Integrated solution with low temperature dry development for EUV photoresists

Abstract

Embodiments disclosed herein may include a method for developing a photopatterned metal-oxo photoresist. In one embodiment, the method may include pretreating the photopatterned metal-oxo photoresist using a pretreatment process and developing the photopatterned metal-oxo photoresist using a thermal dry development process to selectively remove portions of the photopatterned metal-oxo photoresist and form a resist mask. In one embodiment, the thermal dry development process includes a first sub-step and a second sub-step different from the first sub-step. In one embodiment, the process further includes post-treating the resist mask using a post-treatment process.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Patent Application No. 18 / 222,897, filed July 17, 2023, which claims the benefit of U.S. Provisional Application No. 63 / 466,891, filed May 16, 2023, and U.S. Provisional Application No. 63 / 425,264, filed November 14, 2022, the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate to the field of semiconductor processing, and more particularly to a method for developing metal-oxo photoresists using a gas phase process. [Background technology]

[0003] Lithography has been used for decades in the semiconductor industry to create 2D and 3D patterns for microelectronic devices. The lithography process involves spin-on deposition of a film (photoresist), irradiating (exposing) the film with an energy source in a selected pattern, and dissolving (etching) the exposed (positive tone) or unexposed (negative tone) areas of the film in a solvent. A bake is then performed to remove any remaining solvent.

[0004] Photoresist should be a radiation-sensitive material, and when irradiated, a chemical change occurs in the exposed portions of the film, allowing for a change in solubility between the exposed and unexposed areas. This change in solubility is used to remove (etch) either the exposed or unexposed areas of the photoresist. This develops the photoresist, allowing the pattern to be transferred by etching into the underlying thin film or substrate. After the pattern is transferred, the remaining photoresist is removed, and this process can be repeated multiple times to create the 2D and 3D structures used in microelectronic devices.

[0005] Several properties are important in lithography processes. These properties include sensitivity, resolution, low line edge roughness (LER), etch resistance, and the ability to form thinner layers. The higher the sensitivity, the less energy is required to change the solubility of the deposited film. This can improve the efficiency of the lithography process. Resolution and LER determine how narrow features can be achieved in the lithography process. Pattern transfer to form deep structures requires materials with higher etch resistance. Materials with higher etch resistance also enable thinner films. Thinner films improve the efficiency of the lithography process. Summary of the Invention

[0006] Embodiments disclosed herein may include a method for developing a photopatterned metal-oxo photoresist. In one embodiment, the method may include pretreating the photopatterned metal-oxo photoresist with a pretreatment process, developing the photopatterned metal-oxo photoresist with a thermal dry develop process to selectively remove portions of the photopatterned metal-oxo photoresist and form a resist mask, and post-treating the resist mask with a post-treatment process.

[0007] Embodiments disclosed herein may also include a semiconductor processing tool. In one embodiment, the semiconductor processing tool may include a transfer chamber. The transfer chamber is equipped with a substrate handling robot. The tool may further include a first processing chamber fluidly coupled to the transfer chamber. The first processing chamber is configured to deposit a metal oxo resist on the substrate using a dry deposition process. The tool may further include a second processing chamber fluidly coupled to the transfer chamber. The second processing chamber is configured to pre-treat or post-treat the metal oxo resist using a thermal treatment, an irradiation treatment, and / or a plasma treatment. The tool may further include a third processing chamber fluidly coupled to the transfer chamber. The third processing chamber is configured to develop the metal oxo resist using a dry development process. [Brief explanation of the drawings]

[0008] [Figure 1A] 1 is a flowchart illustrating a process for treating and developing a metal-oxo photoresist, according to an embodiment. [Figure 1B] 1 is a flowchart illustrating a process for treating and developing a metal-oxo photoresist, according to an embodiment. [Figure 2] 1 is a flow chart illustrating a process for developing a metal-oxo photoresist using a gas phase process with a halogenating agent according to one embodiment of the present disclosure. [Figure 3] 3A-3C are cross-sectional views of a substrate and photoresist illustrating steps in the flowchart of FIG. 2 according to an embodiment of the present disclosure. [Figure 4] 1 is a flow chart illustrating a process for developing a metal-oxo photoresist using a gas phase process with a halogenated agent and a protonated ligand according to an embodiment of the present disclosure. [Figure 5] 5A-C are cross-sectional views of a substrate and photoresist illustrating steps in the flowchart of FIG. 4 according to an embodiment of the present disclosure. [Figure 6] 1 is a flow chart illustrating a process for developing a metal-oxo photoresist using a vapor phase process with an organic acid according to an embodiment of the present disclosure. [Figure 7] 7A and 7B are cross-sectional views of a substrate and photoresist illustrating steps in the flowchart of FIG. 6 according to an embodiment of the present disclosure. [Figure 8A] 7 is a cross-sectional view of a processing tool that may be used to perform portions of the processes of FIG. 1, FIG. 2, FIG. 4, or FIG. 6 according to an embodiment of the present disclosure. [Figure 8B] FIG. 1 is a top schematic view of a cluster tool that may be used to process metal-oxo photoresist according to an embodiment of the present disclosure. [Figure 9] 1 illustrates a block diagram of an exemplary computer system according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0009] Described herein is a method for developing metal-oxo photoresist using a vapor-phase process. The following description sets forth numerous specific details for developing photoresist (such as thermal vapor-phase processes and material regimes) in order to provide a comprehensive understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that embodiments of the present disclosure may be practiced without these specific details. In other instances, well-known aspects, such as integrated circuit fabrication, have not been described in detail so as not to unnecessarily obscure embodiments of the present disclosure. Furthermore, it should be understood that the various embodiments illustrated in the figures are illustrative representations and are not necessarily drawn to scale.

[0010] Specifically, photoresist systems used in extreme ultraviolet (EUV) lithography suffer from low efficiency. Existing photoresist material systems for EUV lithography require high dosages to provide the necessary solubility switch that makes the photoresist material developable. Organic-inorganic hybrid materials (e.g., metal-oxo material systems) have been proposed as material systems for EUV lithography due to their high sensitivity to EUV radiation. Such material systems typically contain metals (e.g., Sn, Hf, Zr), oxygen, and carbon. Metal-oxo-based organic-inorganic hybrid materials have also been demonstrated to provide low LER and high resolution, which are necessary properties for forming narrow features.

[0011] In metal-oxo photoresist systems, carbon is removed by exposure to EUV radiation. The difference in carbon percentage between exposed and unexposed areas is used as a solubility switch during development. Specifically, in negative-tone development, unexposed areas with high carbon content are preferentially etched by the developer.

[0012] Metal-oxo photoresist systems are currently developed using wet chemistry. That is, after exposure, the unexposed areas of the photoresist are developed with an organic solvent / base solution used in a spin-on dry process. A post-bake anneal may also be included. However, when addressing high aspect ratio features, wet methods can be challenging due to the risk of pattern collapse (especially for line and pillar structures). Additionally, wet processes may not remove all of the material that should be removed, and may trap film material, by-products, solvents, etc. within small features.

[0013] Accordingly, embodiments of the present disclosure provide a gas-phase thermal etching process for developing metal-oxo photoresists. Specifically, the gas-phase thermal etching process offers the following advantages: 1) elimination of wet by-product generation, 2) reduced defects and impurities, 3) reduced waste stream due to destruction of dry chemistry in the abatement system, 4) improved LER, and 5) reduced damage from dry thermal etching compared to plasma damage in reactive ion etching (RIE). For example, at pitches less than 30 nm (e.g., line CDs less than 14 nm) and photoresist thicknesses less than 15 nm, the plasma can damage the photoresist mask, which can result in poor LER / LWR or even destroyed line patterns when the pattern is transferred to the underlying layer.

[0014] Embodiments disclosed herein provide various gas-phase thermal etching processes that are performed after a metal-oxo photoresist is partially exposed to an appropriate electromagnetic radiation source (e.g., an EUV source). In a first embodiment, the gas-phase thermal etching process includes vaporizing a halogenating agent in a vacuum chamber. The halogenating agent reacts with either the unexposed or exposed regions of the photoresist to produce volatile by-products, which are removed from the vacuum chamber. In a second embodiment, the gas-phase thermal etching process includes vaporizing a halogenating agent in a vacuum chamber. The halogenating agent can react with either the unexposed or exposed regions of the photoresist to produce non-volatile products. A ligand can then be vaporized in the chamber. The ligand can react with the non-volatile products to produce volatile by-products, which can be removed from the vacuum chamber. In a third embodiment, the gas-phase thermal etching process includes vaporizing an organic acid in a vacuum chamber. The organic acid reacts with either the unexposed or exposed areas of the photoresist to produce volatile by-products that are removed from the vacuum chamber.

[0015] In embodiments disclosed herein, the dry development process may be performed after a pretreatment of the metal-oxo photoresist. The pretreatment may include a thermal treatment, an irradiation treatment, and / or a plasma treatment. Additionally, embodiments may include a post-treatment after the dry development process. The post-treatment may include a thermal treatment, an irradiation treatment, and / or a plasma treatment.

[0016] Referring now to FIG. 1A, a process flow diagram illustrating a process 110 for developing a metal-oxo photoresist is shown, according to an embodiment. In an embodiment, the process 110 may begin at step 111 with providing a substrate with a metal-oxo photoresist. The photoresist may be disposed on the surface of the substrate using any suitable deposition process. In an embodiment, the photoresist is disposed on the substrate surface with wet chemistry using a spin-on process. In another embodiment, the photoresist is disposed on the substrate surface using a gas-phase process (i.e., a dry process). In a gas-phase process, a metal precursor and an oxidizer may be vaporized into a vacuum chamber. The metal precursor and the oxidizer then react to deposit a metal-oxo photoresist on the substrate surface. Such dry processes may be characterized as a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, a plasma-enhanced CVD (PE-CVD) process, or a plasma-enhanced ALD (PE-ALD) process.

[0017] In one embodiment, process 110 can include an exposure step after the metal-oxo photoresist is deposited. The exposure step (e.g., EUV exposure) converts exposed areas of the metal-oxo photoresist into a material that can be selectively etched relative to unexposed areas. The EUV exposure can be performed through a mask layer or by reflection from the mask layer. Although referred to as EUV, it should be understood that in some embodiments, other wavelengths (e.g., deep ultraviolet (DUV) wavelengths or ultraviolet (UV) wavelengths) can also be used.

[0018] In one embodiment, after the metal-oxo photoresist is provided on the substrate and exposed to EUV, the process 110 may continue with step 112. Step 112 may include pre-treating the metal-oxo photoresist. The pre-treatment may occur before the exposure and / or development of the metal-oxo photoresist. In an embodiment, the pre-treatment may include one or more of a thermal treatment, an irradiation treatment, and a plasma treatment.

[0019] For the thermal treatment, the photoresist may be exposed to a temperature between about -100°C and about 300°C. The duration of the thermal treatment may be between about 0.1 seconds and about 600 seconds. In one embodiment, the thermal treatment may be carried out in an atmosphere containing one or more gases. For example, the gas may include O2, N2, CO2, H2, D2, HO, DO, Ar, He, Cl2, Br2, I2, HCl, HBr, HI, CH4, TDMA-Me (where Me includes Sn, Zr, Al, Hf, Cr, Ta, Ru, Mo, Te, Ti, Zn, etc.), NH4X (X = F, CL, Br, or I), particularly NH4Cl, or a combination thereof.

[0020] In the case of irradiation treatment, the metal oxo photoresist can be exposed to electromagnetic radiation of a specific wavelength. For example, the wavelength can be between about 150 nm and about 700 nm. The irradiation treatment can be carried out in an atmosphere containing one or more gases. For example, the gas can include O2, N2, CO2, H2, D2, H2O, DO, Ar, He, Cl2, Br2, I2, HCl, HBr, HI, CH4, TDMA-Me (where Me includes Sn, Zr, Al, Hf, Cr, Ta, Ru, Mo, Te, Ti, Zn, etc.), NH4X (X = F, CL, Br, or I), particularly NHCl, or a combination thereof.

[0021] For plasma processing, the plasma may include plasma from H2, D2, Ar, and / or He source gases. The flow rate of one or more gases may be between about 1 sccm and about 2,000 sccm. The chamber pressure may be between about 1 mTorr and about 500 mTorr. The source power may be supplied at 0 W to 3,000 W using inductively coupled plasma (ICP), capacitively coupled plasma (CCP), or transformer coupled plasma (TCP). The bias power may be between 0 W and 1,000 W using frequencies of 13 MHz and / or 2 MHz.

[0022] In one embodiment, process 110 may continue with step 113, which includes developing the metal-oxo photoresist using a dry development process, such as a vapor-phase thermal etching process. In a first embodiment, the vapor-phase thermal etching process includes vaporizing a halogenating agent into a vacuum chamber. The halogenating agent reacts with either the unexposed or exposed regions of the photoresist to produce volatile by-products, which are removed from the vacuum chamber. In a second embodiment, the vapor-phase thermal etching process includes vaporizing a halogenating agent into a vacuum chamber. The halogenating agent may react with either the unexposed or exposed regions of the photoresist to produce non-volatile products. A ligand may then be vaporized into the chamber. The ligand may react with the non-volatile products to produce volatile by-products, which may be removed from the vacuum chamber. In a third embodiment, the vapor-phase thermal etching process includes vaporizing a halogen-containing inorganic / organic acid into a vacuum chamber. The one or more halogen-containing acids react with either the unexposed or exposed areas of the photoresist to produce volatile by-products, which are removed from the vacuum chamber. A more detailed description of the gas-phase thermal etching process is provided below.

[0023] In an embodiment, the process 110 may continue with step 114, which includes post-treating the developed metal-oxo photoresist. In one embodiment, the post-treatment may include a thermal treatment, an irradiation treatment, and / or a plasma treatment.

[0024] For the thermal treatment, the photoresist may be exposed to a temperature between about -100°C and about 300°C. The duration of the thermal treatment may be between about 0.1 seconds and about 600 seconds. In one embodiment, the thermal treatment may be carried out in an atmosphere containing one or more gases. For example, the gas may include O2, N2, CO2, H2, D2, HO, DO, Ar, He, Cl2, Br2, I2, HCl, HBr, HI, CH4, TDMA-Me (where Me includes Sn, Zr, Al, Hf, Cr, Ta, Ru, Mo, Te, Ti, Zn, etc.), NH4X (X = F, CL, Br, or I), particularly NH4Cl, or a combination thereof.

[0025] In the case of irradiation treatment, the metal oxo photoresist can be exposed to electromagnetic radiation of a specific wavelength. For example, the wavelength can be between about 150 nm and about 700 nm. The irradiation treatment can be carried out in an atmosphere containing one or more gases. For example, the gas can include O2, N2, CO2, H2, D2, H2O, DO, Ar, He, Cl2, Br2, I2, HCl, HBr, HI, CH4, TDMA-Me (where Me includes Sn, Zr, Al, Hf, Cr, Ta, Ru, Mo, Te, Ti, Zn, etc.), NH4X (X = F, CL, Br, or I), particularly NHCl, or a combination thereof.

[0026] For plasma processing, the plasma may include plasma from H2, D2, Ar, and / or He source gases. The flow rate of one or more gases may be between about 1 sccm and about 2,000 sccm. The chamber pressure may be between about 1 mTorr and about 500 mTorr. The source power may be supplied at 0 W to 3,000 W using an ICP, CCP, or TCP. The bias power may be between 0 W and 1,000 W using frequencies of 13 MHz and / or 2 MHz.

[0027] In one embodiment, process 100 may include a pre-treatment that is substantially similar to a post-treatment. In other embodiments, the pre-treatment may be different from the post-treatment. For example, the pre-treatment may include a thermal treatment and the post-treatment may include a plasma treatment. However, it will be understood that any combination of pre-treatment steps and any combination of post-treatment steps may be used to improve the performance of a metal-oxo photoresist.

[0028] 1B, a process flow diagram of process 180 is shown, according to an embodiment. In one embodiment, process 180 may begin with step 181, which includes depositing an underlayer on a substrate. The underlayer may be a material that improves the performance of an overlying metal-oxo resist. For example, the underlayer may be an adhesion-promoting layer. In other embodiments, the underlayer may improve the image quality of an overlying metal-oxo resist. The underlayer may be considered a high-Z metal oxide.

[0029] In one embodiment, process 180 may then continue with step 182, which includes depositing a metal-oxo photoresist over the underlayer. In one embodiment, the metal-oxo photoresist may be deposited by a wet process (e.g., spin coating, etc.). In other embodiments, a dry deposition process, such as a gas-phase process, is used to form the metal-oxo photoresist. In a gas-phase process, a metal precursor and an oxidizer may be vaporized into a vacuum chamber. The metal precursor and the oxidizer then react to deposit the metal-oxo photoresist on the substrate surface. Such dry processes may be characterized as CVD processes, ALD processes, PE-CVD processes, or PE-ALD processes.

[0030] In one embodiment, process 180 may then continue with step 183, which includes exposing a portion of the metal-oxo photoresist using an EUV exposure tool. In one embodiment, the EUV exposure may cause a chemical change in the composition of the metal-oxo photoresist. The chemical change activates a solubility switch, allowing the exposed areas of the metal-oxo photoresist to be selectively etched relative to the unexposed areas of the metal-oxo photoresist. While EUV exposure is described in more detail herein, it should be understood that in some embodiments, deep UV or UV exposure may also be used.

[0031] In one embodiment, process 180 may then continue with step 184, which includes performing a post-exposure bake (PEB) of the metal-oxo photoresist. In one embodiment, the PEB may include raising the temperature of the substrate to a temperature (e.g., 100° C.) or higher and holding it for a desired period of time. The elevated temperature may allow chemical reactions initiated by the EUV exposure to proceed further. In other embodiments, the PEB may be used to remove solvents or other components of the metal-oxo photoresist.

[0032] In one embodiment, process 180 may then continue with step 185, which includes pre-treating the metal-oxo photoresist. The pre-treatment process may be similar to the pre-treatment process described in more detail above with respect to Figure 1A. For example, the pre-treatment process may include a thermal treatment, an irradiation treatment, and / or a plasma treatment.

[0033] In one embodiment, process 180 may then continue with step 186, which includes developing the metal-oxo photoresist. The development process may be a dry development process. For example, to develop the exposed metal-oxo photoresist, a process gas containing a halogenating agent, a halogenating agent and a ligand, or an organic acid may be flowed into the chamber.

[0034] In certain embodiments, the dry development process may include two or more sub-steps. For example, a first sub-step may be followed by a second sub-step. The first sub-step may be different from the second sub-step. The difference between the sub-steps may include one or more different process parameters.

[0035] In one embodiment, the pressure of the first substep can be different from the pressure of the second substep. The first substep can be at a lower pressure than the second substep. For example, the first substep can be performed at a pressure of about 100 mTorr or less, and the second substep can be performed at a pressure of about 100 mTorr or more. In a specific embodiment, the first substep can be performed at a pressure of about 60 mTorr or less, and the second substep can be performed at a pressure of about 350 mTorr or more. In yet another embodiment, the first substep can be performed at a higher pressure than the second substep.

[0036] In one embodiment, the temperature process parameters may differ between the first sub-step and the second sub-step. For example, the first sub-step may be at a lower temperature than the second sub-step. However, in other embodiments, the first sub-step may be at a higher temperature than the second sub-step. In one embodiment, the temperature range for the first sub-step and the second sub-step may be between about -90°C and about 350°C. More specifically, the temperature range may be between about -90°C and 50°C.

[0037] In yet another embodiment, the gas flow ratio can vary between the first and second sub-steps. In a two-gas system, the first gas can have a flow rate between about 100 sccm and about 1,000 sccm, and the second gas can have a flow rate between 0 sccm and about 1,000 sccm. For example, the first ratio in the first sub-step can be about 1:1, and the second ratio in the second sub-step can be about 10:1. While various gases can be used (as described in more detail below), specific gases can include HBr as the first gas and Ar as the second gas.

[0038] In one embodiment, the durations of the substeps may be different. For example, a first substep may have a longer or shorter duration than a second substep. The durations of the different substeps may range from about 1 second to about 10 minutes. In a specific embodiment, the first substep may have a duration of about 60 seconds, and the second substep may have a duration of about 30 seconds.

[0039] In one embodiment, the substeps may be sequential; that is, a first substep is followed by a second substep. After the last substep (e.g., the second substep, the third substep, etc.), the process 180 may continue with the next step 187. However, in other embodiments, the substeps may be looped any number of times. In such a case, after the last substep is completed, the process 180 loops back to the first substep. This sequence may be repeated for any number of cycles. For example, two or more cycles, or ten or more cycles may be used.

[0040] In one embodiment, process 180 may then continue with step 187, which includes post-treatment of the patterned metal-oxo photoresist. In one embodiment, the post-treatment may be substantially similar to any of the post-treatments described in more detail above. For example, the post-treatment may include a thermal treatment, an irradiation treatment, and / or a plasma treatment. In certain embodiments, the post-treatment is different from the pre-treatment. In other embodiments, the post-treatment is substantially similar to the pre-treatment.

[0041] 2, a flow chart illustrating a process 220 for developing a metal-oxo photoresist on a substrate surface is provided, according to an embodiment of the present disclosure. Figures 3A-3C are cross-sectional views of a substrate 361 and a metal-oxo photoresist 362 after various steps in the process 220.

[0042] In one embodiment, process 220 may begin with step 221, which includes providing a substrate with a metal-oxo photoresist. FIG. 3A is a cross-sectional view of substrate 361 with metal-oxo photoresist 362 disposed on the surface of substrate 361. In an embodiment, substrate 361 may include any substrate material or materials typical of a semiconductor manufacturing environment. For example, substrate 361 may include a semiconductor material. Substrate 361 may include a semiconductor device or portion of a semiconductor device. Examples of such semiconductor devices include, but are not limited to, memory devices or complementary metal-oxide-semiconductor (CMOS) transistors fabricated on a silicon substrate and encased in a dielectric layer. Substrate 361 may also include a plurality of metal interconnects formed in the surrounding dielectric layer above the devices or transistors and may be used to electrically couple the devices or transistors to form an integrated circuit. In one embodiment, substrate 361 may be a wafer.

[0043] In one embodiment, the metal-oxo photoresist 362 (also referred to simply as "photoresist 362") can be any metal-oxo material system. Such material systems typically include a metal (e.g., Sn, Zr, Al, Hf, Cr, Ta, Ru, Mo, Te, Ti, Zn, etc.), oxygen, and carbon. In a particular embodiment, the photoresist 362 includes SnOC. In a more general sense, the photoresist 362 can be any material of the form (R a M) b O c (OH) d wherein R is a ligand and M is a metal. In one embodiment, a is equal to or less than b, and b is between 2 and 125. In one embodiment, c+d is equal to or less than b, and x is 2 to 8.

[0044] The photoresist 362 may be disposed on the surface of the substrate 361 using any suitable deposition process. In one embodiment, the photoresist is disposed on the surface of the substrate 361 using wet chemistry using a spin-on process. In an alternative embodiment, the photoresist is disposed on the surface of the substrate 361 using a gas-phase process (i.e., a dry process). In a gas-phase process, a metal precursor and an oxidant may be vaporized into a vacuum chamber. The metal precursor and oxidant then react to deposit a metal-oxo photoresist 362 on the surface of the substrate 361. Such dry processes may be characterized as chemical vapor CVD processes, ALD processes, PE-CVD processes, or PE-ALD processes.

[0045] In one embodiment, process 220 may continue with step 222, which includes exposing portions of the metal-oxo photoresist to form exposed and unexposed areas. Figure 3B is a cross-sectional view illustrating the exposure process. As shown, electromagnetic radiation 364 passes through mask 363 to expose exposed areas 362. E The non-exposed area 362 is exposed. U is shielded from electromagnetic radiation by a mask 363. In one embodiment, the electromagnetic radiation is EUV radiation. If EUV radiation is used, the EUV radiation 364 may reflect off the mask rather than passing through it. While EUV radiation is specifically disclosed herein, it should be understood that any suitable wavelength of electromagnetic radiation capable of initiating a solubility switch in the metal-oxo photoresist 362 may be used. For example, in some embodiments, DUV radiation may be used.

[0046] In one embodiment, the solubility switch is effected by the loss of carbon. In particular, exposure to electromagnetic radiation causes the exposed region 362 E Carbon is removed from the unexposed area 362. U The higher carbon content of the non-exposed areas makes them more susceptible to etching in the subsequent gas phase development process.

[0047] In one embodiment, process 220 may continue with step 223, which includes placing the substrate in a vacuum chamber. In one embodiment, the vacuum chamber may be any suitable chamber for providing sub-atmospheric pressure conditions. The vacuum chamber may also include heating / cooling features to provide thermal control of the gas-phase process. For example, the pedestal on which the substrate 361 rests may be an actively heated and / or cooled pedestal. Additionally, the walls of the vacuum chamber may be actively heated and / or cooled in some embodiments.

[0048] In particular, it should be appreciated that the embodiments disclosed herein do not require a plasma source to perform gas-phase etching of the metal-oxo photoresist. Thus, the construction of the vacuum chamber can be simplified compared to processes involving plasma-based development of the metal-oxo photoresist. A more detailed description of a suitable vacuum chamber is provided below in connection with FIG. 8.

[0049] In one embodiment, process 220 may continue with step 224, which includes vaporizing a halogenating agent in a vacuum chamber. In one embodiment, the halogenating agent may be vaporized in unexposed regions 362. U The halogenating agent reacts with the unexposed region 362 to form volatile by-products. U 3C, the reaction with the unexposed region 362 is removed from the substrate 361. U In other embodiments, the halogenating agent is removed from the exposed region 362. E may react with SnCl to produce a volatile by-product. In one embodiment, the by-product of the reaction is a volatile metal halide. Some metal halides are more volatile than others. For example, SnCl is more volatile than SnCl, CoClL (where L is a ligand) is more volatile than CoCl, and MoOCl is more volatile than MoCl. Thus, the reaction may preferentially produce a more volatile by-product. In one embodiment, the by-product has the formula RMX x , RMO y Xx , or MX X where M is a metal or metalloid, X is a halide, R is a ligand, x is 1-6, and y is 1-5.

[0050] In one embodiment, the halogenating agent has the formula MX a or MX a L b where M is a metal or metalloid (e.g., Mo, W, Ta, Nb, Sn, V, Ti, or Si), X is a halide (e.g., Cl or Br), L is a volatile ligand (e.g., alkyl, ethylenediamine, or Cp), a is 1 to 6, and b is 1 to 5. For example, the metal halide can include MoCl5, TaCl5, NbCl5, or WCl5.

[0051] In additional embodiments, the halogenating agent has the formula MO a X b or MO a X b L c where M is a metal or metalloid (e.g., Mo, W, Ta, Nb, Sn, V, Ti, or Si), X is a halide (e.g., Cl or Br), L is a volatile ligand (e.g., alkylethylenediamine, or Cp), a is 1 to 5, b is 1 to 5, and c is 1 to 5. For example, the metal oxyhalide can include MoOCl4, MoO2Cl2, WOCl4, or WO2Cl2.

[0052] In yet another embodiment, the halogenating agent may be an organic halogenating agent. For example, the halogenating agent may be thionyl chloride (SOCl), methanesulfonyl chloride (CHSOCl), trichloromethanesulfonyl chloride (CClSOCl), 4-toluenesulfonyl chloride (tosyl chloride), oxalyl chloride (ClCOCOCl), tert-butyl hypochlorite ((CH)COCl), N-chlorophthalimide, 1,3-dichloro-5,5-dimethylhydantoin, trimethylsilyl chloride, HCl, Cl, PCl, may include BCl3, HBr, Br2, CCl3Br, CBr4, 1,2-dibromo-1,1,2,2-tetrachloroethane (Cl2CBrCBrCl2), BBr3, PBr3, N-bromosuccinimide, N-bromoacetamide, 2-bromo-2-cyano-N,N-dimethylacetamide, 1,3-dibromo-5,5-dimethylhydantoin, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, or trimethylsilyl bromide.

[0053] In yet another embodiment, the halogenating agent may include one or more of SOBr2 (thionyl bromide), SO2Cl2 (sulfuryl chloride), and SO2Br2 (sulfuryl bromide).

[0054] In one embodiment, the halogenating agent may be diluted with an inert gas. For example, an inert gas such as Ar, N, or He may be used to dilute the halogenating agent. In other embodiments, gases such as O, N, CO, H, D, H0, DO, Ar, He, Cl, Br, I, HCl, HBr, HI, CH, TDMA-Me (where Me includes Sn, Zr, Al, Hf, Cr, Ta, Ru, Mo, Te, Ti, Zn, etc.), NHX (X = F, CL, Br, or I), particularly NHCl, or combinations thereof, may also be mixed with the halogenating agent. Generally, photoresist 362 E Photoresist 362 for the exposed area UThe etch selectivity of the unexposed regions of the silicon nitride film has been shown to increase with increasing pressure. In one embodiment, the pressure can be between about 1 torr and about 100 torr. In a particular embodiment, the pressure can be between about 3 torr and about 10 torr. In additional embodiments, the gas flow rate can be between 1 sccm and 2,000 sccm, and the pressure can be between 1 mTorr and 500 mTorr.

[0055] In one embodiment, the substrate 361 may be temperature controlled during step 224. For example, the temperature may vary between about −90° C. and about 350° C. In a particular embodiment, the temperature may vary between about −90° C. and about −60° C. In one embodiment, the source power may range between 0 W and 3,000 W using an ICP tool, a CCP tool, or a TCP tool. In one embodiment, the bias power may be between 0 W and 1,000 W, for example, at a frequency of about 13 MHz or about 2 MHz.

[0056] In one embodiment, step 224 may be performed through the use of two or more sub-steps, similar to the embodiment described in more detail above. For example, the first and second sub-steps may include different processing parameters, such as, but not limited to, duration, pressure, temperature, gas ratio, etc. In other embodiments, the sub-steps may be looped for any number of cycles to complete step 224.

[0057] In one embodiment, process 220 may continue with step 225, which includes purging the vacuum chamber. Purging the vacuum chamber removes by-products from the reaction in step 224 from the vacuum chamber. In one embodiment, step 224 may be performed as a soak followed by a single purge in step 225. In an alternative embodiment, steps 224 and 225 may define a cycle including a pulse of halogenating agent followed by a purge. In such an embodiment, photoresist 362 U Multiple cycles can be repeated to remove the unexposed areas.

[0058] Referring now to FIG. 4, a flow chart illustrating a process 430 for patterning a metal-oxo photoresist according to an embodiment of the present disclosure is shown. FIGS. 5A-5C are corresponding cross-sectional views illustrating various processing steps in process 430. In one embodiment, process 430 can be beneficial when the halogenating agent is unable to completely convert the unexposed regions of the photoresist to volatile by-products. In particular, process 430 further includes vaporizing a protonated ligand in a vacuum chamber to convert the unexposed regions of the photoresist to volatile by-products.

[0059] In an embodiment, process 430 may begin with step 431, which includes providing a substrate with a metal-oxo photoresist. In one embodiment, the substrate and metal-oxo photoresist may be substantially similar to the substrate and metal-oxo photoresist described above with respect to step 221 of process 220.

[0060] In one embodiment, process 430 may continue with step 432, which includes exposing portions of the metal oxo photoresist to form exposed and unexposed regions. In an embodiment, the exposure process of step 432 may be substantially similar to the exposure process of step 222 of process 220. FIG. 5A illustrates a substrate 561, exposed regions 562 of the photoresist, and E and unexposed areas of the photoresist 562 U FIG.

[0061] In one embodiment, process 430 may continue with step 433, which includes placing the substrate in a vacuum chamber. The vacuum chamber used in process 430 may be substantially similar to the vacuum chamber used in process 220.

[0062] In one embodiment, process 430 may continue with step 434, which includes vaporizing a halogenating agent in a vacuum chamber. In one embodiment, the halogenating agent may be added to photoresist 562. U reacts with the unexposed areas of theU That is, in some embodiments, the halogenating agent may not, by itself, provide a photoresist 562 U In other embodiments, the halogenating agent may not completely convert the unexposed regions 562 into volatile products that can be removed from the vacuum chamber. E In one embodiment, the non-volatile product 562 U 'MX x or MO y X x The metal halide or metal oxyhalide may have the chemical formula: where M is a metal or metalloid, X is a halide, x is 1-6, and y is 1-5.

[0063] In one embodiment, the halogenating agent has the formula MX a or MX a L b where M is a metal or metalloid (e.g., Mo, W, Ta, Nb, Sn, V, Ti, or Si), X is a halide (e.g., Cl or Br), L is a volatile ligand (e.g., alkylethylenediamine, or Cp), a is 1 to 6, and b is 1 to 5. For example, the metal halide can include MoCl5, TaCl5, NbCl5, or WCl5.

[0064] In additional embodiments, the halogenating agent has the formula MO a X b or MO a X b L c where M is a metal or metalloid (e.g., Mo, W, Ta, Nb, Sn, V, Ti, or Si), X is a halide (e.g., Cl or Br), L is a volatile ligand (e.g., alkylethylenediamine, or Cp), a is 1 to 5, b is 1 to 5, and c is 1 to 5. For example, the metal oxyhalide can include MoOCl4, MoO2Cl2, WOCl4, or WO2Cl2.

[0065] In yet another embodiment, the halogenating agent may be an organic halogenating agent. For example, the halogenating agent may be thionyl chloride (SOCl), methanesulfonyl chloride (CHSOCl), trichloromethanesulfonyl chloride (CClSOCl), 4-toluenesulfonyl chloride (tosyl chloride), oxalyl chloride (ClCOCOCl), tert-butyl hypochlorite ((CH)COCl), N-chlorophthalimide, 1,3-dichloro-5,5-dimethylhydantoin, trimethylsilyl chloride, HCl, Cl, PCl, may include BCl3, HBr, Br2, CCl3Br, CBr4, 1,2-dibromo-1,1,2,2-tetrachloroethane (Cl2CBrCBrCl2), BBr3, PBr3, N-bromosuccinimide, N-bromoacetamide, 2-bromo-2-cyano-N,N-dimethylacetamide, 1,3-dibromo-5,5-dimethylhydantoin, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, or trimethylsilyl bromide.

[0066] In one embodiment, the halogenating agent may be diluted with an inert gas. For example, an inert gas such as Ar, N2, or He may be used to dilute the halogenating agent. In other embodiments, a gas such as O2, N2, CO2, H2, D2, HO, DO, Ar, He, Cl2, Br2, HCl, HBr, CH4, THMA-Me (where Me includes Sn, Zr, Al, Hf, Cr, Ta, Ru, Mo, Te, etc.), or a combination thereof, may also be mixed with the halogenating agent. In one embodiment, the pressure may be between about 1 torr and about 100 torr. In certain embodiments, the pressure may be between about 5 torr and about 10 torr. In additional embodiments, the gas flow rate may be between 1 sccm and 2,000 sccm, and the pressure may be between 1 mTorr and 500 mTorr. For example, the temperature may vary between about -90°C and about 350°C. In certain embodiments, the temperature can vary between about −90° C. and about −60° C. In one embodiment, the source power can range between 0 W and 3,000 W using an ICP tool, a CCP tool, or a TCP tool. In one embodiment, the bias power can be between 0 W and 1,000 W, for example, at a frequency of about 13 MHz or about 2 MHz.

[0067] In one embodiment, step 434 may be performed through the use of two or more sub-steps, similar to the embodiment described in more detail above. For example, the first and second sub-steps may include different processing parameters, such as, but not limited to, duration, pressure, temperature, gas ratio, etc. In other embodiments, the sub-steps may be looped for any number of cycles to complete step 434.

[0068] In one embodiment, process 430 may continue with step 435, which includes purging the vacuum chamber with an inert purge. In one embodiment, the purging process removes any by-products and unreacted halogenating agent.

[0069] In one embodiment, process 430 may continue with step 436, which includes vaporizing the ligand into a vacuum chamber. In one embodiment, the ligand is vaporized into non-volatile product 562. U ' to produce volatile by-products, i.e., vaporized ligand and non-volatile products 562 U The reaction between the ' and the non-exposed regions is removed from the substrate 561 as shown in FIG. 5C. The non-volatile product is then released into the exposed regions 562. E When the exposed region is generated from the substrate 561, the exposed region can be removed from the substrate 561. In one embodiment, the ligand is a protonated ligand such as an amine. In one embodiment, the ligand can be diluted with an inert gas such as Ar, N, or He. In one embodiment, the volatile by-products can be a compound having the formula MX x L y or MO x X y L z where M is a metal or metalloid (e.g., Mo, W, Ta, Nb, Sn, V, Ti, or Si), X is a halide (e.g., Cl or Br), L is a volatile ligand (e.g., an amine), x is 1-5, y is 1-5, and z is 1-5.

[0070] In one embodiment, the pressure can be between about 1 torr and about 100 torr. In a specific embodiment, the pressure can be between about 5 torr and about 10 torr. In additional embodiments, the gas flow rate can be between 1 sccm and 2,000 sccm, and the pressure can be between 1 mTorr and 500 mTorr. In one embodiment, the substrate 561 can be temperature controlled during step 436. For example, the temperature can vary between about -90°C and about 350°C. In a specific embodiment, the temperature can vary between about -90°C and about -60°C. In one embodiment, the source power can range between 0 W and 3,000 W using an ICP tool, a CCP tool, or a TCP tool. In one embodiment, the bias power can be between 0 W and 1,000 W, for example, at a frequency of about 13 MHz or about 2 MHz.

[0071] In one embodiment, step 436 may be performed through the use of two or more sub-steps, similar to the embodiment described in more detail above. For example, the first and second sub-steps may include different processing parameters, such as, but not limited to, duration, pressure, temperature, gas ratio, etc. In other embodiments, the sub-steps may be looped for any number of cycles to complete step 436.

[0072] In one embodiment, process 430 may continue with step 437, which includes purging the vacuum chamber. Purging with an inert gas may remove volatile by-products and vaporized residual ligands.

[0073] In one embodiment, steps 434-437 may define one cycle. U This cycle can be repeated any number of times to completely (or substantially) remove the halogenated compound. For example, the cycle can include a sequence including a pulse introducing a vaporized halogenated agent into the vacuum chamber, followed by an inert purge, followed by a pulse introducing a vaporized ligand into the vacuum chamber, followed by an inert purge. In other embodiments, a single cycle can be used. In such an embodiment, a soak of the vaporized halogenated agent can be introduced into the vacuum chamber, followed by an inert purge, followed by a soak of the vaporized ligand into the vacuum chamber, followed by an inert purge.

[0074] Generally, exposed areas 562 of the photoresist E unexposed areas 562 of the photoresist U It has been shown that the etch selectivity of the photoresist increases with increasing pressure. Furthermore, generally, increasing the substrate temperature during one or more of steps 434-437 increases the etch selectivity of the photoresist in the exposed regions 562. E unexposed areas 562 of the photoresist U It has been shown that the etching selectivity of

[0075] 6, a flow chart illustrating a process 640 for patterning a metal-oxo photoresist is shown, according to an embodiment of the present disclosure. Figures 7A-7B are corresponding cross-sectional views illustrating various processing steps in process 640. In one embodiment, process 640 may be similar to process 220, except that the halogenating agent is replaced with a vaporized organic acid. That is, the organic acid is vaporized into a vacuum chamber, where it reacts with either the unexposed or exposed regions of the metal-oxo photoresist to generate volatile by-products.

[0076] In one embodiment, process 640 may begin with step 641, which includes providing a substrate with a metal-oxo photoresist. In one embodiment, the substrate and metal-oxo photoresist may be substantially similar to the substrate and metal-oxo photoresist described above with respect to step 221 of process 220.

[0077] In one embodiment, process 640 may continue with step 642, which includes exposing portions of the metal oxo photoresist to form exposed and unexposed regions. In an embodiment, the exposure process of step 642 may be substantially similar to the exposure process of step 222 of process 220. FIG. 7A illustrates a substrate 761, a photoresist 762, and a photoresist 762. E and the photoresist 762 U FIG.

[0078] In one embodiment, process 640 may continue with step 643, which includes placing the substrate in a vacuum chamber. The vacuum chamber used in process 640 may be substantially similar to the vacuum chamber used in process 220.

[0079] In one embodiment, process 640 may continue with step 644, which includes vaporizing an organic acid in a vacuum chamber. In one embodiment, the organic acid is vaporized in unexposed regions 762. U or exposure area 762 EThe organic acid reacts with either the organic acid or the unexposed region 762 to form volatile by-products. U The reaction between the substrate 761 and the unexposed region 762 U is removed (as shown in FIG. 7B), or the exposed area 762 is treated with an organic acid. E The reaction between the substrate 761 and the exposed region 762 E is removed.

[0080] In one embodiment, the organic acid can be a carboxylic acid having the formula RCO2H. For example, R can be H, CH3, tBu, or iPr. In one embodiment, the by-product of the reaction is a volatile carboxylate salt. For example, a carboxylate can have the formula M(RCO2). x where M is the metal from the metal oxo photoresist and R is the R used in the organic acid.

[0081] In one embodiment, the organic acid may be diluted with an inert gas. For example, an inert gas such as Ar, N2, or He may be used to dilute the organic acid. In other embodiments, O2, N2, CO2, H2, D2, H2O, D2O, Ar, He, Cl2, Br2, HCl, HBr, CH4, 、 Gases such as THMA-Me (where Me includes Sn, Zr, Al, Hf, Cr, Ta, Ru, Mo, Te, etc.), or combinations thereof, can also be mixed with organic acids. Generally, the exposed areas 762 of the photoresist are E unexposed areas 762 of the photoresist U The etch selectivity of the etched silicon dioxide has been shown to increase with increasing pressure. In one embodiment, the pressure can be between about 1 torr and about 100 torr. In a particular embodiment, the pressure can be between about 5 torr and about 10 torr.

[0082] In one embodiment, the substrate 761 may be temperature controlled during step 644. For example, the temperature may vary between about −90° C. and about 350° C. In a particular embodiment, the temperature may vary between about −90° C. and about −60° C. In one embodiment, the source power may range between 0 W and 3,000 W using an ICP tool, a CCP tool, or a TCP tool. In one embodiment, the bias power may be between 0 W and 1,000 W, for example, at a frequency of about 13 MHz or about 2 MHz.

[0083] In one embodiment, step 644 may be performed through the use of two or more sub-steps, similar to the embodiment described in more detail above. For example, the first and second sub-steps may include different processing parameters, such as, but not limited to, duration, pressure, temperature, gas ratio, etc. In other embodiments, the sub-steps may be looped for any number of cycles to complete step 644.

[0084] In one embodiment, process 640 may continue with step 645, which includes purging the vacuum chamber. Purging the vacuum chamber removes by-products from the reaction in step 644 from the vacuum chamber. In one embodiment, step 644 may be performed as a soak followed by a single purge in step 645. In an alternative embodiment, steps 644 and 645 may define a cycle including a pulse of organic acid followed by a purge. In such an embodiment, photoresist 762 U Multiple cycles can be repeated to remove the unexposed areas.

[0085] Therefore, the embodiments described herein include a thermal vapor process for developing the metal-oxo photoresist. As such, the embodiments disclosed herein may not require a vacuum chamber capable of generating a plasma. Eliminating the plasma process also reduces damage to the metal-oxo photoresist. This is particularly beneficial when the photoresist thickness is thin (e.g., photoresist thickness of about 15 nm or less). When the photoresist thickness is thin, plasma damage can cause LER / LWR defects or even line pattern destruction when transferring the pattern to an underlying layer.

[0086] Additionally, wet chemical reactions are avoided, and by-products produced by the reactions disclosed herein can be destroyed in abatement systems common in the semiconductor manufacturing industry, thereby significantly reducing waste streams. Additionally, because gas-phase processes do not use wet chemical reactions, defects and impurities in the final developed metal-oxo photoresist can be reduced, especially at small feature sizes.

[0087] 8A is a schematic diagram of a vacuum chamber configured to develop unexposed areas of a metal-oxo photoresist, according to one embodiment of the present disclosure. Vacuum chamber 800 includes a grounded chamber 805. In one embodiment, chamber 805 can be temperature-controlled; that is, the walls of chamber 805 can be actively cooled or heated during the processes disclosed herein. Substrate 810 is loaded through opening 815 and positioned on temperature-controlled pedestal 820.

[0088] Process gases are supplied to the interior of the chamber 805 from gas sources 844 through respective mass flow controllers 849. In certain embodiments, a gas distribution plate 835 is provided for supplying process gases 844, such as, for example, halogenating agents, ligands, organic acids, and / or inert gases. The chamber 805 is evacuated by an exhaust pump 855.

[0089] Vacuum chamber 800 is controlled by a controller 870. Controller 870 may include a CPU 872, a memory 873, and an I / O interface 874. CPU 872 may perform processing operations within vacuum chamber 800 according to instructions stored in memory 873. For example, one or more processes, such as processes 220, 430, and 740 described above, may be performed within the vacuum chamber by controller 870.

[0090] Although vacuum chamber 800 is described above as not having features suitable for forming a plasma within the chamber, it should be understood that embodiments of the present disclosure may be practiced in a vacuum chamber 800 capable of generating a plasma within the chamber.

[0091] 8B, a top view schematic of a cluster tool 800 is shown, according to an embodiment. In one embodiment, the cluster tool 800 may include a load port 892. The load port 892 may be configured to accept one or more front-opening unified pods (FOUPs) containing a plurality of substrates 861. The substrates 861 may be retrieved by a robot 895 positioned within a central transfer chamber of the cluster tool 800. The robot 895 may distribute the substrates 861 between an aligner 896 and one or more processing chambers 890. The processing chambers 890 may include a vacuum chamber for performing dry deposition and / or dry development processes of a metal-oxo layer on the substrates 861, similar to the embodiments described in more detail above. For example, a first chamber 890 may deposit a metal oxo resist on the substrate 861, a second chamber 890 may expose the metal oxo resist to EUV radiation to form a latent image in the metal oxo resist, and a third chamber 890 may be used to pre-treat and / or post-treat the metal oxo resist. Chamber 890 may also be used to develop the metal oxo resist. In some embodiments, cluster tool 800 may further include a chamber for depositing an underlayer. Cluster tool 800 may further include a chamber for performing a post-exposure bake process after an EUV exposure tool exposes the metal oxo resist to form a latent image in the metal oxo resist. In this manner, the entire process (from deposition to final post-treatment) may be performed in a single processing environment (e.g., tool 800).

[0092] FIG. 9 illustrates a schematic diagram of a machine in the exemplary form of a computer system 900 within which a set of instructions for causing the machine to perform any one or more of the methodologies described herein may be executed. In alternative embodiments, the machine may be connected (e.g., networked) to other machines in a local area network (LAN), an intranet, an extranet, or the Internet. The machine may operate as a server or a client machine in a client-server network environment, or as a peer machine in a peer-to-peer (or distributed) network environment. The machine may be a personal computer (PC), a tablet PC, a set-top box (STB), a personal digital assistant (PDA), a mobile phone, a web appliance, a server, a network router, switch, or bridge, or any machine capable of executing a set of instructions (sequential or other) that specify actions to be performed by the machine. Furthermore, while only a single machine is illustrated, the term "machine" is intended to include any collection of machines (e.g., computers) that individually or jointly execute a set of instructions (or sets) to perform any one or more of the methodologies described herein.

[0093] The exemplary computer system 900 includes a processor 902, a main memory 904 (e.g., read-only memory (ROM), flash memory, dynamic random access memory (DRAM) (e.g., synchronous DRAM (SDRAM) or Rambus DRAM (RDRAM)), etc.), a static memory 906 (e.g., flash memory, static random access memory (SRAM), MRAM, etc.), and a secondary memory 918 (e.g., a data storage device, etc.), which communicate with each other via a bus 930.

[0094] Processor 902 represents one or more general-purpose processing devices, such as a microprocessor, a central processing unit, or the like. More specifically, processor 902 may be a complex instruction set computing (CISC) microprocessor, a reduced instruction set computing (RISC) microprocessor, a very long instruction word (VLIW) microprocessor, a processor implementing other instruction sets, or a processor implementing a combination of instruction sets. Processor 902 may also be one or more special-purpose processing devices, such as an application-specific integrated circuit (ASIC), a field-programmable gate array (FPGA), a digital signal processor (DSP), a network processor, or the like. Processor 902 is configured to execute processing logic 926 for performing the operations described herein.

[0095] Computer system 900 may further include a network interface device 908. Computer system 900 may also include a video display unit 910 (e.g., a liquid crystal display (LCD), a light emitting diode display (LED), or a cathode ray tube (CRT)), an alphanumeric input device 912 (e.g., a keyboard), a cursor control device 914 (e.g., a mouse), and a signal generation device 916 (e.g., a speaker).

[0096] The secondary memory 918 may include a machine-accessible storage medium (or more specifically, a computer-readable storage medium) 932 having stored thereon one or more sets of instructions (e.g., software 922) that embody any one or more of the methods or functions described herein. The software 922 may also reside, completely or at least partially, within the main memory 904 and / or the processor 902 during execution by the computer system 900. The main memory 904 and the processor 902 also constitute machine-readable storage media. The software 922 may further be transmitted or received over the network 920 via the network interface device 908.

[0097] While the exemplary embodiment depicts machine-accessible storage medium 932 as a single medium, the term "machine-readable storage medium" should be interpreted to include a single medium or multiple media (e.g., a centralized or distributed database, and / or associated caches and servers) that store one or more sets of instructions. The term "machine-readable storage medium" should also be interpreted to include any medium capable of storing or encoding a set of instructions that are executed by a machine, causing the machine to perform any one or more of the methodologies of the present disclosure. Accordingly, the term "machine-readable storage medium" should be interpreted to include, but is not limited to, solid-state memory, optical media, and magnetic media.

[0098] According to one embodiment of the present disclosure, a machine-accessible storage medium stores instructions that cause a data processing system to perform a method for developing metal-oxo photoresist on a substrate using a vapor-phase process. The method includes exposing the metal-oxo photoresist to light to provide exposed and unexposed regions, and placing the substrate containing the exposed photoresist in a vacuum chamber. In one embodiment, a gas that reacts with the unexposed regions of the photoresist is vaporized in the vacuum chamber. For example, the reactive gas may include one or more of a halogenating agent, a ligand, and an organic acid. The reactive gas reacts with the unexposed regions of the metal-oxo photoresist to form volatile by-products. The by-products may be removed from the chamber by an inert gas purge.

[0099] Thus, a method for developing metal-oxo photoresists using a gas phase process has been disclosed.

Claims

1. 1. A method for developing a photopatterned metal-oxo photoresist, comprising: pretreating the photopatterned metal-oxo photoresist using a pretreatment process; developing the photo-patterned metal-oxo photoresist using a thermal dry development process to selectively remove portions of the photo-patterned metal-oxo photoresist and form a resist mask, the thermal dry development process comprising: A first sub-step, and a second sub-step, wherein the first sub-step is different from the second sub-step; developing the photopatterned metal-oxo photoresist, post-treating the resist mask using a post-treatment process; A method comprising:

2. 2. The method of claim 1, wherein the first sub-step has a first duration that is different from a second duration of the second sub-step.

3. The method of claim 2 , wherein the first duration is greater than or equal to 60 seconds and the second duration is less than or equal to 30 seconds.

4. 10. The method of claim 1, wherein the first sub-step has a first pressure and the second sub-step has a second pressure different from the first pressure.

5. 5. The method of claim 4, wherein the first pressure and the second pressure are between 20 mTorr and 350 mTorr.

6. 2. The method of claim 1, wherein the first sub-step has a first temperature and the second sub-step has a second temperature different from the first temperature.

7. 7. The method of claim 6, wherein the first temperature and the second temperature are between -90°C and 350°C.

8. 2. The method of claim 1, wherein the first sub-step has a first gas ratio and the second sub-step has a second gas ratio that is different from the first gas ratio.

9. 9. The method of claim 8, wherein the first gas ratio and the second gas ratio are a ratio of HBr to Ar.

10. repeating the first sub-step and the second sub-step multiple times; The method of claim 1 further comprising:

11. The method of claim 1 , wherein the pre-treatment process and the post-treatment process include a thermal treatment, an irradiation treatment, and / or a plasma treatment.

12. The method of claim 11 , wherein the post-treatment process is the same as the pre-treatment process.

13. The method of claim 11 , wherein the post-treatment process is different from the pre-treatment process.

14. The method of claim 1 , wherein the thermal dry development process includes a development chemistry comprising a halogenated agent and an inert gas.

15. The developing chemistry is ２ , N ２ , CO ２ , CO, H ２ , D ２ , H ２ O.D. ２ O, Ar, He, Cl ２ ,Br ２ , HCl, HBr, CH ４ , TDMA‐Me, and NH ４ 15. The method of claim 14, comprising at least one gas selected from the group consisting of Cl.

16. 1. A semiconductor processing tool comprising: a transfer chamber, the transfer chamber having a substrate handling robot disposed therein; a first processing chamber fluidly coupled to the transfer chamber, the first processing chamber configured to deposit a metal oxo resist on a substrate using a dry deposition process; a second processing chamber fluidly coupled to the transfer chamber, the second processing chamber configured to pre-treat or post-treat the metal oxo resist using a thermal treatment, an irradiation treatment, and / or a plasma treatment; a third processing chamber fluidly coupled to the transfer chamber, the third processing chamber configured to develop the metal oxo resist using a dry development process, the dry development process comprising: A first sub-step, and a second sub-step different from the first sub-step; a third processing chamber including:

1. A semiconductor processing tool comprising:

17. an extreme ultraviolet (EUV) exposure tool coupled to the transfer chamber, the EUV exposure tool exposing the metal oxo resist to form a latent image in the metal oxo resist; The semiconductor processing tool of claim 16 further comprising:

18. a fourth processing chamber coupled to the transfer chamber, the fourth processing chamber configured to deposit an underlayer on the substrate, the underlayer comprising a high-Z metal oxide; The semiconductor processing tool of claim 16 further comprising:

19. 17. The semiconductor processing tool of claim 16, further comprising a fifth processing chamber coupled to the transfer chamber, the fifth processing chamber configured to perform a post-exposure bake process after the EUV exposure tool exposes the metal oxo resist to form the latent image in the metal oxo resist.

20. 17. The semiconductor processing tool of claim 16, wherein the dry development process is carried out at a temperature between −90° C. and 350° C. with developer chemistry that renders a portion of the metal-oxo photoresist volatile.

Images