Baking method for improving the lithographic performance of metal-containing resists - Patent Application 20070122999

Abstract

SOLUTION: Various embodiments herein relate to methods, apparatus, and systems for baking metal-containing on a semiconductor substrate in the presence of a reactive gas species. For example, the method may include: receiving the substrate in a process chamber, the substrate having a photoresist layer thereon, where the photoresist layer includes a metal-containing photoresist material; causing a reactive gas species to flow from a gas source, through a gas delivery line, into the process chamber; and exposing the substrate to the reactive gas species in the process chamber; and baking the photoresist layer while the substrate is exposed to the reactive gas species.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Incorporation by Reference A PCT application is filed concurrently herewith as a part of this application. Each application to which this application claims benefit or priority, as identified in the concurrently filed PCT application, is incorporated herein by reference in its entirety for all purposes.

[0002] The present disclosure relates generally to the field of semiconductor processing. In particular aspects, the present disclosure relates to processes and apparatus for photoresist processing associated with lithographic patterning and film development to form pattern masks. [Background technology]

[0003] As semiconductor manufacturing advances, feature sizes continue to shrink, requiring new processing methods. One area of ​​advancement relates to patterning, for example, using photoresist materials that are patterned by exposure to radiation.

[0004] The discussion of the background art provided herein is for the purpose of generally presenting the contents of the present disclosure, and the inventions of the presently named inventors are not admitted expressly or impliedly as prior art to the present disclosure, to the extent that they are described in this background art section or in aspects of the description that are not prior art at the time of filing. Summary of the Invention

[0005] Various embodiments herein relate to methods, apparatus, and systems for baking a photoresist layer on a substrate. In one aspect of the embodiments of the present disclosure, a method of baking a photoresist layer on a substrate is provided, the method comprising: receiving the substrate into a processing chamber; the substrate having a photoresist layer thereon, the photoresist layer comprising a metal-containing photoresist material; flowing reactive gas species from a gas source through a gas supply line into the processing chamber; exposing the substrate to the reactive gas species in the processing chamber; and baking the photoresist layer while the substrate is exposed to the reactive gas species.

[0006] In various embodiments, the photoresist layer comprises an extreme ultraviolet (EUV) photoresist material. In some embodiments, the reactive gas species comprises a gas selected from the group consisting of water, hydrogen, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, ammonia, nitrous oxide, nitric oxide, alcohol, acetylacetone, formic acid, oxalyl chloride, pyridine, a carboxylic acid, an amine, and combinations thereof. In some cases, the reactive gas species may include water. In these or other cases, the reactive gas species may include hydrogen. In these or other cases, the reactive gas species may include oxygen. In these or other cases, the reactive gas species may include ozone. In these or other cases, the reactive gas species may include hydrogen peroxide. In these or other cases, the reactive gas species may include carbon monoxide. In these or other cases, the reactive gas species may include carbon dioxide. In these or other cases, the reactive gas species may include ammonia. In some such cases, baking the photoresist occurs after the photoresist is exposed to EUV radiation to pattern the photoresist, and any of the following conditions is met: (i) the process chamber is maintained at atmospheric pressure during the photoresist bake and ammonia is provided at a concentration of about 0.001-5% (by volume), and (ii) the process chamber is maintained at subatmospheric pressure during the photoresist bake and ammonia is provided at a partial pressure of about 1-100 mTorr. In these and other cases, the reactive gas species may include nitrous oxide and / or nitric oxide. In these and other cases, the reactive gas species may include alcohol. In these and other cases, the reactive gas species may include acetylacetone. In these and other cases, the reactive gas species may include formic acid. In these and other cases, the reactive gas species may include oxalyl chloride. In these and other cases, the reactive gas species may include a carboxylic acid. In these and other cases, the reactive gas species may include an amine. Examples of amines may include, in certain cases, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and / or triethylamine.In various embodiments, the reactive gas species may be oxidizing. In these and other cases, the reactive gas species may be polar.

[0007] In certain embodiments, exposure of the substrate to reactive gas species may promote crosslinking in the photoresist layer. In these or other embodiments, exposure of the substrate to reactive gas species may promote removal of low molecular weight species within the photoresist layer. For example, the low molecular weight species may contain zero, one, or two metal atoms per molecule. In some embodiments, exposure of the substrate to reactive gas species may oxidize metal hydride species within the photoresist layer to metal hydroxide species.

[0008] In certain embodiments, the method may further comprise applying a vacuum to the processing chamber while baking the photoresist layer. In these or other embodiments, the method may further comprise controlling the moisture concentration in the processing chamber to remain within a target moisture concentration range while baking the photoresist layer. Similarly, the method may comprise controlling the oxygen concentration in the processing chamber to remain within a target oxygen concentration range while baking the photoresist layer. In some embodiments, the processing chamber may be maintained at sub-atmospheric pressure while baking the photoresist layer. For example, in some cases, the processing chamber may be maintained at less than atmospheric pressure while baking the photoresist layer.

[0009] The support on which the substrate is placed may be temperature controlled during baking of the photoresist layer. For example, in some embodiments, the method may further comprise increasing the temperature of the substrate support on which the substrate is placed during baking of the photoresist layer. In these or other embodiments, the method may further comprise decreasing the temperature of the substrate support on which the substrate is placed during baking of the photoresist layer. In some cases, the method may comprise controlling the flow of reactants into the processing chamber to achieve a target degree of crosslinking. A variety of different types of heat may be provided. In some embodiments, baking the photoresist includes heating the substrate on a hotplate. In some embodiments, baking the photoresist includes exposing the substrate to infrared and / or ultraviolet light. In some embodiments, baking the photoresist layer may include heating the substrate from above. In these or other embodiments, baking the photoresist layer may include heating the substrate from below.

[0010] The methods described herein may be used for different applications. In some cases, a photoresist layer is applied to a substrate but not yet patterned, and the baking is a post-apply bake (PAB). In other cases, a photoresist layer is applied to a substrate and patterned by partial exposure to EUV radiation, resulting in exposed and unexposed portions of the photoresist layer, and the baking is a post-exposure bake (PEB). In these or other embodiments, the reactive gas species may include polar and oxidizing molecules. For example, the reactive gas species may include hydrogen peroxide.

[0011] In another aspect of an embodiment of the present disclosure, there is provided an apparatus for baking a photoresist layer on a substrate, the apparatus comprising: a process chamber, an inlet for introducing reactive gas species into the process chamber, an outlet for removing material from the process chamber, a substrate support within the process chamber, a heater configured to heat the substrate by conduction, convection, and / or radiation, and a controller having at least one processor configured to control the apparatus to perform a method of the present application or methods described herein.

[0012] These and other aspects are further described below with reference to the drawings. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a flowchart illustrating a lithographic patterning process in accordance with various embodiments.

[0014] [Figure 2] 1 is a simplified diagram of a processing chamber in accordance with certain embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0015] Reference will be made in detail herein to specific embodiments of the present disclosure. Examples of specific embodiments are illustrated in the accompanying drawings. While the present disclosure will be described in conjunction with these specific embodiments, it will be understood that there is no intention to limit the disclosure to such specific embodiments. To the contrary, the present disclosure is intended to include alternatives, modifications, and equivalents which may be included within the spirit and scope of the present disclosure. In the following description, several specific details are set forth in order to provide a thorough understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the present disclosure.

[0016] Patterning of thin films in semiconductor processing is often a critical step in semiconductor manufacturing. Patterning involves lithography. In traditional photolithography (such as 193 nm photolithography), a pattern is printed onto a light-sensitive photoresist film by exposing the photoresist to photons in selected areas defined by a photomask, causing a chemical reaction in the photoresist that creates a chemical contrast that can be exploited in a development process to remove specific portions of the photoresist and form the pattern. The patterned and developed photoresist film can then be used as an etch mask to transfer the pattern into underlying films made of metals, oxides, etc.

[0017] Advanced technology nodes (as defined by the International Technology Roadmap for Semiconductors), including the 22 nm node, 16 nm node, and beyond, require continued improvements in lithographic resolution. For example, at the 16 nm node, via or line widths in damascene structures are typically about 30 nm or less, which are not possible using simple 193 nm photolithography or would otherwise involve complex multi-patterning methods.

[0018] Extreme ultraviolet (EUV) lithography can expand lithography technology by moving to shorter image source wavelengths than are achievable with conventional photolithography methods. EUV light sources with wavelengths of approximately 10-20 nm or 11-14 nm (e.g., 13.5 nm wavelength) can be used in cutting-edge lithography tools (also called scanners). EUV radiation is strongly absorbed by a wide range of solid and liquid materials, including quartz, water vapor, and atmospheric pressure gases, so EUV scanners operate in a vacuum.

[0019] EUV lithography utilizes EUV resists that can be patterned using EUV light to form masks for use in etching underlying layers. The EUV resists can be polymer-based chemically amplified resists (CARs) applied by liquid spin-on techniques. An alternative to CARs are metal oxide-based EUV photoresist (PR) films that can be directly photopatterned. Such PR films may be formed by (wet) spin-on techniques, such as those available from Inpria of Corvallis, Oregon, such as those described in U.S. Patent Applications US2017 / 0102612 and US2016 / 0116839, which are incorporated by reference herein for at least their disclosure of photopatternable metal oxide-containing films, or the dry-deposited films described in PCT Application No. PCT / US19 / 31618, filed May 9, 2019, entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," which is incorporated by reference herein for at least its disclosure regarding the composition and patterning of directly photopatternable metal oxide films to form EUV resist masks. These directly photopatternable EUV resists may consist of or include high EUV absorbance metals, their organometallic oxides / hydroxides, and other derivatives. Upon EUV exposure, EUV photons and generated secondary electrons are converted into SnO x These compounds can induce chemical reactions, such as beta-H elimination reactions, in resists (and other metal oxide-based resists), providing chemical functionality that promotes crosslinking and other changes in the resist film. These chemical changes can then be exploited in a development step to selectively remove exposed or unexposed areas of the resist film, forming an etch mask for pattern transfer.

[0020] While this disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, it should be understood that it is also applicable to other next-generation lithography technologies. In addition to EUV, with the standard 13.5 nm EUV wavelength currently in use and under development, the most relevant radiation source for such lithography is DUV (deep ultraviolet), which generally refers to the use of 248 nm or 193 nm excimer laser sources, X-rays (formally including EUV in the lower energy range of X-rays), and electron beams (which may include a wide energy range). Specific methods may depend on the specific materials and applications used in the semiconductor substrate and final semiconducting device. Thus, the methods described herein are merely examples of methods and materials that may be used with the present techniques.

[0021] Photolithography processes typically include one or more bake steps to promote the chemical reactions necessary to create chemical contrast between exposed and unexposed areas of the photoresist. Such bake steps are typically performed on a track-based basis for high volume manufacturing (HVM), where the wafer is baked in an atmosphere or, in some cases, on a hotplate at a predetermined temperature under a N2 flow. During these bake steps, tighter control of the bake atmosphere as well as the introduction of additional reactive gas components into the atmosphere can help further reduce dose requirements and / or improve pattern fidelity.

[0022] This disclosure describes a new baking method that includes thorough control of the baking atmosphere and reactive gas introduction, and in some cases, thorough control of the baking temperature ramp rate. Such a method can be particularly effective for metal oxide-based EUV photoresists (PRs). Examples of effective reactive gases include water, hydrogen, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, ammonia, nitrous oxide, nitric oxide, methylamine, dimethylamine, alcohols, acetylacetone, formic acid, oxalyl chloride, carboxylic acids, other amines, substitutions of these materials, and the like. Reactive gases may be provided in the gas phase and vaporized prior to delivery to the reaction chamber. Various exemplary gases are further described below.

[0023] Although the present disclosure is not limited to a particular logic or mechanism of operation, it is understood that these reactive gas molecules may accelerate the crosslinking reaction of the metal oxide-based EUV photoresist in the EUV-exposed regions (in this example, the regions remaining for mask formation following development of the patterned film) through oxidation, coordination, or acid-base chemistry, while having limited impact on crosslinking in the unexposed regions. Alternatively, or in addition, in some cases, the reactive gas molecules may facilitate the removal of volatile species from the metal oxide-based EUV photoresist, further enhancing the stability of the resist.

[0024] FIG. 1 shows a flowchart according to various embodiments. In operation 101, resist is deposited on a substrate. The substrate on which the resist is deposited typically includes an underlying material that will ultimately be etched after the resist is patterned and developed. In various embodiments, the substrate on which the resist is deposited may have an exposure layer such as amorphous carbon, spin-on carbon (SoC), spin-on glass (SoG), silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, or silicon oxycarbide. Often, the exposure layer is an ashable hard mask (AHM). The resist deposited in operation 101 is a metal oxide-based EUV photoresist. This deposition may occur by a wet spin-on technique or a dry vapor-based technique such as chemical vapor deposition (CVD) and / or atomic layer deposition (ALD), which may be operated by thermal energy, plasma energy, or both. Next, in operation 103, the substrate is exposed to heat in a first baking step, often referred to as a post-apply bake (PAB). In operation 105, the substrate is exposed to EUV radiation to pattern the resist, thereby forming exposed and unexposed regions in the resist. Then, in operation 107, the substrate is exposed to heat in a second baking step, often referred to as a post-exposure bake (PEB). Then, in operation 109, the resist is developed to selectively remove the unexposed regions. In various embodiments herein, the atmosphere to which the substrate is exposed may be controlled during the PAB in operation 103 and / or during the PEB in operation 107. For example, the substrate may be exposed to one or more reactive gases during these steps. Each baking step is described further below. 1. Post-apply bake (PAB)

[0025] A post-apply bake is performed after the resist is deposited on a substrate and before the resist is exposed to EUV radiation for patterning. See operation 103 in Figure 1. A PAB may be performed to remove excess solvent (e.g., if the resist is deposited using a spin-on method), remove other low molecular weight or volatile species, and promote a desired degree of cross-linking in the resist. These features act to enhance the stability of the resist. For example, by removing unbonded or only loosely bound low molecular weight or volatile species in the resist, outgassing of metal-containing molecules can be reduced to an acceptable amount (e.g., <1E10 molecules / (cm 2 The PAB process can be reduced to 100 times the normal PAB time. Removal of these materials is advantageous because they can contaminate downstream processes, equipment, and substrates if not removed. Crosslinking achieved during PAB also enhances resist stability, but too much crosslinking can result in increased linewidth roughness. Therefore, crosslinking can be controlled to a desired degree during PAB.

[0026] In various embodiments herein, the substrate may be exposed to a reactive gas during PAB. The reactive gas may promote the removal of low-molecular-weight or volatile species. In various embodiments, the low-molecular-weight species removed during PAB may have zero metal atoms, one metal atom, or two metal atoms. In some cases, the low-molecular-weight species removed may include bimetallic species. Molecules with three or more metal atoms typically have a relatively heavy molecular weight and are relatively less volatile, and may substantially remain in the resist during PAB. In addition to removing the low-molecular-weight species, the reactive gas may promote a desired degree of crosslinking within the resist. As a result of these characteristics, the use of a reactive gas during PAB may help stabilize the resist.

[0027] Exemplary processing equipment and reactive gases are provided below. In various embodiments, the substrate may be exposed to one or more of these reactive gases during PAB. In certain examples, the substrate may be exposed to a processing atmosphere having a controlled amount of oxygen and / or moisture (e.g., water vapor) along with an inert gas during PAB. In some embodiments, suitable gas sensors and feedback mechanisms may be used to ensure that the components of the processing atmosphere are controlled within desired ranges.

[0028] In various embodiments, one or more process conditions may be controlled during the PAB as follows: The substrate may be heated to an elevated temperature of about 100-170°C (e.g., about 100-130°C in some cases). The pressure may be maintained at about 0.1-760 Torr (e.g., about 0.1-1 Torr in some cases). The substrate may be exposed to the elevated temperature for about 1-10 minutes (e.g., about 2-5 minutes). An inert gas may be flowed into the process chamber at a rate of about 10-10,000 sccm. In certain examples, the oxygen (e.g., O) concentration in the process chamber may be controlled during the PAB. In these or other embodiments, the moisture (e.g., HO vapor) concentration may be controlled during the PAB.

[0029] In some embodiments, PAB may be omitted. For example, if the resist is deposited by a dry vapor-based technique rather than a wet spin-on technique, PAB may not be necessary because excess solvent used to deposit the resist does not need to be removed. However, even if the resist is deposited by a dry vapor-based technique, it may be advantageous to perform PAB to promote the desired degree of crosslinking and to remove low molecular weight or non-volatile species that may be of greater concern with dry vapor-based deposition techniques than with wet spin-on techniques. In some embodiments, the PAB may be conventional PAB. That is, the PAB may occur without exposing the substrate to reactive gas species and / or in an uncontrolled atmosphere. In such embodiments, the substrate may be exposed to reactive gas species during a post-exposure bake, as described further below. 2. Post-Exposure Bake (PEB)

[0030] A post-exposure bake is performed after the resist is exposed to EUV radiation for patterning and before the resist is developed to remove the unexposed portions thereof. See operation 107 in Figure 1. PEB may be performed for several purposes, for example, 1) to promote complete evaporation of organic fragments generated during EUV exposure, 2) to oxidize metal hydride species (other products from the beta-H elimination reaction during EUV exposure) to metal hydroxides, and 3) to promote cross-linking between adjacent -OH groups to form a cross-linked metal oxide network.

[0031] The baking temperature is carefully selected to achieve optimal EUV lithography performance. A PEB temperature that is too low will result in incomplete removal of organic fragments as well as insufficient crosslinking, resulting in insufficient chemical contrast for development at a given dose. A PEB temperature that is too high will also result in adverse effects, including severe oxidation and film shrinkage in unexposed areas (in this example, areas removed by development of the patterned film to form the mask) and undesirable interdiffusion at the interface between the PR and the underlayer (UL) (typically a spin-on carbon material), both of which will result in reduced chemical contrast and increased defect density due to insoluble debris. With baking temperature and baking time as the only knobs, tunability and process window are often quite limited.

[0032] As described herein, thorough control of the baking atmosphere and introduction of reactive gas species during the PEB process provides additional chemical knobs for fine-tuning the crosslinking process. For example, because exposed regions tend to be more polar than unexposed regions due to the loss of alkyl groups and the formation of hydride / hydroxide moieties, having polar and oxidizing molecules, such as H2O2, present during the bake step can promote oxidation of metal hydrides in the exposed regions. Other gases, such as those described in the Reactive Gases section below, may similarly alter the rate of hydride oxidation and hydroxide crosslinking reactions through oxidation, acid-base chemicals, coordinating chemicals, and combinations thereof. Reactive gases may be provided in a controlled atmosphere, for example, using any of the equipment described in the Bake Apparatus section below. Reactive gases may be provided along with non-reactive gases, such as N2, Ar, He, Ne, Kr, or Xe. In some cases, air or clean, dry air may be provided to the atmosphere during PEB.

[0033] The ability to tune the rate of crosslinking reactions in metal oxide-based EUV photoresist materials provides a wider process window, enabling further optimization of lithographic performance by minimizing interdiffusion and other related defect formation mechanisms. For example, if reactive gases can efficiently lower bake temperature requirements, interdiffusion concerns at the PR / UL interface can be alleviated, which would be beneficial for defect reduction.

[0034] In certain embodiments, one or more process conditions may be controlled during the PEB as follows: The substrate may be heated to an elevated temperature of about 100-250°C (e.g., about 120-200°C in some cases). The pressure may be maintained at about 0.1-760 Torr (e.g., about 0.1-1 Torr in some cases). The substrate may be exposed to the elevated temperature for about 1-10 minutes (e.g., about 2-5 minutes). An inert gas may be flowed into the process chamber at a rate of about 10-10,000 sccm. In certain examples, the oxygen (e.g., O) concentration in the process chamber may be controlled during the PEB. In these or other embodiments, the moisture (e.g., HO vapor) concentration may be controlled during the PEB.

[0035] In certain embodiments, the substrate may be exposed to ammonia during the PEB. In some cases, ammonia may be the only reactive gas present during the PEB, while in other cases, one or more additional reactive gases may be provided along with the ammonia. In some embodiments, ammonia may be provided at a concentration of about 0.001-5.0% (by volume), and in some cases, at a concentration of about 0.001-0.5% (by volume) at atmospheric pressure or at a partial pressure of about 1-100 mTorr, or at a partial pressure of about 1-10 mTorr if the processing chamber is under vacuum. The duration of the PEB (and / or the duration of the substrate exposure to ammonia during the PEB) may be about 5 seconds to about 10 minutes, and in some cases, about 5 seconds to 1 minute. After the substrate is exposed to ammonia, the processing chamber may be purged with an inert gas. In various embodiments, the inert gas purge period may be the same length as or longer than the period during which the substrate is exposed to ammonia. These processes may promote the alkali-catalyzed reaction of M-OH condensation / crosslinking to form relatively high molecular weight, low volatility species, resulting in a more stable photoresist film as described above. These processes may harden and densify film regions exposed to EUV radiation (or other types of lithographic patterning radiation) and may enable these effects at lower bake temperatures than those required to achieve the same film properties. In some embodiments, these same reaction conditions may be used during PAB. In some cases, these same reaction conditions may be used during PAB and / or PEB using alternative or additional reactant gases described herein, including other volatile amines such as, but not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, pyridine, and the like.

[0036] In some embodiments, the PEB may be a conventional PEB, i.e., the PEB may be performed without providing reactive gases to the substrate and / or in an uncontrolled atmosphere, in which case one or more reactive gases may be provided to the substrate during the PEB. 3. Reactive gas

[0037] In various embodiments herein, the substrate may be exposed to one or more reactive gases during a photoresist baking operation, which may promote a desired degree of crosslinking, promote removal of low molecular weight or volatile species, and / or stabilize the photoresist, as described above.

[0038] A number of different reactant gases may be used. Examples of useful reactant gases are water (H2O), hydrogen (H2), oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), carbon monoxide (CO), carbon dioxide (CO2), ammonia (NH3), nitrous oxide (NO), nitric oxide (NO), methylamine (CH3NH2), dimethylamine ((CH3)2NH), trimethylamine (N(CH3)3), ethylamine (CH3CH2NH2), diethylamine ((CH3CH2)2NH), triethylamine (N(CH2CH3)3), alcohols (C n H 2n+1 OH (including but not limited to methanol, ethanol, propanol, and butanol), acetylacetone (CH3COCH2COCH3), formic acid (HCOOH), oxalyl chloride ((COCl)2), carboxylic acids (C n H 2n+1 COOH), and other small molecule amines (NR 1 R 2 R 3 (R 1 , R 2 , R 3 are each independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or combinations thereof. Substitutes for these reactive gases may also be used. In some cases, the substrate may be exposed to more than one reactive gas during the photoresist bake operation.

[0039] The reactive gas may interact with the photoresist through oxidation, coordination, or acid-base chemistry. If the reactive gas is provided during the PEB operation, the reactive gas may preferentially interact with the photoresist in areas exposed to EUV radiation. This preferential interaction may occur due to chemical changes that occur during EUV exposure (e.g., loss of alkyl groups in the photoresist).

[0040] Following exposure of the substrate to reactive gases during PAB and / or PEB, the chamber in which the substrate is processed may be evacuated and / or purged, for example with an inert gas. In some cases, the inert gas purge period may be at least as long as the period during which the substrate is exposed to the reactive gas. 4. Temperature gradient

[0041] In some embodiments, the rate at which the substrate temperature is changed may be controlled during the baking process. In some cases, rapid heating and cooling can be problematic. By controlling the rate at which the substrate temperature increases and decreases, problems associated with rapid heating and cooling can be avoided. Furthermore, the rate at which the baking temperature increases and / or decreases may be controlled to fine-tune the cross-linking reaction in the resist. 5.Baking equipment

[0042] The baking operations described herein may occur in a variety of different types of processing equipment. In some cases, the processing equipment may have a closed chamber that is sealed from the ambient environment. In other cases, the processing equipment may have an open chamber that is not sealed from the ambient environment. In certain cases where an open chamber is used, the substrate may be processed based on a track that can operate continuously or discontinuously. Closed chambers generally offer greater control over the processing atmosphere and provide additional safety against potentially harmful reactive chemicals. However, open chambers may be preferred, for example, in mass production where non-hazardous chemicals are used.

[0043] The chamber may include one or more inlets for providing a desired processing atmosphere. The desired processing atmosphere may include one or more reactive gases, as described above. The inlets may therefore be fluidly connected to a reactive gas source. The reactive gas may flow from the reactive gas source through a gas supply line and into the chamber through an inlet. If the reactive gas is a liquid at an appropriate temperature, it may be stored as a liquid and vaporized before being delivered to the gas supply line / inlet / chamber. In certain embodiments, air and / or an inert gas (e.g., N2, Ar, He, Ne, Kr, Xe, etc.) may also be provided to the processing atmosphere. These may also flow from a gas source through a gas supply line and into the chamber through an inlet. In some cases, the processing atmosphere may be air-free.

[0044] The chamber may also include one or more outlets for removing materials from the chamber. The outlets may be fluidly connected to a vacuum source to allow active removal of gaseous species from the chamber. Vacuum-connected outlets may be used in both sealed and open chambers. When used in sealed chambers, the vacuum-connected outlets may allow processing at subatmospheric pressures. When the processing chamber is an open chamber that is not sealed from the environment, the outlets may be a path by which gases can passively escape from the chamber.

[0045] As described above, in certain embodiments, the atmosphere within the chamber may be controlled during the baking process. In some cases, the concentration of reactive gases (e.g., oxygen and / or water and / or other reactive gases described herein) may be actively controlled during the baking process. In addition to the inlets and outlets described above, the chamber may further include sensors (e.g., residual gas analyzers, Fourier transform infrared spectroscopy sensors, etc.) to monitor the composition of its atmosphere. These sensors may be used to provide feedback for actively controlling the composition of the baking atmosphere.

[0046] To bake the photoresist, the chamber includes one or more heating elements configured to heat the substrate. The heating elements may heat the substrate from above and / or below. The heating elements may heat the front side of the substrate (e.g., where the semiconductor devices / structures are formed) and / or the back side of the substrate. Various different types of heating elements may be used alone or in combination with each other. Examples of heating elements may include a heated substrate support (e.g., pedestal, chuck, etc.) and a radiation source such as an infrared lamp and / or an ultraviolet lamp.

[0047] In some embodiments, the chamber may include one or more cooling elements configured to cool the substrate. For example, the substrate support may be configured to cool the substrate. In one embodiment, the substrate support may include cooling channels through which a heat exchange fluid flows to cool the substrate. Other heat exchange devices may be used as needed for a particular application. The cooling elements may be particularly useful for controlling the rate at which the substrate cools after a bake operation.

[0048] The chamber may also include a temperature sensor for monitoring the temperature of the substrate and / or substrate support during the baking operation. In one example, the chamber includes a pyrometer for measuring the temperature of the substrate surface during baking. Temperature measurements from the pyrometer or other temperature sensor may be used as feedback to actively control the substrate temperature during baking.

[0049] FIG. 2 depicts a simplified diagram of a processing chamber 200 according to one embodiment. In this example, the processing chamber 200 is a sealed chamber with a controllable atmosphere. A substrate 201 may be placed on a substrate support 202, which may also heat and / or cool the substrate. In some cases, alternative or additional heating and cooling elements may be provided. Processing gases enter the processing chamber 200 through an inlet 203. Materials are removed from the processing chamber 200 through an outlet 204, which may be connected to a vacuum source (not shown). Operation of the processing chamber 200 may be controlled by a controller 206, which is described further below. Additionally, a sensor 205 may be provided to monitor, for example, the temperature and / or composition of the atmosphere in the processing chamber 200. Values ​​from the sensor 205 may be used by the controller 206 in an active feedback loop.

[0050] The chamber in which baking occurs may be configured in several ways. In some embodiments, this chamber is the same as the chamber used to deposit photoresist, and / or the same as the chamber used to expose photoresist to EUV radiation, and / or the same as the chamber used to develop photoresist. In some embodiments, this chamber is a dedicated bake chamber that is not used for other processes, such as deposition, etching, EUV exposure, or photoresist development. This chamber may be a stand-alone chamber or may be integrated with a larger processing tool, such as a deposition tool used to deposit photoresist, an EUV exposure tool used to expose photoresist to EUV radiation, and / or a development tool used to develop photoresist. The chamber used for baking may be combined with one or more of these tools as needed for a particular application.

[0051] The chamber may include a controller. In some embodiments, the controller is part of a system, which may be part of the examples above. Such systems may include semiconductor processing equipment, including processing tools, chambers, processing platforms, and / or specific processing components (such as wafer pedestals and gas flow systems). These systems may be integrated with electronics for controlling operations before, during, and after processing of semiconductor wafers or substrates. These electronics may be referred to as "controllers" and may control various components or subcomponents of the system. Depending on the processing requirements and / or type of system, the controller may be programmed to control any of the processes disclosed herein, including supply of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid supply settings, position operation settings, wafer loading and unloading from tools and other transfer tools connected or coupled to a particular system, and / or load locks.

[0052] Generally, a controller may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. Integrated circuits may include chips in firmware format that store program instructions, digital signal processors (DSPs), chips defined as application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various personalizations (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or system. In some embodiments, the operational parameters may be part of a recipe defined by a process engineer to accomplish one or more processing steps during the manufacture of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0053] In some embodiments, the controller may be part of or coupled to a computer integrated with, coupled to, or otherwise networked to the system. For example, the controller may be in the “cloud” that enables remote access of wafer processing or may be all or part of a fab host computer system. The computer may enable remote access to the system to monitor the progress of manufacturing operations, examine the history of past manufacturing operations, examine trends or performance metrics from multiple manufacturing operations, modify parameters of a current process, set processing steps following a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings that are then communicated from the remote computer to the system. In some examples, the controller receives instructions in the form of data specifying parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool the controller is configured to couple to or control. Thus, as noted above, the controller may be distributed, for example, by including one or more separate controllers networked together and cooperating toward a common purpose, such as the process or control described herein. An example of a controller distributed for such a purpose would be one or more integrated circuits on the chamber that are located remotely (e.g., at the platform level or as part of a remote computer) and communicate with one or more integrated circuits that cooperate to control the process in the chamber.

[0054] Without being limited thereto, example systems may include plasma etch chambers or modules, deposition chambers or modules, spin rinse chambers or modules, metal plating chambers or modules, cleaning chambers or modules, bevel edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, ALD chambers or modules, atomic layer etch (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and other semiconductor processing systems related to or usable in the fabrication and / or manufacturing of semiconductor wafers.

[0055] As noted above, depending on the processing steps being performed by the tool, the controller may be in communication with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used to transport materials to and from tool locations and / or load ports in a semiconductor fabrication factory to transport wafer containers. conclusion

[0056] A baking method is disclosed that improves the EUV lithographic performance of metal-containing EUV resists.

[0057] It is understood that the examples and embodiments described herein are for illustrative purposes, and that various modifications or changes in light thereof will be suggested to those skilled in the art. Various details have been omitted for clarity, but various conceptual changes may be implemented. Thus, the examples should be considered illustrative rather than restrictive, and the disclosure should not be limited to the details described herein, but may be modified within the scope of the disclosure. [Application Example 1] A method for baking a photoresist layer on a substrate, comprising: receiving the substrate in a processing chamber, the substrate having the photoresist layer thereon, the photoresist layer comprising a metal-containing photoresist material; flowing reactive gas species from a gas source through a gas supply line into the processing chamber and exposing the substrate to the reactive gas species within the processing chamber; baking the photoresist layer while the substrate is exposed to the reactive gas species; A method comprising: [Application Example 2] The method according to Application Example 1, The method, wherein the photoresist layer comprises an extreme ultraviolet (EUV) photoresist material. [Application Example 3] The method according to Application Example 2, The method of claim 1, wherein the reactive gas species comprises a gas selected from the group consisting of water, hydrogen, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, ammonia, nitrous oxide, nitric oxide, alcohol, acetylacetone, formic acid, oxalyl chloride, pyridine, carboxylic acids, amines, and combinations thereof. [Application Example 4] The method according to Application Example 3, The method wherein the reactive gas species comprises the water. [Application Example 5] The method according to Application Example 3, The method wherein the reactive gas species comprises hydrogen. [Application Example 6] The method according to Application Example 3, The method wherein the reactive gas species comprises the oxygen. [Application Example 7] The method according to Application Example 3, The method wherein the reactive gas species comprises the ozone. [Application Example 8] The method according to Application Example 3, The method wherein the reactive gas species comprises the hydrogen peroxide. [Application Example 9] The method according to Application Example 3, The method wherein the reactive gas species comprises the carbon monoxide. [Application Example 10] The method according to Application Example 3, The method wherein the reactive gas species comprises the carbon dioxide. [Application Example 11] The method according to Application Example 3, The method wherein the reactive gas species comprises the ammonia. [Application Example 12] The method according to Application Example 11, Baking the photoresist occurs after the photoresist has been exposed to EUV radiation to pattern the photoresist, and one of the following conditions is met: (i) the processing chamber is maintained at atmospheric pressure during baking of the photoresist, and the ammonia is provided at a concentration of about 0.001 to 5% (by volume); and (ii) the process chamber is maintained at sub-atmospheric pressure during baking of the photoresist, and the ammonia is provided at a partial pressure of about 1 to 100 mTorr. [Application Example 13] The method according to Application Example 3, The method, wherein the reactive gas species comprises the nitrous oxide and / or the nitric oxide. [Application Example 14] The method according to Application Example 3, The method wherein the reactive gas species comprises the alcohol. [Application Example 15] The method according to Application Example 3, The method wherein the reactive gas species comprises the acetylacetone. [Application Example 16] The method according to Application Example 3, The method wherein the reactive gas species comprises the formic acid. [Application Example 17] The method according to Application Example 3, The method wherein the reactive gas species comprises the oxalyl chloride. [Application Example 18] The method according to Application Example 3, The method wherein the reactive gas species comprises the carboxylic acid. [Application Example 19] The method according to Application Example 3, The method wherein the reactive gas species comprises the amine. [Application Example 20] The method according to Application Example 19, The method, wherein the amine comprises methylamine, dimethylamine, and / or trimethylamine. [Application Example 21] The method according to Application Example 19, The method, wherein the amine comprises ethylamine, diethylamine, and / or triethylamine. [Application Example 22] The method according to any one of Application Examples 2 to 21, The method wherein the reactive gas species is oxidizing. [Application Example 23] The method according to any one of Application Examples 2 to 22, The method wherein the reactive gas species is polar. [Application Example 24] The method according to any one of Application Examples 2 to 23, The method, wherein exposing the substrate to the reactive gas species promotes cross-linking in the photoresist layer. [Application Example 25] The method according to any one of Application Examples 2 to 24, The method, wherein exposing the substrate to the reactive gas species increases the stability of the photoresist layer. [Application Example 26] The method according to any one of Application Examples 2 to 25, The method, wherein exposing the substrate to the reactive gas species promotes removal of low molecular weight species within the photoresist layer. [Application Example 27] The method according to Application Example 26, The method wherein the low molecular weight species comprises zero, one, or two metal atoms per molecule. [Application Example 28] The method according to any one of Application Examples 2 to 27, The method, wherein exposing the substrate to the reactive gas species oxidizes metal hydride species in the photoresist layer to metal hydroxide species. [Application Example 29] The method according to any one of Application Examples 2 to 28, further comprising: applying a vacuum to the processing chamber while baking the photoresist layer. [Application Example 30] The method according to any one of Application Examples 2 to 29, further comprising: controlling a moisture concentration in the processing chamber to remain within a target moisture concentration range while baking the photoresist layer. [Application Example 31] The method according to any one of Application Examples 2 to 30, further comprising: controlling an oxygen concentration in the processing chamber to remain within a target oxygen concentration range while baking the photoresist layer. [Application Example 32] The method according to any one of Application Examples 2 to 31, The method wherein the processing chamber is maintained at sub-atmospheric pressure while baking the photoresist layer. [Application Example 33] The method according to Application Example 32, The method wherein the processing chamber is maintained at sub-atmospheric pressure while baking the photoresist layer. [Application Example 34] The method according to any one of Application Examples 2 to 33, further comprising: The method includes increasing the temperature of a substrate support on which the substrate is mounted while baking the photoresist layer. [Application Example 35] The method according to any one of Application Examples 2 to 34, further comprising: The method includes reducing the temperature of a substrate support on which the substrate is mounted while baking the photoresist layer. [Application Example 36] The method according to any one of Application Examples 2 to 35, further comprising: controlling the flow of the reactive species into the processing chamber to achieve a target degree of crosslinking. [Application Example 37] The method according to any one of Application Examples 2 to 36, The method, wherein baking the photoresist layer comprises heating the substrate on a hotplate. [Application Example 38] The method according to any one of Application Examples 2 to 37, The method, wherein baking the photoresist layer comprises exposing the substrate to infrared and / or ultraviolet radiation. [Application Example 39] The method according to any one of Application Examples 2 to 38, The method, wherein baking the photoresist layer comprises heating the substrate from above. [Application Example 40] The method according to any one of Application Examples 2 to 39, The method, wherein baking the photoresist layer comprises heating the substrate from below. [Application Example 41] The method according to any one of Application Examples 2 to 40, The method wherein the photoresist layer is applied to the substrate but not yet patterned, and the baking is a post-apply bake (PAB). [Application Example 42] The method according to any one of Application Examples 2 to 41, The method wherein the photoresist layer is applied to the substrate and patterned by partial exposure to EUV radiation resulting in exposed and unexposed portions of the photoresist layer, and the baking is a post-exposure bake (PEB). [Application Example 43] The method according to Application Example 42, The method wherein the reactive gas species include polar and oxidizing molecules. [Application Example 44] The method according to Application Example 43, The method wherein the reactive gas species comprises hydrogen peroxide. [Example 45] An apparatus for baking a photoresist layer on a substrate, comprising: a processing chamber; an inlet for introducing reactive gas species into the processing chamber; an outlet for removing material from the processing chamber; a substrate support within the processing chamber; a heater configured to heat the substrate by conduction, convection, and / or radiation; a controller having at least one processor, said at least one processor configured to control said device to perform any of the methods of claims 1 to 44; An apparatus comprising:

Claims

1. 1. A method of baking a photoresist layer on a substrate, comprising: receiving the substrate in a processing chamber, the substrate having the photoresist layer thereon, the photoresist layer comprising a metal-containing photoresist material; flowing a reactive gas from a gas source through a gas supply line into the processing chamber and exposing the substrate to the reactive gas in the processing chamber, the reactive gas comprising a gas selected from the group consisting of hydrogen, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, ammonia, nitrous oxide, nitric oxide, acetylacetone, formic acid, oxalyl chloride, pyridine, a carboxylic acid, an amine, and combinations thereof; baking the photoresist layer while the substrate is exposed to the reactive gas, a concentration of which is actively controlled via the gas supply line during the baking, and which reacts with the metal-containing photoresist material to create cross-links within the metal-containing photoresist material.

2. 10. The method of claim 1, The method wherein the reactive gas is a mixture of at least two gas species.

3. 10. The method of claim 1 further comprising:

1. A method comprising flowing a second, different reactant gas from a separate gas source, wherein the second, different reactant gas comprises a gas selected from the group consisting of water, hydrogen, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, ammonia, nitrous oxide, nitric oxide, alcohol, acetylacetone, formic acid, oxalyl chloride, pyridine, a carboxylic acid, an amine, and combinations thereof.

4. 10. The method of claim 1, The method wherein the reaction gas is a mixture further comprising water.

5. 5. The method of claim 4, The method wherein the mixture of the reactive gases comprises the hydrogen and the water.

6. 5. The method of claim 4, The method wherein the mixture of the reactive gases comprises the oxygen and the water.

7. 5. The method of claim 4, The method wherein the mixture of the reactive gases comprises the ozone and the water.

8. 5. The method of claim 4, The method wherein the mixture of the reactive gases comprises the hydrogen peroxide and the water.

9. 5. The method of claim 4, The method wherein the mixture of the reactive gases comprises the ammonia and the water.

10. 10. The method of claim 9, Baking the photoresist layer occurs after the photoresist layer is exposed to EUV radiation to pattern the photoresist layer, and any of the following conditions is met: (i) the processing chamber is maintained at atmospheric pressure during baking of the photoresist layer, and the ammonia is provided at a concentration of about 0.001 to 5% (by volume); and (ii) the process chamber is maintained at sub-atmospheric pressure during baking of the photoresist layer, and the ammonia is provided at a partial pressure of about 1 to 100 mTorr.

11. 5. The method of claim 4, The method wherein the mixture of the reactive gases comprises the amine and the water.

12. 12. The method of claim 11, The method, wherein the amine comprises ethylamine, diethylamine, and / or triethylamine.

13. 10. The method of claim 1, The method wherein the reaction gas is a mixture further comprising an alcohol.

14. 14. The method of claim 13, The method wherein the mixture of the reactant gases comprises the hydrogen and the alcohol.

15. 14. The method of claim 13, The method wherein the mixture of the reactive gases comprises the oxygen and the alcohol.

16. 14. The method of claim 13, The method wherein the mixture of the reactive gases comprises the ozone and the alcohol.

17. 14. The method of claim 13, The method wherein the mixture of the reactive gases comprises the hydrogen peroxide and the alcohol.

18. 14. The method of claim 13, The method wherein the mixture of the reactive gases comprises the ammonia and the alcohol.

19. 19. A method according to any one of claims 2 to 18, comprising: The method wherein at least one of the reactive gases is oxidizing.

20. 19. A method according to any one of claims 2 to 18, comprising: A method wherein at least one of the reactive gases is polar.

21. 1. A method of baking a photoresist layer on a substrate, comprising: receiving the substrate in a processing chamber, the substrate having the photoresist layer thereon, the photoresist layer comprising a metal-containing photoresist material; flowing a reactive gas from a gas source through a gas supply line into the processing chamber and exposing the substrate to the reactive gas in the processing chamber, the reactive gas comprising a gas selected from the group consisting of water, hydrogen, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, ammonia, nitrous oxide, nitric oxide, alcohol, acetylacetone, formic acid, oxalyl chloride, pyridine, a carboxylic acid, an amine, and combinations thereof; flowing an inert gas into the processing chamber and exposing the substrate to the reactive gas and the inert gas in the processing chamber; baking the photoresist layer while the substrate is exposed to the reactive gas and the inert gas, wherein a concentration of the reactive gas is actively controlled via the gas supply line during the baking, and the reactive gas reacts with the metal-containing photoresist material to create cross-links within the metal-containing photoresist material.

22. 22. The method of claim 21, The method wherein the reactive gas is a mixture of at least two gas species.

23. 22. The method of claim 21 further comprising:

1. A method comprising flowing a second, different reactant gas from a separate gas source, wherein the second, different reactant gas comprises a gas selected from the group consisting of water, hydrogen, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, ammonia, nitrous oxide, nitric oxide, alcohol, acetylacetone, formic acid, oxalyl chloride, pyridine, a carboxylic acid, an amine, and combinations thereof.

24. 1. An apparatus for baking a photoresist layer on a substrate, comprising: a processing chamber; an inlet for introducing reactive gas species into the processing chamber; an outlet for removing material from the processing chamber; a substrate support within the processing chamber; a heater configured to heat the substrate by conduction, convection, and / or radiation; a controller having at least one processor, said at least one processor configured to control said device to perform any of the methods of claims 1 to 23; An apparatus comprising:

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