Metallization precursors and onboard combinatorial chemical synthesis

Abstract

Methods and apparatuses for forming gas mixtures remotely to deposit metal using a mixed metal halide precursor are provided herein, the method for processing a substrate comprising: providing a substrate including a plurality of features, each feature comprising a feature opening and a feature bottom, in a process chamber; introducing a mixed metal halide precursor into the process chamber; and introducing a reducing agent into the process chamber, wherein the mixed metal halide precursor reacts with the reducing agent to deposit a metal film in the feature.

Description

METALLIZATION PRECURSORS AND ONBOARD COMBINATORIAL CHEMICAL SYNTHESISCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] A PCT Request Form is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in their entireties and for all purposes.BACKGROUND

[0002] Semiconductor processing involves deposition of various metal-containing materials and there exists challenges for depositing such materials as devices shrink. The background description provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.SUMMARY

[0003] One aspect involves a method for processing a substrate including: providing a substrate including a plurality of features, each feature including a feature opening and a feature bottom, in a process chamber; introducing a mixed metal halide precursor into the process chamber; and introducing a reducing agent into the process chamber; where the mixed metal halide precursor reacts with the reducing agent to deposit a metal film in the feature.

[0004] In various embodiments, the metal film includes molybdenum or tungsten.

[0005] In various embodiments, the reducing agent is hydrogen.

[0006] In various embodiments, the mixed metal halide precursor includes a mixed molybdenum halide precursor or a mixed tungsten halide precursor.

[0007] In various embodiments, the method also includes introducing a metal-containing halogen-containing gas and a halogen-containing gas to a remote reaction chamber to form the mixed metal halide precursor, such that the mixed metal halide precursor is delivered from the remote reaction chamber to the process chamber.

[0008] In some embodiments, the metal-containing halogen-containing gas includesmolybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride, molybdenum hexafluoride or molybdenum fluoride.

[0009] In some embodiments, the tungsten halide precursor includes tungsten hexafluoride, tungsten pentafluoride, tungsten hexachloride, tungsten pentachloride or a combination thereof.

[0010] Another aspect involves an apparatus for filling a feature of a semiconductor substrate, the apparatus including: one or more process chambers; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, such that the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the associated flow-control hardware, and the memory stores computerexecutable instructions for controlling the at least one processor to at least control the associated flow-control hardware to: cause introduction of a mixed metal halide precursor into the process chamber; and cause introduction of a reducing agent into the process chamber.

[0011] In various embodiments, the apparatus also includes a remote reaction chamber for synthesizing the mixed metal halide precursor.

[0012] In various embodiments, the controller further includes instructions for causing delivery of the mixed metal halide precursor from the remote reaction chamber to the process chamber to cause introduction of the mixed metal halide precursor into the process chamber.

[0013] These and other aspects are described further below with reference to the drawings.BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 is a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments.

[0015] Figure 2 is a schematic illustration of a process chamber that may be used to perform certain disclosed embodiments.

[0016] Figures 3 and 4 are schematic illustrations of apparatuses that may be used to perform certain disclosed embodiments.DETAIEED DESCRIPTION

[0017] In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may bepracticed without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments.

[0018] Chemical vapor deposition (CVD) is a process used to deposit thin films for semiconductor fabrication. CVD typically includes introducing one or more reagents (i.e., precursors) to a substrate in a processing chamber. The reagents react and / or decompose to deposit the films. Plasma enhanced CVD (PECVD) uses plasma in the processing chamber to increase the reaction rates of the reagents and can allow deposition at lower temperatures. Plasma species can also be used to modify the resulting film properties.

[0019] ALD is a technique that deposits thin layers of material using sequential self-limiting reactions. ALD processes use surface-mediated deposition reactions to deposit films on a layer-by-layer basis in cycles. As an example, an ALD cycle may include the following operations: (i) delivery / adsorption of a precursor, (ii) purging of precursor from the chamber, (iii) delivery of a second reactant and optionally ignite plasma, and (iv) purging of byproducts from the chamber. The reaction between the second reactant and the adsorbed precursor to form a film on the surface of a substrate affects the film composition and properties, such as nonuniformity, stress, wet etch rate, dry etch rate, electrical properties (e.g., breakdown voltage and leakage current), etc. In ALD deposition of molybdenum films, this reaction involves introducing a molybdenum-containing precursor, and reacting the molybdenum-containing precursor with a reducing agent.

[0020] Unlike a chemical vapor deposition (CVD) technique, ALD processes use surface-mediated deposition reactions to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface that includes a population of surface active sites is exposed to a gas phase distribution of a first precursor, such as a silicon-containing precursor, in a dose provided to a chamber housing a substrate. Molecules of this first precursor are adsorbed onto the substrate surface, including chemisorbed species and / or physisorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorbed layer may include the compound as well as derivatives of the compound. For example, an adsorbed layer of a metal-containing precursor may include the metal-containing precursor as well as derivatives of the metal-containing precursor. After a first precursor dose, the chamber is then evacuated to remove most or all of first precursor remaining in gas phase so that mostly or only theadsorbed species remain. In some implementations, the chamber may not be fully evacuated.For example, the reactor may be evacuated such that the partial pressure of the first precursor in gas phase is sufficiently low to mitigate a reaction. A second reactant, such as a reducing agent gas, is introduced to the chamber so that some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after a source of activation is applied temporally, The chamber may then be evacuated again to remove unbound second reactant molecules, As described above, in some embodiments the chamber may not be completely evacuated, Additional ALD cycles may be used to build film thickness.

[0021] Embodiments herein may also be relevant to spatial ALD processes. In spatial ALD, gases used for each exposure are continuously flowed in spatially different locations or “zones” in a process chamber. Each zone includes a point of injection of gases for example, one zone may include the first precursor, one zone may include first purge gases, one zone may include second reactant, and a fourth zone may include a second purge gas. The substrate is rotated between zones to expose the substrate surface to different exposures to implement the surface reactions described above with respect to temporal ALD. That is, instead of temporally separating the exposures, exposures are separated by location.

[0022] In some implementations, the ALD methods include plasma activation. As described herein, the ALD methods and apparatuses described herein may be conformal film deposition (CED) methods, which are described generally in U.S. Patent Application No. 13 / 084,399 (now U.S. Patent No. 8,728,956), filed April 11, 2011, and titled “PLASMA ACTIVATED CONEORMAL EILM DEPOSITION,” and in U.S. Patent Application No. 13 / 084,305, filed April 11, 2011, and titled “SILICON NITRIDE FILMS AND METHODS,” which are herein incorporated by reference in their entireties.

[0023] Certain disclosed embodiments may be performed in thermal, spatial, or plasma- enhanced ALD processes. In some embodiments, conversion time is modulated while maintaining the same plasma power during conversion of all ALD cycles. In some embodiments, conversion time is modulated as well as plasma power and other process conditions to achieve a desired film property.

[0024] FIG. 1 is a flow chart which depicts method 100 of deposition process that may be performed in accordance with certain disclosed embodiments. In certain embodiments, the method is a low temperature process, in which the process chamber is maintained at a temperature of about 350 °C or less, 300 °C or less, 250 °C or less, 200 °C or less, 150 °C orless or 100 °C or less.

[0025] The substrate may be a silicon wafer, e.g., a 200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semi-conducting material deposited thereon. In various embodiments, the substrate is patterned. A patterned substrate may have “features” such as pillars, poles, trenches, via or contact holes, which may be characterized by one or more of narrow and / or re-entrant openings, constrictions within the feature, and high aspect ratios. One example of a negative feature is a hole or via in a semiconductor substrate or in a layer on the substrate. Another example is a trench in a substrate or layer. A further example of a feature is a pillar or pole in a semiconductor substrate or a layer on the substrate.

[0026] A feature typically has an aspect ratio (depth to lateral dimension). A feature having a high aspect ratio can have a depth to lateral dimension aspect ratio equal to or greater than about 10:1, equal to or greater than about 15:1, equal to or greater than about 20:1, equal to or greater than about 25:1, equal to or greater than about 30:1, equal to or greater than about 40:1, equal to or greater than about 50:1, or equal to or greater than about 100:1.

[0027] In various embodiments, the feature may have an under-layer, such as a barrier layer or adhesion layer. Non-limiting examples of under-layers include dielectric layers and conducting layers, e.g., silicon oxides, silicon nitrides, undoped silicon carbides, oxygen- doped silicon carbides, nitrogen-doped silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers.

[0028] The feature(s) may be formed in one or more of the above-described layers.

[0029] The methods described herein can be used to fill vertically oriented features formed in a substrate. Such features may be referred to as gaps, recessed features, negative features, unfilled features, or simply features. Filling such features may be referred to as gapfill.

[0030] In some embodiments, the feature(s) such as a pillar may have an aspect ratio of at least about 1:1, at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, or higher. The feature(s) may also have a dimension near the opening, e.g., an opening diameter or line width of between about 10 nm to 500 nm, for example between about 25 nm and about 300 nm. Disclosed methods may be performed on substrates with feature(s) having an opening less than about 150 nm.

[0031] A via, trench or other recessed feature may be referred to as an unfilled feature or a feature. According to various embodiments, the feature profile may narrow gradually and / or include an overhang at the feature opening. A re-entrant profile is one that narrows from the bottom, closed end, or interior of the feature to the feature opening. A re-entrant profile maybe generated by asymmetric etching kinetics during patterning and / or the overhang due to non-conformal film step coverage in the previous film deposition, such as deposition of a diffusion barrier.

[0032] Features of a substrate can be of various types. In some embodiments, a feature can have straight sidewalls, positively sloped sidewalls, or negatively sloped sidewalls. In some embodiments, a feature can have sidewall topography or sidewall roughness, which may occur as a result of an etch process to form the feature. In some embodiments, a feature can have a feature opening that is greater at the top of the feature than at the bottom, or a feature can have a feature opening that is greater at the bottom of the feature than at the top. In some embodiments, a feature can be partially filled with material or have one or more under-layers. Gapfill of features such as any of foregoing embodiments can depend on feature type and profile.

[0033] The deposition method according to the present disclosure can be used to deposit transition metals such as nickel (Ni), cobalt (Co), copper (Cu), molybdenum (Mo), ruthenium (Ru), iridium (Ir), platinum (Pt), palladium (Pd) and tungsten (W). In some embodiments, the deposition method is used for metal gapfill in contact holes and middle of line (MOL) and back end of line (BEOL) trenches / vias. In some embodiments, the liner layer includes titanium / titanium nitride (TiN), tungsten carbonitride (WCN), or tantalum / tantalum nitride (TaN). Alternatively, the deposition process can be used with oxide sidewalls or with any other metal or dielectric barrier materials.

[0034] Returning to FIG. 1, operation 102 is an introduction of a metal precursor into the processing chamber which houses a semiconductor substrate. Selection of the precursor depends upon the metal film to be deposited on the substrate. In certain embodiments the metal is tungsten (W) or molybdenum (Mo). The precursor can be introduced in a vaporized form in a flow of inert gas such as argon, helium, or nitrogen (N2).

[0035] Deposition of tungsten may be achieved with a variety of volatile precursors. In some embodiments, mixed halogen-containing metal precursors, which may have the formula:MaXbYzwhere:M is a metal,X is a halogen (e.g., F, Cl, Br, and / or I), Fis a halogen (e.g., F, Cl, Br, and / or I), a is any number (including integers and non-integers) such as about 1-4, and b is any number (including integers and non-integers) such as about 1-4.

[0036] The metal may be tungsten, molybdenum, aluminum, gallium, indium, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, cobalt, copper, technicum, rhodium, osmium, platinum, rhenium, and combinations thereof. In some embodiments, the mixed metal halide is a fluorine-containing mixed metal halide. In some embodiments, the mixed metal halide is a chlorine-containing mixed metal halide. In some embodiments, the mixed metal halide is a bromine-containing mixed metal halide. In some embodiments, the mixed metal halide is a iodine-containing mixed metal halide.

[0037] Specific examples of fluorine-containing mixed metal halides include but are not limited to: M0F5CI, M0F5CI2, MoF5Br, M0FCI4, M0F2CI3, M0F3CI2, M0F4CI, MO2FC18, M02F2CI7, M02F3CI6, M02F4CI5, M02F5CI4, M02F6CI3, M02F7CI2, M02F8CI, M03F7CI7, M03F10CI5, M03F14CI, M03F13CI2, M04F19CI, M0F4.75CI0.25, MoFBr4, MoF2Br3, MoF3Br2, MoF4Br, Mo2FBr8, Mo2F2Br?, Mo2F3Bre, Mo2F4Brs, Mo2FsBr4, Mo2FeBr3, Mo2F?Br2, Mo2F8Br, MosFyBr?, MosFioBrs, MosFuBr, Mo3Fi3Br2, Mo4Fi9Br, MoF4.75Bro.25, M0FI4, M0F2I3, M0F3I2, M0F4I, MO2FI8, M02F2I7, M02F3I6, M02F4I5, M02F5I4, M02F6I3, M02F7I2, MO2F8I, M03F7I7, M03F10I5, M03F14I, M03F13I2, M04F19I, M0F4.75I0.25, WFCI4, WF2CI3, WF3CI2, WF4CI, W2FC18, W2F2CI7, W2F3CI6, W2F4CI5, W2F5CI4, W2F6CI3, W2F7CI2, W2F8C1, W3F7CI7, W3F10CI5, W3F14CI, W3F13CI2, W4F19CI, WF4.75Clo.25, WFBr4, WF2Br3, WF3Br2, WErBr, W2FBr8, W2F2Br?, W2F3Bre, W2F4Brs, W2FsBr4, W2FeBr3, W2F?Br2, W2F8Br, WsF / Br?, WsFioBrs, WsFuBr, W3Fi3Br2, W4FigBr, WF4.75Bro.25, WFI4, WF2I3, WF3I2, WF4I, W2FI8, W2F2I7, W2F3I6, W2F4I5, W2F5I4, W2F6I3, W2F7I2, W2F8I, W3F7I7, W3F10I5, W3F14I, W3F13I2, W4F19I, WF4.75I0.25, and combinations thereof.

[0038] The mixed metal halide precursor may be flowed for from about 50 ms to about 10000 ms.

[0039] Operation 104 is an optional purge step. Purging the chamber may involve flowing a purge gas or a sweep gas, which may be a carrier gas used in other operations or may be a different gas. In some embodiments, purging may involve evacuating the chamber. Examples of purge gases include argon (Ar), nitrogen (N2), hydrogen (H2), helium (He), oxygen (O2), krypton (Kr), xenon (Xe), neon (Ne), and combinations thereof. In various embodiments, the purge gas is an inert gas. The purge gas may include one or more gases. In some embodiments, operation 104 may include one or more evacuation subphases for evacuating the process chamber. Alternatively, it will be appreciated that purges may be omitted in some embodiments. Operation 104 may have any suitable duration, such as between about 0 seconds and about 60 seconds, for example about 0.01 seconds.

[0040] In some embodiments, increasing a flow rate of one or more purge gases maydecrease the duration of a purge. For example, a purge gas flow rate may be adjusted according to various reactant thermodynamic characteristics and / or geometric characteristics of the process chamber and / or process chamber plumbing for modifying the duration of the purge. In one non-limiting example, the duration of a purge phase may be adjusted by modulating purge gas flow rate. This may reduce deposition cycle time, which may improve substrate throughput.

[0041] The purge gas can be flowed to a chamber housing the substrate at a flow rate between about 1000 seem and about 40000 seem (e.g., about 100 to 2000 seem). The purge gas can be flowed for any useful period (e.g., about 0.1 to 10 seconds) and any useful pressure (e.g., about 0.5 to 25 Torr).

[0042] In operation 106, at least one reducing agent is introduced into the process chamber.

[0043] The reducing agent is typically a reducing gas. Suitable examples of reducing agents include H2, SiFU, NH3, or B2H6. In some embodiments, the reducing agent may be in plasma form, such as a hydrogen plasma. For example, in CVD processes the precursor may react with the second reactant in the body of the processing chamber. The reaction may be conducted thermally or with plasma activation. In ALD processes the reaction occurs only on the surface and is limited by the amount of the adsorbed material on the surface (by the amount of molybdenum precursor and / or by the amount of adsorbed second reactant). In surface-limited reactions (such as in ALD) plasma activation is also possible. For example, an adsorbed layer of a molybdenum precursor may be reacted with a plasma formed in a gas that includes a hydrogen-containing second reactant (e.g., H2, NH3, CO, alcohol, etc.) to form a molybdenum metal layer. Generally, the plasma may be generated directly in the process chamber housing the substrate (direct plasma) or remotely in a separate compartment with the resulting plasma- activated species being fed to the process chamber (remote plasma). The temperature during the reaction process can be, for example, between about 20 - 600 °C. Low temperature deposition at about 450 °C or less such as about 400 °C or less, e.g., between about 100 - 400 °C is conducted in some embodiments and is particularly advantageous for deposition of molybdenum metal. The pressure in the process chamber can be in a range of between about 0.1 - 100 Torr, such as between about 0.5 - 5 Torr in PEALD methods and 1 - 60 Torr in thermal ALD.

[0044] In some embodiments, the reducing agent is hydrogen, ammonia, hydrazine, silane, disilane, trisilane, germane, digermane, diborane or a combination thereof.

[0045] Exposing the substrate to the reducing agent may include contacting the substrate with the reducing agent for a time of between about 0.1 seconds and about 180 seconds; betweenabout 0.5 seconds and 60 seconds; or between about 0.1 seconds at 10 seconds. The flow rate of the reducing agent during the exposure of the substrate may be less than 30 slm, or less than 15 slm, or less than 10 slm, or less than 5 slm, or less than 2 slm or even less than 0.1 slm in some embodiments. The flow rate of the reducing agent may range from about 0.1 to 30 slm, from about 5 to 15 slm, or equal to or greater than 10 slm.

[0046] Operation 108 is a second optional purge step. In process 100, either purge 104 or 108 may be included; both purge 104 and 108 may be included; or no purge may be utilized.

[0047] In operation 110, a determination of whether or not the metal deposited is of a desired thickness. As used herein, “metal” refers to a film only including metal or a film which contains a metal with additional components. Metal can be deposited for a variety of semiconductor applications. Therefore, the desired thickness will depend upon the particular application. In some embodiments metal may be deposited as a conformal layer to a thickness of between about 0.1-10 nm on a substrate.

[0048] If a thicker film is desired, operation 112 is a process flow path indicating that after operation 106, operation 102 can commence again, repeating n times. In process flow path 112, n is the number of cycles which may be from 1 to 50 or from 20 to 40. The cycle of operations 102 and 106 with optional purge 104 can be repeated as many times as necessary. As used herein, the term “cycle” refers to a particular set of sequential operations.

[0049] Certain disclosed embodiments also include performing deposition and etching, deposition only, and / or etching only. For example, a mixed metal halide may be used for deposition in cycles of dep-etch-dep where the etchant is a single metal halide. One example is using MoFxCly for deposition and MoC15 or MoF6 for etching.

[0050] By ‘ ‘etchant” is meant any compound used to remove a material such as a layer, byproduct or contaminant from a surface. In some embodiments, the etchant is a halogencontaining etchant such as chlorine (Ch), fluorine (F2), bromine (Br2), iodine (I2), hydrogen chloride (HC1), hydrogen fluoride (HF), hydrogen iodide (HI), chlorine trifluoride (CIF3), trifluoromethane (CHF3), fluoromethane (CH3F), octafluorocyclobutane (C4F8), hexafluorobutadiene (C4F6), hexafluorocyclopentadiene (CsFe), carbon tetrafluoride (CF4), nitrogen trifluoride (NF3), boron trichloride (BCI3), boron trifluoride (BF3), hydrogen iodide (HI), hydrogen bromide (HBr), sulfur tetrafluoride (SF4), sulfur hexafluoride (SFe), thionyl chloride (SOCI2), phosphorus pentafluoride (PF5) or a combination thereof.

[0051] In some embodiments, a single etchant may be sufficiently effective. In some embodiments a combination including more than one etchant may be utilized. Examples of combinations include oxygen (02) with one of the above halogen-containing etchants such aschlorine and oxygen; or fluorine and oxygen. Alternatively, carbon dioxide (CO2) may be combined with one of the above halogen-containing etchants. If a combination of etchants is utilized, they may be flowed through delivery lines together (concomitantly), or sequentially (one following the other). The etchant may be co-flowed with an inert gas, such as argon. In some embodiments, etchants are combined. For example, the halogen-containing etchant may be co-flowed with a non-halogen containing etchant.

[0052] In some embodiments, the etchant is M0CI5, MoFe or any of the other metal halides described above.COMBINATORIAL CHEMICAL SYNTHESIS

[0053] In various embodiments, the method may include synthesizing the mixed metal halide precursor in-situ, or in a remote reaction chamber, integrated into the apparatus for depositing the metal using the mixed metal halide precursor. For example, a remote reaction chamber may be configured to deliver at least a first gas and a second gas, the first gas having a metalcontaining and halogen-containing compound, and the second gas having a halogencontaining compound. For example, the first gas may be molybdenum trifluoride. In another example, the second gas may be chlorine. The remote reaction chamber may be upstream of the substrate upon which the metal is to be deposited.

[0054] One example reaction that may occur in the remote reaction chamber may be as follows, which produces molybdenum trifluorodichloride:MoF3+ Cl2-> MoF3Cl2

[0055] The first gas may be any metal halide, which may have a chemical formula MnXm where M is a metal, X is a halogen, and n is a number 0 to 3, and m is a number 0 to 7, where n and m may be integers or non-integers (e.g., substoichiometric or non-stoichiometric variations may be used).

[0056] In some embodiments, a metal fluorochloride is used as the first gas. Example molybdenum fluorochlorides include but are not limited to M0F4CI, M0F3CI2, M0F2CI3, MoFCL, and M02F6CI3.

[0057] Deposition of molybdenum may be achieved, for example, using molybdenum precursors having from two (M0L2) to six (MoLe) ligands where the molybdenum may be in a wide range of oxidation states ranging from 0 to +6. Suitable molybdenum precursors may also be dimolybdenum compounds having 1) two molybdenum atoms singly or multiply bonded to one another; or 2) two molybdenum atoms connected by a linking group such as a bidentate ligand.

[0058] In some embodiments, the molybdenum precursors include molybdenumhexacarbonyl (Mo(CO)e), molybdenum oxyhalide precursors such as molybdenum oxytetrachloride (MoOCU) or molybdenum dichloride dioxide (MOO2CI2) and molybdenum halide precursors such as molybdenum chloride ([MoClsh) or molybdenum hexafluoride (MOF6).

[0059] Other metals such as aluminum, gallium, indium, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, technetium, rhenium, rhodium, ruthenium, osmium or platinum may be deposited using the metal precursors AlCh, GaCh, InCh, BiCh, BiF5, TiF4, TiCU, ZrCl4, HfCl4, VF5, VC14, NbF5, NbCls, TaF5, TaCls, CrF5, CrFs, TcF6, ReFe, ReFy, Re2Clio, RhFs, RhFe, RuFs, RuFe, OsFe and PtFe respectively. In some embodiments, the first gas is M0CI5, MoFe, Til4, AII3, BI3 M0I2, M0I3, or any of the other metal halides described above.

[0060] The second gas may be any halogen-containing gas. Examples include chlorine (CI2), fluorine (F2), bromine (Br2), iodine (I2), silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), and combinations thereof.

[0061] Flow rates of the first gas and / or the second gas typically depend on a size of the chamber, relative reactivity of the gases, process conditions, and other parameters.

[0062] In some embodiments, the first gas and the second gas are introduced to the remote reaction chamber together. In some embodiments, the first gas and the second gas are introduced to the remote reaction chamber in pulses. A pulse may be characterized as a duration upon which flow of a gas is started and stopped or started and diverted to a process chamber. In some embodiments, the first gas and the second gas are introduced to the remote reaction chamber in temporally separated pulses. In some embodiments, the first gas and the second gas are cycled. In some embodiments, the first gas is continuously flowed while the second gas is pulsed. In some embodiments, the first gas is pulsed while the second gas is continuously flowed. In some embodiments, the second gas is used both as a carrier gas and as a reactant such that only the volume of flow is adjusted to increase its reactivity with the first gas to form the mixed metal halide. The mixed metal halide may be delivered to the process chamber housing the chamber to be used in metal deposition.

[0063] In various embodiments, a plasma may be used during formation of the mixed metal halide. For example, in some embodiments, M0CI5 or MoFe may be exposed to plasmas of HBr, F2, NF3 or CIF3 or CI2 or combinations thereof to form a metastable mixed metal halide species. In some embodiments, oxygen plasma may be used to form a metal oxychloride such as MOO2CI2 or MOOC14.APPARATUS

[0064] The deposition methods described herein can be carried out in a variety of apparatuses. A suitable apparatus includes a processing chamber having one or more inlets for introduction of reactants, a substrate holder in the process chamber configured to hold the substrate in place during deposition, and, optionally, a plasma generating mechanism configured for generating a plasma in a process gas. The apparatus may include a controller having program instructions for causing any of the method steps described herein. The deposition methods described herein may be carried out in corresponding ALD and CVD apparatuses.

[0065] An example of a deposition apparatus suitable for depositing metal using provided methods is shown in FIG. 2 which schematically illustrates an embodiment of a process station 200 that may be used to deposit material using atomic layer deposition (ALD) and / or chemical vapor deposition (CVD), either of which may be plasma enhanced. For simplicity, the process station 200 is depicted as a standalone process station having a process chamber body 202 for maintaining a low-pressure environment. However, it will be appreciated that a plurality of process stations 200 may be included in a common process tool environment. Further, it will be appreciated that, in some embodiments, one or more hardware parameters of process station 200, including those discussed in detail below, may be adjusted programmatically by one or more computer controllers.

[0066] Process station 200 fluidly communicates with reactant delivery system 201 for delivering process gases to a distribution showerhead 206. Reactant delivery system 201 includes a mixing vessel 204 for blending and / or conditioning process gases for delivery to showerhead 206. One or more mixing vessel inlet valves 220 may control introduction of process gases to mixing vessel 204. Similarly, a showerhead inlet valve 205 may control introduction of process gasses to the showerhead 206.

[0067] Some metal-containing precursors or molybdenum-containing precursors may be stored in solid or liquid form prior to vaporization and subsequent delivery to the process station. For example, the embodiment of FIG. 2 includes a vaporization point 203 for vaporizing solid reactant to be supplied to mixing vessel 204. In some embodiments, vaporization point 203 may be a heated vaporizer. In some embodiments a flow of an inert gas is passed over the heated solid molybdenum precursor, or bubbled through the heated liquid molybdenum precursor, under sub-atmospheric pressure, and carries the precursor vapor to the process chamber. The precursor vapor produced from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensedreactant may create small particles. These small particles may clog piping, impede valve operation, contaminate substrates, etc. Some approaches to addressing these issues involve sweeping and / or evacuating the delivery piping to remove residual reactant. However, sweeping the delivery piping may increase process station cycle time, degrading process station throughput. Thus, in some embodiments, delivery piping downstream of vaporization point 203 may be heat traced. In some examples, mixing vessel 204 may also be heat traced. In one non-limiting example, piping downstream of vaporization point 203 has an increasing temperature profile extending from approximately 100°C to approximately 200°C at mixing vessel 204.

[0068] Showerhead 206 distributes process gases toward substrate 212. In the embodiment shown in FIG. 2, substrate 212 is located beneath showerhead 206, and is shown resting on a pedestal 208. It will be appreciated that showerhead 206 may have any suitable shape and may have any suitable number and arrangement of ports for distributing processes gases to substrate 212. While not explicitly shown, in some embodiments the showerhead 206 is a dual plenum showerhead that includes at least two types of conduits, where the first type of conduit is dedicated to delivery of molybdenum-containing precursor vapor, and the second type of conduit is dedicated to delivery of the second (or other) reactant. In these embodiments the molybdenum-containing precursor and the reactant are not allowed to mix in the conduits prior to entry to the process chamber, and do not share the conduits if delivered to the chamber consecutively.

[0069] In some embodiments, a microvolume 207 is located beneath showerhead 206. Performing an ALD and / or CVD process in a microvolume rather than in the entire volume of a process station may reduce reactant exposure and sweep times, may reduce times for altering process conditions (e.g., pressure, temperature, etc.), may limit an exposure of process station robotics to process gases, etc. Example microvolume sizes include, but are not limited to, volumes between 0.1 liter and 2 liters. This microvolume also impacts productivity throughput. While deposition rate per cycle drops, the cycle time also simultaneously reduces. In certain cases, the effect of the latter is dramatic enough to improve overall throughput of the module for a given target thickness of film.

[0070] In some embodiments, pedestal 208 may be raised or lowered to expose substrate 212 to microvolume 207 and / or to vary a volume of microvolume 207. For example, in a substrate transfer phase, pedestal 208 may be lowered to allow substrate 212 to be loaded onto pedestal 208. During a deposition process phase, pedestal 208 may be raised to position substrate 212 within microvolume 207. In some embodiments, microvolume 207 maycompletely enclose substrate 212 as well as a portion of pedestal 208 to create a region of high flow impedance during a deposition process.

[0071] Optionally, pedestal 208 may be lowered and / or raised during portions the deposition process to modulate process pressure, reactant concentration, etc., within microvolume 207. In one scenario where process chamber body 202 remains at a base pressure during the deposition process, lowering pedestal 208 may allow microvolume 207 to be evacuated. Example ratios of microvolume to process chamber volume include, but are not limited to, volume ratios between 1:700 and 1:10. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller.

[0072] While the example microvolume variations described herein refer to a height- adjustable pedestal, it will be appreciated that, in some embodiments, a position of showerhead 206 may be adjusted relative to pedestal 208 to vary a volume of microvolume 207. Further, it will be appreciated that a vertical position of pedestal 208 and / or showerhead 206 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, pedestal 208 may include a rotational axis for rotating an orientation of substrate 212. It will be appreciated that, in some embodiments, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers.

[0073] Returning to the embodiment shown in FIG. 2, showerhead 206 and pedestal 208 electrically communicate with RF power supply 214 and matching network 216 for powering a plasma. In other embodiments apparatuses without a plasma generator are used for depositing molybdenum-containing films using provided methods. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, a radio frequency (RF) source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 214 and matching network 216 may be operated at any suitable power to form a plasma having a desired composition of radical species. Eikewise, RF power supply 214 may provide RF power of any suitable frequency. In some embodiments, RF power supply 214 may be configured to control high- and low-frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 200 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions. In one non-limiting example, the plasma power may be intermittently pulsed to reduce ionbombardment with the substrate surface relative to continuously powered plasmas.

[0074] In some embodiments, the plasma may be monitored in- situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and / or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0075] In some embodiments, the plasma may be controlled via input / output control (IOC) sequencing instructions. In one example, the instructions for setting plasma conditions for a plasma process phase may be included in a corresponding plasma activation recipe phase of a deposition process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a deposition process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more plasma parameters may be included in a recipe phase preceding a plasma process phase. For example, a first recipe phase may include instructions for setting a flow rate of an inert and / or a reactant gas, instructions for setting a plasma generator to a power set point, and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for enabling the plasma generator and time delay instructions for the second recipe phase. A third recipe phase may include instructions for disabling the plasma generator and time delay instructions for the third recipe phase. It will be appreciated that these recipe phases may be further subdivided and / or iterated in any suitable way within the scope of the present disclosure.

[0076] In some embodiments, pedestal 208 may be temperature controlled via heater 210. Further, in some embodiments, pressure control for deposition process station 200 may be provided by butterfly valve 218. As shown in the embodiment of FIG. 2, butterfly valve 218 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 200 may also be adjusted by varying a flow rate of one or more gases introduced to process station 200.

[0077] FIG. 3 shows a schematic view of an embodiment of a multi-station processing tool 300 with an inbound load lock 302 and an outbound load lock 304, either or both of whichmay comprise a remote plasma source. Such tool may be used for processing the substrates using the methods provided herein. A robot 306, at atmospheric pressure, is configured to move wafers from a cassette loaded through a pod 308 into inbound load lock 302 via an atmospheric port 310. A wafer is placed by the robot 306 on a pedestal 312 in the inbound load lock 302, the atmospheric port 310 is closed, and the load lock is pumped down. Where the inbound load lock 302 comprises a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock prior to being introduced into a processing chamber 314. Further, the wafer also may be heated in the inbound load lock 302 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 316 to processing chamber 314 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of a first station shown in the reactor for processing. While the embodiment depicted in FIG. 3 includes load locks, it will be appreciated that, in some embodiments, direct entry of a wafer into a process station may be provided.

[0078] The depicted processing chamber 314 comprises four process stations, numbered from 1 to 4 in the embodiment shown in FIG. 3. Each station has a heated pedestal (shown at 318 for station 1), and gas line inlets. It will be appreciated that in some embodiments, each process station may have different or multiple purposes. While the depicted processing chamber 314 comprises four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments a processing chamber may have three or fewer stations.

[0079] FIG. 3 also depicts an embodiment of a wafer handling system 390 for transferring wafers within processing chamber 314. In some embodiments, wafer handling system 390 may transfer wafers between various process stations and / or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots. FIG. 3 also depicts an embodiment of a system controller 350 employed to control process conditions and hardware states of process tool 300. System controller 350 may include one or more memory devices 356, one or more mass storage devices 354, and one or more processors 352. Processor 352 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0080] In some embodiments, system controller 350 controls all of the activities of process tool 300. System controller 350 executes system control software 358 stored in mass storage device 354, loaded into memory device 356, and executed on processor 352. System controlsoftware 358 may include instructions for controlling the timing, mixture of gases, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequencies, substrate, pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by process tool 300. System control software 358 may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components necessary to carry out various process tool processes in accordance with the disclosed methods. System control software 358 may be coded in any suitable computer readable programming language.

[0081] In some embodiments, system control software 358 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of an ALD process may include one or more instructions for execution by system controller 350. The instructions for setting process conditions for an ALD process phase may be included in a corresponding ALD recipe phase. In some embodiments, the ALD recipe phases may be sequentially arranged, so that all instructions for an ALD process phase are executed concurrently with that process phase.

[0082] Other computer software and / or programs stored on mass storage device 354 and / or memory device 356 associated with system controller 350 may be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0083] A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal 318 and to control the spacing between the substrate and other parts of process tool 300.

[0084] A process gas control program may include code for controlling gas composition and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. The process gas control program may include code for controlling gas composition and flow rates within any of the disclosed ranges. A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc. The pressure control program may include code for maintaining the pressure in the process station within any of the disclosed pressure ranges.

[0085] A heater control program may include code for controlling the current to a heatingunit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate. The heater control program may include instructions to maintain the temperature of the substrate within any of the disclosed ranges.

[0086] A plasma control program may include code for setting RF power levels and frequencies applied to the process electrodes in one or more process stations, for example using any of the RF power levels disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

[0087] In some embodiments, there may be a user interface associated with system controller 350. The user interface may include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0088] In some embodiments, parameters adjusted by system controller 350 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF power levels, frequency, and exposure time), etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.

[0089] Signals for monitoring the process may be provided by analog and / or digital input connections of system controller 350 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of process tool 300. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0090] Any suitable chamber may be used to implement the disclosed embodiments. Two or more of the stations may perform the same functions. Similarly, two or more stations may perform different functions. Each station can be designed / configured to perform a particular function / method as desired.

[0091] FIG. 4 is a block diagram of a processing system suitable for conducting thin film deposition processes in accordance with certain embodiments. The system 400 includes a transfer module 403. The transfer module 403 provides a clean, pressurized environment to minimize risk of contamination of substrates being processed as they are moved between various reactor modules. Mounted on the transfer module 403 are two multi- station reactors 409 and 410, each capable of performing atomic layer deposition (ALD) and / or chemicalvapor deposition (CVD) according to certain embodiments. Reactors 409 and 410 may include multiple stations 411, 413, 415, and 417 that may sequentially or non- sequentially perform operations in accordance with disclosed embodiments. The stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate.

[0092] Also mounted on the transfer module 403 may be one or more single or multi- station modules 407 capable of performing plasma or chemical (non-plasma) pre-cleans, or any other processes described in relation to the disclosed methods. The module 407 may in some cases be used for various treatments to, for example, prepare a substrate for a deposition process. The module 407 may also be designed / configured to perform various other processes such as etching or polishing. The system 400 also includes one or more wafer source modules 401, where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 419 may first remove wafers from the source modules 401 to loadlocks 421. A wafer transfer device (generally a robot arm unit) in the transfer module 403 moves the wafers from loadlocks 421 to and among the modules mounted on the transfer module 403.

[0093] In various embodiments, a system controller 429 is employed to control process conditions during deposition. The controller 429 will typically include one or more memory devices and one or more processors. A processor may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0094] The controller 429 may control all of the activities of the deposition apparatus. The system controller 429 executes system control software, including sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored on memory devices associated with the controller 429 may be employed in some embodiments.

[0095] Typically, a user interface will be associated with the controller 429. The user interface may include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0096] System control logic may be configured in any suitable way. In general, the logic can be designed or configured in hardware and / or software. The instructions for controlling the drive circuitry may be hard coded or provided as software. The instructions may be provided by “programming.” Such programming is understood to include logic of any form, including hard coded logic in digital signal processors, application- specific integrated circuits, andother devices which have specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general purpose processor. System control software may be coded in any suitable computer readable programming language.

[0097] The computer program code for controlling the germanium-containing reducing agent pulses, hydrogen flow, and tungsten-containing precursor pulses, and other processes in a process sequence can be written in any conventional computer readable programming language: for example, assembly language, C, C++, Pascal, Fortran, or others. Compiled object code or script is executed by the processor to perform the tasks identified in the program. Also as indicated, the program code may be hard coded.

[0098] The controller parameters relate to process conditions, such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe and may be entered utilizing the user interface. Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 429. The signals for controlling the process are output on the analog and digital output connections of the deposition apparatus 400.

[0099] The system software may be designed or configured in many different ways. For example, various chamber component subroutines or control objects may be written to control operation of the chamber components necessary to carry out the deposition processes (and other processes, in some cases) in accordance with the disclosed embodiments. Examples of programs or sections of programs for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0100] In some implementations, a controller 429 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and / or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The controller 429, depending on the processing requirements and / or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency(RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0101] Broadly speaking, the controller may be defined as electronics having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0102] The controller, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e.g., a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, which are then communicated to the system from the remote computer.

[0103] In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus as described above, the controller may be distributed, such as by comprisingone or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.

[0104] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and / or manufacturing of semiconductor wafers.

[0105] As noted above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing factory.

[0106] The apparatus and processes described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like. Typically, though not necessarily, such apparatus and processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically comprises some or all of the following steps, each step enabled with a number of possible tools: (1) application of photoresist on a work piece, i.e., a substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or work piece by using a dry or plasma- assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.DEFINITIONS

[0107] As used herein, the term “about” is understood to account for minor increases and / ordecreases beyond a recited value, which changes do not significantly impact the desired function of the parameter beyond the recited value(s). In some cases, “about” encompasses + / -10% of any recited value. As used herein, this term modifies any recited value, range of values, or endpoints of one or more ranges.

[0108] As used herein, the terms “top”, “bottom”, “upper”, “lower”, “above”, and “below” are used to provide a relative relationship between structures. The use of these terms does not indicate or require that a particular structure must be located at a particular location in the apparatus.

[0109] As used herein, the phrase “at least one of A, B, and C” should be construed to mean a logical (A or B or C), using a non-exclusive logical “or”, and should not be construed to mean “at least one of A, at least one of B and at least one of C”.

[0110] For the purposes of this disclosure, “metal” used in this context should be understood to mean conductor with a maximum resistivity of 500 micro Ohm cm, including metals and conductive metal salts, in particular conductive metal nitrides, e.g., TiN.

[0111] In the present disclosure, the terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably. One of ordinary skill in the art would understand that the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of many stages of integrated circuit fabrication thereon. A wafer or substrate used in the semiconductor device industry typically has a diameter of 200 mm, or 300 mm, or 450 mm. The following detailed description assumes the present disclosure is implemented on a wafer. However, the present disclosure is not so limited. The work piece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other work pieces that may take advantage of the present disclosure include various articles such as printed circuit boards and the like.CONCLUSION

[0112] Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the embodiments are not to be limited to the details given herein.

Claims

1. CLAIMSWhat is claimed is:

1. A method for processing a substrate comprising: providing a substrate including a plurality of features, each feature comprising a feature opening and a feature bottom, in a process chamber; introducing a mixed metal halide precursor into the process chamber; introducing a reducing agent into the process chamber; and wherein the mixed metal halide precursor reacts with the reducing agent to deposit a metal film in the feature.

2. The method of claim 1, wherein the metal film comprises molybdenum or tungsten.

3. The method of claim 1, wherein the reducing agent is hydrogen.

4. The method of claim 1, wherein the mixed metal halide precursor comprises a mixed molybdenum halide precursor or a mixed tungsten halide precursor.

5. The method of claim 1, further comprising introducing a metal-containing halogen-containing gas and a halogen-containing gas to a remote reaction chamber to form the mixed metal halide precursor, wherein the mixed metal halide precursor is delivered from the remote reaction chamber to the process chamber.

6. The method of claim 5, wherein the metal-containing halogen-containing gas comprises molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride, molybdenum hexafluoride or molybdenum fluoride.

7. The method of claim 5, wherein the tungsten halide precursor comprises tungsten hexafluoride, tungsten pentafluoride, tungsten hexachloride, tungsten pentachloride or a combination thereof.

8. An apparatus for filling a feature of a semiconductor substrate, the apparatus comprising: one or more process chambers; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, wherein the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the associated flowcontrol hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the associated flow-control hardware to: cause introduction of a mixed metal halide precursor into the process chamber; and cause introduction of a reducing agent into the process chamber.

9. The apparatus of claim 8, further comprising a remote reaction chamber for synthesizing the mixed metal halide precursor.

10. The apparatus of claim 9, wherein the controller further comprises instructions for causing delivery of the mixed metal halide precursor from the remote reaction chamber to the process chamber to cause introduction of the mixed metal halide precursor into the process chamber.

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