Fluorination processing method for fluorination object of semiconductor device and fluorination processed component

Abstract

The present invention relates to a fluorination processing method for a fluorinated object of a semiconductor device and a component fluorinated by this method. That is, the fluorinated object can be fluorinated by exciting a fluorination gas into plasma, thereby achieving high density and high strength, and at the same time, plasma contamination particles can be significantly reduced during fluorination coating.

Description

Technical Field

[0001] The present invention relates to a method for fluorinating a fluorinated object of a semiconductor device and a component fluorinated by the method. More specifically, the present invention relates to a method for fluorinating a fluorinated object of a semiconductor device and a component fluorinated by the method, wherein the fluorinating object can be fluorinated by exciting a fluorinated gas into plasma, thereby achieving high density and high strength. At the same time, the plasma contamination particles can be significantly reduced by controlling the F composition rate in a specific range in the surface layer, and the productivity can be significantly improved by shortening the aging performed in the debugging step. The method is particularly suitable for the normal etching rate of large-area semiconductor devices. Background Art

[0002] After semiconductor dry etching equipment in semiconductor equipment is shut down for regular equipment inspection or component replacement (maintenance), it must undergo a back-up process before restarting the equipment to enable normal operation of the semiconductor manufacturing equipment.

[0003] In semiconductor dry etching equipment, the back-up process is carried out through the following steps: removing gaseous contamination such as moisture from the equipment (out-gasing); reducing contamination factors (particles) within the equipment; aging the fluorination equipment; and using mass-produced wafers for sample quality testing (in the factory database In Fab.Data).

[0004] Among them, an aging process will be accompanied to form a fluorinated atmosphere inside the semiconductor dry etching equipment that can achieve a normal etching rate. This aging process allows a specified level of corrosive gas to adhere to the surface of the plasma-resistant coating (Al2O3, Y2O3, YAG, etc.) installed inside the equipment, thereby arbitrarily forming a fluorinated layer with a yttrium oxyfluoride (YOF) component of several nm to several hundred nm on the surface.

[0005] If a fluorinated atmosphere is not sufficiently formed inside the semiconductor dry etching equipment, the operating time of the semiconductor equipment will be greatly reduced as the time of repeated aging processes increases, which may lead to a decrease in the productivity of the semiconductor equipment and an increase in manufacturing costs.

[0006] On the other hand, as an example of a conventional method for forming a fluorinated layer, there is a known method in which a component to be fluorinated is placed in a vacuum chamber and a low-pressure vacuum plasma containing fluorine-containing gases such as CF4, SF6, and NF3 is generated, thereby fluorinating the surface by fluorine-containing radicals ("Fabrication, characterization, and fluorine-plasma exposure behavior of dense yttrium oxyfluoride ceramic", T Tsunoura et al, Japanese Journal of Applied Physics 56, 06HC02(2017), "Fluorination mechanisms of Al2O3and Y2O3 surfaces irradiated by high-density CF4 / O2 and SF6 / O2 plasmas", K Miwa et al, J Vac Sci Technol A 27(4), Jul / Aug 2009).

[0007] However, this method has the following disadvantages: since it requires the construction of a vacuum tank and vacuum equipment, it is not conducive to mass production and has low economic efficiency. Moreover, since a low-pressure plasma process is used, the density of fluorine-containing free radicals is low, resulting in a slow fluorination rate, thereby reducing productivity.

[0008] As another example, there is a known method of fluorinating the surface of a part to be fluorinated by immersing it in a solution of HF, SF4, CHF3, etc. and then raising the temperature to ~250°C ("Preparation of Fluorinated-Alumina", E. Kemnitz et al, "Efficient Preparations of Fluorine Compounds", Edited by H. W. Roesky, 2013, 442).

[0009] However, this method has the disadvantage that it is disadvantageous in terms of process safety because hazardous solutions are used during operation and handling.

[0010] As another example, U.S. Patent No. 8,206,829 and / or U.S. Patent Publication No. US2017 / 0114440 disclose methods for coating a component surface with powder materials such as AlF3, YF3, AlOF, and YOF by plasma spraying or the like.

[0011] However, the raw material price of AlF3 or YF3, which is the coating raw material for coating ceramic protective films such as aluminum oxide (Al2O3) or yttrium oxide (Y2O3), is very high, and the limited number of raw material suppliers leads to poor supply, so there is a problem of low economy. In addition, there is a problem that relatively more plasma particles are generated during fluorination coating, thereby reducing the reliability of the fluorination coating. Summary of the Invention

[0012] Technical issues

[0013] Therefore, the purpose of the present invention for solving the above-mentioned problems is to provide a fluorination processing method for a fluorinated object of a semiconductor device and a component fluorinated by this method, which minimizes the generation of contamination particles. That is, the fluorination object can be fluorinated by exciting the fluorination gas into plasma, thereby achieving high density and high strength. At the same time, the plasma contamination particles can be significantly reduced by the F composition rate in a specific range in the surface layer, and the productivity can be significantly improved by shortening the aging performed in the debugging step. It is particularly suitable for the normal etching rate of large-area semiconductor equipment.

[0014] Furthermore, another object of the present invention is to provide a fluorination processing method for a fluorination object of a semiconductor device and a component fluorinated by this method, which minimizes the generation of contamination particles. That is, by adjusting parameters according to various process environments or conditions, a specific range of F composition can be formed in the surface layer, thereby significantly reducing plasma contamination particles.

[0015] The technical problems of the present invention are not limited to the above-mentioned contents, and those skilled in the art can clearly understand other technical problems not mentioned from the following description.

[0016] Technical Solution

[0017] According to one aspect of the present invention for achieving the above-mentioned purpose and other features of the present invention, a fluorination processing method for a fluorinated object is provided, which is used for fluorinating the surface of the fluorinated object, and comprises: a first step of placing the fluorinated object in a processing chamber having a plasma reaction space; a second step of introducing a working gas into the processing chamber, wherein the working gas is a discharge gas selected from He, Ne, Ar, Kr, and Xe, a non-fluorine reaction gas selected from O2, N2, and air, a fluorine-containing fluorocarbon gas selected from CF4, C2F6, C4F8, or a nitrogen trifluoride (NF3) gas; A mixed gas of fluorine reaction gas, i.e., the mixed gas is introduced into the above-mentioned processing chamber; a third step is to introduce the mixed gas introduced into the above-mentioned processing chamber into the above-mentioned plasma reaction space; and a fourth step is to generate plasma in the above-mentioned plasma reaction space by applying high-frequency power to the above-mentioned processing chamber, and fluorinate the surface of the above-mentioned fluorination object with the generated fluorine-containing free radical gas and plasma, thereby forming a fluorinated modified layer, wherein the F component in the YOF of the surface layer forming the above-mentioned fluorinated modified layer is 1 atomic percentage to 10 atomic percentages.

[0018] Effects of the Invention

[0019] The fluorination method of a fluorination target object of a semiconductor device and the component fluorinated by the method according to the present invention provide the following effects.

[0020] First, the effect of the present invention is to provide a new concept component fluorination technology, that is, taking the plasma-resistant coating installed in semiconductor dry etching equipment as the target, the component can be fluorinated using high-frequency plasma with specific process factors under normal temperature and atmospheric pressure.

[0021] Second, the present invention has the effect of significantly reducing plasma contamination particles.

[0022] Thirdly, the present invention has the effect that productivity can be improved by shortening the aging step which is one of the debugging processes performed in semiconductor dry etching equipment.

[0023] Fourthly, the present invention has the effect of achieving high density and high strength, being applicable to large-area components, while relatively reducing costs, and improving productivity by increasing the speed of fluorination (process) performed in the aging step. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a flow chart showing the fluorination method of the fluorination object of the present invention.

[0025] Figure 2The present invention provides a graph showing experimental results related to the flow ratio of Ar, O2, and CF4 (Ar:O2:CF4) used as gases in the fluorination processing method of the fluorination object of the present invention, including a graph showing a scanning electron microscope image (a) of the surface layer of the fluorination object with respect to the flow ratio of Ar and a bar graph (b) showing the content of F and Al components.

[0026] Figure 3 The present invention provides a graph showing experimental results related to the flow ratio of Ar, O2, and CF4 (Ar:O2:CF4) used as gases in the fluorination processing method of the fluorination object of the present invention, including a graph showing a scanning electron microscope image (a) of the surface layer of the fluorination object with respect to the flow ratio of O2 and a bar graph (b) showing the content of F and Al components.

[0027] Figure 4 The present invention provides a graph showing experimental results related to the flow ratio of Ar, O2, and CF4 (Ar:O2:CF4) used as the gases in the fluorination processing method of the fluorination object of the present invention, including a graph showing a scanning electron microscope image (a) of the surface layer of the fluorination object with respect to the flow ratio of CF4 and a bar graph (b) showing the contents of F and Al components.

[0028] Figure 5 The figures show experimental results related to high-frequency power in the fluorination processing method of the fluorination object of the present invention, which are figures showing a scanning electron microscope image (a) of the surface layer of the fluorination object and a bar graph (b) of the content of F and Al components in relation to plasma power.

[0029] Figure 6 These are diagrams showing experimental results related to the temperature of a fluorinated object in the fluorination method of the present invention, and are diagrams showing a surface layer scanning electron microscope image (a) and a histogram (b) showing the contents of F and Al components with respect to temperature.

[0030] Figure 7 The present invention provides a diagram showing experimental results related to the step of introducing a mixed gas and the number of repetitions of the fluorination step in the fluorination processing method of the fluorination object of the present invention, including a diagram showing a scanning electron microscope image (a) of the surface layer of the fluorination object and a bar graph (b) showing the content of F and Al components with respect to the number of repetitions.

[0031] Figure 8 The figures show experimental results related to the distance between the fluorinated object (base material) and plasma in the fluorination processing method of the fluorinated object of the present invention, and are figures showing a scanning electron microscope image (a) of the surface layer of the fluorinated object with respect to the distance and a bar graph (b) of the content of F and Al components.

[0032] Figure 9 This is a table showing cross-sectional images and component analysis of a fluorinated object related to the temperature factor in the fluorination method of the fluorinated object of the present invention.

[0033] Figure 10 This is a table showing cross-sectional images and component analysis of a fluorinated object in relation to the number of repetitions in the fluorination method of the present invention.

[0034] Figure 11 This is a table showing cross-sectional images and component analysis of a fluorinated object related to the power factor in the fluorination method of the fluorinated object of the present invention.

[0035] Figure 12 This is a table showing the X-ray photoelectron spectroscopy analysis of the fluorinated object in relation to the content of the F component in the fluorination method of the fluorinated object of the present invention.

[0036] Figure 13 This is a table showing transmission electron microscope images and component analysis of fluorinated objects related to the content of the F component in the fluorination method of the fluorinated object of the present invention.

[0037] Figure 14 This is a bar graph showing the hardness analysis of the fluorinated object in relation to the content of the F component in the fluorination method of the fluorinated object of the present invention.

[0038] Figure 15 The graph shows the chemical resistance evaluation of the fluorinated object in a hydrogen chloride (HCl) solution in relation to the content of the F component in the fluorination method of the fluorinated object of the present invention.

[0039] Figure 16 This is a schematic diagram illustrating a method of exposing a fluorinated object to which the fluorination method of the present invention is applied to a plasma containing a corrosive gas containing an F component and measuring the number of contaminant particles changing with time in real time.

[0040] Figure 17 The photographs show the fluorinated objects of Examples and Comparative Examples before and after being exposed to plasma according to the F component content.

[0041] Figure 18 This is a bar graph showing the total number of contaminant particles of the fluorinated object according to the F content after exposure to the plasma of the corrosive gas containing the F component in the present invention.

[0042] Figure 19 This is a line graph showing in real time the number of contaminant particles of the fluorinated object depending on the F component content during exposure to the plasma of the corrosive gas containing the F component.

[0043] Figure 20 This is a table showing the results of X-ray photoelectron spectroscopy analysis of the F component content before exposure to plasma containing a corrosive gas containing a F component in the present invention.

[0044] Figure 21 This table shows the atomic bonding state by analyzing the binding energy equivalent to the Y3d orbital function at different depths from the surface to the inside of the fluorinated object based on the F component content before exposure to the plasma of the F component-containing corrosive gas in the present invention.

[0045] Figure 22 The table shows the results of X-ray photoelectron spectroscopy analysis of the F component content after exposure to plasma of a corrosive gas containing the F component.

[0046] Figure 23 and Figure 24 This is a table showing transmission electron microscope images and diffraction patterns of the F component content before and after exposure to plasma containing a corrosive gas containing a F component in the present invention.

[0047] Description of Reference Signs

[0048] S100: Fluoridation object placement step

[0049] S200: Mixed gas introduction step

[0050] S300: Mixed gas introduction step

[0051] S400: Fluorination step DETAILED DESCRIPTION

[0052] Other objects, features and advantages of the present invention will be more clearly understood from the following detailed description and accompanying drawings.

[0053] Hereinafter, a fluorination method for a fluorination object of a semiconductor device according to a preferred embodiment of the present invention and a component fluorinated by the method will be described in detail with reference to the accompanying drawings.

[0054] refer to Figure 1 The fluorination processing method of the fluorination object of the semiconductor device of the present invention will be described in detail.

[0055] Figure 1 This is a flow chart showing the fluorination method of the fluorination object of the present invention.

[0056] like Figure 1As shown, the fluorination processing method of the fluorination object of the present invention is a processing method for fluorinating the surface of a fluorination object including components used in semiconductor processes, and generally includes a fluorination object placement step S100, a mixed gas introduction step S200, a mixed gas introduction step S300 and a fluorination step S400.

[0057] Specifically, if Figure 1 As shown, the fluorination processing method of the fluorination object of the present invention is used to fluorinate the surface of the fluorination object including components used in semiconductor processes, which includes: a first step S100 as a fluorination object placement step, in which the fluorination object is placed facing the plasma jet outlet in a processing chamber of a fluorination processing device having a plasma jet outlet and a plasma reaction space; a second step S200 as a mixed gas introduction step, in which a working gas is introduced into the processing chamber, wherein the working gas is a discharge gas selected from He, Ne, Ar, Kr, and Xe, a non-fluorine reaction gas selected from O2, N2, and air, a fluorine-containing fluorocarbon gas selected from CF4, C2F6, C4F8, or a fluorine-containing reaction gas selected from nitrogen trifluoride (NF3) gas, and a mixed gas thereof. The mixed gas is introduced into the processing chamber; in the third step S300 as a mixed gas introduction step, the mixed gas introduced into the processing chamber is introduced into the plasma reaction space; and in the fourth step S400 as a fluorination step, plasma is generated in the plasma reaction space by applying high-frequency power to the metal electrode rod in the processing chamber, and the generated fluorine-containing free radical gas and plasma are sprayed toward the fluorination object through the plasma jet outlet to fluorinate the surface of the fluorination object, thereby forming a fluorination modified layer. In the first step S100 to the fourth step S400, the atmosphere in the processing chamber is formed into an atmospheric pressure atmosphere, and the third step S300 and the fourth step S400 are performed more than once and less than 10 times.

[0058] In the present invention, the F component in the YOF forming the surface layer of the fluorinated modified layer is formed within a specific composition ratio range: 1 to 10 atomic percent, preferably 2 to 9 atomic percent, and more preferably 3 to 7 atomic percent. The inventors of the present invention have confirmed through repeated experiments that this F composition ratio significantly reduces the generation of plasma contamination particles. This will be described later.

[0059] Furthermore, in the fluorination processing method, the composition of the above-mentioned F component can be formed by adjusting parameters (gas flow ratio, plasma intensity (high-frequency power intensity), chamber atmosphere, chamber temperature, etc.) according to various process environments or conditions.

[0060] The fluorination object placement step S100 as the first step is a process of placing the fluorination object facing the plasma jet outlet in a processing chamber having a plasma jet outlet and a plasma reaction space, and placing the fluorination object to be fluorinated on the upper part of a bracket (a bracket having a heater) located inside the processing chamber, and isolating the inside from the outside by closing the door of the processing chamber.

[0061] For example, the fluorination processing device with a processing chamber used in the above-mentioned fluorination object placement step S100 may include: a metal electrode rod, the surface of which is insulated by an insulator; a non-conductive ceramic tube, which is coaxially arranged with the above-mentioned metal electrode rod and forms a gap with the above-mentioned metal electrode rod and extends; a grounding conduit, which is a grounding conduit that extends around the outer circumference of the above-mentioned non-conductive ceramic tube and is electrically grounded, and the inner circumference of the above-mentioned grounding conduit is in contact with the above-mentioned non-conductive ceramic tube as a whole; and a plasma jet head module, which forms an annular space portion between the outer circumference of the above-mentioned metal electrode rod and the inner circumference of the above-mentioned non-conductive ceramic tube, extending along the length direction, and the open part at the lower end of the above-mentioned annular space portion becomes a plasma reaction space with a plasma jet outlet.

[0062] Furthermore, the processing chamber may include: a high-frequency power supply device, which applies high-frequency power to the metal electrode rod and is connected to the metal electrode rod via a high-frequency matcher for impedance matching; a gas supply portion, which supplies a working gas including a fluorine-containing reaction gas to the plasma reaction space; and a sample holder, which is arranged at the lower end of the plasma jet outlet and places the sample.

[0063] The upper part of the above-mentioned plasma injection head module is fixed on the upper part of this processing chamber. The above-mentioned metal electrode rod is formed in the form of passing through the above-mentioned gas introduction chamber and extends vertically downward. The upper end is connected to the above-mentioned high-frequency matcher. The upper end of the above-mentioned non-conductor ceramic tube is located in the above-mentioned gas introduction chamber and extends downward along the length direction to introduce the used gas from the above-mentioned gas introduction chamber into the above-mentioned plasma reaction space.

[0064] Then, the mixed gas introduction step S200 as the above-mentioned second step is a process of introducing the working gas into the above-mentioned processing chamber, and the above-mentioned working gas is a discharge gas selected from He, Ne, Ar, Kr, Xe, a non-fluorine reaction gas selected from O2, N2, and air, a mixed gas selected from fluorine-containing fluorocarbon gases such as CF4, C2F6, C4F8, or a fluorine-containing reaction gas in nitrogen trifluoride (NF3) gas, that is, a process of introducing the above-mentioned mixed gas into the above-mentioned processing chamber.

[0065] In the mixed gas introduction step S200, argon (Ar) gas as a discharge gas, oxygen (O2) as a non-fluorine reaction gas, and carbon tetrafluoride (CF4) as a fluorine-containing reaction gas are used as working gases and introduced into the processing chamber from the gas tanks of the gas supply unit.

[0066] In this case, the introduced working gas is introduced into the processing chamber by adjusting the flow ratio of the mixed gas through the gas flow regulator, and the mixed gas is introduced into the above-mentioned plasma reaction space through the mixed gas introduction step S300 as the above-mentioned third step.

[0067] In addition to Ar gas, the discharge gas may also include inert gases such as He, Ne, Ar, Kr, and Xe. Furthermore, in addition to oxygen (O2) gas, non-fluorine-containing reaction gases may include nitrogen (N2) or air. Furthermore, in addition to CF4 gas, fluorine-containing reaction gases may include fluorine-containing fluorocarbon gases such as C2F6 and C4F8, or nitrogen trifluoride (NF3) gas. However, in the present invention, preferably, the discharge gas is argon (Ar) gas, the non-fluorine-containing reaction gas is oxygen (O2), and the fluorine-containing reaction gas is carbon tetrafluoride (CF4).

[0068] Furthermore, in the mixed gas introduction step S200, the flow ratio of Ar, O2, and CF4 used as the working gas (Ar:O2:CF4) is 0.1-60:0.1-10:0.1-10, preferably 25-40:0.1-0.4:0.3-1.0.

[0069] The inventors of the present invention have experimentally confirmed that the flow ratio of Ar, O2, and CF4 (Ar:O2:CF4) used as the working gas through the fluorinated coating of the present invention is the optimal ratio, and plasma contamination particles are significantly reduced.

[0070] For the flow ratio experiment

[0071] Figures 2 to 4 This is a diagram showing experimental results related to the flow rate ratio (Ar:O2:CF4) of Ar, O2, and CF4 used as gases in the fluorination processing method of the fluorination object of the present invention. Figure 2 Graphs showing (a) a scanning electron microscope image of the surface layer of a fluorinated object and (b) a bar graph of the contents of F and Al components relative to the Ar flow rate ratio. Figure 3 Graph showing a scanning electron microscope image (a) of the surface layer of a fluorinated object and a histogram (b) of the contents of F and Al components in relation to the O2 flow rate ratio. Figure 4 Graphs showing a scanning electron microscope image (a) of a surface layer of a fluorinated object and a histogram (b) of the contents of F and Al components in relation to the CF4 flow rate ratio.

[0072] like Figure 2 As shown, the inventors of the present invention have confirmed the existence of the following problems: when the Ar flow ratio is greater than 40, a small amount of particles (P / C: particle) are generated, and especially when it is greater than 60, particles are significantly generated, and when the Ar flow ratio is less than 0.1, the plasma is unstable and unsuitable. In particular, when the Ar flow ratio is within 25, the plasma is stable, and based on this, the fluorination object can be optimally fluorinated.

[0073] And, as Figure 3 As shown in FIG, it is confirmed that there is a problem that when the flow rate ratio of O2 is greater than 0.4, a small amount of particles are generated, and in particular, when the flow rate ratio is greater than 10, particles are significantly generated, and as shown in FIG. Figure 4 As shown, when the flow rate ratio of CF4 is greater than 1.0, a small amount of particles are generated. In particular, when the flow rate ratio is greater than 10, particles are significantly generated, so it is not suitable.

[0074] Then, the fluorination step S400 is a process of applying high-frequency power to the metal electrode rod arranged in the processing chamber to generate plasma in the plasma reaction space, and spraying the generated fluorine-containing free radical gas and plasma toward the fluorination object through the plasma jet outlet to fluorinate the surface of the fluorination object.

[0075] In the fluorination step S400 of the present invention, the frequency of the high-frequency power applied by the high-frequency power supply device is preferably 1 MHz to 100 MHz, and the high-frequency power is preferably 300 W to 400 W.

[0076] Figure 5 The figures show experimental results related to the high-frequency power in the fluorination processing method of the fluorination object of the present invention. Part (a) is a figure showing a scanning electron microscope image of the surface layer of the fluorination object, and part (b) is a figure showing a bar chart of the content of F and Al components.

[0077] like Figure 5 As shown, it was confirmed that there was a problem that, in the fluorination step S400 , when the power of the applied high-frequency power source was less than 100 W or greater than 1000 W, particles were generated and the plasma became unstable, which was not suitable.

[0078] On the other hand, in the fluorination method of the present invention, the temperature in the processing chamber, that is, the temperature at which the fluorination object is heated, is preferably 400° C. or lower at room temperature. Figure 6These are graphs showing experimental results related to the temperature of the fluorinated object in the fluorination processing method of the fluorinated object of the present invention. Part (a) is a graph showing a scanning electron microscope image of the surface layer of the fluorinated object, and part (b) is a graph showing a bar chart of the contents of F and Al components.

[0079] It was confirmed that the method for fluoriding a fluorided object of the present invention is not suitable because the coating peels off or separates from the fluorided object when the temperature at which the fluorided object is heated exceeds 400°C.

[0080] Furthermore, in the fluorination method of the fluorinated object of the present invention, the mixed gas introducing step S300 and the fluorination step S400 are preferably repeated one or more times.

[0081] Figure 7 The figures show experimental results related to the introduction step of the mixed gas and the number of repetitions of the fluorination step in the fluorination processing method of the fluorination object of the present invention. Part (a) is a figure showing a scanning electron microscope image of the surface layer of the fluorination object, and part (b) is a figure showing a bar chart of the content of F and Al components.

[0082] Among these, when the mixed gas introduction step and the fluorination step performed when the number of repetitions is one or more is regarded as one cycle, it is preferable that the maintenance time between cycles is 60 seconds to 10 minutes.

[0083] On the other hand, the inventors of the present invention have confirmed that the distance between the fluoridation object and the plasma in the processing chamber is an important process factor in the fluoridation processing method of the present invention. The distance between the fluoridation object and the plasma is the distance from the surface of the fluoridation object to the inlet of the plasma injection port.

[0084] Figure 8 These are figures showing experimental results related to the distance between the fluoridation object (base material) and plasma in the fluoridation processing method of the fluoridation object of the present invention. Part (a) is a figure showing a scanning electron microscope image of the surface layer of the fluoridation object, and part (b) is a figure showing a bar chart of the content of F and Al components.

[0085] In the fluorination method of the fluorination object of the present invention, the distance between the fluorination object and the plasma is preferably 1 mm or more and 50 mm or less.

[0086] The inventors of the present invention have confirmed the following problem: when the distance between the fluorination object and the plasma is less than 1 mm, particles are generated and discharge is difficult. When the distance is greater than 50 mm, a large-capacity high-frequency power supply device is required to increase the discharge voltage, but this leads to increased costs and is therefore not suitable.

[0087] In the fluorination method of the fluoridation object of the present invention, the thickness of the fluoridation coating layer of the fluoridation object is preferably 0.001 μm to 10 μm.

[0088] On the other hand, the inventors of the present invention evaluated the process factors (power, temperature, number of repetitions) that can form a fluorinated layer by reacting a Y2O3 coating prepared by atmospheric plasma spraying with F as a corrosive gas.

[0089] The surface of the Y2O3 coating prepared by atmospheric plasma spraying uses particle powder of several tens of μm as raw material, and therefore has a surface roughness of several μm. In order to correctly confirm the surface fine structure and composition changes caused by the fluorination reaction layer after fluorination modification, the surface is mirror polished to 0.1 μm, and the fluorination processing method of the present invention (new process for fluorination modification of coating) is applied.

[0090] In order to confirm the cross-sectional fine structure changes, reaction depth and distribution of the fluorination layer of the Y2O3 coating prepared by the atmospheric plasma spraying method applying the fluorination processing method of the present invention, the coating was processed with a focused ion beam, observed with a scanning electron microscope, and the content of the F component was analyzed by energy dispersive spectroscopy.

[0091] Furthermore, high-resolution X-ray diffraction analysis was performed to confirm the crystal phase change caused by the reaction of the Y2O3 coating prepared by atmospheric plasma spraying with the F component as a corrosive gas.

[0092] Figure 9 This is a table showing cross-sectional images and component analysis of a fluorinated object related to the temperature factor in the fluorination method of the fluorinated object of the present invention.

[0093] First, the fine structure of the cross section of a Y2O3 coating prepared by atmospheric plasma spraying and subjected to surface mirror polishing was analyzed. It was confirmed that almost no micropores were observed on the surface, but there were some scratches caused by mirror polishing. The Y, O, and C components were detected, and the contents of Y, O, and C were 27 atomic percent, 58 atomic percent, and 15 atomic percent, respectively.

[0094] Furthermore, observation of the fine structure within the processed coating using a focused ion beam revealed some vertical cracks due to typical volume shrinkage during atmospheric plasma spray coating. However, energy dispersive spectroscopy analysis and mapping to confirm the compositional distribution within the coating revealed that the Y and O components were uniformly distributed overall.

[0095] On the other hand, in the fluorination processing method of the fluorination object of the present invention, in order to confirm the fluorination layer generation trend of the fluorination object with respect to the temperature factor, the temperature is changed to 100°C, 250°C, and 350°C to perform the fluorination processing method of the present invention on the Y2O3 coating prepared by the atmospheric plasma spraying method, thereby forming a fluorination layer.

[0096] The results of observing the surface fine structure of the coating after applying the fluorination processing method of the present invention confirmed that it showed the same fine structure as the Y2O3 coating prepared by atmospheric plasma spraying before the application of the fluorination processing method. Therefore, there was no change in the fine structure caused by fluorination modification. On the contrary, it can be confirmed that the coating composition contains an additional F component in addition to Y, O, and C components. This component increases proportionally with the increase in temperature and exists in a distribution of 3 atomic percent to 7 atomic percent. Therefore, a YOF fluorination layer is effectively formed on the coating surface.

[0097] Furthermore, as a result of observing the fine structure inside the processed coating using a focused ion beam, no YOF fluoride layer was clearly confirmed near the surface of the coating, but the results of mapping using energy dispersion spectroscopy confirmed the presence of a color equivalent to the F component inside the coating, and that as the temperature increased, the color near the surface became brighter than that inside. As mentioned above, this is consistent with the trend that the F component content on the coating surface increases to 3 atomic percent, 5 atomic percent, and 7 atomic percent as the temperature increases.

[0098] Figure 10 This is a table showing cross-sectional images and component analysis of a fluorinated object in relation to the number of repetitions in the fluorination method of the present invention.

[0099] Then, in order to confirm the trend of fluorination layer formation of the fluorination object with respect to the number of repetitions, the temperature factor is fixed at 350°C, and the number of repetitions is changed to 1, 5, and 10 times to perform the fluorination processing method of the present invention (new process for fluorination modification of coating) on ​​the Y2O3 spray coating prepared by atmospheric plasma spraying, thereby forming a fluorination layer.

[0100] The results of observing the fine structure inside the processed coating using a focused ion beam showed that, similar to the previous evaluation of the temperature factor, no YOF fluorination layer of the fluorinated object was clearly confirmed. However, mapping using energy dispersive spectroscopy analysis showed the presence of a color equivalent to the F component inside the coating. As the number of repetitions increased, the color brightness became more clearly distinguished on the surface, and the reaction of the F component occurred more actively, with the content increasing to a maximum of 12 atomic percent.

[0101] This is because, as the number of repetitions increases, the amount of F components diffused on the coating surface also increases as the coating surface is exposed to dissociated F ions for an increased time, thereby increasing the F content.

[0102] Figure 11 This is a table showing cross-sectional images and component analysis of a fluorinated object related to the power factor in the fluorination method of the fluorinated object of the present invention.

[0103] The temperature is fixed at 350°C and the number of repetitions is fixed at 10 times, and the power factor is increased to 300W to 400W to perform the fluorination processing method of the present invention (new coating fluorination modification process) on the atmospheric plasma Y2O3 spray coating to form a fluorinated layer.

[0104] As the power increases, the F content increases to a maximum of 15 atomic percent. However, similar to the evaluation of temperature and repetition factors, the YOF fluorination layer of the fluorinated object is not clearly confirmed. However, the presence of a color equivalent to the F component inside the coating mapped by energy dispersion spectroscopy analysis shows that the color brightness is clearly distinguished on the surface as the power increases.

[0105] This is also because, with the increase of power, the decomposition of F-based corrosive gas is further accelerated, resulting in an increase in the density of dissociated F radicals, and thus the reactivity of the coating surface increases, resulting in an increase in the F content.

[0106] Next, the inventors of the present invention used the Y2O3 coating prepared by atmospheric plasma spraying method to measure the changes in temperature, number of repetitions, and power factor through energy dispersive spectroscopy as a benchmark, screened out conditions with F content of 5 atomic percent, 9 atomic percent, and 15 atomic percent, and analyzed the YOF fluorination layer of the fluorinated object by X-ray photoelectron spectroscopy and transmission electron microscopy to confirm the composition changes and thickness at different depths.

[0107] Figure 12 This is a table showing the X-ray photoelectron spectroscopy analysis of the fluorinated object in relation to the content of the F component in the fluorination method of the fluorinated object of the present invention.

[0108] First, X-ray photoelectron spectroscopy is used to confirm the change in F content at different depths from the surface to the interior of the coating. Then, the binding energy equivalent to the Y3d orbital function on the surface of the fluorinated object is analyzed to confirm the atomic bonding state.

[0109] By analyzing the changes in the F content at different depths while sputtering in units of a few nm from the surface, it was confirmed that the Y component and O component of the Y2O3 coating prepared by atmospheric plasma spraying before the fluorination processing method were uniformly distributed at 42 atomic percent and 58 atomic percent, respectively.

[0110] In contrast, in the fluorinated object to which the fluorination processing method of the present invention is applied, F components are detected on all coating surfaces, showing maximum values ​​of 33 atomic percent, 44 atomic percent, and 36 atomic percent, respectively, and showing a trend of a sharp decrease until a depth of 100 nm. However, it slowly decreases after a depth of 100 nm, and contents of 5 atomic percent, 9 atomic percent, and 11 atomic percent are confirmed at a depth of about 500 nm.

[0111] The reason for the difference in F content at different depths is that the concentration of F radicals plasma-dissociated at the surface is high, causing a rapid chemical reaction. The F radicals then diffuse into the interior of the coating through micropores and cracks, resulting in a low concentration of F radicals and a slow chemical reaction rate.

[0112] On the other hand, the F content measured by energy dispersive spectroscopy on the coating surface increases with increasing temperature, number and power factor. The results measured by depth profiling are inconsistent with the results measured by energy dispersive spectroscopy. Under the conditions where the F content is measured at 9 atomic percent and 15 atomic percent, it is shown as 44 atomic percent and 36 atomic percent, respectively. However, in the depth profiling results, the slope of the F content under the condition of 15 atomic percent decreases gradually as the coating is deeper, compared with the slope of the F content under the condition of 9 atomic percent measured by energy dispersive spectroscopy, and it is shown as 11 atomic percent at a depth of about 500 nm, which is higher than the value under the condition of 9 atomic percent measured by energy dispersive spectroscopy, which is consistent with the change in the F content measured on the coating surface by energy dispersive spectroscopy.

[0113] As mentioned above, the difference in the content of F components based on this analysis method is judged to be due to the fact that the analysis depth of the EDS is relatively deep, with a minimum range of 1μm, while the analysis depth of X-ray photoelectron spectroscopy (XPS) is about 1nm, which is used to analyze the composition of the local surface. In addition, the results of the analysis of the Y3d orbital function of the Y2O3 coating prepared by the atmospheric plasma spraying method showed that two peaks corresponding to the YO single bond were confirmed at 158.5eV and 156.7eV. This is consistent with the following report that the total binding energy of the Y3d orbital function constitutes a pair of peaks caused by the Y3d. 5 / 2 With Y3d 3 / 2 The two binding energies have an intensity ratio of 3:2, and the binding energy difference is 2eV.

[0114] In addition, the results of analyzing the atmospheric plasma Y2O3 spray coating that applied the fluorination processing method to form a YOF fluorination layer showed that four peaks could be confirmed in all Y3d orbital functions. Based on the analysis of the Y, O, and F components confirmed by depth analysis and dispersion spectrum, it was confirmed that the two peaks other than the YO bond were YF bonds, which means that the Y2O3 spray coating reacted with the F component to form a YOF fluorination layer and moved to the YF bond with higher binding energy than the YO bond.

[0115] Generally, electronegativity refers to a scale that measures the tendency of an atom to attract electrons to form anions. It is known that the binding energy of an atom with higher electronegativity increases. Since the electronegativity of the F atom is 4, which is higher than the electronegativity of the O atom of 3.5, the binding energy of the YF bond is measured in a higher region compared to the binding energy of the YO bond. Therefore, it can be confirmed that when exposed to the F series corrosive gas plasma, the YO bond is partially decomposed and reacts with the F radical to form a new YF bond, thereby forming a YOF fluorinated layer.

[0116] Figure 13 This is a table showing transmission electron microscope images and component analysis of fluorinated objects related to the content of the F component in the fluorination method of the fluorinated object of the present invention.

[0117] Then, as a result of analyzing the cross-sectional fine structure using a transmission electron microscope (TEM), a color corresponding to the F component was detected in the coating having a YOF fluoride layer slightly thicker than 20 nm on all coating surfaces, showing a difference in brightness with increasing F component content.

[0118] Figure 14 This is a bar graph showing the hardness analysis of the fluorinated object in relation to the content of the F component in the fluorination method of the fluorinated object of the present invention.

[0119] The fluorinated object to which the fluorination processing method of the present invention is applied is compared with the Y2O3 coating prepared by atmospheric plasma spraying before the fluorination processing method is applied. Since the object includes a YOF fluorination layer, the Vickers hardness is measured to confirm the change in hardness with the change in the F component content.

[0120] Compared to the 475 Hv hardness of a Y2O3 coating produced by atmospheric plasma spraying before fluorination, all hardness values ​​measured for the fluorinated object containing the YOF fluoride layer fell within the standard deviation, regardless of the F content. As confirmed by these results, the YOF fluoride layer is very thin, ranging from tens to hundreds of nanometers, indicating that variations in hardness due to varying F content on the surface are minimal.

[0121] Figure 15 The graph shows the chemical resistance evaluation of the fluorinated object in a hydrogen chloride (HCl) solution in relation to the content of the F component in the fluorination method of the fluorinated object of the present invention.

[0122] In the semiconductor dry etching process, chemical etching occurs by generating highly chemically active free radicals to promote chemical reactions with the coating. The time the coating is corroded by hydrochloric acid is evaluated by directly exposing the coating surface to a 5% hydrochloric acid solution, and the corrosion resistance of the coating is evaluated. The standard is selected as 3 hours.

[0123] In this evaluation, similarly, fluorinated objects to which the fluorination processing method is applied were prepared at different contents of the F component and evaluated.

[0124] The results of analyzing the changes in chemical resistance showed that in the fluorinated objects, when the F content of the YOF fluorination layer was 5 atomic percent and 9 atomic percent, and when the Y2O3 coating was prepared by atmospheric plasma spraying before the fluorination processing method was applied, bubbles began to form after 5 hours of reaction with hydrochloric acid. On the contrary, when the F content was the highest at 15 atomic percent, bubbles were formed after more than 6 hours of reaction with hydrochloric acid.

[0125] Therefore, the fact that the reaction time increases by more than 1 hour under the condition where the content of component F is the highest indicates that the resistance to corrosive chemicals increases under the condition where the content of component F is greater than a certain level.

[0126] Experiment to confirm the generation of plasma contamination particles

[0127] On the other hand, the inventors of the present invention have confirmed the generation of plasma contamination particles through experiments.

[0128] Figure 16 This is a schematic diagram illustrating a method of exposing a fluorinated object to which the fluorination method of the present invention is applied to a plasma containing a corrosive gas containing an F component and measuring the number of contaminant particles changing with time in real time.

[0129] The chamber has an inner diameter of 30 cm and a height of 30 cm. The radius between the powered electrode and the grounded electrode is 7.6 cm (= 3 inches). Plasma discharge is generated between the powered and grounded electrodes, with a distance of approximately 10 cm between them. The fluorinated object is prepared by depositing a Y2O3 coating on a 3-inch circular surface using atmospheric plasma spraying. The fluorination process is then performed using an atmospheric pressure high-frequency plasma source. The fluorinated object is then placed on the powered electrode.

[0130] In addition, Ar, CF4, and O2 gases were used as plasma to generate contaminant particles. 5sccm, 30sccm, and 25sccm of Ar, CF4, and O2 gases were supplied through a nozzle equipped with a mass flow meter. Magnets were inserted into the powered electrodes to increase the density of the plasma. A dry vacuum pump and a turbo pump were used to create a vacuum for approximately 60 minutes at an RF input current of 150W and an operating pressure of 300mTorr.

[0131] A light scattering sensor attached to the exhaust pipe measures the contaminant particles generated in the fluorinated object during etching by the corrosive gas containing the F component and the plasma in real time according to the plasma exposure time. Based on the principle of laser light scattering, the amount and number of contaminant particles larger than 0.2μm can be measured.

[0132] Figure 17 The photographs show the fluorinated objects of Examples and Comparative Examples before and after being exposed to plasma according to the F component content.

[0133] It was confirmed that after exposure to plasma, the color of the fluorinated object darkened depending on the arrangement of magnets inserted into the power supply electrodes to increase the plasma density.

[0134] Figure 18 This is a bar graph showing the total amount of contaminant particles of the fluorinated object according to the F content after exposure to the plasma of the corrosive gas containing the F component in the present invention.

[0135] First, in a comparative example of a Y2O3 coating prepared by atmospheric plasma spraying before the fluorination process, a total of 152 ea / cm2 was measured after 60 minutes of exposure to the plasma. 3 However, in Example 1, which is a fluorinated object to which the fluorination processing method is applied, a total of 115 ea / cm 3 The minimum number of contaminant particles represents a reduction rate of approximately 23.3%.

[0136] On the contrary, in Examples 2 and 3, the number of pollutant particles gradually increased and totaled 167 ea / cm 3 、419ea / cm 3 , which is similar to or produces more contamination particles than the Y2O3 coating prepared by atmospheric plasma spraying before the application of the fluorination processing method.

[0137] Figure 19 This is a line graph showing in real time the number of contaminant particles of the fluorinated object depending on the F component content during exposure to the plasma of the corrosive gas containing the F component.

[0138] First, it was confirmed that the Y2O3 coating (comparative example) prepared by atmospheric plasma spraying before the fluorination process was applied gradually increased the number of contaminant particles within 60 minutes after exposure to the plasma containing the corrosive gas containing the F component, reaching a total of 152 ea / cm 3 In the comparative example of the fluorinated object to which the fluorination processing method of the present invention is applied, a similar trend as that of the Y2O3 coating prepared by the atmospheric plasma spraying method is shown within 10 minutes, but the slope begins to decrease after 10 minutes and decreases to a total of 115 ea / cm within 60 minutes. 3 .

[0139] In contrast, in Example 2, a trend almost identical to that of the Y2O3 coating produced by the atmospheric plasma spraying method was observed within 60 minutes of exposure to the plasma containing a corrosive gas of the F component, and in Example 3, the slope began to increase after 10 minutes and increased rapidly within 30 minutes. This indicates that in fluorinated objects subjected to the fluorination method, the fluorinated layer formed during exposure to the plasma containing a corrosive gas of the F component at a specific F content acts as a protective film that suppresses chemical reactions between ions dissociated from the reaction gas and free radicals.

[0140] Figure 20 This is a table showing the results of X-ray photoelectron spectroscopy analysis of the F component content before exposure to plasma containing a corrosive gas containing a F component in the present invention.

[0141] First, the fluorinated object, before exposure to a plasma containing a corrosive gas containing F, is examined using X-ray photoelectron spectroscopy to determine the variation in F content at different depths from the coating surface. The atomic bonding state is then determined by analyzing the binding energy equivalent to the Y3d orbital function on the surface of the fluorinated object.

[0142] By analyzing the changes in the F content at different depths while sputtering in units of a few nm from the surface, it was confirmed that the Y component and O component of the Y2O3 coating (comparative example) prepared by atmospheric plasma spraying before the fluorination processing method was applied were evenly distributed from the surface to the inside, at 38.4 atomic percent and 59.43 atomic percent, respectively, and the F component was 0 atomic percent and was not detected at all.

[0143] In contrast, in the fluorinated object to which the fluorination processing method of the present invention is applied, F components are detected on all coating surfaces, showing maximum values ​​of 47.3 atomic percent, 59.0 atomic percent, and 50.2 atomic percent, respectively. The F components show a trend of rapid decrease as the coating goes deeper, but slowly decrease after a depth of 200 nm.

[0144] The reason for the difference in F content at different depths is that the concentration of the reaction gas dissociated by plasma and the ions dissociated from free radicals are high on the surface, causing a rapid chemical reaction. The ions then diffuse into the interior through micropores or cracks, causing the ion concentration to decrease, resulting in a slower chemical reaction rate.

[0145] On the other hand, the Y3d orbital function of the Y2O3 coating (comparative example) prepared by atmospheric plasma spraying before the fluorination process was analyzed by depth profiling of the fluorinated object according to the F content before exposure to the plasma of the corrosive gas containing the F component was confirmed to be two peaks corresponding to the YO bond at binding energies of 156.3 eV and 158.3 eV. It was confirmed that this is consistent with the following report that the total binding energy of the Y3d orbital function constitutes a pair of peaks caused by the Y3d 5 / 2 With Y3d 3 / 2 The two binding energies have a ratio of 3:2 and a binding energy difference of 2eV.

[0146] Furthermore, analysis of the fluorinated object to which the fluorination processing method was applied similarly revealed that four peaks were identified in all Y3d orbital functions. Analysis based on the Y, O, and F components identified by depth profiling and dispersion spectroscopy revealed that two binding energies corresponding to 156.9 eV and 158.1 eV, 157.9 eV and 159.5 eV, and 157.9 eV and 159.56 eV, respectively, were YO bonds forming a pair. The remaining two peaks were YF bonds, indicating that the Y2O3 spray coating reacted with the reaction gas in the plasma containing the corrosive gas of the F component and with ions dissociated from free radicals, etc., to form a YOF fluorination layer, and then moved to the YF bond having a higher binding energy than the YO bond.

[0147] Generally, electronegativity is a measure of the tendency of an atom to attract electrons to form anions. It is known that the binding energy of an atom with higher electronegativity increases. Since the electronegativity of the F atom is 4, which is higher than the electronegativity of the O atom of 3.5, the binding energy of the YF bond is measured in a higher region compared to the binding energy of the YO bond. Therefore, it can be demonstrated that when exposed to a plasma containing a corrosive gas containing an F component, the YO bond is decomposed and reacts with the reactive gas and ions dissociated from free radicals to form a new YOF fluorination layer.

[0148] Figure 21 This table shows the atomic bonding state by analyzing the binding energy equivalent to the Y3d orbital function at different depths from the surface to the inside of the fluorinated object based on the F component content before exposure to the plasma of the F component-containing corrosive gas in the present invention.

[0149] By analyzing the changes in the binding energy corresponding to the Y3d orbital function while sputtering in units of a few nm from the surface, it was confirmed that the surface of the Y2O3 coating (comparative example) prepared by atmospheric plasma spraying before the fluorination processing method was applied had no change in binding energy to a depth of 1000 nm, but all coatings of the fluorinated object to which the fluorination processing method of the present invention was applied tended to move to lower binding energies from the surface to the inside.

[0150] This is like Figure 19 As described above, it can be confirmed that the fluorinated object to which the fluorination processing method of the present invention is applied shows a trend in which the F component content decreases from the surface to the inside while the O component content relatively increases. If the O component content increases, the concentration of O atoms having lower electronegativity than F atoms increases, so the YO bond is relatively larger than the YF bond, and the binding energy gradually shifts to a lower value.

[0151] Figure 22 The table shows the results of X-ray photoelectron spectroscopy analysis of the F component content after exposure to plasma of a corrosive gas containing the F component.

[0152] Similar to exposure to plasma containing a corrosive gas containing an F component, the change in the F component of the fluorinated object according to the F component content is confirmed at different depths from the coating surface to the inside, and then the atomic bonding state is confirmed by analyzing the binding energy equivalent to the Y3d orbital function on the surface of the fluorinated object.

[0153] By analyzing the changes in the F content at different depths while sputtering in units of a few nm from the surface, it was confirmed that F was detected not only in the Y2O3 coating prepared by the atmospheric plasma spraying method before the fluorination processing method was applied (comparative example), but also in all coatings of the fluorinated objects to which the fluorination processing method of the present invention was applied, and that the F component first decreased sharply and then became slower as it went deeper.

[0154] The reason for the difference in F content at different depths is that the concentration of F radicals dissociated from plasma is high on the surface, causing a rapid chemical reaction. The F radicals then diffuse into the coating through micropores and cracks and penetrate into the coating. Therefore, the low concentration of F radicals slows the chemical reaction rate.

[0155] On the other hand, the results of depth profiling of the Y3d orbital function of the Y2O3 coating (comparative example) prepared by atmospheric plasma spraying before the fluorination processing method was applied to the fluorinated object according to the F component content before exposure to the plasma of the corrosive gas containing the F component showed that in addition to two peaks corresponding to the YO bond at binding energies of 156.6 eV and 158.2 eV, YF bonds at higher binding energies of 159.1 eV and 161.1 eV were also confirmed. This clearly indicates that when exposed to the plasma of the corrosive gas containing the F series components, the YO bond is decomposed and reacts with the ions dissociated in the reaction gas and free radicals to form a new YOF fluorination layer.

[0156] Figure 23 and Figure 24 This is a table showing transmission electron microscope images and diffraction patterns of the F component content before and after exposure to plasma containing a corrosive gas containing a F component in the present invention.

[0157] First, the results of the Y2O3 coating prepared by atmospheric plasma spraying before the fluorination processing method was applied (comparative example) were analyzed. Before exposure to plasma, only single crystals equivalent to Y2O3 with a constant crystal direction were observed, but after exposure to plasma, a triple structure was confirmed, that is, single crystals equivalent to YOF were formed adjacent to the single crystals equivalent to Y2O3, and further, polycrystals equivalent to YOF were observed across the surface.

[0158] On the contrary, in the fluorination object to which the fluorination processing method of the present invention is applied before exposure to plasma, a double structure is confirmed in Examples 1 and 2, that is, a single phase equivalent to YOF is formed adjacent to the single crystal equivalent to Y2O3, but in Example 3, the same as the comparative example after exposure to plasma, a triple structure is confirmed, that is, a single phase equivalent to YOF is formed adjacent to the single crystal equivalent to Y2O3, and further, polycrystals equivalent to YOF are observed beyond the surface.

[0159] On the other hand, after the fluorination object to which the fluorination processing method of the present invention is applied is exposed to plasma, Example 1 maintains a double structure as before exposure to plasma, that is, a single phase equivalent to YOF is formed adjacent to the single crystal equivalent to Y2O3, but Examples 2 and 3 confirm a triple structure as in the comparative example, that is, a single phase equivalent to YOF is formed adjacent to the single crystal equivalent to Y2O3, and further, polycrystals equivalent to YOF are observed beyond the surface.

[0160] Recently, it was discovered that when a Y2O3 bulk is exposed to a plasma containing a corrosive gas containing a fluorine component at a bias voltage of 150V for 120 minutes, it exhibits differential etching across multiple grains, with more etching occurring in certain grain directions. (“Erosion behavior of Y2O3 in fluorine-based etching plasmas: Orientation dependence and reaction layer formation fluorinated-alumina,” MoritzKindelmann et al., Journal of American Ceramistry Society 2021, 104, 1465-1474)

[0161] Therefore, by comparison Figure 18 and Figure 19 If we explain the number of contamination particles mentioned in , Example 1, which does not include a polycrystal corresponding to YOF, shows the smallest number of contamination particles. This indicates that one of the causes of the generation of contamination particles is due to the orientation of the crystal grains.

[0162] On the other hand, in the description of the fluorination processing method of the present invention, it is explained that the atmosphere in the processing chamber in the first step to the fourth step (S100 to S100) is composed of an atmospheric pressure atmosphere, but as mentioned above, if the F component in the YOF surface layer of the fluorinated modified layer has a composition ratio as described above, the atmosphere in the processing chamber is composed of other atmospheres, rather than a vacuum atmosphere or an atmospheric pressure atmosphere, and the composition ratio of the F component in this atmosphere can be achieved by the parameters (gas flow ratio, plasma intensity (high-frequency power intensity), chamber atmosphere, chamber temperature, etc.) according to various process environments or conditions as described above.

[0163] The advantages of the fluorination processing method for the fluorination object of the semiconductor device of the present invention and the components fluorinated by this method as described above are that a new concept component fluorination technology is provided, that is, with the plasma-resistant coating installed in the semiconductor dry etching equipment as the object, the components can be fluorinated by high-frequency plasma with specific process factors under normal temperature and atmospheric pressure conditions, and the plasma contamination particles generated during the fluorination coating can be significantly reduced, thereby improving the reliability of the fluorination coating.

[0164] Furthermore, the advantages of the present invention are that productivity can be improved by shortening the aging step of one of the debugging processes performed in semiconductor dry etching equipment, high density and high strength can be achieved, costs can be relatively reduced while being applied to large-area components, and productivity can be improved by increasing the speed of fluorination (process) performed in the aging step.

Claims

1. A method for fluorinating a fluorinated object, wherein the method is used to fluorinate the surface of the fluorinated object, wherein a Y2O3 coating is formed on the surface by an atmospheric plasma spraying method, wherein: include: In the first step, a fluorinated object is placed in a processing chamber having a plasma reaction space; In the second step, a working gas is introduced into the processing chamber, wherein the working gas is a mixed gas of Ar as a discharge gas, O2 as a non-fluorine reaction gas, and CF4 as a fluorine-containing reaction gas; The third step is to introduce the mixed gas introduced into the processing chamber into the plasma reaction space; as well as In the fourth step, high frequency power is applied to the processing chamber to generate plasma in the plasma reaction space, and the generated fluorine-containing radical gas and plasma are used to fluorinate the surface of the fluorinated object, thereby forming a fluorinated modified layer. In the second step of introducing the mixed gas, the flow ratio of Ar, O2, and CF4 (Ar:O2:CF4) is 0.1-60:0.1-10:0.1-10. In the above fluorination step, the frequency of the high-frequency power supply is 1 MHz to 100 MHz, and the high-frequency power is 300 W to 400 W. In the first to fourth steps above, the atmosphere in the processing chamber is composed of an atmospheric pressure atmosphere. The thickness of the fluorinated coating formed on the fluorinated object is 0.001 μm to 10 μm. In the yttrium oxyfluoride forming the surface layer of the fluorinated modified layer, the F component is 1 to 2 atomic percent.

2. The fluorination method of a fluorinated object according to claim 1, wherein: Repeat the third and fourth steps above.

3. The fluorination method of a fluorinated object according to claim 1, wherein: The distance between the fluorination object and the plasma is 2 mm or more and 5 mm or less. 4 . A component processed by the fluorination processing method for a fluorinated object according to claim 1 .

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