Bake-sensitive underlayers for reducing dose-to-size of EUV photoresists

Abstract

A patterning structure underlayer deposited between the substrate and the imaging layer is provided, the underlayer having chemically labile activatable bonds useful for extreme ultraviolet lithography, where reactive moieties can be released from the activatable bonds of the underlayer into the overlying imaging layer in the presence of heat, oxidizing gas, and / or inert gas.

Description

[Technical Field]

[0001] [Incorporated by reference] A PCT application is being filed contemporaneously herewith as part of this application, and each application identified in that contemporaneous application data sheet to which this application claims benefit or priority 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 fabrication continues to advance, feature sizes continue to shrink, requiring new processing methods. One area where advances are being made is in the area of ​​patterning, for example, using photoresist materials that are sensitive to lithographic radiation.

[0004] The background description provided herein is intended to present the contents of the present disclosure generally. Work by the presently named inventors within the scope of what is described in this Background section, as well as aspects of the description that may not otherwise be considered prior art at the time of filing, are not admitted, expressly or impliedly, as prior art against the present disclosure. Summary of the Invention

[0005] A patterning structure underlayer is provided, deposited between a substrate and an imaging layer, and the underlayer has chemically labile (activatable) bonds useful for EUV lithography. Reactive moieties can be released from the activatable bonds of the underlayer into the overlying imaging layer in the presence of heat, oxidizing gas, and / or inert gas. Their interaction within the imaging layer induces desirable reactions, such as crosslinking, which provides many benefits, including reduced dose-to-size and increased adhesion. The use of the underlayer provides synergistic effects when performing a post-exposure bake after EUV exposure. Scum and roughness after development can also be reduced. Various embodiments herein relate to underlayers, methods for optimizing their use, patterning structures, and apparatus for depositing underlayers on substrates.

[0006] Thus, in a first aspect, the present invention encompasses a method of optimizing the formation of a patterned structure. In some embodiments, the method comprises:

[0007] The method includes providing a substrate; selecting a carbon-containing underlayer having an activatable moiety for deposition on the substrate, the underlayer selected to generate reactive species upon activation by heating, treatment with an oxidizing gas, treatment with an inert gas, or a combination thereof; depositing the selected carbon-containing underlayer on the substrate; and forming a film of a radiation-sensitive imaging layer on the selected underlayer, whereby interaction of the reactive species with the film reduces radiation dose for effective photoresist exposure of the patterned structure.

[0008] In some embodiments, the activatable moiety is a hydroxyl group, a carboxyl group, a peroxy group, a sp 2 carbon, sp carbon, unsaturated carbon-containing bond, allylic C-H bond, ether alpha C-H bond, vinylic C-H bond, aldehyde C-H bond, tertiary C-H bond, benzylic C-H bond, ketone alpha C-H bond, or combinations thereof.

[0009] In some embodiments, the carbon-containing underlayer comprises a carbon-containing doped film.

[0010] In some embodiments, the carbon-containing doped film is doped with a halogen, a metal, an organometallic complex, hydrogen, oxygen, or a combination thereof.

[0011] In some embodiments, the metal comprises antimony, tin, bismuth, indium, tellurium, gold, platinum, palladium, osmium, iridium, titanium, ruthenium, rhodium, silver, tungsten, or a combination thereof.

[0012] In some embodiments, the organometallic complex is an organometallic complex having an oxidizable metal-carbon bond.

[0013] In some embodiments, the heating comprises heating to a temperature of about 100°C to 250°C.

[0014] In some embodiments, the oxidizing gas comprises chlorine, nitric oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, ozone, oxygen, or a combination thereof.

[0015] In some embodiments, the oxidizing gas is provided as a mixture of oxidizing gas in an inert gas.

[0016] In some embodiments, the oxidizing gas is provided in an amount of about 10% to about 100% of the oxidizing gas mixture.

[0017] In some embodiments, the inert gas is helium, neon, argon, krypton, xenon, radon, nitrogen, or a combination thereof.

[0018] In some embodiments, the carbon-containing doped film is doped with a halogen, antimony, tin, indium, tellurium, or bismuth, and the activation is heating.

[0019] In some embodiments, the activatable moiety is sp 2The alkylene may contain carbon, sp carbon, unsaturated carbon-containing bonds, allylic C-H bonds, ether alpha C-H bonds, vinylic C-H bonds, tertiary C-H bonds, benzylic C-H bonds, or combinations thereof, and activation is by heating and treatment with an oxidizing gas.

[0020] In a second aspect, the present invention encompasses a method of fabricating a patterned structure. In some embodiments, the method includes providing a substrate, depositing a bake-sensitive underlayer on the substrate, forming a film of a radiation-sensitive imaging layer on the bake-sensitive underlayer, and The method includes exposing the film to extreme ultraviolet light to produce a film having exposed and unexposed regions; baking the film having the exposed and unexposed regions to activate a bake-sensitive underlayer and generate reactive species, wherein the reactive species generated in the bake-sensitive underlayer preferentially interact with the exposed regions to form exposed cross-linked regions; and developing the film having the exposed cross-linked and unexposed regions, whereby the interaction of the reactive species with the exposed regions reduces the radiation dose for effective photoresist exposure of the patterned structure, and the exposed cross-linked regions increase the contrast between the exposed and unexposed regions.

[0021] In a third aspect, the present invention encompasses a method of fabricating a patterning structure. In some embodiments, the method includes providing a substrate; The method includes depositing a bake-sensitive underlayer having a top underlayer surface and a bottom underlayer surface on a substrate, forming a film having a radiation-sensitive imaging layer on the top underlayer surface of the bake-sensitive underlayer, and baking the film to activate the bake-sensitive underlayer and generate reactive species, wherein the reactive species generated in the bake-sensitive underlayer interact with the film, whereby the interaction of the reactive species with the film reduces the radiation dose for effective photoresist of the patterned structure.

[0022] In a fourth aspect, the present invention encompasses a method of fabricating a patterning structure. In some embodiments, the method includes providing a substrate; depositing a bake-sensitive underlayer on a substrate; and forming a film having a radiation-sensitive imaging layer on the bake-sensitive underlayer; The method includes exposing the film to extreme ultraviolet light to produce an exposed film, and baking the exposed film to activate a bake-sensitive underlayer and generate reactive species, whereby the reactive species generated in the bake-sensitive underlayer interact with the exposed film, whereby the interaction of the reactive species with the exposed film reduces the radiation dose for effective photoresist exposure of the patterned structure.

[0023] In some embodiments, baking comprises heating, contacting the film with an inert gas, contacting the film with an oxidizing gas, or a combination thereof.

[0024] In some embodiments, the reactive species interacts with the exposed film and promotes crosslinking of the exposed film.

[0025] In some embodiments, the reactive species is an oxygen-containing reactive species.

[0026] In some embodiments, baking comprises heating to a temperature of about 75°C to 280°C.

[0027] In some embodiments, the oxidizing gas comprises chlorine, nitric oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, hydrogen peroxide, ozone, oxygen, or a combination thereof.

[0028] In some embodiments, the oxidizing gas is provided as a mixture of oxidizing gas in an inert gas.

[0029] In some embodiments, the oxidizing gas is provided in an amount of about 10% to about 100% of the oxidizing gas mixture.

[0030] In some embodiments, the method also includes increasing adhesion between the substrate and the radiation-sensitive imaging layer as a result of the interaction of the reactive species with the exposed film.

[0031] In some embodiments, the inert gas comprises helium, neon, argon, krypton, xenon, radon, nitrogen, or a combination thereof.

[0032] In some embodiments, the bake-sensitive underlayer is a carbon-containing or silicon-containing film.

[0033] In some embodiments, the bake-sensitive underlayer is a carbon-containing film.

[0034] In some embodiments, the bake-sensitive underlayer has activatable moieties, and the activatable moieties are hydroxyl groups, carboxyl groups, peroxy groups, sp 2 carbon, sp carbon, unsaturated carbon-containing bond, allylic C-H bond, ether alpha C-H bond, vinylic C-H bond, aldehyde C-H bond, tertiary C-H bond, benzylic C-H bond, ketone alpha C-H bond, or combinations thereof.

[0035] In some embodiments, the bake-sensitive underlayer comprises a carbon-containing doped film or a silicon-containing doped film.

[0036] In some embodiments, the carbon-containing doped film is doped with a halogen, a metal, an organometallic complex, hydrogen, oxygen, or a combination thereof.

[0037] In some embodiments, the metal comprises antimony, tin, bismuth, indium, tellurium, gold, platinum, palladium, osmium, iridium, titanium, ruthenium, rhodium, silver, tungsten, or a combination thereof.

[0038] In some embodiments, the organometallic complex comprises an organometallic complex having an oxidizable metal-carbon bond.

[0039] In some embodiments, the organometallic complex having an oxidizable metal-carbon bond is an organoruthenium, organoplatinum, organopalladium, organoiridium, organogold, organosmium, or organorhodium.

[0040] In some embodiments, the silicon-containing doped film is doped with a halogen, a metal, carbon, hydrogen, oxygen, or a combination thereof.

[0041] In some embodiments, the bake-sensitive underlayer has a thickness of 60 nm or less.

[0042] In some embodiments, the reactive species comprises a peroxy radical, a hydroperoxy radical, an oxy radical, a hydroxyl radical, a hydrogen radical, a formate radical, an iodine radical, carbon dioxide, carbon monoxide, water, iodine, hydrogen iodide, hydrogen antimonide, hydrogen telluride, bismuthine, formate anion, superoxide anion, or a combination thereof.

[0043] In some embodiments, the substrate is a film stack of a partially fabricated semiconductor device, the substrate further comprises or is 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 radiation-sensitive imaging layer is a tin oxide-based photoresist or a tin oxide hydroxide-based photoresist, the bake-sensitive underlayer is a vapor-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, and the film has a thickness of 60 nm or less.

[0044] In some embodiments, the bake-sensitive underlayer is vapor-deposited onto a substrate using a hydrocarbon precursor in the presence or absence of an oxocarbon precursor, thereby providing a carbon-containing film, optionally the oxocarbon precursor co-reacting with hydrogen (H) or a hydrocarbon, and optionally further co-reacting with a silicon (Si) source dopant.

[0045] In some embodiments, the hydrocarbon precursor is an alkane, alkene, or alkyne.

[0046] In some embodiments, the bake-sensitive underlayer is vapor-deposited using a hydrocarbon precursor in the presence of a nitrogen-containing precursor, a tungsten-containing precursor, a boron-containing precursor, a chlorine-containing precursor, a bromine-containing precursor, a fluorine-containing precursor, an iodine-containing precursor, a platinum-containing precursor, a ruthenium-containing precursor, an iridium-containing precursor, a gold-containing precursor, a palladium-containing precursor, a rhodium-containing precursor, an osmium-containing precursor, an antimony-containing precursor, an indium-containing precursor, a bismuth-containing precursor, a tellurium-containing precursor, a tin-containing precursor, a silver-containing precursor, a titanium-containing precursor, or a combination thereof, thereby providing a doped film.

[0047] In some embodiments, the doped film comprises iodine, a combination of iodine and silicon, or a combination of iodine, silicon, and nitrogen.

[0048] In some embodiments, the bake-sensitive underlayer is vapor-deposited onto the substrate by using a silicon-containing precursor that co-reacts with an oxidizing agent, and the silicon-containing precursor optionally further co-reacts with a carbon (C) source dopant.

[0049] In some embodiments, the bake-sensitive underlayer is vapor-deposited onto the substrate by plasma-enhanced chemical vapor deposition as a final operation of vapor deposition onto the substrate.

[0050] In some embodiments, the bake-sensitive underlayer is vapor-deposited onto the substrate by plasma-enhanced chemical vapor deposition or atomic layer deposition.

[0051] In some embodiments, the method also includes 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 after deposition.

[0052] In a fifth aspect, the invention encompasses a patterning structure. In some embodiments, the patterning structure includes a radiation-sensitive imaging layer disposed over a substrate and a bake-sensitive underlayer disposed between the substrate and the imaging layer, the bake-sensitive underlayer configured to reduce radiation dose for effective photoresist exposure of the imaging layer.

[0053] In some embodiments, the bake-sensitive underlayer is a carbon-containing or silicon-containing film.

[0054] In some embodiments, the bake-sensitive underlayer is a carbon-containing film.

[0055] In some embodiments, the carbon-containing film may contain hydroxyl groups, carboxyl groups, peroxy groups, sp 2 carbon, sp carbon, unsaturated carbon-containing bond, allylic C-H bond, ether alpha C-H bond, vinylic C-H bond, aldehyde C-H bond, tertiary C-H bond, benzylic C-H bond, ketone alpha C-H bond, or combinations thereof.

[0056] In some embodiments, the bake-sensitive underlayer is a carbon-containing doped film or a silicon-containing doped film.

[0057] In some embodiments, the carbon-containing doped film is doped with a halogen, a metal, an organometallic complex, hydrogen, oxygen, or a combination thereof.

[0058] In some embodiments, the metal is antimony, tin, bismuth, indium, tellurium, gold, platinum, palladium, osmium, iridium, titanium, ruthenium, rhodium, silver, tungsten, or a combination thereof.

[0059] In some embodiments, the organometallic complex is an organometallic complex having an oxidizable metal-carbon bond.

[0060] In some embodiments, the organometallic complex having an oxidizable metal-carbon bond is an organoruthenium, organoplatinum, organopalladium, organoiridium, organogold, organosmium, or organorhodium.

[0061] In some embodiments, the silicon-containing doped film is doped with a halogen, a metal, carbon, hydrogen, or a combination thereof.

[0062] In some embodiments, the carbon-containing doped film is about 0.01 to 20 atomic percent dopant.

[0063] In some embodiments, the imaging layer comprises an extreme UV sensitive inorganic photoresist layer, a chemical vapor deposited film, a spin-on film, a tin oxide film, or a tin oxide hydroxide film.

[0064] In some embodiments, the substrate is or comprises a hard mask, an amorphous carbon film, a boron (B) doped amorphous carbon film, a tungsten (W) doped 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.

[0065] In some embodiments, the bake-sensitive underlayer has a thickness of about 2 to 60 nm.

[0066] In some embodiments, the bake-sensitive underlayer has a coating 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 roughness and line width roughness and / or reduced dose to size.

[0067] In a sixth aspect, the invention encompasses a spin-coating method. In some embodiments, the method includes spin-coating an organometallic imaging layer onto a bake-sensitive underlayer on a substrate, the bake-sensitive underlayer configured to reduce radiation dose for effective photoresist exposure of the organometallic imaging layer.

[0068] In some embodiments, the method also includes exposing the organometallic imaging layer to extreme ultraviolet radiation.

[0069] In some embodiments, the method also includes developing the organometallic imaging layer using wet development after exposing the organometallic imaging layer to extreme ultraviolet light.

[0070] In some embodiments, wet development is carried out using an alkaline developer, an ammonium-based ionic liquid, a glycol ether, an organic acid, a ketone, or an alcohol.

[0071] In some embodiments, wet development is carried out using tetramethylammonium hydroxide, propylene glycol methyl ether, propylene glycol methyl ether acetate, 2-heptanone, ethanol, or combinations thereof.

[0072] In some embodiments, the method also includes performing a post-apply bake at a temperature less than 250° C. after spin coating.

[0073] In some embodiments, the method also includes performing a post-exposure bake at a temperature less than 280°C.

[0074] In some embodiments, the method also includes performing a post-development bake at a temperature less than 280°C.

[0075] In some embodiments, the bake-sensitive underlayer is provided by plasma-enhanced chemical vapor deposition.

[0076] In some embodiments, the organometallic imaging layer comprises an organotin.

[0077] In some embodiments, the organometallic imaging layer comprises organozirconium, organoantimony, organozinc, organohafnium, organozinc, organotellurium, organoindium, or a combination thereof.

[0078] In some embodiments, the method also includes providing a hard mask between the substrate and the bake-sensitive underlayer.

[0079] In some embodiments, the hardmask is an ashable hardmask.

[0080] In some embodiments, the bake-sensitive underlayer comprises hydrogenated carbon.

[0081] In some embodiments, the bake-sensitive underlayer comprises hydrogenated carbon doped with oxygen (O), silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), bromine (Br), fluorine (F), platinum, ruthenium, iridium, gold, palladium, rhodium, osmium, antimony, indium, bismuth, tellurium, tin, silver, titanium, or a combination of any two or more thereof, optionally with iodine doped hydrogenated carbon configured to improve secondary electron generation upon exposure to radiation.

[0082] In some embodiments, the bake-sensitive underlayer has a coating density of about 0.7 to 2.9 g / cm 3 and optionally the bake-sensitive underlayer further provides increased etch selectivity, and optionally the bake-sensitive underlayer further provides reduced line edge roughness and line width roughness, and / or reduced dose to size.

[0083] In a seventh aspect, the invention encompasses a method. In some embodiments, the method includes providing a bake-sensitive underlayer on a substrate, the bake-sensitive underlayer comprising a vapor-deposited film of hydrogenated carbon, spin-coating an organotin imaging layer onto the bake-sensitive underlayer, exposing the organotin imaging layer to extreme ultraviolet light, and developing the organotin imaging layer using wet development.

[0084] In some embodiments, wet development is carried out using an alkaline developer, an ammonium-based ionic liquid, a glycol ether, an organic acid, a ketone, or an alcohol.

[0085] In some embodiments, wet development is carried out using tetramethylammonium hydroxide, propylene glycol methyl ether, propylene glycol methyl ether acetate, 2-heptanone, ethanol, or combinations thereof.

[0086] In some embodiments, the method also includes performing a post-apply bake at a temperature less than 250° C. after spin coating.

[0087] In some embodiments, the method also includes performing a post-exposure bake at a temperature of less than 250°C after exposure.

[0088] In some embodiments, the method also includes performing a post-development bake at a temperature less than 250°C after development.

[0089] In some embodiments, the bake-sensitive underlayer is provided by plasma-enhanced chemical vapor deposition.

[0090] In some embodiments, the method also includes providing an ashable hard mask between the substrate and the underlayer after spin coating.

[0091] In some embodiments, the carbon-containing doped film is an organometallic complex-doped carbon-containing film, which is formed by vapor deposition of a carbon-containing film precursor and an organometallic complex.

[0092] In some embodiments, the carbon-containing doped film is an organometallic complex-doped carbon-containing film, which is formed by alternating deposition of a carbon-containing film precursor and an organometallic complex.

[0093] In some embodiments, the carbon-containing doped film is an organometallic complex-doped carbon-containing film, which is formed by immersing the deposited bake-sensitive underlayer in a solution of the organometallic complex.

[0094] In some embodiments, the organometallic complex-doped carbon-containing film comprises a layer of an organometallic complex over a bake-sensitive underlayer.

[0095] In some embodiments, the organometallic complex-doped carbon-containing film has an organometallic complex dispersed within a bake-sensitive underlayer.

[0096] In some embodiments, the organometallic complex-doped carbon-containing film includes a layer of an organometallic complex over a bake-sensitive underlayer and an organometallic complex dispersed within the bake-sensitive underlayer.

[0097] In an eighth aspect, the invention encompasses a method of fabricating a patterned structure. In some embodiments, the method includes providing a substrate, depositing a doped bake-sensitive underlayer on the substrate, the doped bake-sensitive underlayer being doped with a dopant including iodine, antimony, bismuth, tellurium, and combinations thereof, forming a film of a radiation-sensitive imaging layer on the doped bake-sensitive underlayer, exposing the film to extreme ultraviolet light to produce a film having exposed and unexposed regions, baking the film having exposed and unexposed regions to activate the doped bake-sensitive underlayer and generate reactive species, wherein the generated reactive species in the doped bake-sensitive underlayer preferentially interact with the exposed regions to form exposed crosslinked regions, and developing the film having exposed crosslinked and unexposed regions, whereby the interaction of the reactive species with the exposed regions reduces the radiation dose for effective photoresist exposure of the patterned structure, and the exposed crosslinked regions increase the contrast between the exposed and unexposed regions.

[0098] In some embodiments, exposing the film to extreme ultraviolet light also activates the doped bake-sensitive underlayer to generate reactive species.

[0099] In a ninth aspect, the invention encompasses a method of fabricating a patterned structure. In some embodiments, the method includes providing a substrate, depositing a doped bake-sensitive underlayer on the substrate, the doped bake-sensitive underlayer having a top underlayer surface and a bottom underlayer surface, the doped bake-sensitive underlayer being doped with a dopant including antimony, bismuth, tellurium, and combinations thereof, vapor-depositing a film having a radiation-sensitive imaging layer on the top underlayer surface of the doped bake-sensitive underlayer, and baking the film to release dopants from the doped bake-sensitive underlayer and generate dopant reactive species, which interact with the film, whereby interaction of the dopant reactive species with the film reduces the radiation dose for effective photoresist of the patterned structure.

[0100] In some embodiments, vapor depositing a film having a radiation-sensitive imaging layer on the upper underlayer surface of a doped bake-sensitive underlayer also generates dopant reactive species.

[0101] In a tenth aspect, the present invention encompasses an apparatus for processing a substrate. In some embodiments, the apparatus includes a process chamber with a substrate support, process gas sources and flow control hardware connected to the process chamber, substrate handling hardware connected to the process chamber, and a controller having a processor and memory, wherein the processor and memory are communicatively connected to each other, the processor is at least operatively connected to the flow control hardware and the substrate handling hardware, and the memory stores computer-executable instructions for performing the operations described in any of the methods described herein.

[0102] These and other aspects are further described below with reference to the drawings. [Brief explanation of the drawings]

[0103] [Figure 1] FIG. 1 is a process flow diagram for a non-limiting method 100 according to certain disclosed embodiments.

[0104] [Figure 2A] 2A is a schematic diagram of an exemplary patterning structure, illustrating stages in the fabrication of an exemplary patterning structure described herein. [Figure 2B] 2A and 2B are schematic diagrams of exemplary patterning structures, illustrating stages in the fabrication of exemplary patterning structures described herein. [Figure 2C] 2C is a schematic diagram of an exemplary patterning structure, illustrating a stage in the fabrication of an exemplary patterning structure described herein. [Figure 2D]2D is a schematic diagram of an exemplary patterning structure, showing a cross-sectional view illustrating possible interactions between the imaging layer 218 and the underlayer 216. [Figure 2E] 2E is a schematic diagram of an exemplary patterning structure, showing a non-limiting reaction scheme within the imaging layer. [Figure 2F] 2F is a schematic diagram of an exemplary patterning structure illustrating a non-limiting reaction scheme between imaging layer 228 and underlayer 226, according to certain disclosed embodiments.

[0105] [Figure 3A] FIG. 3A is a diagram illustrating the interaction of exposed and unexposed photoresist on a bake-sensitive underlayer in the presence of an oxidizing agent, according to certain disclosed embodiments.

[0106] [Figure 3B] FIG. 3B is a bar chart illustrating CH loss resulting from post-exposure baking of patterned structures having underlayers treated with various amounts of oxidizing gas, according to certain disclosed embodiments.

[0107] [Figure 4] FIG. 4 is a graphical illustration of CH loss resulting from post-exposure baking of patterned structures having underlayers treated with various amounts of oxidizing gas, according to certain disclosed embodiments.

[0108] [Figure 5A] FIG. 5A illustrates a formula for calculating synergy, in accordance with certain disclosed embodiments.

[0109] [Figure 5B] FIG. 5B is a graphical illustration of CH loss resulting from post-exposure baking of a control patterned structure without an underlayer (lacking activatable moieties) at different temperatures, in accordance with certain disclosed embodiments.

[0110] [Figure 5C]FIG. 5C is a graphical illustration of CH loss resulting from post-exposure baking of a patterned structure having an activatable underlayer at different temperatures, in accordance with certain disclosed embodiments.

[0111] [Figure 6A] FIG. 6A is a bar chart illustrating C—H loss resulting from baking alone (without EUV exposure) compared to a non-bake-sensitive underlayer for a patterned structure having a bake-sensitive underlayer, according to certain disclosed embodiments.

[0112] [Figure 6B] FIG. 6B is a graph demonstrating the correlation of dose versus size and CH loss as measured by FTIR, in accordance with certain disclosed embodiments.

[0113] [Figure 7] FIG. 7 is a schematic diagram of one embodiment of a process station 300 for dry development, in accordance with certain disclosed embodiments.

[0114] [Figure 8] FIG. 8 is a schematic diagram of one embodiment of a multi-station processing tool 400, in accordance with certain disclosed embodiments.

[0115] [Figure 9] FIG. 9 is a schematic diagram of one embodiment of an inductively coupled plasma apparatus 500, in accordance with certain disclosed embodiments.

[0116] [Figure 10] FIG. 10 is a schematic diagram of one embodiment of a semiconductor process cluster tool architecture 600, in accordance with certain disclosed embodiments.

[0117] [Figure 11] FIG. 11 is a cross-sectional schematic view of an example dry deposition apparatus 700, according to certain disclosed embodiments.

[0118] [Figure 12] FIG. 12 is a detailed cross-sectional side view and plan view of a portion of the top plate, substrate, and edge ring in accordance with certain disclosed embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0119] Reference will be made in detail herein to specific embodiments of the present disclosure. Examples of specific embodiments are illustrated in the accompanying drawings. While the present disclosure will be described in conjunction with these specific embodiments, it will be understood that 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. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the present disclosure.

[0120] definition "Acyloxy" or "alkanoyloxy," as used interchangeably herein, 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 Alkanoyloxy groups. Exemplary alkanoyloxy groups include acetoxy.

[0121] "Aliphatic" means a group consisting of at least 1 carbon atom and at least 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), which includes alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic versions thereof, as well as 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.

[0122] "Alkenyl" refers to an optionally substituted C alkyl group having one or more double bonds. 2-24 The alkenyl group is a cyclic group (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.

[0123] "Alkenylene" means a polyvalent (e.g., divalent) form of an alkenyl group, which is an optionally substituted C alkyl group having one or more double bonds. 2-24 Alkenylene groups are cyclic (e.g., C 3-24 The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substituents described herein for alkyl. Exemplary non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0124] "Alkoxy" refers to -OR, where R is an optionally substituted alkyl group as described herein. Exemplary alkoxy groups 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. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12, C 1-16 , C 1-18 , C 1-20 , or C 1-24 Examples include alkoxy groups.

[0125] The terms "alkyl" and "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 can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can include a haloalkyl, where the alkyl group is substituted with one or more halo groups as described herein. In another example, the alkyl group can be substituted with 1, 2, 3, or, in the case of an alkyl group of 2 or more carbons, 4 substituents independently selected from the group consisting of: (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 , R N1 and R N2 each is independently H or optionally substituted alkyl, or R N1 and R N2each taken 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 3-8 hydrocarbon group), (10) halo (e.g., F, Cl, Br, or I), (11) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms such as nitrogen, oxygen, phosphorus, sulfur, or halo, unless otherwise specified), (12) heterocyclyloxy (e.g., —O-Het, where Het is a heterocyclyl as described herein), (13) heterocyclyloyl (e.g., —C(O)-Het, where Het is a 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 , R A is (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) (C 4-18 Aryl)C 1-6 (19) —C(O)NR B R C , R B and R C each independently being (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) (C 4-18 Aryl)C 1-6alkyl (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 , R G and R H each of which is independently (a) hydrogen, (b) an N-protecting group, (c) C 1-6 Alkyl, (d) C 2-6 alkenyl (e.g., optionally substituted alkyl having one or more double bonds); (e) C 2-6 alkynyl (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 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, there are no two groups attached to the nitrogen atom via 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.

[0126] "Alkylene" refers to the polyvalent (e.g., divalent) form of the alkyl groups described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, an alkylene group is a C1-3 , 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 2-24 It is an alkylene group. The alkylene group can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more of the substituents described herein for alkyl.

[0127] "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 are exemplified by 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.

[0128] "Alkynylene" means a polyvalent (e.g., divalent) form of the alkynyl group, which is an optionally substituted C alkyl group having one or more triple bonds. 2-24 It 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. Exemplary non-limiting alkynylene groups include -C≡C- or -C≡CCH2-.

[0129] "Amino" means -NR N1 R N2 means R N1 and R N2 each is independently H, optionally substituted alkyl, or optionally substituted aryl, or R N1 and RN2 taken together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0130] "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, or 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 can 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.

[0131] "Aryl" refers to fused benzo-C groups such as, but not limited to, indanyl, tetrahydronaphthyl, and fluorenyl. 4-8 The term aryl refers to any carbon-based aromatic group, including phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including cycloalkyl radicals (e.g., as defined herein). The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having 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 within the term aryl, defines a group containing an aromatic group without a heteroatom. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted with 1, 2, 3, 4, or 5 substituents, such as those described herein for alkyl.

[0132] "Arylene" refers to a polyvalent (e.g., divalent) form of the aryl groups described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenylether, 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 It 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 substituents described herein for alkyl or aryl.

[0133] "(Aryl)(alkyl)ene" refers to a divalent form comprising an arylene group, as described herein, linked to an alkylene group or a heteroalkylene group, as described herein. In some embodiments, the (aryl)(alkyl)ene 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.

[0134] "Atomic layer deposition" (ALD) refers to a vapor deposition process in which deposition cycles, preferably multiple consecutive deposition cycles, are performed in a process chamber (i.e., a deposition chamber). Typically, during each cycle, a precursor is chemisorbed to the deposition surface (i.e., the substrate assembly surface or a previously deposited underlying surface, such as material from a previous ALD cycle), forming a monolayer or submonolayer that does not readily react with additional precursors (i.e., self-limiting reaction). If desired, a reactant (i.e., another precursor or reactant gas) can then be introduced into the process chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. Typically, this reactant is capable of reacting with the already chemisorbed precursor. Additionally, a purge step can be utilized during each cycle to remove excess precursor from the process chamber and / or to remove excess reactant and / or reaction by-products from the process chamber after conversion of the chemisorbed precursor.

[0135] "Carbonyl" refers to the group -C(O)-, which can also be depicted as a >C=O, or CO group.

[0136] "Carboxyl" means a -CO2H group.

[0137] "Carboxyalkyl" means an alkyl group, as defined herein, substituted with one or more carboxyl groups, as defined herein.

[0138] "Carboxyaryl" means an aryl group, as defined herein, substituted with one or more carboxyl groups, as defined herein.

[0139] "Cyclic anhydride" refers to a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., a 5-, 6-, or 7-membered ring) having a -C(O)-OC(O)- group within the ring, unless otherwise specified. The term "cyclic anhydride" also includes bicyclic, tricyclic, and tetracyclic groups, any of which 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. Exemplary 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 exemplary cyclic anhydride groups include dioxotetrahydrofuranyl, dioxodihydroisobenzofuranyl, and the like. The cyclic anhydride group can also be substituted or unsubstituted. For example, the cyclic anhydride group can be substituted with one or more groups, including those described herein for heterocyclyl.

[0140] "Cycloalkenyl" means, unless otherwise specified, a monovalent unsaturated non-aromatic or aromatic cyclic hydrocarbon group of 3 to 8 carbons having one or more double bonds. Cycloalkenyl groups can also be substituted or unsubstituted. For example, cycloalkenyl groups can be substituted with one or more groups, including those described herein for alkyl.

[0141] "Cycloalkyl," unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group of 3 to 8 carbons, exemplified by 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 groups, including those described herein for alkyl.

[0142] "Halo" means F, Cl, Br, or I.

[0143] "Haloalkyl" means an alkyl group, as defined herein, that is substituted with one or more halo.

[0144] "Heteroalkyl" means an alkyl group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo).

[0145] "Heteroalkylene" refers to a divalent form of an alkyl group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). Heteroalkylene groups can be substituted or unsubstituted. For example, heteroalkylene groups can be substituted with one or more substituents described herein for alkyl.

[0146] "Heterocyclyl," unless otherwise specified, refers to a 3-, 4-, 5-, 6-, or 7-membered ring (e.g., a 5-, 6-, or 7-membered ring) containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). A 3-membered ring has 0 to 1 double bond, a 4- and 5-membered ring has 0 to 2 double bonds, and a 6- and 7-membered ring has 0 to 3 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 such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. A heterocyclyl group can be substituted or unsubstituted. For example, heterocyclyl groups can be substituted with one or more of the substituents described herein for alkyl.

[0147] "Hydrocarbyl" refers to 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, which groups contain only carbon and hydrogen atoms. Hydrocarbyl groups can be substituted or unsubstituted. For example, hydrocarbyl groups can be substituted with one or more of the substituents described herein for alkyl. In other embodiments, any alkyl or aryl group herein can be replaced with a hydrocarbyl group as defined herein.

[0148] "Hydroxyl" means --OH.

[0149] "Hydroxyalkyl" means an alkyl group, as defined herein, substituted with one to three hydroxyl groups, with the proviso that not more than one hydroxyl group can be attached to a single carbon atom of the alkyl group; such groups are exemplified by hydroxymethyl, dihydroxypropyl, and the like.

[0150] "Hydroxyaryl" means an aryl group, as defined herein, substituted with one to three hydroxyl groups, with the proviso that not more than one hydroxyl group can be attached to a single carbon atom of the aryl group; this group is exemplified by hydroxyphenyl, dihydroxyphenyl, and the like.

[0151] "Isocyanato" means --NCO.

[0152] "Oxide" means -O - means a group.

[0153] "Oxo" means the radical =O.

[0154] "Phosphine" means trivalent or tetravalent phosphorus having a hydrocarbyl moiety. In some embodiments, the phosphine is -PR P There are three R P are independently H, optionally substituted alkyl, or optionally substituted aryl. The phosphine group can be substituted or unsubstituted. For example, the phosphine group can be substituted with one or more of the substituents described herein for alkyl.

[0155] "Selenol" refers to the group -SeH.

[0156] "Tellurol" refers to the group -TeH.

[0157] "Thioisocyanato" means -NCS.

[0158] "Thiol" refers to the group --SH.

[0159] "Deposition" or "vapor deposition" refers to a process in which a metal layer is formed on one or more surfaces of a substrate from a vaporized precursor composition containing one or more metal-containing compounds. The metal-containing compounds are vaporized and directed toward and / or contact one or more surfaces of a substrate (i.e., a semiconductor substrate or semiconductor assembly) placed in a deposition chamber. Typically, the substrate is heated. These metal-containing compounds form a non-volatile, thin, uniform metal-containing layer on the surface of the substrate. One operation of the method is one cycle, and the process can be repeated as many times as necessary to obtain the desired metal thickness.

[0160] "Etchant" means any compound used to remove material, such as a layer, by-product, or contaminant, from a surface.

[0161] "Bake sensitivity" means sensitivity to a particular temperature threshold in combination with a particular gaseous atmosphere.

[0162] By "bake-sensitive underlayer" is meant an underlayer material that is sensitive to a particular temperature threshold and a particular gaseous atmosphere (i.e., oxidizing / reducing / inert...) combination that results in a chemical change that causes a beneficial DtS reduction for the imaging layer.

[0163] As used herein, the terms "top," "bottom," "upper," "lower," "above," and "below" are used to provide relative relationships between structures. The use of these terms does not indicate or require that a particular structure must be located in a particular location within the device.

[0164] As used herein, the term "about" is understood to allow for slight increases and / or decreases beyond the recited value, but these variations do not significantly affect the desired function of the parameter beyond the recited value. In some cases, "about" encompasses + / - 10% of the recited value. As used herein, the term modifies a recited value, a range of values, or one or more end points of a range.

[0165] Extreme ultraviolet (EUV) lithography (typically at a wavelength of 13.5 nm) is considered the next technology to enable lithographic patterning. However, a number of technical obstacles have slowed the widespread adoption and implementation of this technique. EUV photoresists (PR) are one of the barriers.

[0166] 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 sensitivity and resolution limitations due to random variations in the use of polymers. 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, including metal hydroxides and oxides. The small molecular size of metal oxides improves the final resolution of the patterning step, and metal oxide photoresists generally exhibit higher etch resistance than CARs, allowing the thickness of the CAR to be reduced to reduce the aspect ratio of the structure.

[0167] 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-rich (C) film that has poor etch resistance and line width roughness (LWR). Common hardmask materials such as silicon oxide (e.g., silicon dioxide, SiO2), silicon nitride, and ashable hardmask (AHM) can be used directly underneath PR to improve etch selectivity and achieve good LER and LWR. However, delamination between EUV PR and hardmask materials remains a problem, especially after wet development of EUV-exposed PR. Only about 20% 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 show that EUV inorganic PR placed directly on common hardmask materials requires a higher dose than EUV inorganic PR on SOC to resolve the same line critical dimension.

[0168] As described herein, a thin underlayer film disposed directly beneath an EUV inorganic PR allows for improved performance of the EUV inorganic PR film stack. In particular, the bake-sensitive underlayer is one that has chemically unstable or activatable moieties. In some embodiments, the underlayer may be carbon- or silicon-containing. The activatable moieties may be a constituent part of the underlayer, may be added to the underlayer as a dopant, or may be a constituent part of the underlayer and derived from a dopant.

[0169] Sources of carbon-containing films can include, but are not limited to, methane, acetylene, ethylene, propylene, propyne, allene, cyclopropene, butane, cyclohexane, benzene, and toluene.

[0170] In some embodiments, when the underlayer is a carbon-containing underlayer, it may have certain types of bonds that are susceptible to cleavage under appropriate conditions, which may include heat, oxidizing gas, or a combination of heat and oxidizing gas. Some examples of activatable C-H bonds include, but are not limited to, allylic C-H, ether alpha C-H, vinylic C-H, C-H bonds alpha to a ketone group, C-H bonds alpha to an aldehyde or to a carbonyl carbon, tertiary C-H, and benzylic C-H.

[0171] In such carbon-containing sublayers, the synergistic action of the oxidizing gas causes the release of reactive moieties, which may be reactive species including peroxy radicals, hydroperoxy radicals, oxy radicals, hydroxy radicals, hydrogen radicals, formate radicals, iodine radicals, carbon dioxide, carbon monoxide, water, iodine, hydrogen iodide, hydrogen antimonide, hydrogen telluride, bismuthine, formate anions, superoxide anions, or combinations thereof.

[0172] Without wishing to be bound by theory, reactive species (once released from the bake-sensitive underlayer having activatable moieties) can diffuse into the imaging layer and crosslink the imaging layer material, which reduces dose-to-size.

[0173] When a carbon-containing underlayer is doped with, for example, a halide, the CX bond can be broken by heat alone, and an oxidizing gas may not be necessary. For such underlayers, the reactive species may include halogen radicals or anions.

[0174] Sources of iodine dopants for carbon-containing underlayers include the precursors HI, CH2I2, CH3I, ICH2CH2I, C2H4I, CF3I, or ICF2CF2I in some embodiments.

[0175] Sources of bromine dopants for carbon-containing underlayers include the precursors HBr, CH2Br2, CH3Br, BrCH2CH2Br, C2H4Br, CF3Br, or BrCF2CF2Br in some embodiments.

[0176] Sources of chlorine dopants for carbon-containing underlayers include the precursors HCl, CH2Cl2, CH3Cl, ClCH2CH2Cl, C2H4Cl, CF3Cl, or ClCF2CF2Cl in some embodiments.

[0177] Sources of fluorine dopants for carbon-containing underlayers include the precursors HF, CH2F2, CH3F, CF4, FCH2CH2F, C2H4F, CF3F, or C2F6 in some embodiments.

[0178] Similar to the example of the halide-doped carbon-containing underlayer, when the carbon-containing underlayer is doped with a metal or organometallic complex, the C-M bond can be broken by heat alone, and an oxidizing gas may not be necessary.

[0179] In some embodiments, suitable metals include antimony, tin, bismuth, indium, tellurium, gold, platinum, palladium, osmium, iridium, titanium, ruthenium, rhodium, silver, tungsten, or combinations thereof. The metal may be applied as a thin layer onto the underlayer or may be deposited with the underlayer precursor.

[0180] In some embodiments, suitable organometallic complexes include complexes having an oxidizable metal-carbon bond, such as organoruthenium, organoplatinum, organopalladium, organoiridium, organogold, organosmium, or organorhodium.

[0181] An underlayer doped with an organometallic complex can be produced by a variety of techniques. In one embodiment, the underlayer is first deposited on a substrate. The underlayer is then immersed in the organometallic complex dissolved in a solution and optionally heated. As a result of the immersion, the organometallic complex can be 1) deposited as a thin layer covering the underlayer, 2) dispersed throughout the underlayer, or 3) deposited as a thin layer and dispersed throughout the underlayer.

[0182] In some embodiments, solvents that can be used to dissolve the organometallic complex include tetrahydrofuran, n-hexane, acetonitrile, ethanol, isopropyl alcohol, or dimethyl sulfoxide. The immersion time can be from about 20 seconds to about 5 minutes. During immersion, the solution can optionally be heated to a temperature of from about 25°C to about 150°C.

[0183] Suitable organorhodium complexes include, in some embodiments, dicarbonyl(pentamethylcyclopentadienyl)rhodium(I).

[0184] Suitable organic osmium complexes include bis(pentamethylcyclopentadienyl)osmium and bis(cyclopentadienyl)osmium.

[0185] Suitable organogold complexes include dimethyl(acetylacetonate)gold(III).

[0186] Suitable organic iridium complexes include (methylcyclopentadienyl)(1,5-cyclooctadiene)iridium(I) and 1-ethylcyclopentadienyl-1,3-cyclohexadieneiridium(I).

[0187] Suitable organopalladium complexes include allyl(cyclopentadienyl)palladium(II).

[0188] Suitable organoplatinum complexes include (trimethyl)pentamethylcyclopentadienylplatinum(IV) and trimethyl(methylcyclopentadienyl)platinum(IV).

[0189] Suitable organo-ruthenium complexes include those with cyclopentadienyl, cyclic unsaturated hydrocarbon, alkyl, alkenyl, or beta-diketonate ligands.

[0190] The underlayer may also be comprised of a silicon-containing film, which may be silicon oxide. In any embodiment, the silicon-containing film may be doped with a halogen, a metal, carbon, hydrogen, or a combination thereof.

[0191] If heating is required, heating may be performed at a pedestal temperature of about 75° C. to about 280° C., or at a temperature of about 75° C. to about 280° C. In some embodiments, two or more different temperatures with different bake gas atmospheres may be utilized (i.e., a first bake in an oxidizing gas with heating, and a second bake in an inert gas (i.e., 100% N) at a higher temperature than the first bake).

[0192] The duration of heating is variable and can be optimized for the selected underlayer. In some embodiments, the duration may be from about 1 to about 10 minutes. In some embodiments, when two or more different temperatures are utilized, a first temperature may be maintained for a first duration of from about 1 to about 5 minutes, and a second temperature may be maintained for a second duration of from about 1 to about 10 minutes. The two durations may be the same or different.

[0193] The choice of oxidizer can be variable and depends on the nature of the selected underlayer. If utilized, the oxidizer can include chlorine, nitric oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, hydrogen peroxide, ozone, oxygen, or combinations thereof.

[0194] The oxidizing agent can be delivered to the process chamber in the form of an inert gas. In addition, the underlayer precursor can also be delivered in the form of an inert gas. When the oxidizing gas is delivered as an oxidizing gas mixture (with an inert gas), the oxidizing gas can be delivered in an amount of about 10% to about 100% of the oxidizing gas mixture.

[0195] In certain embodiments, the inert gas is helium, neon, argon, krypton, xenon, radon, nitrogen, or a combination thereof.

[0196] In certain embodiments, dose-to-size reduction can be achieved based on the selection of an appropriate underlayer and treatment that releases reactive species in the underlayer to promote crosslinking in the imaging layer, so the underlayers described above can be utilized to optimize or fine-tune the production of patterned structures. The treatment (bake or bake-type process) can be heating alone or heating with exposure to an oxidizing gas. Beneficial effects can be measured even when the treatment is simply a bake-only type process or without EUV exposure. The selection criteria for the underlayer depend on the specific product or effect desired. In some embodiments, a doped underlayer can be selected. For example, if it is preferable to avoid the use of oxidizing agents, a halo-doped bake-sensitive underlayer can be selected because the halo-doped bake-sensitive underlayer can be activated in the presence of heat alone. In some embodiments, other dopants may be preferred to achieve the desired effect. In still other embodiments, if the underlayer material itself already contains activatable bonds, doping may not be required to form the bake-sensitive underlayer.

[0197] In certain embodiments, the above-described underlayers can be used to prepare patterned structures by EUV exposure and post-exposure bake processes. The reduction in dose-to-size and / or increased adhesion are some of the beneficial effects of synergistically combining these two steps of the lithography process. The dose-to-size reduction can be approximately 20% to 60% compared to a non-bake-sensitive underlayer (one lacking activatable moieties).

[0198] In certain embodiments, the above-described underlayer can be used to prepare a patterned structure by a method that involves EUV exposure, post-exposure baking, and development processes. In such a method, reactive species generated from the bake-sensitive underlayer (during PEB) preferentially interact with the EUV-exposed regions of the image compared to the unexposed regions. This means that the reactive species do not indiscriminately interact with the exposed and unexposed regions, but contribute to an increased amount of crosslinking in the exposed regions of the imaging layer. This creates additional chemical / material contrast in the imaging layer between the unexposed and exposed regions. The beneficial end result of such a method is reduced pattern edge roughness and / or reduced scum.

[0199] The resulting multilayer (e.g., bilayer) hardmask scheme using the above-described underlayers has comparable or better DtS performance compared to EUV inorganic PR applied directly on the SOC stack. The underlayer also functions as an adhesion layer between the EUV inorganic PR and the hardmask, potentially improving etch selectivity and LER / LWR performance, regardless of the hardmask film composition. Surfaces other than hardmasks can be used below the underlayer, in which case the underlayer can function as an adhesion layer between the EUV PR and any useful substrate (e.g., hardmask, wafer, film stack of a partially fabricated semiconductor device, etc.).

[0200] As further described 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 vapor deposition methods (e.g., sputter deposition, physical vapor deposition (PVD), including PVD co-sputtering). The underlayer deposition process can be performed in either an etching tool (e.g., Kiyo® or Flex®, available from Lam Research, Inc., Fremont, California) or a deposition tool (e.g., Lam Striker®). In some embodiments, the underlayer deposition process can be integrated as a final step in the hard mask deposition process. Depending on the film stack, different film compositions of the underlayer can be selected.

[0201] While this disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, it should be understood that the disclosure is also applicable to other next-generation lithography techniques. In addition to EUV, including the standard 13.5 nm EUV wavelength currently in use and under development, the most relevant radiation sources for such lithography are DUV (deep UV), which generally refers to the use of excimer laser sources at 248 nm or 193 nm, X-ray, which formally includes EUV at the lower 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. Specific methods may depend on the specific materials and applications used in the semiconductor substrate and final semiconductor device. Therefore, the methods described herein are merely exemplary of methods and materials that can be used with the present technology.

[0202] FIG. 1 illustrates a process flow for one aspect of the present disclosure, namely, a method for fabricating a patterned structure. The method 100 involves providing a substrate, at 101. The substrate may be, for example, a hard mask, film, stack, film stack of a partially fabricated semiconductor device, or the like, fabricated by any suitable method. In some embodiments, the substrate may include a hard mask disposed on a workpiece, such as a film stack of a partially fabricated semiconductor device. The hard mask on the top layer of the film stack can have a variety of compositions, such as SiO, silicon nitride, ashable hard mask material, and can be formed by chemical vapor deposition, e.g., PECVD. An ashable hard mask comprised 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.

[0203] Still other substrates can be used, for example, the substrate can be or include amorphous hydrogenated carbon, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon boronitride, amorphous silicon, polysilicon, or any combination described herein, and can be in any form (e.g., bulk film, thin film, another film, stack, etc.).

[0204] At 103, a photoresist underlayer is deposited on the substrate. The underlayer is configured to increase 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 vapor-deposited film of hydrogenated carbon doped with O, silicon (Si), nitrogen (N), tungsten (W), boron (B), iodine (I), chlorine (Cl), or any combination thereof (e.g., a combination of Si and O). In one embodiment, the film is deposited by introducing or delivering a hydrocarbon precursor (e.g., to provide carbon atoms) and a dopant precursor (e.g., to provide non-carbon atoms for doping). In another embodiment, the film is deposited by introducing or delivering a heteroatom-containing precursor, such as an iodine-containing precursor, that provides a doped film after deposition. In particular, iodine-doped hydrogenated carbon films can improve secondary electron generation upon exposure to EUV radiation. Further non-limiting precursors and dopants for providing such underlayers are described herein.

[0205] The film can have a thickness of about 60 nm or less. For example, the photoresist underlayer may have a thickness of about 2-20 nm, e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 nm, and may optionally contain about 0-30 atomic % O and / or about 20-50 atomic % hydrogen (H), 0-16 atomic % halogen, such as iodine, fluorine, bromine, or chlorine, and / or 30-70 atomic % C. Other underlayer properties are described herein.

[0206] In some implementations, the underlayer may be vapor-phase deposited onto the substrate by PECVD or ALD using a hydrocarbon precursor with or without carbon monoxide (CO) and / or carbon dioxide (CO). In certain embodiments, the vapor deposition includes introducing or delivering a hydrocarbon precursor without CO and CO.

[0207] In some embodiments, the underlayer may be vapor-phase deposited onto the substrate by PECVD or ALD using an oxocarbon precursor that co-reacts with hydrogen (H) or a hydrocarbon. In a variation of this embodiment, 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 can impart hydroxyl (-OH) groups or other oxygen-containing groups to the underlayer, resulting in a hydrophilic surface or a surface with increased hydrophilicity (compared to an underlayer lacking such -OH groups or oxygen-containing groups). In a non-limiting example, a hydrophilic surface can improve adhesion between the underlayer and the PR layer.

[0208] In other embodiments, the underlayer may be vapor-deposited onto 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 embodiment, 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, such as silanes, halosilanes, aminosilanes, alkoxysilanes, and organosilanes.

[0209] In some embodiments, the underlayer may be vapor-deposited onto the substrate by PECVD, for example, by adjusting the flow of precursors into the PECVD process chamber to achieve the desired composition of the photoresist underlayer as a final operation of vapor deposition onto the substrate.

[0210] In other embodiments, the underlayer may be vapor deposited onto 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 0.7-1.4 g / cm 3In yet another embodiment, the doped film has a density of about 0.7-1.4 g / cm 3 It has a density of

[0211] 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.

[0212] Deposition of the underlayer can involve the use of plasmas (e.g., those in PECVD processes) including transformer-coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP). In certain embodiments, deposition can use low TCP power (e.g., about 100-1000 W) with minimal bias (e.g., no bias) to provide low-density films. Of course, higher-power plasmas can also be used, as described herein. In certain embodiments, generation of the plasma (e.g., TCP or ICP) can be controlled by power in continuous wave (CW) mode.

[0213] Deposition (e.g., using TCP or ICP power in CW mode) can include a bias (regardless of frequency) applied in a pulsed manner (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, an applied pulsed bias can be provided to control ion energy. Non-limiting applied pulsed bias power can be about 10-1000 W, as well as other ranges described herein.

[0214] In yet other embodiments, deposition can include an applied CW bias. The CW bias can also be used to control ion energy. In some embodiments, the applied CW bias power can be 10-1000 W (e.g., 10-500 W, 10-400 W, as well as other ranges described herein).

[0215] Still other conditions (e.g., useful for low density films) include the use of specific pressure conditions (e.g., 5-1000 milliTorr (mTorr), including 10-1000 mTorr, 10-500 mTorr, or 10-400 mTorr) and specific temperature conditions (e.g., including about 0-100°C, 0-50°C, and 10-40°C).

[0216] Pulsed or continuous bias can be used to fine-tune the film properties. In one embodiment, pulsed bias can provide a denser film compared to a low-density film prepared with 0 W bias power. Such denser films can, in some cases, have increased etch resistance compared to a low-density film. In another example, such denser films can have reduced undercut compared to a low-density film prepared with 0 W bias power. Additional plasma conditions and processes are also described herein.

[0217] 1, at 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, entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," filed May 9, 2019, and published as WO2019 / 217749, and PCT / US2019 / 060742, entitled "METHODS FOR MAKING HARD MASKS USEFUL IN NEXT GENERATION LITHOGRAPHY," filed November 11, 2019, and published as WO2020 / 102085, the disclosures of which relating to the composition, deposition, and patterning of directly photopatternable organometallic-based metal oxide films to form EUV resist masks are incorporated herein by reference. As described herein, according to various embodiments, the EUV-sensitive inorganic photoresist may be a spin-on film or a vapor-deposited film.

[0218] 2A-2C illustrate stages in the fabrication of a non-limiting patterning structure described herein. The patterning structure shown in FIG. 2C has a hard mask 204 disposed on a substrate 202 (e.g., a wafer or a film stack of a partially fabricated semiconductor device). An imaging layer 208 is disposed on top of the hard mask 204. And an underlayer 206 is disposed between the hard mask 204 and the imaging layer 208. The underlayer 206 can be configured to increase adhesion between the hard mask and the imaging layer and to reduce radiation dose for effective photoresist exposure.

[0219] In test structures according to the described embodiments, the DtS performance of EUV PR on amorphous carbon AHM with an underlayer described herein is comparable to or better than EUV PR on SOC, in some cases reducing the required dose by 10% or more. Furthermore, the EUV PR is not observed to delaminate from the hardmask bilayer (amorphous carbon AHM with a photoresist underlayer) after development.

[0220] The underlayer 206 can further provide increased etch selectivity and / or reduced line edge roughness and line width roughness (LER / LWR) within the structure. In test structures according to the described embodiments, LER / LWR improved from nearly good to over 25% compared to EUV PR on AHM or SOC.

[0221] 2A-2C, an embodiment of the fabrication of the structure of FIG. 2C is shown in FIG. 2A-2B. As discussed 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 deposited on the hard mask 204.

[0222] The use of an underlayer in the stack can improve properties. In one example, interactions between the underlayer and the imaging layer reduce 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 productive interactions between the underlayer and the imaging layer, which in turn can contribute to improved adhesion and / or DtS.

[0223] Additionally, the compositions of the underlayer and imaging layer can be designed to promote favorable reactions, thereby improving DtS. For example, as seen in Figure 2E, the imaging layer can include a tin-based photoresist with radiation-cleavable ligands. Upon exposure to radiation (e.g., EUV), the ligands (R) are detached from the tin (Sn) center, forming Sn-H bonds instead. After a post-exposure bake (PEB) step, the Sn-H bonds participate in further thermally activated crosslinking reactions, thereby increasing the difference in material properties between the exposed and unexposed photoresists.

[0224] Thus, in one example, as seen in FIG. 2F , underlayer 226 includes a ligand (R1) that provides a releasable H atom upon exposure to EUV radiation, thereby forming a reacted ligand (R1*). Possible R1 groups include, for example, optionally substituted alkyl, which may be linear or branched. In imaging layer 228, EUV-cleavable ligand R provides a leaving ligand R* and a reactive metal center Sn. The H atoms released from underlayer 226 can promote the formation of Sn-H bonds within imaging layer 228, thereby reducing DtS. If the underlayer also contains oxygen (O) atoms, such atoms can form M-O bonds (e.g., Sn-O bonds) in the imaging layer, further reducing DtS. Additionally, Sn atoms from imaging layer 228 can diffuse into underlayer 226, thereby generating additional secondary electrons.

[0225] Embodiment 1: Dry deposition of the underlayer The underlayer can be deposited in any useful manner. In one example, the deposition includes vapor-phase deposition of a hydrocarbon precursor or a carbon-containing precursor (e.g., any of those described herein). The deposition can include the use of a process gas (e.g., as a plasma or an inert gas) during deposition, non-limiting process gases including carbon monoxide (CO), helium (He), argon (Ar), krypton (Kr), neon (Ne), nitrogen (N), and / or hydrogen (H).

[0226] Deposition conditions include controlling 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 processing chamber. The precursor flow rate can be about 1-100 standard cubic centimeters per minute (sccm). The gas flow rate 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 can 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 can 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 can be about 0-1000 W using pulsed or continuous wave (CW) plasma. The processing chamber can 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 can be about 10-400 mTorr, and the TCP power can be about 200-500 W.

[0227] Table 1 shows non-limiting examples of processing regimes for the underlayer. In embodiment 1, the hydrocarbon precursor is methane (CH4) and the additional gas is He. In embodiment 2, the hydrocarbon precursor is CH4 and the process gas includes CO, H2, and He. [Table 1]

[0228] [Table 2]

[0229] Embodiment 2: Pulsed Bias Process for Use in Underlayer Deposition Additional processes have been developed to improve the etch resistance of the underlayer. Specifically, bias power has been used to modify the density of the underlayer. For example, deposition of the underlayer can involve a DC pulsed (e.g., in the range of about 1 Hz to about 10 kHz) bias (regardless of frequency) of about 1% to 99% DC. Such bias can be provided at any useful power, such as about 10 to 500 W.

[0230] It is understood that plasma pulses involve repeating periods, each lasting for a duration T. The duration T includes the duration for the pulse ON time (the duration the plasma is ON) and the duration for the plasma OFF time (the duration the plasma is OFF) for a given period. The pulse frequency is understood to be 1 / T. For example, if the 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 of the period T that the plasma is ON; therefore, the duty cycle or duty ratio is the pulse ON time divided by T. For example, if the plasma pulse period T = 100 μs, the pulse ON time is 70 μs (and therefore the duration of the plasma ON state within the period is 70 μs) and the pulse OFF time is 30 μs (and therefore the duration of the plasma OFF state within the period is 30 μs), then the duty cycle is 70%.

[0231] Further deposition conditions may include controlling precursor flow rates, gas flow rates, process pressure, temperature (e.g., ESC temperature), plasma power, bias power, pulse frequency, DC, and TCCT parameters in the processing 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 can 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 can 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 can be about 10-1000 W, using a pulsed plasma of 1-100% DC (100% indicates CW (e.g., 1-99%)). The RF bias power can be pulsed at a frequency less than 5000 Hz, for example, about 10-2000 Hz. The TCCT parameter can 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 processing chamber can be an ICP chamber or a CCP chamber.

[0232] Table 3 shows an example of a processing regime for a non-limiting underlayer formed using a pulsed bias process (embodiment 3). Using embodiment 3, various underlayer films were formed with bias powers of 70 W or 140 W and DC varied from 10 to 50%. Compared to films formed with 0 W bias, the pulsed bias process resulted in increased density (e.g., about 1.09 g / cm).3 Films with densities exceeding 1000 Å have been obtained. In this way, the density of the underlayer can be fine-tuned by applying a bias power. In some cases, a denser film can reduce the etch rate, thereby improving etch resistance. [Table 3]

[0233] Embodiment 3: Deposition of a doped underlayer The underlayer can include one or more dopants (e.g., non-carbon dopants when a hydrocarbon precursor is used). The dopants can be provided by using a hydrocarbon precursor (e.g., to provide carbon atoms) and a separate dopant precursor (e.g., to provide non-carbon atoms for doping). In another embodiment, the dopants are provided by 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 described herein.

[0234] The use of dopants can improve etch resistance in some cases. Any of the process regimes herein can be modified to incorporate dopants into the underlayer. For example, deposition can include the use of dopant precursors (e.g., any of those described herein), and the process regimes (e.g., flow rate, pressure, temperature, plasma power, bias power, pulse frequency, duty cycle, TCCT, etc.) for the precursors generally described herein can also be used for the dopant precursors.

[0235] For example, the flow rate of the precursors (e.g., hydrocarbon precursors and / or dopant precursors) can be about 1-100 sccm. The flow rate of the process gas 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 can 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 can be about 0.3 to 600 MHz (e.g., 13.56 MHz, 60 MHz, 27 MHz, 2 MHz, 400 kHz, or a combination thereof). The RF bias power can be about 0 to 1000 W using pulsed plasma with about 1 to 99% DC or CW plasma (100% DC). The RF bias power can be pulsed at a frequency less than 5000 Hz, for example, about 10 to 2000 Hz. The TCCT parameter can be 0.1 to 1.5. The processing chamber can be an ICP chamber or a CCP chamber.

[0236] In one example, the dopant is or includes nitrogen (N), forming 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.

[0237] Table 4 shows non-limiting examples of processing regimes for N-doped underlayers. In embodiment 4, the hydrocarbon precursor is CH4 and the N-containing precursor is N2. In embodiment 5, the hydrocarbon precursor is CH4 and the N-containing precursor is NH3. [Table 4]

[0238] In certain embodiments, the N-doped underlayer has N-H bonds (e.g., at about 3500-3100 cm in a Fourier transform infrared spectroscopy (FTIR) spectrum). -1 and / or approximately 1635cm -1 peak at about 2260-2222 cm in the FTIR spectrum) and / or C≡N bonds (e.g., -1 , approx. 2244cm -1 , and / or approximately 2183 cm -1 The peaks can be characterized by the presence of

[0239] The etch rate of the doped underlayer can be improved in some cases.

[0240] In another example, the dopant is or includes tungsten (W), providing a W-doped underlayer. Non-limiting W-containing precursors can include any 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.

[0241] In certain embodiments, the W-doped underlayer exhibits W—OH…HO bonds (e.g., at about 3500-3400 cm in the FTIR spectrum). -1 a peak at about 981 cm in the FTIR spectrum), a W=O bond (for example, -1 ) and / or WOW bonds (e.g., peaks at about 837 cm in the FTIR spectrum) -1 , 800cm -1 , and / or 702cm -1 The peaks can be characterized by the presence of

[0242] Table 5 shows non-limiting examples of processing regimes for W-doped underlayers. In each embodiment, the hydrocarbon precursor is CH4. In embodiment 6, the W-containing precursor is WF6 at a lower flow rate of 1 sccm. In embodiment 7, the W-containing precursor is WF6 at a higher flow rate of 2 sccm. In embodiment 8, the W-containing precursor is WF6 at a lower flow rate of 1 sccm but at a higher pressure of 50 mTorr. [Table 5]

[0243] The density of the doped underlayer can be increased. Table 6 shows the refractive index (RI at 633 nm), deposition rate (Dep. Rate), and density of the underlayer. As further seen in Example 7, co-flow of a hydrocarbon precursor and a W-containing dopant precursor increased the density and RI compared to a baseline deposited without a dopant precursor. [Table 6]

[0244] In yet another example, the dopant is or includes boron (B), providing a B-doped underlayer. Non-limiting B-containing precursors can include any 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, a B-doped underlayer is formed by co-flowing a hydrocarbon precursor and a B-containing precursor.

[0245] In certain embodiments, the B-doped underlayer contains B...OH bonds (e.g., at about 3200 cm in the FTIR spectrum). -1 a peak at about 1340 cm in the FTIR spectrum), a B-O bond (for example, -1 and / or BOH bonds (e.g., peaks at about 1194 cm in the FTIR spectrum). -1The peaks can be characterized by the presence of

[0246] Table 7 shows non-limiting examples of treatment regimes for B-doped underlayers. In embodiment 9, the hydrocarbon precursor is CH4 and the B-containing precursor is BCl3. In embodiment 10, the deposition conditions are the same as embodiment 9, but the film is further treated with H2. In Table 7, the H2 treatment conditions are pressure = 5 mTorr, TCP = 300 W, bias power = 100 W, H2 flow rate = 200 sccm, and treatment time = 1 second. [Table 7]

[0247] In certain embodiments, both the deposition rate and density of the doped underlayer can be increased. Table 8 shows the RI at 633 nm, deposition rate (Dep. Rate), and density of the underlayer. As can be seen in Example 9, co-flow of a hydrocarbon precursor and a B-containing dopant precursor increased the deposition rate and density compared to a baseline deposited without a dopant precursor. [Table 8]

[0248] As described herein, dopant precursors can be used during deposition to provide a doped underlayer, which in certain embodiments can have enhanced properties, such as improved etch resistance, etch rate, refractive index, deposition rate, and / or density.

[0249] Embodiment 4: Deposition of various hydrocarbon precursors The underlayer can be deposited using 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).

[0250] A variety of compounds can be used as hydrocarbon precursors. For example, hydrocarbon precursors can include aliphatic and aromatic compounds (e.g., alkanes, alkenes, alkynes, benzene, etc.), including their substituted forms. By using different hydrocarbon precursors, the type and amount of specific chemical bonds within the underlayer can be modified. For example, using unsaturated hydrocarbon precursors can increase the unsaturated bond content (e.g., increase the C=C and / or C≡C bond content), sp 2 Increased carbon content, increased sp carbon content, decreased saturated bond content (e.g., decreased C-C bond content), sp 3 The underlayer can be provided with a reduced carbon content and / or a reduced C-H bond content (e.g., compared to a film formed using an increased amount of saturated hydrocarbon precursor or a decreased amount of unsaturated hydrocarbon precursor). The selection of the hydrocarbon precursor can depend on various factors. In one non-limiting example, the hydrocarbon precursor includes a saturated precursor capable of providing sufficient H atoms (e.g., an increased C-H bond content compared to a C-C, C=C, or C≡C content). While not wishing to be limited by mechanism, selecting 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. However, in another non-limiting example, the hydrocarbon precursor includes an unsaturated precursor (e.g., an increased C-C, C=C, or C≡C bond content compared to a C-H bond content). While not wishing to be limited by mechanism, selecting such a precursor can improve etch resistance compared to the use of saturated precursors.

[0251] In certain embodiments, the underlayer may contain C═CH bonds (e.g., at about 3310 cm in an FTIR spectrum). -1 peak at about 1650-1600 cm in the FTIR spectrum) and / or C=C bonds (e.g., -1 or 1000~660cm -1 The peaks can be characterized by the presence of

[0252] Table 9 shows example processing regimes for non-limiting hydrocarbon precursors. In embodiment 1, the hydrocarbon precursor is CH4. In embodiment 11, the hydrocarbon precursor is acetylene (C2H2). In embodiment 12, the hydrocarbon precursor is propyne (C3H4). Different plasma types (e.g., ICP or CCP) can be used. In one example, ICP is used to allow for separate control of ion energy and ion density. Process conditions can be optimized to obtain similar films using either ICP or CCP. For example, CCP generally uses 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, thus achieving an equivalent processing environment to provide film properties similar to those obtained using ICP. Therefore, the processes herein can include the use of ICP or CCP with one or more processing 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]

[0253] In certain embodiments, the use of unsaturated hydrocarbon precursors improves etch resistance. Figure 7 shows the etch rates of 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 etching 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. As can be seen, the use of unsaturated hydrocarbon precursors (e.g., with triple bonds) improved the etch resistance of the underlayer compared to saturated hydrocarbon precursors (e.g., with only single bonds).

[0254] Embodiment 5: Use of highly EUV absorbing atoms The underlayer has a high patterning radiation absorption cross section (e.g., 1×10 7 cm 2 The dopant precursor may also include one or more atoms having an EUV absorption cross section of 1 / mol or greater. Such atoms include, for example, iodine (I). The iodine can be provided by any useful source. For example, the precursor used during deposition can 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), as well as benzene). Still other examples of 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).

[0255] Any of the deposition conditions herein can be combined to provide a beneficial underlayer. For example, a pulse bias process can be used with any of the precursors described herein (e.g., hydrocarbon precursors, dopant precursors, or combinations thereof). In another example, a dopant precursor can be combined with any of the hydrocarbon precursors described herein. Furthermore, the process can include the use of 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.

[0256] A combination of precursors can be selected to provide desired film properties. For example, a particular hydrocarbon precursor (e.g., an unsaturated hydrocarbon precursor) can be selected to improve etch resistance. A particular heteroatom can then be selected to 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.

[0257] Finally, still other non-carbon heteroatoms can be selected to provide films with enhanced EUV absorption (e.g., heteroatoms such as I, or 1×10 7 cm 2 / mol or more). The thickness of the underlayer can be controlled (e.g., about 5 nm or more).

[0258] Precursor (e.g., for the underlayer) The underlayers herein may employ any useful precursor or combination of precursors. Such precursors may include hydrocarbon precursors containing only carbon (C) and hydrogen (H) atoms, and the precursors may be saturated (having only a single bond) or unsaturated (having one or more double or triple bonds), and linear or cyclic. Still other precursors may contain one or more non-carbon heteroatoms, and such precursors are referred to herein as dopant precursors. Such dopant precursors may optionally contain a combination of carbon and non-carbon atoms. In some embodiments, any hydrocarbon precursor herein may be modified with one or more heteroatoms to provide a dopant precursor. The general term "precursor" may refer to a hydrocarbon precursor and / or a dopant precursor. Such precursors may optionally be gases, thereby enabling vapor-phase deposition within a process chamber.

[0259] The hydrocarbon precursor generally includes a carbon-containing precursor. In some cases, the hydrocarbon precursor includes only C and H atoms. The hydrocarbon precursor may be, for example, a precursor of the 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 include 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).

[0260] The hydrocarbon precursors are aliphatic compounds (e.g., C 1-10 Alkane, C 2-10 Alkene, C 2-10The hydrocarbon precursor may be an alkyne, including linear or cyclic forms thereof, or an aromatic compound (e.g., benzene, as well as polycyclic forms thereof). 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).

[0261] 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.

[0262] 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 (e.g., t-amyl alcohol, ethanol, propanol, etc.), polyols (e.g., diols such as ethylene glycol), ketones, aldehydes, ethers, esters, carboxylic acids, alkoxysilanes, oxolanes, or furans.

[0263] Si-containing precursors can include silanes, halosilanes, aminosilanes, alkoxysilanes, organosilanes, and the like. In certain embodiments, the Si-containing precursor is co-reacted with an oxidizing agent (e.g., any of those described herein, including O-containing precursors or oxocarbon precursors, CO and CO). Non-limiting Si-containing precursors include polysilanes (HSi-(SiH) n —SiH3) (n>0). Examples of silanes include silane (SiH4), disilane (Si2H6), and organosilanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-t-butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, and di-t-butyldisilane.

[0264] Halosilanes contain at least one halogen group and may or may not contain H and / or C 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 trimethylsilyl iodide.

[0265] 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 tetraaminosilanes (HSi(NH), HSi(NH), HSi(NH), and Si(NH), respectively), as well as substituted mono-, di-, tri-, and tetraaminosilanes, such as t-butylaminosilane, methylaminosilane, t-butylsilaneamine, bi(t-butylamino)silane (SiH(NHC(CH))(BTBAS), t-butylsilylcarbamate, SiH(CH)-(N(CH)), SiHCl(N(CH), (Si(CH)NH), etc. A further example of an aminosilane is trisilylamine (N(SiH).

[0266] 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 include mono-, di-, tri-, and tetraalkoxysilanes (HSi(OR), HSi(OR), HSi(OR), and Si(OR), respectively, where each R can independently be an optionally substituted alkyl or aryl), as well as substituted mono-, di-, tri-, and tetraalkoxysilanes, such as trimethoxymethylsilane (CHSi(OCH), (3-aminopropyl)trimethoxysilane (NH(CH)Si(OCH). 3)3), (3-aminopropyl)triethoxysilane (NH2(CH2)3Si(OCH2CH3)3), triethoxyvinylsilane (CH2=CHSi(OCH2CH3)3), triethoxyethylsilane (CH3CH2Si(OCH2CH3)3), trimethoxyphenylsilane (PhSi(OCH3)3), isobutyltriethoxysilane (i-BuSi(OCH2CH3)3), diacetoxydimethylsilane ((CH3)2Si(OCOCH3)2). Still other examples include tetraethoxysilane (Si(OCH2CH3)4), triethoxysilane (HSi(OCH2CH3)3), tetramethoxysilane (Si(OCH3)4), and trimethoxysilane (HSi(OCH3)3).

[0267] The N-containing precursor may contain at least one nitrogen atom, such as nitrogen gas (N), ammonia (NH), hydrazine (NH), methylamine, dimethylamine, ethylmethylamine, ethylamine, isopropylamine, t-butylamine, di-t-butylamine, cyclopropylamine, sec-butylamine, cyclobutylamine, isoamylamine, 2-methylbutan-2-amine, trimethylamine, diisopropylamine, diethylisopropylamine, di-t-butylhydrazine, and other amines (carbon-containing amines), as well as aromatic-containing amines such as aniline, pyridine, and benzylamine. Still other N-containing precursors may include nitriles (e.g., acetonitrile), amides, N-containing heterocyclic compounds, or aminoalcohols (e.g., ethanolamine). The amine may be primary, secondary, tertiary, or quaternary (e.g., tetraalkylammonium compounds). The N-containing precursor can contain heteroatoms other than N, for example, hydroxylamine, t-butyloxycarbonylamine, and Nt-butylhydroxylamine are N-containing precursors.

[0268] 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 (WCl), tungsten(V) chloride (WCl), and tungsten(VI) oxychloride (WOCl). In some embodiments, tungsten hexacarbonyl (W(CO)), mesitylenetungsten tricarbonyl ([CH(CH)]W(CO), bis(t-butylimido)bis(dimethylamino)tungsten(VI) ([(CH)CN]W[N(CH)]), bis(cyclopentadienyl)tungsten(IV) dihydride (HWCp), or other metalloorganic tungsten-containing precursors can be used.

[0269] B-containing precursors include boron halides (e.g., BC), boranes (e.g., B2H6), borates (e.g., B(OH)3), and organoboron compounds (e.g., B(CH3)3). Non-limiting B-containing precursors include diborane (B2H6), trimethylborate (B[OCH3]3), triethylborate (B[OCH2CH3]3), triisopropylborate (B[OCH(CH3)2]3), trimethylborane (B(CH3)3), triethylborane (B(C2H5)3), triphenylborane (BPh3), tetrakis(dimethylamino)diboron (B2(N(CH3)2)4), boron trifluoride (BF3), boron trichloride (BCl3), boron tribromide (BBr3), and boron iodide (BI3).

[0270] I-containing precursors include iodinated hydrocarbon compounds such as iodoacetylene (C2HI), diiodoacetylene (C2I2), vinyl iodide (C2H3I), iodomethane (CHI), diiodomethane (CHI2), 1,1-diiodoethylene (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).

[0271] 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).

[0272] Other heteroatoms, such as phosphorus (P), may be included. P-containing precursors may include phosphates, phosphines, phosphorus halides, organophosphorus compounds, etc. Non-limiting P-containing precursors include triethylphosphate (PO[OCH]), trimethylphosphate (PO[OCH]), trimethylphosphite (P(OCH)), trisdimethylaminophosphorus (P[N(CH)]), phosphorus trichloride (PCl), trismethylsilylphosphine (P[Si(CH)]), and phosphorus oxychloride (POCl).

[0273] Properties of the lower layer Any of the processes and precursors described herein can be used to provide a useful underlayer. The composition of the underlayer can be tailored to include specific atoms. In one embodiment, the underlayer includes about 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 includes the presence of unsaturated bonds (e.g., C=C, C≡C, and / or C≡N bonds). In yet other embodiments, the underlayer includes about 0.7-2.9 g / cm. 3 It has a density of

[0274] The underlayer can be characterized by increased etch selectivity and / or reduced undercutting compared to the control film. In other embodiments, the underlayer can be characterized by reduced line edge roughness and line width roughness and / or reduced dose-to-size compared to the control film. Non-limiting control films include films formed using saturated hydrocarbon precursors, films formed under pulsed bias, and / or films formed without dopants. In one example, the control film is an AHM formed using methane. In another example, the control film is an AHM formed using acetylene.

[0275] Patterning Structure The patterning structures (or films) herein can include an imaging layer on the surface of a hard mask or substrate, and an underlayer below the imaging layer, hi certain embodiments, the presence of the underlayer increases the radiation absorption and / or patterning performance of the imaging layer.

[0276] In general, photon absorption through a layer is depth-dependent. When a homogeneous layer or film is exposed to radiation, the lower portions of the layer are exposed to a lower dose of radiation compared to the upper portions of the same layer because fewer photons reach the lower portions. Therefore, to ensure sufficient and uniform exposure throughout the entire 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 cases, the underlayer can effectively generate more secondary electrons, allowing for better exposure of the lower portions of the patterning structure.

[0277] One or both of the underlayer and imaging layer may include a high absorption element. In one example, both the underlayer and imaging layer may have a high absorption of 1×10 for EUV absorption. 7 cm 2 / mol or more of high-absorption elements. The elements in each of the absorbing layer and imaging layer can be the same or different. In certain embodiments, the improved adhesion can reduce the required radiation dose to provide desired patterned features in the imaging layer and / or underlayer.

[0278] The imaging layer can comprise any useful resist, such as the metal-organic-based resists described herein. If the photoresist material used has a significant inorganic component, e.g., exhibits a predominantly metal-oxide framework, the underlayer can be advantageously a carbon-based film. If device features exist on the substrate to be patterned, thereby creating significant topography, another important function of the underlayer can be to overcoat and planarize the existing topography, allowing subsequent patterning steps to be performed on a flat surface with the entire pattern in focus. In such applications, the underlayer (or at least one of multiple underlayers) can be applied using dry deposition or spin-coating techniques. Layers include various AHM films with carbon- and hydrogen-based compositions, which may be doped with additional elements such as tungsten, boron, nitrogen, or fluorine.

[0279] The underlayer and the 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 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).

[0280] The precursor can be used to provide a radiation-sensitive, patternable film (or a patterned radiation-sensitive or photopatternable film). Such radiation can include EUV, DUV, or UV radiation provided by irradiating through a patterned mask, thereby resulting in patterned radiation. The film itself can be modified by exposure to such radiation to become radiation-sensitive or photosensitive. In certain embodiments, the precursor is an organometallic compound containing at least one metal center.

[0281] The precursor can have any useful number and type of ligands. In some embodiments, the ligands can be characterized by their ability to react in the presence of a back-reactant or in the presence of patterned radiation. For example, the precursor can include a ligand that reacts with a back-reactant, which can introduce a linkage (e.g., an -O- linkage) between the metal centers. In another example, the precursor can include a ligand that detaches in the presence of patterned radiation. Such EUV-labile ligands can include branched or straight-chain alkyl groups with beta hydrogens, as well as any of those described herein for R in formula (I) or (II).

[0282] The precursor can be any useful metal-containing precursor, such as an organometallic agent, a metal halide, or a capping agent (e.g., as described herein). In a non-limiting example, the precursor has the formula (I): M a R b (I) and M is a metal or atom with a high EUV absorption cross section, 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, and b≧1.

[0283] In another non-limiting example, the precursor has the formula (II): M a R b L c (II) and 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 reverse reactant; R and L together with M can optionally form a heterocyclyl group, or R and L together can optionally form a heterocyclyl group; a≧1, b≧1, and c≧1.

[0284] In some embodiments, each ligand in the precursor can be a ligand that reacts with a reverse reactant. In one example, the precursor comprises a structure having formula (II), where each R is independently L. In another example, the precursor comprises a structure having formula (IIa): M a L c (IIa) and 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 reverse reactant; two Ls 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.

[0285] For any formula herein, M represents a high patterning radiation absorption cross section (e.g., 1×10 7 cm 2M can be a metal, metalloid, or atom having an EUV absorption cross section of 1 / 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 periodate).

[0286] For any formula herein, each R is independently H, halo, optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy (e.g., -OR 1 , R 1 may be optionally substituted alkyl), optionally substituted alkanoyloxy, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, oxo, anionic ligand (e.g., oxide, chloride, hydride, acetate, iminodiacetate, propanoate, butanoate, benzoate, etc.), neutral ligand, or multidentate ligand.

[0287] In some embodiments, the optionally substituted amino is —NR 1 R 2 and each R 1 and R 2 are independently H or alkyl, or R 1 and R 2 taken together with the nitrogen atom to which each is attached form a heterocyclyl group, as defined herein. In other embodiments, an optionally substituted bis(trialkylsilyl)amino is —N(SiR 1 R 2 R 3 )2, and each R 1 , R 2 , and R 3 is independently an optionally substituted alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is —SiR 1 R 2 R 3 and each R 1 , R 2 , and R 3 is independently an optionally substituted alkyl.

[0288] In other embodiments, the formula is —NR 1 R 2 The first R (or the first L) and -NR 1 R 2 and each R 1 and R 2 are independently H or optionally substituted alkyl, or R from the first R (or first L) and R from the second R (or second L), 1 taken together with the nitrogen atom and metal atom to which each is attached, form a heterocyclyl group as defined herein. In yet another embodiment, the formula is -OR 1 The first R and -OR 1 and each R 1 are independently H or optionally substituted alkyl, or the first R to R 1 and R from the second R 1taken together with the oxygen atom and metal atom to which each is attached, form a heterocyclyl group as defined herein.

[0289] In some embodiments, at least one of R or L (e.g., in Formula (I), (II), or (IIa)) is an optionally substituted alkyl. Non-limiting alkyl groups include C, where n is 1, 2, 3, or more, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. n H 2n+1 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).

[0290] 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.

[0291] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (I), (II), or (IIa)) can contain a nitrogen atom. In certain embodiments, one or more R or L can be an optionally substituted amino, an optionally substituted monoalkylamino (e.g., —NR 1 H, R 1 is optionally substituted alkyl), optionally substituted dialkylamino (e.g., —NR 1 R 2 , 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).

[0292] In some embodiments, each R or L, or at least one R or L (e.g., in Formula (I), (II), or (IIa)) can include a silicon atom. In certain embodiments, one or more R or L can be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl)amino. Non-limiting R or L substituents can include, for example, -SiMe, -SiEt, -N(SiMe), and -N(SiEt).

[0293] 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 optionally substituted alkoxy or optionally substituted alkanoyloxy. Non-limiting R or L substituents include, for example, methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), acetate (-OC(O)-CH), and -O=C(CH)-CH=C(CH)-O-(acac).

[0294] Any of the formulas 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 can independently be H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is optionally substituted alkylene), optionally substituted phosphines (e.g., PR or RP-Ak-PR, where each R can independently be H, optionally substituted alkyl, optionally substituted hydrocarbyl, or optionally substituted aryl, and Ak is optionally substituted alkylene), optionally substituted ethers (e.g., OR, where each R can independently be 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.

[0295] Any formula herein can 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(R1 )-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 1 is independently H, optionally substituted alkyl, optionally substituted haloalkyl, or optionally substituted aryl, and each R 2 are independently H or optionally substituted alkyl, and R 3 and R 4 taken together form an optionally substituted heterocyclyl, Ak is an optionally substituted alkylene, and Ar is an optionally substituted arylene.

[0296] 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 replaced by 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 1 In certain embodiments, each R 1 , R2 , and R 3 are independently 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 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), dibutyltin, tetramethyl ... Diphenyltin (SnBu2Ph2), trimethyl(phenyl)tin (SnMe3Ph), trimethyl(phenylethynyl)tin, tricyclohexyltin hydride, tributyltin hydride (SnBu3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acac)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)(NMe2 )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-diazastanolidine-2-ylidene), or bis[bis(trimethylsilyl)amino]tin (Sn[N(SiMe3)2]2).

[0297] In other embodiments, the precursor comprises bismuth, such as BiR3, where each R is independently halo, optionally substituted C 1-12 Alkyl, mono-C 1-12 Alkylamino (e.g., -NR 1 H), Di-C 1-12Alkylamino (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 independently, 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 BiCl, BiMe, BiPh, Bi(NMe), Bi[N(SiMe)], and Bi(thd), where thd is 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0298] In other embodiments, the precursor comprises tellurium, such as TeR2 or TeR4, 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, 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)), hydride t-butyltellurium (Te(t-Bu)(H)), Te(OEt), bis(trimethylsilyl)tellurium (Te(SiMe)), and bis(triethylsilyl)tellurium (Te(SiEt)).

[0299] The precursor can include antimony, such as 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 , each R 1 and R 2 are independently H or optionally substituted C 1-12 Non-limiting antimony precursors include SbCl, Sb(OEt), Sb(On-Bu), and Sb(NMe).

[0300] Other precursors include indium precursors such as 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-, each R 4 and R 5 are independently H or C 1-12 Non-limiting indium precursors include InCp, where Cp is cyclopentadienyl, InCl, InMe, In(acac), In(CFCOCHCOCH), and In(thd).

[0301] The precursor can include iodine, such as RI, where R is iodine (I), optionally substituted C 1-12 alkyl, or periodate. Non-limiting iodine precursors include iodine gas (I), diiodomethane (CHI), and periodate.

[0302] Further precursors and non-limiting substituents are described herein. For example, the precursor can be any of the precursors having the structure of formula (I), (II), and (IIa) described above, or formula (III), (IV), (V), (VI), (VII), or (VIII) described below. Any of the substituents M, R, X, or L described herein can be used in any of formulas (I), (II), (IIa), (III), (IV), (V), (VI), (VII), or (VIII).

[0303] Still other exemplary EUV-sensitive materials, as well as 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 herein by reference in its entirety.

[0304] As described herein, the films, layers, and methods herein can be used with any useful precursor. In some cases, the precursor has the following formula (III): MX n (III) and a metal halide having the formula: Depending on the selection of M, M is a metal, X is halo, and n is 2 to 4. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary metal halides include SnBr4, SnCl4, SnI4, and SbCl3.

[0305] Another non-limiting precursor is represented by formula (IV): MR n (IV) and 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. Exemplary 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 more. Exemplary organometallic agents include SnMe4, SnEt4, TeR n , RTeR, 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, etc.

[0306] Another non-limiting precursor is represented by the following formula (V): ML n (V) and a capping agent having the formula: M is a metal and each L is independently an optionally substituted alkyl, amino (e.g., —NR 1 R 2 , R 1 and R 2where each of R can be H or alkyl as any described herein), alkoxy (e.g., —OR, where R is alkyl as any described herein), halo, or other organic substituent, and depending on the selection of M, n is 2-4. Exemplary metals for M include Sn, Te, Bi, or Sb. Exemplary ligands include 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-tertbutyl-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.

[0307] The precursor has the following formula (VI): R n MX m (VI) and a hydrocarbyl-substituted capping agent having the formula: M is a metal and R is a C with beta hydrogen 2-10R is alkyl or substituted alkyl, and X is a suitable leaving group 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, as long as m>0 (or 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 with a heteroatom substituent at the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I) or oxygen (—OH or —OR). X can also 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).

[0308] In various embodiments, the precursor comprises at least one alkyl group on each metal atom that can withstand the gas phase reaction, and other ligands or ions coordinated to the metal atom can be displaced by the counter-reactant. Thus, another non-limiting precursor is represented by formula (VII): M a R b L c (VII) and an organometallic agent having the formula: M is a metal, R is an optionally substituted alkyl, L is a ligand, ion, or other moiety that reacts with a reverse 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 , R 1 and R 2 wherein each of R can be H or alkyl as any described herein), alkoxy (e.g., —OR, where R is alkyl as any described herein), or halo (e.g., F, Cl, Br, or I). Exemplary agents include SnMeCl, SnMeCl, SnMeCl, SnMe(NMe), SnMe(NMe), SnMe(NMe), and the like.

[0309] In other embodiments, the precursor is a compound of formula (VIII): M a L c (VIII) and an organometallic agent having the formula: M is a metal and L is a ligand, ion, or other moiety that reacts with the counter-reactant, where a > 1 and c > 1. In certain embodiments, c = n-1 and n is 2, 3, or 4. In some embodiments, M is Sn, Te, Bi, or Sb. The counter-reactant preferably has the ability to replace the reactive moiety ligand or ion (e.g., L in the formulas herein) so as to link at least two metal atoms via a chemical bond.

[0310] In any embodiment herein, R is optionally substituted alkyl (e.g., C 1-10In one embodiment, the alkyl can be substituted with one or more halo (e.g., halo-substituted C, including one, two, three, four, or more halo, such as F, Cl, Br, or I). 1-10 Exemplary R substituents include C alkyl, preferably where n≧3. n H 2n+1 , and C with 2n+1≦x≦1 n F x H( 2n+1-x 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.

[0311] In any embodiment herein, L is an M-OH moiety, such as an amino (e.g., —NR 1 R 2 , R 1 and R 2 may be any moiety that is readily displaced by a reverse reactant to produce a moiety selected from the group consisting of: alkyl (e.g., —OR, where R is alkyl as described herein), carboxylate, halo (e.g., F, Cl, Br, or I), and mixtures thereof.

[0312] The reverse reactant preferably has the ability to replace a reactive moiety, ligand, or ion (e.g., L in the formulas herein) so as to link at least two metal atoms via a chemical bond. Exemplary reverse reactants include oxygen-containing reverse 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 reverse reactant reacts with the precursor by forming oxygen bridges between adjacent metal atoms. Other potential reverse 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 may be utilized to incorporate iodine into the film.

[0313] Still other non-limiting reverse 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.

[0314] Exemplary organometallic agents include SnMeCl, (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 similar 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.

[0315] In some embodiments, the patterning structures are formed by exposing hydroxyl groups or hydroxyl-terminated SnO. x Without limiting the mechanism, function, or utility of the present technology, a surface layer or film comprising hydroxyl-terminated SnO x It is believed that the SnO layer can 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 and resolution to EUV or other radiation depend on the thickness, density, and short-range charge transport properties of the SnO layer. x In various embodiments, SnO 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.

[0316] In some embodiments, hydroxyl-terminated SnO x The layer is deposited on the surface of the substrate by vapor deposition. In such a method, the deposition is carried out using a Sn-X nwith an oxygen-containing reverse 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 reverse reactant may be selected from the group consisting of water, hydrogen peroxide, formic acid, alcohol, oxygen, ozone, and combinations thereof.

[0317] Suitable vapor 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 a Sn-X n The CVD method involves simultaneously flowing SnO and an oxygen-containing counter-reactant. x Materials and processes useful herein for depositing the layers 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.

[0318] A surface activation operation can be used to activate the surface for future operations, e.g., SiO xFor surfaces, water or oxygen / hydrogen plasma can be used to form hydroxyl groups on the surface. For carbon- or hydrocarbon-based surfaces, water, hydrogen / oxygen, or CO2 plasma, or ozone treatment can be used to form carboxylic acid and / or hydroxyl groups. Such approaches have proven important for improving adhesion of resist features to the substrate, which in some cases may peel or lift off in the solvent used for development.

[0319] Adhesion can also be enhanced by inducing roughness on 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 be used to first create a rough surface. The surface can then be terminated with desired surface functional groups (e.g., hydroxyl and / or carboxylic acid groups) as described above. On carbon, a combination approach can be used, using chemically reactive oxygen-containing plasmas such as CO2, O2, or HO (or a mixture of H2 and O2) to etch away a thin layer of film with localized inhomogeneities and simultaneously terminate with -OH, -OOH, or -COOH groups. This approach 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 and chemically activating the substrate surface for direct adhesion to inorganic metal oxide-based resists or as an intermediate surface modification for further functionalization.

[0320] The patterning structure can comprise any useful substrate. For example, a subsequent wafer can be prepared with a substrate surface of the desired material, with the top material being the layer to which the resist pattern will be transferred. While the choice of material can vary depending on the integration, it is generally desirable to select a material that can be etched with high selectivity to (i.e., much faster than) the EUV resist or imaging layer. In some embodiments, the substrate is a hard mask 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), or other materials. x ), silicon oxide (e.g., SiO containing SiO x ), silicon oxynitride (e.g., SiO x N y ), silicon oxycarbide (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 ), hafnium oxide (e.g., HfO), zirconium oxide (e.g., ZrO), antimony oxide (SbO), zinc oxide (ZNO), indium oxide (InO), tellurium (Te) and tellurium oxide (TeO), and aluminum oxide (e.g., AlO). Suitable substrate materials include various carbon-based films (e.g., ashable hard masks (AHMs), silicon-based films (e.g., SiO x , SiC x , SiO x C y , SiO x N y , SiO x C y N z ), a-Si:H, poly-Si, or SiN), or any other (generally sacrificial) film applied to facilitate the patterning process. For example, the substrate is preferably a SnO substrate, such as SnO. xIn various embodiments, the layer may be 1 nm to 100 nm thick, or 2 nm to 10 nm thick.

[0321] In various embodiments, the surface (e.g., of a substrate and / or film) contains exposed hydroxyl groups on its surface. Generally, the surface can be any surface that contains or has been treated to provide an exposed hydroxyl surface. Such hydroxyl groups can be formed on the surface by surface treatment of the substrate using oxygen plasma, water plasma, or ozone. In other embodiments, the surface of the film can be treated to provide exposed hydroxyl groups, over which a capping layer can be applied. In various embodiments, the hydroxyl-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.

[0322] The embodiments disclosed herein describe the deposition of materials onto a substrate, such as a wafer, substrate, or other workpiece. The workpiece may be of various shapes, sizes, and materials. In this application, the terms "semiconductor wafer," "wafer," "substrate," "wafer substrate," and "partially fabricated integrated circuit" are used interchangeably. Those skilled in the art will understand that the term "partially fabricated integrated circuit" can refer to a silicon wafer during any of the many stages of integrated circuit fabrication. 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.) listed herein relate to the processing of 300 mm diameter substrates or processing chambers configured to process 300 mm diameter substrates and can be appropriately scaled for other sized substrates or chambers. In addition to semiconductor wafers, other workpieces that may be used in the embodiments disclosed herein include various articles, such as printed circuit boards. The processes and apparatus can be used in the fabrication of semiconductor devices, displays, and the like.

[0323] Lithography Process EUV lithography utilizes an EUV resist, which can be a polymer-based, chemically amplified resist applied by a liquid-based spin-on technique or a metal oxide-based resist applied by a dry vapor deposition technique. Such an EUV resist can include any EUV-sensitive film or material described herein. The lithography method can include, for example, patterning the resist by exposing the EUV resist to EUV radiation to form a photopattern, and subsequently developing the pattern by removing portions of the resist according to the photopattern to form a mask.

[0324] While the present disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, it should be understood that the present disclosure is also applicable to other next-generation lithography techniques. In addition to EUV, which includes the standard 13.5 nm EUV wavelength currently in use and under development, the most relevant radiation sources for such lithography are DUV (deep UV), which generally refers to the use of excimer laser sources at 248 nm or 193 nm; X-ray, which formally includes EUV at the lower energy range of 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 of those described herein) to form a metal oxide film (e.g., a layer comprising a network of metal oxide bonds, which may also include other non-metallic and non-oxygen groups) as an imaging / PR layer on the surface of the substrate. Specific methods may depend on the specific materials and applications used in the semiconductor substrate and final semiconductor device. Therefore, the methods described herein are merely exemplary of methods and materials that can 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.

[0325] Directly photopatternable EUV resists can be composed of or include metals and / or metal oxides. Metals / metal oxides hold great promise in that they can enhance EUV photon absorption, generate secondary electrons, and / or exhibit increased 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 onto 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 the fine features.

[0326] Dry development techniques have been proposed to overcome these issues by eliminating substrate delamination and interfacial defects. Dry development presents its own challenges, including 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 result in rounded PR corners due to longer exposure times under etching gases, increasing line CD variation in the subsequent transfer etch step. Additional processes used during lithography are described in detail below.

[0327] Deposition processes, including dry deposition As described herein, the present disclosure provides methods for fabricating underlayers and imaging layers on semiconductor substrates, which can be patterned using EUV or other next-generation lithography techniques. In some embodiments, dry deposition can use any useful precursor (e.g., hydrocarbon precursors, dopant precursors, metal halides, capping agents, or organometallic agents described herein) to provide the underlayers and imaging layers. Methods include generating a polymerized organometallic material in vapor and depositing it onto the underlayer. In other embodiments, spin-on formulations can be used. The deposition process can include applying an EUV-sensitive material as a resist film or an EUV-sensitive film.

[0328] Such EUV-sensitive films include materials that undergo a transformation upon exposure to EUV, such as the loss of bulky pendant ligands bonded to metal atoms in low-density M-OH-rich materials, allowing crosslinking to higher-density MOM-bonded metal oxide materials. In other embodiments, EUV exposure further promotes crosslinking between ligands bonded to metal atoms, thereby providing higher-density MLM-bonded organometallic materials (where L is a ligand). In yet other embodiments, EUV exposure results in the loss of ligands, providing M-OH materials that can be removed by a positive tone developer.

[0329] 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 dissolving either the unexposed or exposed regions, or selectively depositing 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 is recognized that the hydrophilic properties of the exposed and unexposed regions are interrelated). For example, material removal can be achieved by exploiting differences in the film's chemical composition, density, and crosslinking. Removal can be by wet or dry processing, as further described herein.

[0330] The thickness of the EUV-patternable film formed on the surface of a substrate can vary depending on the surface characteristics, materials used, and processing conditions. In various embodiments, the film thickness can range from about 0.5 nm to about 100 nm. Preferably, the film has a thickness sufficient to absorb a majority of the EUV light under EUV patterning conditions. For example, the overall 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 disclosure, it is believed that, unlike wet spin-coating processes of the art, the processes of the present disclosure have fewer limitations on the surface adhesion properties of the substrate and therefore can be applied to a wider variety of substrates. Furthermore, as discussed above, the deposited film can closely conform to surface features, providing advantages when forming a mask over a substrate, such as a substrate with underlying features, without "filling" or planarizing such features.

[0331] The film (e.g., underlayer and / or imaging layer) can be comprised of a metal oxide layer deposited in any useful manner. Such a metal oxide layer can 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) combined with a reverse 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 can be used as a film, an adhesion layer, or a capping layer.

[0332] Optionally, the metal oxide layer can include a hydroxyl-terminated metal oxide layer, which can be deposited by using a capping agent (e.g., any described herein) in conjunction with an oxygen-containing reverse reactant. Such a hydroxyl-terminated metal oxide layer can be used 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.

[0333] Exemplary deposition techniques (e.g., for films, underlayers, or imaging layers) include any described herein, such as ALD (e.g., thermal ALD and plasma-enhanced ALD), spin-coat deposition, PVD including PVD co-sputtering, CVD (e.g., PE-CVD or LP-CVD), sputter deposition, e-beam deposition including e-beam co-evaporation, or the like, or combinations thereof, such as ALD with a CVD component, or discontinuous ALD-like processes, such as precursors and back-reactants, separated in either time or space.

[0334] Further description of precursors and methods for their deposition as EUV photoresist films applicable to the present disclosure can be found in International Application No. PCT / US19 / 31618, entitled "METHODS FOR MAKING EUV PATTERNABLE HARD MASKS," filed May 9, 2019, and published as International Publication No. WO2019 / 217749. In addition to the precursors and back-reactants, the thin films can include optional materials to modify the film's chemical or physical properties, such as to modify its sensitivity to EUV or enhance its etch resistance. Such optional materials may be introduced, such as by doping during vapor formation before deposition on the substrate, after film deposition, or both. In some embodiments, introducing a mild remote H plasma can, for example, replace some Sn-L bonds with Sn-H, thereby increasing the reactivity of the resist under EUV.

[0335] Generally, the method can include mixing a vapor flow of a precursor (e.g., a metal-containing precursor such as an organometallic agent) with an optional vapor flow of a reverse reactant to form a polymerized organometallic material, and depositing the organometallic material onto a surface of a semiconductor substrate. In some embodiments, mixing the precursor and the optional reverse reactant can form the polymerized organometallic material. As will be appreciated by those skilled in the art, the mixing and deposition aspects of the process can be simultaneous in a substantially continuous process.

[0336] In an exemplary continuous CVD process, two or more gas streams of precursors and optional reverse reactants are introduced into a deposition chamber of a CVD apparatus via separate inlet paths, where they mix and react in the gas phase to form a coagulated polymeric material or film on a substrate (e.g., via metal-oxygen-metal bond formation). The gas streams can be introduced using, for example, separate injection inlets or a dual plenum showerhead. The apparatus is configured so that the precursor and optional reverse reactant flows mix within the chamber, thereby allowing the precursor and optional reverse reactant to react and form a polymerized organometallic material or film (e.g., a metal oxide coating or coagulated polymeric material via metal-oxygen-metal bond formation, etc.).

[0337] 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.

[0338] To deposit cohesive polymeric materials, CVD processes are generally performed at reduced pressures, such as 10 mTorr to 10 Torr. In some embodiments, the process is performed at 0.5 to 2 Torr. The substrate temperature is preferably at or below the reactant flow temperature. 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 the 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 from such gas-phase reactions become heavier in molecular weight as metal atoms are crosslinked by the co-reactant, and then condense or, in some cases, deposit onto the substrate. In various embodiments, the steric hindrance of the bulky alkyl groups further prevents the formation of a densely packed network, resulting in a low-density film with increased porosity.

[0339] A potential advantage of using dry deposition methods is the ease with which the film's composition can be adjusted as it grows. In CVD processes, this can be achieved by varying the relative flows of the first and second precursors during deposition. Deposition can occur at pressures between 0.01 Torr and 100 Torr and between 30°C and 200°C, but more commonly at pressures between about 0.1 Torr and 10 Torr.

[0340] Films (e.g., metal oxide coatings or aggregated polymeric materials, such as via metal-oxygen-metal bond formation) can also be deposited by ALD processes. For example, precursors and optional back-reactants are introduced at separate times, representing ALD cycles. The precursors react on the surface, forming up to a monolayer of material at a time in each cycle. This can allow for excellent control over 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 can be between 0°C and 250°C, or between ambient temperature (e.g., 23°C) and 150°C. The process can be a thermal process, or preferably, plasma-assisted deposition.

[0341] 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 using a metal alkoxide precursor having a first metal (e.g., Sn) and a silyl-based precursor having a different second metal (e.g., Te).

[0342] The process herein can be used to achieve surface modification. In several iterations, precursor vapors can be passed over the wafer. The wafer can be heated to provide thermal energy for the reaction to proceed. In several iterations, heating can be from about 50°C to about 250°C. In some cases, pulses of precursors separated by pumping and / or purging steps can be used. For example, a first precursor can be pulsed between pulses of a second precursor, resulting in ALD or ALD-like growth. In other cases, both precursors can be flowed simultaneously. Examples of elements useful for surface modification include I, F, Sn, Bi, Sb, Te, and oxides or alloys of these compounds.

[0343] 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. Following deposition, the films can be prepared using M as described elsewhere herein. a R b L c The surface can be capped with an alkyl-substituted precursor in the form of a tetrakis(dimethylamino)tin. A back-reactant can be used to better remove the ligands, and multiple cycles can 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 generate a thin film of SnOx. Possible chemistries include growing SnO2 by cycling a back-reactant such as tetrakis(dimethylamino)tin and water or O2 plasma. After growth, a capping agent can be used. For example, isopropyltris(dimethylamino)tin vapor can be flowed over the surface.

[0344] The deposition process can be used on any useful surface. As referred to herein, the "surface" refers to the surface on which the film of the present technology is deposited or the surface that is exposed to EUV during processing. Such a surface can be on a substrate (e.g., on which the film is deposited), on a film (e.g., on which a capping layer can be deposited), on a hard mask, or on an underlayer.

[0345] Any useful substrate can be used, including any material structure suitable for lithographic processing, particularly for the manufacture of integrated circuits and other semiconductor devices. In some embodiments, the substrate is a silicon wafer. The substrate can be a silicon wafer on which features having irregular surface topography ("underlying topographical features") are formed.

[0346] Such underlying topographical features may include areas from which material has been removed (e.g., by etching) or added (e.g., by deposition) during processing prior to performing the methods of the present technology. Such pre-processing may include other processing methods in the methods of the present technology or in an iterative process, whereby two or more layers of features are formed on the 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 that deposit photolithographic films onto the surface of a substrate using spin-casting techniques. Such advantages may stem from the conformity of the films of the present technology to underlying features without "filling" or planarizing such features, and the ability to deposit films on a wide variety of material surfaces.

[0347] EUV exposure process EUV exposure of the membrane can provide EUV-exposed regions with activated reactive centers containing a metal atom (M) resulting from an EUV-mediated cleavage event. Such reactive centers can include a dangling metal bond, a M-H group, a cleaved M-ligand group, a dimerized M-M bond, or a M-O-M bridge.

[0348] The EUV exposure can have a wavelength in a vacuum atmosphere ranging from about 10 nm to about 20 nm, for example, 10 nm to 15 nm, for example, 13.5 nm. In particular, patterning can provide EUV-exposed regions and EUV-unexposed regions to form a pattern.

[0349] The present technology can include patterning using EUV, DUV, or e-beam. In such patterning, radiation is focused on 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 can include multiple exposed and unexposed regions, forming a pattern that corresponds to the formation of transistors or other features of a semiconductor device, formed by adding or removing material from the substrate during subsequent processing of the substrate. EUV, DUV, and e-beam radiation methods and equipment useful herein include methods and equipment known in the art.

[0350] In some EUV lithography techniques, an organic hard mask (e.g., a PECVD amorphous hydrogenated carbon ashable hard mask) is patterned using a conventional photoresist process. During photoresist exposure, EUV radiation is absorbed by the resist and the underlying substrate, generating high-energy photoelectrons (e.g., approximately 100 eV) and then a cascade of low-energy secondary electrons (e.g., approximately 10 eV) that diffuse laterally by a few nanometers. These electrons increase the extent of chemical reactions within the resist and its EUV dose sensitivity. However, an essentially random secondary electron pattern is superimposed on the optical image. This unwanted secondary electron exposure results in loss of resolution, observable line edge roughness (LER), and linewidth variations in the patterned resist. These defects are then replicated in the patterned material during subsequent pattern-transfer etching.

[0351] Disclosed herein is a vacuum-integrated metal hard mask process and associated vacuum-integrated hardware that combines film formation (deposition / condensation) and optical lithography, resulting in significantly improved EUV lithography (EUVL) performance, e.g., reduced line edge roughness.

[0352] 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 thin films of metal-containing films, such as photosensitive metal salts or metal-containing organic compounds (organometallic compounds), that have strong absorption in EUV (e.g., at wavelengths on the order of 10 nm to 20 nm), for example, at the wavelength of an EUVL light source (e.g., 13.5 nm = 91.8 eV). This film photodecomposes upon EUV exposure and forms a metal mask, which is a pattern transfer layer, during subsequent etching (e.g., in a conductor etching tool such as a Lam 2300™ Kiyo®).

[0353] Following deposition, the EUV-patternable thin film is patterned by exposure to a beam of EUV light, typically under a relatively high vacuum. For EUV exposure, the metal-containing film can be deposited in a chamber integrated with the lithography platform (e.g., a wafer stepper such as the TWINSCAN® NXE:3300B platform supplied by ASML, Veldhoven, The Netherlands) and transferred under vacuum so that it is not reactive prior to exposure. Integration with the lithography tool is facilitated by the fact that EUVL also requires significantly reduced pressure, given the strong optical absorption of incident photons by ambient gases such as HO and O. In other embodiments, photosensitive metal film deposition and EUV exposure can occur in the same chamber.

[0354] 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 by using one or more dry development processes (e.g., halide chemistries). In other embodiments, M-M bonds can be selectively removed by a wet development process, for example, using hot ethanol and water, to produce soluble M(OH) n In yet other embodiments, the EUV-exposed regions are removed by wet development (e.g., using a positive developer). In some embodiments, the EUV-unexposed regions are removed by dry development.

[0355] Dry development processes can include the use of halides, such as HCl- or HBr-based processes. While this disclosure is not limited to a particular theory or mechanism of operation, it is understood that the approach leverages the chemical reactivity of dry-deposited EUV photoresist films with clean chemicals (e.g., HCl, HBr, and BCl3) to form volatile products using vapor or plasma. Dry-deposited EUV photoresist films can be removed at etch rates of up to 1 nm / sec. Rapid removal of dry-deposited EUV photoresist films with these chemistries is applicable to chamber cleaning, backside cleaning, bevel cleaning, and PR development. Films can be removed using vapor at various temperatures (e.g., HCl or HBr at temperatures above -10°C, or BCl3 at temperatures above 80°C), although plasma can also be used to further accelerate or enhance reactivity.

[0356] Plasma processes include transformer coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP) using equipment and techniques known in the art. For example, the process can 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 can be 30°C to 300°C (e.g., 30°C to 120°C) for a time of 1 to 3000 seconds (e.g., 10 seconds to 600 seconds), with a flow rate of 100 to 1000 standard cubic centimeters per minute (sccm), e.g., about 500 sccm.

[0357] 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 and contacted with the patterned EUV photoresist on the wafer substrate layer. Suitable plasma power, without bias, can range from 100 W to 500 W. These conditions are suitable for some process reactors, such as the Kiyo etch tool available from Lam Research, Inc., Fremont, California. However, it should be understood that a wider range of process conditions can be used depending on the capabilities of the process reactor.

[0358] In a thermal development process, the substrate is exposed to a dry development chemical (e.g., a Lewis acid) in a vacuum chamber (e.g., an oven). A suitable chamber can include a vacuum line, a dry development hydrogen halide chemical gas (e.g., HBr, HCl) line, and a heater for temperature control. In some embodiments, the interior of the chamber can 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 used in the thermal processes of the present disclosure without the risk of removal by plasma exposure.

[0359] The process conditions for dry development can be about 10 seconds to 1 minute without plasma, reactant flow rate of 100 sccm to 500 sccm (e.g., 500 sccm HBr or HCl), temperature of -10°C to 120°C (e.g., -10°C), and pressure of 1 mTorr to 500 mTorr (e.g., 300 mTorr), depending on the photoresist film and its composition and properties.

[0360] In various embodiments, the disclosed methods combine all dry steps: film deposition, vapor deposition formation, (EUV) lithography photopatterning, and dry development. In such a process, the substrate can be directly directed to a dry development / etch chamber following photopatterning in an EUV scanner. Such a process can avoid the material and productivity costs associated with wet development. The dry process can allow for additional tuning and further improve CD control and / or scum removal.

[0361] In various embodiments, the EUV photoresist containing some amount of metal, metal oxide, and organic components has the formula R x Z y Dry development can be achieved by heat, plasma (including possible photoactivated plasma, e.g., lamp-heated or UV-lamp-heated), or a combination of heat and plasma methods, while flowing a dry development gas containing a compound of the formula: R = B, Al, Si, C, S, SO, x > 0, Z = Cl, H, Br, F, CH4, y > 0. x Z yThe species can selectively remove the exposed material, leaving the unexposed counterpart as a mask, resulting in a positive tone. In some embodiments, the exposed portions of the organotin oxide-based photoresist film are removed by dry development in accordance with the present disclosure. Positive tone dry development can be achieved by selective dry development (removal) of the EUV-exposed areas by exposure to a flow containing hydrogen halide or hydrogen and a halide (including HCl and / or HBr) without plasma application, or to a flow of H and Cl and / or Br using remote plasma or plasma-generated UV radiation to generate radicals.

[0362] Wet development methods can also be used. In certain embodiments, such wet development methods are used to remove EUV-exposed regions to provide a positive or negative photoresist. Exemplary, non-limiting wet development methods can include the use of an alkaline developer (e.g., an aqueous alkaline developer), such as a developer containing ammonium, e.g., ammonium hydroxide ([NH4OH), an ammonium-based ionic liquid, e.g., tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), or other quaternary alkylammonium hydroxides, an organic amine, e.g., mono-, di-, and tri-organic amines (e.g., dimethylamine, diethylamine, ethylenediamine, triethylenetetramine), or an alkanolamine, e.g., monoethanolamine, diethanolamine, triethanolamine, or diethyleneglycolamine. In other embodiments, the alkaline developer can be a developer containing a nitrogen-containing base, e.g., a compound of formula R N1 NH2, R N1 R N2 N.H., R. N1 R N2 R N3 N or R N1 R N2 R N3 R N4 N + X N1- and compounds having R N1 , RN2 , R N3 , and R N4 is independently an organic substituent (e.g., an optionally substituted alkyl, an optionally substituted hydroxyalkyl, or any of those described herein), or two or more organic substituents that can be linked together; and X N1- OH - , F - , Cl - , Br - , I - or other quaternary ammonium cation species known in the art. These bases may also include heterocyclyl nitrogen compounds known in the art, some of which are described herein.

[0363] Other development methodologies 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 such as 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 such as glycol ethers (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), as well as combinations thereof.

[0364] In certain embodiments, the positive developer is an aqueous alkaline developer (e.g., comprising NHOH, TMAH, TEAH, TPAH, or TBAH). In other embodiments, the negative 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 a combination thereof).

[0365] Post-application process The methods herein can include any useful post-application process, as described below.

[0366] In the backside and bevel cleaning process, the vapor and / or plasma can be confined to specific areas of the wafer to ensure removal of only the backside and bevel without degrading the film on the front side of the wafer. The dry-deposited EUV photoresist film being removed is generally composed of Sn, O, and C, but the same cleaning approach can be extended to films of other metal oxide resists and materials. In addition, this approach can also be used for film strip and PR rework.

[0367] Suitable process conditions for dry bevel edge and backside cleaning can be reactant flow rates of 100 sccm to 500 sccm (e.g., 500 sccm HCl, HBr, or H and Cl or Br, BCl, or H) for a time of about 10 seconds to 20 seconds, depending on the photoresist film and its composition and properties; temperatures of -10°C to 120°C (e.g., 20°C); pressures of 20 mTorr to 500 mTorr (e.g., 300 mTorr); and plasma powers 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 available from Lam Research, Inc., Fremont, California; however, it should be understood that a wider range of process conditions can be used depending on the capabilities of the process reactor.

[0368] Photolithography processes typically involve one or more bake steps to promote the chemical reactions necessary to create chemical contrast between exposed and unexposed areas of the photoresist. For 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 during these bake steps, as well as the introduction of additional reactive gas components into the atmosphere, can help further reduce dose requirements and / or improve pattern fidelity.

[0369] 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 exposure (e.g., post-exposure bake (PEB)) and / or 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 width roughness (LER / LWR) after subsequent dry development. Such treatments can involve thermal processes that control temperature, gas atmosphere, and moisture, resulting in improved dry development performance in subsequent processing. In some cases, remote plasma may be used.

[0370] For post-application treatments (e.g., PAB), thermal processes that control 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 moisture can be used after deposition and before exposure to alter the composition of unexposed metal and / or metal oxide photoresists. This alteration can increase the EUV sensitivity of the material, thereby achieving reduced dose-to-size and edge roughness after exposure and dry development.

[0371] For post-exposure treatment (e.g., PEB), a thermal process can be used to control 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 moisture to alter the composition of both the unexposed and exposed photoresists. This alteration can increase the difference in composition / material properties between the unexposed and exposed photoresists and the difference in the etch rates of dry development etch gases between the unexposed and exposed photoresists. This can achieve higher etch selectivity. Improved selectivity can result in squarer PR profiles with improved surface roughness and / or less photoresist residue / scum. In certain embodiments, PEB can be performed in air, optionally in the presence of moisture and CO.

[0372] For post-development treatments (e.g., post-develop bake or PDB), the composition of the unexposed photoresist can be altered using a thermal process that controls 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., using UV), and moisture. In certain embodiments, the conditions also include the use of plasma (e.g., containing O, O, Ar, He, or mixtures thereof). This alteration can increase the hardness of the material, which can be beneficial if the film is used as a resist mask in etching the underlying substrate.

[0373] In these cases, an alternative embodiment can replace the thermal process with a remote plasma process, increasing the reactive species, lowering the energy barrier to the reaction, and increasing productivity. Remote plasma can generate more reactive radicals, thus lowering the reaction temperature / time for processing, leading to increased productivity.

[0374] Therefore, one or more processes can be applied to modify the photoresist itself, increasing the selectivity of dry development. This thermal or radical modification can increase the contrast between unexposed and exposed materials, thus increasing the selectivity of the subsequent dry development step. The resulting difference between the material properties of unexposed and exposed materials can be controlled by adjusting process conditions, including temperature, gas flow, moisture, pressure, and / or RF power. Because the process latitude enabled by dry development is broad and not limited by the solubility of materials in wet developer solvents, more aggressive conditions can be applied, further increasing the achievable material contrast. The resulting high material contrast allows for a wider process window for dry development, thereby increasing productivity, reducing costs, and improving defect performance.

[0375] A practical limitation of wet-developable resist films is their limited bake temperature. Because wet development relies on the solubility of the material, heating to temperatures above 220 °C, for example, can significantly increase the degree of crosslinking in both the exposed and unexposed regions of a metal-containing PR film, rendering both regions insoluble in the wet development solvent. As a result, the film can no longer be reliably wet-developed. For dry-developable resist films, the difference in etch rate (i.e., selectivity) between the exposed and unexposed regions of the PR is utilized to remove only the exposed or unexposed portions of the resist. Therefore, the processing temperature during PAB, PEB, or PDB can be varied over a much wider window to adjust and optimize the processing process. For example, the temperature ranges are approximately 90 °C to 250 °C, e.g., 90 °C to 190 °C, for PAB, and approximately 170 °C to 250 °C or higher, e.g., 190 °C to 240 °C, for PEB and / or PDB. It has been shown that increasing the processing temperature within the stated ranges decreases the etch rate and increases etch selectivity.

[0376] In certain embodiments, the PAB, PEB, and / or PDB treatments can be performed at a gas atmosphere flow ranging from 100 sccm to 10,000 sccm, with a water content ranging from a few percent up to 100% (e.g., 20% to 50%), at a pressure between atmospheric pressure and vacuum, for a duration of about 1 to 15 minutes, e.g., about 2 minutes.

[0377] These findings can be used to adjust process conditions to tailor or optimize processes for specific materials and situations. For example, the selectivity achieved for a given EUV dose using a PEB thermal treatment at 220°C to 250°C in air at approximately 20% humidity for approximately 2 minutes can be similar to that achieved at 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 lower the required EUV dose. Alternatively, if higher selectivity is required and a higher dose can be tolerated, it is possible to obtain much higher selectivity (up to 100x exposed vs. unexposed) than is possible in wet development situations.

[0378] Still other steps may include in situ metrology capable of assessing physical and structural properties (e.g., critical dimensions, film thickness, etc.) during the photolithography process. Modules for performing in situ metrology include, for example, a scatterometry module, an ellipsometry module, a downstream mass spectrometry module, and / or a plasma-enhanced downstream optical emission spectroscopy module.

[0379] 3A illustrates the interaction of an oxidizing gas with activatable moieties on and within a bake-sensitive underlayer underlying an imaging layer having exposed and unexposed regions. The bake-sensitive underlayer includes a top underlayer surface and a bottom underlayer surface, and the imaging layer thereover includes a top imaging layer surface and a bottom imaging layer surface. The oxidizing gas diffuses from the top imaging layer surface through the imaging layer and also through the bottom imaging layer surface, oxidizing activatable moieties, such as C-H bonds (shown), on and within the top surface of the bake-sensitive underlayer and releasing reactive species, such as oxygen radicals. These released reactive species can then diffuse into the imaging layer through the bottom imaging layer surface and from the top underlayer surface into the imaging layer, where they can interact with the imaging layer, e.g., react with the imaging layer to promote crosslinking. While crosslinking can occur to some extent in both the exposed and unexposed regions of the imaging layer, crosslinking occurs preferentially and more strongly in the exposed regions. The contribution of reactive species generated in and on the underlayer results in more effective and efficient crosslinking than reactive species generated by oxidizing gas alone, heating alone, or delivering oxidizing gas while heating the substrate pedestal. Preferential crosslinking in exposed regions can be exploited to 1) improve patterned structure properties such as dose-to-size reduction, 2) increase adhesion, and 3) sharpen the contrast between exposed and unexposed regions of the photoresist.

[0380] FIG. 3B is a bar chart showing CH loss resulting from post-exposure baking of patterned structures having underlayers treated with various amounts of oxidizing gas, according to certain disclosed embodiments. Four different underlayers (SHD2, S0, SHD1, and SHD DC10) with activatable moieties and a control (a silicon wafer without a Si-underlayer) were post-exposure baked in the presence of various amounts of oxygen, ranging from 0% to 50%, as the oxidizing gas. The processing temperature was 210° C. for 240 seconds. CH loss was measured by FTIR, with an increase in CH loss indicating a reduction in dose versus size. The data shows that, depending on the underlayer selected, different amounts of oxidizer may be required to produce results.

[0381] Figure 4 is a graphical representation of the data in Figure 3B, demonstrating the synergistic interaction between a particular underlayer and an oxidizing gas atmosphere. With 0% O2, there is no change in CH loss, but as O2 is increased, a sharp increase in CH loss is observed for photoresist deposited on a bake-sensitive underlayer (compared to a control underlayer, Si, with no activatable moieties). In addition, different underlayers do not react identically and therefore have different sensitivities to the addition of O2.

[0382] The formula for the synergistic effect is provided as Figure 5A, where CH Loss Total represents the total CH loss due to EUV + PEB ​​(post-exposure bake), and CH Loss Bake = CH loss due to PEB component, CH Loss EUV = CH loss due to EUV exposure component, CH Loss Synergy = CH loss due to the synergistic effect of EUV and PEB (i.e., when performed sequentially). The formula is used to interpret CH loss data measured by FTIR under different conditions and represents the data plotted in Figures 5B and 5C. The degree of synergy depends on the underlayer selected. The CH loss from the combined EUV and bake step is greater than the sum of the CH losses from the individual steps (the definition of synergy). The amount of this synergy (measured by CH loss) depends on the type of underlayer. This is important because it is a measure of the degree to which reactive species generated from EUV preferentially interact with the exposed pattern on the resist over unexposed regions. This increases the chemical / material contrast between the two regions, allowing for differentiation of the exposed pattern and unexposed material within the photoresist film. Synergy refers to an unexpected positive effect resulting from a combination of conditions and / or materials that is greater than a simple additive effect. Synergy can result from the synchronized interaction of process conditions (use of oxidizing gas), process steps (bake and EUV exposure), and / or materials (e.g., bake-sensitive underlayers).

[0383] Figure 5B is a graphical illustration of CH loss as a function of EUV exposure dose resulting from post-exposure bake of a patterned structure without an underlayer. The control is a bare silicon wafer. The control was also tested without bake and at two different bake temperatures. The calculated CH loss shown already subtracts the contribution to CH loss from the bake step (determined from the equation in Figure 5A). The difference in CH loss between "no bake" (i.e., treated with EUV exposure only) and 200 °C or 210 °C (i.e., treated with EUV exposure and post-exposure bake of the underlayer) demonstrates the synergistic effect of subjecting a wafer to both EUV exposure and post-exposure bake relative to the control sample (no bake-sensitive underlayer).

[0384] FIG. 5C is a graphical illustration of CH loss as a function of EUV exposure dose resulting from post-exposure baking of a patterned structure having a bake-sensitive underlayer SHD2 at different temperatures, demonstrating the synergistic effect of EUV exposure followed by a post-exposure bake according to certain disclosed embodiments. The bake-sensitive underlayer was tested without a bake and at two different bake temperatures. The calculated CH loss shown already includes the contribution to CH loss from the bake step (determined from the equation in FIG. 5A). The difference in CH loss for the control between "no bake" (i.e., treated with EUV exposure only) and 200°C or 210°C (i.e., treated with EUV exposure and a post-exposure bake) demonstrates the synergistic effect of treating a patterned structure including a bake-sensitive underlayer with both EUV exposure and a post-exposure bake. Comparing the gap between the no-bake and EUV-baked conditions shows that the effect on CH loss with a bake-sensitive underlayer (Figure 5C) is much greater than without (Figure 5B), going beyond a mere additive effect. Additionally, the dose at which this synergistic effect is observed is much lower when a bake-sensitive underlayer is included in the patterned structure.

[0385] Figure 6A is a bar chart showing CH loss measured by FTIR for four different bake-sensitive underlayers (UL1, UL2, UL3, and UL4) beneath the imaging layer after the imaging layer deposited on control Si (without an underlayer) was baked at 210 °C for 240 seconds at 600 Torr in the presence of an oxidizing gas mixture. The mixture was 21% O and 79% N. The data suggest that CH loss results directly from interactions between the bake-sensitive underlayer and the overlying imaging layer.

[0386] Figure 6B is a graph showing the CH loss from Figure 6A plotted against experimentally observed dose versus size for a 14 nM L / S patterned wafer. The linear correlation between dose versus size and CH loss (determined by FTIR) clearly demonstrates that the CH loss data can predict dose versus size.

[0387] 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 comprising a chamber for depositing one or more precursors to provide an underlayer and / or imaging layer, a patterning module comprising an EUV photolithography tool having a radiation source at a wavelength of less than 30 nm, and a development module comprising a chamber for developing a film including such layers.

[0388] The apparatus can 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 encoded with instructions for depositing the film. Such instructions can include depositing one or more precursors to provide an underlayer and / or an imaging layer in a deposition module, patterning the layer directly with EUV exposure at a resolution of less than 30 nm to thereby form a pattern in the film in a patterning module, and developing the film in a development module. In certain embodiments, the development module removes EUV-exposed or non-EUV-exposed areas, thereby providing a pattern in the film.

[0389] 7 illustrates a schematic diagram of one embodiment of a process station 300 having a process chamber body 302 for maintaining a low-pressure environment suitable for carrying out the vapor deposition and dry development embodiments described herein. Multiple process stations 300 may be included in a common low-pressure process tool environment. For example, FIG. 8 illustrates one embodiment of a multi-station processing tool 400, such as a VECTOR® processing tool available from Lam Research, Inc. of Fremont, California. In some embodiments, one or more hardware parameters of the process stations 300 (including those described in detail below) may be programmatically adjusted by one or more computer controllers 350.

[0390] The process stations can be configured as modules within a cluster tool. Figure 10 illustrates a semiconductor process cluster tool architecture having a vacuum-integrated deposition and patterning module suitable for practicing embodiments described herein. Such a cluster process tool architecture can include a PR and underlayer deposition module, a resist exposure (EUV scanner) module, a resist dry develop module, and an etch module, as described above and further below with reference to Figures 11-12.

[0391] In some embodiments, certain processing functions, such as vapor deposition (e.g., PECVD), dry development, and etching, can be performed sequentially within the same module.

[0004] Embodiments of the present disclosure are also directed to an apparatus for processing a substrate, the apparatus comprising: a process chamber with a substrate support; a process gas source and associated flow control hardware coupled to the process chamber; substrate handling hardware coupled to the process chamber; and a controller having a processor and memory. In some implementations, the processor and 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 operations in the methods of fabricating patterned structures described herein.

[0392] For example, the memory can store computer-executable instructions for providing a hard mask to be disposed on the substrate, for example, by chemical vapor deposition (e.g., PECVD). As mentioned above, a suitable hard mask may be, for example, an ashable hard mask film of amorphous carbon, undoped or doped with B or W.

[0393] The memory can further store instructions for depositing an underlayer on the substrate and / or hard mask, the underlayer configured to increase 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 include a vapor-deposited film of hydrogenated carbon doped with a non-carbon heteroatom (e.g., any of those described herein, e.g., O, Si, N, W, B, I, Cl, etc.), and the film may have a thickness of about 25 nm or less and contain about 0-30% O. In some embodiments, the underlayer may be vapor-deposited on the substrate and / or hard mask by PECVD or ALD using hydrocarbon precursors and / or dopant precursors. In other embodiments, the underlayer may be vapor-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 embodiment, the oxocarbon precursor may further co-react with a Si-source dopant during deposition. In other embodiments, the underlayer may be vapor-deposited onto the substrate and / or hardmask by PECVD or ALD using a Si-containing precursor (e.g., any O-containing precursor described herein) that co-reacts with an oxidizer. In a variation of this embodiment, the Si-containing precursor further co-reacts with a C-source dopant. In some embodiments, the underlayer may be vapor-deposited onto the substrate and / or hardmask by PECVD as a termination operation of the vapor deposition onto the substrate or the vapor deposition of the hardmask onto the substrate, for example, by adjusting the flow of precursors into the PECVD process chamber to achieve the desired composition of the underlayer.

[0394] The memory can further store instructions for forming an EUV-sensitive inorganic photoresist on the photoresist underlayer. A suitable EUV-sensitive inorganic photoresist can be a metal oxide film, such as the EUV-sensitive tin oxide-based photoresist described above.

[0395] 7, the process station 300 is in fluid communication with a reactant delivery system 301a for delivering process gases to a distribution showerhead 306. The reactant delivery system 301a optionally includes a mixing vessel 304 for blending and / or adjusting the process gases delivered to the showerhead 306. One or more mixing vessel inlet valves 320 can control the introduction of process gases into the mixing vessel 304. If plasma exposure is used, the plasma can also be delivered to the showerhead 306 or can be generated in the process station 300. As noted above, in at least some embodiments, non-plasma thermal exposure is preferred.

[0396] 7 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) can be provided upstream of the vaporization point 303 to control the mass flow rate of the liquid being vaporized and delivered to the process station 300. For example, the LFC can include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC can then be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM.

[0397] The showerhead 306 distributes process gases toward the substrate 312. In the embodiment shown in Figure 7, the substrate 312 is shown positioned below the showerhead 306 and resting 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.

[0398] In some embodiments, the pedestal 308 can be raised or lowered to expose the substrate 312 to the volume between the substrate 312 and the showerhead 306. It will be appreciated that in some embodiments, the height of the pedestal can be programmatically adjusted by a suitable computer controller 350.

[0399] In some embodiments, the pedestal 308 may be temperature controlled via heater 310. In some embodiments, the pedestal 308 may be heated to a temperature of greater than 0° C. to 300° C. or greater, such as 50-120° C., for example, about 65-80° C., during non-plasma thermal exposure of the photopatterned resist to a hydrogen halide dry development chemistry such as HBr or HCl.

[0400] Additionally, in some embodiments, pressure control for the process station 300 may be provided by a butterfly valve 318. As shown in the embodiment of Figure 7, the butterfly valve 318 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control for the process station 300 may also be adjusted by varying the flow rate of one or more gases introduced to the process station 300.

[0401] In some embodiments, the position of the showerhead 306 can be adjusted relative to the pedestal 308 to vary the volume between the substrate 312 and the showerhead 306. Furthermore, it will be understood that the vertical position of the pedestal 308 and / or the showerhead 306 may be varied 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 will be understood that in some embodiments, one or more of these exemplary adjustments can be implemented programmatically by one or more suitable computer controllers 350.

[0402] When plasma may be used, such as 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 can 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 can operate at any suitable power to form a plasma having a desired composition of radical species. An example of a suitable power is up to approximately 500 W. Similarly, the RF power source 314 can provide RF power at any suitable frequency. In some embodiments, the RF power source 314 can be configured to control high-frequency and low-frequency RF power sources independently of each other. Examples of low-frequency RF frequencies can 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 will be appreciated that any suitable parameters may be adjusted discretely or continuously to provide plasma energy for surface reactions. In one non-limiting example, the plasma power may be intermittently pulsed to reduce ion bombardment at the substrate surface compared to a continuously powered plasma. The RF power source may operate 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.

[0403] In some examples, the RF power can be continuous or pulsed between one or more levels. If pulsed operation is used, the pulsing can 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.

[0404] In some deposition processes, plasma strikes last several seconds or longer. In certain implementations, much shorter strikes may be used. These may be on the order of 10 ms to 1 second, typically about 20 to 80 ms, with 50 ms being a specific example. Such very short RF strikes require extremely rapid stabilization of the plasma. 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 approximately 13.56 MHz. In various embodiments disclosed herein, the frequency is allowed to vary to values ​​different from this standard value. By allowing the frequency to vary while the impedance match is fixed at a predetermined voltage, the plasma can stabilize much more quickly, which may be important when using very short strikes associated with certain types of deposition cycles.

[0405] In some embodiments, instructions for the controller 350 may be provided via input / output control (IOC) sequence instructions. In one example, instructions for setting conditions for a process step may be included in the corresponding recipe step of a process recipe. In some cases, process recipe steps may be arranged in sequence so 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 flow rates of an oxocarbon precursor and H or hydrocarbon co-reactant and optional dopants for a photoresist underlayer. In some embodiments, the controller 350 may include any of the features described below with respect to the system controller 450 of FIG. 8.

[0406] As described above, one or more process stations can be included in a multi-station processing tool. FIG. 8 shows a schematic diagram of one embodiment of a multi-station processing tool 400 including an inbound load lock 402 and an outbound load lock 404, either or both of which may include a remote plasma source. A robot 406 is configured to move wafers at atmospheric pressure from a cassette loaded via a pod 408 to the inbound load lock 402 through an atmospheric pressure port 410. The wafer is placed by the robot 406 on a pedestal 412 of the inbound load lock 402, the atmospheric pressure port 410 is closed, and the load lock is pumped down. If the inbound load lock 402 includes a remote plasma source, the wafer may undergo remote plasma processing to treat its surface within the load lock before being introduced into the processing chamber 414. Additionally, the wafer may also be heated in the inbound load lock 402, for example, to remove moisture and absorbed gases. The chamber transfer port 416 to the processing chamber 414 is then opened and another robot (not shown) places the wafer into the reactor on a pedestal in the first station shown in the reactor for processing. While the embodiment shown in Figure 8 includes a load lock, it will be understood that in some embodiments the wafer may enter the process station directly.

[0407] The illustrated processing chamber 414 includes four process stations, numbered 1 through 4 in the embodiment shown in FIG. 8 . Each station has a heated pedestal (shown at 418 for station 1) and a gas line inlet. It will be understood that in some embodiments, each process station may have a different purpose or multiple purposes. For example, in some embodiments, a process station may be switchable between a dry development mode and an etch process mode. Additionally or alternatively, in some embodiments, the processing chamber 414 may include one or more corresponding pairs of dry development and etch process stations. While the illustrated processing chamber 414 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, the processing chamber may have five or more stations, while in other embodiments, the processing chamber may have three or fewer stations.

[0408] FIG. 8 illustrates one embodiment of a wafer handling system 490 for transferring wafers within the processing chamber 414. In some embodiments, the wafer handling system 490 can transfer wafers between various process stations and / or between process stations and load locks. It will be understood that any suitable wafer handling system may be used. Non-limiting examples include a wafer carousel and a wafer handling robot. FIG. 8 also illustrates one embodiment of a system controller 450 used to control the process conditions and hardware states of the process 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, stepper motor controller boards, etc.

[0409] In some embodiments, the system controller 450 controls all of the activity of the process 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 on the processor 452. Alternatively, the 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. In the following description, whenever "software" or "code" is used, functionally equivalent hard-coded logic may be used instead. The system control software 458 may include instructions for controlling the timing, mixture of gases, gas flow rates, chamber and / or station pressures, chamber and / or station temperatures, wafer temperature, target power levels, RF power levels, substrate pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by the process 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 various process tool processes. The system control software 458 may be coded in any suitable computer-readable programming language.

[0410] In some embodiments, the system control software 458 may include input / output control (IOC) sequence instructions for controlling the various parameters described above. In some embodiments, 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 be used. Examples of programs or sections of programs 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.

[0411] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal 418 and control the spacing between the substrate and other parts of the process tool 400 .

[0412] The process gas control program can include code for controlling the hydrogen halide gas composition (e.g., HBr or HCl gas as described herein) and flow rate to stabilize the pressure of the process station, and optionally, code for flowing gas to one or more process stations prior to deposition. The pressure control program can include code for controlling the pressure of the process station by, for example, adjusting a throttle valve in the exhaust system of the process station, gas flow to the process station, etc.

[0413] 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 delivery of a heat transfer gas (such as helium) to the substrate.

[0414] The plasma control program may include code for setting RF power levels applied to process electrodes in one or more process stations in accordance with embodiments herein.

[0415] The pressure control program can include code for maintaining pressure in the reaction chamber according to embodiments herein.

[0416] In some embodiments, there may be a user interface associated with the system controller 450. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0417] 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 rates, 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.

[0418] 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 can 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 can be used with data from these sensors to maintain process conditions.

[0419] The system controller 450 can provide program instructions for carrying out the deposition processes described above. The program instructions can control various process parameters such as direct current (DC) power levels, RF bias power levels, pressure, temperature, etc. The instructions can control the parameters that operate the photoresist underlayer deposition process according to various embodiments described herein.

[0420] System controller 450 typically includes one or more memory devices and one or more processors configured to execute instructions such that the apparatus performs methods according to the disclosed embodiments. Machine-readable media containing instructions for controlling process operations according to the disclosed embodiments may be coupled to system controller 450.

[0421] In some embodiments, the system controller 450 is part of a system, such as may be part of the examples described above. Such systems may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (e.g., wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling system operation before, during, and after semiconductor wafer or substrate processing. Such electronics may be referred to as a "controller" and may control various components or subcomponents of one or more systems. The system controller 450 may be programmed to control any of the processes disclosed herein, depending on the processing conditions and / or type of system. Such processes may include process gas delivery, 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 delivery settings, position and motion settings, wafer transfer to and from tools and other transfer tools connected or interfaced with a particular system, and / or wafer transfer to and from load locks.

[0422] Broadly, 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, i.e., microcontrollers, that execute program instructions (e.g., software). Program instructions may be instructions communicated to system controller 450 in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters, in some embodiments, may be part of a recipe defined by a process engineer to implement one or more processing steps in the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0423] In some embodiments, the system controller 450 may be part of, coupled to, or a combination of a computer integrated with, coupled to, or otherwise networked to the system. For example, the system controller 450 may be in the “cloud” or all or part of a fab host computer system. This allows for remote access to wafer processing. The computer may provide remote access to the system to monitor the current progress of a fabrication operation, review the history of past fabrication operations, review trends or performance criteria from multiple fabrication operations, modify parameters of a current process, set processing steps following a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide process recipes to the system over a network. Such a network 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 then communicated from the remote computer to the system. In some examples, the system controller 450 receives instructions in the form of data. Such data may identify parameters for each processing step performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool that the system controller 450 is configured to interface with or control. Thus, as described above, the system controller 450 may be distributed, for example, by including one or more individual controllers that are networked together and cooperate toward a common purpose (such as the processes and controls described herein).An example of a distributed controller for such purposes would include one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) and coupled to control the process in the chamber.

[0424] Exemplary systems may include, but are not limited to, 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 tracker 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 used in the fabrication and / or manufacturing of semiconductor wafers.

[0425] As noted above, depending on the process step or steps being performed by the tool, the system controller 450 may communicate with one or more 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 and from tool locations and / or load ports in a semiconductor fabrication factory.

[0426] 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.

[0427] 9 shows a schematic cross-sectional view of an inductively coupled plasma apparatus 500 suitable for practicing certain embodiments or aspects of embodiments, such as gas phase (dry) deposition, dry development, and / or etching, an example of which is the Kiyo® reactor manufactured by Lam Research, Inc. of Fremont, Calif. Other embodiments may be practiced using other tools or tool types having the functionality to perform the dry deposition, development, and / or etching processes described herein.

[0428] The inductively coupled plasma apparatus 500 includes an overall process chamber 524 structurally defined by a chamber wall 501 and a window 511. The chamber wall 501 can be fabricated from stainless steel or aluminum. The window 511 can be fabricated from quartz or other dielectric material. An optional internal plasma grid 550 divides the overall process chamber into an upper subchamber 502 and a lower subchamber 503. In many embodiments, the plasma grid 550 can be removed, thereby utilizing the chamber space consisting of the subchambers 502 and 503. A chuck 517 is positioned 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. If present, the chuck 517 can be an electrostatic chuck for supporting the wafer 519. In some embodiments, an edge ring (not shown) surrounds the chuck 517 and, if present on the chuck 517, has an upper surface that is approximately planar with the upper surface of the wafer 519. 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 circuit 521 through connection 527. The matching circuit 521 is connected to the chuck 517 through connection 525. In this manner, 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 approximately 50 V or may be set to a different bias power depending on the process being performed in accordance with the disclosed embodiments. For example, the bias power may be between approximately 20 V and approximately 100 V, or between approximately 30 V and approximately 150 V.

[0429] The elements for plasma generation include a coil 533 positioned over the window 511. In some embodiments, a coil is not used in the disclosed embodiments. The coil 533 is fabricated from a conductive material and includes at least one full turn. The exemplary coil 533 shown in FIG. 9 includes three turns. A cross section of the coil 533 is indicated by symbols, with the coil having an "X" extending into the page and the coil having a "●" extending out 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 circuit 539 through connection 545. The matching circuit 539 is connected to the coil 533 through connection 543. In this manner, the RF power supply 541 is connected to the coil 533. An optional Faraday shield 549a is positioned between the coil 533 and the window 511. The Faraday shield 549a may be maintained in a spaced apart relationship relative 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 not 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 parallel to one another. The Faraday shield 549a can prevent metals or other species from depositing on the window 511 of the process chamber 524.

[0430] Process gases can enter the process chamber through one or more main gas inlets 560 and / or one or more side gas inlets 570 positioned in the upper subchamber 502. Similarly, although not explicitly shown, similar gas inlets can be used to supply process gases to the capacitively coupled plasma processing chamber. A vacuum pump, e.g., a single-stage or two-stage mechanical dry pump and / or turbomolecular pump 540, can be used to draw process gases from the process chamber 524 and maintain pressure within the process chamber 524. For example, the vacuum pump can be used to evacuate the lower subchamber 503 during an ALD purge operation. A valve-controlled conduit can be used to fluidly connect the vacuum pump to the process chamber 524 to selectively control the application of the vacuum environment provided by the vacuum pump. This can be done using a closed-loop controlled flow restriction device, such as a throttle valve (not shown) or a pendulum valve (not shown), during plasma processing operations. Similarly, a vacuum pump and valve-controlled fluid connection to the capacitively coupled plasma processing chamber can also be used.

[0431] During operation of the apparatus 500, one or more process gases can be supplied through the gas inlets 560 and / or 570. In certain embodiments, process gases can be supplied only through the main gas inlet 560 or only through the side gas inlet 570. In some cases, the gas inlets shown in the figure can be replaced with more complex gas inlets, such as one or more showerheads. The Faraday shield 549a and / or the optional grid 550 can include internal channels and holes that allow delivery of process gases to the process chamber 524. Either or both of the Faraday shield 549a and the optional grid 550 can serve as showerheads for delivering process gases. In some embodiments, a liquid vaporization and delivery system can be positioned upstream of the process chamber 524, whereby 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.

[0432] Radio frequency power is supplied from RF power supply 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 generated ions and radicals with wafer 519 etch features in wafer 519 and selectively deposit layers on wafer 519.

[0433] When a plasma grid 550 is used such that both the upper subchamber 502 and the lower subchamber 503 are present, induced currents act on the gas present in the upper subchamber 502, generating an electron-ion plasma in the upper subchamber 502. The optional internal plasma grid 550 limits the number of thermal electrons in 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.

[0434] Both the upper electron-ion plasma and the lower ion-ion plasma can 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 can be removed from the lower subchamber 503 through port 522. The chuck 517 disclosed herein can operate at high temperatures ranging from about 10° C. to about 250° C. The temperature depends on the process operation and the specific recipe.

[0435] The apparatus 500 may be coupled to equipment (not shown) when installed in a clean room or fabrication facility. The equipment includes plumbing to provide process gases, vacuum, temperature control, and environmental particle control. These equipment are coupled to the apparatus 500 when installed in the target fabrication facility. Additionally, the apparatus 500 may be coupled to a transfer chamber that allows a robot to move semiconductor wafers in and out of the apparatus 500 using typical automated operations.

[0436] 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 flow rates and durations when the disclosed embodiments are implemented. 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 flowing chemistry, the selected recipe, the reactor architecture, and other factors.

[0437] In some embodiments, the system controller 530 is part of a system, such as may be part of the examples described above. Such systems may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (e.g., wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling system operation before, during, and after semiconductor wafer or substrate processing. Such electronics may be integrated into the system controller 530 and control various components or subcomponents of one or more systems. The system controller may be programmed to control any of the processes disclosed herein, depending on the processing parameters and / or type of system. Such processes may include process gas delivery, 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 delivery settings, position and motion settings, wafer transfer to and from tools and other transfer tools connected or interfaced with a particular system, and / or wafer transfer to and from load locks.

[0438] Broadly, 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, i.e., microcontrollers, that execute program instructions (e.g., software). The program instructions may be instructions communicated to the controller in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters, in some embodiments, may be part of a recipe defined by a process engineer to accomplish one or more processing steps in the fabrication or removal of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer die.

[0439] In some embodiments, the system controller 530 may be part of, coupled to, or a combination of a computer integrated with, coupled to, or otherwise networked to the system. For example, the controller may be in the “cloud” or all or part of a fab host computer system. This allows for remote access of wafer processing. The computer may provide remote access to the system to monitor the current progress of a fabrication operation, review the history of past fabrication operations, review trends or performance criteria from multiple fabrication operations, modify parameters of a current process, set processing steps following a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide process recipes to the system over a network. Such a network 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 then communicated from the remote computer to the system. In some examples, the system controller 530 receives instructions in the form of data. Such data may identify parameters for each processing step performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool the controller is configured to interface with or control. Thus, as described above, the system controller 530 may be distributed, for example, by including one or more individual controllers networked together and working together toward a common purpose (such as the processes and controls described herein).An example of a distributed controller for such purposes would include one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) and coupled to control the process in the chamber.

[0440] Exemplary systems may include, but are not limited to, 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 (e.g., PECVD) chamber or module, an ALD chamber or module, an ALE chamber or module, an ion implantation chamber or module, a tracker 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 used in the fabrication and / or manufacturing of semiconductor wafers.

[0441] As noted above, depending on the process step or steps being performed by the tool, the controller may communicate with one or more 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 and from tool locations and / or load ports in a semiconductor fabrication factory.

[0442] EUVL patterning can be performed using any suitable tool, often referred to as a scanner, such as the TWINSCAN® NXE:3300B platform supplied by ASML, Veldhoven, The Netherlands. The EUVL patterning tool may be a standalone device from 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. 10 illustrates a semiconductor process cluster tool architecture 600 having vacuum-integrated deposition, EUV patterning, and dry develop / etch modules interfaced with a vacuum transfer module, suitable for carrying out the processes described herein. While the processes can be performed without such vacuum-integrated equipment, such equipment may be advantageous in some embodiments.

[0443] 10 illustrates a semiconductor process cluster tool architecture having a vacuum-integrated deposition and patterning module interfaced with a vacuum transfer module suitable for carrying out the processes described herein. The arrangement of transfer modules for "transferring" wafers between multiple storage facilities and 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, can also be included in the cluster.

[0444] A vacuum transfer module (VTM) 638 interfaces with four processing modules 620a-620d, which can be individually optimized to perform various fabrication processes. By way of example, processing modules 620a-620d can be implemented to perform deposition, evaporation, ELD, dry develop, etch, strip, and / or other semiconductor processes. For example, module 620a can be an ALD reactor that can be operated to perform the non-plasma thermal atomic layer deposition described herein, such as a Vector tool available from Lam Research, Inc. of Fremont, California. And module 620b can be a PECVD tool, such as a Lam Vector®. It should be understood that the figures are not necessarily drawn to scale.

[0445] Airlocks 642 and 646, also known as load locks or transfer modules, interface with VTM 638 and patterning module 640. For example, as noted above, a suitable patterning module could be a TWINSCAN® NXE:3300B platform supplied by ASML, 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 significantly reduced pressure, given the strong optical absorption of incident photons by ambient gases such as HO and O.

[0446] As noted above, this integrated architecture is just one possible embodiment of a tool for carrying out the described process. The process can also be carried out with more conventional standalone EUVL scanners and modularly with deposition reactors such as the Lam Vector tool described with reference to FIG. 9 but without an integrated patterning module, either standalone or integrated in a cluster architecture with other tools such as etch, strip, etc. (e.g., a Lam Kiyo or Gamma tool).

[0447] Airlock 642 may be an "outgoing" load lock, referring to the transfer of substrates from VTM 638, which services deposition module 620a, to patterning module 640, and airlock 646 may be an "incoming" load lock, referring to the transfer of substrates from patterning module 640 back to VTM 638. Incoming load lock 646 may also provide an interface to the outside of the tool for substrate access and egress. Each process module has a facet that interfaces the module to VTM 638. For example, deposition process module 620a has facet 636. Within each facet, sensors, such as sensors 1-18 shown, are used to detect the passage of wafer 626 as it moves between its respective stations. Patterning module 640 and airlocks 642 and 646 may similarly include additional facets and sensors not shown.

[0448] The 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 lifts wafers, such as wafer 626, for transfer. A front-end robot 644 is used therein 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 can also transfer wafers 626 between the input load lock and the exterior of the tool for substrate access and egress. Because the input airlock module 646 has the ability to adapt environments between atmospheric pressure and vacuum, wafers 626 can move between the two pressure environments without damage.

[0449] It should be noted that EUVL tools typically operate at a higher vacuum than deposition tools. In this case, it is desirable to increase the vacuum environment of the substrate during transfer between the deposition tool and the EUVL tool to allow for degassing of the substrate before entering the patterning tool. The unloading airlock 642 can provide this function by holding the transferred wafer at a low pressure no higher than the pressure in the patterning module 640 for a period of time and venting the 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 exhaust off-gas airlock is 1E-8 Torr or less.

[0450] 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 local to the cluster architecture, located outside the cluster architecture on the manufacturing floor, or located at a remote location and connected to the cluster architecture 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 on 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.

[0451] The system control software may include instructions for controlling the timing of application and / or magnitude of any aspect of tool or module operation. The system control software 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 process tool components necessary to perform various process tool processes. The system control software may be coded in any suitable computer-readable programming language. In some embodiments, the system control software includes input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each stage of a semiconductor fabrication process may include one or more instructions executed by the system controller. For example, instructions for setting process conditions for condensation, deposition, vapor deposition, patterning, and / or etching stages may be included in the corresponding recipe stage.

[0452] In various embodiments, an apparatus for forming a negative tone patterned mask is provided. The apparatus can include a process chamber for patterning, depositing, and etching, and a controller including instructions for forming the negative tone patterned mask. The instructions can include code for patterning features in a chemically amplified (CAR) resist on a semiconductor substrate by EUV exposure in the process chamber to expose a surface of the substrate, code for dry developing the photopatterned resist, and code for etching an underlying layer or layer stack using the patterned resist as a mask.

[0453] It should be noted that the computer controlling the movement of the wafers may be local to the cluster architecture, may be located outside the cluster architecture on the manufacturing floor, or may be located at a remote location and connected to the cluster architecture via a network. The controller described above with respect to any of Figures 7, 8, or 9 may be implemented using the tool of Figure 10.

[0454] 11 illustrates an example of a deposition chamber (e.g., for vapor-based deposition of an imaging layer and / or 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 through 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 seal or open 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.

[0455] The wafer support 724 may include an ESC 726 that provides a wafer support surface for the substrate 722. The ESC 726 may include a base plate 734 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 that generate an electric charge in the substrate 722, causing the substrate 722 to be attracted to the wafer support surface of the top plate 728.

[0456] Another system is a thermal control system that controls the temperature of the substrate 722 during processing conditions. In FIG. 11 , the thermal control system features four annular resistive heater traces 730a, 730b, 730c, and 730d positioned below the clamping electrode 732. Each resistive heater trace 730a / b / c / d can be individually controlled to provide various radial heating profiles to the top plate 728, maintaining the substrate 722 with temperature uniformity of, for example, ±0.5°C in some cases. In other embodiments, a single zone or a multi-zone heating system having more or less than four zones can be used. For example, in some implementations of the temperature control mechanism described above, a heat pump or Peltier junction may be used instead of the resistive heating traces.

[0457] ESC 726 may also include a base plate 734 that provides structural support to the underside of top plate 728 and may also act as a heat distribution 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.

[0458] The ESC 726 may be supported by a wafer support housing 742 connected to and supported by wafer support columns 744. The wafer support columns 744 may have other passageways for wire passages 748 for routing cabling (e.g., to provide electrical power), fluid flow conduits (e.g., to carry heat exchange media), and other equipment to the underside of the base plate 734 and / or top plate 728.

[0459] 11 also includes a substrate support Z actuator 746 that can provide movable support to the wafer support column 744. The wafer support Z actuator 746 can be actuated to move the wafer support column 744, and the wafer support 724 supported thereby, vertically up and down, for example, by up to several inches, within the reaction volume 720 of the processing chamber 702. In doing so, the gap distance X between the substrate 722 and the underside of the showerhead 710 can be adjusted in response to various process conditions.

[0460] The wafer support 724 may also include one or more edge rings that may be used to control and / or fine-tune various process conditions. In Figure 11, for example, an upper edge ring 738 is provided that sits above lower edge rings 740a and 740b, which are supported by a wafer support housing 742 and a third lower edge ring 740c.

[0461] The apparatus 700 may also include a system for removing process gases from the processing chamber 702 during and after processing. For example, the processing chamber 702 may include an annular plenum 756 surrounding the wafer support column 744. The annular plenum 756 may in turn be fluidly connected to a vacuum foreline 752, which may be connected to a vacuum pump. A regulator valve 754 may be provided between the vacuum foreline 752 and the processing chamber 702 and may be actuated to control flow into the vacuum foreline 752. In some implementations, a baffle 750, e.g., an annular plate or other structure, may be provided that may serve to more evenly distribute flow into the annular plenum 756 around the wafer support column 744, reducing the likelihood of flow non-uniformities in the reactants flowing across the substrate 722.

[0462] The showerhead 710, as shown, is a dual-plenum showerhead 710 and includes 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 can be used to maintain separation between the precursors and the reverse reactant prior to release. In some cases, a single plenum is used to deliver precursors to the reaction space 720 of the processing chamber 702. Each plenum may have a corresponding set of gas distribution ports that fluidly connect the respective plenum with the reaction space 720 through the faceplate of the showerhead 710 (the faceplate is the portion of the showerhead 710 interposed between the lowermost plenum and the reaction space 720).

[0463] The first inlet 716 and the second inlet 718 of the showerhead 710 can be supplied with process gases via a gas delivery system, which can be configured to provide one or more precursors and / or counter reactants as described herein. A first valve manifold 768a can be configured to supply one or more precursors to the first inlet 716, while a second valve manifold 768b can be configured to supply 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 can 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 on another three-way valve A3. Similarly, valve A4 may be another three-way valve having 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 on another three-way valve A5. One of the other ports on valve A5 may be fluidly connected to first inlet 716, and the remaining port on valve A5 may be fluidly connected to one of the remaining ports on valve A3. The remaining port on 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 suitable inert gas (for precursor and / or back reactant). In some embodiments, only the first valve manifold is used.

[0464] For purposes of this disclosure, the term "fluidically connected" is used in reference to volumes, plenums, holes, etc. that may be connected to one another to form a fluid connection, similar to the way the term "electrically connected" is used in reference to components that are connected to one another to form an electrical connection. The term "fluidically interposed," when used, may be used to refer to a component, volume, plenum, or hole that is fluidly connected to at least two other components, volumes, plenums, or holes, such that fluid flowing from one of those other components, volumes, plenums, or holes to the other or another of those components, volumes, plenums, or holes first flows through the "fluidically interposed" component before reaching the other or another of those components, volumes, plenums, or holes. For example, if a pump is fluidly interposed between a reservoir and an outlet, fluid flowing from the reservoir to the outlet first flows through the pump before reaching the outlet.

[0465] First valve manifold 768a may be controllable, such as by controlled actuation of valves A1-A5, to flow vapor from one or both of vaporizers 772a and 772b into processing chamber 702 or through first bypass line 770a to vacuum foreline 752. First valve manifold 768a may also be controllable to flow purge gas from purge gas source 774 to first inlet 716.

[0466] It will be appreciated that second valve manifold 768b can be controlled in a similar manner, 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 will further be appreciated that different manifold arrangements can be utilized as well, including a single integral manifold that includes valves for controlling the flow of precursors, counter reactants, and other reactants to first inlet 716 and second inlet 718.

[0467] 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.

[0468] As described above, an apparatus such as apparatus 700 that may be used to perform dry deposition of a film may be configured to maintain a particular temperature profile within the process chamber 702. In particular, such an apparatus 700 may be configured to maintain the substrate 722 at a lower temperature, e.g., at least 25° C. to 50° C. lower, than most of the equipment in the apparatus 702 that comes into direct contact with the precursors and / or counter reactants.

[0469] 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; for example, vertical holes for receiving the cartridge heater 758 may be drilled in the four corners of the housing of the chamber 702. In some implementations, the showerhead 710 may be covered with a heater blanket 760, which may be used to apply heat across the entire 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 772 to the showerhead 710. For example, resistive heater tape may be wrapped around such gas lines and used to heat them to a high temperature. Any of the gas lines in FIG. 11, as well as the fate valve 706, may also be actively or indirectly heated.

[0470] The various operating systems of apparatus 700 can be controlled by a controller 784, which can include one or more processors 786 and one or more memory devices 788 operably connected to each other and communicatively connected to the various systems and subsystems of apparatus 700 to provide control functionality for those systems. For example, controller 784 can be configured to control valves A1-A5 and B1-B5, various heaters 758, 760, vaporizer 772, regulator valve 754, gate valve 706, wafer support Z actuator, etc.

[0471] Another feature that the apparatus 700 may include is shown in FIG. 12 , which illustrates an enlarged side cross-sectional view and plan view of a portion of the substrate 722, top plate 728, and upper edge ring 738 of FIG. 11 . As can be seen, in some implementations, the substrate 722 may be elevated from the majority of the top plate 728 by a plurality of small mesas 776, which may be shallow bosses that protrude a small distance from the nominal top surface of the top plate 728 to provide a backside gap 778 between the lower surface 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 typically inert gas, such as helium, may be flowed into the backside gap 778 through one or more gas ports 782. This gas can then flow radially outward before encountering the peripheral wall feature 777, thereby restricting such radially outward flow and trapping a high-pressure region of gas between the substrate 722 and the top plate 728. Inert gas that leaks beyond the peripheral wall 777 can eventually escape through the radial gap 780 between the outer edge of the substrate 722 and a portion of the upper edge ring 738. Such gas can act to protect the underside of the substrate from undesirable effects of processing operations being performed by preventing gases emitted by the showerhead 710 from reaching the underside of the substrate 722. At the same time, gas emitted in the backside gap 778 region can also act to increase thermal coupling between the substrate 722 and the top plate 728, thereby allowing the top plate 728 to more effectively heat or cool the substrate 722. Due to the high pressure provided by the peripheral wall, the gas in the backside gap 778 region can be denser than the gas in the rest of the chamber, thus providing more effective thermal coupling between the substrate 722 and the top plate 728.

[0472] Controller 784 can be configured, for example, through the execution of computer-executable instructions, to cause device 700 to perform various operations consistent with the above disclosure.

[0473] 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 additional operations (e.g., any described herein), as described above. Additional deposition apparatus are described in International Patent Application No. PCT / US2020 / 038968, filed June 22, 2020, entitled "APPARATUS FOR PHOTORESIST DRY DEPOSITION," the disclosure of which is incorporated herein by reference in its entirety.

[0474] conclusion Patterning structures and schemes, as well as related processes and apparatus, for incorporating photoresist underlayers configured to increase adhesion between a substrate (e.g., a hard mask) and photoresist and / or reduce EUV dose for effective photoresist exposure during EUV lithography are disclosed and described.

[0475] It will be understood that the examples and embodiments described herein are for illustrative purposes only, and that various modifications or changes will be suggested to those skilled in the art in light thereof. Various details have been omitted for clarity, and various design alternatives can be implemented. Therefore, the examples should be considered illustrative rather than restrictive, and the disclosure is not limited to the details given herein, but can be modified within the scope of the disclosure.

[0476] The following sample claims are provided to further describe certain embodiments of the present disclosure, but the present disclosure is not necessarily limited to these embodiments.

Claims

1. 1. A method for optimizing formation of a patterning structure, comprising: providing a substrate; selecting a carbon-containing underlayer including an activatable moiety for deposition on the substrate, the carbon-containing underlayer being selected to generate reactive species upon activation by heating, treatment with an oxidizing gas, treatment with an inert gas, or a combination thereof; depositing the selected carbon-containing underlayer on the substrate; forming a film of a radiation-sensitive imaging layer over the selected carbon-containing underlayer; Including, whereby the interaction of the reactive species with the film reduces the radiation dose for effective photoresist exposure of the patterned structure. method.

2. 10. The method of claim 1, The activatable moieties include hydroxyl groups, carboxyl groups, peroxy groups, sp 2 carbon, sp carbon, unsaturated carbon-containing bond, allylic C—H bond, ether alpha C—H bond, vinylic C—H bond, aldehyde C—H bond, tertiary C—H bond, benzyl C—H bond, ketone alpha C—H bond, or combinations thereof.

3. 10. The method of claim 1, The method, wherein the carbon-containing underlayer comprises a carbon-containing doped film.

4. 4. The method of claim 3, The method, wherein the carbon-containing doped film is doped with a halogen, a metal, an organometallic complex, hydrogen, oxygen, or a combination thereof.

5. 5. The method of claim 4, The method wherein the metal comprises antimony, tin, bismuth, indium, tellurium, gold, platinum, palladium, osmium, iridium, titanium, ruthenium, rhodium, silver, tungsten, or a combination thereof.

6. 5. The method of claim 4, The method, wherein the organometallic complex comprises an organometallic complex having an oxidizable metal-carbon bond.

7. 7. The method of claim 6, The method wherein the organometallic complex having an oxidizable metal-carbon bond comprises an organoruthenium, organoplatinum, organopalladium, organoiridium, organogold, organosmium, or organorhodium.

8. 10. The method of claim 1, The method wherein heating comprises heating to a temperature of about 100°C to 250°C.

9. 10. The method of claim 1, The method, wherein the oxidizing gas comprises chlorine, nitric oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, hydrogen peroxide, ozone, oxygen, or a combination thereof.

10. 10. The method of claim 1, The method wherein the oxidizing gas is provided as a mixture of oxidizing gas in an inert gas.

11. 11. The method of claim 10, The method wherein the oxidizing gas is provided in an amount of about 10% to about 100% of the oxidizing gas mixture.

12. 10. The method of claim 1, The method, wherein the inert gas comprises helium, neon, argon, krypton, xenon, radon, nitrogen, or a combination thereof.

13. 4. The method of claim 3, The method, wherein the carbon-containing doped film is doped with a halogen, antimony, tin, bismuth, indium, or tellurium, and the activation comprises heating.

14. 10. The method of claim 1, The activatable moiety is sp 2 the carbon, sp carbon, unsaturated carbon-containing bond, allylic C—H bond, ether alpha C—H bond, vinylic C—H bond, tertiary C—H bond, benzylic C—H bond, or a combination thereof, and said activation comprises heating and treatment with an oxidizing gas.

15. 1. A method of fabricating a patterning structure, comprising: providing a substrate; depositing a bake-sensitive underlayer on the substrate; forming a film of a radiation-sensitive imaging layer on the bake-sensitive underlayer; exposing the film to extreme ultraviolet light to produce a film comprising exposed and unexposed regions; baking the film, including exposed and unexposed regions, to activate the bake-sensitive underlayer and generate reactive species, wherein the reactive species generated in the bake-sensitive underlayer preferentially interact with the exposed regions to form exposed crosslinked regions; developing the film to include exposed crosslinked regions and unexposed regions; Including, whereby interaction of the reactive species with the exposed areas reduces the radiation dose for effective photoresist exposure of the patterned structure; The exposed crosslinked regions increase the contrast between the exposed and unexposed regions. method.

16. 1. A method of fabricating a patterning structure, comprising: providing a substrate; depositing a bake-sensitive underlayer on the substrate, the bake-sensitive underlayer having a top underlayer surface and a bottom underlayer surface; forming a film comprising a radiation-sensitive imaging layer on the upper underlayer surface of the bake-sensitive underlayer; baking the film to activate the bake-sensitive underlayer and generate reactive species, wherein the reactive species generated in the bake-sensitive underlayer interact with the film; Including, whereby the interaction of the reactive species with the film reduces the radiation dose for effective photoresist of the patterned structure; method.

17. 1. A method of fabricating a patterning structure, comprising: providing a substrate; depositing a bake-sensitive underlayer on the substrate; forming a film comprising a radiation-sensitive imaging layer on the bake-sensitive underlayer; exposing the film to extreme ultraviolet light to produce an exposed film; baking the exposed film to activate the bake-sensitive underlayer and generate reactive species, wherein the reactive species generated in the bake-sensitive underlayer interact with the exposed film; Including, whereby the interaction of the reactive species with the exposed film reduces the radiation dose for effective photoresist exposure of the patterned structure. method.

18. 18. The method of claim 17, The method, wherein the baking comprises heating, contacting the film with an inert gas, contacting the film with an oxidizing gas, or a combination thereof.

19. 18. The method of claim 17, The method wherein the reactive species interacts with the exposed film and promotes crosslinking of the exposed film.

20. 18. The method of claim 17, The method, wherein the reactive species is an oxygen-containing reactive species.

21. 20. The method of claim 18, The method wherein baking comprises heating to a temperature of about 75°C to 280°C.

22. 20. The method of claim 18, The method, wherein the oxidizing gas comprises chlorine, nitric oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, hydrogen peroxide, ozone, oxygen, or a combination thereof.

23. 20. The method of claim 18, The method wherein the oxidizing gas is provided as a mixture of oxidizing gas in an inert gas.

24. 24. The method of claim 23, The method wherein the oxidizing gas is provided in an amount of about 10% to about 100% of the oxidizing gas mixture.

25. 18. The method of claim 17, The method further comprises increasing adhesion between the substrate and the radiation-sensitive imaging layer as a result of the interaction of the reactive species with the exposed film.

26. 20. The method of claim 18, The method, wherein the inert gas comprises helium, neon, argon, krypton, xenon, radon, nitrogen, or a combination thereof.

27. 18. The method of claim 17, The method, wherein the bake-sensitive underlayer comprises a carbon-containing film or a silicon-containing film.

28. 28. The method of claim 27, The method, wherein the bake-sensitive underlayer comprises a carbon-containing film.

29. 18. The method of claim 17, The bake-sensitive underlayer has activatable moieties, and the activatable moieties are hydroxyl groups, carboxyl groups, peroxy groups, sp 2 carbon, sp carbon, unsaturated carbon-containing bond, allylic C—H bond, ether alpha C—H bond, vinylic C—H bond, aldehyde C—H bond, tertiary C—H bond, benzyl C—H bond, ketone alpha C—H bond, or combinations thereof.

30. 28. The method of claim 27, The method, wherein the bake-sensitive underlayer comprises a carbon-containing doped film or a silicon-containing doped film.

31. 31. The method of claim 30, The method, wherein the carbon-containing doped film is doped with a halogen, a metal, an organometallic complex, hydrogen, oxygen, or a combination thereof.

32. 32. The method of claim 31 , The method wherein the metal comprises antimony, tin, bismuth, indium, tellurium, gold, platinum, palladium, osmium, iridium, titanium, ruthenium, rhodium, silver, tungsten, or a combination thereof.

33. 32. The method of claim 31 , The method, wherein the organometallic complex comprises an organometallic complex having an oxidizable metal-carbon bond.

34. 34. The method of claim 33, The method wherein the organometallic complex having an oxidizable metal-carbon bond comprises an organoruthenium, organoplatinum, organopalladium, organoiridium, organogold, organosmium, or organorhodium.

35. 31. The method of claim 30, The method, wherein the silicon-containing doped film is doped with a halogen, a metal, carbon, hydrogen, oxygen, or a combination thereof.

36. 18. The method of claim 17, The method wherein the bake-sensitive underlayer has a thickness of 60 nm or less.

37. 18. The method of claim 17, wherein the reactive species comprises a peroxy radical, a hydroperoxy radical, an oxy radical, a hydroxyl radical, a hydrogen radical, a formate radical, an iodine radical, carbon dioxide, carbon monoxide, water, iodine, hydrogen iodide, hydrogen antimonide, hydrogen telluride, bismuthine, formate anion, superoxide anion, or a combination thereof.

38. 18. The method of claim 17, the substrate is a film stack of a partially fabricated semiconductor device; the substrate further comprises or is 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 radiation-sensitive imaging layer comprises a tin oxide-based photoresist or a tin oxide hydroxide-based photoresist; the bake-sensitive underlayer comprises a vapor-deposited film of hydrogenated carbon doped with oxygen, silicon, nitrogen, tungsten, boron, iodine, chlorine, or a combination of any two or more thereof, the film having a thickness of 60 nm or less; method.

39. 39. The method of claim 38, The method of claim 1, wherein the bake-sensitive underlayer is vapor-deposited onto the substrate using a hydrocarbon precursor in the presence or absence of an oxocarbon precursor, thereby providing a carbon-containing film, wherein the oxocarbon precursor optionally co-reacts with hydrogen or a hydrocarbon, and optionally further co-reacts with a silicon source dopant.

40. 40. The method of claim 39, The method, wherein the hydrocarbon precursor comprises an alkane, an alkene, or an alkyne.

41. 40. The method of claim 39, the bake-sensitive underlayer is vapor-deposited using a hydrocarbon precursor in the presence of a nitrogen-containing precursor, a tungsten-containing precursor, a boron-containing precursor, an iodine-containing precursor, a chlorine-containing precursor, a bromine-containing precursor, a fluorine-containing precursor, a platinum-containing precursor, a ruthenium-containing precursor, an iridium-containing precursor, a gold-containing precursor, a palladium-containing precursor, a rhodium-containing precursor, an osmium-containing precursor, an antimony-containing precursor, an indium-containing precursor, a bismuth-containing precursor, a tellurium-containing precursor, a tin-containing precursor, a silver-containing precursor, a titanium-containing precursor, or a combination thereof, thereby providing a doped film.

42. 42. The method of claim 41 , The method wherein the doped film comprises iodine, a combination of iodine and silicon, or a combination of iodine, silicon, and nitrogen.

43. 39. The method of claim 38, The method wherein the bake-sensitive underlayer is vapor-deposited onto the substrate by using a silicon-containing precursor that co-reacts with an oxidizing agent, and the silicon-containing precursor optionally further co-reacts with a carbon source dopant.

44. 39. The method of claim 38, The method, wherein the bake-sensitive underlayer is vapor-deposited onto the substrate by plasma-enhanced chemical vapor deposition as a final operation of vapor deposition onto the substrate.

45. 39. The method of claim 38, The method wherein the bake-sensitive underlayer is vapor-deposited onto the substrate by plasma-enhanced chemical vapor deposition or atomic layer deposition.

46. 18. The method of claim 17, The method further comprising modifying the bake-sensitive underlayer to provide a roughened surface, and optionally exposing the bake-sensitive underlayer or the roughened surface to an oxygen-containing plasma to provide an oxygen-containing surface after deposition.

47. A patterning structure comprising: a radiation-sensitive imaging layer disposed over the substrate; a bake-sensitive underlayer disposed between the substrate and the radiation-sensitive imaging layer, the bake-sensitive underlayer configured to reduce radiation dose for effective photoresist exposure of the radiation-sensitive imaging layer; A patterning structure comprising:

48. 48. The patterning structure of claim 47, The patterned structure, wherein the bake-sensitive underlayer comprises a carbon-containing film or a silicon-containing film.

49. 49. The patterning structure of claim 48, The patterned structure, wherein the bake-sensitive underlayer comprises a carbon-containing film.

50. 50. The patterning structure of claim 49, The carbon-containing film may contain a hydroxyl group, a carboxyl group, a peroxy group, a sp 2 The patterned structure comprises carbon, sp carbon, unsaturated carbon-containing bonds, allylic C—H bonds, ether alpha C—H bonds, vinylic C—H bonds, aldehyde C—H bonds, tertiary C—H bonds, benzyl C—H bonds, ketone alpha C—H bonds, or combinations thereof.

51. 49. The patterning structure of claim 48, The patterned structure, wherein the bake-sensitive underlayer comprises a carbon-containing doped film or a silicon-containing doped film.

52. 52. The patterning structure of claim 51, The patterned structure, wherein the carbon-containing doped film is doped with a halogen, a metal, an organometallic complex, hydrogen, oxygen, or a combination thereof.

53. 53. The patterning structure of claim 52, The patterned structure, wherein the metal comprises antimony, tin, bismuth, indium, tellurium, gold, platinum, palladium, osmium, iridium, titanium, ruthenium, rhodium, silver, tungsten, or a combination thereof.

54. 53. The patterning structure of claim 52, The patterned structure, wherein the organometallic complex comprises an organometallic complex having an oxidizable metal-carbon bond.

55. 55. The patterning structure of claim 54, A patterned structure, wherein the organometallic complex having an oxidizable metal-carbon bond comprises organoruthenium, organoplatinum, organopalladium, organoiridium, organogold, organosmium, or organorhodium.

56. 52. The patterning structure of claim 51, The patterned structure, wherein the silicon-containing doped film is doped with a halogen, a metal, carbon, hydrogen, or a combination thereof.

57. 52. The patterning structure of claim 51, The patterned structure, wherein the carbon-containing doped film comprises about 0.01 to 20 atomic percent of a dopant.

58. 48. The patterning structure of claim 47, The patterned structure, wherein the radiation-sensitive imaging layer comprises an extreme ultraviolet-sensitive inorganic photoresist layer, a chemical vapor deposition film, a spin-on film, a tin oxide film, or a tin oxide hydroxide film.

59. 48. The patterning structure of claim 47, The substrate is a patterned structure that is or includes a hard mask, an amorphous carbon film, a boron-doped amorphous carbon film, a tungsten-doped 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 boron nitride film, an amorphous silicon film, a polysilicon film, or a combination thereof.

60. 48. The patterning structure of claim 47, The patterned structure wherein the bake-sensitive underlayer has a thickness of about 2 to 60 nm.

61. 48. The patterning structure of claim 47, The bake-sensitive underlayer has a coating density of about 0.7 to 2.9 g / cm 3 and optionally the bake-sensitive underlayer further provides increased etch selectivity, and optionally the bake-sensitive underlayer further provides reduced line-edge roughness and line-width roughness, and / or reduced dose to size.

62. Spin-coating a metalorganic imaging layer onto a bake-sensitive underlayer on a substrate, the bake-sensitive underlayer configured to reduce radiation dose for effective photoresist exposure of the metalorganic imaging layer. A method comprising:

63. 63. The method of claim 62, The method further comprises exposing the organometallic imaging layer to extreme ultraviolet radiation.

64. 64. The method of claim 63, exposing the organometallic imaging layer to extreme ultraviolet light and then developing the organometallic imaging layer using wet development. The method further comprises:

65. 65. The method of claim 64, The method, wherein the wet development is carried out using an alkaline developer, an ammonium-based ionic liquid, a glycol ether, an organic acid, a ketone, or an alcohol.

66. 65. The method of claim 64, The method, wherein the wet development is carried out using tetramethylammonium hydroxide, propylene glycol methyl ether, propylene glycol methyl ether acetate, 2-heptanone, ethanol, or a combination thereof.

67. 63. The method of claim 62, The method further comprising performing a post-apply bake at a temperature less than 250° C. after spin coating.

68. 63. The method of claim 62, The method further comprising performing a post-exposure bake at a temperature less than 280°C.

69. 69. The method of claim 68, The method further comprising performing a post-development bake at a temperature less than 280°C.

70. 63. The method of claim 62, The method wherein the bake-sensitive underlayer is provided by plasma-enhanced chemical vapor deposition or vapor phase deposition.

71. 63. The method of claim 62, The method wherein the organometallic imaging layer comprises an organotin.

72. 63. The method of claim 62, The method wherein the organometallic imaging layer comprises organozirconium, organoantimony, organozinc, organohafnium, organozinc, organotellurium, organoindium, or a combination thereof.

73. 63. The method of claim 62, The method further comprising providing a hard mask between the substrate and the bake-sensitive underlayer.

74. 74. The method of claim 73, The method wherein the hard mask is an ashing hard mask.

75. 63. The method of claim 62, The method wherein the bake-sensitive underlayer comprises hydrogenated carbon.

76. 63. The method of claim 62, 1. The method of claim 1, wherein the bake-sensitive underlayer comprises hydrogenated carbon doped with oxygen, silicon, nitrogen, tungsten, boron, iodine, chlorine, bromine, fluorine, platinum, ruthenium, iridium, gold, palladium, rhodium, osmium, antimony, indium, bismuth, tellurium, tin, silver, titanium, or a combination of any two or more thereof, and optionally the iodine-doped hydrogenated carbon is configured to improve secondary electron generation upon exposure to radiation.

77. 63. The method of claim 62, The bake-sensitive underlayer has a coating density of about 0.7 to 2.9 g / cm 3 and optionally the bake-sensitive underlayer further provides increased etch selectivity, and optionally the bake-sensitive underlayer further provides reduced line-edge roughness and line-width roughness, and / or reduced dose to size.

78. providing a bake-sensitive underlayer on a substrate, the bake-sensitive underlayer comprising a vapor-deposited film of hydrogenated carbon; spin-coating an organotin imaging layer onto the bake-sensitive underlayer; exposing the organotin imaging layer to extreme ultraviolet light; developing said organotin imaging layer using wet development; A method comprising:

79. 79. The method of claim 78, The method, wherein the wet development is carried out using an alkaline developer, an ammonium-based ionic liquid, a glycol ether, an organic acid, a ketone, or an alcohol.

80. 79. The method of claim 78, The method, wherein the wet development is carried out using tetramethylammonium hydroxide, propylene glycol methyl ether, propylene glycol methyl ether acetate, 2-heptanone, ethanol, or a combination thereof.

81. 79. The method of claim 78, The method further comprising performing a post-apply bake at a temperature less than 250° C. after spin coating.

82. 79. The method of claim 78, The method further comprising performing a post-exposure bake at a temperature less than 280° C. after exposure.

83. 83. The method of claim 82, The method further comprising performing a post-development bake at a temperature less than 280° C. after development.

84. 79. The method of claim 78, The method wherein the bake-sensitive underlayer is provided by plasma-enhanced chemical vapor deposition.

85. 79. The method of claim 78, The method further comprising providing an ashable hard mask between the substrate and the bake-sensitive underlayer after spin coating.

86. 32. The method of claim 31 , The method, wherein the carbon-containing doped film is an organometallic complex-doped carbon-containing film, and the organometallic complex-doped carbon-containing film is formed by vapor deposition of a carbon-containing film precursor and an organometallic complex.

87. 32. The method of claim 31 , The method, wherein the carbon-containing doped film is an organometallic complex-doped carbon-containing film, and the organometallic complex-doped carbon-containing film is formed by alternating deposition of a carbon-containing film precursor and an organometallic complex.

88. 32. The method of claim 31 , The method, wherein the carbon-containing doped film is an organometallic complex-doped carbon-containing film, and the organometallic complex-doped carbon-containing film is formed by immersing the deposited bake-sensitive underlayer in a solution of an organometallic complex.

89. 89. The method of claim 88, The method, wherein the organometallic complex-doped carbon-containing film comprises a layer of an organometallic complex over the bake-sensitive underlayer.

90. 89. The method of claim 88, The method, wherein the organometallic complex-doped carbon-containing film comprises an organometallic complex dispersed within the bake-sensitive underlayer.

91. 89. The method of claim 88, The method, wherein the organometallic complex-doped carbon-containing film comprises a layer of an organometallic complex over the bake-sensitive underlayer and an organometallic complex dispersed within the bake-sensitive underlayer.

92. 1. A method of fabricating a patterning structure, comprising: providing a substrate; depositing a doped bake-sensitive underlayer on the substrate, the doped bake-sensitive underlayer being doped with a dopant comprising iodine, antimony, bismuth, tellurium, and combinations thereof; forming a film of a radiation-sensitive imaging layer on the doped bake-sensitive underlayer; exposing the film to extreme ultraviolet light to produce a film comprising exposed and unexposed regions; baking the film, including exposed and unexposed regions, to activate the doped bake-sensitive underlayer and generate reactive species, wherein the reactive species generated in the doped bake-sensitive underlayer preferentially interact with the exposed regions to form exposed crosslinked regions; developing the film to include exposed crosslinked regions and unexposed regions; Including, whereby interaction of the reactive species with the exposed areas reduces the radiation dose for effective photoresist exposure of the patterned structure; The exposed crosslinked regions increase the contrast between the exposed and unexposed regions. method.

93. 93. The method of claim 92, The method wherein exposing the film to extreme ultraviolet light activates the doped bake-sensitive underlayer to generate reactive species.

94. 1. A method of fabricating a patterning structure, comprising: providing a substrate; depositing a doped bake-sensitive underlayer on the substrate, the doped bake-sensitive underlayer comprising a top underlayer surface and a bottom underlayer surface, the doped bake-sensitive underlayer being doped with a dopant comprising antimony, bismuth, tellurium, and combinations thereof; vapor depositing a film comprising a radiation-sensitive imaging layer on the upper underlayer surface of the doped bake-sensitive underlayer; baking the film to release the dopant from the doped bake-sensitive underlayer and generate dopant reactive species, wherein the generated dopant reactive species interact with the film; Including, whereby interaction of the dopant reactive species with the film reduces radiation dose for effective photoresist of patterned structures; method.

95. 95. The method of claim 94, The method, wherein vapor depositing a film comprising a radiation-sensitive imaging layer on the upper underlayer surface of the doped bake-sensitive underlayer generates dopant reactive species.

96. 1. An apparatus for processing a substrate, comprising: a process chamber including a substrate support; a process gas source and flow control hardware connected to the process chamber; substrate handling hardware coupled to the process chamber; a controller having a processor and a memory, the processor and the memory being communicatively coupled to each other, the processor being operatively coupled to at least flow control hardware and substrate handling hardware, the memory storing computer-executable instructions for performing the operations of the method of claim 1; An apparatus comprising:

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