Method for processing substrate and sublimable material

Abstract

To provide a method for processing a substrate using sublimation materials.SOLUTION: The present disclosure relates to a method and composition for processing a semiconductor substrate having a pattern arranged on its surface.SELECTED DRAWING: None

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority from U.S. Provisional Patent Application No. 62 / 889,615, filed August 21, 2019, the contents of which are incorporated herein by reference in their entirety.

[0002] FIELD OF THE DISCLOSURE The present disclosure relates generally to surface treatments and related compositions and methods. [Background technology]

[0003] At linewidths (critical dimensions) below 20 nm, pattern collapse of fin field-effect transistors (FinFETs) and dielectric stacks during wet cleaning and drying has become a major issue in semiconductor manufacturing processes. The conventional theory of pattern collapse posits that high capillary forces during rinsing and drying are the primary factor leading to the collapse phenomenon. However, other chemical and substrate properties may also play important roles, including the surface tension and viscosity of the liquid, the mechanical strength of the substrate, the pattern density and aspect ratio, and damage to the substrate surface by the cleaner chemicals. Summary of the Invention [Problem to be solved by the invention]

[0004] It has been found that certain surface treatment compositions can provide a hydrophobic layer (e.g., a hydrophobic monolayer) on the surface of a semiconductor substrate (e.g., a wafer such as a silicon wafer or a copper wafer), which reduces capillary forces that cause pattern collapse in subsequent semiconductor manufacturing processes. These surface treatment compositions (also referred to as sublimable materials) can be removed by sublimation, which further minimizes pattern collapse by eliminating subsequent rinsing or drying processes. [Means for solving the problem]

[0005] In one aspect, the disclosure features a method of processing a substrate, including: a) applying a sublimable material to a substrate having a pattern disposed on a surface of the substrate, where the sublimable material includes a sublimable compound and a surface modifier; b) maintaining the sublimable material on the surface for a time sufficient to modify the surface; c) solidifying the sublimable material on the surface; and d) removing the sublimable material located on the surface by sublimation.

[0006] In another aspect, the disclosure features a method of processing a substrate, including: a) applying a sublimable material to a substrate having a pattern disposed on a surface of the substrate, where the sublimable material includes a sublimable compound, and the sublimable compound is a surface modifier; b) maintaining the sublimable material on the surface for a time sufficient to modify the surface; c) solidifying the sublimable material on the surface; and d) removing the sublimable material located on the surface by sublimation.

[0007] In another aspect, the disclosure features a sublimable material including a sublimable compound in an amount of about 40% to about 99.5% by weight of the sublimable material, and a surface modifier in an amount of about 0.5% to about 10% by weight of the sublimable material.

[0008] In another aspect, the disclosure features a sublimable material that includes (e.g., comprises, consists essentially of, or consists of) a sublimable compound in an amount of about 40% to about 99.5% by weight relative to the sublimable material, a catalyst in an amount of about 0.1% to about 10% by weight relative to the sublimable material, and a solvent in an amount of about 0.1% to about 50% by weight relative to the sublimable material.

[0009] In yet another aspect, the disclosure features a sublimable material comprising (e.g., comprises, consists essentially of, or consists of) a sublimable compound in an amount of about 40% to about 99.5% by weight of the sublimable material, and a solvent in an amount of about 0.1% to about 50% by weight of the sublimable material. The sublimable compound can be octamethylcyclotetrasiloxane, trimethylsilanol, t-hexyldimethylchlorosilane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane, triisopropyldimethylaminosilane, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate.

[0010] Other features, objects, and advantages of the present invention will become apparent from the specification and claims. DETAILED DESCRIPTION OF THE INVENTION

[0011] In the definitions of this disclosure, unless otherwise specified, the stated percentages should be understood as weight percents based on the total weight of the composition. Unless otherwise specified, the properties described in this disclosure are measured at atmospheric pressure. The term "solvent" as used in this disclosure refers to a single solvent or a combination of two or more (e.g., three or four) solvents, unless otherwise specified. In this disclosure, "ppm" means parts per million, "ppb" means "parts per billion," and "ppt" means parts per trillion.

[0012] The present disclosure generally relates to surface treatment compositions and methods. The surface treatment compositions described herein are also referred to as sublimable materials because they can be removed by sublimation. In some embodiments, the surface treatment methods described herein can be performed, for example, by a) applying a sublimable material to a substrate (e.g., a semiconductor substrate) having a pattern disposed thereon; b) maintaining the sublimable material on the surface for a time sufficient to modify the surface; c) solidifying the sublimable material on the surface; and d) removing the sublimable material located on the surface by sublimation. The pattern can include features having dimensions of about 20 nm or less. In some embodiments, the sublimable material can form a surface treatment layer (e.g., a hydrophobic monolayer) on the surface of the substrate to reduce pattern collapse (e.g., by forming a surface with a water contact angle of about 50° or greater).

[0013] In some embodiments, semiconductor substrates that can be treated with the sublimable materials described herein may be composed of silicon, silicon germanium, silicon nitride, copper, III-V compounds such as GaAs, or any combination thereof. In some embodiments, the semiconductor substrate may be a silicon wafer, a copper wafer, a silicon dioxide wafer, a silicon nitride wafer, a silicon oxynitride wafer, a carbon-doped silicon oxide wafer, a SiGe wafer, or a GaAs wafer. The semiconductor substrate may additionally include exposed integrated circuit structures on its surface, such as interconnect features (e.g., metal lines and dielectric materials). Metals and metal alloys used for interconnect features include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, nickel, silicon, polysilicon titanium nitride, tantalum nitride, tin, tungsten, SnAg, SnAg / Ni, CuNiSn, CuCoCu, and / or CoSn. The semiconductor substrate may also include layers of interlayer dielectrics, silicon oxide, silicon nitride, titanium nitride, silicon carbide, silicon oxycarbide, silicon oxynitride, titanium oxide, and / or carbon-doped silicon oxide.

[0014] In some embodiments, a semiconductor substrate surface treated with a sublimable material described herein comprises features comprising SiO2, SiN, TiN, SiOC, SiON, Si, SiGe, Ge, and / or W. In some embodiments, the semiconductor substrate surface comprises features comprising SiO2 and / or SiN.

[0015] Typically, the semiconductor substrate surface treated with the sublimable materials described herein includes a pattern formed by a prior semiconductor fabrication process (e.g., a lithography process including applying a photoresist layer, exposing the photoresist layer to actinic radiation, developing the photoresist layer, etching the semiconductor substrate beneath the photoresist layer, and / or removing the photoresist layer). In some embodiments, the pattern may include features having one or more (e.g., two or three) dimensions (e.g., length, width, and / or depth) that are about 20 nm or less (e.g., about 15 nm or less, about 10 nm or less, or about 5 nm or less) and / or about 1 nm or greater (e.g., about 2 nm or greater, or about 5 nm or greater).

[0016] Generally, the sublimable material described herein comprises at least one (e.g., two or three) sublimable compound, which may be a liquid or a solid at 25° C. In some embodiments, the sublimable compound is a component in the sublimable material that may be sublimed in the surface treatment method described herein.

[0017] In some embodiments, the sublimable compound may have a melting point at atmospheric pressure of about −20° C. or higher (e.g., about −15° C. or higher, about −10° C. or higher, about −5° C. or higher, or about 0° C. or higher) and / or about 60° C. or lower (e.g., about 55° C. or lower, about 50° C. or lower, about 45° C. or lower, about 40° C. or lower, about 35° C. or lower, about 30° C. or lower, about 25° C. or lower, or about 20° C. or lower). Without wishing to be bound by theory, it is believed that compounds having such melting points may be suitable for sublimation.

[0018] In some embodiments, the sublimable compound may have a vapor pressure at 25° C. of about 1 mmHg or more (e.g., about 2 mmHg or more, about 3 mmHg or more, about 5 mmHg or more, about 10 mmHg or more, about 15 mmHg or more, or about 20 mmHg or more) and / or about 100 mmHg or less (e.g., about 90 mmHg or less, about 80 mmHg or less, about 70 mmHg or less, about 60 mmHg or less, about 50 mmHg or less, or about 25 mmHg or less). Without wishing to be bound by theory, it is believed that compounds having a vapor pressure of less than about 1 mmHg at 25° C. may not readily sublimate. Also, without wishing to be bound by theory, it is believed that compounds having a vapor pressure of more than about 100 mmHg at 25° C. may evaporate too easily and may not remain on the surface of the semiconductor substrate long enough to treat the surface.

[0019] In some embodiments, the sublimable compound may have a surface tension of about 15 mN / m or more (e.g., about 20 mN / m or more, about 25 mN / m or more, or about 30 mN / m or more) and / or about 65 mN / m or less (e.g., about 60 mN / m or less, about 55 mN / m or less, about 50 mN / m or less, about 45 mN / m or less, about 40 mN / m or less, or about 35 mN / m or less) at 25° C. Without wishing to be bound by theory, it is believed that in some embodiments, compounds having a surface tension within the above ranges can form a surface with a relatively large water contact angle (e.g., about 50° or more), which can reduce pattern collapse.

[0020] In some embodiments, the sublimable compound may have a viscosity at 25°C of about 0.5 centistokes or more (e.g., about 0.6 centistokes or more, about 0.8 centistokes or more, about 1 centistokes or more, about 1.2 centistokes or more, about 1.4 centistokes or more, about 1.6 centistokes or more, about 1.8 centistokes or more, or about 2 centistokes or more) and / or about 5 centistokes or less (e.g., about 4.8 centistokes or less, about 4.6 centistokes or less, about 4.5 centistokes or less, about 4.4 centistokes or less, about 4.2 centistokes or less, about 4 centistokes or less, about 3.5 centistokes or less, or about 3 centistokes or less).

[0021] In some embodiments, the sublimable compounds described herein have high purity. In some embodiments, the purity of the sublimable compounds is about 99.9% or greater (e.g., about 99.99% or greater or about 99.999% or greater) or 100%. In some embodiments, the sublimable compounds may have a total metal content of 0-1 ppb by mass (e.g., 0-500 ppt or 0-300 ppt). In some embodiments, the total number of particles with a diameter of 0.1 μm or greater in the sublimable compounds described herein is 200 or less (e.g., 150 or less, 100 or less, 80 or less, 60 or less, or 50 or less) per mL of sublimable compound. The number of "particles" in a liquid medium can be counted using a light-scattering liquid particle counter, referred to as "LPC" (liquid particle count).

[0022] In some embodiments, the sublimable compounds described herein do not have a substantial volume change during the liquid-to-solid phase change upon freezing, which may reduce pattern collapse or damage. In some embodiments, during sublimation, the sublimable compounds can be uniformly removed without the need for subsequent rinsing or drying, which further reduces pattern collapse or damage.

[0023] Generally, the sublimable compounds described in the present disclosure may have at least one (e.g., two, three, or all) of the above properties. Examples of suitable sublimable compounds include t-butanol, glacial acetic acid, octamethylcyclotetrasiloxane, pentafluorophenol, 2-acetyl-5-methylfuran, p-chlorotoluene, acrylic acid, pyrimidine, 4-methylthiazole, p-xylene, ethylene dibromide, paraldehyde, ethylenediamine, 1,4-dioxane, formic acid, hexafluorobenzene, benzene, cyclohexane, 4-pyridinol, camphene, 2,2-dimethyl-1-propanol, cyanamide, dimethyl carbonate, trimethylsilanol, dimethyl sulfoxide, cyclohexanol, and trimethylacetonitrile.

[0024] In some embodiments, the sublimable compounds described herein also function as surface modifiers (e.g., to form a hydrophobic layer (e.g., a hydrophobic monolayer) on the semiconductor substrate surface, thereby reducing pattern collapse during rinsing or drying processes). Examples of such sublimable compounds include Si-containing compounds such as octamethylcyclotetrasiloxane, trimethylsilanol, t-hexyldimethylchlorosilane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane, triisopropyldimethylaminosilane, N-(trimethylsilyl)acetamide, and tris(trimethylsilyl)phosphate.

[0025] In some embodiments, the sublimable compound is present in an amount of about 40% by weight or more (e.g., about 50% by weight or more, about 60% by weight or more, about 70% by weight or more, about 80% by weight or more, about 90% by weight or more, about 92% by weight or more, or about 95% by weight or more) to about 99.5% by weight or less (e.g., about 99% by weight or less, about 98% by weight or less, about 97% by weight or less, about 96% by weight or less, about 95% by weight or less, about 90% by weight or less, about 85% by weight or less, or about 80% by weight or less) based on the weight of the sublimable material.

[0026] Some properties of exemplary sublimable compounds described in this disclosure are included in Table 1 below. [Table 1]

[0027] In some embodiments, the sublimable material described in the present disclosure may optionally further comprise at least one (e.g., two or three) surface modifier. Without wishing to be bound by theory, it is believed that the surface modifier can form a hydrophobic layer (e.g., a hydrophobic monolayer) on a semiconductor substrate having a pattern disposed on its surface, thereby reducing pattern collapse in a subsequent semiconductor manufacturing process (e.g., a rinsing process or a drying process). In some embodiments, if the sublimable compound in the sublimable material itself is a surface modifier, or if there is no subsequent rinsing or drying process, the sublimable material may not comprise an additional surface modifier.

[0028] In some embodiments, the surface modifier may include a Si-containing compound. In some embodiments, the Si-containing compound may be a disilazane. For example, the disilazane may be hexamethyldisilazane, heptamethyldisilazane, N-methylhexamethyldisilazane, 1,3-diphenyltetramethyldisilazane, or 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane.

[0029] In some embodiments, the Si-containing compound may include a trimethylsilyl group. For example, the Si-containing compound may be trimethylsilyl triflate, N-(trimethylsilyl)dimethylamine, N-(trimethylsilyl)diethylamine, 4-trimethylsilyloxy-3-penten-2-one, bis(trimethylsilyl)sulfate, methoxytrimethylsilane, ethoxytrimethylsilane, N-allyl-N,N-bis(trimethylsilyl)amine, N-(trimethylsilyl)diethylamine, N,N-bis(trimethylsilyl)urea, trimethylsilanol, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate.

[0030] In some embodiments, the Si-containing compound may be an aminosilane. For example, the aminosilane may be triisopropyl(dimethylamino)silane. In some embodiments, the Si-containing compound may be a siloxane. The siloxane compound may be a disiloxane, oligosiloxane, cyclosiloxane, or polysiloxane. In this disclosure, the term "oligosiloxane" refers to a compound having 3 to 6 siloxane units, and the term "polysiloxane" refers to a compound having more than 6 siloxane units. Examples of suitable siloxanes include octamethylcyclotetrasiloxane or 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane.

[0031] In some embodiments, the surface modifier is present in an amount of about 0.5% by weight or more (e.g., about 1% by weight or more, about 1.5% by weight or more, about 2% by weight or more, about 2.5% by weight or more, about 3% by weight or more, about 3.5% by weight or more, about 4% by weight or more, or about 5% by weight or more) to about 10% by weight or less (e.g., about 9% by weight or less, about 8% by weight or less, about 7% by weight or less, or about 6% by weight or less) of the sublimable material described herein.

[0032] Some properties of exemplary surface modifiers described in this disclosure are included in Table 2 below. [Table 2]

[0033] In some embodiments, the sublimable material described herein may optionally further comprise at least one (e.g., two or three) catalyst. For example, the catalyst may be triflic acid, triflic anhydride, methanesulfonic acid, acetic acid, or acetic anhydride. In some embodiments, the catalyst is present in an amount of about 0.1 wt. % or more (e.g., about 0.2 wt. % or more, about 0.3 wt. % or more, about 0.4 wt. % or more, about 0.5 wt. % or more, about 0.8 wt. % or more, about 1 wt. % or more, about 2 wt. % or more, or about 3 wt. % or more) to about 10 wt. % or less (e.g., about 9 wt. % or less, about 8 wt. % or less, about 7 wt. % or less, or about 6 wt. % or less) of the sublimable material described herein. Without wishing to be bound by theory, it is believed that the catalyst promotes the reaction between the surface modifier and reactive groups (e.g., silanol groups) in the semiconductor substrate surface, thereby improving surface treatment with sublimable materials.

[0034] Some properties of exemplary catalysts described in this disclosure are included in Table 3 below. [Table 3]

[0035] In some embodiments, the sublimable material described herein may optionally further comprise at least one (e.g., two or three) solvent (e.g., organic solvent). For example, the solvent may be hexyl acetate, n-butyl acetate, t-butyl acetate, propylene glycol methyl ether acetate (PGMEA), or anisole. In such embodiments, the surface treatment method described herein may further comprise a solvent evaporation step to remove the solvent before removing the sublimable compound by sublimation.

[0036] In some embodiments, the solvent is present in an amount of about 0.1 wt % or more (e.g., about 0.5 wt % or more, about 1 wt % or more, about 2 wt % or more, about 5 wt % or more, about 10 wt % or more, about 15 wt % or more, about 20 wt % or more, or about 25 wt % or more) to about 50 wt % or less (e.g., about 45 wt % or less, about 40 wt % or less, about 35 wt % or less, or about 30 wt % or less) of the sublimable material described herein.

[0037] Some properties of exemplary solvents described in this disclosure are included in Table 4 below. [Table 4]

[0038] In some embodiments, the sublimable material described herein may contain only two components: (1) at least one sublimable compound and (2) at least one surface modifier or at least one solvent. In some embodiments, when the sublimable compound itself is a surface modifier, the surface treatment composition described herein may contain only one component (i.e., at least one sublimable compound), or may contain only three components (i.e., (1) at least one sublimable compound, (2) at least one catalyst, and (3) at least one solvent).

[0039] Without wishing to be bound by theory, it is believed that in some embodiments, the sublimable materials described herein can form a surface treatment layer (e.g., a hydrophobic layer, such as a hydrophobic monolayer) on the patterned surface of a semiconductor substrate such that the patterned surface has a water contact angle of about 50° or greater (e.g., about 55° or greater, about 60° or greater, about 65° or greater, about 70° or greater, about 75° or greater, about 80° or greater, about 85° or greater, about 89° or greater, about 90° or greater, about 95° or greater, or about 100° or greater) and / or about 175° or less. Without wishing to be bound by theory, it is believed that such a surface treatment layer can prevent or minimize collapse of patterned features (e.g., having dimensions of about 20 nm or less) on the semiconductor substrate surface during subsequent semiconductor fabrication processes after the semiconductor substrate surface has been treated with the sublimable materials described herein. Additionally, it is believed that removal of the sublimable material by sublimation can eliminate subsequent rinsing or drying processes, further reducing pattern collapse.

[0040] In some embodiments, the sublimable materials described herein may specifically exclude or be substantially free of one or more additional components (in any combination, if two or more).Such additional components include non-aromatic hydrocarbons, protic solvents (e.g., alcohols or amides), lactones (e.g., lactones having a five- or six-membered ring), propylene glycol methyl ether acetate, Si-containing compounds (e.g., siloxanes such as disiloxanes; silanes such as alkoxysilanes; silazanes such as disilazanes; cyclic or heterocyclic silazanes; and compounds having Si-H groups or aminosilyl groups), polymers, oxygen scavengers, quaternary ammonium hydroxides or quaternary ammonium hydroxides. quaternary ammonium compounds such as ammonium salts, amines, bases (e.g., alkali bases (e.g., NaOH, KOH, LiOH, Mg(OH)2, and Ca(OH)2) and organic bases), surfactants, antifoaming agents, fluorine-containing compounds (e.g., HF, H2SiF6, H2PF6, HBF4, NHF, and tetraalkylammonium fluorides), oxidizing agents (e.g., peroxides, hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, nitric acid, ammonium chlorite, ammonium chlorate, ammonium iodate, the anti-rust agent is selected from the group consisting of: ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, urea hydrogen peroxide, and peracetic acid), abrasives, silicates, hydroxycarboxylic acids, carboxylic acids, and polycarboxylic acids (e.g., those without an amino group), cyclic compounds other than the cyclosiloxanes described herein (e.g., cyclic compounds containing two or more rings, such as substituted or unsubstituted naphthalene or substituted or unsubstituted biphenyl ether), chelating agents (e.g., azoles, diazoles, triazoles, or tetrazoles), rust inhibitors (e.g., azole and non-azole rust inhibitors), buffers, guanidine, guanidine salts, pyrrolidone, polyvinylpyrrolidone, metal salts (e.g., metal halides), and metal-containing catalysts.

[0041] In some embodiments, the sublimable materials described herein (including at least one sublimable compound and optionally one or more other components) have a relatively low metal content and a relatively low particle content. In some embodiments, the sublimable materials may have a total metal content of 0 to 1 ppb by mass (e.g., 0 to 500 ppt or 0 to 300 ppt). In some embodiments, the total number of particles with a particle size of 0.1 μm or larger in the sublimable materials described herein may be 200 or less (e.g., 150 or less, 100 or less, 80 or less, 60 or less, or 50 or less) per mL of sublimable material.

[0042] In some embodiments, the surface treatment methods described herein may optionally further comprise contacting the surface of the substrate with at least one aqueous cleaning solution prior to contacting the surface of the substrate with the sublimable material. In such embodiments, the at least one aqueous cleaning solution may comprise water, an alcohol, an aqueous ammonium hydroxide solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an organic solvent, or a combination thereof.

[0043] In some embodiments, the surface treatment method described herein may optionally further include contacting the surface of a substrate with a first rinse solution (e.g., water, an organic solvent such as isopropanol, or a combination thereof) after contacting the surface with at least one aqueous cleaning solution and before contacting the surface with a sublimable material. In some embodiments, the surface treatment method described herein may optionally further include contacting the surface with a second rinse solution (e.g., water, an organic solvent such as isopropanol, or a combination thereof) after contacting the surface with a sublimable material. In some embodiments, the surface treatment method described herein may optionally further include drying the surface (e.g., after any of contacting the surface with the first rinse solution, contacting the surface with the sublimable material, and contacting the surface with the second rinse solution). In some embodiments, the surface treatment method described herein may further include removing a surface treatment layer from the surface.

[0044] In some embodiments, the present disclosure provides methods for cleaning a semiconductor substrate (e.g., a wafer) having a pattern disposed on the surface of the substrate. Such methods may include, for example: a) optionally contacting the surface with an aqueous cleaning solution; b) optionally contacting the surface with a first rinse solution; c) contacting said surface with a sublimable material described herein, wherein said sublimable material comprises at least one sublimable compound; d) maintaining the sublimable material on the surface for a time sufficient to modify the surface; e) optionally removing solvent (if present) on said surface; f) solidifying the sublimable material on the surface; g) removing the sublimable material (which may form a surface treatment layer) disposed on the surface by sublimation; h) optionally contacting the surface with a second rinse solution; i) optionally drying the surface; and j) optionally removing the surface treatment layer to form a cleaned, patterned surface; This can be done by: In such embodiments, the pattern on the semiconductor substrate surface may include features having dimensions of about 20 nm or less.

[0045] In step a) of the method, a substrate (e.g., a wafer) bearing a patterned surface may optionally be treated with one or more aqueous cleaning solutions. When the patterned surface is treated with two or more aqueous cleaning solutions, the cleaning solutions may be applied sequentially. The aqueous cleaning solution may be water alone, an organic solvent alone, or a solution containing water, a solute, and optionally an organic solvent. In some embodiments, the aqueous cleaning solution may contain water, an alcohol (e.g., a water-soluble alcohol such as isopropanol), an aqueous ammonium hydroxide solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an organic solvent (e.g., a water-soluble organic solvent), or a combination thereof.

[0046] In step b), the cleaning solution from step a) is optionally rinsed off with a first rinse solution. The first rinse solution may comprise water, an organic solvent (e.g., isopropanol), or an aqueous solution containing an organic solvent. In some embodiments, the first rinse solution is at least partially miscible with the cleaning solution used in step a). In some embodiments, step b) may be omitted if the cleaning solution used in step a) is not moisture-sensitive or does not contain appreciable amounts of water. In some embodiments, step (b) is used without step a).

[0047] In step c), the substrate surface may be treated with a sublimable material described herein to form a modified surface having a surface treatment layer (e.g., a hydrophobic layer). The semiconductor substrate may be contacted with the sublimable material in any suitable manner, including, for example, placing the sublimable material in a tank and immersing and / or submerging the semiconductor substrate in the sublimable material, spraying the sublimable material onto the semiconductor substrate, flowing the sublimable material onto the semiconductor substrate, or any combination thereof. In some embodiments, this step may be performed at a temperature of about 20°C to 35°C. In some embodiments, the sublimable material may be pretreated using an ion exchange process, a distillation process, a sublimation process, or a filtration process to meet the ultra-pure material requirements for this process.

[0048] In step d), the sublimable material may be maintained on the surface for a time ranging from about 10 seconds to about 300 seconds to modify the surface.

[0049] In step e), if the sublimable material includes a solvent, the solvent may be removed (e.g., by evaporation) prior to sublimation of the sublimable material. In some embodiments, the solvent may be removed by evaporation, for example, by heating the semiconductor substrate using a heating means such as a hot plate or infrared lamp, by placing the semiconductor substrate under reduced pressure (e.g., in a chamber), or both. In some embodiments, if the sublimable material includes a solvent, solvent saturation and blanket gas (N, clean dry air, etc.) for the tool tank and chamber (holding the sublimable material) can be used to control evaporation to prevent "bumping" of micro- and nano-bubbles that can cause patterned substrate defects during the solvent removal process. It is believed that this additional process may improve the uniformity of the sublimation process, provide a better stiction-free drying process, and minimize substrate defectivity.

[0050] In step f), the sublimable material can be solidified by reducing the temperature of the semiconductor substrate, for example, by cooling the backside of the semiconductor substrate or by cooling the chamber in which the semiconductor substrate is placed. The temperature for solidifying or freezing the sublimable material can be about 15°C or lower (e.g., about 10°C or lower, about 5°C or lower, about 0°C or lower, about -5°C or lower, about -10°C or lower, or -20°C or lower) or about -30°C or higher. In some embodiments, when using a sublimable material with a melting point of about 18°C ​​or higher, it may be necessary to use a heating jacket for the dispense canister and transfer line to prevent premature fluid solidification when transferring the sublimable material to the substrate. In such embodiments, the sublimable material can be solidified at ambient temperature.

[0051] In step g), the sublimable material can be sublimated by increasing the substrate temperature, decreasing the pressure of the substrate chamber (e.g., after the substrate is placed in the chamber), or both to achieve acceptable conditions for uniform sublimation based on the phase diagram of the sublimable material. In some embodiments, an in-line endpoint detector can be used to verify completion of the sublimation process. The pressure and temperature of the substrate chamber can then be slowly changed to standard temperature and pressure (STP) conditions under a nitrogen gas flow. The substrate can then be removed from the substrate chamber. The chamber can then be cleaned using cycles of increasing temperature and / or decreasing pressure (with N flow) to remove any traces of sublimable material from the chamber. Without wishing to be bound by theory, it is believed that this sublimation step can minimize pattern collapse on the semiconductor substrate (e.g., by eliminating subsequent rinsing and / or drying steps).

[0052] In step h), after treating the substrate surface with the sublimable material, the surface can be rinsed with a second rinse solution. The second rinse solution can be water, an organic solvent (e.g., isopropanol), or an aqueous solution containing an organic solvent. In some embodiments, this step can be performed at a temperature between about 20°C and 70°C. In some embodiments, this rinse step can be omitted if all of the sublimable material is removed by sublimation and no substantial residue remains on the semiconductor substrate.

[0053] In step i), the substrate surface can be dried (e.g., by using pressurized gas). Without wishing to be bound by theory, it is believed that this drying step minimizes pattern collapse on the substrate surface after it has been treated with a sublimable material as described herein. In some embodiments, this drying step may be omitted if a post-sublimation rinse step is eliminated.

[0054] In step j), once the surface treatment layer (e.g., a hydrophobic layer) has been formed on the semiconductor substrate, the surface treatment layer can be optionally removed. Generally, depending on the chemical properties of the modified surface, the surface treatment layer can be removed by a number of methods. Suitable methods for removing the surface treatment layer include plasma sputtering; plasma ashing; thermal treatment at atmospheric pressure or below atmospheric pressure; treatment with a solvent containing an acid, a base, an oxidizing agent, or a condensed fluid (e.g., a supercritical fluid such as supercritical CO2); treatment with a gas or liquid; UV irradiation; or a combination thereof.

[0055] A semiconductor substrate having a cleaned and patterned surface produced by the methods described herein may be further processed to form one or more circuits on the substrate, or may be processed into a semiconductor device (e.g., an integrated circuit device such as a semiconductor chip), for example, by assembly (e.g., dicing and bonding) and packaging (e.g., chip sealing).

[0056] In some embodiments, the present disclosure also features an article (e.g., an intermediate semiconductor article formed during the manufacture of a semiconductor device) that includes a semiconductor substrate and a sublimable material described herein supported on the semiconductor substrate.

[0057] The present disclosure will be described in more detail with reference to the following examples, which are for illustrative purposes and should not be construed as limiting the scope of the disclosure. [Example]

[0058] Example 1 The patterned substrates were cleaned with an RCA cleaning sequence (dilute hydrofluoric acid / ammonium hydrogen peroxide / hydrogen peroxide and hydrochloric acid) using a single wafer tool (SWT) processor with substrate spinning, temperature control, and chemical dispensing, and rinsed with water, isopropanol, or other rinses or combinations of rinses. To prevent stiction drying, the substrates were kept with liquid on the surface prior to surface modification and sublimation.

[0059] A sublimable material containing 97% dimethyl carbonate (i.e., the sublimable compound) and 3% trimethylsilyl triflate (i.e., the surface modifier) ​​at 25°C is used to rinse away any potentially damaging residual chemicals (e.g., any cleaning or other rinsing solutions that may be present) from the surface of the substrate while simultaneously surface modifying the substrate to minimize surface free energy. Once the substrate is surface modified, the sublimable material is subjected to a phase change (i.e., from liquid to solid) using substrate, substrate chamber, and / or chemical tank temperature control. In this example, the substrate temperature is reduced to 0°C to solidify the dimethyl carbonate solution. After this substrate pattern solidification step, the dimethyl carbonate is sublimated by increasing the substrate temperature, reducing the substrate chamber pressure, or both, to achieve acceptable conditions for uniform sublimation based on the phase diagram of the sublimable compound. For this example, the substrate temperature is maintained at 0°C, and the chamber pressure is slowly reduced to 16.5 mmHg to provide suitable sublimation conditions.

[0060] An in-line endpoint detector is used to verify completion of the sublimation process. The pressure and temperature of the substrate chamber are then slowly brought to STP (standard temperature and pressure) conditions under dry nitrogen gas. An optional surface modification removal step can be performed by treating the patterned substrate with plasma, UV radiation, or chemical vapors that cleave the Si-O-C—R bonds of the modified surface and reconstruct a hydroxylated surface for subsequent processing steps. The substrate is then removed from the chamber.

[0061] Sublimation-processed substrate patterns containing cylindrical silicon pillars with an aspect ratio of 22:1, an average width at half height of 10-15 nm, and an average height of 550 nm, are analyzed by scanning electron microscopy at 50,000x magnification at three randomly selected locations, and the number of uncollapsed silicon pillars is tallied. The average number of uncollapsed silicon pillars at the three locations is then calculated and compared to the average number of total silicon pillars at the three locations on the unprocessed sample. The % uncollapsed is calculated by dividing the number of uncollapsed pillars by the total number of original pillars and multiplying by 100. In this way, the effectiveness of the sublimation process in preventing pattern collapse can be evaluated.

[0062] Example 2 The patterned substrates were cleaned in an RCA cleaning sequence (DHF / SC-1 / SC-2) using a single wafer tool (SWT) processor with substrate spinning, temperature control, and chemical dispensing, and rinsed with water, isopropanol, or other rinses or combinations of rinses. To prevent stiction drying, the substrates were kept with liquid on the surface prior to surface modification and sublimation.

[0063] The substrate surface is rinsed to remove any residual chemicals (e.g., any previous cleaning or rinsing solutions) that may be present from the substrate surface using a sublimable material containing 60% octamethylcyclotetrasiloxane (i.e., a sublimable compound with a surface-modifying function), 1% triflic acid (i.e., a catalyst), and 39% n-butyl acetate (i.e., a solvent), and then the substrate is surface-modified at 25°C. The n-butyl acetate slowly evaporates from the substrate as the wafer temperature is increased and the pressure is reduced, achieving smooth evaporation without bumping. Bumping occurs when a liquid is heated too quickly or its pressure is reduced, during which small vapor bubbles rapidly grow into large vapor bubbles and displace surrounding liquid at high speeds, potentially damaging surrounding features. The sublimable material is then phase-changed (i.e., from liquid to solid) within the substrate pattern using substrate, substrate chamber, and / or chemical tank temperature control. In this example, the substrate temperature is reduced to 15° C. to solidify the octamethylcyclotetrasiloxane. After this substrate pattern solidification step, the octamethylcyclotetrasiloxane is sublimated by increasing the substrate temperature, reducing the pressure in the substrate chamber, or both, to achieve acceptable conditions for uniform sublimation based on the phase diagram of the sublimable compound. For this example, the substrate temperature is maintained at 15° C. and the chamber pressure is slowly reduced to 0.25 mmHg to provide suitable sublimation conditions.

[0064] An in-line endpoint detector is used to verify the completion of the sublimation process. Then, under dry nitrogen gas, the pressure and temperature are slowly brought to STP (standard temperature and pressure) conditions. An optional surface modification removal step can be performed by treating the patterned substrate with plasma, UV radiation, or chemical vapors that cleave the Si-O-C—R bonds of the modified surface and reconstruct a hydroxylated surface for subsequent processing steps. The substrate is then removed from the chamber.

[0065] Sublimation-processed substrate patterns containing cylindrical silicon pillars with an aspect ratio of 22:1, an average width at half height of 10-15 nm, and an average height of 550 nm, are analyzed by scanning electron microscopy at 50,000x magnification at three randomly selected locations, and the number of uncollapsed silicon pillars is tallied. The average number of uncollapsed silicon pillars at the three locations is then calculated and compared to the average number of total silicon pillars at the three locations on the unprocessed sample. The % uncollapsed is calculated by dividing the number of uncollapsed pillars by the total number of original pillars and multiplying by 100. In this way, the effectiveness of the sublimation chemistry and process in preventing pattern collapse can be evaluated.

[0066] Although the invention has been described in detail with reference to specific embodiments thereof, it will be understood that modifications and variations are within the spirit and scope of what has been described and claimed. The present application includes the following aspects. [Section 1] a) applying a sublimable material to a substrate having a pattern disposed on a surface of the substrate, wherein the sublimable material includes a sublimable compound and a surface modifier; b) maintaining the sublimable material on the surface for a time sufficient to modify the surface; c) solidifying the sublimable material on the surface; and d) removing the sublimable material located on the surface by sublimation; A method for processing a substrate, comprising: [Section 2] Item 1. The method according to Item 1, wherein the sublimable compound has a melting point of about −20° C. to about 60° C. and a vapor pressure of about 1 mmHg or more at 25° C. [Section 3] Item 1. The method according to Item 1, wherein the sublimable compound has a melting point of about 0°C to about 20°C. [Section 4] Item 1. The method according to Item 1, wherein the sublimable compound has a surface tension of about 65 mN / m or less at 25°C. [Section 5] Item 10. The method of claim 1, wherein the sublimable compound has a viscosity of about 5 centistokes or less at 25°C. [Section 6] Item 2. The method according to item 1, wherein the sublimable compound is selected from the group consisting of t-butanol, glacial acetic acid, octamethylcyclotetrasiloxane, pentafluorophenol, 2-acetyl-5-methylfuran, p-chlorotoluene, acrylic acid, pyrimidine, 4-methylthiazole, p-xylene, ethylene dibromide, paraldehyde, ethylenediamine, 1,4-dioxane, formic acid, hexafluorobenzene, benzene, cyclohexane, 4-pyridinol, camphene, 2,2-dimethyl-1-propanol, cyanamide, dimethyl carbonate, trimethylsilanol, dimethyl sulfoxide, cyclohexanol, and trimethylacetonitrile. [Section 7] Item 1. The method according to item 1, wherein the sublimable compound is present in an amount of about 40% by weight to about 99.5% by weight based on the sublimable material. [Section 8] Item 1. The method according to item 1, wherein the surface modifier comprises a Si-containing compound. [Section 9] Item 9. The method according to Item 8, wherein the Si-containing compound is a disilazane. [Section 10] Item 10. The method according to item 9, wherein the disilazane is hexamethyldisilazane, heptamethyldisilazane, N-methylhexamethyldisilazane, 1,3-diphenyltetramethyldisilazane, or 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane. [Section 11] Item 9. The method according to Item 8, wherein the Si-containing compound comprises a trimethylsilyl group. [Section 12] Item 12. The method according to Item 11, wherein the Si-containing compound is trimethylsilyl triflate, N-(trimethylsilyl)dimethylamine, N-(trimethylsilyl)diethylamine, 4-trimethylsilylsilyloxy-3-penten-2-one, bis(trimethylsilyl)sulfate, methoxytrimethylsilane, ethoxytrimethylsilane, N-allyl-N,N-bis(trimethylsilyl)amine, N-(trimethylsilyl)diethylamine, N,N-bis(trimethylsilyl)urea, trimethylsilanol, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate. [Section 13] Item 9. The method according to Item 8, wherein the Si-containing compound is an aminosilane. [Section 14] Item 14. The method of item 13, wherein the aminosilane is triisopropyl(dimethylamino)silane. [Section 15] Item 9. The method according to item 8, wherein the Si-containing compound is a siloxane. [Section 16] Item 16. The method according to item 15, wherein the siloxane is octamethylcyclotetrasiloxane or 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane. [Section 17] Item 1. The method according to item 1, wherein the surface modifier is present in an amount of about 0.5% by weight to about 10% by weight of the sublimable material. [Section 18] Item 10. The method of claim 1, wherein the sublimable material further comprises a catalyst. [Section 19] The catalyst is triflic acid, triflic anhydride, Item 19. The method according to Item 18, wherein the base is methanesulfonic acid, acetic acid, or acetic anhydride. [Section 20] Item 19. The method of item 18, wherein the catalyst is present in an amount of about 0.1% to 10% by weight relative to the sublimable material. [Section 21] Item 1. The method of claim 1, wherein the sublimable material further comprises a solvent. [Section 22] 22. The method of claim 21, further comprising a solvent evaporation step. [Section 23] Item 22. The method of item 21, wherein the solvent is hexyl acetate, n-butyl acetate, t-butyl acetate, propylene glycol methyl ether acetate (PGMEA), or anisole. [Section 24] Item 1. The method of item 1, wherein the surface comprises SiO2, SiN, TiN, SiOC, SiON, Si, SiGe, Ge, or W. [Section 25] a) applying a sublimable material to a substrate having a pattern disposed on a surface of the substrate, wherein the sublimable material includes a sublimable compound, the sublimable compound being a surface modifier; b) maintaining the sublimable material on the surface for a time sufficient to modify the surface; c) solidifying the sublimable material on the surface; and d) removing the sublimable material located on the surface by sublimation; A method for processing a substrate, comprising: [Section 26] Item 26. The method according to Item 25, wherein the sublimable compound has a melting point of about −20° C. to about 60° C. and a vapor pressure of about 1 mmHg or more at 25° C. [Section 27] Item 26. The method according to Item 25, wherein the sublimable compound has a melting point of about 0°C to about 20°C. [Section 28] Item 26. The method according to item 25, wherein the sublimable compound has a surface tension of about 65 mNm or less at 25°C. [Section 29] 26. The method of claim 25, wherein the sublimable compound has a viscosity of about 5 centistokes or less at 25°C. [Section 30] Item 26. The method according to Item 25, wherein the sublimable compound is octamethylcyclotetrasiloxane, trimethylsilanol, t-hexyldimethylchlorosilane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane, triisopropyldimethylaminosilane, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate. [Section 31] 26. The method of claim 25, wherein the sublimable material further comprises a catalyst. [Section 32] 32. The method of claim 31, wherein the catalyst is triflic acid, triflic anhydride, methanesulfonic acid, acetic acid, or acetic anhydride. [Section 33] Item 32. The method of item 31, wherein the catalyst is present in an amount of about 0.1% to 10% by weight relative to the sublimable material. [Section 34] Item 26. The method of item 25, wherein the sublimable material further comprises a solvent. [Section 35] 35. The method of claim 34, further comprising a solvent evaporation step. [Section 36] Item 35. The method of item 34, wherein the solvent is hexyl acetate, n-butyl acetate, t-butyl acetate, propylene glycol methyl ether acetate (PGMEA), or anisole. [Section 37] 26. The method of claim 25, wherein the surface comprises SiO2, SiN, TiN, SiOC, SiON, Si, SiGe, Ge, or W. [Section 38] a sublimable compound in an amount of about 40% to about 99.5% by weight relative to the sublimable material; and A surface modifier in an amount of about 0.5% to about 10% by weight based on the sublimable material. A sublimable material comprising: [Section 39] a sublimable compound in an amount of about 40% to about 99.5% by weight relative to the sublimable material; a catalyst in an amount of about 0.1% to about 10% by weight relative to the sublimable material; a solvent in an amount of about 0.1% to about 50% by weight relative to the sublimable material; and A sublimable material comprising: [Section 40] a sublimable compound in an amount of about 40% to about 99.5% by weight based on the sublimable material, wherein the sublimable compound is octamethylcyclotetrasiloxane, trimethylsilanol, t-hexyldimethylchlorosilane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane, triisopropyldimethylaminosilane, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate; and A solvent in an amount of about 0.1% to about 50% by weight relative to the sublimable material A sublimable material comprising:

Claims

1. a) applying a sublimable material to a substrate having a pattern disposed on a surface of the substrate, wherein the sublimable material comprises a sublimable compound and a surface modifier; b) maintaining the sublimable material on the surface for a time sufficient to modify the surface; c) solidifying the sublimable material on the surface; and d) removing the sublimable material located on said surface by sublimation; Including, 1. A method for treating a substrate, wherein the sublimable compound is selected from the group consisting of glacial acetic acid, octamethylcyclotetrasiloxane, 2-acetyl-5-methylfuran, p-chlorotoluene, acrylic acid, pyrimidine, 4-methylthiazole, p-xylene, ethylene dibromide, paraldehyde, ethylenediamine, 1,4-dioxane, formic acid, benzene, 4-pyridinol, cyanamide, dimethyl carbonate, trimethylsilanol, dimethyl sulfoxide, and trimethylacetonitrile.

2. 2. The method of claim 1, wherein the sublimable compound has a melting point of -20°C to 60°C and a vapor pressure of 1 mmHg or more at 25°C.

3. 2. The method of claim 1, wherein the sublimable compound has a melting point of 0°C to 20°C.

4. 10. The method of claim 1, wherein the sublimable compound has a surface tension of 65 mN / m or less at 25°C.

5. 10. The method of claim 1, wherein the sublimable compound has a viscosity of 5 centistokes or less at 25°C.

6. 10. The method of claim 1, wherein the sublimable compound is present in an amount of 40% to 99.5% by weight relative to the sublimable material.

7. The method of claim 1 , wherein the surface modifier comprises a Si-containing compound.

8. The method of claim 7, wherein the Si-containing compound is a disilazane.

9. 9. The method of claim 8, wherein the disilazane is hexamethyldisilazane, heptamethyldisilazane, N-methylhexamethyldisilazane, 1,3-diphenyltetramethyldisilazane, or 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane.

10. The method of claim 7 , wherein the Si-containing compound comprises a trimethylsilyl group.

11. The method of claim 10, wherein the Si-containing compound is trimethylsilyl triflate, N-(trimethylsilyl)dimethylamine, N-(trimethylsilyl)diethylamine, 4-trimethylsilyloxy-3-penten-2-one, bis(trimethylsilyl)sulfate, methoxytrimethylsilane, ethoxytrimethylsilane, N-allyl-N,N-bis(trimethylsilyl)amine, N-(trimethylsilyl)diethylamine, N,N-bis(trimethylsilyl)urea, trimethylsilanol, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate.

12. The method of claim 7 wherein the Si-containing compound is an aminosilane.

13. The method of claim 12 wherein the aminosilane is triisopropyl(dimethylamino)silane.

14. The method of claim 7, wherein the Si-containing compound is a siloxane.

15. The method of claim 14, wherein the siloxane is octamethylcyclotetrasiloxane or 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane.

16. The method of claim 1, wherein the surface modifier is present in an amount of 0.5% to 10% by weight relative to the sublimable material.

17. The method of claim 1 , wherein the sublimable material further comprises a catalyst.

18. The catalyst is triflic acid, triflic anhydride, , methanesulfonic acid, acetic acid, or acetic anhydride.

19. 18. The method of claim 17, wherein the catalyst is present in an amount of 0.1% to 10% by weight relative to the sublimable material.

20. The method of claim 1 , wherein the sublimable material further comprises a solvent.

21. 21. The method of claim 20 further comprising a solvent evaporation step.

22. 21. The method of claim 20, wherein the solvent is hexyl acetate, n-butyl acetate, t-butyl acetate, propylene glycol methyl ether acetate (PGMEA), or anisole.

23. The surface is SiO ２ , SiN, TiN, SiOC, SiON, Si, SiGe, Ge, or W.

24. a) applying a sublimable material to a substrate having a pattern disposed on a surface of the substrate, wherein the sublimable material includes a sublimable compound, the sublimable compound being a surface modifier; b) maintaining the sublimable material on the surface for a time sufficient to modify the surface; c) solidifying the sublimable material on the surface; and d) removing the sublimable material located on said surface by sublimation; Including, A method for treating a substrate, wherein the sublimable compound is octamethylcyclotetrasiloxane, trimethylsilanol, t-hexyldimethylchlorosilane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane, triisopropyldimethylaminosilane, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate.

25. 25. The method of claim 24, wherein the sublimable compound has a melting point of -20°C to 60°C and a vapor pressure of 1 mmHg or more at 25°C.

26. 25. The method of claim 24, wherein the sublimable compound has a melting point of 0°C to 20°C.

27. 25. The method of claim 24, wherein the sublimable compound has a surface tension of 65 mNm or less at 25°C.

28. 25. The method of claim 24, wherein the sublimable compound has a viscosity of 5 centistokes or less at 25°C.

29. 25. The method of claim 24, wherein the sublimable material further comprises a catalyst.

30. 30. The method of claim 29, wherein the catalyst is triflic acid, triflic anhydride, methanesulfonic acid, acetic acid, or acetic anhydride.

31. 30. The method of claim 29, wherein the catalyst is present in an amount of 0.1% to 10% by weight relative to the sublimable material.

32. 25. The method of claim 24, wherein the sublimable material further comprises a solvent.

33. 33. The method of claim 32, further comprising a solvent evaporation step.

34. 33. The method of claim 32, wherein the solvent is hexyl acetate, n-butyl acetate, t-butyl acetate, propylene glycol methyl ether acetate (PGMEA), or anisole.

35. The surface is SiO ２ , SiN, TiN, SiOC, SiON, Si, SiGe, Ge, or W.

36. a sublimable compound in an amount of 40% to 99.5% by weight relative to the sublimable material; and A surface modifier in an amount of 0.5% to 10% by weight relative to the sublimable material Including, The sublimable compound is selected from the group consisting of glacial acetic acid, octamethylcyclotetrasiloxane, 2-acetyl-5-methylfuran, p-chlorotoluene, acrylic acid, pyrimidine, 4-methylthiazole, p-xylene, ethylene dibromide, paraldehyde, ethylenediamine, 1,4-dioxane, formic acid, benzene, 4-pyridinol, cyanamide, dimethyl carbonate, trimethylsilanol, dimethyl sulfoxide, and trimethylacetonitrile.

37. a sublimable compound in an amount of 40% to 99.5% by weight relative to the sublimable material; a catalyst in an amount of 0.1% to 10% by weight relative to the sublimable material; and a solvent in an amount of 0.1% to 50% by weight relative to the sublimable material; Including, The sublimable compound is octamethylcyclotetrasiloxane, trimethylsilanol, t-hexyldimethylchlorosilane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane, triisopropyldimethylaminosilane, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate.

38. a sublimable compound in an amount of 40% to 99.5% by weight based on the sublimable material, wherein the sublimable compound is octamethylcyclotetrasiloxane, trimethylsilanol, t-hexyldimethylchlorosilane, 1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane, triisopropyldimethylaminosilane, N-(trimethylsilyl)acetamide, or tris(trimethylsilyl)phosphate; and A solvent in an amount of 0.1% to 50% by weight relative to the sublimable material A sublimable material comprising:

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