Silicon-containing high-moisture-removable planarization layer

Abstract

Lithographic compositions for use as wet-removable silicon gap fill layers are provided. Methods of using these compositions involve utilizing a silicon gap fill layer over topographic features on a substrate. The silicon gap fill layer can be applied either directly to the substrate or to any intermediate layer that can be applied directly to the substrate. Preferred silicon gap fill layers are formed from spin-coatable polymer compositions with high silicon content, and these layers exhibit good gap fill and planarization performance and high oxygen etch resistance.

Description

Technical Field

[0001] Related Applications This application claims the benefit of priority of U.S. Provisional Patent Application No. 62 / 925,259, filed October 24, 2019, entitled "HIGH-SILICON-CONTENT WET-REMOVABLE PLANARIZING HARDMASK", which is incorporated herein by reference in its entirety.

[0002] The present invention relates to a method of manufacturing microelectronic structures using lithography.

Background Art

[0003] If the semiconductor industry continues to follow Moore's Law, the requirements for ever-smaller feature sizes will necessitate the use of innovative processes and materials to obtain clear features. Importantly, a flat surface must be created to enable shorter lithography wavelengths and the focal lengths necessary to enable smaller features. High silicon content materials (25% - 40%) are not only promising gap-fill materials for creating a flat surface for lithography but also provide good etch resistance, thus enabling a high-fidelity pattern transfer process. However, the high silicon content and siloxane network structure of these materials make their removal difficult. Fluorine-containing plasmas and hydrofluoric acid can be used to remove (or strip) these silicon-containing layers. However, both fluorine plasmas and hydrofluoric acid remove not only these silicon-containing materials but also other materials that should remain intact, such as the substrate. Wet stripping using higher concentrations, for example, ≥ 5 wt% tetramethylammonium hydroxide, can be used to remove at least a portion of these silicon-containing layers, but these higher concentrations of tetramethylammonium hydroxide can also potentially damage the substrate. Silicon-containing layers with a relatively low amount of silicon may sometimes be removable using "piranha solution" (concentrated sulfuric acid and hydrogen peroxide), but such an approach has proven unsuccessful for silicon-containing materials with a higher silicon content. Summary of the Invention Problems to be Solved by the Invention

[0004] As the structure becomes smaller with a very high aspect ratio, it is essential to find a silicon-containing material that can fill the gaps between structures with a very high aspect ratio while achieving good planarization so that multiple lithography patterning processes can be carried out to generate more complex structures. There is a need for a silicon-containing gap-fill material with high etch resistance that can be removed after processing without damaging adjacent structures or the substrate.

Means for Solving the Problems

[0005] In one embodiment, the present disclosure is broadly related to a method of forming a structure, the method including providing a substrate having a surface including topographic features. The substrate optionally includes one or more intermediate layers on its surface. A composition is applied to the substrate surface or, if present, on one or more intermediate layers to form a planarization layer. The composition includes a polymer including a [3-(triethoxysilyl)propyl] succinic anhydride monomer. One of the following (I), (II), (III), (IV), or (V) is performed: (I) Forming a silicon hard mask layer on the planarization layer, Optionally, forming an anti-reflection layer on the silicon hard mask layer, Forming a photoresist layer on the silicon hard mask layer or, if present, on the anti-reflection layer, (II) Forming a silicon hard mask layer on the planarization layer, Forming a carbon-rich layer on the silicon hard mask layer, Optionally, forming an anti-reflection layer on the carbon-rich layer, Forming a photoresist layer on the carbon-rich layer or, if present, on the anti-reflection layer, (III) Forming a carbon-rich layer on the planarization layer, Optionally, forming an anti-reflection layer on the carbon-rich layer, Forming a photoresist layer on the carbon-rich layer or, if present, on the anti-reflection layer, (IV) Form a carbon-rich layer on the planarization layer, form a silicon hard mask layer on the carbon-rich layer, Optionally, form an antireflection layer on the silicon hard mask layer, form a photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer, or (V) Form an antireflection layer on the planarization layer, form a photoresist layer on the antireflection layer.

[0006] In another embodiment, the present invention provides a structure comprising a substrate having a surface with topographic features. The substrate optionally includes one or more intermediate layers on its surface. The planarization layer is on the substrate surface or, if present, on one or more intermediate layers, and the planarization layer includes a polymer containing a [3-(triethoxysilyl)propyl] succinic anhydride monomer. This structure also comprises one of the following (I), (II), (III), (IV), or (V): (I) A silicon hard mask layer on the planarization layer, optionally, an antireflection layer on the silicon hard mask layer, and a photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer, (II) A silicon hard mask layer on the planarization layer, a carbon-rich layer on the silicon hard mask layer, optionally, an antireflection layer on the carbon-rich layer, and a photoresist layer on the carbon-rich layer or, if present, on the antireflection layer, (III) A carbon-rich layer on the planarization layer, optionally, an antireflection layer on the carbon-rich layer, and a photoresist layer on the carbon-rich layer or, if present, on the antireflection layer, (IV) A carbon-rich layer on the planarization layer, a silicon hard mask layer on the carbon-rich layer, optionally, an antireflection layer on the silicon hard mask layer, and A photoresist layer on a silicon hard mask layer or, if present, on an antireflection layer, or (V) an antireflection layer on a planarization layer, and a photoresist layer on the antireflection layer.

[0007] In a further embodiment, the present invention provides a method of forming a structure, the method including providing a substrate having a surface including topographic features. The substrate optionally includes one or more intermediate layers on the substrate surface. To form a planarization layer, a composition is applied to the substrate surface or, if present, on one or more intermediate layers. The composition includes a polymer including from about 1 mol% to about 10 mol% of a [3-(triethoxysilyl)propyl] succinic anhydride monomer. The planarization layer is resistant to oxygen etching, such that it will experience a thickness loss of less than about 5% when exposed to oxygen etching for about 2 minutes. A photoresist layer is formed on the planarization layer.

[0008] In yet a further embodiment, a structure is provided that includes a substrate having a surface including topographic features. The substrate optionally includes one or more intermediate layers on the substrate surface. The planarization layer is on the substrate surface or, if present, on one or more intermediate layers. The planarization layer includes a polymer including from about 1 mol% to about 10 mol% of a [3-(triethoxysilyl)propyl] succinic anhydride monomer, and the planarization layer is resistant to oxygen etching, such that it will experience a thickness loss of less than about 5% when exposed to oxygen etching for about 2 minutes. A photoresist layer on the planarization layer.

[0009] In a further embodiment, a composition is also provided that includes a polymer dispersed or dissolved in a solvent system. The polymer is (i) from about 1 mol% to about 10 mol% of a [3-(triethoxysilyl)propyl] succinic anhydride monomer, from about 35 mol% to about 85 mol% of methyltrimethoxysilane, and from about 15 mol% to about 60 mol% of tetraethoxysilane, (ii) About 1 mol% to about 10 mol% of [3-(triethoxysilyl)propyl] succinic anhydride monomer, about 35 mol% to about 85 mol% of methyltrimethoxysilane, about 15 mol% to about 60 mol% of tetraethoxysilane, and about 1 mol% to about 5 mol% of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, or (iii) About 1 mol% to about 10 mol% of [3-(triethoxysilyl)propyl] succinic anhydride monomer, about 15 mol% to about 60 mol% of tetraethoxysilane, about 1 mol% to about 5 mol% of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, and about 15 mol% to about 70 mol% of methyltriethoxysilane comprises.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0011] More specifically, the present invention broadly provides a composition for use in forming a silicon planarization layer.

[0012] Planarization composition 1. Polymer for use in the composition Preferred polymers for use in the novel planarization composition include [3-(triethoxysilyl)propyl] succinic anhydride ("TEOSPSA") monomer. Preferably, the polymer further comprises one or more additional monomers selected from the following,

Chemical formula

[0013] Preferred additional monomers that fit within the above general structure include (3-glycidoxypropyl)trimethoxysilane, 5,6-epoxyhexyl-triethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (“ECHETMS”), (3-acetamidopropyl)-trimethoxysilane, (1,3-di-2-propen-1-yl)-5-(([3-triethoxysilylpropyl])-(1,3,5triazine-2,4,6(1H,3H,5H)-trione), methyltrimethoxysilane (“MTMS”), methyltriethoxysilane (“MTEOS”), dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenethyl-trimethoxysilane (“PETMS”), 2-(carbomethoxy)ethyltrimethoxysilane (“CMETMS”), acetoxyethyltrimethoxysilane, ethyltrimethoxysilane (“ETMS”), n-butyltrimethoxysilane, tetraethoxysilane (“TEOS”), tetramethyl orthosilicate (“TMOS”), and mixtures thereof. Particularly preferred additional monomers are ECHETMS, MTMS, MTEOS, and / or TEOS, preferably selected from at least two of the foregoing.

[0014] It will be appreciated that the ratio and loading of the monomers can be adjusted to provide suitable properties of the planarizing composition and / or the planarizing layer formed from the composition (e.g., carbon content, silicon content, wet etching rate, dry etching rate, adhesion, and gelation). In a preferred embodiment, the mole percentage of TEOSPSA in the polymer constitutes from about 1 mol% to about 10 mol%, more preferably from about 2 mol% to about 5 mol%.

[0015] In another embodiment, the polymer contains ECHETMS as an additional monomer. In this embodiment, ECHETMS is preferably present in the polymer at from about 1 mol% to about 5 mol%, more preferably from about 1 mol% to about 2 mol%.

[0016] In another embodiment, the MTMS is an additional monomer present in the polymer at about 35 mol% to about 85 mol%, preferably about 40 mol% to about 70 mol%.

[0017] In a further embodiment, TEOS is used as an additional monomer and is present in the polymer at a molar ratio of about 15 mol% to about 60 mol%, preferably about 30 mol% to about 50 mol%. In still further embodiments, TEOS is present as an additional monomer at a molar ratio of less than about 45 mol%, preferably about 15 mol% to about 45 mol%, more preferably about 20 mol% to about 40 mol%, and even more preferably about 25 mol% to about 35 mol%.

[0018] In still further embodiments, MTEOS is an additional monomer present in the polymer at about 15 mol% to about 70 mol%, preferably about 30 mol% to about 60 mol%.

[0019] In another embodiment, the combination of MTMS, TEOS, and MTEOS present in the polymer is about 85 mol% to about 98 mol%, more preferably about 90 mol% to about 96 mol%.

[0020] In one embodiment, the polymer comprises, consists of, or consists essentially of TEOSPSA and one or more (in any combination) of the above-described additional monomers.

[0021] In another embodiment, the polymer preferably comprises, consists of, or consists essentially of TEOSPSA, ECHETMS, MTMS, and TEOS at the above molar percentages.

[0022] In another embodiment, the polymer preferably comprises, consists of, or consists essentially of TEOSPSA, ECHETMS, MTEOS, and TEOS at the above molar percentages.

[0023] In yet another embodiment, the polymer preferably comprises, consists of, or consists essentially of TEOSPSA, MTMS, and TEOS in the molar percentages described above.

[0024] In a further embodiment, the polymer comprises, consists of, or even consists essentially of TEOSPSA, ECHETMS, TEOS, and MTMS in the following molar ratios.

Chemical formula

[0025] In one embodiment, the polymer preferably has a low carbon content. In this embodiment, the polymer contains less than about 33 wt% carbon, preferably about 18% to about 33 wt% carbon, more preferably about 23% to about 33 wt% carbon, and even more preferably about 23% to about 28 wt% carbon, and the carbon weight percentage is calculated by the molecular weight of carbon as a percentage of the molecular weight of the polymer.

[0026] In another embodiment, the polymer preferably has a high silicon content. In this embodiment, the polymer contains at least about 27 wt% silicon, preferably about 27 wt% to about 47 wt% silicon, more preferably about 33% to about 39% silicon, and even more preferably about 35% to about 38% silicon, and the silicon percentage is calculated by the molecular weight of silicon as a percentage of the molecular weight of the polymer.

[0027] Regardless of the embodiment, the weight average molecular weight (Mw) range of the polymer, when determined by gel permeation chromatography (GPC) using polystyrene standards, is preferably from about 1,000 Daltons to about 5,000 Daltons, more preferably from about 1,500 Daltons to about 3,000 Daltons.

[0028] Finally, while a number of polymer embodiments are described above, it will be understood that the foregoing embodiments can "mix and match" with each other as long as they do not directly contradict each other.

[0029] 2. Polymerization Materials and Methods To synthesize the polymer, the monomers are charged into a reactor equipped with a distillation apparatus or a reflux setup in a suitable polymerization solvent with stirring. The polymerization solvent can include, but is not limited to, propylene glycol monomethyl ether acetate ("PGMEA"), propylene glycol methyl ether ("PGME"), acetone, cyclohexanone, ethyl lactate, isopropanol, propanol, butanol, and mixtures thereof. The preferred monomer solid percentage in the reaction mixture is from about 10% to about 25%, more preferably from about 14% to about 20%. The catalyst is then slowly charged into the reactor at ambient temperature. Suitable catalysts include, but are not limited to, nitric acid, hydrochloric acid, acetic acid, trifluoroacetic acid, sulfonic acid, and combinations thereof. The catalyst is preferably added in an amount of 3 to 10 equivalents, more preferably about 5 equivalents, per total monomer, where 1 equivalent is equal to 1 mole of water per mole of monomer, or 18 grams of water per mole of monomer. The reaction mixture is preferably stirred for from about 0 minutes to about 60 minutes, more preferably from about 1 minute to about 60 minutes, even more preferably from about 10 minutes to about 30 minutes.

[0030] Next, the solution is heated to a temperature of about 60°C to about 120°C, preferably about 60°C to about 95°C, more preferably about 65°C to about 75°C, preferably for about 2 hours to about 48 hours, more preferably about 8 hours to about 24 hours, and even more preferably about 24 hours. During this heating step, a distillation setup is used to remove the methanol generated during the polymerization reaction. An additional rotary evaporator or vacuum process may be required to remove excess methanol / ethanol / water by-products from the reaction. The rotary evaporator or vacuum process can be either at ambient temperature or at a heating temperature of about 25°C to about 60°C, preferably less than 40 - 50°C or about 40 - 50°C. The content of the methanol / ethanol / water by-products ranges from about 0% to about 10%, preferably less than about 1%.

[0031] 3. Preparation of the Composition Next, the polymer is dispersed or dissolved in a solvent system, or the polymer mother liquor is further diluted with a solvent to the desired solid level. Preferred solvent systems include solvents selected from the group consisting of PGMEA, PGME, propylene glycol n-propyl ether ("PnP"), ethyl lactate, cyclohexanone, gamma-butyrolactone ("GBL"), methyl isobutyl carbinol, propylene glycol monoethyl ether ("PGEE"), water, ethanol, and mixtures thereof. The solvent system is preferably utilized at about 90 wt% to about 97 wt%, more preferably about 92% - 94%, and even more preferably about 92.5 wt% to about 93 wt% based on 100 wt% of the total weight of the composition. The composition used to form the silicon planarization layer preferably contains a solids content of about 3 wt% to about 10 wt% of solids, more preferably about 6 wt% to about 8 wt% of solids, and even more preferably about 7 wt% to about 7.5 wt% of solids based on 100 wt% of the total weight of the composition.

[0032] By mixing the above components together in a solvent system, a silicon planarization layer composition is formed. Further, any optional components (e.g., surfactants, mineral acids, organic acids, graft / condensation catalysts, thermal acid generators ("TAG"), and / or photoacid generators ("PAG")) are also simultaneously dispersed in the solvent system. If present, the optional components (cumulatively or individually) should be present in the composition at a level of about 0.01 wt% to about 2.0 wt%, preferably about 0.1 wt% to about 1.0 wt%, based on the total weight of the solids in the composition being 100 wt%.

[0033] In one embodiment, the planarization composition consists essentially of, or further consists of, the above-described polymer, one or more of the above optional components, and a solvent system. In a further embodiment, the planarization composition consists essentially of, or further consists of, the above-described polymer and a solvent system.

[0034] Method of using the silicon planarization composition In the method of the present invention, a planarization composition as described above is formed on a substrate surface or on a layer over an intermediate layer present on the substrate surface (e.g., silicon, silicon dioxide, silicon carbide, silicon nitride, silicon oxynitride, metals (including TiN and / or tungsten), carbon (including carbon fibers, carbon nanofibers, carbon nanotubes, diamond, and / or graphene), fluorocarbons, filaments, and high-k dielectrics). Any microelectronic substrate can be utilized. The substrate is preferably a semiconductor substrate such as silicon, SiGe, SiO2, Si3N4, SiON, SiCO:H (such as those sold under the name Black Diamond), aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, glass, or a mixture of the foregoing. The substrate or its intermediate layer includes topographic features (via holes, trenches, contact holes, raised features, lines, etc.). As used herein, "topography" refers to the height or depth of structures within or on the substrate surface.

[0035] Next, the silicon planarization layer of the present invention is applied to the substrate or any intermediate layer. It will be understood that any intermediate layer applied to a substrate having topography will necessarily have a topography similar to that of the surface of the substrate. Thus, whether the planarization layer is applied to the substrate surface or to an intermediate layer, it is used to fill the topography gaps in a void-free (i.e., bubble-free) manner while creating a substantially flat surface for use in subsequent processing steps. By inspecting the cross-section of the planarization layer with a scanning electron microscope and visually confirming the absence of voids, it is possible to determine whether there are voids or not.

[0036] The silicon planarization layer is preferably applied by spin coating at a speed of about 1,000 rpm to about 5,000 rpm, preferably about 1,250 rpm to about 1,750 rpm, for a period of about 30 seconds to about 120 seconds, preferably about 45 seconds to about 75 seconds. After the silicon planarization layer is applied, it is preferably heated by a sol-gel reaction to a temperature of preferably about 100°C to about 400°C, more preferably about 150°C to about 250°C, for a period of about 30 seconds to about 120 seconds, preferably about 45 seconds to about 60 seconds, to evaporate the solvent and crosslink the material. The thickness of the silicon planarization layer after baking (average measured value obtained at 5 locations by ellipsometry) is preferably 80 nm to 300 nm, more preferably 150 nm to 250 nm, even more preferably 180 nm to 220 nm.

[0037] The planarization layer prepared according to the described method has a low bias. Specifically, the method of the present invention results in a profile having an absolute value (i.e., which can be a positive or negative bias) of less than about 60 nm, preferably less than about 40 nm, more preferably about 10 nm to about 30 nm, even if the average film thickness is less than about 80 nm.

[0038] When determining the bias, the thickness of the layer is determined by measuring the thickness of the layer at approximately the midpoint between two via holes whose boundaries are within approximately 1,000 nm of each other and are not separated from each other by intervening features (using an ellipsometer, SEM, or other conventional apparatus). These measurements are repeated up to 49 times for the wafer (or other area as defined herein), and the measured values are averaged to determine the average thickness of the layer. The bias, when measured by SEM, is determined by subtracting the average thickness of the layer across the high-density region from the average thickness of the same layer across the isolated region. The high-density region is defined as a portion of the substrate where at least about 50% of its surface area is filled with via holes or a 1:1 line-to-space ratio, and the isolated region is defined as a portion of the substrate where less than about 20% of its surface area is filled with via holes or a 1:5 line-to-space ratio.

[0039] The silicon planarization layer will have a high silicon content, i.e., the layer is preferably from about 36% silicon to about 42% silicon, more preferably from about 38% to about 41% silicon, with the total weight of the cured planarization layer being 100% by weight. The silicon planarization layer will have a low carbon content, i.e., the layer is preferably from about 15% carbon to about 30% carbon, more preferably from about 15% carbon to about 20% carbon, with the total weight of the cured planarization layer being 100% by weight.

[0040] The silicon planarization layer preferably has an n value from about 1.40 to about 1.50, more preferably from about 1.42 to about 1.46. The silicon planarization layer preferably has a k value of less than about 0.10, more preferably from about 0 to about 0.10, even more preferably from about 0 to about 0.05.

[0041] Next, depending on the specific application, an optional carbon-rich layer or hard mask layer is formed on top of the silicon planarization layer. In embodiments where the carbon-rich layer is formed on top of the silicon planarization layer, the carbon-rich layer can be formed by any known coating method, and one preferred method is spin coating at a speed of about 1,000 to about 5,000 rpm, preferably about 1,250 to about 1,750 rpm, for a period of about 30 to about 120 seconds, preferably about 45 to 75 seconds. The carbon-rich layer can also be formed by other known coating methods such as chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), or plasma-enhanced atomic layer deposition (PEALD).

[0042] The term "carbon-rich" refers to a layer formed from a composition that contains more than about 50 wt% carbon, preferably more than about 70 wt% carbon, more preferably about 75 to about 80 wt% carbon, with the total solids in the composition being 100 wt%. Suitable carbon-rich layers are selected from the group consisting of spin-on carbon layers (SOC), amorphous carbon layers, and carbon planarization layers. Exemplary carbon-rich layers generally contain a polymer dissolved or dispersed in a solvent system along with any of the following optional components: acid and / or base quenchers, catalysts, crosslinking agents, and / or surface modifying additives. Preferred compositions for use as the carbon-rich layer are suitable for forming thick layers and have a solids content of preferably about 0.1% to about 70 wt%, more preferably about 5% to about 40 wt%, even more preferably about 10% to about 30 wt%, based on 100 wt% of the total weight of the carbon-rich composition.

[0043] After the carbon-rich composition is applied, it is preferably heated to a temperature of about 100°C to about 400°C, more preferably about 160°C to about 350°C, for a period of about 30 seconds to about 120 seconds, preferably about 45 seconds to about 60 seconds, to evaporate the solvent. The thickness of the baked carbon-rich layer is preferably about 10 nm to about 120 nm, more preferably about 20 nm to about 100 nm, even more preferably about 50 nm to about 60 nm.

[0044] In an embodiment where a hard mask layer is formed on top of a silicon planarization layer, a conventional silicon hard mask layer can be formed by any known coating method. One preferred method is spin coating at a speed of about 1,000 to about 5,000 rpm, preferably about 1,250 to about 1,750 rpm, for a period of about 30 to about 120 seconds, preferably about 45 to about 75 seconds. A suitable hard mask layer is preferably a high-silicon-containing material selected from the group consisting of silanes, siloxanes, silsesquioxanes, and mixtures thereof, and is preferably chemically different from the planarization layer described herein. Exemplary hard mask layers generally include a polymer dissolved or dispersed in a solvent system together with any of the following optional components: surfactant, acid catalyst, base catalyst, and / or crosslinking agent. A preferred hard mask composition preferably has a solids content of about 0.1% to about 70 wt%, more preferably about 0.5% to about 10 wt%, even more preferably about 1% to about 2 wt%, based on 100 wt% of the total weight of the composition. After the hard mask is applied, it is preferably heated to a temperature of about 100°C to about 300°C, more preferably about 150°C to about 250°C, for a period of about 30 seconds to about 120 seconds, preferably about 45 seconds to about 60 seconds, to evaporate the solvent. The thickness of the baked hard mask layer is preferably about 5 nm to about 50,000 nm, more preferably about 5 nm to about 1,000 nm, even more preferably about 10 nm to about 100 nm. When both a hard mask layer and a carbon-rich layer are used, the hard mask layer should be at least about 0.75 times that of any carbon-rich layer in a fluorine-rich plasma atmosphere and have an etching rate at least 5 times slower than that of the carbon-rich layer in an oxygen-rich plasma etching atmosphere.

[0045] Several commercially available hard mask layers can be used. Other preferred hard mask layers contain copolymers of monomers selected from the group consisting of phenethyltrimethoxysilane (PETMS), 2-(carboxymethoxy)ethyltrimethoxysilane (CMETMS), tetraethoxysilane (TEOS), methyltrimethoxysilane, phenyltrimethoxysilane, and combinations thereof.

[0046] In other embodiments, a carbon-rich layer can be formed on the silicon planarization layer, and a hard mask layer can be formed on the carbon-rich layer. In another embodiment, a hard mask layer can be formed on the silicon planarization layer, and a carbon-rich layer can be formed on top of the hard mask layer. Alternatively, as described above, only one of the carbon-rich layer or the hard mask layer is formed on the planarization layer.

[0047] In a further embodiment, the antireflection coating can be formed on top of any one of the silicon planarization layer, the carbon-rich layer, or the hard mask layer being the topmost (i.e., any one formed being the last layer). A preferred antireflection coating has a k value of at least about 0.2, more preferably from about 0.2 to about 0.9, even more preferably from about 0.25 to about 0.7. In one embodiment, the antireflection coating has a relatively low silicon content. That is, the silicon content of the antireflection layer is less than about 20 wt%, preferably less than about 10 wt%, more preferably less than about 5 wt%, even more preferably about 0 wt%, based on 100 wt% of the total weight of the antireflection layer.

[0048] Regardless of the layer structure, when the uppermost layer (which is a carbon-rich layer, a hard mask layer, or an antireflection layer) above the planarization layer is cured, a photoresist (i.e., an image-forming layer) can be applied to the uppermost layer to form a photoresist layer, or the photoresist can be directly applied to the silicon planarization layer. The photoresist layer can be formed by any conventional method. One preferred method is to spin-coat a 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, the photoresist layer is optionally post-application baked ("PAB") at a temperature of at least about 70 °C, preferably about 80 °C to about 150 °C, more preferably about 100 °C to about 150 °C, for a period of about 30 seconds to about 120 seconds. The thickness of the baked photoresist layer is typically about 5 nm to about 120 nm, preferably about 10 nm to about 50 nm, more preferably about 20 nm to about 40 nm.

[0049] Thereafter, the photoresist layer is exposed to radiation at a dose of about 20 mJ / cm 2 ~ about 45 mJ / cm 2 , preferably about 25 mJ / cm 2 ~ about 40 mJ / cm 2 , more preferably about 30 mJ / cm 2 ~ about 35 mJ / cm 2 to be patterned. More specifically, the photoresist layer is exposed using a mask disposed above the surface of the photoresist layer. The mask has an area designed to allow radiation to pass through the mask 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 a particular area. Those skilled in the art will readily understand that the arrangement of the absorbing portions is designed based on the desired pattern to be formed in the photoresist layer, ultimately on the substrate or any intermediate layer.

[0050] After exposure, the photoresist layer is post-exposure baked (「PEB」) at a temperature of less than about 180°C, preferably about 60°C to about 140°C, 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).

[0051] Next, the photoresist layer is contacted with a developer to form a pattern. Depending on whether the photoresist used is positive or negative processing, the developer removes the exposed portion of the photoresist layer or removes the unexposed portion of the photoresist layer to form a pattern. Next, the pattern is transferred to the hard mask, carbon-rich layer, and / or anti-reflection layer (depending on their presence and order), planarization layer, and finally the substrate. This pattern transfer can be performed via plasma etching (e.g., CF4 etchant, O2 etchant) or wet etching or a development process, depending on the specific layer, the process followed, and / or the user's preference. Advantageously, one of the characteristics of the silicon planarization layer is that they are wet-developable or wet-etchable, which means that they can be removed by wet etching either during or at the end of the pattern transfer process. Preferred wet etching or development materials include, but are not limited to, SC1 (a commercially available developer that is a 1:1:5 volume mixture of NH4OH:H2O2:H2O), tetramethylammonium hydroxide (「TMAH」), and / or dilute HF. Preferably, the wet etching or development rate of the planarization layer in SC1 is at least about 20 nm / min, preferably about 20 nm / min to about 200 nm / min, more preferably about 40 nm / min to about 100 nm / min.

[0052] Furthermore, another characteristic of the planarization layer is that they are resistant to oxygen etching. That is, the planarization layer formed as described herein undergoes a thickness loss of less than about 5%, preferably less than about 2%, more preferably less than about 1%, and even more preferably about 0% after about 2 minutes of oxygen etching.

[0053] Regardless of whether the pattern transfer is performed by etching or by development, the resulting features have high resolution. For example, a resolution of less than about 40 nm half-pitch, preferably less than about 30 nm half-pitch, can be achieved by the method of the present invention.

[0054] Further advantages of the various embodiments will be apparent to those skilled in the art upon consideration of the disclosure herein and the following examples. It is to be understood that the various embodiments described herein are not necessarily mutually exclusive unless otherwise indicated herein. For example, features described or illustrated in one embodiment may be included in other embodiments, but not necessarily. Thus, the present disclosure encompasses various combinations and / or integrations of the specific embodiments described herein.

[0055] 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 can be used alone or any combination of two or more of the listed items can be used. For example, if a composition is described as containing or excluding components A, B, and / or C, the composition can 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.

[0056] This specification also uses numerical ranges to quantify specific parameters for the various embodiments. It should be understood that when a numerical range is provided, such a range is to be construed as providing literal support for claims that limit only the lower limit of the range and for claims that limit only the upper limit of the range. For example, the disclosed numerical range of about 10 to about 100 literally supports claims that recite "greater than about 10" (no upper limit) and claims that recite "less than about 100" (no lower limit).

Examples

[0057] The following examples describe the method according to the present disclosure. However, it should be understood that these examples are provided by way of illustration and that none of them should be construed as a limitation on the overall scope of the invention.

[0058] [Example 1] Synthesis and formulation of silicon planarization material 1 A three-necked round-bottom flask was equipped with a thermocouple, a magnetic stir bar, an N2 supply line, a bubbler, a condenser, and a heating oil bath. Next, 3.41 grams (11.2 mmol) of TEOSPSA (Gelest, Morrisville, PA, USA), 1.38 grams (5.6 mmol) of ECHETMS (Gelest, Morrisville, PA, USA), 24.79 grams (182 mmol) of MTMS (Gelest, Morrisville, PA, USA), and 16.92 grams (81.2 mmol) of TEOS (Gelest, Morrisville, PA, USA) were measured by weight and charged into the reactor with 80 grams (605 mmol) of PGMEA as the solvent (KMG Electronic Chemicals, Fort Worth, TX). Then, 25.2 grams of 0.01 M HNO3 (Fisher Scientific, Ontario, Canada) was slowly charged into the reactor as a catalyst at ambient temperature. A two-phase mixture was obtained after the addition. The batch was stirred at ambient temperature for 30 minutes. A mild exothermic effect was observed (the batch temperature rose from 20 °C to about 25 - 28 °C). Then, the oil bath temperature was adjusted to 70 °C to initiate distillation. The batch was stirred at 65 °C (internal solution temperature) for 24 hours to achieve a molecular weight of 2,500 Daltons. The batch temperature was cooled to ambient temperature. The polymer produced was further diluted to 7 wt% solids with a 50:50 (volume ratio) mixture of PGME and PGMEA.

[0059] [Example 2] Formulation of silicon planarization material 2 In this example, 100 grams of the material prepared in Example 1 was added to a 250 mL round-bottom flask, and 100 grams of PGMEA was also added to the same round-bottom flask. Subsequently, the round-bottom flask was connected to a rotary evaporator apparatus (Buchi Rotovap R124). While heating the polymer solution to 50 °C in a water bath, a vacuum was applied (6 torr). After 30 minutes, the material was taken out from the rotary evaporator, and PGMEA was added to grasp the loss of the solvent. After this process, the methanol / ethanol / water by-product content level was less than 1%. The increase in the molecular weight of the polymer was minimal (less than 500 Da). The prepared polymer was further diluted to 7.7 wt% solids with a 50:50 (volume ratio) mixture of PGEE and PGMEA.

[0060] [Example 3] Formulation of Silicon Planarization Material 3 A three-neck round-bottom flask was equipped with a thermocouple, a magnetic stir bar, an N2 supply line, a bubbler, a condenser, and a heating oil bath. Next, 2.44 grams of TEOSPSA, 0.99 grams of ECHETMS, 17.71 grams of MTMS, and 12.08 grams of TEOS were measured by weight, and 55 grams of PGMEA was charged into the reactor as a solvent. Then, 14.44 grams of 3N acetic acid (VWR, Batavia, IL) in water was slowly charged into the reactor as a catalyst over 30 minutes at ambient temperature. The batch was stirred at ambient temperature for 10 minutes, and then the oil bath temperature was adjusted to 91 °C. The batch was stirred for 5 hours to achieve a molecular weight of 3,000 Daltons. The batch temperature was cooled to ambient temperature. The prepared polymer was further diluted to 3 wt% solids with a 70:30 mixture (volume ratio) of PGMEA and PGME.

[0061] [Example 4] Formulation of Silicon Planarization Material 4 A three-necked round-bottom flask was equipped with a thermocouple, a magnetic stir bar, an N2 supply line, a bubbler, a condenser, and a heating oil bath. 3.41 grams of TEOSPSA, 25.55 grams of MTMS, and 16.92 grams of TEOS were charged into the reactor with 80 grams of PGMEA as the solvent. Next, 25.20 grams of 0.01 M HNO3 was slowly added to the reactor as a catalyst over 30 minutes at ambient temperature. The batch was stirred at ambient temperature for 10 minutes, and then the oil bath temperature was adjusted to 70 °C. The batch was then stirred for 10 hours to achieve a molecular weight of 2,000 Daltons. The batch temperature was cooled to ambient temperature. The polymer produced was further diluted with PGME to 7 wt% solids.

[0062] [Example 5] Formulation of Silicon Planarization Material 5 A three-necked round-bottom flask was equipped with a thermocouple, a magnetic stir bar, an N2 supply line, a bubbler, a condenser, and a heating oil bath. Next, 3.41 grams of TEOSPSA, 25.55 grams of MTMS, and 16.92 grams of TEOS were charged into the reactor with 40 grams of PGMEA as the solvent, and then 20.16 grams of 0.01 M HNO3 was slowly added to the reactor as a catalyst over 30 minutes at ambient temperature. The batch was stirred at ambient temperature for 10 minutes, and then the oil bath temperature was adjusted to 70 °C. The batch was stirred for 8 hours to achieve a molecular weight of 2,000 Daltons. The batch temperature was cooled to ambient temperature. The polymer produced was further diluted with PGME to 7 wt% solids.

[0063] [Example 6] Formulation of Silicon Planarization Material 6 A three-necked round-bottom flask was equipped with a thermocouple, a magnetic stir bar, an N2 supply line, a bubbler, a condenser, and a heating oil bath. Next, 6.82 grams of TEOSPSA, 1.38 grams of ECHTMS, 30.45 grams of MTEOS, and 16.92 grams of TEOS were charged into the reactor with 40 grams of PGMEA as the solvent, and then 20.16 grams of 0.01M HNO3 was slowly charged into the reactor as a catalyst over 30 minutes at ambient temperature. The batch was stirred at ambient temperature for 10 minutes, and then the oil bath temperature was adjusted to 70 °C. The batch was stirred for 8 hours to achieve a molecular weight of 2,000 Daltons. The batch temperature was cooled to ambient temperature. The polymer produced was further diluted with PGME to 7 wt% solids.

[0064] [Example 7] Formulation of Silicon Planarization Material 7 A three-necked round-bottom flask was equipped with a thermocouple, a magnetic stir bar, an N2 supply line, a bubbler, a condenser, and a heating oil bath. Next, 2.44 grams of TEOSPSA, 0.99 grams of ECHETMS, 12.8 grams of MTMS, and 19.58 grams of TEOS were charged into the reactor together with 55.00 grams of PGMEA as the solvent, and then 15.31 grams of 3N acetic acid in water was slowly charged into the reactor as a catalyst over 30 minutes at ambient temperature. The batch was stirred at ambient temperature for 10 minutes, and the oil bath temperature was adjusted to 83 °C. The batch was stirred for 2 hours to achieve a molecular weight of 3,000 Daltons. The batch temperature was cooled to ambient temperature. The polymer produced was further diluted with a 70:30 mixture (by volume) of PGMEA and PGME to 3 wt% solids.

[0065] [Example 8] Spin Coating of the Formulation and Silicon Content The materials from Example 2 were spin-coated onto a silicon wafer at a spin speed of 1,500 rpm for 60 seconds and then baked on a hot plate at 205 °C for 60 seconds to form a crosslinked film having a thickness of about 1,900 Å and a silicon content of about 38.7%. The materials from Example 3 and 7 were each spin-coated onto separate silicon wafers at a spin speed of 1,500 rpm for 60 seconds and then baked on a hot plate at 205 °C for 60 seconds to form crosslinked films having a thickness of about 800 Å and silicon contents of about 38.7% (formulation of Example 3) and 39.5% (formulation of Example 7).

[0066] [Example 9] Spin Coating of Formulations and Silicon Content The material from Example 1 was spin-coated onto a silicon wafer having topography at a spin speed of 1,500 rpm for 60 seconds and then baked on a hot plate at 205 °C for 60 seconds to form a crosslinked film. Cross-sectional images were taken to reveal the gap filling and planarization performance. Figures 1-3 show the planarization and gap filling performance of the material for high-density isolated features.

[0067] [Example 10] Wet Removability Test The materials from Example 1, 3, and 7 were spin-coated onto silicon wafers at a spin speed of 1,500 rpm for 60 seconds and then baked on a hot plate at 205 °C for 60 seconds to form crosslinked films. The coated wafers were then immersed in a 5% aqueous TMAH solution at 40 °C for 1 minute or in an SC1 solution (a developer which is a 1:1:5 volume mixture of NH4OH:H2O2:H2O) at 60 °C for 3 minutes. The wafers were then rinsed with DI water and dried under nitrogen. The film thicknesses before and after this wet cleaning step were measured by ellipsometry and the difference was reported in Table 1 as the percentage loss. These results indicate that the films have good wet cleanability.

[0068]

Table 1

[0069] [Example 11] Processing Example The film of the material from Example 1 was coated on a silicon wafer by spin coating at 1,500 rpm for 60 seconds, and the film was cured at 205 °C for 1 minute to form a cross-linked network structure having a film thickness of about 190 nm. Next, the film was subjected to oxygen plasma etching for 5 seconds, 10 seconds, 20 seconds, 30 seconds, and 60 seconds. The film thickness before and after this etching step was measured using an ellipsometer, and the etching rate was calculated. This data suggests that the film had good oxygen etching resistance. Figure 4 shows these results.

Claims

1. A method of forming a structure, the method comprising: providing a substrate having a surface comprising one or more features selected from one or more of via holes, trenches, contact holes, raised features, lines, and combinations thereof, optionally comprising one or more intermediate layers on the surface of the substrate; applying a composition comprising a polymer comprising [3-(triethoxysilyl)propyl] succinic anhydride monomer, tetraethoxysilane monomer, and one of methyltrimethoxysilane monomer or methyltriethoxysilane monomer, and comprising 15 mol% to 60 mol% tetraethoxysilane monomer, on the surface of the substrate or, if present, on the one or more intermediate layers, to form a planarization layer; performing one of the following (I), (II), (III), (IV), or (V): (I) forming a silicon hard mask layer on the planarization layer, optionally forming an antireflection layer on the silicon hard mask layer, forming a photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer; (II) forming a silicon hard mask layer on the planarization layer, forming a carbon-rich layer on the silicon hard mask layer, optionally forming an antireflection layer on the carbon-rich layer, forming a photoresist layer on the carbon-rich layer or, if present, on the antireflection layer; (III) forming a carbon-rich layer on the planarization layer, optionally forming an antireflection layer on the carbon-rich layer, forming a photoresist layer on the carbon-rich layer or, if present, on the antireflection layer; (IV) forming a carbon-rich layer on the planarization layer, forming a silicon hard mask layer on the carbon-rich layer, Optionally, an antireflection layer is formed on the silicon hard mask layer, forming a photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer, or (V) forming an antireflection layer on the planarization layer, forming a photoresist layer on the antireflection layer. **Claim 2** The method according to claim 1, wherein the polymer further comprises 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane monomer. **Claim 3** The method according to claim 1, wherein the polymer comprises 1 mol% to 10 mol% of [3-(triethoxysilyl)propyl] succinic anhydride monomer. **Claim 4** The method according to claim 1, wherein the planarization layer contains less than 33% by weight of carbon, with the weight of the planarization layer being 100% by weight. **Claim 5** The method according to claim 1, wherein the polymer does not contain phenyltrimethoxysilane monomer. **Claim 6** The method according to claim 1, wherein the substrate is selected from the group consisting of silicon, SiGe, SiO2, Si3N4, SiON, SiCO:H, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, glass, and mixtures thereof. **Claim 7** exposing the photoresist layer to radiation so as to form a pattern in the photoresist layer, and transferring the pattern to any antireflection layer, silicon hard mask layer, or carbon-rich layer present, to the planarization layer, to any intermediate layer present, and to the substrate The method according to claim 1, further comprising. **Claim 8** The method according to claim 7, wherein transferring the pattern comprises contacting the photoresist layer with a developer.

9. A structure comprising: a substrate having a surface comprising one or more features selected from one or more of via holes, trenches, contact holes, raised features, lines, and combinations thereof, optionally comprising one or more intermediate layers on the surface of the substrate; a planarization layer on the surface of the substrate or, if present, on the one or more intermediate layers, the planarization layer comprising a polymer comprising [3-(triethoxysilyl)propyl] succinic anhydride monomer, tetraethoxysilane monomer, and one of methyltrimethoxysilane monomer or methyltriethoxysilane monomer, and comprising 15 mol% to 60 mol% of tetraethoxysilane monomer; a structure comprising one of the following (I), (II), (III), (IV), or (V): (I) a silicon hard mask layer on the planarization layer; optionally, an antireflection layer on the silicon hard mask layer, and a photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer; (II) a silicon hard mask layer on the planarization layer; a carbon-rich layer on the silicon hard mask layer; optionally, an antireflection layer on the carbon-rich layer, and a photoresist layer on the carbon-rich layer or, if present, on the antireflection layer; (III) a carbon-rich layer on the planarization layer; optionally, an antireflection layer on the carbon-rich layer, and a photoresist layer on the carbon-rich layer or, if present, on the antireflection layer; (IV) a carbon-rich layer on the planarization layer; a silicon hard mask layer on the carbon-rich layer; Optionally, an anti-reflection layer on the silicon hard mask layer, and a photoresist layer on the silicon hard mask layer or, if present, on the anti-reflection layer, or (V) an anti-reflection layer on the planarization layer and a photoresist layer on the anti-reflection layer. **Claim 10** The structure according to claim 9, wherein the substrate is selected from the group consisting of silicon, SiGe, SiO2, Si3N4, SiON, SiCO:H, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, glass, and mixtures thereof. **Claim 11** The structure according to claim 9, wherein the polymer further comprises 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane monomer. **Claim 12** The structure according to claim 9, wherein the planarization layer contains less than 33% by weight of carbon, with the weight of the planarization layer being 100% by weight. **Claim 13** A method of forming a structure, the method comprising providing a substrate having a surface comprising one or more features selected from one or more of via holes, trenches, contact holes, raised features, lines, and combinations thereof, optionally providing a substrate comprising one or more intermediate layers on the surface of the substrate; applying to the surface of the substrate or, if present, on the one or more intermediate layers, a composition comprising a polymer comprising 1 mol% to 10 mol% of [3-(triethoxysilyl)propyl] succinic anhydride monomer, 15 mol% to 60 mol% of tetraethoxysilane monomer, and one of methyltrimethoxysilane monomer or methyltriethoxysilane monomer to form a planarization layer; forming a photoresist layer on the planarization layer. A method in which the planarization layer is resistant to oxygen etching, such that when the planarization layer is exposed to oxygen etching for 5 to 60 seconds, it will experience a thickness loss of less than 5%. **Claim 14** The method according to claim 13, wherein the planarization layer contains less than 33% by weight of carbon, with the weight of the planarization layer being 100% by weight. **Claim 15** The method according to claim 13, wherein the polymer further comprises one of the following (i) to (iv): (i) 1 mol% to 5 mol% of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, (ii) 35 mol% to 85 mol% of methyltrimethoxysilane, (iii) 35 mol% to 85 mol% of methyltrimethoxysilane and 1 mol% to 5 mol% of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, (iv) 1 mol% to 5 mol% of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 15 mol% to 70 mol% of methyltriethoxysilane. **Claim 16** A structure comprising: A substrate having a surface comprising one or more features selected from one or more of via holes, trenches, contact holes, raised features, lines, and combinations thereof, optionally including one or more intermediate layers on the surface of the substrate; A planarization layer on the surface of the substrate or, if present, on the one or more intermediate layers, the planarization layer comprising a polymer containing 1 mol% to 10 mol% of [3-(triethoxysilyl)propyl] succinic anhydride monomer, 15 mol% to 60 mol% of tetraethoxysilane monomer, and one of methyltrimethoxysilane monomer or methyltriethoxysilane monomer, the planarization layer being resistant to oxygen etching, such that when the planarization layer is exposed to oxygen etching for 5 to 60 seconds, it will experience a thickness loss of less than 5%. A structure comprising a photoresist layer on the planarization layer.

17. The structure according to claim 16, wherein the planarization layer contains less than 33% by weight of carbon with the weight of the planarization layer being 100% by weight.

18. The structure according to claim 16, wherein the polymer further comprises one of the following (i) to (iv). (i) 1 mol% to 5 mol% of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, (ii) 35 mol% to 85 mol% of methyltrimethoxysilane, (iii) 35 mol% to 85 mol% of methyltrimethoxysilane and 1 mol% to 5 mol% of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, (iv) 1 mol% to 5 mol% of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane and 15 mol% to 70 mol% of methyltriethoxysilane.

19. The method according to claim 1, comprising performing one of (I), (II), (III), or (IV).

20. The structure according to claim 9, comprising one of (I), (II), (III), or (IV).

21. A method of forming a structure, the method comprising: Providing a substrate comprising a surface comprising one or more features selected from one or more of via holes, trenches, contact holes, raised features, lines, and combinations thereof, optionally comprising one or more intermediate layers on the surface of the substrate; Coating a composition comprising a polymer, which contains [3-(triethoxysilyl)propyl] succinic anhydride monomer, 15 mol% to 60 mol% of tetraethoxysilane monomer, and one of methyltrimethoxysilane monomer or methyltriethoxysilane monomer and does not contain phenyltrimethoxysilane monomer, on the surface of the substrate or, if present, on the one or more intermediate layers so as to form a planarization layer. A method comprising: performing any one of the following (I), (II), (III), (IV), or (V). (I) Forming a silicon hard mask layer on the planarization layer. Optionally, forming an antireflection layer on the silicon hard mask layer. Forming a photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer. (II) Forming a silicon hard mask layer on the planarization layer. Forming a carbon-rich layer on the silicon hard mask layer. Optionally, forming an antireflection layer on the carbon-rich layer. Forming a photoresist layer on the carbon-rich layer or, if present, on the antireflection layer. (III) Forming a carbon-rich layer on the planarization layer. Optionally, forming an antireflection layer on the carbon-rich layer. Forming a photoresist layer on the carbon-rich layer or, if present, on the antireflection layer. (IV) Forming a carbon-rich layer on the planarization layer. Forming a silicon hard mask layer on the carbon-rich layer. Optionally, forming an antireflection layer on the silicon hard mask layer. Forming a photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer, or (V) Forming an antireflection layer on the planarization layer. Forming a photoresist layer on the antireflection layer.

22. A structure comprising: A substrate having a surface including one or more features selected from one or more of via holes, trenches, contact holes, raised features, lines, and combinations thereof, optionally a substrate including one or more intermediate layers on the surface of the substrate; A planarization layer on the surface of the substrate or, if present, on the one or more intermediate layers, the planarization layer including a [3-(triethoxysilyl)propyl] succinic anhydride monomer, 15 mol% to 60 mol% of a tetraethoxysilane monomer, and one of a methyltrimethoxysilane monomer or a methyltriethoxysilane monomer, and including a polymer that does not include a phenyltrimethoxysilane monomer; A structure comprising one of the following (I), (II), (III), (IV), or (V): (I) A silicon hard mask layer on the planarization layer, Optionally, an antireflection layer on the silicon hard mask layer, and A photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer; (II) A silicon hard mask layer on the planarization layer, A carbon-rich layer on the silicon hard mask layer, Optionally, an antireflection layer on the carbon-rich layer, and A photoresist layer on the carbon-rich layer or, if present, on the antireflection layer; (III) A carbon-rich layer on the planarization layer, Optionally, an antireflection layer on the carbon-rich layer, and A photoresist layer on the carbon-rich layer or, if present, on the antireflection layer; (IV) A carbon-rich layer on the planarization layer, A silicon hard mask layer on the carbon-rich layer, Optionally, an antireflection layer on the silicon hard mask layer, and A photoresist layer on the silicon hard mask layer or, if present, on the antireflection layer, or (V) an antireflection layer on the planarization layer, and a photoresist layer on the antireflection layer. **Claim 23** A method of forming a structure, the method comprising providing a substrate having a surface comprising one or more features selected from one or more of via holes, trenches, contact holes, raised features, lines, and combinations thereof, optionally providing a substrate comprising one or more intermediate layers on the surface of the substrate; applying to the surface of the substrate or, if present, on the one or more intermediate layers, a composition comprising a polymer comprising 1 mol% to 10 mol% of [3-(triethoxysilyl)propyl] succinic anhydride monomer, 15 mol% to 60 mol% of tetraethoxysilane monomer, and one of methyltrimethoxysilane monomer or methyltriethoxysilane monomer, and not comprising phenyltrimethoxysilane monomer; forming a photoresist layer on the planarization layer, wherein the planarization layer is resistant to oxygen etching such that the planarization layer experiences less than 5% thickness loss when exposed to oxygen etching for 5 to 60 seconds. **Claim 24** A structure comprising a substrate having a surface comprising one or more features selected from one or more of via holes, trenches, contact holes, raised features, lines, and combinations thereof, optionally a substrate comprising one or more intermediate layers on the surface of the substrate; A planarization layer on the surface of the substrate or, if present, on the one or more intermediate layers, comprising from 1 mol% to 10 mol% of [3-(triethoxysilyl)propyl] succinic anhydride monomer, from 15 mol% to 60 mol% of tetraethoxysilane monomer, and one of methyltrimethoxysilane monomer or methyltriethoxysilane monomer, and not containing phenyltrimethoxysilane monomer, the planarization layer being resistant to oxygen etching, whereby the planarization layer experiences a thickness loss of less than 5% when exposed to oxygen etching for 5 to 60 seconds. A structure comprising the photoresist layer on the planarization layer.

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