Method for selectively depositing highly conductive metal films - Patents.com

Abstract

Methods are provided that include selective ruthenium seed layer deposition using an oxygen-free ruthenium precursor, followed by bulk deposition of a metal-containing precursor, such as a tungsten, molybdenum, cobalt, ruthenium, and / or copper-containing precursor. The ruthenium seed layer deposition is highly selective to the conductive portions of the microelectronic device substrate, minimizing deposition on insulating surfaces of the microelectronic device substrate. In certain embodiments, the conductive portions of the substrate are selected from titanium nitride, tungsten nitride, tantalum nitride, tungsten, cobalt, molybdenum, aluminum, and copper.

Description

[Technical field]

[0001]

[0001] The present invention relates generally to the field of vapor deposition. In particular, the present invention relates to the selective deposition of ruthenium-containing precursors followed by bulk deposition of various metals on microelectronic device substrates.

[0002] Priority claim

[0002] This invention claims priority to U.S. Provisional Patent Application No. 63 / 306,287, filed February 3, 2022, which is incorporated herein by reference. [Background technology]

[0003]

[0003] In the manufacture of microelectronic devices, tungsten is typically deposited on a titanium nitride barrier. The method involves depositing a nucleation layer using tungsten hexafluoride and a silicon or boron source, followed by bulk deposition using tungsten hexafluoride and hydrogen as the reducing gas. Unfortunately, the material of such nucleation layers is often very fine grained and exhibits high resistivity. Moreover, because the nucleation step is non-selective, the sidewalls of the device also tend to be covered with this highly resistive metal.

[0004]

[0004] For the deposition of molybdenum-containing films on microelectronic device substrates, molybdenum pentachloride and molybdenum oxytetrachloride have been developed for the chemical vapor deposition of high purity, low resistivity molybdenum metal. However, molybdenum also generally requires similar nonselective pulsed nucleation techniques for deposition on titanium nitride surfaces at temperatures below about 500°C.

[0005]

[0005] Thus, there remains a need for the ability to deposit low resistance nucleation (or seed) layers on metal surfaces, such as titanium nitride, with high selectivity to the surrounding dielectric, thereby enabling bulk deposition of materials such as metal-containing films, such as tungsten, molybdenum, cobalt, ruthenium, copper, etc.

[0006]

[0006] With the scaling of integrated semiconductor devices, the resistance of conductive vias connecting wiring layers has become a significant portion of the overall resistive-capacitive (RC) delay in communication within integrated devices. To minimize the via resistance, it is necessary to minimize the volume consumed by high-resistance barriers, adhesion layers, and nucleation layers. One way to fill the entire volume of a via with a low-resistance metal is to nucleate and grow from the metal contact at the bottom of the via toward the top, without growing from the dielectric sidewalls of the via. Therefore, it is necessary to deposit selectively on such metal contacts. Summary of the Invention

[0007] In summary, the present invention provides a method that includes selective ruthenium seed layer deposition using an oxygen-free ruthenium precursor, followed by bulk deposition of a metal-containing precursor, such as a tungsten, molybdenum, cobalt, ruthenium, and / or copper-containing precursor. The ruthenium seed layer deposition is highly selective to the conductive portions of the microelectronic device substrate, minimizing deposition on the insulating surfaces of the microelectronic device substrate. In certain embodiments, the conductive portions of the substrate are selected from titanium nitride, tungsten nitride, tantalum nitride (all conductive nitrides), tungsten, cobalt, molybdenum, aluminum, and copper (metal 1 in FIG. 6). In certain embodiments, the insulating surface is selected from silicon oxide, silicon nitride, and other dielectrics, as well as low-k dielectrics.

[0008]

[0008] The ruthenium seed layer exhibited a post-deposition electrical resistivity of about 450 μΩ-cm when a 5.3 Å thick ruthenium film was deposited from a p-cymenecyclohexadiene precursor on a titanium nitride substrate at 300° C. The process was also highly selective, as evidenced by only about 0.3 Å of ruthenium deposited on the adjacent silicon oxide surface, demonstrating selectivity to the conductive portions of the substrate over the insulating portions of the substrate. This highly conductive seed layer allows for the bulk deposition of the metals. [Brief description of the drawings]

[0009] [Figure 1]

[0009] Figure 1 is a graph showing the self-limiting deposition and deposition selectivity of titanium nitride to SiO2 as described in Example 1. The deposition selectivity was demonstrated to be 94% with 5 Angstroms of ruthenium. [Diagram 2]

[0010] 1 is a graph showing the as-deposited resistivity of ruthenium films formed on titanium nitride at various thicknesses. [Diagram 3]

[0011] Scanning electron micrograph (SEM) top view of a 5.3 Å thick ruthenium layer deposited on a titanium nitride substrate. (10 min, 446.1 μΩ-cm) [Figure 4]

[0012] 1 is a graph showing the self-limiting deposition and selectivity of titanium nitride over silicon dioxide when depositing ethylbenzyl(1-ethyl-1,4-cyclohexadienyl)Ru with H2 as a coreactant, as described in Example 2. [Diagram 5]

[0013] 1 is a graph showing the as-deposited resistivity of ruthenium on titanium dioxide and silicon dioxide at various thicknesses according to Example 2. [Figure 6]

[0014] FIG. 6b is an illustration of a problem presented in the prior art where voids often occur when filling vias with "metal 2" by non-selective deposition. FIG. 6b is an illustration of a solution to this problem believed to be possible with the process of the present invention, i.e., such a void-free via structure. FIG. 6c is an example where metal 2 is selectively deposited on "metal 1" in a very selective manner, allowing for bottom-up filling of the via with metal 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010]

[0015] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0011]

[0016] The term "about" generally refers to a range of numbers considered equivalent to a stated value (e.g., having the same function or result). In many cases, the term "about" may include numbers that are rounded to the nearest significant figure.

[0012]

[0017] Numeric ranges expressed using endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0013] In a first aspect, the present invention provides a method of depositing a metal-containing film on a microelectronic device substrate, the metal being selected from tungsten, molybdenum, cobalt, ruthenium, and copper, the substrate being selected from titanium nitride, tungsten nitride, tantalum nitride, niobium nitride, tungsten, molybdenum, cobalt, and copper; a. introducing an oxygen-free ruthenium precursor material into a reaction zone containing a substrate under vapor deposition conditions in the presence of a reducing gas until a ruthenium-containing film is formed having a thickness of about 3 to about 15 Å; and b. introducing a tungsten, molybdenum, cobalt, ruthenium or copper metal-containing precursor into a reaction zone under vapor deposition conditions until a tungsten, molybdenum, cobalt, ruthenium or copper metal-containing film of a desired thickness is obtained; The present invention provides a method comprising:

[0014]

[0019] The method of the present invention allows for the bulk deposition of specific metal-containing films on a substrate provided with a highly conductive ruthenium seed layer (step a). This selectively formed highly conductive ruthenium layer can be deposited using the methodology described in U.S. Patent Publication Nos. 2020 / 0149155 and 2020 / 0157680, which are incorporated herein by reference. As mentioned above, step a. utilizes an oxygen-free ruthenium precursor material. In one embodiment, the oxygen-free ruthenium precursor is selected from the following: TIFF2025504116000002.tif41170 In this specification, they are referred to as "p-cymene CHD Ru" and "EBECHD Ru", respectively.

[0015]

[0020] Once a ruthenium seed layer having a thickness of about 3 to about 15 Å has been formed, step b is utilized to introduce a metal-containing precursor of tungsten, molybdenum, cobalt, ruthenium, or copper. In this regard, the ruthenium precursor utilized in step b can be an oxygen-free ruthenium precursor or an oxygen-containing ruthenium precursor, in either case selected from known ruthenium precursor materials. When the ruthenium precursor contains oxygen, it may be desirable to utilize a reducing gas as a co-reactant to properly deposit (i.e., in a zero oxidation state) the desired metal. Exemplary reducing gases include hydrogen, ammonia, hydrazine, methylhydrazine, t-butylhydrazine, 1,2-dimethylhydrazine, and 1,1-dimethylhydrazine.

[0016]

[0021] In certain embodiments, the vapor deposition conditions include reaction conditions known as chemical vapor deposition, pulsed chemical vapor deposition, and atomic layer deposition. In the case of pulsed chemical vapor deposition, a series of alternating pulses of precursor composition and co-reactant, with or without intermediate (inert gas) purge steps, can be utilized to build up film thickness to a desired endpoint.

[0017]

[0022] In certain embodiments, the pulse time of the precursor compounds indicated above (i.e., the duration that the precursor is exposed to the substrate) ranges from about 1 second to 30 seconds. If a purge step is utilized, the duration is about 1 to 20 seconds or 1 to 30 seconds. In other embodiments, the pulse time of the co-reactant ranges from 5 seconds to 60 seconds.

[0018]

[0023] In one embodiment, the vapor deposition conditions for step a, ie, deposition of the ruthenium seed layer, include a temperature in the reaction zone of from about 100° C. to about 400° C., or from about 200° C. to about 350° C., and a pressure of from about 1 Torr to about 100 Torr.

[0019]

[0024] The bulk deposition of the metal film in step b depends on the particular metal precursor selected and involves a variety of temperatures, pressures and co-reactant gases.

[0020]

[0025] For example, for molybdenum hexacarbonyl and tungsten carbonyl, U.S. Patent Publication No. 2021 / 0062331, incorporated herein by reference, describes temperatures of about 250° C. to about 750° C.

[0021]

[0026] U.S. Patent Publication No. 2020 / 0199743 describes temperatures of less than about 480° C. and pressures of less than about 100 Torr for precursors such as MoCl5, MoOCl4, MoO2Cl2, WCl6, WCl5, WOCl4, and WO2Cl3.

[0022]

[0027] For various ruthenium precursors, the vapor deposition temperature is generally from about 100° C. to about 500° C., and the pressure is generally from about 10 mTorr to about 30 Torr.

[0023]

[0028] For various cobalt precursors, the vapor deposition temperature is generally from about 70° C. to about 480° C., and the pressure is generally from about 0.2 mTorr to about 760 Torr.

[0024]

[0029] For various copper precursors, the vapor deposition temperature is generally from about 40° C. to about 200° C., and the pressure is generally from about 0.2 mTorr to about 30 Torr.

[0025]

[0030] In one embodiment, the ruthenium-containing precursor compound in step a or step b is selected from one or more compounds selected from: TIFF2025504116000003.tif236170TIFF2025504116000004.tif241170TIFF2025504116000005.tif140170[Wherein, R is selected from C1 to C4 alkyl.]

[0026]

[0031] In one embodiment, R is t-butyl.

[0027]

[0032] The precursor composition comprising at least one of the compounds described above can be used to form a low-resistance ruthenium seed film on various surfaces. In one embodiment, in step (a) above, the ruthenium seed layer is formed using a chemical vapor deposition technique.

[0028]

[0033] In one embodiment, the tungsten, molybdenum, cobalt, ruthenium or copper metal precursor shown in step (b) is a. MoCl5, MoOCl4, and MoO2Cl2; Mo(CO)6, MoH2( i a molybdenum precursor such as PrCp; (iPr = isopropyl, Cp = cyclopentadienyl); b. WF6 and W(t-butyl-N)2(N(CH3)2)2; WCl5 and WCl6, WOCl4; W(CO)6, WH2( i a tungsten precursor such as PrCp2; c.Co(t-Butyl-NCHCHN-t-Butyl) 2、cobalt precursors such as Co2(CO)6(HCCCF3) and Co2(CO)6(HCC(CH3)3), other cobalt precursors as described in Alain E. Kaloyeros et al., ECS Journal of Solid State Science and Technology, 8 (2) P119-P152 (2019), “Cobalt Thin Films: Trends in Processing Technologies and Emerging Applications”, Seong Ho Han et al., “New Heteroleptic Cobalt Precursors for Deposition of Cobalt-based Thin Films, ACS Omega, http: / / pubs.acs.org / journal / acsodf, and U.S. Pat. No. 10,872,770 and U.S. Patent Publication No. 2018 / 044788, which are incorporated herein by reference; d. Copper precursors, such as copper(I) amidinates, copper(I) guanidate precursors, such as copper(I) 2-methoxy-1,3-diisopropylamidinate; copper(I) 2-ethoxy-1,3-diisopropylamidinate; copper(I) 2-t-butoxy-1,3-diisopropylamidinate; copper(I) 2-isopropyl-1,3-diisopropylamidinate; copper(I) 2-dimethylamino-1,3-diisopropylamidinate; (see U.S. Patent Publication No. 2005 / 0281952 and WO 2007 / 1422700, which are incorporated herein by reference). In one embodiment, the copper precursor is copper(I) N',N''-diisopropyl-N,N-dimethylguanidate, hereinafter referred to as "CuDMAPA". See also Peter G. Gordon et al 2015 ECS J. Solid State Sci. Technol. 4 N3188, U.S. Patent Nos. 7,964,746, 7,858,525, and U.S. Patent Publication No. 2008 / 0281476, which are incorporated herein by reference.

[0029]

[0034] The desired microelectronic device substrate may be placed in the reaction zone in any suitable manner, such as, for example, single wafer CVD or ALD, or a furnace containing multiple wafers.

[0030]

[0035] In one alternative, the method of the present invention can be carried out as an ALD or ALD-like process. As used herein, the term "ALD or ALD-like" refers to a process in which (i) each reactant, including a precursor composition comprising a compound described herein, co-reactant, is introduced sequentially into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor, or (ii) each reactant is exposed to the substrate or microelectronic device surface by moving or rotating the substrate to different sections of the reactor, each section being separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor. In certain embodiments, the thickness of the resulting bulk ALD metal film may range from about 0.5 nm to about 40 nm.

[0031]

[0036] The deposition methods disclosed herein may require one or more purge gases. Purge gases used to remove unconsumed reactants and / or reaction by-products are inert gases that do not react with the precursor composition or the co-reactants. Exemplary purge gases include, but are not limited to, argon, nitrogen, helium, neon, and mixtures thereof. In certain embodiments, a purge gas, such as Ar, is fed into the reactor at a flow rate of about 10 to about 2000 sccm for about 0.1 to 1000 seconds to purge unreacted materials and by-products that may remain in the reactor. Such purge gases may also be utilized as inert carrier gases for either or both of the precursor composition and the co-reactant.

[0032]

[0037] Energy is applied to the precursor composition and co-reactants in the reaction zone to induce a reaction and form a film on the surface of the microelectronic device. Such energy can be provided by, but is not limited to, heat, pulsed heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments involving a plasma for deposition, the plasma generation process can include a direct plasma generation process in which the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process in which the plasma is generated "remotely" from the reaction zone and substrate and fed into the reactor.

[0033]

[0038] The term "microelectronic device" as used herein corresponds to semiconductor substrates, including 3D NAND structures, flat panel displays, and microelectromechanical systems (MEMS), fabricated for use in microelectronic, integrated circuit, or computer chip applications. It should be understood that the term "microelectronic device" is not limiting in any way and includes any substrate that contains negative channel metal oxide semiconductor (nMOS) and / or positive channel metal oxide semiconductor (pMOS) transistors and that ultimately becomes a microelectronic device or microelectronic assembly. Such microelectronic devices include at least one substrate, which may be selected from, for example, tin, SiO2, Si3N4, OSG, FSG, tin carbide, hydrogenated tin carbide, tin nitride, hydrogenated tin nitride, tin carbonitride, hydrogenated tin carbonitride, boron nitride, anti-reflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, porous inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, WN, etc.

[0034]

[0039] Example - Example 1 - CVD deposition of p-cymene (1,3-cyclohexadiene)Ru with H2 coreactant Ru metal was deposited at 300° C. and 30 Torr using 4 μmol / min of p-cymene CHDRu and 0.4 lpm (liters per minute) of H 2 .

[0035] In this example, ruthenium metal was deposited at 300° C. and 30 Torr. The data from this example is shown in Figure 1 and shows the superior selectivity of deposition of titanium nitride over silicon dioxide.

[0036] Example 2 - CVD Deposition of Ethylbenzyl(1-ethyl-1,4-cyclohexadienyl)Ru [EBECHD Ru] Using H2 Coreactant Ruthenium films were deposited at 300 °C and 30 Torr using ethylbenzyl(1-ethyl-1,4-cyclohexadienyl)Ru (flow rate of 4 μmol / min) as the precursor and 0.4 lpm of H2 coreactant. The data for this example is shown in Figure 4 and shows self-limiting deposition and selectivity of titanium nitride over silicon dioxide.

[0037] Example 3 (second step is predictive) In the first step, 6 Å of Ru is selectively deposited on the TiN regions of the substrate under the following conditions: 300°C, 30 Torr, 4 μmol / min p-cymene CHD Ru and 0.4 lpm (liters per minute) H2, with a deposition time of 3 minutes (less than 1 Å of Ru on the surrounding dielectric surface).

[0038] In the second step, the substrate is held at 400°C in 60 Torr of H2 flowing at 2 slm (standard liters per minute). MoCl5 vapor is delivered from a ProE-Vap ampoule held at 105°C using 300 sccm of Ar carrier gas. In approximately 10 minutes, 100 Å of Mo metal is deposited with <30 mW-cm (microohm-cm) resistivity.

[0039] Example 4a (Ru deposition) In this example, 6 Å of Ru is selectively deposited on the TiN regions of the substrate under the following conditions: 300°C, 30 Torr, 4 μmol / min p-cymene CHD Ru and 0.4 lpm (liters per minute) H2, for a deposition time of 3 minutes (less than 1 Å of Ru on the surrounding dielectric surface).

[0040] Example 4b (Cu deposition on sputtered Ru surface) In this example, 230 Å of Cu is selectively deposited on the Ru layer under the following conditions: The substrate is held at 65°C and the process pressure is controlled at 1 Torr. There are constant flow rates of 470 sccm H2 and 490 sccm Ar. CuDMAPA vapor is delivered in 18 second long pulses from a ProE-Vap ampoule held at 95°C using 95 Torr Ar carrier gas upstream of the ampoule. The flow of Cu precursor is stopped for a 0.5 second purge time. A 150 W direct plasma is struck for 1.5 seconds, then the plasma is followed by a 0.05 second purge. After 550 cycles, the film is 230 Å thick and has a resistivity of 5.1 mW-cm (microohm-cm).

[0041] Example 5a (Ru deposition) In this example, 6 Å of Ru is selectively deposited on the TiN regions of the substrate under the following conditions: 300°C, 30 Torr, 4 μmol / min p-cymene CHD Ru and 0.4 lpm (liters per minute) H2, with a deposition time of 3 minutes (less than 1 Å of Ru on the surrounding dielectric surface).

[0042] Example 5b (Co deposition on sputtered Ru surface) In this example, the substrate is held at 200°C with 30 Torr of H2 flowing at 0.5 slm. 10 micromoles of Co(t-Butyl-NCHCHN-t-Butyl)2 vapor are delivered per minute from a vaporizer held at 130°C with 100 sccm of He carrier gas. In approximately 15 minutes, 300 Å of Co metal is selectively deposited with <12 mW-cm (microohm-cm) resistivity.

[0043] Aspects In a first aspect, the present invention provides a method of depositing a metal-containing film on a microelectronic device substrate, the metal being selected from tungsten, molybdenum, cobalt, ruthenium and copper, the substrate being selected from titanium nitride, tungsten nitride, tantalum nitride, niobium nitride, tungsten, molybdenum, cobalt and copper; a. introducing an oxygen-free ruthenium precursor material into a reaction zone containing a substrate under vapor deposition conditions in the presence of a reducing gas until a ruthenium-containing film is formed having a thickness of about 3 to about 15 Å; and b. introducing a tungsten, molybdenum, cobalt, ruthenium or copper metal-containing precursor into a reaction zone under vapor deposition conditions until a tungsten, molybdenum, cobalt, ruthenium or copper metal-containing film of a desired thickness is obtained; The present invention provides a method comprising:

[0044] In a second aspect, the invention provides a process of the first aspect, wherein (a) the ruthenium precursor material is introduced into the reaction zone under chemical vapor deposition conditions.

[0045] In a third aspect of the present invention, there is provided the process of the first aspect, wherein a metal-containing precursor of tungsten, molybdenum, cobalt, ruthenium or copper is introduced into the reaction zone under chemical vapor deposition conditions.

[0046] In a fourth aspect, the present invention provides a method of the first aspect, wherein a metal-containing precursor of tungsten, molybdenum, cobalt, ruthenium or copper is introduced into the reaction zone under atomic layer deposition or pulsed CVD conditions.

[0047] In a fifth aspect, the present invention provides a tungsten, molybdenum, cobalt, ruthenium or copper metal-containing precursor comprising: MoCl5, MoOCl4, MoO2Cl2; Mo(CO)6, MoH2( i PrCp)2; WF6, W(t-butyl-N)2(N(CH3)2) 2、WCl5, WCl6, and WOCl4; W(CO)6, WH2( i PrCp)2; Co(t-Butyl-NCHCHN-t-Butyl)2, Co2(CO)6(HCCCF3), and Co2(CO)6(HCC(CH3)3); Copper(I) 2-methoxy-1,3-diisopropylamidinate, copper(I) 2-ethoxy-1,3-diisopropylamidinate, copper(I) 2-t-butoxy-1,3-diisopropylamidinate, copper(I) 2-isopropyl-1,3-diisopropylamidinate, and copper(I) 2-dimethylamino-1,3-diisopropylamidinate The present invention provides a method according to any one of the first to fourth aspects, wherein the method is selected from the following:

[0048]

[0046] In a sixth aspect, the present invention provides the method of any one of the first to fifth aspects, wherein the molybdenum metal-containing precursor is selected from MoCl5, MoOCl4, or MoO2Cl2.

[0049]

[0047] In a seventh aspect, the present invention provides the method of any one of the first to fourth aspects, wherein the tungsten metal-containing precursor is selected from WF6 and W(t-butyl-N)2(N(CH3)2)2.

[0050]

[0048] In an eighth aspect, the present invention provides the method of any one of the first to fourth aspects, wherein the copper metal-containing precursor is copper(I) N',N''-diisopropyl-N,N-dimethylguanidate.

[0051] In a ninth aspect, the present invention provides a ruthenium metal-containing precursor comprising one or more compounds selected from the following: TIFF2025504116000006.tif236170TIFF2025504116000007.tif241170TIFF2025504116000008.tif140170[wherein R is selected from C1 to C4 alkyl] The method according to any one of the first to fourth aspects is provided.

[0052] In a tenth aspect, the present invention provides the method of the ninth aspect, wherein R is t-butyl.

[0053] In an eleventh aspect, the present invention provides an oxygen-free ruthenium precursor comprising a compound selected from the following formulas: TIFF2025504116000009.tif29170A method according to any one of the first to tenth aspects is provided.

[0054] In a twelfth aspect, the present invention provides a ruthenium metal-containing precursor comprising a compound selected from the following: TIFF2025504116000010.tif241170TIFF2025504116000011.tif193170[wherein R is selected from C1 to C4 alkyl] The method according to any one of the first to fourth or ninth aspects is provided.

[0055] In a thirteenth aspect, the present invention provides a ruthenium metal-containing precursor comprising one or more compounds selected from the following: TIFF2025504116000012.tif144170A method according to any one of the first to fourth or ninth aspects is provided.

[0056]

[0053] In a fourteenth aspect, the present invention provides the method of any one of the first to twelfth aspects, wherein the ruthenium-containing film of step 1 exhibits an electrical resistivity of about 450 μΩ-cm for a film having a thickness of about 5.3 Å.

[0057]

[0054] Although several exemplary embodiments of the present disclosure have been described above, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the claims appended hereto. Numerous advantages of the disclosure set forth in this document have been set forth in the foregoing description. It will be understood, however, that this disclosure is, in many respects, merely illustrative. The scope of the disclosure is, of course, defined in the language in which the appended claims are expressed.

Claims

1. 1. A method for depositing a metal-containing film on a microelectronic device substrate, wherein the metal is selected from tungsten, molybdenum, cobalt, ruthenium, and copper, and the substrate is selected from titanium nitride, tungsten nitride, tantalum nitride, niobium nitride, tungsten, molybdenum, cobalt, and copper; a. introducing an oxygen-free ruthenium precursor material into a reaction zone containing a substrate under vapor deposition conditions in the presence of a reducing gas until a ruthenium-containing film is formed having a thickness of about 3 to about 15 Å; followed by b. introducing a tungsten, molybdenum, cobalt, ruthenium or copper metal-containing precursor into a reaction zone under vapor deposition conditions until a tungsten, molybdenum, cobalt, ruthenium or copper metal-containing film of a desired thickness is obtained; The method includes:

2. The method of claim 1 , wherein the ruthenium precursor material of (a) is introduced into the reaction zone under chemical vapor deposition conditions.

3. 10. The method of claim 1, wherein a metal-containing precursor of tungsten, molybdenum, cobalt, ruthenium or copper is introduced into the reaction zone under chemical vapor deposition conditions.

4. 10. The method of claim 1, wherein a metal-containing precursor of tungsten, molybdenum, cobalt, ruthenium or copper is introduced into the reaction zone under atomic layer deposition or pulsed CVD conditions.

5. a metal-containing precursor of tungsten, molybdenum, cobalt, ruthenium or copper; a!|l ５ 、|o｣l ４ 、||o﯁ ２ . ２ ,7, sort of))le ６ 、||oH ２ ( ｉ pi) ２ 4 b. WF ６ , W(t-butyl-N) ２ (N(CH ３ ) ２ ) ２ , W.C.L. ５ , W.C.L. ６ , and WOCl ４ ; W(CO) ６ , W.H. ２ ( ｉ PrCp) ２ ; c. Co(t-butyl-NCHCHN-t-butyl) ２ , Co ２ (CO) ６ (HCCCF ３ ), and Co ２ (CO) ６ (HCC (CH ３ ) ３ );and d. Copper(I) 2-methoxy-1,3-diisopropylamidinate; copper(I) 2-ethoxy-1,3-diisopropylamidinate; copper(I) 2-t-butoxy-1,3-diisopropylamidinate, copper(I) 2-isopropyl-1,3-diisopropylamidinate; and copper(I) 2-dimethylamino-1,3-diisopropylamidinate. The method of claim 1 , wherein the compound is selected from the group consisting of

6. The molybdenum metal-containing precursor is MoCl ５ , MoOCl ４ , or MoO ２ C ２ The method of claim 1 , wherein the compound is selected from the group consisting of

7. The tungsten metal-containing precursor is WF ６ and W(t-butyl-N) ２ (N(CH ３ ) ２ ) ２ The method of claim 1 , wherein the compound is selected from the group consisting of

8. The method of claim 1, wherein the copper metal-containing precursor is copper(I) N',N''-diisopropyl-N,N-dimethylguanidate.

9. The ruthenium metal-containing precursor comprises [In the formula, R is C １ ~C ４ alkyl] The method of claim 1, comprising one or more compounds selected from:

10. 10. The method of claim 9, wherein R is t-butyl.

11. The oxygen-free ruthenium precursor is The method of claim 1 , comprising a compound selected from:

12. The ruthenium metal-containing precursor comprises [In the formula, R is C １ ~C ４ alkyl] The method of claim 1 , comprising a compound selected from:

13. The ruthenium metal-containing precursor comprises 8. The method of claim 7, comprising one or more compounds selected from:

14. 10. The method of claim 1 , wherein the ruthenium-containing film of step a. exhibits an electrical resistivity of about 450 μΩ·cm for a film having a thickness of about 5.3 Å.

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