Composition comprising a siloxane and an alkane for avoiding pattern collapse when treating patterned materials with line-space dimensions of 50 nm or below

Abstract

This invention relates to a non-aqueous composition, which is essentially composed of: (a) an organic solvent selected from: (i) straight-chain, branched, or cyclic C5 to C12 alkanes, and (ii) benzene substituted with 1 to 3 C1 to C4 alkyl groups; and (b) at least one additive of formula I or II: wherein R1 is H, R2 is selected from H, C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl, and C6 to C10 aryl, R3 is selected from R2, R4 is selected from C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl, and C6 to C10 aryl, R10 and R12 are independently selected from C1 to C10 alkyl and C1 to C10 alkoxy, m is 1, 2, or 3, and n is 0 or an integer from 1 to 100.

Description

[Technical Field]

[0001] This invention relates to a composition for anti-pattern collapse processing, and its use and method in manufacturing integrated circuit devices, optical devices, micromechanical devices and precision mechanical devices. [Previous Technology]

[0002] In methods for manufacturing ICs using LSI, VLSI, and ULSI, patterned material layers, such as patterned photoresist layers, patterned barrier material layers containing or composed of titanium nitride, tantalum, or tantalum nitride, patterned multi-stacked material layers containing or composed of, for example, alternating stacks of polycrystalline silicon and silicon dioxide or silicon nitride layers, and patterned dielectric material layers containing or composed of silicon dioxide or low-k or ultra-low-k dielectric materials, are manufactured using photolithography. Currently, such patterned material layers contain structures with dimensions even below 22 nm and high aspect ratios.

[0003] However, regardless of the exposure technology, wet chemical processing of small patterns involves several issues. With technological advancements and increasingly stringent size requirements, patterns need to include relatively thin and tall structures or features on the substrate, i.e., features with high aspect ratios. Due to excessive capillary forces from the liquid or solution of deionized water, the rinsing liquid remaining between adjacent patterned structures during chemical rinsing and spin drying, these structures may suffer bending and / or collapse, especially during the spin drying process.

[0004] Due to the shrinkage in size, removing particles and plasma etching residues to achieve defect-free patterned structures has become a key factor. This certainly applies to photoresist patterns, but also to other patterned materials produced during the manufacture of optical devices, micromechanical devices, and precision mechanical devices.

[0005] WO 2012 / 027667 A2 discloses a method for modifying a surface with a high aspect ratio feature by contacting the surface with an additive composition to produce a modified surface, wherein the forces acting on the high aspect ratio feature when the rinsing solution contacts the modified surface are sufficiently minimized to prevent bending or collapse of the high aspect ratio feature, at least during the removal of the rinsing solution or at least during the drying of the high aspect ratio feature. The modified surface should have a contact angle in the range of about 70 degrees to about 110 degrees. In addition to many other types of acids, bases, nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants, it also discloses some siloxane-type surfactants. It mentions a variety of organic solvents, including ethylene glycol, isopropanol, 1-methoxy-2-propyl acetate, isopropyl acetate, ethyl carbonate, dimethyl sulfoxide, and hydrocarbons (such as hexane).

[0006] US 2018 / 0254182 A discloses the use of silanes (such as hexamethyldisilazane) in compositions for surface treatment, which can highly hydrophobically (silanize) the surface of the target, while suppressing the deterioration of PVC when the surface treatment of the target (such as inorganic patterns and resin patterns) is performed using an apparatus having a liquid contact portion provided with a component made of PVC.

[0007] WO 2019 / 086374 discloses a water-based anti-pattern collapse solution containing siloxane additives.

[0008] US 2013 / 255534 A1 discloses a clean composition containing silane and an organic solvent to resist pattern collapse.

[0009] Unpublished European Patent Application No. 19168153.5 discloses a composition comprising an ammonia-activated silicate and a polar protic solvent (such as isopropanol), which may be combined with alkanes as needed. This composition is used to prevent pattern collapse when processing patterned materials with line spacing dimensions of 50 nm or less.

[0010] However, these compositions still exhibit high pattern collapse in structures below 50 nm, especially when SC1 pretreatment with ammonia and hydrogen peroxide is required.

[0011] The object of the present invention is to provide a composition and method for manufacturing integrated circuits for nodes of 50 nm and below, particularly 32 nm and below, especially 22 nm and below, which does not have the disadvantages of prior art manufacturing compositions and methods.

[0012] In particular, the compounds of the present invention should allow chemical rinsing of patterned material layers containing patterns having a high aspect ratio and line spacing dimensions of 50 nm and below, particularly 32 nm and below, especially 22 nm and below, without causing pattern collapse. Furthermore, an object of the present invention is to provide a composition that provides reduced pattern collapse on substrates (such as, but not limited to, silicon, silicon oxide, and silicon nitride) requiring alkali pretreatment (such as SC1 treatment). [Summary of the Invention]

[0013] This invention completely avoids all the disadvantages of prior art by using a non-aqueous composition comprising a combination of a nonpolar organic solvent and the siloxane-type nonionic additives described herein. Surprisingly, it has been found that only combinations of H-silanes with straight-chain, branched, or cyclic C5 to C12 alkanes or benzenes substituted with 1 to 3 C1 to C4 alkyl groups can solve the problems associated with prior art compositions, particularly the high non-collapse rate.

[0014] A first specific example of the present invention is a non-aqueous composition, which is substantially composed of: (a) an organic solvent selected from: (i) a straight-chain, branched or cyclic C5 to C12 alkane, and (ii) a benzene substituted with 1 to 3 C1 to C4 alkyl groups; and (b) at least one additive of formula I or II: (I) (II) wherein R1 is H, R2 is selected from H, C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl and C6 to C10 aryl, R3 is selected from R2, R4 is selected from C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl and C6 to C10 aryl, R10 and R12 are independently selected from C1 to C10 alkyl and C1 to C10 alkoxy, m is 1, 2 or 3, and n is an integer from 0 or 1 to 100.

[0015] When used for cleaning, the additive according to the invention, which contains at least one H atom bonded to a Si atom, provides a better pattern collapse rate than the additive in which the H atom is fully substituted.

[0016] Another specific example of the present invention is the use of the composition described herein for processing a substrate comprising a patterned material layer having a line spacing dimension of 50 nm or less, an aspect ratio of 4 or greater, or a combination thereof.

[0017] Another specific embodiment of the present invention is a method for manufacturing integrated circuit devices, optical devices, micromechanical devices, and precision mechanical devices, the method comprising the following steps: (a) providing a substrate comprising a patterned material layer having a line spacing dimension of 50 nm or less, an aspect ratio of 4 or greater, or a combination thereof; (b) contacting the substrate with an aqueous pretreatment composition comprising ammonia and hydrogen peroxide; (c) removing the aqueous pretreatment composition from the substrate; (d) contacting the substrate with a non-aqueous composition described herein at least once; and (e) removing the non-aqueous composition from the contact with the substrate.

[0018] Compositions comprising a combination of a nonpolar organic protic solvent and H-silanes are particularly suitable for anti-pattern collapse treatment of substrates containing patterns having a line spacing dimension of 50 nm or less, particularly 32 nm or less, and most particularly 22 nm or less. Furthermore, the composition according to the invention is particularly useful for aspect ratios greater than or equal to 4 without causing pattern collapse. Finally, and equally importantly, due to the use of a nonpolar organic solvent and, if desired, an alkane as the solvent, the composition exhibits excellent compatibility with substrates containing polyvinyl chloride.

[0019] It should be noted that cleaning or rinsing solutions containing a combination of nonpolar organic solvents and H-silanes are generally used to avoid pattern collapse of photoresist structures, as well as pattern collapse of non-photoresist patterns with high aspect ratios stack (HARS), especially patterned multi-stacked material layers containing or composed of silicon, silicon dioxide or silicon nitride layers, and pattern collapse of stacks containing alternating polycrystalline silicon and silicon dioxide or silicon nitride layers.

Implementation Method

[0021] The present invention relates to a composition that is particularly suitable for manufacturing patterned materials containing features of less than 50 nm in size, such as integrated circuit (IC) devices, optical devices, micromechanical and mechanical precision devices, especially IC devices.

[0022] Any conventional and known substrate used for manufacturing IC devices, optical devices, micromechanical devices, and precision mechanical devices can be used in the method of the present invention. Preferably, the substrate is a semiconductor substrate, more preferably a silicon wafer, which is typically used to manufacture IC devices, particularly IC devices comprising ICs having LSI, VLSI, and ULSI.

[0023] This composition is particularly suitable for processing substrates comprising patterned material layers having line spacing dimensions of 50 nm and below, particularly 32 nm and below, especially 22 nm and below, i.e., patterned material layers below the 22 nm technology node. The patterned material layer preferably has an aspect ratio greater than 4, more preferably greater than 5, more preferably greater than 6, even more preferably greater than 8, even more preferably greater than 10, even more preferably greater than 12, even more preferably greater than 15, even more preferably greater than 20. The smaller the line spacing dimension and the higher the aspect ratio, the more advantageous it is to use the composition described herein.

[0024] The components of the present invention can be applied to substrates of any patterned material, as long as the structure tends to collapse due to its geometry.

[0025] For example, the patterned material layer may be (a) a silicon layer coated with patterned silicon oxide or silicon nitride, (b) a patterned barrier material layer containing or composed of ruthenium, cobalt, titanium nitride, tantalum or tantalum nitride, (c) a patterned multi-stacked material layer containing or composed of at least two different materials selected from the group consisting of silicon, polycrystalline silicon, silicon dioxide, SiGe, low-k and ultra-low-k materials, high-k materials, semiconductors other than silicon and polycrystalline silicon, and metals, and (d) a patterned dielectric material layer containing or composed of silicon dioxide or low-k or ultra-low-k dielectric materials.

[0026] Particularly preferred patterned material layers may be: • patterned silicon layers; • silicon layers coated with silicon oxide or silicon nitride; and • patterned multi-stacked material layers containing or composed of at least two different materials selected from the group consisting of: silicon, polycrystalline silicon, silicon dioxide, SiGe, low-k and ultra-low-k materials, high-k materials, semiconductors other than silicon and polycrystalline silicon, and metals; and • patterned dielectric material layers containing or composed of silicon dioxide or low-k or ultra-low-k dielectric materials.

[0027] These materials do not require HF pretreatment solution but do require alkaline SC1 pretreatment, and the effects of the composition and method of the present invention are particularly significant for these materials and pretreatment. Solvent

[0028] The non-aqueous anti-pattern collapse composition comprises a non-polar organic solvent, which may be (i) a straight-chain, branched or cyclic C5 to C12 alkane, or (ii) a phenyl substituted with one to three C1 to C4 alkyl groups, or (iii) a combination thereof.

[0029] Even if a nonpolar organic solvent has low hygroscopicity and contains a considerable amount of residual water, it is still advantageous to remove the residual water by drying before using it in anti-pattern collapse compositions.

[0030] As used herein, "non-aqueous" means that the composition may contain only about 1% by weight of water. Preferably, the non-aqueous composition contains less than 0.5% by weight, more preferably less than 0.2% by weight, even more preferably less than 0.1% by weight, even more preferably less than 0.05% by weight, even more preferably less than 0.02% by weight, even more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight of water. Bestly, the composition is essentially free of water. "Essentially" here means that the water present in the composition has no significant effect on the performance of the additives in the non-aqueous solution in terms of pattern collapse on the substrate to be treated.

[0031] The organic solvent needs to have a sufficiently low boiling point so that it can be removed by heating without negatively affecting the substrate treated with the composition. For a typical substrate, the boiling point of the organic solvent should be 150°C or below, preferably 100°C or below.

[0032] In a preferred embodiment, the solvent is basically composed of one or more nonpolar organic solvents, preferably a single nonpolar organic solvent, that is, the composition does not contain any other solvents other than nonpolar solvents.

[0033] In another preferred embodiment, the nonpolar organic solvent may be straight-chain, branched, or cyclic hexane, heptane, octane, nonane, decane, or mixtures thereof; particularly straight-chain, branched, or cyclic hexane, heptane, or octane. The preferred C5 to C12 alkanes are straight-chain or branched heptanes, particularly n-heptane, cyclohexane, cycloheptane, and methylcyclohexane.

[0034] In yet another preferred embodiment, the nonpolar organic solvent is selected from toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, ethylbenzene, 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, particularly 1,2-xylene, 1,3-xylene, 1,4-xylene, or mixtures thereof. Additives of Formula I or II

[0035] In a first specific example, the nonionic H-silane additive of the present invention (also referred to as an additive or more specifically as silane or siloxane) may be selected from formula I or II: (I) (II) where R1 is H, that is, the additive of the present invention is H-silane or H-siloxane. Compared with other silanes or siloxanes (such as tetraethyl orthosilicate), H-silanes or H-siloxanes exhibit better performance.

[0036] In formulas I and II, R2 may be selected from H, C1-C10 alkyl, C1-C10 alkoxy, C6-C12 aryl, and C6-C10 aryloxy. Preferably, R2 may be selected from C1 to C8 alkyl and C1 to C8 alkoxy. More preferably, R2 may be selected from C1 to C6 alkyl and C1 to C6 alkoxy. Most preferably, R2 may be selected from C1 to C4 alkyl and C1 to C4 alkoxy. The most preferred group R2 may be selected from methyl, ethyl, methoxy, and ethoxy.

[0037] R3 may be selected from H, C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl, and C6 to C10 aryl. Preferably, R3 may be selected from H, C1 to C8 alkyl, and C1 to C8 alkoxy. More preferably, R3 may be selected from H, C1 to C6 alkyl, and C1 to C6 alkoxy. Even more preferably, R3 may be selected from H, C1 to C4 alkyl, and C1 to C4 alkoxy. The most preferred group R3 may be selected from H, methyl, ethyl, methoxy, and ethoxy.

[0038] R4 may be selected from C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl, and C6 to C10 aryloxy. Preferably, R4 may be selected from C1 to C8 alkyl and C1 to C8 alkoxy. More preferably, R4 may be selected from C1 to C6 alkyl and C1 to C6 alkoxy. Most preferably, R4 may be selected from C1 to C4 alkyl and C1 to C4 alkoxy. The most preferred group R4 may be selected from methyl, ethyl, methoxy, and ethoxy.

[0039] R10 and R12 can be independently selected from C1 to C10 alkyl and C1 to C10 alkoxy groups. Preferably, R10, R12, and R4 can be selected from C1 to C8 alkyl and C1 to C8 alkoxy groups. More preferably, R10 and R12 can be selected from C1 to C6 alkyl and C1 to C6 alkoxy groups. Most preferably, R10 and R12 can be selected from C1 to C4 alkyl and C1 to C4 alkoxy groups. The preferred group R4 can be selected from methyl, ethyl, methoxy, and ethoxy groups.

[0040] In Formula I, n can be 0 or an integer from 1 to 100, preferably 0 or an integer from 1 to 50, even more preferably 0 or an integer from 1 to 20, and most preferably 0. In Formula II, m can be 1, 2 or 3, preferably 1.

[0041] Preferably, R2, R4, R10 and R12 are independently selected from methyl, methoxy, ethyl, ethoxy, propyl and propoxy.

[0042] In a particularly preferred embodiment, the additive is selected from trimethoxysilane, triethoxysilane, trimethylsilane and triethylsilane.

[0043] The concentration should be high enough to properly prevent pattern collapse, but should be as low as possible for economic reasons. The concentration of additives of formula I or II in non-aqueous solutions is generally in the range of about 0.00005% by weight to about 15% by weight. Preferably, the concentration of additives is about 0.001% by weight to about 12% by weight, more preferably about 0.005% by weight to about 12% by weight, even more preferably about 0.05% by weight to about 10% by weight, and most preferably 0.1% by weight to 5% by weight, which weight percentage is based on the total weight of the components.

[0044] One or more additives may be present in the composition; however, it is preferred to use only one additive of formula I or II. Other additives

[0045] Other additives may be present in the cleaning solution of the present invention. Such additives may be (I) buffer components for adjusting pH, such as, but not limited to, (NH4)2CO3 / NH4OH, Na2CO3 / NaHCO3, hydroxymethylaminomethane / HCl, Na2HPO4 / NaH2PO4, or organic acids such as acetic acid, methanesulfonic acid; (II) one or more other additives, nonionic or anionic, to improve the surface tension and solubility of the mixture; (III) dispersants to prevent removed dirt or polymer particles from re-adhering to the surface; (IV) ammonia, as described in unpublished European Patent Application No. 19168153.5, to further activate the above-mentioned H-silane additives. This activation is generally possible by adding about 0.05% by weight to about 8% by weight of ammonia to the solution. Below 0.05% by weight, the activation will be insufficient, and due to the limited solubility of ammonia in proton organic solvents, it is difficult to achieve using more than about 8% by weight. The activation is preferably performed using 0.2% to 6% by weight, more preferably 0.3% to 4% by weight, and most preferably 0.5% to 2% by weight. Rinse solution

[0046] Preferably, the non-aqueous component is basically composed of an organic nonpolar solvent, at least one additive of formula I or II, ammonia and its reaction products as needed.

[0047] If ammonia is used, it is preferable to add it in place before using the ammonia. Therefore, it is advantageous to provide a composition as a two-component kit comprising (a) ammonia dissolved in an organic protic solvent and, if desired, C5 to C12 alkanes, and (b) at least one additive of formula I or II as described herein. Application

[0048] The composition described herein can be used to process a substrate containing a patterned material layer having a line spacing of 50 nm or less, an aspect ratio of 4 or greater, or a combination thereof.

[0049] The composition described herein can be used in a method of manufacturing an integrated circuit device, an optical device, a micromechanical device, and a precision mechanical device, the method comprising the steps of: (a) providing a substrate comprising a patterned material layer having a line spacing dimension of 50 nm or less, an aspect ratio of 4 or greater, or a combination thereof; (b) contacting the substrate with an aqueous pretreatment composition comprising ammonia and hydrogen peroxide; (c) removing the aqueous pretreatment composition from the substrate; (d) contacting the substrate with a non-aqueous composition as claimed in any one of claims 1 to 8 at least once; and (e) removing the non-aqueous composition from the contact with the substrate.

[0050] In the first step (a), a substrate is provided comprising a patterned material layer having a line spacing dimension of 50 nm or less, an aspect ratio of 4 or greater, or a combination thereof.

[0051] The substrate is preferably provided by a photolithography process, comprising the following steps: (i) providing the substrate with an immersion photoresist, EUV photoresist or electron beam photoresist layer, (ii) exposing the photoresist layer to photochemical radiation through a photomask with or without an immersion solution, (iii) developing the exposed photoresist layer with a developer to obtain a pattern with a line spacing dimension of 32 nm or less and an aspect ratio of 4 or more, and (iv) spin-drying the semiconductor substrate after applying the composition.

[0052] Any conventional and known immersion photoresist, EUV photoresist, or electron beam photoresist may be used. The immersion photoresist may contain at least one siloxane additive or a combination thereof. In addition, the immersion photoresist may contain other nonionic additives. Suitable nonionic additives are described, for example, in US 2008 / 0299487 A1, page 6, paragraph

[0078] . Preferably, the immersion photoresist is a positive photoresist.

[0053] In addition to electron beam exposure or extreme ultraviolet radiation of about 13.5 nm, UV radiation with a wavelength of 193 nm is also preferably used as photochemical radiation.

[0054] In the case of a better immersion lithography, ultrapure water is used as the immersion solution.

[0055] Any conventional and known developer solution can be used to develop the exposed photoresist layer. Preferably, an aqueous developer solution containing tetramethylammonium hydroxide (TMAH) is used.

[0056] According to the method of the present invention, photolithography can be performed using conventional and known equipment commonly used in the semiconductor industry.

[0057] A so-called SC1 pretreatment is performed in step (b). Preferably, the aqueous SC1 pretreatment composition comprises 0.1% to 5% by weight, more preferably 0.5% to 3% by weight, of ammonia (as NH4OH) and 1% to 20% by weight, more preferably 5% to 17% by weight, of hydrogen peroxide. The pretreatment is typically carried out for about 10 seconds to about 10 minutes, more preferably about 20 seconds to about 5 minutes, and most preferably about 30 seconds to about 3 minutes.

[0058] As used herein, "aqueous" means that the solvent comprises water, preferably deionized water, and most preferably ultrapure water as the primary solvent. Aqueous compositions may contain polar organic solvents miscible with water, although they may be present only in small amounts without compromising the aqueous properties of the composition. The solvent is preferably substantially composed of water, preferably deionized water, and most preferably ultrapure water. Examples of ultrapure water are those having a concentration of 5 ppt (ng / kg) or better, an anion concentration of 5 ppb (ng / g) or better, a total organic matter content (TOC) of 50 ppb (ng / g) or better, and containing particles >0.2 mm per milliliter of less than 10,000.

[0059] In step (c), the pretreatment components from step (b) are removed from the substrate. This is typically accomplished by rinsing the substrate with ultrapure water. Preferably, this step is performed once, but it can be repeated if necessary.

[0060] In step (d), the substrate is brought into contact with the non-aqueous composition described herein at least once. This APCC process is typically performed for about 10 seconds to about 10 minutes, more preferably about 20 seconds to about 5 minutes, and most preferably about 30 seconds to about 3 minutes.

[0061] Typically, all steps (a) to (d) can be used at any temperature between about 10 and about 40°C. At higher temperatures, the composition becomes unstable as the amount of ammonia decreases rapidly due to evaporation. Lower temperatures may generally be used, but strong cooling is required. Preferred temperatures are between 10 and 35°C, and even more preferably between 15 and 30°C.

[0062] In the fourth step (e) of the method, the non-aqueous solution is removed from the contact area with the substrate. Any known method commonly used to remove liquids from solid surfaces can be used. In a preferred embodiment, this is accomplished by: (i) contacting the substrate with a polar protic solvent, preferably a C1 to C4 alkanol, most preferably 2-propanol, methanol, or ethanol; and (ii) evaporating the polar protic solvent of step (i), preferably in the presence of an inert gas. The inert gas is preferably nitrogen.

[0063] Unless otherwise stated, all percentages, ppm, or comparable values ​​refer to weight relative to the total weight of the respective components. All referenced documents are incorporated herein by reference. Examples

[0064] Patterned silicon wafers with circular nanopillar patterns were used to determine the pattern collapse performance of the formulation during drying. The (aspect ratio) AR 20 pillars used for testing had a height of 600 nm and a diameter of 30 nm. The spacing was 90 nm. 1x1 cm wafers were processed in the following order without intermediate drying:

[0065] The process sequence without intermediate drying is as follows: • SC1 (NH4OH (28%) / H2O2 (31%) / ultrapure water (UPW), weight ratio 1 / 8 / 60) immersion for 40 seconds, • ultrapure water (UPW) immersion for 60 seconds, • isopropanol (IPA) immersion for 30 seconds, • siloxane additive solution in non-polar organic solvent immersion for 60 seconds at room temperature, • IPA immersion for 60 seconds, • N2 drying.

[0066] The water content of the solvent is less than 0.01% by weight.

[0067] The dry silicon wafers and collapse rates analyzed by top-down SEM in Examples 1.1 to 1.14 are shown in Table 1.

[0068] Table 1 Example additive Concentration [wt%] solvent Concentration [wt %] Stiffness [mN / m] Non-collapse rate [%) C1.1 n / a 0 Isopropanol 100 44 0.4 C1.2 Triethoxysilane 5 Isopropanol 95 43 0.8 C1.3 n / a 0 n-Heptane 100 43 1 1.4 Triethoxysilane 0.2 n-Heptane 99.8 43 5.9 1.5 Triethoxysilane 2.5 n-Heptane 97.5 42.5 9.2 1.6 Triethoxysilane 5 n-Heptane 95 43 61.3 1.7 Triethoxysilane 10 n-Heptane 90 42.5 48.7 1.8 Triethoxysilane 20 n-Heptane 80 42.5 36.8 C1.9 n / a 0 n-Decane 100 43 1.6 1.10 Triethoxysilane 2.5 n-Decane 97.5 42 40.5 1.11 Triethoxysilane 5 n-Decane 95 42.5 63.3 1.12 Triethoxysilane 10 n-Decane 90 42 45.3 C1.13 n / a 0 p-xylene 100 43 1.7 1.14 Triethoxysilane 5 p-xylene 95 42 43.1 C1.15 n / a 0 n-Heptane 100 77 4.3 1.16 Triethoxysilane 5 n-Heptane 95 77 77.7 C1.17 Triethoxysilane 4 PGMEA*** 96 43 0.6 C1.18 Triethoxysilane 5 n-Heptane* 94 45 n / a** * Adding 1 wt% trifluoromethanesulfonic acid to this composition. ** The composition becomes cloudy. *** PGMEA = propylene glycol methyl ether acetate.

[0069] Table 1 shows that, under alkaline SC1 pretreatment, the combination of additives and nonpolar solvents has a remarkable effect on the degree of pattern collapse compared to solutions without any additives or using polar proton solvents. C1.17 shows that the nonpolar solvent of the present invention results in a much higher non-collapse rate compared to other nonproton but more polar solvents in the prior art. C1.18 shows that nonpolar solvents cannot be used in combination with acids. In this case, the additives cannot be completely dissolved in the nonpolar solvent, rendering them unusable.

[0070] It should be noted that, due to the different preprocessing and histories of the various wafers used, the results can only be compared under comparable conditions, especially under the same stiffness. [Simplified Explanation of the Diagram]

[0020] None

Claims

1. A non-aqueous composition comprising essentially the following: (a) an organic solvent selected from: (i) a straight-chain, branched, or cyclic C5 to C12 alkane, or (ii) a benzene substituted with one to three C1 to C4 alkyl groups, or (iii) combinations thereof; and (b) at least one additive of formula I or II: (I) (II) wherein R1 is H, R2 is selected from H, C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl, and C6 to C10 aryl, R3 is selected from H, C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl, and C6 to C10 aryl, R4 is selected from C1 to C10 alkyl, C1 to C10 alkoxy, C6 to C10 aryl, and C6 to C10 aryl, R10 and R12 are independently selected from C1 to C10 alkyl and C1 to C10 alkoxy, m is 1, 2 or 3, and n is 0 or an integer from 1 to 100; wherein the water content in the non-aqueous component is less than 1% by weight.

2. The composition of claim 1, wherein the organic solvent is selected from hexaane, heptane, octane, nonane and decane.

3. The composition of claim 1, wherein the organic solvent is selected from toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, ethylbenzene, 1,2-diethylbenzene, 1,3-diethylbenzene, and 1,4-diethylbenzene.

4. The composition of any one of claims 1 to 3, wherein the water content in the non-aqueous composition is less than 0.1% by weight.

5. The composition of any one of claims 1 to 3, wherein the at least one additive of formula I or II is present at a concentration of 2.5% by weight to 15% by weight.

6. A composition of any one of claims 1 to 3, wherein the at least one additive is a compound of formula I, wherein n is 0, 1 or 2.

7. A composition of any one of claims 1 to 3, wherein R2, R4, R10 and R12 are independently selected from methyl, methoxy, ethyl, ethoxy, propyl and propoxy.

8. A composition of any one of claims 1 to 3, wherein the additive is selected from trimethoxysilane, triethoxysilane, trimethylsilane and triethylsilane.

9. Use of a composition as claimed in any one of claims 1 to 8 for processing a substrate comprising a patterned material layer having a line spacing dimension of 50 nm or less, an aspect ratio of 4 or greater, or a combination thereof.

10. A method of manufacturing an integrated circuit device, an optical device, a micromechanical device, and a precision mechanical device, the method comprising the steps of: (a) providing a substrate comprising a patterned material layer having a line spacing dimension of 50 nm or less, an aspect ratio of 4 or greater, or a combination thereof; (b) contacting the substrate with an aqueous pretreatment composition comprising ammonia and hydrogen peroxide; (c) removing the aqueous pretreatment composition from the substrate; (d) contacting the substrate with a non-aqueous composition as claimed in any one of claims 1 to 8 at least once; and (e) removing the non-aqueous composition from the contact point with the substrate.

11. The method of claim 10, wherein the patterned material layer has a line spacing dimension of 32 nm or less and an aspect ratio of 10 or more.

12. The method of claim 10 or 11, wherein the patterned material layer comprises silicon, silicon oxide or silicon nitride.

13. The method of claim 10 or 11, wherein 0.1% to 5% by weight of ammonia (as NH4OH) and 1% to 20% by weight of hydrogen peroxide are used in step (b).

14. The method of claim 10 or 11, wherein the patterned material layer is selected from the group consisting of: patterned multi-stacked material layers and patterned dielectric material layers.