All-in-one dry development for metal-containing photoresists

Abstract

Process condition management facilitates the combination of dry development and post-development processing into a single process chamber, thereby eliminating the need for a baking step after dry development in individual chambers during semiconductor manufacturing. Thermal dry development and plasma dry development can be performed in the same chamber. Thermal dry development, plasma dry development, and passivation, e.g., O2 flash processing; or thermal dry development, plasma dry development, passivation, and curing operations can be performed without wafer transfer.

Description

Technology Field

[0001] Cross-reference

[0002] A PCT request is submitted concurrently with this specification as part of this application. As confirmed in the concurrently submitted PCT request, each application claiming its advantage or priority in this application is incorporated herein by reference in its entirety for all purposes. 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 using lithography techniques to form structural features of the semiconductor device (e.g., transistors and circuits). Steps of a typical photolithography process include: preparing a substrate; applying a photoresist, for example, by spin coating; exposing the photoresist to light in a desired pattern so that the exposed area of ​​the photoresist becomes nearly soluble in a developer solution; developing the photoresist by applying a developer solution to remove the exposed or unexposed area of ​​the photoresist; and subsequent process steps for creating features on the substrate area from which the photoresist has been removed, for example, by etching or material deposition.

[0004] The evolution of semiconductor design has necessitated the creation of increasingly smaller features on semiconductor substrate materials and has been driven by the ability to do so. One challenge in manufacturing devices with such small features is the ability to reliably and reproducibly produce photolithography masks with sufficient resolution. Current photolithography processes typically use 193 nm ultraviolet (UV) light to expose photoresist. The fact that the light has a wavelength significantly larger than the desired size of the features to be created on the semiconductor substrate presents an inherent problem. To achieve feature sizes smaller than the wavelength of the light, complex resolution enhancement techniques such as multipatterning must be used. Consequently, there is significant interest and research regarding the development of photolithography techniques using shorter wavelengths of light, such as extreme ultraviolet (EUV) with wavelengths of 10 nm to 15 nm, e.g., 13.5 nm.

[0005] However, the EUV photolithography process can present challenges including low power output, optical loss during patterning, and metal cross-contamination caused by metal degassing. Therefore, there is still a need for improved EUV photoresist processes to produce materials with desired properties in a more efficient manner.

[0006] The background art description provided herein is intended for the purpose of generally indicating the context of the disclosure. The work of the inventors currently named is not explicitly or implicitly recognized as prior art to the disclosure, to the extent described in this background art section, as well as in modes of description that may not otherwise be recognized as prior art at the time of filing.

[0007] The present disclosure relates to a method and apparatus for integrating a dry development process into the same process chamber. In some embodiments, the present disclosure relates to a method and apparatus for integrating a dry development process and a dry development post-process into the same process chamber. Such integration of the surface of a metal-containing photoresist increases throughput and reduces wafer handling; thereby increasing the efficiency of semiconductor manufacturing through higher wafer productivity and better lithography control. The integrated process also improves device yield / defectivity performance. The dry development post-process may include plasma passivation. Additionally or alternatively, the dry development post-process may include curing. The dry development post-process of plasma flash processing, passivation, and / or curing can all be performed together with the dry development in a single process chamber, thereby eliminating the need for dry development post-baking, which would otherwise have to be performed in a different chamber or instrument. The integrated method also achieves surface smoothing and mitigates the degassing of contaminants through passivation.

[0008] Accordingly, in a first aspect, the present disclosure comprises a method for performing both dry development and passivation of a metal-containing photoresist in a single process chamber. In some embodiments, the method comprises the steps of: providing a patterned metal-containing photoresist on a semiconductor substrate to a process chamber; thermally dry developing the patterned metal-containing photoresist with a process gas at a first pressure to form a thermally dry developed patterned metal-containing photoresist; and passivating the thermally dry developed patterned metal-containing photoresist in the same process chamber as the thermally dry developing at a second pressure that is different from or equal to the first pressure to form a patterned substrate. In some embodiments, the second pressure is lower than the first pressure.

[0009] In some embodiments, passivation includes exposure to an oxygen-containing, nitrogen-containing, or hydrogen-containing plasma.

[0010] In some embodiments, passivation is O2, O3, CO, CO2, H2, C x H y Flash treatment using , H2O, H2O2, SO2, NO, NO2, N2O, NH3 or a mixture thereof, where x is an integer from 1 to 6 and y is an integer from 2 to 14.

[0011] In some embodiments, flash processing is performed for a period of about 0.5 to about 10 seconds.

[0012] In some embodiments, the semiconductor substrate throughput is increased by at least about 50%.

[0013] In some embodiments, the metal-containing photoresist is a photopatterned EUV-sensitive organometallic oxide, a photopatterned EUV-sensitive metal oxide, or an organometallic-containing thin film EUV resist.

[0014] In some embodiments, the photopatterned EUV-sensitive metal oxide is tin oxide.

[0015] In some embodiments, tin degassing from tin oxide is mitigated.

[0016] In some embodiments, the thermal drying phenomenon involves exposure to halogen-containing gases.

[0017] In some embodiments, the method also includes the step of plasma dry developing a thermally dry developed patterned metal-containing photoresist, wherein the thermal dry developing, plasma dry developing, and passivation are all performed in the same process chamber.

[0018] In some embodiments, the thermal drying phenomenon and the plasma drying phenomenon are repeated alternately.

[0019] In some embodiments, the plasma drying phenomenon includes a cyclic plasma drying phenomenon, a direct plasma drying phenomenon, a remote plasma drying phenomenon, or a continuous plasma drying phenomenon.

[0020] In some embodiments, the plasma dry phenomenon includes a continuous plasma dry phenomenon, and the continuous plasma dry phenomenon is performed at variable power, at constant power and pulsing bias, or at variable power and pulsing bias.

[0021] In some embodiments, the plasma dry phenomenon includes exposure to a plasma of at least one halogen-containing gas among inert carrier gases.

[0022] In some embodiments, the halogen-containing gas is HBr, Br2, HCl, Cl2, HI, I2, or BCl3.

[0023] In some embodiments, the first pressure is about 5 mTorr to 760 Torr, and the second pressure is about 5 mTorr to 200 mTorr.

[0024] In some embodiments, the second pressure is lower than the first pressure.

[0025] In some embodiments, the method also includes the step of switching the pressure in the same process chamber from a first pressure to a second pressure within 10 seconds or less; the step of returning the pressure in the same process chamber from the second pressure to the first pressure within 20 seconds or less after plasma drying and passivation; and the step of maintaining one or more process parameters uniformly.

[0026] In some embodiments, the method also includes the step of curing the metal-containing photoresist in the same process chamber used for the thermal dry development.

[0027] In some embodiments, the method also includes the step of curing the metal-containing photoresist after passivation in the same process chamber used for thermal dry development, plasma dry development, and passivation.

[0028] In some embodiments, curing is performed by treatment using an inert gas plasma, treatment using an oxidizing gas plasma, heat treatment, UV light exposure, or a combination thereof.

[0029] In a second aspect, the present disclosure comprises an apparatus for performing both dry development and passivation of a metal-containing photoresist in a single process chamber. In some embodiments, the apparatus comprises one or more process chambers; one or more pressure control devices; one or more pumps fluidly coupled to one or more pressure control devices; a plasma process system; one or more gas inlets to the process chambers and associated flow control hardware; and a controller having at least one processor and memory, wherein at least one processor and memory are communicably connected to each other, at least one processor is operably connected to associated flow control hardware, and memory stores computer-executable instructions for controlling at least one processor to control associated flow control hardware to perform thermal dry development in one of the process chambers and to perform passivation in the same process chamber as the thermal dry development. In some embodiments, thermal dry development is performed at a first pressure, and passivation is performed at a second pressure lower than or equal to the first pressure.

[0030] In some embodiments, the device also includes a photoresist thickness sensor module.

[0031] In some embodiments, the photoresist thickness sensor module includes a spectral reflectometer.

[0032] In some embodiments, the device also performs a plasma drying phenomenon by controlling at least one related flow control hardware, including computer-executable instructions for controlling at least one processor, and the thermal drying phenomenon, the plasma drying phenomenon, and the passivation are all performed in the same process chamber.

[0033] In some embodiments, the plasma drying phenomenon includes a cyclic plasma drying phenomenon, a direct plasma drying phenomenon, a remote plasma drying phenomenon, or a continuous plasma drying phenomenon.

[0034] In some embodiments, the plasma dry phenomenon includes a continuous plasma dry phenomenon, and the continuous plasma dry phenomenon is performed at variable power, at constant power and pulsing bias, or at variable power and pulsing bias.

[0035] In some embodiments, passivation includes exposure to an oxygen-containing, nitrogen-containing, or hydrogen-containing plasma.

[0036] In some embodiments, passivation is O2, O3, CO, CO2, H2, C x H y Flash treatment using , H2O, H2O2, SO2, NO2, N2O, NH3 or a combination thereof, where x is an integer from 1 to 6 and y is an integer from 2 to 14.

[0037] In some embodiments, the second pressure is lower than the first pressure.

[0038] In some embodiments, the device also controls at least one related flow control hardware, including computer-executable instructions for controlling at least one processor, to switch the pressure in the same process chamber from a first pressure to a second pressure within 10 seconds or less; to return the pressure in the same process chamber from the second pressure to the first pressure within 20 seconds or less after plasma drying and passivation; and to maintain one or more process parameters uniformly.

[0039] In a third aspect, the present disclosure comprises an apparatus for performing dry development, passivation, and curing of a metal-containing photoresist all in a single process chamber. In some embodiments, the apparatus comprises one or more process chambers; one or more pressure control devices; one or more pumps fluidly coupled to one or more pressure control devices; one or more gas inlets to the process chambers and associated flow control hardware; a plasma process system; and a controller having at least one processor and memory, wherein at least one processor and memory are communicably connected to each other, at least one processor is operably connected to associated flow control hardware, and memory stores computer-executable instructions for controlling at least one processor to control associated flow control hardware to perform dry development in one of the process chambers; and perform passivation and curing in the same process chamber as the dry development. In some embodiments, the dry development includes thermal dry development and plasma dry development. In some embodiments, the dry development is performed at a first pressure, and the passivation and curing are performed at a second pressure. In some embodiments, the second pressure is lower than the first pressure or equal to the first pressure.

[0040] In some embodiments, the device also includes a photoresist thickness sensor module.

[0041] In some embodiments, the photoresist thickness sensor module includes a spectral reflectometer.

[0042] In some embodiments, curing is performed by treatment using an inert gas plasma, treatment using an oxidizing gas plasma, heat treatment, UV light exposure, or a combination thereof.

[0043] In some embodiments, passivation includes exposure to an oxygen-containing, nitrogen-containing, or hydrogen-containing plasma.

[0044] In some embodiments, passivation is O2, O3, CO, CO2, H2, C x H y Flash treatment using , H2O, H2O2, SO2, NO, NO2, N2O, NH3 or a combination thereof, where x is an integer from 1 to 6 and y is an integer from 2 to 14.

[0045] In some embodiments, the plasma drying phenomenon includes a cyclic plasma drying phenomenon, a direct plasma drying phenomenon, a remote plasma drying phenomenon, or a continuous plasma drying phenomenon.

[0046] In some embodiments, the plasma dry phenomenon includes a continuous plasma dry phenomenon, and the continuous plasma dry phenomenon is performed at variable power, at constant power and pulsing bias, or at variable power and pulsing bias.

[0047] In some embodiments, the device also includes a UV exposure module.

[0048] In some embodiments, the second pressure is lower than the first pressure.

[0049] In some embodiments, the device also controls at least one related flow control hardware, including computer-executable instructions for controlling at least one processor, to switch the pressure in the same process chamber from a first pressure to a second pressure within 10 seconds or less; to return the pressure in the same process chamber from the second pressure to the first pressure within 20 seconds or less after plasma drying and passivation; and to maintain one or more process parameters uniformly.

[0050] In a fourth aspect, the present disclosure comprises a method for performing both thermal dry development and plasma dry development in a single process chamber. In some embodiments, the method comprises the steps of: providing a metal-containing photoresist on a semiconductor substrate to a process chamber; thermally dry developing the metal-containing photoresist in the process chamber; and plasma dry developing the metal-containing photoresist in the process chamber.

[0051] In some embodiments, the thermal dry phenomenon comprises exposure to a first process gas, and the plasma dry phenomenon comprises exposure to a plasma of a second process gas different from the first process gas. In some embodiments, the first process gas comprises a halogen-containing gas, and the second process gas comprises an inert gas, a halogen-containing gas, or a combination thereof. In some embodiments, the first process gas comprises a hydrogen halide.

[0052] In some embodiments, the thermal drying phenomenon is performed at a first pressure, and the plasma drying phenomenon is performed at a second pressure different from the first pressure.

[0053] In some embodiments, the thermal drying phenomenon and the plasma drying phenomenon are performed in a process chamber at a temperature of about -20°C to about 50°C.

[0054] In some embodiments, the thermal drying phenomenon and the plasma drying phenomenon are repeated alternately.

[0055] In some embodiments, the method further comprises the step of performing a dry development post-process in a process chamber. In some embodiments, the dry development post-process comprises passivating the metal-containing photoresist in the process chamber. Passivation may include exposure to an oxygen-containing, nitrogen-containing, or hydrogen-containing plasma. Additionally or alternatively, the dry development post-process comprises curing the metal-containing photoresist in the process chamber. Curing may include treatment using an inert gas plasma, treatment using an oxidizing gas plasma, heat treatment, UV light exposure, or a combination thereof.

[0056] In a fifth aspect, the present disclosure comprises an apparatus for performing both thermal dry development and plasma dry development of a metal-containing photoresist in a single process chamber. In some embodiments, the apparatus comprises one or more process chambers; one or more pressure control devices; one or more pumps fluidly coupled to the pressure control devices; a plasma process system; one or more gas inlets to the process chambers and associated flow control hardware; and a controller having at least one processor and memory, wherein at least one processor and memory are communicably connected to each other, at least one processor is operably connected to the associated flow control hardware, and the memory stores computer-executable instructions for controlling at least one processor to control the associated flow control hardware to perform thermal dry development in one of the process chambers and perform plasma dry development in the same process chamber as the thermal dry development.

[0057] These and other embodiments are further described below with reference to the drawings. Brief explanation of the drawing

[0058] Fig. 1 This represents a process flowchart for depositing, developing, and processing photoresist. Fig. 2a inside Fig. 2c This is a schematic cross-sectional view of various process steps including the development and processing of photoresist. Fig. 3 ...shows a flowchart of an exemplary method of an entire process including the development of photoresist in a single process chamber according to a specific disclosed embodiment. Fig. 4a This shows a flowchart of an exemplary method for performing dry development and passivation operations in the same process chamber according to a specific disclosed embodiment. Fig. 4b This shows a flowchart of an exemplary method for performing thermal drying and plasma drying operations in the same process chamber according to a specific disclosed embodiment. Fig. 4c This shows a flowchart of an exemplary method for performing dry development and curing operations in the same process chamber according to a specific embodiment disclosed. Fig. 4d This shows a flowchart of an exemplary method for performing thermal drying, plasma drying, and passivation operations in the same process chamber according to a specific disclosed embodiment. Fig. 4e This shows a flowchart of an exemplary method for performing dry development, passivation, and curing operations in the same process chamber according to a specific embodiment disclosed. Fig. 5a inside Fig. 5e is a schematic cross-sectional view of various process steps including thermal drying, plasma drying, and passivation according to specific embodiments disclosed. Fig. 6 The diagram illustrates a schematic representation of an exemplary process station for maintaining an environment suitable for performing photoresist development and other photoresist processing operations according to a specific embodiment disclosed. Fig. 7 It illustrates a schematic diagram of an exemplary multi-station process tool suitable for implementing the photoresist development and other photoresist processing operations described herein, according to a specific embodiment disclosed herein. Fig. 8[It] shows a schematic cross-sectional view of an exemplary inductively coupled plasma device for implementing the specific embodiments and operations described herein according to the specific embodiments disclosed herein. Fig. 9 It illustrates a semiconductor process cluster tool having a vacuum integrated deposition and patterning module interfacing with a vacuum transfer module suitable for implementing the process described herein according to a specific embodiment disclosed herein. Specific details for implementing the invention

[0059] In the following description, numerous specific details are provided to provide a thorough understanding of the provided embodiments. The disclosed embodiments may be practiced with or without some or all of these specific details. In other examples, well-known process operations have not been described in detail to avoid unnecessarily obscuring the disclosed embodiments. It will be understood that while the disclosed embodiments will be described together with specific embodiments, this is not intended to limit the disclosed embodiments.

[0060] definition

[0061] The term "flow control hardware" generally refers to a component configured to place one or more chemical sources in fluid communication with a process chamber. Flow control hardware may include, for example, one or more mass flow controllers and / or valves. Examples of chemical sources include dielectric membrane precursor sources, halogen-containing precursor sources, reactant gas sources, and inert gas sources.

[0062] The term "forming a gas mixture" generally refers to mixing multiple gases before introducing multiple gases into a process chamber or mixing multiple gases in a process chamber, or both.

[0063] The term "inert gas" generally refers to a gaseous material that does not react with other chemicals in a process chamber during substrate processing. Examples of inert gases include helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe), as well as nitrogen (N2) in some processes.

[0064] The term "plasma" generally refers to a gas containing cations, free radicals, and free electrons. The term "in-situ plasma" generally refers to plasma formed at a process station within a process chamber. The term "remote plasma" generally refers to plasma formed at a location away from a process station within a process chamber.

[0065] The term "plasma generator" generally refers to a combination of components that can be used to form plasma. Examples of components include a radio frequency power source, an impedance matching network, and one or more electrodes.

[0066] The term "precursor" generally refers to a chemical species that adsorbs onto the substrate surface in the ALD process. The precursor reacts with the reactant to convert the adsorbed precursor into a film layer.

[0067] The term "processing chamber" or "process chamber" generally refers to an enclosure where chemical and / or physical processes are performed on a substrate. The pressure, substrate temperature, and atmospheric composition within the process chamber can be controlled to perform chemical and / or physical processes.

[0068] The term "process tool" may generally refer to a machine comprising a process chamber and other hardware configured to enable the process to be performed in the process chamber.

[0069] The term "process station" generally refers to a location within a process chamber where a substrate is placed during the process.

[0070] The term "reactant" generally refers to a chemical species that reacts with a precursor adsorbed on the substrate surface to form a film layer in the ALD process. The reaction between the reactant and the precursor can be facilitated by thermal energy and / or plasma in various processes.

[0071] As used herein, the term “semiconductor substrate” refers to a substrate at any stage of fabricating a semiconductor device containing semiconductor material anywhere within its structure. It is understood that the semiconductor material within the semiconductor substrate does not need to be exposed. An example of a semiconductor substrate is a semiconductor wafer having multiple layers of other material (e.g., dielectric) covering the semiconductor material. The following detailed description assumes that the disclosed embodiment is implemented on a semiconductor wafer, e.g., a 200 mm, 300 mm, or 450 mm semiconductor wafer. However, the disclosed embodiment is not so limited. Workpieces may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces to which the disclosed embodiment can be utilized include various articles, e.g., printed circuit boards.

[0072] The embodiments disclosed below describe the deposition of material on a substrate, such as a wafer, a substrate, or other workpiece. Workpieces may be of various shapes, sizes, and materials. In this application, 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” may refer to a silicon wafer at any stage of integrated circuit fabrication. Wafers or substrates used in the semiconductor device industry typically have a diameter of 200 mm, 300 mm, or 450 mm. Unless otherwise specified, process details mentioned herein (e.g., flow rate, power level, etc.) relate to processing a 300 mm diameter substrate or processing a chamber configured to process a 300 mm diameter substrate and may be scaled to suit substrates or chambers of other sizes. In addition to semiconductor wafers, other workpieces that may be used in the embodiments disclosed herein include various articles, such as printed circuit boards. The process and device can be used to manufacture semiconductor devices, displays, LEDs, photovoltaic panels, etc.

[0073] As used herein, the term “photoresist” and derivatives thereof refer to photosensitive materials used to form a patterned coating on a surface in processes such as photolithography, photoetching, or photoengraving. Photoresist materials change their solubility in a developer solution when exposed to light of a specific wavelength. A photoresist layer may consist of a positive (exposed area becomes soluble) or negative (exposed area becomes insoluble) photoresist material.

[0074] For the purposes of this disclosure, the term “metal” as used in this context should be understood to mean a conductor having a maximum resistivity of 500 micro ohms cm, including metals and conductive metal salts, in particular conductive metal nitrides, e.g., TiN.

[0075] As used herein, "metal-containing photoresist" includes, but is not limited to, metal photoresists, metal oxide photoresists, or organometal oxide photoresists.

[0076] "Tin oxide" is Sn containing integer values ​​x and y, and non-integer values ​​x and y. x O y It means including any stoichiometric possibilities for. For example, "tin oxide" is the chemical formula SnO n It includes a compound having, where 1 ≤ n ≤ 2, where n can be an integer or non-integer value. "Tin oxide" refers to a sub-stoichiometric compound, e.g., SnO₂ 1.8 It may include. "Tin oxide" also includes tin dioxide (SnO2 or stannous oxide) and tin monooxide (SnO or stannous oxide). "Tin oxide" also includes both natural and synthetic variations, and also includes any crystalline and molecular structure. "Tin oxide" also includes amorphous tin oxide.

[0077] As used herein, the phrase “at least one of A, B and C” should be interpreted to mean logic (A or B or C) using the non-exclusive logic “or”, and should not be interpreted to mean “at least one of A, at least one of B and at least one of C”.

[0078] As used herein, the term “about” is understood to describe a minor increase and / or decrease beyond a stated value, and such difference does not significantly affect the desired function of the parameter beyond the stated value(s). In some cases, “about” includes + / - 10% of any stated value. As used herein, this term modifies any stated value, a range of values, or an endpoint of one or more ranges.

[0079] As used herein, the terms "top," "bottom," "upper," "lower," "top," and "bottom" are used to provide relative relationships between structures. The use of these terms does not indicate or require that a specific structure be located at a specific position within the device.

[0080] Introduction and Background

[0081] The present disclosure generally relates to the field of semiconductor processes. In particular, the present disclosure relates to the development of photoresists, including metal-containing photoresists. Such metal and / or metal oxide-containing photoresists may undergo one or both of thermal dry development and plasma dry development. Such metal and / or metal oxide-containing photoresists may undergo treatment to alter the chemical, physical and / or optical properties of the photoresist after development and before pattern transfer. Treatment of the photoresist improves the performance of the photoresist. For example, photoresist treatment may reduce dose-to-size (DtS), reduce LWR, increase line CD, improve etching resistance, increase throughput, reduce degassing of tin or other elements, or reduce defects / line breakage. Throughput can be increased by at least about 40%, 50%, about 60%, about 70%, about 80%, or about 90%.

[0082] In semiconductor processes, thin film patterning is often a critical step in semiconductor fabrication. Patterning involves lithography. In conventional photolithography, such as 193 nm photolithography, a pattern is printed onto a photosensitive photoresist film by exposing the photoresist to photons in a selected area defined by a photomask. This induces a chemical reaction in the exposed photoresist to create a chemical contrast, which is then utilized in the development stage to remove specific parts of the photoresist and form a pattern. Subsequently, the patterned and developed photoresist film can be used as an etching mask to transfer the pattern onto a base film composed of metal, oxide, etc.

[0083] Advanced technology nodes (defined by the International Technology Roadmap for Semiconductors) include 22 nm, 16 nm nodes, and nodes beyond these. At the 16 nm node, for example, the width of vias or lines in a damascene structure typically does not exceed about 30 nm. Scaling of features on advanced semiconductor integrated circuits (ICs) and other devices is leading to improvements in lithography resolution.

[0084] Extreme ultraviolet (EUV) lithography can expand lithography techniques by shifting to image source wavelengths smaller than those achievable with conventional photolithography methods. At wavelengths of approximately 10 to 20 nm or 11 to 14 nm, for example at 13.5 nm, EUV light sources can be used in state-of-the-art lithography tools, also referred to as scanners. Since EUV radiation is strongly absorbed by a wide range of solid and fluid materials, including quartz and water vapor, it operates in a vacuum.

[0085] EUV lithography utilizes a patterned EUV resist to form a mask for use in etching a base layer. The EUV resist may be a polymer-based chemical amplification resist (CAR) prepared by a liquid-based spin-on technique. An alternative to CAR is a directly photopatternable metal oxide-containing film, which is available, for example, from Inpria Corp. (Corvallis, Oregon) and described, for example, in U.S. Patent Publications Nos. US 2017 / 0102612, US 2016 / 0216606 and US 2016 / 0116839, which are incorporated herein by reference at least for the disclosure of their photopatternable metal oxide-containing films. Such films may be prepared by a spin-on technique or by dry vapor deposition. Metal oxide-containing films can be patterned directly (i.e., without the use of a separate photoresist) by EUV exposure in a vacuum environment providing a patterning resolution of less than 30 nm, as described in, for example, U.S. Patent No. 9,996,004, issued on June 12, 2018, under the title “EUV PHOTOPATTERNING OF VAPOR-DEPOSITED METAL OXIDE-CONTAINING HARDMASKS”, and / or in International Application No. PCT / US19 / 31618, filed on May 9, 2019, under the title “METHODS FOR MAKING EUV PATTERNABLE HARD MASKS”, and the disclosures thereof relating at least to the composition, deposition, and patterning of a directly photopatternable metal oxide film for forming an EUV resist mask are incorporated herein by reference. Generally, patterning involves exposing an EUV resist to EUV radiation to form a photo pattern on the resist, and then developing it to remove a portion of the resist according to the photo pattern to form a mask.

[0086] Direct photopatternable EUV or DUV resists may consist of or include metals and / or metal oxides mixed within organic components. The metals / metal oxides may enhance EUV or DUV photon absorption and / or generate secondary electrons, or exhibit increased etching selectivity for the underlying film stack and device layer. Such resists may be developed using a wet (solvent) approach that requires moving the wafer to a track, exposing it to a developing solvent therein, drying, and then baking. Such resists may also be developed using a dry approach or a combination of the wet and dry approaches, as described herein.

[0087] Generally, a resist can be used as a positive tone resist or a negative tone resist by controlling the resist's chemicals and / or the solubility or reactivity of the developer. It would be beneficial to have an EUV or DUV resist capable of acting as a negative tone resist or a positive tone resist.

[0088] The following describes techniques related to the EUV process, but these techniques may also be applicable to other next-generation lithography technologies. Various radiation sources may be used, including EUV (typically about 13.5 nm), DUV (deep-UV in the 248 nm or 193 nm range using an excimer laser source), X-rays (including EUV in the lower energy range of the X-ray range) and e-beams (including a wide energy range).

[0089] Fig. 1 This shows a flowchart of the steps of a conventional method for depositing, developing, and processing photoresist. Fig. 1In the patterning process flow, the term often refers to an EUV-sensitive resist, but it will be understood that the process flow is not limited to an EUV resist. An EUV resist may be a resist that is responsive to EUV radiation. The operations of the process (100) may be performed in a different order and / or may be performed with different operations, fewer operations, or additional operations. In some implementations, the operations of the process (100) may be implemented at least partially according to software stored on one or more non-transient computer-readable media.

[0090] A layer of photoresist is deposited in block (102) of process (100). This may be a dry deposition process, such as a vapor deposition process, or a wet deposition process, such as a spin-on deposition process. In one embodiment, the metal-containing precursor is deposited as a solution by using a liquid-based spin-on technique. In another embodiment, the metal-containing precursor is deposited in vapor form by using a dry technique (e.g., chemical vapor deposition).

[0091] A photoresist film can be deposited on a substrate. Such a film can be deposited by using a wet or dry deposition process, wherein a metal-containing precursor (e.g., a tin-containing precursor, any of which is described herein) is provided in close proximity to the substrate. In one embodiment, the metal-containing precursor is deposited as a solution by using a liquid-based spin-on technique. In another embodiment, the metal-containing precursor is deposited in vapor form by using a dry technique (e.g., chemical vapor deposition). Although the present disclosure often indicates that the metal-containing precursor is a tin-containing precursor, other metal atoms may be used.

[0092] The layers and membranes described herein are 1x10 7 cm 2It may include elements having a high light absorption cross-section, such as / mol or higher (e.g., metal atoms or nonmetal atoms). These elements may be provided by depositing one or more precursor(s) to provide an imaging layer.

[0093] In some embodiments, the membrane is a radiation-sensitive membrane (e.g., an EUV-sensitive membrane). This membrane can, ultimately, serve as an EUV resist as further described herein. In certain embodiments, the layer or membrane may comprise one or more ligands (e.g., EUV-unstable ligands) that can be removed, cut, or cross-linked by radiation (e.g., EUV or DUV radiation).

[0094] The precursor may provide a patternable film that is responsive to radiation (or a patternable radiation-responsive film or a photopatternable film). Such radiation may include EUV radiation, DUV radiation, or UV radiation that is provided by irradiation through a patterned mask and becomes patterned radiation. The film itself may be altered by exposure to such radiation so that the film becomes radiation-responsive or photosensitive. In certain embodiments, the precursor is an organometallic compound comprising at least one metal center.

[0095] The precursor may have any useful number and type of ligand(s). In some embodiments, the ligand may be characterized by its ability to react in the presence of a counter-reactor or in the presence of patterned radiation. For example, the precursor may include a ligand that reacts with the counter-reactor, capable of introducing a link (e.g., -O- link) between metal centers. In another example, the precursor may include a ligand that is removed in the presence of patterned radiation.

[0096] The precursor has a high patterning radiation absorption cross-section (e.g., 1x10⁻⁶). 7 cm 2It may include a metal or metalloid or an atom having an EUV absorption cross-section of at least / mol. In some embodiments, M is tin (Sn), bismuth (Bi), tellurium (Te), cesium (Cs), antimony (Sb), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), and lead (Pb).

[0097] In certain embodiments, the precursor includes tin. Non-limiting tin precursors include SnF2, SnH4, SnBr4, SnCl4, SnI4, tetramethyltin (SnMe4), tetraethyltin (SnEt4), trimethyltin chloride (SnMe3Cl), dimethyltin dichloride (SnMe2Cl2), methyltin trichloride (SnMeCl3), tetraallyltin, tetravinyltin, hexaphenyltin(IV) (Ph3Sn-SnPh3, where Ph is phenyl), dibutyldiphenyltin (SnBu2Ph2), trimethyl(phenyl)tin (SnMe3Ph), trimethyl(phenylethynyl)tin, tricyclohexyltin hydride, tributyltin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acac)2), and tributyltin. Ethoxide (SnBu3(OEt)), dibutyltin dimethoxide (SnBu2(OMe)2), tributyltin methoxide (SnBu3(OMe)), tin(IV) tert-butoxide (Sn( t -BuO)4), n-butyltin tributoxide(Sn( n -Bu)( t -BuO)3), tetrakis(dimethylamino)tin(Sn(NMe2)4), tetrakis(ethylmethylamino)tin(Sn(NMeEt)4), tetrakis(diethylamino)tin(IV)(Sn(NEt2)4), (dimethylamino)trimethyltin(IV)(Sn(Me)3(NMe2), Sn( i -Pr)(NMe2)3, Sn( n-Bu)(NMe2)3, Sn( s -Bu)(NMe2)3, Sn( i -Bu)(NMe2)3, Sn( t -Bu)(NMe2)3, Sn( t -Bu)2(NMe2)2, Sn( t It includes -Bu)(NEt2)3, Sn(tbba), Sn(II)(1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2-diazastanolidine-2-ylidene) or bis[bis(trimethylsilyl)amino]tin(Sn[N(SiMe3)2]2).

[0098] Exemplary deposition techniques (for example, for films) include any of those described herein, such as ALD (e.g., thermal ALD and plasma-enhanced ALD), spin coating deposition, PVD including PVD co-sputtering, CVD (e.g., PE-CVD or LP-CVD), sputter deposition, e-beam deposition including e-beam co-evaporation, or combinations thereof, such as ALD with a CVD component, such as discontinuous ALD-like processes in which a precursor and a counter-reactant are separated in time or space.

[0099] Further description of precursors and methods for depositing the same as EUV photoresist films applicable to the present disclosure can be found in international application number PCT / US19 / 31618, filed on May 9, 2019, under the title "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS" and published as international publication number WO 2019 / 217749. The thin film may include optional materials in addition to the precursor and counter-reactant to modify the chemical or physical properties of the film, such as changing the sensitivity of the film to EUV or improving etching resistance. These optional materials may be introduced by doping, for example, during vapor phase formation before deposition on the substrate, during deposition on the substrate, and / or after film deposition. In some embodiments, a weak remote H2 plasma may be introduced to replace some Sn-L bonds with Sn-H, for example, which can increase the reactivity of the resist under EUV. In another embodiment, CO2 may be introduced to replace some Sn-O bonds with Sn-CO3 bonds, which may be more resistant to wet phenomena.

[0100] Various atoms present in the precursor and / or counter-reactant may be provided within a capping layer, which is ultimately placed over any useful layer or structure. The capping layer may be of any useful thickness (e.g., any thickness described herein including about 0.1 nm to about 5 nm).

[0101] Furthermore, two or more different precursors may be used within each layer (e.g., a film or a capping layer). For example, two or more of any metal-containing precursors of the present invention may be used to form an alloy. Another exemplary EUV-sensitive material, as well as process methods and apparatuses, are described in U.S. Patent No. 9,996,004; International Patent Publication No. WO 2020 / 102085; and International Patent Publication No. WO 2019 / 217749, each of which is incorporated herein by reference in its entirety.

[0102] In some embodiments, a photoresist film may be deposited on an underlayer. In some embodiments, the underlayer may be deposited on a hard mask, such as an Ashable Hard Mask (AHM). The underlayer is configured to increase adhesion between the subsequently formed EUV resist and the substrate. The underlayer is also configured to reduce the EUV dose for effective EUV exposure of the EUV resist. The underlayer comprises a vapor-deposited film of hydronated carbon doped with non-carbon heteroatoms, such as oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or a combination thereof. For example, an underlayer comprising a hydronated carbon film doped with iodine may improve the generation of secondary electrons in the EUV resist upon exposure to EUV radiation. The underlayer may have a thickness of about 25 nm or less, for example, about 2 nm to about 20 nm. In some implementations, the lower layer can be deposited using vapor deposition techniques, such as PECVD or ALD.

[0103] In block (104) of process (100), the backside surface or bevel of the substrate may be optionally cleaned and / or the edge beads of the photoresist deposited in a preliminary step may be removed. Such cleaning or removal steps may be useful for removing particles that may be present after the photoresist layer has been deposited. The removal step may include processing the wafer into a wet metal oxide (MeOx) edge bead removal (EBR) step.

[0104] In block (106) of process (100), post-coating baking (PAB) or post-coating treatment may be optionally performed. Such treatment can improve the etching resistance of materials that have not been exposed to an aqueous or non-aqueous solution. In one example, since such treatment can improve the chemical composition difference (or contrast) between the non-exposed area and the exposed area, a PAB operation is performed. In another example, since such treatment can reduce the chemical composition difference (or contrast) between the non-exposed area and the exposed area, a PAB operation is not performed. In yet another example, the use of PAB removes residual moisture from the layer to form a cured resist film. PAB may include some combination of heat treatment, chemical exposure, and / or moisture to develop a pattern on the film by reducing the EUV dose by increasing the EUV sensitivity of the film. In certain embodiments, the PAB step is performed at a temperature greater than about 100°C, or at a temperature between about 100°C and about 200°C, or at a temperature between about 100°C and about 250°C. In other embodiments, the PAB step is performed at a temperature between about 190°C and about 350°C in the absence of an O-containing gas. In other examples, post-coating treatment includes exposing the film to an inert gas or CO2, which may optionally include cooling or heating. Using an inert gas may provide metal-oxygen-metal species, and using CO2 may provide metal carbonate species within the film.

[0105] In block (108) of process (100), the film is exposed to EUV radiation to develop a pattern. Generally, EUV exposure alters the chemical composition of the film, creating contrast in etching selectivity that can be used to remove a portion of the film. This contrast may provide a positive tone resist. However, it will be understood that EUV exposure may alternatively induce contrast so that unexposed areas (or less exposed areas) are selectively removed. This contrast may provide a negative tone resist as described herein. More exposed areas of the photoresist having altered physical or chemical properties compared to less exposed areas are created through photopatterning. The difference in properties between the more exposed areas and the less exposed areas may be utilized in subsequent processes. EUV exposure may include exposures having wavelengths in the range of about 10 nm to about 20 nm (e.g., about 13.5 nm in a vacuum environment) in a vacuum environment.

[0106] In block (110) of process (100), post-exposure baking (PEB) is performed on the exposed film to further remove residual moisture, promote chemical condensation within the film, increase contrast in etching selectivity of the exposed film, or post-process the film in any useful way. In one example, since this treatment can reduce the difference in chemical composition (or contrast) between the non-exposed area and the exposed area, the PEB operation is not performed. In another example, the exposed film is heat-treated (e.g., at a low temperature and / or optionally in the presence of various chemical species) to promote reactivity within the EUV exposed or non-exposed portion of the resist upon exposure to a stripping agent or positive tone developer (e.g., an aqueous solution of a halide-based acid, such as HCl, HBr, HI, or a combination thereof). In another example, the exposed film may be heat-treated (e.g., at a low temperature) to further crosslink ligands within the EUV-unexposed portions of the resist, thereby providing EUV-exposed portions that can be selectively removed upon exposure to a stripper (e.g., a positive tone developer). In yet another example, the PEB is omitted.

[0107] In block (112) of process (100), the photoresist pattern is developed through positive tone development or negative tone development. In various embodiments of development, non-exposed areas are selectively removed (to provide a pattern within the negative tone resist). These steps may be wet processes followed by an optional rinsing operation (e.g., using deionized water or other solvents) or an optional drying operation (e.g., under inert conditions with optional heating or using air) after using one or more developers or developing solutions. In certain embodiments, the development step is a wet process. In other embodiments, the development step is a dry process. For example, the dry process involves a halide-containing chemical.

[0108] The dry development process may include a thermal (plasma-free) dry development process, a plasma dry development process, or a combination of a thermal dry development process and a plasma dry development process. In some embodiments, the dry development gas may include halide-containing chemicals, such as hydrogen halides. Thus, the development chemistry may include hydrogen halides (e.g., HBr, HCl, etc.), hydrogen and halogen gases (e.g., H2 and Cl2, H2 and Br2, etc.), boron trichloride, organic halides, acyl halides, carbonyl halides, thionyl halides, or mixtures thereof. Organic halides are C x H y F z , C x H y Cl z , C x H y Br z and C x H y I zIt may include, but is not limited to, x, y, and z, where x, y, and z are values ​​greater than or equal to 0. Acyl halides may include, but are not limited to, CH3COF, CH3COCl, CH3COBr, and CH3COI. Carbonyl halides include, but are not limited to, COF2, COCl2, COBr2, and COI2. Thionyl halides include, but are not limited to, SOF2, SOCl2, SoBr2, and SOI2. In some embodiments, the dry developing gas may be flowed in the presence or absence of an inert / carrier gas, such as He, Ne, Ar, Xe, and N2. In some embodiments, the dry developing may include a thermal process, a plasma process, or a combination of a thermal process and a plasma process. Parameters, such as chamber pressure, gas flow rate, substrate temperature, and exposure duration, may be adjusted. In some embodiments, the chamber pressure may be from about 5 mTorr to about 760 Torr. In some embodiments, the substrate temperature may be from about -60°C to about 300°C. In some embodiments where plasma is applied, the RF level may be adjusted to an RF power level of about 1000 W or less. The selection of the development method may affect development selectivity, roughness, decumming, and other characteristics of the development, along with the optimization of development parameters.

[0109] After block (112), post-development inspection may be performed. If necessary, the process (102) is repeated to perform rework. In block (114) of process (100), the photoresist undergoes treatment before pattern transfer. The treatment may be thermal treatment, plasma treatment, chemical treatment, selective deposition treatment, or a combination of the aforementioned treatments. Thermal treatment may expose the photoresist to an elevated temperature of about 200°C to about 300°C to reduce the defect rate and LWR. Plasma treatment may expose the photoresist to a plasma, such as direct (in-situ) plasma or remote plasma, to densify the photoresist and reduce the LWR. In some embodiments, plasma treatment may include passivation. Passivation may include flash treatment, which includes exposure to an oxygen-containing plasma, a nitrogen-containing plasma, or a hydrogen-containing plasma. In some embodiments, plasma treatment may include curing. Curing may include exposure to an inert gas plasma and / or exposure to UV light. Chemical treatment may expose the photoresist to reactive chemical species, such as halide-based species (e.g., tungsten hexafluoride) or carbon-containing precursors (e.g., carbon monoxide, metal-organic precursors), to improve etching resistance, reduce degassing, and increase line CD. Selective deposition treatment may expose the photoresist to chemical precursors for selectively depositing a protective coating on the photoresist to reduce DtS, improve etching resistance, reduce degassing, and increase line CD. One or more of the aforementioned treatments are applied to the photoresist after development to improve the performance of the photoresist during pattern transfer.

[0110] In block (116) of process (100), one or more substrate layers are etched using a photoresist mask for pattern transfer. These substrate layers are located beneath the photoresist mask and may be removable by lithographic etching. Pattern transfer etching can etch the material to a desired depth to form a plurality of patterned features. In some embodiments, one or more substrates are amorphous carbon (aC), amorphous silicon (a-Si), tin oxide (e.g., SnO₂). x ), silicon oxide (e.g., SiO2), silicon oxynitride (e.g., SiO2) x N y ), silicon oxycarbide (e.g., SiO x C y ), silicon nitride (e.g., Si3N4), titanium oxide (e.g., TiO2), titanium nitride (e.g., TiN), tungsten (e.g., W), doped carbon (e.g., W-doped C), tungsten oxide (e.g., WO x It may include hafnium oxide (e.g., HfO2), zirconium oxide (e.g., ZrO2), and aluminum oxide (e.g., Al2O3). Any defect or variation within the CD of the photoresist mask is replicated in the material being patterned during pattern transfer etching. Additionally, poor etching resistance negatively affects the transfer of the pattern to the base substrate layer during the etching process. Post-development processing of the photoresist mask mitigates the aforementioned problems to ensure successful pattern transfer during pattern transfer etching.

[0111] After the pattern transfer, an inspection can be performed after etching. If necessary, go back and repeat the operation (102) to perform the rework.

[0112] Fig. 2a inside Fig. 2cIt illustrates a schematic cross-sectional view providing an overview of various process steps, including the development and processing of photoresist. Fig. 2a As shown in the figure, the wafer (200) comprises a substrate (202) to be etched and a substrate layer (204). The patterning structure may include any useful substrate. For example, the incoming wafer may be prepared with a substrate surface of a desired material, wherein the top layer material is a layer on which a resist pattern is transferred. The choice of material may vary depending on the degree of integration, but generally, it is desirable to select a material that can be etched with high selectivity (i.e., at a much faster rate than these) for the EUV resist or imaging layer.

[0113] In some embodiments, the substrate is a hard mask used for lithographic etching of a base semiconductor material. The hard mask is amorphous carbon (aC), tin oxide (e.g., SnO₂). x ), silicon oxide (e.g., SiO containing SiO2) x ), silicon oxynitride (e.g., SiO x N y ), silicon oxycarbide (e.g., SiO x C y ), silicon nitride (e.g., Si3N4), titanium oxide (e.g., TiO2), titanium nitride (e.g., TiN), tungsten (e.g., W), doped carbon (e.g., W-doped C), tungsten oxide (e.g., WO x It may include any of various materials including ), hafnium oxide (e.g., HfO2), zirconium oxide (e.g., ZrO2), and aluminum oxide (e.g., Al2O3). Suitable substrate materials include various carbon-based films (e.g., ashable hardmasks (AHM)), silicon-based films (e.g., SiO2). x , SiC x , SiO x C y , SiOx N y , SiO x C y N z It may include ), a-Si:H, poly-Si, or SiN), or any other (typically sacrificial) film applied to facilitate the patterning process. For example, the substrate is preferably SnO x , for example, may include SnO2. In various embodiments, the layer may have a thickness of 1 nm to 100 nm, or 2 nm to 10 nm.

[0114] In some embodiments, the substrate layer (204) comprises an ashable hardmask, such as amorphous carbon, spin-on carbon, or other materials, such as silicon, silicon oxide, silicon nitride, silicon carbide, etc. In some embodiments, the substrate layer (204) may be a layer stack deposited on the substrate (202). The wafer (200) further comprises a photopatterned metal-containing EUV resist film (206). For example, the photopatterned metal-containing EUV resist film (206) may be an organometal-containing layer deposited on the substrate layer (204) to be etched. The photopatterned metal-containing EUV resist film (206) may have a thickness of about 5 nm to about 50 nm, or about 10 nm to about 30 nm. The photopatterned metal-containing EUV resist film (206) may be provided to a process chamber after photopatterning in an EUV scanner and / or after PEB processing. The photopatterned metal-containing EUV resist film (306) includes a non-EUV exposed area (206a) and an EUV exposed area (206b).

[0115] Fig. 2bAs shown in [Figure], the non-EUV exposed area (206a) of the photopatterned metal-containing EUV resist film (206) is removed during the development process. Development may use wet development chemistry or dry development chemistry. If dry development chemistry is applied, dry development may proceed with or without plasma striking. In some embodiments, dry development chemistry may include halide-containing chemistry. A photoresist mask of the photopatterned metal-containing EUV resist film (206) is formed after development by the removal of the non-EUV exposed area (206a). Fig. 2a inside Fig. 2c While it illustrates a negative tone phenomenon, it will be understood that a positive tone phenomenon may alternatively be applied in this disclosure.

[0116] Fig. 2c As shown in the figure, the substrate layer (204) is etched using a photoresist mask (208) to form a recessed feature defined by the photoresist mask (208) on the wafer (200). The wafer (200) undergoes pattern transfer etching so that the substrate layer (204) is selectively removed by the photoresist mask (208) to which the etchant is chemically modified. Pattern transfer etching can be performed by dry etching or wet etching. For example, dry etching may utilize a fluorine-based plasma etching process or an oxygen-based plasma etching process. Pattern transfer etching can be performed through the substrate layer (204) according to a pattern defined by the photoresist mask (208). In some embodiments, the photoresist mask (208) preserves, or at least substantially preserves, the increased line CD after pattern transfer etching.

[0117] Fig. 1Returning to the above, various steps of process (100), including the transfer of a wafer from one process chamber to the next process chamber for subsequent operations, are typically performed in separate chambers. For example, steps of process (100), such as block (112) for development and block (114) for post-development processing, are typically performed in separate chambers. Dry development may be performed in a dry development chamber (e.g., a thermal dry development chamber). Post-development processing, such as baking after development, may be performed in a baking chamber. Optionally, subsequent post-development processing, such as line curing, may be performed in a UV chamber. This may result in a longer waiting time between dry development and dry development post-process(s). In some examples, this may potentially cause contamination on the back of the wafer due to degassing. To improve process efficiency and throughput and to limit potential sources of contamination, the number of steps and / or chambers for various operations may be reduced by the method disclosed herein.

[0118] especially, Fig. 1 The efficiency of the conventional process (100) as illustrated in the figure can be improved by performing the step indicated by the block (112) together with post-development processing in the same process chamber in a manner that eliminates the need for a separate chamber. Specifically, Fig. 1 The efficiency of the process (100) as shown in the figure can be improved by performing passivation, or passivation and curing together in the same process chamber in a way that eliminates the need for baking after separate development in a separate chamber.

[0119] The present disclosure relates to an all-in-one dry development of a photoresist. The dry development process may be performed in the same process chamber. The dry development process and the post-dry development process may be performed in the same process chamber. A metal or metal oxide-containing photoresist may be wet or dry deposited. The metal or metal oxide-containing photoresist may have high absorption of EUV radiation, so that the photoresist may be patterned by EUV exposure to form exposed and non-exposed regions. After the dry development selectively removes the exposed or non-exposed regions of the photopatterned metal or metal oxide-containing photoresist, the post-developed photoresist may be processed. Such processing may include one or more of the following operations: (i) thermal annealing, (ii) plasma exposure, (iii) reactive gas exposure, and (iv) selective deposition of a protective layer. This treatment can improve the performance of metal or metal oxide-containing photoresist during etching by achieving one or more of the following benefits: reduced defect rate, reduced LWR, reduced DtS, reduced degassing (e.g., tin degassing), increased etching resistance, and increased line CD.

[0120] The present invention refers 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 together with these specific embodiments, it will be understood that the present disclosure is not intended to be limited to these specific embodiments. On the contrary, it is intended to encompass alternatives, modifications, and equivalents that may be included within the spirit and scope of the present disclosure. In the following description, numerous specific details are provided to provide a complete understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other examples, well-known process operations have not been described in detail to avoid unnecessarily obscuring the present disclosure.

[0121] As previously discussed, the present disclosure provides a method for a film on a semiconductor substrate that can be patterned using EUV or other next-generation lithography techniques. The method comprises generating a polymerized organometallic material in vapor and depositing it onto a substrate. In some embodiments, dry deposition may utilize any useful precursor (e.g., metal halides, capping agents, or organometallic agents described herein). In other embodiments, spin-on formulations may be used. The deposition process may include applying an EUV-sensitive material as a resist film or an EUV-sensitive film.

[0122] These EUV-sensitive films include materials that undergo changes, such as the loss of bulky pendant ligands bonded to metal atoms, upon exposure to EUV. If the unexposed area contains dense MOM-rich material, EUV-induced cutting can provide intermediates that are more easily removed by a positive tone developer.

[0123] Through EUV patterning, film regions with altered physical or chemical properties compared to non-exposed regions are created. These properties can be utilized in subsequent processes, for example, to dissolve non-exposed or exposed regions, or to selectively deposit material onto exposed or non-exposed regions. In some embodiments, under the conditions in which these subsequent processes are performed, the non-exposed film has a hydrophobic surface, and the exposed film has a hydrophilic surface (the hydrophilic properties of the exposed and non-exposed regions are recognized as relative to each other). For example, material removal can be performed by utilizing differences in the chemical composition, density, and crosslinking of the films. Removal can be achieved by a wet process or a dry process, as further described herein.

[0124] The thickness of the EUV patternable film formed on the substrate surface may vary depending on surface features, materials used, and process conditions. In various embodiments, the film thickness may be in the range of about 0.5 nm to about 100 nm. Preferably, the film has a thickness sufficient to absorb most of the EUV light under EUV patterning conditions. For example, the total absorption rate of the resist film may be 30% or less (e.g., 10% or less, or 5% or less) so that the resist material at the bottom of the resist film is sufficiently exposed. In some embodiments, the film thickness is 10 nm to 20 nm. Without limiting the mechanism, function, or utility of the present disclosure, the process of the present disclosure is considered to be applicable to a wide variety of substrates. Furthermore, as previously discussed, the deposited film may closely match the surface features, thereby providing an advantage in forming a mask on a substrate, such as a substrate having underlying features, without "filling" or otherwise planarizing said features.

[0125] The film may consist of a metal oxide layer deposited in any useful manner. Such a metal oxide layer may be deposited or applied by using any EUV-sensitive material described herein, such as a precursor (e.g., a metal-containing precursor, a metal halide, a capping agent, or an organometallic agent), in combination with a counter-reactor. In an exemplary process, to provide a metal oxide layer, a polymerized organometallic material is formed in a vapor phase or formed in situ on the surface of a substrate. The metal oxide layer may be used as a film, an adhesive layer, or a capping layer.

[0126] Generally, the method may include the steps of mixing a vapor stream of a precursor (e.g., a metal-containing precursor such as an organometallic agent) with a selective vapor stream of a counter-reactor to form a polymerized organometallic material, and depositing the organometallic material onto the surface of a semiconductor substrate. In some embodiments, mixing the precursor and the selective counter-reactor may form a polymerized organometallic material. As will be understood by those skilled in the art, the mixing and deposition modes of the process may take place simultaneously in a substantially continuous process.

[0127] In an exemplary continuous CVD process, two or more gas streams of a source of precursor and an optional counter-reactor are introduced into the deposition chamber of a CVD apparatus from separate inlet paths, where they are mixed and reacted in the gaseous phase to form an aggregated polymer material (e.g., through the formation of a metal-oxygen-metal bond) or to form a film on a substrate. The gas streams may be introduced, for example, using separate inlets or a dual-plenum showerhead. The apparatus is configured so that the streams of the precursor and the optional counter-reactor are mixed in the chamber to react the precursor and the optional counter-reactor, thereby forming a polymerized organometallic material or a film (e.g., a metal oxide coating through the formation of a metal-oxygen-metal bond or an aggregated polymeric material).

[0128] To deposit metal oxides, the CVD process is generally performed at a reduced pressure, such as 0.1 Torr to 10 Torr. In some embodiments, the process is performed at a pressure of 1 Torr to 2 Torr. The temperature of the substrate is preferably lower than the temperature of the reactant stream. For example, the substrate temperature may be 0°C to 250°C, or ambient temperature (e.g., 23°C) to 150°C.

[0129] To deposit aggregated polymeric materials, the CVD process is generally performed at reduced pressure, e.g., 10 mTorr to 10 Torr. In some embodiments, the process is performed at 0.5 to 2 Torr. The temperature of the substrate is preferably below the temperature of the reactant stream. For example, the substrate temperature may be from 0°C to 250°C, or from ambient temperature (e.g., 23°C) to 150°C. In various processes, the deposition of the polymerized organometallic material on the substrate occurs at a rate inversely proportional to the surface temperature. Without limiting the mechanism, function, or utility of this disclosure, the product from this vapor phase reaction is believed to have a heavier molecular weight as the metal atoms are crosslinked by the counter-reactants, and then condense or otherwise deposit on the substrate. In various embodiments, the steric hindrance of the large alkyl group further prevents the formation of a densely packed network and produces a low-density film with increased porosity.

[0130] A potential advantage of using a dry deposition method is that the composition of the film can be easily adjusted as the film grows. In a CVD process, this can be achieved by changing the relative flow of the first precursor and the second precursor during deposition. Deposition can take place at 30°C to 200°C at a pressure of 0.01 Torr to 100 Torr, more generally at a pressure of about 0.1 Torr to 10 Torr.

[0131] Films (e.g., metal oxide coatings or aggregated polymeric materials via the formation of metal-oxygen-metal bonds) can also be deposited by an ALD process. For example, precursor(s) and optional counter-reactants are introduced at distinct times representing an ALD cycle. The precursor reacts on the surface to form a monolayer of the material at a time during each cycle. This can enable excellent control over the uniformity of film thickness across the entire surface. The ALD process is generally performed at reduced pressure, e.g., 0.1 Torr to 10 Torr. In some embodiments, the process is performed at 1 Torr to 2 Torr. The substrate temperature may be 0°C to 250°C, or ambient temperature (e.g., 23°C) to 150°C. The process may be a thermal process, or preferably a plasma-assisted deposition.

[0132] Any deposition method of the present invention may be modified to enable the use of two or more different precursors. In one embodiment, the precursor may comprise the same metal but different ligands. In another embodiment, the precursor may comprise different metal groups. In one non-limiting example, an alternating flow of various volatile precursors may provide a mixed metal-containing layer, such as the use of a metal alkoxide precursor having a first metal (e.g., Sn) and a silyl-based precursor having a second metal (e.g., Te) different from the first metal.

[0133] The process of the present invention can be used to achieve surface modification. In some iterations, vapor of the precursor may be passed over a wafer. The wafer may be heated to provide thermal energy to allow the reaction to proceed. In some iterations, heating may be performed at about 50°C to about 250°C. In some cases, pulses of the precursor may be used, which may be separated by a pump and / or purging step. For example, the first precursor may be pulsed between pulses of the second precursor pulse to result in ALD or ALD-like growth. In other cases, both precursors may be flowed simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of their compounds.

[0134] The process of the present invention can be used to deposit thin metal oxides or metals by ALD or CVD. An example is tin oxide (SnO₂). x ), bismuth oxide (BiO₂) x It includes ) and Te. After deposition, the film is M as described elsewhere in this application. a R b L c It can be capped with an alkyl-substituted precursor of the form. A counter-reactant can be used to better remove ligands, and several cycles can be repeated to ensure complete saturation of the substrate surface. Subsequently, the surface can be prepared for the EUV-sensitive film to be deposited. One possible method is SnO x The purpose is to manufacture a thin film. Possible chemistry involves the growth of SnO2 by a tetrakis(dimethylamino)tin cycle with a counter-reactant such as water or O2 plasma. After growth, a capping agent may be used. For example, isopropyltris(dimethylamino)tin vapor may be flowed over the surface.

[0135] The deposition process may be used on any useful surface. As referred to herein, a “surface” is a surface on which a film of the present technology is to be deposited or a surface to be exposed to EUV during processing. Such a surface may exist on a substrate (e.g., on which a film is to be deposited) or on a film (e.g., on which a capping layer may be deposited).

[0136] These underlying topographic features may include areas where material is removed (e.g. by etching) or areas where material is added (e.g. by deposition) during processing prior to performing the method of the present invention. These preliminary processes may include the method of the present invention or other process methods of iterative processes in which a layer of two or more features is formed on a substrate. Without limiting the mechanism, function, or utility of the present disclosure, in some embodiments, the method of the present disclosure is thought to provide advantages, such as the conformance of the film of the present disclosure to the underlying features without "filling" or otherwise planarizing the underlying features, and the ability to deposit the film on a wide variety of material surfaces.

[0137] Exposure of metal-containing resist materials

[0138] The photoresist film can be exposed to radiation. The photoresist film is exposed to radiation according to a desired pattern to form exposed and non-exposed areas of the photoresist film. It will be understood that the "exposed area" can be understood as a "more exposed area" relatively speaking, and the "non-exposed area" can be understood as a "less exposed area" relatively speaking. Exposure causes changes in the chemical composition and crosslinking of the photoresist film, creating a contrast in etching selectivity, which can be utilized in subsequent development.

[0139] EUV exposure of the membrane can provide an EUV-exposed region having an activated reactive center containing a metal atom (M) generated by an EUV-mediated cleavage event. This reactive center may include a dangling metal bond, an MH group, a cleaved M-ligand group, a dimerized MM bond, or a MOM bridge.

[0140] EUV exposure in a vacuum environment may have wavelengths in the range of about 10 nm to about 20 nm, e.g., 10 nm to 15 nm, e.g., 13.5 nm. In particular, patterning can form a pattern by providing EUV exposed areas and EUV non-exposed areas. In some embodiments, such patterning is about 1 to 50 mJ / cm² 2 , 1 to 40 mJ / cm² 2 , 1 to 30 mJ / cm² 2 , 1 to 20 mJ / cm² 2 or 1 to 10 mJ / cm² 2 Includes the radiation dose of.

[0141] The present disclosure may include patterning using EUV as well as DUV or e-beam. In such patterning, radiation is focused on one or more regions of the imaging layer. Exposure may be performed such that the imaging layer film includes one or more regions that are not exposed to radiation. The resulting imaging layer may include a plurality of exposed and non-exposed regions, which create a pattern corresponding to the creation of other features of a semiconductor device or transistors formed by the addition or removal of material from the substrate during subsequent processing of the substrate. EUV, DUV, and e-beam radiation methods and equipment useful herein include methods and equipment known in the art.

[0142] In some EUV lithography techniques, organic hard masks (e.g., PECVD amorphous carbon hydride washable hard masks) are patterned using a photoresist process. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate to generate high-energy photoelectrons (e.g., about 100 eV), which consequently create a cascade of low-energy secondary electrons (e.g., about 10 eV) that diffuse laterally over several nanometers. These electrons increase the degree of chemical reaction in the resist, thereby increasing EUV dose sensitivity. However, virtually random secondary electron patterns overlap in the optical image. This unwanted secondary electron exposure results in a loss of resolution, observable line edge roughness (LER), and changes in the linewidth of the patterned resist. These defects are replicated in the material to be patterned during subsequent pattern transfer etching.

[0143] In the various embodiments described herein, a thin film of a metal-containing film, such as a photosensitive metal salt or a metal-containing organic compound (organometallic compound), which exhibits strong absorption at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV), can be formed using a deposition (e.g., condensation) process (e.g., ALD or MOCVD performed in a PECVD tool) at EUV (e.g., wavelengths in the order of approximately 10 nm to 20 nm). Such a film is photodegraded upon EUV exposure to form a metal mask that is a pattern transfer layer during subsequent etching (e.g., in a conductor etching tool).

[0144] After deposition, the EUV patternable thin film is patterned by exposure to a beam of EUV light under a relatively high vacuum in some examples. For EUV exposure, the metal-containing film is subsequently deposited in a chamber integrated with a lithography platform (e.g., a wafer stepper) and transferred under vacuum to prevent reaction prior to exposure. Integration with lithography tools is facilitated in that EUVL also requires significantly reduced pressure, considering the strong optical absorption of incident photons by ambient gases such as H2O, O2, etc. In other embodiments, the deposition of the photosensitive metal film and EUV exposure can be performed within the same chamber.

[0145] The photolithography process may include one or more baking steps to facilitate the chemical reactions necessary to create chemical contrast between the exposed and unexposed areas of the photoresist. For high-volume manufacturing (HVM), these baking steps may be performed on a track where wafers are baked on a hot plate at a preset temperature under ambient air or, in some cases, N2 flow. More careful control of the baking environment, as well as the introduction of additional reactive gas components into the surroundings during these baking steps, can help further reduce dose requirements and / or improve pattern fidelity.

[0146] According to various embodiments of the present disclosure, one or more post-treatments for metal and / or metal oxide-based photoresists after deposition (e.g., baking after coating (PAB) or another post-coating treatment) and / or exposure (e.g., baking after exposure (PEB) or another post-exposure treatment, which may be omitted) and / or development (e.g., baking after development (PDB) or another post-development treatment) increase the difference in material properties between the exposed photoresist and the non-exposed photoresist, thereby reducing the dose-to-size (DtS) after subsequent dry development, improving the PR profile, and improving line edge and line width roughness (LER / LWR). Such processes may include thermal processes that control temperature, ambient gas, and moisture, which may lead to improved dry development performance in subsequent processes. In some examples, remote plasma may be used. However, in certain examples, PAB and / or PEB and / or PDB are not performed.

[0147] In the case of post-coating processing (e.g., PAB), the composition of the unexposed metal and / or metal oxide photoresist can be changed by using a thermal process that controls temperature (e.g., heating or cooling), gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or a mixture thereof), or vacuum, and moisture after deposition and before exposure. Since such change can increase the EUV sensitivity of the material, lower irradiation dose and edge roughness can be achieved after exposure and dry development.

[0148] For post-exposure processing (e.g., PEB), the composition of both the non-exposed and exposed photoresists can be changed using a thermal process that controls temperature, gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or a mixture thereof), or vacuum and moisture. Such changes can increase the difference in composition / material properties between the non-exposed and exposed photoresists and the difference in etching rates of the dry development etching gas between the non-exposed and exposed photoresists. This allows for higher etching selectivity to be achieved. Due to improved selectivity, surface roughness is improved, and / or a more square PR profile with less photoresist residue / scum can be obtained. In certain embodiments, PEB can be performed in air and in the optional presence of moisture and CO2. In other embodiments, the PEB may be omitted.

[0149] For post-development processing (e.g., post-development baking or PDB), the composition of the non-exposed photoresist can be changed by using a thermal process that controls temperature, a gas atmosphere (e.g., air, H2O, CO2, CO, O2, O3, CH4, CH3OH, N2, H2, NH3, N2O, NO, Ar, He, or a mixture thereof) or a vacuum (e.g., using UV), and moisture. In certain embodiments, conditions also include the use of plasma (e.g., including O2, O3, H2O2, Ar, He, or a mixture thereof). The change may increase the hardness of the material, which may be beneficial when the film is used as a resist mask when etching the base substrate.

[0150] In such cases, in an alternative implementation, the thermal process can be replaced with a remote plasma process to increase reactive species, thereby lowering the energy barrier to the reaction and increasing productivity. Since remote plasma can generate more reactive radicals, it can lead to increased productivity by lowering the reaction temperature / time for processing.

[0151] Accordingly, one or multiple processes may be applied to modify the photoresist itself to increase wet or dry development selectivity. Such thermal or radical modification can increase the selectivity of subsequent development steps by increasing the contrast between the non-exposed material and the exposed material. The resulting difference in material properties between the non-exposed and exposed materials can be adjusted by controlling process conditions including temperature, gas flow, moisture, pressure, and / or RF power.

[0152] In the case of a wet-developed or dry-developed resist film, the processing process can be adjusted and optimized by varying the processing temperature in PAB or PEB, which is, for example, about 90°C to 250°C in the case of PAB and about 170°C to 250°C or higher in the case of PEB.

[0153] In certain embodiments, PAB and / or PEB treatment may be performed at a pressure between atmospheric pressure and vacuum with an ambient gas flow in the range of 100 sccm to 10,000 sccm, with a moisture content of several percent to up to 100% (e.g., 20% to 50%), for a period of about 30 seconds to 15 minutes, e.g., about 1 to 2 minutes. In certain embodiments, PEB is omitted.

[0154] Depending on the selectivity requirements / constraints of the semiconductor process operation, the heat treatment as described herein may be used to lower the required EUV dose. Alternatively, where higher selectivity is required and a higher dose is acceptable, much higher selectivity of up to 100 times can be obtained in the case of exposure compared to the case of non-exposure.

[0155] Another step may include in-situ metrology in which physical and structural features (e.g., critical dimensions, film thickness, etc.) can be evaluated during the photolithography process. Modules for implementing in-situ metrology include, for example, scatterometry, ellipsometry, downstream mass spectroscopy, and / or plasma-enhanced downstream optical emission spectroscopy modules.

[0156] A substrate may be provided in a process chamber, wherein the substrate is a semiconductor substrate comprising a substrate layer and a post-development photoresist mask on the substrate layer. The substrate layer may be located beneath the post-development photoresist mask and may comprise any suitable material that facilitates the patterning process. The substrate layer may be etched with high selectivity onto the post-development photoresist mask. In some embodiments, the substrate layer is spin-on carbon (SoC), spin-on glass (SOG), amorphous carbon (aC), tin oxide (e.g., SnO₂). x ), silicon (e.g., a-Si), silicon oxide (e.g., SiO x ), silicon oxynitride (e.g., SiO x N y ), silicon oxycarbide (e.g., SiO x C y ), silicon nitride (Si3N4), silicon carbide (SiC x), titanium oxide (e.g., TiO2), titanium nitride (e.g., TiN), tungsten (e.g., W), doped carbon (e.g., W-doped C), tungsten oxide (e.g., WO x It may include hafnium oxide (HfO2), zirconium oxide (e.g., ZrO2) or aluminum oxide (Al2O3).

[0157] A metal-containing photoresist can be dry- or wet-deposited on a substrate layer. The metal-containing photoresist can be provided as a positive-tone or negative-tone resist having EUV-exposed regions and EUV-non-exposed regions after EUV exposure. After deposition, the metal-containing photoresist can be photopatterned in an EUV lithography chamber (scanner). After exposure and selective PEB treatment, the metal-containing photoresist can be developed to selectively remove a portion of the metal-containing photoresist (e.g., EUV-non-exposed portion) to form a patterned photoresist mask on the substrate layer. In some embodiments, the metal-containing photoresist is a metal-containing EUV photoresist, wherein the metal-containing EUV photoresist is an organometallic oxide or an organometallic-containing film. For example, the metal-containing EUV photoresist may contain Sn, O, and C atoms.

[0158] A process chamber may provide a sealed space for processing a substrate after development. The chamber walls of the process chamber may be made of stainless steel, aluminum, plastic, or other suitable materials. In some embodiments, the chamber walls are coated with a corrosion-resistant film, such as a polymer or inorganic coating. The process chamber may include a substrate support (e.g., a pedestal or an electrostatic chuck) upon which the substrate is supported. In some embodiments, the process chamber for post-development processing may be a deposition chamber, a bevel edge and / or back cleaning chamber, a PAB processing chamber, a PEB processing chamber, a development chamber, or an etching chamber. In this way, the process chamber for post-development processing may be the same as the chamber used in the previous operation for the photoresist process or the same as the chamber used in the subsequent operation for the photoresist process, thereby minimizing substrate transfer and reducing exposure to air breaks between operations. The process chamber may include one or more heating elements for exposing the substrate to an elevated temperature. In some embodiments, one or more heating elements may include one or more infrared (IR) lamps or one or more light-emitting diodes (LEDs) located on the substrate support to control the temperature of the substrate. The process chamber may include one or more gas lines for delivering gas to the process chamber. For example, one or more gas lines may include showerheads for supplying reactive gas from the process chamber toward the substrate. In some embodiments, the process chamber may be a plasma generation chamber or may be coupled to a plasma generation chamber separate from the process chamber. The plasma generation chamber may be an inductively coupled plasma (ICP) reactor, a transformer-coupled plasma (TCP) reactor, or a capacitively coupled plasma (CCP) reactor.In some cases, the process chamber additionally includes one or more gas outlets for discharging gas, which may or may not be coupled to a vacuum pump to maintain a desired pressure within the process chamber.

[0159] The metal-containing photoresist mask after development is processed using one or more of the following operations: (i) thermally annealing the metal-containing photoresist mask after development, (ii) exposing the metal-containing photoresist mask after development to plasma, (iii) exposing the metal-containing photoresist mask after development to one or more reactive gases, and (iv) selectively depositing a protective layer on the metal-containing photoresist mask after development. Post-development processing of the substrate may utilize one or a combination of the aforementioned thermal annealing, plasma, chemical, or selective deposition processes. Post-development processing improves the performance of the metal-containing photoresist mask during pattern transfer etching. The aforementioned thermal annealing, plasma, chemical, and selective deposition techniques are discussed in detail below.

[0160] The substrate layer is etched to form concave features using a metal-containing photoresist mask after development. This process may be referred to as pattern transfer or pattern transfer etching. Etching can selectively remove a portion of the substrate layer without removing the metal-containing photoresist mask after development. Etching can be performed through the portion of the substrate layer exposed by the metal-containing photoresist mask after development using a wet or dry etchant. The metal-containing photoresist mask can define a pattern in which the feature is to be etched. The feature is etched through the substrate layer according to the pattern defined by the metal-containing photoresist mask. After post-development processing, the metal-containing photoresist mask may have improved etching resistance and / or increased line CD during pattern transfer etching. The feature to be etched may retain or substantially retain the line CD provided by the metal-containing photoresist mask. In some cases, metal-containing photoresist masks may have reduced defect rates and / or roughness. Consequently, defects and roughness are not transferred to features formed after pattern transfer etching.

[0161] heat treatment

[0162] In some implementations, the substrate may be thermally treated by heating the substrate to an elevated temperature. This may also be referred to as post-phase baking (PDB). Thermal treatment of the substrate can contribute to reducing defects and roughness from the metal-containing photoresist mask prior to pattern transfer etching. In particular, thermal treatment of the substrate can improve chemical contrast in the metal-containing photoresist mask by removing scum. Thermal treatment of the substrate can cure residues / scum and also reduce degassing.

[0163] After wet or dry development, residues or scum may remain on the substrate. Residues or scum may remain in areas of the photoresist mask removed by development. Residues or scum may include residual etching byproducts adsorbed onto the surface of the substrate. For example, halogen vapors used in certain development chemistry can react with moisture or oxygen to form residual etching byproducts that are difficult to remove. Wet process techniques often use moisture and / or oxygen, which leads to the formation of scum and residues more easily. In some cases, the residues consist of high concentrations of metal or metal oxide (e.g., SnO₂), which can contribute to a loss of chemical contrast during pattern transfer and contaminate downstream process tools. x It may include particles or clusters of ).

[0164] After wet or dry development, roughness may form on the sidewalls of etched features with the developed pattern of the photoresist mask. Part of this may be due to light stochastics or non-optimal Gaussian distributions, which can cause the material to be partially or completely exposed in areas where the photoresist should remain unexposed, and vice versa. Furthermore, scumming on the sidewalls of etched features of the photoresist mask can worsen the roughness.

[0165] During heat treatment, the substrate may be heated to an elevated temperature of about 50°C to about 500°C, about 100°C to about 400°C, about 100°C to about 300°C, or about 100°C to about 250°C. The substrate may be heated to an elevated temperature using one or more temperature-controllable elements in a process chamber. Pressure may be maintained at about 0.1 Torr to about 760 Torr in some cases, for example, about 0.1 Torr to about 1 Torr. The substrate may be exposed to the elevated temperature for a duration of about 1 minute to about 10 minutes in some cases, for example, about 2 minutes to about 5 minutes. In some embodiments, the heat treatment is performed with one or more inert gases. For example, the heat treatment may be performed with a flow of nitrogen (N2), helium (He), neon (Ne), argon (Ar), or xenon (Xe). In some embodiments, the heat treatment is performed in the atmosphere.

[0166] Higher temperatures during post-development heat treatment can lead to increased decomposing, reduced defect rates, and reduced roughness. However, higher temperatures can simultaneously lead to a reduction in line CD. It has been observed that as the temperature increases during thermal annealing, the photoresist sides and photoresist height shrink. A reduction in line CD results in a higher irradiation dose. Post-development heat treatment may experience a tradeoff between reduced defect rates and reduced roughness depending on the higher irradiation dose. This optimizes the benefits of reduced defect rates and roughness while minimizing the increase in irradiation dose by limiting the heat treatment to a desired temperature range and duration.

[0167] Plasma treatment

[0168] In some implementations, the substrate may be exposed to plasma for post-development processing. Plasma treatment can contribute to densifying the metal-containing photoresist mask and reducing roughness prior to pattern transfer etching. In some cases, plasma treatment can further improve chemical contrast in the metal-containing photoresist mask by removing scum. Plasma treatment may utilize plasma of inert gas species or plasma of reactive gas species. Plasma of reactive gas species can chemically react with the metal-containing photoresist mask or selectively deposit a protective film on the metal-containing photoresist mask. Plasma treatment may exhibit the effects of passivation and / or curing.

[0169] Exposure to plasma can be facilitated by generating plasma in a remote plasma generator or in a process chamber where the substrate is processed. One or more gases may flow into a plasma generation region, which may be a remote plasma generator or a process chamber, and the plasma is ignited. The plasma generation chamber may be an inductively coupled plasma (ICP), transformer coupled plasma (TCP), or capacitively coupled plasma (CCP) reactor. Plasma energy is provided to activate one or more gases into ions, radicals, neutral species, and other plasma-activated species. The ions, radicals, neutral species, and other plasma-activated species may interact with the metal-containing photoresist mask to improve the performance of the metal-containing photoresist mask during pattern transfer etching.

[0170] One or more gases may include oxygen-containing species, such as oxygen (O2), carbon dioxide (CO2), carbon monoxide (CO), ozone (O3), and sulfur dioxide (SO2). Additionally or alternatively, one or more gases may include halogen-containing species, such as boron trichloride (BCl3), silicon tetrachloride (SiCl4), tin tetrachloride (SnCl4), tungsten hexafluoride (WF6), and difluoromethane (CH2F2). Additionally or alternatively, one or more gases may include inert gas species, such as nitrogen (N2), helium (He), neon (Ne), argon (Ar), and xenon (Xe). Other gases include hydrogen (H2), ammonia (NH3), water (H2O), hydrogen peroxide (H2O2), nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), hydrogen halides (HCl, HBr, HF, HI), and various hydrocarbons (C x H y ), for example, may include methane (CH4). In some cases, the plasma may be an oxygen-based plasma, a nitrogen-based plasma, a hydrogen-based plasma, an inert gas plasma, and / or a carbon-based plasma. In some implementations, the plasma is a remote plasma. In some other implementations, the plasma is an in-situ plasma.

[0171] Process conditions for plasma treatment can be adjusted to achieve desired results. These process conditions include, but are not limited to, plasma power, plasma frequency, plasma exposure time, bias voltage, duty cycle, temperature (e.g., pedestal temperature), pressure (e.g., chamber pressure), and the flow rate of one or more gases. The plasma in operation may be generated at a plasma power of less than about 6 kW, e.g., about 50 W to about 4000 W, about 50 W to about 1000 W, or about 100 W to about 500 W. In some examples, the plasma may be provided at low plasma power and high ion energy. The directionality of the plasma may be controlled by the bias voltage. In some implementations, the bias voltage may be applied at about 1 V to about 500 V, about 10 V to about 400 V, or about 30 V to about 300 V. Plasma treatment may be applied for a period of about 0.5 seconds to about 120 seconds, about 1 second to about 60 seconds, or about 2 seconds to about 40 seconds. Plasma treatment may modulate the duty cycle of the plasma being worked to achieve the desired result, wherein the RF power supply may deliver the plasma at any suitable duty cycle, for example, about 1% to about 99%, or about 10% to about 90%. In some embodiments, the chamber pressure may be about 0.1 Torr to about 760 Torr, and in some cases, about 0.1 Torr to about 1 Torr. In some embodiments, the substrate temperature may be about 0°C to about 400°C, about 50°C to about 300°C, or about 100°C to about 250°C.

[0172] In some embodiments, a useful plasma process system may include a radio frequency power amplifier that can be operated continuously or pulsed.

[0173] As discussed below, plasma treatment can be accompanied by reactive gas species. Plasma of reactive gas species can induce chemical reactions in metal-containing photoresist masks to improve mask properties such as etching resistance. Plasma of reactive gas species can selectively deposit a protective film on metal-containing photoresist masks to increase line CD and reduce irradiation dose.

[0174] In certain embodiments, the plasma treatment may be a cyclic plasma treatment. This process includes a first step of immersion in a halogen-containing gas, such as HBr, where HBr is absorbed onto the exposed patterned surface, followed by purging of the excess HBr. After purging the process chamber, the second step of the cyclic plasma treatment process is to ignite a helium plasma with a specific bias to activate the HBr absorbed onto the exposed patterned surface for decomposing. Then, the two steps are repeated as many times as necessary to remove all scum.

[0175] In certain embodiments, the plasma treatment may be a continuous plasma dry development. In this process, an inert gas comprising, but not limited to, helium, argon, or a combination thereof is co-flowed into a process chamber with about 1 to about 10% of a halogen-containing gas, e.g., HBr, and then the plasma is decomposed by igniting it with a bias at a voltage of about 40 volts to about 500 volts. The halogen-containing gas flow rate may be about 200 to about 800 sccm. The plasma may be modulated by 1) ramping up the TCP power from high to low, 2) maintaining a constant TCP power with a pulsing bias, or 3) pulsing the bias and TCP simultaneously to clean the scum on the photoresist surface. The entire process may take about 7 seconds to about 30 seconds in some embodiments. The pressure of the continuous dry development plasma process may be about 5 mTorr to about 50 mTorr.

[0176] Chemical treatment

[0177] In some embodiments, the metal-containing photoresist mask may be exposed to one or more reactive gas species. The reactive gas species may chemically react with the metal-containing photoresist mask. In practice, certain reactive gas species may react with the metal-containing photoresist mask but not with the substrate layer of the substrate. In some embodiments, the reactive gas species may convert the entire or substantially the entire metal-containing photoresist mask from a first material to a second material. The chemical change of the metal-containing photoresist mask may alter one or more properties of the metal-containing photoresist mask. In some embodiments, the reactive gas species may convert only the outer portion of the metal-containing photoresist mask from the first material to a second material, which may be used as a protective film, as further described below.

[0178] Reactive gas species can react with a metal-containing photoresist mask to increase line CD and decrease irradiation dose. Reactive gas species can react with a metal-containing photoresist mask to reduce roughness (e.g., LWR / LER) or at least maintain the same roughness. Reactive gas species can densify the metal-containing photoresist mask. In some cases, reactive gas species can react with a metal-containing photoresist mask to reduce defect rate (e.g., skimming). Additionally, reactive gas species can reduce degassing, such as tin degassing, from the metal-containing photoresist mask. In some cases, reactive gas species can react with a metal-containing photoresist mask to increase the etching resistance of the photoresist mask during a subsequent etching operation. For example, after pattern transfer etching, reactive gas species can increase line CD and at least substantially maintain the increased line CD of the photoresist mask.

[0179] Reactive gas species may be more reactive with the metal-containing photoresist compared to the underlying substrate layer(s). In certain implementations, chemical treatment using reactive gas species can leverage the chemistry of the EUV photoresist mask. The EUV photoresist mask may consist of an organometallic oxide film, such as an organotin oxide film containing Sn, O, and C atoms. The organotin oxide film may consist of a network of Sn-Sn bonds, Sn-H bonds, Sn-C bonds, Sn-OH bonds, Sn-O bonds, Sn-O-Sn bonds, and Sn-OC bonds. Reactive gas species may react with one or more elements of the organotin oxide film via oxidation, reduction, insertion, extraction, or other chemical reaction mechanisms to induce chemical changes in the EUV photoresist mask. In some examples, the reactive gas species may include carbon monoxide (CO), where the tin species may undergo a catalytic reaction with carbon monoxide. Without being limited to any theory, SnOC x The compound reacts with CO to form SnOC x (CO) y A new compound is formed. The chemical reaction extends the line CD, inducing a change in the EUV photoresist mask. In some implementations, the etching resistance of the new compound in the EUV photoresist mask is improved.

[0180] Chemical reactions can be induced in EUV photoresist masks using reactive gas species other than CO. Examples of useful reactive gas species are air, water vapor (H2O), hydrogen peroxide (H2O2), carbon dioxide (CO2), oxygen (O2), ozone (O3), methane (CH4), methanol (CH3OH), ethanol (CH3CH2OH), nitrogen (N2), hydrogen (H2), ammonia (NH3), nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), acetylacetone (C5H8O2), formic acid (CH2O2), acetic acid (CH3COOH), hydrogen cyanide (HCN), boron trichloride (BCl3), silicon tetrachloride (SiCl4), chlorine (Cl2), bromine (Br2), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), hydrogen fluoride (HF), and fluoromethane (CH3F). Difluoromethane (CH2F2) and combinations thereof may be included, but not limited to. In some cases, the reactive gas species may include oxygen-containing gas, carbon-containing gas, hydrogen-containing gas, nitrogen-containing gas, halogen-containing gas, or combinations thereof. Other reactive gas species may include metal precursors, such as tungsten hexafluoride (WF6), tin tetrachloride (SnCl4), molybdenum hexafluoride (MoF6), molybdenum dichloride dioxide (MoO2Cl2) and molybdenum chloride (MoCl5). Other reactive gas species are metal-organic precursors, e.g., tin tetrakis(dimethylamide) (Sn(N(CH3)2)4), hafnium tetrakis(dimethylamide) (Hf(N(CH3)2)4), dimethyl aluminum ((CH3)2Al), trimethyl aluminum ((CH3)3Al), titanium isopropoxide (Ti(OCH(CH3)2)4), tungsten carbonyl (W(CO x )), molybdenum carbonyl (Mo(CO) x ), ruthenium carbonyl (Ru(CO) x ), iron carbonyl (Fe(CO) xIt may include ) and combinations thereof. Accordingly, in some cases, the reactive gas species may include metal halides or organometallic precursors, such as metal carbonyl precursors. While conventional polymer-based photoresist materials may not react with metal halides or certain organometallic precursors, the metal-containing or metal oxide-containing photoresist materials of the present disclosure may have a greater tendency to react with metal halides and organometallic precursors. Without being limited to any theory, if the organometallic photoresist has M-OH bonds, MOM' bridges may be formed, where M' is derived from a metal precursor (e.g., a metal halide or an organometallic precursor).

[0181] Reactive gas species can be co-flowed with other gases. In some embodiments, reactive gas species can be co-flowed with inert gas species, such as helium, neon, argon, or xenon. In some embodiments, combinations of reactive gas species can be co-flowed with each other. For example, a halogen-containing gas, such as boron trichloride, can be co-flowed with a carbon-containing gas, such as methane. In another example, a metal precursor, such as tungsten hexafluoride, can be co-flowed with a carbon-containing gas, such as difluoromethane. Reactive gas species, alone or in combination with other reactive gas species, can convert the photoresist mask into another material or selectively deposit a protective film on the photoresist mask.

[0182] In some embodiments, reactive gas species may be supplied to the process chamber from a gas source fluidically coupled to the process chamber. A gas source, such as a gas storage tank, may be fluidly coupled to the process chamber via a gas supply line. The gas reactants may be pre-mixed before entering the process chamber or mixed upon entering the process chamber. In some embodiments, reactive gas species may be generated in-situ within the process chamber. The gas reactants may react with each other to form reaction products, which react with the metal-containing photoresist mask to induce a chemical change. Alternatively, the gas reactants may react with one or more chamber components (e.g., a metal-based chamber line) to form reaction products, which react with the metal-containing photoresist mask to induce a chemical change. The gas reactants may be carbon-containing precursors that react with the metal chamber components to form organometallic precursors. These reactions may be thermally driven to produce organometallic precursors. For example, carbon monoxide supplied to the process chamber reacts with the iron-containing chamber line, and iron carbonyl (Fe(CO)₂) that readily reacts with the EUV photoresist mask x It forms ), thereby increasing the line CD of the EUV photoresist mask. Without being limited to any theory, iron carbonyl causes the deposition of iron oxide on the EUV photoresist mask. In another example, carbon monoxide or carbon dioxide supplied to the process chamber reacts with tungsten-containing chamber lines (e.g., hotwires) to form tungsten carbonyl (W(CO)) that readily reacts with the EUV photoresist mask. x It can form ).

[0183] Chemical treatment of a metal-containing photoresist mask containing one or more reactive gas species can be used in combination with one or both of heat treatment and plasma treatment. While heat treatment or plasma treatment alone may result in trade-offs, these trade-offs can be offset by additionally applying chemical treatment to the metal-containing photoresist mask. Specifically, chemical treatment can be combined with heat treatment so that one or more reactive gas species flow into the metal-containing photoresist mask at an elevated temperature. While elevated temperature can decrease line CD, one or more reactive gas species can increase line CD in the metal-containing photoresist mask. In practice, the increased line CD resulting from one or more reactive gas species can exceed the decreased line CD resulting from elevated temperature. This reduces the irradiation dose while decreasing the defect rate and roughness of the metal-containing photoresist mask. In some embodiments, chemical treatment may be combined with plasma treatment so that radicals and / or ions of reactive gas species flow into the metal-containing photoresist mask. Radicals and / or ions may increase the reactivity of the metal-containing photoresist mask and the reactive gas species. The metal-containing photoresist mask may be exposed to one or more reactive gas species in the plasma, which may alter the chemical composition of the metal-containing photoresist mask and increase line CD and density. This can be performed without inevitably damaging the defect rate or roughness of the metal-containing photoresist mask. The plasma may be applied at a power that avoids damage to the substrate.

[0184] Induction of surface or bulk reactions in a metal-containing photoresist mask can occur by applying energy to the reaction. Some amount of energy from thermal exposure and / or plasma exposure may be sufficient to induce a surface or bulk reaction. Accordingly, process conditions, such as temperature and plasma power, can be adjusted to achieve the desired results. In some embodiments, the substrate temperature may be about 0°C to about 400°C, about 50°C to about 300°C, or about 100°C to about 250°C during chemical treatment using one or more reactive gas species. In some embodiments, the plasma power may be less than about 6 kW, about 50 W to about 4000 W, about 50 W to about 1000 W, or about 100 W to about 500 W during chemical treatment using one or more reactive gas species.

[0185] Other process conditions, such as plasma frequency, exposure time, bias voltage, pressure, and flow rate, may be adjusted to facilitate chemical treatment using one or more reactive gas species. In some embodiments, the bias voltage may be applied at less than about 800 V, about 0 V to about 500 V, about 10 V to about 400 V, or about 30 V to about 300 V. In some embodiments, exposure to one or more reactive gas species may be applied for a period of about 1 second to about 10 minutes, about 5 seconds to about 8 minutes, or about 30 seconds to about 4 minutes. In some embodiments, the chamber pressure may be about 0.1 Torr to about 760 Torr, or in some cases, 1 mTorr to about 100 mTorr. The first reactive gas species may be flowed into the process chamber at a flow rate of about 1 sccm to about 1000 sccm, about 2 sccm to about 500 sccm, or about 5 sccm to about 300 sccm. An optional second reactive gas species may be co-flowed into the process chamber at a flow rate of about 5 sccm to about 1000 sccm, about 10 sccm to about 500 sccm, or about 20 sccm to about 300 sccm. An optional inert gas species may be co-flowed into the process chamber at a flow rate of about 20 sccm to about 2000 sccm, about 30 sccm to about 1000 sccm, or about 50 sccm to about 500 sccm. For example, carbon monoxide can be flowed into a process chamber at a flow rate of about 500 sccm at a substrate temperature of about 240°C for a period of about 20 seconds to about 5 minutes. Carbon monoxide can react with the EUV photoresist mask to change the chemical composition of the EUV photoresist mask. In an alternative example, tungsten hexafluoride can replace carbon monoxide and react with the EUV photoresist mask to change the chemical composition of the photoresist mask.EUV photoresist masks can exhibit increased etching resistance during subsequent pattern transfer etching.

[0186] A specific embodiment of the disclosed method is Fig. 3 This is exemplified by. The work of process (300) may be performed in a different order and / or may be performed with different work, fewer work, or additional work. One or more of the work of process (300) Fig. 6 inside Fig. 9 It may be performed using a device described in any one of the above. In some embodiments, the operation of the process (300) may be implemented at least partially according to software stored on one or more non-transient computer-readable media.

[0187] Fig. 3 In this, blocks (302 to 310 and 314) are Fig. 1 It represents the same operation as blocks (102 to 110 and 116). The operation of block (312) represents an integrated dry development operation, wherein the integrated dry development operation may include thermal and plasma dry development, or the integrated dry development operation may include dry development and post-development processing, all of which are performed in a single process chamber. The operation (312) Fig. 1 This can be performed instead of the operations (112 and 114). By doing so, productivity is improved, and defects, overlays, and CD can be controlled more effectively. Integrating both dry development and post-development operations into a single process chamber promotes the reduction of metal degassing, such as tin degassing, without the need to add the additional step of baking after dry development, which typically occurs in different process chambers.

[0188] In a single chamber, a combination of dry processes and passivation, or a combination of thermal dry processes and plasma dry processes, is counterintuitive due to the diametrically opposed process conditions required by each operation, particularly regarding pressure. These are typically performed in different chambers using different process tools to substantially manage pressure requirements. Thermal processes require high pressure to obtain high etching rates. High partial pressures lead to better selectivity. Conversely, for plasma processes, low pressure is required to achieve anisotropic etching. When performed in a single process chamber, a pressure drop of several times must be achieved rapidly within about 1 to about 10 seconds. By using throttle valves, specialized pumps, multiple pumps, or control of process gas flow, a rapid pressure drop can be achieved in about 10 seconds or less. In some embodiments, the pressure drop occurs within 8, 7, 6, 5, 4, 3, or 2 seconds. The device enables one or more process parameters to be uniformly maintained, wherein one or more process parameters include pumping, gas delivery, or pumping and gas delivery.

[0189] In addition, the all-in-one process enables wafer surface passivation, residue cleaning, and pattern edge roughness smoothing in-situ in a single chamber.

[0190] When the metal-containing photoresist is a metal oxide, such as tin oxide, metal degassing, such as tin degassing, can be controlled without the need for baking after dry development.

[0191] "Tin oxide" is Sn containing integer values ​​x and y, and non-integer values ​​x and y. x O y It refers to including any stoichiometric possibility for. For example, "tin oxide" is the chemical formula SnO nIt includes a compound having, where 1 ≤ n ≤ 2, and n can be an integer or non-integer value. "Tin oxide" is a substoichiometric compound, e.g., SnO₂ 1.8 It may include. "Tin oxide" also includes tin dioxide (SnO2 or stannous oxide) and tin monooxide (SnO or stannous oxide). "Tin oxide" also includes both natural and synthetic variations, and also includes any crystalline and molecular structure. "Tin oxide" also includes amorphous tin oxide.

[0192] An exemplary method for performing the integration of blocks (312) is Fig. 4a , Fig. 4b , Fig. 4c , Fig. 4d and Fig. 4e It is explained in more detail in. Fig. 4a , Fig. 4b , Fig. 4c , Fig. 4d and Fig. 4e The embodiments described herein are merely exemplary and are not intended to be limited to the scope of block (312) of process (300). Fig. 4a This can describe an aspect of a block (312) in which dry development and passivation are performed in the same process chamber. Fig. 4b This can describe an aspect of block (312) in which thermal drying and plasma drying phenomena are performed in the same process chamber. Fig. 4c This can describe an aspect of a block (312) in which the drying phenomenon and curing are performed in the same process chamber. Fig. 4d This can describe an embodiment of a block (312) in which thermal drying, plasma drying, and passivation are performed in the same process chamber. Fig. 4e This can describe an embodiment of a block (312) in which thermal drying, plasma drying, passivation, and curing are performed in the same process chamber.

[0193] Fig. 4aThis shows a flowchart for an example process (410) that performs dry development and passivation operations in the same process chamber according to a specific embodiment disclosed. For some photoresists, under certain process conditions, only a thermal dry development process is required. That is, plasma dry development may not be necessary.

[0194] The operation of block (412) may be a dry development process. As described herein, a dry development process may be used to process a photoresist film. Non-limiting processes may include the use of halides, such as hydrogen halides (e.g., HBr, HCl, etc.), hydrogen and halogen gases (e.g., H2 and Cl2, H2 and Br2, etc.), boron trichloride, organic halides, acyl halides, carbonyl halides, thionyl halides, or mixtures thereof. Although the present disclosure is not limited to any specific theory or operating mechanism, the approach is understood to utilize the chemical reactivity of the EUV photoresist film and cleaning chemicals (e.g., HCl, HI, HBr and / or BCl3) to form volatile products using vapor or plasma. These volatile products may be removed by any method (e.g., by treatment with an aqueous acid solution as described herein). The EUV photoresist film may be removed at an etching rate of up to 1 nm / sec. Rapid removal of EUV photoresist films by such chemistry is applicable to chamber cleaning, back cleaning, bevel edge cleaning, and PR development. The film can be removed using vapors at various temperatures (e.g., HCl or HBr at temperatures above -20°C, or BCl3 at temperatures above 50°C), but plasma can also be used to further accelerate or enhance reactivity.

[0195] The dry development process may include a thermal process, a plasma process, or a combination of a thermal process and a plasma process. The thermal process may expose the photoresist film to a process gas that may contain one or more halides in a plasma-free process. The plasma process may expose the photoresist film to a plasma of an inert gas, a halogen-containing gas, or a combination of an inert gas and a halogen-containing gas. Thermal dry development and plasma dry development may be performed in the same process chamber in block (412). In negative tone development, the dry development process selectively removes less exposed areas of the photoresist film compared to more exposed areas of the photoresist film.

[0196] In some implementations, the dry phenomenon is merely a thermal dry phenomenon. Between block (412) and block (414), the flow path (413) may represent a change in process conditions to transition from the dry phenomenon of block (412) to the passivation of block (414). For example, the flow path (413) may represent a change in pressure occurring within the process chamber, such as a sudden pressure drop. The pressure drop may occur within the process chamber, enabling both high-pressure and low-pressure processes to occur within the same chamber. The pressure change may be managed by a throttle valve, a special pump, multiple pumps, flow control of the process gas, or a combination of these techniques. If more than one pump is utilized, one of the pumps may be a roughing pump and one of the pumps may be a turbo pump. Optional purging with an inert gas may be performed before, after, or during the pressure drop operation.

[0197] After the drying process of block (412), the operation of block (414) represents a passivation step, such as flash plasma treatment. The drying process of block (412) and the passivation of block (414) may be performed in the same process chamber. In some embodiments, the drying process of block (412) may be performed at a first pressure, and the passivation of block (414) may be performed at a second pressure. For example, the second pressure may be equal to or lower than the first pressure. In some embodiments, the first pressure is in the range of about 5 mTorr to about 760 Torr, and the second pressure is in the range of about 5 mTorr to about 200 mTorr. In some embodiments, the transition of the pressure in the process chamber from the first pressure to the second pressure may occur within 10 seconds or less.

[0198] Passivation is useful when the photoresist has surface bromine or chlorine substituents that can destabilize the photoresist. As used herein, “passivation” refers to a surface treatment that causes stabilization of the photoresist by creating a thin layer of a stable film on the photoresist or by reducing volatile moiety on the photoresist. In some embodiments, when passivation is performed using an oxygen-containing plasma, the thin layer of the stable film is oxide, whereas in other embodiments, when passivation is performed using a hydrogen-containing plasma or a nitrogen-containing plasma, volatile moiety may be removed. Surface smoothing may also be achieved during the operation of block (414). The plasma process may include transformer-coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP) using equipment and techniques known in the art. For example, the process may be carried out at a pressure greater than 0.5 mTorr (e.g., 1 mTorr to 100 mTorr) at a power level of less than 1000 W (e.g., less than 500 W). The temperature may be 30°C to 300°C (e.g., 30°C to 120°C). The flow rate may be 100 to 5000 standard cubic centimeters / min (sccm), e.g., about 500 sccm, for 1 to 3000 seconds (e.g., 10 seconds to 600 seconds).

[0199] In some embodiments, passivation is a treatment using an oxygen-containing plasma, a nitrogen-containing plasma, or a hydrogen-containing plasma. In some embodiments, passivation is O2, O3, CO, CO2, H2, C x H yPlasma treatment using H2O, H2O2, SO2, NO, NO2, N2O, NH3, or a mixture thereof, wherein x is an integer from 1 to 6 and y is an integer from 2 to 14. The gas may be introduced into the process chamber at a flow rate of about 100 to about 10,000 sccm. Passivation may be performed at a pressure of about 5 mTorr to about 500 mTorr. Passivation may be performed at a plasma power of about 50 W to about 300 W. Passivation may be performed at a step time of about 3 seconds to about 30 seconds. In some implementations, passivation is a flash treatment, wherein the flash treatment occurs relatively quickly for about 0.5 seconds to about 4 seconds, or about 0.5 seconds to about 10 seconds.

[0200] In some embodiments, passivation includes an O2 flash treatment that delivers a flash gas of oxygen (O2) at a rate of 1,000 sccm to 2,000 sccm from block (412) to the process chamber. In certain embodiments, radio frequency power of 100 W to 3,000 W is delivered at 13.56 MHz to convert the flash gas into plasma. A pressure of 20 mTorr to 100 mTorr is provided. This process may be referred to as an “O2 flash” operation because the time during which power is delivered is relatively fast, ranging from about 0.5 seconds to about 10 seconds, or from about 0.5 seconds to about 10 seconds. Optional purging with an inert gas may be performed after the dry development and before passivation.

[0201] The task (416) was previously Fig. 1 It is a pattern transfer process similar to the one described for the operation (116).

[0202] The operation (418) is an optional cleaning process that can be performed to remove metal oxides as well as other contaminants. The cleaning process occurs after the process chamber is opened. For the back and bevel edge cleaning process, the vapor and / or plasma can be restricted to specific areas of the wafer to ensure that only the material on the back and bevel edges is removed without any film degradation on the front of the wafer. The photoresist film to be removed is typically composed of Sn, O, and C, but the same cleaning approach can be extended to films of other metal oxide resists and materials. Additionally, this approach can be used for film stripping and photoresist rework.

[0203] For wet cleaning, the solution comprises a compound, such as tetramethylammonium hydroxide (TMAH), a complexed amine, such as ethylenediamine or diethylenetriamine, a semi-aqueous fluoride stripper, or a dilute hydrofluoric acid stripper. Metal oxides can be removed by using an acid, such as citric acid, acetic acid, or octanoic acid, or other organic or inorganic acids may be used. Additionally, a very dilute (i.e., less than 0 / 1%) peroxide-containing acid, such as a sulfuric acid-peroxide mixture, may also be used. Any combination of the wet cleaning agents described above may also be utilized.

[0204] Fig. 4bThis illustrates a process (420) for integrated thermal dry development and plasma dry development in a single process chamber according to a specific embodiment disclosed. The operation of block (422) is thermal dry development. A non-limiting process may include the use of halides, e.g., hydrogen halides (e.g., HBr, HCl, etc.), hydrogen and halogen gases (e.g., H2 and Cl2, H2 and Br2, etc.), boron trichloride, organic halides, acyl halides, carbonyl halides, thionyl halides, or mixtures thereof. While the present disclosure is not limited to any specific theory or operating mechanism, the approach is understood to utilize the chemical reactivity of the EUV photoresist film and cleaning chemicals (e.g., HCl, HI, HBr and / or BCl3) to form volatile products. These volatile products may be removed by any method (e.g., treatment with an aqueous acid solution as described herein). EUV photoresist films can be removed at an etching rate of up to 1 nm / second. Rapid removal of EUV photoresist films by these chemicals is applicable to chamber cleaning, back-side cleaning, bevel edge cleaning, and PR development. The film can be removed using vapors at various temperatures (e.g., HCl or HBr at temperatures above -20°C, or BCl3 at temperatures above 50°C).

[0205] In the thermal development process, the substrate is exposed to dry developing chemicals (e.g., Lewis acids) in a vacuum chamber (e.g., an oven). A suitable chamber may include a vacuum line, a dry developing chemical gas line (e.g., HBr, HCl), and a heater for temperature control. In some embodiments, the interior of the chamber may be coated with a corrosion-resistant film, such as an organic polymer or an inorganic coating. One such coating is polytetrafluoroethylene (PTFE), e.g., Teflon TM )am.

[0206] The thermal process may expose the photoresist film to a process gas that may contain one or more halides in a plasma-free process. In the thermal dry development process, the thermal dry development may be performed at a pressure of about 5 mTorr to about 760 Torr, e.g., about 300 mTorr. The temperature may be about -60°C to about 120°C, or about -20°C to about 60°C, e.g., about -10°C. In the thermal dry development process, the flow rate of the process gas(s) may be about 10 sccm to about 10,000 sccm, about 100 sccm to about 3,000 sccm, e.g., about 500 sccm HBr or HCl. The thermal dry development process may expose the substrate to the process gas(s) for a time of about 10 seconds to about 1 minute, depending on the photoresist film and its composition and characteristics. In some embodiments, the pressure is 400 to 500 mTorr for a period of 10 to 20 seconds.

[0207] Between block (422) and block (424), the flow path (423) may represent a change in process conditions to transition from the thermal drying phenomenon of block (422) to the plasma drying phenomenon of block (424). For example, the flow path (423) may represent a change in pressure occurring within the process chamber, such as a sudden pressure drop. The pressure drop may occur within the process chamber, which enables both high-pressure and low-pressure processes to occur in the same chamber. The pressure change may be managed by a throttle valve, a special pump, multiple pumps, flow control of the process gas, or a combination of these techniques. If more than one pump is utilized, one of the pumps may be a roughing pump and one of the pumps may be a turbo pump. Optional purging using an inert gas may be performed before, after, or during the pressure drop operation.

[0208] After the thermal drying phenomenon of block (422), the operation of block (424) exhibits a plasma drying phenomenon. The thermal drying phenomenon of block (422) and the plasma drying phenomenon of block (424) may be performed in the same process chamber. In some embodiments, the thermal drying phenomenon of block (422) may be performed at a first pressure, and the plasma drying phenomenon of block (424) may be performed at a second pressure. For example, the second pressure may be equal to or lower than the first pressure. In some embodiments, the first pressure is in the range of about 5 mTorr to about 760 Torr, and the second pressure is in the range of about 5 mTorr to about 200 mTorr. In some embodiments, the transition of the pressure in the process chamber from the first pressure to the second pressure may occur within 10 seconds or less.

[0209] After the thermal dry phenomenon of block (422), the operation of block (424) represents a plasma dry phenomenon step, where both operations are performed in the same process chamber. The plasma dry phenomenon may perform decomposing and / or smoothing operations. The plasma process includes transformer coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP) using equipment and techniques known in the art. The plasma dry phenomenon may be performed at a pressure greater than about 0.5 mTorr, for example, from about 1 mTorr to about 200 mTorr, or from about 5 mTorr to about 100 mTorr. The plasma dry phenomenon may apply plasma power of less than about 1000 W, for example, from about 1 W to about 1000 W, or from about 1 W to about 500 W. The plasma dry phenomenon may occur at a temperature of about -60°C to about 120°C, for example, from about -20°C to about 60°C. The flow rate can be 100 to 1,000 standard cubic centimeters (sccm) per minute, for example, about 500 sccm, for 1 to 3,000 seconds (for example, 10 to 600 seconds).

[0210] In some embodiments, the plasma dry phenomenon utilizes an inert carrier gas, such as argon (Ar) or helium (He). In some embodiments, the plasma dry phenomenon utilizes at least one halogen-containing gas. For example, the halogen-containing gas may include HBr, HCl, HF, HI, Br2, Cl2, F2, I2, BCl3, or a combination thereof. The halogen-containing gas may be delivered to the inert carrier gas. In some cases, the halogen-containing gas(s) may be efficiently used to remove scum during the plasma dry phenomenon. In some embodiments, the plasma dry phenomenon utilizes at least one carbon-containing gas. For example, the carbon-containing gas may include methane (CH4). In some embodiments, the plasma dry phenomenon utilizes at least one hydrogen-containing gas. For example, the hydrogen-containing gas may include hydrogen gas (H2). In some embodiments, the plasma dry phenomenon utilizes at least one nitrogen-containing gas. For example, the nitrogen-containing gas may include nitrogen gas (N2).

[0211] Under specific dry phenomenon process conditions, specific combinations of reactants may be advantageous for plasma dry phenomena. Combinations may include, but are not limited to, HBr and N2; HBr and H2; HBr and Cl2; HBr and HCl; HBr and BCl3; BCl3 and Cl2; BCl3 and HBr; BCl3 and CH4; CH4 and Cl2; CH4, Cl2 and N2; CH4 and HCl; or CH4 and HBr. In some embodiments, the aforementioned combination for plasma dry phenomena of block (424) may be followed by thermal dry phenomena of block (422) utilizing a hydrogen halide, such as HBr.

[0212] When the halide reactant flow consists of hydrogen gas and halide gas, remote plasma / UV radiation is used to generate radicals from H2 and Cl2 and / or Br2, and the hydrogen and halide radicals flow into the reaction chamber to contact the EUV photoresist on the substrate layer of the wafer. The appropriate plasma power can be in the range of 100 W to 500 W without bias. While these conditions are suitable for some process reactors, it should be understood that a wider variety of process conditions may be used depending on the performance of the process reactor. Fig. 4b Although not illustrated, it will be understood that post-development processes, such as passivation and / or curing, may be performed in the same process chamber as the thermal dry development and plasma dry development.

[0213] The task (426) was previously Fig. 1 It is a pattern transfer process similar to that described for the operation (116).

[0214] Fig. 4b Returning to the pattern transfer, a selective cleaning process (428) may be performed to remove metal oxides as well as other contaminants. The cleaning process occurs after the chamber is opened. For the back and bevel edge cleaning process, the vapor and / or plasma may be restricted to specific areas of the wafer to ensure that only the material on the back and bevel edges is removed without any film degradation on the front of the wafer. The EUV photoresist film to be removed is typically composed of Sn, O, and C, but the same cleaning approach can be extended to films of other metal oxide resists and materials. Additionally, this approach can be used for film stripping and photoresist rework.

[0215] For wet cleaning, the solution comprises a compound, such as tetramethylammonium hydroxide (TMAH), a complexed amine, such as ethylenediamine or diethylenetriamine, a hemihydrofluoric acid stripper, or a dilute hydrofluoric acid stripper. Metal oxides can be removed by using an acid, such as citric acid, acetic acid, or octanoic acid, or other organic or inorganic acids may be used. Additionally, a very dilute (i.e., less than 0 / 1%) peroxide-containing acid, such as a sulfuric acid-peroxide mixture, may also be used. Any combination of the wet cleaning agents described above may also be utilized.

[0216] Fig. 4c ... exemplifies a process (430) for integrated dry developing and curing in a single process chamber according to a specific disclosed embodiment. The operation of block (432) is thermal dry developing. The operation of block (432) Fig. 4b It is similar to what is described in block (422).

[0217] Between block (432) and block (434), the flow path (433) may represent a change in process conditions to transition from the thermal drying phenomenon of block (432) to the plasma drying phenomenon and hardening of block (434). Specifically, the flow path (433) may represent a change in pressure occurring within the process chamber, such as a sudden pressure drop. The pressure drop may occur within the process chamber, which enables both high-pressure and low-pressure processes to occur in the same chamber. The pressure change may be managed by a throttle valve, a special pump, multiple pumps, flow control of the process gas, or a combination of these techniques. If more than one pump is utilized, one of the pumps may be a roughing pump and one of the pumps may be a turbo pump. Optional purging using an inert gas may be performed before, after, or during the pressure drop operation.

[0218] After the thermal drying phenomenon of block (432), the operation of block (434) represents a plasma drying phenomenon and / or curing. In some cases, the operation of block (434) is only a curing step. In some other cases, the operation of block (434) is both a plasma drying phenomenon and a curing step. The thermal drying phenomenon of block (432) and the plasma drying phenomenon and / or curing of block (434) may be performed in the same process chamber. In some embodiments, the thermal drying phenomenon of block (432) may be performed at a first pressure, and the plasma drying phenomenon and curing of block (434) may be performed at a second pressure. For example, the second pressure may be equal to or lower than the first pressure. In some embodiments, the first pressure is in the range of about 5 mTorr to about 760 Torr, and the second pressure is in the range of about 5 mTorr to about 200 mTorr. In some implementations, switching the pressure in the process chamber from the first pressure to the second pressure may occur within 10 seconds or less.

[0219] The aspect of the plasma dry phenomenon of block (434) is Fig. 4b It is similar to that described in block (424). The curing mode of block (434) is described below. A post-processing step, such as curing, can be performed in the same process chamber as the thermal drying step of block (432).

[0220] For certain applications, curing of the photoresist is desirable. As used herein, “curing” refers to a treatment of the surface and interior of the photoresist that condenses the material by a process such as the crosslinking and / or cutting of the metal-carbon bonds of the photoresist. This can contribute to densifying the material of the photoresist. In some embodiments, curing may be achieved by treatment using a plasma of an inert gas. In one example, curing by treatment using plasma may include plasma ignition to generate argon, nitrogen, xenon, or helium reactive species (e.g., ions and / or radicals). In some embodiments, curing may be achieved by a flash treatment, such as an O2 flash treatment, which can perform both passivation and curing. The pressure may be about 5 mTorr to about 500 mTorr, and the plasma power (e.g., TCP power) may be about 50 W to about 300 W in certain embodiments. The gas flow rate can be about 100 sccm to about 1000 sccm, and the step time is about 5 mTorr to about 500 mTorr.

[0221] In some alternative implementations, curing may be achieved by exposure to UV light. For example, exposure to UV light for curing may include exposure from one or more UV lamps at a power of about 10 W to about 1000 W and a pressure of about 5 mTorr to about 760 Torr. In some implementations, curing may be achieved by a combination of exposure to a plasma of inert gas and exposure to UV light.

[0222] In some embodiments, curing may occur during or after the plasma drying phenomenon. In some embodiments, curing may occur without the plasma drying phenomenon.

[0223] The task (436) was previously Fig. 1 It is a pattern transfer process similar to the one described for the operation (116).

[0224] The operation (438) is an optional cleaning process. The aspect of the cleaning process of the block (438) is Fig. 4b It is similar to what is described in block (428).

[0225] Fig. 4d This illustrates a process (440) for integrated thermal dry phenomenon, plasma dry phenomenon, and passivation in a single process chamber according to a specific disclosed embodiment. The operation of block (442) is a thermal dry phenomenon. The operation of block (442) Fig. 4b It is similar to what is described in block (422).

[0226] Between block (442) and block (444), the flow path (443) may represent a change in process conditions to transition from the thermal drying phenomenon of block (442) to the plasma drying phenomenon and passivation of block (444). In particular, the flow path (443) may represent a change in pressure occurring within the process chamber, such as a sudden pressure drop. The pressure drop may occur within the process chamber, which enables both high-pressure and low-pressure processes to occur in the same chamber. The pressure change may be managed by a throttle valve, a special pump, multiple pumps, flow control of the process gas, or a combination of these techniques. If more than one pump is utilized, one of the pumps may be a roughing pump and one of the pumps may be a turbo pump. Optional purging using an inert gas may be performed before, after, or during the pressure drop operation.

[0227] After the thermal drying phenomenon of block (442), the operation of block (444) involves plasma drying and passivation. The thermal drying phenomenon of block (442) and the plasma drying phenomenon and passivation of block (444) can be performed in the same process chamber. In some embodiments, the thermal drying phenomenon of block (442) can be performed at a first pressure, and the plasma drying phenomenon and passivation of block (444) can be performed at a second pressure. For example, the second pressure may be equal to or lower than the first pressure. In some embodiments, the first pressure is in the range of about 5 mTorr to about 760 Torr, and the second pressure is in the range of about 5 mTorr to about 200 mTorr. In some embodiments, the transition of the pressure in the process chamber from the first pressure to the second pressure may occur within 10 seconds or less.

[0228] The aspect of the plasma dry phenomenon of block (444) is Fig. 4b It is similar to that described in block (424). The mode of passivation of block (444) is Fig. 4a It is similar to that described in block (414). In some implementations, passivation is a plasma flash process, e.g., an O2 plasma flash process. A post-phenomenal process such as passivation can be performed in the same process chamber as the thermal dry phenomenon of block (442). In some embodiments, passivation may occur during or after the plasma dry phenomenon.

[0229] The task (446) was previously Fig. 1 It is a pattern transfer process similar to the one described for the operation (116).

[0230] The operation (448) is an optional cleaning process. The aspect of the cleaning process of the block (448) is Fig. 4b It is similar to what is described in block (428).

[0231] Fig. 4eThis illustrates an alternative process (450) for dry development, passivation, and curing, all integrated into a single process chamber according to a specific disclosed embodiment. The operation of block (452) is as previously described. Fig. 4b It exhibits a thermal drying phenomenon as described for block (422).

[0232] Between block (452) and block (454), the flow path (453) represents a pressure change procedure occurring within the process chamber. As previously described for the flow path (453), the necessary pressure drop is made within the process chamber, making it possible for both high-pressure and low-pressure processes to occur in the same chamber. The pressure change can be managed by a throttle valve, a special pump, multiple pumps, flow control of the process gas, or a combination of these techniques. If more than one pump is utilized, one of the pumps may be a roughing pump and one of the pumps may be a turbo pump.

[0233] After the thermal drying phenomenon of block (452), the operation of block (454) involves plasma drying, passivation, and curing processes, all of which can be performed in a single (same) process chamber.

[0234] Plasma dry phenomena and passivation are Fig. 4a , Fig. 4b , Fig. 4c and Fig. 4d It is the same as previously described with reference to. The mode of hardening is Fig. 4c It is described above with reference to

[0235] Fig. 4e Returning to the point, selective purging using an inert gas can be performed with operation (453), between operation (454) and operation (456), as well as between the plasma drying phenomenon and passivation and / or between the plasma drying phenomenon and curing.

[0236] The task (456) was previously Fig. 1It is a pattern transfer process similar to the one described for the operation (116).

[0237] Following the work (456), as before Fig. 4b An optional cleaning process (458) similar to the operation described for block (428) can be performed.

[0238] Fig. 5a inside Fig. 5e is a schematic cross-sectional view of various process steps including thermal drying, plasma drying, and passivation according to specific embodiments disclosed. The process steps may be performed in a single process chamber.

[0239] Fig. 5a In this, a photoresist (510), such as a metal-containing photoresist, is provided on a semiconductor substrate (501). The photoresist (510) may be photopatterned to include an exposed area (503) (or a more exposed area) and a non-exposed area (505) (or a less exposed area). Fig. 5a As illustrated in [Image], particles or clusters (507) of metal / metal oxide may occupy the non-exposed area (505). In some implementations, photopatterned photoresist (510) may be provided to a process chamber after EUV exposure in an EUV scanner.

[0240] Fig. 5bIn this case, the photoresist (510) is developed in a process chamber using a thermal dry development process. As the thermal dry development proceeds, clusters (507) of metal / metal oxide become more concentrated. Clusters (507) of metal / metal oxide are generally difficult to remove. Thermal dry development can selectively remove the non-exposed area (505) compared to the exposed area (503). Bulk removal of the non-exposed area (505) can occur under thermal dry development. Thermal dry development can be selective for the removal of organic material. After bulk removal of the non-exposed area (505), clusters (507) of metal / metal oxide may remain as scum on the surface of the semiconductor substrate (501). In some embodiments, thermal dry development may be performed by exposure to a halide chemical, such as a hydrogen halide. For example, the hydrogen halide may include HBr. In some embodiments, the thermal dry phenomenon may be performed in a process chamber at a first pressure, wherein the first pressure may be from about 5 mTorr to about 760 Torr. In some embodiments, the thermal dry phenomenon may be performed at a temperature from about -20°C to about 60°C, and the flow rate of the process gas may be from about 100 sccm to about 3000 sccm.

[0241] Fig. 5cIn this case, the photoresist (510) is developed in a process chamber using a plasma dry development process. As the plasma dry development proceeds, clusters (507) of metal / metal oxide are removed. Additionally, the plasma dry development can remove or substantially remove the remaining non-exposed area (505). In some embodiments, the plasma dry development may utilize a plasma of an inert gas species, such as He or Ar. In some embodiments, the plasma dry development may utilize a plasma of a halogen-containing species. For example, the halogen-containing gas may include HBr, HCl, HF, HI, Br2, Cl2, F2, I2, BCl3, or a combination thereof. The halogen-containing gas may be delivered by an inert carrier gas. In some embodiments, the plasma dry development may utilize a combination of a plasma of an inert gas species and a plasma of a halogen-containing gas. In some embodiments, the plasma dry development includes cyclic plasma dry development. In one example, the cyclic plasma drying phenomenon may alternate exposure to an inert gas plasma and exposure to a halogen-containing gas plasma. In some embodiments, the plasma drying phenomenon includes a continuous plasma drying phenomenon. The continuous plasma drying phenomenon may be performed at variable power, at constant power and pulsing bias, or at variable power and pulsing bias. In some embodiments, the plasma drying phenomenon is efficiently used to remove scum from the surface of a semiconductor substrate (501). In some embodiments, a specific combination of reactants may be used in the plasma drying phenomenon. The combination may include, but is not limited to, HBr and N2; HBr and H2; HBr and Cl2; HBr and HCl; HBr and BCl3; BCl3 and Cl2; BCl3 and HBr; BCl3 and CH4; CH4 and Cl2; CH4, Cl2 and N2; CH4 and HCl; or CH4 and HBr.In some embodiments, the plasma dry phenomenon may be performed in a process chamber at a second pressure, wherein the second pressure may be from about 5 mTorr to about 200 mTorr. In some embodiments, the plasma dry phenomenon may be performed at a temperature of about -20°C to about 60°C, the flow rate of the process gas may be from about 100 sccm to about 3000 sccm, the TCP power may be from about 1 W to about 500 W, and the bias voltage may be from about 1 V to about 300 V.

[0242] Fig. 5d In this example, a photoresist (510) after plasma dry processing is shown. Clusters (507) of metal / metal oxide are removed, and non-exposed areas (505) of the photoresist (510) are removed. In some embodiments, critical dimension (CD) loss (509) occurs as a result of plasma dry processing. However, the directional characteristics of the plasma dry processing and other conditions associated with the plasma dry processing can remove clusters (507) of metal / metal oxide with minimal CD loss (509). Additionally, plasma dry processing can be utilized to improve linewidth roughness (LWR) performance.

[0243] Fig. 5e In this example, the photoresist (510) after passivation is shown. Passivation may be performed in the same process chamber as the thermal dry development and plasma dry development. Passivation may occur under the same pressure as the plasma dry development. In some embodiments, passivation may create a passivation layer (511) on the exposed surface of the photoresist (510). For example, the passivation layer (511) may contain oxides and / or nitrides and / or carbon. In some embodiments, passivation is a process using an oxygen-containing plasma, a nitrogen-containing plasma, or a hydrogen-containing plasma. For example, passivation may be O2, O3, CO, CO2, H2, C x H yPlasma treatment using H2O, H2O2, SO2, NO, NO2, N2O, NH3, or a mixture thereof, wherein x is an integer from 1 to 6 and y is an integer from 2 to 14. In one example, passivation includes O2 flash treatment, wherein the photoresist (510) is exposed to O2 plasma for a relatively fast timing, such as about 0.5 seconds to about 4 seconds. Passivation may provide in-situ surface stabilization to prevent degassing of the photoresist (510). Passivation may additionally or alternatively perform curing of the photoresist (510). Passivation may additionally or alternatively provide surface smoothing of the photoresist (510).

[0244] The foregoing description is by nature merely illustrative and is not intended to limit the disclosure, its application, or use in any way. The broad teachings of this disclosure may be embodied in various forms. Accordingly, while this disclosure includes specific examples, the actual scope of this disclosure should not be limited in this way, as other modifications will become apparent from studying the drawings, the specification, and the following claims. It should be understood that one or more steps within the method may be executed in a different order (or simultaneously) without altering the principles of this disclosure. Furthermore, although each embodiment is described above as having specific features, any one or more of these features described with respect to any embodiment of this disclosure may be embodied in combination with features of any other embodiment and / or features of any other embodiment, even if the combination is not explicitly described. In other words, the described embodiments are not mutually exclusive, and substitutions between one or more embodiments remain within the scope of this disclosure.

[0245] device

[0246] The apparatus of the present disclosure is configured for dry development of a photoresist and, in some cases, also configured for post-development processing of a photoresist mask. The apparatus may be configured for other process operations, such as deposition, bevel and back cleaning, baking after coating, EUV scanning, baking after exposure, development, etching, and other operations. In some embodiments, the apparatus is configured to perform a number of dry operations. In some embodiments, 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 process chamber. With multiple stations within the same process chamber, various process operations as described in the present disclosure may be performed at different stations within the same process chamber. In some embodiments, the process chamber for post-development processing of the present disclosure may be performed in the same chamber as development, in the same chamber as pattern transfer etching, or in the same chamber as both development and pattern transfer etching.

[0247] An apparatus configured for dry development, and in some cases also configured for dry development and post-development processing, comprises a process chamber equipped with a substrate support. The apparatus may include at least a reactive gas source in fluid communication with the process chamber. The apparatus may include one or more gas lines for the delivery of one or more reactive gas species. In some embodiments, one or more reactive gas species may include an organic gas species, an organometallic gas species, a metal-containing gas species, or a combination thereof. In some embodiments, one or more reactive gas species may include an oxygen-containing gas, a carbon-containing gas, a hydrogen-containing gas, a nitrogen-containing gas, a halogen-containing gas, or a combination thereof. One or more reactive gas species may be delivered to the process chamber through one or more gas lines to develop the photoresist and / or process the photoresist mask after development. The apparatus may include one or more heating elements for temperature control. These heating elements may be provided to the process chamber and / or to the substrate support. Alternatively, these heating elements may be provided outside the process chamber. In some embodiments, the device may include a plasma source for generating plasma during the development and / or processing of the post-development photoresist mask. In some embodiments, one or more reactive species may optionally deposit a protective film on the post-development photoresist mask. The device may further include one or more sensors for detecting particle counts, wafer counts, thickness counts, or other parameters to trigger the endpoint of the post-development process.

[0248] Fig. 6The schematic diagram illustrates an exemplary process station for maintaining an environment suitable for performing photoresist development and photoresist processing operations, according to some embodiments. For simplification, the process station (600) is illustrated as a standalone process station having a process chamber body (602) for maintaining a low-pressure environment. However, it will be recognized that multiple process stations (600) may be included in a common process tool environment. Additionally, it will be recognized that in some embodiments, one or more hardware parameters of the process station (600), including those discussed in detail below, may be programmatically adjusted by one or more computer controllers.

[0249] Multiple process stations (600) may be included in a common low-pressure process tool environment. For example, Fig. 7 The figure illustrates an implementation of a multi-station process tool (700). In some implementations, one or more hardware parameters of the process tool (700), including those discussed in detail below, may be programmatically adjusted by one or more computer controllers (750).

[0250] The process station can be configured as a module of the cluster tool. Fig. 9 [It] illustrates a semiconductor process cluster tool architecture having a suitable vacuum integrated deposition and patterning module for implementing the embodiments described herein. This cluster process tool architecture is, Fig. 6 and Fig. 7 As described above and further below with reference, it may include resist deposition, resist exposure (EUV scanner), resist development, resist rework, and etching modules.

[0251] Fig. 6Returning to the above, the process station (600) is fluidly connected to a reactant delivery system (601) to deliver process gas to a showerhead (606). The reactant delivery system (601) optionally includes a mixing vessel (604) to blend and / or condition the process gas for delivery to the showerhead (606). One or more mixing vessel inlet valves (620) can control the introduction of process gas into the mixing vessel (604). If plasma exposure is used, the plasma can also be delivered to the showerhead (606) or generated at the process station (600). As previously indicated, in at least some implementations, non-plasma thermal exposure is preferred.

[0252] Fig. 6 It includes an optional vaporization point (603) for vaporizing a liquid reactant to be supplied to a mixing vessel (604). In some embodiments, a liquid flow controller (LFC) upstream of the vaporization point (603) may be provided to control the mass flow of the liquid for vaporization and delivery to the process station (600). For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. Then, the plunger valve of the LFC may be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller that communicates electrically with the MFM.

[0253] The showerhead (606) distributes process gas toward the substrate (612). Fig. 6 In the embodiment illustrated in the figure, the substrate (612) is shown positioned under the showerhead (606) and placed on the pedestal (608). The showerhead (606) may have any suitable shape and may have any suitable number and arrangement of ports for dispensing process gas to the substrate (612).

[0254] In some embodiments, the pedestal (608) may be raised or lowered to expose the substrate (612) to the volume (607) between the substrate (612) and the showerhead (606). In some embodiments, it will be noted that the pedestal height may be programmed by a suitable computer controller. In some embodiments, the showerhead (606) may have multiple plenum volumes with multiple temperature controls.

[0255] In some embodiments, the pedestal (608) may be temperature-controlled via a heater (610). In some embodiments, the pedestal (608) may be heated to a temperature greater than -20°C and up to 300°C, e.g., 50°C to 280°C, e.g., about 100°C to 240°C, during development or post-development processing as described in the disclosed embodiment. In some embodiments, the heater (610) of the pedestal (608) may include a plurality of independently controllable temperature control zones.

[0256] Additionally, in some implementations, pressure control for the process station (600) may be provided by a butterfly valve (618). Fig. 6 As illustrated in the implementation, the butterfly valve (618) throttles the vacuum provided by the downstream vacuum pump (not shown). However, in some implementations, the pressure control of the process station (600) can also be adjusted by changing the flow rate of one or more gases introduced into the process station (600).

[0257] In some embodiments, the position of the shower head (606) may be adjusted relative to the pedestal (608) to change the volume between the substrate (612) and the shower head (606). Additionally, it will be recognized that the vertical position of the pedestal (608) and / or the shower head (606) may be varied by any suitable mechanism within the scope of this disclosure. In some embodiments, the pedestal (608) may include a rotation axis for rotating the orientation of the substrate (612). In some embodiments, it will be recognized that one or more of these exemplary adjustments may be performed programmatically by one or more suitable computer controllers.

[0258] For example, where plasma may be used in decomposing, developing, processing, deposition, or smoothing operations, the showerhead (606) and pedestal (608) electrically communicate with a radio frequency (RF) power supply (614) and a matching network (616) to power the plasma. 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 supply (614) and the matching network (616) may be operated at any appropriate power to form a plasma having radical species of a desired composition. An example of appropriate power is up to about 1000 W.

[0259] In some implementations, instructions to a computer controller (not shown) may be provided via input / output control (IOC) sequencing instructions. In one example, instructions for setting conditions for a process step may be included in the corresponding recipe step of the process recipe. In some cases, process recipe steps may be arranged sequentially so that all instructions for a process step are executed concurrently with that process step. In some implementations, instructions for setting one or more reactor parameters may be included in the recipe step. For example, the recipe step may include instructions for setting the flow rate of an etching gas, such as a hydrogen halide, and time-delay instructions for the recipe step. In some implementations, the controller Fig. 7 In relation to the controller (750), any of the features described below may be included.

[0260] The process chamber may also include a UV exposure module (not shown).

[0261] In some embodiments, the process chamber may also include a photoresist thickness sensor module (not shown). The photoresist thickness sensor module may be a spectral reflectometer comprising a lamp source, an optical cable, and a spectrometer system operating within a spectral range of about 200 to about 900 nm. The reflectometer may be useful for measuring in-situ wafer refractive index versus time and thereby monitoring the thickness of the photoresist during dry development.

[0262] As previously described, one or more process stations may be included in a multi-station process tool. Fig. 7A schematic diagram of an implementation of a multi-station process tool (700) having an inbound load lock (702) and an outbound load lock (704) is illustrated, and either or both of the inbound load lock (702) and the outbound load lock (704) may include a remote plasma source. At atmospheric pressure, a robot (706) is configured to move a wafer from a cassette loaded via a pod (708) to the inbound load lock (702) via a standby port (710). The wafer is placed by the robot (706) on a pedestal (712) within the inbound load lock (702), the standby port (710) is closed, and the load lock is pumped down. If the inbound load lock (702) includes a remote plasma source, the wafer may be exposed to remote plasma treatment to process the substrate surface within the load lock before being introduced into the process chamber (714). Additionally, the wafer may also be heated in an inbound load lock (702) to remove moisture and adsorbed gases, for example. Next, a chamber transfer port (716) to a process chamber (714) 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 the process. Fig. 7 The implementation described herein includes a load lock, but it will be noted that in some implementations, direct entry of the wafer into the process station may be provided.

[0263] The illustrated process chamber (714) Fig. 7The embodiment shown includes four process stations numbered 1 through 4. Each station has a heated pedestal (illustrated as 718 for station 1) and a gas line inlet. It will be recognized that in some embodiments, each process station may have different or multiple purposes. For example, in some embodiments, the process station may be switchable between developing and etching process modes. Additionally or alternatively, in some embodiments, the process chamber (714) may include one or more matched pairs of developing and etching process stations. Although the illustrated process chamber (714) includes four stations, it will be understood that the process chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, the process chamber may have five or more stations, while in other embodiments, the process chamber may have three or fewer stations.

[0264] Fig. 7 The illustration depicts an implementation of a wafer handling system (790) for transferring wafers within a process chamber (714). In some implementations, the wafer handling system (790) may transfer wafers between various process stations and / or between a process station and a load lock. It will be noted that any suitable wafer handling system may be used. Non-limiting examples include wafer carousels and wafer handling robots. Fig. 7 It also illustrates an implementation of a controller (750) (e.g., a system controller) used to control process conditions and hardware status of a process tool (700). The controller (750) may include one or more memory devices (756), one or more mass storage devices (754), and one or more processors (752). The processor (752) may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, etc.

[0265] In some implementations, the controller (750) controls all activities of the process tool (700). The controller (750) executes system control software (758) that is stored in a mass storage device (754), loaded into a memory device (756), and executed on a processor (752). Alternatively, control logic may be hardcoded into the controller (750). An application-specific integrated circuit (ASIC), a programmable logic device (e.g., a field-programmable gate array, or an FPGA) may be used for this purpose. In the following discussion, whenever "software" or "code" is used, functionally similar hardcoded logic may be used instead. System control software (758) may include instructions for controlling timing, gas mixture, gas flow rate, chamber and / or station pressure, chamber and / or station temperature, wafer temperature, target power level, RF power level, substrate pedestal, chuck and / or susceptor position, and other parameters of a specific process performed by the process tool (700). The system control software (758) may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be created to control the operation of process tool components used to perform various process tool processes. The system control software (758) may be coded in any suitable computer-readable programming language.

[0266] In some implementations, the system control software (758) may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. Other computer software and / or programs stored in a mass storage device (754) and / or memory device (756) associated with the controller (750) 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.

[0267] The substrate positioning program may include program code for a process tool component used to load the substrate onto the pedestal (718) and to control the gap between the substrate and other parts of the process tool (700).

[0268] The process gas control program may include code for controlling the process gas composition and flow rate, and optionally code for flowing gas into one or more process stations prior to deposition to stabilize the pressure within the process station. The pressure control program may include code for controlling the pressure in the process station by controlling, for example, a throttle valve in the process station's exhaust system, the flow of gas into the process station, etc.

[0269] The heater control program may include code to control the current to the heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (e.g., helium) to the substrate.

[0270] A plasma control program may include code for setting the RF power level applied to a process electrode at one or more process stations according to an implementation of the present invention.

[0271] The pressure control program may include code for maintaining pressure within the reaction chamber according to the implementation of the present invention.

[0272] In some implementations, there may be a user interface associated with the controller (750). The user interface may include a display screen, a graphic software display of the device and / or process conditions, and a user input device, such as a pointing device, a keyboard, a touch screen, a microphone, etc.

[0273] In some implementations, parameters adjusted by the controller (750) may be related to process conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (e.g., RF bias power level), etc. These parameters may be provided to the user in the form of a recipe that can be entered using a user interface.

[0274] Signals for monitoring the process may be provided from various process tool sensors by analog and / or digital input connections of the controller (750). Signals for controlling the process may be output to analog and digital output connections of the process tool (700). Non-limiting examples of process tool sensors that can be monitored include mass flow controllers, pressure sensors (e.g., manometers), thermocouples, etc. Suitablely programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0275] The controller (750) may provide program instructions for implementing the deposition process described above. The program instructions may control various process parameters such as DC power level, RF bias power level, pressure, temperature, etc. The instructions may control parameters to operate the developing, cleaning, and / or etching processes according to the various implementations described herein.

[0276] The controller (750) will typically include one or more memory devices and one or more processors configured to execute instructions so that the device performs a method according to the disclosed implementation. A machine-readable medium containing instructions for controlling a process operation according to the disclosed implementation may be coupled to the controller (750).

[0277] In some embodiments, the controller (750) is part of the system, which is part of the example described above. Such a system may include semiconductor process equipment including process tools or tools, chambers or chambers, a platform or platforms for the process, and / or specific process components (wafer pedestals, gas flow systems, etc.). Such a system may be integrated with an electronic device to control its operation before, during, and after the rotation of a semiconductor wafer or substrate. The electronic device may be referred to as a “controller” capable of controlling the system or various components or sub-parts of the systems. The controller (750) may be programmed to control any process among the processes disclosed herein, depending on the process conditions and / or type of the system, including the delivery of process gas, temperature setting (e.g., heating and / or cooling), pressure setting, vacuum setting, power setting, radio frequency (RF) generator setting, RF matching circuit setting, frequency setting, flow rate setting, fluid delivery setting, position and operation setting, and wafer delivery into and out of a load lock connected to or interfacing with tools and other delivery tools and / or specific systems.

[0278] Generally speaking, the controller (750) may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receives instructions, issues instructions, controls operations, enables cleaning operations, enables endpoint measurement, etc. The integrated circuit may include a chip in the form of firmware that stores program instructions, a digital signal processor (DSP), a chip defined as an application-specific integrated circuit (ASIC), and / or one or more microprocessors, or a microcontroller that executes program instructions (e.g., software). The program instructions may be instructions communicated to the controller (750) in the form of various individual settings (or program files) that define operation parameters for performing a specific process on or for a semiconductor wafer, or for a system. In some implementations, the operation parameter may be part of a recipe defined by a process engineer to achieve one or more process steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0279] In some implementations, the controller (750) may be integrated with the system, coupled to the system, otherwise networked to the system, coupled to a computer that combines these, or be part of the same. For example, the controller (750) may be located within a “cloud” or may be all or part of a fab host computer system capable of allowing remote access to the wafer process. The computer may enable remote access to the system to monitor the current progress of a fabrication job, examine the history of past fabrication jobs, examine trends or performance measurements from multiple fabrication jobs, change parameters of the current process, set process steps following the current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system via a local network or a network that may include the Internet. The remote computer may include a user interface that enables the input or programming of parameters and / or settings that are subsequently communicated from the remote computer to the system. In some examples, the controller (750) receives instructions in the form of data specifying parameters for each process step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of tool configured to be controlled or interfaced by the controller (750) and the type of process to be performed. Thus, as previously described, the controller (750) may be distributed by including one or more individual controllers that are networked and operated together toward a common purpose, such as the process and control described herein. An example of a distributed controller for this purpose would be one or more integrated circuits in a chamber communicating with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) that are combined to control the process in the chamber.

[0280] The exemplary system may include, without limitation, a plasma etching 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 etching 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 etching (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a developing chamber or module, and any other semiconductor process system that may be used or associated in the manufacture and / or fabrication of a semiconductor wafer.

[0281] As previously indicated, depending on the process steps or steps to be performed by the tool, the controller (750) may communicate with one or more of the tools used in material transport, such as other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, main computers, other controllers, or in the semiconductor manufacturing plant, for taking a container of wafers from a tool location and / or load port and bringing it to a tool location and / or load port.

[0282] In certain embodiments, an ICP reactor that may be suitable for etching operations suitable for the implementation of some embodiments is now described. Although an ICP reactor is described herein, it should be understood that in some embodiments, a capacitively coupled plasma reactor may also be used.

[0283] Fig. 8The figure schematically illustrates a cross-sectional view of an inductively coupled plasma device (800) suitable for implementing a specific implementation or aspect of the implementation, such as dry development, development-post-processing (e.g., passivation and curing) and / or etching. In other implementations, other tools or tool types having the function of performing the dry development, development-post-processing and / or etching processes described herein may be used for the implementation.

[0284] The inductively coupled plasma device (800) comprises an entire process chamber (824) structurally defined by chamber walls (801) and a window (811). The chamber walls (801) may be made of stainless steel, aluminum, or plastic. The window (811) may be made of quartz or other dielectric materials. An optional internal plasma grid (850) divides the entire process chamber into an upper subchamber (802) and a lower subchamber (803). In most implementations, the plasma grid (850) may be removed, thereby utilizing the chamber space consisting of the subchambers (802 and 803). A chuck (817) is located within the lower subchamber (803) near the lowest inner surface. The chuck (817) is configured to receive and secure a semiconductor wafer (819) on which etching and deposition processes are performed. The chuck (817) may be an electrostatic chuck for supporting the wafer (819), if present. In some implementations, an edge ring (not shown) surrounds the chuck (817) and has an upper surface that is approximately flat with the top surface of the wafer (819) when present on the chuck (817). The chuck (817) also includes an electrostatic electrode for chucking and dechucking the wafer (819). A filter and a DC clamp power supply (not shown) may be provided for this purpose. Another control system for lifting off the wafer (819) from the chuck (817) may also be provided. The chuck (817) may be electrically charged using an RF power supply (823). The RF power supply (823) is connected to a matching network (821) via a connection (827). The matching network (821) is connected to the chuck (817) via a connection (825). In this way, the RF power supply (823) is connected to the chuck (817). In various implementations, the bias power of the electrostatic chuck can be set to about 50 V, or it can be set to a different bias power depending on the process performed according to the disclosed implementation.For example, the bias power can be about 20 V to about 100 V, or about 30 V to about 150 V.

[0285] The element for generating plasma includes a coil (833) positioned over a window (811). In some embodiments, the coil is not used in the disclosed embodiment. The coil (833) is made of an electrically conductive material and includes at least one full turn. Fig. 8 An example of a coil (833) illustrated in the figure includes three turns. The cross-section of the coil (833) is illustrated by a symbol, and the coil with an “X” rotates and extends into the page, while the coil with a “●” rotates and extends outward from the page. The element for plasma generation also includes an RF power supply (841) configured to supply RF power to the coil (833). Generally, the RF power supply (841) is connected to a matching network (839) via a connection (845). The matching network (839) is connected to the coil (833) via a connection (843). In this way, the RF power supply (841) is connected to the coil (833). An optional Faraday shield (849) is positioned between the coil (833) and the window (811). The Faraday shield (849) may be maintained in a spaced-away relationship with respect to the coil (833). In some implementations, the Faraday shield (849) is positioned directly above the window (811). In some implementations, the Faraday shield (849) is located between the window (811) and the chuck (817). In some implementations, the Faraday shield (849) is not maintained in a spaced-away relationship with respect to the coil (833). For example, the Faraday shield (849) may be located directly below the window (811) without a gap. The coil (833), the Faraday shield (849), and the window (811) are each configured to be substantially parallel to each other. The Faraday shield (849) can prevent metal or other paper from being deposited on the window (811) of the process chamber (824).

[0286] Process gas may flow into the process chamber through one or more main gas flow inlets (860) located within the upper subchamber (802) and / or one or more side gas flow inlets (870). Similarly, although not explicitly shown, similar gas flow inlets may be used to supply process gas to the capacitively coupled plasma process chamber. A vacuum pump, for example, a one or two-stage mechanical dry pump and / or a turbomolecular pump (840), may be used to draw process gas out of the process chamber (824) and maintain pressure within the process chamber (824). For example, a vacuum pump may be used to exhaust the lower subchamber (803) during a purging operation. A valve-controlled conduit may be used to fluidly connect the vacuum pump to the process chamber (824) to selectively control the application of the vacuum environment provided by the vacuum pump. This can be achieved by using a closed-loop controlled flow limiting device, such as a throttle valve (not shown) or a pendulum valve (not shown), during the working plasma process. Similarly, a vacuum pump and valve-controlled fluid connection to the capacitively coupled plasma process chamber can also be used. A wide range of pressures to be modulated within the process chamber for coupled dry development and etching can be achieved by using a variable-speed vacuum system, a throttle valve to adjust the flow of the process gas, or by using two pressure control systems.

[0287] During operation of the device (800), one or more process gases may be supplied through the gas flow inlets (860 and / or 870). In a specific implementation, the process gas may be supplied only through the main gas flow inlet (860) or only through the side gas flow inlet (870). In some cases, the gas flow inlets shown in the drawings may be replaced with more complex gas flow inlets, for example, one or more showerheads. The Faraday shield (849) and / or optional grid (850) may include internal channels and holes that allow the transfer of process gas to the process chamber (824). One or both of the Faraday shield (849) and the optional grid (850) may serve as showerheads for the transfer of process gas. In some implementations, the liquid vaporization and transfer system may be located upstream of the process chamber (824) so ​​that when the liquid reactant or precursor is vaporized, the vaporized reactant or precursor is introduced into the process chamber (824) through the gas flow inlet (860 and / or 870).

[0288] Radio frequency power is supplied from the RF power supply (841) to the coil (833), causing RF current to flow through the coil (833). The RF current flowing through the coil (833) generates an electromagnetic field around the coil (833). The electromagnetic field generates an induced current within the upper subchamber (802). The physical and chemical interactions between the various generated ions and radicals and the wafer (819) etch features of the wafer (819) and selectively deposit a layer on the wafer (819).

[0289] If a plasma grid (850) is used such that both the upper subchamber (802) and the lower subchamber (803) exist, an induced current acts on the gas present in the upper subchamber (802) to generate an electron-ion plasma within the upper subchamber (802). An optional internal plasma grid (850) limits the amount of high-temperature electrons within the lower subchamber (803). In some implementations, the device (800) is designed and operated such that the plasma present in the lower subchamber (803) is an ion-ion plasma.

[0290] Both the upper electron-ion plasma and the lower ion-ion plasma may contain cations and anions, but the ion-ion plasma will have a larger anion-to-cation ratio. Volatile etching and / or deposition byproducts can be removed from the lower subchamber (803) through the port (822). The chuck (817) disclosed herein may operate at an elevated temperature in the range of about 10°C to about 250°C. The temperature will depend on the process operation and the specific recipe.

[0291] The device (800) may be coupled to equipment (not shown) when installed in a clean room or manufacturing facility. The equipment includes piping that provides process gas, vacuum, temperature control, and environmental particle control. These equipment is coupled to the device (800) when installed in a target manufacturing facility. Additionally, the device (800) may be coupled to a transfer chamber that allows a robot to transfer semiconductor wafers into and out of the device (800) using typical automation.

[0292] In some implementations, a controller (830) (which may include one or more physical or logical controllers) controls some or all of the operations of the process chamber (824). The controller (830) may include one or more memory devices and one or more processors. In some implementations, the device (800) includes a switching system for controlling the flow rate and duration when the disclosed implementation is performed. In some implementations, the device (800) may have a switching time of up to about 500 ms, or up to about 750 ms. The switching time may depend on the flow chemistry, selected recipe, reactor architecture, and other factors.

[0293] In some implementations, the controller (830) is part of the system, which may be part of the example described above. Various aspects of the controller (830) are described above.

[0294] EUVL patterning can be performed using any suitable tool, often referred to as a scanner. The EUVL patterning tool may be a standalone device in which the substrate is moved in and out for deposition and etching as described herein. Alternatively, as described below, the EUVL patterning tool may be a module of a larger multi-component tool.

[0295] Fig. 9 The invention illustrates a semiconductor process cluster tool architecture (900) having vacuum-integrated deposition, patterning, and processing modules that interface with a vacuum transfer module suitable for the implementation of the process described herein. An arrangement of transfer modules for "transferring" wafers between multiple storage facilities and process modules may be referred to as a "cluster tool architecture" system. The deposition, patterning, and processing modules are vacuum-integrated according to the requirements of a specific process. Other modules, such as etching modules, may also be included in the cluster.

[0296] The vacuum transport module (VTM) (938) interfaces with four process modules (920a-920d) that can be individually optimized to perform various fabrication processes. For example, the process modules (920a-920d) can be implemented to perform deposition, evaporation, ELD, dry development, cleaning, etching, treatment, stripping, and / or other semiconductor processes. For example, module (920a) may be an ALD reactor that can be operated to perform non-plasma, thermal atomic layer deposition as described herein. Module (920b) may be a PECVD tool. It should be understood that the drawings are not necessarily drawn to scale.

[0297] The airlock (942 and 946), also known as the load lock or transfer module, interfaces with the VTM (938) and the patterning module (940). This tool architecture allows workpieces, such as semiconductor substrates or wafers, to be transferred under vacuum so that they do not react before exposure. The integration of the lithography tool and the deposition module is facilitated by the fact that the EUVL also requires significantly reduced pressure, considering the strong optical absorption of incident photons by ambient gases such as H2O, O2, etc.

[0298] As previously indicated, this integrated architecture is merely one possible implementation among the tools for implementing the described process. The process is also, for example, Fig. 9 It can be implemented as a more traditional standalone EUVL scanner and deposition reactor integrated into a cluster architecture, such as a module without an integrated patterning module as described with reference to, but without, standalone or other tools, such as etching, stripping, etc.

[0299] The airlock (942) may be an "outgoing" load lock referring to the transfer of a substrate from the VTM (938) providing the deposition module (920a) to the patterning module (940), and the airlock (946) may be an "ingoing" load lock referring to the transfer of a substrate from the patterning module (940) back to the VTM (938). The inoing airlock (946) may also provide an interface outside the tool for accessing and egressing the substrate. Each process module has a facet that interfaces the module to the VTM (938). For example, the deposition process module (920a) has a facet (936). Inside each facet, sensors, for example, sensors 1 through 18 as illustrated, are used to detect the passage of the wafer (926) as it moves between individual stations. The patterning module (940) and airlock (942 and 946) may similarly be equipped with additional facets and sensors not shown.

[0300] The main VTM robot (922) transfers a wafer (926) between modules including airlocks (942 and 946). In one implementation, the robot (922) has one arm, and in another implementation, the robot (922) has two arms, each arm having an end effector (924) for picking up a wafer, e.g., wafer (926), for transport. The front-end robot (944) is used to transfer the wafer (926) from the withdrawal airlock (942) into the patterning module (940), and from the patterning module (940) into the inflow airlock (946). The front-end robot (944) can also transport the wafer (926) between the inflow load lock and the outside of the tool for access and exit of the substrate. Because the inlet airlock module (946) has the ability to match an environment between atmospheric pressure and vacuum, the wafer (926) can move between the two pressure environments without damage.

[0301] 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 EUVL tool and the deposition tool so that the substrate is degassed before entering the patterning tool. The withdrawal airlock (942) can provide this function by securing the transferred wafer at a lower pressure, not higher than the pressure inside the patterning module (940), while exhausting any off-gassing so that the optics of the patterning module (940) are not contaminated by off-gassing from the substrate. The appropriate pressure for the withdrawal, off-gassing airlock is 1E-8 Torr or less.

[0302] In some implementations, a controller (950) (which may include one or more physical or logical controllers) controls some or all of the operations of the cluster tool and / or its separate modules. It should be noted that the controller may be local to the cluster architecture, located outside the cluster architecture or at a remote location at the manufacturing site, and connected to the cluster architecture via a network. The controller (950) 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, a stepper motor controller board, and other similar components. Instructions for implementing suitable control operations are executed by the processor. These instructions may be stored in memory devices associated with the controller, or they may be provided via a network. In a specific implementation, the system controller executes system control software.

[0303] System control software may include instructions for controlling the timing and / or magnitude of the application of any mode of tool or module operation. 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 operations of process tool components necessary to perform various process tool processes. System control software may be coded in any suitable computer-readable programming language. In some implementations, system control software includes input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each step of the semiconductor fabrication process may include one or more instructions for execution by a controller. Instructions for setting process conditions for condensation, deposition, evaporation, patterning, and / or etching steps may be included, for example, in the corresponding recipe steps.

[0304] An apparatus for post-development processing is provided in various configurations. The apparatus may include a process chamber for patterning, processing, deposition, and etching, and a controller comprising instructions for post-development processing of a patterned photoresist mask. The instructions may include code for processing a patterned metal-containing photoresist mask after development in the process chamber. Such processing may include thermal processing, plasma processing, chemical processing, or the selective deposition of a protective layer on the patterned metal-containing photoresist mask.

[0305] It should be noted that the computer controlling wafer movement can be local to the cluster architecture, located outside the cluster architecture at the manufacturing site, or situated at a remote location and connected to the cluster architecture via a network. Fig. 6 , Fig. 7 , or Fig. 8In relation to any of the above, the controller described above Fig. 9 It can be implemented as a tool in.

[0306] Additional implementation

[0307] The apparatus and process described herein may be used in conjunction with lithography patterning tools or processes for the manufacture or fabrication of, for example, semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, but not necessarily, such tools and processes will be used or performed together in a common fabrication facility. Lithography patterning of a film typically comprises some or all of the following steps, each step performed with a number of possible tools: (1) applying a photoresist onto a workpiece, i.e., a substrate, using a spin-on or spray-on tool; (2) curing the photoresist using a hot plate, furnace, or UV curing tool; (3) exposing the photoresist to visible light, UV, or X-ray light using a tool such as a wafer stepper; (4) selectively removing the resist and developing the resist for patterning using a tool such as a wet bench; (5) transferring the resist pattern onto a base film or workpiece by using a dry or plasma-assisted etching tool; and (6) remove the resist using a tool such as an RF or microwave plasma resist stripper.

[0308] conclusion

[0309] Although the foregoing embodiments have been described in some detail for the sake of clarity of understanding, it will be apparent that specific changes and modifications may be made within the scope of the appended claims. It should be noted that there are many alternative ways to implement the processes, systems, and apparatus of the embodiments. Accordingly, the embodiments are to be regarded as exemplary rather than restrictive, and are not limited to the details given herein.

Claims

Claim 1 A method for performing a dry development, comprising: a step of performing a thermal dry development on a semiconductor substrate including an EUV-sensitive photoresist film using a halogen-containing gas during a plasma-free process in a process chamber, wherein the EUV-sensitive photoresist film includes an EUV-exposed portion and a non-exposed portion, and the thermal dry development selectively removes the non-exposed portion compared to the EUV-exposed portion to form a patterned photoresist mask; and a step of performing a plasma dry development on a semiconductor substrate by forming a plasma using at least one reactive gas in the same process chamber after performing the thermal dry development, wherein the plasma dry development removes a residue including a byproduct of the thermal dry development compared to the EUV-exposed portion, and the byproduct has a composition different from the non-exposed portion and the EUV-exposed portion of the EUV-sensitive photoresist film. Claim 2 A method according to claim 1, wherein at least one reactive gas comprises one or more halogen-containing gases, one or more hydrogen-containing gases, or a combination thereof. Claim 3 A method according to claim 1, wherein at least one reactive gas comprises one or more hydrogen-containing gases, and one or more hydrogen-containing gases comprise CH4. Claim 4 A method according to claim 1, wherein at least one reactive gas comprises a plurality of halogen-containing gases, and each of the halogen-containing gases is selected from the group consisting of HBr, HCl, Cl2 and BCl3. Claim 5 In paragraph 4, the method comprises at least one reactive gas comprising HBr and Cl2, HBr and HCl, HBr and BCl3, or BCl3 and Cl2. Claim 6 A method according to claim 1, wherein at least one reactive gas comprises a combination of one halogen-containing gas selected from HBr, HCl, Cl2 and BCl3, and one hydrogen-containing gas selected from H2 and CH4. Claim 7 In claim 6, the method comprises at least one reactive gas comprising HBr and H2, BCl3 and CH4, Cl2 and CH4, HCl and CH4, or HBr and CH4. Claim 8 A method according to claim 1, wherein a plasma dry phenomenon is performed by forming a plasma using at least one reactive gas, wherein the plasma is formed using at least one reactive gas and at least one non-reactive gas, and the non-reactive gas is selected from the group consisting of N2, He, Ne, Ar, Kr, and Xe. Claim 9 A method according to claim 8, wherein at least one reactive gas comprises HBr and at least one non-reactive gas comprises N2. Claim 10 A method according to claim 8, wherein at least one reactive gas comprises Cl2 and at least one non-reactive gas comprises N2. Claim 11 A method according to claim 1, wherein the halogen-containing gas comprises a hydrogen halide. Claim 12 A method according to claim 1, wherein the halogen-containing gas comprises hydrogen bromide (HBr). Claim 13 A method according to claim 1, wherein the thermal dry phenomenon is performed in a process chamber at a first pressure, the plasma dry phenomenon is performed in the same process chamber at a second pressure lower than the first pressure, and the transition from the first pressure to the second pressure in the process chamber is performed within 10 seconds or less. Claim 14 A method according to claim 1, wherein the thermal dry phenomenon and the plasma dry phenomenon are performed at a temperature of -60℃ to 120℃. Claim 15 delete Claim 16 A method according to claim 1, wherein the performance of a thermal drying phenomenon and the performance of a plasma drying phenomenon are repeated alternately in the same process chamber. Claim 17 A method according to claim 1, wherein the plasma drying phenomenon is a circulating plasma drying phenomenon, a direct plasma drying phenomenon, a remote plasma drying phenomenon, or a continuous plasma drying phenomenon. Claim 18 A method according to claim 17, wherein the plasma dry phenomenon is a continuous plasma dry phenomenon, and the continuous plasma dry phenomenon is performed at variable power, at constant power and pulsing bias, or at variable power and pulsing bias. Claim 19 An apparatus for performing dry development, comprising: a process chamber; and a controller having at least one processor and memory, wherein the controller performs a process in which a thermal dry development is performed in the process chamber on a semiconductor substrate including an EUV-sensitive photoresist film using a halogen-containing gas during a plasma-free process, wherein the EUV-sensitive photoresist film includes an EUV-exposed portion and a non-exposed portion, and the thermal dry development is performed to selectively remove the non-exposed portion compared to the EUV-exposed portion to form a patterned photoresist mask; and a process in which a plasma of at least one reactive gas is formed in the same process chamber after performing the thermal dry development to perform a plasma dry development on the semiconductor substrate by decomposing, wherein the plasma dry development is performed to remove a residue including a byproduct of the thermal dry development compared to the EUV-exposed portion, and the byproduct has a composition different from the non-exposed portion and the EUV-exposed portion of the EUV-sensitive photoresist film. Claim 20 An apparatus according to claim 19, wherein at least one reactive gas comprises one or more halogen-containing gases, one or more hydrogen-containing gases, or a combination thereof. Claim 21 An apparatus according to claim 19, wherein at least one reactive gas comprises a plurality of halogen-containing gases, each of which is selected from the group consisting of HBr, HCl, Cl2 and BCl3. Claim 22 An apparatus according to claim 19, wherein at least one reactive gas comprises a combination of one halogen-containing gas selected from HBr, HCl, Cl2 and BCl3, and one hydrogen-containing gas selected from H2 and CH4. Claim 23 In claim 19, a controller comprising instructions for performing a plasma dry phenomenon by forming a plasma using at least one reactive gas comprises instructions for forming a plasma using at least one reactive gas and at least one non-reactive gas, wherein the non-reactive gas is selected from the group consisting of N2, He, Ne, Ar, Kr and Xe. Claim 24 In paragraph 19, the apparatus wherein the halogen-containing gas comprises a hydrogen halide. Claim 25 In paragraph 19, the apparatus wherein the halogen-containing gas comprises hydrogen bromide (HBr). Claim 26 In claim 19, the apparatus further comprises one or more pressure regulating devices; and one or more pumps fluidically coupled to one or more pressure regulating devices, wherein a thermal drying phenomenon is performed at a first pressure and a plasma drying phenomenon is performed at a second pressure lower than the first pressure. Claim 27 In paragraph 19, the device comprises a controller composed of instructions for performing a thermal dry phenomenon and a plasma dry phenomenon, wherein the controller is composed of instructions for performing the thermal dry phenomenon and the plasma dry phenomenon at a temperature of -60°C to 120°C. Claim 28 delete Claim 29 A device according to claim 19, wherein the controller is additionally configured with instructions that alternately repeat thermal drying phenomena and plasma drying phenomena. Claim 30 A device in which, in paragraph 19, the plasma drying phenomenon is a circulating plasma drying phenomenon, a direct plasma drying phenomenon, a remote plasma drying phenomenon, or a continuous plasma drying phenomenon. Claim 31 In paragraph 30, the plasma dry phenomenon is a continuous plasma dry phenomenon, and the continuous plasma dry phenomenon is performed at variable power, at constant power and pulsing bias, or at variable power and pulsing bias, in a device. Claim 32 delete Claim 33 delete Claim 34 delete Claim 35 delete Claim 36 delete Claim 37 delete Claim 38 delete Claim 39 delete Claim 40 delete Claim 41 delete Claim 42 delete Claim 43 delete Claim 44 delete Claim 45 delete Claim 46 delete Claim 47 delete Claim 48 delete Claim 49 delete Claim 50 delete Claim 51 delete Claim 52 delete Claim 53 delete Claim 54 delete Claim 55 delete Claim 56 delete Claim 57 delete Claim 58 delete Claim 59 delete Claim 60 delete

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