Bimodal photoresist

Abstract

Embodiments disclosed herein include a method of patterning a metal oxo photoresist. In one embodiment, the method includes depositing a metal oxo photoresist on a substrate, processing the metal oxo photoresist in a first process, exposing the metal oxo photoresist by EUV exposure to form an exposed region and an unexposed region, processing the exposed metal oxo photoresist in a second process, and developing the metal oxo photoresist.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of priority of U.S. Patent Application No. 17 / 862,283, filed on July 11, 2022, the entire content of which is incorporated herein by reference.

[0002] Field Embodiments of the present disclosure relate to the field of semiconductor processing, and more particularly, to a method of depositing a positive photoresist layer on a substrate using dry deposition and oxidation processes.

Background Art

[0003] Lithography has been used for decades in the semiconductor industry to create 2D and 3D patterns in microelectronic devices. The lithography process includes spin - on deposition of a film (photoresist), irradiation (exposure) of the film with a selected pattern by an energy source, and removal (etching) of the exposed (positive - type) or unexposed (negative - type) regions of the film by dissolution in a solvent. Baking is performed to remove the remaining solvent.

[0004] The photoresist must be a radiation - sensitive material, and upon irradiation, a chemical transformation occurs in the exposed portion of the film, which can change the solubility between the exposed and unexposed regions. Using such a change in solubility, the exposed or unexposed regions of the photoresist are removed (etched). The photoresist is then developed, and the pattern can be transferred to the underlying thin film or substrate by etching. After the pattern is transferred, the remaining photoresist is removed, and by repeating this process multiple times, 2D and 3D structures used in microelectronic devices can be obtained.

[0005] Several characteristics are important in the lithography process. Such important characteristics include sensitivity, resolution, lower line-edge roughness (LER), etching resistance, and the ability to form thinner layers. The higher the sensitivity is, the lower the energy required to change the solubility of the film during deposition. This can increase the efficiency in the lithography process. Resolution and LER determine how narrow features can be achieved by the lithography process. For pattern transfer to form deep structures, materials with higher etching resistance are required. Also, the higher the etching resistance of the material, the thinner the film that can be obtained. Thinner films increase the efficiency of the lithography process.

Summary of the Invention

[0006] Embodiments disclosed herein include a method of patterning a metal oxo photoresist. In one embodiment, the method includes depositing a metal oxo photoresist on a substrate, processing the metal oxo photoresist in a first process, exposing the metal oxo photoresist by EUV exposure to form an exposed region and an unexposed region, processing the exposed metal oxo photoresist in a second process, and developing the metal oxo photoresist.

[0007] In one embodiment, a method of depositing and patterning a photoresist is provided. In one embodiment, the method includes depositing a photoresist on a substrate using a dry deposition process, where the photoresist contains a metal oxo material, exposing the photoresist by EUV exposure to form an exposed region and an unexposed region, and developing the photoresist by removing the exposed region or the unexposed region.

[0008] An embodiment is depositing a photoresist on a substrate using a dry deposition process, depositing a photoresist where the photoresist is a metal oxo material, exposing the photoresist by EUV exposure to form an exposed region and an unexposed region, developing the photoresist by removing the exposed region or the unexposed region to form an opening that penetrates the photoresist, and etching the substrate through the opening of the photoresist, and may further include a method of patterning the substrate.

Brief Description of Drawings

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DETAILED DESCRIPTION OF THE INVENTION

[0010] This specification describes a method of depositing a positive photoresist on a substrate using a dry deposition process and an oxidation treatment process. In the following description, numerous specific details, such as chemical vapor deposition (CVD) processes and atomic layer deposition (ALD) processes, as well as the types of materials for depositing the positive photoresist, are presented to provide a complete understanding of the embodiments of the present disclosure. It will be apparent to those skilled in the art that the embodiments of the present disclosure can be practiced without these specific details. In other instances, well-known aspects, such as the manufacture of integrated circuits, are not described in detail so as not to unnecessarily obscure the embodiments of the present disclosure. Further, it should be understood that the various embodiments shown in the figures are exemplary representations and are not necessarily drawn to scale.

[0011] To explain the background, photoresist systems used in extreme ultraviolet (EUV) lithography have the drawback of being inefficient. That is, existing photoresist material systems for EUV lithography require high application amounts to provide the solubility switching necessary to enable the development of the photoresist material. Conventionally, carbon-based films, commonly referred to as organic chemically amplified photoresists (CARs), have been used as photoresists. However, recently, organic-inorganic hybrid materials (metal-oxo) have been used as photoresists for extreme ultraviolet (EUV) radiation. Such materials typically contain a metal (e.g., Sn, Hf, Zr), oxygen, and carbon. The conversion from deep ultraviolet (DUV) to EUV in the lithography industry makes it easier to obtain narrow features with a high aspect ratio. Metal-oxo-based organic-inorganic hybrid materials have been shown to exhibit lower line edge roughness (LER) and higher resolution required for forming narrow features. Also, such films have the properties of higher sensitivity and etching resistance and can be implemented to produce relatively thin films.

[0012] Currently, metal-oxo photoresists are deposited by a wet spin-on method. A post-baking process is required to remove any remaining solvent from the film and to stabilize the film. Also, the wet method can generate large amounts of wet waste that are desirable to eliminate in the industry. Photoresist films deposited by the spin-on method often present non-uniformity problems. According to embodiments of the present disclosure, a process for the vacuum deposition of metal-oxo positive photoresists is described herein to address one or more of the above problems.

[0013] According to one or more embodiments of the present disclosure, dry deposition techniques and oxidation treatment techniques for forming positive photoresist films are described herein. In some embodiments, thermal chemical vapor deposition (CVD) is used for the dry deposition of positive photoresist films. In other embodiments, plasma-enhanced chemical vapor deposition (PECVD) is used for the dry deposition of positive photoresist films. In one embodiment, the dry deposition process is not a condensation process. In another embodiment, the dry deposition process is a condensation process. In one embodiment of such a condensation process, the wafer / substrate is maintained at a temperature at which the metal precursor can condense. Condensation of the precursor can be achieved by maintaining the wafer temperature at a temperature lower than the precursor ampoule temperature.

[0014] FIG. 1A is a cross-sectional view showing various steps in a patterning process using a positive photoresist material formed by the process described herein according to an embodiment of the present disclosure.

[0015] As shown in part (a) of FIG. 1A, the starting structure 100 includes a positive photoresist layer 104 on a substrate or lower layer 102. In one embodiment, the positive photoresist layer 104 is deposited using dry deposition. In part (b) of FIG. 1A, the starting structure 100 is irradiated 106 at selected locations to form an irradiated photoresist layer 104A having an irradiated region 105B and a non-irradiated region 105A. In part (c) of FIG. 1A, a removal or etching process 108 is used to provide a developed photoresist layer in the non-irradiated region 105A. In part (d) of FIG. 1A, an etching process 110 that uses the non-irradiated region 105A as a mask is used to pattern the substrate or lower layer 102 to form a patterned substrate or patterned lower layer 102A including an etching feature 112.

[0016] As shown in FIG. 1A, the positive photoresist 104 is a radiation-sensitive material, and when irradiated, a chemical conversion occurs in the exposed portion of the film, which can cause a change in solubility between the exposed region and the non-exposed region. The change in solubility is used to remove (etch) the exposed region of the positive photoresist. The positive photoresist is then developed, and the pattern can be transferred by etching to the underlying thin film or substrate. After the pattern is transferred, the remaining positive photoresist is removed. This process can be repeated many times to fabricate 2D and 3D structures, for example, for use in microelectronic devices.

[0017] FIG. 1B is a cross-sectional view showing various steps in a patterning process using a negative photoresist material formed by the process described herein according to an embodiment of the present disclosure.

[0018] As shown in part (a) of FIG. 1B, the starting structure 100 includes a negative photoresist layer 103 on a substrate or lower layer 102. In one embodiment, the negative photoresist layer 103 is deposited using dry deposition. In part (b) of FIG. 1B, the starting structure 100 is irradiated 106 at selected locations to form an irradiated photoresist layer 103A having an irradiated region 105B and a non-irradiated region 105A. In part (c) of FIG. 1B, a removal or etching process 108 is used to provide a developed photoresist layer in the irradiated region 105B. In part (d) of FIG. 1B, an etching process 110 using the irradiated region 105B as a mask is used to pattern the substrate or lower layer 102 to form a patterned substrate or patterned lower layer 102A including an etching feature 112.

[0019] As shown in FIG. 1B, the negative photoresist 103 must be a radiation-sensitive material, and when irradiated, a chemical conversion occurs in the exposed portion of the film, which can cause a change in solubility between the exposed region and the non-exposed region. The change in solubility is used to remove (etch) the non-exposed region of the negative photoresist. The negative photoresist is then developed, and the pattern can be transferred by etching to the underlying thin film or substrate. After the pattern is transferred, the remaining negative photoresist is removed. This process can be repeated many times to fabricate 2D and 3D structures, for example, for use in microelectronic devices.

[0020] As described in more detail below, both positive resists and negative resists can be made into metal oxo photoresist films. In some cases, the same material system can be used for both positive and negative resists. In particular, the chemical nature of the developer used will determine whether the photoresist film is a negative resist or a positive resist. For example, for a negative resist, the developer is an organic solvent, and for a positive resist, the developer is an aqueous basic medium. That is, positive or negative resists can be formed using dry deposition with EUV exposure.

[0021] To explain the background, the lithography industry is accustomed to operating with positive photoresist (PR) materials. However, many metal-oxo PR materials are negative photoresists. Positive photoresists have advantages such as higher resolution, dryness, dry etching resistance, and contrast compared to negative photoresists. According to one or more embodiments of the present disclosure, a method for manufacturing a positive PR material by dry deposition such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) by a dry deposition method is described.

[0022] In one embodiment, an Sn precursor is used in the vacuum deposition process of the Sn oxo PR material. The SnOC film can be an attractive photoresist film due to its high sensitivity to exposure. Generally, the TiN-oxo photoresist film contains Sn-O and Sn-C bonds in the SnOC network. When exposed (e.g., UV / EUV), the Sn-C bonds are broken and the proportion of carbon in the film decreases. This causes selective etching during the development process. Sn-C can be incorporated into the film by using a metal precursor containing one or more Sn-C bonds. In one embodiment, the precursor described herein has Sn-C (where R contains C bonded to Sn) which is advantageous for exposure sensitivity, and has a ligand (L) that reacts with an oxidant (water as an example) to form a photoresist film. In one embodiment, the reactivity between the precursor and the oxidant can be adjusted by changing R and / or L on the Sn precursor. Also, the sensitivity can be adjusted by changing the R group in the precursor. In one embodiment, indium-oxo or TiN-indium-oxo films can also be used as positive photoresist films. The techniques described herein can be extended to many other metal-containing films. In this case, it should be noted that while specific attention is required for positive photoresist films, a similar material system can be used as a negative photoresist film. In particular, the choice of developer can determine whether a positive resist or a negative resist is obtained upon exposure (e.g., EUV exposure).

[0023] According to one embodiment of the present disclosure, a positive or negative photoresist is manufactured by using a specific type of R group in a metal precursor deposition method or a plasma-assisted deposition method. As an example, a phenyl group (R) (PhSn(NMe2)3) containing an Sn precursor can be used. After exposing the resist to UV under the atmosphere, the exposed area showed an acid moiety by FTIR. Then, the resist was immersed in an aqueous basic medium (e.g., sodium hydroxide (NaOH) or tetramethylammonium hydroxide (TMAH)) to develop the resist as a positive type. The acidic portion of the resist (exposed area) reacts with the basic NaOH and dissolves in the aqueous medium to yield a positive resist. Also, when Sn(nBu)4 was used for PECVD, a positive resist was obtained. Thus, a method for manufacturing a positive photoresist is described herein. In the opposite case (e.g., for a negative photoresist), the resist can be immersed in an organic solvent. The organic solvent can dissolve the unexposed area of the resist film. Thus, a method for manufacturing a negative resist is described herein.

[0024] In the first aspect, an R group with low radical stability is used. For example, radicals of R groups such as phenyl, alkenyl, and methyl have low stability (Sn-C→Sn·+C·). Figure 2A includes the general formula and specific examples of metal precursors suitable for use in the manufacture of positive or negative photoresist films according to embodiments of the present disclosure. In one embodiment, the two specific examples on the left can be used for thermal CVD, and the two on the right may require PECVD for the development process described later.

[0025] In the lithography industry, it is typically geared towards dealing with positive photoresists (PRs), and it should be understood that almost all new metal-oxo PRs are negative PRs. Positive PRs have advantages such as higher resolution, dryness, dry etching resistance, and contrast compared to negative PRs. However, metal-oxo PRs may require oxidation during or after exposure in order to behave as positive PRs. Here, a method of fabricating positive PRs using an oxidation process is described. It should be understood that the same or similar methods can be used for negative PR manufacturing as well.

[0026] In a second aspect, for the exposure environment, when the photoresist is exposed by an energy source (e.g., EUV), the exposure chamber (environment) can be in a state containing oxygen or an inert state. In one embodiment, the exposure is carried out under vacuum containing an oxygen source such as O2, H2O, CO2, CO, NO2, or NO. The repetition of EUV exposure and subsequent oxygen exposure can be between 1 and 100 times in one embodiment.

[0027] In a third aspect, post-annealing is carried out in an oxygen-containing environment. In one embodiment, the oxygen source is O3, NO2, NO, or O2, which can be used to form a plasma and / or can be used together with N2, Ar, or He. In one embodiment, the post-annealing is carried out at a temperature in the range of 25 to 200 degrees Celsius. In one embodiment, the post-annealing is carried out at a pressure of less than 200 torr. In a specific embodiment, the post-annealing is carried out using ozone (O3) as the oxygen source gas, at a temperature in the range of 25 to 250 degrees Celsius and at a pressure of less than 200 torr.

[0028] In a fourth aspect, a basic developer containing an inorganic base that can be prepared in water can be used, and the concentration and development time are adjustable. In one embodiment, the hydroxides of Groups 1 and 2 shown in FIG. 2B (e.g., NaOH, KOH), NH4OH, NaHCO3, NaCO3, N(CH3)4OH, or amines can be used.

[0029] In the fifth aspect, an organic solvent can be used to prepare a negative photoresist. The organic solvent can dissolve the less polar organic portion of the photoresist film (i.e., the unexposed region). Suitable organic solvents include, but are not limited to, 2-heptanone, MIBC, MINK, anisole, D-limonene, methyl benzoate, n-butyl acetate, GBL, and supercritical CO2.

[0030] In addition, Figure 2C includes specific metal precursors and a list of specific examples of those metal precursors. Materials having the general formula MR X L Y (where x = 0-6 and y = 0-6) are shown. The R component can include, for example, alkyl, alkenyl, alkynyl, aryl, carbene, or R groups containing silicon, germanium, and TiN. The L component can be a water-reactive ligand such as an amine or an alkoxide. The metal component can be any of those listed in Figure 2C. The material system described in Figure 2C can be used as an alternative to or in combination with that described in Figure 2A. In addition, it should be understood that there may be an overlap between the material system described in Figure 2A and the material system described in Figure 2C. In one embodiment, the oxidant co-reactant is selected from the group consisting of water, O2, N2O, NO, CO2, CO, ethylene glycol, alcohols (e.g., methanol, ethanol), peroxides (e.g., H2O2), and acids (e.g., formic acid and acetic acid).

[0031] According to the embodiments of the present disclosure, the first method, the chemical vapor deposition (CVD) method for forming a positive or negative photoresist includes the following. (A) One or more metal precursors of FIG. 2A and one or more oxidants listed above are vaporized into a vacuum chamber where the substrate wafer is maintained at a predetermined substrate temperature. The substrate temperature can be varied from 0°C to 500°C. The precursor / oxidant can be diluted with an inert gas such as Ar, N2, He when vaporized into the chamber. Due to the reactivity of the precursor and the oxidant, a metal-oxo film is deposited on the wafer. Vaporization into the chamber can be carried out simultaneously with all the precursors, or by alternately pulsing one or more metal precursors and one or more oxidants. This process is described as thermal CVD. (B) Plasma can also be turned on during this process. In this case, the process can be described as plasma enhanced (PE)-CVD. Examples of plasma sources are CCP, inductively coupled plasma, remote plasma, microwave plasma. (C) Deposition of the photoresist film can be carried out by thermal deposition followed by plasma treatment. In this case, the film is deposited thermally and then a plasma treatment step is carried out. The plasma treatment may include plasma from an inert gas such as Ar, N2, He, or those gases can be mixed with O2, CO2, CO, NO, NO2, H2O. The process can be run periodically, and the thermal deposition and subsequent plasma treatment can repeat this cycle or perform one plasma treatment (post-treatment) after the deposition part is completed. It is also possible to perform plasma treatment after PECVD. In any case, in one embodiment, post-annealing is carried out in an oxygen-containing environment. In one embodiment, the post-annealing is carried out using ozone (O3) as the oxygen source gas at a temperature in the range of 25 to 250 degrees Celsius and at a pressure of less than 200 torr.

[0032] In the second method, according to an embodiment of the present disclosure, the atomic layer deposition (ALD) method for forming a positive or negative photoresist includes the following. (A) Vaporize the metal precursor of FIG. 2A into a vacuum chamber where the substrate wafer is maintained at a predetermined substrate temperature. The substrate temperature can be varied from 0 to 500 °C. Next, purge with an inert gas to remove by-products and excess metal precursor. Then, vaporize one or more oxidants into the chamber. One or more oxidants react with the metal precursor absorbed on the surface. Next, apply an inert gas purge to remove by-products and unreacted oxidants. Repeat this cycle to obtain the desired thickness. The precursor or oxidant can be diluted with an inert gas such as Ar, N2, or He when vaporized into the chamber. This process is described as thermal ALD. By using this method and incorporating additional metal precursor pulsing into the ALD cycle, multiple metals can be incorporated into the film. Also, different oxidants can be pulsed after the first oxidant. (B) Plasma can be turned on during the pulsing of the oxidant, in which case the process can be described as PE-ALD. (C) Also, the deposition can be performed by thermal ALD followed by plasma treatment. In this case, the film is deposited thermally and then a plasma treatment step is performed. The plasma treatment can include plasma from an inert gas such as Ar, N2, or He, or those gases can be mixed with O2, CO2, CO, NO, NO2, or H2O. The process can be performed periodically, and X (X = 1 to 5000) thermal ALD cycles followed by plasma treatment can repeat the entire cycle the desired number of times, or a single plasma treatment can be performed after completing the deposition part. It is also possible to perform plasma treatment after PE-ALD. In any case, in one embodiment, post-annealing is performed in an oxygen-containing environment. In one embodiment, post-annealing is performed using ozone (O3) as the oxygen source gas at a temperature in the range of 25 to 250 °C and a pressure of less than 200 torr.

[0033] In a third approach, according to embodiments of the present disclosure, atomic layer deposition (ALD) or chemical vapor deposition (CVD) methods for forming positive or negative photoresists include providing a composition gradient across the entire film. As an example, the first few nanometers of the film have a different composition from the remainder of the film. The main part of the film can be optimized for dose, but target a different composition near the interface layer to change adhesion, sensitivity to EUV photons, and sensitivity to development chemistry, thereby controlling the profile after lithography (especially scum), and improving defects and resist collapse / lift-off. The gradation can be optimized according to the type of pattern, for example, optimized for pillars that require improved adhesion and line / space patterns where adhesion can be reduced to improve dose.

[0034] In one embodiment, the method of depositing a photoresist film described herein is a vacuum deposition method that does not use a wet method. The positive or negative photoresist described herein has advantages such as higher resolution, dry etching resistance, and contrast than negative photoresists.

[0035] Among the advantages of implementing one or more of the techniques described herein is that the deposition technique of the positive or negative photoresist film is a dry deposition technique and does not use a wet method. The wet method may produce a large amount of wet by-products that are preferably avoided. Also, spin-on (wet method) often leads to non-uniformity problems, which can be successfully addressed by the vacuum deposition method described herein. Also, the ratio of metal and carbon (C) in the film can be adjusted by the vacuum deposition method. In spin-on, the ratio of metal and C is often fixed in a given deposition system. The precursors used to deposit the positive or negative photoresist film under vacuum need to be volatile, and the precursors described herein are volatile based on the L and R structures. The dry deposition method may require a lower temperature than other vacuum deposition methods such as ALD or CVD. When the deposition is carried out at a low temperature, a relatively large amount of carbon can be retained in the film, which can be useful for patterning.

[0036] In one embodiment, the vacuum deposition process relies on a chemical reaction between a metal precursor and an oxidant. The metal precursor and the oxidant are vaporized into the vacuum chamber. In some embodiments, the metal precursor and the oxidant are provided together to the vacuum chamber. In other embodiments, the metal precursor and the oxidant are provided to the vacuum chamber by alternately pulsing. After a metal-oxo positive photoresist film having a desired thickness is formed, the process may be stopped. In one embodiment, optionally, a plasma treatment step may be performed after a metal-oxo positive photoresist film having a desired thickness is formed.

[0037] In one embodiment, a cycle including a pulse of metal precursor vapor and a pulse of oxidant vapor can be repeated multiple times to provide a metal-oxo-pos photoresist film having a desired thickness. In one embodiment, the order of the cycles can be switched. For example, the oxidant vapor can be pulsed first and the metal precursor vapor can be pulsed second. In one embodiment, the duration of the pulse of the metal precursor vapor can be substantially the same as the pulse duration of the oxidant vapor. In other embodiments, the pulse duration of the metal precursor vapor may be different from the pulse duration of the oxidant vapor. In one embodiment, the pulse duration can be between 0 seconds and 1 minute. In certain embodiments, the pulse duration can be between 1 second and 5 seconds. In one embodiment, each iteration of the cycle uses the same process gas. In other embodiments, the process gas may be changed between cycles. For example, the first cycle can utilize a first metal precursor vapor, and the second cycle can utilize a second metal precursor vapor. Subsequent cycles can alternately continue with the first metal precursor vapor and the second metal precursor vapor. In one embodiment, multiple oxidant vapors can similarly be used alternately between cycles. In one embodiment, any plasma treatment may be performed after all the cycles. That is, each cycle can include a pulse of metal precursor vapor, a pulse of oxidant vapor, and a plasma treatment. In an alternative embodiment, any plasma treatment may be performed after a plurality of cycles. In yet another embodiment, any plasma treatment may be performed after completion of all the cycles (i.e., as a post-treatment).

[0038] Metal-oxo positive and negative photoresist films using the dry deposition process and oxidation process as described in the above embodiments can achieve significant advantages over wet chemical methods. One such advantage is the elimination of wet by-products. In the dry deposition process, liquid waste is eliminated and the removal of by-products is simplified. Additionally, the dry deposition process can provide more uniform positive and negative photoresist layers. Uniformity in this sense can refer to the uniformity of the thickness across the wafer and / or the uniformity of the distribution of the metal component of the metal-oxo film.

[0039] In addition, the use of the dry deposition process provides the ability to finely tune the ratio of metal in the positive or negative photoresist and the composition of the metal in the positive or negative photoresist. The ratio of metal can be adjusted by increasing / decreasing the flow rate of the metal precursor into the vacuum chamber and / or by adjusting the length of the metal precursor / oxidant pulse. The use of the dry deposition process can also include multiple different metals in the metal-oxo film. For example, a single pulse flowing two different metal precursors can be used, or alternating pulses of two different metal precursors can be used.

[0040] Furthermore, metal-oxo positive and negative photoresists formed using the dry deposition process have been shown to be more resistant to post-exposure thickness reduction. Without being bound to a particular mechanism, the resistance to thickness reduction is thought to be at least partially due to a reduction in carbon loss upon exposure.

[0041] FIG. 3 shows a schematic diagram of a chemical reaction for forming a negative-type metal oxo photoresist according to an embodiment. As shown, the metal precursor 320 can be supplied to a chamber (e.g., a vacuum chamber). At 321, an oxygen source as described in more detail above can be supplied to the chamber to form the metal oxo photoresist 322. As shown, the metal oxo film can include a metal center (e.g., Sn) that binds to oxygen at a site previously occupied by the ligand L. In step 323, the negative-type photoresist film can be exposed (e.g., by EUV exposure). Upon exposure, a chemical reaction occurs in which the reactive group R in the exposed region 325 is replaced by oxygen. That is, the proportion of carbon in the exposed region is reduced. The cross-linking bonds in the exposed region can be more numerous than in the unexposed region. In the unexposed region 324, the chemical structure can maintain the organic portion. Thus, the polarity of the unexposed region 324 is lower than that of the exposed region 325. The organic nature of the unexposed region allows the unexposed region 324 to dissolve in an organic solvent as described in more detail above.

[0042] FIG. 4 shows a schematic diagram of a chemical reaction for forming a positive-type metal oxo photoresist according to an embodiment. As shown, the metal precursor 420 can be supplied to a chamber containing an oxygen source 421. A reaction between the metal precursor 420 and the oxygen source 421 forms the metal oxo film 422. In step 423, the metal oxo film 422 is exposed (e.g., by EUV exposure) to produce an exposed region 425 and an unexposed region 424. Due to the organic nature of the unexposed region 424, the unexposed region 424 does not dissolve in an aqueous basic medium that dissolves the exposed region 425.

[0043] That is, the choice of developer can allow for the formation of either a negative-type resist or a positive-type resist. The material systems used for negative-type and positive-type resists can be substantially similar to each other. Thus, a single material system can be used flexibly to provide either a negative-type or a positive-type system. Therefore, the material systems disclosed herein are of increased value due to their ability to be used as either positive-type or negative-type resists.

[0044] FIG. 5 shows a process flow diagram of a process 580 for developing a metal oxo film according to one embodiment. In one embodiment, process 580 begins at step 581, which includes depositing a metal oxo photoresist on a substrate. In one embodiment, the metal oxo photoresist can be deposited by any of the processing steps described in more detail above. For example, CVD, PE-CVD, ALD, PE-ALD processes can be used to deposit a metal oxo film on a substrate. Dry deposition processes are described in detail herein, and two types of resist materials can optionally be deposited using a spin-on deposition process or other wet deposition process.

[0045] In one embodiment, process 580 continues to step 582, which includes processing the metal oxo photoresist. In one embodiment, the processing can be an annealing process. For example, annealing can be performed between 50°C and 200°C. Annealing can be performed in an inert environment or an oxidizing environment. For example, O2, O3, H2O, H2O2, or alcohol can be used as the annealing environment. The ambient environment can also be used for annealing. In some embodiments, the processing can include UV processing. The UV processing can be provided in addition to annealing or without annealing. The UV processing can include exposure to light having a wavelength between 172 nm and 900 nm at a power in the range of 1 mW to 400 W.

[0046] In one embodiment, process 580 may continue to step 583, which includes exposing the metal oxo photoresist to EUV exposure. The EUV exposure can form an exposed region and an unexposed region.

[0047] In one embodiment, process 580 may follow step 584, which includes treating the exposed metal oxo photoresist with post-exposure treatment. In one embodiment, the post-exposure treatment may include annealing. For example, the annealing temperature can be between 50°C and 300°C. The annealing can be carried out in an inert environment or an oxidizing environment (e.g., O2, O3, H2O 、 H2O2, or alcohol). In some embodiments, the ambient environment can be used for annealing. In some embodiments, the post-exposure treatment may include UV treatment. The UV treatment may be provided in addition to annealing or without annealing. The UV treatment may include exposure to light having a wavelength between 172 nm and 900 nm at a power in the range of 1 mW to 400 W.

[0048] In one embodiment, process 580 may follow step 585, which includes developing the metal oxo photoresist. In one embodiment, the metal oxo photoresist can be a positive-type film resist or a negative-type resist. For example, an organic solvent can be used to selectively dissolve the unexposed areas to form a negative-type resist, or an aqueous basic medium can be used to selectively dissolve the exposed areas to form a positive-type resist. In one embodiment, the temperature of the substrate can be maintained between -10°C and 90°C during the development process.

[0049] In one embodiment, process 580 may follow step 586, which includes treating the developed metal oxo photoresist with post-development treatment. In one embodiment, the post-development treatment may include annealing. For example, the annealing temperature can be between 50°C and 300°C. The annealing can be carried out in an inert environment or an oxidizing environment (e.g., O2, O3, H2O 、It can be carried out in H2O2 or alcohol. In some embodiments, the ambient environment can be used for annealing. In some embodiments, the post-exposure treatment can include a UV treatment. The UV treatment can be provided in addition to annealing or provided without annealing. The UV treatment can include exposure to light having a wavelength between 172 nm and 900 nm at a power in the range of 1 mW to 400 W.

[0050] In one embodiment, the vacuum chamber utilized in the dry deposition process is any suitable chamber capable of providing a pressure below atmospheric pressure. In one embodiment, the vacuum chamber can include a temperature control function for controlling the temperature of the chamber wall and / or for controlling the temperature of the substrate. In one embodiment, the vacuum chamber can also include a function for providing plasma inside the chamber. A more detailed description of a suitable vacuum chamber will be provided later with reference to FIG. 6. FIG. 6 is a schematic diagram of a vacuum chamber configured to perform dry deposition of a metal-oxo-posi type photoresist according to an embodiment of the present disclosure.

[0051] The vacuum chamber 600 includes a grounded chamber 605. The substrate 610 is loaded through the opening 615 and fixed to the temperature-controlled chuck 620. In one embodiment, the substrate 610 can be temperature-controlled during the dry deposition process. For example, the temperature of the substrate 610 can be between approximately -40 degrees Celsius and 200 degrees Celsius. In certain embodiments, the substrate 610 can be maintained at a temperature between room temperature and 150 °C.

[0052] Process gas is supplied from gas source 644 through respective mass flow controllers 649 into the interior of chamber 605. In some embodiments, gas distribution plate 635 distributes process gas 644 such as metal precursor, oxidant, and inert gas. Chamber 605 is evacuated via exhaust pump 655. In one embodiment, one or more of the process gases are stored / contained in one or more ampoules. In one embodiment, the dry deposition process is a chemical vapor condensation process, and the one or more ampoules are maintained at a temperature above the substrate temperature, for example, at a temperature 25 degrees Celsius or more above the substrate temperature in degrees Celsius.

[0053] When RF power is applied during processing of substrate 610, a plasma is formed above substrate 610 within the chamber processing region. Bias power RF generator 625 is connected to temperature-controlled chuck 620. Bias power RF generator 625 provides bias power to supply energy to the plasma as needed. Bias power RF generator 625 can have, for example, a low frequency between about 2 MHz and 60 MHz and, in certain embodiments, is in the 13.56 MHz band. In some embodiments, vacuum chamber 600 includes a third bias power RF generator 626 having a frequency in the approximately 2 MHz band that connects to the same RF match 627 as bias power RF generator 625. Source power RF generator 630 is connected through a match (not shown) to a plasma generating element (e.g., gas distribution plate 635) to provide source power to supply energy to the plasma. Source RF generator 630 can have, for example, a frequency between 100 and 180 MHz and, in certain embodiments, is in the 162 MHz band. Since the diameter of the substrate has evolved over time from 150 mm to 200 mm, 300 mm, etc., in the art it is common to normalize the source and bias power of a plasma etching system to the area of the substrate.

[0054] The vacuum chamber 600 is controlled by a controller 670. The controller 670 may include a CPU 672, a memory 673, and an I / O interface 674. The CPU 672 can execute a processing step inside the vacuum chamber 600 according to instructions stored in the memory 673. For example, one or more processes, such as the above-described processes 120 and 440, can be executed by the controller 670 in the vacuum chamber.

[0055] In another aspect, the embodiments disclosed herein include a processing tool that includes an architecture particularly suitable for optimizing dry deposition. For example, the processing tool may include a pedestal for supporting a temperature-controlled wafer. In some embodiments, the temperature of the pedestal can be maintained between approximately -40°C and approximately 200°C. Additionally, an edge purge flow and shadow ring may be provided around the column that supports the substrate. The edge purge flow and shadow ring prevent the positive photoresist from depositing along the edge or back side of the wafer. In one embodiment, the pedestal can provide any desired chucking architecture, such as, but not limited to, a vacuum chuck, a monopole chuck, or a bipolar chuck, depending on the operating regime of the processing tool.

[0056] In some embodiments, the processing tool may be suitable for deposition processes that do not use plasma. Alternatively, the processing tool may include a plasma source that enables plasma-enhanced operations. Further, it should be noted that the embodiments disclosed herein are particularly suitable for the deposition of metal-oxo positive photoresists for EUV patterning, but the embodiments are not limited to such a configuration. For example, the processing tools described herein are suitable for depositing any positive photoresist material for any type of lithography using a dry deposition process.

[0057] FIG. 7 shows a cross-sectional view of a processing tool 700 according to one embodiment. In one embodiment, the processing tool 700 may include a chamber 705. The chamber 705 can be any suitable chamber capable of supporting a sub-atmospheric pressure (e.g., a vacuum pressure). In one embodiment, an evacuation device (not shown) including a vacuum pump may be coupled to the chamber 705 to provide a sub-atmospheric pressure. In one embodiment, the chamber 705 can be sealed by a lid. For example, the lid may include a showerhead assembly 740. The showerhead assembly 740 can include a fluid path through which a processing gas and / or an inert gas can flow into the chamber 705. In some embodiments where the processing tool 700 is suitable for plasma-enhanced operations, the showerhead assembly 740 can be electrically coupled to an RF source and a matching circuit 750. In another embodiment, the tool 700 can be configured with an RF bottom feed architecture. That is, the pedestal 730 is connected to an RF source and the showerhead assembly 740 is grounded. In such an embodiment, the filtering circuit may remain connected to the pedestal. In one embodiment, the precursor gas is stored in an ampoule 799.

[0058] In one embodiment, a replaceable column for supporting the wafer 701 is provided in the chamber 705. In one embodiment, the wafer 701 can be any substrate on which a positive photoresist material is to be deposited. For example, the wafer 701 can be a 300 mm wafer or a 450 mm wafer, although other wafer diameters may be used. Additionally, in some embodiments, the wafer 701 may be replaced with a non-circular shaped substrate. The replaceable column can include a pillar 714 that protrudes from the chamber 705. The pillar 714 can have ports that provide electrical and fluid paths from the outside of the chamber 705 to various components of the column.

[0059] In one embodiment, the column may include a base plate 710. The base plate 710 may be grounded. As described in more detail below, the base plate 710 may include fluid channels that allow for the flow of an inert gas to provide an edge purge flow.

[0060] In one embodiment, an insulating layer 715 is disposed on the base plate 710. The insulating layer 715 can be any suitable dielectric material. For example, the insulating layer 715 can be a ceramic plate or the like. In one embodiment, a pedestal 730 is disposed on the insulating layer 715. The pedestal 730 may include a single material or may be formed from different materials. In one embodiment, the pedestal 730 can hold the wafer 701 using any suitable chucking system. For example, the pedestal 730 can be a vacuum chuck or a monopole chuck. In embodiments where no plasma is generated within the chamber 705, the pedestal 730 can utilize a bipolar chucking architecture.

[0061] The pedestal 730 may include a plurality of cooling channels 731. The cooling channels 731 can be connected to a fluid input and a fluid output (not shown) that pass through the pillars 714. In one embodiment, the cooling channels 731 enable controlling the temperature of the wafer 701 during operation of the processing tool 700. For example, the cooling channels 731 enable controlling the temperature of the wafer 701 to be between approximately -40°C and approximately 200°C. In one embodiment, the pedestal 730 is connected to ground through a filtering circuit 745, thereby enabling biasing the pedestal with respect to ground with DC and / or RF.

[0062] In one embodiment, the edge ring 720 surrounds the insulating layer 715 and the pedestal 730. The edge ring 720 can be a dielectric material such as ceramic. In one embodiment, the edge ring 720 is supported by the base plate 710. The edge ring 720 can support the shadow ring 735. The shadow ring 735 has an inner diameter smaller than the diameter of the wafer 701. Thus, the shadow ring 735 prevents the positive photoresist from depositing on a portion of the outer edge of the wafer 701. A gap is provided between the shadow ring 735 and the wafer 701. The gap prevents the shadow ring 735 from contacting the wafer 701 and provides an outlet for the edge purge flow. This will be described in more detail below. In one embodiment, a dual-channel showerhead can be used to provide a positive photoresist manufacturing process.

[0063] The shadow ring 735 protects the upper and end faces of the wafer 701 to some extent, and the processing gas can flow / diffuse along the path between the edge ring 720 and the wafer 701. Thus, the embodiments disclosed herein can include a fluid path between the edge ring 720 and the pedestal 730 that enables an edge purge flow. By providing an inert gas to the fluid path, the local pressure within the fluid path increases, preventing the processing gas from reaching the edge of the wafer 701. Thus, the deposition of the positive photoresist is prevented along the edge of the wafer 701.

[0064] FIG. 8 shows an enlarged partial cross-sectional view of a column 860 inside a processing tool according to one embodiment. FIG. 8 shows the edge on the left side of the column 860. However, it should be understood that the edge on the right side of the column 860 is substantially a left-right reversal of the left side edge.

[0065] In one embodiment, the column 860 can include a base plate 810. The insulating layer 815 can be disposed on the base plate 810. In one embodiment, the pedestal 830 includes a first portion 830 A and a second portion 830B may include. The cooling channel 831 may be disposed in the second portion 830 B may be disposed in the first portion 830 A may include features for chucking the wafer 801.

[0066] In one embodiment, the edge ring 820 surrounds the base plate 810, the insulating layer 815, the pedestal 830, and the wafer 801. In one embodiment, the edge ring 820 is positioned spaced apart from other components of the column 850 and provides a fluid path 812 from the base plate 810 to the top of the column 860. For example, the fluid path 812 can exit the column between the wafer 801 and the shadow ring 835. In certain embodiments, the inner surface of the fluid path 812 includes the end face of the insulating layer 815, the end faces of the pedestal 830 (i.e., the first portion 830 A and the second portion 830 B ), and the end face of the wafer 801. In one embodiment, the outer surface of the fluid path 812 includes the inner end face of the edge ring 820. In one embodiment, the fluid path 812 may follow over the top surface of a portion of the pedestal 830 as it progresses towards the end face of the wafer 801. Thus, when an inert gas (e.g., helium, argon, etc.) flows through the fluid path 812, the process gas is prevented from flowing / diffusing along the side of the wafer 801.

[0067] In one embodiment, the width W of the fluid path 812 is minimized to prevent plasma collisions along the fluid path 812. For example, the width W of the fluid path 812 may be approximately 1 mm or less. In one embodiment, the seal 817 prevents the fluid path 812 from exiting the bottom of the column 860. The seal 817 may be disposed between the edge ring 820 and the base plate 810. The seal 817 may be a flexible material such as a gasket material. In certain embodiments, the seal 817 includes silicone.

[0068] In one embodiment, channel 811 is disposed on base plate 810. Channel 811 sends an inert gas from the center of column 860 to the inner end face of edge ring 820. Note that only a portion of channel 811 is shown in FIG. 8. A more comprehensive description of channel 811 will be described later with reference to FIG. 10B.

[0069] In one embodiment, edge ring 820 and shadow ring 835 may have features suitable for aligning shadow ring 835 with respect to wafer 801. For example, notch 821 on the upper surface of edge ring 820 may engage with protrusion 836 on the bottom surface of shadow ring 835. Notch 821 and protrusion 836 may have tapered surfaces that allow for a rough alignment of these two components such that they are sufficient to provide a more precise alignment when edge ring 820 contacts shadow ring 835. In additional embodiments, an alignment feature (not shown) may be provided between pedestal 830 and edge ring 820. The alignment feature between pedestal 830 and edge ring 820 may include a tapered notch and protrusion architecture similar to the alignment feature between edge ring 820 and shadow ring 835.

[0070] FIGS. 9A and 9B are a pair of partial cross-sectional views showing a processing tool having pedestals at different positions (in the Z direction) according to one embodiment. In FIG. 9A, the pedestal is in a lowered position inside the chamber. The position of the pedestal in FIG. 9A is the position where the wafer is inserted into or removed from the chamber through the slit valve. In FIG. 9B, the pedestal is in a raised position inside the chamber. The position of the pedestal in FIG. 9B is the position where the wafer is processed.

[0071] FIG. 9A shows a cross-sectional view of a replaceable column 960 in a first position according to one embodiment. As shown in FIG. 9A, the column includes base plate 910, insulating layer 915, pedestal 930 (i.e., the first portion 930 A and the second portion 930B ) and includes an edge ring 920. Such components may be substantially similar to components having similar names described above. For example, the cooling channel 931 is in the second portion 930 of the pedestal 930 B provided, the channel 911 is disposed on the base plate 910, and the seal 917 may be provided between the edge ring 920 and the base plate 910.

[0072] As shown in FIG. 9A, the wafer 901 is disposed on the upper surface of the pedestal 930. The wafer 901 is inserted into the chamber through a slit valve (not shown). In addition, the shadow ring 935 is shown in the raised position above the edge ring 920. Since the inner diameter of the shadow ring 935 is smaller than the diameter of the wafer 901, the wafer 901 must be disposed on the pedestal before the shadow ring 935 contacts the edge ring 920.

[0073] In one embodiment, the shadow ring 935 is supported by a chamber liner 970. The chamber liner 970 may surround the outer periphery of the column 960. In one embodiment, a holder 971 is positioned on the upper surface of the chamber liner 970. The holder 971 is configured to hold the shadow ring 935 in a high position above the edge ring 920 when the column 960 is in the first position. In one embodiment, the shadow ring 935 includes a protrusion 936 for aligning with the notch 921 of the edge ring 920.

[0074] FIG. 9B shows a cross-sectional view of column 960 after shadow ring 935 has engaged. As shown, column 960 is displaced in the vertical direction (i.e., the Z direction) until shadow ring 935 engages edge ring 920. As column 960 is further displaced vertically, shadow ring 935 is lifted from holder 971 on chamber liner 970. In one embodiment, shadow ring 935 is properly aligned by alignment features (i.e., notch 921 and protrusion 936) of shadow ring 935 and edge ring 920. In additional embodiments, alignment features (not shown) may be provided between pedestal 930 and edge ring 920. Alignment features between pedestal 930 and edge ring 920 may include a tapered notch and protrusion architecture similar to the alignment features between edge ring 920 and shadow ring 935.

[0075] While in the second position, wafer 901 can be processed. In particular, this processing can include depositing a positive photoresist material on the top surface of wafer 901. For example, this process can be a dry deposition and oxidation process that may or may not employ plasma. In certain embodiments, the positive photoresist is a metal-oxo positive photoresist suitable for EUV patterning. However, it should be understood that the positive photoresist can be any type of positive photoresist and the patterning can include any lithography regime. While depositing the positive photoresist on wafer 901, an inert gas can be flowed along the fluid channel between the inner surface of edge ring 910 and the outer surface of insulating layer 915, pedestal 930, and wafer 901. In this way, deposition of the positive photoresist along the edge or backside of wafer 901 is substantially eliminated. In one embodiment, wafer temperature 901 can be maintained between approximately -40°C and approximately 200°C by cooling channel 931 in the second portion of pedestal 930 B and.

[0076] FIG. 10A shows a cross-sectional view of a processing tool 1000 according to a further embodiment. As shown in FIG. 10A, the column includes a base plate 1010. The base plate 1010 can be supported by pillars 1014 protruding from the chamber. That is, in some embodiments, the base plate 1010 and the pillars 1014 may be separate components rather than a single monolithic component as shown in FIG. 7. The pillar 1014 may have a central channel that serves as a path for electrical connections and fluids (e.g., cooling fluid and inert gas for purge flow).

[0077] In one embodiment, an insulating layer 1015 is disposed on the base plate 1010, and a pedestal 1030 (i.e., the first portion 1030 A and the second portion 1030 B ) is disposed on the insulating layer 1015. In one embodiment, a coolant channel 1031 is provided in the second portion 1030 of the pedestal 1030 B . The wafer 1001 is disposed on the pedestal 1030.

[0078] In one embodiment, an edge ring 1020 is provided around the base plate 1010, the insulating layer 1015, the pedestal 1030, and the wafer 1001. The edge ring 1020 can be coupled to the base plate 1013 by a fastening mechanism 1013, such as bolts, pins, or screws. In one embodiment, a seal 1017 prevents purge gas from exiting through the gap between the base plate 1010 and the edge ring 1020 at the bottom of the column.

[0079] In the illustrated embodiment, the pedestal 1030 is in a first position. Accordingly, the shadow ring 1035 is supported by the holder 1071 and the chamber liner 1070. When the pedestal 1030 is displaced vertically, the edge ring 1020 engages the shadow ring 1035 and lifts the shadow ring 1035 from the holder 1071.

[0080] FIG. 10B shows a cross-sectional view of chamber 1000 according to a further embodiment. In the example of FIG. 10B, the insulating layer 1015 and the pedestal 1030 are omitted so that the structure of the base plate 1010 can be seen more clearly. As shown, the base plate 1010 may include a plurality of channels 1011 that provide a fluid path from the center of the base plate 1010 to the edge of the base plate 1010. In the illustrated embodiment, a plurality of first channels connect the center of the base plate 1010 to the first ring channel, and a plurality of second channels connect the first ring channel to the outer edge of the base plate 1010. In one embodiment, the first channels and the second channels are not aligned with each other. Although a particular configuration of the channels 1011 is shown in FIG. 10B, it should be understood that any channel configuration can be used to send an inert gas from the center of the base plate 1010 to the edge of the base plate 1010.

[0081] FIG. 11 shows a schematic diagram of a machine within an exemplary form of computer system 1100 within which a set of instructions for causing a machine to execute any one or more of the methods described herein can be executed. In alternative embodiments, the machine can be connected (e.g., networked) to other machines in a local area network (LAN), intranet, extranet, or the Internet. The machine can 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 can be a personal computer (PC), tablet PC, set-top box (STB), personal digital assistant (PDA), cellular phone, web appliance, server, network router, switch or bridge, or any machine capable of executing a set of instructions (sequential or otherwise) that specify actions to be taken by that machine. Further, while a single machine is shown, the term "machine" shall also be taken to include any collection of machines (e.g., computers) that individually or jointly execute a set of instructions (or multiple sets of instructions) for performing any one or more of the methods described herein.

[0082] The exemplary computer system 1100 includes a processor 1102, main memory 1104 (e.g., read only memory (ROM), flash memory, dynamic random access memory (DRAM) such as synchronous DRAM (SDRAM) or Rambus DRAM (RDRAM)), static memory 1106 (e.g., flash memory, static random access memory (SRAM), MRAM, etc.), and auxiliary memory 1118 (e.g., a data storage device) that communicate with each other via bus 1130.

[0083] Processor 1102 represents one or more general-purpose processing devices such as a microprocessor or a central processing unit. Specifically, processor 1102 can 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 1102 can 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), or a network processor. Processor 1102 is configured to execute processing logic 1126 to perform the processes described herein.

[0084] Computer system 1100 may further include a network interface device 1108. Computer system 1100 may also include a video display unit 1110 (e.g., a liquid crystal display (LCD), a light-emitting diode display (LED), or a cathode ray tube (CRT)), an alphanumeric input device 1112 (e.g., a keyboard), a cursor control device 1114 (e.g., a mouse), and a signal generation device 1116 (e.g., a speaker).

[0085] Auxiliary memory 1118 may include a machine-accessible storage medium (or specifically a computer-readable storage medium) 1132 in which one or more sets of instructions (e.g., software 1122) that embody any one or more of the methods or functions described herein are stored. While being executed by computer system 1100, software 1122 may be stored completely or at least partially resident in main memory 1104 and / or inside processor 1102, and main memory 1104 and processor 1102 also constitute machine-readable storage media. This software 1122 can further be transmitted or received over network 1120 via network interface device 1108.

[0086] In an illustrative embodiment, machine-accessible storage medium 1132 is shown as a single medium, but the term "machine-readable storage medium" should be interpreted to include a single medium or multiple media (e.g., a centralized database or a distributed database, and / or associated caches and servers) that store one or more instruction sets. The term "machine-readable storage medium" should also be interpreted to include any medium that can store or encode a set of instructions for execution by a machine, where the set of instructions causes the machine to perform any one or more of the methods of the present disclosure. Thus, the term "machine-readable storage medium" should be interpreted to include, but not be limited to, solid state memories, optical media, and magnetic media.

[0087] According to an embodiment of the present disclosure, a machine-accessible storage medium stores instructions that cause a data processing system to perform a method of forming a positive photoresist layer on a substrate within a vacuum chamber. The method includes providing a metal precursor vapor into the vacuum chamber. The method also includes providing an oxidant vapor into the vacuum chamber. A reaction between the metal precursor vapor and the oxidant vapor forms the positive photoresist layer on the surface of the substrate.

[0088] As described above, methods for forming positive or negative photoresists using dry processes have been disclosed.

Claims

1. A method for patterning a metal oxo photoresist, comprising: depositing the metal oxo photoresist on a substrate; processing the metal oxo photoresist with a first treatment; exposing the metal oxo photoresist by EUV exposure to form an exposed region and an unexposed region; processing the exposed metal oxo photoresist with a second treatment; and developing the metal oxo photoresist. A method as described above.

2. The method according to claim 1, wherein the metal oxo photoresist is a positive photoresist.

3. The method according to claim 2, wherein developing the metal oxo photoresist includes removing the exposed region.

4. The method according to claim 2, wherein the developer contains an aqueous basic medium.

5. The method according to claim 4, wherein the developer contains tetramethylammonium hydroxide (TMAH).

6. The method according to claim 1, wherein the metal oxo photoresist is a negative photoresist.

7. The method according to claim 6, wherein developing the metal oxo photoresist includes removing the unexposed region.

8. The method according to claim 6, wherein the developer contains an organic solvent.

9. The organic solvent is 20-heptanone, MIBC, MIBK, anisole, D-limonene, methyl benzoate, n-butyl acetate, GBL, or supercritical CO ２ The method according to claim 8, comprising.

10. The method according to claim 1, wherein the first treatment includes annealing between 50°C and 200°C.

11. The method according to claim 1, wherein the first treatment includes UV treatment at a wavelength of 172 nm or more.

12. The method according to claim 1, wherein the second treatment includes annealing between 50°C and 300°C and / or UV treatment at a wavelength of 172 nm or more.

13. Further including processing the developed metal oxo photoresist with a post-treatment including annealing and / or UV treatment. The method according to claim 1.

14. A method for depositing and patterning a photoresist, comprising: depositing the photoresist on a substrate using a dry deposition process, wherein the photoresist contains a metal oxo material; exposing the photoresist by EUV exposure to form an exposed region and an unexposed region; and developing the photoresist by removing the exposed region or the unexposed region. A method as described above.

15. The method according to claim 14, wherein the exposed region is removed with an aqueous basic medium.

16. The method according to claim 14, wherein the non-exposed area is removed with an organic solvent.

17. The method according to claim 14, wherein the metal-carbon bond is broken by exposing the photoresist to the EUV exposure, and the metal of the metal-carbon bond is replaced by oxygen.

18. A method of patterning a substrate, depositing a photoresist on the substrate using a dry deposition process, wherein the photoresist is a metal oxo material, exposing the photoresist by EUV exposure to form an exposed area and a non-exposed area, developing the photoresist to form an opening penetrating the photoresist by removing the exposed area or the non-exposed area, and etching the substrate through the opening of the photoresist comprising the method.

19. The method according to claim 18, wherein the exposed area is removed with an aqueous basic medium.

20. The method according to claim 18, wherein the non-exposed area is removed with an organic solvent.

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