Metal-containing material ETCH methods

Abstract

Exemplary semiconductor processing methods may include providing an oxygen-containing precursor to a processing region of a semiconductor processing chamber. A metal-containing material may be disposed on a substrate housed within the processing region. The oxygen-containing precursor may be provided from a gas box of the semiconductor processing chamber, through a showerhead defining an upper surface of the processing region, and into the processing region without passing an intervening gas flow component. The methods may include contacting the substrate with the oxygen-containing precursor to oxidize a portion of the metal-containing material to form a metal-and-oxygen-containing material. The methods may include providing a halogen-containing precursor to the processing region of the semiconductor processing chamber. The methods may include contacting the substrate with the halogen-containing precursor to etch the metal-and-oxygen-containing material.

Description

PATENT KTS No.: 080042-44025062W001-1468600METAL-CONTAINING MATERIAL ETCH METHODSTECHNICAL FIELD

[0001] The present technology relates to semiconductor processes and equipment. More specifically, the present technology relates to etching metal-containing materials.BACKGROUND

[0002] Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods for removal of exposed material. Chemical etching is used for a variety7of purposes including transferring a pattern in photoresist into underlying layers, thinning layers, or thinning lateral dimensions of features already present on the surface. Often it is desirable to have an etch process that etches one material faster than another facilitating, for example, a pattern transfer process. Such an etch process is said to be selective to the first material. As a result of the diversity of materials, circuits, and processes, etch processes have been developed with a selectivity towards a variety of materials.

[0003] Etch processes may be termed wet or dry based on the materials used in the process. For example, a wet etch may preferentially remove some oxide dielectrics over other dielectrics and materials. However, wet processes may have difficulty penetrating some constrained trenches and also may sometimes deform the remaining material. Dry etches produced in local plasmas formed within the substrate processing region can penetrate more constrained trenches and exhibit less deformation of delicate remaining structures. However, local plasmas may damage the substrate through the production of electric arcs as they discharge.

[0004] Thus, there is a need for improved systems and methods that can be used to produce high quality devices and structures. These and other needs are addressed by the present technology.SUMMARY

[0005] Exemplary semiconductor processing methods may include providing an oxygencontaining precursor to a processing region of a semiconductor processing chamber. A metal-containing material may be disposed on a substrate housed within the processing region. The oxy gen-containing precursor may be provided from a gas box of the semiconductor processing chamber, through a showerhead defining an upper surface of the processing region, and into the processing region without passing an intervening gas flow component. The methods may include contacting the substrate with the oxy gen-containing precursor to oxidize a portion of the metal-containing material to form a metal-and-oxy gencontaining material. The methods may include providing a halogen-containing precursor to the processing region of the semiconductor processing chamber. The methods may include contacting the substrate with the halogen-containing precursor to etch the metal-and-oxygen-containing material.

[0006] In some embodiments, the metal-containing material may be or include a metal-and-nitrogen-containing material. A metal of the metal-containing material may be or include molybdenum (Mo), niobium (Nb). titanium (Ti), or tungsten (W). The oxygen-containing precursor may be or include atomic oxygen (O), diatomic oxygen (O2), ozone (O3), steam (H2O), nitric oxide (NO), nitrous oxide (N2O), or nitrogen dioxide (NO2). The methods may include forming plasma effluents of oxy gen-containing precursor prior to providing the oxygen-containing precursor to the processing region of the semiconductor processing chamber. A sihcon-containing material, a second metal-and-oxy gen-containing material, or both may be disposed on the substrate. The metal-and-oxygen-containing material may be characterized by a thickness of greater than or about 2 nm. The methods may include halting a flow of the oxy gen-containing precursor prior to providing the halogen-containing precursor to the processing region of the semiconductor processing chamber. The halogencontaining precursor may be or include diatomic chlorine (Ch), diatomic fluorine (F2), boron trichloride (BCls), thionyl chloride (SOCI2), nitrogen trifluoride (NFs), or tungsten hexafluoride (WFe). The processing region may be maintained plasma-free while providing the halogen-containing precursor and contacting the substrate with the halogen-containing precursor. A temperature of a pedestal supporting the substrate may be maintained at greater than or about 150 °C. A pressure within the processing region may be maintained at greater than or about 1 Torr. The methods may include alternating (i) providing the oxygencontaining precursor to the processing region of the semiconductor processing chamber andcontacting the substrate with the oxygen-containing precursor and (ii) providing the halogencontaining precursor to the processing region of the semiconductor processing chamber and contacting the substrate with the halogen-containing precursor to iteratively etch the metalcontaining material.

[0007] Some embodiments of the present technology may encompass semiconductor processing methods. The methods may include providing an oxygen-containing precursor and a halogen-containing precursor to a processing region of a semiconductor processing chamber. A metal-and-nitrogen-containing material may be disposed on a substrate housed within the processing region. The oxy gen-containing precursor may be provided from a gas box of the semiconductor processing chamber to the processing region without passing an intervening gas flow component. The methods may include contacting the substrate with the oxygen-containing precursor and the halogen-containing precursor to oxidize a portion of the metal-and-nitrogen-containing material to form a metal-and-oxygen-containing material and etches the metal-and-oxygen-containing material.

[0008] In some embodiments, the gas box of the semiconductor processing chamber may be seated on a showerhead defining an upper portion of the processing region. The metal-and-nitrogen-containing material may be or include a titanium-and-nitrogen-containing material. The processing region may be maintained plasma-free.

[0009] Some embodiments of the present technology may encompass semiconductor processing methods. The methods may include i) providing an oxy gen-containing precursor to a processing region of a semiconductor processing chamber. A titanium-and-nitrogen-containing material may be disposed on a substrate housed within the processing region. A gas box of the semiconductor processing chamber may be seated on a showerhead defining an upper portion of the processing region. The methods may include ii) contacting the substrate with the oxy gen-containing precursor to oxidize a portion of the titanium-and-nitrogen-containing material to form a titanium-and-oxygen-containing material. The methods may include iii) halting a flow of the oxygen-containing precursor. The methods may include iv) providing a halogen-containing precursor to the processing region of the semiconductor processing chamber. The methods may include v) contacting the substrate with the halogen-containing precursor to etch the titanium-and-oxygen-containing material.

[0010] In some embodiments, a pressure within the processing region may be maintained at greater than or about 10 Torr. The methods may include repeating operations i) through v) for a plurality of cycles.

[0011] Such technology may provide numerous benefits over conventional systems and techniques. For example, the processes may allow dry etching to be performed that may protect features of the substrate. Additionally, the processes may selectively remove metalcontaining materials, such as titanium-and-nitrogen-containing materials, relative to other exposed materials on the substrate with reduced chamber complexity. These and other embodiments, along with many of their advantages and features, are described in more detail in conjunction with the below description and attached figures.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] A further understanding of the nature and advantages of the disclosed technology may be realized by reference to the remaining portions of the specification and the drawings.

[0013] FIG. 1 shows a top plan view of one embodiment of an exemplary processing system according to some embodiments of the present technology.

[0014] FIG. 2A shows a schematic cross-sectional view of an exemplary processing chamber according to some embodiments of the present technology.

[0015] FIG. 2B shows a detailed view of a portion of the processing chamber illustrated in FIG. 2A according to some embodiments of the present technology.

[0016] FIG. 3 shows a bottom plan view of an exemplary showerhead according to some embodiments of the present technology.

[0017] FIG. 4 shows exemplary7operations in a method according to some embodiments of the present technology.

[0018] FIGS. 5A-5D show schematic cross-sectional views of materials etched according to some embodiments of the present technology.

[0019] Several of the figures are included as schematics. It is to be understood that the figures are for illustrative purposes, and are not to be considered of scale unless specifically stated to be of scale. Additionally, as schematics, the figures are provided to aidcomprehension and may not include all aspects or information compared to realistic representations, and may include additional or exaggerated material for illustrative purposes.

[0020] In the appended figures, similar components and / or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the letter.DETAILED DESCRIPTION

[0021] Diluted acids may be used in many different semiconductor processes for cleaning substrates and removing materials from those substrates. For example, diluted hydrofluoric acid (“DHF”) can be an effective etchant for silicon oxide, aluminum oxide, titanium oxide, and other materials, and may be used to remove these materials from substrate surfaces. After the etching or cleaning operation is complete, the acid may be dried from the wafer or substrate surface. Using DHF may be termed a “wet” etch where the diluent is often water. Additional etching processes may be used that utilize precursors delivered to the substrate. For example, plasma enhanced processes may also selectively etch materials by enhancing precursors through the plasma to perform a dry etch.

[0022] Although wet etchants using aqueous solutions or water-based processes may operate effectively for certain substrate structures, the water may pose challenges in a variety of conditions. For example, utilizing water during etch processes may cause issues when disposed on substrates including metal materials. For example, certain later fabrication processes, such as recessing gaps, removing oxide dielectric, or other processes to remove oxygen-containing materials, may be performed after an amount of metallization has been formed on a substrate. If water is utilized in some fashion during the etching, an electrolyte may be produced, which when contacting the metal material, may cause galvanic corrosion to occur between dissimilar metals, and the metal may be corroded or displaced in various processes. In addition, because of the surface tension of the water diluent, pattern deformation and collapse may occur with minute structures. The water-based material may also be incapable of penetrating some high aspect ratio features due to surface tension effects. Plasma etching may overcome the issues associated with water-based etching, although additional issues may occur. For example, a reactive ion etch process may expose the metalto ion activity', which through bombardment can damage the structure, and affect electrical characteristics.

[0023] The present technology overcomes these issues by performing a dry etch process that, in some embodiments, may be plasma-free and purely thermal during the etching. Additionally, the present technology' may not require complex chamber configurations and may be able to provide some or all of the precursors into the processing region by only passing a showerhead. The present technology may also protect, or passivate, a number of materials relative to a material to be etched. By utilizing particular precursors that may facilitate halogen dissociation to provide etchant materials, an etch process may be performed that may protect the surrounding structures. Additionally, the materials and conditions used may allow improved etching relative to conventional techniques. Finally, the present technology may utilize sequential oxidation and etch, such that the etch may proceed selectively and with a high degree of control.

[0024] Although the remaining disclosure will routinely identify specific etching processes utilizing the disclosed technology7, it will be readily understood that the systems and methods are equally applicable to deposition and cleaning processes as may occur in the described chambers, as well as other etching technology and other etching that may be performed with a variety of exposed materials that may be maintained or substantially maintained.Accordingly, the technology' should not be considered to be so limited as for use with the exemplary etching processes or chambers alone. Moreover, although an exemplary7chamber is described to provide foundation for the present technology, it is to be understood that the present technology can be applied to virtually any semiconductor processing chamber that may allow the operations described.

[0025] FIG. 1 shows a top plan view of one embodiment of a processing system 100 of deposition, etching, baking, and curing chambers according to embodiments. In the figure, a pair of front opening unified pods (FOUPs) 102 supply substrates of a variety of sizes that are received by robotic arms 104 and placed into a low pressure holding area 106 before being placed into one of the substrate processing chambers 108a-f, positioned in tandem sections 109a-c. A second robotic arm 110 may be used to transport the substrate wafers from the holding area 106 to the substrate processing chambers 108a-f and back. Each substrate processing chamber 108a-f, can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layerdeposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation, and other substrate processes.

[0026] The substrate processing chambers 108a-f may include one or more system components for depositing, annealing, curing and / or etching a dielectric film on the substrate wafer. In one configuration, two pairs of the processing chambers, e.g., 108c-d and 108e-f, may be used to deposit dielectric material on the substrate, and the third pair of processing chambers, e.g., 108a-b, may be used to etch the deposited dielectric. In another configuration, all three pairs of chambers, e.g., 108a-f, may be configured to etch a dielectric film on the substrate. Any one or more of the processes described may be carried out in chamber(s) separated from the fabrication system shown in different embodiments. It will be appreciated that additional configurations of deposition, etching, annealing, and curing chambers for dielectric films are contemplated by system 100.

[0027] FIG. 2A shows a cross-sectional view of an exemplary process chamber system 200 with partitioned plasma generation regions within the processing chamber. During film etching, e.g., titanium nitride, tantalum nitride, tungsten, silicon, poly silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon oxy carbide, etc., a process gas may be flowed into the first plasma region 215 through a gas inlet assembly 205. A remote plasma system (RPS) 201 may optionally be included in the system, and may process a first gas which then travels through gas inlet assembly 205. The inlet assembly 205 may include two or more distinct gas supply channels where the second channel (not shown) may bypass the RPS 201, if included.

[0028] A cooling plate 203, faceplate 217, ion suppressor 223, showerhead 225, and a pedestal 265 or substrate support, having a substrate 255 disposed thereon, are shown and may each be included according to embodiments. The pedestal 265 may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate, which may be operated to heat and / or cool the substrate or wafer during processing operations. The wafer support platter of the pedestal 265, which may include aluminum, ceramic, or a combination thereof, may also be resistively heated in order to achieve relatively high temperatures, such as from up to or about 100 °C to above or about 1100 °C, using an embedded resistive heater element.

[0029] The faceplate 217 may be pyramidal, conical, or of another similar structure with a narrow top portion expanding to a wide bottom portion. The faceplate 217 may additionallybe flat as shown and include a plurality' of through-channels used to distribute process gases. Plasma generating gases and / or plasma excited species, depending on use of the RPS 201, may pass through a plurality of holes, shown in FIG. 2B, in faceplate 217 for a more uniform delivery into the first plasma region 215.

[0030] Exemplary configurations may include having the gas inlet assembly 205 open into a gas supply region 258 partitioned from the first plasma region 215 by faceplate 217 so that the gases / species flow through the holes in the faceplate 217 into the first plasma region 215. Structural and operational features may be selected to prevent significant backflow of plasma from the first plasma region 215 back into the supply region 258, gas inlet assembly 205, and fluid supply system 210. The faceplate 217, or a conductive top portion of the chamber, and showerhead 225 are shown with an insulating ring 220 located between the features, which allows an AC potential to be applied to the faceplate 217 relative to showerhead 225 and / or ion suppressor 223. The insulating ring 220 may be positioned between the faceplate 217 and the showerhead 225 and / or ion suppressor 223 enabling a capacitively coupled plasma (CCP) to be formed in the first plasma region. A baffle (not shown) may additionally be located in the first plasma region 215, or otherwise coupled with gas inlet assembly 205, to affect the flow of fluid into the region through gas inlet assembly 205.

[0031] The ion suppressor 223 may comprise a plate or other geometry that defines a plurality of apertures throughout the structure that are configured to suppress the migration of ionically-charged species out of the first plasma region 215 while allow ing uncharged neutral or radical species to pass through the ion suppressor 223 into an activated gas delivery region between the suppressor and the showerhead. In embodiments, the ion suppressor 223 may comprise a perforated plate with a variety of aperture configurations. These uncharged species may include highly reactive species that are transported with less reactive carrier gas through the apertures. As noted above, the migration of ionic species through the holes may be reduced, and in some instances completely suppressed. Controlling the amount of ionic species passing through the ion suppressor 223 may advantageously provide increased control over the gas mixture brought into contact with the underlying wafer substrate, which in turn may increase control of the deposition and / or etch characteristics of the gas mixture. For example, adjustments in the ion concentration of the gas mixture can significantly alter its etch selectivity. In alternative embodiments in which deposition is performed, it can also shift the balance of conformal-to-flow able style depositions for dielectric materials.

[0032] The plurality of apertures in the ion suppressor 223 may be configured to control the passage of the activated gas, i.e.. the ionic, radical, and / or neutral species, through the ion suppressor 223. For example, the aspect ratio of the holes, or the hole diameter to length, and / or the geometry of the holes may be controlled so that the flow of ionically-charged species in the activated gas passing through the ion suppressor 223 is reduced. The holes in the ion suppressor 223 may include a tapered portion that faces the plasma excitation region 215, and a cylindrical portion that faces the showerhead 225. The cylindrical portion may be shaped and dimensioned to control the flow of ionic species passing to the showerhead 225. An adjustable electrical bias may also be applied to the ion suppressor 223 as an additional means to control the flow of ionic species through the suppressor.

[0033] The ion suppressor 223 may function to reduce or eliminate the amount of ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may still pass through the openings in the ion suppressor to react with the substrate. It should be noted that the complete elimination of ionically charged species in the reaction region surrounding the substrate may not be performed in embodiments. In certain instances, ionic species are intended to reach the substrate in order to perform the etch and / or deposition process. In these instances, the ion suppressor may help to control the concentration of ionic species in the reaction region at a level that assists the process.

[0034] Showerhead 225 in combination with ion suppressor 223 may allow- a plasma present in first plasma region 215 to avoid directly exciting gases in substrate processing region 233, while still allowing excited species to travel from chamber plasma region 215 into substrate processing region 233. In this way, the chamber may be configured to prevent the plasma from contacting a substrate 255 being etched. This may advantageously protect a variety of intricate structures and films patterned on the substrate, which may be damaged, dislocated, or otherwise warped if directly contacted by a generated plasma. Additionally, when plasma is allowed to contact the substrate or approach the substrate level, the rate at which oxide species etch may increase. Accordingly, if an exposed region of material is oxide, this material may be further protected by maintaining the plasma remotely from the substrate.

[0035] The processing system may further include a power supply 240 electrically coupled with the processing chamber to provide electric power to the faceplate 217, ion suppressor223, showerhead 225, and / or pedestal 265 to generate a plasma in the first plasma region 215 or processing region 233. The power supply may be configured to deliver an adjustable amount of power to the chamber depending on the process performed. Such a configuration may allow for a tunable plasma to be used in the processes being performed. Unlike a remote plasma unit, which is often presented with on or off functionality, a tunable plasma may be configured to deliver a specific amount of power to the plasma region 215. This in turn may allow development of particular plasma characteristics such that precursors may be dissociated in specific ways to enhance the etching profiles produced by these precursors.

[0036] A plasma may be ignited either in chamber plasma region 215 above showerhead 225 or substrate processing region 233 below showerhead 225. Plasma may be present in chamber plasma region 215 to produce the radical precursors from an inflow of, for example, a fluorine-containing precursor or other precursor. An AC voltage typically in the radio frequency (RF) range may be applied between the conductive top portion of the processing chamber, such as faceplate 217, and showerhead 225 and / or ion suppressor 223 to ignite a plasma in chamber plasma region 215 during deposition. An RF power supply may generate a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency.

[0037] FIG. 2B shows a detailed view 253 of the features affecting the processing gas distribution through faceplate 217. As shown in FIGS. 2A and 2B, faceplate 217, cooling plate 203, and gas inlet assembly 205 intersect to define a gas supply region 258 into which process gases may be delivered from gas inlet 205. The gases may fill the gas supply region 258 and flow to first plasma region 215 through apertures 259 in faceplate 217. The apertures 259 may be configured to direct flow in a substantially unidirectional manner such that process gases may flow into processing region 233, but may be partially or fully prevented from backflow into the gas supply region 258 after traversing the faceplate 217.

[0038] The gas distribution assemblies such as showerhead 225 for use in the processing chamber section 200 may be referred to as dual channel showerheads (DCSH) and are additionally detailed in the embodiments described in FIG. 3. The dual channel showerhead may provide for etching processes that allow for separation of etchants outside of the processing region 233 to provide limited interaction with chamber components and each other prior to being delivered into the processing region.

[0039] The showerhead 225 may comprise an upper plate 214 and a lower plate 216. The plates may be coupled with one another to define a volume 218 between the plates. The coupling of the plates may be so as to provide first fluid channels 219 through the upper and lower plates, and second fluid channels 221 through the lower plate 216. The formed channels may be configured to provide fluid access from the volume 218 through the lower plate 216 via second fluid channels 221 alone, and the first fluid channels 219 may be fluidly isolated from the volume 218 between the plates and the second fluid channels 221. The volume 218 may be fluidly accessible through a side of the showerhead 225.

[0040] FIG. 3 is a bottom view of a showerhead 325 for use with a processing chamber according to embodiments. Showerhead 325 may correspond with the showerhead 225 shown in FIG. 2A. Through-holes 365, which show a view of first fluid channels 219, may have a plurality of shapes and configurations in order to control and affect the flow of precursors through the showerhead 225. Small holes 375, which show a view of second fluid channels 221, may be distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 365, and may help to provide more even mixing of the precursors as they exit the showerhead than other configurations.

[0041] The chamber discussed previously may be used in performing exemplary methods. Turning to FIG. 4, exemplary operations in a method 400 according to embodiments of the present technology are illustrated. Method 400 may include one or more operations prior to the initiation of the method, including front end processing, deposition, gate formation, etching, polishing, cleaning, or any other operations that may be performed prior to the described operations. The method may include a number of optional operations, which may or may not be specifically associated with some embodiments of methods according to the present technology. For example, many of the operations are described in order to provide a broader scope of the processes performed, but are not critical to the technology, or may be performed by alternative methodology as will be discussed further below. Method 400 may describe operations shown schematically in FIGS. 5A-5D, the illustrations of which will be described in conjunction with the operations of method 400. It is to be understood that the figures illustrate only partial schematic views, and a substrate may contain any number of additional materials and features having a variety of characteristics and aspects as illustrated in the figures.

[0042] Method 400 may or may not involve optional operations to develop the semiconductor structure for a particular fabrication operation. It is to be understood that method 400 may be performed on any number of semiconductor structures 500 or substrates 505, as illustrated in FIG. 5A, including exemplary structures on which a metal-containing material, such as a metal nitride, removal operation may be performed. Stacked layers may overly the substrate 505. The stacked layers may include a first material 510 and a second material 515. The first matenal 510 and the second material 515 may be alternated to form pairs of the stacked layers. As illustrated in FIG. 5A, one of the materials may be recessed, such as the second material 515 relative to the first material 510. The first material 510 and the second material 515 may each be any material useful in semiconductor structures, such as dielectric materials, such as silicon, silicon oxide material, silicon nitride material, or silicon germanium material, as well as metal materials that may include metal oxide materials, such as hafnium oxide or aluminum oxide. One or more trenches or features 520 may be formed through the stacked layers overlying the substrate 505. A metal-containing material 525 may be formed in the trenches or features 520 and may extend into recesses defined by the stacked layers, such as into the recesses formed by the recessed portions of the second layer of material 515. In embodiments, the metal-containing material 525 may be a metal-and-nitrogen-containing material. A metal of the metal-containing material 525 may be or include, for example, moly bdenum (Mo), niobium (Nb), titanium (Ti), or tungsten (W). As shown in FIG. 5A. the metal-containing material 525 may be exposed relative to one or more other materials including metal -containing materials including oxides or nitrides thereof, dielectric materials including silicon oxide, silicon nitride, silicon germanium, or any number of other semiconductor materials relative to which the metal-containing material, such as titanium-containing material, is to be removed.

[0043] Although FIG. 5A illustrates only seven layers of material on the substrate 505, the processed structure 500 may include any number of layers of each material, such as up to or greater than about 10, greater than or about 15, greater than or about 20, greater than or about 25, greater than or about 30, greater than or about 35, greater than or about 40, greater than or about 45. greater than or about 50. greater than or about 55. greater than or about 60. greater than or about 65, greater than or about 70, greater than or about 80, greater than or about 90, greater than or about 100, or more layers of materials. This may produce trenches or features 520 with a width of a few hundreds of nanometers, or tens of nanometers, or less, while the height thereof may be on the order of a few microns, or tens of microns, or more. Theresulting aspect ratios, or height to width ratios, of the trenches or features 520 may be greater than 20: 1, greater than 50: 1, greater than 75: 1. greater than 100: 1. or even greater. In embodiments, the trenches or features 520 may be characterized by a width of less than or about 200 nm or less, and / or a depth of greater than or about 5 microns, greater than or about 10 microns, greater than or about 15 microns, greater than or about 20 microns, or more.

[0044] It is to be understood that the noted structure is not intended to be limiting, and any of a variety of other semiconductor structures including metal-containing materials, such as titanium-containing materials, are similarly encompassed. Other exemplary structures may include two-dimensional and three-dimensional structures common in semiconductor manufacturing, and within which a metal-containing material 525, such as a titanium-and-nitrogen-containing material, is to be removed relative to one or more other materials, as the present technology may selectively remove metal-containing materials, such as a titanium-and-nitrogen-containing materials, relative to other exposed materials, such as silicon-containing materials, metal-containing materials, oxides, and other nitrides, as well as any of the other materials discussed elsewhere. Additionally, although a high-aspect-ratio structure may benefit from the present technology, the technology may be equally applicable to lower aspect ratios and any other structures.

[0045] Method 400 may be performed to remove an exposed metal -containing material 525 in embodiments, although any number of metal-containing materials, such as nitrides or titanium-containing materials, may be removed in any number of structures in embodiments of the present technology. The methods may include specific operations for the removal of metal-containing materials, and may include one or more optional operations to prepare or treat the metal-containing materials. For example, an exemplary substrate structure may have previous processing residues on a film to be removed, such as metal-containing material 525. In embodiments, residual photoresist or byproducts from previous processing may reside on the metal-containing material 525. These materials may prevent access to the metalcontaining material 525, or may interact with etchants differently than a clean metalcontaining material 525 surface, which may frustrate one or more aspects of the etching. Accordingly, in some embodiments an optional pre-treatment of the metal-containing material 525 may be performed at optional operation 405. Exemplary pre-treatment operations may include a thermal treatment, wet treatment, or plasma treatment, for example, which may be performed in chamber 200 as well as any number of chambers that may be included in system 100 described above. The pre-treatment operations may remove previousprocessing residues or other materials to provide a clean metal-containing material 525 surface.

[0046] In one exemplary plasma treatment, a remote or local plasma may be developed from a precursor intended to interact with residues in one or more ways. For example, utilizing chambers such as chamber 200 described above, either a remote or local plasma may be produced from one or more precursors. For example, an oxygen-containing precursor, a hydrogen-containing precursor, a nitrogen-containing precursor, a helium-containing precursor, or some other precursor may be flowed into a remote plasma region or into the processing region, where a plasma may be struck. The plasma effluents may be flowed to the substrate, and may contact the residue material. The plasma process may be either phy sical or chemical depending on the material to be removed to expose the metal-containing material. For example, plasma effluents may be flowed to contact and physically remove the residue, such as by a sputtering operation, or the precursors may be flowed to interact with the residues to produce volatile byproducts that may be removed from the chamber.

[0047] Exemplary precursors used in the pre-treatment may be or include hydrogen, a hydrocarbon, water vapor, an alcohol, hydrogen peroxide, or other materials that may include hydrogen as would be understood by the skilled artisan. Exemplary oxygen-containing precursors may be or include atomic oxygen (O), diatomic oxygen (O2), ozone (Os), steam (H2O), nitric oxide (NO), nitrous oxide (N2O), or nitrogen dioxide (NO2), or any other oxygen-containing precursor useful in semiconductor processing. A nitrogen-containing precursor may also be used, or a combination precursor having one or more of hydrogen, oxygen, and / or nitrogen may be utilized to remove particular residues. Once the residue or byproducts have been removed, a clean metal-containing material 525 surface may be exposed for etching.

[0048] At operation 410. method 400 may include providing an oxygen-containing precursor into the processing region of the semiconductor processing chamber housing the substrate 505. In embodiments, the oxy gen-containing precursor may be flowed directly to contact the substrate 505, although in some embodiments a plasma may be formed of the oxygen-containing precursor. The oxygen-containing precursor may be flowed through a remote plasma region of the processing chamber, such as region 215 described above, and a plasma may be formed of the oxy gen-containing precursor to produce plasma effluents. Although a substrate-level plasma may be produced, in some embodiments the plasma maybe a remote plasma, which may protect exposed materials in structure 500 from ion bombardment that may occur due to the substrate-level plasma. Whether plasma-enhanced or not, at operation 415, method 400 may include contacting the substrate 505, including the metal-containing material 525, with the oxygen-containing precursor or plasma effluents of the oxygen-containing precursor. As illustrated in FIG. 5B, the contacting may oxidize the metal-containing material 525 to form a metal-and-oxygen-containing material 530. The metal-and-oxy gen-containing material 530 may be formed by converting an exposed region of metal-containing material 525 to an oxidized version of the metal-containing material 525. Additionally, some portion of the nitrogen in the metal-containing material 525 may be outgassed as one or more volatiles including, but not limited to. diatomic nitrogen, nitrous oxide, nitric oxide, or nitrogen dioxide. In embodiments, subsequent to the contacting at operation 415 and the resultant oxidation, the plasma, if formed, may be extinguished, and the processing region may be purged.

[0049] As previously discussed, after the oxidation, a flow of the oxygen-containing precursor may be halted. The processing region may be purged to remove any residual oxygen-containing precursor or oxidation byproducts. At operation 420, method 400 may include providing a halogen-containing precursor to the processing region. In embodiments, the halogen-containing precursor may be flowed directly to contact the substrate 505, although in some embodiments a plasma may be formed of the halogen-containing precursor. Similar to the oxy gen-containing precursor previously discussed, the halogen-containing precursor may be flowed through a remote plasma region of the processing chamber, such as region 215 described above, and a plasma may be formed of the halogen-containing precursor to produce plasma effluents. Again, although a substrate-level plasma may be produced, in some embodiments the plasma may be a remote plasma, which may protect exposed materials in structure 500 from ion bombardment that may occur due to the substrate-level plasma. Whether plasma-enhanced or not, at operation 425, method 400 may include contacting the substrate 505, including the metal-and-oxygen-containing material 530, with the halogen-containing precursor or plasma effluents of the halogen-containing precursor. As illustrated in FIG. 5C, the contacting may etch the metal-and-oxygen-containing material 530. The contacting may selectively remove the metal-and-oxygen-containing material 530 relative to other materials on the substrate 505. Additionally, the contacting may only remove the metal-and-oxygen-containing material 530 with the metal-containing material 525 serving as an etch stop layer, limiting the etch and maintaining precise control of theetch. In embodiments, subsequent to the contacting at operation 425 and the resultant etching, the plasma, if formed, may be extinguished, and the processing region may be purged.

[0050] After the etching, a flow of the halogen-containing precursor may be halted. The processing region may be purged to remove any residual halogen-containing precursor or etch byproducts. An optional operation may be performed to clear the substrate or chamber of residues and may include a post-treatment at optional operation 430. The post-treatment may include similar operations as the pre-treatment at optional operation 405, and may include any of the precursors or operations discussed above for the pre-treatment at optional operation 405. The post-treatment may clear residual etchant from the substrate or chamber in some embodiments. It is to be understood that although the pre-treatment and / or posttreatment may include plasma generation and plasma effluent delivery to the processing region, plasma may or may not be formed during operations 410-425. For example, in some embodiments, no plasma may be generated while the oxygen-containing precursor and halogen-containing precursor or precursors are being delivered into the processing chamber.

[0051] The oxidation at operations 410-415 and the etching at operations 420-425 may then be repeated in any number of cycles to remove additional metal-containing material 525 selectively to exposed materials on the substrate 505. More specifically, method 400 may include alternating (i) providing the oxygen-containing precursor to the processing region of the semiconductor processing chamber and contacting the substrate with the oxygencontaining precursor and (ii) providing the halogen-containing precursor to the processing region of the semiconductor processing chamber and contacting the substrate with the halogen-containing precursor to iteratively etch the metal -containing material 530. For example, the operations may be repeated for two cycles, three cycles, four cycles, five cycles, ten cycles, fifteen cycles, twenty-five cycles, fifty cycles, one hundred cycles, or more to iteratively remove metal-containing material 525. Each cycle may be the same as the previous cycle or may be different. For example, each cycle may include each of operations 405-430. Alternatively, cycles may not include either or both of the pre-treatment at optional operation 405 and the post-treatment at optional operation 430. As illustrated in FIG. 5D, the operations may be repeated for any number of cycles to etch the metal -containing material 525 to result in metal-containing material 525 remaining in recesses defined by the first material 510 and the second material 515.

[0052] While embodiments of the present technology may include alternating (i) providing the oxy gen-containing precursor and (ii) providing the halogen-containing precursor, as previously discussed, it is also contemplated that the oxy gen-containing precursor and the halogen-containing precursor may be provided together. For example, the oxygen-containing precursor may be provided from the gas box, through the showerhead, and into the processing region. Simultaneously, the halogen-containing precursor may be provided in a similar manner. Alternatively, the halogen-containing precursor may be provided through a side of the showerhead 225. In such an embodiment, unlike alternating the oxy gen-containing precursor and the halogen-containing precursor, the precursors may be provided simultaneously, or co-flowed, to the processing region.

[0053] Oxygen-containing precursors provided at operation 410 may include, but are not limited to, O, O2, O3, H2O. NO, N2O, or NO2. The oxy gen-containing precursor may be selected based on oxidative ability. Some oxygen-containing precursors may oxidize an increased thickness of the metal-containing material. For example, O2 may be a weaker oxidant compared to O3. Additionally, non-plasma enhanced oxygen-containing precursors may oxidize a reduced thickness of the metal-containing material. As such, the oxygencontaining precursor may be selected based on the desired degree of oxidation. The oxygen-containing precursor may also be provided with any number of carrier gases, which may include nitrogen (N), helium (He), argon (Ar), xenon (Xe), or other noble, inert, or useful precursors. The carrier gases may serve to dilute the oxy gen-containing precursor, which may control oxidation, as well as distribute the oxygen-containing precursor.

[0054] Flow rates of the oxy gen-containing precursor may be tuned, including in situ, to control the etch process. In embodiments, a flow rate of the oxy gen-containing precursor may be between about 5 seem and about 1,000 seem. For example, the flow rate of the oxygen-containing precursor may be maintained below or about 900 seem, below or about 800 seem, below or about 700 seem, below or about 600 seem, below or about 500 seem, below or about 400 seem, below or about 300 seem, below or about 200 seem, below or about 100 seem, or less. Additionally, the flow rate of the oxygen-containing precursor may be maintained at greater than or about 10 seem, greater than or about 25 seem, greater than or about 50 seem, greater than or about 75 seem, greater than or about 100 seem, greater than or about 250 seem, greater than or about 500 seem, greater than or about 750 seem, or more. The flow rate may also be between any of these stated flow rates, or within smaller ranges encompassed by any of these numbers. The flow rate of the oxy gen-containing precursormay be reduced, maintained, or increased during operation 415 or during individual cycles of method 400. By increasing the flow rate of the oxygen-containing precursor, oxidation may be increased up to a point of saturation. By reducing the flow rate of the oxy gen-containing precursor, a reduced amount of metal-containing material 525 may be oxidized, resulting in a reduced thickness of metal-and-oxygen-containing material 530, and more limited and precise removal.

[0055] Based on the oxygen-containing precursor and process conditions, the oxidation may be limited to a depth of the metal -containing material 530 of less than or about 10 A, and may be limited to a depth of less than or about 9 A, less than or about 8 A, less than or about 7 A, less than or about 6 A, less than or about 5 A, less than or about 4 A, less than or about 3 A, less than or about 2 A, or less. Conversely, when using a stronger oxidant, the oxidation may be increased to a depth of the metal-containing material 530 of greater than or about 1 nm, and may be limited to a depth of greater than or about 1.2 nm, greater than or about 1.4 nm, greater than or about 1.6 nm, greater than or about 1.8 nm, greater than or about 2 nm, greater than or about 2.5 nm, greater than or about 3 nm, greater than or about 3.5 nm, greater than or about 4 nm, greater than or about 4.5 nm, greater than or about 5 nm. greater than or about 5.5 nm, greater than or about 6 nm, greater than or about 6.5 nm, greater than or about 7 nm, greater than or about 7.5 nm, greater than or about 8 nm, or more.

[0056] Once metal-and-oxygen-containing material 530 has been produced, no further oxidation of metal-containing material 525 may occur. This may limit the subsequent etch to substantially halt after metal-and-oxygen-containing material 530 has been removed, which may provide precise control over the depth at which the metal-containing material 525 is removed, and which may allow controlled thinning and removal without damaging underlying materials as a substantially self-limiting etch process. Accordingly, techniques according to aspects of the present technology may be performed to remove metal-containing material 525 from narrow features, as well as high aspect ratio features, and thin dimensions that may otherwise be unsuitable for wet etching or reactive ion etching.

[0057] The halogen-containing precursor provided at operation 420 may be a fluorine-containing precursor, a chlorine-containing precursor, or any other halogen-containing precursor. Exemplary fluorine-containing precursors may be or include diatomic fluorine (F2), nitrogen trifluoride (NF3), tungsten hexafluoride (WFe), or other fluorine-containing precursors useful in semiconductor processing. Exemplary chlorine-containing precursorsmay be or include diatomic chlorine (Ch), boron trichloride (BCh). thionyl chloride (SOCh), or other chlorine-containing precursors useful in semiconductor processing. The halogencontaining precursor may also be provided with any number of carrier gases, which may include N, He, Ar, Xe, or other noble, inert, or useful precursors. The carrier gases may serve to dilute the halogen-containing precursor, which may control etching and maintain selectivity, as well as distribute the halogen-containing precursor.

[0058] Flow rates of the halogen-containing precursor may also be tuned, including in situ, to control the etch process. For example, a flow rate of the halogen-containmg precursor may be reduced, maintained, or increased during operation 425 or during individual cycles of method 400. By increasing the flow rate of the etchant precursor, etch rates may be increased up to a point of saturation. The flow rate of the halogen-containing precursor may be between about 5 seem and about 1,000 seem. For example, the flow rate of the halogencontaining precursor may be maintained below or about 900 seem, below or about 800 seem, below or about 700 seem, below or about 600 seem, below or about 500 seem, below or about 400 seem, below or about 300 seem, below or about 200 seem, below or about 100 seem, or less. Additionally, the flow rate of the halogen-containing precursor may be maintained at greater than or about 10 seem, greater than or about 25 seem, greater than or about 50 seem, greater than or about 75 seem, greater than or about 100 seem, greater than or about 250 seem, greater than or about 500 seem, greater than or about 750 seem, or more. The flow rate may also be between any of these stated flow rates, or within smaller ranges encompassed by any of these numbers.

[0059] While FIG. 2A illustrates multiple components between the gas inlet assembly 205 and the showerhead 225, method 400 may be performed in a simpler chamber without components between the gas inlet assembly 205 and the showerhead 225. As such, one or more of the precursors, such as the oxygen-containing precursor provided at operation 410, may be provided from the gas box of the semiconductor processing chamber, through the showerhead defining an upper surface of the processing region, and into the processing region. As such, the gas box of the semiconductor processing chamber may be seated on the showerhead defining the upper portion of the processing region. The gas box may be seated directly or indirectly on the showerhead. In this manner, one or more of the precursors, such as the oxygen-containing precursor, may be provided without passing an intervening gas flow component. Intervening gas flow components may be any component that impacts or substantially impacts gas flow. Impacting gas flow is to be understood to mean any sort ofchange in gas flux, distribution, etc. Even if the gas box is not seated directly on the showerhead, such that the gas box is indirectly seated on the showerhead, any intervening component may not alter flow of the precursor being provided. Examples of components that do not impact gas flow include, but are not limited to, spacers or other annular components that do not impact or substantially impact gas flow. Examples of components that do impact gas flow include may include, but are not limited to, blockers, faceplates, ion filters, etc.

[0060] As previously discussed, some of the precursors may be provided from the gas box, through the showerhead, and into the processing region. For example, the oxy gen-containing precursor may be provided from the gas box, through the showerhead, and into the processing region. The halogen-containing precursor may be provided in a similar manner.Alternatively, the halogen-containing precursor may be provided through a side of the showerhead 225. such as previously discussed in FIG. 2A. As such, the precursors may be provided in the same manner or may be provided differently.

[0061] Processing conditions may impact and facilitate oxidation and etching according to the present technology. Because the etch reaction may proceed based on thermal dissociation of a halogen from the halogen-containing precursor, the temperatures may be at least partially dependent on the particular halogen and / or other atoms of the etchant precursor in order to initiate dissociation. As temperature increases above or about 250 °C, for example, etching begins to occur or increase, which may indicate dissociation of the precursor, and / or activation of the reaction with metal-and-oxygen-containing material 530. As temperature continues to increase, dissociation may be further facilitated as may the reaction with metal-and-oxygen-containing material 530.

[0062] Accordingly, in some embodiments of the present technology, the method 400 may be performed at substrate, pedestal, and / or chamber temperatures less than or about 450 °C, and may be performed at temperatures less than or about 440 °C, less than or about 430 °C, less than or about 420 °C, less than or about 410 °C, less than or about 400 °C. less than or about 390 °C, less than or about 380 °C, less than or about 370 °C, less than or about 360 °C, less than or about 350 °C, or lower. The temperature may also be maintained at any temperature within these ranges, within smaller ranges encompassed by these ranges, or between any of these ranges. In some embodiments the method may be performed on substrates that may have a number of produced features, which may produce a thermal budget. In embodiments, a greater temperature may increase etching of the metal-containingmaterial 525. Accordingly, in some embodiments, the methods may be performed at temperatures greater than or about 150 °C, and may be performed at temperatures greater than or about 200 °C, greater than or about 250 °C, greater than or about 300 °C, greater than or about 310 °C, greater than or about 320 °C, greater than or about 330 °C, greater than or about 340 °C, greater than or about 350 °C, greater than or about 360 °C, or higher.Additionally, increased temperatures may increase the amount of oxidation and, therefore, throughput.

[0063] The pressure within the chamber may also affect the operations performed as well as affect at what temperature the etchant precursor may dissociate. Accordingly, in some embodiments the pressure may be maintained above or about 0.5 Torr, above or about 1 Torr, above or about 2 Torr, above or about 3 Torr, above or about 4 Torr, above or about 5 Torr, above or about 6 Torr, above or about 7 Torr, above or about 8 Torr, above or about 9 Ton, above or about 10 Torr, above or about 15 Torr, above or about 20 Torr, above or about 25 Torr, above or about 30 Torr, above or about 40 Torr, above or about 50 Torr, above or about 60 Torr, above or about 70 Torr, above or about 80 Torr, or higher. Additionally, the pressure may be maintained below or about 100 Torr, and may be maintained at below or about 90 Torr, below or about 80 Torr, below or about 70 Torr, below or about 60 Torr, below or about 50 Torr, below or about 40 Torr, below or about 30 Torr, below or about 25 Torr, below or about 20 Torr, below or about 15 Torr, below or about 10 Torr, below or about 9 Torr, below or about 8 Torr, below or about 7 Torr, below or about 6 Torr, below or about 5 Torr, below or about 4 Torr, below or about 3 Torr, below or about 2 Torr, below or about 1 Torr, below or about 0. 1 Torr, or less. The pressure may also be maintained at any pressure within these ranges, within smaller ranges encompassed by these ranges, or between any of these ranges. Higher pressures, such as greater than or about 30 Torr or more, including the previous ranges, may be increase efficiency of thermal, non-plasma enhanced oxidation and / or etching operations. Conversely, plasma-enhanced oxidation and / or etching operations may be performed at lower pressures, such as below or about 20 Torr, including the previous ranges. Lower pressure may allow for increased mean free path of plasma effluents and increased oxidation and / or etching effect.

[0064] Without being bound to any particular theory, pressure within the chamber may affect processing with precursors described above. At low pressures, flow across a substrate may be reduced, and dissociation may similarly be reduced. As pressure increases, interactions between the halogen-containing precursor and the metal-and-oxygen-containingmaterial 530 may increase, which may increase etch rates. However, as pressure continues to increase, recombination of the halogen-containing precursor atoms may increase due to the relative stability of the molecules. Thus, the precursors may effectively be pumped back out of the chamber without reacting with the metal-and-oxygen-containing material 530.Additionally, interactions with the metal-and-oxygen-containing material 530 may be suppressed as pressure continues to increase, or byproduct material may be reintroduced to the metal-containing material 525 and / or the metal-and-oxygen-containing material 530. further limiting removal.

[0065] By performing operations according to embodiments of the present technology, metal-containing materials may be etched selectively relative to other materials, including other oxides or nitrides. For example, the present technology may selectively etch metalcontaining materials, such as titanium-and-nitrogen-containing materials, relative to exposed regions of other metals, dielectrics including silicon-containing materials including silicon oxide, or other materials. Embodiments of the present technology7may etch metal-containing materials, such as titanium-and-nitrogen-containing materials, relative to silicon oxide or any of the other materials that have been mentioned at a rate of greater than or about 2: 1. greater than or about 3: 1, greater than or about 4: 1, greater than or about 5: 1, greater than or about 6: 1, greater than or about 7: 1, greater than or about 8: 1, greater than or about 9: 1 , greater than or about 10: 1, greater than or about 15: 1, greater than or about 20: 1, greater than or about 25: 1, greater than or about 30: 1, greater than or about 35: 1, greater than or about 40: 1, greater than or about 45: 1. greater than or about 50: 1. or more. For example, etching performed according to some embodiments of the present technology may etch metal -containing material 530, such as titanium-and-nitrogen-containing material that has been oxidized to titanium-and-oxygen-containing material, while substantially or essentially maintaining silicon oxide or other materials, such as nitrides or oxides of silicon, aluminum, or hafnium, metals such as tungsten or molybdenum, or materials such as polysilicon for example.

[0066] Selectivity may be based in part on precursors used and the ability to dissociate at more controlled temperature ranges. Conventional dry etchants may be incapable of producing etch selectivities of embodiments of the present technology. Similarly, because wet etchants readily remove silicon oxide, wet etchants may also be incapable of etching selectively at rates comparable to embodiments of the present technology. The previously discussed methods may allow the removal of various metal -containing materials, such as a titanium-containing material or a titanium-and-nitrogen-containing material, relative to anumber of other exposed materials. By utilizing etchants at operating conditions as previously described, improved etching of metal-containing material may be performed, which may both increase selectivity over conventional techniques, as well as improve etching access in small pitch features.

[0067] In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details.

[0068] Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present technology. Accordingly, the above description should not be taken as limiting the scope of the technology. Additionally, methods or processes may be described as sequential or in steps, but it is to be understood that the operations may be performed concurrently, or in different orders than listed.

[0069] Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherw ise, between the upper and lower limits of that range is also specifically disclosed. Any narrow er range betw een any stated values or unstated intervening values in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the technology, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0070] As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, reference to “a precursor” includes a plurality of such precursors, and reference to “the material” includes reference to one or more materials and equivalents thereof known to those skilled in the art. and so forth. “About” and / or “approximately” as used herein when referring to a measurable value such as an amount, a temporal duration, and the like,encompasses variations of ±20% or ±10%, ±5%, or ±0.1% from the specified value, as such variations are appropriate to in the context of the systems, devices, circuits, methods, and other implementations described herein. “Substantially’’ as used herein when referring to a measurable value such as an amount, a temporal duration, a physical attribute (such as frequency), and the like, also encompasses variations of ±20% or ±10%, ±5%, or ±0.1% from the specified value, as such variations are appropriate to in the context of the systems, devices, circuits, methods, and other implementations described herein.

[0071] Also, the words “comprise(s)”, “comprising”, “contain(s)”, “containing”, “include(s)”, and “including”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or operations, but they do not preclude the presence or addition of one or more other features, integers, components, operations, acts, or groups.

Claims

CLAIMS:

1. A semiconductor processing method comprising:providing an oxy gen-containing precursor to a processing region of a semiconductor processing chamber, wherein a metal-containing material is disposed on a substrate housed within the processing region, and wherein the oxy gen-containing precursor is provided from a gas box of the semiconductor processing chamber, through a showerhead defining an upper surface of the processing region, and into the processing region without passing an intervening gas flow component;contacting the substrate with the oxygen-containing precursor to oxidize a portion of the metal-containing material to form a metal-and-oxy gen-containing material;providing a halogen-containing precursor to the processing region of the semiconductor processing chamber; andcontacting the substrate with the halogen-containing precursor to etch the metal-and-oxy gen-containing material.

2. The semiconductor processing method of claim 1, wherein the metalcontaining material comprises a metal-and-nitrogen-containing material.

3. The semiconductor processing method of claim 1, wherein a metal of the metal-containing material comprises molybdenum (Mo), niobium (Nb), titanium (Ti), or tungsten (W).

4. The semiconductor processing method of claim 1, wherein the oxy gencontaining precursor comprises atomic oxygen (O), diatomic oxygen (O2), ozone (O3), steam (H2O), nitric oxide (NO), nitrous oxide (N2O), or nitrogen dioxide (NO2).

5. The semiconductor processing method of claim 1, further comprising: forming plasma effluents of oxy gen-containing precursor prior to providing the oxygen-containing precursor to the processing region of the semiconductor processing chamber.

6. The semiconductor processing method of claim 1, w herein a silicon -containing material, a second metal-and-oxygen-containing material, or both are disposed on the substrate.

7. The semiconductor processing method of claim 1, wherein the metal -and-oxygen-containing material is characterized by a thickness of greater than or about 2 nm.

8. The semiconductor processing method of claim 1, further comprising: halting a flow of the oxygen-containing precursor prior to providing the halogen-containing precursor to the processing region of the semiconductor processing chamber.

9. The semiconductor processing method of claim 1, wherein the halogen-containing precursor comprises diatomic chlorine (CI2), diatomic fluorine (F2), boron trichloride (BCk), thionyl chloride (SOCI2), nitrogen trifluoride (NFs), or tungsten hexafluoride (WFe).

10. The semiconductor processing method of claim 1, wherein the processing region is maintained plasma-free while providing the halogen-containing precursor and contacting the substrate with the halogen-containing precursor.

11. The semiconductor processing method of claim 1 , wherein a temperature of a pedestal supporting the substrate is maintained at greater than or about 150 °C.

12. The semiconductor processing method of claim 1, wherein a pressure within the processing region is maintained at greater than or about 1 Torr.

13. The semiconductor processing method of claim 1, further comprising: alternating (i) providing the oxygen-containing precursor to the processing region of the semiconductor processing chamber and contacting the substrate with the oxygen-containing precursor and (ii) providing the halogen-containing precursor to the processing region of the semiconductor processing chamber and contacting the substrate with the halogen-containing precursor to iteratively etch the metal-containing material.

14. A semiconductor processing method comprising:providing an oxy gen-containing precursor and a halogen-containing precursor to a processing region of a semiconductor processing chamber, wherein a metal-and-nitrogen-containing material is disposed on a substrate housed within the processing region, and wherein the oxy gen-containing precursor is provided from a gas box of the semiconductorprocessing chamber to the processing region without passing an intervening gas flow component; andcontacting the substrate with the oxygen-containing precursor and the halogen-containing precursor to oxidize a portion of the metal-and-nitrogen-containing material to form a metal-and-oxygen-containing material and to etch the metal-and-oxygen-containing material.

15. The semiconductor processing method of claim 14, wherein the gas box of the semiconductor processing chamber is seated on a showerhead defining an upper portion of the processing region.

16. The semiconductor processing method of claim 14, wherein the metal-and-nitrogen-containing material comprises a titanium-and-nitrogen-containing material.

17. The semiconductor processing method of claim 14, wherein the processing region is maintained plasma-free.

18. A semiconductor processing method comprising:i) providing an oxy gen-containing precursor to a processing region of a semiconductor processing chamber, wherein a titanium-and-nitrogen-containing material is disposed on a substrate housed within the processing region, and wherein a gas box of the semiconductor processing chamber is seated on a showerhead defining an upper portion of the processing region;ii) contacting the substrate with the oxy gen-containing precursor to oxidize a portion of the titanium-and-nitrogen-containing material to form a titanium-and-oxygen-containing material;iii) halting a flow of the oxy gen-containing precursor;iv) providing a halogen-containing precursor to the processing region of the semiconductor processing chamber; andv) contacting the substrate with the halogen-containing precursor to etch the titanium-and-oxy gen-containing material.

19. The semiconductor processing method of claim 18, wherein a pressure within the processing region is maintained at greater than or about 10 Torr.

20. The semiconductor processing method of claim 18, further comprising:repeating operations i) through v) for a plurality of cycles.

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