Selective etching of silicon-containing materials relative to metal-doped boron films

Abstract

An exemplary semiconductor processing method may include depositing a metal-doped boron-containing material on a substrate disposed in a processing region of a semiconductor processing chamber. The metal-doped boron-containing material may include a metal dopant including tungsten. The substrate may include a silicon-containing material. The method may include depositing one or more additional materials over the metal-doped boron-containing material. The one or more additional materials may include a patterned photoresist material. The method may include transferring a pattern from the patterned photoresist material to the metal-doped boron-containing material. The method may include etching the metal-doped boron-containing material with a chlorine-containing precursor. The method may include etching the silicon-containing material with a fluorine-containing precursor. The metal dopant may enhance the etch rate of the silicon-containing material. The method may include removing the metal-doped boron-containing material from the substrate with a halogen-containing precursor.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. patent application Ser. No. 18 / 106,697, filed Feb. 7, 2023, entitled "SELECTIVE ETCHING OF SILICON-CONTAINING MATERIAL RELATIVE TO METAL-DOPED BORON FILMS," the entire contents of which are incorporated herein by reference.

[0002]

[0002] The present technology relates to semiconductor deposition and etching processes. More particularly, the present technology relates to methods of using materials having metal dopants as masking materials to enhance the etch rate and / or selectivity to underlying materials during patterning steps. [Background technology]

[0003]

[0003] Integrated circuits are realized through processes that create intricately patterned layers of material on a substrate surface. Creating patterned structures on a substrate requires controlled methods for forming and removing exposed material. As device sizes continue to shrink and structures become more complex, material properties can affect subsequent processing steps. For example, masking materials can affect both the ability to develop structures as well as the ability to selectively remove material.

[0004]

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

[0005] An exemplary semiconductor processing method can include depositing a metal-doped boron-containing material on a substrate disposed in a processing region of a semiconductor processing chamber. The metal-doped boron-containing material can include a metal dopant including tungsten. The substrate can include a silicon-containing material. The method can include depositing one or more additional materials over the metal-doped boron-containing material. The one or more additional materials can include a patterned photoresist material. The method can include transferring a pattern from the patterned photoresist material to the metal-doped boron-containing material. The method can include etching the metal-doped boron-containing material with a chlorine-containing precursor. The method can include etching the silicon-containing material with a fluorine-containing precursor. The metal dopant can enhance the etch rate of the silicon-containing material. The method can include removing the metal-doped boron-containing material from the substrate with a halogen-containing precursor.

[0006] In some embodiments, the metal dopant concentration in the metal-doped boron-containing material can be maintained at about 80 atomic % or less. The one or more additional materials can include an oxide hard mask deposited on the metal-doped boron-containing material, a carbon hard mask deposited on the oxide hard mask, and one or more antireflective coatings deposited on the carbon hard mask. The patterned photoresist material can be on the one or more antireflective coatings. The chlorine-containing precursor can be or can include diatomic chlorine (Cl). The method can include applying plasma power to the processing region during etching of the metal-doped boron-containing material. The method can include intermittently delivering a silicon-containing precursor and an oxygen-containing precursor to form a passivation material on sidewalls of the metal-doped boron-containing material during etching of the metal-doped boron-containing material. The silicon-containing precursor can be or can include silicon tetrachloride (SiCl). The oxygen-containing precursor may be or may include molecular oxygen (O). The fluorine-containing precursor may be or may include a fluorocarbon. The metal dopant may promote the formation of fluorine radicals during etching of silicon-containing materials. The halogen-containing precursor may be or may include diatomic chlorine (Cl) or hydrogen bromide (HBr).

[0007] Some embodiments of the present technology include a semiconductor structure. The structure can include a substrate. The structure can include a silicon-oxygen material overlying the substrate. The structure can include a silicon-carbon-nitrogen material overlying the silicon-oxygen material. The structure can include a metal-doped boron-containing material overlying the silicon-carbon-nitrogen material. The metal-doped boron-containing material can include a metal dopant comprising tungsten. The structure can include one or more additional materials overlying the metal-doped boron-containing material. The one or more additional materials can include a patterned photoresist material.

[0008] In some embodiments, the one or more additional materials may include an oxide hard mask overlying the metal-doped boron-containing material, a carbon hard mask overlying the oxide hard mask, and one or more antireflective coatings overlying the carbon hard mask. The patterned photoresist material may be overlying the one or more antireflective coatings. The metal dopant concentration in the metal-doped boron-containing material may be maintained at or below about 80 atomic %. The metal-doped boron-containing material may be characterized by a hardness of at least about 25 GPa. The thickness of the silicon-oxygen material may be greater than the thickness of the metal-doped boron-containing material.

[0009] Some embodiments of the present technology include a semiconductor processing method. The method can include depositing a metal-doped boron-containing material over a silicon-containing material overlying a substrate disposed in a processing region of a semiconductor processing chamber. The metal-doped boron-containing material can include a metal. The method can include delivering a fluorine-containing precursor and an oxygen-containing precursor to the processing region of the semiconductor processing chamber. The method can include forming a plasma of the fluorine-containing precursor and the oxygen-containing precursor in the processing region of the semiconductor processing chamber. The method can include etching the silicon-containing material. The etching can remove a portion of the metal-doped boron-containing material. The metal can increase the etch rate of the silicon-containing material.

[0010] In some embodiments, the metal-doped boron-containing material may further comprise one or more of tungsten, molybdenum, titanium, aluminum, cobalt, ruthenium, tantalum, hafnium, zirconium, silicon, carbon, or nitrogen. The method may include depositing a photoresist material over the metal-doped boron-containing material. The method may include patterning the photoresist material. The method may include transferring a pattern from the patterned photoresist material to the metal-doped boron-containing material. The fluorine-containing precursor may be or may include a fluorocarbon. The fluorine-containing precursor may passivate sidewalls of the metal-doped boron-containing material.

[0011] Such technology can offer many advantages over conventional systems and techniques. For example, the process can produce films characterized by improved selectivity to underlying materials. Furthermore, steps of embodiments of the technology can form improved mask materials that can facilitate processing steps. These and other embodiments, along with many of their advantages and features, are described in more detail in conjunction with the following description and accompanying figures.

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

[0013] [Figure 1] 1 is a schematic top view illustrating an exemplary processing system according to some embodiments of the present technique; [Figure 2] 1 is a schematic cross-sectional view of an exemplary processing system according to some embodiments of the present technique; [Figure 3] 1A-1D illustrate exemplary steps in a semiconductor processing method according to some embodiments of the present technique. [Figure 4A] 1A-1D are schematic cross-sectional views illustrating substrate materials undergoing selected processes in accordance with some embodiments of the present technique. [Figure 4B] 1A-1D are schematic cross-sectional views illustrating substrate materials undergoing selected processes in accordance with some embodiments of the present technique. [Figure 4C] 1A-1D are schematic cross-sectional views illustrating substrate materials undergoing selected processes in accordance with some embodiments of the present technique. [Figure 4D] 1A-1D are schematic cross-sectional views illustrating substrate materials undergoing selected processes in accordance with some embodiments of the present technique. [Figure 4E] 1A-1D are schematic cross-sectional views illustrating substrate materials undergoing selected processes in accordance with some embodiments of the present technique. DETAILED DESCRIPTION OF THE INVENTION

[0014]

[0017] Some of the figures are included as schematic diagrams. It should be understood that the figures are for illustrative purposes and should not be considered to scale unless scale is specifically stated. Furthermore, as schematic diagrams, the figures are provided to aid in understanding and may not include all aspects or information compared to realistic representations and may include exaggerated material for illustrative purposes.

[0015]

[0018] In the accompanying figures, similar components and / or features may be labeled with the same reference label. Furthermore, various components of the same type may be distinguished by following the reference label with a letter that distinguishes between the similar components. When only a first reference label is used herein, the description is applicable to any one of the similar components having the same first reference label, regardless of the letter.

[0016]

[0019] During semiconductor manufacturing, structures can be formed on a substrate using various deposition and etching processes. Mask materials can be used to at least partially etch materials to form features across the substrate. As device sizes continue to shrink and improved selectivity between materials allows for easier structure formation, improved hard masks can facilitate manufacturing. For example, future DRAM nodes may require taller capacitor structures, which may involve forming deeper trenches in the substrate. Conventional hard masks may reach their selectivity limits to the underlying silicon material. Consequently, many semiconductor manufacturing processes use thicker hard mask films for larger vertical device structures or work to develop mask materials featuring increased hardness. However, while hard masks may be sufficiently transparent at certain thicknesses, the film's transparency may decrease as the thickness increases. If the film becomes sufficiently opaque, the process may require additional steps to create openings near alignment markers to ensure proper orientation. Furthermore, thicker hard mask films can make patterning more difficult and affect the uniformity of transfer to the underlying structures.

[0017]

[0020] The present technique can overcome these limitations by fabricating mask materials incorporating metal dopants. While these materials may counterintuitively reduce transparency and hardness, they may offer greater material selectivity to the underlying material, resulting in masks with reduced thickness and overall improved etching and structuring of semiconductor substrates. It should be understood that the technique described can be used to improve many film formation processes and may be applicable to a variety of processing chambers and steps, and therefore the present technique is not intended to be limited to the specific films and processes described.

[0018]

[0021] Figure 1 illustrates a top view of one embodiment of a deposition, etch, bake, and / or cure chamber processing system 10 according to embodiments. The tool or processing system 10 shown in Figure 1 can include multiple process chambers 24a-d, a transfer chamber 20, a service chamber 26, an integrated metrology chamber 28, and a pair of load lock chambers 16a-b. The process chambers can include any number of structures or components and any number or combination of processing chambers.

[0019]

[0022] To transport substrates between chambers, the transfer chamber 20 can include a robotic transport mechanism 22. The transport mechanism 22 can have a pair of substrate transport blades 22a, each attached to the distal end of an extendable arm 22b. The blades 22a can be used to transport individual substrates to and from process chambers. In a process, one of the substrate transport blades, such as blade 22a of the transport mechanism 22, can retrieve a substrate W from one of the load lock chambers, such as chambers 16a-b, and transport the substrate W to a first processing stage, e.g., a processing process, as described below, in chambers 24a-d. Chambers can be included to perform individual or combinations of the described techniques. For example, one or more chambers can be configured to perform a deposition or etching process, while one or more other chambers can be configured to perform a described pre-processing step and / or one or more post-processing steps. Any number of configurations capable of performing any number of additional manufacturing steps typically performed in semiconductor processing are encompassed by the present technology.

[0020]

[0023] If a chamber is in use, the robot can wait until processing is complete and then remove the processed substrate from the chamber using one blade 22a and insert a new substrate using a second blade. Once the substrate has been processed, it can be moved to a second processing stage. For each move, the transport mechanism 22 may generally have one blade transporting the substrate and one empty blade to perform a substrate swap. The transport mechanism 22 can wait at each chamber until the swap can be accomplished.

[0021]

[0024] Once processing in the process chambers is complete, the transport mechanism 22 can remove the substrate W from the last process chamber and transfer the substrate W to a cassette in the load lock chambers 16a-b. The substrate moves from the load lock chambers 16a-b into the factory interface 12. The factory interface 12 generally operates to transfer substrates between the pod loaders 14a-d and the load lock chambers 16a-b in an atmospheric pressure clean environment. The clean environment within the factory interface 12 may generally be provided through an air filtration process, such as HEPA filtration. The factory interface 12 may also include a substrate orienter / aligner that may be used to properly align substrates before processing. At least one substrate robot, such as robots 18a-b, may be positioned within the factory interface 12 to transport substrates between various locations within the factory interface 12 and to other locations coupled thereto. The robots 18a-b may be configured to move from a first end to a second end of the factory interface 12 along a track system within the factory interface 12.

[0022]

[0025] The processing system 10 may further include an integrated metrology chamber 28 for providing control signals that may provide adaptive control for any of the processes being performed in the processing chambers. The integrated metrology chamber 28 may include any of a variety of metrology devices for measuring various film properties such as thickness, roughness, composition, etc., and the metrology devices may also be capable of characterizing grating parameters such as critical dimensions under vacuum, sidewall angle, and feature height in an automated manner.

[0023]

[0026] Each of the processing chambers 24a-d can be configured to perform one or more process steps in the fabrication of semiconductor structures, and any number and combination of processing chambers can be used on the multichamber processing system 10. For example, any of the processing chambers can be configured to perform multiple substrate processing steps, including any number of deposition processes, including cyclical layer deposition, atomic layer deposition, chemical vapor deposition, physical vapor deposition, and other steps, including etching, pre-cleaning, pre-treatment, post-treatment, annealing, plasma treatment, degassing, alignment, and other substrate processes. Specific processes that can be performed in any chamber, or any combination of chambers, can be metal deposition, surface cleaning and preparation, thermal annealing such as rapid thermal processing, and plasma treatment. As one skilled in the art will readily appreciate, any other process, including any of the processes described below, can similarly be performed in a particular chamber incorporated into the multichamber processing system 10.

[0024]

[0027] FIG. 2 is a schematic cross-sectional view illustrating an exemplary processing chamber 200 suitable for patterning a material layer disposed on a substrate 202 therein. While the exemplary processing chamber 200 is suitable for performing a patterning process, it should be understood that aspects of the present technology can be performed in any number of chambers, and that a substrate support according to the present technology can be included in an etch chamber, a deposition chamber, a treatment chamber, or any other processing chamber. The plasma processing chamber 200 can include a chamber body 205 defining a chamber region 201 in which a substrate can be processed. The chamber body 205 can have sidewalls 212 and a bottom 218 coupled to ground 226. The sidewalls 212 can have a liner 215 that protects the sidewalls 212 and extends the time between maintenance cycles for the plasma processing chamber 200. The dimensions of the chamber body 205 and associated components of the plasma processing chamber 200 are not limited and can generally be proportionally larger than the size of the substrate 202 to be processed therein. Examples of substrate sizes include diameters of 200 mm, 250 mm, 300 mm, and 450 mm, and the same applies to display substrates or solar cell substrates.

[0025]

[0028] The chamber body 205 may support a chamber lid assembly 210 to enclose the chamber region 201. The chamber body 205 may be fabricated from aluminum or other suitable materials. A substrate access port 213 may be formed through a sidewall 212 of the chamber body 205 to facilitate transfer of the substrate 202 into and out of the plasma processing chamber 200. The access port 213 may be coupled to a transfer chamber and / or other chambers of a substrate processing system, as previously described. A pumping port 245 may be formed through the sidewall 212 of the chamber body 205 and connected to the chamber region 201. A pumping system may be coupled to the chamber region 201 through the pumping port 245 to evacuate and control the pressure within the processing region. The pumping system may include one or more pumps and a throttle valve.

[0026]

[0029] A gas panel 260, which supplies process gases into the chamber region 201, may be coupled to the chamber body 205 by gas lines 267. The gas panel 260 may include one or more process gas sources 261, 262, 263, 264 and may further include inert, non-reactive, and reactive gases for use in any number of processes. Examples of process gases that may be supplied by the gas panel 260 include, but are not limited to, hydrocarbon-containing gases including methane, sulfur hexafluoride, silicon chloride, carbon tetrafluoride, hydrogen bromide, hydrocarbon-containing gases, argon gas, chlorine, nitrogen, helium, or oxygen gas, as well as any number of additional materials. Additionally, the process gas can include nitrogen, chlorine, fluorine, oxygen, silicon, and hydrogen-containing gases such as BCl3, Cl2, SiCl4, CF4, C2F4, C4F8, C4F6, CHF3, CH2F2, CH3F, NF3, NH3, CO2, SO2, CO, COS, N2, NO2, N2O, O2, HBr, and H2, among any number of additional precursors.

[0027]

[0030] A valve 266 can control the flow of process gas from sources 261, 262, 263, and 264 from the gas panel 260 and can be managed by a controller 265. The flow of gas supplied to the chamber body 205 from the gas panel 260 can include a combination of gases from one or more sources. The lid assembly 210 can include a nozzle 214. The nozzle 214 can be one or more ports for introducing process gases from the sources 261, 262, 264, and 263 of the gas panel 260 into the chamber region 201. After the process gases are introduced into the plasma processing chamber 200, a voltage can be applied to the gases to form a plasma. An antenna 248, such as one or more inductor coils, can be located adjacent to the plasma processing chamber 200. An antenna power supply 242 can supply power to the antenna 248 through a matching circuit 241 to inductively couple energy, such as RF energy, to the process gases to maintain a plasma formed from the process gases in the chamber region 201 of the plasma processing chamber 200. Instead of, or in addition to, the antenna power supply 242, process electrodes below and / or above the substrate 202 can be used to capacitively couple RF power to the process gases to maintain the plasma in the chamber region 201. The operation of the power supply 242 can be controlled by a controller, such as controller 265, which also controls the operation of other components in the plasma processing chamber 200.

[0028]

[0031] A substrate support pedestal 235 may be disposed within the chamber region 201 to support the substrate 202 during processing. The substrate support pedestal 235 may include an electrostatic chuck 222 for holding the substrate 202 during processing. The electrostatic chuck (“ESC”) 222 may hold the substrate 202 to the substrate support pedestal 235 using electrostatic attraction. The ESC 222 may be powered by an RF power supply 225 integrated with a matching circuit 224. The ESC 222 may include an electrode 221 embedded in a dielectric. The electrode 221 may be coupled to the RF power supply 225 and may provide a bias that attracts plasma ions formed by process gases in the chamber region 201 to the ESC 222 and the substrate 202 seated on the pedestal. The RF power supply 225 may be cycled on and off or pulsed during processing of the substrate 202. The ESC 222 may include an isolator 228 to prevent plasma from being attracted to the sidewalls of the ESC 222, thereby extending the maintenance life of the ESC 222. Additionally, the substrate support pedestal 235 may include a cathode liner 236 to protect the sidewalls of the substrate support pedestal 235 from plasma gases and extend the maintenance intervals of the plasma processing chamber 200.

[0029]

[0032] The electrode 221 may be coupled to a power supply 250. The power supply 250 may provide a chucking voltage of approximately 200 volts to approximately 2000 volts to the electrode 221. The power supply 250 may also include a system controller for controlling the operation of the electrode 221 by sending a direct current to the electrode 221 to chuck and dechuck the substrate 202. The ESC 222 may include a heater disposed within the pedestal and connected to a power supply for heating the substrate, and the cooling base 229 supporting the ESC 222 may include conduits for circulating a heat transfer fluid to maintain the temperature of the ESC 222 and the substrate 202 disposed thereon. The ESC 222 may be configured to operate within a temperature range dictated by the thermal budget of devices fabricated on the substrate 202. For example, the ESC 222 may be configured to maintain the substrate 202 at a temperature of approximately −150° C. or lower to approximately 500° C. or higher, depending on the process being performed.

[0030]

[0033] A cooling base 229 may be provided to assist in temperature control of the substrate 202. To mitigate process drift and shorten process time, the temperature of the substrate 202 may be maintained substantially constant by the cooling base 229 throughout the substrate 202's time in the chamber. In some embodiments, the temperature of the substrate 202 may be maintained at a temperature of about −150° C. to about 500° C. throughout subsequent processes, although any temperature may be utilized. A cover ring 230 may be disposed on the ESC 222 and along the periphery of the substrate support pedestal 235. The cover ring 230 may be configured to confine etching gases to a desired portion of the exposed upper surface of the substrate 202 while shielding the upper surface of the substrate support pedestal 235 from the plasma environment inside the plasma processing chamber 200. Lift pins may be selectively translated through the substrate support pedestal 235 to elevate the substrate 202 above the substrate support pedestal 235 to facilitate access to the substrate 202 by a transfer robot or other suitable transfer mechanism, as described above.

[0031]

[0034] The controller 265 can be used to control process sequences, regulate gas flow from the gas panel 260 into the plasma processing chamber 200, and other process parameters. The software routines, when executed by the CPU, transform the CPU into a special-purpose computer, such as a controller, that can control the plasma processing chamber 200 so that processes are performed in accordance with the present disclosure. The software routines can also be stored and / or executed by a second controller that can be associated with the plasma processing chamber 200.

[0032]

[0035] FIG. 3 illustrates exemplary steps in a deposition method 300 according to some embodiments of the present technology. The method can be performed in a variety of processing chambers, including any one of the processing chambers 24a-d and / or processing chamber 200 described above. Method 300 can include numerous optional steps that may or may not be particularly relevant to some embodiments of methods according to the present technology. For example, many of the steps are described to provide a broader scope for structure formation, but may be performed by alternative methodologies that are not critical to the present technology or will be readily understood. Method 300 can be described by steps shown generally in FIGS. 4A-4E, which will be described in conjunction with the steps of method 300. It should be understood that the figures are only partially schematic and that the substrate can include any number of additional materials and features having various properties and aspects as illustrated in the figures.

[0033]

[0036] Method 300 may include additional steps prior to the commencement of the recited steps. For example, the additional processing steps may include forming structures on the substrate, which may include both the formation and removal of materials. Pre-processing steps may be performed in the chamber in which method 300 may be performed, or processing may be performed in one or more other processing chambers prior to delivering the substrate to the semiconductor processing chamber in which method 300 may be performed. In either case, method 300 may optionally include delivering the substrate to a processing region of a semiconductor processing chamber, such as processing chambers 24a-d or processing chamber 200 described above, or other chambers that may include components as described above. The substrate may be disposed on a substrate support, which may be a pedestal that may reside in the processing region of the chamber.

[0034]

[0037] As shown in FIG. 4A , the substrate 405 can be or include any number of materials onto which a material can be deposited. The substrate 405 can be or include silicon, germanium, a dielectric material including silicon oxide or silicon nitride, a metallic material, or any combination of these materials, and can be the substrate 405 or a material formed on the substrate 405. In some embodiments, optional treatment steps, such as pretreatment, can be performed to prepare the surface of the substrate 405 for deposition. For example, pretreatment can be performed to provide specific ligand terminations on the surface of the substrate 405 to promote nucleation of the deposited film. For example, other molecular terminations including hydrogen, oxygen, carbon, nitrogen, or any combination of these atoms or radicals can be adsorbed, reacted, or formed on the surface of the substrate 405. Additionally, material removal, such as reduction of native oxides or etching of materials, or any other step that can prepare one or more exposed surfaces of the substrate 405 for deposition can be performed.

[0035]

[0038] In optional step 305, one or more precursors can be delivered to the processing region of the chamber. For example, the film to be deposited can be a mask film used in semiconductor processing. The deposition precursors can include any number of mask precursors, including one or more boron-containing precursors. The precursors can be flowed together or separately. For example, in an exemplary embodiment in which a boron-containing film can be formed, at least one boron-containing precursor can be delivered to the processing region of the processing chamber. In some embodiments of the present technique, plasma deposition can be performed, which can facilitate material reaction and deposition. For example, in optional step 310, a plasma of the boron-containing precursor can be formed, and in optional step 315, a boron-containing material can be deposited.

[0036]

[0039] Boron-containing hard masks may be characterized by desirable mechanical properties, such as a relatively high Young's modulus and hardness, which may improve etch selectivity. However, to further improve etch selectivity relative to underlying silicon-containing materials, such as silicon oxide or silicon nitride, the present technology may incorporate one or more dopant materials, which may include one or more metals. Incorporating a metal may be counterintuitive in hard mask formation, particularly for the purpose of improving properties for selective etching. For example, incorporating a metal into a hard mask may actually decrease the film's hardness, and many conventional techniques avoid this in favor of a harder mask film. Furthermore, metal dopants may decrease the film's transparency, which can interfere with lithography processes by forming more opaque films, making increased mask thicknesses, as previously used, problematic. However, the present technology utilizes metal dopants to increase the selectivity of the etch process and overcome the decrease in film hardness. Furthermore, because etch selectivity may be improved compared to non-metal-doped films, masks according to some embodiments of the present technology may improve the transparency of films that may be characterized by reduced thicknesses. For example, conventional techniques may provide thicker hard masks to increase the depth of the structures being formed. Increasing the thickness of silicon, boron, and germanium films can result in increasingly opaque features that can make lithography difficult. By incorporating metal materials, the present technology reverses the need for thicker mask films.

[0037]

[0040] Accordingly, some embodiments of the present technique may include, in optional step 320, additionally delivering a dopant-containing precursor, which may be delivered along with the other deposition precursors. All of the delivered precursors may be used to form a plasma in the processing region of the semiconductor processing chamber in step 310, as described above; therefore, the sequence of steps shown in method 300 may include steps performed in a different order, including simultaneously. In step 325, a material including a metal dopant in the deposition material, such as a metal-doped boron-containing material 420, may be deposited on the substrate 405. In embodiments, the metal-doped boron-containing material 420 may be formed on a silicon-containing material 410, such as silicon oxide or silicon nitride. In some embodiments, a silicon-carbon-nitrogen-containing material 415 may be on the silicon-containing material 410, and the metal-doped boron-containing material 420 may be formed on the silicon-carbon-nitrogen-containing material 415. In some embodiments, the incorporation of dopant-containing precursors can form films with controlled hardness and transparency while increasing etch selectivity to the underlying silicon-containing material 410 and / or silicon-carbon-nitrogen-containing material 415, if present.

[0038]

[0041] Depending on the precursor used, the flow rate of the dopant precursor can be used to control the incorporation of the dopant. For example, in the case of transition metal dopants, the dopant precursor can be flowed at a flow rate of about 250 sccm or less, and can be delivered at a flow rate of about 200 sccm or less, about 150 sccm or less, about 100 sccm or less, about 50 sccm or less, about 40 sccm or less, about 30 sccm or less, about 25 sccm or less, about 20 sccm or less, about 15 sccm or less, about 10 sccm or less, about 5 sccm or less, or less, compared to flow rates of several hundred sccm or more for other deposition precursors.

[0039]

[0042] Regarding boron-containing precursors, any number of precursors can be used in the present technique. For example, the boron-containing material can include boron, such as borane, diborane, or other multi-core boron materials, as well as any other boron-containing material that can be used to form a boron-containing material. The incorporation of boron into the formed film can be based on any percentage incorporation. For example, the formed film can include about 20 atomic % or greater boron incorporation, and in some embodiments, about 25 atomic % or greater boron incorporation, about 30 atomic % or greater boron incorporation, about 35 atomic % or greater boron incorporation, about 40 atomic % or greater boron incorporation, about 45 atomic % or greater boron incorporation, about 50 atomic % or greater boron incorporation, about 55 atomic % or greater boron incorporation, about 60 atomic % or greater boron incorporation, about 65 atomic % or greater boron incorporation, about 70 atomic % or greater boron incorporation, or more, including films that are substantially or essentially boron minus the amount of dopants in the film. It should be understood that trace substances due to exposure to the atmosphere or other process environment may be incorporated into the film, but the film may still be essentially boron-based.

[0040]

[0043] The dopant precursor can include any metal-containing precursor, such as any metal or transition metal that can be delivered to the processing region in a stable form. Exemplary dopants can include one or more of tungsten, molybdenum, titanium, aluminum, cobalt, ruthenium, tantalum, hafnium, zirconium, or any other metal or transition metal that can be incorporated into the mask material with boron. The dopant precursor can also additionally or alternatively include one or more of silicon, carbon, or nitrogen. Exemplary precursors can include any number of metal-containing materials that can dissociate in the plasma to provide a metal dopant for incorporation. For example, non-limiting examples of dopant-containing precursors that may be used in embodiments of the present technology include tungsten hexafluoride, tungsten hexacarbonyl, molybdenum hexafluoride, molybdenum pentachloride, molybdenum hexacarbonyl, titanium tetrachloride, tetrakis(dimethylamido)titanium, titanium tetrafluoride, trimethylaluminum, aluminum chloride, bis(N,N'-diisopropylacetamidinato)cobalt, cobaltocene, bis(ethylcyclopentadienyl)cobalt, bis(pentamethylcyclopentadienyl)cobalt, bis(cyclopentadienyl)ruthenium, bis(ethylcyclopentadienyl)ruthenium, tantalum pentachloride, pentakis(dimethylamido)tantalum, or any other metal-containing precursor that may be used to provide a metal dopant material for incorporation into a boron-containing material.

[0041]

[0044] In some embodiments, the deposited metal-doped boron-containing material 420 may consist essentially or substantially of boron and one or more metal dopant materials. Furthermore, in some embodiments, additional dopant precursors may be delivered along with the metal-containing precursor, which may include oxygen or nitrogen, or any other dopant that can tailor the structure of the deposited film to improve transparency, stress, hardness, and thermal resistance. Any number of nitrogen-containing or oxygen-containing precursors may be used in embodiments of the present technology. Furthermore, combination precursors containing multiple of these elements may be used. For example, the oxygen-containing precursor used in some embodiments may be nitrous oxide, which may provide both oxygen and nitrogen for incorporation into the film. The dopant incorporation may be within any range, which may be related to the extinction coefficient; the higher the dopant incorporation, the lower the extinction coefficient of the formed film. In some embodiments, the dopant may be selected for compatibility with the other deposition precursors.

[0042]

[0045] The one or more dopants may be present in any amount or concentration, and may individually or collectively be present in the deposited film at about 0.5 atomic % or greater, and in some embodiments may be present at about 1 atomic % or greater, about 2 atomic % or greater, about 3 atomic % or greater, about 4 atomic % or greater, about 5 atomic % or greater, about 6 atomic % or greater, about 7 atomic % or greater, about 8 atomic % or greater, about 9 atomic % or greater, about 10 atomic % or greater, about 11 atomic % or greater, about 12 atomic % or greater, about 13 atomic % or greater, about 14 atomic % or greater, about 15 atomic % or greater, about 16 atomic % or greater, about 17 atomic % or greater, about 18 atomic % or greater, about 19 atomic % or greater, about 20 atomic % or greater, about 30 atomic % or greater, about 40 atomic % or greater, about 50 atomic % or greater, about 60 atomic % or greater, about 70 atomic % or greater, about 80 atomic % or greater, or more. However, as discussed above, metal dopants can reduce transparency as well as hardness. Therefore, in some embodiments, metal dopant concentrations can be maintained at about 80 atomic % or less, about 70 atomic % or less, about 60 atomic % or less, about 50 atomic % or less, about 40 atomic % or less, about 30 atomic % or less, about 20 atomic % or less, about 15 atomic % or less, about 12 atomic % or less, about 10 atomic % or less, or less. Oxygen and / or nitrogen dopants can also be maintained at levels within these ranges, as discussed above, to further tailor film properties. While incorporation of oxygen and / or nitrogen can promote improvements in extinction coefficient or film stress, the material can also reduce etch selectivity. Therefore, to maintain higher etch selectivity, incorporation of oxygen and nitrogen can be limited or eliminated. In embodiments, a carbon precursor can be included in the deposition precursor to maintain higher etch selectivity. Additional hydrogen precursors, such as diatomic hydrogen, can be included in the deposition precursor, which can affect film transparency. Furthermore, one or more carrier gases, such as argon, can be delivered to facilitate the deposition process.

[0043]

[0046] The temperature of the substrate 405 can further affect the deposition. For example, in some embodiments, the substrate 405 can be maintained at a temperature of about 300°C or higher during deposition, and can be maintained at a temperature of about 325°C or higher, about 350°C or higher, about 375°C or higher, about 400°C or higher, about 425°C or higher, about 450°C or higher, about 475°C or higher, about 500°C or higher, about 525°C or higher, about 550°C or higher, about 575°C or higher, about 600°C or higher, or higher. By performing deposition according to some embodiments of the present technique, hydrogen can be reduced or limited in the film. Increased hydrogen incorporation can increase compressive stress in the film, and therefore, films according to embodiments of the present technique can be characterized by higher tensile properties due to less hydrogen incorporation. Additionally, in some embodiments, the method 300 can include steps that can further reduce hydrogen incorporation in the film. Unlike some prior art techniques, incorporating dopants in accordance with embodiments of the present technique can, in some embodiments, reduce or limit damage from subsequent processing, such as by performing a thermal anneal following deposition of the hard mask material.

[0044]

[0047] As described above, the present technique can increase the selectivity of the hard mask film while limiting loss of hardness. For example, the metal-doped boron-containing material 420 according to some embodiments of the present technique can be characterized by a film hardness that can be maintained at about 20 GPa or greater, and can be maintained at about 22 GPa or greater, about 24 GPa or greater, about 26 GPa or greater, about 28 GPa or greater, about 30 GPa or greater, about 32 GPa or greater, about 34 GPa or greater, about 36 GPa or greater, about 38 GPa or greater, about 40 GPa or greater, about 42 GPa or greater, about 44 GPa or greater, or even greater, despite the incorporation of some metal materials that can reduce the film's hardness. Furthermore, the film can have high selectivity during subsequent etching steps. For example, in some embodiments, the method 300 can further include etching a material on the substrate 405, as further described below.

[0045]

[0048] Metal-doped boron-containing hard mask films according to some embodiments of the present technology can be characterized by extinction coefficients for light of different wavelengths, which can affect lithography processes when implemented. By controlling the incorporation of dopants, including adding oxygen and / or nitrogen dopants, to limit the mask thickness according to embodiments of the present technology, the extinction coefficient at 633 nm can be reduced to about 0.45 or less, about 0.44 or less, about 0.43 or less, about 0.42 or less, about 0.41 or less, about 0.40 or less, about 0.39 or less, about 0.38 or less, about 0.37 or less, about 0.36 or less, about 0.35 or less, about 0.34 or less, about 0.33 or less, about 0.32 or less, about 0.31 or less, about 0.30 or less, about 0.29 or less, about 0.28 or less, about 0.27 or less, about 0.26 or less, about 0.25 or less, or less. This may allow lithography to be extended to thicknesses of about 300 nm or greater, about 350 nm or greater, about 400 nm or greater, or even greater, without performing an additional alignment key opening step.

[0046]

[0049] Furthermore, some embodiments of the present technique can form a bilayer hard mask that can further limit the impact of metal material incorporation while providing improved selectivity to the etched material. For example, as previously described using optional deposition step 315, method 300 can first include forming a plasma of one or more boron-containing precursors in the semiconductor processing region. This process can include maintaining the processing region free of metal-containing dopant precursors during this initial process, thereby initially depositing a boron-containing layer on the substrate 405. A first layer, which can be maintained free of metal dopants, can be formed on the substrate 405 to a first thickness. Then, after a first period of time to develop the thickness of the first layer, a dopant precursor can be supplied in optional step 320. A second layer including a boron-doped material can then be deposited on the first layer of the boron-containing film to form a bilayer film or hard mask. The plasma and flow of the boron-containing precursors are maintained during the process, and after the first period of time, the dopant-containing precursor is added. Deposition can then proceed for a second period of time until a second layer of desired thickness, which may be a metal-doped layer, can be formed.

[0047]

[0050] The first and second periods can be based on the desired thickness of the layers. For example, in some embodiments, the first period can be less than or equal to the second period, and the formed bilayer can have equal thicknesses or the second doped layer can be thicker than the first layer. Thus, in some embodiments, the second layer of metal-doped boron-containing material may be about 25% or more of the thickness of the bilayer, and the second layer may be about 30% or more of the thickness of the bilayer, about 35% or more of the thickness of the bilayer, about 40% or more of the thickness of the bilayer, about 45% or more of the thickness of the bilayer, about 50% or more of the thickness of the bilayer, about 55% or more of the thickness of the bilayer, about 60% or more of the thickness of the bilayer, about 65% or more of the thickness of the bilayer, about 70% or more of the thickness of the bilayer, about 75% or more of the thickness of the bilayer, about 80% or more of the thickness of the bilayer, about 85% or more of the thickness of the bilayer, about 90% or more of the thickness of the bilayer, or more. Utilizing metal-doped mask materials according to embodiments of the present technology can improve selectivity, as described below, and facilitate manufacturing in future process nodes.

[0048]

[0051] In optional step 330, the method 300 may include depositing one or more additional materials on the metal-doped boron-containing material 420. The one or more additional materials may form a stack of materials on the substrate 405. As shown in FIG. 4A , the one or more additional materials may include an oxide hard mask 425 deposited on the metal-doped boron-containing material 420. A carbon hard mask 430 may be deposited on the oxide hard mask 425. One or more antireflective coatings may be deposited on the carbon hard mask. The one or more antireflective coatings may include, but are not limited to, a dielectric antireflective coating 435, a bottom antireflective coating 440, or any other antireflective coating useful in semiconductor processing. A patterned photoresist material 445 may be deposited on the one or more antireflective coatings. The patterned photoresist material 445 may include one or more openings 450 exposing the bottom antireflective coating, such as the bottom antireflective coating 440.

[0049]

[0052] In optional step 335, the pattern from the patterned photoresist 345 can be transferred through one or more additional materials to the metal-doped boron-containing material 420 to expose the metal-doped boron-containing material 420. In an embodiment, as shown in Figure 4B, each layer of material between the patterned photoresist 445 and the metal-doped boron-containing material 420 can be sequentially patterned and removed to transfer the pattern through the one or more additional materials. As shown in Figure 4B, the oxide hard mask 425 can be patterned to transfer the pattern to expose the metal-doped boron-containing material 420.

[0050]

[0053] As shown in FIG. 4C , in step 340, the method 300 can include etching the metal-doped boron-containing material 420. Etching the metal-doped boron-containing material 420 can include supplying a halogen-containing precursor, such as a chlorine-containing precursor and / or a bromine-containing precursor, to a processing region. In embodiments, the chlorine-containing precursor can be or include diatomic chlorine (Cl) or any other chlorine-containing precursor. The bromine-containing precursor can be or include hydrogen bromide (HBr) or any other bromine-containing precursor. Using both a chlorine-containing precursor, such as diatomic chlorine (Cl), and a bromine-containing precursor, such as hydrogen bromide (HBr), can achieve desired etch selectivity. Etching the metal-doped boron-containing material 420 can include forming a plasma effluent of one or more halogen-containing precursors, such as a chlorine-containing precursor and / or a bromine-containing precursor. The chlorine-containing precursor or its plasma effluent can selectively remove the exposed metal-doped boron-containing material 420 relative to the patterned oxide hard mask 425. Etching the metal-doped boron-containing material 420 with a chlorine-containing precursor or its plasma effluent may form non-volatile by-products, such as tungsten hexachloride (WC16) and / or boron trichloride (BC13). The etching in step 340 may also etch the underlying silicon-carbon-nitrogen material 415 (if present) and / or a portion of the underlying silicon-containing material 410. However, to maintain high selectivity, the flow of the chlorine-containing precursor may be stopped once the underlying silicon-containing material 410 is exposed. As described further below, a different etch chemistry may be used to continue transferring the pattern into the underlying silicon-containing material 410.

[0051]

[0054] While etching the metal-doped boron-containing material 420 in step 340, the silicon-containing precursor and / or oxygen-containing precursor are intermittently delivered. The flow of the chlorine-containing precursor can be paused or reduced during delivery of the silicon-containing precursor and / or oxygen-containing precursor. However, it is also contemplated that the flow of the chlorine-containing precursor can be maintained while delivering the silicon-containing precursor and / or oxygen-containing precursor. The silicon-containing precursor and / or oxygen-containing precursor can react to form a passivation material on the sidewalls of the metal-doped boron-containing material 420. While some embodiments can include simultaneously flowing the silicon-containing precursor and / or oxygen-containing precursor to form the passivation material, in other embodiments, flowing only one of the silicon-containing precursor or oxygen-containing precursor can be sufficient to form the passivation material. The passivation material can limit lateral etching of the metal-doped boron-containing material 420 to maintain openings with uniform opening sizes in the metal-doped boron-containing material 420. The passivation material can also increase selectivity during removal. In embodiments, the silicon-containing precursor may be or include silicon tetrachloride (SiCl) or any other silicon-containing precursor, and the oxygen-containing precursor may be or include molecular oxygen (O) or any other oxygen-containing precursor.

[0052]

[0055] As shown in FIG. 4D, in step 345, the silicon-containing material 410 below the metal-doped boron-containing material 420 can be etched. Etching the silicon-containing material 410 can include delivering a fluorine-containing precursor to the processing region. An oxygen-containing precursor can be delivered along with the fluorine-containing precursor. In an embodiment, the fluorine-containing precursor is a fluorocarbon (C x F yThe oxygen-containing precursor may be or may include molecular oxygen (O) or any other oxygen-containing precursor. Etching the silicon-containing material 410 against the metal-doped boron-containing material 420 may include forming a plasma effluent of the fluorine-containing precursor and the oxygen-containing precursor.

[0053]

[0056] The fluorocarbon precursor and oxygen-containing precursor, as well as their plasma effluent, can simultaneously passivate the sidewalls of the metal-doped boron-containing material 420 and etch the underlying silicon-containing material 410. Specifically, plasma generation can dissociate fluorine and / or carbon from the fluorocarbon precursor. Fluorine can function as an etchant species, and carbon can combine with the oxygen-containing precursor to form carbon monoxide (CO) or carbon dioxide (CO), which can be removed from the processing region. Simultaneously, the fluorocarbon can passivate the sidewalls of the metal-doped boron-containing material 420. Metals in the metal-doped boron-containing material, such as tungsten, can further promote fluorine radical formation in the generated plasma effluent. Increased fluorine radical formation can improve the etch rate of the underlying silicon-containing material 410. Furthermore, the generated tungsten fluoride by-product can also contribute to the passivation of the sidewalls of the metal-doped boron-containing material. This passivation, in combination with the fluorocarbon passivation, can reduce clogging of the patterned metal-doped boron-containing material 420 in the openings 450 and also protect the sidewalls of the metal-doped boron-containing material 420 from being etched.

[0054]

[0057] In some embodiments, the metal-doped boron-containing material 420 may be characterized by an etch selectivity relative to the underlying silicon-containing material 410, such as an oxide and / or nitride material, such that the underlying material may be etched at a rate greater than, or about twice as fast as, the rate at which the metal-doped boron-containing material 420 can be etched. Furthermore, the silicon-containing material 410, such as silicon oxide or silicon nitride, may be etched at a rate greater than or equal to about 3.0 times, e.g., greater than or equal to about 3.5 times, greater than or equal to about 4.0 times, greater than or equal to about 4.5 times, greater than or equal to about 5.0 times, greater than or equal to about 5.5 times, greater than or equal to about 6.0 times, greater than or equal to about 6.5 times, greater than or equal to about 7.0 times, greater than or equal to about 7.5 times, greater than or equal to about 8.0 times, greater than or equal to about 8.5 times, greater than or equal to about 9.0 times, greater than or equal to about 9.5 times, greater than or equal to about 10.0 times, or more, the rate at which the metal-doped boron-containing material 420 may be etched. This can at least double the selectivity to the underlying film compared to other hard mask materials, such as amorphous silicon. As a result, by increasing the etch selectivity to the underlying film, a metal-doped boron-containing material 420 with reduced thickness can be formed, improving or maintaining the transparency of the film despite the incorporation of the metal material.

[0055]

[0058] The metal-doped boron-containing material 420 according to the present technology can increase the etch rate of the underlying silicon-containing material 410. In embodiments, the silicon-containing material 410 can be etched at an etch rate of 4400 Å / min or greater, e.g., about 4450 Å / min or greater, about 4500 Å / min or greater, about 4550 Å / min or greater, about 4600 Å / min or greater, about 4650 Å / min or greater, about 4700 Å / min or greater, about 4750 Å / min or greater, about 4800 Å / min or greater, or greater. While not intending to be bound by any particular theory, the metal in the metal-doped boron-containing material 420 may catalyze the formation of etchant radicals, such as fluorine radicals. Furthermore, etchants, such as fluorine, may interact with the metal-doped boron-containing material 420 to form metal-fluorine materials. The metal-fluorine materials may accumulate around the metal-doped boron-containing material 420 and act as a protective layer. WF for tungsten-doped boron materials xMetal fluorine materials, such as materials found in conventional etching processes without the presence of metal dopants, e.g., CF x It can act as a better protective material than the original material. x The metal-fluorine material, such as a metal-doped boron-containing material, can at least partially dissociate after a period of time to provide additional fluorine radicals for etching the underlying silicon-containing material 410. These additional fluorine radicals can further increase the etch rate of the silicon-containing material 410. Generally, etching can etch a portion of the metal-doped boron-containing material 420, and some of the metal in the etched metal-doped boron-containing material 420 may increase the etch selectivity as well as the etch rate of the silicon-containing material 410. After the silicon-containing material 410 has been etched to a desired depth, e.g., to expose the substrate 405, the flow of the fluorine-containing precursor and the flow of the oxygen-containing precursor can be stopped.

[0056]

[0059] As shown in FIG. 4E, in step 350, the method 300 can include removing the metal-doped boron-containing material 420 from the substrate 405. Removing the metal-doped boron-containing material 420 can include providing a halogen-containing precursor to the processing region. The halogen-containing precursor can include, for example, chlorine and / or bromine. In embodiments, the halogen-containing precursor can be or include, for example, diatomic chlorine (Cl), hydrogen bromide (HBr), or any other halogen-containing precursor. In embodiments, a plasma effluent of the halogen-containing precursor can be generated during the removal or stripping of the metal-doped boron-containing material 420. In embodiments, molecular oxygen (O) can be added during the stripping step of the metal-doped boron-containing material 420 to control stripping and prevent undesired removal of adjacent materials, such as the silicon-carbon-nitrogen material 415, if present.

[0057]

[0060] As previously described, plasma effluents of various precursors may be generated during steps 340-350. During each step, source power and / or bias power may be applied to enhance etching or removal. In an exemplary embodiment, source power may be provided at 13.56 MHz and bias power may be provided at 2 MHz, although any other frequency may be used. In embodiments, source power of about 5000 W or less may be provided. Bias power of about 10,000 V or less may be provided. In embodiments, bias power may be maintained at about 2500 V or less during steps 340 and 350, while bias power may be maintained at a higher level, e.g., about 2500 V or more, during step 345.

[0058]

[0061] In embodiments, one or more of steps 340-350 can be performed with varying amounts of source power and bias power to vary the effect of the precursors on the substrate 405 and the materials present on the substrate. For example, during a first period of any of steps 340-350, the source power can be "on" and the bias power can be "off" or "on" at a low level. During the first period, sidewalls of the silicon-containing material 410 and / or the metal-doped boron-containing material 420 can be passivated to limit etching of the material. During a second period, the bias power can be turned "on" or increased from the first period. Furthermore, the source power can be maintained or reduced during the second period. Increasing the bias power can increase the bombardment and directionality of the plasma effluent. The increased bombardment and directionality can result in deeper etching of the silicon-containing material 410 and / or the metal-doped boron-containing material 420. During a third period, both the source power and the bias power can be turned "off" to allow byproducts to be removed from the processing region. Turning the source power and bias power "off" removes by-products to prevent unintentional clogging. The three periods can be repeated in various orders during each of steps 340-350. Furthermore, the source power and bias power can be supplied at different RF powers and voltages throughout steps 340-350 or sequentially during one of steps 340-350.

[0059]

[0062] In embodiments, the temperature can be varied during steps 340-350. For example, during steps 340 and 350, in which the metal-doped boron-containing material 420 is patterned or removed, respectively, the substrate 405 can be maintained at a temperature of about 400° C. or less, and can be maintained at about 375° C. or less, about 350° C. or less, about 325° C. or less, about 300° C. or less, about 275° C. or less, about 250° C. or less, about 225° C. or less, about 200° C. or less, about 175° C. or less, about 150° C. or less, about 125° C. or less, about 100° C. or less, about 75° C. or less, about 50° C. or less, about 25° C. or less, about 0° C. or less, or less. During step 345, during which the silicon-containing material 410 beneath the metal-doped boron-containing material 420 may be etched, the substrate 405 may be maintained at a temperature of about 150° C. or less, and may be maintained at a temperature of about 125° C. or less, about 100° C. or less, about 75° C. or less, about 50° C. or less, about 25° C. or less, about 0° C. or less, about −25° C. or less, about −50° C. or less, about −75° C. or less, about −100° C. or less, about −125° C. or less, about −150° C. or less, or less.

[0060]

[0063] During steps 340 and 350, the metal-containing by-products may have a relatively high boiling or sublimation point, for example, about 100° C. or higher, about 125° C. or higher, about 150° C. or higher, or even higher. Performing at higher temperatures, such as about 150° C. or higher, about 200° C. or higher, may increase the etch rate of the metal-doped boron-containing material 420 and / or increase selectivity relative to the silicon-containing material 410. The increased etch rate and / or selectivity may also allow for more uniform critical dimensions to be maintained during step 340. Furthermore, higher temperatures may facilitate easier transport of the etch by-products. During step 345, the temperature may be maintained lower than the temperature during steps 340 and 350. Performing at a lower temperature, for example, at or below about 150° C., may protect the sidewalls of the silicon-containing material 410 and / or the sidewalls of the metal-doped boron-containing material 420.

[0061]

[0064] In the foregoing description, for purposes of explanation, numerous details are set forth in order to provide an understanding of various embodiments of the present technology. However, it will be apparent to one skilled in the art that particular embodiments may be practiced without some of these details or with additional details.

[0062]

[0065] Although several embodiments have been disclosed, those skilled in the art will recognize that various modifications, alternative structures, and equivalents can be used without departing from the spirit of the embodiments. Moreover, to avoid unnecessarily obscuring the present technology, some well-known processes and elements have not been described. Therefore, the above description should not be construed as limiting the scope of the present technology. Furthermore, while a method or process may be described sequentially or stepwise, it should be understood that steps may be performed simultaneously or in an order different from that listed.

[0063]

[0066] 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, between the upper and lower limit of that range is also specifically disclosed, unless the context clearly dictates otherwise. Any narrower range between any stated value or unstated intervening value in a stated range and any other stated or intervening value in that stated range is also included. The upper and lower limits of these smaller ranges may independently be included or excluded, and each range where the smaller range includes one, both, or neither limit is also included within the technology, subject to any specifically excluded limit in the stated range. Where a stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0064]

[0067] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, a reference to "a precursor" includes a plurality of such precursors; a reference to "the layer" includes a reference to one or more layers and equivalents thereof known to those skilled in the art, and so forth.

[0065]

[0068] Also, as used in this specification and the claims that follow, the terms "comprise," "comprising," "contain," "containing," "include," and "including" specify the presence of stated features, integers, components, or steps, but do not exclude the presence or addition of one or more other features, integers, components, steps, operations, or groups.

Claims

1. 1. A semiconductor processing method comprising: depositing a metal-doped boron-containing material on a substrate disposed in a processing region of a semiconductor processing chamber, the metal-doped boron-containing material comprising a metal dopant comprising tungsten, and the substrate comprising a silicon-containing material; depositing one or more additional materials over the metal-doped boron-containing material, the one or more additional materials comprising a patterned photoresist material; transferring a pattern from the patterned photoresist material to the metal-doped boron-containing material; Etching the metal-doped boron-containing material with a chlorine-containing precursor; etching the silicon-containing material with a fluorine-containing precursor, wherein the metal dopant enhances an etch rate of the silicon-containing material; removing the metal-doped boron-containing material from the substrate with a halogen-containing precursor; A semiconductor processing method comprising:

2. 10. The semiconductor processing method of claim 1, wherein the metal dopant concentration in said metal-doped boron-containing material is maintained at or below about 80 atomic percent.

3. The one or more additional materials are an oxide hard mask deposited on the metal-doped boron-containing material; a carbon hard mask deposited on the oxide hard mask; one or more anti-reflective coatings deposited on the carbon hard mask; 10. The semiconductor processing method of claim 1, wherein the patterned photoresist material overlies the one or more anti-reflective coatings.

4. The chlorine-containing precursor is diatomic chlorine (Cl ２ 10. The semiconductor processing method of claim 1, comprising:

5. applying plasma power to the processing region during etching of the metal-doped boron-containing material. The semiconductor processing method of claim 1 further comprising:

6. intermittently delivering a silicon-containing precursor and an oxygen-containing precursor to form a passivation material on sidewalls of the metal-doped boron-containing material during etching of the metal-doped boron-containing material. The semiconductor processing method of claim 1 further comprising:

7. The silicon-containing precursor is silicon tetrachloride (SiCl ４ ) or The oxygen-containing precursor is molecular oxygen (O ２ 7. The semiconductor processing method of claim 6, comprising:

8. The semiconductor processing method of claim 1 , wherein the fluorine-containing precursor comprises a fluorocarbon.

9. 10. The semiconductor processing method of claim 1, wherein said metal dopant promotes the formation of fluorine radicals during etching of said silicon-containing material.

10. The halogen-containing precursor is diatomic chlorine (Cl ２ 2. The semiconductor processing method of claim 1, wherein the oxidizing agent comprises hydrogen bromide (HBr) or hydrogen bromide (HBr).

11. 1. A semiconductor structure comprising: A substrate; a silicon-oxygen material overlying the substrate; a silicon-carbon-nitrogen material overlying the silicon-oxygen material; and a metal-doped boron-containing material overlying the silicon-carbon-nitrogen material, the metal-doped boron-containing material comprising a metal dopant comprising tungsten; and one or more additional materials overlying the metal-doped boron-containing material, the one or more additional materials including a patterned photoresist material; 1. A semiconductor structure comprising:

12. The one or more additional materials are an oxide hard mask overlying the metal-doped boron-containing material; a carbon hard mask overlying the oxide hard mask; one or more anti-reflective coatings overlying the carbon hard mask; 12. The semiconductor structure of claim 11, wherein the patterned photoresist material overlies the one or more antireflective coatings.

13. 12. The semiconductor structure of claim 11, wherein the metal dopant concentration in the metal-doped boron-containing material is maintained at or below about 80 atomic percent.

14. 12. The semiconductor structure of claim 11, wherein the metal-doped boron-containing material is characterized by a hardness of greater than or equal to about 25 GPa.

15. 12. The semiconductor structure of claim 11, wherein a thickness of the silicon-oxygen material is greater than a thickness of the metal-doped boron-containing material.

16. 1. A semiconductor processing method comprising: depositing a metal-doped boron-containing material over a silicon-containing material overlying a substrate disposed in a processing region of a semiconductor processing chamber, the metal-doped boron-containing material comprising a metal; delivering a fluorine-containing precursor and an oxygen-containing precursor to the processing region of the semiconductor processing chamber; forming a plasma from the fluorine-containing precursor and the oxygen-containing precursor in the processing region of the semiconductor processing chamber; Etching the silicon-containing material, wherein the etching removes a portion of the metal-doped boron-containing material, and the metal increases an etch rate of the silicon-containing material. A semiconductor processing method comprising:

17. 17. The semiconductor processing method of claim 16, wherein the metal-doped boron-containing material further comprises one or more of tungsten, molybdenum, titanium, aluminum, cobalt, ruthenium, tantalum, hafnium, zirconium, silicon, carbon, or nitrogen.

18. 17. The semiconductor processing method of claim 16, wherein said metal-doped boron-containing material further comprises tungsten.

19. depositing a photoresist material over the metal-doped boron-containing material; patterning the photoresist material; transferring a pattern from the patterned photoresist material to the metal-doped boron-containing material; and 17. The semiconductor processing method of claim 16, further comprising:

20. 17. The semiconductor processing method of claim 16, wherein the fluorine-containing precursor comprises a fluorocarbon, and wherein the fluorine-containing precursor passivates sidewalls of the metal-doped boron-containing material.

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