Dual-property photoresist

Abstract

Embodiments disclosed herein include a method of patterning a metal oxide photoresist. In one embodiment, the method includes depositing a metal oxide photoresist on a substrate, treating the metal oxide photoresist with a first treatment, exposing the metal oxide photoresist with EUV exposure to form exposed and unexposed regions, treating the exposed metal oxide photoresist with a second treatment, and developing the metal oxide photoresist.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. patent application No. 17 / 862,283, filed on July 11, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure relate to the field of semiconductor processing, and more particularly to methods of depositing a positive photoresist layer onto a substrate using dry deposition and oxidation processes. Background Art

[0004] For decades, lithography has been used in the semiconductor industry to create two-dimensional (2D) and three-dimensional (3D) patterns in microelectronic devices. The lithography process involves depositing a film (photoresist) by spin coating, irradiating the film in a selected pattern with an energy source (exposing), and removing (etching) the exposed (positive) or non-exposed (negative) areas of the film by dissolving in a solvent. A bake is performed to drive off the remaining solvent.

[0005] The photoresist should be a radiation-sensitive material, and after irradiation, a chemical transformation occurs in the exposed parts of the film, so that the solubility changes between the exposed and non-exposed areas. Using this solubility change, the exposed or non-exposed areas of the photoresist are removed (etched). The photoresist is then developed and the pattern can be transferred to the underlying film or substrate by etching. After the pattern is transferred, the remaining photoresist is removed, and this process is repeated many times to obtain 2D and 3D structures for microelectronic components.

[0006] Several properties are important in the lithography process. These important properties include sensitivity, resolution, lower line-edge roughness (LER), etch resistance, and the ability to form thinner layers. When sensitivity is higher, the energy required to change the solubility of the deposited film is lower. This makes the lithography process more efficient. Resolution and LER determine how narrow features can be achieved in the lithography process. Pattern transfer requires higher etch resistance materials to form deep structures. Higher etch resistance materials also allow for thinner films. Thinner films increase the efficiency of the lithography process. Summary of the invention

[0007] Embodiments disclosed herein include a method for patterning a metal oxide photoresist. In one embodiment, the method includes depositing a metal oxide photoresist on a substrate, treating the metal oxide photoresist with a first process, exposing the metal oxide photoresist with EUV exposure to form exposed areas and unexposed areas, treating the exposed metal oxide photoresist with a second process, and developing the metal oxide photoresist.

[0008] In one embodiment, a method for depositing and patterning a photoresist is provided. In one embodiment, the method comprises depositing a photoresist on a substrate using a dry deposition process, wherein the photoresist comprises a metal oxide material, exposing the photoresist using EUV exposure to form exposed areas and unexposed areas, and developing the photoresist by removing the exposed areas or the unexposed areas.

[0009] An embodiment may further include a method for patterning a substrate, the method comprising: placing a photoresist on a substrate using a dry deposition process, wherein the photoresist is a metal oxide material; exposing the photoresist using EUV exposure to form exposed areas and unexposed areas, developing the photoresist by removing the exposed areas or the unexposed areas to form openings through the photoresist, and etching the substrate through the openings in the photoresist. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1A Cross-sectional views representing various operations in a patterning process using a positive photoresist material formed by the processes described herein are shown in accordance with an embodiment of the present disclosure.

[0011] Figure 1B Cross-sectional views representing various operations in a patterning process using a negative photoresist material formed by the processes described herein are shown in accordance with an embodiment of the present disclosure.

[0012] Figure 2A Included are general formulas and specific examples of metal precursors suitable for manufacturing positive photoresist films according to embodiments of the present disclosure.

[0013] Figure 2B Amines that can be used as developers for negative photoresists according to embodiments of the present disclosure are shown.

[0014] Figure 2C Included are general formulas and specific examples of metal precursors suitable for fabricating positive or negative photoresist films according to embodiments of the present disclosure.

[0015] Figure 3 FIG. 4 is a schematic diagram of a chemical reaction occurring in a negative photoresist film according to an embodiment of the present disclosure.

[0016] Figure 4FIG. 4 is a schematic diagram of a chemical reaction occurring in a positive photoresist film according to an embodiment of the present disclosure.

[0017] Figure 5 FIG. 4 is a process flow chart of a process for patterning a metal oxide photoresist film according to an embodiment of the present disclosure.

[0018] Figure 6 is a cross-sectional view of a processing tool that may be used to perform the dry deposition and oxidation treatment processes described herein, according to an embodiment of the present disclosure.

[0019] Figure 7 is a cross-sectional view of a processing tool for depositing a positive photoresist layer on a substrate using a dry deposition and oxidation treatment process according to an embodiment of the present disclosure.

[0020] Figure 8 is an enlarged illustration of an edge of a displaceable post in a processing tool for depositing a positive photoresist layer on a substrate using a dry deposition and oxidation treatment process according to an embodiment of the present disclosure.

[0021] Fig.9A is an enlarged illustration of an edge of a displaceable post in a processing tool, wherein the shaded ring does not engage the edge ring, according to an embodiment of the present disclosure.

[0022] Fig. 9B is an enlarged illustration of an edge of a displaceable post in a processing tool with a shaded ring engaged with an edge ring according to an embodiment of the present disclosure.

[0023] Fig. 10A is a cross-sectional view of a processing tool for depositing a positive photoresist layer on a substrate using a dry deposition and oxidation treatment process according to an embodiment of the present disclosure.

[0024] Fig. 10B is a cross-sectional view of a processing tool according to an embodiment of the present disclosure, with a base removed to expose channels in the bottom plate.

[0025] Fig.11 A block diagram of an exemplary computer system according to an embodiment of the present disclosure is shown. DETAILED DESCRIPTION

[0026] Methods for depositing positive photoresists on substrates using dry deposition and oxidation treatment processes are described herein. In the following description, many specific details, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes and material schemes for depositing positive photoresists, are set forth in order to provide a thorough 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 may be practiced without these specific details. In other cases, well-known aspects such as integrated circuit manufacturing are not described in detail to avoid unnecessarily confusing the embodiments of the present disclosure. In addition, it should be understood that the various embodiments shown in the figures are illustrative representations and are not necessarily drawn to scale.

[0027] To provide background, photoresist systems used in extreme ultraviolet (EUV) lithography suffer from inefficiencies. That is, existing photoresist material systems for EUV lithography require high doses to provide the required solubility transitions to allow the development of the photoresist material. Traditionally, carbon-based films called organic chemically amplified photoresists (CARs) have been used as photoresists. However, recently, organic-inorganic hybrid materials (metal-oxygen) have been used as photoresists under extreme ultraviolet (EUV) radiation. Such materials typically include metals (e.g., Sn, Hf, Zr), oxygen, and carbon. The transition of the lithography industry from deep UV (DUV) to extreme ultraviolet (EUV) has facilitated narrow features with high aspect ratios. Metal-oxygen-based organic-inorganic hybrid materials have shown lower line edge roughness (LER) and higher resolution, which is required to form narrow features. In addition, such films have higher sensitivity and etch resistance characteristics, and can be implemented to manufacture relatively thin films.

[0028] Currently, metal-oxygen photoresists are deposited by spin coating methods including wet chemistry. A post-bake process is required to drive off any residual solvent in the film and stabilize the film. In addition, the wet process produces a large amount of wet waste that the industry wants to get rid of. Photoresist films deposited by spin coating methods often result in non-uniformity issues. According to embodiments of the present disclosure, in response to one or more of the above-mentioned problems, a vacuum deposition process for metal-oxygen positive photoresists is described herein.

[0029] According to one or more embodiments of the present disclosure, dry deposition and oxidation treatment methods for forming positive photoresist films are described herein. In some embodiments, thermal chemical vapor deposition (CVD) is used for dry deposition of positive photoresist films. In other embodiments, plasma enhanced chemical vapor deposition (PECVD) is used for 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 such condensation process embodiment, the wafer / substrate is maintained at a temperature at which the metal precursor can condense. Precursor condensation can be achieved by maintaining the wafer temperature at a temperature below the precursor ampoule temperature.

[0030] Figure 1A Cross-sectional views representing various operations in a patterning process using a positive photoresist material formed by the processes described herein are shown in accordance with an embodiment of the present disclosure.

[0031] refer to Figure 1A In part (a), a starting structure 100 includes a positive photoresist layer 104 over a substrate or underlying layer 102. In one embodiment, the positive photoresist layer 104 is deposited using dry deposition. Figure 1A In part (b), the starting structure 100 is irradiated 106 at selected locations to form an irradiated photoresist layer 104A having irradiated areas 105B and unirradiated areas 105A. Figure 1A In part (c), a removal or etching process 108 is used to provide a developed photoresist layer in the un-irradiated area 105A. Figure 1A In part (d), an etching process 110 using the un-irradiated area 105A as a mask is used to pattern the substrate or underlying layer 102 to form a patterned substrate or patterned underlying layer 102A including etched features 112 .

[0032] Reference again Figure 1A The positive photoresist 104 is a radiation sensitive material and upon irradiation, a chemical transformation occurs in the exposed portion of the film, which causes a change in solubility between the exposed and unexposed areas. Using the change in solubility, the exposed areas of the positive photoresist are removed (etched). The positive photoresist is then developed and the pattern can be transferred to an underlying film or substrate by etching. After the pattern is transferred, the remaining positive photoresist is removed. This process can be repeated multiple times to produce 2D and 3D structures, such as for microelectronic components.

[0033] Figure 1B Cross-sectional views representing various operations in a patterning process using a negative photoresist material formed by the processes described herein are shown in accordance with an embodiment of the present disclosure.

[0034] refer to Figure 1B In part (a), the starting structure 100 includes a negative photoresist layer 103 over a substrate or underlying layer 102. In one embodiment, the negative photoresist layer 103 is deposited using dry deposition. Figure 1B In part (b), the starting structure 100 is irradiated 106 at selected locations to form an irradiated photoresist layer 103A having irradiated areas 105B and unirradiated areas 105A. Figure 1B In part (c), a removal or etching process 108 is used to provide a developed photoresist layer in the irradiated area 105B. Figure 1B In part (d), an etching process 110 using the irradiated region 105B as a mask is used to pattern the substrate or underlying layer 102 to form a patterned substrate or patterned underlying layer 102A including etched features 112 .

[0035] Reference again Figure 1B The negative photoresist 103 is a radiation sensitive material and upon irradiation, a chemical transformation occurs in the exposed portion of the film, which causes a change in solubility between the exposed and unexposed areas. Using the change in solubility, the unexposed areas of the negative photoresist are removed (etched). The negative photoresist is then developed and the pattern can be transferred to an underlying film or substrate by etching. After the pattern is transferred, the remaining negative photoresist is removed. This process can be repeated multiple times to produce 2D and 3D structures, such as for microelectronic components.

[0036] As will be described in more detail below, both positive resists and negative resists may be metal oxide photoresist films. In some cases, the same material system may be used for both positive and negative resists. Specifically, the developer chemistry used will specify whether the photoresist film is a negative or positive resist. For example, in a negative resist, the developer may be an organic solvent; and in a positive resist, the developer may be an aqueous alkaline medium. That is, dry deposition using EUV exposure may be used to form either a positive resist or a negative resist.

[0037] To provide background, the lithography industry is accustomed to operating with positive photoresist (PR) materials. However, most metal-oxygen PR materials are negative photoresists. Positive photoresists have advantages over negative photoresists, such as higher resolution, higher dry etch resistance, and higher contrast. According to one or more embodiments of the present disclosure, methods of manufacturing positive PR materials by dry deposition methods such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) are described.

[0038] In one embodiment, a Sn precursor is used in a vacuum deposition process of a Sn-oxygen PR material. SnOC films can be attractive photoresist films due to their high sensitivity to exposure. Typically, tin-oxygen photoresist films contain Sn-O and Sn-C bonds in the SnOC network, and upon exposure (e.g., UV / EUV), the Sn-C bonds break and the carbon percentage in the film decreases. This results in selective etching during the development process. Sn-C can be incorporated into the film by using a metal precursor with a Sn-C bond. In one embodiment, the precursor described herein has Sn-C for exposure sensitivity (R contains C bound to Sn) and has a ligand (ligand; L) to react with an oxidant (e.g., water) 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. In addition, the sensitivity can be adjusted by changing the R group in the precursor. In one embodiment, indium-oxygen or tin-indium-oxygen films can also be used as positive photoresist films. The methods described herein can be extended to many other metal-containing films. Although this article specifically focuses on positive photoresist films, it should be understood that similar material systems can be used as negative photoresist films. Specifically, the choice of developer solution can specify whether the exposure (e.g., EUV exposure) produces a positive resist or a negative resist.

[0039] According to an embodiment of the present disclosure, a positive or negative photoresist is manufactured by using a specific type of R group in a metal precursor or a plasma assisted deposition method. For example, a Sn precursor (PhSn(NMe2)3) containing phenyl (R) can be used. After the resist is exposed to UV under ambient conditions, the exposed area shows an acidic portion by FTIR. Subsequently, the resist is immersed in an aqueous alkaline medium (e.g., sodium hydroxide (NaOH) or tetramethylammonium hydroxide (TMAH)) and the resist is developed to be positive. The acidic portion (exposed area) of the resist reacts with the alkaline NaOH and dissolves in the aqueous medium, producing a positive resist. In addition, when Sn(nBu)4 is used in PECVD, a positive resist is obtained. Therefore, 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 areas of the resist film. Thus, methods for making negative tone resists are described herein.

[0040] In the first aspect, an R group with low radical stability is used. For example, R groups such as phenyl, alkenyl, and methyl have low radical stability (Sn-C → Sn• +C•). Figure 2AIncluded are general formulas and specific examples of metal precursors suitable for making 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 with thermal CVD, while the two specific examples on the right may require PECVD in order to use the development process described below.

[0041] It should be understood that the lithography industry is generally used to process positive PR, and almost all new metal-oxygen PRs are negative PRs. Positive PRs may have advantages such as higher resolution, higher resistance to dry etching, and higher contrast than negative PRs. However, metal-oxygen PRs may need to be oxidized during or after exposure to function as positive PRs. Here, a method for making positive PRs using an oxidation operation is described. It should be understood that the same or similar methods can also be used for negative PR manufacturing.

[0042] In a second aspect, for the exposure environment, when the photoresist is exposed to an energy source (e.g., EUV), the exposure chamber (environment) may be oxygen-containing or inert. In one embodiment, the exposure is under vacuum using an oxygen source such as O2, H2O, CO2, CO, NO2, or NO. In one embodiment, the EUV exposure followed by the oxygen exposure may be repeated between 1 and 100 times.

[0043] In a third aspect, the post anneal is performed 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 with N2, Ar or He. In one embodiment, the post anneal is performed at a temperature in the range of 25-200 degrees Celsius. In one embodiment, the post anneal is performed at a pressure of less than 200 Torr. In a specific embodiment, ozone (O3) is used as the oxygen source gas, and the post anneal is performed at a temperature in the range of 25-250 degrees Celsius and a pressure of less than 200 Torr.

[0044] In a fourth aspect, the alkaline developer that can be used includes an inorganic base that can be prepared in water, and the concentration and development time can be adjusted. In one embodiment, Group 1 and Group 2 hydroxides (e.g., NaOH, KOH), NH4OH, NaHCO3, NaCO3, N(CH3)4OH or Figure 2B The amines shown in .

[0045] In a fifth aspect, an organic solvent may be used to prepare a negative photoresist. The organic solvent may dissolve the organic portion (i.e., the unexposed area) of the photoresist film having a lower polarity. 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.

[0046] Additionally, Figure 2CA list of certain metal precursors and specific examples of those metal precursors is included. X L Y wherein x=0-6 and y=0-6. The R component may include, for example, an alkyl, alkenyl, alkynyl, aryl, carbene, or an R group containing silicon, germanium, and tin. The L component may be a water-reactive ligand, such as an amine or an alkoxide. The metal component may be Figure 2C Any of those components listed in . Figure 2C The material system described in can be used as Figure 2A Alternatives to those material systems described in, or with Figure 2A In addition, it should be understood that in Figure 2A and Figure 2C There may be overlap in the material systems described in 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, acetic acid).

[0047] In a first method, according to an embodiment of the present disclosure, a chemical vapor deposition (CVD) method for forming a positive or negative photoresist includes: (A) Figure 2AOne or more metal precursors and one or more oxidants listed above are vaporized into a vacuum chamber in which the substrate wafer is maintained at a predetermined substrate temperature. The substrate temperature can vary between 0°C and 500°C. When the precursor / oxidant is vaporized into the chamber, it can be diluted with an inert gas such as Ar, N2, He. Due to the reactivity of the precursors and the oxidant, a metal-oxygen film is deposited on the wafer. The chamber can be vaporized by all precursors simultaneously or by alternating pulses of metal precursors and oxidants. This process can be described as thermal CVD. (B) A plasma can also be turned on during this process, and the process can then be described as plasma enhanced (PE)-CVD. Examples of plasma sources are CCP, ICP, remote plasma, microwave plasma. (C) Photoresist film deposition can be performed by thermal deposition followed by plasma treatment. In this case, the film is thermally deposited and then a plasma treatment operation is performed. Plasma treatment may involve plasma from an inert gas such as Ar, N2, He, or such gases may be mixed with O2, CO2, CO, NO, NO2, H2O. These processes may be performed in a cyclical manner; thermal deposition followed by plasma treatment and the cycle repeated or the deposition portion completed and then followed by a plasma treatment (post-treatment). Plasma treatment after PECVD is also possible. In either case, in one embodiment, post-annealing is performed in an oxygen-containing environment. In one embodiment, post-annealing is performed at a pressure of less than 200 Torr in a temperature range of 25-250 degrees Celsius using ozone (O3) as the oxygen source gas.

[0048] In a second method, according to an embodiment of the present disclosure, an atomic layer deposition (ALD) method for forming a positive or negative photoresist includes: (A) Figure 2A(A) A metal precursor in a vacuum chamber is vaporized into a vacuum chamber in which a substrate wafer is maintained at a predetermined substrate temperature. The substrate temperature may vary between 0 and 500 degrees Celsius. Subsequently, an internal gas purge is provided to remove byproducts and excess metal precursor. Subsequently, one or more oxidants are vaporized into the chamber. The oxidants react with the metal precursor adsorbed on the surface. Subsequently, an inert gas purge is applied to remove byproducts and unreacted oxidants. This cycle may be repeated to achieve the desired thickness. When the precursor or oxidant is vaporized into the chamber, it may be diluted with an inert gas such as Ar, N2, He. This process may be described as thermal ALD. Using this method, more than one metal may be incorporated into the film by incorporating additional metal precursor pulses into the ALD cycle. In addition, a different oxidant may be pulsed after the first oxidant. (B) A plasma may be turned on during the oxidant pulse, and then this process may be described as PE-ALD. (C) In addition, deposition may be performed by thermal ALD and then plasma treatment may be performed. In this case, the film is thermally deposited and then a plasma treatment operation is performed. The plasma treatment may involve a plasma from an inert gas such as Ar, N2, He, or such gases may be mixed with O2, CO2, CO, NO, NO2, H2O. These processes can be performed in a cyclic manner; X thermal ALD cycles (X=1-5000) followed by plasma treatment, and the entire cycle is repeated as many times as required, or the deposition portion is completed and then a plasma treatment is performed. It is also possible to perform a plasma treatment after PE-ALD. In either case, in one embodiment, a post anneal is performed in an oxygen-containing environment. In one embodiment, the post anneal is performed using ozone (O3) as the oxygen source gas, at a temperature range of 25-250 degrees Celsius and a pressure of less than 200 Torr.

[0049] In a third approach, according to an embodiment of the present disclosure, an atomic layer deposition (ALD) or chemical vapor deposition (CVD) method for forming a positive or negative photoresist includes providing a composition gradient throughout the film. For example, the first few nanometers of the film have a different composition than the rest of the film. The main portion of the film can be optimized for dose, but for different compositions near the interface layer to change adhesion, sensitivity to EUV photons, sensitivity to development chemistry to improve post-lithography profile control (specifically scum) and defects and collapse / peeling resistance. The gradient can be optimized for pattern type, for example, pillars need to improve adhesion, while line / space patterns can reduce adhesion to increase dose.

[0050] In one embodiment, the photoresist film deposition method described herein is a vacuum deposition method that does not involve wet chemistry. The positive or negative photoresist described herein has advantages such as higher resolution, higher dry etching resistance and higher contrast than negative photoresist.

[0051] Advantages of implementing one or more methods described herein include that the positive or negative photoresist film deposition method is a dry deposition method and does not involve wet chemistry. Wet chemical methods produce a large amount of wet byproducts, and it is preferred to avoid these byproducts. In addition, spin coating (wet method) usually leads to non-uniformity problems, which can be successfully solved by the vacuum deposition method described herein. In addition, the percentage of metal and carbon (C) in the film can be tuned by vacuum deposition. In spin coating, the metal percentage and C are usually fixed in a given deposition system. The precursors used to deposit positive or negative photoresist films under vacuum need to be volatile, and the precursors described herein are volatile based on L and R structures. The dry deposition method may require a lower temperature than other vacuum deposition methods (such as ALD or CVD). When deposited at low temperatures, a relatively high amount of carbon can be retained in the film, which helps patterning.

[0052] 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 a vacuum chamber. In some embodiments, the metal precursor and the oxidant are provided to the vacuum chamber together. In other embodiments, the metal precursor and the oxidant are provided to the vacuum chamber in alternating pulses. After forming a metal-oxygen positive photoresist film having a desired thickness, the process may be stopped. In one embodiment, an optional plasma treatment operation may be performed after forming a metal-oxygen positive photoresist film having a desired thickness.

[0053] In one embodiment, a cycle including a metal precursor vapor pulse and an oxidant vapor pulse may be repeated multiple times to provide a metal-oxygen positive photoresist film having a desired thickness. In one embodiment, the order of the cycles may be switched. For example, the oxidant vapor may be pulsed first, and the metal precursor vapor may be pulsed second. In one embodiment, the pulse duration of the metal precursor vapor may be substantially similar to 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 may be between 0 seconds and 1 minute. In a particular embodiment, the pulse duration may be between 1 second and 5 seconds. In one embodiment, each iteration of the cycle uses the same processing gas. In other embodiments, the processing gas may change between cycles. For example, the first cycle may utilize the first metal precursor vapor, and the second cycle may utilize the second metal precursor vapor. Subsequent cycles may continue to alternate between the first metal precursor vapor and the second metal precursor vapor. In one embodiment, multiple oxidant vapors may alternate between cycles in a similar manner. In one embodiment, an optional plasma treatment operation may be performed after each cycle. That is, each cycle may include a metal precursor vapor pulse, an oxidant vapor pulse, and a plasma treatment. In an alternative embodiment, an optional plasma treatment operation may be performed after multiple cycles. In yet another embodiment, an optional plasma treatment operation may be performed after all cycles are completed (i.e., as a post-treatment).

[0054] Providing metal-oxygen positive and negative photoresist films using dry deposition and oxidation treatment processes such as described in the above embodiments can achieve significant advantages over wet chemical methods. One such advantage is the elimination of wet byproducts. With dry deposition processes, liquid waste is eliminated and removal of byproducts is simplified. In addition, dry deposition processes can provide more uniform positive and negative photoresist layers. Uniformity in this sense can refer to thickness uniformity across the wafer and / or uniformity of the metal component distribution of the metal-oxygen film.

[0055] In addition, the use of a dry deposition process provides the ability to fine tune the percentage of metal in the positive or negative photoresist and the composition of the metal in the positive or negative photoresist. The percentage of metal can be changed by increasing / decreasing the flow rate of the metal precursor into the vacuum chamber and / or by changing the pulse length of the metal precursor / oxidant. The use of a dry deposition process also allows a variety of different metals to be included in the metal-oxygen 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.

[0056] Furthermore, metal-oxygen positive and negative photoresists formed using dry deposition processes have been shown to be more resistant to thickness reduction after exposure. It is believed that, independent of a particular mechanism, the resistance to thickness reduction is at least partially due to reduced carbon loss upon exposure.

[0057] Reference Figure 3 , a schematic diagram of a chemical reaction for forming a negative metal oxide photoresist according to an embodiment is shown. As shown, a metal precursor 320 may be supplied to a chamber (e.g., a vacuum chamber). At 321, an oxidation source, such as those described in more detail above, may be supplied to the chamber to form a metal oxide photoresist 322. As shown, the metal oxide film may include a metal center (e.g., Sn) that is bound to oxygen at a position previously occupied by a ligand L. At operation 323, the negative photoresist film may be exposed (e.g., by EUV exposure). The exposure produces a chemical reaction in which the reactant group R in the exposed region 325 is replaced by oxygen. That is, the carbon percentage in the exposed region is reduced. The crosslinking in the exposed region may be higher than that in the unexposed region. In the unexposed region 324, the chemical structure may retain an organic portion. Therefore, the unexposed region 324 may have a lower polarity than the exposed region 325. The organic nature of the unexposed region allows the unexposed region 324 to be dissolved in an organic solvent, such as those described in more detail above.

[0058] Reference Figure 4 , a schematic diagram of a chemical reaction for forming a positive metal oxide photoresist according to an embodiment is shown. As shown, a metal precursor 420 can be supplied to a chamber having an oxidation source 421. The reaction between the metal precursor 420 and the oxidation source 421 results in the formation of a metal oxide film 422. At operation 423, the metal oxide 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 will not dissolve in an aqueous alkaline medium that will dissolve the exposed region 425.

[0059] That is, the choice of developer solution can allow the formation of a negative resist or a positive resist. The material systems used for negative resists are generally similar to those used for positive resists. Therefore, a single material system with flexibility can be used to provide a negative system or a positive system. Therefore, the material systems disclosed herein have increased value due to their ability to be used as positive resists or negative resists.

[0060] View now Figure 5, a process flow diagram of a process 580 for developing a metal oxide film according to an embodiment is shown. In one embodiment, the process 580 begins with operation 581, which includes depositing a metal oxide photoresist on a substrate. In one embodiment, the metal oxide photoresist can be deposited using any of the processing operations described in more detail above. For example, CVD, PE-CVD, ALD, PE-ALD processes can be used to deposit the metal oxide film on the substrate. Although dry deposition processes are described in detail herein, it should be understood that the amphoteric resist material can be deposited via a spin-on deposition process or other wet deposition process as appropriate.

[0061] In one embodiment, process 580 may continue with operation 582, which includes treating the metal oxide photoresist. In one embodiment, the treatment may be an annealing treatment. For example, an annealing between 50° C. and 200° C. may be performed. The annealing may be in an inert environment or an oxidizing environment. For example, O2, O3, H2O, H2O2, or alcohol may be used as an annealing environment. The surrounding environment may also be used for annealing. In some embodiments, the treatment may include ultraviolet treatment. Ultraviolet treatment may be provided in addition to annealing, or ultraviolet treatment may be provided without annealing. Ultraviolet treatment may include exposure to light with a wavelength between 172 nm and 900 nm and a power in the range of 1 mW to 400 W.

[0062] In one embodiment, process 580 may continue with operation 583, which includes exposing the metal oxide photoresist with EUV exposure. The EUV exposure may result in the formation of exposed areas or unexposed areas.

[0063] In one embodiment, process 580 may continue with operation 584, which includes treating the exposed metal oxide photoresist with a post-exposure treatment. In one embodiment, the post-exposure treatment may include annealing. For example, the annealing temperature may be between 50° C. and 300° C. The annealing may be performed in an inert environment or an oxidizing environment (e.g., O2, O3, H2O, H2O2, or alcohol). In some embodiments, an ambient environment may be used for annealing. In some embodiments, the post-exposure treatment may include ultraviolet treatment. The ultraviolet treatment may be provided in addition to the annealing, or the ultraviolet treatment may be provided without the annealing. The ultraviolet treatment may include exposure to light having a wavelength between 172 nm and 900 nm and a power in the range of 1 mW to 400 W.

[0064] In one embodiment, process 580 may continue with operation 585, which includes developing the metal oxide photoresist. In one embodiment, the metal oxide photoresist may produce a positive film resist or a negative resist. For example, an organic solvent may be used to selectively dissolve the unexposed areas to form a negative resist, or an aqueous alkaline medium may be used to selectively dissolve the exposed areas to form a positive resist. In one embodiment, during the development process, the temperature of the substrate may be maintained at from -10°C to 90°C.

[0065] In one embodiment, process 580 may continue with operation 586, which includes treating the developed metal oxide photoresist with a post-development treatment. In one embodiment, the post-development treatment may include annealing. For example, the annealing temperature may be between 50° C. and 300° C. The annealing may be performed in an inert environment or an oxidizing environment (e.g., O2, O3, H2O, H2O2, or alcohol). In some embodiments, an ambient environment may be used for annealing. In some embodiments, the post-exposure treatment may include ultraviolet treatment. The ultraviolet treatment may be provided in addition to the annealing, or the ultraviolet treatment may be provided without the annealing. The ultraviolet treatment may include exposure to light having a wavelength between 172 nm and 900 nm and a power in the range of 1 mW to 400 W.

[0066] In one embodiment, the vacuum chamber used in the dry deposition process is any suitable chamber capable of providing sub-atmospheric pressure. In one embodiment, the vacuum chamber may include temperature control features for controlling chamber wall temperature and / or for controlling substrate temperature. In one embodiment, the vacuum chamber may also include features for providing a plasma within the chamber. Figure 6 A more detailed description of a suitable vacuum chamber is provided. Figure 6 is a schematic diagram of a vacuum chamber configured to perform dry deposition of metal-oxygen positive photoresist according to an embodiment of the present disclosure.

[0067] The vacuum chamber 600 includes a grounded chamber 605. A substrate 610 is loaded through an opening 615 and clamped on a temperature controlled chuck 620. In one embodiment, the substrate 610 can be temperature controlled during dry deposition. For example, the temperature of the substrate 610 can be between about -40 degrees Celsius and 200 degrees Celsius. In a particular embodiment, the substrate 610 can be maintained at a temperature between room temperature and 150°C.

[0068] The process gases are supplied from the gas source 644 to the interior of the chamber 605 via respective mass flow controllers 649. In certain embodiments, the gas distribution plate 635 provides distribution of the process gases 644, such as metal precursors, oxidants, and inert gases. The chamber 605 is evacuated via an exhaust pump 655. In one embodiment, one or more process gases are contained / stored 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 higher than the substrate temperature, such as a temperature 25 degrees Celsius or greater than the substrate temperature.

[0069] When RF power is applied during processing of the substrate 610, plasma is formed in the chamber processing region above the substrate 610. A bias power RF generator 625 is coupled to the temperature controlled chuck 620. The bias power RF generator 625 provides bias power to ignite the plasma if necessary. The bias power RF generator 625 may have a low frequency, for example, between about 2 MHz and 60 MHz, and in a specific embodiment, a low frequency in a 13.56 MHz bandwidth. In certain embodiments, the vacuum chamber 600 includes a third bias power RF generator 626 having a frequency of about 2 MHz bandwidth, which is connected to the same RF match 627 as the bias power RF generator 625. The source power RF generator 630 is coupled to the plasma generation assembly (e.g., gas distribution plate 635) via a match (not depicted) to provide source power to ignite the plasma. The source RF generator 630 may have a frequency, for example, between 100 and 180 Mhz, and in a particular embodiment, a frequency in a 162 MHz bandwidth. As substrate diameters have evolved over time from 150 mm, 200 mm, 300 mm, etc., it is common in the art to normalize the source and bias power of a plasma etch system to the substrate area.

[0070] 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 may perform processing operations within the vacuum chamber 600 according to instructions stored in the memory 673. For example, one or more processes such as processes 120 and 440 described above may be performed in the vacuum chamber by the controller 670.

[0071] In another aspect, embodiments disclosed herein include a processing tool that includes an architecture that is 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 may be maintained between about -40°C and about 200°C. In addition, an edge purge flow and a shadow ring may be provided around the periphery of a column supporting a substrate. The edge purge flow and the shadow ring prevent positive photoresist from being deposited along the edge or back of the wafer. In one embodiment, the pedestal may also provide any desired clamping architecture, such as but not limited to vacuum clamping, monopolar clamping, or bipolar clamping, depending on the operating state of the processing tool.

[0072] In some embodiments, the processing tool may be adapted for a deposition process without plasma. Alternatively, the processing tool may include a plasma source to enable plasma enhanced operation. In addition, while the embodiments disclosed herein are particularly adapted for depositing metal-oxygen positive photoresists for EUV patterning, it should be understood that the embodiments are not limited to such configurations. For example, the processing tools described herein may be adapted for depositing any positive photoresist material for any lithography scheme using a dry deposition process.

[0073] View now Figure 7 , showing a cross-sectional view of a processing tool 700 according to an embodiment. In one embodiment, the processing tool 700 may include a chamber 705. The chamber 705 may be any suitable chamber capable of supporting a sub-atmospheric pressure (e.g., a vacuum pressure). In one embodiment, an exhaust device (not shown) including a vacuum pump may be coupled to the chamber 705 to provide the sub-atmospheric pressure. In one embodiment, a lid may seal the chamber 705. For example, the lid may include a showerhead assembly 740, etc. The showerhead assembly 740 may include a fluid passage that enables a process gas and / or an inert gas to flow into the chamber 705. In some embodiments where the processing tool 700 is suitable for plasma enhanced operation, the showerhead assembly 740 may be electrically coupled to an RF source and matching circuitry 750. In yet another embodiment, the tool 700 may be configured in an RF bottom feed architecture. That is, the base 730 is connected to the RF source, and the showerhead assembly 740 is grounded. In such embodiments, the filter circuitry may still be connected to the base. In one embodiment, the precursor gas is stored in an ampoule 799.

[0074] In one embodiment, a displaceable post is provided in chamber 705 for supporting wafer 701. In one embodiment, wafer 701 can be any substrate on which a positive photoresist material is deposited. For example, wafer 701 can be a 300 mm wafer or a 450 mm wafer, although other wafer diameters can also be used. Additionally, in some embodiments, a substrate having a non-circular shape can be substituted for wafer 701. The displaceable post can include a post member 714 that extends out of chamber 705. Post member 714 can have ports to provide electrical and fluid paths from outside of chamber 705 to various components of the post.

[0075] In an embodiment, the column can include a base plate 710. The base plate 710 can be grounded. As will be described in more detail below, the base plate 710 can include fluid channels to allow an inert gas to flow to provide an edge purge flow.

[0076] In one embodiment, an insulating layer 715 is disposed above 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, etc. In one embodiment, a pedestal 730 is disposed above the insulating layer 715. The pedestal 730 can include a single material, or the pedestal 730 can be formed of different materials. In one embodiment, the pedestal 730 can utilize any suitable clamping system to hold the wafer 701. For example, the pedestal 730 can be a vacuum chuck or a monopolar chuck. In embodiments where no plasma is generated in the chamber 705, the pedestal 730 can utilize a bipolar clamping architecture.

[0077] The pedestal 730 may include a plurality of cooling channels 731. The cooling channels 731 may be connected to a fluid input and a fluid output (not shown) that pass through the column 714. In one embodiment, the cooling channels 731 allow the temperature of the wafer 701 to be controlled during operation of the processing tool 700. For example, the cooling channels 731 may allow the temperature of the wafer 701 to be controlled between about -40°C and about 200°C. In one embodiment, the pedestal 730 is connected to ground via the filtering circuitry 745, which enables DC and / or RF biasing of the pedestal relative to ground.

[0078] In one embodiment, edge ring 720 surrounds the periphery of insulating layer 715 and base 730. Edge ring 720 can be a dielectric material, such as ceramic. In one embodiment, edge ring 720 is supported by base plate 710. Edge ring 720 can support shadow ring 735. The inner diameter of shadow ring 735 is smaller than the diameter of wafer 701. Therefore, shadow ring 735 prevents positive photoresist from being deposited on a portion of the outer edge of wafer 701. A gap is provided between shadow ring 735 and wafer 701. This gap prevents shadow ring 735 from contacting wafer 701 and provides an outlet for edge purge flow, which will be described in more detail below. In one embodiment, a dual channel shower head can be used for positive photoresist manufacturing process.

[0079] Although the shadow ring 735 provides some protection to the top surface and edge of the wafer 701, the process gas may flow / diffuse downward along the path between the edge ring 720 and the wafer 701. Therefore, embodiments disclosed herein may include a fluid path between the edge ring 720 and the pedestal 730 to achieve an edge purge flow. Providing an inert gas in the fluid path increases the local pressure in the fluid path and prevents the process gas from reaching the edge of the wafer 701. Therefore, deposition of positive photoresist along the edge of the wafer 701 is prevented.

[0080] Reference Figure 8 , an enlarged cross-sectional view of a portion of a column 860 within a processing tool is shown, according to one embodiment. Figure 8 , only the left edge of the column 860 is shown. However, it should be understood that the right edge of the column 860 can be substantially a mirror image of the left edge.

[0081] In one embodiment, the column 860 may include a bottom plate 810. The insulating layer 815 may be disposed on the bottom plate 810. In one embodiment, the base 830 may include a first portion 830. A and Part II 830 B The cooling channel 831 may be disposed in the second portion 830 B Part 1 830 A Features for clamping wafer 801 may be included.

[0082] In one embodiment, edge ring 820 surrounds base plate 810, insulating layer 815, pedestal 830, and wafer 801. In one embodiment, edge ring 820 is spaced apart from other components of post 850 to provide a fluid path 812 from base plate 810 to the top side of post 860. For example, fluid path 812 can exit the post between wafer 801 and shadow ring 835. In one particular embodiment, the inner surface of fluid path 812 includes the edge of insulating layer 815, the edge of pedestal 830 (i.e., first portion 830), and the inner surface of fluid path 812. A and Part II 830 B ) and the edge of the wafer 801. In one embodiment, the outer surface of the fluid path 812 includes the inner edge of the edge ring 820. In one embodiment, when a portion of the pedestal 830 advances to the edge of the wafer 801, the fluid path 812 can also continue on the top surface of the portion of the pedestal 830. In this way, when an inert gas (e.g., helium, argon, etc.) flows through the fluid path 812, the process gas is prevented from flowing / diffusing downward along the side of the wafer 801.

[0083] In one embodiment, the width W of the fluid path 812 is minimized to prevent plasma from being struck along the fluid path 812. For example, the width W of the fluid path 812 can be about 1 mm or less. In one embodiment, a seal 817 prevents the fluid path 812 from leaving the bottom of the column 860. The seal 817 can be positioned between the edge ring 820 and the bottom plate 810. The seal 817 can be a flexible material, such as a gasket material, etc. In a specific embodiment, the seal 817 includes silicone.

[0084] In one embodiment, a channel 811 is disposed in the base plate 810. The channel 811 directs the inert gas from the center of the column 860 to the inner edge of the edge ring 820. It should be understood that Figure 8 Only a portion of channel 811 is shown. Fig. 10B A more complete description of channel 811 is provided.

[0085] In one embodiment, the edge ring 820 and the shadow ring 835 may have features suitable for aligning the shadow ring 835 relative to the wafer 801. For example, a groove 821 in the top surface of the edge ring 820 may interface with a protrusion 836 on the bottom surface of the shadow ring 835. When the edge ring 820 and the shadow ring 835 are in contact, the groove 821 and the protrusion 836 may have tapered surfaces to allow for a rough alignment of the two components sufficient to provide a more precise alignment. In another embodiment, an alignment feature (not shown) may also be provided between the base 830 and the edge ring 820. The alignment feature between the base 830 and the edge ring 820 may include a tapered groove and protrusion structure similar to the alignment feature between the edge ring 820 and the shadow ring 835.

[0086] Reference Fig.9A and Fig. 9B , shows a pair of cross-sectional views depicting a portion of a processing tool having a susceptor in different positions (in the Z direction) according to an embodiment. Fig.9A In the embodiment, the base is located at a lower position within the chamber. Fig.9A The position of the susceptor in the middle is where the wafer is inserted into or removed from the chamber via the slit valve. Fig. 9B In the embodiment, the base is in a raised position within the chamber. Fig. 9B The position of the middle susceptor is the position for processing the wafer.

[0087] Reference Fig.9A , showing a cross-sectional view of a displaceable post 960 in a first position according to an embodiment. Fig.9A As shown, the column includes a bottom plate 910, an insulating layer 915, a base 930 (ie, a first portion 930 A and Part II 930 B ), and edge ring 920. Such components may be substantially similar to the components similarly noted above. For example, cooling channel 931 may be disposed in second portion 930 of base 930. B In the embodiment, the channel 911 can be disposed in the bottom plate 910 , and the seal 917 can be disposed between the edge ring 920 and the bottom plate 910 .

[0088] like Fig.9A As shown, wafer 901 is placed on the top surface of susceptor 930. Wafer 901 can be inserted into the chamber via a slit valve (not shown). In addition, shadow ring 935 is shown in an elevated position above edge ring 920. Since the inner diameter of shadow ring 935 is smaller than the diameter of wafer 901, wafer 901 needs to be placed on the susceptor before shadow ring 935 contacts edge ring 920.

[0089] In one embodiment, the shadow ring 935 is supported by a chamber liner 970. The chamber liner 970 can surround the outer perimeter of the post 960. In one embodiment, a retainer 971 is positioned on the top surface of the chamber liner 970. The retainer 971 is configured to retain the shadow ring 935 in an elevated position above the edge ring 920 when the post 960 is in the first position. In one embodiment, the shadow ring 935 includes a protrusion 936 for aligning with a groove 921 in the edge ring 920.

[0090] Reference Fig. 9B , a cross-sectional view of post 960 after engaging shadow ring 935 is shown, according to one embodiment. As shown, post 960 is displaced in a vertical direction (i.e., Z direction) until shadow ring 935 engages edge ring 920. Additional vertical displacement of post 960 lifts shadow ring 935 off retainer 971 on chamber liner 970. In one embodiment, shadow ring 935 is properly aligned due to alignment features in shadow ring 935 and edge ring 920 (i.e., groove 921 and protrusion 936). In another embodiment, alignment features (not shown) may also be provided between base 930 and edge ring 920. The alignment features between base 930 and edge ring 920 may include a tapered groove and protrusion configuration similar to the alignment features between edge ring 920 and shadow ring 935.

[0091] While in the second position, the wafer 901 can be processed. Specifically, the processing can include depositing a positive photoresist material on the top surface of the wafer 901. For example, this process can be a dry deposition and oxidation treatment process with or without plasma assistance. In a specific embodiment, the positive photoresist is a metal-oxygen 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 scheme. During the deposition of the positive photoresist onto the wafer 901, an inert gas can flow along the fluid channel between the inner surface of the edge ring 910 and the insulating layer 915, the pedestal 930 and the outer surface of the wafer 901. Therefore, positive photoresist deposition along the edge or back side of the wafer 901 is substantially eliminated. In one embodiment, the temperature of the wafer 901 can be controlled by the second portion 930 of the pedestal. B The cooling channel 931 in is maintained between about -40°C and about 200°C.

[0092] View now Fig. 10A , a schematic diagram of a processing tool 1000 according to another embodiment is shown. Fig. 10A As shown in FIG. 1 , the column includes a base plate 1010. The base plate 1010 can be supported by a column 1014 extending out of the chamber. That is, in some embodiments, the base plate 1010 and the column 1014 can be separate components rather than being a single component. Figure 7A single monolithic component is shown. Post 1014 may have a central channel for conducting electrical connections and fluids (eg, cooling fluid and inert gas for purge flow).

[0093] In one embodiment, the insulating layer 1015 is disposed above the base 1010, and the base 1030 (ie, the first portion 1030 A and Part II 1030 B ) is disposed above the insulating layer 1015. In one embodiment, the coolant channel 1031 is disposed in the second portion 1030 of the base 1030. B The wafer 1001 is disposed on the susceptor 1030 .

[0094] In one embodiment, edge ring 1020 is disposed around base plate 1010, insulating layer 1015, pedestal 1030, and wafer 1001. Edge ring 1020 may be coupled to base plate 1013 by a fastening mechanism 1013 such as bolts, pins, screws, etc. In one embodiment, seal 1017 prevents purge gas from leaving the column from the bottom between the gap between base plate 1010 and edge ring 1020.

[0095] In the illustrated embodiment, the base 1030 is in the first position. Therefore, the shadow ring 1035 is supported by the retainer 1071 and the chamber liner 1070. When the base 1030 is vertically displaced, the edge ring 1020 will engage with the shadow ring 1035 and lift the shadow ring 1035 off the retainer 1071.

[0096] Reference Fig. 10B , shows a cross-sectional view of chamber 1000 according to additional embodiments. Fig. 10B In the illustration of FIG. 1 , the insulating layer 1015 and the base 1030 are omitted so as to more clearly see the construction of the bottom plate 1010. As shown, the bottom plate 1010 may include a plurality of channels 1011 that provide a fluid path from the center of the bottom plate 1010 to the edge of the bottom plate 1010. In the illustrated embodiment, a plurality of first channels connect the center of the bottom plate 1010 to the first annular channel, and a plurality of second channels connect the first annular channel to the outer edge of the bottom plate 1010. In one embodiment, the first channel and the second channel are offset from each other. Although the specific configuration of the channels 1011 is not limited to the embodiment of FIG. 1 , the first channel and the second channel are offset from each other. Fig. 10B 1010 , but it should be understood that any channel configuration can be used to direct the inert gas from the center of the substrate 1010 to the edge of the substrate 1010 .

[0097] Fig.11A diagrammatic representation of a machine in the exemplary form of a computer system 1100 is marked, in which a set of instructions can be executed to cause the machine to perform any one or more of the methods described herein. In alternative embodiments, the machine may be connected (e.g., networked) to other machines in a local area network (LAN), an intranet, an inter-net, or the Internet. The machine may operate in the role of a server or client machine in a client-server network environment, or as a peer machine in a peer-to-peer (distributed) network environment. The machine may be a personal computer (PC), a tablet computer, a set-top box (STB), a personal digital assistant (PDA), a cellular phone, a network appliance, a server, a network router, a switch or a bridge, or any machine capable of executing a set of instructions (sequentially or otherwise) specifying actions to be taken by the machine. In addition, although only a single machine is illustrated, the term "machine" should also be understood to include any machine (e.g., computer) collection that executes a set (or multiple sets) of instructions individually or jointly to perform any one or more of the methods described herein.

[0098] The exemplary computer system 1100 includes a processor 1102, a 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)), etc.), a static memory 1106 (e.g., flash memory, static random access memory (SRAM), MRAM, etc.), and an auxiliary memory 1118 (e.g., a data storage device), which communicate with each other via a bus 1130.

[0099] The processor 1102 represents one or more general-purpose processing devices, such as a microprocessor, a central processing unit, and the like. More specifically, the processor 1102 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. The processor 1102 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, and the like. The processor 1102 is configured to execute processing logic 1126 for performing the operations described herein.

[0100] The computer system 1100 may further include a network interface device 1108. The 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 generating device 1116 (e.g., a speaker).

[0101] The secondary memory 1118 may include a machine-accessible storage medium (or more specifically, a computer-readable storage medium) 1132 on which is stored one or more sets of instructions (e.g., software 1122) embodying any one or more of the methods or functions described herein. The software 1122 may also reside completely or at least partially within the main memory 1104 and / or within the processor 1102 during its execution by the computer system 1100, the main memory 1104 and the processor 1102 also constituting machine-readable storage media. The software 1122 may further be transmitted or received over the network 1120 via the network interface device 1108.

[0102] Although the machine-accessible storage medium 1132 is shown as a single medium in the exemplary embodiment, the term "machine-readable storage medium" should be taken 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 taken to include any medium that is capable of storing or encoding a set of instructions for execution by a machine and causing the machine to perform any one or more methods of the present disclosure. The term "machine-readable storage medium" should accordingly be taken to include, but is not limited to, solid-state memories and optical and magnetic media.

[0103] According to an embodiment of the present disclosure, a machine-accessible storage medium has instructions stored thereon that cause a data processing system to perform a method of forming a positive photoresist layer on a substrate in 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 results in the formation of a positive photoresist layer on a surface of the substrate.

[0104] Thus, a method of forming a positive or negative photoresist using a dry process has been disclosed.

Claims

1. A method for patterning a metal oxide photoresist, comprising the following steps: Depositing the metal oxide photoresist on a substrate; treating the metal oxide photoresist with a first treatment; exposing the metal oxide photoresist using EUV exposure to form exposed areas and unexposed areas; treating the exposed metal oxide photoresist with a second treatment; as well as The metal oxide photoresist is developed. 2 . The method according to claim 1 , wherein the metal oxide photoresist is a positive photoresist.

3. The method of claim 2, wherein the step of developing the metal oxide photoresist comprises the following steps: The exposed area is removed.

4. The method of claim 2, wherein the developer solution comprises an aqueous alkaline medium.

5. The method of claim 4, wherein the developer solution comprises tetramethylammonium hydroxide (TMAH). The method according to claim 1 , wherein the metal oxide photoresist is a negative photoresist.

7. The method of claim 6, wherein the step of developing the metal oxide photoresist comprises the following steps: The unexposed areas are removed.

8. The method of claim 6, wherein the developer solution comprises an organic solvent.

9. The method of claim 8, wherein the organic solvent comprises 20 heptanone, MIBC, MIBK, anisole, D-limonene, methyl benzoate, n-butyl acetate, GBL or supercritical CO2.

10. The method of claim 1, wherein the first treatment comprises annealing at between 50°C and 200°C.

11. The method of claim 1, wherein the first treatment comprises ultraviolet treatment having a wavelength of 172 nm or more.

12. The method of claim 1, wherein the second treatment comprises annealing between 50°C and 300°C, and / or ultraviolet treatment having a wavelength of 172 nm or more.

13. The method of claim 1, further comprising the steps of: The developed metal oxide photoresist is treated by post-treatment, wherein the post-treatment includes annealing and / or ultraviolet treatment.

14. A method for depositing and patterning a photoresist, comprising the following steps: Depositing a photoresist on a substrate using a dry deposition process, wherein the photoresist comprises a metal oxide material; exposing the photoresist using EUV exposure to form exposed areas and unexposed areas; as well as The photoresist is developed by removing the exposed areas or the unexposed areas.

15. The method of claim 14, wherein the exposed areas are removed using an aqueous alkaline medium.

16. The method of claim 14, wherein the unexposed area is removed using an organic solvent.

17. The method of claim 14, wherein the step of exposing the photoresist to the EUV exposure results in breaking of metal-carbon bonds, and wherein the metal of the metal-carbon bonds is replaced by oxygen.

18. A method for patterning a substrate, comprising the following steps: Placing a photoresist on the substrate using a dry deposition process, wherein the photoresist is a metal oxide material; exposing the photoresist using EUV exposure to form exposed areas and unexposed areas; developing the photoresist to form openings through the photoresist by removing the exposed areas or the unexposed areas; as well as The substrate is etched through the opening in the photoresist.

19. The method of claim 18, wherein the exposed areas are removed using an aqueous alkaline medium.

20. The method of claim 18, wherein the unexposed area is removed using an organic solvent.

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