Chemically homogeneous silicon hardmasks for lithography

Abstract

This invention discloses silicon hard masks comprising a single-component polymer. These hard masks provide high optical and chemical homogeneity, thus minimizing or avoiding negative stochastic effects on characteristic critical dimensions. These hard masks further provide low porosity, higher density, and higher silicon content, and improve performance factors such as LER / LWR, defect rate, uniformity, and DoF.

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing microelectronic structures using offset printing. Related applications

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 129,807, filed December 23, 2020, entitled "Chemical Homogeneous Silicon Hard Masks for EUV Lithography," which is incorporated herein by reference in its entirety. Prior Technology

[0003] Several techniques, such as multilayer lithography and directed self-assembly (DSA), rely on etching to transfer the resulting pattern to the underlying substrate. However, as feature sizes decrease, random effects and nanoscale inhomogeneities lead to suboptimal lithography and patterned resist transfer. For conventional hard masks, these inhomogeneities can range from about 0.5 to 2 nanometers or larger. Silicon hard masks (Si-HMs) with excellent photochemical homogeneity are needed to achieve consistent lithography and etching characteristics.

[0004] Hypothetical and modeled, the homogeneity and distribution of components play an increasingly important role in the performance of resist materials. For example, in EUV lithography, electron and hole migration between resist components, and more specifically, materials in contact with the resist, such as hard masks, can determine the degree of uniformity of PAG activation after EUV electrons have been generated. This becomes increasingly important for future nodes where stochastic effects can significantly influence the critical dimensions of features. Most efforts to improve photochemical homogeneity target the homogeneity and distribution of active components in the resist. Summary of the Invention

[0005] This disclosure generally relates to a method of forming a structure. The method includes providing a substrate comprising one or more intermediate layers, if applicable. A composition is applied to the substrate or one or more intermediate layers (if present) to form a silicon hard masking layer. The composition comprises a first polymer or oligomer formed from a monomer, the monomer comprising at least two parts (I): (I) in: Each R is individually selected from hydrogen, alkyl, alkoxy, and halogen; and " "" indicates the connection point between the silicon atom and the rest of the monomer.

[0006] One or more intermediate layers are formed on the silicon hard mask layer, as appropriate. The photoresist layer is formed on one or more intermediate layers (if present) on the silicon hard mask layer, or on the silicon hard mask layer if no intermediate layers are present. At least a portion of the photoresist layer is subjected to radiation.

[0007] In another specific example, a structure is provided. The structure includes: a substrate having a surface; one or more intermediate layers, present as appropriate, situated on the substrate surface; a silicon hard masking layer situated on the substrate surface or on the intermediate layers (if present) on the substrate surface; one or more intermediate layers, present as appropriate, situated on the silicon hard masking layer; and a photoresist layer situated on one or more intermediate layers (if present) on the silicon hard masking layer, or situated on the silicon hard masking layer if no intermediate layers are present. The silicon hard masking layer comprises a polymer or oligomer, which includes repeating units of one or both of the following: , in: Each R1 is individually selected from hydrogen, alkyl, alkoxy, halogen, and -O-; and The X series is selected from: (IV) (V) , or (VI) (VII) in: m ranges from 1 to approximately 16; n is from 1 to approximately 8; and Each Y is individually selected from one or more of the following: , Where p ranges from 1 to 6; Simple Explanation of the Diagram

[0008] [Fig. 1(a)] is a scanning electron microscope (SEM, 150kx) image showing the dense features formed as described in Example 14; [Figure 1(b)] is a SEM (150kx) image showing the individual features formed as described in Example 14; [Figure 2(a)] is a graph illustrating the process window analysis described in Example 15 using the hard mask material of Example 7; [Figure 2(b)] is a diagram illustrating the process window analysis described in Example 15 using a commercially available hard masking material; [Figure 3(a)] is a top view SEM image (150kx) of the trench formed using the hard masking material of Example 7 as described in Example 15; [Figure 3(b)] is a top view SEM image (150kx) of the trench formed using a commercially available rigid masking material as described in Example 15; [Figure 4] shows the exposure matrix of the hard mask material of Example 13 processed as described in Example 16; [Figure 5] is a top view SEM image (164kx) of the printed line obtained as described in Example 16; [Figure 6] shows the Bossung curve of the hard mask material in Example 13 (see Example 16); [Figure 7] shows the exposure matrix of the hard mask material of Example 18 processed as described in Example 19; [Figure 8] is a top view SEM image of the printed L / S feature obtained as described in Example 19 (150kx in the x direction and 49kx in the y direction); [Figure 9] shows the exposure matrix of the hard mask material of Example 18 processed as described in Example 20; [Figure 10] is a top view SEM image (164kx) of the contact hole formed as described in Example 20; [Figure 11] Comparison of critical size uniformity and SEM images of single-monomer and multi-monomer polymers (Example 22); [Figure 12] is a diagram depicting the defect-free process window of the test described in Example 22; [Figure 13] is a graph comparing the CF 4 etching rates of the hard mask formulation of Example 13 with those of a conventional hard mask (Example 23); and [Figure 14] is a graph comparing the O2 etching rate of the hard mask formulation of Example 13 with that of a conventional hard mask (Example 23). Implementation

[0009] This disclosure relates to silicon hard mask compositions and methods for forming microelectronic structures using such compositions. These compositions are useful across a wide range of wavelengths, but are particularly well-suited for EUV lithography processes. Silicon hard masking components 1. Polymers or oligomers used in the composition

[0010] The polymers and / or oligomers (i.e., two to ten monomers or repeating units) used in the silicon hard mask (“Si-HM”) composition are preferably formed by polymerizing and / or oligomerizing monomers comprising one or more parts (I): (I) in: Each R is individually selected (i.e., each R may be the same or different) from hydrogen, alkyl (preferably C1 to about C6, and more preferably C1 to about C3), alkoxy (preferably C1 to about C6, and more preferably C1 to about C3), and halogen (preferably -Cl, -F, -Br, and / or -I); and " The symbol "" indicates the point of connection between the silicon atom and the rest of the monomer. In a specific example, the Si atom is not bonded to alkoxy and / or methyl groups at the point of connection with the rest of the monomer.

[0011] In part (I), preferably no more than one R is hydrogen and / or no more than one R is halogen. That is, preferably, at least two R groups in part (I) are alkyl and / or alkoxy, and in some specific examples, all three R groups in part (I) are alkyl and / or alkoxy.

[0012] In some specific instances, a monomer comprises at least two (and preferably three) parts (I).

[0013] A preferred monomer comprising at least one moiety (I) that can be oligomerized and / or polymerized for use in Si-HM compositions preferably has a structure selected from one or both of the following: , Wherein R is as previously defined (with regard to part (I)), and X is selected from one or more of the following: (IV) (V) , or (VI) (VII) in: m is 1 to about 16, preferably 1 to about 12, and even more preferably 1 to about 8; n is 1 to approximately 8, preferably 1 to approximately 6, and even more preferably 1 to approximately 3; and Each Y is individually selected from one or more of the following: , Where p is from 1 to about 6, and more preferably from 1 to about 4.

[0014] In one specific instance, the monomers that have been polymerized or oligomerized do not contain any Si-OH groups.

[0015] In another specific example, the polymer or oligomer contains less than about 5 mol%, preferably less than about 3 mol%, and more preferably about 0 mol% of 3-(triethoxysilyl)propyl]succinic anhydride monomer.

[0016] Examples of monomers that can be polymerized or oligomerized to be included in Si-HM compositions as described herein include monomers selected from the group consisting of: 1,2-bis(triethoxysilyl)ethylene, 1,2-bis(methyldiethoxysilyl)ethylene, 1,1-bis(trimethoxysilylmethyl)ethylene, 1,6-bis(trimethoxysilyl)hexane, 1,4-bis(triethoxysilyl)benzene, 1, 2-Bis(trimethoxysilyl)ethane, n,n'-bis[3-(triethoxysilyl)propyl]urea, n,n'-bis[3-(triethoxysilyl)propyl]thiourea, 1,8-bis(triethoxysilyl)octane, bis(triethoxysilyl)methane, bis(trimethoxysilylethyl)benzene, 1,3-bis(chlorodimethylsilyl)propane, 1,2-bis(chlorodimethylsilyl)ethane, bis... [3-(triethoxysilyl)propyl]disulfide, n,n'-bis[(3-trimethoxysilyl)propyl]ethylenediamine, n,n'-bis(2-hydroxyethyl)-n,n'-bis(trimethoxysilylpropyl)ethylenediamine, bis(methyldimethoxysilylpropyl)-n-methylamine, bis[3-(triethoxysilyl)propyl]tetrasulfide, bis(triethoxysilylethyl)ethylene Methylsilane, bis(3-trimethoxysilylpropyl) fumarate, 4,4'-bis(dimethylsilyl)biphenyl, n,n'-bis(3-trimethoxysilylpropyl)thiourea, 1,11-bis(trimethoxysilyl)-4-oxa-8-azaunde-6-ol, bis(methyldiethoxysilylpropyl)amine, sphenanthrene[3-(trimethoxysilyl)propyl] isocyanurate, and combinations thereof. 2. Polymer materials and methods

[0017] To synthesize the polymer, one or more desired monomers are fed into a reactor, equipped with a distillation apparatus or reflux device as appropriate, in a suitable polymerization solvent under stirring. The polymerization solvent includes propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), propanol, propylene glycol ethyl ether (PGEE), cyclohexanone, ethyl lactate, 3-methyl-1,5-pentanediol, 1,2-propanediol, 1,3-propanediol, ethylene glycol, and mixtures thereof. The monomer solids percentage in the reaction mixture (including monomers, catalyst, and solvent) is preferably from about 10% to about 40% by weight, and more preferably from about 25% to about 35% by weight, based on the combined weight of 100% by weight of the reaction mixture. The catalyst is then slowly fed into the reactor at a temperature of about 20°C to about 100°C, and more preferably from about 25°C to about 85°C.

[0018] Catalysts suitable for sol polymerization include, but are not limited to, nitric acid, hydrochloric acid, acetic acid, trifluoroacetic acid, sulfonic acid, and combinations thereof. The catalyst is added in aqueous solution. The catalyst solution is preferably prepared in water as a solution of about 0.001 N to about 10 N, more preferably about 0.01 N to about 5 N, and even more preferably about 3 N for weaker acids and about 0.01 N for stronger acids. These aqueous catalyst solutions are added in an amount relative to the total monomers, preferably about 0.5 equivalents to about 20 equivalents, more preferably about 5 equivalents to about 15 equivalents, and even more preferably about 10 equivalents, where one equivalent is approximately equal to one mole of water per mole of monomer (or about 18 grams of water per mole of monomer). The reaction mixture is preferably stirred for about 10 minutes to about 300 minutes, more preferably about 10 minutes to about 60 minutes, and even more preferably about 10 minutes to about 30 minutes. The reaction is carried out, as appropriate, in an inert atmosphere such as nitrogen.

[0019] In one specific example, the polymer is purified and / or separated by a rotary evaporator process (also referred to herein as "rotavap"). In this process, the reaction mixture is processed in a rotary evaporator at a temperature of about 30°C to about 100°C, preferably about 45°C to about 55°C. The rotary evaporation process continues until the solvent is removed. Prior to rotary evaporation, a co-solvent may be added to the reaction mixture if necessary. Suitable co-solvents include, but are not limited to, PGEE, PGMEA, PGME, and combinations thereof.

[0020] The resulting polymer will preferably include repeating units of one or both of the following: , in: X is as previously defined; and Each R1 is selected individually from: hydrogen; Alkyl group (preferably C1 to about C6, and more preferably C1 to about C3); Alkyl group (preferably C1 to about C6, and more preferably C1 to about C3); Halogens (preferably -Cl, -F, -Br and / or -I); and -O-. In a specific instance, the polymer or oligomer is preferably composed substantially of a single monomer type or even solely of a single monomer type. That is, the resulting polymer or oligomer is primarily formed from a single type of monomer (i.e., the same monomer), and therefore primarily contains repeating units of a single type (i.e., the same repeating units). As used herein, monomers are considered the same or a single type as long as there are no differences in their chemical structure (regardless of the inherent presence of minor impurities or defects). A polymer or oligomer is considered the same or a single type if each repeating unit contains the same X group (in the case of structure (VIII)) or, in the case of structure (IX), each contains the following groups: .

[0021] In one specific instance, the monomers that have been polymerized or oligomerized do not contain any Si-OH groups.

[0022] In one specific instance, at least about 95 mol%, more preferably at least about 97 mol%, even more preferably at least about 99%, and most preferably about 100 mol%, of the polymer or oligomer is formed from a single monomer type.

[0023] In some specific instances, the resulting polymers or oligomers have a high silicon content. The polymers or oligomers preferably contain about 20% to about 47% silicon, and more preferably about 35% to about 45% silicon, wherein the silicon percentage is calculated as a percentage of the molecular weight of silicon relative to the molecular weight of the fully hydrolyzed polymer. The weight-average molecular weight (Mw) of the polymer preferably ranges from about 500 Daltons to about 50,000 Daltons, more preferably from about 1,000 Daltons to about 10,000 Daltons, as determined by gel permeation chromatography (GPC) using polystyrene standards. 3. Preparation of the constituents

[0024] The polymer and / or oligomers are then dispersed or dissolved in a solvent system. Preferred solvent systems include one or more solvents, such as PGMEA, PGME, PGEE, propylene glycol n-propyl ether (PnP), ethyl lactate, cyclohexanone, gamma-butyrolactone (GBL), 3-methyl-1,5-pentanediol, 1,2-propanediol, 1,3-propanediol, ethylene glycol, and / or mixtures thereof. Based on the total weight of the components considered as 100% by weight, the solvent system is preferably used at a content of about 95% by weight to about 99.9% by weight, more preferably about 97.5% by weight to 99.9% by weight, and even more preferably about 99% by weight to about 99.9% by weight. Based on the total weight of the composition considered as 100% by weight, the composition used to form the silicon hard mask layer will preferably contain about 0.1% by weight to about 5% by weight of solids, more preferably about 0.1% by weight to about 2.5% by weight of solids, and even more preferably about 0.1% by weight to about 1% by weight of solids.

[0025] In one specific example, the composition comprises less than about 3% by weight, preferably less than about 1% by weight and preferably 0% by weight of polymers other than the polymers mentioned above, based on the total weight of solids in the composition.

[0026] In another specific example, the composition comprises less than about 3% by weight, preferably less than about 1% by weight and preferably 0% by weight of organic polymer, based on the total weight of solids in the composition.

[0027] The above components are mixed together in a solvent system to form a silicon hard masking layer composition. In addition, any components selected as appropriate (e.g., surfactants, inorganic acids, organic acids, grafting / condensation catalysts, thermal acid generators (TAG), photoacid generators (PAG), inhibitors, and / or pH adjusters) are also dispersed in the solvent system.

[0028] When used, suitable TAGs include, but are not limited to, capped acids, such as quaternary ammonium-capped trifluoromethanesulfonic acid, such as those sold under the names: K-PURE® TAG-2689, K-PURE® TAG-2678 (King Industries, Norwalk, CT), TAG-2700, CXC-1889, TAG-2789, and combinations thereof. Based on the total weight of the composition considered as 100% by weight, the TAG is present in the composition in an amount of about 0.01% by weight to about 1% by weight, more preferably about 0.05% by weight to about 0.5% by weight, and even more preferably about 0.1% by weight to about 0.3% by weight.

[0029] Suitable catalysts for use include, but are not limited to, ethyltriphenylphosphonium bromide (EtPPB), benzyltriethylammonium chloride (BTEAC), tetrabutylphosphonium bromide (TBPB), and combinations thereof. The catalyst is present in the composition in an amount of about 0.001% to about 5% by weight, more preferably about 0.005% to about 1% by weight, and even more preferably about 0.01% to about 0.05% by weight, based on the total weight of the composition as 100% by weight.

[0030] When used, suitable inhibitors include inhibitors that protect double bonds (e.g., hydroquinone), inhibitors that maintain sol stability and / or slow down aging (e.g., 3-methyl-1,5-pentanediol), and combinations thereof. Inhibitors may be included to slow down aging and / or improve spin-bowl compatibility. Based on the total weight of the composition considered as 100% by weight, the inhibitor is present in the composition in an amount of about 0.001% by weight to about 1.0% by weight, more preferably about 0.001% by weight to about 0.1% by weight, and even more preferably about 0.001% by weight to about 0.01% by weight.

[0031] Suitable pH adjusters for use include maleic acid, malonic acid, malic acid, and combinations thereof. pH adjusters may be included to slow aging and / or improve rotating bowl compatibility. When used, the pH adjuster is present in the composition in an amount of about 0.001% to about 1.0% by weight, more preferably about 0.001% to about 0.1% by weight, and even more preferably about 0.001% to about 0.01% by weight, based on the total weight of the composition as 100% by weight.

[0032] In one specific example, the silicon hard masking composition is essentially composed of, or even entirely composed of, the aforementioned polymer / oligomer, one or more of the aforementioned components selected as appropriate, and a solvent system. In another specific example, the silicon hard masking composition is essentially composed of, or even entirely composed of, the aforementioned polymer / oligomer, a solvent system, and one or more of a catalyst, an acid generator, a free radical inhibitor, or a pH adjuster. In yet another specific example, the silicon hard masking composition is essentially composed of, or even entirely composed of, the aforementioned polymer / oligomer and a solvent system. Method using silicon hard masking composition

[0033] A method for forming microelectronic structures particularly suitable for offset printing is also provided, wherein the hard mask composition as described above is formed on the surface of a substrate or on an intermediate layer (described below) existing on the surface of a substrate.

[0034] Any microelectronic substrate can be used. The substrate is preferably a semiconductor substrate, such as silicon, SiGe, SiO2, Si3N4, SiON, SiCO:H (such as those sold by SVM, Santa Clara, CA, US under the name Black Diamond), tetramethyl silate and tetramethylcyclotetrasiloxane combinations (such as those sold under the name CORAL), aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, coral, glass, or mixtures thereof. The substrate may have a planar surface, or may include topographic features (vias, trenches, contact holes, bumps, lines, etc.). As used herein, "topography" refers to the height or depth of a structure on or on the surface of the substrate.

[0035] If necessary, a primer can be applied to the substrate surface before the hard mask or other layers are formed. Preferred primers include hexamethyldisilizane (HMDS). In this process, the wafer is exposed to primer vapor in a sealed chamber while being heated at 150°C for 90 seconds. As used herein, the primered surface is considered an intermediate layer, even if the primer process only modifies the surface of the layer being primered, rather than forming separate layers.

[0036] As noted above, an intermediate layer, selected as appropriate, may be formed on the substrate (with or without primer) prior to the formation of the hard mask layer. The carbon-rich layer is a layer, selected as appropriate, that may be formed on top of the substrate or any intermediate layer. The carbon-rich layer can be formed by any known application method, one preferred method being spin-coating at a speed of about 1,000 to about 5,000 rpm, more preferably about 1,250 to about 1,750 rpm, for a duration of about 30 to about 120 seconds, more preferably about 45 to 75 seconds. The term "carbon-rich" refers to a layer formed from a composition, wherein, based on the total solids of the composition considered as 100% by weight, the composition contains more than about 50% by weight of carbon, more preferably more than about 70% by weight of carbon, and more preferably about 75% to about 80% by weight of carbon. Suitable carbon-rich layers are selected from a group consisting of spin-on carbon layers (SOC), amorphous carbon layers, and carbon planarization layers.

[0037] An exemplary carbon-rich layer typically comprises a polymer dissolved or dispersed in a solvent system, and, where appropriate, the following components: acid and / or base quenchers, catalysts, crosslinking agents, and surface-modifying additives. A preferred composition is suitable for forming a thick layer, and the solids content of the preferred composition, considered as 100% by weight, is preferably from about 0.1% to about 70% by weight, more preferably from about 5% to about 40% by weight, and even more preferably from about 10% to about 30% by weight. After applying the carbon-rich composition, it is preferably heated to a temperature of about 100°C to about 400°C, more preferably from about 160°C to about 350°C, for a period of about 30 seconds to about 120 seconds, more preferably from about 45 seconds to about 60 seconds, to evaporate the solvent. The thickness of the carbon-rich layer after baking is preferably from about 10 nm to about 120 nm, more preferably from about 20 nm to about 100 nm, and even more preferably from about 50 nm to about 60 nm. Carbon-rich layers can be formed by other known application methods, such as chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), or plasma-enhanced atomic layer deposition (PEALD).

[0038] The silicon hard masking layer of the present invention can be formed directly on the substrate surface (with or without primer) or on a carbon-rich layer (if using) by any known application method. A preferred application method involves spin-coating the hard masking composition at a speed of about 1,000 rpm to about 2,000 rpm, preferably about 1,250 rpm to about 1,750 rpm, for a period of about 15 seconds to about 120 seconds, preferably about 30 seconds to about 75 seconds. After applying the silicon hard masking composition, it is preferably heated to a temperature of about 150°C to about 300°C, and more preferably about 200°C to about 250°C, for a period of about 15 seconds to about 120 seconds, preferably about 30 seconds to about 75 seconds, to evaporate the solvent. The thickness of the hard masking layer after baking is preferably about 2 nm to about 50 nm, more preferably about 5 nm to about 30 nm, and even more preferably about 10 nm to about 25 nm. The hard mask layer should have an etch rate at least 1.5 times that of the photoresist (e.g., chemically amplified, metal oxide, or chain-breaking photoresist) in a fluorine-rich (e.g., CF4) plasma atmosphere, and the SOC or carbon-rich layer should be etched at least 1.5 times faster than the hard mask layer in an oxygen-rich (e.g., O2) plasma etching atmosphere. The etch rate of the hard mask layer in O2 should be slow enough to block etching and allow pattern transfer to the SOC or carbon layer.

[0039] In one specific example, when etched in O2, the hard mask layer will exhibit a less varied etch rate compared to a layer with a multi-monomer polymer, even when using similar functional groups. That is, the standard deviation of the etch rate measurements performed three times as described in Example 23 will be less than about 0.5 nm / min, preferably less than about 0.25 nm / min, and more preferably less than about 0.15 nm / min.

[0040] The silicon hard masking layer will exhibit good optical and chemical homogeneity; that is, the monomer ratio of the hard masking layer in one sample will preferably be at least 90% the same as that in the hard masking layer of the second sample, more preferably at least 99%, and even more preferably about 99.9% to about 100%. This will ensure that the functional groups penetrate the polymer and the density of the layer will be substantially uniformly distributed, and preferably completely uniformly distributed.

[0041] In one specific example, the silicon hard masking layer will exhibit high critical dimension uniformity (CDU), as measured as described in Example 22. That is, the CDU will be less than about 5 nm, preferably less than about 3 nm, and even more preferably about 1 nm to about 2.5 nm.

[0042] In one specific example, the silicon hard masking layer will preferably have a surface energy of about 20 mN / m to about 70 mN / m, and more preferably 25 mN / m to about 60 mN / m, which is determined by measuring the surface contact angle using a variety of liquids on a contact angle tool such as the VCA Optima contact angle tool.

[0043] After baking the silicon hard mask layer, a photoresist (i.e., an imaging layer) can be applied to the silicon hard mask layer to form a photoresist layer. The photoresist layer can be formed by any known method, one preferred method being to spin-coat the photoresist composition at a speed of about 350 rpm to about 4,000 rpm (preferably about 1,000 rpm to about 2,500 rpm) for a period of about 10 seconds to about 60 seconds (preferably about 10 seconds to about 30 seconds). Subsequently, a post-application bake (PAB) photoresist layer is applied at a temperature of at least about 70°C, preferably about 80°C to about 150°C, and more preferably about 100°C to about 150°C, for a period of about 30 seconds to about 120 seconds, depending on the situation. After baking, the thickness of the photoresist layer (an average measurement obtained by ellipsometer at five locations) will typically be about 5 nm to about 120 nm, preferably about 10 nm to about 50 nm, and even more preferably about 20 nm to about 40 nm.

[0044] A primer coating process can be applied before photoresist coating. Preferred primers include hexamethyldisilazane. In this process, the wafer is exposed to primer vapor in a sealed chamber while being heated at 150°C for 90 seconds.

[0045] The photoresist layer is then patterned by exposure to radiation at wavelengths preferably from about 10 nm to about 400 nm, more preferably from about 13 nm to about 193 nm. In one specific example, the layer is exposed to EUV radiation (i.e., wavelengths less than about 20 nm and typically about 13.5 nm). In any case, the preferred exposure dose is from about 5 mJ / cm² to about 120 mJ / cm², more preferably from about 10 mJ / cm² to about 80 mJ / cm², and more preferably from about 20 mJ / cm² to about 60 mJ / cm². More specifically, the photoresist layer is exposed using a mask positioned above the surface of the photoresist layer. The mask has areas designed to allow radiation to reflect off the mask (in the case of EUV) or pass through the mask (in the case of ArF or higher wavelengths) and contact the surface of the photoresist layer. The remaining portion of the mask is designed to absorb light to prevent radiation from contacting the surface of the photoresist layer in certain areas. Those skilled in the art will readily understand that the arrangement of the reflective and absorptive portions is designed based on the desired pattern to be formed in the photoresist layer and ultimately in the substrate or any intermediate layer.

[0046] After exposure, the photoresist layer is preferably subjected to a post-exposure bake (PEB) at a temperature of less than about 180°C, more preferably about 60°C to about 140°C, and more preferably about 80°C to about 130°C for a period of about 30 seconds to about 120 seconds (preferably about 30 seconds to about 90 seconds).

[0047] The photoresist layer is then contacted with a developer to form a pattern. Depending on whether the photoresist used is positive or negative, the developer removes either the exposed or unexposed portions of the photoresist layer to form the pattern. The pattern is then transferred to a silicon hard mask layer, any existing intermediate layers, and finally to the substrate. This pattern transfer can occur via plasma etching (e.g., CF4 etchant, O2 etchant) or a wet etching or development process. In a specific instance where the pattern is transferred from the photoresist layer to the substrate via etching, preferably, the etching rate of the silicon hard mask layer is at least about 1 times that of a typical photoresist, and more preferably about 1.5 times to about 2 times.

[0048] Regardless of whether pattern transfer is performed by etching or development, the resulting features exhibit high resolution. For example, the method of this invention can achieve a resolution of less than about 40 nm half-pitch, preferably less than about 30 nm half-pitch, and even more preferably less than about 20 nm half-pitch. The silicon hard mask layer preferably improves the collapse margin of the final feature. Collapse margin is quantified by the difference in dose to size between the maximum dose from which the structure remains upright for positive tone imaging resist, or the minimum dose from which the structure remains upright for negative tone developing resist or negative tone imaging resist.

[0049] Those skilled in the art will appreciate the additional advantages of the various specific examples upon reviewing the disclosure herein and the working embodiments described below. It should be understood that, unless otherwise indicated herein, the various specific examples described herein are not necessarily mutually exclusive. For example, a feature described or depicted in one specific example may be included in other specific examples, but is not required to be included. Therefore, this disclosure covers various combinations and / or integrations of the particular specific examples described herein.

[0050] As used herein, the phrase "and / or" when used in a list of two or more items means that any one of the listed items may be used alone or any combination of two or more of the listed items. For example, if a composition is described as containing or excluding components A, B and / or C, then the composition may contain or exclude A alone; B alone; C alone; a combination of A and B; a combination of A and C; a combination of B and C; or a combination of A, B and C.

[0051] This specification also uses numerical ranges to quantify certain parameters relevant to various specific instances. It should be understood that when numerical ranges are provided, such ranges are to be interpreted as providing textual support for asserting limitations on only the lower limit of the range and limitations on only the upper limit of the range. For example, the disclosed numerical range of approximately 10 to approximately 100 provides textual support for assertions of "greater than approximately 10" (without an upper boundary) and assertions of "less than approximately 100" (without a lower boundary). Example

[0052] The following embodiments illustrate methods according to this disclosure. However, it should be understood that these embodiments are provided by way of illustration, and nothing therein should be considered as a limitation on the overall scope. Example 1 Synthesis of poly(1,2-bis(triethoxysilyl)ethylene)

[0053] In a 250 ml three-necked round-bottom flask, 10.08 g of 1,2-bis(triethoxysilyl)ethylene (Gelest, Morrisville, PA) and 84.88 g of acetone were added. A stir bar was added to the mixture, and 5.15 g of 0.01 N HCl was added dropwise while stirring. After a reaction time of 2.5 hours, 84 g of PGEE (Fujifilm Ultra Pure Solutions, Carrollton, TX) was added to the flask, and the mixture was rotary evaporated to remove the acetone. This stock solution was used for further testing in subsequent examples. Example 2 Si-HM formulation of polymer from Example 1

[0054] In a 250 ml Aicello vial, add 1.57 g of the polymer synthesized in Example 1, 0.02 g of K-PURE® TAG-2689 (King Industries, Norwalk, CT), 78.81 g of PGEE, and 19.7 g of PGME (KMG Electronic Chemicals, Fort Worth, TX) and mix for 30 minutes. This formulation was filtered using a 0.1-micron PTFE filter (GE Healthcare UK Limited, Buckinghamshire, UK). Example 3 Synthesis of poly(1,2-bis(triethoxysilyl)ethylene)

[0055] In a 250 ml Aicello flask, add 12.04 g of 1,2-bis(triethoxysilyl)ethylene and 101.9 g of acetone. Then, add 6.21 g of 0.01 N HCl dropwise while mixing the contents of the flask. Invert the mixture on a wheel and mix for 3 hours at room temperature, then add 102 g of PGEE. Transfer the mixture to a 500 ml round-bottom flask. Rotate the mixture at room temperature for 5 minutes, immersing it in a rotary evaporator water bath maintained at 50°C, until the distillation of acetone stops. Continue rotary evaporation for another 5 minutes. Cool the mixture to room temperature and filter the mother liquor using a 0.2 micron PTFE filter. Example 4 Si-HM formulation of polymer from Example 3

[0056] In a 250 ml Aicello flask, add 0.603 g of the mother liquor synthesized in Example 3, 0.006 g of ethyltriphenylphosphonium bromide ("EtPPB", a catalyst obtained from Sigma-Aldrich, St. Louis, MO), 78.72 g of PGEE, and 20.67 g of PGME, and mix for 30 minutes. Filter this formulation using a 0.1-micron PTFE filter. Example 5 Si-HM formulation of polymer from Example 3

[0057] In a 100 ml Aicello flask, add 0.347 g of the mother liquor synthesized in Example 3, 0.003 g of EtPPB, 79.727 g of PGEE, and 19.923 g of PGME, and mix for 30 minutes. Filter this formulation using a 0.1 micron PTFE filter. Example 6 Synthesis of poly(1,2-bis(methyldiethoxysilyl)ethylene)

[0058] In a 500 ml round-bottom flask, add 10.09 g of 1,2-bis(methyldiethoxysilyl)ethylene (Gelest, Morrisville, PA) and 83.87 g of acetone. Next, add 6.2 g of 0.01 N HCl dropwise at room temperature with stirring for 30 minutes. Heat the mixture to reflux at 80 °C for 4 hours, then add 84 g of PGEE to the reaction flask. Rotate the mixture at room temperature for 5 minutes, immersing it in a rotary evaporator water bath maintained at 50 °C, until the distillation of acetone stops. Continue rotary evaporation for another 5 minutes. Cool the mixture to room temperature and store at -20 °C. Example 7 Si-HM formulation of polymer from Example 6

[0059] In a 250 ml Aicello flask, 1.67 g of the mother liquor synthesized in Example 6, 0.02 g of benzyltriethylammonium chloride (“BTEAC”, a catalyst obtained from Sigma-Aldrich, St. Louis, MO), 78.62 g of PGEE, and 19.69 g of PGME were added and mixed together for 30 minutes. This formulation was filtered using a 0.1-micron PTFE filter. Example 8 Synthesis of poly(1,2-bis(methyldiethoxysilyl)ethylene)

[0060] In a 250 ml three-necked round-bottom flask, add 5.18 g of 1,2-bis(methyldiethoxysilyl)ethylene and 43.46 g of PGMEA. Next, add 3.21 g of 0.01 M HCl dropwise at room temperature with stirring for 30 minutes. Heat the mixture to reflux at 80 °C for 4 hours. Cool the mixture to room temperature, transfer to a clean Aicello flask, and store at -20 °C. Example 9 Si-HM formulation of polymer from Example 8

[0061] In a 250 ml Aicello flask, add 35.32 g of the mother liquor synthesized in Example 8, 0.883 g of PGMEA containing 1% hydroquinone (a free radical inhibitor) (KMG Electronic Chemicals, Fort Worth, TX), 211.31 g of PGMEA, and 2.48 g of 3-methyl-1,5-pentanediol (Sigma-Aldrich, St. Louis, MO) and mix for 30 minutes. Filter this formulation using a 0.1-micron PTFE filter. Example 10 Synthesis of poly(1,4-bis(triethoxysilyl)benzene)

[0062] In a 100 ml round-bottom flask, add 1.50 g of 1,4-bis(triethoxysilyl)benzene (Gelest, Morrisville, PA) and 12.83 g of PGMEA. Next, add 0.67 g of 0.01 M HCl dropwise to the stirred flask. Stir the mixture at room temperature for 30 minutes. The solution is then purged with nitrogen in a reflux apparatus and heated to 80°C for 6 hours with constant stirring. The mother liquor is then removed from heating and cooled with stirring. Once at room temperature, the mother liquor is transferred to 100 ml Aicello flasks for storage. Example 11 Si-HM formulation of polymer from Example 10

[0063] In a 100 ml Aicello flask, add 8.2931 g of the mother liquor synthesized in Example 10, 10.0109 g of PGME, and 82.7083 g of PGMEA and mix for 30 minutes. Filter the mixture using a 0.1 micron filter. Example 12 Synthesis of poly(1,2-bis(methyldiethoxysilyl)ethylene)

[0064] In a 100 ml round-bottom flask, 7.83 g of 1,2-bis(methyldiethoxysilyl)ethylene (Gelest, Morrisville PA) and 65.34 g of PGMEA were added. Next, 4.85 g of 0.01 M HCl was added dropwise to the stirred flask. The mixture was stirred at room temperature for 30 minutes, then purged with nitrogen in a reflux apparatus and heated to 80°C for 6 hours with continuous stirring. The mother liquor was then removed from heating and cooled with stirring. Once at room temperature, the mother liquor was transferred to 100 ml Aicello flasks for storage. Example 13 Si-HM formulation of polymer from Example 12

[0065] In a 100 ml Aicello flask, add 11.9434 g of the mother liquor synthesized in Example 12, 0.2985 g of TBPB (Sigma-Aldrich, St. Louis, MO), 9.5819 g of PGME, and 78.1605 g of PGMEA and mix for 30 minutes. Filter the mixture using a 0.1 micron filter. Example 14 Screening of negative tone developing lithography performance

[0066] Using a Sokudo DUO coating and developing system (track), 12-inch silicon wafers were dehydrated at 230°C for 60 seconds and undercoated with hexamethyldisilazane at 110°C for 50 seconds prior to SOC coating. Spin-coating carbon or the "SOC" composition, sold under the name OptiStack® SOC110D (Brewer Science, Rolla, MO), was spin-coated onto the undercoated wafers at 1,727 rpm for 30 seconds, followed by baking at 205°C for 60 seconds. Silicon hard masks were then spin-coated onto different SOC-coated wafers as follows: the Example 2 formulation was spin-coated at 1,280 rpm for 30 seconds, followed by baking at 240°C for 60 seconds; and the Example 4 formulation was spin-coated at 1,000 rpm for 30 seconds, followed by baking at 205°C for 60 seconds. The stacks of hard mask coatings were undercoated with hexamethyldisilazane at 150°C for 80 seconds. Photoresist (AN02 resist from FujiFilm) was applied to the top of the stack (on a base-coated hard mask) at a rotation speed of 1,930 rpm for 30 seconds, followed by baking at 90°C for 60 seconds. The wafer was exposed via a photomask to generate a focal dosing matrix using an immersion tool (TWINSCAN NXT:1950i, available from ASML, the Netherlands). For the hard mask formulation of Example 2, the dosing ranged from 18 mJ / cm² to 46 mJ / cm², and the focal length ranged from -0.23 µm to 0.13 µm. For the hard mask formulation of Example 4, the dosing ranged from 18 mJ / cm² to 46 mJ / cm², and the focal length ranged from -0.21 µm to 0.11 µm. This was followed by a development step using FN-DP001 / 20 developer (FujiFilm, North Kingstown, RI).

[0067] CD-SEM measurements (Hitachi CG5000-2, 150Kx; beam = 500 V, 8Pa) were performed to evaluate the effectiveness of these hard masks. Data are presented in Table 1, while Figures 1(a) to (b) show images of the clean, formed trenches. The resist profile is also straight in both dense (Figure 1(a)) and isolated (Figure 1(b)) features. Table 1. Effective energy obtained by high-photochemical homogeneous hard mask [Hard mask] [Nested] [DoF] [(] [nm] [)] [Nested structure biased] [LWR] [(] [nm] [)] [Dense Dosage] [(] [mJ] [)] [Collapse Tolerance] [(] [mJ] [)] Bridge tolerance () [bridge margin] [)] [(] [mJ] [)] [Under intensive doses] [Iso DoF] [(] [nm] [)] [Iso LWR] [(] [nm] [)] Example 2 >280 (Focus Offset) 3.9 32 28 45 > 40 4.4 Example 4 >360 3.7 32 twenty two 46 80 4.8 Example 15 Screening of positive tone developing lithographic printing performance

[0068] Using the Sokudo DUO coating and developing system, 12-inch silicon wafers were dehydrated at 230°C for 60 seconds and undercoated with hexamethyldisilazane at 110°C for 50 seconds prior to SOC coating. SOC, sold under the name OptiStack® SOC120 (Brewer Science, Rolla, MO), was spin-coated onto the undercoated wafer at 1,368 rpm for 30 seconds, followed by baking at 205°C for 60 seconds. Silicon hard masks were then spin-coated onto different SOC-coated wafers as follows: Example 7: 1,110 rpm for 30 seconds, followed by baking at 205°C for 60 seconds; and a commercially available hard mask composition sold under the name OptiStack® HM825-303.2 (Brewer Science, Rolla, MO): 1,171 rpm for 30 seconds, followed by baking at 205°C for 60 seconds. Both hard masks were coated to a target thickness of 30 nm. A commercially available resist (AIM5484, JSR Micro) was applied to the top of the stack at a spin speed of 1,185 rpm for 30 seconds, followed by a post-bake at 120°C for 60 seconds. The wafer was then exposed via a photomask (TM07-40) to generate a focal dose matrix using an immersion tool (TWINSCAN NXT:1950i). σ(outer / inner) was (0.98 / 0.821). The illumination mode of Dipole35Y Gen2 was used. NA was 1.35. For the hard mask formulation from Example 7, the dose varied from 6.4 mJ / cm² to 28.8 mJ / cm², and the focal spot varied from 0.15 µm to -0.21 µm. After exposure, a bake at 100°C for 60 seconds was performed. The pattern was then developed for 20 seconds using a developer (OPD262, available from FujiFilm). This exposure produced a series of grooves and spaces. These features were analyzed using a scanning electron microscope (CG5000-2, Hitachi) at 150Kx magnification with 500 V and 8 pA. The data are shown in Table 2. As shown in Figures 2(a) and (b), the process window of the material formulated in Example 7 is larger than that of the commercially available silicon hard mask layer (OptiStack® HM825-303.2). Figures 3(a) and (b) are top views of the two samples. Table 2. Performance metrics obtained from the hard mask of Example 7 and commercially available hard masks [Hard mask] [Dense] [DoF] [(] [nm] [)] [PW DoF] [(] [nm] [)] [PW EL] [(] [%] [)] [Dense] [LWR] [(] [nm] [)] [Dense Dosage] [(] [mJ] [)] [Collapse Tolerance] [(] [mJ] [)] [Bridge Capacity] [(] [mJ] [)] Example 7 80 51 19.9 3.7 20.8 25.6 10.4 Commercially available hard shields 60 42 23.0 3.4 19.2 23.2 9.6 Example 16 lithographic printing results from the formulation of Example 13

[0069] The material from Example 13 was spin-coated onto a carbon layer of OptiStack® SOC120 material (Brewer Science, Rolla, MO) at 1340 rpm for 30 seconds and then baked at 205°C for 60 seconds. This carbon layer was formed by spin-coating onto a Si wafer at 1406 rpm for 30 seconds and then baking at 205°C for 60 seconds to form a 25 nm film. EUV resist (JSR4267, available from JSR Corporation; supplied by IMEC) was applied onto a hard mask layer by spin-coating at 1040 rpm for 25 seconds and then baked at 130°C for 60 seconds to form a 35 nm thick coating. The resulting resist was exposed using an EUV scanner (TWINSCAN NXE:3400B, available from AMSL) for the imaging step and a coating and developing system (CLEAN TRACK TMLITHIUS Pro TMZ, TEL, Tokyo, JP) for the wafer fabrication process. After exposure, the resist was baked at 110°C for 60 seconds. The pattern was then developed using a developer (OPD262, available from FujiFilm). The characteristics were analyzed using a scanning electron microscope (CG5000-2, Hitachi) at 164Kx magnification with 500 V and 8 pA. Figure 4 shows the exposure matrix, Figure 5 shows a top view of the sample, and Figure 6 shows the Poisson curve of the material from Example 13. Example 17 Synthesis of poly(trimethoxysilyl)propyl isocyanurate [3-(trimethoxysilyl)propyl] ester

[0070] In a 100 ml round-bottom flask, add 6.16 g of trimethylolpropanoate [3-(trimethoxysilyl)propyl] ester (Gelest, Morrisville, PA) and 17 g of PGME (KMG Electronic Chemicals, Fort Worth, TX). Next, while stirring at room temperature for 30 minutes, add dropwise 0.88 g of 0.01 N HNO₃ (Sigma-Aldrich, St. Louis, MO). Heat the mixture to reflux at 90 °C for 20 minutes, then cool to room temperature and store at -20 °C. Example 18 Si-HM formulation of polymer from Example 17

[0071] In a 1-liter Aiello flask, add 5.43 g of the stock solution synthesized in Example 17, 0.11 g of 2% TBPB / PGME stock solution (TBPB from Sigma-Aldrich, St. Louis, MO), 1.09 g of 2% maleic acid / PGME stock solution (pH adjuster; maleic acid from Sigma-Aldrich, St. Louis, MO), 257.18 g of PGME, and 29.19 g of PGMEA, and mix for 30 minutes. Filter this formulation using a 0.1-micron filter. Example 19 Example 18: EUV line / space (L / S) patterning results of formulations

[0072] The material from Example 18 was spin-coated on top of a carbon layer (sold by Brewer Science, Rolla, MO under the name OptiStack® SOC120) at 1521 rpm for 30 seconds and baked at 205°C for 60 seconds. This carbon layer was formed into a 25 nm film by spin-coating on a Si wafer at 1521 rpm for 30 seconds and baking at 205°C for 60 seconds. EUV resist (JSR4267, available from JSR Corporation; supplied by IMEC) was then applied by spin-coating at 1040 rpm for 25 seconds and subsequently baked at 130°C for 60 seconds to form a 35 nm thick coating. The resulting resist was exposed using an EUV scanner (TWINSCAN NXE:3400B, available from AMSL) for the imaging step and a coating and developing system (CLEAN TRACK TMLITHIUS Pro TMZ, TEL, Tokyo, JP) for the wafer fabrication process. After exposure, the resist was baked at 110°C for 60 seconds. The pattern was then developed using a developer (OPD262, available from FujiFilm). The characteristics were analyzed using a scanning electron microscope (CG6300, Hitachi) at 164Kx magnification with 500 V and 8 pA. Figure 7 shows the exposure matrix of the L / S pattern, and Figure 8 shows a top view of the printed L / S sample. Example 20 Example 18: Patterning of EUV Contact Holes in the Formulation

[0073] The material from Example 18 was spin-coated onto a bare silicon wafer at 1,900 rpm for 30 seconds and baked at 205°C for 60 seconds to form a 5 nm thick hard mask layer. EUV resist (JSR4267, available from JSR Corporation; supplied by IMEC) was applied onto the hard mask layer by spin-coating at 1,040 rpm for 25 seconds, followed by baking at 130°C for 60 seconds to form a 35 nm thick resist layer. The formed resist was exposed using an EUV scanner (TWINSCAN NXE:3400B, available from AMSL) for the imaging step and a coating and developing system sold under the name CLEAN TRACK TMLITHIUS Pro TMZ (TEL, Tokyo, JP) for the wafer fabrication process. After exposure, it was baked at 110°C for 60 seconds. The pattern was then developed using a developer (OPD262, available from FujiFilm). The features were analyzed using a scanning electron microscope (CG6300, Hitachi) at 164Kx magnification with 500 V and 8 pA. Figure 9 shows the exposure matrix of the contact hole patterning, and Figure 10 shows a top view of the printed contact hole features. Example 21 Si-HM formulation of polymer from Example 17

[0074] In a 250 ml Aicello flask, add 8.85 g of the mother liquor synthesized in Example 17, 1.77 g of 2% maleic acid / PGME stock solution, 145.72 g of PGME, and 17.17 g of PGMEA, and mix for 30 minutes. Filter this formulation using a 0.1 micron filter. Example 22 Example 21: Patterning of EUV Contact Holes in the Formulation

[0075] The material from Example 21 was spin-coated onto a bare silicon wafer at 1,900 rpm for 30 seconds and then baked at 205°C for 60 seconds to form a 5 nm thick hard mask layer. EUV resist (JSR4267, available from JSR Corporation; supplied by IMEC) was applied onto the hard mask layer by spin-coating at 1,040 rpm for 25 seconds and then baked at 130°C for 60 seconds to form a 35 nm thick resist layer. The resist was then exposed using an EUV scanner (TWINSCAN NXE:3400B, available from AMSL) and developed with OPD262 developer for 20 seconds. The critical size uniformity (CDU) of the pattern was analyzed by CD-SEM measurements (Hitachi CG5000-2, 150Kx; beam = 500 V, 8 pA) and compared with a linear control polymer formed from trimethylolpropionate isocyanurate, tetraethyl orthosilicate (TEOS), and phenyltrimethoxysilane, applied using the same parameters as the material in Example 21. CDU information and SEM images of each polymer are shown in Figure 11.

[0076] The defect-free process window analyzed a total of 8,600 contact holes using Kolona software and compared them with a control group. This data is shown in Figure 12, where the x-axis represents the diameter of the feature in nanometers. Example 23 Etching results of the formulation in Example 13

[0077] The etching rate in the O2 and CF4-based plasma etching chemistry was tested using materials from Example 13 and a conventional (multi-monomer) Si-HM sample with a 2:1 ratio of methyltrimethoxysilane and vinyltrimethoxysilane, designed to have functional groups similar to those of the polymer used in Example 13 (i.e., 1,2-bis(methyldiethoxysilyl)ethylene). The samples were spin-coated onto 100 mm silicon wafers, baked at 205°C for 60 seconds, diced into 2.5 mm × 2.5 mm wafers, and subsequently etched using an Oxford Plasma Lab 80+ etcher. O2-based etching was used with one set of these wafers, and CF4-based etching was used with another set. The etching process settings were 50 sccm flow rate (O2 or CF4), 50 mTorr chamber pressure, 50 W power, and 30 seconds etching time. The etching rates of the samples for the two etching chemistries were calculated using film thickness measurements obtained before and after etching using a Gaertner ellipsometer. These etching rate results are shown in Figures 13 and 14, with the multi-monomer material on the left and the single-monomer material (i.e., the formulation of Example 13) on the right.

[0078] The CF4 etch rate results show that the etch rate of the single-monomer polymer sample (18.47 nm / min) is higher than that of the conventional multi-monomer Si-HM sample. A higher CF4 etch rate is desirable during semiconductor processing with Si-HM. In the case of O2 plasma, the average etch rate is equal for both samples, but compared to the conventional Si-HM sample (standard deviation 0.945 nm / min), the single-component polymer sample exhibits a smaller variation in etch rate (standard deviation 0.115 nm / min), which will produce more uniform etching and clearer features.

[0079] none

Claims

1. A method of forming a structure, the method comprising: providing a substrate, the substrate including one or more intermediate layers thereon, as appropriate; applying a composition to the substrate, or, if one or more intermediate layers are present on the substrate, applying it to one or more intermediate layers on the substrate to form a silicon hard masking layer, the composition comprising a first polymer or oligomer composed of monomers of formula (II): wherein: Each R is individually selected from hydrogen, alkyl, alkoxy, or halogen; and X is selected from one or more of the following: (IV), (V), (VI), or (VII), wherein: m is 1 to about 16; n is 1 to about 8; and each Y is individually selected from one or more of the following: , wherein p is 1 to 6; one or more intermediate layers are formed on the silicon hard mask layer as appropriate; if one or more intermediate layers are present on the silicon hard mask layer, a photoresist layer is formed on one or more intermediate layers on the silicon hard mask layer, or if no intermediate layer is present, a photoresist layer is formed on the silicon hard mask layer; and at least a portion of the photoresist layer is subjected to radiation.

2. The method of claim 1, wherein the first polymer or oligomer does not contain any Si-OH groups.

3. The method of claim 1, wherein the composition does not include any polymer other than the first polymer.

4. The method of claim 1, wherein the first polymer or oligomer does not include the [3-(triethoxysilyl)propyl]succinic anhydride monomer.

5. The method of claim 1, wherein the first polymer or oligomer is formed from one or more of the following: 1,2-bis(triethoxysilyl)ethylene, 1,2-bis(methyldiethoxysilyl)ethylene, 1,1-bis(trimethoxysilylmethyl)ethylene, 1,6-bis(trimethoxysilyl)hexane, 1,4-bistriethoxysilylbenzene, 1,2-bis(triethoxysilyl)benzene, etc. Methoxysilyl)-ethane, n,n'-bis[3-(triethoxysilyl)propyl]urea, n,n'-bis[3-(triethoxysilyl)propyl]thiourea, 1,8-bis(triethoxysilyl)octane, bis(triethoxysilyl)methane, bis(trimethoxysilylethyl)benzene, 1,3-bis(chlorodimethylsilyl)propane, 1,2-bis(chlorodimethylsilyl) Ethane, bis[3-(triethoxysilyl)propyl] disulfide, n,n'-bis[(3-trimethoxysilyl)propyl]ethylenediamine, n,n'-bis(2-hydroxyethyl)-n,n'-bis(trimethoxysilylpropyl)ethylenediamine, bis(methyldimethoxysilylpropyl)-n-methylamine, bis[3-(triethoxysilyl)propyl]tetrasulfide bis(triethoxysilylethyl)-vinylmethylsilane, bis(3-trimethoxysilylpropyl) fumarate, 4,4'-bis(dimethylsilyl)biphenyl, n,n'-bis(3-trimethoxysilylpropyl)thiourea, 1,11-bis(trimethoxysilyl)-4-oxa-8-azaunde-6-ol or bis(methyldiethoxysilylpropyl)amine.

6. The method of claim 1, wherein the substrate is selected from the group consisting of: silicon, SiGe, SiO2, Si3N4, SiON, SiCO:H, tetramethyl silicate and tetramethylcyclotetrasiloxane combination, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, coral, glass and mixtures thereof.

7. The method of claim 1, wherein the radiation is EUV radiation.

8. The method of claim 1, further comprising forming a pattern in the photoresist layer after subjecting the photoresist layer to radiation.

9. The method of claim 8, further comprising transferring the pattern to the silicon hard mask layer, transferring it to the intermediate layer if an intermediate layer exists, and transferring it to the substrate.

10. The method of claim 1, wherein an intermediate layer exists and the intermediate layer is a carbon-rich layer.

11. A structure comprising: a substrate having a surface; one or more intermediate layers present, as appropriate, on the surface of the substrate; a silicon hard masking layer on the surface of the substrate, or, if an intermediate layer is present on the surface of the substrate, a silicon hard masking layer on the intermediate layer of the substrate, the silicon hard masking layer comprising a polymer or oligomer, the polymer or oligomer comprising repeating units of one or both of the following: , wherein: Each R1 is individually selected from hydrogen, alkyl, alkoxy, halogen or -O-; and the X series is selected from: (IV), (V), (VI), or (VII), wherein: m is 1 to about 16; n is 1 to about 8; and each Y is individually selected from one or more of the following: , wherein p is 1 to 6; one or more intermediate layers present as appropriate on the silicon hard masking layer; and a photoresist layer, if one or more intermediate layers are present on the silicon hard masking layer, then the photoresist layer is located on one or more intermediate layers on the silicon hard masking layer, or if no intermediate layer is present, then the photoresist layer is located on the silicon hard masking layer.

12. The structure of claim 11, wherein the substrate is selected from the group consisting of: silicon, SiGe, SiO2, Si3N4, SiON, SiCO:H, tetramethyl silicate and tetramethylcyclotetrasiloxane combination, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, coral, glass and mixtures thereof.

13. The structure of claim 11, wherein the silicon hard mask layer and the photoresist layer have respective etch rates in CF4, the etch rate in CF4 of the silicon hard mask layer being at least about 1.5 times the etch rate in CF4 of the photoresist layer.

14. The structure of claim 11, wherein the silicon hard mask layer has an etch rate in O2 and the standard deviation between the three etch rate measurements is less than about 0.5 nm / min.

15. The structure of claim 11, wherein the polymer or oligomer is composed of a single monomer type.

16. A method of forming a structure, the method comprising: providing a substrate, the substrate including one or more intermediate layers thereon, as appropriate; applying a composition to the substrate, or, if one or more intermediate layers are present on the substrate, applying it to one or more intermediate layers on the substrate to form a silicon hard masking layer, the composition comprising a first polymer or oligomer formed from a monomer, the monomer comprising at least two portions (I): (I), wherein: Each R is individually selected from hydrogen, alkyl, alkoxy, or halogen; and "" indicates the junction of a silicon atom with the remainder of the monomer; one or more intermediate layers are formed on the silicon hard mask layer as appropriate; if one or more intermediate layers are present on the silicon hard mask layer, a photoresist layer is formed on one or more intermediate layers on the silicon hard mask layer, or if no intermediate layers are present, a photoresist layer is formed on the silicon hard mask layer; and at least a portion of the photoresist layer is subjected to radiation, wherein the radiation is EUV radiation.

17. A method of forming a structure, the method comprising: providing a substrate, the substrate including one or more intermediate layers thereon, as appropriate; applying a composition to the substrate, or, if one or more intermediate layers are present on the substrate, applying it to one or more intermediate layers on the substrate to form a silicon hard masking layer, the composition comprising a first polymer or oligomer formed from a monomer, the monomer comprising at least two portions (I): (I), wherein: Each R is individually selected from hydrogen, alkyl, alkoxy, or halogen; and "" indicates the connection point between the silicon atom and the remainder of the monomer; one or more intermediate layers are formed on the silicon hard mask layer as appropriate; if one or more intermediate layers are present on the silicon hard mask layer, a photoresist layer is formed on one or more intermediate layers on the silicon hard mask layer, or if no intermediate layers are present, a photoresist layer is formed on the silicon hard mask layer; at least a portion of the photoresist layer is subjected to radiation; and a pattern is formed in the photoresist layer after the photoresist layer has been subjected to radiation.

18. A structure comprising: a substrate having a surface; one or more intermediate layers present, as appropriate, on the surface of the substrate; a silicon hard masking layer on the surface of the substrate, or, if an intermediate layer is present on the surface of the substrate, a silicon hard masking layer on the intermediate layer on the surface of the substrate, the silicon hard masking layer comprising a polymer or oligomer, the polymer or oligomer being composed of repeating units of: wherein: Each R1 is individually selected from hydrogen, alkyl, alkoxy, halogen or -O-; and the X series is selected from: (IV), (V), (VI), or (VII), wherein: m is 1 to about 16; n is 1 to about 8; and each Y is individually selected from one or more of the following: , wherein p is 1 to 6; one or more intermediate layers present as appropriate on the silicon hard mask layer; and a photoresist layer, if an intermediate layer is present, the photoresist layer is located on one or more intermediate layers on the silicon hard mask layer, or if no intermediate layer is present, the photoresist layer is located on the silicon hard mask layer.

Images