Articles coated with a crack-resistant fluoroannealed film, and methods for producing such articles.

Abstract

The present invention provides articles related to coatings that have excellent plasma etching resistance and can extend the lifespan of RIE components. [Solution] The article comprises a vacuum-compatible substrate and a protective film on at least a portion of the substrate. The film contains a fluorinated metal oxide containing yttrium, and the yttrium oxide is deposited using an AC power supply. The film has at least 10% fluorine atoms at a depth of 30% of the total thickness of the film, and the film does not have subsurface cracks below the surface of the film that are visible when a laser confocal microscope is used to observe the total depth of the film at a magnification of 1000x.

Description

Background Art

[0001] Reactive ion etching (RIE) is an etching technique used in semiconductor manufacturing processes. RIE uses a chemically reactive plasma generated by ionizing a reactive gas (e.g., a gas containing fluorine, chlorine, bromine, oxygen, or a combination thereof) to remove the material deposited on the wafer. However, the plasma erodes not only the material deposited on the wafer but also the components installed inside the RIE chamber. Moreover, the components used to supply the reactive gas into the RIE chamber can also be corroded by the reactive gas. Damage caused to the components by the plasma and / or the reactive gas can result in low production yields, process instability, and contamination.

[0002] Semiconductor manufacturing etch chambers use components coated with a chemically resistant material to reduce degradation of underlying components, to improve etch process consistency, and to reduce particle generation in the etch chamber. Despite being chemically resistant, the coating can be degraded during cleaning and regular maintenance in a corrosive condition where an etchant gas combined with water or other solution creates a corrosive state, e.g., hydrochloric acid. The corrosive condition can shorten the useful life of the coated component and can also lead to etch chamber contamination when the component is reinstalled in the chamber. There is a continuing need for improved coatings for etch chamber components.

Summary of the Invention

[0003] Articles and methods related to a coating having excellent plasma etch resistance and capable of lengthening the life of RIE components are provided. The coating also has minimal to no visible surface cracks on the surface of the coating or visible subsurface cracks within the coating.

[0004] In a first aspect of the present disclosure, an article comprises a substrate and a protective film on at least a portion of the substrate, wherein the film comprises a fluorinated metal oxide containing yttrium, the film has at least 10% fluorine atoms at a depth of 30% of the total thickness of the film, and the film does not have subsurface cracks below the surface of the film that are visible when a laser confocal microscope is used to observe the entire depth of the film at a magnification of 1000x.

[0005] In the second embodiment according to the first embodiment, after fluoroannealing, the film does not have visible surface cracks on its surface when the film surface is observed using a laser confocal microscope at a magnification of 400x.

[0006] In a third embodiment according to the first or second embodiment, the substrate is alumina.

[0007] In the fourth embodiment according to the first or second embodiment, the substrate is silicon.

[0008] In a fifth embodiment according to any of the preceding embodiments, the film has at least 20% fluorine atoms at a depth of 30% of the total thickness of the film.

[0009] In a sixth embodiment according to any of the preceding embodiments, the film has at least 30% of fluorine atoms at a depth of 30% of the total thickness of the film.

[0010] In a seventh embodiment according to any of the preceding embodiments, the film has at least 10% of fluorine atoms at a depth of 50% of the total thickness of the film.

[0011] In the eighth embodiment according to any of the preceding embodiments, the film has at least 20% fluorine atoms at a depth of 50% of the total thickness of the film.

[0012] In the ninth embodiment according to any of the preceding embodiments, the film has at least 30% of fluorine atoms at a depth of 50% of the total thickness of the film.

[0013] In a tenth aspect of the present disclosure, the method comprises depositing a yttrium-containing metal oxide on a substrate using a physical vapor deposition technique with an alternating current (AC) power source, wherein the metal oxide forms a film on the substrate, and fluoroannealing the film, wherein after fluoroannealing, the film has at least 10% fluorine atoms at a depth of 30% of the total thickness of the film.

[0014] In the eleventh aspect according to the tenth aspect, after fluoroannealing, the film does not have visible surface cracks on its surface when the surface of the film is observed using a laser confocal microscope at a magnification of 400x.

[0015] In the twelfth embodiment according to the tenth or eleventh embodiment, after fluoroannealing, the film does not have subsurface cracks below the surface of the film, which are visible when a laser confocal microscope is used to observe the total depth of the film at a magnification of 1000x.

[0016] In the 13th embodiment according to any of the 10th to 12th embodiments, after fluoroannealing, the film has at least 20% fluorine atoms at a depth of 30% of the total thickness of the film.

[0017] In the 14th embodiment according to any of the 10th to 12th embodiments, after fluoroannealing, the film has at least 30% fluorine atoms at a depth of 30% of the total thickness of the film.

[0018] In the 15th embodiment according to any of the 10th to 14th embodiments, after fluoroannealing, the film has at least 20% fluorine atoms at a depth of 50% of the total thickness of the film.

[0019] In the 16th embodiment according to any of the 10th to 14th embodiments, after fluoroannealing, the film has at least 30% fluorine atoms at a depth of 50% of the total thickness of the film.

[0020] In the 17th embodiment according to any of the 10th to 16th embodiments, fluoroannealing is carried out in a fluorine-containing atmosphere at a temperature of about 300°C to about 650°C.

[0021] In the 18th embodiment according to any of the 10th to 17th embodiments, the substrate is alumina.

[0022] In the 19th embodiment according to any of the 10th to 17th embodiments, the substrate is silicon.

[0023] In the 20th aspect, the article is manufactured according to the process of any of the 10th to 19th aspects.

[0024] The above will become apparent from the following more detailed description of exemplary embodiments of the present disclosure, such that similar reference numerals are shown in the accompanying drawings referring to the same parts through different figures. The drawings are not necessarily to a constant scale, and instead, emphasis is made in illustrating embodiments of the present disclosure. [Brief explanation of the drawing]

[0025] [Figure 1] This figure shows a plot of data, with the percentage of fluorine atoms shown on the Y-axis and the depth in microns on the X-axis. [Figure 2] This is a cross-sectional view of the silicon coupon from Example 1 after fluoroannealing, taken by scanning electron microscopy (SEM). [Figure 3] This is a photograph taken using a Keyence laser confocal microscope at a magnification of 1000x, showing multiple surface cracks in a fluorinated yttrium oxide film subjected to condition 10 in Example 1. [Figure 4] This photograph, taken at 1000x magnification using a Keyence laser confocal microscope, shows that there are no surface cracks in the fluorinated yttrium oxide film subjected to condition 10 in Example 2.

Best Mode for Carrying Out the Invention

[0026] The present disclosure will be shown and described in detail with reference to exemplary embodiments of the present disclosure. It will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the present disclosure as encompassed by the appended claims.

[0027] Although various compositions and methods are described, it should be understood that the present disclosure is not limited to the specific molecules, compositions, designs, methodologies or protocols described, as these may vary. Also, the terminology used in the description is for the purpose of describing one or more specific versions only and is not intended to limit the scope of the present disclosure. It should be understood that the scope of the present disclosure is limited only by the appended claims.

[0028] It should also be noted that, as used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural references unless the context clearly indicates otherwise. Thus, for example, a reference to “film” refers to one or more films and their equivalents known to those skilled in the art. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Methods and materials similar to or equivalent to those described herein may be used in the practice or testing of the version of this disclosure. All publications mentioned herein are incorporated in their entirety by reference. Nothing herein should be construed as an acknowledgment that this disclosure is not given priority over any prior disclosure. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes instances in which the event occurs and instances in which the event does not occur. All numerical values ​​in this specification, whether expressly indicated or not, may be modified by the term “about.” The term “about” generally refers to a range of numbers that a person skilled in the art would consider equivalent to (in other words, having the same function or result as) the stated value. In some versions, the term “about” refers to ±10% of the stated value, and in other versions, the term “about” refers to ±2% of the stated value. Compositions and methods are described in terms of “comprising” (to be interpreted as “including but not limiting”) various components or steps, but compositions and methods may also “consist essentially of” various components and steps or “consist of” those components and steps, and such terminology should be interpreted as defining essentially closed groups of components.

[0029] A description of exemplary embodiments of this disclosure follows below.

[0030] Yttria (yttrium oxide) coatings are used on RIE components to provide plasma etching resistance. Such coatings can be applied to RIE components by various methods, including thermal spraying, aerosols, physical vapor deposition (PVD), chemical vapor deposition (CVD), and electron beam evaporation. However, yttria coatings can be corroded by hydrogen chloride (HCl) during maintenance of the RIE chamber and components.

[0031] After a chlorine plasma RIE process, residual chlorine remains on the RIE components. When the components are cleaned with deionized (DI) water during maintenance, the residual chlorine and DI water become HCl, which can corrode the yttria coating and prevent it from protecting the underlying substrate during subsequent RIE processes. In addition, the yttria coating in the RIE chamber can become particulate during the plasma etching process. These particles can adhere to silicon wafers, causing defects in the manufactured semiconductor devices and resulting in a loss of wafer production yield.

[0032] Versions of this disclosure provide improved articles and methods for protecting RIE components by fluoroannealing metal oxide yttrium-containing films, such as yttria and yttrium aluminum oxide, which have minimal to no surface cracks on the film surface and minimal to no subsurface cracks within the film. Previous films with surface and subsurface cracks were formed when the yttria deposition process relied on pulsed direct current (DC) power. The use of alternating current (AC) power during the yttria deposition process, as disclosed herein, can unexpectedly minimize or prevent the formation of surface and subsurface cracks during the fluoroannealing process. As used herein, “surface cracks” are cracks on the surface of the film that are visible when the surface of the film is observed using a laser confocal microscope at 400x magnification. As used herein, “subsurface cracks” are cracks below the surface of the film that are visible when a laser confocal microscope is used to observe the entire depth of the film at 1000x magnification.

[0033] The fluoroannealing process involves introducing fluorine into a yttrium metal oxide-containing film by annealing the film in a fluorine-containing atmosphere at 300°C to 650°C. The heating ramp rate for the fluoroannealing process may be between 50°C and 200°C per hour.

[0034] Fluoroannealed yttria films offer several advantages and possess several desirable properties, including high fluorine plasma etch resistance (e.g., about 0.1 to about 0.2 microns / hour), high wet chemical etch resistance (e.g., about 5 to about 120 minutes in 5% HCl), good adhesion to chamber components (e.g., second critical load (LC2) adhesion of about 5N to about 15N), and conformal coating capability. In addition, fluoroannealed yttria films are tunable with respect to material, mechanical properties, and microstructure. Films containing yttria, fluoroannealed yttria, or mixtures of both yttria and fluoroannealed yttria can be produced to meet the needs of specific applications or etching environments. For example, the fluorine content of the film can be manipulated to range from about 4 atomic percent to about 60 atomic percent when measured by scanning electron microscopy (SEM) in combination with an energy-dispersive spectroscopy (EDS) probe, and the fluorine depth can be manipulated to range from about 0.5 microns to about 20 microns. The etch resistance of fluorinated yttria increases with the fluorine content in the film. The fluoroannealed yttria films disclosed herein, deposited using an AC power supply, also offer the additional advantages of superior crack resistance (with respect to both surface and subsurface cracks) and improved bonding at higher temperatures compared to fluoroannealed yttria films deposited using a DC or pulsed DC power supply.

[0035] In some embodiments, yttria is deposited on a substrate using an alternating current (AC) power supply, followed by a fluoroannealing process to convert the yttria to yttrium oxyfluoride, or a mixture of yttria and yttrium oxyfluoride. The yttria and / or yttrium oxyfluoride form a film on the substrate that protects it. The film provides an outermost layer that is in contact with the etching environment in a vacuum chamber.

[0036] A film of a yttrium-containing metal oxide, such as yttria and yttrium aluminum oxide, is first deposited on the substrate. The deposition of the metal oxide film can be carried out by various methods of physical vapor deposition (PVD) using an AC power supply, including sputtering and ion beam-assisted deposition. The AC power supply can be operated at a frequency in the range of approximately 30 kHz to approximately 100 kHz. Following deposition, the film is fluoroannealed in a fluorine-containing environment at approximately 300°C to approximately 650°C. The fluorination process can be carried out as described in U.S. Publication No. 2016 / 0273095, which is incorporated herein by reference in its entirety. The fluorination process can be carried out using several methods, including, for example, fluorine ion implantation followed by annealing, fluorine plasma treatment at temperatures above 300°C, fluoropolymer combustion methods, fluorine gas reactions at elevated temperatures, and UV treatment with fluorine gas, or any combination of the above.

[0037] Various fluorine sources can be used depending on the fluoroannealing method employed. In the case of fluoropolymer combustion methods, fluoropolymer materials are required and may include, for example, PVF (polyvinyl fluoride), PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PCTFE (polychlorotrifluoroethylene), PFA, MFA (perfluoroalkoxy polymer), FEP (fluorinated ethylene-propylene), ETFE (polyethylene tetrafluoroethylene), ECTFE (polyethylene chlorotrifluoroethylene), FFPM / FFKM (perfluoroelastomer), FPM / FKM (fluorocarbon [chlorotrifluoroethylene vinylidene fluoride]), PFPE (perfluoropolyether), PFSA (perfluorosulfonic acid), and perfluoropolyoxetane.

[0038] In other fluoroannealing methods, where annealing is followed by fluoride ion implantation, fluorine plasma treatment at temperatures above 300°C, fluorine gas reaction during heating, and UV treatment with fluorine gas, fluorinated gas and oxygen gas are required for the reaction. The fluorinated gas may be, for example, hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulfur hexafluoride (SF6), HF vapor, NF3, and gases from fluoropolymer combustion.

[0039] Yttria or aluminum yttrium oxide films preferably have a columnar structure, which allows fluorine to penetrate the film through particle boundaries during the fluoroannealing process. Amorphous yttria (in other words, non-columnar or less columnar) structures do not allow fluorine to penetrate easily during the fluoroannealing process.

[0040] The fluoroannealed films of this disclosure may be applied to vacuum-compatible substrates, such as components in semiconductor manufacturing systems. Etching chamber components may include showerheads, shields, nozzles, and windows. Etching chamber components may also include stages for substrates, wafer handling fixtures, and chamber liners. Chamber components may be made from ceramic materials. Examples of ceramic materials include alumina, silicon carbide, and aluminum nitride. Although this specification refers to etching chamber components, the embodiments disclosed herein are not limited to etching chamber components and other ceramic articles, and substrates that would benefit from improved corrosion resistance may also be coated as described herein. Examples include ceramic wafer carriers and wafer holders, susceptors, spindles, chucks, rings, baffles, and fasteners. Vacuum-compatible substrates may also be silicon, quartz, steel, metal, or metal alloys. Vacuum-compatible substrates may also be plastics used in the semiconductor industry, such as polyetheretherketone (PEEK) and polyimide in dry etching, or may include such plastics.

[0041] Fluoroannealed films are tunable, and the fluoroannealing process allows for variations in the depth and density of fluorination of the film. In some embodiments, the fluoroannealed film is fully fluorinated (fully saturated), with fluorine distributed throughout the entire depth of the film. In other embodiments, the fluoroannealed film is partially fluorinated, with fluorine distributed along the outer portion of the film but not throughout the entire depth of the film. Additionally, the film can be a graded film, where the fluorine content varies throughout the film depth. For example, the top (outermost) portion of the film may contain the highest fluorine content, and the fluorine content gradually decreases throughout the film depth towards the bottom (innermost) portion of the film, which is closest to the substrate and interfaces with the substrate. The outermost portion of the film is the portion facing the etching environment. In some embodiments, the film may contain surface fluorine amounts of about 60 atomic% or less, about 55 atomic% or less, about 50 atomic% or less, about 45 atomic% or less, about 40 atomic% or less, about 35 atomic% or less, about 30 atomic% or less, about 25 atomic% or less, about 20 atomic% or less, or about 15 atomic% or less. All atomic percent of the fluorine values ​​disclosed herein are measured using a scanning electron microscope (SEM) in combination with an energy-dispersive spectroscopy (EDS) probe. In some embodiments, the film may have a thickness in the range of about 1 micron to about 20 microns. In some embodiments, the amount of fluorine at a depth of 10% of the film thickness (when measured from the surface furthest from the substrate) is at least about 10 atomic%, about 15 atomic%, about 20 atomic%, about 25 atomic%, about 30 atomic%, or about 35 atomic%. In some embodiments, the amount of fluorine at a depth of 30% of the film thickness (measured from the surface furthest from the substrate) is at least about 10 atomic%, about 15 atomic%, about 20 atomic%, about 25 atomic%, about 30 atomic%, or about 35 atomic%. In some embodiments, the amount of fluorine at a depth of 50% of the film thickness (measured from the surface furthest from the substrate) is at least about 10 atomic%, about 15 atomic%, about 20 atomic%, about 25 atomic%, about 30 atomic%, or about 35 atomic%.

[0042] The depth of fluorination of the film can be controlled during fluoroannealing by varying process parameters such as fluoroannealing time and temperature. As shown in Figure 1 (and described in more detail in Example 1 below), fluorine diffuses deeper into the film as the fluoroannealing time and temperature increase.

[0043] The film provides a protective layer on the substrate, which is the outermost layer of the coated article that is in contact with the environment inside the vacuum chamber.

[0044] In some embodiments where the film is not completely fluorinated, the top or outermost portion of the film is yttrium oxyfluoride, and the remaining depth of the film is yttria. In other embodiments where the film is not completely fluorinated, the top or outermost portion of the film is yttrium aluminum oxyfluoride, and the remaining depth of the film is yttrium aluminum oxide.

[0045] In some embodiments, the substrate was coated with yttrium through physical vapor deposition (PVD) in an oxygen-containing atmosphere using an AC power supply. In some embodiments, the substrate was coated with yttrium through reactive sputtering in a reactive gas atmosphere. The reactive gas can be a gas, which is an oxygen source and may include air. Thus, the film can be a ceramic material containing yttrium and oxygen, which can be fabricated using physical vapor deposition (PVD) techniques such as reactive sputtering. The oxygen-containing atmosphere during deposition may also include an inert gas such as argon.

[0046] In some embodiments, ceramic substrates are disclosed herein that are coated with an yttria film deposited by reactive sputtering using an AC power supply, wherein the coating and the substrate are annealed in an oven containing a fluorine atmosphere at 300°C to 650°C. The fluoroannealed coating is a ceramic material containing yttrium, oxygen, and fluorine. The substrate and the fluoroannealed film can be fired at 150°C under high vacuum (5E to 6 Torr) without loss of fluorine from the coating.

[0047] The time required to anneal the yttria film during heating can range from approximately 0.5 hours to approximately 6.5 hours, or even longer.

[0048] Fluoroannealing of yttria on ceramic substrates such as alumina significantly improves the wet chemical (5% HCl) etching resistance of yttria films.

[0049] The fluoroannealed yttria film disclosed herein may be characterized as a film that adheres to a ceramic substrate, wherein the film adheres to the ceramic substrate after contact with 5% aqueous hydrochloric acid at room temperature for 5 minutes or more. In some versions, the fluoroannealed yttria film adheres to the ceramic substrate for 15 to 30 minutes, in some cases for 30 to 45 minutes, and in other cases, the film adheres to the substrate after 100 to 120 minutes when contacted with or immersed in 5% aqueous HCl at room temperature. The yttria film disclosed herein may be used as a protective coating for components used in halogen-containing plasma etchers. For example, the halogen-containing gas may include NF3, F2, Cl2, etc.

[0050] Fluoroannealed yttria films are particularly advantageous in fluorine-based etching systems because the presence of fluorine in the film allows the chamber to stabilize or dry more quickly. This helps eliminate process drift during drying and use, and reduces etcher downtime for drying with fluorine or chlorine-containing gases.

[0051] As discussed above, the fluoroannealed yttria films disclosed herein have minimal to no surface cracks and / or subsurface cracks. The excellent crack resistance of the films is thought to be due to the use of AC power for depositing the yttria films. Yttria films deposited using AC power rather than DC or pulsed DC power have minimal (e.g., 5 or fewer, 4 or fewer, 3 or fewer, or 2 or fewer) to no surface cracks and / or subsurface cracks, including in the case of substrates with significant differences in thermal expansion coefficients using yttria, such as quartz substrates. The formation of minimal (e.g., 5 or fewer, 4 or fewer, 3 or fewer, or 2 or fewer) to no surface cracks and / or subsurface cracks is also present after fluorinating the yttria film, including when fluoroannealing is performed at high temperatures and / or for extended periods, thereby leading to higher fluorine atom percentages throughout the film's depth. For example, for a film having at least 10% fluorine atoms at a depth of 30% of its total thickness, at least 20% fluorine atoms at a depth of 30% of its total thickness, at least 30% fluorine atoms at a depth of 30% of its total thickness, at least 10% fluorine atoms at a depth of 50% of its total thickness, at least 20% fluorine atoms at a depth of 50% of its total thickness, and at least 30% fluorine atoms at a depth of 50% of its total thickness, minimal to no surface cracks are visible on the film surface when the film surface is observed using a laser confocal microscope at 400x magnification, and / or minimal to no subsurface cracks are visible below the film surface when a laser confocal microscope is used to observe the entire film depth at 1000x magnification. These results are unexpected, as yttria films deposited using DC or pulsed DC power supplies with similar fluorine atom percent depth profiles develop surface and / or subsurface cracks. [Examples]

[0052] Example 1 A yttrium oxide film approximately 5 microns thick was deposited on a silicon coupon-sized substrate (approximately 0.75 inches × 0.75 inches) by yttrium physical vapor deposition (in other words, reactive sputtering) in an oxygen-containing atmosphere using an alternating current (AC) power supply. The coupon was then subjected to fluoroannealing, during which it was heated in an oven in a fluorine-containing atmosphere under one of the following conditions listed in Table 1 below. Conditions 9 and 10 had twice the amount of fluorine precursor as conditions 1-8 to ensure that not all fluorine was used up before the fluoroannealing process was complete. The atomic percentage of fluorine was measured over the entire 5-micron thickness of the film for each of the 10 conditions listed in Table 1 using a scanning electron microscope in combination with an electron dispersion spectroscopy (EDS) probe. A plot of the data is shown in Figure 1, with the atomic percentage of fluorine shown on the Y-axis and the depth into the thickness in microns shown on the X-axis. For 500C / 5hr 2X and 550C / 5hr 2X, "2X" in the legend of Figure 1 indicates the presence of twice the amount of fluorine precursor for those conditions. The coating surface of each coupon was observed under a laser confocal microscope at 400X magnification to examine visible surface cracks on the coating surface. The coating of each coupon was also observed using a laser confocal microscope to observe the total depth of the film at 1000X magnification to examine subsurface cracks below the coating surface. Table 1 also reports whether surface and subsurface cracks were visible for each of the 10 conditions. TIFF2026108682000002.tif105170

[0053] As seen in Figure 1, there is a general trend from Condition 1 to Condition 10 in which the fluorine atom percentage on the coating surface increases with increasing fluoroannealing temperature and duration. Furthermore, fluorination across the coating thickness is achieved for Conditions 6, 7, 8, and 9, as can be seen in Figure 1. Figure 2 is a cross-sectional view of a coupon subjected to one of the above fluoroannealing conditions, taken by scanning electron microscopy (SEM). As shown in Table 1, no surface or subsurface cracks occurred up to Condition 10 at 550 degrees Celsius. Figure 3 is a photograph taken using a Keyence laser confocal microscope at 1000x magnification, showing multiple surface cracks. The absence of visible surface and subsurface cracks in the coating for Conditions 1-9 is thought to be due to the use of alternating current (AC) power during yttrium oxide deposition.

[0054] Example 2 A yttrium oxide film approximately 5 microns thick was deposited on a coupon-sized alumina substrate (a disk approximately 0.75 inches in diameter) by yttrium physical vapor deposition (in other words, reactive sputtering) in an oxygen-containing atmosphere using an alternating current (AC) power supply. The coupons were then subjected to fluoroannealing, during which they were heated in an oven in a fluorine-containing atmosphere under one of the following conditions listed in Table 2 below. Conditions 9 and 10 had twice the amount of fluorine precursor as conditions 1-8 to ensure that not all fluorine was used up before the fluoroannealing process was complete. For each coupon subjected to conditions 1-10, the plots of fluorine atoms % shown on the Y axis and depth into thickness in microns shown on the X axis are considered to be similar to those shown in Figure 1. The surface of the coating of each coupon was observed under a laser confocal microscope at 400X magnification to inspect for visible surface cracks on the coating surface. The coating on each coupon was also observed using a laser confocal microscope to examine the total depth of the film at 1000x magnification to inspect for subsurface cracks beneath the surface of the coating. Table 2 also reports whether surface and subsurface cracks were visible for each of the 10 conditions. TIFF2026108682000003.tif106170

[0055] The absence of visible and subsurface cracks during coating under conditions 1-10 is thought to be due to the use of an AC power supply during yttrium oxide deposition. Figure 4 shows a photograph taken with a Keyence laser confocal microscope at 1000x magnification, demonstrating the absence of surface cracks.

[0056] Example 3 A yttrium oxide film approximately 5 microns thick was deposited on quartz and sapphire coupon-sized substrates (approximately 0.75 inches in diameter) using an alternating current (AC) power supply by yttrium physical vapor deposition (in other words, reactive sputtering) in an oxygen-containing atmosphere. The coupons were then subjected to fluoroannealing, during which the coupons were heated in an oven in a fluorine-containing atmosphere under conditions 1-10 used in Examples 1 and 2. While no surface or subsurface cracks were present in the yttrium oxide film upon coating, cracks and subsurface cracks formed after fluoroannealing under each of conditions 1-10.

[0057] All patents, published applications, and reference teachings cited herein are incorporated in their entirety by reference.

[0058] While this disclosure shows and describes one or more implementations, other persons skilled in the art will likely conceive of equivalent modifications and alterations based on reading and understanding this specification and the accompanying drawings.

[0059] This disclosure, including all such modifications and alterations, is limited only to the following claims. In addition, certain features or aspects of this disclosure may be disclosed in relation to only one of several implementations, but such features or aspects may be combined with one or more other features or aspects of other implementations when desired and may be advantageous for any given or particular application. Furthermore, to the extent that the terms “includes,” “having,” “has,” “with,” or their variations thereof are used in any form for carrying out the invention or in the claims, such terms are intended to be inclusive in a similar manner to the term “comprising.” Also, the term “exemplary” means merely an example, not a best example. Furthermore, please understand that the features and / or elements depicted herein are illustrated with specific dimensions and / or orientations relative to each other for the purpose of simplicity and ease of understanding, and that actual dimensions and / or orientations may differ substantially from those illustrated herein.

[0060] While this disclosure has been shown and described in detail with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various modifications of form and detail may be made within this disclosure without departing from the scope of the disclosure as encompassed by the appended claims.

Claims

1. circuit board and A protective film located on at least a portion of the substrate and Equipped with, The aforementioned film contains a fluorinated metal oxide containing yttrium, The film has at least 10% of fluorine atoms at a depth of 30% of the total thickness of the film, and The film does not have subsurface cracks below the surface of the film that are visible when a laser confocal microscope is used to observe the entire depth of the film at a magnification of 1000x. Goods.

2. The article according to claim 1, wherein, after fluoroannealing, the film does not have visible surface cracks on its surface when the surface of the film is observed using a laser confocal microscope at a magnification of 400x.

3. The article according to claim 1 or 2, wherein the substrate is alumina.

4. The article according to claim 1 or 2, wherein the substrate is silicon.

5. The article according to any one of claims 1 to 4, wherein the film has at least 20% of fluorine atoms at a depth of 30% of the total thickness of the film.

6. The article according to any one of claims 1 to 5, wherein the film has at least 30% of fluorine atoms at a depth of 30% of the total thickness of the film.

7. The article according to any one of claims 1 to 6, wherein the film has at least 10% of fluorine atoms at a depth of 50% of the total thickness of the film.

8. The article according to any one of claims 1 to 7, wherein the film has at least 20% of fluorine atoms at a depth of 50% of the total thickness of the film.

9. The article according to any one of claims 1 to 8, wherein the film has at least 30% of fluorine atoms at a depth of 50% of the total thickness of the film.

10. A method of depositing a yttrium-containing metal oxide onto a substrate using a physical vapor deposition technique with an alternating current (AC) power supply, wherein the metal oxide forms a film on the substrate. The film is fluoroannealed. Includes, After fluoroannealing, the film has at least 10% of fluorine atoms at a depth of 30% of the total thickness of the film. method.

11. The method according to claim 10, wherein, after fluoroannealing, the film does not have visible surface cracks on its surface when the surface of the film is observed using a laser confocal microscope at a magnification of 400x.

12. The method according to claim 10 or 11, wherein, after fluoroannealing, the film does not have subsurface cracks below the surface of the film that are visible when a laser confocal microscope is used to observe the total depth of the film at a magnification of 1000x.

13. The method according to any one of claims 10 to 12, wherein, after fluoroannealing, the film has at least 20% of fluorine atoms at a depth of 30% of the total thickness of the film.

14. The method according to any one of claims 10 to 12, wherein, after fluoroannealing, the film has at least 30% of fluorine atoms at a depth of 30% of the total thickness of the film.

15. The method according to any one of claims 10 to 14, wherein, after fluoroannealing, the film has at least 20% of fluorine atoms at a depth of 50% of the total thickness of the film.

16. The method according to any one of claims 10 to 14, wherein, after fluoroannealing, the film has at least 30% of fluorine atoms at a depth of 50% of the total thickness of the film.

17. The method according to any one of claims 10 to 16, wherein the fluoroannealing is carried out in a fluorine-containing atmosphere at a temperature of about 300°C to about 650°C.

18. The method according to any one of claims 10 to 17, wherein the substrate is alumina.

19. The method according to any one of claims 10 to 17, wherein the substrate is silicon.

20. An article manufactured according to the process described in any one of claims 10 to 19.

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