WO2021067362A1 - Gravure sélective verticale de cobalt - Google Patents

Gravure sélective verticale de cobalt Download PDF

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Publication number
WO2021067362A1
WO2021067362A1 PCT/US2020/053411 US2020053411W WO2021067362A1 WO 2021067362 A1 WO2021067362 A1 WO 2021067362A1 US 2020053411 W US2020053411 W US 2020053411W WO 2021067362 A1 WO2021067362 A1 WO 2021067362A1
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Prior art keywords
cobalt
plasma
substrate
containing precursor
containing material
Prior art date
Application number
PCT/US2020/053411
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English (en)
Inventor
Zhenjiang Cui
Ryo Wakabayashi
Anchuan Wang
Nitin K. Ingle
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Applied Materials, Inc.
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Publication date
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Publication of WO2021067362A1 publication Critical patent/WO2021067362A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F4/00—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32357—Generation remote from the workpiece, e.g. down-stream
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32422—Arrangement for selecting ions or species in the plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3244—Gas supply means
    • H01J37/32449—Gas control, e.g. control of the gas flow

Definitions

  • the present technology relates to gas-phase etching cobalt metal. More specifically, the present technology relates to selectively etching cobalt with directionality.
  • 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 variety of 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 which etches one material faster than another helping e.g. a pattern transfer process proceed. 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.
  • Dry etch processes are often desirable for selectively removing material from semiconductor substrates. The desirability stems from the ability to gently remove material from minute structures with minimal physical disturbance. Dry etch processes also allow the etch rate to be abruptly stopped by removing the gas phase reagents. However, dry-etch processes are still needed, which delicately remove metals directionally, e.g., vertically, while substantially maintaining the metal laterally. [0005] 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.
  • Exemplary methods for selectively etching cobalt-containing material from a substrate may include forming a plasma of a carbon-containing precursor in a substrate processing region housing the substrate.
  • the substrate may include exposed cobalt-containing material.
  • the methods may include forming a conformal carbon-containing film on the exposed cobalt- containing material.
  • the methods may include forming a local plasma of a hydrogen-containing precursor in the substrate processing region.
  • the methods may include removing a portion of the carbon-containing film to expose at least a portion of a surface of the cobalt-containing material.
  • the methods may include forming a local plasma of a chlorine-containing precursor in the substrate processing region to produce chlorine-containing plasma effluents.
  • the methods may include contacting the exposed portion of the surface of the cobalt-containing material with the chlorine-containing plasma effluents to form cobalt chloride complexes.
  • the methods may include flowing a nitrogen-containing precursor into the processing region and contacting the cobalt chloride complexes with the nitrogen-containing precursor.
  • the methods may include recessing the surface of the cobalt-containing material.
  • the methods may be repeated for at least two cycles to achieve a desired etch depth.
  • the carbon-containing precursor may be or include a hydrocarbon, or a carbon-and-nitrogen-containing precursor.
  • Plasma effluents of the hydrogen-containing precursor may be accelerated toward the surface of the cobalt-containing material by biasing the local plasma relative to the substrate.
  • a chlorinated cobalt residue may remain subsequent the recessing.
  • the methods may include a post-treatment to remove the chlorinated cobalt residue.
  • the post-treatment may include forming a local plasma of a hydrogen-containing precursor.
  • the post-treatment may include removing the chlorinated cobalt residue using plasma effluents of the hydrogen-containing precursor.
  • the post-treatment may include forming a local plasma of a nitrogen-containing precursor.
  • the post-treatment may include removing the chlorinated cobalt residue with plasma effluents of the nitrogen-containing precursor.
  • the post-treatment may include forming a local plasma of a hydrogen-containing precursor.
  • the post-treatment may include removing residual chlorine residue with plasma effluents of the hydrogen-containing precursor.
  • the hydrogen-containing precursor may be or include Th.
  • the carbon-containing precursor may be or include tetramethylethylenediamine.
  • the carbon-containing film may be, include, or consist of carbon, nitrogen, and hydrogen. Subsequent to removing the carbon-containing film locally to expose the surface of the cobalt- containing material, the carbon-containing film may be at least partially maintained on sidewalls composed of at least one of cobalt-containing material or silicon oxide hard mask material, the sidewalls adjacent to and extending vertically from the exposed surface.
  • the cobalt-containing material may be substantially planar, and the method may recess the cobalt-containing material vertically into the substrate.
  • a hard mask may overly the cobalt-containing material, and may define an opening to expose a surface of the cobalt-containing material. The methods may form a recess vertically into the cobalt-containing material.
  • Some embodiments of the present technology may encompass methods of selectively etching cobalt-containing material from a substrate.
  • the methods may include forming a plasma of an oxygen-containing precursor in a substrate processing region housing the substrate.
  • the substrate may include exposed cobalt-containing material.
  • the methods may include forming a conformal oxide-containing film on the exposed cobalt-containing material.
  • the methods may include flowing a chlorine-containing precursor into the substrate processing region while forming a local plasma of the chlorine-containing precursor to produce chlorine-containing plasma effluents.
  • the methods may include contacting the exposed surface of the cobalt- containing material with the chlorine-containing plasma effluents to form cobalt chloride complexes.
  • the methods may include flowing a nitrogen-containing precursor into the substrate processing region and contacting the cobalt chloride complexes with the nitrogen-containing precursor.
  • the methods may include recessing the surface of the cobalt-containing material.
  • the methods may be repeated for at least two cycles to achieve a desired etch depth.
  • the methods may include, subsequent to forming the oxide-containing film, flowing a hydrogen-containing precursor into the substrate processing region while forming a local plasma from the hydrogen-containing precursor to form hydrogen-containing plasma effluents.
  • the methods may include removing the oxide-containing film from the cobalt- containing material with the hydrogen-containing plasma effluents.
  • the substrate may include a hard mask thereon, the hard mask defining an opening to expose a horizontal surface of the cobalt-containing material. The methods may form a recess vertically into the substrate without expanding laterally.
  • the exposed cobalt-containing material may be substantially planar and the methods may form a recess vertically into the substrate without expanding laterally.
  • the exposed cobalt-containing material may include a silicon oxide hard mask thereon.
  • the mask may define an opening to expose a horizontal surface of the cobalt-containing material.
  • the methods may form a recess vertically into the cobalt-containing material while limiting lateral expansion [0011]
  • Such technology may provide numerous benefits over conventional systems and techniques. For example, the processes may produce a controlled etch of partial regions of cobalt material. Additionally, the methods may perform a more uniform recess of cobalt materials from substrate.
  • FIG. 1 shows a top plan view of one embodiment of an exemplary processing system according to embodiments of the present technology.
  • FIG. 2A shows a schematic cross-sectional view of an exemplary processing chamber according to embodiments of the present technology.
  • FIG. 2B shows a detailed view of a portion of the processing chamber illustrated in FIG. 2A according to embodiments of the present technology.
  • FIG. 3 shows a bottom plan view of an exemplary showerhead according to embodiments of the present technology.
  • FIG. 4 shows exemplary operations in a method according to embodiments of the present technology.
  • FIGS. 5A-5E show cross-sectional views of substrates being processed according to embodiments of the present technology.
  • FIGS. 6A-6E show cross-sectional views of substrates configuration being processed according to embodiments of the present technology.
  • Cobalt may be in the form of a blanket layer on a substrate or cobalt may reside in discrete regions of a patterned substrate surface.
  • the substrate structure may be planar or substantially planar or may include hard masking thereon.
  • the hard mask may be or include any number of materials to allow selective removal relative to cobalt, and in some embodiments the hard mask material may be, for example, silicon oxide.
  • the exposed surfaces of the substrate including cobalt-containing material are deposited with a protective film. The film may be removed locally to expose the cobalt-containing material only in the area upon which recessing is desired.
  • FIG. 1 showing a top plan view of one embodiment of a processing system 100 of deposition, etching, baking, and curing chambers according to embodiments.
  • 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.
  • FOUPs front opening unified pods
  • 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 layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation, and other substrate processes.
  • CLD cyclical layer deposition
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • etch pre-clean, degas, orientation, and other substrate processes.
  • the substrate processing chambers 108a-f may include one or more system components for depositing, annealing, curing and/or etching a dielectric or metallic film on the substrate wafer.
  • two pairs of the processing chambers e.g., 108c-d and 108e-f
  • the third pair of processing chambers e.g., 108a-b
  • all three pairs of chambers e.g., 108a-f
  • Any one or more of the processes described may be carried out in chamber(s) separated from the fabrication system shown in different embodiments.
  • FIG. 2A shows a cross-sectional view of an exemplary process chamber system 200 with partitioned plasma generation regions within the processing chamber.
  • film etching e.g., titanium nitride, tantalum nitride, tungsten, copper, cobalt, silicon, polysilicon, 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.
  • a cooling plate 203, faceplate 217, ion suppressor 223, showerhead 225, and a substrate support 265, 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 be or 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 600° C, using an embedded resistive heater element.
  • 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 additionally be flat as shown and include a plurality of through-channels used to distribute process gases.
  • Plasma generating gases and/or plasma excited species 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.
  • 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.
  • the ion suppressor 223 may be 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 allowing uncharged neutral or radical species to pass through the ion suppressor 223 into an activated gas delivery region between the suppressor and the showerhead.
  • the ion suppressor 223 may be 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.
  • adjustments in the ion concentration of the gas mixture can significantly alter its etch selectivity, e.g., SiNx:SiOx etch ratios, Si:SiOx etch ratios, etc.
  • it can also shift the balance of conformal-to-flowable style depositions for dielectric materials.
  • 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.
  • 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 may be 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 suppressor 223, 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.
  • 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.
  • FIG. 2B shows a detailed view 253 of the features affecting the processing gas distribution through faceplate 217.
  • 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.
  • 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.
  • the showerhead 225 may be 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 gas distribution assembly 225.
  • 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.
  • a substrate Prior to the first operation of the method, a substrate may be processed in one or more ways before being placed within a processing region of a chamber in which method 400 may be performed. For example, features may be produced, and vias or trenches may be formed or defined within the substrate.
  • the vias or trenches may have an aspect ratio, or a ratio of their height to width, greater than or about 2, greater than or about 5, greater than or about 10, greater than or about 20, greater than or about 30, greater than or about 50, or more in embodiments.
  • a first portion of cobalt may be deposited within a processing chamber positioned on a processing tool.
  • a flow of a precursor suitable to form local plasma and plasma effluents for forming a protective film may be introduced into the substrate processing region in operation 405.
  • a carbon-containing precursor may be flowed into the substrate processing region in operation 405 of cobalt etch process 400.
  • the carbon-containing precursor may include a hydrocarbon, such as methane, ethane, or any other hydrocarbon.
  • the carbon-containing precursor may also be or include a carbon-and-nitrogen-containing precursor.
  • the carbon-and- nitrogen-containing precursor may include or consist of carbon, nitrogen, and hydrogen in embodiments.
  • the carbon-and-nitrogen-containing precursor may include at least two, three, or four methyl groups according to embodiments.
  • An exemplary carbon-and-nitrogen-containing precursor may be or include tetramethylethylenediamine (“TMEDA”).
  • TMEDA may be dissociated in the local plasma to form a carbon-containing film over the substrate surface as in operation 410.
  • the surface may be planar or substantially planar or have an irregular topography including vias or trenches.
  • the protective film may be formed conformally onto the substrate surface.
  • the protective film may be a carbon-containing film, which may be a hydrocarbon film or a film containing carbon, hydrogen, and nitrogen.
  • a hydrogen precursor may be flowed into the substrate processing region in operation 405 of cobalt etch process 400, which may be a flow of hydrogen (Th) or may be oxygen-free and/or carbon-free according to embodiments.
  • the hydrogen precursor forms a local plasma to reduce the cobalt to form a conformal oxide-containing film on the exposed cobalt-containing material to form the protective film as in operation 410.
  • the oxide-containing protective film may be a film containing cobalt and oxygen or a cobalt oxide.
  • the chamber in which the protective film deposition is performed may be on the same tool as an etching chamber used in method 400, or in embodiments may be on a different tool than the chamber used in method 400. In some embodiments, both formation of the protective film and the etching process may occur within the same chamber, such as chamber 200 described above, and transfer between the chambers may occur without breaking vacuum.
  • the deposition onto the substrate surface may include the sidewalls and bottom of a recess. This bottom may be referred to as a horizontal surface or surface to which selective etching is targeted of cobalt etch process 400.
  • a planar or substantially planar surface may utilize a hard mask, which may be silicon oxide.
  • a portion of the substrate surface may remain exposed, such as an exposed cobalt- containing material which is then covered by the protective film at operation 410 as well as sidewalls that are at least one of hard mask material and or the cobalt-containing substrate surface material.
  • an amount of carbon- containing or oxide-containing protective film may be formed or deposited at the bottom of the recess and along the sidewalls or onto the exposed surface left by the hard mask material.
  • Method 400 may include flowing a precursor into a processing region of a semiconductor processing chamber at operation 415.
  • the processing region may be region 233 of chamber 200 previously discussed, where the substrate including a portion of cobalt- containing material may be housed, at least a portion of the cobalt-containing material may be covered with a protective film as in operation 410.
  • a treatment with a hydrogen-containing precursor forming plasma effluents may remove only a portion of the protective film from the substrate surface as targeted or desired.
  • only a portion of the protective film may be removed on surfaces normal to the direction of delivery, while other surface, such as sidewalls for example, may have the protective film maintained.
  • the hydrogen treatment may include contacting the substrate with effluents of a hydrogen-containing plasma at operation 415.
  • the plasma effluents may remove locally the protective film to expose a horizontal cobalt surface such as between the hard mask or the bottom of a recess at operation 420.
  • the hydrogen treatment may be performed in the same chamber as the other operations of method 400 such that the entire method 400 may be performed in a single chamber, such as chamber 200 as previously described. Additionally, in some embodiments one or more operations may be performed in a different chamber as other operations of method 400.
  • the hydrogen treatment at operation 415 may include forming the plasma effluents remotely or at the substrate level.
  • the hydrogen-containing precursor may be flowed into a remote plasma region, such as a remote plasma unit, or a remote section of a processing chamber, such as region 215 discussed previously with respect to chamber 200.
  • the hydrogen-containing precursor may be flowed into the processing region in which the substrate is housed, and a plasma may be formed.
  • the hydrogen plasma effluents are accelerated toward the substrate in operation 420 to selectively expose a cobalt-containing surface, i.e. a horizontal surface.
  • the plasma may be a bias plasma formed within the chamber region that may direct plasma effluents to the substrate surface and provide low- energy ion bombardment to the substrate.
  • the hydrogen plasma effluents may optionally interact with impurities and residue materials and remove them from exposed cobalt surfaces within the recess, including sidewalls and material along the bottom of the recess.
  • Hydrogen formed by plasma processes may not interact with cobalt, and may not affect the cobalt on which the residue may be located. In this way, the cobalt surfaces may be cleared of residue material prior to additional deposition material or reflow, which may maintain a high quality cobalt fill.
  • Method 400 may include flowing a precursor into a processing region of a semiconductor processing chamber at operation 425.
  • the precursor may be or include a chlorine-containing precursor in embodiments.
  • a halogen-containing precursor may also be used instead or to augment the chlorine-containing precursor.
  • a halogen-containing precursor may be used in place of the chlorine-containing precursor of cobalt etch process 400.
  • the halogen-containing precursor may include at least one of chlorine or bromine in embodiments.
  • the halogen-containing precursor may be a diatomic halogen, a homonuclear diatomic halogen or a heteronuclear diatomic halogen according to embodiments.
  • Exposing the cobalt to chlorine may occur with plasma or without any plasma in the substrate processing region in embodiments.
  • the substrate processing region may be plasma-free during operation 425 of cobalt etch process 400.
  • the cobalt may react with the chlorine to form cobalt-chloride adsorbates on or near the surface of the substrate.
  • the cobalt- chloride adsorbates may facilitate the subsequent removal of cobalt from the substrate.
  • a plasma may be formed at operation 425 within the processing region of the chamber.
  • the plasma may be formed from the chlorine-containing precursor to produce plasma effluents.
  • the plasma may be formed by two electrodes within the processing chamber, which may include, for example, one or both of the showerhead 255 and support pedestal 265 previously described.
  • the plasma may be a bias plasma formed within the chamber region that may direct plasma effluents to the substrate surface and provide low-energy ion bombardment to the substrate.
  • An exposed region of the cobalt-containing material may be contacted with the plasma to remove cobalt-containing material at an exposed horizontal surface to form a recess at operation 430.
  • the plasma effluents at operation 425 may include chlorine plasma effluents, which when contacting cobalt-containing material, may modify the cobalt, and may form cobalt chloride at the locations of contact.
  • the chlorine plasma effluents may contact cobalt-containing material preferentially at a desired location such as at a region exposed by the hard mask and/or a bottom horizontal surface of a recess.
  • the chlorine plasma may be halted, and the chamber may be purged with one or more inert precursors in some embodiments.
  • a carbon-and-nitrogen- containing precursor may be delivered to the substrate processing region to form volatile metal complexes which desorb from the surface of the cobalt-containing material.
  • the carbon-and- nitrogen-containing precursor may be flowed into the processing region of the semiconductor processing chamber at operation 430.
  • the carbon-and-nitrogen-containing precursor may contact the substrate and modified cobalt at operation 430.
  • the modified cobalt may include the regions of cobalt chloride, and may interact with the cobalt chloride.
  • the carbon-and-nitrogen- containing precursor may interact with the cobalt chloride to produce volatile substances, which may then be removed from the chamber. Creating volatile reaction products from cobalt may remove material during cobalt etch process 400.
  • the volatile reaction products are thought to include methyl cobalt complexes such as Co(CH3)4.
  • Exposing cobalt first to chlorine (operation 425) and then to the carbon-and-nitrogen-containing precursor (operation 430) has been found to produce the production worthy etch rate of cobalt and may form volatile reaction products which leave the surface by desorption.
  • Cobalt chloride complexes have been found to be nonvolatile with or without plasma treatment. However, the formation of cobalt chloride complexes have been found to be a conducive intermediate state toward volatization and desorption.
  • the exposed portion of cobalt-containing material may have been at least partially converted or modified into cobalt chloride, and when contacted with the nitrogen-containing precursor, the exposed portion of cobalt-containing material may be at least partially recessed at operation 430.
  • the methods presented may remove cobalt while substantially maintaining the other exposed materials.
  • a thin metal oxide layer may be present on the surface of the metal layer, in which case a local plasma from hydrogen may be used to remove the oxygen or amorphize the near surface region, which has been found to increase the overall etch rate.
  • the process may involve cycling certain operations.
  • method 400 may be repeated for at least two cycles, and may be repeated for at least 3 cycles, at least 4 cycles, at least 5 cycles, at least 6 cycles, at least 7 cycles, at least 8 cycles, at least 9 cycles, or more. The number of cycles may be dependent on the amount of removal provided by each cycle.
  • Method 400 may represent one cycle of a process for recessing or removing cobalt selectively from a substrate where the removal is vertical and does not expand laterally, or substantially maintains sidewall critical dimensions, due to the protective film remaining in place on sidewalls during the cobalt removal at operation 430.
  • the plasma formed in the processing region with the chlorine-containing precursor may be a low-power plasma in embodiments to limit the effect on cobalt.
  • the plasma power may be maintained relatively low to provide slight directionality to the chlorine plasma effluents. However, by using a low power, the effluents may not extend deep into the recess. Additionally, the higher the plasma power the more likely to cause sputtering at the surfaces of materials being contacted. Accordingly, by maintaining the plasma power low, the underlying materials may remain unmodified while a surface-amount of cobalt may be modified.
  • the plasma power may be below or about 300 W in embodiments, depending on the thickness of the desired modification.
  • Higher plasma power may provide additional modification to the recess during an operation cycle. However, a higher plasma power may allow more material within the recess to be modified and removed.
  • the plasma power may be below or about 250 W, below or about 200 W, below or about 150 W, below or about 100 W, below or about 50 W, between about 10 W and about 80 W, or between about 30 W and about 60 W. Utilizing a plasma power below 100 W may afford more control on the amount of cobalt modified at the bottom of the recess, and may allow increased control on the modification.
  • the chlorine-containing precursor flowing into the processing region may be provided in a low dose in embodiments to ensure an un-saturated reactant, such as chlorine, in this operation.
  • an un-saturated reactant such as chlorine
  • the plasma effluents may not extend deep into the recess during the operations. Accordingly, by maintaining the low dose of chlorine- containing precursor flow and/or delivering the chlorine-containing precursor for a reduced time period, such as with a pulsed operation, the underlying materials may remain unmodified while a surface-amount of cobalt may be modified.
  • the flow rate of the chlorine-containing precursor may be less than or about 50 seem in embodiments, and may be less than or about 45 seem, less than or about 40 seem, less than or about 35 seem, less than or about 30 seem, less than or about 25 seem, less than or about 20 seem, less than or about 15 seem, less than or about 10 seem, less than or about 5 seem, or less. Additionally, the chlorine-containing precursor delivery may be pulsed for time periods of less than or about 40 seconds in embodiments, and may be pulsed for time periods of less than or about 35 seconds, less than or about 30 seconds, less than or about 25 seconds, less than or about 20 seconds, less than or about 15 seconds, less than or about 10 seconds, less than or about 5 seconds, or less.
  • the flow rate and pulsing may be combined for any of the listed numbers.
  • the chlorine-containing precursor flow rate may be below or about 10 seem and may be delivered in pulses from about 5 to about 10 seconds in embodiments, depending on the thickness of the desired modification. Because only the modified regions of cobalt chloride may be subject to removal by the nitrogen-containing precursor, controlling the amount of material that is converted provides control over the material that is removed.
  • a temperature within the processing chamber or at the substrate level may be maintained between about 50° C and about 500° C in embodiments.
  • the temperature may be maintained below or about 500° C in embodiments, and may be maintained below or about 450° C, below or about 400° C, below or about 350° C, below or about 300° C, below or about 250° C, below or about 200° C, below or about 150° C, below or about 100° C, or lower.
  • the temperature may also be maintained between about 100° C and about 300° C in embodiments, and may be maintained between about 175° C and about 250° C during operations of the etching method 400. In embodiments the temperature may be maintained within this range for all operations of method 400. In some embodiments the temperature may be adjusted up or down between the contacting operations 410, 420, and 425.
  • a higher processing temperature may allow the nitrogen-containing precursor to remove the cobalt chloride without further excitation in embodiments.
  • contacting the cobalt chloride with the precursor at operation 425 may be performed between about 175° C and about 250° C.
  • the nitrogen-containing precursor may interact with the cobalt chloride at this temperature producing volatile materials that may be expelled from the chamber. Additionally, the nitrogen-containing precursor may not interact or chemically react with unmodified portions of cobalt.
  • the temperature based reaction of the nitrogen-containing precursor may be limited to the modified portions of cobalt, and may maintain the unmodified regions, including sidewalls within the recess or on the hard mask silicon oxide. Accordingly, in some embodiments, the processing region of the chamber may be maintained plasma-free during operation 425 of contacting the cobalt chloride with the nitrogen-containing precursor.
  • a pressure within the chamber may be maintained below or about 5 Torr in embodiments.
  • a lower pressure may provide a more anisotropic process.
  • the pressure may be maintained below or about 4 Torr in embodiments, and may be maintained below or about 3 Torr, below or about 2 Torr, below or about 1 Torr, below or about 100 mTorr, or lower. In embodiments the pressure may be maintained between about 500 mTorr and about 2 Torr.
  • the modification depth may affect the degree of cobalt removal during the etching method 400. This may also impact the amount of cobalt material removed from within the recess, where a smaller amount of modification may reduce an amount of cobalt removed from within the recess.
  • the low plasma power and/or low chlorine-containing precursor flow rate discussed previously may allow the removal to be limited to less than or about 5 nm of cobalt during the operation.
  • the low plasma treatment and/or low chlorine-containing precursor flow rate may provide a removal of less than or about 4 nm, less than or about 3 nm, less than or about 2 nm, less than or about 1 nm, 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 in embodiments, down to a few molecules of cobalt.
  • the removal may be at least about 5 A, and may be between about 4 A and about 2 nm of removal, or between about 5 A and about 1 nm of removal.
  • each cycle may remove between about 5 A and about 10 A of cobalt, and a total amount of cobalt of a few nanometers may be performed with additional cycles.
  • the cycling of method 400 may remove at least about 10 A of cobalt, and may remove at least about 15 A, at least about 20 A, at least about 25 A, at least about 30 A, at least about 40 A, at least about 45 A, at least about 50 A, or more depending on the amount of cobalt deposited, and the amount sought for removal.
  • the method may preferentially remove cobalt-containing material vertically at the horizontal or bottom surface of the recess without removing cobalt-containing material laterally.
  • the first cycle, two cycles, three cycles, or more may perform a recess of increasing depth.
  • the process may be halted when cobalt within the recess has been removed to a desired depth.
  • a slight lateral undercut may occur in some embodiments, the present technology may vertically etch the cobalt material while maintaining or substantially maintaining lateral expansion of the etch process.
  • the precursors used to form plasma at operation 425 may include a chlorine-containing precursor, or a halogen-containing precursor in embodiments.
  • the precursor may include chlorine, bromine, fluorine, or other etchants that may interact with the cobalt under plasma conditions.
  • a chlorine-containing precursor may include diatomic chlorine , or may include a diatomic precursor including chlorine or a halogen.
  • the nitrogen-containing precursor may include nitrogen, carbon, and/or hydrogen in any combination.
  • the nitrogen- containing precursor may include one or more methyl moieties coupled with nitrogen, or some other carbon based moiety.
  • Exemplary nitrogen-containing precursors include amines, diamines, including aliphatic and aromatic diamines, including linear aliphatic diamines, branched aliphatic diamines, phenylenediamines, and other nitrogen-containing precursors.
  • Exemplary precursors may include tetramethylethylenediamine (TMEDA) in embodiments.
  • Either precursor may include additional carrier gases including chemically inert precursors including helium, argon, xenon, and other noble gases or precursors that may not chemically react with cobalt.
  • Method 400 may optionally include deposition operations that may occur on the same tool as the etching method, or on a different tool.
  • a vacuum may be maintained between the operations, which may reduce contaminants, moisture, and other handling issues.
  • the etching operations of method 400 may then be repeated in a subsequent set of cycles as previously explained.
  • a recess of the desired depth may be realized. Additional operations may be performed in between the iterations and cycles, including reflow in embodiments.
  • the methods may also optionally include a hydrogen treatment between deposition operations such as forming a protective film and subsequent recess or removal operations. Modification of the material to produce cobalt chloride and then removal of cobalt chloride may produce residue on the cobalt that may cause peeling of subsequently formed or deposited materials. By conducting a treatment with a hydrogen-containing precursor, residue materials may be removed to ensure a clean surface of the formed film.
  • the hydrogen treatment may include contacting the substrate with effluents of a hydrogen-containing plasma at optional operation 435. The plasma effluents may remove residue from exposed cobalt surfaces at optional operation 440.
  • the optional hydrogen treatment may be performed in the same chamber as the other operations of method 400 such that the entire method 400 is performed in a single chamber, such as chamber 200 as previously described. Additionally, in some embodiments one or more operations may be performed in a different chamber as other operations of method 400.
  • the optional hydrogen post-treatment at operation 440 may include forming the plasma effluents remotely or at the substrate level.
  • the hydrogen-containing precursor may be flowed into a remote plasma region, such as a remote plasma unit, or a remote section of a processing chamber, such as region 215 discussed previously with respect to chamber 200.
  • the hydrogen-containing precursor may be flowed into the processing region in which the substrate is housed, and a plasma may be formed.
  • the hydrogen plasma effluents may interact with impurities and residue materials and remove them from exposed cobalt surfaces.
  • the plasma process performed may interact with liner or barrier materials formed along the recess, and in embodiments may interact with materials within which the recesses are defined or formed. Based on the temperature and plasma characteristics used in the operations, the present technology may etch cobalt selectively over liner material and other substrate materials.
  • the liner may include one or more metals, including transition metals, as well as nitrides of metals.
  • the metals may include, for example, titanium, titanium nitride, tantalum, tantalum nitride, ruthenium, and other materials and nitrides.
  • the present technology may selectively etch cobalt over liner materials, such as titanium nitride, at an etch rate ratio greater than or about 20: 1, and in embodiments may etch cobalt at an etch ratio greater than or about 30:1, greater than or about 40: 1, greater than or about 50:1, greater than or about 60: 1, greater than or about 70: 1, or more in embodiments.
  • liner materials such as titanium nitride
  • the present technology may also etch cobalt over silicon-containing materials, including silicon oxide and silicon nitride, at an etch rate ratio greater than or about 50:1.
  • the present technology may etch cobalt at an etch rate ratio compared to silicon- containing materials greater than or about 60: 1, greater than or about 70: 1, greater than or about 80: 1, greater than or about 90: 1, greater than or about 100: 1, greater than or about 110:1, greater than or about 120: 1, greater than or about 150: 1, or higher.
  • FIGS. 5A-5E are shown cross-sectional views of substrates on which the present technology may be performed.
  • FIG. 5A illustrates a cross-sectional view of a substrate 505 on which a recess may be formed.
  • Substrate 505 may include a cobalt-containing material for selective etching.
  • the substrate may optionally include a hard mask 510, which may be silicon oxide.
  • the hard mask may be formed to expose a horizontal surface 515, which may be the local area onto which the etch process 400 will form a recess.
  • a first amount of cobalt 505 may be removed to form a recess as described in etch process 400.
  • the substrate may further include a liner or a base material.
  • a liner may include titanium nitride, tantalum nitride, other transition metals or transition metal nitrides, and may protect the substrate 505 from metal diffusion.
  • a base material for the substrate may predominantly include silicon dioxide or other suitable material.
  • FIG. 5B illustrates a plasma modification in which plasma effluents 520 of a carbon- and-nitrogen-containing precursor are produced.
  • the carbon-and-nitrogen-containing precursor may be flowed into a substrate processing region where a plasma may be formed to produce the plasma effluents 520 forming a protective film 525 on the exposed areas of substrate 505 and also on the sidewalls of hard mask 515 as shown.
  • Substrate 505 may alternatively be substantially planar, as further described below, without a hard mask 515.
  • the protective film 525 may be or include carbon, nitrogen, and/or hydrogen.
  • an oxygen-containing precursor may be flowed into a substrate processing region where a plasma may be formed to produce the plasma effluents 520 to oxidize the cobalt to form a protective oxide-containing film 525.
  • a plasma may be formed to produce the plasma effluents 520 to oxidize the cobalt to form a protective oxide-containing film 525.
  • the protective film 525 covers the sidewalls of the substrate and/or hard mask as well as the horizontal surface corresponding to the bottom of the recess or recess to be formed.
  • FIG. 5B is an example illustration to show a protective film, and is not necessarily to scale or with an accurate amount of protection.
  • a hydrogen-containing precursor may be flowed into the processing region to form a hydrogen plasma to contact the protective film at the horizontal surface or bottom to produce volatile materials 530, which may be extracted from the chamber.
  • the volatile material 530 may be removed to leave an exposed horizontal surface of cobalt-containing material, which may provide access to forming the recess. The modification and removal may be performed multiple times in order to provide an adequate depth to the recess.
  • a chlorine- containing precursor may be flowed into the processing region.
  • the chlorine-containing precursor may contact the horizontal surface to produce cobalt chloride complexes 540 as illustrated in FIG. 5D.
  • a nitrogen-containing precursor may then be flowed into the processing region to contact the cobalt chloride complexes 540 with the nitrogen-containing precursor.
  • a recess 550 may be produced by one or more cycles of etch process 400 as illustrated in FIG. 5E.
  • FIGS. 6A-6E are shown cross-sectional views of substrates on which the present technology may be performed, which may be characterized by additional substrate configurations.
  • FIG. 6A-6E are shown cross-sectional views of substrates on which the present technology may be performed, which may be characterized by additional substrate configurations.
  • Substrate 600 may include a cobalt-containing material 605 for selective etching.
  • the substrate may be planar or substantially planar.
  • An exposed horizontal surface 615 may be the local area onto which the etch process 400 will form a recess.
  • a first amount of cobalt 605 may be removed to form a recess as described in etch process 400.
  • the substrate may further include a liner or a base material.
  • a liner (not shown) may include titanium nitride, tantalum nitride, other transition metals or transition metal nitrides, and may protect the substrate 505 from metal diffusion.
  • FIG. 6B illustrates a plasma modification in which plasma effluents 620 of a carbon- and-nitrogen-containing precursor are produced.
  • the carbon-and-nitrogen-containing precursor may be flowed into a substrate processing region where a plasma may be formed to produce the plasma effluents 620 forming a protective film 625 on the exposed areas of substrate 600.
  • the protective film 625 may be or include carbon, nitrogen, and hydrogen.
  • an oxygen- containing precursor may be flowed into a substrate processing region where a plasma may be formed to produce the plasma effluents 620 to form a protective film 625 on the exposed area 615 of substrate 600, which may be an oxide-containing film 625.
  • a plasma may be formed to produce the plasma effluents 620 to form a protective film 625 on the exposed area 615 of substrate 600, which may be an oxide-containing film 625.
  • the protective film 625 covers the sidewalls of the substrate as well as the horizontal surface corresponding to the bottom of the recess or recess to be formed.
  • FIG. 6B is an example illustration to show a protective film, and is not necessarily to scale or with an accurate amount of protection.
  • a hydrogen-containing precursor may be flowed into the processing region.
  • the hydrogen-containing precursor may contact the protective film at the horizontal surface or bottom to produce volatile materials 630, which may be extracted from the chamber.
  • the volatile material 630 may be removed to leave an exposed horizontal surface of cobalt-containing material, which may provide access to forming the recess.
  • the modification and removal may be performed multiple times in order to provide an adequate depth to the recess. Additional operations may be performed as described above with reference to FIGS. 5A- 5E.
  • a chlorine-containing precursor may be flowed into the processing region.
  • the chlorine-containing precursor may contact the horizontal surface to produce cobalt chloride complexes 640 as illustrated in FIG. 6D.
  • a nitrogen- containing precursor is then flowed into the processing region to contact the cobalt chloride complexes 640 with the nitrogen-containing precursor.
  • a recess 650 is formed (by one or more cycles of etch process 400) as illustrated in FIG. 6E.

Abstract

La présente invention concerne des procédés de gravure sélective, donnés à titre d'exemples, d'un matériau contenant du cobalt à partir d'un substrat qui peuvent comprendre la formation d'un plasma d'un précurseur contenant du carbone dans une région de traitement de substrat comprenant le substrat. Le substrat peut comprendre un matériau contenant du cobalt exposé. Les procédés peuvent comprendre la formation d'un film contenant du carbone adapté sur le matériau contenant du cobalt exposé. Les procédés peuvent comprendre la formation d'un plasma local d'un précurseur contenant de l'hydrogène et l'élimination d'une partie du film contenant du carbone pour exposer au moins une partie d'une surface du matériau contenant du cobalt. Les procédés peuvent comprendre la formation d'un plasma local d'un précurseur contenant du chlore et la mise en contact de la partie exposée de la surface du matériau contenant du cobalt avec des effluents de plasma contenant du chlore pour former des complexes de chlorure de cobalt. Les procédés peuvent comprendre l'écoulement d'un précurseur contenant de l'azote dans la région de traitement et la mise en contact des complexes de chlorure de cobalt avec le précurseur contenant de l'azote. Les procédés peuvent comprendre le retrait de la surface du matériau contenant du cobalt.
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