Underlayer for photoresist adhesion and dose reduction

Abstract

SOLUTION: This disclosure relates generally to a patterning structure including an underlayer and an imaging layer, as well as methods and apparatuses thereof. In particular embodiments, the underlayer enhances radiation absorptivity and / or patterning performance of the imaging layer.SELECTED DRAWING: Figure 2D

Description

[Technical Field]

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

[0002] The present disclosure relates generally to the field of semiconductor processing, and more particularly to extreme ultraviolet (EUV) photoresist (PR) lithography techniques and materials. [Background technology]

[0003] As semiconductor processing continues to advance, feature sizes continue to shrink, requiring new processing methods. One area of ​​advancement is in the context of patterning, for example, using photoresist materials that are sensitive to lithographic radiation.

[0004] The background art provided herein is intended to provide a general background to the present disclosure, and the work of the inventors named herein, to the extent described in this background art, along with aspects of the description that would not normally be considered prior art at the time of filing, are not admitted expressly or impliedly as prior art to the present disclosure. Summary of the Invention

[0005] Various embodiments herein relate to methods, materials, apparatus, and systems for depositing an underlayer on a substrate.

[0006] In a first aspect, the present disclosure includes a patterning structure comprising a radiation-sensitive imaging layer disposed over a substrate and an underlayer disposed between the substrate and the imaging layer, In some embodiments, the underlayer is configured to enhance adhesion between the substrate and the imaging layer and / or reduce the radiation dose for effective photoresist exposure of the imaging layer.

[0007] In some embodiments, the substrate further comprises a hard mask disposed on the substrate.

[0008] In some embodiments, the imaging layer comprises an extreme ultraviolet (EUV)-sensitive inorganic photoresist layer. In certain embodiments, the imaging layer is a chemical vapor deposition (CVD) film, an atomic layer deposition (ALD) film, or a spin-on film. In other embodiments, the imaging layer comprises a tin oxide film or a tin oxide hydroxide film.

[0009] In some embodiments, the substrate is or includes a hard mask, an amorphous carbon film, an amorphous hydrogenated carbon film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbide film, a silicon boronitride film, an amorphous silicon film, a polysilicon film, or a combination thereof. In certain embodiments, the amorphous carbon film is doped with boron (B) or tungsten (W).

[0010] In some embodiments, the underlayer has a thickness of 25 nm or less, hi other embodiments, the underlayer has a thickness of about 2-20 nm.

[0011] In certain embodiments, the underlayer comprises hydrogenated carbon doped with oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or a combination of any two or more thereof. In certain embodiments, the underlayer comprises about 0-30 atomic % oxygen (O) and / or about 20-50 atomic % hydrogen (H) and / or 30-70 atomic % carbon (C). In other embodiments, the underlayer comprises hydrogenated carbon doped with iodine configured to improve secondary electron generation upon exposure to radiation. In still other embodiments, the surface of the underlayer comprises hydroxyl groups (e.g., —OH), carboxyl groups (e.g., —COH), peroxy groups (e.g., —OOH), sp 2 It contains carbon, sp carbon, and / or unsaturated carbon-containing bonds (e.g., C=C and / or C≡C bonds).

[0012] In some embodiments, the underlayer has a density of about 0.7 to 2.9 g / cm 3 In other embodiments, the underlayer further provides increased etch selectivity. In yet other embodiments, the underlayer further provides reduced line edge and line width roughness and / or reduced dose to size.

[0013] In certain embodiments, the underlayer further comprises beta hydrogen atoms configured to be released upon exposure to radiation and / or oxygen atoms configured to form oxygen bonds to atoms in the imaging layer.

[0014] In a second aspect, the present disclosure includes a patterning structure comprising a substrate comprising a partially fabricated semiconductor device film stack, a radiation-sensitive imaging layer disposed over the substrate, and an underlayer disposed between the substrate and the imaging layer. In certain embodiments, the underlayer comprises a deposited film of hydrogenated carbon doped with O, Si, N, W, B, I, Cl, or a combination of any two or more thereof, the film having a thickness of 25 nm or less, or a thickness of about 2-20 nm. In yet other embodiments, the substrate further comprises an amorphous carbon hard mask disposed on the substrate and / or the partially fabricated semiconductor device film stack. In some embodiments, the amorphous carbon hard mask is doped.

[0015] In a third aspect, the present disclosure includes a method of forming a patterned structure, the method comprising providing a substrate, depositing an underlayer (e.g., any underlayer described herein) on the substrate, and forming a radiation-sensitive imaging layer on the underlayer. In some embodiments, the underlayer is configured to enhance adhesion between the substrate and photoresist and / or reduce the radiation dose for effective photoresist exposure.

[0016] In some embodiments, the substrate is a semiconductor device film stack under fabrication. In other embodiments, the substrate further comprises a hard mask, an amorphous carbon film, an amorphous hydrogenated carbon film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbide film, a silicon boronitride film, an amorphous silicon film, a polysilicon film, or a combination thereof, disposed on the substrate and / or the semiconductor device film stack under fabrication, the imaging layer comprises a tin oxide-based photoresist or a tin hydroxide oxide-based photoresist, and the underlayer comprises a deposited film of hydrogenated carbon doped with O, Si, N, W, B, I, Cl, or a combination of any two or more thereof, the film having a thickness of 25 nm or less.

[0017] In some embodiments, the underlayer is deposited on the substrate using a hydrocarbon precursor, thereby providing a carbon-containing film. In certain embodiments, the hydrocarbon precursor comprises an alkane, alkene, alkyne, or other hydrocarbon precursor described herein. In other embodiments, the underlayer is deposited using a hydrocarbon precursor in the presence or absence of an oxocarbon precursor (e.g., any precursor described herein that contains carbon and oxygen atoms).

[0018] In yet other embodiments, the underlayer is deposited using a hydrocarbon precursor in the presence of a nitrogen-containing precursor, a tungsten-containing precursor, a boron-containing precursor, and / or an iodine-containing precursor, thereby providing a doped film. In some embodiments, the doped film comprises iodine, a combination of iodine and silicon, or a combination of iodine, silicon, and nitrogen.

[0019] In some embodiments, the underlayer is deposited on the substrate using an oxocarbon precursor that co-reacts with hydrogen (H) or a hydrocarbon. In other embodiments, the oxocarbon precursor reacts with H or a hydrocarbon and, optionally, further co-reacts with a Si-source dopant. In certain embodiments, the underlayer may be deposited on the substrate using a Si-containing precursor that co-reacts with an oxidant (e.g., an oxocarbon or O-containing precursor). In further embodiments, the Si-containing precursor further co-reacts with a C-source dopant (e.g., a hydrocarbon precursor).

[0020] In some embodiments, depositing further includes applying a bias at a bias power of 0 W to about 1000 W (e.g., 0 to 500 W, 0 to 400 W, or 0 to 300 W) and utilizing a duty cycle of about 1% to 100% or about 5% to 100%. In certain embodiments, applying a bias provides an underlayer having a higher density compared to an underlayer formed without applying a bias.

[0021] In some embodiments, the underlayer is deposited on the substrate by plasma-enhanced chemical vapor deposition (PECVD) as a final deposition operation on the substrate. In other embodiments, the underlayer is deposited on the substrate by PECVD or ALD.

[0022] In further embodiments, the method includes modifying the layer (e.g., after deposition) to provide a roughened surface. In some embodiments, modifying may include sputtering by non-reactive ion bombardment of the underlying surface to provide the roughened surface. Non-limiting non-reactive ions may include argon (Ar), helium (He), krypton (Kr), or other non-reactive species. In other embodiments, modifying may comprise exposing the underlying surface or the roughened surface to an oxygen-containing plasma to provide an oxygen-containing surface. Non-limiting oxygen-containing plasmas may include carbon dioxide (CO), oxygen (O), or water (as H2O or as a mixture of H2 and O2).

[0023] In a fourth aspect, the present disclosure includes a method of depositing an underlayer, the method comprising: providing a substrate in a process chamber; and depositing a hydrogenated carbon film on a surface of the substrate by a PECVD process, the hydrogenated carbon film being a low-density film. In some embodiments, the substrate is or includes a hardmask.

[0024] In some embodiments, the PECVD process is carried out using methane (CH), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), propyne (C3H4), allene (C3H4), cyclopropene (C3H4), butane (C4H 10 ), cyclohexane (CH 12 ), benzene (C6H6), and toluene (C7H8). In another embodiment, the PECVD process further includes introducing a nitrogen-containing precursor, a tungsten-containing precursor, a boron-containing precursor, and / or an iodine-containing precursor to provide a doped film.

[0025] In some embodiments, the PECVD process comprises a transformer coupled plasma (TCP) or an inductively coupled plasma (ICP). In certain embodiments, the TCP power is about 100-1000 W without bias. In other embodiments, the PECVD process further comprises a pressure of about 10-1000 mTorr and / or a temperature of about 0-100°C. In yet other embodiments, the PECVD process further comprises an applied pulsed bias having a power of about 10-1000 W or an applied continuous wave bias having a power of about 10-500 W. In further embodiments, the applied pulsed bias comprises a duty cycle of about 1-99% and a pulsing frequency of about 10-2000 Hz.

[0026] In further embodiments, the method includes modifying the hydrogenated carbon film (e.g., after deposition) to provide a roughened surface. In some embodiments, modifying may include sputtering by non-reactive ion bombardment of the surface of the film to provide the roughened surface. Non-limiting non-reactive ions may include argon (Ar), helium (He), krypton (Kr), or other non-reactive species. In other embodiments, modifying may comprise exposing the film surface or the roughened surface to an oxygen-containing plasma to provide an oxygen-containing surface. Non-limiting oxygen-containing plasmas may include carbon dioxide (CO), oxygen (O), or water (as H2O or as a mixture of H2 and O2).

[0027] In a fifth aspect, the disclosure features an apparatus for processing a substrate, the apparatus including a process chamber including a substrate support, a process gas source connected to the process chamber and associated flow control hardware, substrate handling hardware connected to the process chamber, and a controller having a processor and memory, the processor and memory communicatively coupled to each other. In certain embodiments, the processor is operatively coupled to at least the flow control hardware and the substrate handling hardware.

[0028] In certain embodiments, the substrate support may be a chuck or a pedestal. In other embodiments, the apparatus includes one or more gas inlets into the processing chamber, the gas inlets fluidly connected to a processing gas source and associated flow control hardware, and one or more gas outlets for removing materials from the processing chamber and associated flow control hardware.

[0029] In some embodiments, the memory stores computer-executable instructions for performing the operations described in the methods described herein. In one embodiment, the computer-executable instructions include machine-readable instructions for providing a substrate or a hard mask disposed on the substrate, depositing an underlayer (e.g., any of those described herein) on the substrate and / or hard mask, and forming a radiation-sensitive imaging layer (e.g., any of those described herein) on the underlayer.

[0030] In another embodiment, the computer-executable instructions include machine-readable instructions for depositing a hydrogenated carbon film (e.g., any of those described herein) on a surface of a substrate or hard mask by PECVD. In a further embodiment, the computer-executable instructions include machine-readable instructions for forming a radiation-sensitive imaging layer (e.g., any of those described herein) on the hydrogenated carbon film.

[0031] In certain embodiments, depositing the underlayer includes introducing or supplying one or more precursors (e.g., a hydrocarbon precursor, an oxocarbon precursor, a C-containing precursor, an O-containing precursor, a Si-containing precursor, an N-containing precursor, a W-containing precursor, a B-containing precursor, an I-containing precursor, or a Cl-containing precursor) and / or one or more process gases (e.g., any of those described herein).

[0032] In other embodiments, depositing the underlayer includes a plasma (e.g., a transformer coupled plasma (TCP), an inductively coupled plasma (ICP), or a capacitively coupled plasma (CCP)). In certain embodiments, the plasma is a TCP or ICP having a power of about 100-1000 W, a pressure of about 10-1000 mTorr, and / or a temperature of about 0-100°C. In yet other embodiments, the plasma further includes an applied pulsed bias (e.g., a power of about 10-1000 W) or an applied continuous wave bias (e.g., a power of about 10-500 W).

[0033] In some embodiments, forming the imaging layer comprises depositing an element having a high patterning radiation absorption cross section. In certain embodiments, the element has a high EUV absorption cross section (e.g., 1×10 7 cm 2 / mol or more).

[0034] In other embodiments, forming the imaging layer includes introducing or providing one or more precursors (e.g., a structure having formula (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII)). In some embodiments, forming the imaging layer may further include providing one or more precursors in the presence of a counter reactant. Non-limiting counter reactants include oxygen-containing counter reactants such as oxygen (O), ozone (O), water, peroxide, hydrogen peroxide, oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohols, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof.

[0035] In any embodiment herein, the substrate is or includes a partially fabricated semiconductor device film stack.

[0036] In any embodiment herein, the substrate is a hardmask. In other embodiments, the substrate comprises a hardmask. In yet other embodiments, the substrate comprises a hardmask disposed on a workpiece (e.g., disposed on a wafer, semiconductor wafer, stack, partially fabricated integrated circuit, partially fabricated semiconductor device film stack, film, surface, etc.). In a non-limiting example, the hardmask comprises an amorphous carbon hardmask, which may optionally be doped.

[0037] In any embodiment herein, the imaging layer comprises an EUV-sensitive inorganic photoresist layer. In certain embodiments, the imaging layer comprises a tin oxide film, a tin oxide hydroxide film, a tin oxide-based photoresist, or a tin oxide hydroxide-based photoresist. In other embodiments, the imaging layer comprises an EUV-sensitive film, a DUV-sensitive film, a UV-sensitive film, a photoresist film, or a photopatternable film.

[0038] In any embodiment herein, the substrate is or includes a hard mask, an amorphous carbon film, an amorphous hydrogenated carbon film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbide film, a silicon boronitride film, an amorphous silicon film, a polysilicon film, or a combination thereof. In some embodiments, the hard mask is or includes an amorphous carbon film, an amorphous hydrogenated carbon film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbide film, a silicon boronitride film, an amorphous silicon film, a polysilicon film, or a combination thereof.

[0039] In any embodiment herein, the underlayer comprises hydrogenated carbon doped with oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or a combination of any two or more thereof.

[0040] In any embodiment herein, the underlayer or the underlayer surface may contain hydroxyl groups (e.g., -OH), carboxyl groups (e.g., -COH), peroxy groups (e.g., -OOH), sp 2 It contains carbon, sp carbon, and / or unsaturated carbon-containing bonds (e.g., C=C and / or C≡C bonds).

[0041] In any embodiment herein, the underlayer comprises a doped film. In certain embodiments, the doped film comprises I, a combination of I and Si, or a combination of I, Si, and N. In some embodiments, the doped film comprises Cl, a combination of Cl and Si, or a combination of Cl, Si, and N. In other embodiments, the doped film comprises N, a combination of N and Si, or a combination of N, Si, and O. In still other embodiments, the doped film comprises B or W.

[0042] In any embodiment herein, the underlayer comprises 0-30 atomic % O (e.g., 1-30%, 2-30%, or 4-30%), about 20-50 atomic % H (e.g., 20-45%, 30-50%, or 30-45%), and / or 30-70 atomic % C (e.g., 30-60%, 30-65%, or 30-68%).

[0043] In any embodiment herein, the underlayer may have a density of about 1.5 g / cm 3 Density less than or about 0.7-1.4g / cm 3 In yet another embodiment, the doped membrane has a density of about 0.7-1.4 g / cm 3 It has a density of

[0044] In any embodiment herein, the underlayer further provides increased etch selectivity. In yet other embodiments, the underlayer further provides reduced line edge and line width roughness and / or reduced dose to size. In certain embodiments, the underlayer further comprises beta hydrogen atoms configured to be released upon exposure to radiation and / or oxygen atoms configured to form oxygen bonds to atoms in the imaging layer.

[0045] In any embodiment herein, depositing comprises providing or depositing a precursor in vapor form. In other embodiments, depositing comprises providing one or more counter reactants in vapor form. In certain embodiments, depositing comprises CVD, ALD, or plasma-enhanced forms thereof (e.g., PECVD).

[0046] In any embodiment herein, depositing can include supplying or introducing one or more precursors described herein. Non-limiting precursors include hydrocarbon precursors, oxocarbon precursors, and / or dopant precursors (e.g., O-containing precursors, Si-containing precursors, N-containing precursors, W-containing precursors, B-containing precursors, I-containing precursors, or Cl-containing precursors). Depositing can also include supplying or introducing one or more process gases, such as an inert gas, carbon monoxide (CO), carbon dioxide (CO), helium (He), argon (Ar), krypton (Kr), neon (Ne), nitrogen (N), hydrogen (H), or a combination thereof.

[0047] In any embodiment herein, depositing may include providing a plasma. Providing may include a PECVD process. Non-limiting plasma processes may include TCP, ICP, or CCP. Other non-limiting process conditions include a pressure of >1 milliTorr (mTorr) (e.g., about 5-1000 mTorr), a power level of <400 Watts (W) (e.g., about 10-3000 W), and / or a temperature of <200°C (e.g., about 0-100°C). The plasma may be generated using a radio frequency (RF) source operating at 0.3-600 MHz with a power of about 10-3000 W. A bias may be applied using an applied pulsed bias (e.g., about 10-1000 W of power) or an applied continuous wave bias (e.g., about 10-500 W of power) as described herein.

[0048] Other features and advantages of the invention will become apparent from the following description and claims. [Brief explanation of the drawings]

[0049] [Figure 1] 1 is a process flow diagram of a non-limiting method 100.

[0050] [Figure 2A] 1A-1C are schematic diagrams illustrating examples of patterned structures at processing stages described herein. [Figure 2B] 1A-1C are schematic diagrams illustrating examples of patterned structures at processing stages described herein. [Figure 2C] 1A-1C are schematic diagrams illustrating examples of patterned structures at processing stages described herein. [Figure 2D] 2A-2C are schematic diagrams illustrating examples of patterning structures, with cross-sectional views showing possible interactions between imaging layer 218 and underlying layer 216. [Figure 2E] Schematic diagrams showing examples of patterning structures and non-limiting illustrations of reactions within the imaging layer. [Figure 2F] Schematic diagram showing an example of a patterning structure, illustrating a non-limiting reaction between an imaging layer 228 and an underlayer 226. FIG.

[0051] [Figure 3] 1 shows film properties for various embodiments including an ashable hard mask (AHM), two underlayer embodiments (embodiments 1 and 2), and a spin-on carbon (SOC) film. Critical dimension scanning electron micrographs (CDSEM) and parameters such as the ratio of line critical dimension (LnCD) to line width roughness without bias (LWRunbi), a ratio shown as LnCD / LWRunbi, are provided.

[0052] [Figure 4] 1 illustrates the effect of pulse bias on density for non-limiting embodiments of the underlayer (Embodiments 1 and 3). As shown in the graph, films produced using bias powers of 0 W, 70 W, or 140 W, and 0% (no bias power applied), 10%, 20%, 30%, 40%, or 50% are provided.

[0053] [Figure 5] 10 illustrates the effect of pulse bias on undercut for a non-limiting embodiment of the bottom layer (Embodiment 3). Parameters such as dose versus size (DtS), pulse bias (140 W RF bias power and 10% or 50% duty cycle (DC) are shown), CDSEM, LnCD, ratio of LWR without bias to spatial width roughness (SpWR) (ratio shown as LWR without bias / SpWR), various frequency components of SpWR (including low frequency (LF), mid frequency (MF), and high frequency (HF) components, shown as LF / MF / HFspwr), and undercut characteristics are provided.

[0054] [Figure 6] FIG. 1 shows the etch rates for non-limiting embodiments of an underlayer (AL412) and an N-doped spin-on carbon film used as an underlayer (Embodiments 1, 4, and 5).

[0055] [Figure 7] FIG. 1 shows etch rates for non-limiting embodiments of underlayers (Embodiments 11, 12, and 1).

[0056] [Figure 8] Schematic diagram illustrating one embodiment of a processing station 300 for dry development.

[0057] [Figure 9] 4 is a schematic diagram illustrating an embodiment of a multi-station processing tool 400. FIG.

[0058] [Figure 10] 5 is a schematic diagram illustrating an embodiment of an inductively coupled plasma device 500. FIG.

[0059] [Figure 11] 6 is a schematic diagram illustrating one embodiment of a semiconductor processing cluster tool architecture 600. FIG.

[0060] [Figure 12] FIG. 7 is a schematic cross-sectional view showing an example of a dry deposition apparatus 700.

[0061] [Figure 13] FIG. 1 is a detailed cross-sectional plan view showing a portion of the top plate, substrate, and edge ring. DETAILED DESCRIPTION OF THE INVENTION

[0062] Reference will now be made in detail 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 it is not intended to limit the disclosure to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the present disclosure. In the following description, numerous 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. Additionally, detailed descriptions of well-known process operations have been omitted to avoid unnecessarily obscuring the present disclosure.

[0063] Extreme ultraviolet (EUV) lithography (typically at a wavelength of 13.5 nm) is considered to be the next enabling technology for lithographic patterning. However, a number of technical obstacles have slowed the widespread adoption and implementation of this technology. EUV photoresists (PR) are one of these obstacles.

[0064] Conventional chemically amplified resists (CARs) offer a cost-effective approach. However, organic polymer CARs produce line-edge roughness (LER) and line-width roughness (LWR) and have limited sensitivity and resolution due to random variations in polymer utilization. Recent research and development efforts have focused on developing new EUV inorganic photoresist platforms. Such systems offer several advantages over polymer-based CAR systems. These inorganic photoresists are generally based on metal oxides, such as metal hydroxide oxides. The small molecular size of metal oxides enhances the final resolution of the patterning process, and metal oxide photoresists generally exhibit higher etch resistance than CARs, allowing for reduced PR thickness and smaller aspect ratio structures.

[0065] However, inorganic PR also presents various challenges. Spin-on-carbon (SOC) hardmask materials are often used in hardmask film stacks where EUV PR is applied for patterning. However, SOC has a soft carbon (C)-rich film with low etch resistance and poor LWR. Common hardmask materials, such as silicon oxide (e.g., silicon dioxide, SiO2), silicon nitride, and ashable hardmask (AHM), can be used underneath the PR for better etch selectivity and good LER and LWR. However, delamination between EUV PR and hardmask materials, especially after wet development of EUV-exposed PR, is a persistent problem. Furthermore, only about 20 percent of EUV photons are absorbed by typical PR, meaning that a large amount of primary and secondary electrons are often generated in the PR underlayer. Dose to size (DtS) data showed that a higher dose was required for EUV inorganic PR deposited directly on a typical hardmask material than for EUV inorganic PR on SOC to resolve the same line critical dimension.

[0066] As described herein, a thin underlayer film disposed beneath an EUV inorganic PR film stack can improve the performance of the EUV inorganic PR. With this underlayer, the resulting multilayer (e.g., bilayer) hard mask scheme has comparable or better DtS performance compared to an EUV inorganic PR film directly above the SOC stack. The underlayer can also function as an adhesion layer between the EUV inorganic PR and the hard mask, regardless of the hard mask film composition, which can improve etch selectivity and LER / LWR performance. Surfaces other than hard masks can be used beneath the underlayer, in which case the underlayer can function as an adhesion layer between the EUV inorganic PR and any useful substrate (e.g., hard mask, wafer, partially fabricated semiconductor device film stack, etc.).

[0067] As described in more detail below, suitable underlayer thin films can be deposited by chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), or other deposition methods (e.g., sputter deposition, physical vapor deposition (PVD) methods, including PVD co-sputtering). The underlayer deposition process can be performed in either an etching tool (e.g., Kiyo® or Flex®, manufactured by Lam Research, Fremont, California) or a deposition tool (e.g., Lam Striker®). In some embodiments, it can be integrated as a final step in a hard mask deposition process. Depending on the film stack, various underlayer film compositions can be selected.

[0068] It should also be understood that while the present disclosure relates to lithographic patterning techniques and materials using EUV lithography as an example, it is also applicable to other next-generation lithography technologies. In addition to EUV, including the standard 13.5 nm EUV wavelength currently being used and developed, the most suitable radiation sources for such lithography are DUV (deep UV) (generally referring to the use of 248 nm or 193 nm excimer laser sources), X-ray (which formally includes EUV in the relatively low energy range of the X-ray range), and e-beam (which can cover a wide energy range). Such methods include contacting a substrate having exposed hydroxyl groups with a hydrocarbyl-substituted tin capping agent to form a hydrocarbyl-terminated tin oxide (SnOx) film as an imaging / PR layer on the surface of the substrate. The specific method may depend on the specific materials and applications used for the semiconductor substrate and the final semiconductor device. Therefore, the methods described herein are merely exemplary of methods and materials that may be used with current technology.

[0069] FIG. 1 illustrates a process flow for a method of forming a patterned structure according to one embodiment of the present disclosure. The method 100 includes step 101 of providing a substrate. The substrate may be, for example, a hard mask, film, stack, partially fabricated semiconductor device film stack, or the like, processed by any suitable method. In some embodiments, the substrate may include a hard mask disposed on a workpiece (such as a partially fabricated semiconductor device film stack). The hard mask on the top layer of the film stack may have a variety of compositions, such as SiO, silicon nitride, or an ashable hard mask material, and may be formed by chemical vapor deposition (e.g., PECVD). An ashable hard mask composed of an amorphous carbon film is desirable in some embodiments. The amorphous carbon film in this context may be undoped or doped, for example, with boron (B) or tungsten (W). Suitable amorphous carbon films may have a composition including, for example, about 50-80 atomic % carbon (C), 10-20 atomic % hydrogen (H), and 5-40 atomic % B or W dopant.

[0070] Still other substrates may be used, for example, the substrate may be or include amorphous hydrogenated carbon, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon boronitride, amorphous silicon, polysilicon, or a combination of any of those described herein, in any form (e.g., bulk film, thin film, another film, stack, etc.).

[0071] In step 103, a photoresist underlayer is deposited on the substrate. The underlayer may be configured to enhance adhesion between the substrate and a subsequently formed EUV-sensitive inorganic photoresist and reduce the EUV dose for effective EUV exposure of the photoresist. The underlayer may be or include a deposited film of hydrogenated carbon doped with O, silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or a combination of any of these (e.g., a combination of Si and O). In one embodiment, the film is deposited by introducing or supplying a hydrocarbon precursor (e.g., to provide carbon atoms) and a dopant precursor (e.g., to provide doped non-carbon atoms). In another embodiment, the film is deposited by introducing or supplying a heteroatom-containing precursor (e.g., an iodine-containing precursor) that provides a doped film after deposition. In particular, an iodine-doped hydrogenated carbon film may improve secondary electron generation upon exposure to EUV radiation. Additionally, non-limiting precursors and dopants for providing such underlayers are described herein.

[0072] The film can have a thickness of about 25 nm or less. For example, the photoresist underlayer can be about 2-20 nm (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 nm) thick and can optionally contain about 0-30 atomic % O and / or about 20-50 atomic % hydrogen (H) and / or 30-70 atomic % C. Other underlayer properties are also described herein.

[0073] In some examples, the underlayer may be deposited on the substrate by PECVD or ALD using a hydrocarbon precursor, which may or may not include carbon monoxide (CO) and / or carbon dioxide (CO). In certain embodiments, the deposition includes introducing or delivering the hydrocarbon precursor without CO and without CO.

[0074] In some embodiments, the underlayer may be deposited on the substrate by PECVD or ALD using an oxocarbon precursor that co-reacts with hydrogen (H) or a hydrocarbon. In a variation of this example, the oxocarbon precursor may further co-react with a Si-source dopant during deposition. In certain embodiments, the oxocarbon precursor may include CO or CO. While not wishing to be limited by mechanism, the use of an oxocarbon precursor may include hydroxyl (—OH) groups or other oxygen-containing groups in the underlayer, thereby providing a hydrophilic surface or a surface with increased hydrophilicity (compared to an underlayer lacking such —OH or oxygen-containing groups). In a non-limiting example, the hydrophilic surface may improve adhesion between the underlayer and the PR layer.

[0075] In another example, the underlayer may be deposited on the substrate by PECVD or ALD using a Si-containing precursor that co-reacts with an oxidant (e.g., an oxocarbon, an O-containing precursor, CO, or CO). In a variation of this example, the Si-containing precursor further co-reacts with a C-source dopant (e.g., a hydrocarbon precursor described herein). Non-limiting Si-containing precursors are described herein, including silanes, halosilanes, aminosilanes, alkoxysilanes, and organosilanes.

[0076] In some embodiments, the underlayer may be deposited onto the substrate by PECVD, for example, as a final act of deposition onto the substrate by adjusting the flow of precursors into a PECVD processing chamber to achieve a desired composition of the photoresist underlayer.

[0077] In another example, the underlayer may be deposited on the substrate by PECVD to provide a hydrogenated carbon film. In some embodiments, the film may be a low density film (e.g., 0.7-2.9 g / cm). 3 In another embodiment, the undoped membrane (or membrane before doping) has a density of about 1.5 g / cm 3 Density less than or about 0.7-1.4g / cm 3In yet another embodiment, the doped membrane has a density of about 0.7-1.4 g / cm 3 It has a density of

[0078] The PECVD process can include any useful precursor or combination of precursors. In one embodiment, the precursor is a hydrocarbon precursor (e.g., any of those described herein). Optionally, a doped hydrogenated carbon film is formed by using a heteroatom-containing precursor (e.g., a nitrogen-containing precursor, a tungsten-containing precursor, a boron-containing precursor, and / or an iodine-containing precursor) during the PECVD process.

[0079] Deposition of the underlayer can involve the use of a plasma (e.g., as in a PECVD process), such as a transformer-coupled plasma (TCP), an inductively coupled plasma (ICP), or a capacitively coupled plasma (CCP). In certain embodiments, deposition can utilize low TCP power (e.g., about 100-1000 W) with minimal bias (e.g., no bias) to provide a low-density film. Of course, higher power plasmas can also be utilized as described herein. In certain embodiments, generation of the plasma (e.g., TCP or ICP) can be controlled by power, and the power is in continuous wave (CW) mode.

[0080] Deposition (e.g., with TCP or ICP power in CW mode) can include a pulsed (regardless of frequency) applied bias (e.g., in the range of about 1 Hz to about 10 kHz (e.g., 10-2000 Hz)) with a duty cycle of about 1% to 99%. Additional pulse frequencies and duty cycles are described herein. In some embodiments, the applied pulsed bias can be provided to control ion energy. Non-limiting applied pulsed bias power can be about 10-1000 W and other ranges described herein.

[0081] In yet other embodiments, deposition may include an applied CW bias. The CW bias may also be used to control ion energy. In some embodiments, the applied CW bias power may be between 10 and 1000 W (e.g., between 10 and 500 W, between 10 and 400 W, and other ranges described herein).

[0082] Still other conditions (e.g., useful for low density films) include utilizing specific pressure conditions (e.g., 5-1000 milliTorr (mTorr) (e.g., 10-1000 mTorr, 10-500 mTorr, or 10-400 mTorr, etc.)) and specific temperature conditions (e.g., about 0-100°C (e.g., 0-50°C and 10-40°C, etc.)).

[0083] Pulsed or continuous bias can be used to fine-tune the film's properties. In one embodiment, pulsed bias can provide a denser film compared to a lower density film prepared with 0 W bias power. Such denser films can, in some instances, provide higher etch resistance compared to lower density films. In other instances, such denser films can provide reduced undercut compared to lower density films prepared with 0 W bias power. Additional plasma conditions and processes are also described herein.

[0084] 1, in step 105, a radiation-sensitive imaging layer is formed on the underlayer. The imaging layer may comprise, for example, an EUV-sensitive inorganic photoresist. A suitable EUV-sensitive inorganic photoresist may be a metal oxide film, such as an EUV-sensitive tin oxide-based photoresist. Such resists (also referred to as imaging layers) and their formation and use are described, for example, in International Patent Application No. PCT / US2019 / 031618, "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," filed May 9, 2019, and published as WO2019 / 217749, and International Patent Application No. PCT / US2019 / 060742, "METHODS FOR MAKING HARD MASKS USEFUL IN NEXT GENERATION LITHOGRAPHY," filed November 11, 2019, and published as WO2020 / 102085, which are incorporated herein by reference for their disclosure regarding the composition, deposition, and patterning of directly photopatternable organometallic-based metal oxide films to form EUV resist masks. As described therein, according to various embodiments, the EUV-sensitive inorganic photoresist can be a spin-on film or a vapor-deposited film.

[0085] 2A-2C illustrate stages in the fabrication of a non-limiting patterning structure described herein. The patterning structure shown in FIG. 2C includes a hard mask 204 disposed on a substrate 202 (e.g., a wafer or an in-process semiconductor device film stack). An imaging layer 208 is disposed on the hard mask 204. An underlayer 206 is disposed between the hard mask 204 and the imaging layer 208. The underlayer 206 can be configured to enhance adhesion between the hard mask and the imaging layer and to reduce the radiation dose for effective photoresist exposure.

[0086] In test structures according to the described embodiments, the DtS performance of EUV PR on amorphous carbon AHM with an underlayer as described herein is comparable to or better than EUV PR on SOC, in some cases reducing the required dose by 10% or more. Furthermore, no post-development delamination of EUV PR from the hardmask bilayer (amorphous carbon AHM with a photoresist underlayer) is observed.

[0087] The underlayer 206 may further increase etch selectivity and / or reduce line edge roughness and line width roughness (LER / LWR) in the structure. In test structures according to the described embodiments, LER / LWR was improved by about 25% or more for EUV PR on AHM or SOC.

[0088] 2A-2C, an example of processing the structure of FIG. 2C is shown in FIG. 2A-2B. As described above with reference to FIG. 1, FIG. 2A shows a hard mask 204 disposed on a substrate 202, and FIG. 2B shows an underlayer 206 disposed on the hard mask 204.

[0089] The use of an underlayer in the stack can improve properties. In one example, an interaction between the underlayer and the imaging layer provides a reduction in DtS. As seen in FIG. 2D , the patterning structure includes a hard mask 214 disposed on the surface of the substrate 212 and an underlayer 216 disposed between the imaging layer 218 and the hard mask 214. Possible interactions include migration (or diffusion) of metal (M) atoms 218A from the imaging layer 218 to the underlayer 216 and / or migration (or diffusion) of hydrogen (H) atoms 216A from the underlayer 216 to the imaging layer 218. While not wishing to be limited by mechanism, such migration events can provide a productive interaction between the underlayer and the imaging layer, which in turn can contribute to improved adhesion and / or DtS.

[0090] Furthermore, the compositions of the underlayer and imaging layer can be designed to promote favorable reactions, which in turn can improve DtS. For example, as seen in FIG. 2E, the imaging layer can include a tin-based photoresist with radiation-cleavable ligands. Upon exposure to radiation (e.g., EUV), the ligand (R) is dissociated from the tin (Sn) center, and an Sn-H bond is formed in its place. After a post-exposure bake (PEB) step, the Sn-H bond further participates in a thermally activated cross-linking reaction, thereby increasing the difference in material properties between the exposed and unexposed photoresist.

[0091] Thus, in one example, as seen in FIG. 2F , underlayer 226 can include a ligand (R1) that, upon exposure to EUV radiation, provides a releasable H atom, thereby forming a reacted ligand (R1*). Possible R1 groups include, for example, optionally substituted alkyl groups, which can be linear or branched. In imaging layer 228, EUV-cleavable ligand R provides a detached ligand R* and a reactive metal center Sn. H atoms released from underlayer 226 can reduce DtS by promoting the formation of Sn-H bonds within imaging layer 228. If the underlayer also includes oxygen (O) atoms, such atoms can form M-O bonds (e.g., Sn-O bonds) within the imaging layer, further reducing DtS. Additionally, Sn atoms from imaging layer 228 can diffuse into underlayer 226, enabling the generation of additional secondary electrons.

[0092] Example 1: Dry deposition of underlayer The underlayer can be deposited by any useful method. In one example, deposition includes deposition of a hydrocarbon precursor or a carbon-containing precursor (e.g., any of those described herein). Deposition can include utilizing a process gas (e.g., as a plasma or as an inert gas) during deposition. Non-limiting process gases include carbon monoxide (CO), helium (He), argon (Ar), krypton (Kr), neon (Ne), nitrogen (N), and / or hydrogen (H).

[0093] Deposition conditions include control of precursor flow rates, gas flow rates, process pressure, temperature (e.g., electrostatic chuck (ESC) temperature), plasma (e.g., TCP) power, bias power, and duty cycle (DC) in the process chamber. The precursor flow rates can be about 1-100 standard cubic centimeters per minute (sccm). The gas flow rates can be about 1-1600 sccm. The chamber pressure can be about 5-1000 mTorr (e.g., 5-800 mTorr, 10-500 mTorr, 10-400 mTorr, 30-500 mTorr, 10-1000 mTorr, or 30-1000 mTorr). The ESC temperature can be about 0-100°C (e.g., 0-50°C or 10-40°C). The power used to generate the plasma may be about 10-3000 W per station (e.g., 100-1000 W, 200-1000 W, 200-800 W, or 200-500 W). The RF frequency used to generate the plasma may be about 0.3-600 MHz (e.g., 13.56 MHz, 60 MHz, 27 MHz, 2 MHz, 400 kHz, or a combination thereof). The RF bias power may be about 0-1000 W using pulsed or continuous wave (CW) plasma. The processing chamber may be an ICP chamber or a CCP chamber. In some embodiments of an ICP chamber, the frequency of both the upper ICP generator and the bias generator is 13.5 MHz. Depending on the underlying layer, in some embodiments, the pressure may be about 10-400 mTorr and the TCP power may be about 200-500 W.

[0094] Table 1 provides non-limiting examples of underlayer treatment regimes. For embodiment 1, the hydrocarbon precursor is methane (CH4) and the additional gas is He. For embodiment 2, the hydrocarbon precursor is CH4 and the treatment gas includes CO, H2, and He. [Table 1]

[0095] Figure 3 provides performance characteristics of Embodiments 1 and 2 compared to AHM and SOC layers. In one embodiment, the use of an underlayer of Embodiment 1 improves DtS (e.g., 5%, 10%, 15%, 20%, 25%, 30%, or more). Table 2 provides the etch resistance of the underlayer compared to AHM, where the underlayer exhibited a higher relative etch rate compared to AHM. Film composition was also determined by x-ray photoelectron spectroscopy (XPS). The underlayers (Embodiments 1 and 2) had higher H and O content compared to AHM. [Table 2]

[0096] Example 2: Pulsed bias treatment used for deposition of underlayer Further processes have been developed to improve the etch resistance of the underlayer. In particular, bias power has been used to modify the density of the underlayer. For example, deposition of the underlayer can include a pulsed (regardless of frequency) bias from about 1% to 99% DC (e.g., in the range of about 1 Hz to about 10 kHz). Such bias can be provided at any effective power, such as from about 10 to 500 W.

[0097] It is understood that plasma pulsing may include repeating cycles, each lasting for a duration T. The duration T includes the duration of the pulse ON time (the duration the plasma is ON) and the duration of the plasma OFF time (the duration the plasma is OFF) during a given period. The pulse frequency is understood to be 1 / T. For example, for a plasma pulse period T = 100 μs, the frequency is 1 / T = 1 / 100 μs or 10 kHz. The duty cycle or duty ratio is the fraction or percentage that the plasma is ON during the period T, and the duty cycle or duty ratio is the pulse ON time divided by T. For example, for a plasma pulse period T=100 μs, if the pulse ON time is 70 μs (i.e., the duration that the plasma is ON during one period is 70 μs) and the pulse OFF time is 30 μs (i.e., the duration that the plasma is OFF during one period is 30 μs), then the duty cycle is 70%.

[0098] Further deposition conditions may include control of precursor flow rates, gas flow rates, process pressure, temperature (e.g., ESC temperature), plasma power, bias power, pulse frequency, DC, and TCCT parameters within the process chamber. The precursor flow rate may be about 1-100 sccm. The process gas flow rate may be about 1-1600 sccm. The chamber pressure may be about 5-1000 mTorr (e.g., 5-800 mTorr, 10-500 mTorr, 10-400 mTorr, 30-500 mTorr, 10-1000 mTorr, or 30-1000 mTorr). The ESC temperature may be about 0-100°C (e.g., 0-50°C or 10-40°C). The power used to generate the plasma may be about 10-3000 W (e.g., 100-1000 W, 200-1000 W, 200-800 W, or 200-500 W). The RF frequency used to generate the plasma may be about 0.3-600 MHz (e.g., 13.56 MHz, 60 MHz, 27 MHz, 2 MHz, 400 kHz, or a combination thereof). The RF bias power may be about 10-1000 W, with the plasma pulsed at 1-100% (e.g., 1-99%) DC (where 100% indicates CW). The RF bias power may be pulsed at less than 5000 Hz, such as at a frequency of about 10-2000 Hz. The TCCT parameter may be 0.1-1.5. In some non-limiting processes, the plasma exposure can include a high frequency (HF) RF component (e.g., typically about 2-60 MHz) and a low frequency (LF) RF component (e.g., typically about 100 kHz-2 MHz). The process chamber can be an ICP chamber or a CCP chamber.

[0099] Table 3 provides examples of processing regimes for non-limiting underlayers formed with pulse bias processing (embodiment 3). Various underlayer films were formed using embodiment 3, where the bias power was either 70 W or 140 W and the DC was varied from 10 to 50%. The densities of such non-limiting films are provided in Figure 4. Compared to films formed with 0 W bias, pulse bias processing resulted in higher densities (e.g., about 1.09 g / cm). 3) was provided. Thus, the density of the underlayer can be fine-tuned by adding bias power. In some instances, a denser film may improve etch resistance by providing a lower etch rate. [Table 3]

[0100] In addition to increasing density, decreasing etch rate, and / or increasing etch resistance, pulsing may improve other film properties. As seen in Figure 5, pulsing can reduce undercut without sacrificing DtS. The processing conditions included a CH flow rate of 30 sccm, a He flow rate of 660 sccm, a pressure of 150 mTorr, an ESC temperature of 20°C, a TCP power of 400 W, a bias power of 140 W, a bias frequency of 100 Hz, a DC of 10% (film on the left in Figure 5) or 50% (film on the right in Figure 5), and a TCCT of 1.4.

[0101] Example 3: Deposition of a doped underlayer The underlayer may include one or more dopants (e.g., non-carbon dopants when hydrocarbons are used). The dopants may be provided using a hydrocarbon precursor (e.g., to provide carbon atoms) and a separate dopant precursor (e.g., to provide doping non-carbon atoms). In another embodiment, the dopant is provided using a single dopant precursor containing carbon atoms and heteroatoms. Non-limiting non-carbon heteroatoms include oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or any combination thereof. Other dopants and heteroatom-containing dopant precursors are also described herein.

[0102] The use of dopants can improve etch resistance in some instances. Any of the process regimes described herein can be modified to incorporate dopants into the underlayer. For example, deposition can include the use of a dopant precursor (e.g., any of those described herein), and the process regimes described herein for the precursor (e.g., flow rate, pressure, temperature, plasma power, bias power, pulse frequency, duty cycle, TCCT, etc.) can generally be used for the dopant precursor.

[0103] For example, the flow rate of the precursor (e.g., hydrocarbon precursor and / or dopant precursor) may be about 1-100 sccm. The flow rate of the process gas may be about 1-1600 sccm. The chamber pressure may be about 5-1000 mTorr (e.g., 5-800 mTorr, 10-500 mTorr, 10-400 mTorr, 30-500 mTorr, 10-1000 mTorr, or 30-1000 mTorr). The ESC temperature may be about 0-100°C (e.g., 0-50°C or 10-40°C). The power used to generate the plasma may be about 10-3000 W (e.g., 100-1000 W, 200-1000 W, 200-800 W, or 200-500 W). The RF frequency used to generate the plasma may be about 0.3-600 MHz (e.g., 13.56 MHz, 60 MHz, 27 MHz, 2 MHz, 400 kHz, or a combination thereof). The RF bias power may be about 0-1000 W, using a pulsed plasma with about 1-99% DC or a CW plasma (100% DC). The RF bias power may be pulsed at less than 5000 Hz, such as at a frequency of about 10-2000 Hz. The TCCT parameter may be 0.1-1.5. The processing chamber may be an ICP chamber or a CCP chamber.

[0104] In one example, the dopant is or includes nitrogen (N) to provide an N-doped underlayer. Non-limiting N-containing precursors can include any of those described herein, such as nitrogen (N), ammonia (NH), hydrazine (NH), amines, and aminosilanes. In one example, the N-doped underlayer is formed by co-flowing a hydrocarbon precursor and an N-containing precursor.

[0105] Table 4 provides non-limiting examples of N-doped underlayer processing regimes. For embodiment 4, the hydrocarbon precursor is CH4 and the N-containing precursor is N2. For embodiment 5, the hydrocarbon precursor is CH4 and the N-containing precursor is NH3. [Table 4]

[0106] In certain embodiments, the N-doped underlayer has a peak at about 3500-3100 cm in a Fourier transform infrared (FTIR) spectrum. -1 and / or approximately 1635cm -1 NH bonds (e.g., peaks at about 2260-2222 cm in the FTIR spectrum) and / or -1 , approx. 2244cm -1 , and / or approximately 2183 cm -1 The peaks can be characterized by the presence of C≡N bonds.

[0107] The etch rate of a doped underlayer can be improved in several examples. Figure 6 provides the etch rates of an undoped underlayer (Embodiment 1), a first N-doped underlayer using N as the dopant precursor (Embodiment 4), a second N-doped underlayer using NH as the dopant precursor (Embodiment 5), and an Al412 underlayer. Non-limiting etch conditions included utilizing an ICP chamber with a pressure of 5 mTorr, TCP of 350 W, TCCT of 2, bias power of 0 V, a CH flow rate of 10 sccm, an O flow rate of 60 sccm, an Ar flow rate of 200 sccm, and an ESC temperature of 30°C. As can be seen, flowing a hydrocarbon precursor with the NH dopant precursor improved the etch resistance of the underlayer compared to an undoped underlayer.

[0108] In another example, the dopant is or includes tungsten (W) to provide a W-doped underlayer. Non-limiting W-containing precursors can include any of those described herein, such as tungsten halides (e.g., WF, WCl, or WCl), tungsten carbonyl (e.g., W(CO)). In one example, the W-doped underlayer is formed by co-flowing a hydrocarbon precursor and a W-containing precursor.

[0109] In certain embodiments, the W-doped underlayer has a peak at about 3500-3100 cm in the FTIR spectrum. -1 W-OH···H2O bond (for example, a peak at about 981 cm in the FTIR spectrum) -1 W=O bonds (e.g., peaks at about 837 cm in the FTIR spectrum) and / or -1 , 800cm -1 , and / or 702cm -1 It can be characterized by the presence of WOW bonds (with a peak at

[0110] Table 5 provides non-limiting examples of W-doped underlayer processing regimes. For each embodiment, the hydrocarbon precursor is CH4. For embodiment 6, the W-containing precursor is WF6 at a low flow rate of 1 sccm. For embodiment 7, the W-containing precursor is WF6 at a high flow rate of 2 sccm. For embodiment 8, the W-containing precursor is WF6 at a low flow rate of 1 sccm but at a high pressure of 50 mTorr. [Table 5]

[0111] The density of the doped underlayer can be increased. Table 6 provides the refractive index (RI at 633 nm), deposition rate (Dep. Rate), and density of the underlayer. As can be further seen for Example 7, flowing a hydrocarbon precursor with a W-containing dopant precursor increased the density and RI compared to a reference deposited without the dopant precursor. [Table 6]

[0112] In yet another example, the dopant is or includes boron (B) to provide a B-doped underlayer. Non-limiting B-containing precursors can include any of those described herein, such as boron halides (e.g., BCl), boranes (e.g., BH), borates (e.g., B(OH)), and organoboron compounds (e.g., B(CH)). In one example, the B-doped underlayer is formed by co-flowing a hydrocarbon precursor and a B-containing precursor.

[0113] In certain embodiments, the B-doped underlayer has a peak at about 3200 cm in the FTIR spectrum. -1 B···OH bond (for example, a peak at about 1340 cm in the FTIR spectrum) -1 a B-O bond (e.g., a peak at about 1194 cm in the FTIR spectrum) and / or -1 It can be characterized by the presence of BOH bonds (with a peak at

[0114] Table 7 provides non-limiting examples of treatment regimes for B-doped underlayers. For Example 9, the hydrocarbon precursor is CH4 and the B-containing precursor is BCl3. For Example 10, the deposition conditions are the same as Example 9, but the film is further treated with H2. In Table 7, the H2 treatment conditions included pressure = 5 mTorr, TCP = 300 W, bias power = 100 W, H2 flow rate = 200 sccm, and treatment time = 1 second. [Table 7]

[0115] In certain embodiments, both the deposition rate and density of the doped underlayer can be increased. Table 8 provides the RI at 633 nm, deposition rate (Dep. Rate), and density of the underlayer. As can be seen for Example 9, flowing a hydrocarbon precursor with a B-containing dopant precursor increased the deposition rate and density compared to a reference deposited without the dopant precursor. [Table 8]

[0116] As described herein, dopant precursors can be utilized during deposition to provide a doped underlayer, which in certain embodiments can have improved characteristics, such as improved etch resistance, etch rate, refractive index, deposition rate, and / or density.

[0117] Example 4: Deposition of various hydrocarbon precursors The underlayer can be deposited with any useful precursor. For example, the precursor can include a hydrocarbon precursor having only carbon and hydrogen atoms. In another example, the precursor can be a heteroatom-containing hydrocarbon precursor having carbon atoms, hydrogen atoms, and non-carbon heteroatoms. In yet another example, the precursor can be a dopant precursor (e.g., as described herein).

[0118] A variety of hydrocarbon precursors are available. For example, hydrocarbon precursors may include aliphatic and aromatic compounds (e.g., alkanes, alkenes, alkynes, benzene, etc.) and their substitutions. Using different hydrocarbon precursors can alter the type and amount of specific chemical bonds within the underlayer. For example, using unsaturated hydrocarbon precursors can result in increased unsaturated bond content (e.g., increased C=C and / or C≡C bond content), increased sp 2 carbon content, increased sp carbon content, decreased saturated bond content (e.g., decreased C-C bond content), decreased sp 3 The underlayer can be provided with a carbon content and / or a reduced C-H bond content. The selection of the hydrocarbon precursor can depend on various factors. In one non-limiting example, the hydrocarbon precursor includes a saturated precursor (e.g., having a high C-H bond content compared to a C-C, C=C, or C≡C content), which can provide sufficient H atoms. While not wishing to be limited by mechanism, the selection of such a precursor can provide releasable H atoms that interact with atoms in the imaging layer, resulting in improved DtS compared to the use of unsaturated precursors. Nevertheless, in another non-limiting example, the hydrocarbon precursor includes an unsaturated precursor (e.g., having a high C-C, C=C, or C≡C bond content compared to a C-H bond content). While not wishing to be limited by mechanism, the selection of such a precursor can increase etch resistance compared to the use of saturated precursors.

[0119] In certain embodiments, the underlayer has a peak at about 3310 cm in an FTIR spectrum. -1 C=CH bonds (e.g., peaks at about 1650-1600 cm in the FTIR spectrum) and / or ー1 or 1000~660cm -1 It can be characterized by the presence of C=C bonds (with a peak at

[0120] Table 9 provides non-limiting examples of hydrocarbon precursor processing regimes. For Embodiment 1, the hydrocarbon precursor is CH4. For Embodiment 11, the hydrocarbon precursor is acetylene (C2H2). For Embodiment 12, the hydrocarbon precursor is propyne (C3H4). Different plasma types can be utilized (e.g., ICP or CCP). In one example, ICP is utilized to allow independent control of ion energy and ion density. Optimizing process conditions can achieve similar films using either ICP or CCP. For example, CCP generally utilizes a higher self-bias voltage than ICP, resulting in a plasma characterized by higher ion energy. This higher energy can be reduced, for example, by using a higher process pressure, achieving an equivalent process environment to provide film properties similar to those obtained using ICP. Thus, processes herein can include utilizing ICP or CCP with one or more process conditions (e.g., pressure, temperature, precursor or inert gas flow rate, process time, etc.) modified to achieve target film compositions and film properties. [Table 9]

[0121] In certain embodiments, the use of unsaturated hydrocarbon precursors improves etch resistance. Figure 7 provides etch rates for underlayers formed with a CH precursor (or HC≡CH, embodiment 11), a CH precursor (HC≡CCH, embodiment 12), and a CH precursor (embodiment 1). Non-limiting etch conditions included the use of an ICP chamber with a pressure of 5 mTorr, TCP of 350 W, TCCT of 2, bias power of 0 V, a CH flow rate of 10 sccm, an O flow rate of 60 sccm, an Ar flow rate of 200 sccm, and an ESC temperature of 30°C. Thus, the use of unsaturated hydrocarbon precursors (e.g., with triple bonds) improved the etch resistance of underlayers compared to saturated hydrocarbon precursors (e.g., with only single bonds).

[0122] Example 5: Use of highly EUV absorbing atoms The underlayer also has a high patterning radiation absorption cross section (e.g., 1×10 7 cm 2 The iodine may include one or more atoms having an EUV absorption cross section of 1000 uV / mol or greater. Such atoms include, for example, iodine (I). The iodine may be provided by any useful source. For example, the precursor used during vapor deposition may be a dopant precursor that is a hydrocarbon having one or more iodine atoms. Non-limiting precursors include aliphatic or aromatic compounds having one or more I atoms (e.g., alkanes, alkenes, or alkynes (including cyclic forms thereof), and benzene). Further exemplary precursors include iodoacetylene (C2HI), diiodoacetylene (C2I2), vinyl iodide (C2H3I), iodomethane (CHI), diiodomethane (CHI2), 1,1-diiodoethene (C2H2I2), (E)-1,2-diiodoethylene (trans-C2H2I2), (Z)-1,2-diiodoethylene (cis-C2H2I2), allyl iodide (C3H5I), 1-iodo-1-propyne (C3H3I), iodocyclopropane (C3H5I), and 1,1-diiodocyclopropane (C3H4I2).

[0123] Any of the deposition conditions herein can be combined to provide a beneficial underlayer. For example, a pulse bias treatment can be used in conjunction with any of the precursors described herein (e.g., hydrocarbon precursors, dopant precursors, or combinations thereof). In another example, a dopant precursor can be used in conjunction with a hydrocarbon precursor described herein. Furthermore, the treatment can include utilizing one, two, three, or more different precursors (e.g., two or more hydrocarbon precursors and / or two or more dopant precursors). In yet another example, a dopant precursor can be produced by modifying any of the hydrocarbon precursors described herein (e.g., saturated or unsaturated hydrocarbon precursors) with one or more non-carbon heteroatoms.

[0124] The combination of precursors can be selected to provide desired film properties. For example, selecting a particular hydrocarbon precursor (e.g., an unsaturated hydrocarbon precursor) can improve etch resistance. Then, selecting a particular heteroatom can provide a film with increased density or refractive index (e.g., a heteroatom such as O, Si, N, W, B, or I). In one example, the underlayer can include I, C, H, and O atoms; I, C, H, and Si atoms; I, H, N, O, and Si atoms; or I, C, H, N, O, and Si atoms.

[0125] Finally, the selection of still other non-carbon heteroatoms can provide films with enhanced EUV absorption (e.g., 1x10 7 cm 2 a heteroatom (such as I or another heteroatom) having an EUV absorption cross section of 1 / mol or greater. The thickness of the underlayer is controllable (e.g., greater than about 5 nm).

[0126] Precursors (e.g., precursors for the underlayer) The underlayers herein can utilize any useful precursor or combination of precursors. Such precursors can include hydrocarbon precursors containing only carbon (C) and hydrogen (H) atoms, where the precursors can be saturated (having only single bonds) or unsaturated (having one or more double or triple bonds) and can be straight or cyclic chains. Still other precursors can contain one or more non-carbon heteroatoms, and such precursors are referred to herein as dopant precursors. Such dopant precursors can optionally contain carbon atoms in combination with non-carbon atoms. In some embodiments, any hydrocarbon precursor herein can be modified with one or more heteroatoms to provide a dopant precursor. The general term "precursor" can refer to hydrocarbon precursors and / or dopant precursors. Such precursors can, in some instances, be gaseous, thereby enabling deposition within a processing chamber.

[0127] The hydrocarbon precursor generally includes a carbon-containing precursor. In some instances, the hydrocarbon precursor includes only C atoms and H atoms. The hydrocarbon precursor may be, for example, a precursor having the chemical formula C x H y where x is an integer from 1 to 10 and y is an integer from 2 to 24. Examples of such precursors are methane (CH), acetylene (C2H2), ethane (C2H6), ethylene (C2H4), propane (C3H8), propylene (C3H6), propyne (C3H4), allene (C3H4), cyclopropene (C3H4), butane (C4H 10 ), butylene (C4H8), butadiene (C4H6), cyclohexane (C6H 12 ), benzene (C6H6), and toluene (C7H8).

[0128] The hydrocarbon precursors are aliphatic compounds (e.g., C 1-10 Alkane, C 2-10 Alkene, C 2-10 The hydrocarbon precursor may be an alkyne, including its linear or cyclic forms, or an aromatic compound (e.g., benzene and its polycyclic forms). The hydrocarbon precursor may contain saturated bonds (single bonds, e.g., C═C or C≡C bonds) and / or unsaturated bonds (double or triple bonds, e.g., C═C, C≡C, or C≡N bonds).

[0129] Useful precursors for the underlayer may also contain one or more heteroatoms. Such heteroatoms may be any useful non-carbon atom, such as oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), and combinations thereof. Thus, non-limiting heteroatom-containing precursors (also referred to herein as dopant precursors) may include O-containing precursors, Si-containing precursors, N-containing precursors, W-containing precursors, B-containing precursors, I-containing precursors, or Cl-containing precursors. Such dopant precursors may be inorganic (lacking carbon atoms) or organic (containing carbon atoms), as described herein.

[0130] The O-containing precursor may include an oxocarbon precursor containing O and C atoms. In certain embodiments, the oxocarbon precursor reacts with hydrogen (H) or a hydrocarbon, and optionally further co-reacts with a Si source or Si-containing precursor. Still other O-containing precursors may include carbon monoxide (CO), carbon dioxide (CO), water (H0), oxygen (O), ozone (O), hydrogen peroxide (H0), alcohols (t-amyl alcohol, ethanol, propanol, etc.), polyols (e.g., diols such as ethylene glycol), ketones, aldehydes, ethers, esters, carboxylic acids, alkoxysilanes, oxolanes, or furans.

[0131] Si-containing precursors can include silanes, halosilanes, aminosilanes, alkoxysilanes, organosilanes, etc. In certain embodiments, the Si-containing precursor is co-reacted with an oxidizing agent (e.g., any of those described herein, such as an O-containing precursor or an oxocarbon precursor, including CO and CO). Non-limiting Si-containing precursors include polysilanes (HSi-(SiH) n —SiH3), where n≧0. Examples of silanes are silane (SiH4), disilane (Si2H6), and organosilanes (e.g., methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-t-butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, di-t-butyldisilane, etc.).

[0132] Halosilanes contain at least one halogen group and may or may not contain hydrogen and / or carbon atoms. Examples of halosilanes include iodosilane, bromosilane, chlorosilane, and fluorosilane. Specific chlorosilanes include tetrachlorosilane, trichlorosilane, dichlorosilane, monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t-butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, and hexyldimethylchlorosilane. Specific iodosilanes include tetraiodosilane, triiodosilane, diiodosilane, monoiodosilane, and iodotrimethylsilane.

[0133] Aminosilanes contain at least one N atom bonded to a Si atom, but may also contain H, O, halogen, and / or C atoms. Examples of aminosilanes are mono-, di-, tri-, and tetra-aminosilanes (HSi(NH), HSi(NH), HSi(NH), and Si(NH), respectively), as well as substituted mono-, di-, tri-, and tetra-aminosilanes (e.g., t-butylaminosilane, methylaminosilane, t-butylsilaneamine, bi(t-butylamino)silane (SiH(NHC(CH))(BTBAS), tert-butylsilylcarbamate SiH(CH)-(N(CH)), SiHCl(N(CH)), (Si(CH)NH), etc. A further example of an aminosilane is trisilylamine (N(SiH)).

[0134] Alkoxysilanes contain at least one O atom bonded to a Si atom, but may also contain H, N, halogen, and / or C atoms. Examples of alkoxysilanes are mono-, di-, tri-, and tetra-alkoxysilanes (HSi(OR), HSi(OR), HSi(OR), and Si(OR), respectively, where each R can independently be an optionally substituted alkyl or aryl group), as well as substituted mono-, di-, tri-, and tetra-alkoxysilanes (e.g., trimethoxymethylsilane (CHSi(OCH)), (3-aminopropyl)trimethoxysilane (NH(CH)Si(OCH), (3-aminopropyl)triethoxysilane (NH(CH)Si(OCH)). Examples include tetraethoxysilane (Si(OCHCH)), triethoxyvinylsilane (CH=CHSi(OCHCH)), triethoxyethylsilane (CHCHSi(OCHCH)), trimethoxyphenylsilane (PhSi(OCH)), isobutyltriethoxysilane (i-BuSi(OCHCH)), diacetoxydimethylsilane ((CH)Si(OCOCH)), etc. Still other examples include tetraethoxysilane (Si(OCHCH)), triethoxysilane (HSi(OCHCH)), tetramethoxysilane (Si(OCH)), and trimethoxysilane (HSi(OCH)).

[0135] N-containing precursors include any containing at least one N atom, such as nitrogen gas (N), ammonia (NH), hydrazine (NH), amines (carbon-containing amines) (methylamine, dimethylamine, ethylmethylamine, ethylamine, isopropylamine, t-butylamine, di-t-butylamine, cyclopropylamine, sec-butylamine, cyclobutylamine, isoamylamine, 2-methylbutan-2-amine, trimethylamine, diisopropylamine, diethylisopropylamine, etc.), di-t-butylhydrazine, and aromatic-containing amines (aniline, pyridine, benzylamine, etc.). Still other N-containing precursors can include nitriles (e.g., acetonitrile), amides, N-containing heterocyclic compounds, or aminoalcohols (e.g., ethanolamine). The amines can be primary, secondary, tertiary, or quaternary amines (e.g., tetraalkylammonium compounds). The N-containing precursor may contain a heteroatom other than N, for example, hydroxylamine, t-butyloxycarbonylamine, and Nt-butylhydroxylamine are N-containing precursors.

[0136] W-containing precursors include tungsten-containing halide precursors, which may include tungsten fluorides (such as tungsten(VI) fluoride (WF)) and tungsten chlorides (such as tungsten(VI) chloride (WC1), tungsten(V) chloride (WC1), and tungsten(VI) oxychloride (WOC1). In some embodiments, metalloorganic tungsten-containing precursors may be used, such as tungsten hexacarbonyl (W(CO)), mesitylenetungsten tricarbonyl ([CH(CH)]W(CO), bis(t-butylimido)bis(dimethylamino)tungsten(VI) ([(CH)CN]W[N(CH)]), and bis(cyclopentadienyl)tungsten(IV) dihydride (HWCp).

[0137] B-containing precursors include boron halides (e.g., BCl), boranes (e.g., BH), borates (e.g., B(OH)), and organoboron compounds (e.g., B(CH)). Non-limiting B-containing precursors include diborane (BH), trimethyl borate (B[OCH]), triethyl borate (B[OCHCH]), triisopropyl borate (B[OCH(CH)]), trimethylborane (B(CH), triethylborane (B(CH)), triphenylborane (BPh), tetrakis(dimethylamino)diboron (B(N(CH)), boron trifluoride (BF), boron trichloride (BCl), boron tribromide (BBr), and boron iodide (BI).

[0138] I-containing precursors include iodinated hydrocarbon compounds such as iodoacetylene (C2HI), diiodoacetylene (C2I2), vinyl iodide (C2H3I), iodomethane (CHI), diiodomethane (CHI2), 1,1-diiodoethene (C2H2I2), (E)-1,2-diiodoethylene (trans-C2H2I2), (Z)-1,2-diiodoethylene (cis-C2H2I2), allyl iodide (C3H5I), 1-iodo-1-propyne (C3H3I), iodocyclopropane (C3H5I), and 1,1-diiodocyclopropane (C3H4I2).

[0139] Cl-containing precursors include chlorinated hydrocarbon compounds such as chloroacetylene (CHCl), vinyl chloride (CHCl), chloromethane (CHCl), dichloromethane (CHCl), 1,1-dichloroethene (CHCl), (E)-1,2-dichloroethylene (trans-CHCl), (Z)-1,2-dichloroethylene (cis-CHCl), allyl chloride (CHCl), 1-chloro-1-propyne (CHCl), chlorocyclopropane (CHCl), and 1,1-dichlorocyclopropane (CHCl).

[0140] Other heteroatoms may be included, such as phosphorus (P). P-containing precursors may include phosphates, phosphines, phosphorus halides, organophosphorus compounds, etc. Non-limiting P-containing precursors include triethyl phosphate (PO[OCH]), trimethyl phosphate (PO[OCH]), trimethyl phosphite (P(OCH)), trisdimethylaminophosphorus (P[N(CH)]), phosphorus trichloride (PCl), trismethylsilylphosphine (P[Si(CH)]), and phosphorus oxychloride (POCl).

[0141] Characteristics of the lower layer Any of the processes and precursors described herein can be used to provide a useful underlayer (primer layer). The composition of the underlayer can be tailored to include specific atoms. In one embodiment, the underlayer contains 0-30 atomic % O (e.g., 1-30%, 2-30%, or 4-30%), about 20-50 atomic % H (e.g., 20-45%, 30-50%, or 30-45%), and / or 30-70 atomic % C (e.g., 30-60%, 30-65%, or 30-68%). In other embodiments, the underlayer contains unsaturated bonds (e.g., C=C, C≡C, and / or C≡N bonds). In yet another embodiment, the underlayer contains about 0.7-2.9 g / cm. 3 It has a density of

[0142] The underlayer may be characterized by a high etch selectivity and / or reduced undercut compared to the control film. In other embodiments, the underlayer may be characterized by low line edge and line width roughness and / or low dose-to-size compared to the control film. Non-limiting control films include films formed with saturated hydrocarbon precursors, formed in a pulsed bias, and / or formed without dopants. In one example, the control film is an AHM formed with methane. In another example, the control film is an AHM formed with acetylene.

[0143] Patterning Structure The patterning structures (or films) herein can include an imaging layer on the surface of the hard mask or substrate and an underlayer below the imaging layer, hi certain embodiments, the presence of the underlayer enhances the radiation absorption and / or patterning performance of the imaging layer.

[0144] In general, photon absorption through a layer is depth-dependent. When a homogeneous layer or film is exposed to radiation, lower portions of the layer are exposed to a lower radiation dose compared to upper portions of the same layer because fewer photons reach the lower portions. Therefore, to ensure sufficient and uniform exposure throughout the depth of the layer, the layer must provide sufficient penetration of the radiation. In certain embodiments, the underlayer described herein increases radiation absorption through the imaging layer. Furthermore, in some instances, the underlayer can effectively generate more secondary electrons that can better expose the lower portions of the patterning structure.

[0145] One or both of the underlayer and imaging layer may include a highly absorbing element. In one example, both the underlayer and imaging layer have a high EUV absorption of 1x10 7 cm 2 The imaging layer may include a highly absorbing element, such as 1 / mol or more. The elements in each of the absorbing layer and the imaging layer may be the same or different. In certain embodiments, improved adhesion can reduce the radiation dose required to provide desired patterned features in the imaging layer and / or underlayer.

[0146] The imaging layer can comprise any useful resist, such as an organometallic-based resist, as described herein. If the photoresist material being used has a significant inorganic component, e.g., if it exhibits a framework that is primarily metal oxide, the underlayer can be advantageously a carbon-based film. If device features that create significant topography are present on the substrate to be patterned, another important function of the underlayer can be to overlay and planarize the existing topography so that subsequent patterning steps can be performed on all areas of the pattern in focus and on a flat surface. For such applications, the underlayer (or at least one of multiple underlayers) can be applied using dry deposition or spin-coating techniques. This layer can include various AHM films with carbon-based and hydrogen-based compositions, and can be doped with additional elements such as tungsten, boron, nitrogen, or fluorine.

[0147] The underlayer and imaging layer, alone or together, can be considered a film. In some embodiments, the film is a radiation-sensitive film (e.g., an EUV-sensitive film). This film can then function as an EUV resist, as further described herein. In certain embodiments, the layer or film can include one or more ligands (e.g., EUV-labile ligands) that can be removed, cleaved, or crosslinked by radiation (e.g., EUV or DUV radiation).

[0148] The precursors can be used to provide radiation-sensitive, patternable films (or patterned radiation-sensitive or photopatternable films). Such radiation can include EUV, DUV, or UV radiation, delivered by irradiating through a patterned mask to provide the patterned radiation. The film itself can be modified by exposure to such radiation to make the film radiation-sensitive or photosensitive. In certain embodiments, the precursor is an organometallic compound and includes at least one metal center.

[0149] The precursor may have any useful number and type of ligands. In some embodiments, the ligands may be characterized by their ability to react in the presence of a counter reactant or in the presence of patterned radiation. For example, the precursor may include a ligand that reacts with a counter reactant, thereby introducing a bond (e.g., an -O- bond) between the metal centers. In another example, the precursor may include a ligand that desorbs in the presence of patterned radiation. Such EUV-labile ligands may include branched or linear alkyl groups with a beta hydrogen and any of those described herein for R in formula (I) or (II).

[0150] The precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., those described herein). In a non-limiting example, the precursor comprises a structure having the following chemical formula (I): M a R b (I), where: M is a metal or atom with a high EUV absorption cross section, each R is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand, neutral ligand, or multidentate ligand; a≧1, b≧1.

[0151] In another non-limiting example, the precursor comprises a structure having the following chemical formula (II): M a R b L c (II), where: M is a metal or atom with a high EUV absorption cross section, each R is independently halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is independently a ligand, anionic ligand, neutral ligand, multidentate ligand, ion, or other moiety that reacts with a counter reactant, where R and L together with M optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a≧1, b≧1, and c≧1.

[0152] In some embodiments, each ligand in the precursor can be a ligand that reacts with a counter reactant. In one example, the precursor has a structure having formula (II), where each R is independently L. In another example, the precursor has a structure having formula (IIa): M a L c (IIa), where: M is a metal or atom with a high EUV absorption cross section, each L is independently a ligand, ion, or other moiety that reacts with a counter reactant, where two L together can optionally form a heterocyclyl group; a≧1 and c≧1. In certain embodiments of Formula (IIa), a is 1. In further embodiments, c is 2, 3, or 4.

[0153] For any formula herein, M is a high patterning radiation absorption cross section (e.g., 1x10 7 cm 2M may be a metal or metalloid or atom having an EUV absorption cross section of 1000 uV / mol or greater. In some embodiments, M is tin (Sn), bismuth (Bi), tellurium (Te), cesium (Cs), antimony (Sb), indium (In), molybdenum (Mo), hafnium (Hf), iodine (I), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), platinum (Pt), and lead (Pb). In further embodiments, in Formula (I), (II), or (IIa), M is Sn, a is 1, and c is 4. In other embodiments, in Formula (I), (II), or (IIa), M is Sn, a is 1, and c is 2. In certain embodiments, M is Sn(II) (e.g., in formula (I), (II), or (IIa)), thereby providing a precursor that is a Sn(II)-based compound. In other embodiments, M is Sn(IV) (e.g., in formula (I), (II), or (IIa)), thereby providing a precursor that is a Sn(IV)-based compound. In certain embodiments, the precursor includes iodine (e.g., as in the case of periodate).

[0154] For any formula herein, each R is independently selected from H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy (e.g., -OR 1 , where R 1 may be an optionally substituted alkyl group), an optionally substituted alkanoyloxy group, an optionally substituted aryl group, an optionally substituted amino group, an optionally substituted bis(trialkylsilyl)amino group, an optionally substituted trialkylsilyl group, an oxo group, an anionic ligand (e.g., oxide, chloride, hydride, acetate, iminodiacetate, propanoate, butanoate, benzoate, etc.), a neutral ligand, or a multidentate ligand.

[0155] In some embodiments, the optionally substituted amino is —NR 1 R 2 where each R 1 and R 2 are independently H or alkyl groups, or R 1 and R 2 together with the nitrogen atom to which each is attached form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino group is —N(SiR 1 R 2 R 3 )2, where each R 1 , R 2 , and ,R 3 are independently an optionally substituted alkyl group. In yet other embodiments, the optionally substituted trialkylsilyl group is -SiR 1 R 2 R 3 where each R 1 , R 2 , and ,R 3 are independently optionally substituted alkyl groups.

[0156] In other embodiments, the formula is —NR 1 R 2 The first R (or first L) and the NR 1 R 2 and a second R (or second L) where each R 1 and R 2 are independently H or optionally substituted alkyl, or R from 1R (or 1L) 1 and R from the 2nd R (or 2nd L) 1 together with the nitrogen atom and metal atom to which each is attached, form a heterocyclyl group, as defined herein. 1 The first R is -OR 1 and a second R, each R 1are independently H or optionally substituted alkyl, or R 1 through R 1 and R from the 2nd R 1 together with the oxygen atom and metal atom to which each is attached, form a heterocyclyl group as defined herein.

[0157] In some embodiments, at least one of R or L (e.g., in formula (I), (II), or (IIa)) is an optionally substituted alkyl group. Non-limiting alkyl groups include, for example, C n H 2n+1 (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl), where n is 1, 2, 3, or 4 or greater. In various embodiments, R or L has at least one beta hydrogen or beta fluorine. In other embodiments, at least one of R or L is a halo-substituted alkyl (e.g., a fluoro-substituted alkyl).

[0158] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (I), (II), or (IIa)) is halo. In particular, the precursor can be a metal halide. Non-limiting metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0159] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (I), (II), or (IIa)) may contain a nitrogen atom. In certain embodiments, one or more R or L is selected from the group consisting of optionally substituted amino, optionally substituted monoalkylamino (e.g., —NR 1 H, where R 1 is optionally substituted alkyl), optionally substituted dialkylamino (e.g., —NR 1 R 2 , where each R 1 and R 2are independently optionally substituted alkyl), or optionally substituted bis(trialkylsilyl)amino. Non-limiting R and L substituents can include, for example, -NMe, -NHMe, -NEt, -NHEt, -NMeEt, -N(t-Bu)-[CHCH]-N(t-Bu)-(tbba), N(SiMe), and N(SiEt).

[0160] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (I), (II), or (IIa)) may include a silicon atom. In particular embodiments, one or more R or L may be an optionally substituted trialkylsilyl group or an optionally substituted bis(trialkylsilyl)amino group. Non-limiting R or L substituents may include, for example, -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2, etc.

[0161] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (I), (II), or (IIa)) can include an oxygen atom. In certain embodiments, one or more R or L can be an optionally substituted alkoxy group or an optionally substituted alkanoyloxy group. Non-limiting R or L substituents can be, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate, (-OC(O)-CH), and -O=C(CH)-CH=C(CH)-O-(acac).

[0162] Any chemical formula herein may include one or more neutral ligands. Non-limiting neutral ligands include optionally substituted amines (e.g., NR or RN-Ak-NR, where each R is independently H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is optionally substituted alkylene), optionally substituted phosphines (e.g., PR or R2P-Ak-PR, where each R is independently H, optionally substituted alkyl, optionally substituted hydroxyl, or optionally substituted aryl). Examples of alkylenes include optionally substituted ethers (e.g., OR, where each R is independently H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl), optionally substituted alkyl, optionally substituted alkene, optionally substituted alkyne, optionally substituted benzene, oxo, or carbon monoxide.

[0163] Any formula herein may include one or more polydentate (e.g., bidentate) ligands. Non-limiting polydentate ligands include diketonates (e.g., acetylacetonate (acac) or -OC(R 1 )-Ak-(R 1 )CO- or -OC(R 1 )-C(R 2 )-(R 1 )CO-), bidentate chelate dinitrogen (e.g., -N(R 1 )-Ak-N(R 1 )- or -N(R 3 )-CR 4 -CR 2 =N(R 1 )-), aromatic (e.g., -Ar-), amidinate (e.g., -N(R 1 )-C(R 2 )-N(R 1 )-), aminoalkoxides (e.g., -N(R 1 )-Ak-O- or -N(R 1)2-Ak-O-), diazadienyl (e.g., -N(R 1 )-C(R 2 )-C(R 2 )-N(R 1 )-), cyclopentadienyl, pyrazolate, optionally substituted heterocyclyl, optionally substituted alkylene, or optionally substituted heteroalkylene. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted haloalkyl, or optionally substituted aryl, and each R 2 are independently H or optionally substituted alkyl, R and R together form an optionally substituted heterocyclyl, A is optionally substituted alkylene, and Ar is optionally substituted arylene.

[0164] In certain embodiments, the precursor comprises tin. In some embodiments, the tin precursor comprises SnR or SnR2 or SnR4 or R3SnSnR3, where each R is independently H, halo, optionally substituted C 1-12 Alkyl, optionally substituted C 1-12 alkoxy, optionally substituted amino (e.g., —NR 1 R 2 ), optionally substituted C 2-12 Alkenyl, optionally substituted C 2-12 Alkynyl, optionally substituted C 3-8 Cycloalkyl, optionally substituted aryl, cyclopentadienyl, optionally substituted bis(trialkylsilyl)amino (e.g., —N(SiR 1 R 2 R 3 )2), optionally substituted alkanoyloxy (e.g., acetate), diketonate (e.g., —OC(R 1 )-Ak-(R 2 )CO-), or bidentate chelate dinitrogen (e.g., -N(R 1 )-Ak-N(R 1In certain embodiments, each R 1 , R 2 , and ,R 3 are independent and can be H or C 1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), and Ak is optionally substituted C 1-6 In certain embodiments, each R is independently selected from the group consisting of halo, optionally substituted C 1-12alkoxy, optionally substituted amino, optionally substituted aryl, cyclopentadienyl, or diketonate. Non-limiting tin precursors include SnF2, SnH4, SnBr4, SnCl4, SnI4, tetramethyltin (SnMe4), tetraethyltin (SnEt4), trimethyltin chloride (SnMe3Cl), dimethyltin dichloride (SnMe2Cl2), methyltin trichloride (SnMeCl3), tetraallyltin, tetravinyltin, hexaphenylditin(IV) (Ph3Sn-SnPh3, where Ph is phenyl), di Butyldiphenyltin (SnBu2Ph2), trimethyl(phenyl)tin (SnMe3Ph), trimethyl(phenylethynyl)tin, tricyclohexyltin hydride, tributyltin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acacac)2), SnBu3(OEt), SnBu2(OMe)2, SnBu3(OMe), Sn( t-BuO)4, Sn(n-Bu)(t-BuO)3, tetrakis(dimethylamino)tin (Sn(NMe2)4), tetrakis(ethylmethylamino)tin (Sn(NMeEt)4), tetrakis(diethylamino)tin(IV) (Sn(NEt2)4), (dimethylamino)trimethyltin(IV) (Sn(Me)3(NMe2), Sn(i-Pr)(NMe2)3, Sn(n-Bu)(NMe2)3, Sn(s-Bu)(NM e2)3, Sn(i-Bu)(NMe2)3, Sn(t-Bu)(NMe2)3, Sn(t-Bu)2(NMe2)2, Sn(t-Bu)(NEt2)3, Sn(tbba), Sn(II) (1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2-diazastannolidin-2-ylidene), or bis[bis(trimethylsilyl)amino]tin (Sn[N(SiMe3)2]2).

[0165] In other embodiments, the precursor comprises bismuth (such as in BiR), where each R is independently halo, optionally substituted C 1-12 Alkyl, mono-C 1-12 Alkylamino (e.g., -NR1 H), Di-C 1-12 Alkylamino (e.g., -NR 1 R 2 ), optionally substituted aryl, optionally substituted bis(trialkylsilyl)amino (e.g., —N(SiR 1 R 2 R 3 )2), or diketonates (e.g., -OC(R 4 )-Ak-(R 5 )CO-). In certain embodiments, each R 1 , R 2 , and ,R 3 is independent and C 1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), and each R 4 and R 5 are independently H or optionally substituted C 1-12 and alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl). Non-limiting bismuth precursors include BiCl3, BiMe3, BiPh3, Bi(NMe2)3, Bi[N(SiMe3)2]3, and Bi(thd)3, where thd is 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0166] In other embodiments, the precursor comprises tellurium (such as TeR2 or TeR4), where each R is independently halo, C 1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl), optionally substituted C 1-12alkoxy, optionally substituted aryl, hydroxyl, oxo, or optionally substituted trialkylsilyl. Non-limiting tellurium precursors include dimethyltellurium (TeMe), diethyltellurium (TeEt), di(n-butyl)tellurium (Te(n-Bu)), di(isopropyl)tellurium (Te(i-Pr)), di(t-butyl)tellurium (Te(t-Bu)), t-butyltellurium hydride (Te(t-Bu)(H)), Te(OEt), bis(trimethylsilyl)tellurium (Te(SiMe)), and bis(triethylsilyl)tellurium (Te(SiEt)).

[0167] The precursor may include antimony (such as in SbR3), where each R is independently halo, optionally substituted C 1-12 Alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl), optionally substituted C 1-12 Alkoxy or optionally substituted amino (e.g., —NR 1 R 2 , where each R 1 and R 2 are independently H or optionally substituted C 1-12 Non-limiting antimony precursors include SbCl3, Sb(OEt)3, Sb(On-Bu)3, and Sb(NMe2)3.

[0168] Other precursors include indium precursors (such as in InR3), where each R is independently halo, optionally substituted C 1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, and neopentyl) or diketonate (e.g., -OC(R 4 )-Ak-(R 5 )CO-, where each R 4 and R 5 are independent and can be H or C 1-12Non-limiting indium precursors include InCp, where Cp is cyclopentadinyl, InCl, InMe, In(acac), In(CFCOCHCOCH), and In(thd).

[0169] The precursor may comprise iodine (RI, where R is iodine (I) or optionally substituted C 1-12 (Alkyl) or periodate, etc.) Non-limiting iodine precursors include iodine gas (I2), diiodomethane (CH2I2), and periodate.

[0170] Further precursors and non-limiting substituents are described herein. For example, the precursor may be any precursor having the structure of formula (I), (II), and (IIa), as described above, or any precursor having the structure of formula (III), (IV), (V), (VI), (VII), or (VIII), as described below. Any of the substituents M, R, X, or L described herein may be used in any of formulas (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII).

[0171] Still other exemplary EUV-sensitive materials and processing methods and apparatus are described in U.S. Pat. No. 9,996,004, International Patent Publication No. WO2020 / 102085, and International Patent Publication No. WO2019 / 217749, each of which is incorporated by reference herein in its entirety.

[0172] As described herein, the films, layers, and methods herein can be used with any useful precursor. In some examples, the precursor comprises a metal halide having the following chemical formula (III): MX n (III), where M is a metal, X is halo, and n is 2-4 depending on the selection of M. Examples of metals for M include Sn, Te, Bi, or Sb. Examples of metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0173] Another non-limiting precursor has a structure having the following formula (IV): MR n (IV), where M is a metal and each R is independently H, optionally substituted alkyl, amino (e.g., -NR2, where each R is independently alkyl), optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR3)2, where each R is independently alkyl), or optionally substituted trialkylsilyl (e.g., -SiR3, where each R is independently alkyl), and n is 2 to 4, depending on the selection of M. Examples of metals for M include Sn, Te, Bi, or Sb. The alkyl group can be C n H 2n+1 where n is 1, 2, 3, or greater than 4. Examples of organometallic agents include SnMe4, SnEt4, TeRn, RTaR, t-butyl tellurium hydride (Te(t-Bu)(H)), dimethyl tellurium (TeMe2), di(t-butyl) tellurium (Te(t-Bu)2)), di(isopropyl) tellurium (Te(i-Pr)2), bis(trimethylsilyl) tellurium (Te(SiMe3)2), bis(triethylsilyl) tellurium (Te(SiEt3)2), tris(bis(trimethylsilyl)amido)bismuth (Bi[N(SiMe3)2]3), Sb(NMe2)3, and the like.

[0174] Another non-limiting precursor may include a capping agent having the following chemical formula (V): ML n (V), where M is a metal and each L is independently an optionally substituted alkyl, amino (e.g., —NR 1 R 2 , where R 1 and R2 Each of may be H or alkyl (such as any described herein), alkoxy (e.g., -OR, where R is alkyl (such as any described herein)), halo, or other organic substituent, and n is 2-4 depending on the selection of M. Examples of metals for M include Sn, Te, Bi, or Sb. Example ligands are dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alkoxy (e.g., t-butoxy and isopropoxy), halo (e.g., F, Cl, Br, and I), or other organic substituent (e.g., acetylacetone or N 2 ,N 3 -di-tert-butyl-butane-2,3-diamino). Non-limiting capping agents include SnCl, SnI, Sn(NR), where each R is independently methyl or ethyl, or Sn(t-BuO). In some embodiments, multiple types of ligands are present.

[0175] The precursor may include a hydrocarbyl-substituted capping agent having the following formula (VI): R n MX m (VI), where M is a metal and R is C 2-12where X is an alkyl or substituted alkyl having a beta hydrogen, and X is a leaving group suitable for reaction with the hydroxyl group of the exposed hydroxyl group. In various embodiments, n=1-3 and m=4-n, 3-n, or 2-n, where m>0 (i.e., m≧1). For example, R can be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, n-hexyl, or a derivative thereof having a heteroatom substituent at the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I) or oxygen (—OH or —OR). X can be dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), alkoxy (e.g., t-butoxy, isopropoxy), halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl-substituted capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe2)3), t-butyltris(diethylamino)tin (Sn(t-Bu)(NEt2)3), di(t-butyl)di(dimethylamino)tin (Sn(t-Bu)2(NMe2)2), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), n-pentyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), tris(dimethylamino)tin (Sn(n-pentyl)(NMe2)3), i-butyltris(dimethylamino)tin (Sn(i-Bu)(NMe2)3), i-propyltris(dimethylamino)tin (Sn(i-Pr)(NMe2)3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO)3), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO)3).

[0176] In various embodiments, the precursor includes at least one alkyl group on each metal atom that can remain after the gas phase reaction, while other ligands or ions coordinated to the metal atom can be replaced by counter reactants. Thus, another non-limiting precursor includes an organometallic agent having the formula (VII): M a R b L c (VII), where M is a metal, R is an optionally substituted alkyl, L is a ligand, ion, or other moiety that reacts with a counter reactant, and a≧1, b≧1, and c≧1. In certain embodiments, a=1, and b+c=4. In some embodiments, M is Sn, Te, Bi, or Sb. In certain embodiments, each L is independently an amino (e.g., —NR 1 R 2 , where R 1 and R 2 Each of R may be H or alkyl (such as any described herein), alkoxyl (e.g., —OR, where R may be alkyl (such as any described herein), or halo (e.g., F, Cl, Br, or I). Examples of organometallic agents include SnMe3Cl, SnMe2Cl2, SnMeCl3, SnMe(NMe2), SnMe2(NMe2), SnMe3(NMe2), and the like.

[0177] In another embodiment, another non-limiting precursor includes an organometallic agent having the formula (VIII). M a L c (VIII), where M is a metal and L is a ligand, ion, or other moiety that reacts with a counter reactant, where a≧1 and c≧1. In certain embodiments, c=n−1, where n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, or Sb. Preferably, the counter reactant can be substituted with a reactive moiety, ligand, or ion (e.g., L in the formulas herein) to join at least two metal atoms in a chemical bond.

[0178] In any embodiment herein, R is optionally substituted alkyl (e.g., C 1-10 In one embodiment, the alkyl can be substituted with one or more halo (e.g., halo-substituted C 1 , including 1, 2, 3, 4, or 5 or more halo (e.g., F, Cl, Br, or I). 1-10 alkyl). Examples of R substituents are C n H 2n+1 (where n≧3 is preferred), and C n F x H (2n+1-x) where 2n+1≦x≦1. In various embodiments, R has at least one beta hydrogen or beta fluorine. For example, R may be selected from the group consisting of i-propyl, n-propyl, t-butyl, i-butyl, n-butyl, sec-butyl, n-pentyl, i-pentyl, t-pentyl, sec-pentyl, and mixtures thereof.

[0179] In any embodiment herein, L is an amino (e.g., —NR 1 R 2 , R 1 and R 2may be any moiety that is readily displaced by a counter reactant to generate the moiety M-OH, such as a moiety selected from the group consisting of H or alkyl (such as any described herein), alkoxy (e.g., —OR, where R may be alkyl (such as any described herein)), carboxylate, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0180] Preferably, the counter reactant can replace a reactive moiety, ligand, or ion (e.g., L in the chemical formulas herein) to chemically bond at least two metal atoms. Examples of counter reactants include oxygen-containing counter reactants such as oxygen (O), ozone (O), water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohols, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof. In various embodiments, the counter reactant reacts with the precursor by forming oxygen bridges between adjacent metal atoms. Other potential counter reactants include hydrogen sulfide and hydrogen disulfide, which can bridge metal atoms via sulfur bridges, and bis(trimethylsilyl)tellurium, which can bridge metal atoms via tellurium bridges. Additionally, hydrogen iodide can be used to incorporate iodine into the film.

[0181] Still other non-limiting counter reactants include chalcogenide precursors having the formula ZR2, where Z is sulfur, selenium, or tellurium, and each R is independently H, optionally substituted alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, etc.), optionally substituted alkenyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or optionally substituted trialkylsilyl.

[0182] Examples of organometallic agents are SnMeCl3, (N 2 ,N 3 -di-t-butyl-butane-2,3-diamido)tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amido)tin(II), tetrakis(dimethylamino)tin(IV) (Sn(NMe2)4), t-butyltris(dimethylamino)tin (Sn(t-butyl)(NMe2)3), i-butyltris(dimethylamino)tin (Sn(i-Bu)(NMe2)3), n-butyltris(dimethylamino)tin (Sn(n-Bu) )(NMe2)3), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe2)3), i-propyl(tris)dimethylaminotin (Sn(i-Pr)(NMe2)3), n-propyltris(diethylamino)tin (Sn(n-Pr)(NEt2)3), and analogous alkyl(tris)(t-butoxy)tin compounds, such as t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO)3). In some embodiments, the organometallic agent is partially fluorinated.

[0183] In some embodiments, the patterning structure comprises exposed hydroxyl groups or hydroxyl-terminated SnO x Without limiting the mechanism, function, or utility of the present technology, the surface layer or film may include hydroxyl-terminated SnO x It is believed that the layer may provide benefits such as improved adhesion of materials deposited on the surface of the substrate and enhanced absorption of EUV (or other radiation) during patterning. Sensitivity to EUV or other radiation and resolution may be improved by using SnO x The properties of the layer (such as thickness, density, and short-range charge transport properties) may be dependent on the layer. x The layer has a thickness of 0.1 nm to 20 nm, or 0.2 nm to 10 nm, or 0.5 nm to 5 nm.

[0184] In some embodiments, hydroxyl-terminated SnO x The layer is deposited on the surface of the substrate by evaporation. In such a method, the deposition is carried out by depositing Sn-X nwith an oxygen-containing reactant, where X is a ligand such as dialkylamino (e.g., dimethylamino, methylethylamino, and diethylamino), alcohol (e.g., t-butoxy and isopropoxy), halogen (e.g., F, Cl, Br, and I), or other organic substituents (e.g., acetylacetone, N2,N3-di-tertbutyl-butane-2,3-diamino). For example, Sn-X n may be SnCl, SnI, or Sn(NR) (where R is methyl or ethyl), or Sn(t-BuO). In some embodiments, multiple types of ligands are present. The oxygen-containing counter reactant may be selected from the group consisting of water, hydrogen peroxide, formic acid, alcohol, oxygen, ozone, and combinations thereof.

[0185] Suitable deposition processes include chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced chemical vapor deposition (PECVD), or plasma-enhanced atomic layer deposition (PEALD). In some embodiments, the deposition is performed using a Sn-X n In some embodiments, the deposition is an ALD process in which deposition of Sn—X is performed in a cyclical manner. n and oxygen-containing reactants. Among those useful herein, SnO x Materials and processes for depositing the SnO layer are described in Nazarov et al., Atomic Layer Deposition of Tin Dioxide Nanofilms: A Review, 40 Rev. Adv. Mater. Sci. 262 (2015). x The substrate may be deposited by a CVD or ALD process as described herein.

[0186] A surface activation operation may be used to activate the surface for future operations. For example, SiO xFor surfaces, water or oxygen / hydrogen plasma may be used to generate hydroxyl groups on the surface. For carbon- or hydrocarbon-based surfaces, water, hydrogen / oxygen, or CO2 plasma, or ozone treatment may be used to generate carboxylic acid and / or hydroxyl groups. Such approaches may prove important for improving adhesion of resist features to the substrate, which may otherwise peel or lift in the solvent used for development.

[0187] Adhesion can also be enhanced by introducing roughness into the substrate surface to increase the surface area available for interaction and directly improve mechanical adhesion. For example, a sputtering process using Ar or other non-reactive ion bombardment can first be used to create a rough surface. The surface can then be terminated with the desired surface functional groups (e.g., hydroxyl and / or carboxylic acid groups) as described above. On carbon, a combination approach can be used, in which a chemically reactive oxygen-containing plasma (such as CO, O, or H, O (or a mixture of H and O)) can be used to etch away a thin layer of the film with localized inhomogeneities while simultaneously terminating with -OH, -OOH, or -COOH groups. This can be performed with or without bias. In conjunction with the surface modification strategies described above, this approach can serve the dual purpose of roughening the surface and chemically activating the substrate surface for direct adhesion to inorganic metal oxide-based resists or as an intermediate surface modification for further functionalization.

[0188] The patterning structure may comprise any useful substrate. For example, an input wafer may be prepared having a substrate surface of a desired material, with the top material being the layer to which the resist pattern will be transferred. The choice of material may vary depending on the integration, but it is generally desirable to select a material that can be etched with high selectivity (i.e., much faster) relative to the EUV resist or imaging layer. In some embodiments, the substrate is a hard mask, and the hard mask is used in the lithographic etching of the underlying semiconductor material. Hard masks can be made of materials such as amorphous carbon (aC), tin oxide (e.g., SnO), x ), silicon oxide (e.g., SiO x ), silicon oxynitride (e.g., SiO x N y ), silicon carbonate (e.g., SiO x C y ), silicon nitride (e.g., Si3N4), titanium oxide (e.g., TiO2), titanium nitride (e.g., TiN), tungsten (e.g., W), doped carbon (e.g., W-doped C), tungsten oxide (e.g., WO x The substrate may comprise any of a variety of materials, such as SnO, hafnium oxide (e.g., HfO), zirconium oxide (e.g., ZrO), and aluminum oxide (e.g., AlO). Suitable substrate materials may include various carbon-based films (e.g., ashable hard masks (AHMs), silicon-based films (e.g., SiOx, SiCx, SiOxCy, SiOxNy, SiOxCyNz), a-Si:H, poly-Si, or SiN), or any other film (typically a sacrificial film) applied to facilitate the patterning process. For example, the substrate is preferably SnO. x (such as SnO2). In various embodiments, the layer may be 1 nm to 100 nm thick, or 2 nm to 10 nm thick.

[0189] In various embodiments, the surface (e.g., of a substrate and / or film) comprises exposed hydroxyl groups on the surface. Generally, the surface can be any surface that comprises, or has been treated to produce, an exposed hydroxyl surface. Such hydroxyl groups can be formed on the surface by surface treatment of the substrate with oxygen plasma, water plasma, or ozone. In other embodiments, the surface of the film can be treated to provide exposed hydroxyl groups, onto which a capping layer can be applied. In various embodiments, the hydroxy-terminated metal oxide layer has a thickness of 0.1 nm to 20 nm, or 0.2 nm to 10 nm, or 0.5 nm to 5 nm.

[0190] The embodiments disclosed herein describe the deposition of materials onto a substrate (e.g., a wafer, substrate, or other workpiece). Workpieces can have a variety of shapes, sizes, and materials. The terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably herein. Those skilled in the art will recognize that the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of the many stages of integrated circuit processing. Wafers or substrates used in the semiconductor device industry typically have diameters of 200 mm, 300 mm, or 450 mm. Unless otherwise specified, process details (e.g., flow rates, power levels, etc.) described herein are suitable for processing 300 mm diameter substrates or chambers configured to process 300 mm diameter substrates and may be scaled to accommodate other sized substrates or chambers. In addition to semiconductor wafers, other workpieces that can be used with the embodiments disclosed herein include various items, such as printed circuit boards. The processes and apparatus can be used in the manufacture of semiconductor devices, displays, and the like.

[0191] Lithography Processing EUV lithography utilizes an EUV resist, which may be a polymer-based chemically amplified resist produced by a liquid-based spin-on technique or a metal oxide-based resist produced by a dry deposition technique. Such an EUV resist may include any EUV-sensitive film or material described herein. The lithography method may include, for example, patterning the resist by exposing the EUV resist to EUV radiation to form a photopattern, and then developing the pattern by removing portions of the resist according to the photopattern to form a mask.

[0192] It should also be understood that while the present disclosure relates to lithographic patterning techniques and materials using EUV lithography as an example, it is also applicable to other next-generation lithography technologies. In addition to EUV, including the standard 13.5 nm EUV wavelength currently being used and developed, the most suitable radiation sources for such lithography are DUV (deep UV) (generally referring to the use of 248 nm or 193 nm excimer laser sources), X-ray (which formally includes EUV at a relatively low energy range in the X-ray range), and e-beam (which can cover a wide energy range). Such methods include contacting a substrate (e.g., optionally having exposed hydroxyl groups) with a precursor (e.g., any precursor described herein) to form a film of metal oxide (e.g., a layer including a network of metal oxide bonds, which may also include other non-metallic and non-oxygen groups) as an imaging / PR layer on the substrate surface. Specific methods may depend on the specific materials and applications used for the semiconductor substrate and final semiconductor device. Accordingly, the methods described herein are merely exemplary of methods and materials that may be used with current technology. In some embodiments, lithography involves the use of a radiation source having a wavelength between 10 nm and 400 nm.

[0193] Directly photopatternable EUV resists may be composed of or include metals and / or metal oxides. Metals / metal oxides are highly promising in that they can enhance EUV photon adsorption, generate secondary electrons, and / or exhibit high etch selectivity relative to underlying film stacks and device layers. To date, these resists have been developed using a wet (solvent) approach, which requires moving the wafer on a track where it is exposed to a developing solvent, dried, and baked. Wet development not only limits productivity, but can also lead to line collapse due to surface tension effects during solvent evaporation between fine features.

[0194] Dry development techniques have been proposed to overcome these challenges by eliminating substrate delamination and interface failure. Dry development presents its own challenges, such as the etch selectivity between unexposed and EUV-exposed resist materials, which can result in higher dose-to-size requirements for effective resist exposure when compared to wet development. Suboptimal selectivity can also cause PR corners to round with longer exposure under etching gases, which can increase line CD variability in the subsequent transfer etch step. Further processing steps used during lithography are detailed below.

[0195] Deposition processes, including dry deposition As discussed herein, the present disclosure provides methods for forming underlayers and imaging layers on semiconductor substrates that can be patterned using EUV or other next-generation lithography techniques. In some embodiments, dry deposition can provide the underlayer and imaging layer using any useful precursor (e.g., hydrocarbon precursors, dopant precursors, metal halides, capping agents, or organometallic agents described herein). Methods include those in which a polymerized organometallic material is generated in vapor and deposited onto the underlayer. In other embodiments, spin-on formulations can be used. The deposition process can include applying the EUV-sensitive material as a resist film or an EUV-sensitive film.

[0196] Such EUV-sensitive films include materials that, upon exposure to EUV, undergo changes such as the loss of bulky pendant ligands bonded to metal atoms within a low-density M-OH-rich material, allowing crosslinking to a denser M-OM-bonded metal oxide material. In other embodiments, EUV exposure results in additional crosslinking between ligands bonded to metal atoms, thereby providing a denser M-OM-bonded organometallic material, where L is a ligand. In yet other embodiments, EUV exposure results in the loss of ligands to provide a M-OH material that can be removed by a positive-tone developer.

[0197] EUV patterning results in the formation of regions of the film with altered physical or chemical properties compared to unexposed regions. These properties can be exploited in subsequent processing, such as to dissolve either the unexposed or exposed regions, or to selectively deposit material in either the exposed or unexposed regions. In some embodiments, the unexposed film has a hydrophobic surface, and the exposed film has a hydrophilic surface under the conditions under which such subsequent processing is carried out (it being understood that the hydrophilicity of the exposed and unexposed regions is relative to one another). For example, material removal may be achieved by exploiting differences in the film's chemical composition, density, and cross-linking. Removal may be by wet or dry processing, as further described herein.

[0198] The thickness of the EUV-patternable film formed on the surface of a substrate can vary depending on the surface characteristics, the materials used, and the process conditions. In various embodiments, the film thickness can range from about 0.5 nm to about 100 nm. The film preferably has a thickness sufficient to absorb most of the EUV light under EUV patterning conditions. For example, the total absorption of the resist film can be 30% or less (e.g., 10% or less, or 5% or less) so that the resist material at the bottom of the resist film is fully exposed. In some embodiments, the film thickness is 10 nm to 20 nm. Without limiting the mechanism, function, or utility of the present technology, unlike wet spin-coating processes in the art, the disclosed process is believed to be applicable to a variety of substrates due to its reduced surface adhesion limitations. Furthermore, as discussed above, the deposited film can closely conform to surface features, providing advantages in forming a mask on a substrate (such as a substrate with underlying features) without "filling" or otherwise planarizing such features.

[0199] The film (e.g., underlayer and / or imaging layer) may be comprised of a metal oxide layer deposited by any useful method. Such a metal oxide layer may be deposited or applied by using any EUV-sensitive material described herein, such as a precursor (e.g., a metal-containing precursor, a metal halide, a capping agent, or an organometallic agent), in combination with a counter reactant. In an exemplary process, a polymerized organometallic material is formed in the vapor phase or in situ on the surface of a substrate to provide a metal oxide layer. The metal oxide layer may be used as a film, an adhesion layer, or a capping layer.

[0200] Optionally, the metal oxide layer may include a hydroxyl-terminated metal oxide layer, which may be deposited by utilizing a capping agent (e.g., any of those described herein) with an oxygen-containing reactant. Such a hydroxyl-terminated metal oxide layer may be utilized as an adhesion layer between two other layers, such as, for example, between a substrate and a film and / or between a photoresist layer and an underlayer.

[0201] Examples of deposition techniques (e.g., for films, underlayers, or imaging layers) include any of the techniques described herein, such as ALD (e.g., thermal ALD and plasma-enhanced ALD), spin-coat deposition, PVD such as PVD co-sputtering, CVD (e.g., PE-CVD or LP-CVD), sputter deposition, e-beam evaporation including e-beam co-evaporation, or combinations thereof (e.g., combining ALD and CVD components, discontinuous ALD-like processes in which precursors and counter reactants are separated in time or space, etc.).

[0202] Further description of precursors applicable to the present disclosure and methods for depositing them as EUV photoresist films can be found in International Application No. PCT / US19 / 31618, "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," filed May 9, 2019, and published as International Publication No. WO2019 / 217749. The thin films may include optional materials in addition to the precursors and counter reactants to alter the chemical or physical properties of the film, such as to modify the film's sensitivity to EUV or increase its etch resistance. Such optional materials may be introduced, such as by doping, during vapor formation prior to deposition on a substrate, after deposition of the film, or both. In some embodiments, a mild remote H plasma may be introduced, for example, to replace some Sn-L bonds with Sn-H, thereby enhancing the reactivity of the resist under EUV.

[0203] In general, the method may comprise mixing a vapor flow of a precursor (e.g., a metal-containing precursor such as an organometallic agent) with a vapor flow of an optional counter reactant to form a polymerized organometallic material, and depositing the organometallic material on a surface of a semiconductor substrate. In some embodiments, mixing the precursor and the optional counter reactant can form a polymerized organometallic material. As will be appreciated by those skilled in the art, the mixing and deposition aspects of the process may be performed in parallel in a substantially continuous process.

[0204] In an example of a sequential CVD process, two or more gas streams of precursors and optional counter reactant sources are introduced into a deposition chamber of a CVD apparatus via separate inlets, where the gases mix and react in the vapor phase to form a coagulated polymer material or film on a substrate (e.g., by forming metal-oxygen-metal bonds). The gas streams may be introduced using, for example, separate inlets or a dual plenum showerhead. The apparatus is configured to allow the precursor and optional counter reactant flows to mix within the chamber, allowing the precursor and optional counter reactant to react to form a polymerized organometallic material or film (e.g., a metal oxide coating or a coagulated polymer material, such as by forming metal-oxygen-metal bonds).

[0205] To deposit metal oxides, CVD processes are typically performed at reduced pressures, such as between 0.1 Torr and 10 Torr. In some embodiments, the process is performed at a pressure between 1 Torr and 2 Torr. The temperature of the substrate is preferably lower than the temperature of the reactant stream. For example, the substrate temperature can be between 0°C and 250°C, or between ambient temperature (e.g., 23°C) and 150°C.

[0206] To deposit cohesive polymeric materials, CVD processes are typically performed at reduced pressures, such as 10 mTorr to 10 Torr. In some embodiments, processes are performed at 0.5 to 2 Torr. The substrate temperature is preferably equal to or less than the temperature of the reactant stream. For example, the substrate temperature can be between 0°C and 250°C, or between ambient temperature (e.g., 23°C) and 150°C. In various processes, deposition of polymerized organometallic materials onto a substrate occurs at a rate inversely proportional to the surface temperature. Without limiting the mechanism, function, or utility of the present technology, it is believed that the products of such vapor-phase reactions have high molecular weights as metal atoms are crosslinked by counter reactants before condensing or otherwise depositing on the substrate. In various embodiments, the steric hindrance of bulky alkyl groups further inhibits the formation of a densely packed network, producing highly porous, low-density films.

[0207] A potential advantage of using dry deposition techniques is the ease of tailoring the film composition as it grows. In CVD processes, this may be achieved by varying the relative flow rates of the first and second precursors during deposition. Deposition can occur at temperatures between 30°C and 200°C and pressures between 0.01 Torr and 100 Torr (more commonly, about 0.1 Torr and 10 Torr).

[0208] Films (e.g., metal oxide coatings or aggregated polymer materials, such as by forming metal-oxygen-metal bonds) may also be deposited by ALD processes. For example, precursors and optional counter reactants are introduced at separate times representing ALD cycles. The precursors react on the surface to form up to a monolayer of material at a time during each cycle. This allows for excellent control of film thickness uniformity across the surface. ALD processes are typically performed at reduced pressures, such as 0.1 Torr to 10 Torr. In some embodiments, the process is performed at 1 Torr to 2 Torr. The substrate temperature may be between 0°C and 250°C, or between ambient temperature (e.g., 23°C) and 150°C. The process may be a thermal process or, preferably, a plasma-assisted deposition.

[0209] Any of the deposition methods herein can be modified to allow for the use of two or more different precursors. In one embodiment, the precursors can contain the same metal but different ligands. In another embodiment, the precursors can contain different metal groups. In one non-limiting example, alternating flows of various volatile precursors can provide mixed-metal-containing layers, such as utilizing a metal alkoxide precursor having a first metal (e.g., Sn) with a silyl-based precursor having a different second metal (e.g., Te).

[0210] The processes described herein can be used to achieve surface modification. Precursor vapors may be passed over the wafer in several iterations. The wafer may be heated to provide thermal energy for the reaction to proceed. During several iterations, heating may be between about 50°C and about 250°C. In some cases, pulses of precursors may be utilized, separated by pumping and / or purging steps. For example, a first precursor may be pulsed between pulses of a second precursor to induce ALD or ALD-like growth. In other cases, both precursors may be flowed simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of these compounds.

[0211] The processes herein can be used to deposit thin metal oxides or metals by ALD or CVD. Examples include tin oxide (SnOx), bismuth oxide (BiOx), and Te. After deposition, the films can be further processed using M as described elsewhere herein. a R b L c The surface may be capped with an alkyl-substituted precursor in the form of . A counter reactant may be used to better remove the ligands, and multiple cycles may be repeated to ensure complete saturation of the substrate surface. The surface is then ready for deposition of an EUV-sensitive film. One possible method is to produce a thin film of SnOx. A possible chemical reaction involves the growth of SnO2 by cycling tetrakis(dimethylamino)tin and a counter reactant (such as water or O2 plasma). After growth, a capping agent may be applied. For example, isopropyltris(dimethylamino)tin vapor may be flowed over the surface.

[0212] The deposition process can be used on any useful surface. As referred to herein, a "surface" is a surface onto which the film of the present technology is deposited or exposed to EUV during the process. Such a surface can be on a substrate (e.g., onto which a film is deposited), on a film (e.g., onto which a capping layer can be deposited), on a hard mask, or on an underlayer.

[0213] Any useful substrate may be used, including any material composition suitable for lithographic processing, particularly for the fabrication of integrated circuits and other semiconductor devices. In some embodiments, the substrate is a silicon wafer. The substrate may be a silicon wafer with features formed thereon ("underlying topographic features"), having an irregular surface topography.

[0214] Such underlying topographical features may include areas where material has been removed (e.g., by etching) or where material has been added (e.g., by deposition) during processing prior to performing the methods of the present technology. Such pre-processing may involve methods of the present technology or other processing methods in an iterative process in which two or more layers of features are formed on a substrate. Without limiting the mechanism, function, or utility of the present technology, in some embodiments, the methods of the present technology are believed to offer advantages over methods known in the art in which photolithographic films are deposited on the surface of a substrate using spin-casting techniques. Such advantages may stem from the conformity of the present technology's films to underlying features without "filling" or otherwise planarizing such features, and the ability to deposit films on a variety of material surfaces.

[0215] EUV exposure processing EUV exposure of the film can provide EUV-exposed regions with activated reactive centers containing metal atoms (M), which are generated by EUV-induced cleavage events. Such reactive centers can include dangling metal bonds, M-H groups, cleaved M-ligand groups, dimerized M-M bonds, or M-O-M bridges.

[0216] The EUV exposure may have a wavelength in the range of about 10 nm to about 20 nm (e.g., a wavelength of 10 nm to 15 nm (e.g., 13.5 nm) in a vacuum atmosphere. In particular, patterning can provide EUV-exposed and non-EUV-exposed regions to form a pattern.

[0217] The present techniques include patterning using not only EUV, but also DUV or electron beam. In such patterning, radiation is focused onto one or more regions of the imaging layer. Exposure is typically performed so that the imaging layer film includes one or more regions that are not exposed to radiation. The resulting imaging layer may include multiple exposed and unexposed regions to create a pattern consistent with the creation of transistors or other features of a semiconductor device that are formed by adding or removing material from the substrate during subsequent processing of the substrate. EUV, DUV, and electron beam radiation methods and apparatus useful herein include methods and apparatus well known in the art.

[0218] In some EUV lithography techniques, an organic hard mask (e.g., a PECVD amorphous hydrogenated carbon ashable hard mask) is patterned using conventional photoresist processing. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate, generating high-energy photoelectrons (e.g., about 100 eV) and then a cascade of lower-energy secondary electrons (e.g., about 10 eV) that diffuse laterally a few nanometers. These electrons enhance the progression of chemical reactions in the resist that enhance EUV dose sensitivity. However, a secondary electron pattern, which is random in nature, is superimposed on the optical image. This unwanted secondary electron exposure causes reduced resolution, observable line-edge roughness (LER), and linewidth variations in the patterned resist. These defects are then carried over to the patterned material during subsequent pattern-transfer etching.

[0219] Disclosed herein is a vacuum-integrated metal hard mask process and associated vacuum-integrated hardware that combines film formation (evaporation / condensation) with optical lithography, resulting in significantly improved performance (e.g., reduced line edge roughness) in Extreme Ultraviolet (EUVL).

[0220] In various embodiments described herein, a deposition (e.g., condensation) process (e.g., ALD or MOCVD performed in a PECVD tool such as a Lam Vector®) can be used to form a thin film of a metal-containing film, such as a photosensitive metal salt or metal-containing organic compound (organometallic compound), that has a strong absorption in EUV (e.g., wavelengths on the order of 10 nm to 20 nm) at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV). This film photodecomposes upon EUV exposure to form a metal mask, which is a pattern transfer layer, during subsequent etching (e.g., in a conductor etching tool such as a Lam2300® Kiyo®).

[0221] After deposition, the EUV-patternable thin film is patterned by exposure to a beam of EUV light, typically under a relatively high vacuum. The metal-containing film can then be deposited in a chamber integrated with a lithography platform (e.g., a wafer stepper such as the TWINSCAN NXE:3300B® manufactured by ASML, Veldhoven, The Netherlands) and transferred under vacuum to prevent reaction prior to exposure. Integration with a lithography tool is facilitated by the fact that EUVL also requires very low pressures, given the strong optical absorption of incident photons by ambient gases (e.g., H2O, O2). In other embodiments, photosensitive metal film deposition and EUV exposure may be performed in the same chamber.

[0222] Development processes including dry development The EUV-exposed or unexposed regions can be removed by any useful development process. In one embodiment, the EUV-exposed regions can have activated reactive centers, such as dangling metal bonds, M-H groups, or dimerized M-M bonds. In certain embodiments, M-M groups can be selectively removed using one or more dry development processes (e.g., halide chemistry). In other embodiments, M-M bonds can be selectively removed using wet development processes (e.g., soluble M(OH) nThe EUV-exposed regions can be selectively removed (e.g., using hot ethanol and water to provide groups). In yet other embodiments, the EUV-exposed regions are removed using wet development (e.g., using a positive tone developer). In some embodiments, the EUV-unexposed regions are removed using dry development.

[0223] Dry development processes can include the use of halides, such as HCl- or HBr-based processes. While this disclosure is not limited to any particular theory or mechanism of operation, it is understood that the approach utilizes the chemical reactivity of dry-deposited EUV photoresist films with cleaning agents (e.g., HCl, HBr, and BCl3) to form volatile products using steam or plasma. Dry-deposited EUV photoresist films can be removed at etch rates up to 1 nm / sec. Rapid removal of dry-deposited EUV photoresist films using these chemistries is applicable to chamber cleaning, backside cleaning, bevel cleaning, and PR development. Films can be removed using steam at various temperatures (e.g., HCl or HBr at temperatures above -10°C, or BCl3 at temperatures above 80°C), although plasma may be used to further accelerate or enhance the reactivity.

[0224] Plasma treatment may utilize equipment and techniques including transformer-coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP), including those well known to those skilled in the art. For example, treatment may be performed at a pressure of >0.5 mTorr (e.g., 1 mTorr to 100 mTorr, etc.) and a power level of <1000 W (e.g., <500 W). The temperature may be 30°C to 300°C (e.g., 30°C to 120°C) for a duration of 1 to 3000 seconds (e.g., 10 to 600 seconds) at a flow rate of 100 to 1000 standard cubic centimeters per minute (sccm) (e.g., about 500 sccm).

[0225] When the halide reactant flow is hydrogen gas and halide gas, remote plasma / UV radiation is used to generate radicals from H2 and Cl2 and / or Br2, and the hydrogen and halide radicals are flowed into the reaction chamber to contact the patterned EUV photoresist on the substrate layer of the wafer. Suitable plasma power, without bias, can range from 100 W to 500 W. These conditions are suitable for some process reactors (e.g., Kiyo etch tools manufactured by Lam Research, Inc., Fremont, California), but it should be understood that a wider range of process conditions may be utilized depending on the capabilities of the process reactor.

[0226] In a thermal development process, the substrate is exposed to a dry developer (e.g., a Lewis acid) in a vacuum chamber (e.g., an oven). A suitable chamber may include a vacuum line, a dry development hydrogen halide compound gas (e.g., HBr, HCl) line, and a heater for temperature control. In some embodiments, the interior of the chamber may be coated with a corrosion-resistant film (such as an organic polymer or inorganic coating). One such coating is polytetrafluoroethylene (PTFE, e.g., Teflon™). Such materials can be utilized in the thermal processes of the present disclosure without the risk of removal by plasma exposure.

[0227] The process conditions for dry development may be, depending on the photoresist film and its composition and properties, a reactant flow rate of 100 sccm to 500 sccm (e.g., 500 sccm HBr or HCl), a temperature of -10°C to 120°C (e.g., -10°C), and a pressure of 1 mTorr to 500 mTorr (e.g., 300 mTorr) for a period of about 10 seconds to 1 minute without plasma.

[0228] In various embodiments, the methods of the present disclosure combine all dry processes: film deposition, deposition-based formation, (EUV) lithography photopatterning, and dry development. In such a process, the substrate may go directly to a dry development / etch chamber after photopatterning in an EUV scanner. Such a process may avoid the material and production costs associated with wet development. Dry processing may also offer additional tunability, providing additional CD control and / or scum removal.

[0229] In various embodiments, the EUV photoresist containing a certain amount of metal, metal oxide, and organic components has the chemical formula R x Z y The dry development may be carried out by a thermal plasma (e.g., a plasma that can be photoactivated by lamp heating or UV lamp heating, etc.) or a combination of thermal and plasma methods while flowing a dry development gas containing a compound of the formula (where R=B, Al, Si, C, S, SO (x>0), and Z=Cl, H, Br, F, CH4 (y>0)). Dry development can result in a positive tone, in which case R x Z y The species selectively removes the exposed material, leaving the remaining unexposed portions as a mask. In some embodiments, the exposed portions of an organotin oxide-based photoresist film are removed by dry development in accordance with the present disclosure. Positive-tone dry development may be achieved by selective dry development (removal) in which the EUV-exposed areas are exposed to a flow containing hydrogen halide or hydrogen and a halide, such as HCl and / or HBr, without igniting a plasma, or to a flow of H and Cl and / or Br together with a remote plasma or UV radiation generated from the plasma to generate radicals.

[0230] Wet development methods may also be utilized. In certain embodiments, such wet development methods are used to remove EUV-exposed regions to provide a positive-tone photoresist or a negative-tone resist. Non-limiting examples of wet development methods may include the use of alkaline developers (e.g., aqueous alkaline developers), such as those containing ammonium (e.g., ammonium hydroxide (NH4OH)), ammonium-based ionic liquids (e.g., tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), or other quaternary alkylammonium hydroxides), organic amines such as mono-, di-, and tri-organoamines (e.g., dimethylamine, diethylamine, ethylenediamine, triethylenetetramine), or alkanolamines (e.g., monoethanolamine, diethanolamine, triethanolamine, or diethyleneglycolamine). In other embodiments, the alkaline developer may be a nitrogen-containing base (e.g., an amine having the chemical formula R N1 NH2, R N 1R N2 N.H., R. N1 R N2 R N3 N or R N1 R N2 R N3 R N4 N + X N1- a compound having the formula: N1 , R N2 , R N 3, and R N4 are each independently an organic substituent (e.g., optionally substituted alkyl or any of the substituents described herein) or two or more organic substituents that can be combined; N1- OH - , F - , Cl - , Br - , I -or other quaternary ammonium cation species known to those skilled in the art. These bases may also include heterocyclyl nitrogen compounds known to those skilled in the art, some of which are described herein.

[0231] Other development methods can include the use of acidic developers (e.g., aqueous acidic developers or acidic developers in organic solvents) containing halides (e.g., HCl or HBr), organic acids (e.g., formic acid, acetic acid, or citric acid), or organic fluorine compounds (e.g., trifluoroacetic acid), or the use of organic developers (ketones (e.g., 2-heptanone, cyclohexanone, or acetone), esters (e.g., γ-butyrolactone or ethyl 3-ethoxypropionate (EEP)), alcohols (e.g., isopropyl alcohol (IPA)), or ethers (glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA))), and combinations thereof.

[0232] In certain embodiments, the positive tone developer is an aqueous alkaline developer (e.g., including NHOH, TMAH, TEAH, TPAH, or TBAH). In other embodiments, the negative tone developer is an aqueous acidic developer, an acidic developer in an organic solvent, or an organic developer (e.g., HCl, HBr, formic acid, trifluoroacetic acid, 2-heptanone, IPA, PGME, PGMEA, or combinations thereof).

[0233] Post-application treatment The methods herein may include any useful post-application treatment, as described below.

[0234] In backside and bevel cleaning processes, the vapor and / or plasma can be limited to specific areas of the wafer to ensure that only the backside and bevel are removed without causing any film degradation on the frontside of the wafer. The dry-deposited EUV photoresist film being removed is typically composed of Sn, O, and C, but the same cleaning approach can be extended to films of other metal oxide resists and materials. Additionally, this approach can be used for film stripping and PR correction.

[0235] Suitable process conditions for dry bevel edge and backside cleaning may be 100 sccm to 500 sccm of reactant flow (e.g., 500 sccm of HCl, HBr, or H with Cl or Br, BCl, or H) for a period of about 10 seconds to 20 seconds, depending on the photoresist film and composition and properties, a temperature of −10° C. to 120° C. (e.g., 20° C.), a pressure of 20 mTorr to 500 mTorr (e.g., 300 mTorr), and a plasma power of 0 to 500 W at high frequency (e.g., 13.56 MHz). These conditions are suitable for some process reactors (e.g., Kiyo® etch tools manufactured by Lam Research, Fremont, California), but it should be understood that a wider range of process conditions may be utilized depending on the capabilities of the process reactor.

[0236] Photolithography processing typically includes one or more bake steps to promote the chemical reactions necessary to create chemical differences between exposed and unexposed areas of the photoresist. In high-volume manufacturing (HVM), such bake steps are typically performed on a track where wafers are baked on a hotplate at a preset temperature under ambient air or, in some cases, N2 flow. More careful control of the bake atmosphere, as well as the introduction of additional reactive gas components into the atmosphere during these bake steps, can help further reduce the required dose and / or improve pattern fidelity.

[0237] According to various aspects of the present disclosure, one or more post-treatments on metal and / or metal oxide-based photoresists after deposition (e.g., post-apply bake (PAB)), and / or after exposure (e.g., post-exposure bake (PEB)), and / or after development (e.g., post-develop bake (PDB)) can increase the difference in material properties between exposed and unexposed photoresists, thus reducing dose-to-size (DtS), improving PR profiles, and improving line edge roughness and line width roughness (LER / LWR) after subsequent dry development. Such treatments can include thermal treatments along with control of temperature, gas atmosphere, and humidity to improve dry development performance in subsequent processing. In some examples, remote plasma may be used.

[0238] For post-application processing (e.g., PAB), thermal treatments can be used in conjunction with temperature, gas atmosphere (e.g., air, HO, CO, CO, O, O, CH, CHOH, N, H, NH, NO, NO, Ar, He, or mixtures thereof) or vacuum, and humidity control to alter the composition of unexposed metal and / or metal oxide photoresists after deposition and before exposure. Such alterations can increase the EUV sensitivity of the material, so that lower dose-to-size and edge roughness can be achieved after exposure and dry development.

[0239] For post-exposure processing (e.g., PEB), thermal treatment can be used with control of temperature, gas atmosphere (e.g., air, HO, CO, CO, O, O, CH, CHOH, N, H, NH, NO, NO, Ar, He, or mixtures thereof) or vacuum, and humidity to alter the composition of both the unexposed and exposed photoresist. The alteration can increase the difference in composition / material properties between the unexposed and exposed photoresist and the difference in the etch rate of dry development etch gases between the unexposed and exposed photoresist. This can achieve a higher etch selectivity. The improved selectivity can result in a more square PR profile, along with improved surface roughness and / or less photoresist residue / scum. In certain embodiments, PEB can be performed in air, optionally with water vapor and CO.

[0240] For post-development treatments (e.g., post-develop bake, or PDB), thermal treatments can be used in conjunction with control of temperature, gas atmosphere (e.g., air, HO, CO, CO, O, O, CH, CHOH, N, H, NH, NO, NO, Ar, He, or mixtures thereof) or under vacuum (e.g., with UV), and humidity to alter the composition of the unexposed photoresist. In certain embodiments, the conditions further include the use of plasma (e.g., containing O, O, Ar, He, or mixtures thereof). The alteration can increase the hardness of the material, which can be useful when the film is used as a resist mask when etching an underlying substrate.

[0241] In these cases, in another embodiment, the thermal treatment may be replaced with a remote plasma treatment to increase the reactive species, thereby lowering the energy barrier for the reaction and increasing productivity. Remote plasma generates more reactive radicals, which may allow the reaction temperature / time of the treatment to be reduced, leading to increased productivity.

[0242] Therefore, one or more treatments may be applied to modify the photoresist itself to enhance the dry development selectivity. This thermal or radical modification increases the difference between unexposed and exposed materials, thereby enhancing the selectivity of the subsequent dry development step. The resulting difference in material properties between unexposed and exposed materials can be tailored by adjusting process conditions, including temperature, gas flow rate, humidity, pressure, and / or RF power. The large process latitude enabled by dry development, which is not limited by material solubility in the wet developer solvent, allows for the application of more aggressive conditions, further enhancing the achievable material differentiation. The resulting large material differentiation feeds back into a wider process window for dry development, thus enabling higher productivity, lower cost, and better defect performance.

[0243] A practical limitation of wet-developed resist films is the temperature-limited bake. Because wet development relies on material solubility, heating to, for example, 220°C or higher can significantly increase the degree of cross-linking in both exposed and unexposed regions of a metal-containing PR film, such that both regions become insoluble in the wet development solvent, resulting in the film no longer being reliably wet-developable. For dry-developed resist films, which rely on the difference in etch rate (i.e., selectivity) between exposed and unexposed regions of the PR to remove only the exposed or unexposed portions of the resist, the processing temperature in PAB, PEB, or PDB can be varied over a much wider window to adjust and optimize the processing process, e.g., from about 90°C to 250°C (e.g., 90°C to 190°C) for PAB and from about 170°C to 250°C or higher (e.g., 190°C to 240°C) for PEB and / or PDB. It has been found that increasing the processing temperature within the aforementioned ranges results in a decrease in etch rate and an increase in etch selectivity.

[0244] In certain embodiments, the PAB, PEB, and / or PDB processes may be performed at a gas atmosphere flow rate ranging from 100 sccm to 10,000 sccm, a humidity of a few percent up to 100% (e.g., 20% to 50%), a pressure between atmospheric pressure and vacuum, and a duration of about 1 to 15 minutes (e.g., about 2 minutes).

[0245] These findings can be used to adjust process conditions to tailor or optimize the process for specific materials and environments. For example, the selectivity achieved for a given EUV dose with a PEB thermal treatment at 220°C to 250°C in air with approximately 20% humidity for approximately 2 minutes can be comparable to the selectivity achieved for approximately 30% higher EUV doses without such a thermal treatment. Thus, depending on the selectivity requirements / constraints of a semiconductor processing operation, thermal treatments such as those described herein can be used to reduce the required EUV dose. Alternatively, when higher selectivity is required and a higher dose can be tolerated, much higher selectivity (up to 100x higher selectivity of exposed to unexposed regions) can be achieved than is possible in the context of wet development.

[0246] Still other steps may include in-situ measurements that can assess physical and structural features (e.g., critical dimensions, film thickness, etc.) during photolithography processing. Modules for achieving in-situ measurements include, for example, scatterometers, polarimetry, downstream mass spectrometry, and / or plasma-enhanced downstream optical emission spectroscopy modules.

[0247] Device The present disclosure also includes any apparatus configured to perform any of the methods described herein. In one embodiment, an apparatus for depositing a film includes a deposition module with a chamber for depositing one or more precursors to provide an underlayer and / or imaging layer, a patterning module with an EUV photolithography tool having a radiation source with a wavelength of less than 30 nm, and a development module with a chamber for developing the film including such layers.

[0248] The apparatus may further include a controller having instructions for such modules. In one embodiment, the controller includes one or more memory devices, one or more processors, and system control software coded with instructions for performing deposition of the film. Such including may include depositing one or more precursors to provide an underlayer and / or an imaging layer in a deposition module, forming a pattern in the film by directly patterning the layer with sub-30 nm resolution by EUV exposure in a patterning module, and developing the film in a development module. In certain embodiments, the development module provides removal of EUV-exposed or non-EUV-exposed regions, thereby providing a pattern in the film.

[0249] 8 is a schematic diagram illustrating one embodiment of a processing station 300 having a processing chamber body 302 for maintaining a low-pressure environment suitable for performing the deposition and dry development embodiments described herein. Multiple processing stations 300 may be included within a common low-pressure processing tool environment. For example, FIG. 9 illustrates one embodiment of a multi-station processing tool 400 (such as a VECTOR® processing tool manufactured by Lam Research, Inc. of Fremont, California). In some embodiments, one or more hardware parameters of the processing stations 300 (such as those described in more detail below) may be programmatically adjusted by one or more computer controllers 350.

[0250] The processing stations may be configured as modules within a cluster tool. Figure 11 illustrates a semiconductor processing cluster tool architecture with vacuum-integrated deposition and patterning modules suitable for implementing embodiments described herein. Such a cluster processing tool architecture may include modules for PR and underlayer deposition, resist exposure (EUV scanner), resist dry development, and etching, as detailed above with reference to Figures 10-11.

[0251] In some embodiments, some of the processing functions (e.g., deposition (e.g., PECVD), dry development, and etching) may be performed sequentially within the same module. Accordingly, embodiments of the present disclosure are directed to an apparatus for processing a substrate, the apparatus comprising: a processing chamber with a substrate support; a processing gas source connected to the processing chamber and associated flow control hardware; substrate handling hardware connected to the processing chamber; and a controller having a processor and a memory. In some implementations, the processor and the memory are communicatively coupled to each other, the processor is at least operatively coupled to the flow control hardware and the substrate handling hardware, and the memory stores computer-executable instructions for performing steps in the methods of forming a patterned structure described herein.

[0252] For example, the memory may store computer-executable instructions for providing a hard mask deposited on a substrate, for example, by chemical vapor deposition (e.g., PECVD). As mentioned above, a suitable hard mask can be, for example, an amorphous carbon ashable hard mask film that is undoped or doped with B or W.

[0253] The memory may further store instructions for depositing an underlayer on the substrate and / or hard mask, the underlayer configured to enhance adhesion between the substrate and / or hard mask and a subsequently formed EUV-sensitive inorganic photoresist and reduce EUV dose for effective EUV exposure of the photoresist. For example, as described above, the underlayer may be or comprise a deposited film of hydrogenated carbon doped with a non-carbon heteroatom (e.g., O, Si, N, W, B, I, Cl, or any of those herein), the film may have a thickness of about 25 nm or less and contain about 0-30% O. In some examples, the underlayer may be deposited on the substrate and / or hard mask by PECVD or ALD using a hydrocarbon precursor and / or a dopant precursor. In other embodiments, the underlayer may be deposited on the substrate and / or hard mask by PECVD or ALD using an oxocarbon precursor that co-reacts with H or a hydrocarbon. In a variation of this example, the oxocarbon precursor may further co-react with a Si-source dopant during deposition. In another example, the underlayer may be deposited on the substrate and / or hardmask by PECVD or ALD using a Si-containing precursor that co-reacts with an oxidant (e.g., any of the O-containing precursors described herein). In a variation of this example, the Si-containing precursor further co-reacts with a C-source dopant. In some embodiments, the underlayer may be deposited on the substrate and / or hardmask by PECVD, for example, as a final operation of deposition on the substrate or deposition of a hardmask on the substrate, by adjusting the flow of precursors into a PECVD processing chamber to reach the desired composition of the underlayer.

[0254] The memory may further store instructions for forming an EUV-sensitive inorganic photoresist that is formed on the photoresist underlayer. A suitable EUV-sensitive inorganic photoresist may be a metal oxide film, such as an EUV-sensitive tin oxide-based photoresist as described above.

[0255] 8 , the processing station 300 is in fluid communication with a reactant delivery system 301 a for supplying process gases to a distribution showerhead 306. The reactant delivery system 301 a optionally includes a mixing vessel 304 for mixing and / or conditioning process gases for delivery to the showerhead 306. One or more mixing vessel inlet valves 320 may control the introduction of process gases into the mixing vessel 304. If plasma exposure is utilized, the plasma may be delivered to the showerhead 306 or generated in the processing station 300. As discussed above, in at least some embodiments, non-plasma thermal exposure is preferred.

[0256] 8 includes an optional vaporization point 303 for vaporizing the liquid reactant supplied to the mixing vessel 304. In some embodiments, a liquid flow controller (LFC) may be provided upstream of the vaporization point 303 to control the mass flow rate of the liquid for vaporization and supply to the processing station 300. For example, the LFC may include a thermal mass flow meter (MFM) disposed downstream of the LFC. A plunger valve of the LFC may then be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM.

[0257] The showerhead 306 distributes process gases to the substrate 312. In the embodiment shown in Figure 8, the substrate 312 is positioned below the showerhead 306 and is shown on a pedestal 308. The showerhead 306 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to the substrate 312.

[0258] In some embodiments, the pedestal 308 may be raised or lowered to expose the substrate 312 to the space between the substrate 312 and the showerhead 306. It is understood that in some embodiments, the height of the pedestal may be programmatically adjusted by a suitable computer controller 350.

[0259] In some embodiments, the pedestal 308 may be temperature controlled using a heater 310. In some embodiments, the pedestal 308 may be heated to a temperature between 0° C. and 300° C. or higher (e.g., 50-120° C., such as about 65-80° C.) during non-plasma thermal exposure of the photopatterned resist to a hydrogen halide dry developer (e.g., HBr or HCl).

[0260] Additionally, in some embodiments, pressure control of the processing station 300 may be provided by a butterfly valve 318. As shown in the embodiment of Figure 8, the butterfly valve 318 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the processing station 300 may be adjusted by varying the flow rate of one or more gases introduced into the processing station 300.

[0261] In some embodiments, the position of the showerhead 306 may be adjusted relative to the pedestal 308 to vary the spacing between the substrate 312 and the showerhead 306. Furthermore, it is understood that the vertical position of the pedestal 308 and / or the showerhead 306 may be altered by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 308 may include a rotation axis for rotating the orientation of the substrate 312. It is understood that in some embodiments, one or more of these exemplary adjustments may be performed programmatically by one or more suitable computer controllers 350.

[0262] When a plasma may be utilized, for example, in a mild plasma-based dry development embodiment and / or an etching operation performed in the same chamber, the showerhead 306 and pedestal 308 are in electrical communication with an RF power source 314 and matching network 316 to power the plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 314 and matching network 316 may be operated at any suitable power to form a plasma having a desired composition of radical species. An example of a suitable power is a power of up to approximately 500 W. Similarly, the RF power source 314 may provide RF power at any suitable frequency. In some embodiments, the RF power source 314 may be configured to independently control high-frequency RF power and low-frequency RF power. Examples of low-frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 1000 kHz. Examples of high frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz (e.g., about 13.56 MHz). It is understood that any suitable parameters may be discretely or continuously adjusted to provide plasma energy for surface reactions. In one non-limiting example, the plasma power may be intermittently pulsed to reduce ion bombardment with the substrate surface compared to a continuously powered plasma. The RF power source may be operated at any suitable duty cycle. Examples of suitable duty cycles include, but are not limited to, a duty cycle between about 5% and 90%. Acceptable process pressures are between about 20 mTorr and 5 Torr.

[0263] In some examples, the RF power may be continuous or pulsed between one or more levels. If pulsed operation is used, the pulsing may be performed at a frequency ranging from 1 Hz to 1 MHz. In some examples, the chamber pressure is maintained at a predetermined pressure ranging from 5 mTorr to 450 mTorr. In other examples, deposition and processing are performed at a pressure ranging from 5 mTorr to 150 mTorr. In yet other examples, deposition and processing are performed at a pressure ranging from 5 mTorr to 35 mTorr.

[0264] In some deposition processes, plasma strikes last for durations on the order of several seconds or longer. In certain embodiments, shorter plasma strikes may be used. These may be on the order of 10 milliseconds to 1 second (typically about 20-80 milliseconds), with 50 milliseconds being a specific example. Such very short RF plasma strikes require very rapid plasma stabilization. To achieve this, the plasma generator may be configured so that the impedance match is preset to a specific voltage while the frequency is allowed to vary. Conventionally, RF plasmas are generated at an RF frequency of about 13.56 MHz. In various embodiments described herein, the frequency is allowed to vary to values ​​different from this standard value. By allowing the frequency to vary while fixing the impedance match at a predetermined voltage, the plasma can stabilize much more quickly, which can be important when utilizing the very short plasma strikes associated with some types of deposition cycles.

[0265] In some embodiments, instructions for the controller 350 may be provided via input / output control (IOC) sequencing instructions. In one example, instructions for setting the conditions of a process step may be included in a corresponding recipe step of a process recipe. In some examples, process recipe steps may be sequenced sequentially, such that all instructions for a process step are executed simultaneously with that process step. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe step. For example, a recipe step may include instructions for setting the flow rates of a photoresist underlayer oxocarbon precursor, H or hydrocarbon co-reactant, and optional dopant. In some embodiments, the controller 350 may include any of the features described below with respect to the system controller 450 of FIG. 9.

[0266] As described above, one or more processing stations may be included in a multi-station processing tool. FIG. 9 is a schematic diagram illustrating one embodiment of a multi-station processing tool 400 including an entry load lock 402 and an exit load lock 404, one or both of which may be equipped with a remote plasma source. A robot 406 at atmospheric pressure is configured to move wafers from a cassette loaded through a pod 408 into the entry load lock 402 through an atmospheric port 410. The wafer is placed on a pedestal 412 in the entry load lock 402 by the robot 406, the atmospheric port 410 is closed, and the load lock is pumped down. If the entry load lock 402 is equipped with a remote plasma source, the wafer may undergo a remote plasma treatment to treat the surface within the load lock before being introduced into the processing chamber 414. Additionally, the wafer may be heated within the entry load lock 402, for example, to remove moisture and adsorbed gases. The chamber transfer port 416 to the processing chamber 414 is then opened and another robot (not shown) loads the wafer into the reactor and places it on the pedestal of the first station shown in the reactor for processing. While the embodiment shown in Figure 9 includes a load lock, it will be appreciated that in some embodiments, the wafer may be loaded directly into the processing station.

[0267] The illustrated processing chamber 414 includes four processing stations, numbered 1 through 4, in the embodiment shown in FIG. 9 . Each station includes a heated pedestal (designated 418 for station 1) and a gas line inlet. It is understood that in some embodiments, each processing station may have a different purpose or multiple purposes. For example, in some embodiments, a processing station may be switchable between a dry development mode and an etch processing mode. Additionally or alternatively, in some embodiments, the processing chamber 414 may include one or more matched pairs of dry development and etch processing stations. While the illustrated processing chamber 414 includes four stations, it is understood that processing chambers according to the present disclosure may include any suitable number of stations. For example, in some embodiments, the processing chamber may include five or more stations, while in other embodiments, the processing chamber may include three or fewer stations.

[0268] FIG. 9 illustrates one embodiment of a wafer handling system 490 for moving wafers within the processing chamber 414. In some embodiments, the wafer handling system 490 may move wafers between various processing stations and / or between processing stations and load locks. It is understood that any suitable wafer handling system may be used. Non-limiting examples include a wafer carousel and a wafer handler robot. FIG. 9 also illustrates one embodiment of a system controller 450 used to control the processing conditions and hardware status of the processing tool 400. The system controller 450 may include one or more memory devices 456, one or more mass storage devices 454, and one or more processors 452. The processor 452 may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, etc.

[0269] In some embodiments, the system controller 450 controls all operations of the processing tool 400. The system controller 450 executes system control software 458 stored on the mass storage device 454, loaded into the memory device 456, and executed by the processor 452. Alternatively, control logic may be hard-coded into the controller 450. Application-specific integrated circuits, programmable logic devices (e.g., field-programmable gate arrays, or FPGAs), or the like may be used for these purposes. Hereinafter, where "software" or "code" is used, functionally equivalent hard-coded logic may be used instead. The system control software 458 may comprise instructions for controlling the timing, mixture of gases, gas flow rates, chamber and / or station pressure, chamber and / or station temperature, wafer temperature, target power levels, RF power levels, substrate pedestal, chuck, and / or susceptor position, and other parameters of a particular process being performed by the processing tool 400. The system control software 458 may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of the process tool components used to perform the processes of the various process tools. The system control software 458 may be coded in any suitable computer-readable programming language.

[0270] In some embodiments, the system control software 458 may comprise input / output control (IOC) sequence instructions for controlling the various parameters described above. Other computer software and / or programs stored on the mass storage device 454 and / or memory device 456 associated with the system controller 450 may also be used in some embodiments. Examples of programs or program sections for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0271] The substrate positioning program may comprise program code for processing tool components used to load a substrate onto the pedestal 418 and control the spacing between the substrate and other parts of the processing tool 400 .

[0272] The process gas control program may include code for controlling the composition and flow rate of the hydrogen halide gas (e.g., HBr or HCl gas, as described herein), and optionally for flowing the gas into one or more process stations prior to deposition to stabilize the pressure within the process station. The pressure control program may include code for controlling the pressure within the process station by, for example, adjusting a throttle valve in the exhaust system of the process station, gas flow rate to the process station, etc.

[0273] The heater control program may include code for controlling the current to a heating unit used to heat the substrate, or the heater control program may control the supply of a heat transfer gas (such as helium) to the substrate.

[0274] A plasma control program may comprise code for setting RF power levels applied to process electrodes in one or more process stations according to embodiments herein.

[0275] The pressure control program may comprise code for maintaining pressure within the reaction chamber according to embodiments herein.

[0276] In some embodiments, there may be a user interface associated with the system controller 450. The user interface may include a display screen (graphical software display of equipment and / or process conditions) and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0277] In some embodiments, the parameters adjusted by the system controller 450 may relate to process conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (such as RF bias power level, frequency, and exposure time), etc. These parameters may be provided to the user in the form of a recipe and may be entered using a user interface.

[0278] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 450 from various process tool sensors. Signals for controlling the process may be output at analog and digital output connections of the process tool 400. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0279] The system controller 450 may provide program instructions for carrying out the deposition processes described above. The program instructions may control various process parameters, such as direct current (DC) power levels, RF bias power levels, pressure, temperature, etc. The instructions may control the parameters for operating a photoresist underlayer deposition process according to various embodiments described herein.

[0280] The system controller 450 typically includes one or more memory devices and one or more processors configured to execute instructions that cause the device to perform methods according to the disclosed embodiments. A machine-readable medium containing instructions for controlling processing operations according to the disclosed embodiments may be coupled to the system controller 450.

[0281] In some embodiments, the system controller 450 is part of a system, which may be part of the examples described above. Such systems may include semiconductor processing equipment, such as one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (e.g., wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling the operation of the system before, during, and after processing of semiconductor wafers or substrates. The electronics may be referred to as a “controller” and may control various components or subcomponents of the system. Depending on the processing conditions and / or type of system, the system controller 450 may be programmed to control any of the processes disclosed herein, such as 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 and motion settings, and wafer movement in and out of tools and other transfer tools and / or load locks connected or coupled to a particular system.

[0282] Generally, system controller 450 may be defined as electronic equipment 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 the form of firmware 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 communicated to system controller 450 in the form of various individual settings (or program files) that define operational parameters for performing particular processes on or for semiconductor wafers or instructions for the system. The operational parameters, in some embodiments, may be part of a recipe defined by a process engineer to accomplish one or more process steps during processing of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0283] In some embodiments, the system controller 450 may be part of or connected to a computer that is integrated with, connected to, or otherwise networked with the system, or a combination thereof. For example, the system controller 450 may be in the “cloud” or may be all or part of a fab host computer system that can enable remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, or examine trends or performance indicators from multiple manufacturing operations, to change parameters of a current process, set up processing steps according to a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) may 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 allows entry or programming of parameters and / or settings, which are communicated to the system from the remote computer. In some examples, the system controller 450 receives instructions in the form of data, where the instructions specify parameters for each of the processing steps 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 as well as the type of tool that the system controller 450 is configured to interface with or control. Thus, as described above, the system controller 450 may be distributed, such as by having one or more separate controllers that are networked and operate toward a common purpose (such as the process and control described herein). One example of a distributed controller for such purposes is one or more integrated circuits on the chamber that communicate with one or more remotely located integrated circuits (e.g., at the platform level or located as part of a remote computer) that cooperate to control the process in the chamber.

[0284] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a dry development chamber or module, and any other semiconductor processing system that may be associated with or utilized in the fabrication and / or manufacturing of semiconductor wafers.

[0285] As described above, depending on the processing step or steps being performed by the tool, the system controller 450 may communicate 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 in material transport to carry containers of wafers to or from tool locations and / or load ports within a semiconductor fabrication factory.

[0286] In certain embodiments, an inductively coupled plasma (ICP) reactor is described herein, which may be suitable for etching operations suitable for practicing some embodiments. Although an ICP reactor is described herein, it should be understood that in some embodiments, a capacitively coupled plasma reactor may also be used.

[0287] 10 is a cross-sectional view of an inductively coupled plasma apparatus 500 suitable for performing certain embodiments or aspects of embodiments, such as (dry) deposition, dry development, and / or etching; one example of such an apparatus is the Kiyo® reactor manufactured by Lam Research, Inc. of Fremont, Calif. In other embodiments, other tools or tool types capable of performing the dry deposition, development, and / or etching processes described herein may be used for implementation.

[0288] The inductively coupled plasma apparatus 500 includes an overall processing chamber 524 structurally defined by a chamber wall 501 and a window 511. The chamber wall 501 may be fabricated from stainless steel or aluminum. The window 511 may be fabricated from quartz or other dielectric materials. An optional internal plasma grid 550 divides the overall processing chamber into an upper subchamber 502 and a lower subchamber 503. In most embodiments, the plasma grid 550 can be removed to utilize the chamber space created by the subchambers 502 and 503. A chuck 517 is disposed within the lower subchamber 503 near the bottom inner surface. The chuck 517 is configured to receive and hold a semiconductor wafer 519 on which etching and deposition processes are performed. The chuck 517 may be an electrostatic chuck for supporting the wafer 519 when the wafer is present. In some embodiments, an edge ring (not shown) surrounds the chuck 517 and has an upper surface that is substantially coplanar with the upper surface of the wafer 519 when the wafer is present on the chuck 517. The chuck 517 also includes an electrostatic electrode for chucking and dechucking the wafer 519. A filter and DC clamp power supply (not shown) may be provided for this purpose. Other control systems for lifting the wafer 519 from the chuck 517 may also be provided. The chuck 517 may be charged using an RF power supply 523. The RF power supply 523 is connected to a matching network 521 through connection 527. The matching network 521 is connected to the chuck 517 through connection 525. Thus, the RF power supply 523 is connected to the chuck 517. In various embodiments, the bias power of the electrostatic chuck may be set to about 50 V or a different bias power depending on the process being performed in accordance with the disclosed embodiments. For example, the bias power may be about 20 V to about 100 V, or about 30 V to about 150 V.

[0289] The elements for plasma generation include a coil 533 disposed above the window 511. In some embodiments, a coil is not utilized in the disclosed embodiments. The coil 533 is fabricated from a conductive material and includes at least one full turn. The example coil 533 shown in FIG. 10 includes three turns. A cross section of the coil 533 is symbolized, with the "X" coil extending from the front to the back of the page and the "●" coil extending from the back to the front of the page. The elements for plasma generation also include an RF power supply 541 configured to provide RF power to the coil 533. Generally, the RF power supply 541 is connected to a matching network 539 through connection 545. The matching network 539 is connected to the coil 533 through connection 543. Thus, the RF power supply 541 is connected to the coil 533. An optional Faraday shield 549a is disposed between the coil 533 and the window 511. The Faraday shield 549a may be maintained in a spaced apart relationship with respect to the coil 533. In some embodiments, the Faraday shield 549a is positioned directly above the window 511. In some embodiments, the Faraday shield 549b is between the window 511 and the chuck 517. In some embodiments, the Faraday shield 549b is maintained in a spaced apart relationship with respect to the coil 533. For example, the Faraday shield 549b may be directly below the window 511 with no gap. The coil 533, the Faraday shield 549a, and the window 511 are each configured to be substantially horizontal with respect to one another. The Faraday shield 549a may prevent metals or other species from depositing on the window 511 of the processing chamber 524.

[0290] Process gases may be flowed into the processing chamber through one or more main gas inlets 560 and / or one or more side gas inlets 570 located in the upper subchamber 502. Similarly, although not explicitly shown, similar gas inlets may be used to supply process gases to a capacitively coupled plasma processing chamber. A vacuum pump (e.g., a one- or two-stage mechanical dry pump and / or turbomolecular pump) 540 may be used to draw process gases from the processing chamber 524 and maintain pressure within the processing chamber 524. For example, the vacuum pump may be used to evacuate the lower subchamber 503 during an ALD purge operation. A valve-controlled conduit may be used to fluidly connect the vacuum pump to the processing chamber 524 and selectively control the application of a vacuum environment provided by the vacuum pump. This may be done using a closed-loop controlled flow restriction device, such as a throttle valve (not shown) or a pendulum valve (not shown), during an operating plasma process. Similarly, a vacuum pump and valve-controlled fluid connection to a capacitively coupled plasma processing chamber may be used.

[0291] During operation of the apparatus 500, one or more process gases may be supplied through the gas inlets 560 and / or 570. In certain embodiments, process gases may be supplied only through the main gas inlet 560 or only through the side gas inlet 570. In some cases, the illustrated gas inlets may be replaced with more complex gas inlets, such as one or more showerheads. The Faraday shield 549a and / or the optional grid 550 may include internal channels and holes that allow process gases to be supplied to the process chamber 524. One or both of the Faraday shield 549a and the optional grid 550 may function as showerheads for the supply of process gases. In some embodiments, a liquid vaporization / delivery system may be located upstream of the process chamber 524 so that liquid reactants or precursors are vaporized and the vaporized reactants or precursors are introduced into the process chamber 524 via the gas inlets 560 and / or 570.

[0292] Radio frequency power is supplied from RF power source 541 to coil 533, causing an RF current to flow through coil 533. The RF current flowing through coil 533 generates an electromagnetic field around coil 533. The electromagnetic field generates an induced current within upper subchamber 502. Physical and chemical interactions of the various ions and radicals generated with wafer 519 etch features in wafer 519 and selectively deposit layers on wafer 519.

[0293] When a plasma grid 550 is utilized such that both an upper subchamber 502 and a lower subchamber 503 are present, induced currents act on the gas present in the upper subchamber 502 to generate an electron-ion plasma within the upper subchamber 502. The optional internal plasma grid 550 limits the amount of hot electrons within the lower subchamber 503. In some embodiments, the apparatus 500 is designed and operated such that the plasma present in the lower subchamber 503 is an ion-ion plasma.

[0294] Both the upper electron-ion plasma and the lower ion-ion plasma contain positive and negative ions, but the ion-ion plasma has a higher ratio of negative ions to positive ions. Volatile etching and / or deposition byproducts may be removed from the lower subchamber 503 through port 522. The chuck 517 disclosed herein may be operated at elevated temperatures ranging from about 10° C. to about 250° C. The temperature depends on the processing operation and the particular recipe.

[0295] The tool 500 may be connected to equipment (not shown) when installed in a clean room or manufacturing facility. The equipment includes plumbing for providing process gases, vacuum, temperature control, and environmental particle control. These equipment will be connected to the tool 500 when installed in the target manufacturing facility. Additionally, the tool 500 may be connected to a transfer chamber that allows semiconductor wafers to be transferred in and out of the tool 500 using robotic techniques, using typical automation.

[0296] In some embodiments, a system controller 530 (which may include one or more physical or logical controllers) controls some or all of the operation of the process chamber 524. The system controller 530 may include one or more memory devices and one or more processors. In some embodiments, the apparatus 500 includes a switching system for controlling the flow rates and durations when the disclosed embodiments are performed. In some embodiments, the apparatus 500 may have a switching time of up to about 500 ms or up to about 750 ms. The switching time may depend on the flow chemistry, the selected recipe, the reactor architecture, and other factors.

[0297] In some embodiments, the system controller 530 is part of a system, which may be part of the examples described above. Such a system may include semiconductor processing equipment, such as one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (e.g., wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling the operation of the system before, during, and after processing of semiconductor wafers or substrates. The electronics may be integrated into the system controller 530, which may control various components or subcomponents of the system. The system controller may be programmed to control any of the processes disclosed herein, such as 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 and motion settings, and wafer movement in and out of tools and other transfer tools and / or load locks connected or coupled to a particular system, depending on the process parameters and / or type of system.

[0298] Generally, the system controller 530 may be defined as electronic equipment having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuits may include chips in the form of firmware 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). The program instructions may be communicated to the controller in the form of various individual settings (or program files) that define operational parameters for performing specific processes on or for semiconductor wafers or instructions for the system. The operational parameters, in some embodiments, may be part of a recipe defined by a process engineer to accomplish one or more process steps during the processing or removal of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of the wafer.

[0299] In some embodiments, the system controller 530 may be part of or connected to a computer that is integrated with, connected to, or otherwise networked with the system, or a combination thereof. For example, the controller may be in the “cloud” or may be all or part of a fab host computer system that can enable remote access for wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, or examine trends or performance indicators from multiple manufacturing operations, to change parameters of a current process, set up processing steps according to a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) may 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 allows entry or programming of parameters and / or settings, which are communicated to the system from the remote computer. In some examples, the system controller 530 receives instructions in the form of data, where the instructions specify parameters for each of the processing steps 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 as well as the type of tool the controller is configured to interface with or control. Thus, as described above, the system controller 530 may be distributed, such as by having one or more separate controllers that are networked and operate toward a common purpose (such as the process and control described herein). One example of a distributed controller for such purposes is one or more integrated circuits on the chamber that communicate with one or more remotely located integrated circuits (e.g., at the platform level or located as part of a remote computer) that cooperate to control the process in the chamber.

[0300] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (PECVD) chamber or module, an ALD chamber or module, an ALE chamber or module, an ion implantation chamber or module, a track chamber or module, an EUV lithography chamber (scanner) or module, a dry develop chamber or module, and any other semiconductor processing system that may be associated with or utilized in the fabrication and / or manufacturing of semiconductor wafers.

[0301] As described above, depending on the processing step or steps being performed by the tool, the controller may communicate 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 in material transport to carry containers of wafers to or from tool locations and / or load ports within a semiconductor fabrication factory.

[0302] EUVL patterning may be performed using any suitable tool (often referred to as a scanner), such as, for example, a TWINSCAN NXE:3300B® platform manufactured by ASML, Veldhoven, The Netherlands. The EUVL patterning tool may be a stand-alone apparatus into which substrates are loaded and unloaded for deposition and etching as described herein. Alternatively, as described below, the EUVL patterning tool may be a module on a larger, multi-component tool. FIG. 11 illustrates a semiconductor processing cluster tool architecture 600 with a vacuum-integrated deposition module, EUV patterning module, and dry develop / etch module coupled to a vacuum transfer module, suitable for performing the processes described herein. While processing may be performed without utilizing such a vacuum-integrated apparatus, such an apparatus may be advantageous in some embodiments.

[0303] 11 illustrates a semiconductor processing cluster tool architecture with vacuum-integrated deposition and patterning modules coupled with a vacuum transfer module suitable for performing the processes described herein. The arrangement of multiple storage facilities and transfer modules that "transfer" wafers between processing modules is sometimes referred to as a "cluster tool architecture" system. The deposition and patterning modules are vacuum-integrated according to the requirements of a particular process. Other modules, such as for etching, may also be included in the cluster.

[0304] A vacuum transfer module (VTM) 638 interfaces with four processing modules 620a-620d, which may be individually optimized to perform various processing operations. For example, processing modules 620a-620d may be implemented to perform deposition, evaporation, ELD, dry development, etching, stripping, and / or other semiconductor processes. For example, module 620a may be an ALD reactor operable to perform plasma-free thermal atomic layer deposition as described herein, such as a Vector tool manufactured by Lam Research, Inc. of Fremont, California. And module 620b may be a PECVD tool, such as a Lam Vector®. It should be understood that the drawings are not necessarily drawn to scale.

[0305] Airlocks 642 and 646 (also known as load locks or transfer modules) connect VTM 638 and patterning module 640. For example, as mentioned above, a suitable patterning module can be a TWINSCAN NXE:3300B® platform manufactured by ASML of Veldhoven, The Netherlands. This tool architecture allows workpieces (such as semiconductor substrates or wafers) to be transferred under vacuum to prevent reaction prior to exposure. Integration of the deposition module with the lithography tool is facilitated by the fact that EUVL also requires very low pressures, given the strong optical absorption of incident photons by ambient gases (e.g., HO, O).

[0306] As noted above, this integrated architecture is just one possible embodiment of a tool for carrying out the described processes. The processes may also be carried out by a more conventional stand-alone EUVL scanner and a deposition reactor (such as a Lam Vector tool) that is standalone or integrated as a module into a cluster architecture with other tools (e.g., a Lam Kiyo or Gamma tool) for etching, stripping, etc., as described with reference to FIG. 11, except that there is no integrated patterning module.

[0307] Airlock 642 may be an "outgoing" load lock, referring to the removal of substrates from VTM 638, which feeds deposition module 620a, to patterning module 640, and airlock 646 may be an "incoming" load lock, referring to the return of substrates from patterning module 640 to VTM 638. Incoming load lock 646 may also provide an interface outside the tool for accessing and unloading substrates. Each processing module has a facet that connects the module to VTM 638. For example, deposition processing module 620a has facet 636. Within each facet, sensors (e.g., sensors 1-18 in the figure) are used to detect the passage of wafer 626 as it is moved between its respective stations. Patterning module 640 and airlocks 642 and 646 may similarly include additional facets and sensors not shown.

[0308] A main VTM robot 622 transfers wafers 626 between modules, including airlocks 642 and 646. In one embodiment, the robot 622 has one arm, and in another embodiment, the robot 622 has two arms, each arm having an end effector 624 that grasps a wafer (such as wafer 626) for transfer. A front-end robot 644 is used to transfer wafers 626 from the output airlock 642 to the patterning module 640 and from the patterning module 640 to the input airlock 646. The front-end robot 644 may also transfer wafers 626 between the input load lock and the exterior of the tool for substrate access and removal. The input airlock module 646 can accommodate environments between atmosphere and vacuum, allowing wafers 626 to move between the two pressure environments without being damaged.

[0309] It should be noted that EUVL tools typically operate at a higher vacuum than deposition tools. In this case, it is preferable to increase the vacuum environment of the substrate during transfer from the deposition tool to the EUVL tool to allow the substrate to degas before entering the patterning tool. The unload airlock 642 provides this function by holding the transferred wafer at a lower pressure (below the pressure in the patterning module 640) for a period of time and evacuating all off-gassing so that the optics of the patterning tool 640 are not contaminated by off-gassing from the substrate. A suitable pressure for the unload off-gas airlock is 1E-8 Torr or less.

[0310] In some embodiments, a system controller 650 (which may include one or more physical or logical controllers) controls some or all of the operation of the cluster tool and / or its separate modules. Note that the controller may be located locally to the cluster structure or may be located outside of the cluster structure, i.e., at a remote location within the manufacturing floor, and connected to the cluster structure via a network. The system controller 650 may include one or more memory devices and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, stepper motor controller boards, and other similar components. Instructions for implementing appropriate control operations are executed by the processor. These instructions may be stored in a memory device associated with the controller or provided over a network. In certain embodiments, the system controller executes system control software.

[0311] The system control software may comprise instructions for controlling the timing and / or extent of application of any aspect of tool or module operation. The system control software may be configured in any suitable manner. For example, various processing tool component subroutines or control objects may be written to control the operation of the processing tool components necessary to perform the various processing tool processes. The system control software may be coded in any suitable computer-readable programming language. In some embodiments, the system control software comprises input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each step of a semiconductor manufacturing process may comprise one or more instructions for execution by the system controller. Instructions for setting process conditions for condensation, deposition, evaporation, patterning, and / or etching steps may be included in the corresponding recipe steps, for example.

[0312] In various embodiments, an apparatus for forming a negative pattern mask is provided. The apparatus may include process chambers for patterning, deposition, and etching, and a controller including instructions for forming the negative pattern mask. The instructions may include code for, in the process chamber, patterning features in a chemically amplified (CAR) resist on a semiconductor substrate by EUV exposure to expose a surface of the substrate, dry developing the photo-patterned resist, and etching an underlying layer or underlying layer stack using the patterned resist as a mask.

[0313] It should be noted that the computer controlling the wafer movement may be located locally to the cluster architecture, or may be located outside or remotely from the cluster architecture within the manufacturing floor and connected to the cluster architecture via a network. A controller such as that described above with respect to any of Figures 8, 9, or 10 may be implemented with the tool of Figure 11.

[0314] 12 illustrates an example of a deposition chamber (e.g., for deposition of an imaging layer and / or an underlayer, etc.). As can be seen, the apparatus 700 includes a processing chamber 702 having a lid 708 and a wafer transfer passage 704 sized to allow a substrate 722 to pass therethrough and be placed on a wafer support 724. The wafer transfer passage 704 may have a gate valve 706 or similar door mechanism operable to open and close the wafer transfer passage. For example, the processing chamber 702 may be provided with a substrate 722 via a wafer handling robot located in an adjacent transfer chamber.

[0315] The wafer support 724 may include an ESC 726 to provide a wafer support surface for the substrate 722. The ESC 726 may include a base plate 734 that is bonded to the upper surface of a top plate 728. In the illustrated example, the top plate 728 has two separate electrical systems embedded therein. One such system is an electrostatic clamping electrode system having one or more clamping electrodes 732 to generate an electric charge within the substrate 722 that causes the substrate 722 to be attracted to the wafer support surface of the top plate 728.

[0316] The other system is a thermal control system for controlling the temperature of the substrate 722 under processing conditions. In FIG. 12 , the thermal control system features four annular resistive heater traces 730 a, 730 b, 730 c, and 730 d disposed beneath the clamping electrode 732. Each resistive heater trace 730 a / b / c / d may be individually controlled to provide a different radial heating profile at the top plate 728, for example, to maintain the substrate 722 with a temperature uniformity of ±0.5° C. in some examples. Other embodiments may use a single-zone heating system or a multi-zone heating system having more or fewer than four zones. For example, in some embodiments of the temperature control mechanisms described above, a heat pump or Peltier junction may be used in place of the resistive heating traces.

[0317] ESC 726 may further include a base plate 734 that provides structural support to the underside of top plate 728 and may also function as a heat dissipation system. For example, base plate 734 may include one or more heat exchange passages 736 through which a heat exchange medium (e.g., water or an inert fluorinated liquid) may be circulated during use.

[0318] The ESC 726 may be supported by a wafer support housing 742 that is connected to and supported by wafer posts 744. The wafer posts 744 may have routing passages 748 or other pass-throughs on the underside of the base plate 734 and / or top plate 728 for routing wiring (e.g., for supplying electrical power), fluid flow conduits (e.g., for carrying heat exchange media), and other equipment.

[0319] 12 further includes a wafer support z-actuator 746 that can provide movable support for the wafer support 744. The wafer support z-actuator 746 can be actuated to vertically raise and lower the wafer support 724, and thereby the wafer support 724, within the reaction volume 720 of the processing chamber 702, for example, by up to several inches. In doing so, the gap distance X between the substrate 722 and the underside of the showerhead 71 can be adjusted for various processing conditions.

[0320] The wafer support 724 may further include one or more edge rings that may be utilized to control and / or fine-tune various processing conditions. In Figure 12, an upper edge ring 738 is provided that sits on top of lower edge rings 740a and 740b, which are supported by a wafer support housing 742 and a third lower edge ring 740c.

[0321] The apparatus 700 may further include a system for removing process gases from the process chamber 702 during and after processing is completed. For example, the process chamber 702 may include an annular plenum 756 surrounding the wafer support 744. The annular plenum 756 may then be fluidly connected to a vacuum foreline 752, which may be connected to a vacuum pump. An adjustable valve 754 may be provided between the vacuum foreline 752 and the process chamber 702 and may be actuated to control flow into the vacuum foreline 752. In some embodiments, a baffle 750 (e.g., an annular plate or other structure operable to direct a flow into the annular plenum 756 that is evenly distributed around the wafer support 744) may be provided to reduce the possibility of flow non-uniformities in reactants flowed across the substrate 722.

[0322] The showerhead 710 is shown as a dual-plenum showerhead 710, including a first plenum 712 supplied with process gas via a first inlet 716 and a second plenum 714 supplied with process gas via a second inlet 718. Two or more plenums may be used to maintain separation between precursors and counter reactants prior to release. In some examples, a single plenum is used to deliver precursors into the reaction space 720 of the processing chamber 702. Each plenum may have a corresponding set of gas distribution ports fluidly connecting the respective plenum to the reaction space 720 through a faceplate of the showerhead 710 (the faceplate is the portion of the showerhead 710 sandwiched between the bottom plenum and the reaction space 720).

[0323] The first inlet 716 and the second inlet 718 of the showerhead 710 may be supplied with process gases via a gas delivery system, which may be configured to deliver one or more precursors and / or counter reactants as discussed herein. A first valve manifold 768a may be configured to deliver one or more precursors to the first inlet 716, while a second valve manifold 768b may be configured to deliver other precursors or other reactants to the second inlet 718. In this example, the first valve manifold 768a includes, for example, multiple valves A1-A5. Valve A2 may be, for example, a three-way valve having one port fluidly connected to a first vaporizer 772a, another port fluidly connected to a bypass line 770a, and a third port fluidly connected to a port of another three-way valve A3. Similarly, valve A4 may be a three-way valve having, for example, one port fluidly connected to second vaporizer 772b, another port fluidly connected to bypass line 770a, and a third port fluidly connected to a port of another three-way valve A5. One of the other ports of valve A5 may be fluidly connected to first inlet 716, while the remaining port of valve A5 may be fluidly connected to one of the remaining ports of valve A3. The remaining port of valve A3 may then be fluidly connected to valve A1, which may be fluidly interposed between valve A3 and a purge gas source 774 (e.g., nitrogen, argon, or other gas with suitable inertness (with respect to precursor and / or reactant)). In some embodiments, only the first valve manifold is used.

[0324] In this disclosure, the term "fluidically connected" is used in reference to spaces, plenums, holes, etc. that can be connected to each other to form a fluid connection, similar to the use of the term "electrically connected" in reference to components that are connected to each other to form an electrical connection. The term "fluidically inserted" is used in reference to a component, space, plenum, or hole that is fluidly connected to at least two other components, spaces, plenums, or holes, to refer to a fluid flowing from one of those other components, spaces, plenums, or holes to another one of those other components, spaces, plenums, or holes first passing through the "fluidically inserted" component before reaching the other one of those other components, spaces, plenums, or holes. For example, if a pump is fluidly inserted between a reservoir and an outlet, fluid flowing from the reservoir to the outlet will first pass through the pump before reaching the outlet.

[0325] First valve manifold 768a may be controllable to allow vapor from one or both of vaporizers 772a and 772b to flow to processing chamber 702 or through first bypass line 770a to vacuum foreline 752, such as by controlling the operation of valves A1-A5. First valve manifold 768a may also be controllable to allow purge gas to flow from purge gas source 774 to first inlet 716.

[0326] It is understood that second valve manifold 768b may be similarly controlled, for example, by controlling valves B1-B5, to supply vapor from vaporizers 772c and 772d to second inlet 718 or second bypass line 770b. It is further understood that different manifold configurations may be utilized, such as a single integrated manifold with valves to control the flow of precursors, counter reactants, or other reactants to first inlet 716 and second inlet 718.

[0327] As previously mentioned, some devices 700 may feature fewer vapor sources (e.g., only two vaporizers 772), in which case valve manifold 768 may be modified to have fewer valves (e.g., only valves A1-A3).

[0328] As described above, an apparatus such as apparatus 700 may be used to provide dry deposition of a film and may be configured to maintain a particular temperature profile within a process chamber 702. In particular, such an apparatus 700 may be configured to maintain a substrate 722 at a lower temperature (e.g., at least 25° C. to 50° C. lower) than most of the equipment of apparatus 702 that is in direct contact with precursors and / or counter reactants.

[0329] Various heating systems may be included in the apparatus 700 to provide temperature control. For example, the processing chamber 702 may have a receptacle for receiving a cartridge heater 758, e.g., vertical holes for receiving the cartridge heater 758 may be drilled into the four corners of the housing of the chamber 702. In some embodiments, the showerhead 710 may be covered with a heater blanket 760, which may be used to apply heat to the exposed top surface of the showerhead 710 to maintain a high showerhead temperature. It may also be beneficial to heat the various gas lines used to direct vaporized reactants from the vaporizer 722 to the showerhead 710. For example, resistive heater tape may be wrapped around such gas lines and used to heat the gas lines to a high temperature. Any of the gas lines and the valve 706 in FIG. 12 may be actively or indirectly heated.

[0330] The various operating systems of the apparatus 700 may be controlled by a controller 784, which may include one or more processors 786 and one or more memory devices 788, which are operatively coupled to each other and communicatively coupled to the various systems and subsystems of the apparatus 700 to provide control functions for those systems. For example, the controller 784 may be configured to control valves A1-A5 and B1-B5, various heaters 758, 760, the vaporizer 772, the regulating valve 754, the gate valve 706, the wafer support z-actuator, etc.

[0331] Another feature that the apparatus 700 may include is shown in FIG. 13, which is an enlarged cross-sectional plan view of the substrate 722, top plate 728, and a portion of the upper edge ring 738 of FIG. 12. As can be seen, in some embodiments, the substrate 722 may be elevated away from most of the top plate 728 by a plurality of small mesas 776, which may be thin bosses that protrude a short distance from the nominal top surface of the top plate 728 to provide a back gap 778 between the underside of the substrate 722 and the majority of the top plate 728. A peripheral wall feature 777 may be provided around the periphery of the top plate 728. The peripheral wall feature 777 may extend around the entire periphery of the top plate 728 and be nominally flush with the mesas 776. During processing operations, a generally inert gas (such as helium) may be flowed into the back gap 778 via one or more gas ports 782. This gas may then flow radially outward until it encounters a peripheral wall feature 777, which may then restrict such radially outward flow, causing a region of higher pressure of gas to be trapped between the substrate 722 and the top plate 728. Any inert gas that leaks beyond the peripheral wall 777 may eventually escape through a radial gap 780 between the outer edge of the substrate 722 and a portion of the upper edge ring 738. Such gas may help protect the underside of the substrate from being undesirably affected by processing operations being performed by acting to prevent gases emitted by the showerhead 710 from reaching the underside of the substrate 722. At the same time, gas emitted in the region of the back gap 778 may also act to increase thermal coupling between the substrate 722 and the top plate 728, allowing the top plate 728 to more effectively heat or cool the substrate 722. Due to the higher pressure provided by the peripheral wall, the gas in the area of ​​the back gap 778 may also be denser than the gas in the rest of the chamber, thereby providing more effective thermal coupling between the substrate 722 and the top plate 728.

[0332] Controller 784 may be configured, for example, by executing computer-executable instructions, to cause device 700 to perform various operations consistent with the above disclosure.

[0333] Once the imaging layer and / or underlayer are deposited on the substrate 722, the substrate 722 may be transferred to one or more subsequent processing chambers or tools for further operations (e.g., any of the operations described herein), as described above. Additional deposition apparatuses are described in International Patent Application No. PCT / US2020 / 038968, filed June 22, 2020, entitled "APPARATUS FOR PHOTORESIST DRY DEPOSITION," which is incorporated herein by reference in its entirety.

[0334] definition As used interchangeably herein, "acyloxy" or "alkanoyloxy" refers to an acyl group or an alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group. In certain embodiments, the alkanoyloxy is -OC(O)-Ak, where Ak is an alkyl group, as defined herein. In some embodiments, the unsubstituted alkanoyloxy is C 2-7 It is an alkanoyl group. Examples of alkanoyl groups include acetoxy.

[0335] "Aliphatic" refers to a group of at least 1 carbon atom to 50 carbon atoms (C 1-50 ) (e.g., 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 "Aliphatic" refers to hydrocarbon groups having an alkyl group, such as a cyclic group, including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), and cyclic forms thereof, including straight-chain and branched-chain arrangements and all stereoisomers and positional isomers. Such aliphatic groups can be unsubstituted or substituted with one or more groups, such as those described herein for alkyl groups.

[0336] "Alkenyl" refers to an optionally substituted C alkyl group having one or more double bonds. 2-2 4 alkyl groups. An alkenyl group is a cyclic (e.g., C 3-24 The alkenyl group may be substituted or unsubstituted. For example, the alkenyl group may be substituted with one or more of the substituents described herein for alkyl.

[0337] "Alkenylene" refers to an optionally substituted C alkyl group having one or more double bonds. 2-24 It refers to the polyvalent (e.g., divalent) form of an alkenyl group, which is an alkyl group. An alkenylene group is a cyclic (e.g., C 3-24 Alkenylene groups can be substituted or unsubstituted. For example, alkenylene groups can be substituted with one or more substituents described herein for alkyl. Non-limiting examples of alkenylene groups include -CH=CH- or -CH=CHCH 2- Includes:

[0338] "Alkoxy" means -OR, where R is an alkyl group optionally substituted as described herein. Examples of alkoxy include methoxy, ethoxy, butoxy, trihaloalkoxy (such as trifluoromethoxy), and the like. Alkoxy groups can be substituted or unsubstituted. For example, an alkoxy group can be substituted with one or more of the substituents described herein for alkyl. Examples of unsubstituted alkoxy groups are C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 Contains an alkoxy group.

[0339] The terms "alkyl" and the prefix "alk" refer to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), cyclopropyl, n-butyl (n-Bu), isobutyl (i-Bu), s-butyl (s-Bu), t-butyl (t-Bu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. An alkyl group can be cyclic (e.g., C 3-24 The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may include a haloalkyl, in which the alkyl group is substituted with one or more halo groups, as described herein. In another example, the alkyl group may be substituted with 1, 2, 3, or 4 (in the case of an alkyl group of 2 or more carbons) substituents independently selected from the following group: (1) C 1-6 Alkoxy (e.g., -O-Ak, where Ak is an optionally substituted C 1-6 alkyl), (2) amino (e.g., NR N1 R N2 , where R N1 and R N2 are independently H or optionally substituted alkyl, or R N1 and R N2 each together with the nitrogen atom to which it is attached forms a heterocyclyl group), (3) aryl, (4) arylalkoxy (e.g., -O-Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl), (5) aryloyl (e.g., -C(O)-Ar, where Ar is an optionally substituted aryl), (6) cyano (e.g., -CN), (7) carboxaldehyde (e.g., -C(O)H), (8) carboxyl (e.g., -COH), (9) C 3-8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3-8hydrocarbon group), (10) halo (e.g., F, Cl, Br, or I), (11) heterocyclyl (e.g., a five-, six-, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms (such as nitrogen, oxygen, phosphorus, sulfur, or halo), unless otherwise specified), (12) heterocyclyloxy (e.g., -O-Het, where Het is heterocyclyl as described herein), (13) heterocyclyloyl (e.g., -C(O)-Het, where Het is heterocyclyl as described herein), (14) hydroxyl (e.g., -OH), (15) N-protected amino, (16) nitro (e.g., NO), (17) oxo (e.g., =O), (18) -COR A , where R A is (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c)(C 4-18 Aryl)C 1-6 alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl), (19) -C(O)NR B R C , where R B and R C are independently (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C 4-18 Aryl)C 1-6 alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl), and (20) -NR G R H , where R G and R H are independently (a) hydrogen, (b) an N-protecting group, or (c) C 1-6 Alkyl, (d) C 2-6 alkenyl (e.g., optionally substituted alkyl having one or more double bonds); (e) C 2-6alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C 4-18 Aryl, (g) (C 4-18 Aryl)C 1-6 alkyl (e.g., Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (h) C 3-8 cycloalkyl, and (i)(C 3-8 Cycloalkyl)C 1-6 and alkyl (e.g., -Lk-Cy, where Lk is a divalent form of an optionally substituted alkyl group and Cy is an optionally substituted cycloalkyl as described herein), and in one embodiment, no two groups are attached to the nitrogen atom through a carbonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is selected from the group consisting of C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 It is an alkyl group.

[0340] "Alkylene" refers to the polyvalent (e.g., divalent) form of an alkyl group as described herein. Examples of alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, an alkylene group is a C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24It is an alkylene group. The alkylene group can be branched or unbranched. Also, the alkylene group can be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more of the substituents described herein for alkyl.

[0341] "Alkynyl" refers to an optionally substituted C alkyl group having one or more triple bonds. 2-24 It refers to an alkyl group. Alkynyl groups can be cyclic or acyclic, and examples include ethynyl, 1-propynyl, and the like. Alkynyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more of the substituents described herein for alkyl.

[0342] "Alkynylene" refers to an optionally substituted C alkyl group having one or more triple bonds. 2-24 It refers to a polyvalent (e.g., divalent) form of an alkynyl group, which is an alkyl group. An alkynylene group can be cyclic or acyclic. An alkynylene group can be substituted or unsubstituted. For example, an alkynylene group can be substituted with one or more substituents described herein for alkyl. Non-limiting examples of alkenylene groups include -C≡C- or -C≡CCH2-.

[0343] "Amino" is -NR N1 R N2 where R N1 and R N2 are independently H, optionally substituted alkyl, or optionally substituted aryl, or R N1 and R N2 together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0344] "Aromatic," unless otherwise specified, refers to a cyclic conjugated group or moiety of 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, pyrazolopyridinyl), i.e., at least one ring and optionally multiple fused rings have a contiguous delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Hückel's rule (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system. Such aromatics may be unsubstituted or substituted with one or more groups, such as those described herein for alkyl or aryl groups. Further substituents may include aliphatic, haloaliphatic, halo, nitrate, cyano, sulfonate, sulfonyl, and the like.

[0345] "Aryl" refers to a group containing any carbon-based aromatic group, including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including fused benzo-C (e.g., as defined herein) groups such as indanyl, tetrahydronaphthyl, fluorenyl, and the like. 4-8 It includes cycloalkyl radicals. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group with at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl (also included in the term aryl) defines a group containing an aromatic group that does not contain a heteroatom. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted with 1, 2, 3, 4, or 5 substituents, such as any of the substituents described herein for alkyl.

[0346] "Arylene" refers to a polyvalent (e.g., divalent) form of an aryl group described herein. Examples of arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, an arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 The arylene group is an arylene group. The arylene group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more of the substituents described herein for alkyl or aryl.

[0347] "Aryl(alkylene)" means a divalent entity comprising an arylene group, as described herein, attached to an alkylene or heteroalkylene group, as described herein. In some embodiments, the arylalkylene group is -L-Ar- or -L-Ar-L- or -Ar-L-, where Ar is an arylene group and each L is independently an optionally substituted alkylene group or an optionally substituted heteroalkylene group.

[0348] "Carbonyl" refers to the -C(O)- group, which may also be expressed as >C=O or -CO group.

[0349] "Carboxyl" means a -CO2H group.

[0350] "Carboxyalkyl" means an alkyl group, as defined herein, substituted with one or more carboxyl groups, as defined herein.

[0351] "Carboxyaryl" means an aryl group, as defined herein, substituted with one or more carboxyl groups, as defined herein.

[0352] "Cyclic anhydride," unless otherwise specified, refers to a three-, four-, five-, six-, or seven-membered ring (e.g., a five-, six-, or seven-membered ring) having a -C(O)-OC(O)- group within the ring. The term "cyclic anhydride" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above rings is fused to one, two, or three rings independently selected from the group consisting of aryl, cyclohexane, cyclohexene, cyclopentane, cyclopentene, and other monocyclic heterocycles. Examples of cyclic anhydride groups include radicals formed by removing one or more hydrogens from succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, isochroman-1,3-dione, oxepanedione, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, naphthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, and the like. Other examples of cyclic anhydride groups include dioxotetrahydrofuranyl, dioxodihydroisobenzofuranyl, etc. Additionally, cyclic anhydride groups can be substituted or unsubstituted. For example, cyclic anhydride groups can be substituted with one or more groups, including those described herein for heterocyclyl.

[0353] "Cycloalkenyl," unless otherwise specified, refers to a monovalent unsaturated non-aromatic or aromatic cyclic hydrocarbon group of 3 to 8 carbon atoms having one or more double bonds. Cycloalkenyl groups can be substituted or unsubstituted. For example, cycloalkenyl groups can be substituted with one or more substituents, including those described herein for alkyl.

[0354] "Cycloalkyl," unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon radical of 3 to 8 carbon atoms, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more substituents, including those described herein for alkyl.

[0355] "Halo" means F, Cl, Br, or I.

[0356] "Haloalkyl" means an alkyl group, as defined herein, that is substituted with one or more halo.

[0357] "Heteroalkyl" means an alkyl group, as defined herein, that contains one, two, three, or four non-carbon heteroatoms (e.g., atoms independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo).

[0358] "Heteroalkylene" means a divalent form of an alkylene group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., atoms independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). A heteroalkylene group can be substituted or unsubstituted. For example, a heteroalkylene group can be substituted with one or more substituents described herein for alkyl.

[0359] "Heterocyclyl," unless otherwise specified, refers to a three-, four-, five-, six-, or seven-membered ring (e.g., a five-, six-, or seven-membered ring) containing one, two, three, or four non-carbon heteroatoms (e.g., atoms independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). Three-membered rings have zero to one double bond; four- and five-membered rings have zero to two double bonds; and six- and seven-membered rings have zero to three double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocycles is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle (e.g., indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, etc.). Heterocyclyl groups can be substituted or unsubstituted, for example, with one or more substituents described herein for alkyl.

[0360] "Hydrocarbyl" means a univalent group formed by removing a hydrogen atom from a hydrocarbon. Non-limiting unsubstituted hydrocarbyl groups include alkyl, alkenyl, alkynyl, and aryl, as defined herein, where these groups contain only carbon and hydrogen atoms. Hydrocarbyl groups can be substituted or unsubstituted. For example, a hydrocarbyl group may be substituted with one or more of the substituents described herein for alkyl. In other embodiments, any alkyl or aryl group herein may be substituted with a hydrocarbyl group, as defined herein.

[0361] "Hydroxyl" means --OH.

[0362] "Hydroxyalkyl" means an alkyl group, as defined herein, substituted with one to three hydroxyl groups, provided that only one hydroxyl group may be attached to a carbon atom of the alkyl group, and examples include hydroxymethyl, dihydroxypropyl, and the like.

[0363] "Hydroxyaryl" means an aryl group, as defined herein, substituted with one to three hydroxyl groups, provided that only one hydroxyl group may be attached to a carbon atom of the aryl group, and is exemplified by hydroxyphenyl, dihydroxyphenyl, and the like.

[0364] "Isocyanate" means --NCO.

[0365] "Oxide" means an --O-- group.

[0366] "Oxo" means the radical =O.

[0367] "Phosphine" means trivalent or tetravalent phosphorus having a hydrocarbyl moiety. In some embodiments, the phosphine is -PR P 3 groups, where each P Rare independently H, optionally substituted alkyl, or optionally substituted aryl. The phosphine group can be substituted or unsubstituted. For example, the phosphine group may be substituted with one or more of the substituents described herein for alkyl.

[0368] "Selenol" refers to the group -SeH.

[0369] "Tellurol" refers to the group -TeH.

[0370] "Thioisocyanate" means -NCS.

[0371] "Thiol" refers to an -SH group.

[0372] As used herein, the terms "top," "bottom," "upper," "lower," "above," and "below" are used to indicate relative relationships between structures. Use of these terms does not indicate or require that a particular structure be located in a particular position on the device.

[0373] Conclusion Patterning structures and schemes, as well as related processes and apparatus, for incorporating photoresist underlayers configured to enhance adhesion between a substrate (e.g., a hard mask) and photoresist and / or reduce the EUV dose for effective photoresist exposure during EUV lithography are disclosed and described.

[0374] It is understood that the examples and embodiments described herein are for illustrative purposes only, and that various modifications or alterations will occur to those skilled in the art in light thereof. Various details have been omitted for simplicity, and various design changes may be implemented. Therefore, the above examples are to be considered as illustrative and not limiting, and the disclosure is not limited to the details set forth herein, but may be modified within the scope of the disclosure.

[0375] The following sample claims are provided to further illustrate certain embodiments of the present disclosure, but the present disclosure is not necessarily limited to these embodiments.

Claims

1. A patterning structure comprising: a radiation-sensitive imaging layer disposed on the substrate; an underlayer disposed between the substrate and the imaging layer; Equipped with The lower layer is enhances adhesion between the substrate and the imaging layer; A patterning structure configured to reduce radiation dose for effective photoresist exposure of the imaging layer.

2. 10. The patterning structure of claim 1, wherein the imaging layer comprises an extreme ultraviolet (EUV) sensitive inorganic photoresist layer, a chemical vapor deposition (CVD) film, a spin-on film, or a tin oxide film.

3. 10. The patterning structure of claim 1, wherein the substrate is or comprises a hard mask, an amorphous carbon film, an amorphous carbon film doped with boron (B), an amorphous carbon film doped with tungsten (W), an amorphous hydrogenated carbon film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbide film, a silicon boron nitride film, an amorphous silicon film, a polysilicon film, or a combination thereof.

4. 4. The patterned structure of claim 1, wherein the underlayer has a thickness of 25 nm or less or a thickness of about 2-20 nm.

5. 10. The patterned structure of claim 1, wherein the underlayer comprises hydrogenated carbon doped with oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or a combination of any two or more thereof, optionally wherein the iodine doped hydrogenated carbon is configured to improve secondary electron generation upon exposure to radiation.

6. 6. The patterning structure according to claim 5, wherein the underlayer comprises about 0 to 30 atomic % of oxygen (O) and / or about 20 to 50 atomic % of hydrogen (H), and / or the surface of the underlayer is free of hydroxyl groups, carboxyl groups, peroxy groups, sp ２ A patterned structure comprising carbon, sp carbon, and / or unsaturated carbon-containing bonds.

7. 7. The patterning structure according to claim 1, wherein the underlayer has a density of about 0.7 to 2.9 g / cm ３ and optionally the underlayer further provides increased etch selectivity, and optionally the underlayer further provides reduced line edge and line width roughness and / or reduced dose to size.

8. 8. The patterned structure of claim 1 , wherein the underlayer further comprises beta hydrogen atoms configured to be released upon exposure to radiation and / or oxygen atoms configured to form oxygen bonds to atoms in the imaging layer.

9. A patterning structure comprising: a substrate comprising a partially fabricated semiconductor device film stack; a radiation-sensitive imaging layer disposed on the substrate; an underlayer disposed between the substrate and the imaging layer; Equipped with the underlayer comprises a deposited film of hydrogenated carbon doped with oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or a combination of any two or more thereof; The film has a thickness of 25 nm or less, or a thickness of about 2-20 nm.

10. 10. The patterning structure of claim 9, wherein the substrate further comprises an optionally doped amorphous carbon hard mask disposed on the substrate.

11. 11. The patterned structure of claim 10, wherein the underlayer comprises about 0-30 atomic % oxygen (O) and / or about 20-50 atomic % hydrogen (H).

12. 1. A method of forming a patterning structure, comprising: Prepare the substrate, depositing an underlayer on the substrate, the underlayer configured to enhance adhesion between the substrate and the photoresist and / or reduce radiation dose for effective photoresist exposure; forming a radiation-sensitive imaging layer over the underlayer; A method comprising:

13. 13. The method of claim 12, the substrate is an in-process semiconductor device film stack; the substrate is or comprises a hard mask, an amorphous carbon film, an amorphous hydrogenated carbon film, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbide film, a silicon boronitride film, an amorphous silicon film, a polysilicon film, or a combination thereof; the imaging layer comprises a tin oxide-based photoresist or a tin oxide hydroxide-based photoresist; the underlayer comprises a deposited film of hydrogenated carbon doped with oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or a combination of any two or more thereof, the film having a thickness of 25 nm or less.

14. 14. The method of claim 13, wherein the underlayer is deposited on the substrate using a hydrocarbon precursor in the presence or absence of an oxocarbon precursor, thereby providing a carbon-containing film, and optionally the oxocarbon precursor is hydrogen (H ２ ) or hydrocarbon, and optionally further co-react with a silicon (Si) source dopant.

15. 15. The method of claim 14, wherein the hydrocarbon precursor comprises an alkane, an alkene, or an alkyne.

16. 15. The method of claim 14, wherein the underlayer is deposited using the hydrocarbon precursor in the presence of a nitrogen-containing precursor, a tungsten-containing precursor, a boron-containing precursor, and / or an iodine-containing precursor, thereby providing a doped film.

17. 17. The method of claim 16, wherein the doped film comprises iodine, a combination of iodine and silicon, or a combination of iodine, silicon, and nitrogen.

18. 14. The method of claim 13, wherein the underlayer is deposited on the substrate using a silicon (Si)-containing precursor that co-reacts with an oxidizing agent, the Si-containing precursor optionally further co-reacting with a carbon (C)-source dopant.

19. 19. The method of claims 12-18, wherein the depositing further comprises applying a bias at a bias power of 0 W to about 1000 W and utilizing a duty cycle of about 5% to 100%.

20. 20. The method of claim 19, wherein applying the bias provides the underlayer with a higher density compared to an underlayer formed without applying the bias.

21. 20. The method of any one of claims 12 to 19, wherein the underlayer is deposited on the substrate by PECVD as a final operation of deposition on the substrate.

22. 20. The method of any one of claims 12 to 19, wherein the underlayer is deposited on the substrate by plasma-enhanced chemical vapor deposition (PECVD) or atomic layer deposition (ALD).

23. 23. The method of any one of claims 12 to 22, further comprising, after said depositing, modifying the underlayer to provide a roughened surface, and optionally exposing the underlayer or the roughened surface to an oxygen-containing plasma to provide an oxygen-containing surface.

24. 1. A method for depositing an underlayer, comprising: Providing a substrate in a processing chamber; depositing a hydrogenated carbon film on a surface of the substrate by a plasma-enhanced chemical vapor deposition (PECVD) process; Equipped with The method, wherein the hydrogenated carbon membrane is a low density membrane.

25. 25. The method of claim 24, wherein the PECVD process is a process using methane (CH ４ ), acetylene (C ２ H ２ ), ethylene (C ２ H ４ ), propylene (C ３ H ６ ), propyne (C ３ H ４ ), Allen (C ３ H ４ ), cyclopropene (C ３ H ４ ), butane (C ４ H １０ ), cyclohexane (C ６ H １２ ), benzene (C ６ H ６ ), and toluene (C ７ H ８ ), and introducing a carbon-containing precursor selected from:

26. 26. The method of claim 25, wherein the PECVD process further comprises introducing a nitrogen-containing precursor, a tungsten-containing precursor, a boron-containing precursor, and / or an iodine-containing precursor to provide a doped film.

27. 25. The method of claim 24, wherein the PECVD process comprises transformer coupled plasma (TCP) or inductively coupled plasma (ICP).

28. 28. The method of claim 27, wherein the TCP power is about 100-1000 W without bias.

29. 28. The method of claim 27, wherein the PECVD process further comprises a pressure of about 10-1000 mTorr and / or a temperature of about 0-100°C.

30. 28. The method of claim 27, wherein the PECVD process further comprises applying a pulsed bias having a power of about 10-1000 W or an applied continuous wave bias having a power of about 10-500 W.

31. 31. The method of claim 30, wherein the applied pulsed bias comprises a duty cycle of about 1-99% and a pulsing frequency of about 10-2000 Hz.

32. 32. The method of claims 24-31, further comprising modifying the hydrogenated carbon film after said depositing to provide a roughened surface, and optionally exposing the roughened surface to an oxygen-containing plasma to provide an oxygen-containing surface.

33. 1. An apparatus for processing a substrate, comprising: a processing chamber including a substrate support; a process gas source connected to the process chamber and associated flow control hardware; substrate handling hardware connected to the processing chamber; a controller having a processor and a memory; Equipped with 33. The apparatus, wherein the processor and the memory are communicatively connected to each other, the processor is operatively connected at least to the flow control hardware and the substrate handling hardware, and the memory stores computer-executable instructions for performing the operations recited in any one of the methods of claims 12 to 32.

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