Method for depositing a ruthenium-containing film on a substrate by a cyclic deposition process

Abstract

Disclosed is a method for depositing a ruthenium-containing film on a substrate by a cyclic deposition process. The method may include: contacting the substrate with a first gaseous reactant including a metal organic precursor, the metal organic precursor including a metal selected from the group consisting of platinum, aluminum, titanium, bismuth, zinc, and combinations thereof. The method may further include: contacting the substrate with a second gaseous reactant including ruthenium tetroxide, wherein the ruthenium-containing film includes at least one of a ruthenium-platinum alloy or ruthenium trioxide. Also disclosed is a device structure including a ruthenium-containing film deposited by the method of the present invention.

Description

[0001] This application is a divisional application of the invention patent application No. 201880088965.7 (invention title: Method for depositing a ruthenium-containing film on a substrate by a cyclic deposition process), which is the national stage entry of the PCT application PCT / IB2018 / 000192 filed on February 14, 2018. Technical Field

[0002] The present disclosure generally relates to a method for depositing a ruthenium-containing film on a substrate by a cyclic deposition process, and more particularly to a method for depositing a ruthenium-containing film using a metal organic precursor and ruthenium tetroxide. Background Art

[0003] Semiconductor device manufacturing processes in advanced technology nodes generally require prior art deposition methods for forming metal-containing films (e.g., ruthenium-containing films).

[0004] Common requirements for depositing metal-containing films are that the deposition process is extremely conformal. For example, conformal deposition is typically required to uniformly deposit a metal-containing film over a three-dimensional structure containing high aspect ratio features. Another common requirement for depositing metal-containing films is that the deposition process is capable of depositing ultrathin films that are continuous over a large substrate area. In the specific case where the metal-containing film is conductive, it may be necessary to optimize the deposition process to produce a low-resistance conductive film.

[0005] Cyclic deposition processes, such as atomic layer deposition (ALD) and cyclic chemical vapor deposition (CCVD), sequentially introduce one or more precursors (reactants) into a reaction chamber, where the precursors react one at a time in a sequentially self-limiting manner on the surface of the substrate. Cyclic deposition processes have been shown to produce metal-containing films with excellent conformality and atomic-level thickness control.

[0006] Cyclic deposition methods can be used to deposit metal alloys. For example, a metal alloy can be deposited by an atomic layer deposition process using a first precursor containing a first metal and a second precursor containing a second metal. Accordingly, methods for depositing metal alloys and semiconductor device structures containing one or more metal alloys are desirable.

[0007] In addition to metal alloys, cyclic deposition methods can be used to deposit metal oxides. For example, a metal oxide can be deposited by atomic layer deposition using a first precursor containing a metal and a second precursor containing an oxygen component. Ternary metal oxides can be particularly valuable for next-generation devices. However, common deposition processes for forming ternary metal oxides may require three separate precursors, such as a first metal precursor, a second metal precursor, and a precursor containing an oxygen component. Accordingly, improved methods for depositing metal oxides, and specifically ternary metal oxides, are desirable. Summary of the Invention

[0008] This summary is provided to introduce a series of concepts in a simplified form. These concepts are further described in detail below in the detailed description of the exemplary embodiments of the present disclosure. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0009] In some embodiments, a method of depositing a ruthenium-containing film on a substrate by a cyclic deposition process is provided. The method may include: contacting the substrate with a first gaseous reactant comprising a metal organic precursor, the metal organic precursor comprising a metal selected from the group consisting of platinum, palladium, aluminum, titanium, bismuth, zinc, and combinations thereof; and contacting the substrate with a second gaseous reactant comprising ruthenium tetroxide; wherein the ruthenium-containing film comprises at least one of a ruthenium-platinum alloy, a ruthenium-palladium alloy, or a ternary ruthenium oxide.

[0010] For the purpose of summarizing the present invention and the advantages achieved over the prior art, certain objectives and advantages of the present invention are described above in this text. Of course, it should be understood that not all of the stated objectives or advantages may be achieved in accordance with any particular embodiment of the present invention. Thus, for example, those skilled in the art will recognize that the present invention may be embodied or practiced in a manner that achieves or optimizes one advantage or a group of advantages taught or suggested herein, without necessarily achieving other objectives or advantages that may be taught or suggested herein.

[0011] All of these embodiments are intended to be within the scope of the present invention disclosed herein. For those skilled in the art, these and other embodiments will become apparent from the following detailed description of certain embodiments with reference to the accompanying drawings, and the present invention is not limited to any one or more of the specific embodiments disclosed. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Although this specification ends with claims that particularly point out and distinctly claim the subject matter regarded as embodiments of the present invention, the advantages of the embodiments of the present disclosure can be more readily determined from a description of certain examples of the embodiments of the present disclosure when read in conjunction with the accompanying drawings, in which:

[0013] Figure 1 Illustrates a process flow of an exemplary cyclic deposition method according to an embodiment of the present disclosure;

[0014] Figure 2 Illustrates a cross-sectional schematic view of a semiconductor device structure including a ruthenium-containing film deposited according to an embodiment of the present disclosure;

[0015] Figure 3 Illustrates a schematic view of a reaction system configured to perform the method of the present disclosure. DETAILED DESCRIPTION

[0016] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and obvious modifications and their equivalents. Accordingly, it is intended that the scope of the invention disclosed herein not be limited to the specific disclosed embodiments described below.

[0017] The illustrations presented herein are not intended as actual views of any particular material, structure, or device, but are merely idealized illustrations for describing embodiments of the present disclosure.

[0018] As used herein, the term "cyclic deposition" may refer to the sequential introduction of precursors (reactants) into a reaction chamber to deposit a film over a substrate and includes deposition techniques such as atomic layer deposition and cyclic chemical vapor deposition.

[0019] As used herein, the term "cyclic chemical vapor deposition" may refer to any process in which a substrate is sequentially exposed to two or more volatile precursors that react and / or decompose on the substrate to produce the desired deposition.

[0020] As used herein, the term "substrate" may refer to any one or more underlying materials that can be used, or on which a device, circuit, or film can be formed. Substrates can include, but are not limited to, wafers, glass, polymers, plastics, solid substances, fibers, and powders.

[0021] As used herein, the term "atomic layer deposition" (ALD) may refer to a vapor deposition process that performs deposition cycles, preferably multiple consecutive deposition cycles, in a process chamber. Generally, during each cycle, a precursor is chemisorbed onto the deposition surface (e.g., the substrate surface or the surface of a previously deposited underlying layer, such as the material from a previous ALD cycle), thereby forming a monolayer or sub-monolayer that is not prone to react with additional precursors (i.e., self-limiting reaction). Subsequently, if necessary, a reactant (e.g., another precursor or reaction gas) can then be introduced into the process chamber to convert the chemisorbed precursor into the desired material on the deposition surface. Generally, this reactant is capable of further reacting with the precursor. In addition, a purge step can also be utilized during each cycle to remove excess precursor and / or remove excess reactant and / or reaction by-products from the process chamber after the conversion of the chemisorbed precursor. Furthermore, when performed using alternating pulses of one or more precursor compositions, reactive gases, and purge gases (e.g., an inert carrier gas), as used herein, the term "atomic layer deposition" is also intended to encompass processes designated by related terms such as "chemical vapor atomic layer deposition", "atomic layer epitaxy" (ALE), molecular beam epitaxy (MBE), gas source MBE or organometallic MBE, and chemical beam epitaxy.

[0022] As used herein, the terms "film" and "thin film" can refer to any continuous or discontinuous structure and material deposited by the methods disclosed herein. For example, "film" and "thin film" can include 2D materials, nanorods, nanotubes, or nanoparticles, or even partial or complete molecular layers or partial or complete atomic layers or atomic and / or molecular clusters. "Film" and "thin film" can include materials or layers that have pinholes but are still at least partially continuous.

[0023] As used herein, the terms "metal organic" or "organometallic" are used interchangeably and can refer to organic compounds containing metal species. Organometallic compounds can be considered a subclass of metal organic compounds having direct metal-carbon bonds.

[0024] Throughout the embodiments of this disclosure, a variety of example materials are given. It should be noted that the chemical formulas given for each of the example materials should not be construed as limiting, and the non-limiting example materials given should not be restricted to the example stoichiometries given.

[0025] This disclosure includes methods that can be used to deposit ruthenium-containing films, and more specifically, deposition methods for depositing ruthenium-platinum alloys, ruthenium-palladium alloys, or ternary ruthenium oxide films.

[0026] Ruthenium (Ru) is a potential high work function electrode material for DRAM capacitors and MOSFETs. Additionally, ruthenium can have applications as a fuel cell electrode, a catalyst, and a seed layer for the electrodeposition of copper (Cu) on barrier layers for integrated circuit interconnects. However, ruthenium precursors are too expensive, making the deposition of elemental ruthenium cost-ineffective. Therefore, the methods of this disclosure include methods for depositing ruthenium-platinum alloys, which can customize the composition of the ruthenium-platinum alloy based on the desired device application, thereby using less ruthenium precursor while depositing a ruthenium-platinum alloy with tailored properties.

[0027] In addition to ruthenium-platinum metal alloys, embodiments of this disclosure can also provide methods for depositing ternary ruthenium oxides. As non-limiting example embodiments, the methods of this disclosure can be used to deposit ruthenium titanium oxide (Ru x Ti y O z ) and bismuth ruthenium oxide (Bi x Ru y O z ), which can have fuel cell applications.

[0028] Therefore, embodiments of this disclosure can include methods for depositing ruthenium-containing films on a substrate by a cyclic deposition process. The method can include: contacting the substrate with a first gaseous reactant comprising a metal organic precursor; and contacting the substrate with a second gaseous reactant comprising ruthenium tetroxide.

[0029] Non-limiting examples of cyclic deposition processes may include atomic layer deposition (ALD), where ALD is based on generally self-limiting reactions, whereby sequential and alternating pulses of reactants are used to deposit approximately one atomic (or molecular) monolayer per deposition cycle of material. Deposition conditions and precursors are typically selected to provide a self-saturating reaction such that an adsorbed layer of one reactant leaves a surface termination that does not react with the gaseous reactant of the same reactant. Subsequently, the substrate is contacted with a different reactant that reacts with the previous termination to effect continued deposition. Thus, each cycle of alternating pulses generally leaves no more than approximately one monolayer of the desired material. However, as mentioned above, one of ordinary skill in the art will recognize that more than one monolayer of material may be deposited in one or more ALD cycles (e.g., if some gas phase reactions occur) regardless of the alternating nature of the process.

[0030] In an ALD-type process for depositing a ruthenium-containing film, one deposition cycle may include exposing a substrate to a first reactant, removing any unreacted first reactant and reaction by-products from the reaction space, and exposing the substrate to a second reactant, followed by a second removal step. The first reactant may include a metal organic precursor (“metal organic precursor”), and the second reactant may include ruthenium tetroxide (“ruthenium precursor”).

[0031] The precursors may be separated by an inert gas, such as argon (Ar) or nitrogen (N2), to prevent gas phase reactions between the reactants and to effect a self-saturating surface reaction. However, in some embodiments, the substrate may be moved to contact the first gas phase reactant and the second gas phase reactant, respectively. Because the reaction is self-saturating, strict temperature control of the substrate and precise dosing control of the precursors are generally not required. However, the substrate temperature is preferably such that incidental gas species neither condense into a monolayer nor decompose on the surface. Residual chemicals and reaction by-products (if present) are removed from the substrate surface, such as by purging the reaction space or by moving the substrate, before contacting the substrate with the next reactive chemical. Undesired gaseous molecules may be effectively evacuated from the reaction space by means of an inert purge gas. A vacuum pump may be used to assist the purge.

[0032] A reactor capable of depositing a ruthenium-containing film may be used for deposition. The reactor includes an ALD reactor and a CVD reactor equipped with suitable equipment and components for providing the precursors. According to some embodiments, a showerhead reactor may be used. According to some embodiments, a crossflow, batch, semi-batch, or spatial ALD reactor may be used.

[0033] Examples of suitable reactors that can be used include commercially available single-substrate (or single-wafer) deposition equipment, such as those available from ASM America, Inc. in Phoenix, Arizona, USA and ASM Europe B.V. in Almere, Netherlands, reactors (such as 2000 and 3000 and XP ALD) and XP and reactors. Other commercially available reactors include those from ASM Japan K.K (Tokyo, Japan) with the trade names XP and XP8. In some embodiments, the reactor is a spatial ALD reactor in which the substrate moves or rotates during processing.

[0034] In some embodiments of the present disclosure, batch reactors can be used. Suitable batch reactors include, but are not limited to, those with the trade names A400 and A412 PLUS available from ASM Europe B.V. (Almere, Netherlands) 400 series reactors. In some embodiments, a vertical batch reactor in which the boat rotates during processing is utilized, such as the A412. Thus, in some embodiments, the wafer rotates during processing. In other embodiments, the batch reactor includes a small batch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 or fewer wafers. In some embodiments using a batch reactor, the non-uniformity between wafers is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

[0035] The deposition processes described herein can optionally be carried out in a reactor or reaction space connected to a cluster tool. In a cluster tool, since each reaction space is dedicated to one type of process, the temperature of the reaction space in each module can be kept constant, which improves throughput compared to a reactor that heats the substrate to the process temperature before each operation. Additionally, in a cluster tool, it is possible to reduce the time required to pump the reaction space to the process pressure level between substrates. In some embodiments of the present disclosure, the deposition process can be carried out in a cluster tool including a plurality of reaction chambers, where each individual reaction chamber can be used to expose the substrate to an individual precursor gas, and the substrate can be transferred between different reaction chambers to be exposed to multiple precursor gases, and the transfer of the substrate is carried out in a controlled environment to prevent oxidation / contamination of the substrate. In some embodiments of the present disclosure, the deposition process can be carried out in a cluster tool including a plurality of reaction chambers, where each individual reaction chamber can be configured to heat the substrate to a different deposition temperature.

[0036] An independent reactor can be equipped with a load lock. In such a case, it is not necessary to cool the reaction space between each operation. In some embodiments, the deposition process for depositing a metal-containing film can include a plurality of deposition cycles, such as ALD cycles or cyclic CVD cycles.

[0037] In some embodiments, a cyclic deposition process is used to form a ruthenium-containing film on a substrate, and the cyclic deposition process can be an ALD-type process. In some embodiments, the cyclic deposition can be a hybrid ALD / CVD or cyclic CVD process. For example, in some embodiments, the growth rate of an ALD process may be lower compared to a CVD process. One way to increase the growth rate can be to operate at a higher substrate temperature compared to the substrate temperature typically used in an ALD process, thereby resulting in a chemical vapor deposition process, but still utilizing the sequential introduction of precursors, and this process can be referred to as cyclic CVD.

[0038] According to some embodiments of the present disclosure, an ALD process can be used to form a ruthenium-containing film on a substrate (such as an integrated circuit workpiece). In some embodiments of the present disclosure, each ALD cycle includes two different deposition steps or stages. In the first stage (“metal stage”) of the deposition cycle, the surface of the substrate on which deposition is desired is contacted with a first gaseous reactant including a metal precursor chemisorbed on the substrate surface, thereby forming no more than about one monolayer of reactant species on the surface of the substrate. In the second stage (“ruthenium stage”) of the deposition, the surface of the substrate on which deposition is desired is contacted with a second gaseous reactant including ruthenium tetroxide, where ruthenium tetroxide can react to form a ruthenium-platinum alloy, a ruthenium-palladium alloy, or ternary ruthenium oxide.

[0039] In some embodiments of the present disclosure, the first gaseous reactant may include a metal-containing precursor, also referred to herein as a "metal compound". In some embodiments, the first gaseous reactant may include a metal-organic precursor, and the metal-organic precursor includes metals selected from the group consisting of platinum, palladium, aluminum, titanium, bismuth, zinc, and combinations thereof. In some embodiments, the metal-organic precursor may be free of or substantially free of metals of Group 2 of the periodic table (i.e., alkaline earth metals). In some embodiments, the metal-organic precursor may be free of or substantially free of metals selected from the group consisting of calcium (Ca), strontium (Sr), and barium (Ba).

[0040] In some embodiments of the present disclosure, the first gaseous reactant may include a metal-containing precursor, also referred to herein as a "metal compound". In some embodiments, the metal-containing precursor may include a metal in an oxidation state of 0, +I, +II, +III, +IV, +V, or +VI. In some embodiments, the oxidation state of the metal in the metal-containing precursor may be +II or +III. In some embodiments, the oxidation state of the metal in the metal-containing precursor may not be equal to 0.

[0041] In some embodiments of the present disclosure, the metal-organic precursor may include a metal-organic platinum precursor, i.e., a metal-organic precursor including the platinum element. In some embodiments, the metal-organic platinum precursor may be selected from the group consisting of: cyclopentadienyl compounds of platinum, such as (trimethyl)methylcyclopentadienyl platinum or (trimethyl)cyclopentadienyl(C5H5)Pt(CH3)3; β-diketonato platinum compounds, such as Pt(acetylacetonate)2; or other platinum compounds, such as Pt(PF3)4, Pt(CO)2Cl2, cis-[Pt(CH3)2((CH3)NC)2], and platinum hexafluoroacetylacetonate.

[0042] In some embodiments of the present disclosure, the metal-organic precursor may include a metal-organic aluminum precursor, i.e., a metal-organic precursor including the aluminum element. In some embodiments, the metal-organic aluminum precursor may include at least one of the following: trimethylaluminum (TMA), triethylaluminum (TEA), dimethylaluminum chloride (AlMe2Cl), dimethylaluminum isopropoxide (AlMe2OPr), or aluminum ethoxide (AlOEt)3.

[0043] In some embodiments of the present disclosure, the metal-organic precursor may include a metal-organic zinc precursor, i.e., a metal-organic precursor including the zinc element. In some embodiments, the metal-organic zinc precursor may include at least one of the following: dimethylzinc (ZnMe2), diethylzinc (ZnEt2), methylzinc isopropoxide (ZnMe(OPr)), or zinc acetate (Zn(CH3CO2)2).

[0044] In some embodiments of the present disclosure, the metal-organic precursor may include a metal-organic palladium precursor, i.e., a metal-organic precursor including palladium element. In some embodiments, the metal-organic palladium precursor may include at least one of Pd(thd)2 or Pd(Hfac)2.

[0045] In some embodiments of the present disclosure, the metal-organic precursor may include a metal-organic titanium precursor, i.e., a metal-organic precursor including titanium element. In some embodiments, the metal-organic titanium precursor may include at least one of the following: tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), pentamethylcyclopentadienyltrimethoxytitanium (CpMe5Ti(OMe)3), titanium methoxide (Ti(OMe)4), titanium ethoxide (Ti(OEt)4), titanium isopropoxide (Ti(OPr)4), or titanium butoxide (Ti(OBu)4). The metal-organic titanium precursor is described in U.S. Patent No. 9,062,390, which is hereby incorporated by reference and assigned to Blomberg.

[0046] In some embodiments of the present disclosure, the metal-organic precursor may include a metal-organic bismuth precursor, i.e., a metal-organic precursor including bismuth element. In some embodiments, the metal-organic bismuth precursor may include at least one of bismuth-alkoxide or bismuth-silyamido. In some embodiments, the metal-organic bismuth precursor is optionally selected from the group consisting of [(dmb)2Bi-O-Bi(dmb)2]2, tris(2,3-dimethyl-2-butoxy)bismuth(III), tris(tert-butoxy)bismuth(III), and tris(isopropoxy)bismuth(III). In some embodiments, the metal-organic bismuth precursor may include at least Bi(N(SiMe3)2)3, Bi(thd)3, Bi(O t Bu)3, Bi(dmb)3, or Bi(CH2SiMe3)3. The metal-organic bismuth precursor is described in U.S. Patent No. 7,713,584, which is hereby incorporated by reference and assigned to Hatanpaa et al.

[0047] In some embodiments of the present disclosure, contacting a substrate with a first gas-phase reactant comprising a metal-organic precursor may include exposing the substrate to the metal-organic precursor for a period of time between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. Additionally, during a pulse of the metal-containing precursor (e.g., metal-organic precursor), the flow rate of the metal-organic precursor may be less than 2000 sccm, or less than 500 sccm, or less than 100 sccm, or less than 50 sccm, or less than 10 sccm, or less than 1 sccm, or even less than 0.1 sccm. Additionally, during a pulse of the metal-organic precursor over the substrate, the flow rate of the metal-organic precursor may be from about 0.05 to 2000 sccm, from about 0.1 to 1000 sccm, or from about 1 to about 500 sccm.

[0048] Excess metal-organic precursor and reaction by-products (if present) can be removed from the surface, for example, by pumping with an inert gas. For example, in some embodiments of the present disclosure, the method may include a purge cycle, wherein the substrate surface is purged for a period of time less than about 2.0 seconds. Excess metal-organic precursor and any reaction by-products can be removed by means of a vacuum generated by a pumping system in fluid communication with the reaction chamber.

[0049] In a second stage of the deposition cycle (“ruthenium tetroxide stage”), the substrate may be contacted with a second gas-phase reactant comprising ruthenium tetroxide (RuO4). In some embodiments of the present disclosure, the ruthenium component of ruthenium tetroxide may have an oxidation state of +VIII or at least +VII. In some embodiments, the ruthenium component of ruthenium tetroxide may have an oxidation state of at least +III or greater than 0.

[0050] In some embodiments of the present disclosure, ruthenium tetroxide (RuO4) may be dissolved in a solvent, such as an inert organic solvent or a fluorocarbon solvent, such as an ethyl-methyl-fluorinated solvent mixture. In some embodiments, the concentration (% w / w) of ruthenium tetroxide (RuO4) in the solvent may be greater than 0.01%, or greater than 0.1%, or greater than 0.5%, or greater than 1.0%, or even greater than 1.5%. In some embodiments, the concentration (% w / w) of ruthenium tetroxide (RuO4) in the solvent may be less than 100%, or less than 50%, or less than 20%, or less than 10%, or less than 5%, or less than 2%, or even less than 1%. The ruthenium tetroxide (RuO4) precursor and its uses are described in U.S. Patent Application 2010 / 0212021712, which is incorporated herein by reference.

[0051] In some embodiments, exposing the substrate to ruthenium tetroxide (RuO4) may include pulsing a ruthenium tetroxide (RuO4) precursor above the substrate for a period of time between 0.1 second and 2.0 seconds, or from about 0.01 second to about 10 seconds, or less than about 20 seconds, less than about 10 seconds or less than about 5 seconds. During the pulsing of the ruthenium tetroxide (RuO4) precursor above the substrate, the flow rate of ruthenium tetroxide (RuO4) may be less than 50 sccm, or less than 25 sccm, or less than 15 sccm, or even less than 10 sccm. In some embodiments of the present disclosure, ruthenium tetroxide (RuO4) may be dissolved in a suitable solvent, and the flow rate of ruthenium tetroxide (RuO4) dissolved in the solvent may be between 0.00001 sccm and 2000 sccm, or between 0.001 sccm and 100 sccm, or between 0.1 sccm and 20 sccm.

[0052] A second gaseous-phase reactant comprising ruthenium tetroxide (RuO4) may react with the metal-containing molecules left on the substrate. In some embodiments, the second-stage precursor may include ruthenium tetroxide (RuO4), and the reaction may deposit a ruthenium-platinum alloy, a ruthenium-palladium alloy, or ternary ruthenium oxide.

[0053] Excess second gaseous-phase reactant (e.g., ruthenium tetroxide (RuO4)) and reaction by-products (if any) may be removed from the substrate surface, for example, by purge gas pulses generated by a pumping system and / or a vacuum. The purge gas is preferably any inert gas such as, but not limited to, argon (Ar), nitrogen (N2), or helium (He). If a purge (i.e., a purge gas pulse) or other reactant removal step is interposed between two stages, then one stage is generally considered to immediately follow the other.

[0054] The deposition cycle in which the substrate is alternately contacted with a first gaseous reactant (i.e., a metal-organic precursor) and a second gaseous reactant (i.e., ruthenium tetroxide (RuO4)) can be repeated two or more times until a ruthenium-containing film of the desired thickness is deposited. It should be understood that in some embodiments of the present disclosure, the order in which the substrate is contacted with the first gaseous reactant and the second gaseous reactant can be such that the substrate is first contacted with the second gaseous reactant and then with the first gaseous reactant. Additionally, in some embodiments, the cyclic deposition process can include contacting the substrate with the first gaseous reactant (i.e., a metal-organic precursor) one or more times before contacting the substrate with the second gaseous reactant (i.e., ruthenium tetroxide (RuO4)) one or more times, and similarly can alternatively include contacting the substrate with the second gaseous reactant one or more times before contacting the substrate with the first gaseous reactant one or more times. Additionally, some embodiments of the present disclosure can include non-plasma reactants, such that the first and second gaseous reactants are substantially free of ionized reactive species. In some embodiments, the first and second gaseous reactants are substantially free of ionized reactive species, excited species, or radical species. For example, the first gaseous reactant and the second gaseous reactant can include non-plasma reactants to prevent ionized damage to the underlying substrate and associated defects therefrom.

[0055] The cyclic deposition process described herein for depositing at least one of a ruthenium-platinum alloy, a ruthenium-palladium alloy, or a ternary ruthenium oxide using a metal-organic precursor and ruthenium tetroxide (RuO4) can be carried out in an ALD or CVD deposition system having a heated substrate. By way of example, in some embodiments, the method can include heating the substrate to a temperature between about 80 °C and about 150 °C, or even heating the substrate to a temperature between about 80 °C and about 120 °C. Of course, the appropriate temperature window for any given cyclic deposition process (e.g., for an ALD reaction) will depend on the surface termination state and reactant species involved. Here, the temperature varies depending on the precursor used and is generally equal to or below about 700 °C. In some embodiments, for a vapor deposition process, the deposition temperature is generally equal to or higher than about 100 °C, in some embodiments, the deposition temperature is between about 100 °C and about 250 °C, and in some embodiments, the deposition temperature is between about 120 °C and about 200 °C. In some embodiments, the deposition temperature is below about 500 °C, below about 400 °C, or below about 300 °C. In some cases, the deposition temperature can be below about 200 °C, below about 150 °C, or below about 100 °C. In some cases, the deposition temperature can be higher than about 20 °C, higher than about 50 °C, and higher than about 75 °C. In some embodiments of the present disclosure, the deposition temperature (i.e., the temperature of the substrate during deposition) is about 150 °C.

[0056] In some embodiments, the growth rate of the ruthenium-containing film is about Cycle to about Cycle, about Cycle to about Cycle. In some embodiments, the growth rate of the ruthenium-containing film is greater than about Cycle, greater than about Cycle, greater than about Cycle, greater than about Cycle, greater than about Cycle or greater than about Cycle. In some embodiments, the growth rate of the ruthenium-containing film is less than about Cycle, less than about Cycle, less than about Cycle, less than about Cycle or less than about Cycle. In some embodiments, the growth rate of the ruthenium-containing film can be between Cycle and Cycle. In some embodiments, the growth rate of the ruthenium-containing film can be between Cycle and Cycle, or between Cycle and Cycle, or between Cycle and Cycle. In some embodiments of the present disclosure, the growth rate of the ruthenium-containing film is about Cycle.

[0057] Embodiments of the present disclosure may include cyclic deposition, which may be illustrated in more detail by exemplary method 100 of Figure 1 . Method 100 may begin with process block 110, which includes providing at least one substrate into a reaction chamber and heating the substrate to a deposition temperature. For example, the substrate may include a bulk silicon substrate, the reaction chamber may include an atomic layer deposition reaction chamber, and the substrate may be heated to a deposition temperature of about 150°C. Method 100 may continue with process block 120, which includes contacting the substrate with a metal-containing gas-phase reactant. For example, the substrate may be contacted with a metal-organic precursor for a period of about 1 second. After contacting the substrate with the metal-organic precursor, excess metal-organic precursor and any reaction by-products may be removed from the reaction chamber through a purge / pump process. Method 100 may continue with process block 130, which includes contacting the substrate with ruthenium tetroxide (RuO4) for a period of about 4 seconds. After contacting the substrate with the ruthenium tetroxide (RuO4) precursor, excess RuO4 precursor and any reaction by-products may be removed from the reaction chamber through a purge / pump process.

[0058] A method in which a substrate is alternately and sequentially contacted with a metal-organic precursor and with a ruthenium tetroxide (RuO4) precursor can constitute one deposition cycle. In some embodiments of the present disclosure, the method of depositing a ruthenium-containing film can include repeating the deposition cycle one or more times. For example, method 100 can continue through decision gate 140, which determines whether method 100 continues or exits. The decision gate of process block 140 makes a determination based on the thickness of the deposited ruthenium-containing film. For example, if the thickness of the metal-containing film is insufficient for the desired device structure, then method 100 can return to process block 120, and the processes of contacting the substrate with the metal-organic precursor and contacting the substrate with the ruthenium tetroxide (RuO4) precursor can be repeated one or more times. Once the ruthenium-containing film has been deposited to the desired thickness, the method can exit 150 and the ruthenium-containing film can undergo additional processes to form the device structure.

[0059] In some embodiments of the present disclosure, method 100 can include additional processing steps that can be used to control the ruthenium content, i.e., the atomic percentage at-% of ruthenium, in the ruthenium-containing film deposited by embodiments of the present disclosure. In some embodiments, the first additional processing step can be performed after contacting the substrate with the metal-organic precursor and before contacting the substrate with ruthenium tetroxide. In some embodiments, the first additional processing step can include contacting the substrate with an oxygen-containing plasma, such as a plasma generated by the excitation of molecular oxygen (O2). In some embodiments of the present disclosure, exposing the substrate to the oxygen-containing plasma can reduce the ruthenium content in the ruthenium-containing layer deposited by the method of the present disclosure. In some embodiments, the second additional processing step can be performed after contacting the substrate with the metal-organic precursor and before contacting the substrate with ruthenium tetroxide. In some embodiments, the second additional processing step can include contacting the substrate with an additional organic precursor (such as an alcohol, an aldehyde, or a carboxylic acid).

[0060] In some embodiments of the present disclosure, the additional organic precursor can include an alcohol, where the alcohol can be a primary alcohol, a secondary alcohol, a tertiary alcohol, a polyhydroxy alcohol, a cyclic alcohol, an aromatic alcohol, and other derivatives of alcohol.

[0061] In some embodiments of the present disclosure, the additional organic precursor can include at least one aldehyde group (-CHO) selected from the group consisting of: a compound having the general formula (I), an alkanediol compound having the general formula (II), a halogenated aldehyde, and other derivatives of aldehyde.

[0062] Thus, in some embodiments, the additional organic precursor can include an aldehyde having the following general formula:

[0063] R3-CHO(I)_

[0064] Wherein R3 is selected from the group consisting of: hydrogen and straight-chain or branched C1-C20 alkyl and alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl or hexyl. In some embodiments, R3 is selected from the group consisting of methyl or ethyl. Exemplary compounds according to formula (I) include, but are not limited to, formaldehyde, acetaldehyde and butyraldehyde.

[0065] In some embodiments of the present disclosure, the additional organic precursor may include an aldehyde having the general formula (II):

[0066] OHC-R4-CHO (II)

[0067] Wherein R4 is a straight-chain or branched C1-C20 saturated or unsaturated hydrocarbon. Alternatively, the aldehyde groups may be directly bonded to each other (R4 is absent).

[0068] In some embodiments of the present disclosure, the additional organic precursor may include at least one -COOH group and may be selected from the group consisting of compounds of general formula (III), polycarboxylic acids, halogenated carboxylic acids and other derivatives of carboxylic acids. Thus, in some embodiments, the additional organic precursor may include a carboxylic acid having the general formula (III):

[0069] R5-COOH (III)

[0070] Wherein R5 is hydrogen or a straight-chain or branched C1-C20 alkyl or alkenyl group, such as methyl, ethyl, propyl, butyl, pentyl or hexyl, for example methyl or ethyl. In some embodiments, R5 is a straight-chain or branched C1-C3 alkyl or alkenyl group. Examples of compounds according to formula (III) are formic acid, propionic acid and acetic acid.

[0071] In some embodiments of the present disclosure, exposing the substrate to the additional organic precursor may increase the ruthenium content in the ruthenium-containing layer relative to the metal supplied by the metal organic in the deposited film.

[0072] In some embodiments of the present disclosure, and specifically for embodiments in which the disclosed deposition method is used to deposit ruthenium trioxide, the substrate may undergo a surface pretreatment before the deposition process. In some embodiments, the surface of the substrate may be pretreated with an alcohol to increase the amount of carbon on the substrate surface. For example, the substrate may be pretreated with an alcohol selected from the group consisting of C1-C10 alcohols, C2-C10 diols and C3-C10 triols. In some embodiments of the present disclosure, the substrate surface may be pretreated with methanol, ethanol, isopropanol or at least one of other organic molecules containing a C x -H y group that can be chemisorbed onto the substrate surface.

[0073] In some embodiments of the present disclosure, a ruthenium-containing film (e.g., pure ruthenium) can be deposited on a suitable substrate using the methods of the present disclosure. In some embodiments, nucleation of the ruthenium-containing film on the substrate may be delayed, i.e., there is an incubation period during which deposition does not occur. For example, for ruthenium deposition on a silica surface, there may be an incubation period of more than 100 deposition cycles before the film is deposited. To improve the incubation period and allow for faster nucleation of the ruthenium-containing film, the substrate can be treated prior to deposition. Thus, in some embodiments of the present disclosure, the substrate surface can be treated with an organic molecule to reduce the incubation time and increase the nucleation of the ruthenium-containing film. In some embodiments, the organic molecule can include an alcohol or a metal organic compound, such as trimethylaluminum (TMA). For example, the substrate surface can include a silica surface, and the silica surface can be exposed to trimethylaluminum (TMA) before the substrate comes into contact with the ruthenium precursor. The pretreatment of the silica surface with trimethylaluminum (TMA) can greatly reduce the incubation time and allow for rapid nucleation of the ruthenium-containing film (e.g., pure ruthenium by a ruthenium tetroxide (RuO4) and hydrogen gas (H2) deposition process).

[0074] A thin film including a ruthenium-containing film (e.g., a ruthenium-platinum alloy, a ruthenium-palladium alloy, or a ternary ruthenium oxide) deposited according to some embodiments described herein can be a continuous film. In some embodiments, a thin film including a ruthenium-containing film deposited according to some embodiments described herein can be continuous at the following thicknesses: less than about 100 nm, less than about 60 nm, less than about 50 nm, less than about 40 nm, less than about 30 nm, less than about 25 nm, or less than about 20 nm, or less than about 15 nm, or less than about 10 nm, or less than about 5 nm, or less. The continuity mentioned herein can be physical continuity or electrical continuity. In some embodiments, the thickness at which the film can have physical continuity may not be the same as the thickness at which the film has electrical continuity, and the thickness at which the film can have electrical continuity may not be the same as the thickness at which the film has physical continuity.

[0075] In some embodiments, the thickness of a ruthenium-containing film deposited according to some embodiments described herein can be from about 20 nm to about 100 nm. In some embodiments, the thickness of a ruthenium-containing film deposited according to some embodiments described herein can be from about 20 nm to about 60 nm. In some embodiments, the thickness of a ruthenium-containing film deposited according to some embodiments described herein can be greater than about 20 nm, greater than about 30 nm, greater than about 40 nm, greater than about 50 nm, greater than about 60 nm, greater than about 100 nm, greater than about 250 nm, greater than about 500 nm, or greater. In some embodiments, the thickness of a ruthenium-containing film deposited according to some embodiments described herein can be less than about 50 nm, less than about 30 nm, less than about 20 nm, less than about 15 nm, less than about 10 nm, less than about 5 nm, less than about 3 nm, less than about 2 nm, or even less than about 1 nm.

[0076] In some embodiments of the present disclosure, a ruthenium-containing film can be deposited on a three-dimensional structure comprising high aspect ratio features. In some embodiments, in structures having an aspect ratio (height / width) greater than about 2, greater than about 5, greater than about 10, greater than about 25, greater than about 50, or even greater than about 100, the step coverage of the ruthenium-containing film can be equal to or greater than about 50%, greater than about 80%, greater than about 90%, about 95%, about 98%, or about 99% or greater.

[0077] In some embodiments of the present disclosure, the metal-organic precursor can include a metal-organic platinum precursor and the ruthenium-containing film deposited by the methods of the present disclosure can include a ruthenium-platinum alloy. In some embodiments, the ruthenium-platinum alloy can include a platinum content greater than 5 atomic %, or greater than 10 atomic %, or greater than 15 atomic %, or greater than 25 atomic %, or greater than 50 atomic %, or greater than 75 atomic %, or even greater than 90 atomic %. In some embodiments, the ruthenium-platinum alloy can include a platinum content of about 15 atomic %.

[0078] In additional embodiments, the ruthenium-platinum alloy can include less than about 20 atomic % oxygen, less than about 10 atomic % oxygen, less than about 5 atomic % oxygen, or even less than about 2 atomic % oxygen. In other embodiments, the ruthenium-platinum alloy can include less than about 10 atomic % hydrogen, or less than about 5 atomic % hydrogen, or less than about 2 atomic % hydrogen, or even less than about 1 atomic % hydrogen. In still other embodiments, the ruthenium-platinum alloy can include less than about 10 atomic % carbon, or less than about 5 atomic % carbon, or less than about 2 atomic % carbon, or less than about 1 atomic % carbon, or even less than about 0.5 atomic % carbon. In the embodiments outlined herein, the atomic concentration of the elements can be determined using Rutherford backscattering (RBS).

[0079] The ruthenium-platinum alloy deposited by the cyclic deposition process disclosed herein can be utilized in a variety of scenarios, such as as an anode catalyst for fuel cell applications and as a work function metal for semiconductor transistor applications.

[0080] More specifically, the ruthenium-platinum alloy deposited by the method of the present disclosure can be used as an electrode, such as an anode catalyst in a direct methanol fuel cell (DMFC). The DMFC is a well-known membrane electrochemical generator in which the oxidation of an aqueous methanol solution occurs at the anode. Compared with other types of low-temperature fuel cells, the DMFC is extremely attractive because it uses a liquid fuel, which provides great advantages in terms of energy density and is easier and faster to refuel or recharge. Many studies have centered on improving the anode catalyst, and in terms of catalytic activity, platinum and ruthenium alloys are largely preferred. However, platinum and ruthenium are extremely difficult to combine into a true alloy using conventional forming methods; therefore, the present disclosure provides a method for forming a high-quality ruthenium-platinum alloy. For example, in some embodiments of the present disclosure, the ruthenium-platinum alloy can be deposited on an inert carrier (such as a carbon carrier) to form a catalytic anode suitable for a fuel cell device.

[0081] In some embodiments of the present disclosure, the ruthenium-platinum alloy deposited by the method in the present disclosure can be used as a work function metal in a transistor structure, such as a planar transistor structure or a multi-gate transistor, such as a FinFET. More specifically, and with reference to Figure 2 , the semiconductor device structure 200 may include a semiconductor body 216 and a gate electrode 210, and the gate electrode includes a ruthenium-platinum alloy disposed above the semiconductor body 216. In some embodiments, the semiconductor device structure 200 may include a transistor structure and may also include a source region 202, a drain region 204, and a channel region 206 therebetween. The transistor gate structure 208 may include an electrode 210, that is, a gate electrode, which may be separated from the channel region 206 by a gate dielectric 212. According to the present disclosure, the gate electrode 210 may include a ruthenium-platinum alloy deposited by the cyclic deposition method described herein. As Figure 2 shown, in some embodiments, the transistor gate structure 208 may further include one or more additional conductive layers 214 formed on the gate electrode 210. The one or more additional conductive layers 214 may include at least one of polysilicon, refractory metal, transition metal carbide, and transition metal nitride.

[0082] In some embodiments of the present disclosure, the metal organic precursor may include a metal selected from the group consisting of aluminum, titanium, bismuth, zinc, and combinations thereof, and the method of the present disclosure may include depositing ruthenium trioxide. For example, the cyclic deposition method disclosed herein can be used to deposit ruthenium trioxide having the general formula M x Ru y O z , where M is a metal selected from the group consisting of aluminum, titanium, bismuth, zinc, and combinations thereof, Ru is ruthenium, and O is oxygen. Therefore, embodiments of the present disclosure can be used to deposit at least one of the following: ruthenium aluminate (Al x Ruy O z ) Ruthenium titanium oxide (Ti x Ru y O z ), ruthenium bismuth oxide (Bi x Ru y O z ), and ruthenium zinc oxide (Zn x Ru y O z ).

[0083] In some embodiments of the present disclosure, the ternary ruthenium oxide (M x Ru y O z ) may include a metal content, i.e., the atomic % of M, which is greater than 1 atomic %, or greater than 10 atomic %, or greater than 15 atomic %, or even greater than 20 atomic %. In some embodiments of the present disclosure, the ternary ruthenium oxide (M x Ru y O z ) may include a ruthenium content, i.e., the atomic % of Ru, which is greater than 1 atomic %, or greater than 10 atomic %, or greater than 15 atomic %, or even greater than 20 atomic %. In some embodiments of the present disclosure, the ternary ruthenium oxide (M x Ru y O z ) may include an oxygen content, i.e., the atomic % of O, which is greater than 20 atomic % or greater than 40 atomic %, or greater than 60 atomic %, or even greater than 65 atomic %.

[0084] In additional embodiments, the ternary ruthenium oxide may include less than about 5 atomic % hydrogen, or less than about 2 atomic % hydrogen, or even less than about 1 atomic % hydrogen. In still other embodiments, the ternary ruthenium oxide may include less than about 10 atomic % carbon, or less than about 5 atomic % carbon, or less than about 2 atomic % carbon, or less than about 1 atomic % carbon, or even less than about 0.5 atomic % carbon. In the embodiments outlined herein, the atomic concentration of elements can be determined using Rutherford backscattering (RBS).

[0085] The ternary ruthenium oxide (M x Ru y O z ) deposited by the cyclic deposition process disclosed herein can be utilized in a variety of scenarios, e.g., in fuel cell applications. For example, ruthenium titanium oxide (Ti x Ru y O z ) can be used as a stable catalyst support for hydrogen fuel cell applications, where ruthenium titanium oxide replaces the commonly used carbon support and platinum nanoparticles are deposited on the support as the catalyst material. In addition, ruthenium bismuth oxide (Bi x Ruy O z ) can be used as a suitable electrode material in a solid oxide fuel cell.

[0086] In some embodiments of the present disclosure, the first gas-phase reactant comprising a metal-organic precursor may further comprise a metal selected from the group consisting of lithium, calcium, barium, cobalt, lead, and combinations thereof. In some embodiments, the metal-organic precursor may comprise lithium metal and the deposited film may comprise lithium ruthenium oxide. For example, lithium ruthenium oxide can be used as an electrode material in lithium-ion battery applications. In some embodiments, the metal-organic precursor may comprise calcium metal and the deposited film may comprise calcium ruthenium oxide. For example, calcium ruthenium oxide can be used as an oxygen evolution anode in electrochemical applications. In some embodiments, the metal-organic precursor may comprise barium metal and the deposited film may comprise barium ruthenium oxide. For example, barium ruthenium oxide can be used in a heterogeneous catalyst structure. In some embodiments, the metal-organic precursor may comprise cobalt metal and the deposited film may comprise cobalt ruthenium oxide. For example, cobalt ruthenium oxide can be used in a thermistor device structure. In some embodiments, the metal-organic precursor may comprise lead metal and the deposited film may comprise lead ruthenium oxide. For example, lead ruthenium oxide can be used in a variety of applications, including but not limited to electrodes for lithium-based batteries, cathode materials in solid oxide fuel cells, and selective oxidation of alcohols.

[0087] In some embodiments of the present disclosure, the ruthenium-containing film deposited by the methods disclosed herein can be used as a heterogeneous catalyst and the ruthenium-containing film can form at least a part of a heterogeneous catalytic structure. For example, the ruthenium-containing film can be deposited over a suitable substrate (such as a catalyst support). In some embodiments, the catalyst support may comprise a high-surface area support on which the ruthenium-containing film is deposited. For example, the catalyst support may comprise carbon, alumina, and silica, and in order to increase the surface area of the catalyst support, and thus the activity of the heterogeneous catalyst, the catalyst support may comprise a powder. The heterogeneous catalytic structure comprising a ruthenium-containing film deposited according to embodiments of the present disclosure can be utilized to enhance a variety of chemical processes, such as gas-phase oxidation, selective hydrogenation, and fuel cell power applications.

[0088] Embodiments of the present disclosure may also include a reaction system configured to form the ruthenium-containing films of the present disclosure. More specifically, Figure 3Schematically illustrate a reaction system 300 including a reaction chamber 302, the reaction chamber further including means for holding a substrate (not shown) under predetermined pressure, temperature and ambient conditions and for selectively exposing the substrate to various gases. A precursor reactant source 304 can be coupled to the reaction chamber 302 through a pipe or other suitable member 304A, and can be further coupled to a manifold, a valve control system, a mass flow control system or means for controlling the gaseous precursor from the precursor reactant source 304. The precursor (not shown), reactant (not shown) supplied by the precursor reactant source 304 can be liquid or solid at room temperature and standard atmospheric pressure conditions. The precursor can be vaporized in a reactant source vacuum container, which can be maintained at or above the vaporization temperature in the precursor source chamber. In this embodiment, an inert gas (e.g., an inert or noble gas) can be used to transport the vaporized precursor, and then the vaporized precursor is fed into the reaction chamber 302 through the pipe 304A. In other embodiments, the precursor can be a vapor under standard conditions. In this embodiment, the precursor does not need to be vaporized and may not need a carrier gas. For example, in one embodiment, the precursor can be stored in a gas cylinder. The reaction system 300 can also include additional precursor reactant sources, and the precursor reactant source 306 can also be coupled to the reaction chamber through a pipe 306A as described above.

[0089] A purge gas source 308 can also be coupled to the reaction chamber 302 through a pipe 308A, and selectively supplies various inert gases or noble gases to the reaction chamber 302 to assist in removing precursor gases or waste gases from the reaction chamber. The various inert gases or noble gases that can be supplied can be from solid, liquid or stored gaseous forms.

[0090] Figure 3 The reaction system 300 can also include a system operation and control means 310, which provides electronic circuits and mechanical components to selectively operate valves, manifolds, pumps and other equipment included in the reaction system 300. The circuits and components operate to introduce precursors, purge gases from the respective precursor sources 304, 306 and the purge gas source 308. The system operation and control means 310 also controls the timing of the gas pulse sequence, the temperature of the substrate and the reaction chamber, and the pressure of the reaction chamber and provides various other operations necessary for the proper operation of the reaction system 300. The operation and control means 310 can include control software and electrically or pneumatically controlled valves to control the flow of precursors, reactants and purge gases into and out of the reaction chamber 302. The control system can include modules that perform certain tasks, such as software or hardware components, such as FPGA or ASIC. The modules can be advantageously configured to reside on an addressable storage medium of the control system, and can be advantageously configured to perform one or more processes.

[0091] Those skilled in the art will understand that other configurations of the reaction system of the present invention are possible, including different numbers and types of precursor reactant sources and purge gas sources. In addition, those skilled in the art should also understand that there are many arrangements of valves, pipes, precursor sources, and purge gas sources that can be used to achieve the goal of selectively feeding gases into the reaction chamber 302. In addition, as a schematic representation of the reaction system, many components have been omitted for the sake of simplicity of description, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0092] The example embodiments of the present disclosure described above do not limit the scope of the present invention, because these embodiments are only examples of the embodiments of the present invention, and the present invention is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to be within the scope of the present invention. In fact, it will be obvious to those skilled in the art from the specification that various modifications to the present disclosure (e.g., alternative applicable combinations of the described elements) other than those shown and described herein. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for depositing a ruthenium-containing film on a substrate by a cyclic deposition process, each cycle of the method comprising: Contact the substrate with a first gaseous reactant comprising a metal-organic precursor, the metal-organic precursor comprising a metal selected from the group consisting of platinum, palladium, aluminum, titanium, bismuth, zinc, and combinations thereof; After contacting the substrate with the first gaseous reactant, contact the substrate with a fourth gaseous reactant comprising an additional organic precursor, wherein the additional organic precursor comprises an aldehyde having the general formula OHC-R4CHO, where R4 is a straight-chain or branched C1-C20 saturated or unsaturated; After contacting the substrate with the additional organic precursor, contact the substrate with a second gaseous reactant comprising ruthenium tetroxide, wherein the ruthenium-containing film comprises at least one of a ruthenium-platinum alloy, a ruthenium-palladium alloy, or ruthenium trioxide.

2. The method according to claim 1, wherein, The cyclic deposition process comprises a cyclic chemical vapor deposition process.

3. The method according to claim 1, wherein, The method comprises at least one deposition cycle, wherein the substrate is alternately and sequentially contacted with the first gaseous reactant and the second gaseous reactant.

4. The method according to claim 1, wherein the metal organic precursor comprises a metal organic platinum precursor selected from the group consisting of (trimethyl)methylcyclopentadienyl platinum, (trimethyl)cyclopentadienyl(C5H5)Pt(CH3)3, Pt(acetylacetonate)2, Pt(PF3)4, Pt(CO)2C12, cis-[Pt(CH3)2((CH3)NC)2], and platinum hexafluoroacetylacetonate.

5. The method according to claim 4, wherein the ruthenium-containing film comprises a ruthenium-platinum alloy.

6. The method according to claim 1, wherein the metal organic precursor comprises a metal organic palladium precursor selected from the group consisting of Pd(thd)2 and Pd(hfac)2.

7. The method according to claim 6, wherein the ruthenium-containing film comprises a ruthenium-palladium alloy.

8. The method according to claim 1, wherein, The metal-organic precursor comprises a metal-organic titanium precursor selected from the group consisting of: tetrakis(dimethylamino)titanium (TDMAT), pentamethylcyclopentadienyltrimethoxytitanium (CpMe5Ti(OMe)3), titanium methoxide (Ti(OMe)4), titanium ethoxide (Ti(OEt)4), titanium isopropoxide (Ti(OPr)4), or titanium butoxide (Ti(OBu)4).

9. The method according to claim 8, wherein, The ruthenium-containing film includes ruthenium titanium oxide (Ti x Ru y O z ).

10. The method according to claim 1, wherein, The metal-organic precursor comprises a metal-organic bismuth precursor selected from the group consisting of: [(dmb)2Bi-O-Bi(dmb)2]2, tris(2,3-dimethyl-2-butoxy)bismuth(III), tris(tert-butoxy)bismuth(III), tris(isopropoxy)bismuth(III), Bi(N(SiMe3)2)3, Bi(thd)3, Bi(OtBu)3, Bi(dmb)3, and Bi(CH2SiMe3)3.

11. The method according to claim 10, wherein, The ruthenium-containing film includes bismuth ruthenium oxide (Bi x Ru y O z ).

12. The method according to claim 1, wherein, The metal-organic precursor comprises a metal-organic aluminum precursor selected from the group consisting of: The metal-organic aluminum precursor may comprise at least one of the following: trimethylaluminum (TMA), triethylaluminum (TEA), dimethylaluminum chloride (AlMe2Cl), dimethylaluminum isopropoxide (AlMe2OPr), or aluminum ethoxide (AlOEt)3.

13. The method according to claim 12, wherein, The ruthenium-containing film includes aluminum ruthenium (Al x Ru y O z ).

14. The method according to claim 1, wherein, The metal-organic precursor comprises a metal-organic zinc precursor selected from the group consisting of: dimethylzinc (ZnMe2), diethylzinc (ZnEt2), methylzinc isopropoxide (ZnMe(OPr)), or zinc acetate (Zn(CH3CO2)2).

15. The method according to claim 14, wherein, The ruthenium-containing film includes ruthenium zinc oxide (Zn x Ru y O z ).

16. The method according to claim 1, wherein, The metal-organic precursor comprises a metal-organic precursor selected from the group consisting of: pentamethylcyclopentadienyltrimethoxytitanium (CpMe5Ti(OMe)3), titanium methoxide (Ti(OMe)4), titanium ethoxide (Ti(OEt)4), titanium butoxide (Ti(OBu)4), Bi(N(SiMe3)2)3, Bi(thd)3, Bi(OtBu)3, or Bi(CH2SiMe3)3.

17. The method according to claim 1 further comprises heating the substrate to a temperature between about 120 °C and 200 °C.

18. The method according to claim 1 further comprises contacting the surface of the substrate with an alcohol prior to the cyclic deposition process.

19. A semiconductor structure comprising a ruthenium-containing film deposited by the method according to claim 1.

20. The semiconductor structure according to claim 19, wherein The ruthenium-containing film comprises at least a portion of the electrode.

21. A reaction system configured to perform the method according to claim 1.

22. A heterogeneous catalyst structure comprising a ruthenium-containing film deposited by the method according to claim 1.

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