# Patent

## Title
Phase-stabilized thin films, structures and devices including the thin films, and methods of forming same

## Abstract

Nitrogen-containing phase-stabilized films, methods of forming phase-stabilized films, and structures and devices including the phase-stabilized films are disclosed. The phase-stabilized films include a matrix material and a phase stabilizer, which provides a morphologically stabilizing effect to a matrix material within the films. The phase-stabilized films may be used as, for example, gate electrodes and similar films in microelectronic devices.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application claims the right of priority based on U.S. Provisional Patent Application No. 61/641,602 entitled “FORMATION OF PHASE-STABILIZED THIN FILMS,” filed on May 2, 2012, which is incorporated herein by reference, to the extent it does not conflict with the present disclosure.


FIELD OF INVENTION
The present disclosure generally relates to thin-film deposition techniques. More particularly, the disclosure relates to thin films including a phase stabilizer, to structures and devices including the films, and to methods of forming the films, structures, and devices.
BACKGROUND OF THE DISCLOSURE
Many semiconductor devices include non-silicon work function materials. For example, metal-oxide semiconductor (MOS) devices may include a gate electrode that includes a metal to assist in setting the effective work function for the gate electrode. Use of metal-containing electrodes in such devices has become increasingly important as the feature size of the devices decreases. Although various processes for forming metal gate electrodes have been developed, many of these processes exhibit unacceptable feature-size dependent performance variations. As a result, as the feature sizes of semiconductor devices decrease, these processes become increasingly problematic.
For example, in some devices, the effective work function of a metal-containing gate electrode may be determined by averaging work functions exhibited by domains within the gate electrode film that may have different crystal orientations and/or morphological phases of the metal gate electrode material. In some settings, the size of these domains may vary according to film deposition conditions and/or film thickness. As a gate length becomes smaller in MOS devices, the domain size may occupy a relatively larger portion of gate electrode, potentially leading to domain-specific work function differences that may have a greater effect on the overall work function of the device. In turn, there may be gate-to-gate work function variation that depends on the gate feature size, which may result in poor device performance.
Metal gate electrodes may also be difficult to integrate into device manufacturing processes because it can be difficult to deposit metal gate electrode films having desired film uniformity or other properties. For example, some semiconductor devices may include a three-dimensional gate dielectric supporting structure, such as a fin extending from the substrate that supports gate dielectric material on one or more of surfaces of the fin, or a replacement gate structure including an opening formed in the substrate surface that supports gate dielectric material on one or more surfaces therein. Depositing thin films of metal gate electrode material on the sidewalls of such structures may be challenging when using some existing deposition processes approaches. For example, mass transport phenomena inherent in physical vapor deposition (PVD) and chemical vapor deposition (CVD) techniques may provide poor step coverage in such structures and may lead to inconsistent film thickness as a function of the gate dielectric supporting structure height.
Further, because some properties of a material that may make it attractive as a potential metal gate electrode material may not be present in a thermodynamically stable phase of the material, it may be difficult to form a desirable but less stable phase of the material using traditional PVD and CVD techniques. For example, a PVD deposition may lead to a film initially having identical composition as the target or targets, and the high energies involved in the PVD process may lead to equilibration into a more thermodynamically stable form of the material, which has less desirable work function properties. As another example, attempts to form desirable metastable phases of material with CVD processes may lead to incomplete conversion and within substrate compositional non-uniformities, potentially leading to downstream processing difficulties and/or device performance problems. Accordingly, improved phase-stabilized films and methods of forming the films are desired.
SUMMARY OF THE DISCLOSURE
Various embodiments of the present disclosure relate to phase-stabilized films, methods of forming phase-stabilized films, and structures and devices including the phase-stabilized films. The phase-stabilized films described herein may be used, for example, for gate electrodes and similar films in microelectronic devices. While the ways in which various embodiments of the disclosure address the drawbacks of the prior art methods and films is discussed in more detail below, in general, the disclosure provides phase-stabilized films that may have more desirable properties when used as a gate electrode in, for example, metal oxide semiconductor devices, compared to films that might otherwise form without a phase stabilizer. However, the invention is not necessarily limited to such applications.
In accordance with various embodiments of the disclosure, methods of forming phase-stabilized nitrogen-containing films include supporting a substrate in a reactor and forming a phase-stabilized nitrogen-containing film on an exposed surface of the substrate. In accordance with various aspects of these embodiments, a method includes the steps of supplying a phase stabilizer precursor and a matrix material precursor to an exposed surface of the substrate and supplying a nitrogen-containing reactant to the reactor so that the nitrogen-containing reactant reacts with active species on the exposed surface of the substrate to form the phase-stabilized film. The steps of supplying a phase stabilizer precursor and a matrix material precursor may be performed concurrently or may be performed as sequential pulses. In accordance with further aspects of these embodiments, the phase-stabilized nitrogen-containing film comprises a phase-stabilized metal nitride film. The phase-stabilized metal nitride film may be formed on a substrate supported in a reactor, where the phase-stabilized metal nitride film comprises a phase stabilizer that stabilizes a matrix material comprising a metal nitride into a selected solid phase. In this example, the phase-stabilized metal nitride film may be formed on the exposed surface of the substrate by concurrently or sequentially (e.g., pulsing) supplying a phase stabilizer precursor and a metal nitride precursor to an exposed surface of the substrate and then supplying a nitrogen-containing reactant to the reactor so that the nitrogen-containing reactant reacts with active species on the exposed surface of the substrate to from the phase-stabilized metal nitride film. In accordance with yet further aspects of these embodiments, the metal nitride film includes a group V transition metal, such as vanadium, niobium, or tantalum. And, in accordance with further aspects, the phase stabilizer comprises a group IV transition metal, such as titanium, zirconium, or hafnium and/or a group VI transition metal, such as chromium, molybdenum, or tungsten. And, in accordance with yet additional exemplary embodiments, the nitrogen-containing film comprises TaxTi(1−x)N. A treatment gas, such as hydrogen may be used during the formation of the film to facilitate formation of nitrogen-containing films having desired morphology and/or properties. The films formed in accordance with these methods may be used as gate electrodes or other layers within electronic devices.
In accordance with additional embodiments of the disclosure, a phase-stabilized nitrogen-containing film includes a solid solution having a stoichiometric ratio of MmzxMs(z−x)X, where MmX represents the matrix material and where Ms represents the phase stabilizer. MmX may be a first metal nitride (e.g., MmxNy) and Ms may be a second metal that stabilizes the matrix material into a selected phase. The matrix material MmxNy, may determine one or more electrical properties of the phase-stabilized film (e.g., a work function) while a second metal nitride MsxNy, may determine or affect morphological characteristics for the phase-stabilized film (e.g., a cubic phase), even if a native metal nitride metal nitride MmaNb would exhibit a different morphology under identical film formation conditions. In accordance with various aspects of these embodiments, X is nitrogen. In accordance with further aspects, Mm is one or more group V transition metals, such as vanadium, niobium, or tantalum. In accordance with further aspects, Ms includes one or more group IV transition metals, such as titanium, zirconium, or hafnium and/or group VI transition metal, such as chromium, molybdenum, and tungsten.
In accordance with yet additional embodiments of the disclosure, a structure, e.g., a semiconductor structure, includes a gate dielectric material and a metal gate electrode material comprising a solid solution formed overlying the gate dielectric material, the solid solution comprising a phase stabilizer that stabilizes a metal nitride in a solution phase that is different from a native phase of the metal nitride that would be formed under identical film formation conditions. The structure may additionally include a substrate, such as a semiconductor substrate, and additional layers typically used in the manufacture of electronic devices. In accordance with various aspects of these embodiments, the metal nitride material includes one or more group V transition metals. In accordance with further aspects, the phase stabilizer includes one or more group IV transition metals, such as titanium, zirconium, or hafnium and/or group VI transition metal, such as chromium, molybdenum, and tungsten. The metal nitride may determine one or more electrical properties of the phase-stabilized film (e.g., a work function) while the phase stabilizer may determine or affect morphological characteristics for the phase-stabilized film (e.g., a cubic phase). Structures in accordance with various aspects of these embodiments may be used to form electronic devices, such as metal oxide semiconductor devices.



BRIEF DESCRIPTION OF THE DRAWING FIGURES
A more complete understanding of the embodiments of the present disclosure may be derived by referring to the detailed description and claims when considered in connection with the following illustrative figures.
FIG. 1 illustrates a phase diagram for a nitrogen-containing films formed in accordance with exemplary embodiments of the disclosure.
FIG. 2 illustrates Gibbs free energy relationships with temperature for nitrogen-containing films formed in accordance with exemplary embodiments of the present disclosure.
FIG. 3 illustrates a method of depositing a nitrogen-containing film according to exemplary embodiments of the present disclosure.
FIG. 4 illustrates a semiconductor structure according to additional exemplary embodiments of the present disclosure.
FIG. 5 illustrates a semiconductor structure according to yet additional exemplary embodiments of the present disclosure.
FIG. 6 illustrates a process tool suitable for forming phase-stabilized nitrogen-containing films in accordance with exemplary embodiments of the present disclosure.



It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of illustrated embodiments of the present disclosure
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS OF THE DISCLOSURE
The description of exemplary embodiments of methods, structures, and devices provided below is merely exemplary and is intended for purposes of illustration only; the following description is not intended to limit the scope of the disclosure or the claims. Moreover, recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features.
The present disclosure relates, generally, to nitrogen-containing phase-stabilized films, to methods of forming the films, and to structures and devices including the films. As set forth in more detail below, nitrogen-containing phase-stabilized films in accordance with various embodiments of the disclosure include a phase stabilizer to stabilize a solid phase of the nitrogen-containing films. It will be appreciated that the embodiments disclosed herein may be used to form any suitable phase-stabilized film. In addition, it may be possible to address mass transfer phenomena affecting film formation processes on non-planar substrate surfaces and to stabilize otherwise metastable phases of some films using the films and techniques described herein.
As used herein, a phase-stabilized film is a film that includes at least a suitable amount of phase stabilizer to cause a matrix material to form into a selected solid phase, within an acceptable tolerance. A phase stabilizer is a material that provides a morphologically-stabilizing effect to the matrix material, so that the presence of the phase stabilizer causes the matrix material to be stabilized into the selected solid phase. Put another way, a phase-stabilized film includes a phase stabilizer that stabilizes the matrix material into a selected solid phase that would not otherwise form under identical conditions. A matrix material is a material that hosts phase stabilizer. For example, the matrix material may be a metal nitride in a phase-stabilized metal nitride film. Generally, the matrix material is present in a higher atomic concentration than the phase stabilizer.
The nitrogen-containing phase-stabilized films described herein may be formed of a variety of materials. For ease of description, exemplary films and methods of forming the films are described in connection with phase-stabilized metal nitride films. In other words, the examples below describe systems where the matrix material includes a metal nitride. However, it will be appreciated that these descriptions are not intended to be limiting in any sense, and that they may apply to matrix material systems other than metal nitride systems. As used herein, a phase-stabilized metal nitride film is a metal nitride film that includes at least a suitable amount of phase stabilizer to cause the metal nitride to form into a selected solid phase, within an acceptable tolerance. Non-limiting examples of metal nitride films include compounds including nitrogen and one or more elements selected from group V transition metals (e.g., vanadium (V), niobium (Nb), and tantalum (Ta)), and by way of one example, the metal nitride film includes tantalum nitride. It will be appreciated that in some embodiments, other suitable elements, including other metals and/or non-metals, may be included in the metal nitride. Non-limiting examples of phase stabilizers that may be used to stabilize various exemplary metal nitride films include one or more elements selected from group IV transition metals (e.g., titanium (Ti), zirconium (Zr), and hafnium (Hf)) and/or group VI transition metals (e.g., chromium (Cr), molybdenum (Mo), and tungsten (W)), and by way of one example, the phase stabilizer includes titanium.
The phase stabilizer may be included at any suitable concentration. It will be understood that such concentrations may vary depending on the particular phase-stabilized film and phase being formed, and may also vary depending on film application parameters, including, but not limited to, film thickness, sublayer type (e.g., an underlying film on which the phase-stabilized film is to be deposited, such as a gate dielectric film), adlayer type (e.g., an overlying film that will be deposited on top of the phase-stabilized film, such as a capping layer, a mask layer, a contact layer, and the like), process thermal budget, and process etch budget. By way of examples, an amount of phase stabilizer within a nitrogen-containing phase-stabilized film ranges from about 5 to about 75 atomic percent.
In some embodiments, the phase stabilizer may be present in an amount that stabilizes the matrix material in the selected solid phase without affecting a particular characteristic of the matrix material beyond an acceptable tolerance. For example, the phase stabilizer may be provided in an amount suitable to stabilize the selected solid phase without altering an electrical property of the matrix, such as the work function of the matrix material. However, it will be appreciated that if the phase stabilizer is not present in at least a concentration sufficient to cause formation of the selected solid phase, a matrix material having a different phase that is native to those conditions may form instead of the phase-stabilized film.
Because the selected solid phase into which the matrix material is phase-stabilized may exhibit one or more different physical and/or electrical properties from a native phase of the matrix material that would be formed under identical conditions, the phase-stabilized film may offer different functionality in an integrated device than a native phase of the matrix material. For example, a phase-stabilized film may exhibit a different work function or morphological state (e.g., grain size, and/or grain orientation) as a consequence of the stabilizing effect of the phase stabilizer that is different from an unstabilized film having a different morphological phase.
In accordance with various exemplary embodiments of the disclosure, a phase-stabilized film includes a solid solution having a stoichiometric ratio of MmzxMs(z−x)X, where MmX represents the matrix material and where Ms represents the phase stabilizer. For example, MmX may be a first metal nitride (e.g., MmxNy) and Ms may be a second metal that stabilizes the matrix material into a selected phase. In this example, matrix material MmxNy, may determine one or more electrical properties of the phase-stabilized film (e.g., a work function) while a second metal nitride MsxNy, may determine morphological characteristics for the phase-stabilized film (e.g., a cubic phase), even if a native metal nitride metal nitride MmaNb would exhibit a different morphology under identical film formation conditions.
FIG. 1 schematically illustrates an exemplary phase diagram 100 for a Ta—Ti—N system. Phase diagram 100 shows a number of non-homogenous mixed phase regions between various tantalum nitrides and titanium nitrides. Phase diagram 100 also shows a dielectric Ta3N5 region, which is typically amorphous, though it may exhibit a hexagonal close-packed (hcp) crystal structure in some settings.
Phase diagram 100 also illustrates δ-TiN, a common, stable form of titanium nitride, and δ-TaN, an uncommon, metastable form of tantalum nitride that is not readily formed by traditional chemical or physical film deposition techniques as the comparatively more stable Ta3N5 film. The dielectric character that accompanies the Ta3N5 film can be unwelcome in applications where tantalum nitride is intended to be used as a conductor, such as a gate electrode, as the effective oxide thickness of the gate dielectric may increase, potentially diminishing device performance.
Phase diagram 100 also depicts a region believed to be a solid solution of δ-TiN and δ-TaN having a stoichiometric ratio of TaxTi(1−x)N. Both δ-TiN and δ-TaN exhibit a cubic crystal structure and each material has a lattice parameter (believed to be a=4.242 Å and a=4.340 Å, respectively); the respective lattice parameters are believed to be within about 2.3% of the other. According to Vegard's Law, at a constant temperature, the lattice parameter may vary linearly according to concentrations of those elements in a solid solution. Thus, without wishing to be bound by theory, where two elements exhibit similar lattice parameters and identical crystal groups, it may be likely that those two elements will form a solid solution with one another.
For a similar reason, phase diagram 100 illustrates another region that may represent a solid solution Ta2xTi(2−x)N formed from Ti2N and Ta2N. While Ti2N and Ta2N have different crystal structures, they exhibit somewhat similar lattice parameters. For example, Ti2N has lattice parameters believed to be a=4.945, b=a, and c=3.034; Ta2N has lattice parameters believed to be a=3.044, b=a, and c=4.914.
FIG. 2 schematically shows a comparison 200 between Gibb's free energy for TiN and TaN deposition processes. As shown in comparison 200, the formation of TaN from a reaction of TaCl5 with NH3 (shown by relationship 202) is believed to be thermodynamically favorable at temperatures of at least 100° C., while relationship 204 indicates that the formation of TiN from the reaction of TiCl4 with NH3 is believed to be thermodynamically favorable at a temperature of at least about 310° C. Accordingly, in some embodiments, it may be possible to form a solid solution of TaxTi(1−x)N or Ti2xTa(2−x)N at temperatures of 310° C. and above.
Moreover, in some embodiments, supplying a treatment gas may increase conversion of some metal-containing precursors into a respective metal compound (e.g., a metal nitride) and decrease the conversion of others. Without wishing to be bound by theory, the presence of a suitable treatment gas may facilitate desorption of ligands dissociated from the chemisorbed precursor and/or may facilitate changes in oxidation state of metal cations included in the lattice by creating lattice vacancies and/or scavenging surface-adsorbed oxygen and/or water molecules. This may offer a potential approach for adjusting the composition of a solid solution.
For example, relationship 206 shows that supplying hydrogen as a treatment gas may decrease the temperature at which formation of TaN is believed to be thermodynamically favorable to about 80° C., while hydrogen may increase the temperature at which formation of TiN is believed to be favorable to about 360° C., as shown in relationship 208. Therefore, if hydrogen is supplied as a treatment gas, it may be possible to form a different solid solution (e.g., having a composition of TayTi(1−y)N) at temperatures of above 360° C. and below 1100° C., a temperature at which hydrogen is believed to reduce TaCl5 to Ta.
FIG. 3 illustrates a flowchart for an exemplary method 300 of forming a phase-stabilized nitrogen-containing film (also referred to herein as a layer) on a substrate. Method 300 may be performed by any suitable hardware and software, including the hardware and software described herein. It will be appreciated that portions of the processes described in method 300 may be omitted, reordered, and/or supplemented without departing from the scope of the present disclosure.
At 302, method 300 includes supporting a substrate in a reactor. A phase-stabilized film may be formed on an exposed surface of any suitable substrate without departing from the present disclosure. Further, the substrate may have any suitable topography, including planar and non-planar surfaces that are exposed for deposition, and the substrate may include layers of various materials, such as materials used to form semiconductor devices.
In some embodiments, the phase-stabilized layer may be formed on top of a nucleation layer provided on the substrate surface. The nucleation layer may help physically align atoms during the deposition process, potentially acting as a physical template that provides some physical stabilization for the phase-stabilized film during the initial deposition of the film. Put another way, as the various atoms forming the initial layers of the phase-stabilized film are deposited on the nucleation layer, such atoms may conform to the morphology of the underlying nucleation layer.
It will be appreciated that the material selected for the nucleation layer may vary depending on the phase-stabilized film to be deposited thereon. For example, the nucleation layer may be selected to have lattice parameters that are acceptably similar to lattice parameters for the selected solid phase of the phase-stabilized film—e.g., within about 2.3% of each other. Further, it will be appreciated that other parameters for the nucleation layer may be selected according to the application for the phase-stabilized film. An example of such an application is described below with reference to FIG. 5.
In cases where a nucleation layer is provided on the substrate, the nucleation layer may be formed in the same reactor prior to forming the phase-stabilized film. In some other embodiments, the nucleation layer may be formed in a common process tool with the reactor, so that the substrate does not experience a vacuum break and/or is not exposed to an ambient atmosphere prior to forming the phase-stabilized film in the reactor.
In accordance with some embodiments, supporting the substrate in the reactor step 302 may include adjusting one or more reactor conditions, such as temperature, pressure, and/or inert gas (e.g., argon (Ar), nitrogen (N2), or helium (He)) flow rate, to conditions suitable for film formation prior to processing the substrate. It will be appreciated that such film formation conditions may vary according to film deposition process chemistry, substrate surface termination, and the like.
For example, reactor conditions may be adjusted to facilitate the formation of surface-active species from suitable film precursors by activating surface adsorption and decomposition processes. Reactor conditions may also be adjusted to facilitate film formation by activating the reaction of such surface-active species with a suitable reactant, whether present in the gas phase or on the surface. In some scenarios, reactor conditions may be adjusted to avoid gas phase decomposition reactions for one or more of precursors and/or reactants, potentially avoiding film contamination from decomposition products and/or poor step coverage resulting from diffusion effects. Further, in some scenarios, reactor conditions may be adjusted to avoid condensation of precursors and/or reactants on various reactor surfaces, potentially avoiding small particle defect generation processes.
For example, non-limiting reactor temperatures for depositing a phase-stabilized film of TaxTi(1−x)N include temperatures between 310° C. and 600° C. in some scenarios and between 450° C. and 600° C. in some other scenarios. Non-limiting reactor pressures for such films include pressures between 0.5 Torr and 10 Torr.
Exemplary method 300 enters a deposition cycle after supporting the substrate in the reactor at 302. As used herein, a deposition cycle refers to a film deposition including a single exposure (e.g., a pulse) of the matrix material and the phase stabilizer precursors and a single exposure of a nitrogen-containing reactant. It will be appreciated that any suitable adjustments to the reactor conditions may be made during the deposition cycle, including adjustments to temperature, pressure, and/or the flow rates of various gases supplied to the reactor during the deposition cycle.
An exemplary deposition cycle 320 includes optional process 304 and processes 306 through 312. It will be appreciated that the arrangement and order of processes shown in the deposition cycle depicted in FIG. 3 are provided for illustrative purposes only, and may be varied in any suitable way in some embodiments.
Method 300 may include, optional step 304 of supplying a treatment gas to the reactor. Supplying a treatment gas may facilitate deposition-related surface reactions (e.g., byproduct desorption reactions and precursor ligand desorption reactions) that may enhance deposition rate of the phase-stabilized film. Additionally or alternatively, supplying a treatment gas may facilitate the formation of selected oxidation states of one or more kinds of metal cations included in the film lattice. In turn, the formation of the selected oxidation states may lead to the formation of a selected composition associated with the phase-stabilized film.
It will be appreciated that any suitable treatment gas may be supplied to the reactor. One non-limiting example treatment gas includes hydrogen. Further, it will be appreciated that, if provided, the treatment gas may be supplied during any suitable portion during the deposition of the phase-stabilized film. For example, a treatment gas may be supplied during an entire deposition cycle configured to deposit a layer of phase-stabilized film. Or, a treatment gas may be supplied during less than an entire deposition cycle, such as during a precursor supply portion of a deposition cycle or during a reactant supply portion of a deposition cycle.
At 306, method 300 includes supplying a matrix material precursor and a phase stabilizer precursor to the reactor during a precursor supply portion of the deposition cycle. The matrix material precursor and a phase stabilizer precursor may be supplied to a reaction chamber simultaneously/concurrently or sequentially—e.g., in separate pulses. Any suitable (e.g., thermally-activated) matrix material precursor and phase stabilizer precursor may be employed without departing from the scope of the present disclosure. For example, in some embodiments, the matrix material precursor and/or the phase stabilizer precursor may comprise various organo-substituted metal compounds and/or halo-substituted metal compounds, which may be employed depending on the particular deposition chemistry that is contemplated. In one non-limiting example, a phase-stabilized film of TaxTi(1−x)N may be formed from a metal nitride precursor that includes TaCl5 and a phase stabilizer precursor that includes TiCl4.
It will be appreciated that the amount of each precursor supplied to the reactor during process 306 may vary according to, among other factors, the topography of the exposed surface of the substrate, the film formation conditions present in the reactor, and the competitive adsorption rates and/or the sticking coefficients of each of the precursors on the surface under those conditions. In one non-limiting process for depositing a phase-stabilized film of TaxTi(1−x)N, TaCl5 and TiCl4 may be supplied to the reactor in concurrent or sequential pulses having durations of between 50 msec and 1 sec each.
Without wishing to be bound by theory, as the matrix material precursor and phase stabilization precursor are supplied to the reactor, gas phase molecules of those precursors may adsorb on the exposed surface of the substrate. Some of the gas phase molecules may become chemically adsorbed (e.g., chemisorbed) to the surface at sites on the surface that activate such chemisorption reactions. Such chemisorbed species form surface-active species of their respective precursors. Because a surface-active species may be bound to at least one surface site until a further reaction occurs, adsorption of the precursors may occur in a self-limiting manner. In turn, the film deposited during a deposition cycle may be moderated by the surface reactions of these active species with a subsequently-supplied reactant, as described in more detail below.
In some embodiments, a full monolayer may be deposited in each deposition cycle 320. In some other embodiments, less than a full monolayer may be deposited in each deposition cycle. For example, in a non-limiting process for depositing a phase-stabilized film of TaxTi(1−x)N, each deposition cycle may deposit approximately 1⁄3 Å of film, so that 3-4 deposition cycles result in approximately 1 monolayer of film.
It will be appreciated that relative amounts of the respective precursors may be supplied to the reactor according to any suitable technique. Non-limiting examples include controlling mass or volume flows of vapor or liquid precursor sources using suitable valves, flow controllers, pressure controllers, and so on. Other examples include, but are not limited to, controlling precursor supply via a phase change from one state to another, such as by controlling temperatures and/or pressures of liquid or solid precursor sources.
In some embodiments, the matrix material and phase stabilizer precursors may be supplied via a common delivery line coupled to sources for each of the precursors, so that there is a simultaneous supply of the matrix material precursor during any supply of the phase stabilizer precursor, within an acceptable tolerance.
In some other embodiments, the matrix material and phase stabilizer precursors may be supplied to the reactor via separate delivery lines. In some of such embodiments, concurrent supply of the precursors may include overlapping a pulse of one precursor with at least a portion of a pulse of the other precursor. This may provide a selected population of surface-active species derived from a particular precursor that is potentially different from an equilibrium surface population that might ordinarily result from differences in competitive adsorption rates for the precursors.
At 308, method 300 includes removing the matrix material precursor and the phase stabilizer precursor from the reactor. Removing the matrix material precursor and the phase stabilizer precursor from the reactor includes removing gas phase molecules of the precursors and molecules of the precursors that are condensed on the surface but that are not chemically adsorbed to it. Such physically adsorbed (e.g., physisorbed) molecules may be condensed on the surface in more than one layer or may be distributed in non-uniform ways (such as being condensed within narrow openings formed in the exposed surface). Removing non-chemisorbed precursor molecules may prevent reaction of such molecules with a subsequently-introduced oxygen-containing reactant. In turn, it may be possible that non-uniform, non-conformal film formation and/or small particle defect generation that may result from residual, non-chemisorbed molecules of the precursor may be avoided. Although illustrated as a single step 308, if matrix material precursor and phase stabilizer precursor are separately pulsed to a reaction chamber, the respective precursor may be removed prior to a pulse of the next precursor.
It will be appreciated that any suitable approach for removing residual matrix material precursor and the phase stabilizer precursor from the reactor may be employed without departing from the scope of the present disclosure. For example, in some embodiments, the reactor may be evacuated to a base pressure for a time suitable to remove the residual precursor. Additionally or alternatively, in some embodiments, the reactor may be supplied with a suitable displacement gas, such as Ar, N2, or He for a suitable time.
At 310, method 300 includes supplying a nitrogen-containing reactant to the reactor. Without wishing to be bound by theory, the nitrogen-containing reactant may be thermally activated to form gas-phase activated species and/or surface-adsorbed activated species. Such activated species may react with active species formed from the matrix material precursor and/or the phase stabilizer precursor on the exposed surface of the substrate to form the phase-stabilized film. Because the population of surface active species may moderate the film deposition rate, the reaction between the surface active species and the activated species formed from the reactant may be comparatively fast, potentially avoiding thickness non-uniformity that might otherwise result from mass transport effects. Although illustrated as a separate step 310, a nitrogen-containing reactant (e.g., N2) may be continuously fed to a reactor and submitted to a plasma pulse to activate the reactant—i.e., form activated species, such as nitrogen ions and/or radicals. Or, if the nitrogen-containing reactant is thermally activated (e.g., ammonia (NH3) or hydrazine (N2H4)) and allowed to continuously flow during the deposition cycle, chemical vapor deposition of the nitrogen-containing film may result—rather than atomic layer deposition of the film.
Any suitable thermally-activated nitrogen-containing reactant may be employed without departing from the scope of the present disclosure. Non-limiting examples of nitrogen-containing reactants that may be used in a process for depositing a phase-stabilized film of TaxTi(1−x)N include ammonia (NH3) and hydrazine (N2H4).
At 312, method 300 includes removing the nitrogen-containing reactant from the reactor. Removing the nitrogen-containing reactant from the reactor includes removing gas phase molecules and surface-adsorbed nitrogen-containing reactant. Removing residual nitrogen-containing reactant may prevent unwanted gas phase or surface reactions when the matrix material precursor and the phase stabilizer precursor are introduced to the reactor during a subsequent layer formation cycle. In turn, it may be possible that non-uniform, non-conformal film formation and/or small particle defect generation that may result from reaction between residual nitrogen-containing reactant molecules and the precursors may be avoided.
It will be appreciated that any suitable approach for removing residual nitrogen-containing reactant from the reactor may be employed without departing from the scope of the present disclosure. For example, in some embodiments, the reactor may be evacuated to a base pressure for a time suitable to remove the residual nitrogen-containing reactant. Additionally or alternatively, in some embodiments, the reactor may be supplied with a suitable displacement gas, such as Ar, N2, or He for a suitable time. It will be appreciated that, in some embodiments, processes for removing residual nitrogen-containing reactant may vary from processes for removing the precursors. For example, the reactant may have a comparatively greater sticking coefficient relative to the precursor(s). Accordingly, the reactor may be purged and/or evacuated for a longer time at 312 relative to 308.
As introduced above, in some embodiments, a single deposition cycle of processes 304 through 312 may result in a consistent thickness of film formed from a self-limiting adsorption and reaction process. Consequently, in some of such embodiments, any suitable thickness of phase-stabilized film may be formed by repeating the deposition cycle a suitable number of times. Thus, method 300 includes, at 314, determining whether to deposit another layer of phase-stabilized film. If another layer is to be deposited, method 300 returns to 304; if not, method 300 continues. In some embodiments, the reactor conditions under which the phase-stabilized film is formed may cause diffusion among individually deposited layers (e.g., within layers deposited during a particular deposition cycle) and between such layers. Such diffusion processes may help mobilize the phase stabilizer so that the phase-stabilized film exhibits the selected solid phase. Such processes may be supplemented with one or more additional thermal treatments, which may include annealing the film at an elevated temperature and/or varying a temperature of the film over time according to a preselected thermal treatment program. Accordingly, thermally treating the film may provide an additional approach for stabilizing the film at the selected solid phase and/or adjusting various physical characteristics of the film (e.g., grain size). Further, thermally treating the film may assist with the removal of one or more film contaminants. For example, thermal treatment may reduce concentrations of carbon and/or halogens introduced by precursor ligands.
In some embodiments, thermal treatment may include treatment with a suitable treatment gas, such as hydrogen, while in some other embodiments, thermal treatment may occur while the reactor is evacuated (e.g., at a base vacuum level) or controlled to a preselected pressure with a suitable inert gas, such as argon, helium, and/or nitrogen.
As an example of such thermal treatments, method 300 includes, at 316, thermally treating the phase-stabilized film. However, it will be appreciated that such treatments may be included at any suitable interval during film deposition in some embodiments. Once film deposition and, if included, thermal treatment, is complete, the substrate is removed from the reactor at 318.
FIG. 4 schematically illustrates an exemplary film stack or structure 400 that includes a nitrogen-containing phase-stabilized film (e.g., TaxTi(1−x)N) that may be formed according to the present disclosure. As illustrated in FIG. 4, film stack 400 includes a substrate 402, a gate dielectric layer 404, and a metal gate electrode layer 406 that comprises the phase-stabilized film. Substrate 402 may include any suitable substrate. One non-limiting example substrate includes a silicon (Si) substrate. Regardless of the type of substrate, it will be appreciated that the substrate may include various films and/or structures resulting from prior processing of the substrate. In the embodiment illustrated in FIG. 4, the surface of substrate 402 is planar. However, it will be appreciated that, in some other embodiments, the substrate surface may be non-planar. For example, the substrate surface may include a non-planar surface topography that may comprise one or more fins, troughs, vias, mesas, or other structures in any suitable density.
Gate dielectric layer 404 is formed on top substrate 402. Non-limiting example gate dielectric materials include silicon oxide (SiO2) and hafnium oxide (HfO2). Gate dielectric layer 404 may be grown from a top surface of substrate 402 (e.g., a layer of SiO2 grown on top of a silicon substrate). Or, gate dielectric layer 404 may be deposited on a top surface of substrate 402. Where the surface of substrate 402 is non-planar, gate dielectric layer 404 may be a conformal layer over part of the surface of substrate 402; alternatively, gate dielectric layer 404 may be formed in a conformal layer over the entire surface of substrate 402.
Metal gate electrode layer 406 is formed on a top surface of gate dielectric layer 404. Metal gate electrode layer 406 includes one or more of the phase-stabilized films described herein, which may be formed according to the phase-stabilized film formation processes of the present disclosure.
As introduced above, in some embodiments, the phase-stabilized layer may be formed on top of a nucleation layer. FIG. 5 schematically illustrates a film stack or structure 500 that includes a phase-stabilized film (e.g., TaxTi(1−x)N) formed on top of a nucleation layer 502. As shown in FIG. 5, film stack 500 includes substrate 402 and gate dielectric layer 404. Metal gate electrode layer 406 comprising the phase-stabilized film is shown on top of a nucleation layer 502. It will be appreciated that nucleation layer 502 may be configured to be work function-transparent in some embodiments, so that the work function setting characteristics of metal gate electrode layer 406 may not be altered/masked.
In some embodiments, the phase-stabilized films described herein may be deposited using a suitable semiconductor processing tool. FIG. 6 schematically illustrates a top view of an exemplary semiconductor processing tool 600 including a plurality of semiconductor processing modules 602. While the depicted embodiment includes two modules, it will be appreciated that any suitable number of semiconductor processing modules may be provided. For example, some processing tools may include just one module while other processing tools may include more than two modules.
FIG. 6 also illustrates load locks 604 for moving substrates between portions of semiconductor processing tool 600 that exhibit ambient atmospheric pressure conditions and portions of the tool that are at pressures lower than atmospheric conditions. An atmospheric transfer module 608, including an atmospheric substrate handling robot 610, moves substrates between load ports 606 and load locks 604, where a portion of the ambient pressure is removed by a vacuum source (not shown) or is restored by backfilling with a suitable gas, depending on whether substrates are being transferred into or out of the tool. Low-pressure substrate handling robot 612 moves substrates between load locks 604 and semiconductor processing modules 602 within low-pressure transfer module 614. Substrates may also be moved among the semiconductor processing modules 602 within low-pressure transfer module 614 using low-pressure substrate handling robot 612, so that sequential and/or parallel processing of substrates may be performed without exposure to air and/or without a vacuum break.
FIG. 6 also shows a user interface 620 connected to a system process controller 622. User interface 620 is adapted to receive user input to system process controller 622. User interface 620 may optionally include a display subsystem, and suitable user input devices such as keyboards, mice, control pads, and/or touch screens, for example, that are not shown in FIG. 6.
FIG. 6 illustrates an exemplary system process controller 622 provided for controlling semiconductor processing tool 600. System process controller 622 may operate process module control subsystems, such as gas control subsystems, pressure control subsystems, temperature control subsystems, electrical control subsystems, and mechanical control subsystems. Such control subsystems may receive various signals provided by sensors, relays, and controllers and make suitable adjustments in response.
Exemplary system process controller 622 includes a computing system that includes a data-holding subsystem 624 and a logic subsystem 626. Data-holding subsystem 624 may include one or more physical, non-transitory, devices configured to hold data and/or instructions executable by logic subsystem 626 to implement the methods and processes described herein. Logic subsystem 626 may include one or more physical devices configured to execute one or more instructions stored in data-holding subsystem 624. Logic subsystem 626 may include one or more processors that are configured to execute software instructions.
In some embodiments, such instructions may control the execution of process recipes. Generally, a process recipe includes a sequential description of process parameters used to process a substrate, such parameters including, but not limited to, time, temperature, pressure, and concentration, as well as various parameters describing electrical, mechanical, and environmental aspects of the tool during substrate processing. The instructions may also control the execution of various maintenance recipes used during maintenance procedures.
In some embodiments, such instructions may be stored on removable computer-readable storage media 628, which may be used to store and/or transfer data and/or instructions executable to implement the methods and processes described herein, excluding a signal per se. It will be appreciated that any suitable removable computer-readable storage media 628 may be employed without departing from the scope of the present disclosure. Non-limiting examples include DVDs, CD-ROMs, floppy discs, and flash drives.
It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, performed in other sequences, or omitted in some cases.
The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts, and/or properties disclosed herein, as well as any and all equivalents thereof.

## Claims

1. A cyclic deposition method of forming a phase-stabilized nitrogen-containing film comprising a solid solution having a stoichiometric ratio of MmzxMs(z-x)X, where Mmzx and Ms(z-x) are transition metals, one belonging to Group V, another belonging either to Group IV or to Group VI of Periodic Table, x varies in a range from greater than 0 to less than 1 and z varies in a range from greater than x to 1, wherein the phase-stabilized nitrogen-containing film comprises a matrix material and a phase stabilizer within the solid solution, wherein the phase-stabilized nitrogen-containing film is formed on a substrate within a reactor by exposing the substrate to a pulse of a matrix material precursor and a phase stabilizer precursor, removing an unreacted matrix material precursor and an unreacted phase stabilizer precursor from the reactor, exposing the substrate to a pulse of a nitrogen-containing reactant, and removing an unreacted nitrogen-containing reactant from the reactor, and wherein the phase stabilizer stabilizes the matrix material in a solution phase that is different from a native phase of the matrix material that would be formed under identical film formation conditions.

2. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material comprises a metal nitride.

3. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material comprises a metal nitride with Group V transition metal.

4. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the phase stabilizer comprises one or more transition metals selected from the Group IV or from Group VI.

5. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein MmzxMs(z-x)X comprises TaxTi(1-x)N.

6. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material determines one or more electrical properties of the phase- stabilized nitrogen-containing film.

7. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material determines a work function of the phase-stabilized nitrogen-containing film.

8. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the phase stabilizer affects morphological characteristics of the phase-stabilized nitrogen-containing film.

9. A method of forming a semiconductor structure, comprising a gate dielectric material and a gate electrode overlying the gate dielectric material, wherein the gate electrode comprising a solid solution having a stoichiometric ratio of MmzxMs(z-x)X, where Mmzx and Ms(z-x) are transition metals, one belonging to Group V, another belonging either to Group IV or Group VI of Periodic Table, x varies in a range from greater than 0 to less than 1 and z varies in a range from greater than x to 1, the solid solution comprising a phase stabilizer that stabilizes a metal nitride in a solution phase that is different from a native phase of the metal nitride that would be formed under identical formation conditions, wherein the solid solution is formed on a substrate within a reactor via a cyclic deposition process by exposing the substrate to a pulse of a matrix material precursor and a phase stabilizer precursor, removing an unreacted matrix material precursor and an unreacted phase stabilizer precursor from the reactor, exposing the substrate to a pulse of a nitrogen-containing reactant, and removing an unreacted nitrogen-containing reactant from the reactor.

10. The method of forming the semiconductor structure of claim 9, wherein the metal nitride comprises one or more transition metals selected from Group V of Periodic Table.

11. The method of forming the semiconductor structure of claim 9, wherein the phase stabilizer comprises one or more transition metals selected from Group IV or from Group VI of Periodic Table.