Coating that contains fluorinated yttrium oxide and metal oxide, and method of preparing and using coating

Abstract

To provide a substrate including a composite coating, and to provide a method for forming a composite coating.SOLUTION: A coating method includes the steps of: disposing a component with a surface in a deposition chamber; depositing a yttrium oxide and a zirconium oxide with atomic layer deposition, where the yttrium oxide and the zirconium oxide do not form individual layers; and exposing the yttrium oxide and the zirconium oxide to a molecular fluorine source vapor at at least a temperature of 300°C to form a fluorinated yttrium oxide-metal oxide composite coating at a surface of the component, where the fluorinated yttrium oxide-metal oxide composite coating includes a mixture of at least two chemically individual materials including a yttrium oxide, a fluorinated yttrium oxide, and a zirconium oxide.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present specification relates to coatings, including protective coatings, that contain a combination of yttrium oxide fluoride (e.g., yttrium fluoride, yttrium oxyfluoride, or combinations thereof) and a metal oxide, such as (but not limited to) zirconium oxide; methods of preparing these coatings; substrates, surfaces, devices, and device components that include coatings that contain a combination of yttrium oxide fluoride and a metal oxide; and methods of preparing and using the substrates. [Background technology]

[0002] Manufacturing processes for semiconductor and microelectronic devices require various processing steps involving highly reactive process materials such as plasmas, acids, accelerated ions, etchants (e.g., halogens and halogenated materials), corrosive materials, cleaning agents, etc.

[0003] Exemplary processes include ion implantation processes (e.g., "doping" processes), etching processes in which plasma or halogen materials may be used, cleaning processes, deposition steps, and the like, each of which may involve the use of reactive, corrosive, or energetic process materials in a "process chamber." Each of these types of processes is carried out inside a process chamber that houses a workpiece (e.g., a "substrate") and process materials. The process chamber also includes various structures and components (sometimes referred to herein as "process chamber components" or "process tool components" for short) that define the process chamber and the items inside or associated with the process chamber and are required for operation. These process chamber components may include chamber walls, flow conduits (e.g., flow lines, flow heads, piping, tubing, etc.), fasteners, trays, supports, and other structures and devices used to support the workpiece or to deliver, contain, or contact reactive process materials for use in the process chamber.

[0004] For use as part of a process chamber, a process tool component should be resistant to the reactive process materials used in the process chamber, and should not be degraded or damaged by contact with the process materials in such a manner as to generate debris or particulates that may be incorporated into the process being performed and contaminate the workpiece being processed.

[0005] Process chamber components used in semiconductor processing equipment for manufacturing semiconductors and microelectronic devices are often made of solid materials ("substrates" or "bases") such as metals (e.g., stainless steel, aluminum alloys that may be anodized, tungsten), minerals, or ceramic materials. The substrate is usually coated with a protective layer that is more resistant to reactive process materials than the substrate material. Traditionally, such protective coatings have typically been disposed on the substrate surface by a variety of useful methods, typically by anodization (e.g., to produce anodized aluminum), spray coating, or deposition methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), atomic layer deposition (ALD), or a variation or derivative of one of these processes. Summary of the Invention

[0006] The present disclosure relates to a deposition coating that can be prepared to contain both yttrium oxide fluoride (e.g., yttrium fluoride, yttrium oxyfluoride, or both) in combination with a metal oxide. The coating can be used as a protective coating, particularly as a protective coating that is chemically resistant to reactive chemicals (process materials) used in methods of processing semiconductor or microelectronic devices. As used herein, the term "yttrium oxide fluoride" refers to yttrium oxide that has been subjected to a step of fluorination. This term includes compounds known as yttrium fluoride (YF3) and yttrium oxyfluoride (YOF). The term "yttrium oxide fluoride" is sometimes used in the chemical arts to refer to the compound yttrium oxyfluoride, which has the formula YOF. However, for purposes of this disclosure, the term "yttrium oxyfluoride" refers to the compound YOF, and "yttrium oxide fluoride" refers to a compound derived by fluorinating yttrium oxide, including both yttrium fluoride (YF3) and yttrium oxyfluoride (YOF).

[0007] Also according to the present specification, the coating can be prepared by a method of disposing a non-fluorinated yttrium oxide precursor coating on a surface using atomic layer deposition techniques, followed by a step of fluorinating the precursor to produce fluorinated yttrium oxide by a fluoro-annealing step. The precursor coating contains yttrium oxide and a metal oxide. The fluoro-annealing step converts a significant portion of the yttrium oxide to fluorinated yttrium oxide, i.e., yttrium fluoride, yttrium oxyfluoride, or a combination thereof, to form a resulting coating containing a combination of metal oxide (not fluorinated) and fluorinated yttrium oxide, i.e., a "fluorinated yttrium oxide-metal oxide coating."

[0008] The method of forming the described yttrium oxide fluoride-metal oxide coating by atomic layer deposition has been identified as being particularly effective in producing coatings containing large amounts of yttrium oxide fluoride and metal oxide.The described method has been shown to be particularly effective in forming coatings containing high concentrations of yttrium oxide fluoride and metal oxide, including zirconium oxide as the preferred metal oxide, compared to alternative deposition methods including other techniques for depositing yttrium oxide (e.g., chemical vapor deposition, physical vapor deposition, or variations thereof) followed by a fluoro-annealing step.The method herein is also particularly effective when the non-yttrium metal oxide is zirconium oxide, which has been identified as being particularly effective in enabling fluorination of the yttrium oxide below the surface of the yttrium oxide-metal oxide coating.

[0009] The described coatings can exhibit a useful combination of the properties and effects of yttrium oxide fluoride and metal oxide materials in a single atomic layer deposition coating. Yttrium oxide fluoride is effective as a protective coating material because both yttrium oxide fluoride and yttrium oxyfluoride contain high levels of fluorine, providing a high level of chemical inertness to reactive process materials that contain fluorine. Yttrium oxide fluoride and yttrium oxyfluoride do not necessarily exhibit the same high level of chemical resistance to other reactive process materials. In many cases, reactive process materials may include a combination of two or more different reactive chemicals, such as a combination of fluorine and another reactive chemical. Non-yttrium metal oxides may be included in the coating to improve resistance to other process materials that may be used in combination with fluorine, for example. One example of such a metal oxide is zirconium oxide, but other metal oxides may also provide complementary chemical resistance to yttrium oxide fluoride. [Brief description of the drawings]

[0010] [Figure 1] 1 shows examples of the coated substrates described. [Figure 2A] 1 shows examples of the described coated substrates having various types of multi-layer coatings. [Figure 2B] 3 shows another example of the described coated substrate having various types of multi-layer coatings. [Figure 2C] 1 shows yet another example of the described coated substrate having various types of multi-layer coatings. [Diagram 3] 1 illustrates an example of the steps of the method herein. [Figure 4] 1 is a table of compositional data for the described coatings. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] All drawings are schematic and not to scale.

[0012] The following description pertains to deposited coatings, e.g., "films," that contain both yttrium oxide fluoride and a metal oxide (different from yttrium oxide) in combination (sometimes referred to herein for convenience as "yttrium oxide fluoride-metal oxide coatings" or "yttrium oxide fluoride-metal oxide films"). "Yttrium oxide fluoride" refers to yttrium oxide, yttrium oxyfluoride, and combinations thereof.

[0013] The present specification also relates to fluorinated yttrium oxide-metal oxide coatings used as protective coatings on substrates, as well as substrates, process equipment, and process equipment components that include the fluorinated yttrium oxide-metal oxide coatings. In an exemplary use, the fluorinated yttrium oxide-metal oxide coatings can act as protective coatings that are chemically resistant to reactive chemicals (process materials) used in methods for processing semiconductor or microelectronic devices.

[0014] The present specification also relates to a method for preparing a fluorinated yttrium oxide-metal oxide coating. The coating can be prepared by a method using atomic layer deposition techniques to place a non-fluorinated yttrium oxide precursor coating on a surface, followed by a step of fluorinating the precursor by a fluoro-annealing step. The precursor coating contains yttrium oxide and a metal oxide, and the fluoro-annealing step converts a substantial portion of the yttrium oxide to fluorinated yttrium oxide, forming the resulting fluorinated yttrium oxide-metal oxide coating.

[0015] The surface of the substrate comprising the yttrium oxide fluoride-metal oxide coating may optionally be a highly three-dimensional surface, e.g., a surface having at least one structure exhibiting a high aspect ratio. The surface may be one used as a component of a chemical processing or manufacturing apparatus, such as semiconductor or microelectronic device processing.

[0016] The described coatings are resistant to reactive process materials, particularly (but not limited to) process materials used in etching techniques used in semiconductor and microelectronic processing methods, and process materials used in methods and processes for cleaning process chambers of equipment ("tools") used in semiconductor and microelectronic processing methods. Specific reactive process materials used in these methods include halogens and halogen-containing materials, such as fluorine, chlorine, fluorine or chlorine-containing materials, and mixed halogens (i.e., combinations of two or more different halogens), such as combinations of fluorine and chlorine. The reactive process materials may be in the form of liquids or vapors (including plasmas).

[0017] According to this specification, coatings containing a combination of yttrium oxide fluoride and a metal oxide other than yttrium oxide have been identified (e.g., are advantageously predicted) as useful or particularly effective as protective chemically resistant (inert) coatings for coatings containing a combination of both yttrium oxide fluoride and another metal oxide. (As used herein, unless otherwise specified, the term "metal oxide" as part of a yttrium oxide fluoride-metal oxide coating or a precursor or derivative thereof refers to a non-yttrium metal oxide.)

[0018] These coatings can provide a useful combination of the properties and effects of yttrium oxide fluoride and metal oxide materials in a single atomic layer deposition coating. yttrium oxide fluoride is effective as a protective coating material because it contains a high level of fluorine and provides a high level of chemical inertness to fluorine-containing reactive process materials. However, yttrium oxide fluoride does not necessarily exhibit the same high level of chemical resistance to other reactive process materials, such as chlorine-containing reactive process materials. To improve resistance to chlorine-containing reactive process materials, non-yttrium metal oxides, such as zirconium oxide, are included in the coating. Zirconium oxide improves chemical resistance to chlorine-containing reactive process materials, and coatings containing both yttrium oxide fluoride and zirconium oxide are effective as coatings that exhibit useful or advantageous chemical resistance to both fluorine-containing and chlorine-containing process materials.

[0019] The described coatings may be included on any surface or substrate that may desirably include a protective (e.g., chemically inert, non-reactive) coating. The coating may be formed on the substrate to form a "coated article" (such as a coated process tool component), where the coating is applied to the surface of the substrate in a solid continuous form or in alternating patterned forms. Examples of coated articles include items such as any of the various components of process chambers ("process tool components") used to prepare semiconductor materials, microelectronic devices, and the like. Because of their resistance to process materials such as halides, the coatings may be used on surfaces of process tool components of process chambers that contain these and other process materials, reducing degradation and particle or debris formation that occurs on the surfaces.

[0020] The atomic layer deposition coatings described include "precursor" coatings containing yttrium oxide and metal oxide, and fluorinated coatings containing yttrium oxide fluoride and metal oxide. For convenience, these two types of coatings are sometimes referred to collectively as "yttrium-metal oxide" coatings. The coatings include a combination of yttrium oxide and metal oxide (as a precursor coating) or a combination of yttrium oxide fluoride and metal oxide (after a fluoro-annealing step), where the two materials are applied in a series of steps by atomic layer deposition techniques to produce the precursor, followed by a fluoro-annealing step to produce the yttrium oxide fluoride.

[0021] Because the coatings are prepared by atomic layer deposition techniques that apply material in multiple deposition steps, the coatings are sometimes referred to as "multilayer" coatings. Depending on the amount of deposition material applied during each individual deposition step, the resulting coating may exhibit a layered structure that is detectable using magnification techniques. When a sufficient amount of material is applied during each deposition step, each applied amount of material can be identified (using magnification) as a separate layer of material.

[0022] In other examples (still considered "multilayer" coatings because they are prepared by a series of atomic layer deposition steps), the amount of material deposited in each individual deposition step is less than sufficient to form a distinct (detectable) layer in the resulting coating structure. For example, a coating may be deposited by atomic layer deposition steps that deposit separate amounts of material (as described) at thicknesses smaller than the roughness of the surface on which the material is deposited. When deposited in succession, the deposited amounts of different deposition materials may not form distinct "layers", but instead form a "composite" material made from the different deposition materials without forming separate layers, e.g., not even a monolayer having a thickness of 1-5 atoms thick. With these methods, the resulting coating does not exhibit distinct layers, but contains at least two chemically distinct materials, including a metal oxide and yttrium oxide (as a precursor coating) or a combination of a metal oxide and yttrium oxide fluoride (after a fluoro-annealing step).

[0023] Thus, as used herein, the term "multilayer" refers to atomic layer deposition coatings having multiple distinguishable layers (e.g., using optical or electronic magnification techniques), and also refers to atomic layer deposition coatings that do not result in multiple distinguishable "layers," but include materials deposited by a series of deposition steps at thicknesses that produce a "composite" structure as described.

[0024] In general, by way of non-limiting example, the thickness of a single deposited "layer" of yttrium-metal oxide coating, whether or not identifiable as a layer, can range from less than a nanometer to a few nanometers, e.g., about 0.1, 0.5, 1, 2, 5, or 10 nanometers, to tens or hundreds of nanometers, e.g., 50, 100, 500, 600, 800, or 900 nanometers (0.9 microns), or more. The total thickness of a multi-layer (including composite) yttrium-metal oxide coating can range from 1, 5, or 10 nanometers, to 100, 500, or 1000 nanometers (1 micron).

[0025] Certain exemplary multi-layer coatings include coatings made of two or more, e.g., 2, 3, 5 or up to 10, 20, 30, 50, 100, 500 or 1000 separate (by magnification) distinguishable layers, where the different layers are made of materials including metal oxides (other than yttrium oxide) and yttrium-containing layers that are yttrium oxide (as a precursor) or yttrium oxide fluoride-containing materials (including combinations of different yttrium oxide fluoride materials) (after the fluoro-annealing step). Each of the different layers may be made of one material that is a metal oxide (other than yttrium oxide) or a yttrium-containing layer that is yttrium oxide (as a precursor) or yttrium oxide fluoride (after the fluoro-annealing step).

[0026] Optionally, the yttrium oxide fluoride-metal oxide coating or precursor thereof may also include one or more layers of additional material, such as a second type of metal oxide. Each layer may be continuous across the area of ​​the coating, may exhibit a discernible (measurable, identifiable) thickness, and may be made entirely or substantially of a single material (metal oxide, yttrium oxide, yttrium oxyfluoride, yttrium fluoride, etc.) having a relatively high level of purity, for example, at least 90, 95, 98, or 99 wt. % of a single metal oxide or yttrium-containing material as described herein. (Note, however, that a layer containing yttrium fluoride may contain yttrium fluoride in combination with an amount of unconverted yttrium oxide or yttrium oxide fluoride).

[0027] The thickness of the individual layers of the coating may be the same, approximately the same, or different. An exemplary coating may include individual deposited layers exhibiting the same thickness, for example two repeated layers A (e.g., yttrium oxide fluoride or yttrium oxide) and B (non-yttrium oxide metal oxide such as zirconium oxide), without the other layer, each of the two different materials formed into layers of the same thickness, for example, each layer having a thickness of 1 nanometer (A=1 nanometer, B=1 nanometer)×N times repeated (N may be 1-50 or 5-100 or 10-500), for a total of 2-100 layers or 10-200 layers or 20-1000 layers.

[0028] Different exemplary coatings may include deposited layers of two different materials, where the layers of the different materials have different thicknesses, but the layers of the same material have the same thickness. An exemplary coating may include two repeating layers A (e.g., yttrium oxide fluoride or yttrium oxide) and B (a non-oxide yttrium metal oxide, such as zirconium oxide). Each of the A layers may all have the same thickness, which may range from 1 nanometer to 50 nanometers. Each of the B layers may all have the same thickness, but their thickness may differ from the thickness of the A layers. The thickness of the B layers may range from 0.1, 0.5 or 1 to 50 nanometers. The coating may have a total of N layers of each material, for example (A=5 nanometers, B=10 to 50 nanometers, e.g., 40 nanometers) x N repetitions, where N may be from 1 or 2 or 5 to 10, 20, 30, 100, 200, etc., producing a total thickness of, for example, up to 1000 nanometers.

[0029] As yet another example, a multilayer coating may include a first (single) layer of layer A (e.g., yttrium oxide fluoride or yttrium oxide) of a first thickness, multiple (N) repeating layers of A and B (non-yttrium metal oxides such as zirconium oxide), and no other layers. The first layer (A1) can be of any thickness as described. The multiple repeating layers (A2) and B can also have any useful thickness, such as A1 having a different thickness than A2, e.g., A1 being thicker than A2.

[0030] As another example, a multilayer coating may include multiple, possibly repeating, pairs of A and B layers, where A is yttrium oxide fluoride or yttrium oxide and B is a non-yttrium metal oxide such as zirconium oxide. The coating may include a first pair of A and B layers, A1 / B1, which may be repeated, with A1 and B1 each having a first thickness. The coating may include a second pair of A and B layers, A2 / B2, which may be repeated, with A2 and B2 each having a second thickness. The coating may include a third pair of A and B layers, A3 / B3, which may be repeated, with A3 and B3 each having a third thickness.

[0031] Referring to FIG. 1, an example of a process chamber component 100 (or another type of coated device, coated article, coated substrate, etc.) of the present invention is shown, which is comprised of a solid body (e.g., substrate) 102 and a coating 104, which includes at least one each of layer A (e.g., yttrium oxide fluoride or yttrium oxide) and layer B (a non-oxidized yttrium metal oxide, such as zirconium oxide). In some embodiments, the coating 104 can include multiple alternating A and B layers, as described herein. The coating 104 can consist of, or consist essentially of, alternating layers of layers A and layers B. Alternatively, the coating 104 can include multiple layers, including one or more layers A and one or more layers B, with optional additional layers or materials as part of the coating 104. The process chamber component 100 can consist of, or consist essentially of, the coating 104 and the solid body 102, or can include one or more optional materials, layers, or coatings as part of the process chamber component 100.

[0032] 2A shows a specific example of a process chamber component 101 of the present invention, which includes a solid body 102 and a multi-layer coating 104 that is composed of two layers of material, a layer (124) of material A (e.g., yttrium oxide fluoride or yttrium oxide) and a layer 128 of material B (a non-yttrium oxide metal oxide such as zirconium oxide) (i.e., a "bi-layer" coating). The illustrated multi-layer coating 104 is shown as consisting of only the two types of layers shown. Each layer 124, 128 can have material A or material B of high purity, e.g., at least 90, 95, 98 or 99% by weight purity. Each layer may be continuous across the surface of the solid body 102 and may have a thickness ranging from less than 1 nanometer, e.g., about 1, 2, 5 or 10 nanometers, up to 50, 100, 200, 500, 800 or 900 nanometers (0.9 microns) or more. In a related example, another different material, such as a different metal oxide, may be included as part of the multi-layer coating 104. That is, although not shown, additional layers of different types of materials (e.g., metal oxides, or other) are not excluded and may be present, but are not necessarily required or preferred as part of the multi-layer coating 104 or the process chamber component 101.

[0033] FIG. 2B shows an example of a different inventive process chamber component 101 composed of a solid body 102 and a multi-layer coating 104 made of the described materials and formed into many (e.g., tens, hundreds, or thousands) of individual layers. Each layer 134 can be made of yttrium oxide (as deposited) or yttrium oxide fluoride (after a fluoro-annealing step). Each layer 138 can be made of a metal oxide, such as zirconium oxide. Each layer can have material A or material B, preferably of high purity, for example at least 90, 95, 98 or 99% by weight. Each layer can be continuous across the surface of the solid body 102 and can have a thickness of less than 1 nanometer, for example in the range of about 0.1, 0.5, 1, 2, 5 or 10 nanometers to 10, 15 or 20 nanometers. Other layers of different materials are not necessarily excluded from the coating 104 or the process chamber 101 and may be present but are not shown.

[0034] The multi-layer coating 104 of FIG. 2B, which includes tens, hundreds, or thousands of layers, may be referred to as a "laminate" coating. A laminate coating may be applied to a surface of the solid body 102 by a series of atomic layer deposition steps by exposing the surface to a series of gaseous precursor materials that sequentially form each individual layer made of a single deposition material. Each successive amount of deposited material is considered to be a "layer." As an example, a series of atomic layer deposition steps may be performed, each step using a single precursor material to form a single deposition layer. The resulting laminate coating includes distinct "layers" due to the multi-step process by which distinct layers of deposition material are deposited.

[0035] The laminate is considered to be made from different layers produced by each atomic layer deposition process, even though the individual "layers" of different deposited materials may be difficult to distinguish by the use of known techniques. In some laminate coatings, the individual layers may be detectable using a tunneling electron microscope. Each layer may be considered to constitute a "monolayer," a term as it is used in chemical deposition techniques, referring to the amount of deposited material deposited on the surface of the substrate or a previous ALD layer such that the deposited material saturates the reactive sites on the substrate or previous ALD layer. A monolayer has a thickness of only a few atoms, i.e., a single layer of atoms or molecules that covers a surface by associating with a limited number of reactive sites on the surface to produce a monolayer having a thickness of about 2, 3, or 5 atoms or less.

[0036] FIG. 2C shows yet another example of the process chamber component 101 of the present invention made from a solid body 102 and a coating 104 in the form of a composite (144) made from a metal oxide and yttrium oxide (as deposited) or yttrium oxide fluoride (after a fluoro-annealing step). The composite can also be formed by atomic layer deposition, similar to a "laminate" coating by a series of atomic layer deposition steps, but the amount of each material deposited during each step in the series is an amount that does not produce a uniformly deposited detectable layer of the deposited barrier material. The composite 144 can preferably have a high purity, such as by containing at least 90, 95, 98 or 99 weight percent of the metal oxide and yttrium oxide (as precursors) or yttrium oxide fluoride (after a fluoro-annealing step). The thickness of the composite 144 can be any useful thickness, such as a thickness in the range of 10 to 1000 nanometers.

[0037] An example of a currently preferred coating is made from two (possibly only two) different materials, namely a metal oxide (preferably zirconium oxide) and yttrium oxide (as deposited) or yttrium oxide fluoride (after a fluoro-annealing step). The coating may have only two layers (i.e. a bilayer coating), may have multiple, but only a few to a few layers (e.g. 3-10), and may be a laminate or composite of the two deposited materials as described. In the case of an yttrium-metal oxide coating that includes only two layers in total, one layer made of a metal oxide and one layer of yttrium oxide (as deposited, as a precursor) or yttrium oxide fluoride (after a fluoro-annealing step), each layer (for example) may be about 50 nanometers, for example 40-60 nanometers. In the case of an yttrium-metal oxide coating that includes 3-10 layers, each layer (for example) may be from 1, 5 or 10 to 20-40 nanometers, for example 10-30 nanometers. These, ie, laminate or composite coatings, may have a total thickness of 50 to 150 nanometers, for example 80 to 120 nanometers.

[0038] The described coatings can be formed by first depositing a coating comprising yttrium oxide and a metal oxide as a precursor coating, followed by converting at least a portion of the yttrium oxide of the deposited coating to yttrium oxide fluoride, e.g., yttrium fluoride, yttrium oxyfluoride, or a combination thereof. The deposited yttrium oxide, as well as the coating comprising yttrium oxide and a metal oxide, may be referred to herein as "precursor" materials or coatings. Yttrium oxide (YO, also known as "yttria") is prepared from and contains yttrium and oxygen in relative amounts (atoms) of about 2:3 (yttrium:oxygen). The precursor coating may include two layers (one each of metal oxide and yttrium oxide), a few to several layers of both yttrium oxide and metal oxide, or may be a laminate or composite made from alternatingly deposited yttrium oxide and metal oxide. Methods for forming yttrium oxide by atomic layer deposition are known. See, for example, U.S. Patent Publication No. 2018 / 0202047.

[0039] After depositing the yttrium oxide-metal oxide coating, the deposited coating is treated by a fluorine annealing step ("fluoro-annealing" step) that converts at least a portion of the total amount of yttrium oxide in the deposited coating to yttrium oxide fluoride (which may be yttrium fluoride, yttrium oxyfluoride, or both).

[0040] Yttrium fluoride is an inorganic material composed of yttrium and fluorine and has the chemical constitution YF3 or approximately Yttrium oxyfluoride is an inorganic material composed of yttrium, fluorine, and oxygen and has the chemical constitution YOF.

[0041] The fluoro-annealing step is carried out at a temperature and for a time effective to produce yttrium fluoride, yttrium oxyfluoride, or both. In certain exemplary embodiments, the method produces a significant or large amount of yttrium oxyfluoride without completely converting yttrium oxide to yttrium fluoride. For example, at least 50, 70, 80, or 90% (atomic) of the yttrium oxide can be converted to yttrium oxyfluoride (YOF), but cannot be fully fluorinated to yttrium fluoride (YF3).

[0042] In another example, the method not only fluorinates yttrium oxide to form yttrium oxyfluoride (YOF), but also produces a large amount of fully fluorinated yttrium fluoride. The temperature and amount of time of the fluoro-annealing step are sufficient to convert at least a significant portion of the yttrium oxide of the deposited yttrium oxide-metal oxide coating to yttrium fluoride (YF3), particularly in the surface portion of the deposited yttrium oxide-metal oxide coating, according to these exemplary methods. According to a useful or preferred method, the yttrium oxide present in at least the outer portion of the yttrium oxide-metal oxide coating, e.g., the "surface portion" of the coating, which includes a portion of the coating thickness between the surface and at least 1, 5 or 10 nanometers deep, is converted to YF3 that contains a small amount of oxygen or is substantially free of oxygen, e.g., less than 20 or 10 atomic percent oxygen, less than 5 or less than 3 atomic percent oxygen.

[0043] A preferred coating can include a yttrium portion (e.g., layer) that contains mainly yttrium and fluorine atoms, i.e., in the form of yttrium fluoride or YF3. The yttrium fluoride of the coating can also contain a certain amount of oxygen, as well as combinations of various elements of yttrium, fluorine, and oxygen, such as yttrium oxyfluoride (YOF). However, certain preferred exemplary coatings as described can contain yttrium mainly in the form of yttrium fluoride (YF3) and an amount (concentration) of oxygen that is less than the amount of oxygen that would be present in a composition called yttrium oxyfluoride (YOF), for example, the coating can contain at least 80 percent (e.g., at least 85, 90, or 95 percent) (atoms) of yttrium fluoride based on the total amount of yttrium fluoride, yttrium oxide, and yttrium oxyfluoride.

[0044] Because the coatings as described are prepared by converting yttrium oxide of a precursor coating to yttrium oxide fluoride, and the process of converting yttrium oxide to yttrium fluoride requires the passage (e.g., diffusion) of fluorine from the surface of the coating to a location below the surface, the coating may contain concentrations of fluorine and oxygen that are non-uniform through the thickness (depth), i.e., the coating or a yttrium oxide fluoride portion (e.g., layer) thereof may contain concentrations of fluorine and oxygen that vary by measurable amounts along the thickness (depth) of the deposited coating.

[0045] In a particular example of a coating, the yttrium oxide fluoride-metal oxide coating includes a portion (referred to as the yttrium fluoride portion) that is substantially converted (fluorinated) from yttrium oxide to yttrium fluoride. The yttrium fluoride portion may be one or more layers of yttrium fluoride, or may be a yttrium fluoride material that is part of a laminate or composite structure. The yttrium fluoride portion may preferably contain substantially only yttrium, fluorine, oxygen, possibly a relatively small amount of carbon ("C") (e.g., up to 4 or 5 atomic percent carbon), and less than or substantially none of other materials. The yttrium fluoride portion of the described coatings may consist of Y, F, O, and C (e.g., up to 4 or 5 atomic percent carbon), or may consist essentially of Y, F, O, and C, e.g., may contain Y, F, O, and C (e.g., 5 or 4 percent (atomic) or less of carbon) and 1, 0.5, 0.1, 0.05, or 0.01 atomic percent or less of any material different from Y, F, O, and C. Preferred yttrium fluoride portions can also contain 20 percent or less (e.g., 10 or 5 percent or less) (atomic percent) of oxygen.

[0046] On another basis, exemplary coatings can contain at least 70, 80 or 90 percent yttrium fluoride, based on the total (atomic) amount of yttrium fluoride, yttrium oxide and yttrium oxyfluoride, to a depth of at least 5, 10, 30, 50 or 60 nanometers below the surface of the coating. Other preferred coatings can contain at least 80 percent yttrium fluoride, based on the total (atomic) amount of yttrium oxide, yttrium fluoride and yttrium oxide fluoride, to a depth of at least 100, 200 or 300 nanometers below the surface of the coating.

[0047] Different portions of a coating can be identified and described by X-ray photoelectron spectroscopy or "XPS" techniques based on the variation in composition at different thickness locations of the coating. These quantitative spectroscopic techniques allow for compositional analysis of the deposited coating, or layers of the coating, at and below the surface of the material, throughout the thickness (depth) of the coating. XPS profiling analysis can identify the elemental composition of the deposited material at different locations along the thickness of the material.

[0048] The coatings of the present invention can also be analyzed by X-ray diffraction to show that a layer or portion of the coating contains a significant or high concentration of yttrium oxide fluoride, e.g., YF3, as opposed to other possible stoichiometric combinations of Y, F, and O. X-ray diffraction (XRD) is a known analytical technique for evaluating the atomic and molecular structure of materials, including materials of deposited films. For example, X-ray diffraction is useful for evaluating the structure and stoichiometric characteristics of deposited films of the type described herein, for example, prepared by atomic layer deposition.

[0049] Referring to Figure 4, this is a table showing exemplary data regarding the chemical makeup of an exemplary precursor coating ("as deposited") and the same coating after a fluoro-annealing step ("F" for fluorination). The data is generated by Energy Dispersive X-ray Spectroscopy, also known as EDAX.

[0050] Data refer to the chemical makeup of three exemplary coatings as determined by 5 keV EDAX. Yttria-zirconia multilayer coatings are: (a) Zr-Y-Comp = composite of yttria and zirconia, (b) Zr-Y-ML = multilayer consisting of 20 alternating layers of zirconia and yttria, (c) Y-Zr-DL = bilayer with zirconia on the bottom and yttria on top, all deposited on Si substrates.

[0051] The table compares the atomic % values ​​measured for the probed elements of Si, Zr, Y, O and F for the coating stack as deposited (before fluorination) and for the coating stack after the fluoro-annealing process. Note that the EDAX atomic % values ​​are not calibrated and serve as a relative comparison between the as-deposited and post-fluoro-annealed states, rather than absolute values. The table shows that yttria (Y2O3) as deposited is highly converted to YF3 as a result of the fluoro-annealing process. Considering the distribution of atomic % to form Y2O3, YF3 and ZrO2, the results in the table show that the majority of Y2O3 is converted to YF3, but ZrO2 is not converted to fluoride. Independent studies on zirconia show that it is not converted to zirconium fluoride or zirconium oxyfluoride.

[0052] Note that the 5 keV EDAX measurements have a probe depth of 150 nm to 200 nm, but have a nonlinear (higher) signal contribution from volumes closer to the surface. For each condition, the coating film thickness is small enough that the EDAX measurements pick up a small percentage of the signal from the substrate (Si). The oxygen atomic % is disproportionately high due to the typical surface oxide formation.

[0053] Methods for converting yttrium oxide to yttrium oxyfluoride (YOF) by a fluoro-annealing step carried out at a temperature below 300° C. have been previously described. See US Patent Publication No. 2018 / 0202047. The methods described herein include specific features of a fluoro-annealing step carried out at a temperature above 300° C. to successfully convert yttrium oxide at least in the surface portion of the described deposited coating to contain a high concentration of yttrium fluoride (YF3) containing a small amount of oxygen, substantially free of oxygen, or containing a small amount of yttrium oxyfluoride (YOF) or substantially free of yttrium oxyfluoride (YOF).

[0054] The method of forming the described yttrium oxide fluoride-metal oxide coating by atomic layer deposition has been identified as being particularly effective in producing coatings containing large amounts of yttrium fluoride and metal oxide.The described method has been shown to be particularly effective in forming coatings containing high concentrations of yttrium fluoride and metal oxide, including zirconium oxide as the preferred metal oxide, compared to alternative deposition methods including other techniques for depositing yttrium oxide (e.g., chemical vapor deposition, physical vapor deposition, or variations thereof) followed by a fluoro-annealing step.The method herein is also particularly effective when the non-yttrium metal oxide is zirconium oxide, which has been identified as being particularly effective in enabling fluorination of the yttrium oxide below the surface of the yttrium oxide-metal oxide coating.

[0055] In terms of deposition techniques, atomic layer deposition has improved effectiveness in forming yttrium fluoride by fluoro-annealing process compared to other deposition techniques.The described yttrium fluoride coating (i.e., coating containing high degree of yttrium oxide converted to yttrium fluoride) can be prepared by converting deposited yttrium oxide thin film to yttrium fluoride using a relatively high temperature fluoro-annealing process, for example, a fluoro-annealing process carried out at a temperature of at least 300°C.Comparable fluoro-annealing techniques at relatively high temperatures that attempt to convert yttrium oxide to yttrium fluoride have not been as effective as those carried out on yttrium oxide deposited by different deposition techniques, such as physical vapor deposition ("PVD") or chemical vapor deposition ("CVD").

[0056] These particular processes have also been determined to be more effective in forming yttrium fluoride as a metal fluoride material compared to methods of forming other types of metal fluorides from other metals by comparable deposition and fluoro-annealing processes. The described high temperature fluoro-annealing processes have not been very effective in converting other metal oxides to metal fluorides, even if the metal oxides are deposited by atomic layer deposition techniques. Specifically, it has been found that fluoro-annealing processes at relatively high temperatures are not very effective in converting metal oxide materials such as zirconium oxide, titanium oxide, or aluminum oxide to fluoride oxide materials (zirconium fluoride, titanium fluoride, or aluminum fluoride), even if the metal oxides are deposited by atomic layer deposition techniques.

[0057] A useful and preferred fluoro-annealing technique involves exposing the surface of a yttrium oxide-metal oxide coating deposited on a surface by atomic layer deposition to a molecular fluorine source vapor at a temperature that causes the fluorine of the molecular fluorine source vapor to react with the yttrium oxide of the deposited yttrium oxide-metal oxide coating to convert the yttrium oxide of the coating to yttrium oxide fluoride, preferably with a high conversion to yttrium fluoride, at and below the surface of the deposited yttrium oxide-metal oxide coating.

[0058] Preferably, the metal oxide of the coating should not be reactive with the molecular fluorine source vapor to allow the molecular fluorine source to penetrate below the surface of the yttrium oxide-metal oxide coating. For example, preferred metal oxides are not decomposed (e.g., are not "etched") by the molecular fluorine source vapor during the fluoro-annealing step. Also, preferably, the molecular fluorine source vapor does not cause fluorination of the metal oxide during the fluoro-annealing step. Although the present specification and the invention are not limited to the use of any particular metal oxide as the non-oxidized yttrium metal oxide of the fluorinated yttrium oxide-metal oxide coating, zirconium oxide is a metal oxide that has been identified as exhibiting the advantageous or preferred properties of being resistant to decomposition by the molecular fluorine source vapor and also resistant to fluorination by the molecular fluorine source vapor during the fluoro-annealing step.

[0059] As used herein, a "molecular fluorine source vapor" is a non-plasma (i.e., molecular) fluorine-containing chemical molecule in vapor (gas) form that is not considered a plasma. A "plasma" is a non-solid vapor phase composition that contains a high density of ionic fragments derived from one or more plasma precursor compounds that have been intentionally exposed to energy (e.g., from a radio frequency power source) for the purpose of breaking down the plasma precursor compounds into ions and using the ions to process a workpiece. In contrast to a plasma, a useful or preferred molecular fluorine source vapor may contain less than 1×10E-5 atomic percent of ionized material, e.g., less than 1×10E-6 atomic percent of ionic species.

[0060] Molecular fluorine source vapor can be provided by any method or from any useful and effective source or location to the process chamber for use in the fluoro-annealing step to form the described fluorinated yttrium oxide-metal oxide coating. In a useful or preferred method, the molecular fluorine source vapor can be generated in situ, i.e., during the fluoro-annealing step and in the process chamber used for the fluoro-annealing step. The molecular fluorine source vapor can be generated in situ from a non-gaseous fluorine source by heating the non-gaseous fluorine source to turn the molecules of the non-gaseous fluorine source into a gas, i.e., molecular vapor. The non-gaseous fluorine source can be a liquid or solid fluorine-containing material, and the heating step generates the gaseous form of the molecules without causing significant decomposition or ionization of the molecules of the liquid or solid fluorine source. The useful or preferred gaseous form of the molecules can be at least 99.9999 atomic percent of the molecules, i.e., the molecules of the liquid or solid fluorine-containing material that are not chemically altered. The gaseous form of the molecule may contain less than 1×10E−5 atomic percent of ionized or decomposed material, such as less than 1×10E−6 atomic percent of ionic species.

[0061] The heating process to generate molecular fluorine source vapor is different from the process to generate plasma used in various semiconductor processing steps. In general, the plasma generation process involves applying one or more forms of energy to a plasma source, typically a gaseous chemical, to ionize the plasma source and chemically break down the molecules of the plasma source to generate ionic fragments of the molecules. The energy may be thermal energy (high temperature), electromagnetic radiation such as RF (radio frequency energy) (generated by a radio frequency power source), or a combination of these.

[0062] As a specific comparison, the heating step herein used to generate a molecular fluorine source vapor is different from the step of generating a fluorine-containing plasma for use in a semiconductor processing tool for the steps of plasma etching, plasma cleaning, or "seasoning" the process chamber of the semiconductor processing tool. An example of a plasma generation step different from the heating step described herein is described in U.S. Patent No. 5,756,222, which describes a fluorine-containing plasma generated in a reaction chamber designed for plasma etching or plasma cleaning processes. The plasma is prepared by exposing a fluorine precursor to RF power.

[0063] The fluoro-annealing step may be carried out in a process chamber at an elevated temperature by placing a substrate having a surface including a yttrium oxide-metal oxide coating deposited thereon by atomic layer deposition inside a process chamber in a removable, temporary, non-operational manner; by distributing a molecular fluorine source vapor into the process chamber or generating a molecular fluorine source vapor within the process chamber by heating a non-gaseous fluorine source to cause molecules of the non-gaseous fluorine source to become a gas, i.e., a vapor, within the process chamber; and by increasing the temperature of the process chamber, the substrate, the deposited yttrium oxide-metal oxide coating, the molecular fluorine source vapor, or a combination thereof, to cause a reaction between the fluorine of the molecular fluorine source vapor and the yttrium oxide of the deposited yttrium oxide-metal oxide coating to convert at least a portion of the yttrium oxide to yttrium oxide fluoride, preferably yttrium fluoride.

[0064] During the fluoro-annealing step, the process chamber may contain process materials including molecular fluorine source vapor, optionally a non-vapor fluorine source, and one or more substrates having a deposited yttrium oxide-metal oxide thin film deposited on the surface by atomic layer deposition techniques. The interior space and atmosphere of the chamber need not be evacuated or depressurized, and may contain a certain amount of atmospheric air. For the fluoro-annealing step, it is not necessary to exclude air or oxygen, nor to introduce an inert gas (purge gas, e.g., N2) into the process chamber. The process chamber need not contain, and may exclude, any other additional gaseous or liquid process materials other than air and molecular fluorine source vapor, and may exclude other gaseous materials, such as inert gases or gaseous co-reactants that may be used in the gaseous atmospheres of other semiconductor processing steps.

[0065] The process chamber need not, and preferably does not, contain other workpieces, such as semiconductor devices, microelectronic devices, or precursors thereof, that are not part of a semiconductor processing tool and are otherwise being processed. The process chamber also does not require or include the use of means for generating a plasma, such as a radio frequency power source, or means for applying an electrical potential (voltage) to components or workpieces.

[0066] Useful process chambers preferably include temperature controls for controlling the temperature within the chamber; means for controlling the composition and purity of the environment inside the chamber, e.g., pressure control, filters, etc.; components for temporarily housing and supporting within the chamber one or more substrates, each having a deposited yttrium oxide-metal oxide coating thereon, for a period of time useful for converting the yttrium oxide of the deposited yttrium oxide-metal oxide coating to yttrium oxide fluoride, preferably to yttrium fluoride; and components for controlling the composition of the atmosphere within the process chamber, including supplying and controlling the amount and concentration of a molecular fluorine source within the process chamber.

[0067] According to certain useful or preferred exemplary fluoro-annealing methods, the molecular fluorine source vapor may be a gaseous fluorinated or perfluorinated organic compound, such as a fluorinated or perfluorinated alkane or alkene, any of which may be linear or branched. Examples include, among others, CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, each of which is in molecular form, i.e., substantially non-ionic, and is not treated (by application of energy other than heat) to decompose or form a plasma.

[0068] According to another useful or preferred exemplary method, the molecular fluorine source vapor can be a gaseous fluorinated polymer that has not been treated with energy to form a plasma. The gaseous fluorinated polymer can be derived from a non-gaseous (e.g., liquid or solid) fluorinated polymer, which is desirably converted to yttrium oxide fluoride by a fluoro-annealing step, for example, by heating the non-gaseous fluorinated polymer in the presence of a deposited yttrium oxide-metal oxide coating in a process chamber.

[0069] The fluorinated polymer may be any fluorinated polymer that is effective according to the described method for forming yttrium fluoride from the deposited yttrium oxide-metal oxide coating present on the surface of the substrate. Examples of useful fluorinated polymers include homopolymers and copolymers that include polymerized fluoroolefin monomers and optionally non-fluorinated comonomers. The polymer may be fluorinated (i.e., partially fluorinated), perfluorinated, or may contain non-fluorine halogen atoms such as chlorine. The molecular fluorine source may be a liquid or solid at room temperature, but becomes a vapor at the temperature of the process chamber used according to the described method.

[0070] Non-limiting examples of specific fluoropolymers include C1-C 10Examples of suitable perfluoroalkyl ethylenes include polymerized perfluoroalkyl groups; polytetrafluoroethylene (PTFE); tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymers (PFA); tetrafluoroethylene / hexafluoropropylene copolymers (FEP); tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymers (EPA); polyhexafluoropropylene; ethylene / tetrafluoroethylene copolymers (ETFE); polytrifluoroethylene; polyvinylidene fluoride (PVDF); polyvinyl fluoride (PVF); polychlorotrifluoroethylene (PCTFE); ethylene / chlorotrifluoroethylene copolymers (ECTFE); or combinations thereof.

[0071] The described fluoro-annealing process can be carried out at any temperature effective to cause the fluorine from the fluorine source vapor to react with the yttrium oxide of the deposited yttrium oxide-metal oxide coating to convert at least a portion of the fluorine of the deposited yttrium oxide-metal oxide coating to yttrium oxide fluoride, preferably to yttrium fluoride (e.g., at the concentrations and depths described herein). A relatively high elevated temperature is generally useful or preferred to cause the fluorine source vapor to react with the yttrium oxide to convert the yttrium oxide to a high concentration of yttrium fluoride (YF3) instead of yttrium oxyfluoride (YOF). However, other conditions may be useful to produce coatings having a relatively low concentration of yttrium fluoride and a relatively high concentration of yttrium oxyfluoride (YOF), as desired.

[0072] Exemplary temperatures for the fluoro-annealing step may be at least 300° C. or 350° C., or higher, for example in the range of 300° C. to 500° C., for example 350° C. or 400° C. to 425° C. or 450° C., to produce a high concentration of YF in at least a surface portion of the deposited yttrium oxide-metal oxide coating.

[0073] The process chamber can be operated at any useful pressure, with exemplary pressures being about atmospheric pressure (760 Torr), such as 100 to 1500 Torr, such as 250 or 500 to 1000 or 1250 Torr. The atmosphere within the process chamber for converting yttrium oxide to yttrium oxide fluoride, such as yttrium fluoride, may include a portion that is air in combination with a molecular fluorine source vapor.

[0074] The amount of time used to form yttrium oxide fluoride by the fluoro-annealing step can be based on factors such as the temperature of the fluoro-annealing step, the type and amount (concentration) of molecular fluorine source vapor in the process chamber, the thickness and composition of the deposited yttrium oxide-metal oxide coating, and the desired amount of fluorination (e.g., depth) of the yttrium oxide-metal oxide coating achieved by the fluoro-annealing step. Examples of useful or preferred amounts of time for the fluoro-annealing step can range from 1 to 48 hours, such as 2 to 24 hours, or 3 to 12 hours. A useful period for performing the fluoro-annealing step can be a period of time that converts a desired amount (e.g., in terms of depth and amount (concentration)) of yttrium oxide of the yttrium oxide-metal oxide coating to yttrium oxyfluoride or yttrium fluoride. The depth of fluorination increases over time during the fluoro-annealing step by continuously exposing the deposited yttrium oxide-metal oxide coating to molecular fluorine source vapor.

[0075] 3, exemplary steps of the described method and exemplary yttrium oxide fluoride-metal oxide coatings are shown. According to the method 10, a substrate 20 is provided, and in step (i), a yttrium oxide-metal oxide layer 22(a) is applied to a surface of the substrate 20 by atomic layer deposition. In step (ii), the substrate 20 with the thin yttrium oxide-metal oxide coating 22(a) deposited thereon is subjected to a fluoro-annealing step to convert at least a portion of the yttrium oxide of the yttrium oxide-metal oxide coating 22(a) to yttrium oxide fluoride, producing a yttrium oxide fluoride-metal oxide coating 24(b).

[0076] The described yttrium oxide fluoride-metal oxide coatings, including at least a portion containing a high concentration of yttrium oxide fluoride, such as yttrium fluoride (YF), can be effective as protective coatings that are chemically resistant to various process materials, particularly (but not limited to) halides that may be present in various types of process chambers during operation to carry out the manufacturing processes, certain exemplary processes of which are described herein, whether known or developed in the future.

[0077] Yttrium oxide fluoride compounds, especially yttrium fluoride, can contain a relatively high concentration of fluorine to provide chemical inertness to fluorine atoms. Furthermore, the presence of non-oxidized yttrium metal oxide enhances chemical resistance to non-fluorine halides such as chlorine. Thus, the level of chemical resistance achieved by the yttrium oxide fluoride-metal oxide coatings described herein can be highly useful or relatively improved compared to the level of chemical resistance achieved by previous protective materials.

[0078] Useful and preferred yttrium oxide fluoride-metal oxide coatings can also be heat resistant for extended periods of time, including during use at high temperatures (e.g., in the range of 350-500° C.) in semiconductor processing tools. More generally, useful or preferred yttrium oxide fluoride-metal oxide coatings can resist decomposition at temperatures up to or exceeding 200, 300, 400, 450 or 500° C. for extended periods of time.

[0079] The equipment, device, or article comprising the yttrium oxide fluoride-metal oxide coating as a protective coating can comprise a substrate comprising the yttrium oxide fluoride-metal oxide coating formed on the surface of the substrate. Advantageously, the yttrium oxide fluoride-metal oxide coating can be prepared using two specific process steps, each of which includes vapor deposition, i.e., atomic layer deposition of the yttrium oxide-containing precursor coating and fluoro-annealing of the deposited yttrium oxide-containing precursor, so that the produced yttrium oxide fluoride-metal oxide coating can be effectively and uniformly applied to substrate surfaces that are highly three-dimensional or have high aspect ratios. Useful yttrium oxide fluoride-metal oxide coatings can be applied to three-dimensional surfaces that include channels, grooves, or openings, such as structures with relatively high aspect ratios, for example, aspect ratios of 10:1, 20:1, 50:1, up to 100:1 or more.

[0080] Examples of substrates to which the described protective fluorinated yttrium oxide-metal oxide coatings can be applied include items such as various components of process chambers ("process chamber components") used to prepare semiconductor materials, microelectronic devices, etc. Because they are resistant to process materials such as halides, including combinations of different halides such as fluorine and chlorine, the fluorinated yttrium oxide-metal oxide coatings can be used to protect process chamber components in the presence of these and other process materials during operation.

[0081] Preferred protective coatings can be prepared to contain low amounts of defects such as cracks, crevices, pinholes, and other physical defects. Defects such as pinholes, cracks, and crevices can be identified by visual inspection, optionally under magnification using an optical microscope or a scanning electron microscope, or other suitable inspection methods. Preferred coatings can also be applied to exhibit a high level of coating thickness uniformity across the surface of the coating, especially when compared to coatings applied by other methods such as physical vapor deposition. For example, a high level of uniformity can refer to a coating that is less than 2 microns thick over an area of ​​1, 5, or 10 square centimeters and does not vary in thickness by more than 20, 10, or 5 percent over that area.

[0082] The described protective coatings can be formed and useful on any surface or substrate to which a fluorinated yttrium oxide-metal oxide coating can be effectively applied. In certain embodiments, the substrate may be made of a vacuum-compatible substrate material or may be in the form of a component of a process chamber used to process substrates, materials, or devices by the use of one or more different process materials that are highly reactive, corrosive, or may violently degrade or react with other materials, including the internal components of the process chamber. In this regard, the described fluorinated yttrium oxide-metal oxide coatings can be advantageously applied to substrates that are referred to herein as "vacuum-compatible substrates" and that are formed to function as components (herein "process chamber components" or "process tool components") of process chambers used to process microelectronic devices, semiconductor equipment and devices, their precursors, and the like, by treatment with process materials that include halides or combinations of halides.

[0083] The process chamber is useful for containing highly corrosive or reactive process materials, which may be in the form of liquids, gases, or plasmas, used to treat microelectronic or semiconductor device substrates, for example, during the process of manufacturing microelectronic or semiconductor devices. Specific examples of reactive process materials include bromine plasmas, chlorine plasmas, and fluorine plasmas, such as plasmas derived from NF3, CF4, C2F6, C3F8, C4F8, F2, Cl2, HCl, HF, CHF3, CH2F2, SF6, BCl3, CCl4, or HBr.

[0084] The process chamber must include process chamber components and surfaces useful for transporting, holding, securing, supporting, or moving the workpiece in, out of, and within the process chamber without being unduly degraded by the process materials present in the process chamber. The process chamber must also include a system of structure effective for flowing, delivering, and removing reactive process materials (e.g., plasma) into and out of the process chamber.

[0085] Examples of process chamber components include articles of any shape that includes a flat, planar, essentially two-dimensional surface, but also articles with more complex shapes. Advantageously, the method and thin film can be used with substrates that have physical shapes or forms that are three-dimensional forms, including features that are considered to have high aspect ratios, such as openings, apertures, channels, tunnels, threaded screws, threaded nuts, porous membranes, filters, three-dimensional networks, holes, channels, forms that include extended surfaces, etc. More specific exemplary structures include flow heads (showerheads), shields, trays, supports, nozzles, valves, conduits, stages for handling or holding substrates, wafer handling fixtures, chamber liners, ceramic wafer carriers, wafer holders, susceptors, spindles, chucks, rings, baffles, and various types of fasteners (screws, nuts, bolts, clamps, rivets, etc.).

[0086] The described atomic layer deposition and fluoro-annealing techniques are vapor phase deposition techniques that are effective for providing uniform, high quality deposited thin films on three-dimensional surfaces, including surfaces having aspect ratios of at least 10:1, 20:1, 50:1, 100:1, or more.

[0087] The substrate of the process chamber component on which the yttrium oxide fluoride-metal oxide coating can be formed can be made from a variety of different solid materials, including materials that are sometimes referred to as "vacuum-compatible" substrate materials. In general, examples can include ceramic materials, metals, and metal alloys, which can be coated with a protective coating and used in the process chamber. Examples of ceramic materials that can be useful as vacuum-compatible substrates include alumina, silicon carbide, silicon, silicon oxide, and aluminum nitride. Examples of metals and metal alloys include nickel, nickel alloys, stainless steel, and aluminum. Vacuum-compatible substrates can also be quartz, sapphire, silica, fused silica, fused quartz, silicon, anodized aluminum, zirconium oxide, glass, and plastics such as certain plastics used in the semiconductor industry, such as polyether ether ketone (PEEK) and polyimide.

[0088] Although the present specification often refers to process chambers and process chamber components (e.g., etch chamber components) as useful substrates for the described protective coatings, the described yttrium oxide fluoride-metal oxide coatings are not limited to use with these items. As described herein, various other ceramic, mineral, metal, and metal alloy articles and substrates that would benefit from a protective coating having a high level of resistance to highly reactive chemical materials can also be treated to place a yttrium oxide fluoride-metal oxide coating on their surface.

[0089] Embodiment 1. A coated substrate comprising a substrate and a coating on a surface of the substrate, the coating comprising yttrium oxide fluoride and zirconium oxide.

[0090] Embodiment 2. The coated substrate of embodiment 1, wherein the yttrium oxide fluoride is selected from yttrium oxyfluoride (YOF), yttrium fluoride (YF3), and combinations thereof.

[0091] Embodiment 3. The coated substrate of embodiment 2, wherein the coating comprises a plurality of layers including at least one yttrium fluoride layer and at least one zirconium oxide layer.

[0092] Example 4. The coated substrate of example 3, wherein the coating comprises a total of 3 to 10 yttrium fluoride and zirconium oxide layers.

[0093] Embodiment 5. The coated substrate of embodiment 4, wherein each layer has a thickness in the range of 2 to 50 nanometers.

[0094] Embodiment 6. The coated substrate of embodiment 3, wherein the coating comprises a total of 5 to 1000 yttrium fluoride and zirconium oxide layers.

[0095] Example 7. The coated substrate of example 6, wherein each layer has a thickness in the range of 0.1 to 10 nanometers.

[0096] Example 8. The coated substrate of example 1, wherein the coating is a composite comprising yttrium fluoride and zirconium oxide.

[0097] Example 9. The coated substrate of any of Examples 1-7, wherein the coating contains less than 20 atomic percent yttrium oxide, based on the total amount of yttrium fluoride, yttrium oxide, and yttrium oxyfluoride.

[0098] Example 10. The coated substrate of any of Examples 1-9, wherein the coating is an atomic layer deposition coating.

[0099] Example 11. The coated substrate of example 10, wherein the coating is a fluoro-annealing coating.

[0100] Example 12. The coated substrate of any one of Examples 1-11, wherein the substrate comprises a three-dimensional structure having an aspect ratio of at least 10:1.

[0101] Embodiment 13. The coated substrate of any one of embodiments 1-12, wherein the substrate is a process tool component of a microelectronic device or semiconductor manufacturing system.

[0102] Embodiment 14. The coated substrate of any of embodiments 1-13, wherein the substrate comprises a wall of a plasma etch chamber, a wafer susceptor, a chuck, a showerhead, a liner, a ring, a nozzle, a baffle, a fastener, a wafer support, a wafer transport structure, or a portion or component of any one of these.

[0103] Embodiment 15. The coated substrate of any of embodiments 1-13, wherein the substrate comprises three-dimensional features selected from a threaded screw, a threaded nut, a porous membrane, a filter, a three-dimensional network, a hole, and a channel.

[0104] Example 16 The coated substrate of any one of Examples 1-15, wherein the substrate comprises aluminum, stainless steel, nickel, quartz, glass, or ceramic.

[0105] Embodiment 17. A method for preparing a coating containing yttrium oxide fluoride and zirconium oxide, comprising depositing a coating comprising yttrium oxide and zirconium oxide on a surface by atomic layer deposition, and exposing the coating to a molecular fluorine source vapor and high temperature to convert the yttrium oxide of the coating to yttrium oxide fluoride.

[0106] Embodiment 18. The method of embodiment 17, wherein the yttrium oxide fluoride is selected from yttrium oxyfluoride (YOF), yttrium fluoride (YF3), and combinations thereof.

[0107] Example 19. The method of example 18, wherein the coating comprises a plurality of layers including at least one yttrium fluoride layer and at least one zirconium oxide layer.

[0108] Example 20. The method of example 19, wherein the coating comprises a total of 3 to 10 yttrium fluoride and zirconium oxide layers.

[0109] Embodiment 21. The method of embodiment 20, wherein each layer has a thickness in the range of 2 to 50 nanometers.

[0110] Example 22. The method of example 19, wherein the coating comprises a total of 5 to 1000 yttrium fluoride layers and zirconium oxide layers.

[0111] Example 23. The method of example 22, wherein each layer has a thickness in the range of 0.1 to 10 nanometers.

[0112] Example 24. The method of example 18, wherein the coating is a composite comprising yttrium fluoride and zirconium oxide.

[0113] Example 25: The method of any of Examples 17-24, wherein at least 80% of the yttrium oxide of the coating is converted to yttrium fluoride by exposing the yttrium oxide to fluorine and high temperature.

[0114] Embodiment 26. The method of any of embodiments 17-25, further comprising exposing the yttrium oxide to a molecular fluorine source vapor at a temperature of at least 300° C. to convert the yttrium oxide to yttrium fluoride.

[0115] Embodiment 27. The method of embodiment 26, wherein the molecular fluorine source vapor is induced by heating the fluorinated polymer.

[0116] Example 28 The method of example 27, wherein the fluorinated polymer is a homopolymer or copolymer comprising polymerized fluoroolefin monomers.

[0117] 29. The fluorinated polymer is C1-C 10 28. The method of embodiment 27, comprising polymerized perfluoroalkyl ethylene having a perfluoroalkyl group; polytetrafluoroethylene (PTFE); tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA); tetrafluoroethylene / hexafluoropropylene copolymer (FEP); tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA); polyhexafluoropropylene; ethylene / tetrafluoroethylene copolymer (ETFE); polytrifluoroethylene; polyvinylidene fluoride (PVDF); polyvinyl fluoride (PVF); polychlorotrifluoroethylene (PCTFE); ethylene / chlorotrifluoroethylene copolymer (ECTFE); or a combination thereof.

[0118] Embodiment 30. The method of embodiment 27, wherein the molecular fluorine source vapor comprises CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, or a combination thereof.

[0119] Embodiment 31. A coated substrate comprising: a substrate; and a coating on a surface of the substrate, the coating comprising yttrium oxide fluoride and a metal oxide different from yttrium oxide.

[0120] Example 32. The coated substrate of example 31, wherein the yttrium oxide fluoride is selected from yttrium oxyfluoride (YOF), yttrium fluoride (YF3), and combinations thereof.

[0121] Example 33. The coated substrate of example 32, wherein the coating comprises a plurality of layers including at least one yttrium fluoride layer and at least one metal oxide layer.

[0122] Example 34. The coated substrate of example 32, wherein the coating is a composite comprising yttrium fluoride and a metal oxide different from yttrium oxide.

[0123] Embodiment 35. The coated substrate of any one of embodiments 30-34, wherein the coating is an atomic layer deposition coating.

[0124] Example 36. The coated substrate of example 35, wherein the coating is a fluoro-annealing coating.

[0125] Embodiment 37. The coated substrate of any one of embodiments 30-36, wherein the substrate is a process tool component of a microelectronic device or semiconductor manufacturing system.

[0126] Aspect 38. A method for preparing a coating containing yttrium fluoride and a metal oxide different from yttrium oxide, comprising depositing a coating comprising yttrium oxide and a metal oxide different from yttrium oxide on a surface by atomic layer deposition, and exposing the coating to a molecular fluorine source vapor and high temperature to convert the yttrium oxide of the coating to yttrium oxide fluoride.

[0127] Embodiment 39. The method of embodiment 38, wherein the coating comprises a plurality of layers including at least one yttrium fluoride layer and at least one metal oxide layer.

[0128] Embodiment 40. The method of embodiment 39, wherein the coating comprises a total of 3 to 10 yttrium fluoride layers and metal oxide layers.

[0129] Embodiment 41. The method of embodiment 40, wherein each layer has a thickness in the range of 2 to 50 nanometers.

[0130] Embodiment 42. The method of embodiment 41, wherein the coating comprises a total of 5 to 1000 yttrium fluoride layers and metal oxide layers.

[0131] Example 43. The method of example 42, wherein each layer has a thickness in the range of 0.1 to 10 nanometers.

[0132] Embodiment 44. The method of embodiment 38, wherein the coating is a composite comprising yttrium fluoride and a metal oxide.

Claims

1. A substrate; A coating on the surface of the substrate; wherein the coating comprises: yttrium oxide fluoride, and Zirconium oxide A coated substrate comprising:

2. Yttrium oxide fluoride is also known as yttrium oxyfluoride (YOF), yttrium fluoride (YF ３ 10. The coated substrate of claim 1, wherein the at least one aryl group is selected from the group consisting of aryl, aryloxy ...

3. The coated substrate of claim 2 , wherein the coating comprises multiple layers including at least one yttrium fluoride layer and at least one zirconium oxide layer.

4. The coated substrate of claim 3, wherein the coating comprises a total of 3 to 10 yttrium fluoride and zirconium oxide layers.

5. The coated substrate of claim 4, wherein each layer has a thickness in the range of 2 to 50 nanometers.

6. The coated substrate of claim 3, wherein the coating comprises a total of 5 to 1000 yttrium fluoride and zirconium oxide layers.

7. The coated substrate of claim 6, wherein each layer has a thickness in the range of 0.1 to 10 nanometers.

8. 10. The coated substrate of claim 1, wherein the substrate comprises a wall of a plasma etch chamber, a wafer susceptor, a chuck, a showerhead, a liner, a ring, a nozzle, a baffle, a fastener, a wafer support, a wafer transfer structure, a threaded screw, a threaded nut, a porous membrane, a filter, a three-dimensional network, a hole, and a channel, or a portion or component of any one of these.

9. The coated substrate of claim 1 , wherein the substrate comprises aluminum, stainless steel, nickel, quartz, glass, or ceramic.

10. 1. A method for preparing a coating containing yttrium oxide fluoride and zirconium oxide, comprising: depositing a coating comprising yttrium oxide and zirconium oxide on the surface by atomic layer deposition; exposing the coating to a molecular fluorine source vapor and elevated temperature to convert the yttrium oxide of the coating to yttrium oxide fluoride; A method comprising:

11. Yttrium oxide fluoride is also known as yttrium oxyfluoride (YOF), yttrium fluoride (YF ３ 11. The method of claim 10, wherein the compound is selected from the group consisting of , , and combinations thereof.

12. The method of claim 10 , wherein the coating comprises multiple layers including at least one yttrium fluoride layer and at least one zirconium oxide layer.

13. The method of claim 10, wherein each layer has a thickness in the range of 2 to 50 nanometers.

14. The method of claim 10, wherein each layer has a thickness in the range of 0.1 to 10 nanometers.

15. 11. The method of claim 10, wherein at least 80% of the yttrium oxide of the coating is converted to yttrium fluoride by exposing the yttrium oxide to fluorine and high temperature.

16. 16. The method of claim 15, further comprising exposing the yttrium oxide to a molecular fluorine source vapor at a temperature of at least 300° C. to convert the yttrium oxide to yttrium fluoride.

17. 17. The method of claim 16, wherein the molecular fluorine source vapor is induced by heating the fluorinated polymer.

18. The fluorinated polymer is C １ ~C １０ 17. The method of claim 16, comprising polymerized perfluoroalkyl ethylene having a perfluoroalkyl group; polytetrafluoroethylene (PTFE); tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA); tetrafluoroethylene / hexafluoropropylene copolymer (FEP); tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA); polyhexafluoropropylene; ethylene / tetrafluoroethylene copolymer (ETFE); polytrifluoroethylene; polyvinylidene fluoride (PVDF); polyvinyl fluoride (PVF); polychlorotrifluoroethylene (PCTFE); ethylene / chlorotrifluoroethylene copolymer (ECTFE); or combinations thereof.

19. The molecular fluorine source vapor is CF ４ , C ２ F ４ , C ３ F ６ , C ４ F ８ , C.H.F. ３ , C ２ H ２ F ２ , C ２ F ６ , H.F., C.H. ３ F, or a combination thereof.

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