TW202407463A - Dual tone photoresists - Google Patents

Abstract

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

Description

Dual type photoresist

This application claims priority from U.S. Patent Application No. 17/862,283, filed on July 11, 2022, the entire contents of which are hereby incorporated by reference.

Embodiments of the present disclosure relate to the field of semiconductor processing, and in particular, to methods of depositing a positive photoresist layer onto a substrate using dry deposition and oxidation processes.

Lithography has been used in the semiconductor industry for decades to create two-dimension (2D) patterns and three-dimension (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 film by dissolving it in a solvent (etching), exposed (positive) or unexposed (negative) area. Bake out to drive out remaining solvent.

The photoresist should be a radiation-sensitive material and, upon irradiation, undergo a chemical transformation in the exposed portions of the film such that the solubility changes between exposed and non-exposed areas. Using this solubility change, 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 pattern transfer, the remaining photoresist is removed and the process is repeated multiple times to obtain 2D and 3D structures for microelectronic components.

Several properties of the lithography process are important. Such important properties include sensitivity, resolution, low line-edge roughness (LER), etch resistance and the ability to form thinner layers. When the 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 the features can be achieved with the lithography process. Pattern transfer requires higher etch-resistant materials to create deep structures. Higher etch-resistant materials also enable thinner films. Thinner films improve the efficiency of the lithography process.

Embodiments disclosed herein include a method of patterning metal oxide photoresists. In one embodiment, the method includes depositing a metal oxide photoresist on a substrate, treating the metal oxide photoresist with a first process, and exposing the metal oxide photoresist with EUV exposure to form exposed areas and unexposed areas, The exposed metal oxide photoresist is treated with a second process and the metal oxide photoresist is developed.

In one embodiment, methods of depositing and patterning photoresists are provided. In one embodiment, the method includes depositing a photoresist on a substrate using a dry deposition process, wherein the photoresist includes a metal oxide material, exposing the photoresist using EUV exposure to form exposed areas and unexposed areas, and The photoresist is developed by removing the exposed areas or the unexposed areas.

Embodiments may further include a method of patterning a substrate, the method comprising: disposing 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 an exposure areas and unexposed areas, developing the photoresist to form openings through the photoresist by removing the exposed areas or the unexposed areas, and etching through the openings in the photoresist substrate.

This article describes a method for depositing positive photoresist on a substrate using a dry deposition and oxidation process. In the following description, many specific details are set forth, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes and materials solutions used to deposit positive photoresists, 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 embodiments of the present disclosure may be practiced without these specific details. In other instances, well-known aspects, such as integrated circuit fabrication, have not been described in detail so as not to unnecessarily obscure the embodiments of the present disclosure. Furthermore, it should be understood that the various embodiments shown in the figures are illustrative representations and are not necessarily drawn to scale.

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 dosages to provide the required solubility transition to allow development of the photoresist material. Traditionally, carbon-based films called chemically amplified photoresist (CAR) have been used as photoresists. Recently, however, organic-inorganic hybrid materials (metal-oxygen) have been used as photoresists under extreme ultraviolet (EUV) radiation. Such materials typically include metals (eg Sn, Hf, Zr), oxygen and carbon. The lithography industry's transition 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, and can be implemented to make relatively thin films.

Currently, metal-oxygen photoresists are deposited by spin coating methods involving wet chemistry. A post-bake process is required to drive out any residual solvent in the film and stabilize the film. Additionally, wet processes produce large amounts of wet waste that industry would like to get rid of. Photoresist films deposited by spin coating often lead to non-uniformity issues. According to embodiments of the present disclosure, in order to address one or more of the above problems, a vacuum deposition process of a metal-oxygen positive photoresist is described herein.

In accordance with one or more embodiments of the present disclosure, described herein are dry deposition and oxidation processing methods for forming positive photoresist films. 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 to dry deposit the positive photoresist film. 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 below the precursor ampoule temperature.

Figure 1A illustrates a cross-sectional view illustrating various operations in a patterning process using a positive photoresist material formed by the processes described herein, in accordance with an embodiment of the present disclosure.

Referring to part (a) of Figure 1A, 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. Referring to part (b) of Figure 1A, the starting structure 100 is illuminated 106 at selected locations to form an illuminated photoresist layer 104A having illuminated areas 105B and unirradiated areas 105A. Referring to part (c) of Figure 1A, a removal or etching process 108 is used to provide a developed photoresist layer in unilluminated areas 105A. Referring to part (d) of FIG. 1A , an etching process 110 using unirradiated areas 105A as a mask is used to pattern the substrate or underlying layer 102 to form a patterned substrate or patterned underlying layer 102A that includes etched features 112 .

Referring again to Figure 1A, positive photoresist 104 is a radiation-sensitive material and, upon irradiation, undergoes a chemical transformation in the exposed portions of the film, which causes a change in solubility between 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 the underlying film or substrate by etching. After pattern transfer, the remaining positive photoresist is removed. This process can be repeated many times and can produce 2D and 3D structures, such as for microelectronic components.

Figure 1B illustrates a cross-sectional view illustrating various operations in a patterning process using negative photoresist materials formed by the processes described herein, in accordance with an embodiment of the present disclosure.

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

Referring again to Figure 1B, negative photoresist 103 is a radiation-sensitive material and, upon irradiation, undergoes a chemical transformation in the exposed portions of the film, which causes a change in solubility between 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 the underlying film or substrate by etching. After pattern transfer, the remaining negative photoresist is removed. This process can be repeated many times and can produce 2D and 3D structures, such as for microelectronic components.

As will be described in more detail below, both the positive resistor and the negative resist can be metal oxide photoresist films. In some cases, the same material system can be used for both positive and negative resistors. 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 can be used to form positive resistors or negative resistors.

To provide context, the lithography industry is accustomed to operating with positive photoresist (PR) materials. However, most metal-oxygen PR materials are negative photoresists. Positive photoresists have the advantages of higher resolution, higher resistance to dry etching and higher contrast than negative photoresists. In accordance with one or more embodiments of the present disclosure, methods of fabricating positive PR materials by dry deposition methods such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) are described.

In one embodiment, the Sn precursor is used in a vacuum deposition process of 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 Sn-C bonds. In one embodiment, a 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 oxidizing agent (eg, water) to A photoresist film is formed. 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, an indium-oxygen or tin-indium-oxygen film can also be used as a positive photoresist film. The methods described here can be extended to many other metal-containing films. Although this article focuses specifically 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 may specify whether the exposure (eg, EUV exposure) produces a positive resist or a negative resist.

According to embodiments of the present disclosure, positive or negative photoresists are made by using specific types of R groups in metal precursors or plasma-assisted deposition methods. For example, a phenyl (R)-containing Sn precursor (PhSn(NMe ₂ ) ₃ ) can be used. After exposing the resist to UV in ambient conditions, the exposed areas showed acidic portions by FTIR. Subsequently, the resist is immersed in an aqueous alkaline medium (eg, sodium hydroxide (NaOH) or tetramethylammonium hydroxide (TMAH)) and developed into a positive type. The acidic portion of the resist (exposed area) reacts with alkaline NaOH and dissolves in the aqueous medium, producing a positive resist. Furthermore, when using Sn(nBu) ₄ in PECVD, a positive resistor was obtained. Therefore, this article describes methods for making positive photoresists. In the opposite case (for example, for negative photoresists), the resist can be immersed in an organic solvent. Organic solvents dissolve unexposed areas of the resist film. Therefore, this article describes methods for making negative resistors.

In a first aspect, R groups with low radical stability are used. For example, R groups such as phenyl, alkenyl, and methyl have low radical stability (Sn-C → Sn• +C•). Figure 2A includes a general formula and specific examples of metal precursors suitable for manufacturing positive or negative photoresist films according to embodiments of the present disclosure. In one embodiment, the two embodiments on the left may be used with thermal CVD, while the two embodiments on the right may require PECVD in order to use the development process described below.

It should be understood that the lithography industry generally deals with positive type PR, and almost all new metal-oxygen PR are negative type PR. Positive PR can have the advantages of higher resolution, higher resistance to dry etching, and higher contrast than negative PR. However, metal-oxygen PR may require oxidation during or after exposure to function as positive PR. Here, a method for making positive-type PR using an oxidation operation is described. It should be understood that the same or similar methods can also be used for negative PR fabrication.

In a second aspect, for the exposure environment, when the photoresist is exposed to an energy source (eg, EUV), the exposure chamber (environment) can 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 repetitions of EUV exposure and subsequent oxygen exposure may be between 1 and 100 times.

In a third aspect, post-annealing 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 the plasma, and/or can be used with _N2 , Ar or He. In one embodiment, the post-annealing is performed at a temperature in the range of 25-200 degrees Celsius. In one embodiment, post-annealing is performed at a pressure of less than 200 Torr. In a specific embodiment, post-annealing is performed at a pressure of less than 200 Torr using ozone ( _O3 ) as the oxygen source gas at a temperature in the range of 25-250 degrees Celsius.

In the 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), NH ₄ OH, NaHCO ₃ , NaCO ₃ , N(CH ₃ ) ₄ OH, or as shown in Figure 2B may be used of amines.

In a fifth aspect, an organic solvent may be used to prepare a negative photoresist. Organic solvents can dissolve organic portions (ie, unexposed areas) of the photoresist film that have 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 .

Additionally, Figure 2C includes a list of certain metal precursors and specific examples of those metal precursors. A material with the general formula MR _{X LY} where x=0-6 and y=0-6 is shown. The R component may 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 alkoxide. The metal component can be any of those listed in Figure 2C. The material systems described in Figure 2C can be used as an alternative to, or in combination with, those material systems described in Figure 2A. Additionally, it should be understood that there may be overlap in the material systems depicted in Figures 2A and 2C. In one embodiment, the oxidant co-reactant is selected from the group consisting of water, O ₂ , N ₂ O, NO, CO ₂ , CO, ethylene glycol, alcohols (e.g., methanol, ethanol), peroxides (e.g., H ₂ O ₂ ) and a group of acids (such as formic acid, acetic acid).

In a first method, according to embodiments of the present disclosure, a chemical vapor deposition (CVD) method for forming a positive or negative photoresist includes: (A) applying one or more metals from Figure 2A The precursors and one or more of the oxidants listed above are vaporized into a vacuum chamber where the substrate wafer is maintained at a predetermined substrate temperature. The substrate temperature can vary from 0°C to 500°C. As the precursor/oxidant vaporizes into the chamber, it can be diluted with an inert gas such as Ar, N2, He. Due to the reactivity of the precursors and oxidants, a metal-oxygen film is deposited on the wafer. Vaporization of the chamber can be performed by all precursors simultaneously or by alternating pulses of metal precursors and oxidants. This process can be described as thermal CVD. (B) 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 a plasma treatment operation is subsequently performed. Plasma treatment may involve plasma from inert gases such as Ar, _N2 , He, or these gases may be mixed with O2 _{, CO2} , CO, NO, _NO2 , _H2O . These processes can be performed in a cyclic fashion; thermal deposition is followed by plasma treatment and the cycle is repeated or the deposition portion is completed and followed by a plasma treatment (post-processing). Plasma treatment after PECVD is also possible. In either case, in one embodiment, the post-annealing is performed in an oxygen-containing environment. In one embodiment, post-annealing is performed at a pressure of less than 200 Torr using ozone ( _O3 ) as the oxygen source gas in a temperature range of 25-250 degrees Celsius.

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) vaporizing the metal precursor in Figure 2A to In a vacuum chamber, the substrate wafer is maintained at a predetermined substrate temperature. The substrate temperature can vary from 0 to 500 degrees Celsius. Subsequently, internal gas purification is provided to remove by-products and excess metal precursors. One or more oxidants are then vaporized into the chamber. The oxidizing agent reacts with the metal precursor adsorbed on the surface. Subsequently, an inert gas purge is applied to remove by-products and unreacted oxidant. This cycle can be repeated to achieve the desired thickness. When the precursor or oxidant vaporizes into the chamber, it can be diluted with inert gases such as Ar, _N2 , and He. This process can be described as thermal ALD. Using this method, more than one metal can be incorporated into the film by pulsing additional metal precursors into the ALD cycle. Additionally, a different oxidizing agent can be pulsed after the first oxidizing agent. (B) The plasma can be turned on during the oxidant pulse, and the process can then be described as PE-ALD. (C) Additionally, deposition can be performed by thermal ALD, followed by plasma treatment. In this case, the film is thermally deposited, and a plasma treatment operation is subsequently performed. Plasma treatment may involve plasma from inert gases such as Ar, _N2 , He, or these gases may be mixed with O2 _{, CO2} , CO, NO, _NO2 , _H2O . These processes can be performed in a cyclic fashion; Plasma treatment after PE-ALD is also possible. In either case, in one embodiment, the post-annealing is performed in an oxygen-containing environment. In one embodiment, post-annealing is performed at a pressure of less than 200 Torr using ozone ( _O3 ) as the oxygen source gas in a temperature range of 25-250 degrees Celsius.

In a third method, according to embodiments of the present disclosure, an atomic layer deposition (ALD) or chemical vapor deposition (CVD) method for forming a positive or negative photoresist includes providing components throughout the film gradient. For example, the first few nanometers of the film have a different composition than the rest of the film. The main part of the film can be optimized for dose, but different components near the interface layer are targeted to alter adhesion, sensitivity to EUV photons, sensitivity to development chemistry to improve post-lithography profile control (specific scum) as well as defects and resistance to collapse/peeling. Gradients can be optimized for pattern type, for example columns need to increase adhesion, while line/space patterns can reduce adhesion to increase dose.

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 photoresists described herein have the advantages of higher resolution, higher dry etching resistance, and higher contrast than negative photoresists.

Advantages of implementing one or more of the 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 large amounts of wet by-products, which are best avoided. Additionally, spin coating (wet) often leads to non-uniformity issues that can be successfully addressed by the vacuum deposition method described in this article. 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 for a given deposition system. Precursors used to deposit positive or negative photoresist films under vacuum need to be volatile, and the precursors described herein are volatile based on the L and R structure. Dry deposition methods may require lower temperatures than other vacuum deposition methods such as ALD or CVD. When deposition is performed at low temperatures, relatively high amounts of carbon can remain in the film, which aids in patterning.

In one embodiment, the vacuum deposition process relies on a chemical reaction between a metal precursor and an oxidant. Vaporize the metal precursor and oxidant into the vacuum chamber. In some embodiments, the metal precursor is provided to the vacuum chamber along with the oxidant. In other embodiments, the metal precursor and oxidant are provided to the vacuum chamber in alternating pulses. After forming a metal-oxygen positive photoresist film with a desired thickness, the process can be stopped. In one embodiment, the optional plasma treatment operation may be performed after forming a metal-oxygen positive photoresist film having a desired thickness.

In one embodiment, a cycle including metal precursor vapor pulses and oxidant vapor pulses may be repeated multiple times to provide a metal-oxygen positive photoresist film with a desired thickness. In one embodiment, the order of the loops 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 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 than the pulse duration of the oxidant vapor. In one embodiment, the pulse duration may be between 0 seconds and 1 minute. In certain embodiments, the pulse duration may be between 1 second and 5 seconds. In one embodiment, each iteration of the loop uses the same process gas. In other embodiments, the process gas may be changed between cycles. For example, a first cycle may utilize a first metal precursor vapor, while a second cycle may utilize a second metal precursor vapor. Subsequent cycles may continue alternating between the first metal precursor vapor and the second metal precursor vapor. In one embodiment, multiple oxidant vapors can be alternated between cycles in a similar manner. In one embodiment, optional plasma processing operations may be performed after each cycle. That is, each cycle may include a metal precursor vapor pulse, an oxidant vapor pulse, and plasma treatment. In alternative embodiments, optional plasma processing operations may be performed after multiple cycles. In yet another embodiment, optional plasma processing operations may be performed after all cycles are completed (ie, as post-processing).

Providing metal-oxygen positive and negative photoresist films using dry deposition and oxidation processes such as those described in the examples above can achieve significant advantages over wet chemical methods. One such advantage is the elimination of wet by-products. With a dry deposition process, liquid waste is eliminated and by-product removal is simplified. In addition, the dry deposition process can provide more uniform positive and negative photoresist layers. Uniformity in this sense may represent thickness uniformity on the wafer and/or uniformity of metal composition distribution of the metal-oxygen film.

In addition, the use of dry deposition processes provides the ability to fine-tune the percentage of metals in positive or negative photoresists and the composition of metals in positive or negative photoresists. 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 dry deposition processes also allows the inclusion of a variety of different metals into the metal-oxygen film. For example, a single pulse flowing through two different metal precursors may be used, or alternating pulses of two different metal precursors may be used.

Additionally, 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 specific mechanism, resistance to thickness reduction is at least partially due to reduced carbon loss upon exposure.

Referring now to Figure 3, a schematic diagram of a chemical reaction to form a negative metal oxide photoresist is shown in accordance with an embodiment. As shown, metal precursor 320 may be supplied to a chamber (eg, a vacuum chamber). At 321 , an oxidation source, such as those described in greater detail above, may be supplied to the chamber to form metal oxide photoresist 322 . As shown, the metal-oxygen film may include a metal center (eg, Sn) bound to oxygen at a site previously occupied by ligand L. At operation 323, the negative photoresist film may be exposed (eg, by EUV exposure). This exposure produces a chemical reaction in which reactant groups R in exposed region 325 are displaced by oxygen. That is, the percentage of carbon in the exposed area decreases. Cross-linking may be higher in exposed areas than in unexposed areas. In unexposed areas 324, the chemical structure may retain the organic portion. Therefore, unexposed area 324 may have a lower polarity than exposed area 325 . The organic nature of the unexposed areas allows the unexposed areas 324 to be dissolved in organic solvents, such as those described in greater detail above.

Referring now to Figure 4, a schematic diagram of a chemical reaction to form a positive metal oxide photoresist is shown, in accordance with an embodiment. As shown, metal precursor 420 may be supplied to a chamber having an oxidation source 421. The reaction between metal precursor 420 and oxidation source 421 results in the formation of metal oxide film 422. At operation 423 , the metal oxide film 422 is exposed (eg, by EUV exposure) to create exposed areas 425 and unexposed areas 424 . Due to the organic nature of unexposed areas 424, unexposed areas 424 will not dissolve in the aqueous alkaline medium that will dissolve exposed areas 425.

That is, the choice of developer solution may allow the formation of a negative resistor or a positive resistor. The material systems used for negative resistors are generally similar to those used for positive resistors. Therefore, a single material system can be used with the flexibility to provide a negative or positive system. Accordingly, the material systems disclosed herein have increased value due to their ability to function as either a positive resistor or a negative resistor.

Referring now to FIG. 5 , a process flow diagram of a process 580 for developing a metal oxide film is shown, in accordance with an embodiment. In one embodiment, 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 greater detail above. For example, CVD, PE-CVD, ALD, and PE-ALD processes can be used to deposit metal oxide films on substrates. Although a dry deposition process is described in detail herein, it should be understood that the dual-type resist material may optionally be deposited via a spin-on deposition process or other wet deposition process.

In one embodiment, process 580 may continue with operation 582, which includes processing the metal oxide photoresist. In one embodiment, the treatment may be an annealing treatment. For example, annealing between 50°C and 200°C may be performed. This annealing can be in an inert annular or oxidizing environment. For example, O ₂ , O ₃ , H ₂ O, H ₂ O ₂ or alcohol can be used as the annealing environment. The surrounding environment can also be used for annealing. In some embodiments, treatment may include ultraviolet treatment. UV treatment can be provided in addition to annealing, or UV treatment can be provided without annealing. UV treatment can include exposure to light with wavelengths between 172 nm and 900 nm and powers in the range of 1 mW to 400 W.

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

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, post-exposure treatment may include annealing. For example, the annealing temperature can be between 50°C and 300°C. The annealing can be performed in an inert or oxidizing environment (eg, _O2 , _O3 , _H2O , _{H2O2 ,} or alcohol). In some embodiments, the ambient environment may be used for annealing. In some embodiments, post-exposure treatment may include UV treatment. UV treatment can be provided in addition to annealing, or UV treatment can be provided without annealing. UV treatment can include exposure to light with wavelengths between 172 nm and 900 nm and powers in the range of 1 mW to 400 W.

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

In one embodiment, process 580 may continue with operation 586, which includes treating the developed metal oxide photoresist with a post-development process. In one embodiment, post-development processing may include annealing. For example, the annealing temperature can be between 50°C and 300°C. The annealing can be performed in an inert or oxidizing environment (eg, _O2 , _O3 , _H2O , _{H2O2 ,} or alcohol). In some embodiments, the ambient environment may be used for annealing. In some embodiments, post-exposure treatment may include UV treatment. UV treatment can be provided in addition to annealing, or UV treatment can be provided without annealing. UV treatment can include exposure to light with wavelengths between 172 nm and 900 nm and powers in the range of 1 mW to 400 W.

In one embodiment, the vacuum chamber used in the dry deposition process is any suitable chamber capable of providing a pressure below 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 plasma within the chamber. A more detailed description of suitable vacuum chambers is provided below with respect to Figure 6. Figure 6 is a schematic diagram of a vacuum chamber configured to perform dry deposition of a metal-oxygen positive photoresist in accordance with an embodiment of the present disclosure.

Vacuum chamber 600 includes grounded chamber 605 . Substrate 610 is loaded via opening 615 and clamped on temperature controlled chuck 620 . In one embodiment, substrate 610 may be temperature controlled during dry deposition. For example, the temperature of the substrate 610 may range from approximately -40 degrees Celsius to 200 degrees Celsius. In a particular embodiment, substrate 610 may be maintained at a temperature between room temperature and 150°C.

Process gases are supplied from gas source 644 to the interior of chamber 605 via respective mass flow controllers 649. In certain embodiments, gas distribution plate 635 provides distribution of process gases 644 such as metal precursors, oxidants, and inert gases. Chamber 605 is evacuated via 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 above the substrate temperature, such as 25 degrees Celsius or more above the substrate temperature.

When RF power is applied during processing of substrate 610, a plasma is formed in the chamber processing region above substrate 610. Bias power RF generator 625 is coupled to temperature controlled chuck 620 . If needed, bias power RF generator 625 provides bias power to excite the plasma. The bias power RF generator 625 may have a low frequency, for example, between approximately 2 Mhz and 60 Mhz, and in a specific embodiment, a low frequency in a 13.56 MHz bandwidth. In some embodiments, the vacuum chamber 600 includes a third bias power RF generator 626 having a frequency of approximately 2 MHz bandwidth and connected to the bias power RF generator 625 Same RF match 627. Source power RF generator 630 is coupled to a plasma generating element (eg, gas distribution plate 635) via matching (not depicted) to provide source power to excite the plasma. Source RF generator 630 may have, for example, a frequency between 100 and 180 Mhz, and in a particular embodiment, a frequency in a 162 MHz bandwidth. As substrate diameters evolve 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.

Vacuum chamber 600 is controlled by controller 670. The controller 670 may include a CPU 672, a memory 673, and an I/O interface 674. CPU 672 may perform processing operations within vacuum chamber 600 according to instructions stored in memory 673 . For example, one or more processes, such as processes 120 and 440 described above, may be performed by controller 670 in a vacuum chamber.

In another aspect, embodiments disclosed herein include a processing tool that includes an architecture particularly suited for optimizing dry deposition. For example, a processing tool may include a pedestal for supporting a temperature-controlled wafer. In some embodiments, the temperature of the base can be maintained between about -40°C and about 200°C. Additionally, edge purge flows and shadow rings can be provided around the perimeter of the pillars supporting the substrate. Edge purge flows and shadow rings prevent positive photoresist deposition along the wafer edge or backside. In one embodiment, the base may also provide any desired clamping architecture, such as, but not limited to, vacuum clamping, monopolar clamping, or bipolar clamping, depending on the operating status of the processing tool.

In some embodiments, the processing tool may be adapted for deposition processes without plasma. Alternatively, the processing tool may include a plasma source to enable plasma enhanced operations. Furthermore, while the embodiments disclosed herein are particularly suitable 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 to deposit any positive photoresist material for any lithography protocol using a dry deposition process.

Referring now to Figure 7, a cross-sectional view of a processing tool 700 is shown in accordance with an embodiment. In an embodiment, processing tool 700 may include chamber 705 . Chamber 705 may be any suitable chamber capable of supporting sub-atmospheric pressure (eg, vacuum pressure). In one embodiment, an exhaust device (not shown) including a vacuum pump may be coupled to chamber 705 to provide sub-atmospheric pressure. In one embodiment, the lid may seal chamber 705. For example, the cover may include a spray head assembly 740 or the like. Showerhead assembly 740 may include fluid passages that enable process gas and/or inert gas to flow into chamber 705 . In some embodiments in which processing tool 700 is suitable for plasma enhancement operations, showerhead assembly 740 may be electrically coupled to an RF source and matching circuitry 750 . In yet another embodiment, tool 700 may be configured in a radio frequency bottom feed architecture. That is, base 730 is connected to the RF source, and showerhead assembly 740 is connected to ground. In such embodiments, the filtering circuitry may still be connected to the base. In one embodiment, the precursor gas is stored in ampoules 799.

In one embodiment, displaceable posts for supporting wafer 701 are provided in chamber 705 . In one embodiment, wafer 701 may be any substrate having a positive photoresist material deposited thereon. For example, wafer 701 may be a 300 mm wafer or a 450 mm wafer, although other wafer diameters may be used. Additionally, in some embodiments, wafer 701 may be replaced with a substrate having a non-circular shape. The displaceable column may include a column member 714 that extends out of the chamber 705. Post member 714 may have ports to provide electrical and fluid paths from outside the chamber 705 to various components of the post.

In one embodiment, the column may include a base plate 710 . Base plate 710 may be grounded. As will be described in greater detail below, the base plate 710 may include fluid channels to allow the flow of inert gas to provide an edge purge flow.

In one embodiment, the insulating layer 715 is disposed above the base plate 710 . Insulating layer 715 may be any suitable dielectric material. For example, the insulating layer 715 may be a ceramic plate or the like. In one embodiment, the base 730 is disposed above the insulating layer 715 . Base 730 may comprise a single material, or base 730 may be formed from different materials. In one embodiment, base 730 may utilize any suitable clamping system to secure wafer 701 . For example, base 730 may be a vacuum chuck or a monopole chuck. In embodiments where no plasma is generated in chamber 705, base 730 may utilize a bipolar clamping architecture.

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

In one embodiment, edge ring 720 surrounds insulation layer 715 and the perimeter of base 730 . Edge ring 720 may be a dielectric material, such as ceramic. In one embodiment, edge ring 720 is supported by base plate 710 . Edge ring 720 may support shadow ring 735. The inner diameter of shadow ring 735 is smaller than the diameter of wafer 701 . Thus, shadow ring 735 prevents deposition of positive photoresist onto portions 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 the edge purge flow, which will be described in more detail below. In one embodiment, a dual-channel nozzle can be used in a positive photoresist manufacturing process.

Although shadow ring 735 provides some protection to the top surface and edges of wafer 701 , process gases may flow/diffusion downward along the path between edge ring 720 and wafer 701 . Accordingly, embodiments disclosed herein may include a fluid path between edge ring 720 and base 730 to achieve 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 wafer 701 . Therefore, deposition of positive photoresist along the edges of wafer 701 is prevented.

Referring now to Figure 8, an enlarged cross-sectional view of a portion of a post 860 within a processing tool is shown, according to one embodiment. In Figure 8, only the left edge of post 860 is shown. However, it should be understood that the right edge of post 860 may substantially mirror the left edge.

In one embodiment, column 860 may include base plate 810 . An insulating layer 815 may be disposed on the base plate 810 . In one embodiment, the base 830 may include a first part _830A and a second part _830B . Cooling channels 831 may be positioned in the second portion _830B . First portion 830 _A may include features for holding wafer 801 .

In one embodiment, edge ring 820 surrounds base plate 810 , insulation layer 815 , base 830 and wafer 801 . In one embodiment, edge ring 820 is spaced apart from other components of column 850 to provide a fluid path 812 from base plate 810 to the top side of column 860 . For example, fluid path 812 may exit the pillar between wafer 801 and shadow ring 835 . In a particular embodiment, the inner surface of fluid path 812 includes the edge of insulating layer 815 , the edge of base 830 (ie, first portion 830 _A and second portion 830 _B ), and the edge of wafer 801 . In one embodiment, the outer surface of fluid path 812 includes the inner edge of edge ring 820 . In one embodiment, the fluid path 812 may also continue on the top surface of the portion of the susceptor 830 as it advances to the edge of the wafer 801 . As such, when an inert gas (eg, helium, argon, etc.) flows through fluid path 812 , the process gas is prevented from flowing/diffusing downward along the sides of wafer 801 .

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

In one embodiment, channels 811 are disposed in base plate 810 . Channel 811 directs the inert gas from the center of column 860 to the inner edge of edge ring 820. It should be understood that only a portion of channel 811 is shown in Figure 8 . A more complete description of channel 811 is provided below with reference to Figure 10B.

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

Referring now to FIGS. 9A and 9B , shown are a pair of cross-sectional views depicting portions of a processing tool with a base in different positions (in the Z direction), in accordance with an embodiment. In Figure 9A, the base is located lower within the chamber. The position of the pedestal in Figure 9A is where the wafer is inserted into or removed from the chamber via the slit valve. In Figure 9B, the base is in an elevated position within the chamber. The position of the base in Figure 9B is the position where the wafer is processed.

Referring now to Figure 9A, a cross-sectional view of the displaceable post 960 in a first position is shown in accordance with an embodiment. As shown in Figure 9A, the column includes a base plate 910, an insulating layer 915, a base 930 (ie, a first portion 930 _A and a second portion 930 _B ), and an edge ring 920. Such components may be substantially similar to the similarly indicated components above. For example, cooling channels 931 may be provided in the second portion _930B of the base 930 , channels 911 may be provided in the base plate 910 , and a seal 917 may be provided between the edge ring 920 and the base plate 910 .

As shown in Figure 9A, wafer 901 is placed on the top surface of susceptor 930. Wafer 901 may be inserted into the chamber via a slit valve (not shown). Additionally, shaded ring 935 is shown in an elevated position above edge ring 920 . Because 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 comes into contact with edge ring 920 .

In one embodiment, shadow ring 935 is supported by chamber liner 670. Chamber liner 970 may surround the outer perimeter of column 960. In one embodiment, retainer 971 is positioned on the top surface of chamber liner 970. Retainer 971 is configured to maintain shadow ring 935 in a raised position above edge ring 920 when post 960 is in the first position. In one embodiment, shadow ring 935 includes protrusions 936 for alignment with grooves 921 in edge ring 920 .

Referring now to Figure 9B, a cross-sectional view of post 960 is shown after engaging shadow ring 935, according to an embodiment. As shown, post 960 is displaced in the vertical direction (ie, the Z direction) until shadow ring 935 engages edge ring 920 . The additional vertical displacement of post 960 lifts shadow ring 935 away from retainer 971 on chamber liner 970. In one embodiment, shadow ring 935 is correctly aligned due to alignment features in shadow ring 935 and edge ring 920 (ie, grooves 921 and protrusions 936). In another embodiment, alignment features (not shown) may also be provided between the base 930 and the edge ring 920 . Alignment features between base 930 and edge ring 920 may include a tapered groove and protrusion architecture similar to the alignment features between edge ring 920 and shadow ring 935 .

Although in the second position, wafer 901 can be processed. Specifically, processing may include depositing a positive photoresist material on the top surface of wafer 901 . For example, the process may be a dry deposition and oxidation 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 deposition of positive photoresist onto wafer 901 , an inert gas may flow along fluid channels between the inner surface of edge ring 910 and insulating layer 915 , pedestal 930 , and the outer surface of wafer 901 . Therefore, positive photoresist deposition along the edges or backside of wafer 901 is essentially eliminated. In one embodiment, wafer temperature 901 can be maintained between about -40°C and about 200°C by cooling channels 931 in the second portion _930B of the base.

Referring now to Figure 10A, a schematic diagram of a processing tool 1000 is shown according to a further embodiment. As shown in Figure 10A, the column includes a base plate 1010. The base plate 1010 may be supported by posts 1014 extending out of the chamber. That is, in some embodiments, the base plate 1010 and the posts 1014 may be discrete components rather than a single monolithic component as shown in FIG. 7 . Column 1014 may have a central channel for conducting electrical connections and fluids (eg, cooling fluid and inert gas for purge flow).

In one embodiment, the insulating layer 1015 is disposed above the base plate 1010 , and the base 1030 (ie, the first part 1030 _A and the second part 1030 _B ) is disposed above the insulating layer 1015 . In one embodiment, coolant channels 1031 are provided in the second portion _1030B of the base 1030. Wafer 1001 is disposed above susceptor 1030.

In one embodiment, edge ring 1020 is disposed around base plate 1010 , insulation layer 1015 , base 1030 and wafer 1001 . Edge ring 1020 may be coupled to base plate 1013 by fastening mechanisms 1013 such as bolts, pins, screws, or the like. In one embodiment, seal 1017 prevents purge gases from exiting the column from the bottom between the gap between base plate 1010 and edge ring 1020 .

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

Referring now to Figure 10B, a cross-sectional view of chamber 1000 is shown in accordance with additional embodiments. In the illustration of FIG. 10B , the insulating layer 1015 and the base 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 edges of the base plate 1010 . In the illustrated embodiment, a plurality of first channels connects the center of the base plate 1010 to a first annular channel, and a plurality of second channels connects the first annular channel to the outer edge of the base plate 1010 . In one embodiment, the first channel and the second channel are offset from each other. Although a specific configuration of channels 1011 is shown in Figure 10B, it should be understood that any channel configuration may be used to direct the inert gas from the center of the substrate 1010 to the edges of the substrate 1010.

Figure 11 shows a diagrammatic representation of a machine in the form of an exemplary computer system 1100 in which a set of instructions may be executed for causing the machine to perform any one or more methodologies described herein. In alternative embodiments, the machine may be connected (eg, network connected) to other machines in a local area network (LAN), an intranet, a business network, or the Internet. The machine can operate as a server or client machine in a client-server network environment, or as a peer machine in a peer (distributed) network environment. The machine can be a personal computer (PC), tablet computer, set-top box (STB), personal digital assistant (PDA), cellular phone, network equipment, server, network A router, switch, or bridge, or any machine capable of executing a set of instructions (sequential or otherwise) that specifies actions to be taken by that machine. Furthermore, although only a single machine is illustrated, the term "machine" shall also be taken to include any machine that individually or jointly executes a set (or sets) of instructions to perform any one or more of the methodologies described herein. (e.g., computer) collection.

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.), static memory 1106 (for example, flash memory, static random access memory (static random access memory; SRAM), MRAM, etc.), and Auxiliary memory 1118 (eg, data storage device), each of which communicates with each other via bus 1130 .

Processor 1102 represents one or more general-purpose processing devices, such as a microprocessor, central processing unit, or the like. More specifically, the processor 1102 may be a complex instruction set computing (CISC) microprocessor, a reduced instruction set computing (RISC) microprocessor, or a very long instruction word (very long instruction) microprocessor. word; VLIW) microprocessor, a processor that implements another instruction set, or a processor that implements 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), or a digital signal processor (digital signal processor). processor; DSP), network processor, etc. Processor 1102 is configured to execute processing logic 1126 for performing the operations described herein.

Computer system 1100 may further include a network interface device 1108. The computer system 1100 may also include a video display unit 1110 (for example, a liquid crystal display (LCD), a light emitting diode display (LED), or a cathode ray tube (CRT)), Alphanumeric input device 1112 (eg, keyboard), cursor control device 1114 (eg, mouse), and signal generation device 1116 (eg, speaker).

Secondary memory 1118 may include machine-accessible storage media (or more specifically computer-readable storage media) 1132 having stored thereon one or more sets embodying any one or more of the methods or functions described herein. Instructions (e.g., software 1122). Software 1122 may also reside fully or at least partially within main memory 1104 and/or within processor 1102 during its execution by computer system 1100, which also constitutes a machine-readable storage medium. Software 1122 may further be transmitted or received over network 1120 via network interface device 1108 .

Although machine-accessible storage medium 1132 is shown in the exemplary embodiment as a single medium, the term "machine-readable storage medium" shall be taken to include a single medium or multiple media that stores one or more sets of instructions (e.g., centralized formal or distributed database, and/or associated caches and servers). The term "machine-readable storage medium" shall also be deemed to include any medium that can store or encode a set of instructions for execution by a machine and any one or more means of causing the machine to perform the present disclosure. The term "machine-readable storage media" shall accordingly be deemed to include, without limitation, solid-state memory and optical and magnetic media.

According to embodiments 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 metal precursor vapor into a vacuum chamber. The method also includes providing oxidant vapor into the vacuum chamber. The reaction between the metal precursor vapor and the oxidant vapor results in the formation of a positive photoresist layer on the surface of the substrate.

Therefore, methods of forming positive or negative photoresists using dry processes have been disclosed.

100: Starting structure 102: Substrate/lower layer 102A: Patterned substrate/Patterned lower layer 103: Negative photoresist layer 103A: Irradiated photoresist 104: Positive photoresist layer 104A: Irradiated photoresist layer 105A: Unirradiated area 105B: Illuminated area 106: Illuminated 108: Removal or etching process 110: Etching process 112: Etched features 320: Metal precursor 321: Operation 322: Metal oxide photoresist 323: Operation 324: Unexposed area 325: Exposed area 420: metal precursor 421: oxidation source 422: metal oxide film 423: operation 424: unexposed area 425: exposed area 580: process 581: operation 582: operation 583: operation 584: operation 585: operation 586: operation 600 : Vacuum chamber 605: Chamber 610: Substrate 615: Opening 620: Temperature controlled chuck 625: Bias power RF generator 626: Third bias power RF generator 627: RF matching 630: Source power RF generator 635 : Gas distribution plate 644: Gas source 649: Mass flow controller 670: Controller 672: CPU 673: Storage 674: I/O interface 700: Processing tool 701: Wafer 705: Chamber 710: Base plate 711: Channel 714 : Pillar 715: Insulation layer 720: Edge ring 730: Base 731: Cooling channel 735: Shadow ring 740: Nozzle assembly 745: Filter circuit system 750: Matching circuit system 799: Ampoule 801: Wafer 810: Base plate 811: Channel 812: Fluid path 815: Insulation layer 817: Seal 820: Edge ring 821: Groove 830 _A : First part 830 _B : Second part 831: Cooling channel 835: Shadow ring 836: Protrusion 860: Pillar 901: Wafer 910 :edge ring 911:channel 915:insulation layer 917:seal 920:edge ring 921:groove 930 _A :first part 930 _B :second part 931: cooling channel 935: shadow ring 936: protrusion 960: column 970: chamber Liner 971: Holder 1000: Processing Tool 1001: Wafer 1010: Base Plate 1011: Channel 1013: Fastening Mechanism 1014: Post 1017: Seal 1020: Edge Ring 1030 _A : First Part 1030 _B : Second Part 1031: Coolant Channel 1035: Shadow ring 1070: Chamber lining 1071: Holder 1100: Computer system 1102: Processor 1104: Main memory 1106: Static memory 1108: Network interface device 1110: Video display unit 1112: Alphanumeric input device 1114: Cursor control device 1116: Signal generation device 1118: Auxiliary memory 1120: Network 1122: Software 1126: Processing logic 1130: Bus 1132: Machine-accessible storage media

Figure 1A illustrates a cross-sectional view illustrating various operations in a patterning process using a positive photoresist material formed by the processes described herein, in accordance with an embodiment of the present disclosure.

Figure 1B illustrates a cross-sectional view illustrating various operations in a patterning process using negative photoresist materials formed by the processes described herein, in accordance with an embodiment of the present disclosure.

Figure 2A includes a general formula and specific examples of metal precursors suitable for manufacturing positive photoresist films according to embodiments of the present disclosure.

Figure 2B illustrates amines that can be used as developers for negative photoresists in accordance with embodiments of the present disclosure.

Figure 2C includes a general formula and specific examples of metal precursors suitable for manufacturing positive or negative photoresist films according to embodiments of the present disclosure.

Figure 3 is a schematic diagram of chemical reactions occurring in a negative photoresist film according to an embodiment of the present disclosure.

Figure 4 is a schematic diagram of chemical reactions occurring in a positive photoresist film according to an embodiment of the present disclosure.

Figure 5 is a process flow diagram of a process for patterning a metal oxide photoresist film according to an embodiment of the present disclosure.

Figure 6 is a cross-sectional view of a processing tool that may be used to perform the dry deposition and oxidation processing processes described herein, in accordance with embodiments of the present disclosure.

Figure 7 is a cross-sectional view of a processing tool for depositing a positive photoresist layer on a substrate using dry deposition and oxidation processing processes in accordance with an embodiment of the present disclosure.

Figure 8 is an enlarged view of an edge of a displaceable pillar in a processing tool for depositing a positive photoresist layer on a substrate using dry deposition and oxidation processing processes in accordance with an embodiment of the present disclosure.

Figure 9A is an enlarged illustration of an edge of a displaceable post in a processing tool, in which the hatched ring does not engage the edge ring, in accordance with an embodiment of the present disclosure.

Figure 9B is an enlarged illustration of an edge of a displaceable post in a processing tool, with the hatched ring engaging the edge ring, in accordance with an embodiment of the present disclosure.

Figure 10A is a cross-sectional view of a processing tool for depositing a positive photoresist layer on a substrate using dry deposition and oxidation processing processes in accordance with an embodiment of the present disclosure.

Figure 10B is a cross-sectional view of a processing tool with the base removed to expose channels in the base plate, in accordance with an embodiment of the present disclosure.

Figure 11 illustrates a block diagram of an exemplary computer system in accordance with embodiments of the present disclosure.

Domestic storage information (please note in order of storage institution, date and number) without Overseas storage information (please note in order of storage country, institution, date, and number) without

580:Process

581:Operation

582:Operation

583:Operation

584:Operation

585:Operation

586:Operation

Claims (20)

A method for patterning a metal oxide photoresist, including the following steps: depositing the metal oxide photoresist on a substrate; Treat the metal oxide photoresist with a first treatment; Exposing the metal oxide photoresist with an EUV exposure to form exposed areas and unexposed areas; Treat the exposed metal oxide photoresist with a second treatment; and The metal oxide photoresist is developed. The method of claim 1, wherein the metal oxide photoresist is a positive photoresist. The method of claim 2, wherein the step of developing the metal oxide photoresist includes the following steps: removing the exposed areas. The method of claim 2, wherein a developer solution contains an aqueous alkaline medium. The method of claim 4, wherein the developer solution contains tetramethylammonium hydroxide (TMAH). The method of claim 1, wherein the metal oxide photoresist is a negative photoresist. The method of claim 6, wherein the step of developing the metal oxide photoresist includes the following steps: removing the unexposed areas. The method of claim 6, wherein a developer solution contains an organic solvent. The method of claim 8, wherein the organic solvent includes 20 heptanone, MIBC, MINK, anisole, D-limonene, methyl benzoate, n-butyl acetate, GBL and supercritical CO ₂ . The method of claim 1, wherein the first treatment includes an annealing between 50°C and 200°C. The method of claim 1, wherein the first treatment includes an ultraviolet treatment with a wavelength of 172 nm or greater. The method of claim 1, wherein the second treatment includes an annealing between 50°C and 300°C, and/or an ultraviolet treatment with a wavelength of 172 nm or greater. The method described in request 1 further includes the following steps: The developed metal oxide photoresist is treated with a post-processing, which includes an annealing and/or an ultraviolet treatment. A method of depositing and patterning a photoresist includes the following steps: Deposit a photoresist on a substrate using a dry deposition process, wherein the photoresist includes a metal oxide material; Expose the photoresist with an EUV exposure to form exposed areas and unexposed areas; and The photoresist is developed by removing the exposed areas or the unexposed areas. The method of claim 14, wherein the exposed areas are removed using an aqueous alkaline medium. The method of claim 14, wherein the unexposed areas are removed using an organic solvent. The method of claim 14, wherein the step of exposing the photoresist with the EUV exposure results in the breaking of metal-carbon bonds, and wherein the metal of the metal-carbon bonds is replaced by oxygen. A method of patterning a substrate includes the following steps: using a dry deposition process to place a photoresist on the substrate, wherein the photoresist is a metal oxide material; Exposing the photoresist with an 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 The substrate is etched through the openings in the photoresist. The method of claim 18, wherein the exposed areas are removed using an aqueous alkaline medium. The method of claim 18, wherein the unexposed areas are removed using an organic solvent.