Metallic article, semiconductor processing system including metallic article, and method of making metallic article

Abstract

To provide a metal article, a semiconductor processing system including the metal article, and a method of making the metal article.SOLUTION: A method of making a metallic article includes forming a workpiece body from a bulk metallic material, forming a metallic oxide layer from the bulk metallic material overlaying the bulk metallic material by exposing the bulk metallic material to ozone (O3), and depositing a ceramic layer onto the metallic oxide layer. The bulk metallic material includes one of aluminum and nickel, and metallic articles and semiconductor processing systems including metallic articles are also described.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure generally relates to metal articles, and more specifically to metal articles having a ceramic layer laminated on a bulk metal material.

Background Art

[0002] Metal articles are commonly used in fluid systems such as semiconductor processing systems, gas turbine engines, and fluid systems used to communicate corrosive and / or high-temperature fluids in chemical processing applications. In some applications, the metal article may have a barrier coating that acts to separate the fluid conveyed by the fluid system from the bulk metal material forming the metal article, for example, to extend the expected service life of the metal article. The barrier coating may contain a suitable metal or rare earth metal for the fluid conveyed by the fluid system.

[0003] Although generally acceptable in terms of separating the fluid passing through the fluid system from the metal structure forming the fluid system, ceramic materials can be prone to delamination. Delamination can potentially expose the underlying bulk metal material to corrosive materials, so metal structures with ceramic barriers generally undergo periodic removal and replacement for scheduled inspections and / or repairs, increasing the ownership cost of fluid systems using such barrier materials.

[0004] Such systems and methods have generally been acceptable for their intended purposes. However, improved metal articles, methods, semiconductor processing systems having such metal articles, and methods of fabricating metal articles are still needed in the art. The present disclosure provides a solution to this need.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] A method of fabricating a metallic article is provided. The method includes forming a workpiece body from a bulk metallic material, where the bulk metallic material includes either aluminum or nickel; forming a metal oxide layer that deposits on the bulk metallic material from the bulk metallic material by exposing the bulk metallic material to ozone (O 3 ); and depositing a ceramic layer on the metal oxide layer.

[0007] In addition to, or instead of, one or more of the above features, a further embodiment of the method may include that the step of forming the workpiece body includes defining a first surface having a circular outer periphery, defining a second surface spaced from the first surface by a thickness, defining a plurality of flow openings within the workpiece body, and fluidly coupling the first surface to the second surface of the workpiece body.

[0008] In addition to, or instead of, one or more of the above features, a further embodiment of the method may include that the step of forming the metal oxide layer includes supporting the workpiece body within an ozone chamber, heating the workpiece body to about 200°C to about 400°C, or about 200°C to about 350°C, or about 200°C to about 300°C, or about 200°C to about 250°C, and exposing the workpiece body to ozone (O 3 ) gas for about 15 minutes to about 5 hours, or about 15 minutes to about 4 hours, or about 15 minutes to about 3 hours, or about 15 minutes to about 2 hours.

[0009] In addition to, or instead of, one or more of the above features, a further embodiment of the method may include wet cleaning the workpiece body before forming the metal oxide layer.

[0010] In addition to, or instead of, one or more of the above features, further embodiments of the method may include that a metal oxide layer is not substantially formed during wet cleaning.

[0011] In addition to, or instead of, one or more of the above features, further embodiments of the method further include that the metal oxide layer is a second metal oxide layer and that the method forms a first metal oxide layer on the workpiece body during wet cleaning, whereby the second metal oxide layer may include covering the first metal oxide layer after exposing the bulk metal material to ozone (O 3 ).

[0012] In addition to, or instead of, one or more of the above features, further embodiments of the method include that the step of depositing the ceramic layer includes depositing aluminum oxide (Al 2 O 3 ) or yttrium(III) oxide (Y 2 O 3 ) on the metal oxide layer.

[0013] In addition to, or instead of, one or more of the above features, further embodiments of the method include indirectly adhering the ceramic layer to the bulk metal material with the metal oxide layer and preventing the formation of a metal-ceramic bonding barrier transition between the bulk metal material and the ceramic layer that can act to limit the adhesion of the ceramic layer to the bulk metal material by exposing the bulk metal material to ozone (O 3 ).

[0014] In addition to, or instead of, one or more of the above features, further embodiments of the method may include fluidly connecting a fluid source to an exhaust source together with a metal article, communicating a corrosive fluid emitted by the fluid source through a pre-cleaning process space of the metal article to the exhaust source, pre-cleaning a substrate fluidly supported between the metal article and the exhaust source, supporting a substrate after pre-cleaning in a deposition process space remote from the pre-cleaning process space, and depositing a silicon-containing material layer on the silicon surface while being supported in the deposition process space. The corrosive fluid may include radical species, and the pre-cleaning may remove at least one of interfacial oxygen and interfacial carbon on the silicon surface of the substrate.

[0015] In addition to, or instead of, one or more of the above features, further embodiments of the method may include disposing a metal article within a chamber body of a semiconductor processing system above a substrate support such that the metal article fluidly connects an inlet port to an outlet port of the chamber body after depositing a ceramic layer on a metal oxide layer covering a bulk metal material.

[0016] In addition to, or instead of, one or more of the above features, further embodiments may include a showerhead metal article fabricated using the method.

[0017] A metal article is provided. The metal article includes a workpiece body formed from a bulk metal material, a metal oxide layer laminated on the bulk metal material, and a ceramic layer laminated on the metal oxide layer, and the metal oxide layer is an oxide formed (or converted) from the bulk metal material forming the workpiece body.

[0018] In addition to, or instead of, one or more of the above features, further embodiments of the metal article may include the bulk metal material including either aluminum or nickel.

[0019] In addition to, or instead of, one or more of the above features, further embodiments of the metal article may include the metal oxide layer being aluminum oxide (Al 2 O3 may include being nickel oxide (NiO).

[0020] In addition to, or instead of, one or more of the above features, a further embodiment of the metal article may include that the metal oxide layer has a thickness of about 10 nanometers to about 100 nanometers, or about 20 nanometers to about 80 nanometers, or about 20 nanometers to about 50 nanometers.

[0021] In addition to, or instead of, one or more of the above features, a further embodiment of the metal article is that alumina, aluminum oxide (Al 2 O 3 ) and yttrium(III) oxide (Y 2 O 3 ) may include a ceramic layer containing at least one of them. The ceramic layer may be formed using chemical vapor deposition technology or atomic layer deposition technology.

[0022] In addition to, or instead of, one or more of the above features, a further embodiment of the metal article may include that the metal workpiece is configured to transfer a corrosive fluid received on a first surface to a second surface through the thickness of a workpiece body formed of a bulk metal material.

[0023] In addition to, or instead of, one or more of the above features, a further embodiment of the metal article may include that the workpiece body defines a showerhead metal article for a semiconductor processing system.

[0024] In addition to, or instead of, one or more of the above features, a further embodiment of the metal article may include that the workpiece body has a first surface having a circular outer periphery, a second surface spaced from the first surface by a thickness, and a plurality of flow openings fluidly connecting the first surface to the second surface of the workpiece body, wherein the metal oxide layer extends continuously and without interruption along the inner surface of the plurality of flow openings.

[0025] In addition to, or instead of, one or more of the above features, a further embodiment of the metal article may include that a plurality of flow openings have an effective flow area width of from about 0.25 millimeter to about 4 millimeters, or from about 0.25 millimeter to about 3 millimeters, or from about 0.25 millimeter to about 2 millimeters, or from about 0.25 millimeter to about 1 millimeter.

[0026] A semiconductor processing system is provided. The semiconductor processing system includes a chamber body having an inlet port and an outlet port, a substrate support disposed inside the chamber body, the above-described metal article installed inside the chamber body and fluidly coupling the inlet port and the outlet port, a corrosive fluid source including a corrosive fluid connected to the inlet port, and an exhaust source connected to the outlet port.

[0027] This summary is provided to introduce selected concepts in a simplified form. These concepts are described in more detail in the following detailed description of examples of the present disclosure. This summary is not intended to identify key features or essential features of the subject matter recited in the claims, nor is it intended to be used to limit the scope of the subject matter recited in the claims.

[0028] These and other features, aspects, and advantages of the invention disclosed herein are described below with reference to the drawings of certain embodiments, which are intended to illustrate the invention and not to limit the invention.

Brief Description of the Drawings

[0029]

Figure 1

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Figure 14

Mode for Carrying Out the Invention

[0030] Of course, the elements in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. For example, the relative sizes of some of the elements in the figures may be exaggerated compared to other elements to assist in the understanding of the illustrated embodiments of the present disclosure.

[0031] Reference is now made to the drawings, in which like reference numerals identify similar structural features or aspects of the present disclosure. For purposes of illustration and example, and not limitation, a partial view of an example of a metal article according to the present disclosure is shown in FIG. 1 and is designated generally by reference numeral 100. Other examples of the metal article, semiconductor processing systems including the metal article, and methods of manufacturing the metal article, or aspects thereof, are provided in FIGS. 2-14, as will be described below. The metal article and method of manufacturing the metal article of the present disclosure may be used in a cluster-type platform for remotely pre-cleaning a substrate prior to depositing a silicon-containing material layer using chemical vapor deposition (CVD) and / or atomic layer deposition (ALD) techniques, such as a pre-cleaning module used in the manufacture of a showerhead for a pre-cleaning process module and a material layer deposition process module, but the present disclosure is not limited to a particular type of processing or to semiconductor processing systems in general.

[0032] Referring to FIG. 1, a portion of a metal article 100 is shown. In the illustrated example, the metal article 100 generally includes a workpiece body 102, a metal oxide layer 104, and a ceramic layer 106. The workpiece body 102 is formed from a bulk metal material 108, in which regard it may be composed of, or consist essentially of, the bulk metal material 108. In certain embodiments of the present disclosure, the bulk metal material 108 may include nickel (e.g., solid nickel (Ni) metal), nickel-based alloys, or nickel-containing alloys such as stainless steel. According to certain embodiments, the bulk metal material 108 may consist of, or consist essentially of, nickel (Ni) metal. Also, according to certain embodiments, it is contemplated that the bulk metal material 108 may include aluminum such as solid aluminum (Al) metal, aluminum-based alloys, or aluminum-containing alloys. In this regard, the bulk metal material 108 may consist of, or consist essentially of, aluminum (Al) metal, aluminum-based alloys, or aluminum-containing alloys.

[0033] The metal oxide layer 104 is laminated on the bulk metal material 108 and may be formed on the bulk metal material 108. In certain embodiments of the present disclosure, the metal oxide layer may be an oxide formed from the bulk metal material 108 that forms the workpiece body 102, and the bulk metal material 108 contributes metal atoms to the metal oxide layer 104 during the formation of the metal oxide layer 104. In this regard, it is contemplated that the metal oxide layer 104 may be conformally disposed on the bulk metal material 108. In a further aspect, the metal oxide layer 104 may seal substantially all of the bulk metal material 108. The metal oxide layer 104 is contemplated to comprise (or consist of, or consist essentially of) the oxides of the bulk metal material 108 that forms the workpiece body 102. For example, in an embodiment where the bulk metal material 108 is solid nickel, the metal oxide layer 104 may comprise (or consist of, or consist essentially of) nickel(II) oxide (NiO), although the metal oxide coating may comprise Ni(III) oxide (Ni 2 O 3 ), and mixtures thereof are contemplated within the scope of the present disclosure. In such embodiments, the nickel (Ni) metal contained within the nickel oxide (NiO) may be derived from the bulk metal material 108 that forms the workpiece body 102, and the nickel oxide (NiO) is formed by exposing the workpiece body to ozone (O 3 ).

[0034] In certain embodiments of the present disclosure, the bulk metal material 108 that forms the workpiece body 102 may be solid aluminum (Al) metal, and the metal oxide layer 104 may comprise (or consist of, or consist essentially of) aluminum oxide (Al 2 O 3 ). The aluminum (Al) component in the aluminum oxide (Al 2 O 3 ) in such embodiments may be derived from the solid aluminum (Al) metal that forms the workpiece body 102 and / or the natural aluminum oxide (Al 2 O 3) may occur through the coating, and aluminum oxide (Al 2 O 3 ) is formed by exposing aluminum (Al) metal (or through a natural aluminum oxide (Al 2 O 3 ) layer) to ozone (O 3 ).

[0035] The ceramic layer 106 is stacked (e.g., formed) on top of the metal oxide layer 104 and may be conformally disposed on the metal oxide layer 104. The ceramic layer 106 may further seal both the metal oxide layer 104 and the underlying bulk metal material 108. In certain embodiments, the ceramic layer 106 may include aluminum oxide (Al 2 O 3 ) or alumina, and in this regard, it may consist of, or consist essentially of, aluminum oxide (Al 2 O 3 ). According to certain embodiments, the ceramic layer 106 may include yttria and may consist of, or consist essentially of, yttrium(III) oxide (Y 2 O 3 ). The ceramic layer 106 may be deposited using ALD techniques, and it is contemplated that the ceramic layer 106 will be relatively high density and / or homogeneous compared to ceramic layers of similar compositions formed using other techniques such as CVD techniques. Also, the ceramic layer 106 may be formed using CVD techniques and it is also contemplated that this will remain within the scope of the present disclosure. As will be understood by those skilled in the art, as seen from the perspective of the present disclosure, in certain embodiments of the present disclosure, by coating the workpiece body 102 with aluminum oxide (Al 2 O 3 ) or alumina, or yttrium(III) oxide (Y 2 O 3 ), for example, without limitation, the recombination tendency of certain radical species such as certain halogen radicals such as hydrogen radicals and fluorine radicals can be restricted and their survival promoted, thereby improving the interaction of the metal workpiece with certain fluids.

[0036] The workpiece body 102 is contemplated to have a thickness 110, the metal oxide layer 104 is contemplated to have a thickness 112, and the ceramic layer is contemplated to have a thickness 114. In certain embodiments of the present disclosure, the thickness 110 of the workpiece body 102 may be greater than the thickness 112 of the metal oxide layer 104. The thickness 110 of the workpiece body 102 may be greater than the thickness 114 of the ceramic layer 106. The thickness 110 of the workpiece body 102 may be greater than either the thickness 112 of the metal oxide layer 104 or the thickness 114 of the ceramic layer 106. In certain embodiments, the thickness 110 may be from about 5 millimeters to about 20 millimeters, or from about 5 millimeters to about 15 millimeters, or even from about 5 millimeters to about 10 millimeters. As would be understood by one of ordinary skill in the art in view of the present disclosure, thicknesses within these ranges can promote the flow stability of the fluid flowing through the flow opening 116 (shown in FIG. 3) extending through the metal article 100.

[0037] In certain embodiments, the thickness 112 of the metal oxide layer 104 may have a thickness thinner than the thickness 110 of the workpiece body 102. According to certain embodiments, the thickness 112 of the metal oxide layer 104 may be greater than the thickness of the ceramic layer 106. For example, the thickness 112 of the metal oxide layer 104 may be from about 10 nanometers to about 100 nanometers, or from about 10 nanometers to about 80 nanometers, or even from about 10 nanometers to about 50 nanometers. Advantageously, thicknesses within these ranges can provide beneficial adhesion (e.g., bonding) of the ceramic layer 106 to the workpiece body 102 by the metal oxide layer 104. For further advantage, such thicknesses are at a relatively low temperature, i.e., lower than the temperature required to form nickel oxide from oxygen (O 2 ) gas and at an oxygen (O 2)It can be formed more rapidly than is required to form nickel oxide from the gas, limiting the cost and time required to manufacture the metal article 100. Also, the thickness 112 of the metal oxide layer 104 may be greater than the thickness 114 of the ceramic layer 106, and the thickness 112 is such that the ceramic layer 106 is aluminum oxide (Al 2 O 3 ) including examples, and the ceramic layer 106 is yttrium(III) oxide (Y 2 O 3 ) is intended to be common in the examples including.

[0038] In certain embodiments, the thickness 114 of the ceramic layer 106 may be greater than the thickness 112 of the metal oxide layer 104. According to certain embodiments, the thickness 114 of the ceramic layer 106 may be less than the thickness 110 of the workpiece body 102. Also contemplated is that the thickness 114 of the ceramic layer 106 is greater than the thickness 112 of the metal oxide layer 104 and less than the thickness 110 of the workpiece body 102. For example, the thickness 114 may be in embodiments where the ceramic layer 106 includes alumina, as well as in embodiments where the ceramic layer 106 includes yttrium(III) oxide (Y 2 O 3 ) from 1 nanometer to 10,000 nanometers, or from about 1 nanometer to about 2,500 nanometers, or from about 100 nanometers to about 500 nanometers. Examples of suitable ceramic layers include those shown and described in Patent Document 1 of Gao et al. filed on October 26, 2018, the content of which is hereby incorporated by reference in its entirety.

[0039] Referring to FIGS. 2-5, the operations for fabricating a metal article 100 are shown. As shown in FIG. 2, the manufacture of the metal article 100 (shown in FIG. 1) can be accomplished by forming a workpiece body 102 from a bulk metal material 108, such as, for example, solid nickel (Ni) metal (nickel alloy Ni-200) or solid aluminum (Al) metal (1050 aluminum). Forming the workpiece body 102 can include, for example, defining a first surface 118 of the workpiece body 102 by defining a generally circular outer peripheral portion, such as a generally circular outer peripheral portion 304 (shown in FIG. 9), that extends around the workpiece body 102. Forming the workpiece body 102 can include defining a second surface 122 that is spaced from the first surface 118 by a thickness of the workpiece body 102, such as a thickness 110 of the workpiece body 102. Forming the workpiece body 102 can further include defining a plurality of flow openings 116 within the workpiece body 102 that fluidly couple the first surface 118 of the workpiece body 102 to the second surface 122 of the workpiece body 102. The plurality of flow openings 116 may be formed using subtractive manufacturing techniques, such as, for example, using a drill or reaming tool 10. The plurality of flow openings 116 may be formed to align with each other, for example, by fusing a plurality of metal layers 12 using additive manufacturing techniques, such as powder bed fusion, and may remain within the scope of the present disclosure.

[0040] As shown in FIG. 3, once the workpiece body 102 is formed, the workpiece body 102 may be wet cleaned. Wet cleaning may be achieved, for example, by immersing the workpiece body 102 in a solvent and / or an etchant 14 contained in a tank or a wet bench 16 after defining a plurality of flow openings 116. The solvent and / or the etchant 14 may serve to collect contaminants present on the workpiece body 102, such as residual cutting fluid and / or cutting debris present in one or more of the plurality of flow openings 116 disposed on the outer peripheral portion of the workpiece body 102 and / or present on the first surface 118 and / or the second surface 122 associated with the subtractive manufacturing technique used to form the workpiece body 102. In certain embodiments, a native oxide may be formed on the workpiece body 102, for example, on a first metal oxide layer 120 on the workpiece body 102. According to certain embodiments, the first metal oxide layer 120 may include (or may consist of, or may consist essentially of) aluminum oxide (Al 2 O 3 ). In such embodiments, the first metal oxide layer 120 may be relatively thin, and the first metal oxide layer 120 may have a thickness 124 that is thinner than either (or both) of the thickness 112 (shown in FIG. 1) and the thickness 114 (FIG. 1). For example, the thickness 124 of the first metal oxide layer 120 may be less than about 20 nanometers, or less than about 10 nanometers, or even less than about 5 nanometers, and may remain within the scope of the present disclosure.

[0041] As shown in FIG. 4, once the workpiece body 102 is formed and wet cleaned as needed, a metal oxide layer 104 may be formed. In this regard, the metal oxide layer 104 may be conformally formed within the plurality of flow openings 116 and may be conformally formed on the surface defined by the bulk metal material 108 and in contact with the plurality of flow openings 116. The formation of the metal oxide layer 104 involves exposing the workpiece body 102, more specifically, the bulk metal material 108 forming the workpiece body 102, to ozone (O 3)18. For example, it can be achieved by exposing to ozone (O 3 ) gas. In this regard, it is contemplated that the metal oxide layer 104 is formed such that the metal oxide layer 104 is laminated on the bulk metal material 108 forming the workpiece body 102 with, for example, a substantially conformal seal. Forming the metal oxide layer 104 can be achieved within the ozone chamber 20. When supported within the ozone chamber 20, the workpiece body 102 can be heated to a predetermined ozone (O 3 ) treatment temperature, for example, using the heater element 22. The workpiece body 102 is at a temperature below the temperature at which nickel oxide is formed in the presence of oxygen (O 2 ) gas, for example, about 200 degrees Celsius to about 400 degrees Celsius, or about 200 degrees Celsius to about 350 degrees Celsius, or about 200 degrees Celsius to about 300 degrees Celsius, or even about 200 degrees Celsius to about 250 degrees Celsius, to a predetermined ozone (O 3 ) treatment temperature. Advantageously, the temperatures within these ranges cooperate with the higher reactivity of ozone (O 2 ) with respect to oxygen (O 3 ) gas, shortening the time required from the metal oxide layer 104 and reducing the time and cost required for the manufacture of the metal article 100 (Figure 1).

[0042] When heated to a predetermined ozone (O 3 ) treatment temperature, the workpiece body 102 is exposed to ozone (O 3 ) during a predetermined ozone (O 3 ) treatment exposure interval, for example, ozone (O 3 ) gas. In this regard, it is contemplated that the predetermined ozone (O 3 ) treatment exposure interval can be about 15 minutes to about 5 hours, or about 15 minutes to about 4 hours, or about 15 minutes to about 3 hours, or even about 15 minutes to about 2 hours. Advantageously, the predetermined ozone (O 3 ) treatment temperature and the predetermined ozone (O 3)The exposure interval can form a metal-ceramic bonding barrier transition 508 (shown in FIG. 11) between the bulk metal material 108 and the ceramic layer 106 without forming a metal-ceramic bonding barrier transition 508 (shown in FIG. 11) between the ceramic layer 106 (shown in FIG. 1) and the bulk metal material 108, and can form a metal oxide layer 104 having a thickness sufficient to allow greater adhesion between the ceramic layer 106 and the bulk metal material 108. The risk that the ceramic layer 106 separates (e.g., peels) from the workpiece body is limited (or eliminated). As will be understood by those skilled in the art from the perspective of the present disclosure, this can limit the risk that the metal article 100 (shown in FIG. 1) generates particles during service. Also, as will be understood by those skilled in the art from the perspective of the present disclosure, as shown and described herein, a final item incorporating a showerhead metal article 300 (shown in FIG. 9) fabricated according to a method 200 (shown in FIG. 6) for manufacturing a metal article, for example, from a semiconductor processing system 400 (shown in FIG. 10), the risk of damaging the ceramic layer 106 during removal and / or attachment of the metal article 100 can be limited (or eliminated).

[0043] As shown in FIG. 5, the ceramic layer 106 may be deposited on the metal oxide layer 104 after forming the metal oxide layer 104 so as to adhere to, for example, on the metal oxide layer 104. For example, the ceramic layer 106 may be conformally deposited on the metal oxide layer 104 on a surface surrounding the plurality of flow openings 116. In certain embodiments, the ceramic layer 106 may be deposited using CVD techniques. According to certain embodiments, the ceramic layer 106 may be deposited using ALD techniques. The ceramic layer 106 may include aluminum oxide (Al 2 O 3 ) such as aluminum oxide (Al 2 O 3 ). It is contemplated that the ceramic layer 106 may also include yttrium(III) oxide (Y 2 O 3 ), and such yttrium(III) oxide (Y 2 O 3) may be deposited using CVD or ALD techniques, for example, by supporting the workpiece body 102 within a CVD or ALD deposition chamber 24 and exposing the workpiece body to a CVD precursor or ALD reactant 26, which is also contemplated. Examples of suitable deposition techniques include the description and explanation of Patent Document 1 to Goa et al., filed on October 26, 2018, which, as described above, is hereby incorporated by reference in its entirety into this specification.

[0044] Referring to FIGS. 6-8, a method 200 for fabricating a metallic article, such as the metallic article 100 (shown in FIG. 1), is shown. As shown in FIG. 6, method 200 includes forming a workpiece body from a bulk metallic material, such as workpiece body 102 (shown in FIG. 1) from bulk metallic material 108 (shown in FIG. 1), as indicated by box 202. Method 200 also includes forming a metal oxide layer, such as metal oxide layer 104 (shown in FIG. 1), deposited on the bulk metallic material by exposing the bulk metallic material to ozone (O 3 ) gas, such as ozone (O 3 ). Method 200 further includes depositing a ceramic layer on the metal oxide layer covering the bulk metallic material, such as ceramic layer 106 (shown in FIG. 1), as indicated by box 206.

[0045] Forming the workpiece body 202 may include forming the workpiece body from nickel (Ni), as shown in box 208. For example, the bulk metal material may be solid nickel (Ni) metal, and in such embodiments, the bulk metal material consists of or consists essentially of nickel, as also shown in box 208. In certain embodiments, the bulk metal material may be a nickel-containing alloy such as a stainless steel material, as further shown in box 208. Forming the workpiece body 202 may include forming the workpiece body from aluminum (Al), as shown in box 210. In this regard, in such embodiments, the bulk metal material may be solid aluminum (Al) metal consisting of or consisting essentially of aluminum (Al), as also shown in box 210. Further, the bulk metal material may be an aluminum-containing alloy such as 6064 aluminum alloy, as further shown in box 210.

[0046] Forming the metal oxide layer 204 may include forming a metal oxide layer on the natural oxide layer that covers the bulk metal material. In such embodiments, the natural oxide layer may be the first metal oxide layer, and the metal oxide layer formed by exposing the workpiece body to ozone (O 3 ) may be a second metal oxide layer laminated on top of the first metal oxide layer and separated from the bulk metal material by the first metal oxide layer, as shown in box 212. Forming the metal oxide layer 204 by exposing the bulk metal material to ozone (O 3 ) may include forming an alumina or aluminum oxide (Al 2 O 3 ) layer on the bulk metal material, as shown in box 214. Forming the metal oxide layer by exposing the bulk metal material to ozone (O 3Forming a metal oxide layer by exposing to (0) can include forming nickel oxide on a bulk metal material as shown in box 216. In this regard, the metal oxide layer may (or consist of, or consist essentially of) include nickel oxide, for example, basic nickel (II) oxide (NiO) as also shown in box 216. Also, the metal oxide layer may (or consist of, or consist essentially of) include non-basic nickel oxide, for example, nickel (III) oxide (Ni 2 O 3 ) and it is also contemplated that it can remain within the scope of the present disclosure.

[0047] Depositing a ceramic layer on the metal oxide layer 206 can include depositing aluminum oxide (Al 2 O 3 ) on the metal oxide layer as shown in box 218. The aluminum oxide (Al 2 O 3 ) layer may (or consist essentially of) consist of aluminum oxide (Al 2 O 3 ) as also shown in box 218. Depositing a ceramic layer on the metal oxide layer 206 can include depositing yttrium (III) oxide (Y 2 O 3 ) on the metal oxide layer as shown in box 220. The yttrium (III) oxide (Y 2 O 3 ) layer may (or consist essentially of) consist of yttrium (III) oxide (Y 2 O 3 ) as also shown in box 220. The ceramic layer is contemplated to be indirectly adhered to the bulk metal material by the metal oxide layer as shown in box 222. Also, the metal oxide layer, for example nickel (Ni) metal and yttrium (III) oxide (Y 2 O 3) so that it can exist differently between them, prevent the formation of a metal-ceramic bonding barrier between the ceramics coating the bulk metal material, and as shown in box 224, it is also contemplated to limit (or remove) the tendency of such a bonding barrier to limit the adhesion of the ceramic layer to the bulk metal material. Advantageously, as demonstrated by an adhesion test between a metal article without a metal oxide layer (shown in FIGS. 11 and 12) and a metal article containing a metal oxide layer formed by exposing to ozone (O 3 ) indirectly bonding the ceramic coating to the bulk material increases the force required to peel the ceramic coating from the metal article produced using the method 200 against the metal article produced without an ozone (O 3 ) treatment and consequently having no resulting metal oxide layer.

[0048] Optionally, the workpiece body may be wet cleaned, for example, as shown in box 226, after forming the workpiece body 202 and before forming a metal oxide on the workpiece body 204. In this regard, the workpiece body may be immersed in a cleaning solvent or etching agent contained within a tank or wet bench, for example, immersed in a cleaning solvent or etching agent 14 (shown in FIG. 3) contained within a tank or wet bench 16 (shown in FIG. 3). Further, wet cleaning of the workpiece body may include degreasing and / or removing chips or swarf from the workpiece body, such as by using a degreaser and / or ultrasonic or megasonic cleaning techniques, as further shown in box 226.

[0049] In certain embodiments, wet cleaning the workpiece body may include forming a native oxide layer on the bulk metal material, as shown in box 228, e.g., the native oxide layer may form a first metal oxide layer 120 (shown in FIG. 3). For example, the bulk metal material forming the workpiece body may include exposed aluminum (Al) metal, and through wet cleaning, aluminum oxide (Al 2 O 3 ) may be formed on the exposed aluminum (Al) metal. In such embodiments, forming the metal oxide layer 204 may include thickening the native oxide layer, and the metal oxide layer 104 is the second metal oxide layer in such an example, and advantageously increases the adhesion of the ceramic layer subsequently deposited on the workpiece body to a higher level than is possible with techniques that use native oxides to deposit ceramic layers. In this regard, the native oxide layer may be a first metal oxide layer of aluminum oxide (Al 2 O 3 ), and the metal oxide layer formed by exposure to ozone (O 3 ) may be a second metal oxide layer of aluminum oxide (Al 2 O 3 ), and it is contemplated that the second metal oxide has a thickness greater than that of the first metal oxide layer. For example, the first metal oxide layer may have a thickness of about 2 nanometers to about 10 nanometers, and the second metal oxide layer may have a thickness of about 25 nanometers to about 7 nanometers.

[0050] Forming the workpiece body 202 may further include, in certain embodiments of the present disclosure, defining a first surface having a generally circular outer perimeter, e.g., a first surface 302 (shown in FIG. 9) having a generally circular outer perimeter 304 (shown in FIG. 9) as shown by box 230. Forming the workpiece body 202 may also include forming a second surface having a generally circular perimeter, e.g., a second surface 306 (shown in FIG. 9) as shown by box 232. Forming the workpiece body 202 may further include defining a plurality of flow openings within the workpiece body and fluidly coupling the first surface to the second surface, e.g., a plurality of flow openings 310 (shown in FIG. 9). In these respects, the metal workpiece may be formed (and thereby configured and adapted) as a showerhead metal article 300 (shown in FIG. 9) for a semiconductor processing system 400 (shown in FIG. 10), such as a semiconductor processing system having a downflow type structure, e.g., as shown by bracket 202. In such embodiments, ozone (O 3 ) may be forced to flow through the plurality of flow openings to form a metal oxide layer adhering with a substantially uniform thickness within the plurality of flow openings, and, as also shown by bracket 202, the metal oxide layer formed within the plurality of flow openings advantageously limits (or eliminates) erosion of a ceramic layer that is subsequently deposited within the plurality of flow openings and adheres to the bulk metal material.

[0051] According to certain embodiments of the present disclosure, forming the metal oxide layer 204 may include supporting the metal workpiece within a reactor, e.g., an ozone chamber 20 (shown in FIG. 4) as shown by box 236. In that, the workpiece body may be heated to a predetermined metal oxide formation temperature as shown by box 238. Heating 238 may be achieved in such embodiments using a heater element in thermal communication with the reactor, e.g., heater element 22 (shown in FIG. 4) as also shown by box 238. Heating the workpiece body 238 may include, as shown by box 240, introducing oxygen (O 2)It may include heating the workpiece body to a temperature lower than the temperature required to oxidize nickel (Ni) metal in a gas-containing atmosphere. For example, the workpiece body may be heated to a predetermined metal oxide formation temperature of about 200 degrees Celsius to about 400 degrees Celsius, such as about 200 degrees Celsius to about 350 degrees Celsius, or about 200 degrees Celsius to about 300 degrees Celsius, or even about 200 degrees Celsius to about 250 degrees Celsius, as also shown in box 240. In a further embodiment, by heating, in embodiments where wet cleaning is not used or where wet cleaning excludes solvent degreasing, residual organic materials (such as oil) present on the surface of the workpiece body can be removed, and the generation of potentially dangerous materials during the manufacture of metal articles is restricted.

[0052] Forming the metal oxide layer 204 may, as shown in box 242, include maintaining the workpiece body at a predetermined metal oxide formation temperature during a predetermined ozone (O 3 ) exposure interval. In this regard, the predetermined ozone (O 3 ) exposure interval may be about 15 minutes to 5 hours, as shown in box 244. For example, the workpiece body may be maintained at a predetermined metal oxide formation temperature during a predetermined ozone (O 3 ) exposure interval of about 15 minutes to about 4 hours, or about 15 minutes to about 3 hours, or about 15 minutes to about 2 hours, or even about 15 minutes to 1 hour, as also shown in box 244. Advantageously, the predetermined metal oxide formation temperature and the predetermined ozone (O 3 ) exposure interval can impart to the metal oxide layer a thickness sufficient to enhance the adhesion of the subsequently deposited ceramic layer more rapidly than exposure to oxygen (O 2 ) gas, relative to specific bulk metal materials such as nickel (Ni) metal and aluminum (Al) metal, to ozone (O 2 ) gas compared to oxygen (O 3By leveraging the reactivity of (), the manufacturing of metal articles can be simplified. Also, as further shown by bracket 204, by forming a metal oxide layer on a bulk metal material that forms the workpiece body 204, it is also contemplated that the porosity and / or surface roughness within a plurality of flow openings otherwise associated with the formation of the workpiece body can be cured using additive manufacturing techniques. As would be understood by one of ordinary skill in the art in view of the present disclosure, this can improve the flow characteristics provided by a metal workpiece, for example, by promoting laminar flow of a fluid through a plurality of flow openings that fluidly couple a first surface and a second surface of the metal workpiece when the metal workpiece is used as a showerhead.

[0053] As shown in FIG. 8, method 200 may further include placing a metal article within a chamber body of a semiconductor processing system, such as within chamber body 402 (shown in FIG. 10) of semiconductor processing system 400 (shown in FIG. 10), as shown by box 246. In this regard, the metal article may be formed as a showerhead, whereby, as shown by box 248, an inlet port of the chamber body may be fluidly coupled to an outlet port of the chamber body, for example, inlet port 412 (shown in FIG. 10) to outlet port 414 (shown in FIG. 10). In a further regard, the metal article may, as shown by box 250, fluidly couple a corrosive fluid source to an exhaust source, for example, fluid source 408 (shown in FIG. 10) to exhaust source 410 (shown in FIG. 10). So arranged, as shown by box 252, a corrosive fluid emitted by the corrosive fluid source may be transmitted by the metal article to the exhaust source through a pre-cleaning space defined within the chamber body, for example, corrosive fluid 28 (shown in FIG. 10) is transmitted through pre-cleaning process space 428 (shown in FIG. 10). Therein, the corrosive fluid may pre-clean a substrate supported within the pre-cleaning space and remove one or more of interfacial oxygen and / or interfacial carbon from a substrate having a silicon surface portion, for example, interfacial carbon 6 (shown in FIG. 10) and / or interfacial oxygen 4 (shown in FIG. 10) may be removed from substrate 2 (shown in FIG. 10) supported within the pre-cleaning space.

[0054] In certain embodiments, the corrosive fluid may contain fluorine radical species, as indicated by box 258. According to certain embodiments, the corrosive fluid may contain hydrogen radical species, as indicated by box 260. The material layer may then be deposited on the substrate, for example, by moving the substrate from a pre-cleaning process space to a deposition process space remote from the pre-cleaning process space, as indicated by box 262. Among them, the material layer, such as an epitaxial silicon-containing material layer, may be deposited on the silicon surface, for example, using CVD technology, as indicated by box 264. As will be understood by those skilled in the art in view of the present disclosure, by pre-cleaning the substrate, interfacial oxygen and / or interfacial carbon that might otherwise potentially be present on the substrate surface can be limited (or eliminated), improving the quality of the material layer deposited on the substrate. As will also be understood by those skilled in the art, the relatively high adhesion provided by the metal oxide layer formed by exposing the workpiece body to ozone (O 3 ) can extend the expected service life of the metal article, for example, by delaying (or preventing) the occurrence of contamination associated with potential erosion and / or delamination of the ceramic layer by the fluid passing through the metal article.

[0055] Referring to FIGS. 9 and 10, a showerhead metal article 300 and a semiconductor processing system 400 including the showerhead metal article 300 are shown. As shown in FIG. 9, the showerhead metal article 300 is similar to the metal article 100 (shown in FIG. 1), and further has a first surface 302 that defines a substantially circular outer peripheral portion 304. The showerhead metal article 300 also has a second surface 306 that defines a substantially circular outer peripheral portion 304 and a thickness 308 (shown in FIG. 10) that separates the second surface 306 from the first surface 302. The showerhead metal article 300 is further contemplated to define a plurality of flow openings 310 therethrough. In this regard, the plurality of flow openings 310 are intended to extend through the thickness 308 of the showerhead metal article 300 and fluidly couple the first surface 302 to the second surface 306 to communicate fluid therethrough. In a further aspect, the plurality of flow openings 310 may have an effective flow area width 312. The effective flow area width 312 may be from about 0.25 millimeters to about 4 millimeters, such as from about 0.25 millimeters to about 3 millimeters, or from about 0.25 millimeters to about 2 millimeters, or even from about 0.25 millimeters to about 1 millimeter.

[0056] The showerhead metal article 300 is configured as a showerhead for a semiconductor processing system, such as semiconductor processing system 400, and in this regard, it is contemplated that the plurality of flow openings 310 may be sized and distributed according to the processes implemented within the semiconductor processing system. In a further aspect, either (or both) of the metal oxide layer 104 (shown in FIG. 1) and the ceramic layer 106 (shown in FIG. 1) are conformally disposed within the plurality of flow openings 310 and may be sized (e.g., in terms of their respective thicknesses) to limit (or remove) delamination and promote the flow of a laminar fluid within the plurality of flow openings 310. Further, in embodiments where the workpiece body 102 (shown in FIG. 1) is formed using an additive manufacturing process, either (or both) of the metal oxide layer 104 and the ceramic layer 106 may act as a countermeasure against potentially harmful properties imparted to the showerhead metal article 300. For example, either (or both) of the metal oxide layer 104 and the ceramic layer 106 may generally act as a countermeasure (e.g., by sealing) against porosity within the bulk metal material 108 (shown in FIG. 1) on the workpiece body. Either (or both) of the metal oxide layer 104 and the ceramic layer 106 act within the plurality of flow openings 310 associated with certain additive manufacturing techniques, such as powder bed fusion, and / or may have a surface roughness, by smoothing the fluid contact surfaces within the plurality of flow openings 310. As will be understood by those skilled in the art in view of the present disclosure, this may, for example, limit (or remove) the need to smooth the internal surfaces of the plurality of flow channels, e.g., using liquid honing techniques, and simplify the manufacture of the showerhead metal workpiece by controlling the thickness 112 (shown in FIG. 1) of the metal oxide layer 104 formed within the plurality of flow openings 310.

[0057] As shown in FIG. 10, the semiconductor processing system 400 may include a chamber body 402, a substrate support 404, a remote plasma unit 406, a fluid source 408, and an exhaust source 410. The chamber body 402 may have an inlet port 412 and an outlet port 414, and generally defines a downflow type chamber structure 416. The substrate support 404 may be disposed inside the interior 418 of the chamber body 402. The substrate support 404 may be further configured to seat the substrate 2 thereon during a pre-cleaning of the substrate 2, for example, while removing one or more of the interfacial oxygen 4 and / or interfacial carbon 6 from the silicon surface portion 8 of the substrate 2 prior to depositing an epitaxial silicon material layer on the substrate 2 in a remote deposition process module on a cluster type platform. The exhaust source 410 may be connected to the outlet port 414 of the chamber body 402, for example, through an exhaust conduit 420, and may be configured to evacuate the interior 418 of the chamber body 402 using one or more vacuum pumps. In this regard, the exhaust source 410 may be configured to remove residual radical species and / or reaction products 32 from the interior 418 of the chamber body 402 during the pre-cleaning of the substrate 2.

[0058] The remote plasma unit 406 may be connected to the inlet port 412 of the chamber body 402 by a supply conduit 422, and may be configured to transmit radical species 30 to the interior 418 of the chamber body 402, and may be configured to, for example, pre-clean the substrate 2. The remote plasma unit 406 may be further connected to the fluid source 408 by a source conduit 424 to receive a corrosive fluid 28 from the fluid source 408 and generate radical species 30 therefrom. The fluid source 408 may be configured to provide the corrosive fluid 28 to the remote plasma unit 406. In a particular embodiment, the corrosive fluid 28 is fluorine (e.g., NF 3 , CF 4 , SF 6 , or C 2 F 6 ) or chlorine (e.g., chlorine Cl 2It may contain halogens such as fluorine radicals and / or chlorine radicals may be generated from the corrosive fluid 28 such as fluorine radicals and / or chlorine radicals. According to a particular embodiment, the corrosive fluid 28 may contain hydrogen, for example, hydrogen (H 2 ) gas, and then the remote plasma unit 406 is configured to generate hydrogen radicals from the corrosive fluid 28. As will be understood by those skilled in the art in view of the present disclosure, other replenishing fluids and / or radical species may be used and may remain within the scope of the present disclosure. Examples of suitable remote plasma units include the Paragon® remote plasma source available from MKS Instruments, Inc. of Andover, Massachusetts.

[0059] The showerhead metal article 300 may be fixed within the interior 418 of the chamber body 402. The showerhead metal article 300 further separates the interior 418 of the chamber body 402 into a supply plenum 426 and a pre-cleaning process space 428, and may additionally fluidly couple the supply plenum 426 to the pre-cleaning process space 428 via a plurality of flow openings 310. As will be understood by those skilled in the art in view of the present disclosure, the ceramic layer 106 (shown in FIG. 1) included in the showerhead metal article 300 may promote the surviving radical species received from the remote plasma unit 406, for example, by reducing the recombination tendency of hydrogen radicals. Also, as will be understood by those skilled in the art in view of the present disclosure, the metal oxide layer 104 (shown in FIG. 1) bonds the ceramic layer 106 and the bulk metal material 108 (shown in FIG. 1) to form the workpiece body 102 (shown in FIG. 1) of the showerhead metal article 300, and by the relatively high adhesion of the ceramic layer 106 to the bulk metal material 108 provided by the metal oxide layer 104, prior to deposition of the ceramic layer, ozone (O 3)Compared with showerhead metal articles of similar composition that have not undergone the treatment, the tendency for delamination and / or erosion of the ceramic layer 106 may be limited (or eliminated) during the transmission of fluid through the plurality of flow openings 310, the expected service life of the showerhead metal article 300 is extended, and the ownership cost of the semiconductor processing system 400 is limited.

[0060] Referring to FIGS. 11-14, it is shown that a metal article 500 having a ceramic layer 502 according to the present disclosure and a metal article 600 having both a metal oxide layer 602 and a ceramic layer 604 are undergoing a ceramic layer adhesion test. As shown in A of FIG. 11 and B of FIG. 12, by applying the adhesive member 34 (shown in FIG. 11) and then removing the adhesive member 34, a portion of the ceramic layer 502 is removed, and the surface portion 504 of the bulk metal material 506 underlying the formation of the metal article 500 is exposed. In contrast, as shown in C of FIG. 13 and B of FIG. 14, by applying and then removing the adhesive member 34 (shown in FIG. 13) that is substantially the same (e.g., with respect to adhesion), substantially none of the ceramic layer 604 is removed, and the metal article 600 remains functional despite trauma to the ceramic layer 604 associated with the removal of the adhesive member 34. As will be understood by those skilled in the art in view of the present disclosure, in addition to providing the aforementioned advantages and benefits, the metal article 600 is more likely to withstand operation and handling during installation and / or service of the metal article.

[0061] Although the present disclosure has been provided in the context of certain embodiments and examples, those skilled in the art will understand that the present disclosure extends beyond the specifically described embodiments to other alternative embodiments, and / or the use of such embodiments, and obvious modifications and equivalents thereof. In addition, while some variations of the embodiments of the present disclosure have been shown and described in detail, other modifications within the scope of the present disclosure will be readily apparent to those skilled in the art based on the present disclosure. Various combinations or partial combinations of the specific features and aspects of the embodiments may be made and are still intended to fall within the scope of the present disclosure. Of course, the various features and aspects of the disclosed embodiments can be combined with or replaced by each other to form various modes of the embodiments of the present disclosure. Therefore, it is intended that the scope of the present disclosure should not be limited by the specific embodiments described above.

[0062] The headings (if any) provided herein are for convenience only and do not necessarily affect the scope or meaning of the apparatus and methods disclosed herein.

Claims

1. 1. A method of making a metal article, comprising: forming a workpiece body from a bulk metal material, the bulk metal material comprising one of aluminum and nickel; The bulk metal material is treated with ozone (O ３ forming a metal oxide layer from the bulk metal material by exposing the bulk metal material to a depositing a ceramic layer onto the metal oxide layer; A method comprising:

2. forming the workpiece body, Defining a first surface having a circular perimeter; defining a second surface spaced from the first surface by a thickness; defining a plurality of flow openings in the workpiece body to fluidly couple the first surface with the second surface of the workpiece body; The method of claim 1 , comprising:

3. The step of forming the metal oxide layer comprises: supporting the workpiece body within an ozone chamber; heating the workpiece body to between 200 degrees Celsius and 400 degrees Celsius, or between 200 degrees Celsius and 350 degrees Celsius, or between 200 degrees Celsius and 300 degrees Celsius, or between 200 degrees Celsius and 250 degrees Celsius; The workpiece body is irradiated with ozone (O ３ ) exposing the gas for 15 minutes to 5 hours, or 15 minutes to 4 hours, or 15 minutes to 3 hours, or 15 minutes to 2 hours; The method of claim 1 , comprising:

4. The method of claim 1 , further comprising wet cleaning the workpiece body prior to forming the metal oxide layer.

5. The method of claim 4 , wherein the metal oxide layer is not formed during the wet cleaning.

6. The method further includes forming a first metal oxide layer on the workpiece body during the wet cleaning, the metal oxide layer being a second metal oxide layer, thereby irradiating the bulk metal material with ozone (O ３ 5. The method of claim 4, wherein after said exposing to a metal oxide layer, said second metal oxide layer is laminated to said first metal oxide layer.

7. The deposition of the ceramic layer comprises depositing aluminum oxide (Al ２ O ３ ) or yttrium (III) oxide (Y ２ O ３ 2. The method of claim 1 comprising depositing a metal oxide layer comprising:

8. The ceramic layer is indirectly bonded to the bulk metal material by the metal oxide layer, thereby insulating the bulk metal material from the ozone (O ３ 2. The method of claim 1 , wherein exposing the ceramic layer to a metal-ceramic bond barrier transition between the bulk metallic material and the ceramic layer prevents formation of a metal-ceramic bond barrier transition between the bulk metallic material and the ceramic layer that can act to limit adhesion of the ceramic layer to the bulk metallic material.

9. 2. The method of claim 1, further comprising, after depositing the ceramic layer on the metal oxide layer laminated to the bulk metal material, placing the metal article within a chamber body of a semiconductor processing system above a substrate support such that the metal article fluidly couples an outlet port and an inlet port of the chamber body.

10. fluidly connecting a fluid source with said metal article to an exhaust source; communicating a corrosive fluid emitted by the fluid source through a pre-cleaning process volume of the metal article to the exhaust source; pre-cleaning a substrate fluidly supported between the metal article and the exhaust source, the corrosive fluid comprising radical species whereby at least one of interfacial oxygen and interfacial carbon is removed from a silicon surface of the substrate; supporting the substrate after pre-cleaning in a deposition process space separate from the pre-clean process space; and depositing a layer of silicon-containing material onto the silicon surface while supported within the deposition process space. The method of claim 1.

11. 13. A showerhead metal article made using the method of claim 1.

12. a workpiece body formed from a bulk metal material; a metal oxide layer laminated to the bulk metal material; a ceramic layer laminated to the metal oxide layer, the metal oxide layer being an oxide formed from the bulk metal material forming the workpiece body. metal articles.

13. The metallic article of claim 12 , wherein the bulk metallic material comprises one of aluminum and nickel.

14. The metal oxide layer is made of aluminum oxide (Al ２ O ３ 13. The metal article of claim 12, wherein the metal is nickel oxide (NiO).

15. 13. The metallic article of claim 12, wherein the metal oxide layer has a thickness of from 10 nanometers to 100 nanometers, or from 20 nanometers to 80 nanometers, or from 20 nanometers to 50 nanometers.

16. The ceramic layer is made of alumina, aluminum oxide (Al ２ O ３ ) and yttrium (III) oxide (Y ２ O ３ 13. The metal article of claim 12, comprising at least one of:

17. 13. The metallic article of claim 12, wherein the metallic workpiece is configured to communicate a corrosive fluid received at a first surface to a second surface through a thickness of the workpiece body formed by the bulk metallic material.

18. The metal article of claim 12 , wherein the workpiece body defines a showerhead metal article for a semiconductor processing system.

19. The workpiece body is a first surface having a circular perimeter; a second surface spaced from the first surface by a thickness; a plurality of flow openings fluidly connecting the first surface with the second surface of the workpiece body, the metal oxide layer extending continuously and uninterruptedly along an interior surface of the plurality of flow openings; 13. The metal article of claim 12, comprising:

20. 20. The metallic article of claim 19, wherein the plurality of flow openings have an effective flow area width of from 0.25 millimeters to 4 millimeters, or from 0.25 millimeters to 3 millimeters, or from 0.25 millimeters to 2 millimeters, or from 0.25 millimeters to 1 millimeter.

21. a chamber body having an inlet port and an outlet port; a substrate support disposed within the chamber body; 13. The metal article of claim 12 disposed within the interior of the chamber body and fluidly connecting the inlet port to the outlet port; a corrosive fluid source including a corrosive fluid connected to the inlet port; an exhaust source coupled to the outlet port. Semiconductor processing systems.

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