Gas-based development of an organometallic resist in an oxidative halogen-donating environment

Abstract

A method for dry developing an organic tin composition that is patterned using radiation and has a latent image is provided. The method includes developing the structure with a gas comprising a halogen-based developer and an oxygen source compound, the structure comprising a substrate having a layer of a composition having a latent image having a region having at least partially condensed tin oxide-hydroxide and another region having an organic tin composition having a carbon-tin bond, the development resulting in at least partial removal of the organic tin composition having a carbon-tin bond. Contact with an oxidative environment can be carried out as a separate step, followed by thermal development based on halogen. A suitable apparatus provides the desired treatment.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 63 / 349,187, entitled "Oxidizing Process and Development of Organometallic Resist" by de Schepper et al., filed on June 6, 2022, which is incorporated herein by reference.

[0002] The present invention relates to dry development of a radiation - patterned organometallic patterning composition using a halide gas developer and an oxygen - containing compound to provide an oxidizing environment during development. The present invention further relates to an apparatus for performing dry development. A further aspect of the present invention relates to an after - irradiation process flow that involves a post - exposure bake in an oxygen - rich atmosphere followed by dry development of the patterned substrate in an oxidizing atmosphere.

Background Art

[0003] Semiconductor patterning requires high - performance and high - resolution photoresists to enable smaller features. The manufacture of semiconductor devices generally involves many iterative processing steps of deposition, patterning, and etching to realize the desired device. Patterning is generally achieved using a lithography process. In lithography, an aerial pattern of radiation is converted into a physical pattern by using a photoresist and a development process. The development process generally involves removing either the irradiated or non - irradiated portions of the irradiated photoresist.

Summary of the Invention

Means for Solving the Problems

[0004] One aspect of the present invention relates to a method of developing a metal - oxide photoresist pattern in a thermal vapor process comprising a halide and an oxidant.

[0005] Another aspect of the present invention is a multi - step method for developing a metal - oxide photoresist pattern, the multi - step method including exposing the metal - oxide photoresist in a thermal process including an oxidizing agent, and developing the metal - oxide photoresist pattern using a halide composition.

[0006] Another aspect of the present invention is a multi - step method for developing a metal - oxide photoresist pattern, the multi - step method including exposing the metal - oxide photoresist to a halide composition in a thermal process, subsequently exposing the metal - oxide photoresist to an oxidizing agent in a thermal process, and then exposing the metal - oxide photoresist to a halide composition in a thermal process. A plasma descum treatment process can be performed after the heat treatment.

[0007] Another aspect of the present invention is a multi - step method for developing a metal - oxide photoresist pattern, the multi - step method including developing the metal - oxide photoresist in a thermal vapor process including a halide, and exposing the metal - oxide photoresist pattern to a liquid rinse / descum composition including an alcohol, an ether, an ester, a carboxylic acid, or a ketone, or a mixture thereof.

[0008] Another aspect of the present invention is a multi - step method for developing a metal - oxide photoresist pattern, the multi - step method including developing the metal - oxide photoresist in a thermal vapor process including a halide, and exposing the metal - oxide photoresist pattern to a gaseous rinse / descum composition including an alcohol, an ether, an ester, a carboxylic acid, or a ketone, or a mixture thereof.

[0009] In a further aspect, the present invention relates to a method for dry developing a radiation-patterned organic tin composition having a latent image. The radiation can be effective to break carbon-tin bonds. The method can include developing the structure with a gas containing a halogen-based developer and an oxygen source compound. The structure can include a substrate having a layer of a composition having a pattern with regions having at least partially condensed tin oxide-hydroxide and other regions having an organic tin composition having carbon-tin bonds, and the contacting can result in at least partial removal of the organic tin composition having carbon-tin bonds.

[0010] In an additional aspect, the present invention a housing configured to achieve a pressure controlled through operation of a pump and a suitable pressure sensor, a substrate support within the housing, a developing energy source including a heater, a cooler, and / or a plasma source configured to supply energy to a substrate placed on the substrate support, a halide developer source configured to supply a gas of a halide developer into the housing from a reservoir through a flow regulator, an oxygen compound source configured to supply a vapor of an oxygen-containing compound into the housing from a reservoir through a flow regulator and relates to a developing chamber.

[0011] In another aspect, the present invention relates to a method for converting an irradiated substrate to form a physical pattern along a surface. The method includes performing a post-exposure bake in a housing and developing the pattern. Performing the post-exposure bake (PEB) involves a substrate having a surface including a pattern generated by irradiated and non-irradiated regions of an organometallic radiation-sensitive material having carbon-metal bonds. For performing the PEB, heating is performed at a temperature of 60°C to about 250°C for about 0.1 minute to about 30 minutes at a pressure of at least about 200 Torr in an atmosphere containing oxygen source molecules. Developing includes introducing a halogen-based developing gas into the housing to substantially remove the non-irradiated organometallic radiation-sensitive material and form a physical pattern.

[0012] In some embodiments, the present invention is a method of converting an irradiated substrate to form a physical pattern along a surface, the method comprising developing the physical pattern, subjecting the substrate having the physical pattern thereon to oxidation, and contacting the oxidized patterned substrate with a halogen developing gas to improve pattern development. Developing the physical pattern can be performed by introducing a halogen developing gas into a chamber to substantially remove the non-irradiated organometallic radiation-sensitive material and form the physical pattern. Subjecting the substrate having the physical pattern thereon to oxidation can be performed for about 0.1 minute to about 30 minutes in an atmosphere containing oxygen source molecules to form the oxidized patterned substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0013]

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[0014] A method for dry developing a latent image in a radiation-sensitive tin-based patterning composition called a resist is presented, which is designed to be more efficient and effective based on maintaining an oxidative environment to reduce residues remaining after pattern development. Dry development is achieved using a halide donor vapor together with an oxidative vapor. This development converts the irradiated resist into a product having a sufficient vapor pressure that can be removed simultaneously or sequentially in a heat-driven process. In addition to or instead of using an oxidative gas during thermal development based on a halide, another oxidation step can also be performed. The tin-based patterning composition usually contains at least one radiation-sensitive carbon-tin bond in the unirradiated composition within an oxo-hydroxone network. By absorption of radiation, the carbon-tin bond can be cleaved. The pattern quality can be further improved by a pre-development process after irradiation and / or a post-development rinse process. In particular, the post-exposure bake step can introduce an oxidative atmosphere that can be carried over to dry development, which can be particularly advantageous in heat-driven dry development. These improvements in pattern formation can be particularly effective in exploiting the potential of extreme ultraviolet (EUV) lithography.

[0015] The overall purpose of patterning is to obtain a structure having a radiation-sensitive coating with a latent image formed by patterned irradiation and to selectively remove material based on the pattern to form a physically patterned structure. The ability to perform selective removal of material depends on the contrast of the material that coincides with the latent image of the radiation, and the development process utilizes this contrast of the material to perform selective removal. The quality of the development process can depend on the contrast, the development process, and the sharpness of the image. Usually, there is one primary development step, during which most or all of the material is removed to form a physical pattern. Additional steps can be added to the development process before and / or after the primary development step. For example, a pre-step can affect the coating material having the latent image to enhance the contrast. Subsequent steps can, for example, remove scum and / or improve the pattern quality in other ways. The main objective here is to improve the halide-based dry development process. Improvements involving the use of oxidizing vapors can be incorporated into the primary development step, and / or the pre-step, and / or subsequent steps. In particular, the post-exposure (before development) bake step can incorporate an oxidizing atmosphere that can prepare the patterning material for the development step with the halide composition. Since tin +4 halides are generally more volatile than tin +2 halides, it is desirable to avoid the reduction of tin +4 to tin +2 and accordingly avoid the possibility of forming less volatile species such as SnCl2. Further, oxidizing Sn+2 compounds to form Sn+4 species can reduce the possibility of disproportionation of Sn+2 species to form tin metal during processing. A rinse step can be performed after development to remove residues formed in the oxidizing environment. Additional or alternative pre-steps and / or subsequent steps can also be used to achieve the desired pattern quality. For example, performing a bake step in an oxidizing environment after the first development with a halide composition may be desirable to convert non-volatile Sn+2 species to Sn+4 species that can be removed better during subsequent development with the halide composition.After the development step based on the halide, the step can be carried out using an oxidizing atmosphere to oxidize the formed tin +2 back to tin +4. Heat may or may not be applied during the oxidation step. After the oxidation step, another vapor development step based on a halide can be carried out to volatilize the tin +4 material, such as by the formation of SnX4 (where X is a halide atom). Optionally, the cycle can be repeated using another oxidation step and another vapor development step based on a halide. When another oxidation step is performed, an oxidizing gas may or may not be used during the development step based on the halide, but usually it is desirable to use an oxidizing gas during the development step based on the halide.

[0016] Recently, metal oxide hydroxide materials have been shown to be effective photoresist compositions capable of achieving very high resolution. To enable high-resolution patterning, these metal oxide hydroxide materials are deposited as thin coatings and have a high etching contrast compared to conventional polymer-based photoresist materials, thus enabling more efficient pattern transfer to the underlying substrate. Examples of metal oxide hydroxide photoresists include the oxide hydroxides of hafnium and zirconium described in U.S. Patent No. 9,176,377B2 entitled "Patterned Inorganic Layers, Radiation Based Patterning Compositions And Corresponding Methods" by Stowers et al. and U.S. Patent No. 9,281,207B2 entitled "Solution Processible Hardmasks for High Resolution Lithography" by Stowers et al., both of which are incorporated herein by reference. In particular, organotin oxide hydroxide photoresists have been shown to achieve high resolution and high sensitivity. Organotin oxide hydroxide photoresists include the organotin materials described in U.S. Patent No. 9,310,684B2 entitled "Organometallic Solution Based High Resolution Patterning Compositions" by Meyers et al. ('684 patent), U.S. Patent No. 10,642,153 entitled "Organometallic Solution Based High Resolution Patterning Compositions and Corresponding Methods" by Meyers et al. and U.S. Patent No. 10,228,618B2 entitled "Organotin Oxide Hydroxide Patterning Compositions, Precursors, and Patterning" by Meyers et al. ('618 patent), all of which are incorporated herein by reference. In particular, organotin compositions, such as those of approximately the formula Rz SnO( 2-z / 2-x / 2 )(OH) x(Where 0 < x < 3, 0 < z ≤ 2, and x + z ≤ 4, and R is a hydrocarbyl or organic group that forms a carbon bond with a tin atom), an organometallic radiation-sensitive resist based on an alkyltin oxide hydroxide has been developed. A particularly effective form of these compositions is a monoalkyltin oxide hydroxide where z = 1 in the above formula. In particular, R is a moiety containing 1 to 31 carbon atoms having one or more carbon atoms optionally substituted with one or more heteroatom functional groups (such as groups containing O, N, Si, Ge, Sn, Te, and / or halogen atoms), or an alkyl group, or a cycloalkyl group further functionalized with phenyl, or a cyano group. In some embodiments, R can contain 10 or fewer carbon atoms and can be, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, or t-amyl. The R group can be a straight-chain, branched (i.e., secondary or tertiary at the carbon atom bonded to the metal) or cyclic hydrocarbyl group. Each R group usually has 1 to 31 carbon atoms, a group having a secondary bonded carbon atom has 3 to 31 carbon atoms, and a group having a tertiary bonded carbon atom has 4 to 31 carbon atoms, and optionally has an unsaturated or aromatic carbon bond. In particular, branched alkyl ligands may be desirable for some patterning compositions. The formation of the oxo-hydroxocoating material can include the deposition of a tin composition having a hydrolyzable bond such as RSnL3 (where L is a hydrolyzable ligand such as an alkoxide, dialkylamine, acetylide, or other suitable hydrolyzable ligand). The hydrolyzable ligand can be hydrolyzed during the deposition of the coating and / or within the coating after deposition to form an oxo-hydroxone network. That is, hydrolysis is completed after deposition.The applicant has developed a methodology for efficiently and effectively forming diverse patterning compositions having C-Sn bonds and optionally containing different R groups with various heteroatoms, which is described in detail in U.S. Patent Application Publication No. 2022 / 00064192 entitled "Methods to Produce Organotin Compositions With Convenient Ligand Providing Reactants" by Edson et al., which is incorporated herein by reference.

[0017] While not wishing to be bound by theory, it is believed that the Sn-C bond is cleaved while being exposed to ionizing radiation such as EUV photons, UV photons, and ion beams. This cleavage can cause the alkyl group to volatilize and form highly reactive Sn sites with insufficient coordination numbers. Although direct measurements to elucidate the specific mechanism of bond cleavage are not known, the mechanism can be speculated. The cleavage mechanism is thought to depend on the composition of the R-ligand. As a result of the cleavage of the Sn-C bond, subsequent crosslinking and / or condensation between Sn sites can occur due to reactions with other sites within the coating and / or reactions with species (e.g., water) in the process environment, resulting in densification. In this case, when the coating is irradiated with a radiation pattern, a latent image corresponding to a density pattern within the coating is formed, where the irradiated region is generally denser than the non-irradiated region. In a typical EUV lithography process, after exposure to EUV radiation, the coating is exposed to ambient air, during which further reactions with water, O2, and / or CO2 can occur within the irradiated region of the coating, promoting the formation of a condensation network, thereby creating a large chemical contrast between the irradiated and non-irradiated regions. The condensation process can be facilitated by a post-exposure heating step, enabling the desired degree of condensation at a lower exposure dose.

[0018] To achieve a physical image of chemical contrast, a photoresist is typically developed in either a negative-tone process where the non-irradiated material is selectively removed or a positive-tone process where the irradiated material is selectively removed. Organotin photoresists are viable in either tone, but for process optimization, it may be advantageous to select specific ligands for favorable development in a particular tone. The irradiated regions of organotin oxide hydroxide coatings are typically hydrophilic and thus soluble in aqueous acids or bases and insoluble in organic solvents. Conversely, the non-irradiated regions are typically hydrophobic and thus soluble in organic solvents and insoluble in aqueous acids or bases. Some useful developer compositions for these organotin oxide photoresists are described in U.S. Patent Application Publication No. 2020 / 0326627, entitled "Organometallic Photoresist Developer Compositions and Processing Methods" by Jiang et al. (hereinafter the '627 application), which is incorporated herein by reference. The dry development process herein relates particularly to negative-tone processing.

[0019] To perform the process, development can be carried out using a vapor treatment process, also referred to as dry development, in which the photoresist coating is exposed to a flowing vapor or gaseous developer composition, unwanted materials are removed, and a physical pattern is formed. Some examples of dry development processes are described in the pamphlet of International Publication No. WO 2020 / 132281A1 named "Dry development of resists" by Volosskiy et al. and in the specification of PCT Patent Application No. PCT / US2020 / 039615 named "Photoresist Development With Halide Chemistries" (hereinafter referred to as the '615 application), and both documents are incorporated herein by reference. These dry development methods typically include a vapor developer composition based on the use of chemicals that are halides. In such dry development processes, development can be achieved by exposing the irradiated substrate to a plasma process or a thermal process while flowing a halide vapor containing small molecules containing halides (F, Cl, Br, I) such as HBr, HCl, BCl3. Optionally, dry development can provide advantages over wet development, such as reduced pattern collapse and precise control of the developer composition (i.e., vapor and / or plasma gas). An alternative form of the process described herein relates to reducing the formation of scum, where scum refers to residues remaining on a portion of the latent image or adjacent edges intended to be removed.

[0020] An improved dry development method for an organotin photoresist coating that uses an oxidizing agent to improve the development of a patterned organotin coating is described herein. Without wishing to be bound by theory, the halide binds to Sn atoms in the coating and a volatile R that is later removed from the substrate by evaporation, etc. n SnX 4-n(X = halide, n = 0, 1, or 2) species are thought to interact with the organotin material. Usually, the non-irradiated region has a lower density than the irradiated region and can thus be more easily removed with a halide developer. However, for some organotin compositions, the products resulting from halogenation may be unstable and decompose within the system and / or upon volatilization and / or prior to removal, leaving unwanted non-volatile and / or insoluble residues such as SnCl2 or SnBr2 on the substrate. It has been recognized, for example, by Haenssgen, D., Puff, H., and Beckerman, N. in J. Organomet. Chem. 1985, 293, 191 (which is incorporated herein by reference), that tert-butyltin trichloride ((CH3)3CSnCl3) rapidly decomposes to SnCl2 and tert-butyl chloride at temperatures higher than cryogenic temperatures. The decomposition reaction involves the reduction of Sn+4 to Sn+2. Although Haenssgen et al. did not describe the stability of tert-butyltin tribromide or tert-butyltin triiodide, it is expected that similar decomposition reactions can occur with these tribromide and triiodide compositions as with the trichloride composition. Tin +2 halides are not volatile under the process conditions described herein. Therefore, it may be desirable to prevent the formation of SnX2 (X is a halide or other Sn+2 species) by promoting oxidation during the development process and / or maintaining oxidized Sn atoms (+4 oxidation state) within the organotin coating. In order to continuously utilize the pattern contrast, it may be particularly desirable to maintain tin in the +4 oxidation state. While it may be desirable to use an oxidizing gas to maintain tin in the +4 oxidation state during development, a separate thermal oxidation step can be used after thermal development based on halide and prior to subsequent thermal development based on halide, regardless of whether an oxidizing gas is present in the atmosphere during the halide-based development step. By repeating the use of the oxidation step and subsequent thermal development based on halide, additional development cycles can be performed.Before the thermal development step based on the halide, an oxidizing agent can be included in the post-exposure (before development) bake step to place the material in an oxidizing environment.

[0021] As described above, in some embodiments, the complete development process may include multiple steps. The process may include a primary development step in which most of the target material is removed. The primary development step in the process mainly targeted herein is a dry process in which vapor reactants and vapor by-products are involved in the removal. To improve the development process, a pre-development step using a reactive gas can be used. In particular, the application of the post-exposure bake is explained in relation to the pre-development step. The post-development step can be used to improve the developed pattern and can be dry or wet (i.e., solution-based). Plasma etching as a post-development descum step will be further described later. The overall development process for realizing the patterned structure can be improved by the interaction between steps and the improvement of the primary development step.

[0022] Fabrication of the coating: The organotin photoresist composition can be effectively used for patterning by radiation, particularly patterning by EUV. Generally, any suitable deposition process can be used to form a radiation-patternable coating on a substrate. Suitable deposition processes include, for example, spin coating, spray coating, dip coating, knife edge coating, printing, such as solution deposition techniques like inkjet printing and screen printing. The fabrication of a radiation-patternable organotin coating is described in the '684 patent and '618 patent cited above.

[0023] In some embodiments, the radiation-patternable organotin coating can be formed by a vapor deposition method. Vapor deposition methods typically include chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), and improved methods thereof. In a typical vapor deposition process, the organotin composition can react with small molecule vapor reagents such as H2O, O2, H2O2, O3, CH3OH, HCOOH, CH3COOH, etc., which function as O and H sources for the production of radiation-sensitive organotin oxide and oxide hydroxide coatings. The vapor deposition of radiation-patternable organotin coatings is described in the '618 patent cited above and in International Publication No. WO 2019 / 217749 entitled "Methods for Making EUV Patternable Hard Masks" by Wu et al., which is incorporated herein by reference. The production of radiation-sensitive organotin coatings can typically be achieved by reacting the volatile organotin precursor, RSnL3, with small gaseous molecules. The reaction can include hydrolyzing / condensing the organotin precursor to hydrolyze the hydrolyzable ligand while substantially leaving the Sn-C bond intact.

[0024] Regarding an overview of a representative process of radiation-based patterning, typically, for example, in an extreme ultraviolet (EUV) lithography process, the photoresist material is deposited or coated as a thin film on a substrate, pre-baked before exposure, exposed with a radiation pattern to form a latent image, post-baked after exposure, and then developed by a solution ("wet") process or a thermal and / or plasma ("dry") process to generate a developed pattern of the resist. Optionally, fewer steps can be used, and additional steps can be used to create a coating with a latent image for development and / or remove residues to improve pattern fidelity. The processes of particular note herein include dry development steps, but in some embodiments, the dry development process can be combined with an initial wet development step and / or a subsequent wet rinse step.

[0025] The selected thickness of the radiation-patternable coating can depend on the desired process. For use in single-patterning EUV lithography, the coating thickness is typically selected such that a pattern with low defect rate and high patterning reproducibility is obtained. In some embodiments, a suitable coating thickness can be from about 1 nm to about 100 nm, in further embodiments from about 1.5 nm to 50 nm, and in further embodiments from about 2 nm to 25 nm. Those skilled in the art will understand that additional ranges of coating thickness are envisioned and are within the scope of the present disclosure. The coating thickness of a radiation-patternable coating made by vapor deposition techniques can typically be controlled by appropriately selecting the reaction time or process cycle. The coating thickness of a solution-deposited coating can be selected based on viscosity, solution usage amount, and wet coating thickness.

[0026] The substrate typically provides a surface on which the coating material can be deposited, which can include multiple layers and the surface relates to the uppermost layer. The substrate is not particularly limited and can include any suitable material, such as silicon, silica, other inorganic materials such as ceramics, semiconductor wafers, and polymeric materials.

[0027] After deposition and formation of the radiation-patternable coating, additional processing can be employed before exposure to radiation. In some embodiments, the coating can be heated at about 30 °C to about 300 °C, in further embodiments at about 50 °C to about 200 °C, and in further embodiments at about 80 °C to about 150 °C. The heating can be carried out over about 10 seconds to about 10 minutes in some embodiments, over about 20 seconds to about 5 minutes in further embodiments, and over about 30 seconds to about 4 minutes in further embodiments. Additional ranges of temperature and heating duration within the ranges specified above are also anticipated and envisioned.

[0028] Patterning and Development: The radiation can typically be directed at a substrate coated through a mask or the radiation beam can be controllably scanned across the entire substrate. Typically, the radiation can include electromagnetic radiation, an electron beam (beta rays) or other suitable radiation. Typically, the electromagnetic radiation can have a desired wavelength or wavelength range such as visible radiation, ultraviolet light or X-rays. The resolution achievable by patterning with radiation generally depends on the radiation wavelength and typically, a higher resolution pattern can be achieved with radiation of a shorter wavelength. Thus, it may be desirable to use ultraviolet light, X-rays or an electron beam, particularly to achieve a particularly high resolution pattern.

[0029] According to the international standard ISO21348 (2007) incorporated herein by reference, ultraviolet light ranges from 100 nm or more to less than 400, 30 nm. A krypton fluoride laser can be used as a 248 nm ultraviolet light source. The ultraviolet range can be subdivided in a plurality of ways, such as extreme ultraviolet (EUV) from 10 nm or more to less than 121 nm and far ultraviolet (FUV) from 122 nm or more to less than 200 nm, based on approved standards. The 193 nm line from an argon fluoride laser can be used as a radiation source for FUV. 13.5 nm EUV light is used in lithography and this light is generated from a Xe or Sn plasma source excited using a high energy laser or a discharge pulse. Soft X-rays can be defined as from 0.1 nm or more to less than 5, 10 nm.

[0030] Based on the design of the coating material, a large contrast in material properties can exist between the irradiated region where the coating material is condensed and the unirradiated coating material where the Sn-C bond is substantially undamaged. In embodiments where post-irradiation heat treatment is used, the post-irradiation heat treatment can be performed at a temperature of about 45°C to about 250°C, in additional embodiments at a temperature of about 50°C to about 190°C, and in further embodiments at a temperature of about 60°C to about 175°C. The post-exposure heating can typically be performed over at least about 0.1 minute, in further embodiments from about 0.5 minute to about 30 minutes, and in additional embodiments from about 0.75 minute to about 10 minutes. One of ordinary skill in the art will recognize that additional ranges of post-irradiation heating temperature and time are envisioned within the explicit ranges above and that they are within the scope of this disclosure. This high contrast in material properties facilitates the formation of high-resolution lines with smooth edges in the pattern after development, as described in the following section.

[0031] Typically, the post-exposure heating step is important to further promote the cleavage of the R group, thereby improving the contrast of the pattern. The applicant has found that the patterning results can be improved by a waiting period (post-exposure delay - PED) after irradiation and before heat treatment and development. The standing time of the waiting period can be at least about 20 minutes, in a further embodiment at least about 25 minutes, and in another embodiment about 30 minutes to about 3 days. The PED can be carried out, for example, under an atmosphere such as an inert gas, oxygen, air or modified air, such as CO2-enriched air (which can be brought to a partial pressure of 450 ppm or more) and / or air with a water content adjusted to a target value in order to obtain a consistent process result, at a pressure of at least about 200 Torr to above atmospheric pressure. The PED can be carried out at room temperature or at a temperature of 40 °C to about 130 °C. Those skilled in the art will recognize that additional ranges of PED parameters are contemplated within the above explicit ranges and that they are within the scope of the present disclosure. The use of PED is described in more detail in U.S. Patent Application Publication No. 2021 / 0271170A, entitled "Process Environment for Inorganic Resist Patterning" by Telecky et al. (hereinafter the '170 application), which is hereby incorporated by reference into this specification.

[0032] Post-exposure baking can be performed in various atmospheres. In the '170 application, it was found that post-exposure processing is desirably performed at a pressure of at least 200 Torr. The atmosphere during post-exposure baking (PEB) can be effectively performed in various atmospheres. As shown in the '170 application, when the CO2 concentration is increased relatively gently, it is suggested that the critical dimension from patterning can be desirably increased and a lower dose can be used for the target resolution. The air used in the '170 application was not dried, so it also contained water vapor. In the context of the dry (meaning gas-based, not meaning without water vapor) patterning of the present invention, the atmosphere used for PEB can correspond to pre-development exposure to desirable vapor species such as O2, O3, H2O, H2O2, NO, NO2, and / or CO2. Some of these species are thought to either remain bound to the resist material or change the resist material for subsequent development steps. Since tin +4 ions can accept up to six ligands, in a material that is not fully condensed, there may be a possibility of the presence of more weakly bound neutral ligands under a specific set of conditions. In particular, species that form an oxidative environment can affect the dry development step.

[0033] The oxidation step after thermal development can proceed in the same manner as the PEB step. The oxidation step may or may not involve heating. During the oxidation step, the atmosphere usually contains O2, O3, H2O, H2O2, NO, and / or NO2. The atmosphere can include the air and / or inert gas described for PEB, and the pressure range and time are similarly applicable here.

[0034] Development can be performed after post-exposure baking. As long as the atmosphere during post-exposure baking is selected to be the same as or similar to the background atmosphere of the vapor development step, development can proceed relatively directly from the PEB, and the PEB can be regarded as at least part of pre-exposing the substrate to the target gas. In relation to the development step caused by the gas, the background atmosphere is intended to refer to additional gas components other than the halide developer in the atmosphere. When the pressure changes, the pumping speed and / or the flow rate can be adjusted accordingly. The PEB treatment can be performed using an atmosphere selected to improve the condensation of the irradiated material, which is different from the atmosphere desirable for dry development. In that case, the atmosphere around the wafer can be appropriately exchanged, and it may be desirable to allow the wafer to equilibrate with the changed atmosphere.

[0035] Regardless of the extent to which the PEB is designed to prepare the substrate for development, the dry development process can be characterized by parameters including the composition of the chamber atmosphere, chamber pressure, flow rate, and temperature. With respect to the composition, in some embodiments, the chamber atmosphere includes a halide developer, an oxidizing gas, and an optional additional gas. When halide-based development is combined with another oxidation step, the chamber atmosphere can include a halide developer and an optional additional gas, such as a dihalide and an inert gas, although an oxidizing gas can still be included in the development step. Suitable halide developers include, for example, HF, HCl, HBr, HI, BCl3, etc. Halogenated acyls (RCOX) such as CH3OCl and carbonyl halides (COX2) such as COF2 and COCl2 react with water to form the corresponding hydrogen halide, where X is F, Cl, Br, or I, and R is an alkyl group having 1 to 5 carbon atoms, which are suitable halide developers. Usually, a mixture of halide developer compounds can be used. By introducing the halide developer into the chamber, the desired partial pressure of the gas can be established, and this partial pressure can be considered independent of the total pressure and other gas components. The partial pressure of the halide developer can be from about 50 milliTorr (mT) to about 25 Torr, in a further embodiment from about 100 mT to about 15 Torr, and in an additional embodiment from about 100 mT to about 10 Torr. The flow rate of the halide developer can depend on the turnover rate of the chamber atmosphere and the chamber size, and can be at least about 10 sccm (standard cubic centimeters per minute), in some embodiments from about 50 sccm to about 10,000 sccm, and in a further embodiment from about 100 sccm to about 2500 sccm. Those skilled in the art will recognize that additional ranges of the parameters of the halide developer are envisioned within the explicit ranges described above and that they are within the scope of this disclosure. The parameters suitable for other gas components of the development process are described below.

[0036] Referring to FIG. 1, a side view of the patterned organotin resist 104 on the substrate 102 before development is schematically shown. The non-irradiated region 106 is mainly an organotin oxide hydroxide composition represented by the formula RSnO 1.5-x / 2 (OH) x (0 < x < 3). The organotin oxide hydroxide composition usually contains an alkyl ligand having an Sn-C bond, and the Sn atoms are incorporated into a network of Sn-O and / or Sn-OH bonds to form an oxide hydroxide network. The irradiated region 108 has significantly less carbon than the non-irradiated region (i.e., a low concentration of Sn-C bonds), is usually denser (i.e., a high concentration of Sn-O-Sn bonds), and is usually represented by the formula R z SnO (2-(z / 2)-(x’ / 2)) (OH) x’ wherein 0 < x' < 4 and z is usually significantly less than 1 (i.e., the ratio of R to Sn is less than 1). It should be understood that the irradiation of the organotin material decomposes Sn-C, and the exact composition of the irradiated region can depend on the amount of radiation supplied and the subsequent processing of the film. For example, additional heating (e.g., post-exposure bake) or exposure to additional radiation (e.g., EUV or UV flood exposure) can affect the composition of both the irradiated and non-irradiated materials. In any case, the non-irradiated region is usually less dense and contains more carbon than the irradiated region. Those skilled in the art will understand that the above formulas for the irradiated and non-irradiated regions are generalizations for educational purposes and are not intended to precisely represent the full complexity of the three-dimensional material, even ignoring approximations due to common trace contaminants (which the applicant has reduced to low levels).

[0037] Referring now to FIG. 2, the reaction of each region of the photoresist with a halide developer (e.g., HBr, BCl3) is shown. In the irradiated region, which typically contains a high density of Sn—O—Sn and Sn—OH networks, a reaction with the halide X can occur to form volatile SnX4. However, in the non-irradiated region, which is typically much less dense (i.e., has a lower concentration of Sn—O—Sn bonds) than the irradiated region, the reaction with the halide proceeds rapidly to form organotin halide species such as RSnX3. Because of the lower density of the non-irradiated region, the reaction in the non-irradiated region occurs much faster, and the maintenance of the R ligand can contribute to the volatility of the halogenated product. For some R groups, due to the instability of RSnX3, rapid decomposition / disproportionation to volatile RX and non-volatile SnX2 products can occur. There is a possibility that unstable organotin halide species other than RSnX3 can be formed during exposure to the halide vapor, and one of ordinary skill in the art will understand that undesirable by-products (e.g., SnX2) can be formed due to their instability. The non-volatile metal species can cause scum to form at the end of the development process.

[0038] Referring now to FIG. 3, a side view of the pattern after development using a halide composition is shown. The irradiated region is essentially intact and remains on the substrate after development, while the non-irradiated region is mostly removed, except for unwanted residues containing non-volatile reaction products with the halide developer composition.

[0039] Here, referring to FIGS. 4 and 5, the improvements obtained by the supply of the oxidizing agent are schematically shown in comparison with the similar FIGS. 2 and 3. When the oxidizing agent is supplied as described herein, the formation of non-volatile materials such as SnX2 can be reduced or eliminated with the reduction of tin +4 to tin +2. By reducing the formation of undesirable by-products, the corresponding yield of the desired volatile product can be improved. Here, FIG. 4 shows the reaction in the presence of an oxidizing agent to avoid the formation of SnX2 by-products. Although the halogenation reaction can be slowed down in the presence of an oxidizing gas, by adjusting the ratio of the gas concentrations, the halogenation reaction can be made to occur at an appropriate rate. The cleaner developed structure obtained is schematically shown in FIG. 5.

[0040] In some embodiments, the present disclosure describes methods and compositions that can reduce the formation of non-volatile residues during the development of organotin coatings using halide vapors. As described herein, introducing an oxidizing agent into the development process can result in improved development using a halide composition. In some embodiments, the developer atmosphere can include a mixture of oxidizing agents that includes a halide composition. The developer atmosphere can further include an inert gas that can be used to maintain the overall pressure within the chamber. In some embodiments, the oxidizing agent can account for at least 1 mol% of the total mixture, and in some embodiments, the oxidizing agent can account for at least 20 mol% of the total mixture. In further embodiments, the oxidizing agent can account for 50 mol% to about 99 mol% of the total mixture, and in further embodiments, the oxidizing agent can account for 75 mol% to about 90 mol% of the total mixture. The amount can depend on the nature of the coating and the strength of the halogenating agent and the oxidizing agent. For relatively strong oxidizing agents such as O3 or H2O2, the development atmosphere can have from about 1 mol% to about 15 mol%, in some embodiments from about 1 mol% to about 12 mol%, and in further embodiments from about 2 mol% to about 10 mol% of the oxidizing agent. For relatively weak oxidizing agents such as O2 or H2O, the development composition can have from about 10 mol% to about 99 mol%, in further embodiments from about 15 mol% to about 95 mol%, in another embodiment from about 50 mol% to about 90 mol% of the oxidizing agent, and ranges formed using combinations of different lower and upper limits from these ranges. The flow rate of the oxidizing agent within the process chamber is typically an amount that balances with the halide developer to obtain the desired ratio of gas species within the chamber. Thus, the flow rate of the oxidizing agent can range from about 1 sccm to about 100,000 sccm, and in further embodiments from about 10 sccm to about 25,000 sccm. Those skilled in the art will recognize that additional ranges of oxidizing gas parameters within the above-explicit ranges are contemplated and are within the scope of the present disclosure.

[0041] The development atmosphere may also desirably further include an optional dihalide, F2, Cl2, Br2, I2, or a mixture thereof to provide another halide source. The development atmosphere, if present, may contain from about 0.5 mole % to about 15 mole %, and in a further embodiment from about 1 mole % to about 10 mole % of the dihalide, excluding the contribution of the inert gas. The flow rate of the dihalide can be set to be proportional to the total flow rate of the halide developer and the oxidizing gas based on the mole percent of the auxiliary compound. The inert gas can be supplied as a regulator and / or to maintain the pressure at a target value without necessarily increasing the amount of the active compound. The flow rate of the inert gas can depend on the target chamber pressure, but can be in the range of about 10 sccm to about 200,000 sccm, and in a further embodiment in the range of about 50 sccm to about 100,000 sccm. In some embodiments, the halide developer can be mixed with air to effect development, and this air may or may not be supplemented with additional oxidizing compounds and / or may or may not be dried, partially dried, or humidified to adjust the water vapor content. The air is mainly supplied with N2 containing natural amounts of inert gas, some Ar, and some CO2, but the air can be supplemented with nitrogen or other inert gases to adjust their concentrations. Similarly, a gas composition containing air components can be formed by mixing appropriate gas species to achieve the target gas concentration. When air is used, the flow rate can be evaluated based on the components of the overall flow, specifically the inert gas, O2, H2O, CO2, the halide developer, and the supplemented species. Additional ranges within the disclosed ranges are also contemplated and are within the scope of the disclosure. The developer composition can be supplied with an inert gas, but this is not considered with respect to the molar concentration of the developer composition described above. The flow of the inert gas can be individually adjusted to affect the development rate and the flow rate through the apparatus.

[0042] In some embodiments, the oxidizing agent can alternatively be supplied in a multi-step process that includes development with a halide composition. For example, in some embodiments, the organic tin coating can be exposed to the oxidizing agent in a thermal process or a plasma process prior to development with the halide composition. As described above, this prior exposure to the oxidizing atmosphere can be combined with PEB and / or can be performed as a separate step. The prior exposure may be desirable to provide a preventative approach to suppressing scum formation, which can be particularly efficient. Similarly, in some embodiments, after development with the halide composition, the organic tin coating can be exposed to the oxidizing agent in a thermal process or a plasma process. In some embodiments, a primary development step including exposure to a halogenated composition can be performed, followed by exposure to the oxidizing agent in a thermal process or a plasma process. Thereafter, a secondary development treatment step (thermal development based on a halide) or a scum removal step can be performed after the processing flow, and these steps can include exposure to a halide composition or a contrast enhancer. The secondary development or scum removal step can be a dry or solution-based process. In some embodiments, a cycle process can be performed in which the organic tin coating is exposed to the oxidizing agent in a thermal process and then the development process including the halide is repeated one or more times. In further embodiments, the oxidizing agent can be continuously present before, during, after the supply of the halide developer, or a portion of this extended time frame, and at that time, the timing of the individual supply steps can be adjusted to obtain the desired patterning result. For example, PEB can be performed using air optionally supplemented with other gases, dry development can be formed using air and an added halide developer, and the chamber can be flushed with air, nitrogen, or other gases after the development step.

[0043] In some embodiments, the oxidizing agent can include oxygen-containing species such as O2, O3, H2O, H2O2, NO2, NO, or mixtures thereof. In some embodiments, suitable oxidizing agents include Sn 2+ to Sn 4+ substantially oxidizable or Sn 4+from Sn 2+ Those that can sacrificially prevent reduction to Sn may be included. With respect to these proposed mechanisms, the Applicant does not wish to be limited by theory. The oxidizing agent can be supplied to the substrate by any suitable method such as flowing oxidizing agent vapor over the substrate in a thermal process or a plasma process, or in some embodiments, can be supplied as a liquid composition that can be supplied as an aerosol.

[0044] In some embodiments, the thermal process can include controlling the temperature of the substrate during contact with the oxidizing agent and / or the developing composition. Such thermal processes can typically include cooling or heating. In some embodiments, it can be beneficial to cool the substrate during exposure of the substrate to the oxidizing agent and / or the developing composition in order to better control the reaction rate and improve the fidelity of the subsequent pattern. Nevertheless, the heat-based dry development step can typically be formed at a suitable temperature in the range of about -80°C to about 400°C, in further embodiments about -25°C to about 250°C, in another embodiment about -10°C to about 150°C, and in some embodiments about 0°C to about 100°C. In some embodiments where cooling is involved, liquid nitrogen can be a particularly useful coolant. In another embodiment, the thermal process can include heating the substrate. The development time can be in the range of about 2 seconds to about 10 minutes, in further embodiments about 5 seconds to about 7 minutes, and in another embodiment about 8 seconds to about 5 minutes. The choice of temperature can depend on the concentration and composition of the developing gas. Those skilled in the art will recognize that additional ranges of temperature and time are contemplated within the explicit ranges above and that they are within the scope of the present disclosure. Typically, the processing time and temperature can be selected in part based on the flow rate and pressure of the gas. The dry development process described herein can be performed after a preliminary development step such as a solution-based development step or a plasma development step, in which case the dry thermal development can be considered a descum step if necessary.

[0045] In some embodiments, it may be desirable to perform a rinse / descum process after the first halide development process. In some embodiments, the rinse / descum composition may include exposing the substrate to a liquid rinse / descum composition. The rinse / descum composition may be supplied to the substrate by any means known in the art, such as dispensing a certain amount of liquid onto the surface of the wafer while the wafer is stationary (i.e., a static process) or rotating (i.e., a dynamic process). The use of a rinse solution for descum is described in U.S. Patent No. 11,480,874B2, entitled "Patterned Organometallic Photoresists and Method of Patterning" by Kocsis et al., which is incorporated herein by reference. The liquid developer described in the '627 application can also be used as a rinse solution. In another embodiment, the rinse / descum process may include exposing the substrate to a descum process in a dry thermal process or a plasma process. In some embodiments, the rinse / descum composition may include an alcohol, a carboxylic acid, a ketone, an ester, an ether, or a mixture thereof. Plasma etching may be desirable to remove scum. For example, a plasma containing helium, argon, or a halide may be effective for scum removal and / or pattern smoothing. Examples of halide compounds suitable for plasma treatment include, for example, SF6, CF4, CHF3, HCl, BCl3, HBr, and mixtures thereof. In contrast to the thermal vapor-based development process described herein, such plasmas typically contain radicals and / or ions and can typically etch resist materials and / or scum by a physical etching process. Plasma treatment can typically be performed at a pressure of less than about 2 Torr, and in further embodiments, from about 50 mTorr to about 1 Torr. The flow rate of plasma etching can be from about 50 sccm to about 1000 sccm. An appropriate RF frequency can be used, and the plasma power can be from about 10 W to about 1000 W at a bias voltage of from about 10 V to about 500 V. Plasma treatment is not particularly sensitive to temperature and can be performed at room temperature.The plasma treatment time can be short, such as about 0.1 second to about 10 seconds. Those skilled in the art will recognize that additional ranges of plasma descum treatment are envisioned within the explicit ranges above and that they are within the scope of this disclosure.

[0046] In some embodiments, the rinse / descum composition can be optionally supplied in the presence of an inert gas such as N2, He, Ne, Ar, Kr, and / or Xe, which typically includes a pulsed or continuous flow through the system. The amount of the inert gas flow can mitigate the development and / or rinse (contrast enhancement) reaction. When present, the inert gas can typically be selected in the range of about 1 mole percent (mol%) to about 99 mol% and any value or range within this range.

[0047] Regarding the plasma treatment herein, it may be desirable to contact the developed substrate with the plasma to remove scum. In plasma treatment, the photoresist is exposed to appropriate species including ions and / or radicals of one or more gases. The plasma process can be performed within or in the vicinity of the plasma generation chamber such that ions and / or radicals can reach the photoresist material. The plasma generation chamber can include any suitable plasma reactor such as an inductively coupled plasma (ICP) reactor, a transformer coupled plasma (TCP) reactor, or a capacitively coupled plasma (CCP) reactor. Such reactors can be configured using suitable techniques and apparatus known in the art. The plasma intensity can be characterized by power, voltage, and frequency. Appropriate plasma power can be about 50 W to about 1000 W. The plasma voltage bias between the substrate and the plasma source can typically be about 10 V to about 500 V. The frequency can typically be in the high radio frequency range. Sub-ranges and values within these ranges of plasma characteristics are also envisioned and are within the scope of this disclosure.

[0048] In some embodiments of the development process, a plurality of inlets and outlets can be attached to the chamber to supply the desired gas and / or vapor to the chamber and to remove the seeds from the chamber by vacuum or gas flow. A mount for a substrate containing a photoresist for which development is desired may be present within or near the chamber to allow ions and / or radicals generated by the associated plasma to reach the photoresist on the substrate surface.

[0049] The rinse / descum composition can be introduced into a plasma process chamber containing a substrate by flowing the rinse / descum composition into the chamber at a desired flow rate and / or constant pressure. The flow rate and pressure can exhibit transient behavior when the target values are set. When two or more rinse / descum compounds (plasma generating compounds) and / or inert gases are used in the process, the partial pressure and / or flow rate of each individual compound and / or inert gas can be controlled. In some embodiments, the partial pressure of each compound in the chamber can be from about 5 milliTorr (mT) to about 1000 mT, in another embodiment from about 50 mT to about 800 mT, in another embodiment from about 100 mT to about 700 mT, and in a further embodiment from about 250 mT to about 500 mT. The concentration of the inert gas can be adjusted to achieve the desired chamber pressure. The pressure can be controlled at a specific pumping speed by varying the flow rate of each individual gas to the process chamber, for example, in some embodiments from about 100 sccm to about 1000 sccm, in another embodiment from about 200 sccm to about 800 sccm, and in a further embodiment from about 300 to about 600 sccm. Those skilled in the art will appreciate that additional ranges of pressure and flow rate within the above ranges are contemplated and are within the scope of the present disclosure.

[0050] Following an initial development process that includes a halide composition, it may be desirable to perform a further thermal process or plasma process on the patterned substrate. In some embodiments, the initial development process may include a solvent development process. Solvent development of organotin resists has been described for both negative tone and positive tone processing. During the initial development, a significant amount of material is removed from the substrate based on the above description, such as a negative tone or positive tone development process. However, in some cases, the initial development process may leave patterns on the substrate with undesirably large line width roughness (LWR) and / or defects (such as scum, residues, microbridges, etc.) due to, for example, incomplete development, material non-uniformity, and probabilistic effects. Therefore, in some embodiments, it may be desirable to perform a further thermal process or plasma process to remove unwanted materials that may be susceptible to the effects of the development chemicals described herein.

[0051] FIG. 6 shows a schematic layout of a suitable process system 300. The process system 300 has a steam supply system 301 and a process chamber 314. In some embodiments, the steam supply system 301 includes a process gas assembly 302. A schematic diagram of the process gas assembly 302 is intended to convey the concept that one or more independently controlled process gas reservoirs may be present within the process gas assembly. In some embodiments, the steam supply system 301 includes a process liquid assembly 303, which may also include one or more independently controlled reservoirs. The process gas assembly 302 and / or the process liquid assembly 303 may include a halide source, an oxidant source, and in some embodiments the auxiliary process gases described above. In some embodiments, the steam supply system 301 includes an inert gas source 304. When air is supplied by the steam supply system, the air may be supplied from a reservoir within the process gas assembly 302 or an intake for drawing in air from the ambient atmosphere. The steam supply system 301 may include an air conditioner for drying and / or humidifying the air to achieve a desired humidity level. The process liquid assembly 303 can be configured to supply a process liquid to a vaporization unit 306 via a liquid flow controller 305, which can be a bubbler, a flash evaporator, or other convenient component. To facilitate the supply of steam, an inert gas from an inert gas assembly 304 etc. can be supplied to the process liquid assembly 303. A mixing unit 307 receives a controlled flow of process gas from the process gas assembly 302, the vaporized process liquid from the vaporization unit 306, and / or the inert gas 304, which are controlled via one or more inlet valves 308, each of which may include a mass flow controller. A temperature controller 309 can be provided to control the temperature of the process steam 312 entering the process chamber 314, and the temperature controller 310 can include a heater and / or a cooler. In some embodiments, the steam supply system 301 has a plasma unit 310.

[0052] The process chamber 314 may include a vapor distribution unit 316. The vapor distribution unit 316 can have various shapes and designs. In some embodiments, the vapor distribution unit 316 has a showerhead shape with a plurality of port designs, one embodiment of which is shown in FIG. 7. The process chamber 314 has a support 318 that can hold a plurality of substrates, such as wafers, in some embodiments. The substrate 320 is positioned under the vapor distribution unit 316 and placed on the support 318. In some embodiments, the support 318 can be temperature-controlled via a heating / cooling unit 322. The support 318 can be connected to a motor for rotating the support 318 for substrate processing. The support 318 can be moved up and down manually or remotely to adjust the distance between the substrate and the vapor distribution unit. A pressure valve 324 is provided to control the pressure and the concentration of volatile reaction products within the process chamber 314. The pressure valve 324 can be connected to a vacuum pump. In some embodiments, the process system 300 has a remote plasma unit directly connected to the process chamber 314. In the embodiment shown in FIG. 6, the remote plasma unit has a matching circuit 328 and an RF power supply 330. In some embodiments, a controller 326 is provided to remotely control the elements of the process system 300. Details of additional devices of the developing apparatus are generally known in the art as described in U.S. Patent Application Publication No. 2014 / 0352736A1, titled "Cleaning Apparatus and Cleaning Method Coater / Developer and Coating and Developing Method, and Computer Readable Storing Medium" by Yamamoto et al. and in International Publication Pamphlet No. 2022 / 125388, titled "Photoresist Development With Organic Vapor" by Dictus et al., both of which are hereby incorporated by reference into this specification.

[0053] After completion of the development step, the coating material can be heat-treated to further condense the material, further dehydrate, densify, or remove residual developer from the material. This heat treatment may be particularly desirable in embodiments where the oxide coating material is incorporated into the final device, but may also be desirable in some embodiments where stabilization of the coating material is desired to facilitate further patterning or where the coating material is used as a resist and ultimately removed. In particular, baking of the patterned coating material can be performed under conditions where the patterned coating material exhibits a desired level of etch selectivity. In some embodiments, the patterned coating material can be heated to a temperature of about 100°C to about 600°C, in further embodiments about 175°C to about 500°C, and in additional embodiments about 200°C to about 400°C. The heating can be carried out for at least about 1 minute, in another embodiment about 2 minutes to about 1 hour, and in further embodiments about 2.5 minutes to about 25 minutes. The heating can be carried out in air, in a vacuum, or in an inert gas atmosphere such as Ar or N2. Those skilled in the art will recognize that additional ranges of heat treatment temperature and time are envisioned within the explicit ranges provided above and that they are within the scope of the present disclosure. Similarly, non-heat treatments such as blanket UV exposure or exposure to oxidative plasmas such as O2, O3, H2O2, etc. can also be used for similar purposes.

[0054] After pattern development and descumming are complete, the patterned material can be used as a mask for further processing of the substrate. The mask can be used for etching the substrate and / or depositing on the substrate. In this case, the substrate can be modified to introduce functionality. Typically, for device formation, patterning is repeated to form the desired structure. A mask formed from a patterning material based on a metal oxide can be removed using appropriate wet etching or dry etching as needed.

[0055] The above embodiments are intended to be illustrative and not limiting. Additional embodiments are within the scope of the claims. Further, although the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that modifications in form and detail may be made without departing from the spirit and scope of the invention. The incorporation by reference of the above documents is limited so that no subject matter contrary to the explicit disclosure herein is incorporated. As used herein, as long as a particular structure, composition, and / or process is described with components, elements, ingredients, or other delineations, the disclosure herein includes a particular embodiment including the particular components, elements, ingredients, other delineations, or combinations thereof, and, unless otherwise indicated, embodiments that consist essentially of such particular components, ingredients, other delineations, or combinations thereof that include additional features that do not change the essential nature of the subject matter, as suggested in the discussion. As will be understood by those skilled in the art, the use of the term "about" herein refers to measurement error of a particular parameter, unless explicitly indicated otherwise.

Claims

1. A method for dry developing an organotin composition patterned with radiation and having a latent image, comprising developing the structure with a gas containing a halogen-based developer and an oxygen source compound, wherein the structure comprises a substrate having a layer of the latent image composition having regions having at least partially condensed tin oxide-hydroxide and other regions having the organotin composition having carbon-tin bonds, and the development results in at least partial removal of the organotin composition having carbon-tin bonds.

2. The halogen-based developer includes HF, HCl, HBr, HI, and acyl halogens (COX ２ The method according to claim 1, comprising a carbonyl halogen (RCOX) or a mixture thereof, wherein X is F, Cl, Br or I, and R is an alkyl group having 1 to 5 carbon atoms.

3. The method according to claim 1, wherein the halogen-based developer comprises HF, HCl, HBr, HI, or a mixture thereof.

4. The oxygen source compound is O ２ , O ３ H ２ O, H ２ O ２ NO ２ The method according to any one of claims 1 to 3, comprising NO or a mixture thereof.

5. The organic tin composition having a carbon-tin bond is of the formula RSnO １．５－ｘ／２ (OH) ｘ (where 0 < x < 3, and R is a hydrocarbyl group that forms a carbon-tin bond and has 1 to 31 carbon atoms, with 3 to 31 carbon atoms for a group having a secondary bonded carbon atom and 4 to 31 carbon atoms for a group having a tertiary bonded carbon atom, and optionally has an unsaturated or aromatic carbon bond), and the method according to any one of claims 1 to 3, comprising a composition represented by this formula.

6. The aforementioned at least partially condensed tin oxide-hydroxide composition is RSnO in which the carbon-tin bond is cleaved by radiation. １．５－ｘ／２ (OH) ｘ The method according to claim 5, formed from

7. The method according to any one of claims 1 to 3, wherein the development is a thermal process, and the development step is carried out at a temperature of about -25°C to about 250°C.

8. The method according to claim 7, wherein the development is a thermal process, and the development step is performed at a temperature of about 0°C to about 150°C.

9. The method according to claim 7, wherein the process is carried out in a chamber at a pressure of at least about 5 Torr.

10. The halogen-based developer is provided at a flow rate of about 50 sccm to about 5000 sccm, according to any one of claims 1 to 3.

11. The method according to any one of claims 1 to 3, wherein the gas, excluding an inert gas, comprises at least about 50 mol% of an oxygen source compound.

12. The method according to any one of claims 1 to 3, wherein the gas includes air.

13. The method according to claim 12, wherein the water content of the air is adjusted to achieve a desired water pressure.

14. The method according to any one of claims 1 to 3, wherein the gas contains about 1 mol% to about 10 mol% of a dihalide, excluding the contribution of an inert gas.

15. The method according to any one of claims 1 to 3, further comprising carrying out an irradiation step for forming the latent image, wherein the irradiation results in the cleavage of a carbon-tin bond.

16. The method according to any one of claims 1 to 3, further comprising a post-exposure bake (PEB) step, which includes heating the structure to a temperature of about 60°C to about 250°C for about 0.1 minutes to about 5 minutes under a pressure of at least about 200 Torr, prior to the developing step.

17. The atmosphere inside PEB is O ２ , O ３ H ２ O, H ２ O ２ CO ２ The method according to claim 16, or a combination thereof.

18. The method according to claim 16, wherein the atmosphere in the PEB includes air.

19. The method according to claim 16, wherein the developing step is performed without purging the PEB atmosphere.

20. The method according to any one of claims 1 to 3, further comprising performing a plasma descam treatment after completing the development to the extent of at least partial removal of the organotin composition having carbon-tin bonds.

21. A housing configured to achieve a controlled pressure through the operation of a pump and appropriate pressure sensors, The substrate support within the housing, A developing energy source including a heater, a cooler and / or a plasma source configured to supply energy to a substrate placed on the substrate support, A halogenated developer source configured to supply halogenated developer gas from a reservoir into the housing through a flow regulator, An oxygen compound source configured to supply vapor of an oxygen-containing compound from a reservoir into the housing through a flow regulator, Includes developing chamber.

22. The developing chamber according to claim 21, wherein the developing energy source includes a heater and / or a cooler.

23. The developing chamber according to claim 21, wherein the halogenated developer source includes a hydrogen halogen source.

24. The developing chamber according to claim 21, wherein the oxygen source includes air.

25. The developing chamber according to claim 24, further comprising an air conditioning device for drying or humidifying the air to achieve a desired humidity level.

26. A developing chamber according to any one of claims 21 to 25, further comprising a controller for monitoring and adjusting temperature, flow rate and / or pumping to maintain target process conditions.

27. The developing chamber according to any one of claims 21 to 25, wherein the halogenated developer source is configured to supply the gas toward a substrate placed on the substrate support.

28. The developing chamber according to any one of claims 21 to 25, wherein the substrate support can support a plurality of substrates.

29. A method for transforming an irradiated substrate to form a physical pattern along its surface, wherein the irradiated substrate comprises a radiation-patterned radiosensitive organotin composition, and the method is The method involves performing post-exposure baking (PEB) on a substrate having a surface with a pattern generated by irradiated and non-irradiated regions of an organometallic radiation-sensitive material having carbon-metal bonds, wherein the heating is carried out in an atmosphere containing oxygen source molecules at a pressure of at least about 200 Torr, at a temperature of 60°C to about 250°C for about 0.1 minutes to about 30 minutes. By introducing a halogen-based developing gas into the housing, the non-irradiated organometallic radiation-sensitive material is substantially removed and a physical pattern is formed, thereby developing the physical pattern. Methods that include...

30. The method according to claim 29, wherein the PEB is performed in an atmosphere containing air.

31. The aforementioned air has a water content and / or CO2 content. ２ The method according to claim 30, which is conditioned to adjust the content.

32. The method according to any one of claims 29 to 31, wherein the halogen developing gas is introduced into the housing after the housing has been adjusted to a temperature of approximately -25°C to approximately 150°C.

33. The method according to any one of claims 29 to 31, wherein the housing is not purged after the PEB and before the introduction of the halogen developing gas.

34. The method according to any one of claims 29 to 31, wherein the irradiation area is formed by contact with EUV radiation.

35. The aforementioned organometallic radiation-sensitive material is of the formula RSnO １．５－ｘ／２ (OH) ｘ The method according to any one of claims 29 to 31, comprising an organotin oxide-hydroxide composition represented by (wherein 0 < x < 3, and R is a hydrocarbyl group that forms a carbon-tin bond and has 1 to 31 carbon atoms, having 3 to 31 carbon atoms in the group having a secondary bond carbon atom and 4 to 31 carbon atoms in the group having a tertiary bond carbon atom, and optionally having an unsaturated or aromatic carbon bond).

36. The method according to claim 35, wherein the carbon-tin bond is broken by radiation to form the irradiated region.

37. The method according to any one of claims 29 to 31, wherein the development is a thermal process, and the development step is carried out at a temperature of about -25°C to about 250°C.

38. The method according to any one of claims 29 to 31, wherein the processing is carried out in a chamber at a pressure of at least about 5 Torr.

39. The method according to any one of claims 29 to 31, wherein the halogen-based developer is provided at a flow rate of about 50 sccm to about 5000 sccm.

40. The method according to any one of claims 29 to 31, wherein the gas, excluding the inert gas, comprises at least about 50 mol% of an oxygen source compound.

41. The method according to any one of claims 29 to 31, wherein the gas includes air.

42. The method according to any one of claims 29 to 31, wherein the gas contains about 1 mol% to about 10 mol% of a dihalide, excluding the contribution of an inert gas.

43. The method according to any one of claims 29 to 31, further comprising performing a plasma descam treatment after completing the development to the extent of at least partial removal of the organotin composition having carbon-tin bonds.

44. A method for transforming an irradiated substrate to form a physical pattern along its surface, wherein the irradiated substrate comprises a radiation-patterned radiosensitive organotin composition, and the method is By introducing a halogen developing gas into the enclosure, non-irradiated organometallic radiation-sensitive material is substantially removed, and a physical pattern is formed, thereby developing the physical pattern. The substrate having the physical pattern on it is subjected to oxidation in an atmosphere containing oxygen source molecules for about 0.1 minutes to about 30 minutes to form an oxidized patterned substrate, The oxidized patterning substrate is brought into contact with a halogen developing gas to improve pattern development. Methods that include...

45. The method according to claim 44, wherein heating is performed at a pressure of at least about 200 Torr and at a temperature of 60°C to about 250°C.

46. The method according to claim 44, wherein the oxidation is carried out under a pressure of at least about 200 Torr.

47. The oxygen source molecule is O ２ , O ３ H ２ O, H ２ O ２ The method according to any one of claims 44 to 46, or a combination thereof.

48. The method according to any one of claims 44 to 46, wherein the atmosphere during oxidation includes air.

49. The method according to any one of claims 44 to 46, wherein the contact step is performed without purging the oxidizing atmosphere.

50. The halogen developing gas is HF, HCl, HBr, HI, acyl halogen (COX ２ The method according to any one of claims 44 to 46, comprising a carbonyl halogen (RCOX) or a mixture thereof, where X is F, Cl, Br or I, and R is an alkyl group having 1 to 5 carbon atoms.

51. The oxygen source compound is O ２ , O ３ H ２ O, H ２ O ２ NO ２ The method according to any one of claims 44 to 46, comprising NO or a mixture thereof.

52. The method according to any one of claims 44 to 46, wherein the developing and contacting are thermal processes carried out at a temperature of about -25°C to about 250°C.

53. The method according to any one of claims 44 to 46, wherein the development is carried out in a chamber at a pressure of at least about 5 Torr.

54. The method according to any one of claims 44 to 46, wherein the halogen developing gas is provided at a flow rate of about 50 sccm to about 5000 sccm.

55. The organotin composition having a carbon-tin bond is of the formula RSnO １．５－ｘ／２ (OH) ｘ The method according to any one of claims 44 to 46, comprising a composition represented by (wherein 0 < x < 3, and R is a hydrocarbyl group that forms a carbon-tin bond and has 1 to 31 carbon atoms, having 3 to 31 carbon atoms in the group having a secondary bond carbon atom and 4 to 31 carbon atoms in the group having a tertiary bond carbon atom, and optionally having an unsaturated or aromatic carbon bond).

56. The method according to any one of claims 44 to 46, wherein the halogen developing gas contains about 1 mol% to about 10 mol% of a dihalide, excluding the contribution of the inert gas.

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