Surface-modified substrates and related methods

Abstract

Surface modified substrates and related methods are provided. A substrate having a modified surface includes a first region and a second region. The first region is located above the second region. The first region includes aluminum fluoride. The second region includes an aluminum alloy. And the concentration of the aluminum fluoride is gradually reduced from the first region to the second region.

Description

Technical Field

[0001] This disclosure relates to surface-modified substrates and related methods.

[0002] Cross-citation of related applications

[0003] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 529,321, filed July 27, 2023, pursuant to 35 USC 119, the entire disclosure of which is hereby incorporated herein by reference. Background Technology

[0004] Semiconductor and microelectronic device manufacturing methods require surface treatment steps using reactive manufacturing process materials (such as plasma). Fabricating substrates with protective coatings to provide chemical, physical, and / or electrical resistance to these surface treatments remains an ongoing challenge. Summary of the Invention

[0005] Some embodiments relate to a substrate. In some embodiments, the substrate includes a first region comprising aluminum fluoride. In some embodiments, the substrate includes a second region comprising an aluminum alloy. In some embodiments, the first region is above the second region. In some embodiments, the concentration of the aluminum fluoride decreases from the first region to the second region.

[0006] Some embodiments relate to a substrate. In some embodiments, the substrate includes a first region comprising magnesium fluoride. In some embodiments, the substrate includes a second region comprising a magnesium-aluminum alloy. In some embodiments, the substrate includes a third region comprising aluminum fluoride. In some embodiments, the third region is located between the first and second regions. In some embodiments, the concentration of magnesium fluoride decreases from the first region to the third region. In some embodiments, the concentration of aluminum fluoride decreases from the third region to the second region.

[0007] Some embodiments relate to a method. In some embodiments, the method includes exposing a substrate to a fluorine-containing vapor sufficient to form at least one of the following: a first region comprising at least one of aluminum fluoride, magnesium fluoride, or any combination thereof; a second region comprising an aluminum alloy; and a third region comprising at least one of aluminum fluoride, magnesium fluoride, or any combination thereof. In some embodiments, the first region is above the second region. In some embodiments, the third region, when present, is between the first and second regions. Attached Figure Description

[0008] Some embodiments of this disclosure are described herein by way of example only, with reference to the accompanying drawings. Detailed reference is now made to the drawings, and it should be emphasized that the illustrated embodiments are exemplary and illustrative discussions for the purpose of implementing embodiments of this disclosure. In this regard, the description taken in conjunction with the drawings will enable those skilled in the art to understand how embodiments of this disclosure can be practiced.

[0009] Figure 1 This is a flowchart of a method for modifying the surface of a substrate according to some embodiments.

[0010] Figure 2 This is a schematic diagram of at least a portion of a cross-section of a substrate having a modified surface according to some embodiments.

[0011] Figure 3 This is a schematic diagram of at least a portion of a cross-section of a substrate having a modified surface according to some embodiments.

[0012] Figure 4 A depth profile of a substrate with a modified surface is depicted according to some embodiments.

[0013] Figure 5 A depth profile of a substrate with a modified surface is depicted according to some embodiments.

[0014] Figure 6 A depth profile of a substrate with a modified surface is depicted according to some embodiments. Detailed Implementation

[0015] Other objects and advantages of this disclosure will become apparent from the following description taken in conjunction with the accompanying drawings, among the disclosed benefits and improvements. Detailed embodiments of this disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the disclosure as it may be embodied in various forms. Furthermore, each of the examples given with respect to the various embodiments of this disclosure is intended to be illustrative and not restrictive.

[0016] Any prior patents and publications referenced in this document are incorporated herein by reference in their entirety.

[0017] Throughout this specification and claims, unless otherwise expressly stated herein, the following terms shall have the meanings explicitly and consequentially used herein. As used herein, the phrases “in one embodiment,” “in an embodiment,” and “in some embodiments” do not necessarily refer to the same embodiment, but may refer to the same embodiment. Furthermore, as used herein, the phrases “in another embodiment” and “in some other embodiments” do not necessarily refer to different embodiments, but may refer to different embodiments. All embodiments of this disclosure are intended to be combined without departing from the scope or spirit of this disclosure.

[0018] As used herein, unless otherwise expressly stated in the text, the term "based on" is non-exclusive and allows for consideration of additional factors not described. Furthermore, throughout this specification, the meanings of "a" and "described" include plural references. The meaning of "in" includes both "in" and "on".

[0019] Conventional coatings can be applied to the surface of substrates suitable for microelectronics manufacturing (e.g., semiconductor manufacturing) to protect them from chemical, physical, and electrical resistance. Due to limitations of conventional coatings and the manufacturing processes used to form them, the resulting coated substrates exhibit several drawbacks. Conventional coatings are non-uniform in thickness and do not conform to the underlying surface. Furthermore, these problems are exacerbated by substrates with high aspect ratio features (e.g., deep trenches). Forming conformally consistent and uniform coatings on high aspect ratio substrates remains an ongoing challenge.

[0020] Some embodiments disclosed herein overcome all or at least some of the challenges of conventional coatings by providing surface-modified substrates and manufacturing processes for the surfaces of the modified substrates. In some embodiments, for example, exposing the surface of the substrate to vapors that react with metals present in the substrate results in modified surfaces exhibiting improved chemical resistance, physical resistance, and / or electrical resistance, etc. These modified surfaces can protect the substrate without depositing coatings or other materials on the surface of the substrate. Using reactive vapors to modify the surface of the substrate provides uniform and conformal surface modification on high aspect ratio substrates with difficult-to-reach characteristics because reactive vapors are readily exposed to all surfaces of the high aspect ratio substrate.

[0021] Figure 1 This is a flowchart of a method 100 for modifying the surface of a substrate according to some embodiments. For example... Figure 1 As shown in the figure, the method includes one or more of the following steps: obtaining a substrate 102; obtaining a reactive vapor 104; and exposing the substrate 106 to a reactive vapor sufficient to modify the surface of the substrate.

[0022] In step 102, a substrate is obtained. The substrate may include a substrate suitable for microelectronics manufacturing (e.g., semiconductor manufacturing, for example, but not limited to). The substrate may be a high aspect ratio substrate, such as (e.g., but not limited to) a substrate having an aspect ratio of 2:1 to 2000:1 or 20:1 to 2000:1. The aspect ratio of the substrate may refer to the ratio of width, depth, height, length, or diameter in any combination. In some embodiments, for example, the aspect ratio refers to the ratio of the depth of a circular hole (e.g., a via) to the diameter of a circular hole (e.g., a via). In some embodiments, the aspect ratio refers to the ratio of the depth of a non-circular hole (e.g., a trench) to the width of a non-circular hole (e.g., a trench). Non-limiting examples of substrates containing high aspect ratio substrates include, but are not limited to, films, showerheads, liners, tubes, gas lines, valves, syringes, trays, or any combination thereof.

[0023] The substrate may have an aspect ratio of any range or subrange between 20:1 and 2000:1. In some embodiments, the substrate may have the following aspect ratios: 50:1 to 2000:1, 100:1 to 2000:1, 200:1 to 2000:1, 300:1 to 2000:1, 400:1 to 2000:1, 500:1 to 2000:1, 600:1 to 2000:1, 700:1 to 2000:1, 800:1 to... 2000:1, 900:1 to 2000:1, 1000:1 to 2000:1, 1100:1 to 2000:1, 1200:1 to 2000:1, 1300:1 to 2000:1, 1400:1 to 2000:1, 1500:1 to 2000:1, 1600:1 to 2000:1, 1700:1 to 2000:1 1. 1800:1 to 2000:1, 1900:1 to 2000:1, 20:1 to 1900:1, 20:1 to 1800:1, 20:1 to 1700:1, 20:1 to 1600:1, 20:1 to 1500:1, 20:1 to 1400:1, 20:1 to 1300:1, 20:1 to 1200:1, 20: 1 to 1100:1, 20:1 to 1000:1, 20:1 to 900:1, 20:1 to 800:1, 20:1 to 700:1, 20:1 to 600:1, 20:1 to 500:1, 20:1 to 400:1, 20:1 to 300:1, 20:1 to 200:1, 20:1 to 100:1, or 20:1 to 50:1.

[0024] In some embodiments, the substrate comprises an aluminum (Al) component. In some embodiments, the aluminum component comprises elemental aluminum (e.g., aluminum metal). In some embodiments, the aluminum component comprises molecular aluminum (e.g., aluminum is part of a molecule). In some embodiments, the aluminum component comprises aluminum cations (e.g., Al). + Al +2 Al +3 (etc.). In some embodiments, the aluminum component includes anodized aluminum. In some embodiments, the aluminum component includes an aluminum alloy. In some embodiments, the aluminum alloy includes at least one of a copper component, an iron component, a manganese component, a silicon component, a zinc component, a magnesium component, a chromium component, a titanium component, or any combination thereof. In some embodiments, reference to a metal component refers to at least one of the elemental form of a metal, the molecular form of a metal, the ionic form of a metal, or any combination thereof. In some embodiments, the substrate does not include a magnesium component. In some embodiments, the substrate includes a magnesium component.

[0025] In some embodiments, the substrate comprises at least 50% to 99% by weight of aluminum composition, or any range or subrange of aluminum composition between 50% and 99% by weight of the total weight of the substrate. In some embodiments, the substrate comprises 50% to 95%, 50% to 90%, 50% to 85%, 50% to 80%, 50% to 75%, 50% to 70%, 50% to 65%, 50% to 60%, 50% to 55%, 55% to 99%, 60% to 99%, 65% to 99%, 70% to 99%, 75% to 99%, 80% to 99%, 85% to 99%, 90% to 99%, or 95% to 99%. In some embodiments, the substrate is entirely aluminum and comprises 100% by weight of aluminum composition based on the total weight of the substrate. In some embodiments, the substrate comprises less than 10% by weight of iron composition based on the total weight of the substrate. For example, in some embodiments, the substrate includes an iron component in amounts of 0.01 wt% to 10 wt%, 0.01 wt% to 9 wt%, 0.01 wt% to 8 wt%, 0.01 wt% to 7 wt%, 0.01 wt% to 6 wt%, 0.01 wt% to 5 wt%, 0.01 wt% to 4 wt%, 0.01 wt% to 3 wt%, 0.01 wt% to 2 wt%, 0.01 wt% to 1 wt%, 0.01 wt% to 0.1 wt%, 0.1 wt% to 10 wt%, 1 wt% to 10 wt%, 2 wt% to 10 wt%, 3 wt% to 10 wt%, 4 wt% to 10 wt%, 5 wt% to 10 wt%, 6 wt% to 10 wt%, 7 wt% to 10 wt%, 8 wt% to 10 wt%, or 9 wt% to 10 wt% based on the total weight of the substrate.

[0026] In step 104, a reactive vapor is obtained. In some embodiments, the reactive vapor includes a fluorine component. In some embodiments, the reactive vapor includes a fluorine-containing vapor. In some embodiments, the fluorine-containing vapor includes a fluorine component that reacts with or undergoes a reaction with the aluminum component of the substrate. In some embodiments, the fluorine-containing vapor includes a fluorine component that reacts with or undergoes a reaction with both the aluminum component and the magnesium component of the substrate.

[0027] In some embodiments, the fluorine component comprises a molecular fluorine source vapor that may be derived from a liquid or solid. In some embodiments, the fluorine component comprises molecular fluorine. In some embodiments, the fluorine component is non-ionic, substantially non-ionic, untreated (e.g., by adding energy other than heat) to form a plasma, or any combination thereof. In some embodiments, the fluorine component comprises at least one of a fluorinated organic compound, a perfluorinated organic compound, or any combination thereof. In some embodiments, for example, the fluorine component may comprise at least one of a fluorinated alkane, a perfluorinated alkane, a fluorinated olefin, a perfluorinated olefin, or any combination thereof, wherein any one or more of these may be linear or branched. In some embodiments, the fluorine-containing vapor comprises at least one of CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, or any combination thereof.

[0028] In some embodiments, the fluorine component comprises a vaporized fluorinated polymer. In some embodiments, for example, obtaining the reactive vapor comprises heating the fluorinated polymer to a temperature sufficient to vaporize at least a portion of the fluorinated polymer. In some embodiments, the fluorine component comprises a gaseous fluorinated polymer derived from a non-gaseous fluorinated polymer (e.g., a solid-phase or liquid-phase fluorinated polymer). In some embodiments, the fluorinated polymer comprises a homopolymer or copolymer. In some embodiments, the fluorinated polymer comprises a copolymer of at least one fluoroolefin monomer and optionally at least one non-fluorinated comonomer. In some embodiments, the fluorinated polymer may be fluorinated (i.e., partially fluorinated), perfluorinated, or may contain non-fluorinated halogen atoms, such as, for example but not limited to, chlorine. In some embodiments, the molecular fluorine source may be liquid or solid at room temperature, but vaporized at the manufacturing process temperatures disclosed herein. Non-limiting examples of fluorinated polymers include, but are not limited to, at least one of the following: having C1 to C2. 10Polymers of perfluoroalkyl groups: perfluoroalkyl ethylene; polytetrafluoroethylene (PTFE); tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA); tetrafluoroethylene / hexafluoropropylene copolymer (FEP); tetrafluoroethylene / perfluoro(alkyl alkenyl ether) / hexafluoropropylene copolymer (EPA); polyhexafluoropropylene; ethylene / tetrafluoroethylene copolymer (ETFE); polytrifluoroethylene; polyvinylidene fluoride (PVDF); polyvinyl fluoride (PVF); polychlorotrifluoroethylene (PCTFE); ethylene / chlorotrifluoroethylene copolymer (ECTFE); or any combination thereof.

[0029] In step 106, the substrate is exposed to reactive vapor sufficient to modify the surface of the substrate. In some embodiments, exposure includes allowing the reactive vapor to flow into a chamber containing the substrate. In some embodiments, exposure includes contacting the reactive vapor with at least one surface of the substrate. In some embodiments, exposure includes pumping the reactive vapor into the chamber containing the substrate. In some embodiments, exposure includes venting the reactive vapor into the chamber containing the substrate. In some embodiments, exposure includes introducing the reactive vapor into the chamber containing the substrate. In some embodiments, exposure includes feeding the reactive vapor into the chamber containing the substrate.

[0030] In some embodiments, exposure is performed under conditions sufficient to modify the surface of the substrate. For example, exposure conditions may include at least one of a temperature of 200°C to 600°C, a pressure of 760 Torr (e.g., atmospheric pressure), a duration of 1 millisecond to 15 hours, or any combination thereof. In some embodiments, exposure is performed or carried out at or up to the following temperatures: 250°C to 600°C, 300°C to 600°C, 350°C to 600°C, 400°C to 600°C, 450°C to 600°C, 500°C to 600°C, 550°C to 600°C, 200°C to 550°C, 200°C to 500°C, 200°C to 450°C, 200°C to 400°C, 200°C to 350°C, 200°C to 300°C, or 200°C to 250°C, or any range or subrange between 200°C and 600°C. In some embodiments, the substrate is exposed to one or more of the following heated temperatures or heated to one or more of the following: the aforementioned temperatures between 200°C and 600°C or any range or subrange between 200°C and 600°C.

[0031] In some embodiments, the exposure is performed at pressures ranging from 100 to 1000 tors or any range or subrange between 100 tors and 1000 tors. In some embodiments, for example, the exposure is performed at pressures of: 100 to 900 tors, 100 to 850 tors, 100 to 800 tors, 100 to 750 tors, 100 to 700 tors, 100 to 650 tors, 100 to 600 tors, 100 to 550 tors, 100 to 500 tors, 100 to 450 tors, 100 to 400 tors, 100 to 350 tors, 100 to 300 tors, 100 to 250 tors, 100 to 200 tors, 100 to 150 tors, 15 0 to 1000 tors, 200 to 1000 tors, 250 to 1000 tors, 300 to 1000 tors, 350 to 1000 tors, 400 to 1000 tors, 450 to 1000 tors, 500 to 1000 tors, 550 to 1000 tors, 600 to 1000 tors, 650 to 1000 tors, 700 to 1000 tors, 750 to 1000 tors, 800 to 1000 tors, 850 to 1000 tors, 900 to 1000 tors, or 950 to 1000 tors. In some embodiments, the operation is performed under atmospheric pressure.

[0032] In some embodiments, the exposure lasts for the following durations: 1 millisecond to 14 hours, 1 millisecond to 13 hours, 1 millisecond to 12 hours, 1 millisecond to 11 hours, 1 millisecond to 10 hours, 1 millisecond to 9 hours, 1 millisecond to 8 hours, 1 millisecond to 7 hours, 1 millisecond to 6 hours, 1 millisecond to 5 hours, 1 millisecond to 4 hours, 1 millisecond to 3 hours, 1 millisecond to 2 hours, 1 millisecond to 1 hour, 1 millisecond to 30 minutes, 1 millisecond to 15 minutes, 1 millisecond to 1 minute, 1 millisecond to 30 seconds, 1 Any range or subrange between milliseconds to 1 second, 1 hour to 15 hours, 2 hours to 15 hours, 3 hours to 15 hours, 4 hours to 15 hours, 1 hour to 15 hours, 5 hours to 15 hours, 6 hours to 15 hours, 7 hours to 15 hours, 1 hour to 15 hours, 8 hours to 15 hours, 9 hours to 15 hours, 10 hours to 15 hours, 11 hours to 15 hours, 12 hours to 15 hours, 13 hours to 15 hours, 14 hours to 15 hours, or 1 millisecond to 15 hours.

[0033] In some embodiments, at least one surface of the substrate is exposed sufficiently to modify the substrate to form at least one of a first region, a second region, a third region, or any combination thereof. In some embodiments, at least one surface of the substrate is exposed sufficiently to modify the substrate to form the first region and the second region, wherein the first region is above the second region. In this application, "above" may mean the outermost layer or exterior of the first layer in a three-dimensional embodiment. In some embodiments, at least one surface of the substrate is exposed sufficiently to modify the substrate to form the first region, the second region, and the third region, wherein the third region is located between the first region and the second region.

[0034] In some embodiments, the first region is the outermost region of the substrate relative to the second and / or third regions. In some embodiments, the first region is a region comprising a modified surface of the substrate. In some embodiments, the surface is modified when at least a portion of the surface or a component thereof reacts with a reactive vapor to, for example, chemically alter the substrate, wherein the chemically altered portion of the substrate is or comprises the first region. In some embodiments, the first region comprises all vapor-exposed and / or gas-exposed surfaces of the substrate. For example, in some embodiments, the first region comprises all surfaces in direct contact or fluid communication with the reactive vapor. In some embodiments, the first region extends from the surface of the substrate to a first depth below the surface of the substrate.

[0035] In some embodiments, the second region is a region that does not include any surface of the substrate. In some embodiments, the second region is a region of the substrate that does not react with reactive vapors. In some embodiments, the second region is a region of the substrate that reacts less with reactive vapors than the first region and / or the third region. In some embodiments, the second region extends from about the first region to a second depth, wherein the second depth is greater than the first depth. In some embodiments, when a third region is present, the second region extends substantially from the third region to a second depth, wherein the second depth is greater than the first depth and the depth of the third region. In some embodiments, the substrate does not include the second region (e.g., when the substrate is exposed for a sufficient duration to chemically alter the entire substrate).

[0036] In some embodiments, the third region is a region that does not contain any surface of the substrate. In some embodiments, the third region is a modified region of the substrate. That is, in some embodiments, the region is modified when at least a portion of the region or its components reacts with a reactive vapor to, for example, chemically alter the substrate, wherein the chemically altered portion in the third region of the substrate differs from the chemically altered portion in the first region of the substrate. In some embodiments, the third region is different (e.g., chemically different) from the first region. In some embodiments, the third region is located between the first and second regions. In some embodiments, the substrate does not include the third region (e.g., when the substrate does not include magnesium).

[0037] In some embodiments, the first region comprises at least one of aluminum fluoride. In some embodiments, the first region comprises magnesium fluoride. In some embodiments, the third region comprises aluminum fluoride. In some embodiments, the second region comprises an aluminum alloy. In some embodiments, the second region comprises a magnesium-aluminum alloy. In some embodiments, the first region comprises aluminum fluoride and the second region comprises an aluminum alloy, wherein the concentration of aluminum fluoride gradually decreases from the first region to the second region. In some embodiments, the first region comprises magnesium fluoride, the second region comprises a magnesium-aluminum alloy, and the third region comprises aluminum fluoride, wherein the third region is located between the first region and the second region, wherein the concentration of magnesium fluoride gradually decreases from the first region to the third region and / or the second region, and wherein the concentration of aluminum fluoride gradually decreases from the third region to the second region.

[0038] In some embodiments, a fluorine component from fluorine vapor reacts with an aluminum component of the substrate to form a first region. In some embodiments, a fluorine component from fluorine vapor reacts with a magnesium component of the substrate to form a first region. In some embodiments, a fluorine component from fluorine vapor reacts with an aluminum component of the substrate to form a third region.

[0039] In some embodiments, the modified surface is present on all exposed surfaces of the substrate and includes features with a high aspect ratio (e.g., holes, channels, chambers, metal films). In some embodiments, the modified surface is a corrosion-resistant surface that is protected from corrosion. In some embodiments, the modified surface is a passivation surface of the substrate.

[0040] In some embodiments, at least a portion of the first region has a depth of any range or subrange from 1 nm to 50 μm. For example, in some embodiments, at least a portion of the first region has a depth of less than 5 μm, less than 1 μm, or less than 250 nm. In some embodiments, at least a portion of the first region has the following depths: 100 nm to 250 nm, 1 nm to 4 μm, 1 nm to 3 μm, 1 nm to 2 μm, 1 nm to 1 μm, 1 nm to 900 nm, 1 nm to 850 nm, 1 nm to 800 nm, 1 nm to 750 nm, 1 nm to 700 nm, 1 nm to 650 nm, 1 nm to 600 nm, 1 nm to 550 nm, 1 nm to 450 nm, 1 nm to 400 nm, 1 nm to 350 nm, 1 nm to 300 nm, 1 nm to 250 nm, 1 nm to 200 nm, 1 nm to 150 nm, 1 nm to 100 nm, 1 nm to 50 nm, 50 nm to 5 μm, 100 nm to 5 μm, 200 nm to 5 μm, 300 nm to 5 μm, 400 nm to 5 μm, 500 nm to 5 μm, 600 nm to 5 μm. μm, 700 nm to 5 μm, 800 nm to 5 μm, 900 nm to 5 μm, 1 μm to 5 μm, 2 μm to 5 μm, 3 μm to 5 μm, 4 μm to 5 μm, 1 nm to 750 nm, 1 nm to 500 nm, 2 nm to 500 nm, 1 nm to 250 nm, 20 nm to 125 nm, 20 nm to 250 nm, 20 nm to 500 nm, 50 nm to 500 nm, 50 nm to 400 nm, 50 nm to 300 nm, 50 nm to 200 nm, 15 nm to 200 nm, 20 nm to 50 nm, 10 nm to 40 nm, 30 nm to 50 nm, 1 nm to 5 μm, 1 μm to 5 μm, 1 μm to 4 μm, 1 μm to 3 μm, 1 μm to 2 μm, 5 nm to 5 μm, 1 nm to 1 μm or 10 nm to 5 μm.

[0041] In some embodiments, at least a portion of the second region has a depth of any range or subrange from 1 nm to 50 μm. For example, in some embodiments, at least a portion of the second region has a depth of less than 5 μm, less than 1 μm, or less than 250 nm. In some embodiments, at least a portion of the second region has the following depths: 100 nm to 250 nm, 1 nm to 4 μm, 1 nm to 3 μm, 1 nm to 2 μm, 1 nm to 1 μm, 1 nm to 900 nm, 1 nm to 850 nm, 1 nm to 800 nm, 1 nm to 750 nm, 1 nm to 700 nm, 1 nm to 650 nm, 1 nm to 600 nm, 1 nm to 550 nm, 1 nm to 450 nm, 1 nm to 400 nm, 1 nm to 350 nm, 1 nm to 300 nm, 1 nm to 250 nm, 1 nm to 200 nm, 1 nm to 150 nm, 1 nm to 100 nm, 1 nm to 50 nm, 50 nm to 5 μm, 100 nm to 5 μm, 200 nm to 5 μm, 300 nm to 5 μm, 400 nm to 5 μm, 500 nm to 5 μm, 600 nm to 5 μm. μm, 700 nm to 5 μm, 800 nm to 5 μm, 900 nm to 5 μm, 1 μm to 5 μm, 2 μm to 5 μm, 3 μm to 5 μm, 4 μm to 5 μm, 1 nm to 750 nm, 1 nm to 500 nm, 2 nm to 500 nm, 1 nm to 250 nm, 20 nm to 125 nm, 20 nm to 250 nm, 20 nm to 500 nm, 50 nm to 500 nm, 50 nm to 400 nm, 50 nm to 300 nm, 50 nm to 200 nm, 15 nm to 200 nm, 20 nm to 50 nm, 10 nm to 40 nm, 30 nm to 50 nm, 1 nm to 5 μm, 1 μm to 5 μm, 1 μm to 4 μm, 1 μm to 3 μm, 1 μm to 2 μm, 5 nm to 5 μm, 1 nm to 1 μm or 10 nm to 5 μm.

[0042] In some embodiments, at least a portion of the third region has a depth of any range or subrange from 1 nm to 50 μm. For example, in some embodiments, at least a portion of the third region has a depth of less than 5 μm, less than 1 μm, or less than 250 nm. In some embodiments, at least a portion of the third region has the following depths: 100 nm to 250 nm, 1 nm to 4 μm, 1 nm to 3 μm, 1 nm to 2 μm, 1 nm to 1 μm, 1 nm to 900 nm, 1 nm to 850 nm, 1 nm to 800 nm, 1 nm to 750 nm, 1 nm to 700 nm, 1 nm to 650 nm, 1 nm to 600 nm, 1 nm to 550 nm, 1 nm to 450 nm, 1 nm to 400 nm, 1 nm to 350 nm, 1 nm to 300 nm, 1 nm to 250 nm, 1 nm to 200 nm, 1 nm to 150 nm, 1 nm to 100 nm, 1 nm to 50 nm, 50 nm to 5 μm, 100 nm to 5 μm, 200 nm to 5 μm, 300 nm to 5 μm, 400 nm to 5 μm, 500 nm to 5 μm, 600 nm to 5 μm. μm, 700 nm to 5 μm, 800 nm to 5 μm, 900 nm to 5 μm, 1 μm to 5 μm, 2 μm to 5 μm, 3 μm to 5 μm, 4 μm to 5 μm, 1 nm to 750 nm, 1 nm to 500 nm, 2 nm to 500 nm, 1 nm to 250 nm, 20 nm to 125 nm, 20 nm to 250 nm, 20 nm to 500 nm, 50 nm to 500 nm, 50 nm to 400 nm, 50 nm to 300 nm, 50 nm to 200 nm, 15 nm to 200 nm, 20 nm to 50 nm, 10 nm to 40 nm, 30 nm to 50 nm, 1 nm to 5 μm, 1 μm to 5 μm, 1 μm to 4 μm, 1 μm to 3 μm, 1 μm to 2 μm, 5 nm to 5 μm, 1 nm to 1 μm or 10 nm to 5 μm.

[0043] In some embodiments, the modified surface of the substrate is formed by a vapor deposition manufacturing process. Examples of vapor deposition manufacturing processes include, but are not limited to, at least one of the following: chemical vapor deposition (CVD) manufacturing processes, digital or pulsed chemical vapor deposition manufacturing processes, plasma-enhanced cyclic chemical vapor deposition (PECCVD) manufacturing processes, flowable chemical vapor deposition (FCVD) manufacturing processes, atomic layer deposition (ALD) manufacturing processes, thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD) manufacturing processes, metal-organic chemical vapor deposition (MOCVD) manufacturing processes, plasma-enhanced chemical vapor deposition (PECVD) manufacturing processes, or any combination thereof.

[0044] In some embodiments, the substrate has an aluminum fluoride content of 60% to 80%, or any range or subrange between 60% and 80%, as measured by XPS. For example, in some embodiments, the fluoride content of the substrate may be 61% to 80%, 62% to 80%, 63% to 80%, 64% to 80%, 65% to 80%, 66% to 80%, 67% to 80%, 68% to 80%, 69% to 80%, 70% to 80%, 71% to 80%, 72% to 80%, 73% to 80%, 74% to 80%, 75% to 80%, 76% to 80%, 77% to 80%, 78% to 80%, or 79% to 80%. In some embodiments, the fluoride content of the substrate may be 60% to 79%, 60% to 78%, 60% to 77%, 60% to 76%, 60% to 75%, 60% to 74%, 60% to 73%, 60% to 72%, 60% to 71%, 60% to 70%, 60% to 69%, 60% to 68%, 60% to 67%, 60% to 66%, 60% to 65%, 60% to 64%, 60% to 63%, 60% to 62%, or 60% to 61%. In some embodiments, the aluminum fluoride content is the aluminum fluoride content in the first region. In some embodiments, the aluminum fluoride content is the aluminum fluoride content in the third region.

[0045] In some embodiments, the substrate comprises magnesium fluoride. In some embodiments, the substrate has an aluminum fluoride content of any range or subrange between 3% and 15% as measured by XPS. For example, in some embodiments, the fluoride content of the substrate may be 4% to 15%, 5% to 15%, 6% to 15%, 7% to 15%, 8% to 15%, 9% to 15%, 10% to 15%, 11% to 15%, 12% to 15%, 13% to 15%, or 14% to 15%. In some embodiments, the fluoride content of the substrate may be 3% to 14%, 3% to 13%, 3% to 12%, 3% to 11%, 3% to 10%, 3% to 9%, 3% to 8%, 3% to 7%, 3% to 6%, 3% to 5%, or 3% to 4%. In some embodiments, the substrate has a magnesium fluoride content of 20% to 40%. For example, in some embodiments, the magnesium fluoride content of the substrate may be 21% to 40%, 22% to 40%, 23% to 40%, 24% to 40%, 25% to 40%, 26% to 40%, 27% to 40%, 28% to 40%, 29% to 40%, 30% to 40%, 31% to 40%, 32% to 40%, 33% to 40%, 34% to 40%, 35% to 40%, 36% to 40%, 37% to 40%, 38% to 40%, or 39% to 40%. In some embodiments, the magnesium fluoride content of the substrate may be 20% to 39%, 20% to 38%, 20% to 37%, 20% to 36%, 20% to 35%, 20% to 34%, 20% to 33%, 20% to 32%, 20% to 31%, 20% to 30%, 20% to 29%, 20% to 28%, 20% to 27%, 20% to 26%, 20% to 25%, 20% to 24%, 20% to 23%, 20% to 22%, or 20% to 21%. In some embodiments, the magnesium fluoride content is the magnesium fluoride content in the first region.

[0046] In some embodiments, the substrate comprises anodized Al. In some embodiments, the substrate has an aluminum fluoride content of any range or subrange between 20% and 40% or between 20% and 40% as measured by XPS. For example, in some embodiments, the fluoride content of the substrate may be 21% to 40%, 22% to 40%, 23% to 40%, 24% to 40%, 25% to 40%, 26% to 40%, 27% to 40%, 28% to 40%, 29% to 40%, 30% to 40%, 31% to 40%, 32% to 40%, 33% to 40%, 34% to 40%, 35% to 40%, 36% to 40%, 37% to 40%, 38% to 40%, or 39% to 40%. In some embodiments, the fluoride content of the substrate may be 20% to 39%, 20% to 38%, 20% to 37%, 20% to 36%, 20% to 35%, 20% to 34%, 20% to 33%, 20% to 32%, 20% to 31%, 20% to 30%, 20% to 29%, 20% to 28%, 20% to 27%, 20% to 26%, 20% to 25%, 20% to 24%, 20% to 23%, 20% to 22%, or 20% to 21%.

[0047] Figure 2 This is a schematic diagram of at least a portion of a cross-section of a substrate 200 having a modified surface according to some embodiments. For example, in some embodiments, the substrate 200 has a first surface and a second surface opposite to the first surface, wherein only the first surface of the substrate 200 is shown. Figure 2 As shown herein, in some embodiments, substrate 200 includes a first region 202 and a second region 204. In some embodiments, the first region 202 is located above the second region 204. In some embodiments, the first region 202 comprises aluminum fluoride. In some embodiments, the second region 204 comprises an aluminum alloy. In some embodiments, substrate 200 does not include magnesium. In some embodiments, the substrate is formed according to the methods disclosed herein. Any of the substrates, first regions, second regions, and other aspects disclosed herein may be used without departing from the scope of this disclosure.

[0048] Figure 3 This is a schematic diagram of at least a portion of a cross-section of a substrate 300 having a modified surface according to some embodiments. For example, in some embodiments, the substrate 300 has a first surface and a second surface opposite to the first surface, wherein only the first surface of the substrate 300 is shown. Figure 3As shown herein, in some embodiments, substrate 300 includes a first region 302, a second region 306, and a third region 304. In some embodiments, the third region 304 is located between the first region 302 and the second region 306. In some embodiments, the first region 302 comprises magnesium fluoride. In some embodiments, the third region 304 comprises aluminum fluoride. In some embodiments, the second region 306 comprises an aluminum alloy. In some embodiments, substrate 300 comprises magnesium. In some embodiments, the substrate is formed according to the methods disclosed herein. Any of the substrates, first regions, second regions, third regions, and other aspects disclosed herein may be used without departing from the scope of this disclosure.

[0049] Figure 4 A depth profile of a substrate with a modified surface, according to some embodiments, is depicted. For example... Figure 4 As shown, the first region 402 of the substrate includes magnesium fluoride, the second region 406 of the substrate (not shown) includes a magnesium-aluminum alloy, and the third region 404 of the substrate includes aluminum fluoride and magnesium fluoride, wherein the third region 404 of the substrate is located between the first region 402 and the second region 406.

[0050] Figure 5 A depth profile of a substrate with a modified surface, according to some embodiments, is depicted. For example... Figure 5 As shown, the first region 502 of the substrate comprises aluminum fluoride and the second region 504 of the substrate comprises an aluminum alloy. The substrate does not include magnesium (e.g., Al1100). The aluminum fluoride (AlF3) content is at least 50% down to a depth of about 200 nm (first region 502). The second region 504 comprises a mixture of aluminum fluoride and aluminum alloy. The fluorine content is at least 20% down to a depth of about 500 nm and at least 5% down to a depth of about 1200 nm. The aluminum content is at least 50% starting from a depth of about 300 nm or greater.

[0051] Figure 6 A depth profile of a substrate with a modified surface, according to some embodiments, is depicted. For example... Figure 6 As shown, a first region 602 of the substrate comprises magnesium fluoride, a second region 606 comprises a magnesium-aluminum alloy, and a third region 604 comprises aluminum fluoride, magnesium fluoride, and an aluminum alloy, wherein the third region 604 is located between the first region 602 and the second region 606. The magnesium fluoride (MgF2) content is at least 50% down to a depth of approximately 800 nm (first region 602). The third region 604 comprises a mixture of magnesium fluoride, aluminum fluoride, and an aluminum alloy. The fluorine content is at least 20% down to a depth of approximately 2500 nm. The aluminum content is at least 50% starting from a depth of approximately 1800 nm.

[0052] aspect

[0053] The following describes various aspects. It should be understood that any one or more of the features listed below may be combined with any one or more other aspects.

[0054] Aspect 1. A substrate comprising:

[0055] The first region includes aluminum fluoride; and

[0056] The second region includes aluminum alloy.

[0057] The first region is above the second region;

[0058] The concentration of aluminum fluoride decreases from the first region to the second region.

[0059] Aspect 2. The substrate as described in aspect 1, wherein the substrate has an aspect ratio of 20:1 to 2000:1, wherein the aspect ratio is a ratio of two of the width, depth, height, length or diameter.

[0060] Aspect 3. The substrate as described in any one of aspects 1 to 2, wherein the substrate comprises:

[0061] Aluminum comprising at least 50% by weight of the total weight of the substrate; and

[0062] Less than 10% by weight of iron based on the total weight of the substrate.

[0063] Aspect 4. The substrate as described in any one of aspects 1 to 3, wherein the substrate comprises anodized Al.

[0064] Aspect 5. The substrate as described in any one of aspects 1 to 4, wherein the substrate does not include magnesium or includes less than 1% magnesium.

[0065] Aspect 6. The substrate as described in any one of aspects 1 to 5, wherein the first region extends from the surface of the substrate to a depth of 2 nm to 5 μm.

[0066] Aspect 7. The substrate as described in any one of aspects 1 to 6, wherein the first region has a fluoride content of up to 100% as measured by XPS.

[0067] Aspect 8. The substrate as described in any one of aspects 1 to 7, wherein the first region has a fluorine content of 60% to 80% as measured by XPS.

[0068] Aspect 9. The substrate as described in any one of Aspects 1 to 8, wherein the first region has a fluorine content of 20% to 40% as measured by XPS.

[0069] Aspect 10. The substrate as described in any one of aspects 1 to 9, wherein the first region is the outermost region of the substrate.

[0070] Aspect 11. A substrate comprising:

[0071] The first region includes magnesium fluoride;

[0072] The second region includes magnesium-aluminum alloys; and

[0073] The third region includes aluminum fluoride;

[0074] The third region is located between the first region and the second region;

[0075] The concentration of magnesium fluoride decreases from the first region to the third region;

[0076] The concentration of aluminum fluoride decreases from the third region to the second region.

[0077] Aspect 12. The substrate as described in aspect 11, wherein the substrate has an aspect ratio of 20:1 to 2000:1, wherein the aspect ratio is a ratio of two of the width, depth, height, length or diameter.

[0078] Aspect 13. The substrate as described in any one of aspects 11 to 12, wherein the substrate comprises:

[0079] Aluminum comprising at least 50% by weight of the total weight of the substrate; and

[0080] Less than 10% by weight of iron based on the total weight of the substrate.

[0081] Aspect 14. The substrate as described in any one of aspects 11 to 13, wherein the substrate comprises anodized Al.

[0082] Aspect 15. The substrate as described in any one of aspects 11 to 14, wherein:

[0083] The first region has a magnesium content of 20% to 40% as measured by XPS;

[0084] The second region has a fluorine content of 10% to 60% as measured by XPS.

[0085] Aspect 16. A method comprising:

[0086] Expose the substrate to a fluorine-containing vapor sufficient to form at least one of the following:

[0087] The first region includes at least one of aluminum fluoride, magnesium fluoride, or any combination thereof;

[0088] The second region includes aluminum alloy; and

[0089] The third region includes at least one of aluminum fluoride, magnesium fluoride, or any combination thereof;

[0090] The first region is above the second region;

[0091] The third region, when present, lies between the first region and the second region.

[0092] Aspect 17. The method of aspect 16, wherein the fluorine component from the fluorine vapor reacts with the magnesium component of the substrate to form the first region.

[0093] Aspect 18. The method of any one of aspects 16 to 17, wherein the fluorine component from the fluorine vapor reacts with the aluminum component of the substrate to form the first region.

[0094] Aspect 19. The method of any one of aspects 16 to 18, wherein the fluorinated vapor comprises at least one of CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, vaporized fluorinated polymers, or any combination thereof.

[0095] Aspect 20. The method of any one of Aspects 16 to 19, wherein the exposure comprises heating at least a portion of the substrate at a temperature of 200°C to 600°C or heating at least a portion of the substrate to a temperature of 200°C to 600°C and exposing the substrate to the fluorine vapor for a duration of 1 millisecond to 15 hours.

[0096] It should be understood that detailed changes may be made without departing from the scope of this disclosure, particularly regarding the construction materials used and the shape, size, and arrangement of parts. This specification and the described embodiments are merely examples, and the true scope and spirit of this disclosure are indicated by the appended claims.

Claims

1. A substrate comprising: The first region includes aluminum fluoride; and The second region includes aluminum alloy. The first region is above the second region; The concentration of aluminum fluoride decreases from the first region to the second region.

2. The substrate of claim 1, wherein the substrate has an aspect ratio of 2:1 to 2000:1, wherein the aspect ratio is a ratio of two of the following: width, depth, height, length, or diameter.

3. The substrate according to claim 1, wherein the substrate comprises: Aluminum comprising at least 50% by weight of the total weight of the substrate; and Less than 10% by weight of iron based on the total weight of the substrate.

4. The substrate according to claim 1, wherein the substrate comprises anodized Al.

5. The substrate according to claim 1, wherein the substrate does not include magnesium.

6. The substrate of claim 1, wherein the first region extends from the surface of the substrate to a depth of 2 nm to 5 μm.

7. The substrate of claim 1, wherein the first region has a fluoride content of up to 100% as measured by XPS.

8. The substrate of claim 1, wherein the first region has a fluorine content of 60% to 80% as measured by XPS.

9. The substrate of claim 5, wherein the first region has a fluorine content of 20% to 40% as measured by XPS.

10. The substrate of claim 1, wherein the first region is the outermost region of the substrate.

11. A substrate comprising: The first region includes magnesium fluoride; The second region includes magnesium-aluminum alloys; and The third region includes aluminum fluoride; The third region is located between the first region and the second region; The concentration of magnesium fluoride decreases from the first region to the third region; The concentration of aluminum fluoride decreases from the third region to the second region.

12. The substrate of claim 11, wherein the substrate has an aspect ratio of 2:1 to 2000:1, wherein the aspect ratio is a ratio of two of the following: width, depth, height, length, or diameter.

13. The substrate of claim 11, wherein the substrate comprises: Aluminum at least 50% by weight based on the total weight of the substrate; and Less than 10% by weight of iron based on the total weight of the substrate.

14. The substrate of claim 11, wherein the substrate comprises anodized Al.

15. The substrate according to claim 11, wherein: The first region has a magnesium content of 20% to 40% as measured by XPS; The second region has a fluorine content of 10% to 60% as measured by XPS.

16. A method comprising: Expose the substrate to a fluorine-containing vapor sufficient to form at least one of the following: The first region includes at least one of aluminum fluoride, magnesium fluoride, or any combination thereof; The second region includes aluminum alloy; and The third region includes at least one of aluminum fluoride, magnesium fluoride, or any combination thereof; The first region is above the second region; The third region, when present, lies between the first region and the second region.

17. The method of claim 16, wherein the fluorine component from the fluorine vapor reacts with the magnesium component of the substrate to form the first region.

18. The method of claim 16, wherein the fluorine component from the fluorine vapor reacts with the aluminum component of the substrate to form the first region.

19. The method of claim 16, wherein the fluorinated vapor comprises at least one of CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, vaporized fluorinated polymers, or any combination thereof.

20. The method of claim 16, wherein the exposure comprises heating at least a portion of the substrate at a temperature of 200°C to 600°C or heating at least a portion of the substrate to a temperature of 200°C to 600°C and exposing the substrate to the fluorine vapor for a duration of 1 millisecond to 15 hours.

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