US 6,649,211 B2Grant
Selective deposition of hydrous ruthenium oxide thin films
Issue Date:2003-11-18
•13 Claims
•4 Drawing Sheets
Abstract
A method for selectively depositing a film of hydrous ruthenium oxide on a substrate, the method comprising the steps of:
selectively functionalizing a substrate surface;
preparing an oxidizing aqueous solution of a Ru-containing composition;
generating RuO4(g) from said oxidizing solution;
selectively depositing a film of hydrous ruthenium oxide from said vapor of said oxidizing solution on said functionalized surface of said substrate; and
depositing by autocatalysis hydrous ruthenium oxide from said vapor of said oxidizing solution on said previously deposited hydrous ruthenium oxide. RuO2.xH2O films are uniformly deposited on substrates that have been selectively surface-modified with or already contain the RuO4-reactive functional groups.
Metadata
Assignee
- The United States of America as represented by the Secretary of the Navy
Inventors
- Karen Swider Lyons
- Debra Rose Rolison
Application Information
Application Number:US 10/084,319
Filing Date:2002-02-28
Priority Date:2002-02-28
Art Unit:7
Classifications
IPC:
B05D 512C23C 1640
Field of Search:
4273074272553142725574271265
Patent Drawings (4 sheets)
Description
BACKGROUND OF THE INVENTION
[0007] 1. Field of the Invention
[0008] The present invention relates generally to a selective deposition of hydrous ruthenium oxide (RuO2or RuO2.xH2O and/or RuOxHy) thin films. More particularly, the invention relates to the selective deposition of hydrous ruthenium oxide thin films by chemical vapor deposition (CVD) on selected or modified substrates. The hydrous ruthenium oxide films made by the method of the invention will be useful for catalytic and electronic applications.
[0009] 2. Description of the Related Art
[0010] RuO2is found in both anhydrous and hydrous forms. The anhydrous form of RuO2exhibits the electrical properties of a metal. It is used as a thick film resistor and as an electrode material in capacitors because of its metallic conductivity and corrosion resistance. Anhydrous RuO2thin films are also used as barrier coatings for some electronic applications, and in catalysis.
[0011] The hydrous form of RuO2is written as RuO2.xH2O, RuO2, and/or RuOxHy. Hydrous ruthenium oxide can contain from 0.03 to 3 moles of structural H2O per mole of RuO2. The structural water in RuO2can be changed by heating the material between 25 and 400° C., see FIG. 4. Like the anhydrous form of RuO2, hydrous ruthenium oxide is a metallic conductor, and in addition, it also conducts protons. Hydrous ruthenium oxide has pseudocapacitive behavior. It is used as a charge-storage medium in ultracapacitors. Charge storage of hydrous ruthenium oxide is optimized when it is heated between 130 and 170° C. and has the approximate formula RuO2.0.5H2O. The hydrous form of ruthenium oxide also has numerous applications in catalysis and electrocatalysis. When combined with platinum, hydrous ruthenium oxide is an excellent electrocatalyst for methanol oxidation and is therefore useful for direct methanol fuel cells. Thin films of hydrous ruthenium oxide are often deposited on Ti and/or TiO2to make the dimensionally stable electrodes used for brine electrolysis by the chlor-alkali industry. Hydrous ruthenium oxide is used for water oxidation when combined with a strong oxidant, e.g., Ce4+, Ru(bpy)33+.
[0012] The deposition of hydrous and anhydrous ruthenium oxide thin films has been the subject of numerous publications and patents. Anhydrous thin films are typically deposited via CVD processes or physical methods, such as pulsed laser deposition. The hydrated forms of the films are deposited from aqueous solutions, usually using RuCl3precursors. Most of the available processes must be carried out at elevated temperatures, i.e.,>300° C., in order to complete the decomposition of the Ru precursors.
[0013] Previous research has shown that RuO4is a precursor for the deposition of solid ruthenium oxide. For instance, the RuO4that forms during nuclear fission processes volatilizes to RuO4(g) and deposits as a ruthenium oxide on the stainless-steel surfaces of the nuclear fuel reprocessing and water treatment equipment. Solid RuO4has been used as a precursor to deposit ruthenium oxide films on polymers substrates at temperatures above 150° C.
[0014] RuO4(g) is generated by dissolving solid RuO4in water or by adding a strong oxidizer (e.g., NaOCl, KBrO3, KMnO4, Ce(SO4)2, NaIO4) to RuO2.xH2O or RuCl3in water. Biological specimens are stained with these ruthenium oxide solutions for microscopy analysis.
[0015] Despite the prior art, there are no reports that disclose the use of RuO4(g) to selectively deposit a thin film of RuO2.xH2O on a substrate.
OBJECTS OF THE INVENTION
[0016] Accordingly, one object of this invention is to provide a method for selectively depositing hydrous ruthenium oxide films on a substrate.
[0017] Another object of this invention is to provide a method of functionalizing a surface of a substrate in order to selectively deposit hydrous ruthenium oxide films at the selectively functionalized locations on the substrate surface.
[0018] A further object of this invention is to deposit a thin film of hydrous ruthenium oxide onto a substrate.
[0019] A still further object of this invention is to deposit a hydrous ruthenium oxide film under ambient or near ambient temperature and pressure conditions.
[0020] A further object of this invention is to deposit a hydrous ruthenium oxide film on a substrate at below 90° C.
[0021] Another object of this invention is to perform such deposition on a range of useful surfaces, including metal and polymer surfaces.
[0022] It is a further object of this invention to selectively deposit hydrous ruthenium oxide on a substrate followed by a subsequent metallization for catalyst formation.
[0023] It is a further object of the invention to control the degree of structural water content of the deposited RuO2by heating at selected temperatures up to 175° C.
[0024] It is a further object of this invention to perform such deposition on flexible substrates, and to have the deposited film have sufficient elasticity to retain conductivity even when slightly bent on flexible substrates.
SUMMARY OF THE INVENTION
[0025] These and other objects of this invention are achieved in a preferred method of the invention.
[0026] An aspect of the present invention is a method for selectively depositing a film of hydrous ruthenium oxide on a substrate, the method comprising the steps of: selectively functionalizing a substrate surface; preparing an oxidizing aqueous solution of a Ru-containing composition; generating RuO4(g) from the oxidizing solution; selectively depositing a film of hydrous ruthenium oxide from the vapor derived from the oxidizing solution on the functionalized surface of the substrate; and depositing by autocatalysis hydrous ruthenium oxide from the vapor of the oxidizing solution on the previously deposited hydrous ruthenium oxide.
[0027] Another aspect of the present invention is a method of selectively depositing a film of hydrous ruthenium oxide on a substrate, the method comprising the steps of: selectively functionalizing a substrate surface; preparing an oxidizing aqueous solution of a ruthenium-containing composition, wherein the oxidizing solution contains RuO2.xH2and Ce(SO4).2H2SO4or RuCl3.xH2O and Ca(OCl)2in water; generating RuO4(g) from the oxidizing solution; selectively depositing a film of hydrous ruthenium oxide from the vapor of the oxidizing solution on the functionalize surface of the substrate; and depositing by autocatalysis hydrous ruthenium oxide from the vapor of the oxidizing solution on the previously deposited hydrous ruthenium oxide.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] These and other objects, features and advantages of the invention, as well as the invention itself, will become better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein like reference numerals designated identical or corresponding parts throughout the several views, and wherein:
[0029] FIG. 1 is a table showing the reactivity of selected compounds with RuO4(g);
[0030] FIG. 2 illustrates a Pourbaix diagram for a Ru—H2O system at 25° C.;
[0031] FIG. 3 illustrates schematically an exemplary device for practicing the CVD method of the invention; and
[0032] FIG. 4 is a table showing how the heat treatment of bulk hydrous ruthenium oxide powder affects the value of x (mole % of water) and the pseudocapacitance.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] Referring now to the drawings, the method for fabrication a thin film of hydrous ruthenium oxide on a selected substrate or a selectively modified substrate involves the following operational steps:
[0034] The specific conditions required for the decomposition of RuO4(g) to ruthenium oxide have not been clearly identified in published literature. In research conducted by these inventors, it has been determined that RuO4(g) decomposes to RuO2.xH2O when it comes in contact only with specific functional groups, such as alcohols (—C—OH), thiols (—SH), amines/amides (—NH,) and clean etched metal surfaces.
[0035] Non-reactive functional groups include hydrocarbons (CxHy), carbon, carboxylic acids (—COOH), nitro groups (—NO2), sulfonic groups (—SO3), and most metal oxides. It should be noted that several prior reports state incorrectly that RuO4reacts with saturated and unsaturated hydrocarbons to form RuO2.
[0036] A wide range of substrates are useful for the present invention, including organic polymers and metals, or substrates with coatings of polymers or metals. Accordingly, in order for most substrates to be used in the present invention, their surfaces must be selectively modified. The substrates are found in two groups, an organic group and a metal group. Possible organic substrates are: polyphenol (BAKELITE®), graphite, carbon paper, perfluorsulfonic ionomer membranes (NAFION®), polyimide (KAPTON®) and paraffin. Possibly metal substrates include: titanium, gold, copper and indium foil or thin films.
[0037] Most substrates require cleaning plus additional surface modification to enable uniform deposition of hydrous ruthenium oxide. Chemical methods can be used to modify or prepare the surfaces of a metal, carbon, or polymer so that hydrous ruthenium oxide may be deposited. The entire surface of Ti is prepared by cleaning and etching in baths of ethanol, acetone and 5% HF. The etched substrate is then rinsed with water and dried under nitrogen. Gold surfaces are cleaned with ethanol and water, etched with oxygenated solution of KOH and KCN, rinsed with water and dried under nitrogen. Alternatively, the native oxide films on the Ti or Au can be physically removed in patterns using standard techniques such as ion milling. The metal surfaces may also be masked and then cleaned to create a desired pattern. The graphite sheet, carbon paper and polyphenol can be cleaned in methanol or ethanol, oxidized by soaking in 5% H2O2, and dried in nitrogen. NAFION® can functionalized by soaking in dilute 4-aminophenol in acetonitrile to provide an alcohol-terminated surface. The paraffin can be prepared by stretching. Thus, the surface of a selected substrate is selectively prepared to have a functional group(s) that will reduce the RuO4(g) to the hydrous ruthenium oxide. Polyimide strips on a silicon substrate will result in the selective deposition of the hydrous ruthenium oxide on the polyimide strips and not on the SiO2-passivated silicon substrate. Specific functional groups, such as alcohols (—C—OH), thiols (—SH), amines/amides (—NHx) and clean metals surfaces are selectively provided to a substrate thereby allowing for the selective deposition of hydrous ruthenium oxide on the substrate.
[0038] Since the method of the invention will not effectively deposit hydrous ruthenium oxide on glass substrates, as they are non-oxidizable, patterned deposition can be achieved by coating a glass substrate in a pattern with some other substrate material, such as an alcohol-terminated organic-containing compound or a suitable metal, that will provide a functional group that allows for the hydrous ruthenium oxide deposition. For instance, it has been demonstrated that when a hydrocarbon-based oil pattern is applied to a glass substrate and mounted over a RuCl3/NaOCl solution, the hydrous ruthenium oxide thin film deposits selectively on the organic pattern (presumably on alcohol functionalities). The glass may also be silanized with an alcohol-containing silane.
[0039] Particular substrates that have been demonstrated with the invention include an oxidized phenolic-based resin (BAKELITE®), and several metals including Cu and In. Particularly valuable substrates for the present invention are perfluorosulfonic ionomer membranes, such as NAFION®. These membranes with deposited hydrous ruthenium oxide can be used in fuel cells for their proton-conducting ability.
[0040] Once the substrate has been cleaned and/or functionalized, the oxidizing ruthenium solution is prepared.
[0041] The ruthenium-containing compound is mixed with water and an oxidizing agent. The ruthenium containing composition can be RuCl3.xH2O and/or RuO2.xH2O. Preferably, RuO2.xH2O is used. Oxidizing agents having a standard potential >1.3 V vs a normal hydrogen electrode (NHE) can be used. Possible oxidizing agents are: NaOCl, Ca(OCl)2, KMnO4, Ce(SO4)2, KBrO3NaIO4and mixtures thereof. Preferably, Ce(SO4).2H2SO4is used.
[0042] An exemplary ruthenium-containing vapor-phase species is RuO4vapor. This vapor can be formed at room temperature and pressure in a number of ways. Yellow RuO4crystals can be dissolved in water, to form a solution of RuO4. Alternatively, RuO4vapor also forms over solid RuO4crystals, i.e., solid RuO4sublimes under ambient conditions. Under ambient conditions, RuO4vapors form over RuO4solid, and over solutions containing RuO4or related molecules, which may also contain Ru3+, Ru4+, Ru6+, Ru7+ and Ru8+ ions, or combinations of these ions. Water-soluble ruthenium-containing precursors, e.g., RuCl3.xH2O, can be converted to these ionic forms in solution via oxidation (e.g., chemical and/or electrochemical oxidation).
[0043] Non-water-soluble ruthenium-containing precursors, such as RuO2.xH2O, are oxidized at their surfaces by oxidizers such as CeSO4.2H2SO4to liberate Ru8+and form RuO4vapor.
[0044] Referring to FIG. 2, the Pourbaix diagram for the Ru—H2O system shows several solution conditions for use in the present invention, including solutions in which RuO4, HRuO5−, and HRuO4− are formed by adjusting the solution pH and EMF. Skilled practitioners will recognize that these various solutions may be created, as indicated by the Pourbaix diagram, by varying the pH and applied EMF of the system, such as occurs when Ce(SO4).2H2SO4is added to RuO2.xH2O. Skilled practitioners will also recognize that a unique Pourbaix diagram exists for each operating temperature, and that these (and perhaps other) solutions may be accessed at somewhat different pH and applied EMF than are indicated in FIG. 2 (which is given for the Ru—H2O system at 25° C.).
[0045] Skilled practitioners will recognize that by using standard chemical equilibrium shifting techniques, e.g., changing the concentration or partial pressure of a reactant or product, or by changing the overall system temperature or pressure, or changing the solution pH, the reaction rate and concentration of RuO4generated may be modulated. For example, with reference to equation (1) below, by increasing or decreasing the partial pressure of oxygen in the system, the reaction can be inhibited or accelerated. A pressure drop imposed near the substrate has been shown to assist the such deposition of RuO2.xH2O films on metals. Other factors affecting the deposition rate (as well as the film thickness, film morphology, hydration, and electrical and catalytic properties) include the activity of the ruthenium in solution, the electrical potential, EMF, of the solution, the partial pressure of the various vapor-phase species, the pH of the solution, substrate temperature, humidity, and the atmospheric temperature and pressure.
[0046] The ruthenium-containing compound is mixed with an oxidizing agent and water to generate RuO4(g) to liberate Ru8+. The RuO4(g) that is generated is reduced on a suitable functional group or surface. The reduction mechanism where R represents a hydrocarbon is as follows:
[0047] RuO4(g)+R—COH+H2O(g)→R—RuO2.xH2O+CO2+O2 1
[0048] A carbonaceous functional group is presumably oxidized to CO2, O2and H2O. Thus, hydrous ruthenium oxide is selectively deposited onto the surface that contains the RuO4−reactive functional groups.
[0049] There is a continuous deposition of the hydrous ruthenium oxide on the previously deposited hydrous ruthenium oxide surface by autocatalysis. This reaction is as follows:
[0050] RuO4(g)+R—RuO2.H2O+H2O(g)→R—2RuO2.xH2O+O2 2
[0051] There can be of from about 0.03 to about 3 moles of H2O per mole of RuO2in hydrous ruthenium oxide. The amount of water is adjusted by heating the material from 25 to 400° C., see FIG. 4.
[0052] As shown in FIG. 3, an exemplary system 10 for depositing a layer of RuO212 on a substrate 14 has a ruthenium-containing solution 16 that produces ruthenium-containing vapor-phase species 18. This ruthenium-containing vapor-phase species 18, which is enclosed in a non-reactive, non-oxidizable chamber 20, is brought into contact with the substrate 14 (typically mounted on a substrate holder 22), where the species deposits as hydrous ruthenium oxide.
[0053] An exemplary ruthenium-containing solution is an aqueous solution of 0.01 M RuCl3at pH 10, with an added oxidizer such as household bleach (active ingredient NaOCl). Oxidizers perform an equivalent function to adjusting the potential, shifting the position on the Pourbaix diagram, FIG. 2. Typically, the oxidizer will be at about 0.01 M concentration, sufficient to modulate the ruthenium-containing vapor-phase species.
[0054] The selective deposition process is preferably carried out at ambient temperature or near ambient temperature and pressure. Specifically, at a temperature of from about 25 to about 90° C., and a pressure of from about 0.05 to 5 atm.
[0055] Having described the invention, the following examples are given to illustrate specific applications of the invention, including the best mode now known to perform the invention. These specific examples are not intended to limit the scope of the invention described in this
EXAMPLE 1
[0056] The reactivity of different chemical functional groups with RuO4(g) was determined qualitatively by surveying the compounds that demonstrated a color change in the presence of the vapor. The color change indicates the deposition of the hydrous ruthenium oxide. Approximately, 110 mg of a powdered sample having a target functional group was placed on top of a clean glass slide under a glass dome for 30-60 min in the presence of a Ru-oxidizer solution, and observed for the color changes. FIG. 1 indicates functional groups that are highly reactive, some that are partially reactive and others that are non-reactive.
EXAMPLE 2
Functionalization of Substrate
[0057] Titanium films (500-Å Ti (100) on Si (100)) were cleaned and etched by sequentially soaking for 5 min in baths of ethanol, acetone, and 5% HF. The substrates were rinsed with H2O and dried under N2after each step.
[0058] Graphite sheets (0.254-mm thick), carbon paper, and polyphenol (Bakelite®) surfaces were prepared by cleaning in methanol or ethanol, and then oxidized by soaking in 5% H2O2for 5 to 10 min and rinsed with water.
[0059] Gold films on glass substrates were cleaned with ethanol and water, etched for 5 min in an oxygenated solution of 1.0 M KOH and 0.01 M KCN, rinsed with H2O, and dried with N2.
[0060] Polyimide strips were patterned in 100-μm wide lines on silicon using photolithography and lift-off processes. Polyimide strips and sheets (KAPTAN®) required no surface preparation to react with the RuO4(g).
[0061] Nafion 117 (DuPont) was treated by boiling sequentially for 1 h intervals in 30% H2O2, 18 M′Ωcm water, and 0.5 M H2SO4. The Nafion membrane was then submerged in a solution of ˜0.1 mM p-aminophenol in acetonitrile for 10 min to modify its surface with alcohol functionalities. The phenol-modified Nafion was washed in water, air dried, and then mounted over a 0.5 M H2SO4solution containing 5 mM RuO2.2.1 H2O and 25 mM Ce(SO4)2for 30 min. The RuOxHy-Nafion films were heated for 1 h at 100° C. in air.
EXAMPLE 3
Preparation of Ru Containing Oxidizing Solution
[0062] Ru-oxidizing solution: 15 mg of RuO2.xH2O plus 70 mg of Ce(SO4)2.2H2(SO4)2were placed in 5 mL of 18 MΩcm water in a 25 mL plastic beaker.
EXAMPLE 4
Deposition Process
[0063] The cleaned and/or surface-modified substrates were mounted on a glass slide that was positioned over the beaker of the fresh Ru-oxidizer solution. This ensemble was tightly covered with a stretched paraffin film (PARAFILM®), and the RuO4(g) allowed to deposit on the substrate for 10 min to 24 h. The resulting RuO2.xH2O thin films were optionally heated in air in a convection oven to 100-150° C. at 2° C./min, held for 60 min, and cooled at 2° C./min.
EXAMPLE 5
Electrodepositing
[0064] For DMFC applications, platinum was electrodeposited on the Nafion-supported RuO2.xH2O thin films from a solution of H2Pt(OH)6(˜4 mM) in 2 M H2SO4. A RuO2.H2O/Nafion film was suspended in the solution from a copper clip and served as the working electrodes, a Pt-mesh was used as the auxiliary electrode, and a saturated calomel electrode was the reference. A controlled potential of 0.4 V vs NHE was applied using a potentiostat to the RuO2.xH2O films for 15 to 240 s (30 s optimum), and then the films were rinsed in 18 MΩcm water and air dried. The deposition area of the RuOxHyranged between 0.2 and 0.3 cm2. The current applied during Pt deposition was predominantly constant but varied for different samples from 40 and 60 mAcm−2.
EXAMPLE 6
Use
[0065] RuO2.xH2O and Pt—RuO2.xH2O films on Nafion were prepared for testing as ultracapacitors or direct methanol fuel cells by hot pressing them at 100° C. between two sheets of Teflon-impregnated porous carbon paper at 1000 psi for 60 s.
[0066] Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.
Claims
What is claimed is:
1. A method for selectively depositing a film of hydrous ruthenium oxide on a substrate, the method comprising the steps of:
selectively functionalizing a substrate surface;
preparing an oxidizing aqueous solution of a Ru-containing composition;
generating RuO4(g) from said oxidizing solution;
selectively depositing a film of hydrous ruthenium oxide from said vapor of said oxidizing solution on said functionalized surface of said substrate; and
depositing by autocatalysis hydrous ruthenium oxide from said vapor of said oxidizing solution on said previously deposited hydrous ruthenium oxide.
2. The selective deposition of claim 1, wherein said substrate is selected from the group consisting of organic compounds and metals, wherein said metal surface is substantially clean and oxide free, wherein said organic compound is selected from the group consisting of graphite, fluorpolymers, hydrocarbons, and carbon paper.
3. The selective deposition method of claim 2, wherein said metal is selected from the group consisting of Ti, Au, Cu and In.
4. The selective deposition method of claim 1, wherein said surface functional group of said substrate is selected from the group consisting of alcohols, thiols, amines/amides, and mixtures thereof.
5. The selective deposition method of claim 1, further including the step of heating said deposited hydrous ruthenium oxide on said substrate thereby adjusting the water composition in said hydrous ruthenium oxide film;
wherein said heated hydrous ruthenium oxide has a formula of RuO2.xH2O, and
wherein the x is from about 0.03 to about 3 moles.
6. The selective deposition method of claim 1, wherein said depositing step is conducted at ambient temperature or at a temperature of from about 15 to about 90° C., and
wherein said depositing step is conducted at ambient pressure or a pressure of from about 0.05 to about 5 atm.
7. The selective deposition method of claim 1, further including the steps of preparing said oxidizing solution by mixing a Ru containing composition, an oxidant and H2O.
8. The selective deposition method of claim 7 where in the Ru-containing composition is selected from the group consisting of RuCl3.xH2O and RuO2.xH2O and wherein said oxidant is selected from the group consisting of NaOCl, Ca(OCl)2, Ce(SO4)2, KMnO4, KBrO3, NaIO4, and mixtures thereof.
9. The selective deposition method of claim 1, further including the step of applying an inert film around said substrate and said oxidizing solution prior to said selective depositing step.
10. The selective deposition method of claim 1, further comprising the step of electrodepositing metal particles on said hydrous ruthenium oxide layer.
11. A method of selectively depositing a film of hydrous ruthenium oxide on a substrate, the method comprising the steps of:
selectively functionalizing a substrate surface;
preparing an oxidizing aqueous solution of a ruthenium-containing composition, wherein said oxidizing solution contains RuO2.xH2O and hydrous Ce(SO4).2H2SO4in water;
generating RuO4(g) from said oxidizing solution;
selectively depositing a film of hydrous ruthenium oxide from said vapor of said oxidizing solution on said functionalize surface of said substrate; and
depositing by autocatalysis hydrous ruthenium oxide from said vapor of said oxidizing solution on said previously deposited hydrous ruthenium oxide.
12. The selective deposition method of claim 11, further comprising the step of: electrodepositing metal particles on said hydrous ruthenium oxide layer.
13. The selective deposition method of claim 11, further including the step of heating said deposited hydrous ruthenium oxide on said substrate thereby adjusting the water composition in said hydrous ruthenium oxide film;
wherein said heated hydrous ruthenium oxide has a formula of RuO2.xH2O, and
wherein the x is from about 0.03 to about 3 moles.
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