Surface-modified substrates and related methods

Abstract

The present disclosure provides surface modified substrates and related methods. A substrate having a modified surface includes a first region and a second region. The first region is positioned over the second region. The first region includes nickel fluoride. The second region includes a nickel alloy. The concentration of the nickel 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-reference of related applications

[0003] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 529,324, filed July 27, 2023, pursuant to 35 USC 119, all disclosures of which are incorporated herein by reference. Background Technology

[0004] Semiconductor and microelectronic device manufacturing methods require surface treatment steps using reactive 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 nickel fluoride. In some embodiments, the substrate includes a second region comprising a nickel alloy. In some embodiments, the first region is above the second region. In some embodiments, the concentration of the nickel fluoride decreases from the first region to the second region.

[0006] 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 nickel fluoride, a second region comprising a nickel alloy, or any combination thereof. In some embodiments, the first region is above the second region. In some embodiments, the concentration of the nickel fluoride decreases from the first region to the second region. Attached Figure Description

[0007] This document describes some embodiments of the present disclosure 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 by way of example and for the purpose of illustrative discussion of embodiments of the present disclosure. In this regard, the description taken in conjunction with the drawings will enable those skilled in the art to understand how embodiments of the present disclosure can be practiced.

[0008] Figure 1 This is a flowchart of a method for modifying the surface of a substrate according to some embodiments.

[0009] 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.

[0010] Figure 3 A depth profile of a substrate with a modified surface is depicted according to some embodiments. Detailed Implementation

[0011] 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 example given with respect to the various embodiments of this disclosure is intended to be illustrative rather than limiting.

[0012] Any prior patents and publications cited herein are incorporated herein by reference in their entirety.

[0013] Throughout this specification and claims, unless the context clearly specifies otherwise, 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 combinable without departing from the scope or spirit of this disclosure.

[0014] As used herein, unless the context clearly specifies otherwise, the term "based on" is not exclusive and may be based on additional factors not described. Furthermore, throughout the specification, "a" and "described" have the meaning of plural references. "In" has the meaning of both "in" and "on".

[0015] Conventional coatings are applied to the surface of substrates used in microelectronics manufacturing (e.g., semiconductor manufacturing) to prevent chemical, physical, and electrical resistance. Due to limitations of conventional coatings and the processes that form them, the resulting coated substrates exhibit several drawbacks. Conventional coatings are non-uniform in thickness and non-conformal to the underlying surface. Furthermore, these problems are exacerbated by substrates with high aspect ratio features (e.g., deep trenches). Forming conformal and uniform coatings on high aspect ratio substrates remains an ongoing challenge.

[0016] Some embodiments disclosed herein overcome all or at least some of the challenges of conventional coatings by providing surface-modified substrates and processes for modifying the surfaces of the substrates. In some embodiments, for example, the surface of the substrate is exposed to vapors that react with metals present in the substrate, thereby resulting 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 a uniform and conformal surface modification close to that on high aspect ratio substrates with hard-to-access features, because reactive vapors are readily exposed to all surfaces of high aspect ratio substrates.

[0017] 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, 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 the reactive vapor sufficient to modify the surface of the substrate.

[0018] In step 102, a substrate is obtained. The substrate may include a substrate suitable for use in microelectronics manufacturing (e.g., but not limited to, semiconductor manufacturing). The substrate may be a high aspect ratio substrate, for example, but not limited to, a substrate having an aspect ratio of 2:1 or from 20:1 to 2000:1. The aspect ratio of the substrate may refer to the ratio of any combination of width, depth, height, length, or diameter. In some embodiments, for example, the aspect ratio refers to the ratio of the depth of a circular hole (e.g., a aperture) to the diameter of a circular hole (e.g., a aperture). 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.

[0019] The substrate may have an aspect ratio of 20:1 to 2000:1 or any range or subrange between 20:1 and 2000:1. In some embodiments, the substrate may have an aspect ratio of 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, or 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, 180 0:1 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 110 Aspect ratios of 0:1, 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.

[0020] In some embodiments, the substrate comprises a nickel (Ni) component. In some embodiments, the nickel component comprises elemental nickel (e.g., nickel metal). In some embodiments, the nickel component comprises molecular nickel (e.g., nickel is a part of a molecule). In some embodiments, the nickel component comprises nickel cations (e.g., Ni... + Ni +2 Ni +3 Ni +4 (etc.). In some embodiments, the nickel component includes a nickel alloy. In some embodiments, the nickel 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, the metal component referred to means 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.

[0021] In some embodiments, the substrate comprises at least 50% to 99% by weight of nickel composition, or any range or subrange of nickel composition between 50% and 99% by weight, based on 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 nickel and comprises 100% by weight of nickel 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, based on the total weight of the substrate, the substrate includes 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% of iron composition.

[0022] 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 is reacting with the nickel component of the substrate.

[0023] In some embodiments, the fluorine component comprises a molecular fluorine source vapor, which may be derived from a liquid or solid. In some embodiments, the fluorine component comprises molecular fluorine. In some embodiments, the fluorine component is not nonionic, substantially nonionic, 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 comprises 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 may be straight-chain 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.

[0024] In some embodiments, the fluorine component comprises a vaporized fluorinated polymer. In some embodiments, for example, obtaining a 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 process temperatures disclosed herein. Non-limiting examples of fluorinated polymers include, but are not limited to, at least one of the following: having C1-C 10 Polymers of perfluoroalkyl groups, including 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.

[0025] In step 106, the substrate is exposed to reactive vapor sufficient to modify the surface of the substrate. In some embodiments, exposure includes flowing the reactive vapor 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.

[0026] 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 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, exposure includes heating the substrate to one or more of the following or heating the substrate to one or more of the following: the aforementioned temperature between 200°C and 600°C or any range or subrange between 200°C and 600°C.

[0027] In some embodiments, 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, 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, or 150 to 1000 tors. The pressure is carried out at 200 to 1000 to 1,000 to 250 to 1000 to 300 to 1000 to 350 to 1000 to 400 to 1000 to 450 to 1000 to 500 to 1000 to 550 to 1000 to 600 to 1000 to 650 to 1000 to 700 to 1000 to 750 to 1000 to 800 to 1000 to 850 to 1000 to 900 to 1000 to 950 to 10 ...

[0028] In some embodiments, exposure is performed from 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 millisecond to 1 second, 1 The duration of any range or subrange between 1 millisecond and 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.

[0029] 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, or any combination thereof. In some embodiments, at least one surface of the substrate is exposed sufficiently to modify the substrate to form both a first region and a second region, wherein the first region is above the second region. In this application, "above" may mean the outermost layer of the 3D structure and may be outside the inner layers.

[0030] In some embodiments, the first region is the outermost region of the substrate relative to the second region. 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.

[0031] In some embodiments, the second region is a region that does not contain any surface of the substrate. In some embodiments, the second region is a region of the substrate that has not reacted with the reactive vapor. In some embodiments, the second region is a region of the substrate that reacts less with the reactive vapor than the first 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, 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). In some embodiments, the first region comprises nickel fluoride (NiF2). In some embodiments, the second region comprises a nickel alloy. In some embodiments, the first region comprises nickel fluoride and the second region comprises a nickel alloy, wherein the concentration of nickel fluoride gradually decreases from the first region to the second region. In some embodiments, a fluorine component from fluorine-containing vapor reacts with a nickel component of the substrate to form the first region.

[0032] 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, internal gas chambers, metal films). In some embodiments, the modified surface is a corrosion-resistant surface. In some embodiments, the modified surface is a passivation surface of the substrate.

[0033] 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 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, 700 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, 600 nm to 5 μm, 700 nm to 250 nm, 1 nm to 200 nm, 300 nm to 5 μm, 400 nm to 5 μm, 50 ... 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 A depth of μm.

[0034] 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 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, 700 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, 600 nm to 5 μm, 700 nm to 250 nm, 1 nm to 200 nm, 300 nm to 5 μm, 400 nm to 5 μm, 50 ... 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 A depth of μm.

[0035] 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 second region has 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, 700 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, 600 nm to 5 μm, 700 nm to 250 nm, 1 nm to 200 nm, 300 nm to 5 μm, 400 nm to 5 μm, 50 ... 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 A depth of μm.

[0036] In some embodiments, the modified surface of the substrate is formed by a vapor deposition process. Examples of vapor deposition processes include, but are not limited to, chemical vapor deposition (CVD), digital or pulsed chemical vapor deposition, plasma-enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), atomic layer deposition (ALD), thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD), metal-organic chemical vapor deposition (MOCVD), plasma-enhanced chemical vapor deposition (PECVD), or any combination thereof.

[0037] In some embodiments, the substrate has a nickel 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 nickel fluoride content is the nickel fluoride content in the first region.

[0038] 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, in some embodiments, substrate 200 includes a first region 202 and a second region 204. In some embodiments, the first region 202 is over the second region 204. In some embodiments, the first region 202 comprises nickel fluoride (NiF2). In some embodiments, the second region 204 comprises a nickel 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.

[0039] Figure 3 A depth profile of a substrate with a modified surface, according to some embodiments, is depicted. For example... Figure 3 As shown, a first region 302 of the substrate comprises nickel fluoride (NiF2), and a second region 304 of the substrate comprises a mixture of nickel fluoride and a nickel alloy, wherein the first region 302 is positioned above the second region 304. The nickel fluoride content is at least 50% up to a depth of about 175 nm (first region 302). The nickel fluoride content is at least 50% up to a depth of about 250 nm (second region 304). The nickel content is at least 50% starting from a depth of about 175 nm or greater.

[0040] aspect

[0041] The following describes various aspects. It should be understood that any or more of the features listed below may be combined with any or more other aspects.

[0042] Aspect 1. A substrate comprising:

[0043] The first region includes nickel fluoride; and

[0044] The second region includes nickel alloys.

[0045] The first region is above the second region;

[0046] The concentration of nickel fluoride decreases from the first region to the second region.

[0047] Aspect 2. The substrate according to 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.

[0048] Aspect 3. A substrate according to any one of aspects 1 to 2, wherein the substrate comprises:

[0049] Based on the total weight of the substrate, at least 50% by weight of nickel.

[0050] Aspect 4. A substrate according to any one of aspects 1 to 3, wherein the substrate comprises:

[0051] Based on the total weight of the substrate, less than 10% by weight of iron.

[0052] Aspect 5. The substrate according to any one of Aspects 1 to 4, wherein the substrate does not contain magnesium or contains less than 1% magnesium.

[0053] Aspect 6. A substrate according to 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.

[0054] Aspect 7. A substrate according to any one of aspects 1 to 6, wherein the first region has a fluorine content of up to 100% as measured by XPS.

[0055] Aspect 8. A substrate according to any one of aspects 1 to 7, wherein the first region has a fluorine content of 10% to 70% as measured by XPS.

[0056] Aspect 9. A substrate according to any one of aspects 1 to 8, wherein the first region is resistant to thermal degradation at a temperature of 200°C to 500°C.

[0057] Aspect 10. The substrate according to any one of aspects 1 to 9, wherein the first region is the outermost region of the substrate.

[0058] Aspect 11. A method comprising:

[0059] Expose the substrate to a fluorine-containing vapor sufficient to form at least one of the following:

[0060] The first region includes nickel fluoride; and

[0061] The second region includes nickel alloys;

[0062] The first region is above the second region;

[0063] The concentration of nickel fluoride decreases from the first region to the second region.

[0064] Aspect 12. The method according to 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.

[0065] Aspect 13. The method according to any one of aspects 11 to 12, wherein the substrate comprises:

[0066] Based on the total weight of the substrate, at least 50% by weight of nickel; and

[0067] Based on the total weight of the substrate, less than 10% by weight of iron.

[0068] Aspect 14. The method according to any one of aspects 11 to 13, wherein the fluorine component from the fluorine vapor reacts with the nickel component of the substrate to form the first region.

[0069] Aspect 15. The method according to any one of aspects 11 to 14, wherein the fluorine vapor comprises at least one of CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, or any combination thereof.

[0070] Aspect 16. The method according to any one of aspects 11 to 15, wherein the fluorinated vapor comprises a vaporized fluorinated polymer.

[0071] Aspect 17. The method according to aspect 16, wherein the vaporized fluorinated polymer is derived from a C1-C2 bond. 10 The product is derived from at least one of the following: poly(perfluoroalkyl) ethylene, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA), polyhexafluoropropylene, ethylene / tetrafluoroethylene copolymer (ETFE), polytrifluoroethylene, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), or any combination thereof.

[0072] Aspect 18. The method according to any one of aspects 11 to 17, 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.

[0073] Aspect 19. The method according to any one of aspects 11 to 18, wherein the exposure comprises exposing the substrate to the fluorine vapor for a duration of 1 millisecond to 15 hours.

[0074] Aspect 20. The method according to any one of aspects 11 to 19, wherein the exposure comprises exposing the substrate to the fluorine vapor at approximately atmospheric pressure.

[0075] It should be understood that detailed changes may be made without departing from the scope of this disclosure, particularly in terms of the construction materials used and the shape, size, and arrangement of components. 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: a first region comprising a fluorinated nickel; and a second region comprising a nickel alloy, wherein the first region is above the second region; wherein a concentration of the fluorinated nickel 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 width, depth, height, length, or diameter.

3. The substrate of claim 1, wherein the substrate comprises: at least 50 wt% nickel, based on a total weight of the substrate.

4. The substrate of claim 1, wherein the substrate comprises: less than 10 wt% iron, based on a total weight of the substrate.

5. The substrate of claim 1, wherein the substrate does not comprise magnesium.

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

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

8. The substrate of claim 1, wherein the first region has a fluorine content of 10% to 70%, as measured by XPS.

9. The substrate of claim 1, wherein the first region is resistant to thermal degradation at a temperature of 200 °C to 500 °C.

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

11. A method comprising: exposing a substrate to a fluorine-containing vapor sufficient to form at least one of: a first region comprising a fluorinated nickel; and a second region comprising a nickel alloy; wherein the first region is above the second region; wherein a concentration of the fluorinated nickel decreases from the first region to the second region.

12. The method 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 width, depth, height, length, or diameter.

13. The method of claim 11, wherein the substrate comprises: at least 50 wt% nickel, based on a total weight of the substrate; and less than 10 wt% iron, based on the total weight of the substrate.

14. The method of claim 11, wherein a fluorine component from the fluorine- containing vapor reacts with a nickel component of the substrate to form the first region.

15. The method of claim 11, wherein the fluorine-containing vapor comprises at least one of CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, or any combination thereof.

16. The method of claim 11, wherein the fluorine-containing vapor comprises a vaporized fluorinated polymer.

17. The method of claim 16, wherein the vaporized fluorinated polymer is derived from at least one of a polymeric perfluoroalkyl ethylene, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA), polyhexafluoropropylene, ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), or any combination thereof. 10 perfluoroalkyl ethylene, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA), polyhexafluoropropylene, ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), or any combination thereof.

18. The method of claim 11, wherein the exposing 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.

19. The method of claim 11, wherein the exposing comprises exposing the substrate to the fluorine-containing vapor for a duration of 1 millisecond to 15 hours.

20. The method of claim 11, wherein the exposing comprises exposing the substrate to the fluorine-containing vapor at about atmospheric pressure.

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