Dry chamber cleaning using thermal and plasma treatments

Abstract

A metal-containing photoresist film may be deposited on a semiconductor substrate. Unintended metal-containing materials may form on the interior surfaces of a processing chamber during deposition, edge and backside cleaning, exposing, baking, developing, etching, or other photolithography operations. Dry chamber cleaning may remove a portion of the unintended metal-containing material by exposure to a plasma. Dry chamber cleaning may remove a portion of the unintended metal-containing material and modify a portion of the unintended metal-containing material by exposure to an etching gas at an elevated temperature without striking a plasma. Dry chamber cleaning may remove the modified metal-containing material using a plasma having a chemical structure configured to form a volatile product of the modified metal-containing material. In some embodiments, the plasma includes a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a mixture thereof.

Description

[Technical Field]

[0001] Incorporation by reference: A PCT Request Form is being filed contemporaneously with this specification as part of the present application. Each application to which this application claims benefit or priority, identified in the contemporaneous PCT Request Form, is incorporated herein by reference in its entirety and for all purposes.

[0002] FIELD OF THE DISCLOSURE This disclosure relates to the removal of photoresist materials in semiconductor fabrication, and more particularly to chamber cleaning of metal-containing photoresist materials in semiconductor fabrication. [Background technology]

[0003] The fabrication of semiconductor devices, such as integrated circuits, is a multi-step process involving photolithography. Generally, the process involves depositing material onto a wafer and patterning the material through lithographic techniques to form structural features (e.g., transistors and circuits) of the semiconductor device. The steps of a typical photolithography process known in the art include preparing a substrate, applying photoresist by, for example, spin coating, exposing the photoresist to light in a desired pattern and causing the exposed areas of the photoresist to become more or less soluble in a developer, developing by applying a developer to remove either the exposed or unexposed areas of the photoresist, and performing subsequent processing, such as by etching or material deposition, to create features on the areas of the substrate where the photoresist was removed.

[0004] The evolution of semiconductor design has created the need for, and been driven by, the ability to create ever-smaller features on semiconductor substrate materials. This technological advancement has been characterized by "Moore's Law," which states that the density of transistors in densely packed integrated circuits doubles every two years. In fact, advances in chip design and manufacturing mean that modern microprocessors can contain billions of transistors and other circuit features on a single chip. Individual features on such chips can be approximately 22 nanometers (nm) or smaller, and in some cases less than 10 nm.

[0005] One challenge in fabricating devices with such small features is the ability to reliably and reproducibly create photolithography masks with sufficient resolution. Current photolithography processes typically use 193 nm ultraviolet (UV) light to expose photoresist. A fundamental problem arises because the light has a wavelength significantly larger than the desired size of the features to be created on the semiconductor substrate. Achieving feature sizes smaller than the wavelength of light requires the use of complex resolution enhancement techniques, such as multi-patterning. Therefore, there has been significant interest and research effort in developing photolithography techniques using shorter wavelength light, such as extreme ultraviolet radiation (EUV), which has a wavelength of 10 nm to 15 nm, e.g., 13.5 nm.

[0006] However, EUV photolithography processes can present challenges, including low power output and light loss during patterning. Conventional organic chemically amplified resists (CARs), similar to those used in 193-nm UV lithography, have potential drawbacks when used in EUV lithography, particularly if they have low absorption coefficients in the EUV region, where diffusion of photoactivated species can result in blurring or line-edge roughness. Furthermore, to provide the etch resistance required to pattern underlying device layers, small features patterned in conventional CAR materials can result in high aspect ratios with the risk of pattern collapse. Therefore, there remains a need for improved EUV photoresist materials with properties such as reduced thickness, greater absorbance, and greater etch resistance.

[0007] The description of the background art provided herein is for purposes of generally presenting the context of the present technology. To the extent described in this background art section, the inventors' work described herein, as well as aspects of the description that do not otherwise qualify as prior art at the time of filing, are not admitted expressly or implicitly as prior art to the present technology. Summary of the Invention

[0008] Provided herein is a method for cleaning a processing chamber. The method includes providing a semiconductor substrate in a processing chamber, the semiconductor substrate having a metal-containing resist film on a surface of the semiconductor substrate and a metalorganic material formed on one or more interior surfaces of the processing chamber. The method further includes exposing the one or more interior surfaces of the processing chamber to a non-plasma etching gas in the processing chamber without the semiconductor substrate in the processing chamber to remove a first portion of the metalorganic material. The method further includes exposing the one or more interior surfaces of the processing chamber to a first plasma in the processing chamber without the semiconductor substrate in the processing chamber to remove a second portion of the metalorganic material.

[0009] In some implementations, exposing one or more interior surfaces to a non-plasma etching gas converts an unremoved portion of the metal-organic material into non-volatile by-products, and the second portion comprises the non-volatile by-products. In some implementations, the first plasma comprises a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a combination thereof. In some implementations, the first plasma comprises a chlorine (Cl) plasma. In some implementations, the non-plasma etching gas comprises a hydrogen halide, boron tribromide, boron trichloride, or a combination thereof. In some implementations, the non-plasma etching gas comprises hydrogen chloride (HCl) or hydrogen bromide (HBr). In some implementations, introducing the non-plasma etching gas comprises heating one or more interior surfaces of the processing chamber to an elevated temperature, the elevated temperature being between about −15° C. and about 200° C., and flowing the non-plasma etching gas into the processing chamber. In some implementations, the method further includes exposing one or more interior surfaces of the processing chamber to a second plasma to remove one or both of residual gases and residual organic materials from the processing chamber. In some implementations, the second plasma includes an oxygen-containing plasma or a hydrogen-containing plasma. In some implementations, the first plasma is configured to form volatile products with a second portion of the organometallic material. In some implementations, the method further includes generating the first plasma in a remote plasma source coupled to the processing chamber. In some implementations, the method further includes generating the first plasma directly in the processing chamber. In some implementations, the metal-containing resist film includes a metal oxide-containing EUV photoresist material. In some implementations, the organometallic material includes at least tin oxide. In some implementations, providing a semiconductor substrate includes depositing a metal-containing resist film on the surface of the semiconductor substrate in the processing chamber. In some implementations, providing a semiconductor substrate includes baking the metal-containing resist film on the surface of the semiconductor substrate in the processing chamber.In some implementations, providing the semiconductor substrate includes dry developing a metal-containing resist film on the surface of the semiconductor substrate in a processing chamber.

[0010] Also provided herein is a method for cleaning a processing chamber. The method includes providing a semiconductor substrate in a processing chamber, the semiconductor substrate having a metal-containing resist film on a surface of the semiconductor substrate and a metalorganic material formed on one or more interior surfaces of the processing chamber. The method further includes exposing one or more interior surfaces of the processing chamber to a first plasma in the processing chamber without the semiconductor substrate in the processing chamber to remove a first portion of the metalorganic material. The method further includes exposing one or more interior surfaces of the processing chamber to a non-plasma etching gas in the processing chamber without the semiconductor substrate in the processing chamber to remove a second portion of the metalorganic material.

[0011] In some implementations, exposing one or more interior surfaces to the first plasma converts an unremoved portion of the organometallic material into non-volatile by-products, and the second portion comprises the non-volatile by-products.

[0012] Also provided herein is a method for cleaning a processing chamber. The method includes providing a semiconductor substrate in a processing chamber, the semiconductor substrate having a metal-containing resist film on a surface of the semiconductor substrate and a metalorganic material formed on one or more interior surfaces of the processing chamber. The method further includes exposing the one or more interior surfaces of the processing chamber to a first plasma in the processing chamber without the semiconductor substrate in the processing chamber to remove at least a substantial portion of the metalorganic material.

[0013] In some implementations, the first plasma comprises a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a combination thereof. In some implementations, the first plasma comprises Cl2, CH4, Ar, or a mixture thereof. In some implementations, the first plasma comprises HBr, Ar, or a mixture thereof. In some implementations, the chamber pressure of the processing chamber during exposure to the first plasma is between about 1 mTorr and about 20 Torr. In some implementations, the method further includes exposing one or more interior surfaces of the processing chamber to a second plasma to remove one or both of residual gases and residual organic materials from the processing chamber without the semiconductor substrate in the processing chamber.

[0014] Also provided herein is an apparatus for cleaning a processing chamber. The apparatus includes a processing chamber having a substrate support configured to support a semiconductor substrate including a metal-containing resist film formed on a surface of the semiconductor substrate, a vacuum line coupled to the processing chamber, and a gas line coupled to the processing chamber. The apparatus further includes a controller configured with instructions for performing the following operations: providing a semiconductor substrate in the processing chamber, wherein a metal-organic material is formed on one or more interior surfaces of the processing chamber; exposing the one or more interior surfaces of the processing chamber to a non-plasma etching gas without the semiconductor substrate in the processing chamber to remove a first portion of the metal-organic material; and exposing the one or more interior surfaces of the processing chamber to a first plasma without the semiconductor substrate in the processing chamber to remove a second portion of the metal-organic material.

[0015] In some implementations, the apparatus further includes a remote plasma source fluidly coupled to the processing chamber, wherein the first plasma is generated in the remote plasma source. In some implementations, the first plasma is generated directly in the processing chamber. In some implementations, the processing chamber is selected from one of the following group: a dry deposition chamber, a beveled edge and / or backside cleaning chamber, a bake chamber, or a dry development chamber. In some implementations, the controller configured with instructions to expose one or more interior surfaces to a non-plasma etching gas is configured with instructions to expose the one or more interior surfaces to the non-plasma etching gas to convert an unremoved portion of the metal-organic material to non-volatile by-products, wherein the second portion includes the non-volatile by-products. In some implementations, the first plasma includes a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a combination thereof, the non-plasma etching gas includes a hydrogen halide, a hydrogen and halogen gas, boron trichloride, or a combination thereof, and the metal-organic material includes at least tin oxide.

[0016] Also provided herein is an apparatus for cleaning a processing chamber. The apparatus includes a processing chamber having a substrate support configured to support a semiconductor substrate including a metal-containing resist film formed on a surface of the semiconductor substrate, a vacuum line coupled to the processing chamber, and a gas line coupled to the processing chamber. The apparatus further includes a controller configured with instructions for performing the following operations: providing a semiconductor substrate in the processing chamber, wherein a metal-organic material is formed on one or more interior surfaces of the processing chamber; exposing the one or more interior surfaces of the processing chamber to a first plasma without the semiconductor substrate in the processing chamber to remove a first portion of the metal-organic material; and exposing the one or more interior surfaces of the processing chamber to a non-plasma etching gas without the semiconductor substrate in the processing chamber to remove a second portion of the metal-organic material.

[0017] In some implementations, the apparatus further includes a remote plasma source fluidly coupled to the processing chamber, wherein the first plasma is generated in the remote plasma source. In some implementations, the first plasma is generated directly in the processing chamber. In some implementations, the processing chamber is selected from one of the following: a dry deposition chamber, a beveled edge and / or backside cleaning chamber, a bake chamber, or a dry development chamber. In some implementations, the controller configured with instructions to expose one or more interior surfaces to the first plasma is configured with instructions to expose the one or more interior surfaces to the first plasma to convert an unremoved portion of the metal-organic material to non-volatile by-products, wherein the second portion includes the non-volatile by-products. In some implementations, the first plasma includes a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, or a combination thereof, the non-plasma etching gas includes a hydrogen halide, a hydrogen and halogen gas, boron trichloride, or a combination thereof, and the metal-organic material includes at least tin oxide.

[0018] Also provided herein is an apparatus for cleaning a processing chamber. The apparatus includes a processing chamber having a substrate support configured to support a semiconductor substrate including a metal-containing resist film formed on a surface of the semiconductor substrate, a vacuum line coupled to the processing chamber, and a gas line coupled to the processing chamber. The apparatus further includes a controller configured with instructions for performing the following operations: providing a semiconductor substrate in the processing chamber, wherein a metal-organic material is formed on one or more interior surfaces of the processing chamber; and exposing the one or more interior surfaces of the processing chamber to a first plasma to remove at least a substantial portion of the metal-organic material without the semiconductor substrate in the processing chamber.

[0019] In some implementations, the first plasma comprises a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a combination thereof, and the organometallic material comprises at least tin oxide. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a flow diagram of an exemplary method for depositing and developing a metal-containing photoresist, according to some implementations.

[0021] [Figure 2A] FIG. 1 is a flow diagram of an exemplary method for performing dry chamber cleaning using thermal and plasma processes, according to some implementations.

[0022] [Figure 2B] FIG. 10 is a flow diagram of an alternative exemplary method for performing dry chamber cleaning using plasma and thermal processes, according to some implementations.

[0023] [Figure 3A] 1A-1C are cross-sectional schematic views of a processing chamber going through various processing stages of dry chamber cleaning using thermal and plasma processes, according to some implementations. [Figure 3B] 1A-1C are cross-sectional schematic views of a processing chamber going through various processing stages of dry chamber cleaning using thermal and plasma processes, according to some implementations. [Figure 3C] 1A-1C are cross-sectional schematic views of a processing chamber going through various processing stages of dry chamber cleaning using thermal and plasma processes, according to some implementations. [Figure 3D] 1A-1C are cross-sectional schematic views of a processing chamber going through various processing stages of dry chamber cleaning using thermal and plasma processes, according to some implementations. [Figure 3E] 1A-1C are cross-sectional schematic views of a processing chamber going through various processing stages of dry chamber cleaning using thermal and plasma processes, according to some implementations. [Figure 3F] 1A-1C are cross-sectional schematic views of a processing chamber going through various processing stages of dry chamber cleaning using thermal and plasma processes, according to some implementations.

[0024] [Figure 4A] 1A-1C are cross-sectional schematic diagrams of various processing stages for the removal of metal-containing EUV photoresist material from chamber walls of a processing chamber according to some implementations. [Figure 4B] 1A-1C are cross-sectional schematic diagrams of various processing stages for the removal of metal-containing EUV photoresist material from chamber walls of a processing chamber according to some implementations. [Figure 4C] 1A-1C are cross-sectional schematic diagrams of various processing stages for the removal of metal-containing EUV photoresist material from chamber walls of a processing chamber according to some implementations. [Figure 4D] 1A-1C are cross-sectional schematic diagrams of various processing stages for the removal of metal-containing EUV photoresist material from chamber walls of a processing chamber according to some implementations.

[0025] [Figure 5] FIG. 1 is a schematic diagram of an exemplary process station suitable for maintaining a low-pressure environment suitable for carrying out the present methods, according to certain disclosed embodiments.

[0026] [Figure 6] FIG. 1 is a schematic diagram of an example multi-station processing tool suitable for implementing various operations in accordance with certain disclosed embodiments.

[0027] [Figure 7] 1 is a cross-sectional schematic diagram of an example inductively coupled plasma device for implementing certain implementations and operations described herein.

[0028] [Figure 8]FIG. 1 depicts a semiconductor process cluster tool architecture having a vacuum-integrated deposition and patterning module interfaced with a vacuum transfer module, suitable for implementing the processes described herein. DETAILED DESCRIPTION OF THE INVENTION

[0029] In this disclosure, the terms "semiconductor wafer," "wafer," "substrate," "wafer substrate," and "partially fabricated integrated circuit" are used interchangeably. Those skilled in the art will understand that the term "partially fabricated integrated circuit" can refer to a silicon wafer during any of the many stages of integrated circuit fabrication. Wafers or substrates used in the semiconductor device industry typically have diameters of 200 mm, 300 mm, or 450 mm. The following detailed description assumes that the present disclosure is implemented on a wafer. However, the present disclosure is not so limited. Workpieces may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces that may utilize the present disclosure include various articles such as printed circuit boards and the like.

[0030] The present disclosure relates generally to the field of semiconductor processing. In certain embodiments, the present disclosure is directed to processes and apparatus for treating photoresists (e.g., EUV-sensitive metal and / or metal oxide-containing photoresists) in the context of EUV patterning or other wavelength patterning, for example, to remove metal oxide-containing materials from a processing chamber. While the following discussion may focus on EUV photoresists, it should be apparent that the photoresists discussed herein may also be suitable for use with other radiation wavelengths, and the techniques and apparatus discussed herein are not limited solely to EUV photoresist production.

[0031] Within this specification, reference will be made in detail to specific embodiments of the present disclosure. Examples of specific embodiments are illustrated in the accompanying drawings. While the present disclosure will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the disclosure to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the present disclosure. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the present disclosure.

[0032] introduction: Patterning thin films in semiconductor processing is often a critical step in semiconductor fabrication. Patterning involves lithography. In traditional photolithography, such as 193 nm photolithography, a pattern is printed by emitting photons from a photon source onto a mask, printing the pattern onto a light-sensitive photoresist, which then triggers a chemical reaction in the photoresist that, after development, removes certain portions of the photoresist to form the pattern.

[0033] Advanced technology nodes (as defined by the International Technology Roadmap for Semiconductors) include nodes 22 nm, 16 nm, and above. At the 16 nm node, for example, the width of a typical via or line in a damascene structure is typically about 30 nm or less. The scaling of features on advanced semiconductor integrated circuits (ICs) and other devices is driving lithography to improve resolution.

[0034] Extreme ultraviolet (EUV) lithography can expand lithography technology by moving to imaging source wavelengths smaller than those achievable with conventional photolithography methods. EUV sources with wavelengths of approximately 10-20 nm, or 11-14 nm, e.g., 13.5 nm, can be used for cutting-edge lithography tools, also known as scanners. EUV radiation is strongly absorbed by a wide range of solid and fluid materials, including quartz and water vapor, and also operates in a vacuum.

[0035] EUV lithography utilizes an EUV resist that is patterned to form a mask for use in etching the underlying layer. The EUV resist can be a polymer-based chemically amplified resist (CAR) produced by a liquid-based spin-on technique. An alternative to CAR is available from Inpria, Corvallis, OR, and is a directly photopatternable metal oxide-containing film, such as those described in U.S. Patent Publication Nos. 2017 / 0102612, 2016 / 021660, and 2016 / 0116839, which are incorporated by reference herein at least for their disclosure of photopatternable metal oxide-containing films. Such films can be produced by spin-on techniques or dry deposition. Metal oxide-containing films can be patterned directly (i.e., without the use of a separate photoresist) by EUV exposure in a vacuum atmosphere providing sub-30 nm patterning resolution, as described, for example, in U.S. Pat. No. 9,996,004, issued June 12, 2018, and entitled "EUV PHOTOPATTERNING OF VAPOR-DEPOSITED METAL OXIDE-CONTAINING HARD MASKS," and / or International Patent Application No. PCT / US2019 / 31618, filed May 9, 2019, and entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," the disclosures of which are incorporated by reference herein, at least with respect to the composition, deposition, and patterning of directly photopatternable metal oxide films to form EUV resist masks. Generally, patterning involves exposing an EUV resist to EUV radiation to form a photopattern in the resist, followed by development to remove portions of the resist with the photopattern to form a mask.

[0036] While this disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, it should also be understood that this disclosure is applicable to other next-generation lithography technologies. In addition to EUV, which includes the standard 13.5 nm EUV wavelength currently in use and under development, the most relevant radiation sources for such lithography are DUV (deep UV), which generally refers to the use of 248 nm or 193 nm excimer laser sources; X-ray, which formally includes EUV in the lower energy range of the X-ray range; and e-beam, which can cover a wide energy range. Particular methods may depend on the specific materials and applications used in the semiconductor substrate and final semiconductor device. Thus, the methods described in this application are merely exemplary of methods and materials that may be used in the present technology.

[0037] These directly photopatternable EUV resists can be composed of or contain highly EUV-absorbing metals and their organometallic oxides / hydroxides and other derivatives. Upon EUV exposure, the EUV photons and secondary electrons generated can induce chemical reactions, such as beta-H elimination reactions, in SnOx-based resists (and other metal oxide-based resists), providing chemical functionality to promote cross-linking and other changes within the resist film. These chemical changes can then be exploited in a development step to selectively remove exposed or unexposed areas of the resist film and to create an etch mask for pattern transfer.

[0038] Metal oxide-containing films can be patterned directly (i.e., without the use of a separate photoresist) by EUV exposure in a vacuum atmosphere providing sub-30 nm patterning resolution, as described, for example, in U.S. Patent No. 9,996,004, entitled "EUV PHOTOPATTERNING OF VAPOR-DEPOSITED METAL OXIDE-CONTAINING HARDMASKS," issued June 12, 2018, the disclosure of which is incorporated herein by reference, at least with respect to the composition, deposition, and patterning of directly photopatternable metal oxide films to form EUV resist masks. Generally, patterning involves exposing an EUV resist to EUV radiation to form a photopattern in the resist, followed by development to remove portions of the resist with the photopattern to form the mask.

[0039] While this disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, it should be understood that this disclosure is also applicable to other next-generation lithography technologies. In addition to EUV, including the standard 13.5 nm EUV wavelength currently in use and under development, the most relevant radiation sources for such lithography are DUV (deep UV), which generally refers to the use of 248 nm or 193 nm excimer laser sources; X-ray, which formally includes EUV in the lower energy range of the X-ray range; and e-beam, which can cover a wide energy range. One such method involves contacting a substrate exposed to hydroxyl groups with a hydrocarbyl-substituted tin capping agent to form a hydrocarbyl-terminated SnOx film as an imaging / PR layer on the surface of the substrate. The specific method may depend on the specific materials and applications used in the semiconductor substrate and final semiconductor device. Therefore, the methods described herein are merely exemplary of methods and materials that may be used in this technology.

[0040] Directly photopatternable EUV resists may be composed of or contain metals and / or metal oxides mixed within an organic component. Metal / metal oxides are very promising in that they can enhance EUV photon absorption, generate secondary electrons, and / or exhibit increased etch selectivity to underlying film stacks and device layers.

[0041] When manufacturing semiconductor devices, it is important that the manufacturing process is accurate and repeatable. Unfortunately, as a semiconductor fabrication reaction chamber processes multiple substrates over time, the processing conditions and chemical structure within the reaction chamber change. During the deposition and application of a metal-containing resist film on a semiconductor substrate, for example, during dry deposition as described herein, there may be some unintentional deposition of metal-containing materials on the chamber surfaces. After several processing operations are performed in the processing chamber, the unintentional formation of metal-containing materials on the chamber surfaces may reach a level that makes the metal-containing material more susceptible to flaking and peeling. In some cases, particles and film impurities originating from the metal-containing materials on the inner surfaces of the processing chamber may fall onto the substrate surface during processing. For example, particles and film impurities may originate from the internal chamber walls, ceiling, showerhead, substrate support, lift pins, gas lines, nozzles, etc. Such particles and film impurities that peel or flake off from the inner surfaces of the processing chamber may result in contamination and defect problems in the semiconductor substrate. Such contamination not only causes contamination in the semiconductor substrate itself, but potentially also in downstream processing tools such as the patterning tool (scanner) and development tool. Additionally, the buildup of metal-containing material can shift deposition conditions due to outgassing or absorption of precursor materials.

[0042] Conventionally, removal of unintentional deposits on the interior surfaces of a processing chamber can be performed by manually opening the processing chamber and mechanically scrubbing / wiping the interior surfaces using one or more cleaning agents. In some cases, these methods can involve replacing parts and can take a day or more to perform chamber maintenance. Such methods are time-consuming, costly, and inefficient.

[0043] Thermal and plasma dry cleaning of metal-containing materials in processing chambers: The present disclosure provides dry cleaning of metal-containing materials from the interior surfaces of a processing chamber. Dry cleaning can be performed using a plasma-only approach, in which all or a substantial portion of the metal-containing material formed on the interior surfaces of the processing chamber is removed by a plasma process. Dry cleaning can be performed using a hybrid thermal and plasma approach, in which some portions of the metal-containing material formed on the interior surfaces of the processing chamber are removed by heat, other portions are modified by a thermal process, and other modified portions are removed or substantially removed by a plasma process. In an alternative implementation, some portions of the metal-containing material formed on the interior surfaces of the processing chamber are removed by a plasma process, other portions are modified by a plasma process, and other modified portions are removed or substantially removed by a thermal process. The thermal process can remove and / or modify the metal-containing material by exposure to a halide-containing chemical structure without applying a plasma. The plasma process can remove and / or modify the metal-containing material by exposure to a plasma, in which the plasma can include a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, or a combination thereof. In some embodiments, dry cleaning of a processing chamber can further involve exposing the interior surfaces of the processing chamber to a plasma to remove residual etching gases and organic materials from the processing chamber. Dry cleaning of a processing chamber can be performed in any processing chamber used in deposition, edge and / or backside cleaning, exposing, baking, developing, or etching operations.

[0044] FIG. 1 presents a flow diagram of an exemplary method for depositing and developing a metal-containing photoresist according to some implementations. Specifically, the flow diagram for process 100 depicts a dry chamber clean when performing metal-containing photoresist deposition, development, and other photolithography operations. The operations of process 100 may be performed in a different order and / or with different, fewer, or additional operations. Aspects of process 100 may be described with reference to FIGS. 2A-2B, 3A-3F, and 4A-4D. One or more operations of process 100 may be performed using an apparatus illustrated in any one of FIGS. 5-8. In some embodiments, the operations of process 100 may be performed, at least in part, according to software stored on one or more non-transitory computer-readable media. In some implementations, a dry chamber clean may be performed after deposition, edge and / or backside clean, post-apply bake, exposure, post-exposure bake, or dry development.

[0045] In block 102 of process 100, a layer of photoresist is deposited. This can be either a dry deposition process, such as an evaporation process, or a wet process, such as a spin-on deposition process.

[0046] The photoresist can be a metal-containing EUV resist. The EUV-sensitive metal or metal oxide-containing film can be deposited on the semiconductor substrate by any suitable technique, including wet (e.g., spin-on) or dry (e.g., CVD) deposition techniques. For example, the described process is demonstrated for organotin oxide-based EUV photoresist compositions, and is applicable to both commercially available spin-coatable formulations (e.g., those available from Inpria Corp, Corvallis, OR) and formulations applied using dry vacuum deposition techniques, as further described below.

[0047] The semiconductor substrate can include any material structure suitable for photolithographic processing, particularly for the production of integrated circuits and other semiconductor devices. In some embodiments, the semiconductor substrate is a silicon wafer. The semiconductor substrate can be a silicon wafer having irregular surface topography and having features fabricated thereon ("sub-features"). As used herein, a "surface" of a substrate is a surface onto which a film of the present disclosure will be deposited or a surface that will be exposed to EUV during processing. Sub-features can include areas from which material has been removed (e.g., by etching) or areas to which material has been added (e.g., by deposition) during processing prior to performing the methods of the present disclosure. Such pre-processing can include the methods of the present disclosure or other processing methods in an iterative process in which two or more layers of features are formed on the substrate.

[0048] EUV-sensitive thin films can be deposited on semiconductor substrates, and such films can act as resists for subsequent EUV lithography and processing. Such EUV-sensitive thin films include materials that undergo changes upon exposure to EUV, such as the loss of bulky pendant substituents bonded to metal atoms in low-density M-OH-rich materials, allowing their cross-linking into denser M-bonded metal oxide materials. Through EUV patterning, regions of the film are created that have modified physical or chemical properties relative to unexposed regions. These properties can be exploited in subsequent processing, such as dissolving either the unexposed or exposed regions, or selectively depositing material in either the exposed or unexposed regions. In some implementations, the unexposed film has a more hydrophobic surface than the exposed film under the conditions under which such subsequent processing is performed. For example, material removal can be achieved by exploiting differences in the film's chemical composition, density, and cross-linking. Removal can occur by dry processing, as further described below.

[0049] In various implementations, the thin film is an organometallic material, such as an organotin material including tin oxide, or other metal oxide material / moiety. The organometallic compound can be made in a gas-phase reaction of an organometallic precursor with a counter-reactant. In various implementations, the organometallic compound is formed by mixing a specific combination of organometallic precursors having bulky alkyl or fluoroalkyl groups with a counter-reactant and polymerizing the mixture in the gas phase to produce a low-density EUV-sensitive material that deposits on the semiconductor substrate.

[0050] In various implementations, organometallic precursors include at least one alkyl group on each metal atom that can survive gas-phase reactions, while other ligands or ions coordinated to the metal atom can be replaced by counter reactants. Organometallic precursors include those of the formula: M a R b L c (Formula 1) where M is an element with a high patterned radiation absorption cross section and R is C n H 2n+1 and the like, preferably n=1-6, L is a ligand, ion, or other moiety that reacts with a counterreactant, a≧1, b≧1, and c≧1.

[0051] In various implementations, M is 1×10 7 cm 2 / mol. M can be selected from the group consisting of, for example, tin, hafnium, tellurium, bismuth, indium, antimony, iodine, germanium, and combinations thereof. In some implementations, M is tin. R can be fluorinated, for example, a compound of formula C n F x H (2n+1)In various implementations, R has at least one beta hydrogen or beta fluorine. For example, R can be selected from the group consisting of methyl, ethyl, i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i-pentyl, t-pentyl, sec-pentyl, and mixtures thereof. L can be any moiety that is readily displaced by a counter reactant to generate an M-OH moiety, such as a moiety selected from the group consisting of an amine (such as a dialkylamino, monoalkylamino), an alkoxy, a carboxylate, a halogen, and mixtures thereof.

[0052] The organometallic precursor can be any of a variety of candidate organometallic precursors. For example, when M is tin, such precursors include t-butyltris(dimethylamino)tin, i-butyltris(dimethylamino)tin, n-butyltris(dimethylamino)tin, sec-butyltris(dimethylamino)tin, i-propyl(tris)dimethylaminotin, n-propyltris(dimethylamino)tin, ethyltris(dimethylamino)tin, and analogous alkyl(tris)(t-butoxy)tin compounds such as t-butyltris(t-butoxy)tin. In some implementations, the organometallic precursor is partially fluorinated.

[0053] Counter-reactants have the ability to replace reactive moieties, ligands, or ions (e.g., L in Formula 1 above) to link at least two metal atoms through a chemical bond. Counter-reactants can include water, peroxides (e.g., hydrogen peroxide), dihydric or polyhydric alcohols, fluorinated dihydric or polyhydric alcohols, fluorinated glycols, and other sources of hydroxy moieties. In various implementations, the counter-reactant reacts with the organometallic precursor by forming oxygen bridges between neighboring metal atoms. Other potential counter-reactants include hydrogen sulfide and hydrogen disulfide, which can cross-link metal atoms via sulfur bridges.

[0054] The thin film may include optional materials in addition to the organometallic precursor and counter-reactant to modify the film's chemical or physical properties, such as to modify the film's sensitivity to EUV or to increase its etch resistance. Such optional materials may be introduced before deposition on the semiconductor substrate, after deposition of the thin film, or both, such as by doping during vapor formation. In some implementations, a mild remote H plasma may be introduced to replace some Sn-L bonds with Sn-H, thereby increasing the reactivity of the resist under EUV.

[0055] In various implementations, EUV-patternable films are fabricated or deposited on semiconductor substrates using vapor deposition equipment and processes, among others known in the art. In such processes, polymerized organometallic materials are formed on the surface of the semiconductor substrate in the gas phase or in situ. Suitable processes include, for example, chemical vapor deposition (CVD), atomic layer deposition (ALD), and ALD with a CVD component, such as discontinuous ALD-like processes in which the metal precursor and counter-reactant are separated in either time or space.

[0056] Generally, the method includes mixing a vapor flow of an organometallic precursor with a vapor flow of a counter-reactant to form a polymerized organometallic material, and depositing the organometallic material onto a surface of a semiconductor substrate. In some implementations, two or more organometallic precursors are included in the vapor flow. In some implementations, two or more counter-reactants are included in the vapor flow. As will be appreciated by those skilled in the art, the mixing and deposition aspects of the process can occur simultaneously in a substantially continuous process.

[0057] In an exemplary continuous CVD process, two or more gas streams of organometallic precursor and counter-reactant sources in separate inlet paths are introduced into a deposition chamber of a CVD apparatus, where they mix and react in the gas phase to form a coagulated polymerized material (e.g., via metal-oxygen-metal bond formation). The streams can be introduced, for example, using separate injection inlets or a dual plenum showerhead. The apparatus is configured to allow the organometallic precursor and counter-reactant flows to mix within the chamber, allowing the organometallic precursor and counter-reactant to react to form a polymerized organometallic material. Without limiting the mechanism, function, or utility of the present technology, it is believed that the product from such a gas-phase reaction will have a heavier molecular weight because the metal atoms are cross-linked by the counter-reactant and then condensed or otherwise deposited onto a semiconductor substrate. In various implementations, the steric hindrance of the bulky alkyl groups prevents the formation of dense networks, producing smooth, amorphous, low-density films.

[0058] In some implementations, the EUV-patternable film is fabricated or deposited on the semiconductor substrate using wet deposition equipment and processes, among others known in the art, for example, an organometallic material is formed by spin coating onto the surface of the semiconductor substrate.

[0059] The thickness of the EUV-patternable film formed on the surface of a semiconductor substrate can vary depending on the surface characteristics, materials used, and processing conditions. In various implementations, the film thickness can range from 0.5 nm to 100 nm and can be thick enough to absorb most of the EUV light under EUV patterning conditions. The EUV-patternable film can correspond to an absorbance equal to or greater than 30%, thereby having significantly fewer EUV photons available toward the bottom of the EUV-patternable film. Higher EUV absorbance leads to more cross-linking and densification near the top of the EUV-exposed film compared to the bottom of the EUV-exposed film. Insufficient cross-linking can make the resist more susceptible to release or disintegration in wet development, but such risks are not present in dry development. Fully dry lithography techniques can facilitate more efficient utilization of EUV photons through more opaque resist films. It should be understood that efficient utilization of EUV photons may occur in EUV-patternable films with higher overall absorbance, but in some cases, the EUV-patternable film may have an absorbance of less than about 30%. For comparison, the maximum overall absorbance of most other resist films may be less than 30% (e.g., 10% or less, or 5% or less), such that the resist material at the bottom of the resist film is fully exposed. In some implementations, the film thickness is 10 nm to 40 nm, or 10 nm to 20 nm. Without limiting the mechanism, function, or utility of the present disclosure, unlike prior art wet spin-coat deposition processes, it is believed that the processes of the present disclosure present fewer limitations on the surface adhesion properties of the substrate and, therefore, may be applicable to a wide range of substrates. Furthermore, as discussed above, the deposited film conforms to surface features, providing the advantage of forming a mask on a substrate, such as a substrate with underlying features, without having to "fill" or separately planarize such features.

[0060] In addition to depositing a metal-containing EUV resist film on a semiconductor substrate in block 102 of process 100, some metal-containing material may form on the interior surfaces of the processing chamber and downstream components. Interior surfaces may include the chamber walls, floor, and ceiling of the processing chamber. Other interior surfaces may include the showerhead, nozzle, ESC / pedestal, and substrate support surfaces, as well as through tunnels or passages connecting the processing chambers. The metal-containing material may form as a result of a dry deposition process, such as a CVD or ALD process. The thickness of the metal-containing material may gradually increase as a result of additional processing (e.g., deposition) operations performed in the processing chamber. The metal-containing material may be prone to spalling, shedding particles, or peeling from the interior surfaces of the processing chamber, causing contamination in downstream processes. The accumulation of metal-containing material may also shift deposition conditions due to outgassing or absorption of precursor materials.

[0061] In block 150 of process 100, a dry chamber clean is performed after the deposition of the metal-containing EUV resist film in block 102 of process 100. This allows the deposition and dry clean to be performed in the same processing chamber. However, it should be understood that in some implementations, the dry chamber clean may be performed in a different processing chamber than the deposition operation. In fact, the dry chamber clean may be performed following an edge and / or backside clean, bake, develop, or etch operation because residues (i.e., metal-containing materials formed on the interior surfaces of the processing chamber) may also form inside the chamber in which any of these operations are performed, which may or may not be the same as the deposition chamber.

[0062] The dry-deposited materials removed are typically composed of Sn, O, C, and N, but the same cleaning techniques can be extended to films of other metal oxide resists and materials. Additionally, this technique can be used for film strip and photoresist rework.

[0063] In block 104, an optional cleaning process is performed to clean the backside and / or beveled edges of the semiconductor substrate. Backside and / or beveled edge cleaning can non-selectively etch the EUV resist film to equally remove films with various levels of oxidation or cross-linking on the substrate backside and beveled edges. During application of the EUV-patternable film by either wet or dry deposition processes, there may be some unintentional deposition of resist material on the substrate beveled edges and / or backside. The unintentional deposition can lead to unwanted particles subsequently migrating to the top surface of the semiconductor substrate and becoming particle defects. Furthermore, this beveled edge and backside deposition can cause downstream processing problems, including contamination of the patterning tool (scanner) and development tool. Traditionally, removal of this beveled edge and backside deposition is performed by wet cleaning techniques. For spin-coated photoresist materials, this process, called edge bead removal (EBR), is performed by directing a flow of solvent from above and below the beveled edge while the substrate is rotating. The same process can be applied to soluble organic tin oxide-based resists deposited by evaporation techniques.

[0064] Substrate bevel edge and / or backside cleaning can also be a dry cleaning process. In some implementations, the dry cleaning process involves vapor and / or plasma with one or more of the following gases: HBr, HCl, BCl3, SOCl2, Cl2, BBr3, H2, O2, PCl3, CH4, methanol, ammonia, formic acid, NF3, and HF. In some implementations, the dry cleaning process can use the same chemistry as the dry development process described herein. For example, the bevel edge and / or backside cleaning can use a hydrogen halide development chemistry. For bevel edge and / or backside cleaning processes, the vapor and / or plasma must be limited to specific areas of the substrate to ensure that only the backside and bevel edge are removed without any film degradation on the front side of the substrate.

[0065] Process conditions can be optimized for beveled edge and / or backside cleaning. In some implementations, higher temperatures, higher pressures, and / or higher reactant flows can lead to increased etch rates. Suitable process conditions for dry beveled edge and backside cleaning can be a reactant flow of 100-10,000 sccm (e.g., 500 sccm HCl, HBr, HI, or H2 and Cl2, or Br2, BCl3, or H2, or other halogen-containing compounds), a temperature of -15°C to 200°C (e.g., 80°C), a pressure of 20-1,000 mTorr (e.g., 100 mTorr) or 50-765 Torr (e.g., 760 Torr), a plasma power of 0 W to 500 W at a high frequency (e.g., 13.56 MHz, 2.45 GHz, 40 KHz, 2 MHz), and a duration of approximately 10-100 seconds, depending on the photoresist film and its composition and properties. Bevel and / or backside cleaning can be accomplished using a Coronus® tool available from Lam Research Corporation, Fremont, CA, although a wider range of process conditions can be used according to the capabilities of the processing reactor.

[0066] The beveled edge and / or backside clean can alternatively be extended to a complete photoresist strip or photoresist “rework” in which the applied EUV photoresist is removed and the semiconductor substrate is prepared for photoresist reapplication, such as when the original photoresist is damaged or otherwise defective. Because photoresist rework must be accomplished without damaging the underlying semiconductor substrate, oxygen-based etches should be avoided. Instead, organic vapor chemistries or variants of halide-containing chemistries may be used. It should be understood that the photoresist rework operation can be applied at any stage during process 100. Thus, the photoresist rework operation can be applied after deposition, after beveled edge and / or backside clean, after PAB processing, after EUV exposure, after PEB processing, after development, or after a hard bake. In some implementations, the photoresist rework can be performed for non-selective removal of exposed and unexposed areas of the photoresist, but selective to the underlying layer.

[0067] In some implementations, the photoresist rework process involves vapor and / or plasma with one or more of the following gases: HBr, HCl, HI, BCl3, Cl2, BBr3, H2, PCl3, CH4, methanol, ammonia, formic acid, NF3, and HF. In some implementations, the photoresist rework may use the same chemistry as the dry chamber cleaning process described herein. For example, the photoresist rework may use a hydrogen halide chemistry.

[0068] Process conditions can be optimized for photoresist rework. In some implementations, higher temperatures, higher pressures, and / or higher reactant flows can lead to increased etch rates. Suitable process conditions for photoresist rework include a reactant flow of 100-5000 sccm (e.g., 500 sccm HCl, HBr, HI, BCl3 or H2 and Cl2 or Br2), a temperature of -20°C to 140°C (e.g., 80°C), a pressure of 20-50,000 mTorr (e.g., 300 mTorr) or 50-765 Torr (e.g., 760 Torr), a plasma power of 0-2000 W (e.g., 500 W) at a high frequency (e.g., 13.56 MHz, 2.45 GHz, 40 KHz, 2 MHz), and a voltage of 0-200 V, depending on the photoresist film and composition and properties. b (Higher biases may be used with harder underlying substrate materials), and a time of about 20 seconds to 30 minutes, sufficient to completely remove the EUV photoresist. These conditions are suitable for some process reactors, e.g., Kiyo etch tools available from Lam Research Corporation, Fremont, CA, but it should be understood that a wider range of process conditions may be used according to the capabilities of the process reactor.

[0069] In block 150 of process 100, a dry chamber clean operation may be performed after the beveled edge and / or backside clean in block 104 of process 100. This allows the beveled edge and / or backside clean and the dry chamber clean to be performed in the same processing chamber. However, it should be understood that in some implementations, the dry chamber clean may be performed in a different processing chamber than the beveled edge and / or backside clean.

[0070] In block 106 of process 100, an optional post-apply bake (PAB) is performed after deposition of the metal-containing EUV resist film and before EUV exposure. The PAB process may involve a combination of thermal treatment, chemical exposure, and moisture to increase the EUV sensitivity of the metal-containing EUV resist film and reduce the EUV dose required to develop a pattern in the metal-containing EUV resist film. The PAB process temperature may be adjusted and optimized to increase the sensitivity of the metal-containing EUV resist film. For example, the process temperature may be about 90°C to about 200°C, or about 150°C to about 190°C. In some implementations, the PAB process may be performed at a pressure between atmospheric and vacuum and for a process duration of about 1 to 15 minutes, e.g., about 2 minutes. In some implementations, the PAB process is performed at a temperature of about 100°C to 230°C for about 1 to 5 minutes.

[0071] In block 150 of process 100, a dry chamber clean operation may be performed after the PAB treatment in block 106 of process 100. This allows the bake and dry chamber clean to be performed in the same processing chamber. However, it should be understood that in some implementations, the dry chamber clean may be performed in a different processing chamber than the PAB treatment.

[0072] In block 108 of process 100, the metal-containing EUV resist film is exposed to EUV radiation to develop a pattern. Generally speaking, the EUV exposure causes changes in chemical composition and cross-linking within the metal-containing EUV resist film, creating a contrast in etch sensitivity that can be exploited for subsequent development.

[0073] The metal-containing EUV resist film can then be patterned by exposing certain regions of the film to EUV light, typically under a relatively high vacuum. Among other useful features, EUV devices and imaging methods herein include methods known in the art. In particular, as discussed above, exposed regions of the film with modified physical or chemical properties relative to unexposed regions are created through EUV patterning. For example, in the exposed regions, metal-carbon bond cleavage can occur through beta-hydrogen elimination, leaving reactive and accessible metal hydride functionality that can be converted to hydroxide and cross-linked metal oxide moieties via metal-oxygen bridges during a subsequent post-exposure bake (PEB) step. This process can be used to create chemical contrast for development as a negative resist. Generally, a higher number of beta-H groups in the alkyl group results in a more sensitive film. This can also be explained as weaker Sn-C bonds with more branching. After exposure, the metal-containing EUV resist film can be baked to induce additional cross-linking of the metal oxide film. The difference in properties between the exposed and unexposed regions can be exploited in subsequent processing, such as dissolving the unexposed regions or depositing materials into the exposed regions. For example, the pattern can be developed using dry methods to form a metal oxide-containing mask.

[0074] In particular, in various implementations, hydrocarbyl-terminated tin oxide present on the surface is converted to hydrogen-terminated tin oxide in the exposed regions of the imaging layer, especially when the exposure is performed in a vacuum using EUV. However, removing the exposed imaging layer from vacuum into air or the controlled introduction of oxygen, ozone, HO, or water can result in the oxidation of surface Sn—H to Sn—OH. The difference in properties between the exposed and unexposed regions can be exploited in subsequent processing, such as by reacting the irradiated regions, the unirradiated regions, or both, with one or more reagents to selectively add or remove material from the imaging layer.

[0075] Without limiting the mechanism, function, or utility of the present technology, e.g., 10 mJ / cm 2 ~100mJ / cm 2 EUV exposure at doses of 1000 nm results in the cleavage of Sn-C bonds, resulting in the loss of alkyl substituents, relieving steric hindrance, and disrupting the low-density film. In addition, the reactive metal-H bonds produced in the beta-hydrogen elimination reaction can react with nearby active groups, such as hydroxyls, in the film, leading to further cross-linking and densification, creating a chemical contrast between exposed and unexposed regions.

[0076] After exposing the metal-containing EUV resist film to EUV light, a photopatterned metal-containing EUV resist is provided, which includes EUV-exposed and unexposed regions.

[0077] In block 150 of process 100, a dry chamber clean operation may be performed after the EUV exposure in block 108 of process 100. This allows the exposure and dry chamber clean to be performed in the same processing chamber. However, it should be understood that in some implementations, the dry chamber clean may be performed in a different processing chamber than the EUV exposure.

[0078] At block 110 of process 100, an optional post-exposure bake (PEB) is performed to further increase the contrast in etch sensitivity of the photopatterned metal-containing EUV resist. The photopatterned metal-containing EUV resist can be heat-treated in the presence of various chemical species to promote cross-linking of the EUV-exposed regions, or can simply be baked on a hotplate in ambient air at, for example, 100°C to 250°C for 1 to 5 minutes (e.g., 190°C for 2 minutes).

[0079] In various implementations, the bake strategy involves careful control of the bake environment, the introduction of reactive gases, and / or the ramping rate of the bake temperature. Examples of useful reactive gases include, for example, air, HO, HO vapor, CO, CO, O, O, CH, CHOH, N, H, NH, NO, NO, alcohol, acetylacetone, formic acid, Ar, He, or mixtures thereof. The PEB process is designed to (1) promote complete vaporization of organic fragments generated during EUV exposure, (2) oxidize any Sn-H, Sn-Sn, or Sn radical species generated by EUV exposure to metal hydroxides, and (3) promote cross-linking of nearby Sn-OH groups to form a more tightly cross-linked SnO-like network. The bake temperature is carefully selected to achieve optimal EUV lithography performance. A PEB temperature that is too low leads to insufficient cross-linking and, consequently, less chemical contrast for development at a given dose. A PEB temperature that is too high also leads to adverse effects, including severe oxidation and film shrinkage in unexposed areas (in this example, areas removed by development of the patterned film to form a mask) and undesirable interdiffusion at the interface between the photopatterned metal-containing EUV resist and the underlayer, both of which can contribute to a loss of chemical contrast and an increase in defect density due to insoluble scum. The PEB processing temperature can be about 100°C to about 300°C, about 170°C to about 290°C, or about 200°C to about 240°C. In some implementations, the PEB process can be performed at a pressure between atmospheric and vacuum and for a processing duration of about 1 to 15 minutes, e.g., about 2 minutes. In some implementations, the PEB thermal treatment can be repeated to further increase etch selectivity.

[0080] In block 150 of process 100, a dry chamber clean operation may be performed after the PEB process in block 110 of process 100. This allows the bake and dry chamber clean to be performed in the same processing chamber. However, it should be understood that in some implementations, the dry chamber clean may be performed in a different processing chamber than the PEB process.

[0081] In block 112 of process 100, the photopatterned metal-containing EUV resist is developed to form a resist mask. In various implementations, either the exposed regions are removed (positive tone) or the unexposed regions are removed (negative tone). In some implementations, development can include selective deposition of the photopatterned metal-containing EUV resist on either the exposed or unexposed regions, followed by an etching operation. In some implementations, development can be performed by exposure to an etching gas containing a halide-containing chemical structure. In some implementations, development can be performed without applying a plasma. Alternatively, development can be performed using a flow of one or more halide-containing etching gases activated in a remote plasma source or by exposure to remote UV radiation. The photoresist for development can include an element selected from the group consisting of tin, hafnium, tellurium, bismuth, indium, antimony, iodine, and germanium. The element can have a high patterning radiation absorption cross section. In some implementations, the element can have a high EUV absorption cross section. In some implementations, the metal-containing EUV resist can have an overall absorbance of greater than 30%. In a fully dry lithography process, this results in more efficient utilization of EUV photons, allowing for the development of thicker and more EUV-opaque resists.

[0082] An example process for development involves subjecting an organotin oxide-containing EUV-sensitive photoresist film (e.g., 10-30 nm thick, e.g., 20 nm) to an EUV exposure dose and post-exposure bake, then developing. The photoresist film can be deposited based on the gas-phase reaction of an organotin precursor, such as isopropyl(tris)(dimethylamino)tin, and water vapor, or it can be a spin-on film containing tin clusters within an organic matrix.

[0083] In block 150 of process 100, a dry chamber clean may be performed after the dry development in block 112 of process 100. This allows the dry development and dry chamber clean to be performed in the same processing chamber. However, it should be understood that in some implementations, the dry chamber clean may be performed in a different processing chamber than the dry development. Furthermore, it should be understood that the dry chamber clean may be performed in the same or a different processing chamber than the etching operation. The etching operation may be applied to etch an underlying substrate layer of a semiconductor substrate.

[0084] In block 114 of process 100, the semiconductor substrate optionally undergoes a hard bake. During the hard bake, the semiconductor substrate is subjected to an elevated temperature. For example, the semiconductor substrate may be subjected to an elevated temperature of about 50° C. or greater, about 100° C. to about 300° C., or about 170° C. to about 290° C. The hard bake may drive off any solvent or etching gases remaining from development.

[0085] FIG. 2A presents a flow diagram of an exemplary method for performing dry chamber cleaning using thermal and plasma processes, according to some embodiments. The operations of process 200 may be performed in a different order and / or with different, fewer, or additional operations. Aspects of process 200 may be described with reference to FIGS. 3A-3F and 4A-4D. One or more operations of process 200 may be performed using an apparatus illustrated in any one of FIGS. 5-8. In some implementations, the operations of process 200 may be performed, at least in part, according to software stored on one or more non-transitory computer-readable media.

[0086] In block 202 of process 200, a semiconductor substrate having a metal-containing resist film on a surface of the semiconductor substrate is provided in a processing chamber. In addition, a metal-organic material is formed on one or more interior surfaces of the processing chamber. The metal-organic material formed on one or more interior surfaces of the processing chamber can have the same or similar chemical composition as the metal-containing resist film on the semiconductor substrate.

[0087] The metal-containing resist film can be deposited on the surface of the semiconductor substrate in the processing chamber or in a separate chamber (i.e., a deposition chamber), where the metal-containing resist film is dry- or wet-deposited on the semiconductor substrate. In some implementations, the metal-containing resist film is provided as a photopatterned metal-containing resist film after development. In some implementations, the metal-containing resist film is provided as a positive- or negative-tone resist film having EUV-exposed and EUV-unexposed regions after EUV exposure. In some implementations, the metal-containing resist film is provided as a photopatternable metal-containing resist film before EUV exposure and development. In some implementations, the metal-containing resist film is a metal-containing EUV resist film, in which case the metal-containing EUV resist film can be an organometallic oxide or an organometallic-containing film. The organometallic oxide film can include tin oxide. Compositions of metal-containing resist films are described, for example, in International Patent Application No. PCT / US2019 / 31618, filed May 9, 2019, which is incorporated by reference in its entirety and for all purposes. Methods include those in which polymerized organometallic materials are produced in the vapor phase and deposited on a semiconductor substrate. For example, elements in the metal-containing resist film can be selected from the group consisting of tin, hafnium, tellurium, bismuth, indium, antimony, iodine, germanium, and combinations thereof.

[0088] The metal-containing resist film may be deposited in a processing chamber or may otherwise undergo processing (e.g., baking, developing, rework, etc.) in the processing chamber. Processing a substrate in a processing chamber may cause unintended resist material to accumulate over time. In some embodiments, the processing chamber in which the semiconductor substrate is provided may be an exposure chamber. The exposure may result in unintended deposits on the chamber surfaces. In some embodiments, the processing chamber in which the semiconductor substrate is provided may be a dry deposition chamber. Providing the semiconductor substrate may involve dry-depositing a metal-containing resist film on the surface of the semiconductor substrate. The unintended metal-containing material may form as an organometallic material on one or more interior surfaces of the processing chamber. The unintended metal-containing material may form as a result of a dry deposition process, such as a CVD or ALD process. In other embodiments, the processing chamber in which the semiconductor substrate is provided may be a beveled edge and / or backside cleaning chamber. Without being limited by any theory, although undesired metal-containing resist films may be removed from certain regions of a semiconductor substrate during beveled edge and / or backside cleaning, such processing may result in redeposition of metal-containing materials on the interior surfaces of the processing chamber. In some other embodiments, the processing chamber in which the semiconductor substrate is provided may be a PAB processing chamber or a PEB processing chamber. In such cases, providing the semiconductor substrate may involve baking a metal-containing resist film on the surface of the semiconductor substrate in the processing chamber. The unintended metal-containing material may form as an organometallic material on one or more interior surfaces of the processing chamber. For example, baking a metal-containing resist film in a PAB processing chamber or a PEB processing chamber may result in outgassing of a material coating on the interior surfaces of the PAB processing chamber or the PEB processing chamber. In some other embodiments, the processing chamber in which the semiconductor substrate is provided may be a development chamber. In such cases, providing the semiconductor substrate may involve dry developing a metal-containing resist film on the surface of the semiconductor substrate. The unintended metal-containing material may form as an organometallic material on one or more interior surfaces of the processing chamber.For example, dry development can result in the formation of volatile by-products that are redeposited as metal-containing materials on one or more interior surfaces of the processing chamber.

[0089] As more and more semiconductor substrates are processed in a processing chamber, unintentional metal-containing materials can grow on the interior surfaces. Unintentional metal-containing materials can form on the chamber walls, ceiling, floor, showerhead surface, nozzle surface, through-hole tunnels and passages, and substrate support surface. Periodic cleaning is required to remove unintentional deposits of metal-containing materials. Cleaning is performed "in situ," where dry chamber cleaning is performed in the same processing chamber where the unintentional metal-containing materials (e.g., organometallic materials) formed.

[0090] 3A shows a cross-sectional schematic view of a processing chamber having a semiconductor substrate supported on a pedestal. A processing chamber 300 for processing a semiconductor substrate 308 may include chamber walls 302 surrounding a processing space of the processing chamber 300 and a pedestal 306 for supporting the semiconductor substrate 308. The chamber walls 302 may include passages 303 connecting the processing chamber 300 to other tools or components, such as a vacuum transport module. In some cases, the processing chamber 300 may further include a showerhead 304 or other gas distributor for introducing process gases into the processing chamber 300. The interior surfaces of the processing chamber 300 may include the chamber walls 302 and other exposed interior surfaces of chamber components. Such other exposed interior surfaces of chamber components may include the exposed surface of the pedestal 306, the exposed surface of the showerhead 304, and the passages 303. In some embodiments, the interior surfaces of the processing chamber 300 may include, for example, aluminum oxide-based ceramic, anodized aluminum, plastic, alloy C22, yttria coating, and stainless steel hardware components (typically downstream). Although the interior surfaces of the processing chamber 300 are not necessarily resistant to plasma and vapors of halogens such as hydrogen halides, the interior surfaces of the processing chamber 300 are typically constructed of materials that are stable in plasma, halogen vapors, and water vapor. In some implementations, the chamber walls 302 of the processing chamber 300 may include aluminum oxide, anodized aluminum, alloy C22, yttria coating, and plastic.

[0091] A semiconductor substrate 308 may be provided in the process chamber 300. The semiconductor substrate 308 may include a substrate layer (not shown) to be etched, where the substrate layer may include spin-on carbon (SoC), spin-on glass (SOG), amorphous carbon, silicon, silicon oxide, silicon nitride, silicon carbide, or silicon oxynitride. A metal-containing photoresist film (not shown) may be dry- or wet-deposited on the substrate layer of the semiconductor substrate 308. The metal-containing photoresist film may be photopatterned to etch the substrate layer of the semiconductor substrate 308. In some implementations, the metal-containing photoresist film is a metal-containing EUV photoresist film, where the metal-containing EUV photoresist is an organometallic oxide or organometallic-containing film. For example, the metal-containing EUV photoresist film may include at least Sn, O, and C atoms.

[0092] FIG. 3B shows a cross-sectional schematic view of a processing chamber having a metal-containing material formed on the interior surfaces of the processing chamber. The metal-containing material 310 is formed on the chamber walls 302 (including the passages 303) of the processing chamber 300. A semiconductor substrate 308 may undergo one or more processing operations, such as lithography processing operations, within the processing chamber 300. In some embodiments, the semiconductor substrate 308 undergoes a deposition operation for depositing a metal-containing resist film. In some embodiments, the semiconductor substrate 308 undergoes an edge and / or backside cleaning operation for removing unwanted metal-containing resist film on the beveled edges and / or backside of the semiconductor substrate 308. In some embodiments, the semiconductor substrate 308 undergoes an exposure operation to create exposed and unexposed regions of the metal-containing resist film. In some embodiments, the semiconductor substrate 308 undergoes a bake operation in a PAB or PEB process of the metal-containing resist film. In some embodiments, the semiconductor substrate 308 undergoes a development operation for removing the exposed or unexposed regions of the metal-containing resist film. During processing of the semiconductor substrate 308, unintentional growth of metal-containing material 310 can accumulate on the chamber walls 302 of the processing chamber 300, as well as on exposed surfaces of the showerhead 304, pedestal 306, and passages 303. The metal-containing material 310 can be undesirable because it can flake or flake off from the interior surfaces of the processing chamber, resulting in contamination, drift, and defect problems in the semiconductor substrate.

[0093] The metal-containing material 310 may have the same composition as the metal-containing photoresist film on the semiconductor substrate 308. In some implementations, the metal-containing material is an organometallic material or an organometallic oxide material. For example, the metal-containing material may include at least Sn, O, and C atoms, or the metal-containing material may include at least Sn, O, C, and N atoms.

[0094] 4A shows a cross-sectional schematic view of a metal-organic material 402 formed on a chamber wall 404 of a processing chamber. The metal-organic material 402 may include metal oxide particles or clusters. In some embodiments, the metal-organic material 402 is formed by a vapor deposition method, such as CVD or ALD. Over time, the metal-organic material 402 may build up a thickness on the chamber wall 404 of the processing chamber. The metal-organic material 402 may be an organic tin oxide.

[0095] Returning to FIG. 2 , in block 204 of process 200, one or more interior surfaces of the processing chamber are exposed to a non-plasma etching gas without a semiconductor substrate in the processing chamber to remove a first portion of the metalorganic material. Some of the other portions may be transformed or otherwise modified by exposure to the non-plasma etching gas. The modified portions of the metalorganic material may constitute non-volatile etching byproducts of the unremoved portions of the metalorganic material. The etching gas may include a halide-containing gas. As used herein, halide refers to anions of F, Cl, Br, or I. In some embodiments, the halide-containing gas may include a hydrogen halide, such as hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), or a combination thereof. The etching gas may include HBr or HCl. In some embodiments, the halide-containing gas may include hydrogen and a halogen gas, such as fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). In some embodiments, the halide-containing gas may include boron trichloride (BCl), boron tribromide (BBr), or a mixture thereof. In other embodiments, the halide-containing gas includes an organic halide, an acyl halide, a carbonyl halide, a thionyl halide, or a mixture thereof. In some cases, the etching gas includes a hydrogen halide, boron trichloride, boron tribromide, or a mixture thereof. In some embodiments, the etching gas is flowed with or without an inert / carrier gas such as He, Ne, Ar, Xe, or N.

[0096] Exposure to an etching gas to remove or modify the metalorganic material can be performed without plasma. The etching gas can remove a first portion of the metalorganic material without applying a plasma. Furthermore, the etching gas can transform or modify other portions of the metalorganic material without applying a plasma. Exposure to a non-plasma etching gas can proceed by heating one or more interior surfaces of the processing chamber to an elevated temperature. One or more heaters can be thermally coupled to one or more surfaces of the processing chamber to heat the one or more surfaces to an elevated temperature. In some embodiments, the elevated temperature can be from about −15° C. to about 200° C., from about −15° C. to about 140° C., or from about 0° C. to about 120° C. Higher temperatures can promote volatilization of etching byproducts. By applying a plasma-free thermal approach, productivity can be significantly improved. However, as discussed below, the thermal process can be followed by exposure to a plasma to further remove the metalorganic material.

[0097] By heating the processing chamber to an elevated temperature, the non-plasma etching gas removes a first portion of the metalorganic material and optionally modifies other portions of the metalorganic material. In some cases, the first portion of the metalorganic material removed by the non-plasma etching gas may represent the bulk or a significant proportion of the metalorganic material. In some implementations, the "significant proportion" of the metalorganic material removed comprises at least 60% by volume, at least 70% by volume, at least 80% by volume, or at least 90% by volume of the metalorganic material formed on one or more interior surfaces of the processing chamber. By way of example, if the metalorganic material has a thickness of about 5 nm, the non-plasma etching gas may remove at least 3.75 nm, at least 4 nm, at least 4.25 nm, at least 4.5 nm, or at least 4.75 nm of the metalorganic material. However, in some other cases, the first portion of the metalorganic material removed by the non-plasma etching gas may represent less than the bulk of the metalorganic material. The non-plasma etching gas may transform or otherwise modify the bulk or a significant proportion of the metalorganic material. The transformed or modified organometallic material may be more easily removable by plasma as discussed below.

[0098] Prior to introducing the non-plasma etching gas, the processing chamber may be prepared at the desired conditions for dry chamber cleaning. Preparation of the processing chamber may achieve specific pressure conditions, levels of loose particles or film impurities, moisture levels, temperature conditions, or protection of surfaces or components (e.g., pedestal) within the processing chamber from the etching gas.

[0099] In some embodiments, preparing the processing chamber may include removing the semiconductor substrate from the processing chamber. In this manner, the processing chamber may be free of the semiconductor substrate or any other processing substrates during the dry chamber clean. Thus, the semiconductor substrate with the metal-containing resist film may be transferred out of the processing chamber prior to the dry chamber clean. In some embodiments, preparing the processing chamber may include providing a dummy substrate on a substrate support in the processing chamber. The dummy substrate may be provided on the substrate support to protect the substrate support (e.g., an electrostatic chuck) from exposure to non-plasma etching gases during the dry chamber clean. The dummy substrate may also be provided on the substrate support to protect the substrate support from exposure to plasma during the dry chamber clean. Alternatively, protection of the substrate support may occur by providing a protective cover on the substrate support during the dry chamber clean.

[0100] In some embodiments, preparing the processing chamber may include purging and / or pumping the processing chamber to remove undesired particles within the processing chamber. A vacuum line or purge line may be coupled to the processing chamber. The vacuum line may include a vacuum pumping system, which may include a one- or two-stage mechanical dry pump and / or a turbomolecular pump. A purge gas may be flowed into the processing chamber to facilitate removal of undesired particles within the processing chamber. Such undesired particles may include particles or fragments from the metal-organic material and its by-products. The vacuum pumping system may reduce the chamber pressure and / or remove the undesired particles from the processing chamber. The vacuum pumping system may be configured to generate a vacuum pressure in a relatively low range (e.g., from about 6 Torr to ambient) or a relatively high range (e.g., from about 1 mTorr to about 6 Torr). In some embodiments, preparing the processing chamber may include a combination of pumping and purging operations.

[0101] Purging the metal organic precursor can be useful to avoid unwanted by-products and ensure sufficient removal of the metal organic CVD precursor before dry chamber cleaning. Sufficient pumping / purging and / or water injection can be performed before dry chamber cleaning to encourage complete reaction. In some embodiments, the chamber walls and other components can be heated to release unreacted precursor.

[0102] In some embodiments, preparing the processing chamber may include increasing the temperature of one or more interior surfaces within the processing chamber. Preheating the interior surfaces of the processing chamber may release unreacted precursors. Preheating the interior surfaces may also release reaction byproducts. The unreacted precursors and byproducts may change the material structure of the metalorganic material on the interior surfaces, which may affect both the thermal and plasma processes of dry chamber cleaning. Preheating the interior surfaces may additionally facilitate the removal of moisture within the processing chamber. Without being limited to any theory, the presence of water vapor retards the reaction between the etching gas and the metalorganic material for removal / conversion of the metalorganic material. Additionally, the increased temperature within the processing chamber promotes a higher etch rate for removal of the metalorganic material. One or more heaters thermally coupled to one or more interior surfaces of the processing chamber heat the one or more interior surfaces to an elevated temperature, such as a temperature of about −20° C. to about 200° C., about −15° C. to about 180° C., or about 0° C. to about 140° C.

[0103] The non-plasma etching gas can be introduced through a showerhead or a separate chamber inlet coupled to the processing chamber. The non-plasma etching gas can flow into the processing chamber to react with the metalorganic material to form volatile products. In some implementations, the non-plasma etching gas can react with the metalorganic material to form volatile products at temperatures below about 200°C. Without being limited to any theory, the metalorganic material can include metalorganic oxide materials with tetrahedral coordination structures, and etching gases with halide-based chemical structures (e.g., HBr or HCl) can add protons to oxygen lone pairs to form volatile byproducts such as R-Sn-Br. Water is also a byproduct. The rate of the reaction can be increased by removing water and increasing the temperature of the processing chamber. After the volatile products are formed, the processing chamber can be pumped and purged to remove the volatile products. Additionally, the processing chamber can be pumped and purged to remove residual etching gas.

[0104] Dry chamber cleaning can be optimized for low etch selectivity or high etch rate of organometallic materials deposited in the processing chamber. In this manner, undesired materials can be removed quickly and efficiently. Low etch selectivity can be achieved due to non-selective removal of photoresist materials and metal oxide materials (e.g., tin oxide). Low etch selectivity can be achieved due to non-selective removal of exposed EUV resist materials and unexposed EUV resist materials. In some embodiments, higher temperatures and / or higher pressures can result in lower etch selectivity of the etching gas. During exposure to the etching gas, the organometallic material on one or more interior surfaces can be subjected to an elevated temperature. The elevated temperature can be from about -20°C to about 200°C, from about -15°C to about 180°C, or from about 0°C to about 140°C. During exposure to the etching gas, the pressure in the processing chamber can be relatively high. In some embodiments, the chamber pressure is from about 0.01 Torr to ambient, from about 0.1 Torr to 100 Torr, or from about 0.1 Torr to about 6 Torr. In some embodiments, the chamber pressure is cycled between a lower pressure and a higher pressure during exposure to the etching gas. The etching gas flow rate can also be adjusted to control the etching selectivity. In some embodiments, the etching gas flow rate is between about 50 sccm and about 10,000 sccm, between about 100 sccm and about 10,000 sccm, or between about 100 sccm and about 5,000 sccm.

[0105] Non-plasma etching gases generally serve to remove metalorganic materials from interior chamber surfaces, where the etch rate can be modulated by adjusting the temperature of one or more interior surfaces of the processing chamber. Metalorganic materials can be removed at etch rates greater than 10 nm / sec. Higher temperatures and / or pressures can increase the etch rate. Resist materials can be removed using steam at various temperatures (e.g., HCl or HBr at temperatures greater than -20°C).

[0106] Due to the ability to thermally remove portions of the as-deposited film (unexposed or uncrosslinked), without the need for the use of plasma, the techniques described herein can clean not only the processing chamber, but also downstream and upstream components of the tool (e.g., exhaust lines running from the processing chamber to the vacuum pump). More generally, this dry chamber cleaning method can be used to clean contaminated parts and components having compositions similar to metals with volatile products involving -Cl, -Br, -F, -H, -CH4, and oxygen and / or R groups.

[0107] In some embodiments, coatings compatible with halogen cleaning chemistries, such as PTFE, anodized aluminum, alloy C22, yttrium oxide (YO), or organic polymer coatings, may be used on chamber walls and other components exposed to dry chamber cleaning. In some embodiments, the processing chamber may include chamber component temperature controls coupled to one or more interior surfaces (e.g., chamber walls) to control the temperature. In some embodiments, the processing chamber may include a gas inlet other than a showerhead for delivery of etching gases. The gas inlet may be located in an area of ​​the processing chamber having a higher concentration of organometallic materials. Alternatively, the gas inlet may be located in an area of ​​the processing chamber that is unlikely to be reached by delivery via the showerhead. In some embodiments, the gas inlet may be located below the substrate support, in a wall of the processing chamber, and / or near the exhaust of the processing chamber. Multiple gas inlets may be used for delivery of etching gases into the processing chamber. This may ensure dry cleaning of the entire processing chamber.

[0108] To prevent corrosion of chamber components, etching gases can be separated from deposition gases / precursors. In various embodiments, etching gases can be delivered to the processing chamber through one or more gas inlets separate from the showerhead, and deposition gases can be delivered to the processing chamber through the showerhead. In some embodiments, the showerhead can provide separate gases by keeping the gases largely separated within the showerhead. The showerhead can include multiple plenum volumes. Multiple exhaust lines can be used to ensure separation of gases downstream from the processing chamber. Switches can be operably coupled to the multiple exhaust lines to enable separation of etching gas chemistries from deposition gases / precursors. For example, hydrogen halide chemistries can be separated from organotin precursors and water vapor. The halides can be exhausted through a first exhaust line during pumping / purging operations, and the deposition precursors and water vapor can be exhausted through a second exhaust line during pumping / purging operations.

[0109] To protect the showerhead, a pressure differential can be used to prevent the etching gas from entering the showerhead (e.g., backflow). In some embodiments, the etching gas can clean the interior surfaces of the showerhead by flowing the etching gas through the showerhead. However, residual halides or moisture can be retained inside the channels of the showerhead. In some embodiments, the showerhead can be made of a transparent material and heated using a suitable light source. For example, an irradiation source tuned to an appropriate wavelength (e.g., IR or blue wavelength) can directly heat the residual halides and / or moisture to remove them. Alternatively, the residual halides and / or moisture can be removed by gas purging.

[0110] In some embodiments, periodic dry chamber cleans may occur upon detection. The detection source may trigger chamber cleans and / or the cleaning endpoint. The detection source may be a sensor installed in the processing chamber, such as a color-based sensor, an intensity-based sensor, a vision-based camera / sensor, or a combination thereof. The sensor may trigger dry chamber cleans by monitoring particle counts or uniformity, wafer counts, or thickness counts. Alternatively, the sensor may trigger dry chamber cleans by an in-situ measurement device for chamber wall deposition. For example, the sensor may detect the presence of photoresist material using infrared (IR) measurements. A dry chamber clean may be triggered after a certain amount of photoresist material is formed or a threshold particle, uniformity, wafer, or thickness count is reached. In some embodiments, a sensor may be installed downstream in the foreline. Such a sensor may detect what gases / byproducts are being exhausted. The dry chamber clean may be terminated when volatile byproducts are no longer detected in the foreline.

[0111] 3C shows a cross-sectional schematic view of the processing chamber during a dry chamber clean using a non-plasma etching gas. The semiconductor substrate 308 of FIGS. 3A and 3B is transferred out of or otherwise removed from the processing chamber 300. An etching gas 320 is flowed into the processing chamber 300 to remove portions of the metal-containing material 310 from the interior surfaces of the processing chamber 300. In this manner, the etching gas 320 may remove portions of the metal-containing material 310 from the chamber walls 302, including the passages 303, and from the exposed surfaces of the showerhead 304 and pedestal 306.

[0112] The etching gas 320 may include a halide-containing gas. In some implementations, the etching gas 320 includes HF, HCl, HBr, HI, BCl3, BBr3, or a mixture thereof. For example, the etching gas includes HBr. The etching gas 320 may remove portions of the metal-containing material 310 without striking a plasma. Thus, some portions of the metal-containing material 310 are removed in a non-plasma thermal process. The interior surfaces of the processing chamber 300 may be heated to a temperature of about −20° C. to about 200° C., about −15° C. to about 180° C., or about 0° C. to about 140° C. to promote removal of the metal-containing material 310. However, some of the unremoved portions of the metal-containing material 310 may remain as residue 312 on the interior surfaces of the processing chamber 300, including the chamber walls 302, the passages 303, and the exposed surfaces of the showerhead 304 and the pedestal 306. The residue 312 may include non-volatile by-products that form as a result of modification / transformation of the metal-containing material 310 by the etching gas 320. The residue 312 may constitute such "decomposed" metal-containing material 310, which may be more easily removable by subsequent plasma exposure, but not by continued exposure to the etching gas 320 in a non-plasma thermal process. In some cases, the non-volatile by-products include non-volatile tin halides (e.g., Sn(II)-Br). The residue 312 may also include redeposited metal-containing material.

[0113] FIG. 4B shows a cross-sectional schematic view of the chamber wall 404 after the etching gas has removed portions of the metalorganic material 402 from the chamber wall 404 and transformed other portions of the metalorganic material 402. The etching gas can be a hydrogen halide, such as HBr. The chamber wall 404 can be heated to an elevated temperature to promote low etch selectivity. The processing chamber can be increased to a high pressure to promote low etch selectivity. The removal and transformation of the metalorganic material 402 can occur without the use of a plasma. Thus, portions of the metalorganic material 402 are removed in a plasma-free thermal process, and the unremoved portions of the metalorganic material 402 are transformed / modified to form residue 406 on the chamber wall 404. The reaction of the etching gas with the metalorganic material 402 can produce volatile as well as non-volatile etching byproducts. The residue 406 can include non-volatile etching byproducts. In some cases, volatile etch by-products may redeposit on the chamber walls 404, in which case the residue 406 may potentially include the redeposited etch by-products along with non-volatile etch by-products.

[0114] Returning to FIG. 2 , in block 206 of process 200, one or more interior surfaces of the processing chamber are exposed to a first plasma to remove a second portion of the metalorganic material without a semiconductor substrate in the processing chamber. The thermal process that removes the first portion of the metalorganic material and converts some other portion of the metalorganic material may be followed by a plasma process that removes or substantially removes some other portion of the converted metalorganic material. The second portion may constitute the converted metalorganic material. As used herein, "substantial removal" of the converted metalorganic material may refer to removal of at least 80% by volume, or even at least 90% by volume, of the converted metalorganic material. The first plasma may be configured to form volatile products with the second portion of the metalorganic material. In some embodiments, the first plasma may include a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a mixture thereof.

[0115] Plasma-activated species of the first plasma can react with a second portion of the metal-organic material to form volatile products. A first process gas, which can be different from the etching gas, can be flowed into the processing chamber or to a remote plasma source to ignite the first plasma. The first process gas can include a halide-containing chemical structure, a hydrogen-containing chemical structure, a hydrocarbon-containing chemical structure, an inert gas-containing chemical structure, or a combination thereof. In some embodiments, the first process gas for generating the first plasma can include Cl2, HCl, BCl3, trichloromethane (CHCl3), dichloromethane (CHCl2), tetrachloromethane (CCl4), HBr, HF, tetrafluoromethane (CF4), nitrogen trifluoride (NF3), trifluoromethane (CHF3), difluoromethane (CH2F2), fluoromethane (CH3F), methane (CH4), hydrogen (H2), or a mixture thereof. As such, the first plasma can be a Cl plasma, an HCl plasma, a BCl plasma, a CHCl plasma, a CHC1 plasma, a CCl plasma, an HBr plasma, an HF plasma, a CF plasma, an NF plasma, a CHF plasma, a CHF plasma, a CHF plasma, a CH plasma, an H plasma, or a mixture thereof. In some embodiments, the first process gas for generating the first plasma can include argon (Ar). Thus, the first plasma can include an Ar plasma.

[0116] In some embodiments, the first plasma is generated directly within the processing chamber. The first process gas can be flowed into the processing chamber and distributed throughout the processing chamber. RF power can be applied to the processing chamber to generate a first plasma containing plasma-activated species (e.g., radicals / ions) of the first process gas. The first plasma can be generated by inductively coupled plasma (ICP) generation, transformer coupled plasma (TCP) generation, capacitively coupled plasma (CCP) generation, or other methods known in the art. For example, the first plasma can be generated within the processing chamber by CCP generation. The first plasma can be controlled to be preferentially directed toward one or more interior surfaces of the processing chamber. Preferentially directing the first plasma in such a manner allows interior surfaces such as the chamber walls, ceiling, floor, through-hole tunnels or passages, exposed surfaces of the showerhead, exposed surfaces of the pedestal, and other chamber components to be exposed to the first plasma.

[0117] In some embodiments, the first plasma is generated in a remote plasma source fluidly coupled to the processing chamber. A first process gas can be flowed into the remote plasma source, and RF power is applied to the remote plasma source to generate plasma-activated species (e.g., radicals / ions) of the first process gas. The first plasma can be generated using ICP, TCP, CCP, or other plasma techniques known in the art. The first plasma can be delivered from the remote plasma source into the processing chamber such that the plasma-activated species are distributed toward one or more interior surfaces of the processing chamber. In some embodiments, the first plasma is delivered from the remote plasma source into the processing chamber through a showerhead. Additionally or alternatively, the first plasma can be delivered into the processing chamber from the remote plasma source through a distributor that preferentially directs the first plasma toward one or more interior surfaces of the processing chamber.

[0118] Process conditions for applying the first plasma can be controlled to remove a second portion of the metal-organic material. In some implementations, the etching gas is composed of a first halide-containing chemical structure, and the first process gas for the first plasma is composed of a second halide-containing chemical structure that may or may not be different from the first halide-containing chemical structure. In one example, the etching gas can include HBr, and the first process gas for the first plasma can include Cl2, BCl3, or a mixture of Cl2 and BCl3. In another example, the etching gas can include HBr, and the first process gas for the first plasma can include HBr, Cl2, H2, Ar, CH4, a mixture of CH4 and H2, a mixture of CH4 and Ar, a mixture of Ar and Cl2, a mixture of CH4 and Cl2, a mixture of HBr and Ar, or a mixture of CH4, Cl2, and Ar. In some implementations, the first process gas flow can be about 50 sccm to about 10,000 sccm, or about 100 sccm to about 5,000 sccm. In some implementations, the temperature can be about -60°C to about 120°C, about -20°C to about 100°C, about -60°C to about 60°C, or about 20°C to about 100°C. In some implementations, the chamber pressure can be about 1 mTorr to about 20 Torr, about 5 mTorr to about 760 Torr, or about 5 mTorr to about 100 mTorr. In some implementations, the plasma power can be about 50 W to about 6,000 W, about 100 W to about 3,000 W, or about 100 W to about 800 W. In some implementations, the wafer bias is about 0 V to about 500 V, about 10 V to about 300 V, or about 20 V to about 200 V. The plasma can be generated using a high RF frequency. In some implementations, the RF frequency is 13.56 MHz, 400 kHz, 2 MHz, 2.45 GHz, or 40 MHz. In some implementations, the duration of exposure to the first plasma is about 5 seconds to about 3000 seconds, about 10 seconds to about 2000 seconds, or about 30 seconds to about 1200 seconds.

[0119] The first plasma may be configured to remove any redeposited and decomposed metalorganic materials remaining in the processing chamber. Without being limited to any theory, the etching gas may form volatile by-products with the metalorganic material in block 204, which may then be redeposited on one or more interior surfaces of the processing chamber. For example, an etching gas including HBr may react with a metalorganic material including SnOx to form volatile R-Sn-Br. Additionally or alternatively, the etching gas may react with a metalorganic material to form non-volatile by-products / compounds. For example, an etching gas including HBr may react with a metalorganic material including SnOx to form volatile R-Sn-Br. x R y The first plasma may react with a photoresist material containing Sn(II)-Br to form a non-volatile salt containing Sn(II)-Br. The second portion of the metalorganic material may be comprised of such a non-volatile salt or by-product. The first plasma may be configured with a suitable chemical structure and reactivity to react with the second portion of the metalorganic material to produce a volatile by-product.

[0120] During plasma exposure, no semiconductor substrate is present in the processing chamber. In some embodiments, the processing chamber may include a dummy substrate on a substrate support within the processing chamber. The dummy substrate may be provided on the substrate support to protect the substrate support (e.g., an electrostatic chuck) from exposure to the plasma during dry chamber cleaning. Alternatively, protection of the substrate support may occur by providing a protective cover over the substrate support during dry chamber cleaning.

[0121] FIG. 3D shows a cross-sectional schematic view of the processing chamber after a dry chamber clean using a non-plasma etching gas. As discussed above, exposure to etching gas 320 in FIG. 3C removes portions of metal-containing material 310 but may leave metal-containing material residue 312. Residue 312 may form on the chamber walls 302 and passages 303, as well as on exposed surfaces of the showerhead 304 and pedestal 306. While etching gas 320 may react with some portions of metal-containing material 310 to form volatile byproducts, etching gas 320 may also react with some other portions of metal-containing material 310 to form non-volatile byproducts / compounds. The non-volatile byproducts formed from the reaction of etching gas 320 with metal-containing material 310 may form residue 312. In some cases, some of the volatile byproducts from etching gas 320 may redeposit on the interior surfaces of processing chamber 300, which may form at least a portion of residue 312. For example, the etching gas 320 may include HBr and the metal-containing material 310 may be SnO x R y If the etching gas 320 contains HBr, the etching gas 320 may react with some of the metal-containing material 310 to produce non-volatile salts of Sn(II)—Br. As a result, continued exposure to HBr in a thermal process may not be sufficient to remove such non-volatile salts from the interior surfaces of the processing chamber 300. The residue 312 may include loose particles that may easily flake or flake off from the interior surfaces of the processing chamber 300, in which case the residue 312 may potentially contaminate the wafer and / or downstream processing tools.

[0122] FIG. 3E shows a cross-sectional schematic view of a processing chamber during a dry chamber clean using a first plasma. The interior surfaces of the processing chamber 300 may be exposed to a first plasma 330 to remove residues 312. After a thermal process using an etching gas 320 to remove portions of the metal-containing material 310, the dry chamber clean may proceed with a plasma process using the first plasma 330 to remove residues 312. The residues 312 may constitute transformed or modified portions of the organometallic material 310, in which case the residues 312 may react with the first plasma 330 to form volatile etching byproducts, but not necessarily with the etching gas 320 to form volatile etching byproducts. Exposure to the first plasma 330 may occur without a semiconductor substrate 308 in the processing chamber 300.

[0123] The first plasma 330 may include radicals and / or ions of a halide-containing gas, a hydrogen-containing gas, a hydrocarbon-containing gas, or a mixture thereof. In some implementations, the first plasma 330 includes plasma-activated species of HBr, Cl, HCl, BCl, CHCl, CHCl, CCl, HBr, HF, CF, NF, CHF, CHF, CHF, CHF, CH, H, Ar, or a mixture thereof. For example, the first plasma 330 includes plasma-activated species of Cl, where such plasma-activated species include chlorine radicals (Cl). * ) Plasma-activated species of halide-containing gases, hydrogen-containing gases, and / or hydrocarbon-containing gases may provide reactive species for etching residue 312.

[0124] In some embodiments, the first plasma 330 is generated directly within the processing chamber 300. The first plasma 330 may be generated using ICP, TCP, CCP, or other suitable plasma generation techniques. For example, the first plasma 330 may be generated in situ within the processing chamber 300 by CCP generation. In such cases, one or both of the showerhead 304 and the pedestal 306 may include electrodes, in which case one or both of the electrodes may be powered to generate the first plasma 330.

[0125] In some embodiments, the first plasma 330 is generated in a remote plasma source (not shown) that is separate from, but fluidly coupled to, the processing chamber 300. The first plasma 330 can be generated using ICP, TCP, CCP, or other suitable plasma generation techniques. In some implementations, the remote plasma source can be located upstream of the processing chamber 300, and radicals of a halide-containing gas, a hydrogen-containing gas, a hydrocarbon-containing gas, and / or an inert gas radical can be delivered into the processing chamber 300 through the showerhead 304.

[0126] All or substantially all of the residue 312 is removed from the interior surfaces of the processing chamber 300 after exposure to the first plasma 330. However, it is possible that some residual contaminants 314 may remain within the processing chamber 300 even after exposure to the first plasma 330. The residual contaminants 314 may be located in areas of the processing chamber 300 that are difficult for the first plasma 330 to reach. Thus, the residual contaminants 314 may include unremoved portions of the residue 312. Additionally or alternatively, the residual contaminants 314 may include residual organic materials, such as carbon, and / or residual etching gases, such as residual halides.

[0127] FIG. 4C shows a cross-sectional schematic view of the chamber wall 404 after plasma exposure removes the residue 406 from the chamber wall 404. The primary plasma can be configured to form volatile byproducts with the residue 406. While the etching gas in a non-plasma thermal process may not be able to remove the residue 406, the primary plasma can have a suitable chemical structure and reactivity for removing the residue 406. In some cases, the primary plasma can include a halide-containing gas such as chlorine, a hydrocarbon-containing gas such as methane, a hydrogen-containing gas such as hydrogen, an inert gas such as argon, or a mixture thereof. After portions of the metalorganic material 402 are removed from the chamber wall 404 by the thermal process, the unremoved portions of the metalorganic material 402 in the form of residue 406 can be removed by a plasma process. In some embodiments, the primary plasma is a direct current plasma generated within the processing chamber. In some embodiments, the primary plasma is a remote plasma generated within a remote plasma source fluidly coupled to the processing chamber. After removal of residue 406, residual etching gas 408 and residual organic material 410 may remain adjacent to or on the chamber walls 404. Other particles or contaminants may remain adjacent to or on the chamber walls 404.

[0128] Returning to FIG. 2 , in block 208 of process 200, one or more interior surfaces of the processing chamber are optionally exposed to a second plasma to remove one or both of residual gases and residual organic materials from the processing chamber. In some embodiments, the second plasma may additionally remove residual salts and other contaminants from the processing chamber. After exposure to the non-plasma etch gas and the first plasma to remove the first and second portions of the organometallic material, some residual impurities or contaminants may still remain in the processing chamber. These residual impurities or contaminants may include residual carbon and / or residual etch gas (e.g., unreacted halides / halogens). In some cases, residual etch products include halides, halide salts, and organic compounds that are sticky and resistant to removal. The accumulation of residual etch products can lead to process drift, resulting in hazardous precautions within the processing chamber. Exposure to the second plasma may quickly remove such residual impurities and contaminants. Exposure to the second plasma restores one or more interior surfaces of the processing chamber to a state free or substantially free of residual organic materials, residual gases, and other contaminants.

[0129] The chemical makeup of the second plasma is different from the chemical makeup of the first plasma. A second process gas different from the first process gas can be flowed into the processing chamber or to a remote plasma source to ignite the second plasma. In some embodiments, the second process gas includes one or both of an oxygen-containing species and a hydrogen-containing species. In some embodiments, the second process gas for generating the second plasma can include oxygen (O), ozone (O), hydrogen (H), water (H), hydrogen peroxide (H), methane (CH), or a mixture thereof. As such, the second plasma can include one or both of an oxygen-containing plasma and a hydrogen-containing plasma. For example, the second plasma can include an O plasma, an O plasma, an H plasma, an H, O plasma, an H, O plasma, a CH plasma, or a mixture thereof.

[0130] In some embodiments, the second plasma is generated directly within the processing chamber. A second process gas can be flowed into the processing chamber and distributed throughout the processing chamber. RF power can be applied to the processing chamber to generate a second plasma containing plasma-activated species (e.g., radicals / ions) of the second process gas. The second plasma can be generated by ICP generation, TCP generation, CCP generation, or other methods known in the art. The second plasma can be controlled to be preferentially directed toward one or more interior surfaces of the processing chamber.

[0131] In some embodiments, the second plasma is generated in a remote plasma source coupled to the processing chamber. A second process gas can be flowed into the remote plasma source, and RF power is applied to the remote plasma source to generate plasma-activated species (e.g., radicals / ions) of the second process gas. The second plasma can be generated using ICP, TCP, CCP, or other plasma techniques known in the art. The second plasma can be delivered from the remote plasma source into the processing chamber such that the plasma-activated species are distributed toward one or more interior surfaces of the processing chamber. In some embodiments, the second plasma is delivered from the remote plasma source into the processing chamber through a showerhead. Additionally or alternatively, the second plasma can be delivered into the processing chamber from the remote plasma source through a distributor that preferentially directs the second plasma toward one or more interior surfaces of the processing chamber.

[0132] The process conditions for applying the second plasma can be controlled to remove residual gases, residual organic materials, and / or other contaminants in the processing chamber. In some implementations, the second process gas can have a different composition from the first process gas. In particular, the first process gas can include a halide-containing chemical structure such as Cl2, and the second process gas can include O2 or H2. In some implementations, the second process gas flow can be from about 50 sccm to about 10,000 sccm, or from about 100 sccm to about 5,000 sccm. In some implementations, the temperature can be from about -60°C to about 140°C, from about -20°C to about 120°C, or from about 20°C to about 100°C. In some implementations, the chamber pressure can be from about 1 mTorr to about 20 Torr, from about 5 mTorr to about 5 Torr, or from about 5 mTorr to about 100 mTorr. In some implementations, the plasma power can be about 50 W to about 6000 W, about 100 W to about 3000 W, or about 100 W to about 800 W. In some implementations, the wafer bias is about 0 V to about 500 V, about 10 V to about 300 V, or about 20 V to about 200 V. The plasma can be generated using a high RF frequency. In some implementations, the RF frequency is 13.56 MHz, 400 kHz, 2 MHz, 2.45 GHz, or 40 mHz. In some implementations, the duration of exposure to the second plasma is about 2 seconds to about 2000 seconds, about 5 seconds to about 1000 seconds, or about 10 seconds to about 500 seconds.

[0133] The second plasma can be configured to remove any residual carbon from the metal-organic material. Additionally, the second plasma can be configured to remove any residual gases, such as residual halides / halogens, used to remove the metal-organic material. An oxidizing gas, such as Cl or Br, can be introduced to oxidize the residual halides / halogens on the inner chamber surfaces. The oxidizing gas can also be effective in removing remaining organic materials, such as carbon-containing residues, on the inner chamber surfaces. Applying the oxidizing gas plasma further accelerates the removal of the residual halides / halogens and organic materials.

[0134] In some embodiments, applying heat along with the second plasma can further accelerate the removal of residual gases, carbon residue, and / or other contaminants within the processing chamber. Higher temperatures can volatilize certain residues. As such, thermal energy can be applied to drive reactions to remove residual gases, carbon residue, and / or other contaminants. One or more heaters can be controlled to adjust the temperature of one or more interior surfaces of the processing chamber. The one or more heaters can adjust the temperature of one or more interior surfaces to an elevated temperature of 20° C. or more to drive the removal of residual gases, carbon residue, and / or other contaminants.

[0135] In some embodiments, purging may follow the exposure to the second plasma to remove excess contaminants. Purging may include flowing an inert gas and / or a reactive gas into the processing chamber. Residual gases may be purged from the processing chamber by purging. In some embodiments, the purging operation may also be referred to as dehalogenation. A purge gas may be flowed into the processing chamber to facilitate removal of unwanted particles within the processing chamber. Such unwanted particles may include particles or fragments from the metalorganic material or byproducts. A vacuum pumping system may reduce the chamber pressure and / or remove the unwanted particles from the processing chamber. Thus, dry chamber cleaning may proceed from a combination of thermal, plasma, and purge processes.

[0136] In some implementations, process 200 may optionally further include conditioning one or more interior surfaces of the processing chamber with a protective coating. This process may also be referred to as chamber "seasoning." In some embodiments, the protective coating may include an organometallic material. The average thickness of the protective coating may be 1 nm or greater, 2 nm or greater, 3 nm or greater, or between about 1 nm and about 5 nm. After a thermal and / or plasma process to perform a dry chamber clean, exposed surfaces of the processing chamber may be susceptible to attack, particularly by halogen-based species. The conditioning operation may provide protection for one or more interior surfaces. In some implementations, conditioning one or more interior surfaces may occur by a vapor-based deposition technique, such as CVD or ALD. By conditioning / seasoning the processing chamber, undesirable first-wafer effects are mitigated when resuming deposition operations on semiconductor substrates.

[0137] 3F shows a cross-sectional schematic view of a processing chamber during a dry chamber clean using a second plasma. The interior surfaces of the processing chamber 300 can be exposed to a second plasma 340 to remove residual contaminants 314 or other impurities. After a plasma process using a first plasma 330 to remove residual contaminants 312, the dry chamber clean can proceed with another plasma process using a second plasma 340 to remove residual contaminants 314. The chemical structure of the first plasma 330 can be different from the chemical structure of the second plasma 340. Exposure to the second plasma 340 can occur without a semiconductor substrate 308 in the processing chamber 300.

[0138] The second plasma 340 may include radicals and / or ions of an oxygen-containing gas, a hydrogen-containing gas, or a mixture thereof. In some implementations, the second plasma 340 includes plasma-activated species of O, O, H, H0, H0, CH, or a mixture thereof. For example, the second plasma 340 includes plasma-activated species of O, where such plasma-activated species include oxygen radicals (O). *) The plasma activated species of the oxygen-containing gas and / or the hydrogen-containing gas may provide reactive species for etching the residual contaminants 314.

[0139] In some embodiments, the second plasma 340 is generated directly within the processing chamber 300. In some embodiments, the second plasma 340 is generated in a remote plasma source (not shown) that is separate from, but fluidly coupled to, the processing chamber 300. The second plasma 340 may be configured to remove residual gases, such as residual halides / halogens. The second plasma 340 may also be configured to remove remaining organic materials as well as any unremoved portions of metal-containing materials. The residual contaminants 314 may include any of the residual substances described above.

[0140] 4D shows a cross-sectional schematic view of the chamber wall 404 after plasma exposure has removed the residual etching gas 408 and residual organic material 410 from the chamber wall 404. A secondary plasma configured to remove the residual etching gas 408 and residual organic material 410 may be generated, in which case the secondary plasma may be different from the primary plasma for removing the residues 406 from the chamber wall 404. In some cases, the secondary plasma may include an oxygen-containing gas, such as oxygen or ozone, a hydrogen-containing gas, such as hydrogen, or a mixture thereof. In some embodiments, a pumping / purging operation may be performed to remove contaminants, such as the residual etching gas 408 and residual organic material 410, from the processing chamber.

[0141] In the present disclosure as discussed above, removal of unintended metal-containing photoresist material may proceed by dry chamber cleaning using a thermal and plasma hybrid approach. In such cases, removal of unintended metal-containing material occurs using a multi-step cleaning process involving a thermal process and a plasma process. The thermal process may remove portions of the metal-containing material and modify other portions of the metal-containing material, and the plasma process may remove or at least substantially remove the modified portions of the metal-containing material. Alternatively, as described below with respect to FIG. 2B, the plasma process may remove portions of the metal-containing material and modify other portions of the metal-containing material, and the thermal process may remove or at least substantially remove the modified portions of the metal-containing material. In some embodiments, the thermal process may involve a halide-based thermal clean without applying a plasma. In some embodiments, the plasma process may involve a halide-based plasma clean followed by an oxygen-based or hydrogen-based plasma process. In some embodiments, exposed surfaces of the processing chamber may be conditioned to protect the chamber surfaces from attack. In some implementations, the plasma process may remove the metal-containing material or at least substantially remove the metal-containing material. In such cases, a subsequent thermal process is unnecessary.

[0142] 2B is a flow diagram of an alternative exemplary method for performing a dry chamber clean using a plasma process or a plasma and thermal process, according to some implementations. The operations of process 250 may be performed in a different order and / or with different, fewer, or additional operations. One or more operations of process 250 may be performed using the apparatus described in any one of FIGS. 5-8. In some implementations, the operations of process 250 may be performed, at least in part, according to software stored on one or more non-transitory computer-readable media.

[0143] In block 252 of process 250, a semiconductor substrate having a metal-containing resist film on a surface thereof is provided in a processing chamber. In addition, a metal-organic material is formed on one or more interior surfaces of the processing chamber. The metal-organic material formed on one or more interior surfaces of the processing chamber may have the same or similar chemical composition as the metal-containing resist film on the semiconductor substrate. Aspects of block 252 of process 250 are described above in block 202 of process 200.

[0144] In block 254 of process 250, one or more interior surfaces of the processing chamber are exposed to a first plasma to remove a first portion of the metal-organic material without a semiconductor substrate in the processing chamber. Some of the other portions may be transformed or otherwise modified by exposure to the first plasma. The modified portions of the metal-organic material may constitute non-volatile etch byproducts of the unremoved portions of the metal-organic material. The first plasma may include a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a mixture thereof. Plasma-activated species of the first plasma may react with the first portion of the metal-organic material to form volatile and non-volatile products. The volatile products may be removed from the processing chamber, while the non-volatile products remain as residue and are later removed by a thermal process.

[0145] A first process gas can be flowed into the processing chamber or into a remote plasma source to ignite the first plasma. In some cases, the first process gas includes a halide-containing gas. In some embodiments, the first plasma is generated directly within the processing chamber. In some embodiments, the first plasma is generated remotely within a remote plasma source that is fluidly coupled to the processing chamber.

[0146] Exposure to the first plasma may remove and / or modify the metalorganic material. In some cases, the first portion of the metalorganic material removed by the first plasma may represent the bulk or a significant proportion of the metalorganic material. However, in some other cases, the first portion of the metalorganic material removed by the first plasma may represent less than the bulk of the metalorganic material. The first plasma may transform or otherwise modify the bulk or a significant proportion of the metalorganic material. The transformed or modified metalorganic material may be more easily removable by non-plasma etching gases, as discussed below.

[0147] The process conditions for applying the first plasma can be controlled to remove a first portion of the metal-organic material. In some implementations, the first process gas for the first plasma is composed of a halide-containing chemical structure. In one example, the first process gas for the first plasma can include HBr, Cl2, BCl3, or a mixture of Cl2 and BCl3. In some implementations, the first process gas for the first plasma is composed of a hydrocarbon-containing chemical structure. For example, the first process gas for the first plasma can include CH4. In some implementations, the first process gas for the first plasma is composed of a halide-containing chemical structure, a hydrocarbon-containing chemical structure, an inert gas, or a mixture thereof. In one example, the first process gas for the first plasma can include Cl2, CH4, Ar, or a mixture thereof. In another example, the first process gas for the first plasma can include HBr, Ar, or a mixture thereof. In some implementations, the first process gas flow can be about 50 sccm to about 10,000 sccm, or about 100 sccm to about 5,000 sccm. In some implementations, the temperature can be about -60°C to about 120°C, about -20°C to about 100°C, about -60°C to about 60°C, or about 20°C to about 100°C. In some implementations, the chamber pressure can be about 1 mTorr to about 20 Torr, about 5 mTorr to about 760 Torr, or about 5 mTorr to about 100 mTorr. In some implementations, the plasma power can be about 50 W to about 6,000 W, about 100 W to about 3,000 W, or about 100 W to about 800 W. In some implementations, the wafer bias is about 0 V to about 500 V, about 10 V to about 300 V, or about 20 V to about 200 V. The plasma can be generated using a high RF frequency. In some implementations, the RF frequency is 13.56 MHz, 400 kHz, 2 MHz, 2.45 GHz, or 40 MHz. In some implementations, the duration of exposure to the first plasma is about 5 seconds to about 3000 seconds, about 10 seconds to about 2000 seconds, or about 30 seconds to about 1200 seconds.

[0148] Prior to exposure to the first plasma, the processing chamber may be prepared in the desired condition for the dry chamber clean. In some embodiments, preparing the processing chamber may include removing the semiconductor substrate from the processing chamber. In this method, the processing chamber may be free of the semiconductor substrate or any other processing substrate during the dry chamber clean. Thus, the semiconductor substrate with the metal-containing resist film may be transferred out of the processing chamber before the dry chamber clean. In some embodiments, preparing the processing chamber may include providing a dummy substrate on a substrate support in the processing chamber. Alternatively, protection of the substrate support may occur by providing a protective cover over the substrate support during the dry chamber clean. In some embodiments, preparing the processing chamber may include purging and / or pumping the processing chamber to remove undesired particles in the processing chamber. In some embodiments, preparing the processing chamber may include increasing the temperature of one or more interior surfaces in the processing chamber.

[0149] In block 256 of process 250, one or more interior surfaces of the processing chamber may be exposed to a non-plasma etching gas to remove a second portion of the metalorganic material without a semiconductor substrate in the processing chamber. The plasma process, which removes a first portion of the metalorganic material and converts some other portion of the metalorganic material, may be followed by a thermal process that removes or substantially removes some other portion of the converted metalorganic material. The second portion may constitute the converted metalorganic material. The non-plasma etching gas may be configured to form volatile products with the second portion of the metalorganic material. In some embodiments, the non-plasma etching gas may include a halide-containing gas. In some embodiments, the halide-containing gas may include a hydrogen halide, such as HF, HCl, HBr, HI, or a combination thereof. In some embodiments, the halide-containing gas may include BCl3, BBr3, or a mixture thereof. In some embodiments, the etching gas is flowed with or without an inert / carrier gas, such as He, Ne, Ar, Xe, or N2.

[0150] The exposure to an etching gas to remove or substantially remove the second portion of the organometallic material can be performed without a plasma. The exposure to a non-plasma etching gas can proceed by heating one or more interior surfaces of the processing chamber to an elevated temperature. One or more heaters can be thermally coupled to one or more surfaces of the processing chamber to heat the one or more surfaces to an elevated temperature. In some embodiments, the elevated temperature can be from about −15° C. to about 200° C., from about −15° C. to about 140° C., or from about 0° C. to 120° C. Higher temperatures can promote volatilization of etching byproducts. By applying plasma-free thermal techniques, productivity can be significantly improved.

[0151] The non-plasma etching gas may react with the second portion of the organometallic material to form volatile products. The non-plasma etching gas may be delivered into the processing chamber through a distributor or other gas inlet that preferentially directs the non-plasma etching gas toward one or more interior surfaces of the processing chamber.

[0152] The non-plasma etching gas can be configured to remove any redeposited and decomposed metalorganic material remaining in the processing chamber. The second portion of the metalorganic material can be comprised of non-volatile salts or by-products. The non-plasma etching gas can be configured with a suitable chemical structure and reactivity to react with the second portion of the metalorganic material to generate volatile by-products.

[0153] During the thermal exposure, no semiconductor substrate is present in the processing chamber. In some embodiments, the processing chamber may include a dummy substrate on a substrate support within the processing chamber. The dummy substrate may be provided on the substrate support to protect the substrate support (e.g., an electrostatic chuck) from exposure to non-plasma etching gases during the dry chamber clean. Alternatively, protection of the substrate support may occur by providing a protective cover over the substrate support during the dry chamber clean.

[0154] Although process 250 is illustrated with a plasma-free thermal process at block 256, the dry chamber cleaning process 250 can proceed without the plasma-free thermal process at block 256. In other words, a dry chamber clean can remove metal-organic materials from one or more interior surfaces of a processing chamber using a first plasma, or using a first plasma and a second plasma (described below). Thus, a dry chamber clean can be achieved using a plasma-only approach.

[0155] In some implementations, in block 258 of process 250, one or more interior surfaces of the processing chamber are optionally exposed to a second plasma to remove one or both of residual gases and residual organic materials from the processing chamber. In some embodiments, the second plasma may additionally remove residual salts and other contaminants from the processing chamber. After exposure to the first plasma, or exposure to the first plasma and non-plasma etching gas, some residual impurities or contaminants may still remain in the processing chamber. Exposure to the second plasma may quickly remove such residual impurities and contaminants.

[0156] The chemical makeup of the second plasma is different from the chemical makeup of the first plasma. A second process gas different from the first process gas can be flowed into the processing chamber or to a remote plasma source to ignite the second plasma. In some embodiments, the second process gas includes one or both of an oxygen-containing species and a hydrogen-containing species. In some embodiments, the second process gas for generating the second plasma can include oxygen (O), ozone (O), hydrogen (H), water (H), hydrogen peroxide (H), methane (CH), or a mixture thereof. As such, the second plasma can include one or both of an oxygen-containing plasma and a hydrogen-containing plasma. For example, the second plasma can include an O plasma, an O plasma, an H plasma, an H, O plasma, an H, O plasma, a CH plasma, or a mixture thereof.

[0157] In some embodiments, the second plasma is generated directly within the processing chamber. A second process gas can be flowed into the processing chamber and distributed throughout the processing chamber. RF power can be applied to the processing chamber to generate a second plasma containing plasma-activated species (e.g., radicals / ions) of the second process gas. The second plasma can be generated by ICP generation, TCP generation, CCP generation, or other methods known in the art. The second plasma can be controlled to be preferentially directed toward one or more interior surfaces of the processing chamber.

[0158] In some embodiments, the second plasma is generated in a remote plasma source coupled to the processing chamber. A second process gas can be flowed into the remote plasma source, and RF power is applied to the remote plasma source to generate plasma-activated species (e.g., radicals / ions) of the second process gas. The second plasma can be generated using ICP, TCP, CCP, or other plasma techniques known in the art. The second plasma can be delivered from the remote plasma source into the processing chamber such that the plasma-activated species are distributed toward one or more interior surfaces of the processing chamber. In some embodiments, the second plasma is delivered from the remote plasma source into the processing chamber through a showerhead. Additionally or alternatively, the second plasma can be delivered into the processing chamber from the remote plasma source through a distributor that preferentially directs the second plasma toward one or more interior surfaces of the processing chamber.

[0159] The process conditions for applying the second plasma can be controlled to remove residual gases, residual organic materials, and / or other contaminants in the processing chamber. In some implementations, the second process gas can have a different composition from the first process gas. In particular, the first process gas can include a halide-containing chemical structure such as Cl2, and the second process gas can include O2 or H2. In some implementations, the second process gas flow can be from about 50 sccm to about 10,000 sccm, or from about 100 sccm to about 5,000 sccm. In some implementations, the temperature can be from about -60°C to about 140°C, from about -20°C to about 120°C, or from about 20°C to about 100°C. In some implementations, the chamber pressure can be from about 1 mTorr to about 20 Torr, from about 5 mTorr to about 5 Torr, or from about 5 mTorr to about 100 mTorr. In some implementations, the plasma power can be about 50 W to about 6000 W, about 100 W to about 3000 W, or about 100 W to about 800 W. In some implementations, the wafer bias is about 0 V to about 500 V, about 10 V to about 300 V, or about 20 V to about 200 V. The plasma can be generated using a high RF frequency. In some implementations, the RF frequency is 13.56 MHz, 400 kHz, 2 MHz, 2.45 GHz, or 40 mHz. In some implementations, the duration of exposure to the second plasma is about 2 seconds to about 2000 seconds, about 5 seconds to about 1000 seconds, or about 10 seconds to about 500 seconds.

[0160] The second plasma can be configured to remove any residual carbon from the metal-organic material. Additionally, the second plasma can be configured to remove any residual gases, such as residual halides / halogens, used to remove the metal-organic material. An oxidizing gas, for example, Cl or Br, can be introduced to oxidize the residual halides / halogens on the inner chamber surfaces. The oxidizing gas can be effective in removing remaining organic materials, such as carbon-containing residues, on the inner chamber surfaces. Applying the oxidizing gas plasma further accelerates the removal of the residual halides / halogens and organic materials.

[0161] In some embodiments, applying heat along with the second plasma can further accelerate the removal of residual gases, carbon residue, and / or other contaminants within the processing chamber. Higher temperatures can volatilize certain residues. As such, thermal energy can be applied to drive reactions to remove residual gases, carbon residue, and / or other contaminants. One or more heaters can be controlled to adjust the temperature of one or more interior surfaces of the processing chamber. The one or more heaters can adjust the temperature of one or more interior surfaces to an elevated temperature of 20° C. or more to drive the removal of residual gases, carbon residue, and / or other contaminants.

[0162] In some embodiments, purging may follow the exposure to the second plasma to remove excess contaminants. Purging may include flowing an inert gas and / or a reactive gas into the processing chamber. Residual gases may be purged from the processing chamber by purging. In some embodiments, the purging operation may also be referred to as dehalogenation. A purge gas may be flowed into the processing chamber to facilitate removal of unwanted particles within the processing chamber. Such unwanted particles may include particles or fragments from the metalorganic material or byproducts. A vacuum pumping system may reduce the chamber pressure and / or remove the unwanted particles from the processing chamber. Thus, dry chamber cleaning may proceed from a combination of thermal, plasma, and purge processes.

[0163] In some implementations, process 250 may optionally further include conditioning one or more interior surfaces of the processing chamber with a protective coating. In some embodiments, the protective coating may include an organometallic material. The average thickness of the protective coating may be 1 nm or greater, 2 nm or greater, 3 nm or greater, or between about 1 nm and about 5 nm. After a thermal and / or plasma process to perform a dry chamber clean, exposed surfaces of the processing chamber may be susceptible to attack, particularly by halogen-based species. The conditioning operation may provide protection for one or more interior surfaces. In some implementations, conditioning one or more interior surfaces may occur by a vapor-based deposition technique, such as CVD or ALD. By conditioning / seasoning the processing chamber, undesirable first-wafer effects are mitigated when resuming deposition operations on semiconductor substrates.

[0164] Various implementations of the present disclosure may include combining all dry operations with deposition, EUV lithography patterning, dry development, and dry chamber cleaning. Various other implementations include a combination of wet and dry processing operations; for example, spin-on EUV photoresist (a wet process) may be combined with dry chamber cleaning or other wet or dry processes as described herein. Also described are various post-deposition (or post-application) processes such as bevel and backside cleaning, chamber cleaning, descumming, smoothing, curing to modify and enhance film features, and photoresist rework processes. Utilizing all dry operations, including dry chamber cleaning, may have certain advantages. Such dry processing operations may avoid the material and productivity costs associated with wet processing operations such as wet chamber cleaning or wet development.

[0165] Although this disclosure often refers to cleaning exposed and / or developed EUV sensitive films, the cleaning processes described may also be used on EUV films of similar composition (e.g., other MO), including unexposed EUV resist films. x R yThis method can be extended to other films containing metal oxides, such as EUV resists, where the metals may form volatile products with -Cl, -Br, -F, -H, -CH, etc., as described herein. Additionally, in some embodiments, films other than EUV resists, such as hard masks, UV resists or films of similar composition having other uses, can be cleaned by this method, and in this regard, the cleaning process described relates to the chemical composition of the film as opposed to its function.

[0166] Device The apparatus of the present disclosure is configured for dry chamber cleaning, such as in-situ dry chamber cleaning. The apparatus may be configured for other processing operations, such as deposition, edge and backside cleaning, post-apply bake, EUV scan, development, post-exposure bake, photoresist rework, descum, smoothing, curing, and other operations. In some implementations, the apparatus is configured to perform all dry operations. In some implementations, the apparatus is configured to perform a combination of wet and dry operations. The apparatus may include a single wafer chamber or multiple stations within the same processing chamber. In the case of multiple stations within the same processing chamber, various processing operations, such as those described in this disclosure, may be performed in different stations within the same processing chamber. In one example, a PEB thermal treatment may be performed in one station and development may be performed in another station.

[0167] An apparatus configured for dry chamber cleaning includes a process chamber having a substrate support. The substrate support can be configured to support a semiconductor substrate having a metal-containing resist film formed thereon. The apparatus can include a gas line coupled to the process chamber for delivery of an etching gas. In some implementations, the etching gas includes a hydrogen halide, such as HBr. The apparatus can include a vacuum line coupled to the process chamber. The vacuum line can be configured for pumping / purging gas from the process chamber. The apparatus can include one or more heaters for thermal control. Such heaters can be provided in the process chamber and / or in the substrate support. In some implementations, there can be multiple gas inlets positioned in the process chamber to flow etching gas near areas prone to the formation of unintended metal-containing materials. The apparatus can further include one or more sensors for detecting particle count, wafer count, thickness count, or other parameters for triggering dry chamber cleaning and / or for the endpoint of the dry chamber cleaning.

[0168] In some implementations, the processing chamber is made of an inexpensive material such as plastic, hi some other implementations, the processing chamber is made of a metal such as anodized aluminum, or a ceramic such as aluminum oxide.

[0169] In some implementations, the processing chamber for performing dry chamber cleaning can be selected from the group consisting of a dry deposition chamber, a beveled edge and / or backside cleaning chamber, a bake chamber, an exposure chamber, a dry development chamber, or an etching chamber. Dry chamber cleaning can be performed in situ with other substrate processing operations when processing photoresist materials. The processing chamber for performing dry chamber cleaning can be configured for cleaning involving one or more plasma processes. The processing chamber for performing dry chamber cleaning can be configured for multi-step cleaning involving thermal and plasma processes. Thus, the processing chamber can be equipped for plasma generation to expose inner chamber surfaces to plasma and for delivery of etching gases to expose inner chamber surfaces to thermal etching gases.

[0170] FIG. 5 depicts a schematic diagram of an example process station suitable for performing dry chamber cleaning, dry developing, bevel and / or backside cleaning, etching, rework, descumming, and smoothing operations, according to some implementations. Multiple process stations 500 may be included in a typical low-pressure process tool environment. For example, FIG. 6 depicts an implementation of a multi-station processing tool 600, such as a VECTOR® processing tool available from Lam Research Corporation, Fremont, CA. In some implementations, one or more hardware parameters of the process tool 600, including those discussed in detail below, may be programmatically adjusted by one or more computer controllers 650.

[0171] The process stations may be configured as modules within a cluster tool. Figure 6 depicts a semiconductor process cluster tool architecture having a vacuum-integrated deposition and patterning module suitable for implementing the implementations described herein. Such a cluster process tool architecture may include a resist deposition module, a resist exposure (EUV scanner) module, a resist development module, and an etch module, as described above and further described below with reference to Figures 7 and 8.

[0172] In some implementations, certain of the processing functions, such as dry development and etching, or dry deposition and dry chamber cleaning, can be performed sequentially in the same module. Implementations of the present disclosure are also directed to methods and apparatus for receiving a wafer, including an EUV resist thin film layer deposited on a layer or layer stack to be etched, into a dry development / etch chamber after being photo-patterned in an EUV scanner, dry developing the photo-patterned EUV resist thin film layer, and then etching the underlying layer using the patterned EUV resist as a mask, as described herein.

[0173] 5, the process station 500 is in fluid communication with a reactant delivery system 501a for delivering process gases to a distribution showerhead 506. The reactant delivery system 501a optionally includes a mixing vessel 504 for mixing and / or conditioning the process gases for delivery to the showerhead 506. One or more mixing vessel inlet valves 520 can control the introduction of process gases into the mixing vessel 504. If plasma exposure is used, the plasma can also be delivered to the showerhead 506 or generated within the process station 500.

[0174] 5 includes an optional evaporation point 503 for evaporating a liquid reactant to be delivered to the mixing vessel 504. In some implementations, a liquid flow controller (LFC) upstream of the evaporation point 503 can be provided to control the mass flow of liquid for evaporation and delivery to the process station 500. For example, the LFC can include a thermal mass flow meter (MFM) located downstream of the LFC, where a plunger valve of the LFC can be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM.

[0175] 5, the substrate 512 is located directly below the showerhead 506 and is shown resting on a pedestal 508. The showerhead 506 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to the substrate 512.

[0176] In some implementations, the pedestal 508 can be raised or lowered to expose the substrate 512 to the volume between the substrate 512 and the showerhead 506. It should be understood that in some implementations, the height of the pedestal can be programmatically adjusted by a suitable computer controller 550. In some implementations, the showerhead 506 can have multiple plenum volumes with multiple temperature controls.

[0177] In some implementations, the stage 508 can be temperature controlled by a heater 510. In some implementations, the stage 508 can be heated to temperatures greater than −20° C. up to 300° C. or more, e.g., 40° C. to 160° C., such as about 80° C. to 140° C., during non-plasma thermal exposure as described in the disclosed implementations. In some implementations, the heater 510 of the stage 508 can include multiple independently controllable temperature control zones.

[0178] Additionally, in some implementations, pressure control for the process station 500 may be provided by a butterfly valve 518. As shown in the implementation of FIG. 5, the butterfly valve 518 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some implementations, pressure control of the process station 500 may also be adjusted by varying the flow rate of one or more gases introduced to the process station 500.

[0179] In some implementations, a portion of the showerhead 506 can be adjusted relative to the pedestal 508 to change the volume between the substrate 512 and the showerhead 506. Furthermore, it should be understood that the vertical position of the pedestal 508 and / or the showerhead 506 can be changed by any suitable mechanism within the scope of the present disclosure. In some implementations, the pedestal 508 can include a rotation axis for rotating the orientation of the substrate 512. It should be understood that in some implementations, one or more of these example adjustments can be programmatically implemented by one or more suitable computer controllers.

[0180] If plasma may be used, for example, in a dry chamber cleaning operation, the showerhead 506 and / or pedestal 508 are in electrical communication with a radio frequency (RF) power source 514 and a matching network 516 to power the plasma. Thus, one or both of the showerhead 506 and the pedestal 508 may be powered for plasma generation. In some implementations, plasma energy may be controlled by controlling one or more of process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 514 and the matching network 516 may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers are up to about 6000 W, up to about 3000 W, or up to about 1000 W.

[0181] In some implementations, instructions for the controller may be provided by input / output control (IOC) sequencing instructions. In one example, instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe. In some cases, process recipe phases may be arranged sequentially such that all instructions for a process phase are executed simultaneously with that process phase. In some implementations, instructions for setting one or more reactor parameters may be included in a recipe phase. For example, a recipe phase may include instructions for setting a flow rate of an etching gas, such as HBr, and a time delay instruction for the recipe phase. In some implementations, the controller may include any of the features described below with respect to the system controller 650 of FIG. 6.

[0182] As described above, one or more process stations may be included in a multi-station processing tool. FIG. 6 shows a schematic diagram of an implementation of a multi-station processing tool 600 having an inbound load lock 602 and an outbound load lock 604, either or both of which may include a remote plasma source. A robot 606 at atmospheric pressure is configured to move wafers from a cassette loaded via a pod 608 into the inbound load lock 602 through an atmospheric port 610. The wafer is placed by the robot 606 on a pedestal 612 in the inbound load lock 602, the atmospheric port 610 is closed, and the load lock is pumped down. If the inbound load lock 602 includes a remote plasma source, the wafer may be exposed to a remote plasma treatment to treat the substrate surface within the load lock before being introduced into a processing chamber 614. Additionally, the wafer may also be heated in the inbound load lock 602 as well, for example, to remove moisture and absorbed gases. Next, a chamber transfer port 616 to the processing chamber 614 is opened, and another robot (not shown) places the wafer into the reactor on the pedestal of the first station shown in the reactor for processing. While the implementation depicted in Figure 6 includes a load lock, it should be understood that in some implementations, direct entry of the wafer into a process station may be provided.

[0183] The depicted processing chamber 614 includes four process stations, numbered 1 through 4 in the implementation shown in FIG. 6 . Each station has a heated pedestal (designated 618 for station 1) and a gas line inlet. It should be understood that in some implementations, each process station may have different or multiple purposes. For example, in some implementations, a process station may be switchable between a thermal processing mode and a plasma processing mode. Additionally or alternatively, in some implementations, the processing chamber 614 may include one or more matched pairs of thermal and plasma processing stations. While the depicted processing chamber 614 includes four stations, it should be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some implementations, the processing chamber may have five or more stations, while in other implementations, the processing chamber may have three or fewer stations.

[0184] FIG. 6 depicts an implementation of a wafer handling system 690 for transferring wafers within the processing chamber 614. In some implementations, the wafer handling system 690 can transfer wafers between various process stations and / or between a process station and a load lock. It should be understood that any suitable wafer handling system can be used. Non-limiting examples include a wafer carousel and a wafer handling robot. FIG. 6 also depicts an implementation of a system controller 650 used to control the process conditions and hardware status of the process tool 600. The system controller 650 can include one or more memory devices 656, one or more mass storage devices 654, and one or more processors 652. The processor 652 can include a CPU or computer, analog and / or digital input / output connections, stepper motor control boards, etc.

[0185] In some implementations, the system controller 650 controls all of the activity of the process tool 600. The system controller 650 executes system control software 658, which is stored on mass storage device 654, loaded into memory device 656, and executed on processor 652. Alternatively, control logic may be hard-coded into the controller 650. Application-specific integrated circuits, programmable logic devices (e.g., field-programmable gate arrays, or FPGAs), and the like may be used for these purposes. In the following discussion, wherever "software" or "code" is used, functionally equivalent hard-coded logic may be used therein. The system control software 658 may include instructions for controlling the timing, mixture of gases, gas flow rates, chamber and / or station pressure, chamber and / or station temperature, wafer temperature, target power levels, RF power levels, substrate stage, chuck and / or susceptor position, and other parameters of a particular process performed by the process tool 600. The system control software 658 may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of the process tool components used to perform the various process tool processes. The system control software 658 may be coded in any suitable computer-readable programming language.

[0186] In some implementations, the system control software 658 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. Other computer software and / or programs stored on the mass storage device 654 and / or memory device 656 associated with the system controller 650 may be used in some implementations. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0187] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal 618 and to control the spacing between the substrate and other parts of the process tool 600.

[0188] The process gas control program may include code for controlling process gas (e.g., etching gas) composition and flow rate, and optionally code for flowing gas into one or more process stations prior to deposition to stabilize the pressure in the process station. The pressure control program may include code for controlling the pressure in the process station by, for example, adjusting a throttle valve in the exhaust system of the process station, gas flow into the process station, etc.

[0189] The heater control program may include code for controlling current to a heating device used to heat the substrate or an inner chamber surface. Alternatively, the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate or an inner chamber surface.

[0190] The plasma control program may include code for setting RF power levels applied to process electrodes in one or more process stations according to implementations herein.

[0191] The pressure control program may include code for maintaining pressure in the reaction chamber according to implementations herein.

[0192] In some implementations, there may be a user interface associated with the system controller 650. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0193] In some implementations, the parameters adjusted by the system controller 650 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), etc. These parameters may be provided to the user in the form of a recipe, which may be entered using a user interface.

[0194] In some implementations, the system controller 650 may be configured with instructions to perform the following operations: providing a semiconductor substrate in a processing chamber, where a metalorganic material is formed on one or more interior surfaces of the processing chamber 614; exposing one or more interior surfaces of the processing chamber 614 to a non-plasma etching gas without the semiconductor substrate in the processing chamber 614 to remove a first portion of the metalorganic material; and exposing one or more interior surfaces of the processing chamber 614 to a first plasma without the semiconductor substrate in the processing chamber 614 to remove a second portion of the metalorganic material. In some implementations, the system controller 650 may be further configured with instructions to expose one or more interior surfaces of the processing chamber 614 to a second plasma to remove one or both of residual gases and residual organic materials from the processing chamber 614.

[0195] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 650 from various process tool sensors. Signals for controlling the process may be output at analog and digital output connections of the process tool 600. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0196] The system controller 650 may provide program instructions for carrying out the deposition processes described above. The program instructions may control various process parameters such as DC power levels, RF bias power levels, pressure, temperature, etc. The instructions may control parameters for operating development processes, cleaning processes, and / or etching processes according to various implementations described herein.

[0197] The system controller 650 typically includes one or more memory devices and one or more processors configured to execute instructions such that the apparatus performs methods according to the disclosed implementations. A machine-readable medium containing instructions for controlling process operations according to the disclosed implementations may be coupled to the system controller 650.

[0198] In some implementations, the system controller 650 is part of a system that may be part of the examples described above. Such systems may include semiconductor processing equipment, including processing tool(s), chamber(s), platform(s) for processing, and / or specific processing components (wafer pedestal, gas flow system, etc.). These systems may be integrated with electronics for controlling the operation of the system before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as a "controller," which may control various components or subparts of the system(s). Depending on the process conditions and / or type of system, the system controller 650 may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer into and out of tools and other transfer tools and / or load locks connected to or interfacing with the particular system.

[0199] Broadly speaking, the system controller 650 may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in firmware form that store program instructions, digital signal processors (DSPs), chips defined as application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). The program instructions may be instructions communicated to the system controller 650 in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or system. The operational parameters, in some implementations, may be part of a recipe defined by a process engineer to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0200] In some implementations, the system controller 650 may be part of or coupled to a computer that is integrated with the system, coupled to the system, separately networked to the system, or a combination thereof. For example, the system controller 650 may be in the “cloud” or in all or part of a fab host computer system, thereby enabling remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a fabrication operation, examine the history of past fabrication operations, examine trends or performance metrics from multiple fabrication operations, vary parameters of a current process, configure processing steps to follow a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) may provide a process recipe to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings that are then communicated from the remote computer to the system. In some examples, the system controller 650 receives instructions in the form of data specifying parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the system controller 650 is configured to interface with or control. Thus, as described above, the system controller 650 may be distributed, such as by including one or more separate controllers networked together and operating toward a common purpose, such as the processes and controls described herein. An example of a distributed controller for such a purpose is one or more integrated circuits on the chamber in communication with one or more remotely located (e.g., at the platform level or as part of a remote computer) integrated circuits that together control the process on the chamber.

[0201] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a development chamber or module, and any other semiconductor processing system that may be associated with or used in the fabrication and / or manufacturing of semiconductor wafers.

[0202] As described above, depending on the process step(s) to be performed by the tool, the system controller 650 may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used in material transfer, bringing containers of wafers to or from tool locations and / or load ports within a semiconductor fabrication factory.

[0203] In certain implementations, an ICP reactor is now described that may be suitable for etching operations suitable for implementation in some implementations. Although an ICP reactor is described herein, it should be understood that in some implementations, a capacitively coupled plasma reactor may also be used.

[0204] 7 schematically illustrates a cross-sectional view of an inductively coupled plasma apparatus 700 suitable for performing particular implementations or aspects of implementations, such as dry developing, cleaning, and / or etching, an example of which is the Kiyo® reactor produced by Lam Research Corp. of Fremont, Calif. In other implementations, other tools or tool types having the functionality to perform the dry developing, cleaning, and / or etching processes described herein may be used for implementation.

[0205] The inductively coupled plasma apparatus 700 includes an overall processing chamber 724 structurally defined by a chamber wall 701 and a window 711. The chamber wall 701 may be fabricated from stainless steel, aluminum, or plastic. The window 711 may be fabricated from quartz or other dielectric materials. An optional internal plasma grid 750 divides the overall processing chamber into an upper subchamber 702 and a lower subchamber 703. In most implementations, the plasma grid 750 may be removed, thereby utilizing the chamber space created by the subchambers 702 and 703. A chuck 717 is positioned within the lower subchamber 703 near the bottom interior surface. The chuck 717 is configured to receive and hold a semiconductor wafer 719 on which etching and deposition processes are performed. The chuck 717 may be an electrostatic chuck for supporting the wafer 719 when present. In some implementations, an edge ring (not shown) surrounds the chuck 717 and has an upper surface that is approximately planar with the upper surface of the wafer 719 when the wafer 719 is present on the chuck 717. The chuck 717 also includes an electrostatic electrode for chucking and dechucking the wafer 719. A filter and DC clamp power supply (not shown) may be provided for this purpose. Other control systems for lifting the wafer 719 from the chuck 717 may also be provided. The chuck 717 may be charged using an RF power supply 723. The RF power supply 723 is connected to a matching circuit 721 through connection 727. The matching circuit 721 is connected to the chuck 717 through connection 725. In this manner, the RF power supply 723 is connected to the chuck 717. In various implementations, the bias power of the electrostatic chuck may be set to approximately 50 V or may be set to a different bias power depending on the process being performed according to the disclosed implementations. For example, the bias power can be from about 20Vb to about 100V, or from about 30V to about 150V.

[0206] The elements for plasma generation include a coil 733 positioned over the window 711. In some implementations, a coil is not used in the disclosed implementations. The coil 733 is fabricated from a conductive material and includes at least one full turn. The example coil 733 shown in FIG. 7 includes three turns. A cross section of the coil 733 is shown with symbols, where the coil with an "X" rotatably extends into the page, while the coil with a "●" rotatably extends out of the page. The elements for plasma generation also include an RF power source 741 configured to supply RF power to the coil 733. Generally, the RF power source 741 is connected to a matching circuit 739 through connection 745. The matching circuit 739 is connected to the coil 733 through connection 743. In this manner, the RF power source 741 is connected to the coil 733. An optional Faraday shield 749a is positioned between the coil 733 and the window 711. The Faraday shield 749a can be maintained in a spaced-apart relationship with respect to the coil 733. In some implementations, the Faraday shield 749a is disposed directly above the window 711. In some implementations, the Faraday shield 749b is between the window 711 and the chuck 717. In some implementations, the Faraday shield 749b is not maintained in a spaced-apart relationship with respect to the coil 733. For example, the Faraday shield 749b can be directly below the window 711 with no gap. The coil 733, the Faraday shield 749a, and the window 711 are each configured to be substantially parallel to one another. The Faraday shield 749a can prevent metals or other species from depositing on the window 711 of the processing chamber 724.

[0207] Process gases may be flowed into the processing chamber through one or more main gas inlets 760 positioned in the upper subchamber 702 and / or through one or more side gas inlets 770. Similarly, although not explicitly shown, similar gas inlets may be used to supply process gases to the capacitively coupled plasma processing chamber. A vacuum pump, such as a one- or two-stage mechanical dry pump and / or turbomolecular pump 740, may be used to draw process gases from the processing chamber 724 and maintain pressure within the processing chamber 724. For example, the vacuum pump may be used to evacuate the lower subchamber 703 during a purge operation. A valve-controlled conduit may be used to fluidly connect the vacuum pump to the processing chamber 724 to selectively control the application of the vacuum environment provided by the vacuum pump. This may be done by using a closed-loop controlled flow-restricting device, such as a throttle valve (not shown) or a pendulum valve (not shown), during operating plasma processing. Similarly, a vacuum pump and a valve-controlled fluid connection to the dose-coupled plasma processing chamber may also be used.

[0208] During operation of the apparatus 700, one or more process gases can be supplied through the gas inlets 760 and / or 770. In certain implementations, process gases can be supplied only through the main gas inlet 760 or only through the side gas inlet 770. In some cases, the gas inlets shown in the figure can be replaced by more complex gas inlets, such as one or more showerheads. The Faraday shield 749a and / or the optional grid 750 can include internal channels and holes that allow delivery of process gases to the processing chamber 724. Either or both the Faraday shield 749a and the optional grid 750 can serve as showerheads for delivery of process gases. In some implementations, a liquid evaporation and delivery system can be located upstream of the processing chamber 724 so that once a liquid reactant or precursor is vaporized, the vaporized reactant or precursor is introduced into the processing chamber 724 via the gas inlets 760 and / or 770.

[0209] Radio frequency power is supplied from RF power supply 741 to coil 733, causing RF current to flow through coil 733. The RF current flowing through coil 733 generates an electromagnetic field around coil 733. This electromagnetic field generates induced currents within upper subchamber 702. Physical and chemical interactions of the various generated ions and radicals with wafer 719 etch features of layers on wafer 719 and selectively deposit layers on wafer 719.

[0210] When a plasma grid 750 is used such that both the upper subchamber 702 and the lower subchamber 703 are present, induced currents act on the gas present in the upper subchamber 702 to generate an electron-ion plasma within the upper subchamber 702. The optional internal plasma grid 750 limits the amount of hot electrons within the lower subchamber 703. In some implementations, the apparatus 700 is designed and operated such that the plasma present in the lower subchamber 703 is an ion-ion plasma.

[0211] Both the upper electron-ion plasma and the lower ion-ion plasma can contain positive and negative ions, but the ion-ion plasma has a greater proportion of negative ions relative to positive ions. Volatile etching and / or deposition byproducts can be removed from the lower subchamber 703 through port 722. The chuck 717 disclosed herein can operate at elevated temperatures ranging from about 10° C. to about 250° C. The temperature depends on the process operation and the particular recipe.

[0212] When installed in a cleaning chamber or fabrication facility, the apparatus 700 can be coupled to equipment (not shown). The equipment includes plumbing to provide process gases, vacuum, temperature control, and environmental particle control. These equipment are coupled to the apparatus 700 when the apparatus 700 is installed in a target fabrication facility. Additionally, the apparatus 700 can be coupled to a transfer chamber that allows a robot to transfer semiconductor wafers in and out of the apparatus 700 using typical automation.

[0213] In some implementations, a system controller 730 (which may include one or more physical or logical controllers) controls some or all of the operation of the processing chamber 724. The system controller 730 may include one or more memory devices and one or more processors. In some implementations, the apparatus 700 includes a switching system for controlling flow rates and durations when the disclosed implementations are implemented. In some implementations, the apparatus 700 may have a switching time of up to about 500 milliseconds or up to about 750 milliseconds. The switching time may depend on the flow chemistry, the selected recipe, the reactor architecture, and other factors.

[0214] In some implementations, the system controller 730 is part of a system that may be part of the examples described above. Such a system may include semiconductor processing equipment, including processing tool(s), chamber(s), platform(s) for processing, and / or specific processing components (wafer pedestal, gas flow system, etc.). These systems may be integrated with electronics for controlling the operation of the system before, during, and after processing of a semiconductor wafer or substrate. The electronics may be integrated into the system controller 730, which may control various components or sub-components of the system(s). Depending on the process parameters and / or type of system, the system controller 730 may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, RF generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer into and out of tools and other transfer tools and / or load locks connected to or interfacing with the particular system.

[0215] As described above, depending on the process step(s) to be performed by the tool, the controller may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used in material transfer, bringing containers of wafers to or from the tool location and / or load ports within the semiconductor fabrication factory.

[0216] EUVL patterning can be performed using any suitable tool, often referred to as a scanner, such as the TWINSCAN NXE:3300B® platform supplied by ASML of Veldhoven, NL. The EUVL patterning tool can be a standalone device into or out of which substrates are moved for deposition and etching as described herein. Alternatively, as described below, the EUVL patterning tool can be a module on a larger, multi-component tool. FIG. 8 depicts a semiconductor process cluster tool architecture with vacuum-integrated deposition, EUV patterning, and dry develop / etch modules interfaced with a vacuum transfer module, suitable for implementing the processes described herein. While the processes can be performed without such vacuum-integrated equipment, such equipment can be advantageous in some implementations.

[0217] 8 depicts a semiconductor process cluster tool architecture with vacuum-integrated deposition and patterning modules interfaced with a vacuum transfer module suitable for implementing the processes described herein. The arrangement of transfer modules for "transferring" wafers between multiple containment facilities and processing modules may be referred to as a "cluster tool architecture" system. The deposition and patterning modules are vacuum-integrated according to the requirements of the particular process. Other modules, such as etching, may also be included on the cluster.

[0218] A vacuum transfer module (VTM) 838 interfaces with four processing modules 820a-820d, which may be individually optimized to perform various fabrication processes. By way of example, processing modules 820a-820d may be implemented to perform deposition, evaporation, ELD, dry develop, clean, etch, strip, and / or other semiconductor processes. For example, module 820a may be an ALD reactor that may be operated to perform non-plasma thermal atomic layer deposition as described herein, such as a Vector tool available from Lam Research Corporation, Fremont, CA. And, module 820b may be a PECVD tool, such as a Lam Vector®. It should be understood that the figures are not necessarily drawn to scale.

[0219] Airlocks 842 and 846, also known as loadlocks or transfer modules, interface with VTM 838 and patterning module 840. For example, as described above, a suitable patterning module may be a TWINSCAN NXE:3300B® platform supplied by ASML of Veldhoven, NL. This tool architecture allows workpieces, such as semiconductor substrates or wafers, to be transferred under vacuum to prevent reaction prior to exposure. Integration of the deposition module with the lithography tool is facilitated by the fact that EUVL also requires greatly reduced pressure given the strong optical absorption of incident photons by ambient gases such as HO and O.

[0220] As described above, this integrated architecture is only one possible implementation of a tool for the practice of the described process. The process can also be practiced using a more conventional standalone EUVL scanner and deposition reactor, such as a Lam Vector tool, either standalone, or integrated into a cluster architecture with other tools such as etch, strip, etc. (e.g., a Lam Kiyo or Gamma tool), as a module, but without an integrated patterning module, as described with reference to FIG.

[0221] Airlock 842 may be an "outgoing" load lock, referring to the transfer of substrates from VTM 838, which serves deposition module 820a, to patterning module 840, and airlock 846 may be an "incoming" load lock, referring to the transfer of substrates from patterning module 840 back to VTM 838. Incoming load lock 846 may also provide an interface to the outside of the tool for substrate access and egress. Each process module has a facet connecting the module with VTM 838. For example, deposition process module 820a has facet 836. Inside each facet, sensors, such as sensors 1-18 as shown, are used to detect the passage of wafer 826 as it is moved between its respective stations. Patterning module 840 and airlocks 842 and 846 may be similarly equipped with additional facets and sensors, not shown.

[0222] The main VTM robot 822 transfers wafers 826 between modules, including airlocks 842 and 846. In one implementation, the robot 822 has one arm; in another implementation, the robot 822 has two arms, each arm having an end effector 824 that picks up a wafer, such as wafer 826, for transfer. The front-end robot 844 is used to transfer wafers 826 from the outward airlock 842 into the patterning module 840 and from the patterning module 840 into the inward airlock 846. The front-end robot 844 can also transfer wafers 826 between the inward load lock and the outside of the tool for substrate access and egress. Because the inward airlock module 846 has the ability to match environments between atmosphere and vacuum, the wafers 826 can move between the two pressure environments without being damaged.

[0223] It should be noted that EUVL tools typically operate at a higher vacuum than deposition tools. In such cases, it is desirable to increase the vacuum environment of the substrate during transfer between the deposition tool and the EUVL tool to allow the substrate to be degassed before entering the patterning tool. Outward airlock 842 may provide this function by holding the transferred wafer at a lower pressure that does not exceed the pressure in patterning module 840 for a period of time and venting any exhaust gases so that the optical elements of patterning module 840 are not contaminated by exhaust gases from the substrate. A preferred pressure for the outward exhaust airlock is no more than 1E-8 Torr.

[0224] In some implementations, a system controller 850 (which may include one or more physical or logical controllers) controls some or all of the operation of the cluster tool and / or its separate modules. Note that the controller may be local to the cluster architecture or may be located outside the cluster architecture on the manufacturing floor or at a remote location and connected to the cluster architecture via a network. The system controller 850 may include one or more memory devices and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, stepper motor control boards, and other similar components. Instructions for performing appropriate control operations are executed on the processor. These instructions may be stored in a memory device associated with the controller, or they may be provided over a network. In certain implementations, the system controller executes system control software.

[0225] The system control software may include instructions for controlling the timing and / or degree of application of any aspect of tool or module operation. The system control software may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of process tool components necessary to perform various process tool processes. The system control software may be coded in any suitable computer-readable programming language. In some implementations, the system control software includes input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of a semiconductor fabrication process may include one or more instructions for execution by the system controller. Instructions for setting process conditions for condensation, deposition, evaporation, patterning, and / or etching phases may be included in the corresponding recipe phase, for example.

[0226] In various implementations, an apparatus for forming a negative pattern mask is provided. The apparatus may include process chambers for patterning, depositing, and etching, and a controller including instructions for forming the negative pattern mask. The instructions may include code for, in the process chamber, patterning features in a chemically amplified (CAR) resist on a semiconductor substrate with EUV exposure to expose a surface of the substrate, developing the photo-patterned resist, and etching an underlying layer or layer stack using the patterned resist as a mask.

[0227] It should be noted that the computer controlling the wafer movement may be local to the cluster architecture, or may be located outside the cluster architecture on the manufacturing floor, or at a remote location, and connected to the cluster architecture via a network. A controller such as those described above with respect to any of Figures 5, 6, or 7 may be implemented with the tool in Figure 8.

[0228] conclusion It should be understood that the examples and implementations described herein are for illustrative purposes only, and that various modifications or changes thereto will be suggested to those skilled in the art. Various details have been omitted for brevity, but various design alternatives may be implemented. Therefore, the examples should be considered illustrative rather than restrictive, and the disclosure should not be limited to the details provided herein, but may be modified within the scope of the disclosure.

Claims

1. 1. A method for cleaning a processing chamber, comprising: providing a semiconductor substrate in the processing chamber, the semiconductor substrate having a metal-containing resist film on a surface of the semiconductor substrate, and an organometallic material formed on one or more interior surfaces of the processing chamber; exposing the one or more interior surfaces of the processing chamber to a non-plasma etching gas in the processing chamber without the semiconductor substrate in the processing chamber to remove a first portion of the organometallic material; exposing the one or more interior surfaces of the processing chamber to a first plasma to remove a second portion of the organometallic material without the semiconductor substrate in the processing chamber; A method comprising:

2. 10. The method of claim 1, wherein exposing the one or more interior surfaces to the non-plasma etching gas converts an unremoved portion of the metal-organic material into non-volatile by-products, and the second portion comprises the non-volatile by-products.

3. 10. The method of claim 1, wherein the first plasma comprises a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a combination thereof.

4. 4. The method of claim 3, wherein the first plasma is a chlorine (Cl 2 ) a method comprising plasma.

5. 10. The method of claim 1, wherein the non-plasma etching gas comprises a hydrogen halide, boron tribromide, boron trichloride, or a combination thereof.

6. 6. The method of claim 5, wherein the non-plasma etching gas comprises hydrogen chloride (HCl) or hydrogen bromide (HBr).

7. 10. The method of claim 1, wherein the introducing of the non-plasma etching gas comprises: heating the one or more interior surfaces of the processing chamber to an elevated temperature, the elevated temperature being from about −15° C. to about 200° C.; flowing the non-plasma etching gas into the processing chamber; A method comprising:

8. 10. The method of claim 1, further comprising exposing the one or more interior surfaces of the processing chamber to a second plasma to remove one or both of residual gases and residual organic materials from the processing chamber.

9. 9. The method of claim 8, wherein the second plasma comprises an oxygen-containing plasma or a hydrogen-containing plasma.

10. 10. The method of claim 1, wherein the first plasma is configured to form volatile product products with the second portion of the organometallic material.

11. 10. The method of claim 1, further comprising generating the first plasma in a remote plasma source coupled to the processing chamber.

12. 10. The method of claim 1, further comprising generating the first plasma directly within the processing chamber.

13. 10. The method of claim 1, wherein the metal-containing resist film comprises a metal oxide-containing EUV photoresist material.

14. The method of claim 1 , wherein the organometallic material comprises at least tin oxide.

15. 10. The method of claim 1, wherein providing the semiconductor substrate comprises depositing the metal-containing resist film on the surface of the semiconductor substrate in the processing chamber.

16. 2. The method of claim 1, wherein providing the semiconductor substrate comprises baking the metal-containing resist film on the surface of the semiconductor substrate in the processing chamber.

17. 10. The method of claim 1, wherein providing the semiconductor substrate comprises dry developing the metal-containing resist film on the surface of the semiconductor substrate in the processing chamber.

18. 1. A method for cleaning a processing chamber, comprising: providing a semiconductor substrate in the processing chamber, the semiconductor substrate having a metal-containing resist film on a surface of the semiconductor substrate and an organometallic material formed on one or more interior surfaces of the processing chamber; exposing the one or more interior surfaces of the processing chamber to a first plasma in the processing chamber without the semiconductor substrate in the processing chamber to remove a first portion of the organometallic material; exposing the one or more interior surfaces of the processing chamber to a non-plasma etching gas to remove a second portion of the organometallic material without the semiconductor substrate in the processing chamber; A method comprising:

19. 20. The method of claim 18, wherein exposing the one or more interior surfaces to the first plasma converts an unremoved portion of the metal-organic material into non-volatile by-products, and the second portion comprises the non-volatile by-products.

20. 1. A method for cleaning a processing chamber, comprising: providing a semiconductor substrate in the processing chamber, the semiconductor substrate having a metal-containing resist film on a surface of the semiconductor substrate and an organometallic material formed on one or more interior surfaces of the processing chamber; exposing the one or more interior surfaces of the processing chamber to a first plasma in the processing chamber without the semiconductor substrate in the processing chamber to remove at least a substantial portion of the organometallic material; A method comprising:

21. 21. The method of claim 20, wherein the first plasma comprises a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a combination thereof.

22. 22. The method of claim 21, wherein the first plasma is Cl 2 , C.H. 4 , Ar, or mixtures thereof.

23. 22. The method of claim 21, wherein the first plasma comprises HBr, Ar, or a mixture thereof.

24. 22. The method of claim 21, wherein the chamber pressure of the processing chamber during exposure to the first plasma is between about 1 mTorr and about 20 Torr.

25. 22. The method of claim 21, further comprising exposing the one or more interior surfaces of the processing chamber to a second plasma to remove one or both of residual gases and residual organic materials from the processing chamber without the semiconductor substrate in the processing chamber.

26. 1. An apparatus for cleaning a processing chamber, comprising: a processing chamber having a substrate support configured to support a semiconductor substrate including a metal-containing resist film formed on a surface of the semiconductor substrate; a vacuum line coupled to the processing chamber; a gas line coupled to the processing chamber; a controller, the controller performing the following operations: providing the semiconductor substrate in the processing chamber, wherein a metal-organic material is formed on one or more interior surfaces of the processing chamber; exposing the one or more interior surfaces of the processing chamber to a non-plasma etching gas to remove a first portion of the organometallic material without the semiconductor substrate in the processing chamber; exposing the one or more interior surfaces of the processing chamber to a first plasma to remove a second portion of the organometallic material without the semiconductor substrate in the processing chamber; An apparatus comprising:

27. 27. The apparatus of claim 26, further comprising a remote plasma source fluidly coupled to the processing chamber, wherein the first plasma is generated within the remote plasma source.

28. 27. The apparatus of claim 26, wherein the first plasma is generated directly within the processing chamber.

29. 27. The apparatus of claim 26, wherein the processing chamber is selected from one of the following group: a dry deposition chamber, a beveled edge and / or backside cleaning chamber, a bake chamber, or a dry development chamber.

30. 27. The apparatus of claim 26, wherein the controller configured with instructions for exposing the one or more interior surfaces to the non-plasma etching gas is configured with instructions for exposing the one or more interior surfaces to the non-plasma etching gas to convert an unremoved portion of the organometallic material into a non-volatile by-product, the second portion including the non-volatile by-product.

31. 27. The apparatus of claim 26, wherein the first plasma comprises a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a combination thereof; the non-plasma etching gas comprises a hydrogen halide, a hydrogen and halogen gas, boron trichloride, or a combination thereof; and the organometallic material comprises at least tin oxide.

32. 1. An apparatus for cleaning a processing chamber, comprising: a processing chamber having a substrate support configured to support a semiconductor substrate including a metal-containing resist film formed on a surface of the semiconductor substrate; a vacuum line coupled to the processing chamber; a gas line coupled to the processing chamber; a controller, the controller performing the following operations: providing the semiconductor substrate in the processing chamber, wherein an organometallic material is formed on one or more interior surfaces of the processing chamber; exposing the one or more interior surfaces of the processing chamber to a first plasma to remove a first portion of the organometallic material without the semiconductor substrate in the processing chamber; exposing the one or more interior surfaces of the processing chamber to a non-plasma etching gas to remove a second portion of the organometallic material without the semiconductor substrate in the processing chamber; An apparatus comprising:

33. 33. The apparatus of claim 32, further comprising a remote plasma source fluidly coupled to the processing chamber, wherein the first plasma is generated within the remote plasma source.

34. 33. The apparatus of claim 32, wherein the first plasma is generated directly within the processing chamber.

35. 33. The apparatus of claim 32, wherein the processing chamber is selected from one of the following: a dry deposition chamber, a beveled edge and / or backside cleaning chamber, a bake chamber, or a dry development chamber.

36. 33. The apparatus of claim 32, wherein the controller configured with instructions for exposing the one or more interior surfaces to the first plasma is configured with instructions for exposing the one or more interior surfaces to the first plasma to convert an unremoved portion of the metal-organic material into a non-volatile by-product, the second portion including the non-volatile by-product.

37. 33. The apparatus of claim 32, wherein the first plasma comprises a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, or a combination thereof; the non-plasma etching gas comprises a hydrogen halide, a hydrogen and halogen gas, boron trichloride, or a combination thereof; and the organometallic material comprises at least tin oxide.

38. 1. An apparatus for cleaning a processing chamber, comprising: a processing chamber having a substrate support configured to support a semiconductor substrate including a metal-containing resist film formed on a surface of the semiconductor substrate; a vacuum line coupled to the processing chamber; a gas line coupled to the processing chamber; a controller, the controller performing the following operations: providing a semiconductor substrate in the processing chamber, wherein a metalorganic material is formed on one or more interior surfaces of the processing chamber; and exposing the one or more interior surfaces of the processing chamber to a first plasma to remove at least a substantial portion of the organometallic material without the semiconductor substrate in the processing chamber; An apparatus comprising:

39. 39. The apparatus of claim 38, wherein the first plasma comprises a halide-containing plasma, a hydrogen-containing plasma, a hydrocarbon-containing plasma, an inert gas-containing plasma, or a combination thereof, and the organometallic material comprises at least tin oxide.

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