Alkaline chemistry formulated for polysilicon etching

Abstract

The disclosed and claimed subject matter relates to etching compositions and methods of using the same to manufacture semiconductor devices that can selectively remove silicon films while minimizing the etch rate of oxide films.

Description

[Technical field]

[0001] Field

[0002] The disclosed and claimed subject matter relates to etching compositions, and more particularly to highly selective etching compositions that can selectively remove silicon films while minimizing the etch rate of oxide films, and semiconductor manufacturing methods including etching processes using the etching compositions. [Background technology]

[0003] Related Technology

[0004] As semiconductor devices become more highly integrated, their reliability and electrical characteristics become more susceptible to damage or deformation of layers that constitute the semiconductor devices. Therefore, when performing an etching process to selectively remove a specific material layer using an etching solution, it is desirable for the etching solution to have a high etching selectivity relative to other material layers, generate fewer by-products in the etching process, and reduce process defects.

[0005] As the number of alternating layers of nitride / oxide increases in 3D NAND flash memory device fabrication, high aspect ratio (HAR) channel etching challenges the physical limits of current plasma etching technology. To overcome these challenges, process flows have shifted from single layer stacking to multi-layer stacking (e.g., 64 layers x 2 decks providing an array equivalent to 128 layers). Figure 1 shows the dual stacking process. After HAR channel etching on deck 1, the vertical channels are filled with sacrificial material. Deck 2 process proceeds on top of deck 1, i.e., nitride / oxide, and channel etching. Finally, the fill material is removed so that a 2X layer HAR channel etch can be achieved. The disclosed and claimed subject matter can be used in these processes as a wet etchant for polysilicon removal.

[0006] Wet etchant compositions are known for removing pyramidal Si etching residues generated after etching processes with high silicon to silicon oxide selectivity.For example, US Patent Application Publication No. 2017 / 0145311 describes an etching composition that can selectively etch specific crystal planes or perform crystal orientation selective wet etching to provide a flat bottom.US Patent Application Publication No. 2020 / 0157422 describes various types of oxide inhibitors that can significantly suppress oxide etching rate in alkaline wet chemical etching formulations and show high silicon to silicon oxide selectivity.

[0007] Despite these known materials, at such high integration densities, the material selectivity requirement for selective silicon sacrificial removal in 3D NAND manufacturing is limited by the need to etch SiO x This becomes even more important in that it is desirable to leave the layer effectively unchanged. x Further suppressing the etching rate and achieving higher silicon SiO x There is a need to achieve selectivity for Summary of the Invention

[0008] In one aspect, the disclosed and claimed subject matter provides an etching composition for selectively removing silicon relative to silicon oxide from a microelectronic device, comprising: A. one or more aqueous solvents; B. one or more alkanolamines; C. One or more quaternary ammonium hydroxides ("QAH"), and D. One or more silicon-containing compounds (sometimes referred to herein as organosilicon compounds).

[0009] Alkanolamines useful in the disclosed and claimed subject matter contain one or more alkanol groups and one or more amine groups. The structure of the alkanolamines useful in the disclosed and claimed subject matter has formula I: [ka] In the formula, R 1 , R 2 and R 3 However, each independently, (a) hydrogen, (b1)C 1 ~C 20 Straight chain alkyl groups, (b2)C 4 ~C 20 Branched chain alkyl groups, (b3)C 3 ~C 20 Cyclic alkyl groups, (c) Unsubstituted C 2 ~C 20 Alkyl ether groups, (d) C 1 ~C 20 Alkanol groups, (e) C substituted with -OH group 2 ~C 20 alkyl ether groups; R 1 , R 2 and R 3 At least one of the following must be (d) or (e):

[0010] Alkanolamines having one alkanol group may be present in the compositions of the disclosed and claimed subject matter. Examples of alkanolamines having one alkanol group that can be used in combination with alkanolamines having two or more alkanol groups include monoethanolamine (MEA), N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol, isobutanolamine, 2-amino-2-ethoxypropanol, and 2-amino-2-ethoxyethanol.

[0011] In some embodiments, the silicon-containing compound has formula II: [ka] During the ceremony, (i) m = 0 to 20; (ii)R 1 , R 2 , R 3 , R 4 and R 5 each independently represents hydrogen, C 1 ~C 10 C substituted with linear alkyl groups, fluorine, nitrogen-containing groups, and oxygen-containing groups 1 ~C 10 Straight chain alkyl group, C 3 ~C 10 Branched chain alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 5 ~C 12 Aryl group, C 2 ~C 10 Linear or branched alkenyl groups and C 2 ~C 10 A straight or branched chain alkynyl group, [ka] is selected from the group (iii)R a and R b Each of the following may be independently selected: C 1 ~C 10 Straight chain alkyl group, C 3 ~C 10 Branched chain alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 5 ~C 12 Aryl group, C 2 ~C 10 Linear or branched alkenyl groups and C 2 ~C 10 A straight or branched chain alkynyl group, [ka] [ka] C replaced with1 ~C 10 is selected from alkyl.

[0012] The embodiments of the disclosed and claimed subject matter may be used alone or in combination with each other. [Brief description of the drawings]

[0013] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter, and which are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and, together with the detailed description, serve to explain the principles of the disclosed subject matter.

[0014] [Figure 1] 3D NAND process flow for HAR vertical channel etch using dual stack. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] All references cited in this specification, including publications, patent applications, and patents, are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0016] In the context of describing the disclosed and claimed subject matter (particularly in the context of the claims below), the use of the terms "a" and "an" and "the" and similar references should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "etc.") provided herein is intended merely to better elucidate the disclosed and claimed subject matter and does not impose limitations on the scope of the disclosed and claimed subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed and claimed subject matter.

[0017] Preferred embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject matter. Variations of these preferred embodiments may become apparent to those of skill in the art upon reading the foregoing description. The inventors anticipate that those of skill in the art will employ such variations as appropriate, and the inventors intend for the disclosed and claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter unless otherwise indicated herein or clearly contradicted by context.

[0018] The disclosed and claimed subject matter relates generally to compositions useful for selectively removing silicon relative to silicon oxide from microelectronic devices having such materials thereon during their manufacture.

[0019] For ease of reference, a "microelectronic device" or "semiconductor substrate" corresponds to a semiconductor wafer, flat panel display, phase change memory device, solar panel and other products including solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS) manufactured for use in microelectronics, integrated circuits, or computer chip applications. Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. It should be understood that the term "microelectronic device" is not intended to be limiting in any way and includes any substrate that will ultimately become a microelectronic device or microelectronic assembly. Microelectronic device or semiconductor substrates may include low-k dielectric materials, barrier materials, and metals such as AlCu alloys, W, Ti, TiN, and other materials thereon.

[0020] As defined herein, "low-k dielectric material" corresponds to any material used as a dielectric material in layered microelectronic devices, which material has a dielectric constant less than about 3.5. Preferably, the low-k dielectric material includes low polarity materials such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It is understood that the low-k dielectric materials may have different densities and different porosities.

[0021] As defined herein, the term "barrier material" corresponds to any material used in the art to encapsulate metal lines, e.g., copper interconnects, to minimize diffusion of the metal, e.g., copper, into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

[0022] "Substantially free" is defined herein as less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, and most preferably less than 0.1% by weight. "Substantially free" also includes 0.0% by weight. The term "free" means 0.0% by weight.

[0023] As used herein, the terms "about" and "approximately" are each intended to correspond to ±5% of the stated value.

[0024] As used herein, "neat" refers to the weight percent amount of undiluted acid or other material. For example, a loading of 100 g of 85% phosphoric acid constitutes 85 g of acid and 15 grams of diluent.

[0025] In addition to the known and understood representations for the points of attachment of covalent bonds, [ka] is also intended to indicate the point of attachment of a covalent bond.

[0026] In all such compositions where a particular component of a composition is discussed with reference to a weight percent range including a lower limit of zero, it will be understood that such component may or may not be present in various specific embodiments of the composition, and that when such component is present, such component may be present in concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such component is used. Note that all defined weight percentages of components are based on the total weight of the composition, unless otherwise indicated. Furthermore, all weight percentages are "neat," meaning that they do not include aqueous compositions present when added to the composition, unless otherwise indicated. Any reference to "at least one" can be replaced with "one or more." "At least one" and / or "one or more" includes "at least two" or "two or more" and "at least three" and "three or more," etc.

[0027] In a broad implementation of the disclosed and claimed subject matter, the present invention relates to an etching composition as described above that comprises, consists essentially of, or consists of components (A), (B), (C) and (D). In some aspects, the etching composition may comprise other components. In some embodiments, the etching compositions disclosed herein are formulated to be free or substantially free of at least one of the following chemical compounds: acids (inorganic and organic), oxidizing agents, hydrogen peroxide and other peroxides, ammonium ions, halide ions (e.g., fluoride ions, chloride ions), inorganic bases, metal-containing chemicals, reducing agents, hydroxylamines, hydroxylamine derivatives, amidoxime compounds, and polishing agents.

[0028] In further embodiments, the etching composition consists essentially of various concentrations of (A), (B), (C), and (D). In such embodiments, the combined amount of (A), (B), (C), and (D) does not equal 100% by weight and can include other components that do not substantially change the effectiveness of the etching composition.

[0029] In another embodiment, the etching composition is comprised of various concentrations of (A), (B), (C), and (D). In such an embodiment, the total amount of (A), (B), (C), and (D) is equal to or is equal to about 100% by weight, but may include other minor and / or trace amounts of impurities present in such small amounts that do not substantially alter the effectiveness of the composition. For example, in one such embodiment, the etching composition may contain 2% or less by weight of impurities. In another embodiment, the etching composition may contain less than 1% by weight of impurities. In a further embodiment, the etching composition may contain less than 0.05% by weight of impurities.

[0030] When referring to compositions of the compositions of the invention described herein in terms of weight percent, it is understood that the weight percent of all components, including non-essential components such as impurities, never exceeds 100 weight percent. In a composition "consisting essentially of" listed components, such components may add up to 100 weight percent of the composition, or may add up to less than 100 weight percent. When components add up to less than 100 weight percent, such compositions may contain small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the etching composition may contain 2 weight percent or less of impurities. In another embodiment, the etching composition may contain less than 1 weight percent of impurities. In a further embodiment, the etching composition may contain less than 0.05 weight percent of impurities. In other such embodiments, the components may form at least 90 weight percent, more preferably at least 95 weight percent, more preferably at least 99 weight percent, more preferably at least 99.5 weight percent, and most preferably at least 99.9 weight percent, and may include other components that do not significantly affect the performance of the etching composition. Otherwise, it is understood that in the absence of significant non-essential impurity ingredients, the combination of all essential components essentially totals 100% by weight.

[0031] composition

[0032] As noted above, the disclosed and claimed subject matter relates to etching compositions comprising, consisting essentially of, or consisting of (A), (B), (C), and (D). In some embodiments, the etching compositions can include other components.

[0033] Component A: Aqueous solvent

[0034] The etching compositions of the present development are aqueous-based and include water. In the disclosed and claimed subject matter, water functions in a variety of ways, such as to dissolve one or more solid components of the composition, as a carrier for the components, as an aid in removing residues, as a viscosity modifier for the composition, and as a diluent. Preferably, the water used in the etching compositions is deionized (DI) water.

[0035] In some embodiments, the aqueous solvent comprises water. In a further aspect of this embodiment, the aqueous solvent consists essentially of water. In a further aspect of this embodiment, the aqueous solvent consists of water.

[0036] Water is included in an amount ranging from the following list of weight percentages with beginning and ending points selected from about 1% to about 65% by weight of the etching composition. In one embodiment, the composition includes about 1% to about 65% by weight of water. In one embodiment, the composition includes about 5% to about 65% by weight of water. In one embodiment, the composition includes about 10% to about 65% by weight of water. In one embodiment, the composition includes about 15% to about 65% by weight of water. In one embodiment, the composition includes about 20% to about 65% by weight of water. In one embodiment, the composition includes about 25% to about 65% by weight of water. In one embodiment, the composition includes about 30% to about 65% by weight of water. In one embodiment, the composition includes about 35% to about 65% by weight of water. In one embodiment, the composition includes about 40% to about 65% by weight of water. In one embodiment, the composition includes about 45% to about 65% by weight of water.

[0037] In one embodiment, the composition comprises about 1% to about 55% water by weight. In one embodiment, the composition comprises about 5% to about 55% water by weight. In one embodiment, the composition comprises about 10% to about 55% water by weight. In one embodiment, the composition comprises about 15% to about 55% water by weight. In one embodiment, the composition comprises about 20% to about 55% water by weight. In one embodiment, the composition comprises about 25% to about 55% water by weight. In one embodiment, the composition comprises about 30% to about 55% water by weight. In one embodiment, the composition comprises about 35% to about 55% water by weight. In one embodiment, the composition comprises about 40% to about 55% water by weight. In one embodiment, the composition comprises about 45% to about 55% water by weight.

[0038] In one embodiment, the composition comprises about 30% water by weight. In one embodiment, the composition comprises about 35% water by weight. In one embodiment, the composition comprises about 40% water by weight. In one embodiment, the composition comprises about 45% water by weight. In one embodiment, the composition comprises about 50% water by weight. In one embodiment, the composition comprises about 51% water by weight. In one embodiment, the composition comprises about 52% water by weight. In one embodiment, the composition comprises about 53% water by weight. In one embodiment, the composition comprises about 54% water by weight. In one embodiment, the composition comprises about 55% water by weight. In one embodiment, the composition comprises about 56% water by weight. In one embodiment, the composition comprises about 57% water by weight. In one embodiment, the composition comprises about 58% water by weight. In one embodiment, the composition comprises about 59% water by weight. In one embodiment, the composition comprises about 60% water by weight.

[0039] In other embodiments, water may be present in an amount defined by the following list of weight percentages: 1, 5, 8, 10, 12, 15, 17, 20, 22, 25, 27, 30, 32, 35, 37, 40, 42, 45, 47, 50, 55, 60, 65, 70, and 75. Still other preferred embodiments of the disclosed and claimed subject matter may include water in an amount to achieve the desired weight percentages of the other components.

[0040] Component B: Alkanolamine

[0041] As noted above, the disclosed and claimed compositions include one or more alkanolamines that contain one or more alkanol groups and one or more amine groups. The structure of the alkanolamines useful in the disclosed and claimed subject matter has the formula I: [ka] In the formula, R 1 , R 2 and R 3 However, each independently, (a) hydrogen, (b1)C 1 ~C 20 Straight chain alkyl groups, (b2)C 4 ~C 20 Branched chain alkyl groups, (b3)C 3 ~C 20 Cyclic alkyl groups, (c) Unsubstituted C 2 ~C 20 Alkyl ether groups, (d) C 1 ~C 20 Alkanol groups, (e) C substituted with -OH group 2 ~C 20 alkyl ether groups; R 1 , R 2 and R 3 At least one of the following must be (d) or (e):

[0042] In one embodiment, the one or more alkanolamines comprise a mixture of two or more alkanolamines. In a further aspect of this embodiment, the one or more alkanolamines comprise a mixture of three or more alkanolamines. In a further aspect of this embodiment, the one or more alkanolamines, the two or more alkanolamines, or the three or more alkanolamines comprise one or more ether-containing alkanolamines. In a further aspect of this embodiment, the one or more alkanolamines comprise a mixture of two alkanolamines. In a further aspect of this embodiment, the one or more alkanolamines comprise a mixture of three alkanolamines.

[0043] In one embodiment, (b1) is C 1 ~C 15 In another embodiment, (b1) is a straight chain alkyl group. 1 ~C 10 In another embodiment, (b1) is a straight chain alkyl group. 1 ~C 7 In another embodiment, (b1) is a straight chain alkyl group. 1 ~C 5 In another embodiment, (b1) is a straight chain alkyl group. 1 ~C 4 In another embodiment, (b1) is a straight chain alkyl group. 1 ~C 3 In another embodiment, (b1) is a straight chain alkyl group. 1 ~C 2 In another embodiment, (b1) is a straight chain alkyl group. 5 In another embodiment, (b1) is a straight chain alkyl group. 4 In another embodiment, (b1) is a straight chain alkyl group. 3 In another embodiment, (b1) is a straight chain alkyl group. 2 In another embodiment, (b1) is a straight chain alkyl group. 1 It is a straight chain alkyl group.

[0044] In one embodiment, (b2) is C 4 ~C 15In another embodiment, (b2) is a branched alkyl group. 4 ~C 10 In another embodiment, (b2) is a branched alkyl group. 4 ~C 7 In another embodiment, (b2) is a branched alkyl group. 4 ~C 5 In another embodiment, (b2) is a branched alkyl group. 8 In another embodiment, (b2) is a branched alkyl group. 7 In another embodiment, (b2) is a C 6 In another embodiment, (b2) is a C 5 In another embodiment, (b2) is a C 4 It is a branched chain alkyl group.

[0045] In one embodiment, (b3) is C 3 ~C 15 In another embodiment, (b3) is a C 3 ~C 10 In another embodiment, (b3) is a C3 1 ~C 7 In another embodiment, (b3) is a C 3 ~C 5 In another embodiment, (b3) is a C 3 ~C 4 In another embodiment, (b3) is a C 6 In another embodiment, (b3) is a C 5 In another embodiment, (b3) is a C 4 In another embodiment, (b3) is a C 3 It is a cyclic alkyl group.

[0046] The alkyl ether group (c) is, for example, 2 ~C 20 (ii) a straight chain alkyl group, 4 ~C 20branched chain alkyl groups, and (iii) C 3 ~C 20 Cyclic alkyl groups include (i), (ii), and (iii) having an oxygen atom (bonded between carbon atoms) in each alkyl group. In (i), (ii), and (iii), the total number of carbon atoms is 2 to 20, or 2 to 15, or 2 to 10, or 2 to 7, or 2 to 5, or 2 to 4, or 2 to 3 carbons.

[0047] The alkanol group (d) is, for example, 1 ~C 20 (ii) a straight chain alkyl group, 4 ~C 20 Branched chain alkyl groups and (iii) C 3 ~C 20 In (i), (ii) and (iii), the total number of carbons is 1 to 20, or 2 to 15, or 2 to 10, or 2 to 7, or 2 to 5, or 2 to 4, or 2 to 3 carbons, as structurally appropriate, and further includes at least one -(R)(R)-OH bonded to a carbon in the alkyl group, where each R is independently H or an alkyl group (including the R 1 , R 2 or R 3 (defined as having fewer carbons than the group).

[0048] The alkyl ether group (e) substituted with an —OH group includes (i) C 2 ~C 20 (ii) a straight chain alkyl group, 4 ~C 20 Branched chain alkyl groups and (iii) C 3 ~C 20 Cyclic alkyl groups are included, in which (i), (ii) and (iii) have an oxygen atom (bonded between carbons) in the alkyl group. In (i), (ii) and (iii), the total number of carbons is 2 to 20, or 2 to 15, or 2 to 10, or 2 to 7, or 2 to 5, or 2 to 4, or 2 to 3 carbons, and further have at least one -(R)(R)-OH bonded to a carbon in the alkyl group, where each R is independently H or an alkyl group (R1 , R 2 or R 3 (defined as having fewer carbons than the group).

[0049] Alkanolamines containing either (c) or (e) are referred to as "ether-containing alkanolamines." Preferred ether-containing alkanolamines have (e) an alkyl ether group further bearing an -OH group. For both (d) and (e), the -(R)(R)-OH attached to the carbon is preferably a terminating group, i.e., both R groups are H.

[0050] In one embodiment, the composition comprises an alkanolamine of formula II, wherein R 1 and R 2 is hydrogen and R 3 is selected from (d) and (e). In a further aspect of this embodiment, the alkanolamine consists essentially of an alkanolamine of formula II, wherein R 1 and R 2 is hydrogen and R 3 is selected from (d) and (e). In a further aspect of this embodiment, the alkanolamine comprises an alkanolamine of formula II, wherein R 1 and R 2 is hydrogen and R 3 is selected from (d) and (e).

[0051] In another embodiment, the composition comprises an alkanolamine of formula II, wherein R 1 is (a), and R 2 is (b1), (b2) or (b3), and R 3 is selected from (d) and (e). In a further aspect of this embodiment, the alkanolamine consists essentially of an alkanolamine of formula II, wherein R 1 is (a), and R 2 is (b1), (b2) or (b3), and R 3 is selected from (d) and (e). In a further aspect of this embodiment, the alkanolamine comprises an alkanolamine of formula II, R1 is (a), wherein R 2 is (b1), (b2) or (b3), and R 3 is selected from (d) and (e).

[0052] In another embodiment, the composition comprises an alkanolamine of formula II, wherein R 1 and R 2 are the same or different (b1), (b2) or (b3), and R 3 is selected from (d) and (e). In a further aspect of this embodiment, the alkanolamine consists essentially of an alkanolamine of formula II, wherein R 1 and R 2 are the same or different (b1), (b2) or (b3), and R 3 is selected from (d) and (e). In a further aspect of this embodiment, the alkanolamine comprises an alkanolamine of formula II, wherein R 1 and R 2 are the same or different (b1), (b2) or (b3), and R 3 is selected from (d) and (e).

[0053] In another embodiment, the composition comprises an alkanolamine of formula II, wherein R 1 , R 2 and R 3 are all the same or different (d). In a further aspect of this embodiment, the alkanolamine consists essentially of an alkanolamine of formula II, wherein R 1 , R 2 and R 3 are all the same or different (d). In a further aspect of this embodiment, the alkanolamine comprises an alkanolamine of formula II, wherein R 1 , R 2 and R 3 However, they are all the same or different (d).

[0054] In another embodiment, the composition comprises an alkanolamine of formula II, wherein R 1is selected from (a), (b1), (b2) or (b3); R 2 and R 3 are the same or different (d). In a further aspect of this embodiment, the alkanolamine consists essentially of an alkanolamine of formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3); R 2 and R 3 are the same or different (d). In a further aspect of this embodiment, the alkanolamine comprises an alkanolamine of formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3); R 2 and R 3 but are the same or different (d).

[0055] In another embodiment, the composition comprises an alkanolamine of formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3); R 2 and R 3 are the same or different (e). In a further aspect of this embodiment, the alkanolamine consists essentially of an alkanolamine of formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3); R 2 and R 3 are the same or different (e). In a further aspect of this embodiment, the alkanolamine comprises an alkanolamine of formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3); R 2 and R 3 but are the same or different (e).

[0056] As indicated by the structures above, in some embodiments, the alkanolamines useful in the compositions of the disclosed and claimed subject matter contain two or more of the same or different (preferably the same) alkanol groups. In some embodiments, the alkanolamines contain three or more of the same or different (preferably the same) alkanol groups.

[0057] Examples of alkanolamines useful in the disclosed and claimed subject matter are preferably miscible in water and include, but are not limited to, monoethanolamine (MEA), aminoethoxyethanol, methanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, diethanolamine, triethanolamine (TEA), tertiary butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol, isobutanolamine, 2-amino-2-ethoxypropanol, 2-amino-2-ethoxyethanol, and mixtures thereof.

[0058] Monoethanolamine (MEA), methanolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol, isobutanolamine and isopropanolamine are examples of alkanolamines. 1 and R 2 is hydrogen and R 3 N-Methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, and N,N-diethylethanolamine are represented by the formula (d). 1 and R 2 is H or either b1 or b2, and R 3 Aminoethoxyethanol, 2-amino-2-ethoxypropanol and 2-amino-2-ethoxyethanol are examples of alkanolamines, R 1 and R 2 is hydrogen and R 3 is (e). N-methyldiethanolamine, N-ethyldiethanolamine, diethanolamine, triethanolamine (TEA), and tertiary butyldiethanolamine are R 1 , R 2 and / or R 3R is an alkanolamine containing two or more alkanol groups (d) which may be the same or different (preferably the same). 1 and R 2 are the same alkanol group, R 3 is often selected from hydrogen, or a straight chain, branched chain, or cyclic alkyl group.

[0059] In one embodiment, the one or more alkanolamines comprise monoethanolamine (MEA). In one embodiment, the one or more alkanolamines consist essentially of monoethanolamine (MEA). In one embodiment, the one or more alkanolamines consist of monoethanolamine (MEA).

[0060] As noted above, in some embodiments, a mixture of two or more alkanolamines is used. Thus, in a further aspect of this embodiment, the at least one alkanolamine comprises a mixture of two or more alkanolamines. In a further aspect of this embodiment, the at least one alkanolamine consists of a mixture of two alkanolamines.

[0061] As noted above, in some embodiments, a mixture of three or more alkanolamines is used. Thus, in a further aspect of this embodiment, the at least one alkanolamine comprises a mixture of three or more alkanolamines. In a further aspect of this embodiment, the at least one alkanolamine consists of a mixture of three alkanolamines.

[0062] In another embodiment, the (i) at least one alkanolamine, (ii) two or more alkanolamines, or (iii) three or more alkanolamines comprise at least one ether-containing alkanolamine.

[0063] In one embodiment, the (i) at least one alkanolamine, (ii) at least two alkanolamines, and (iii) at least three alkanolamines are selected from aminoethoxyethanol, 2-amino-2-ethoxypropanol, 2-amino-2-ethoxyethanol, and mixtures thereof.

[0064] In another embodiment, the (i) at least one alkanolamine, (ii) at least two alkanolamines, and (iii) at least three alkanolamines comprise monoethanolamine, isopropanolamine, and 2-(2-aminoethoxy)ethanol. In a further aspect of this embodiment, the at least three alkanolamines consist essentially of monoethanolamine, and the at least three alkanolamines consist of monoethanolamine, isopropanolamine, and 2-(2-aminoethoxy)ethanol.

[0065] In some embodiments, the mixture of two or more alkanolamines or three or more alkanolamines comprises at least one ether-containing alkanolamine and at least one or two alkanolamines, R 1 and R 2 is hydrogen and R 3 However, the answer is (d).

[0066] In one embodiment, the composition comprises about 20% to about 70% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 20% to about 65% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 35% to about 60% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 40% to about 55% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 45% to about 50% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 43% to about 47% by weight of one or more alkanolamines.

[0067] In one embodiment, the composition comprises about 20% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 25% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 30% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 35% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 40% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 41% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 42% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 43% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 44% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 45% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 46% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 47% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 48% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 49% by weight of one or more alkanolamines. In one embodiment, the composition comprises about 50% by weight of one or more alkanolamines.

[0068] Component C: Quaternary ammonium hydroxide

[0069] As mentioned above, the one or more base components can include one or more quaternary ammonium hydroxides. Suitable quaternary ammonium hydroxides include, but are not limited to, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), ethyltrimethylammonium hydroxide (ETMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, tris-(hydroxyethyl)methylammonium hydroxide, and dimethyldipropylammonium hydroxide (DMDPAH). In some embodiments, TEAH is preferentially included. In such embodiments, TEAH is used as an aqueous solution, for example, a 35% by weight aqueous solution. In other embodiments, DMDPAH is preferentially included. In such embodiments, DMDPAH is used as a 20% by weight solution in propylene glycol. In some embodiments, ETMAH is preferentially included. In such embodiments, ETMAH is used as an aqueous solution, for example, a 20% by weight aqueous solution. In some embodiments, TMAH is preferentially included. In such embodiments, the TMAH is used as an aqueous solution, for example a 25% by weight aqueous solution, hi some embodiments, the solution does not include TMAH.

[0070] The quaternary ammonium hydroxide may be present in any neat amount ranging from about 0.1% to about 20%, 1% to about 15%, or from about 1% to about 14%, or from about 1% to about 13%, or from about 1% to about 12%, or from about 1% to about 11%, or from about 1% to about 10%, or from about 1% to about 9%, or from about 1% to about 8%, or from about 1% to about 7%, or from about 1% to about 6%, or from about 1% to about 5%, or from about 1% to about 4%, or from about 1% to about 3%, or from about 1% to about 2%, or from about 0.1% to about 0.9%, or from about 0.4% to about 0.5%, or from about 0.1% to about 0.2% by weight of the composition. More preferably, the quaternary ammonium hydroxide is present, but in an amount of about 20% by weight or less. In certain preferred compositions, the quaternary ammonium hydroxide is present at about 8% to about 15% by weight. In certain preferred compositions, the quaternary ammonium hydroxide is present at about 8% to about 13% by weight. In certain preferred compositions, the quaternary ammonium hydroxide is present at about 10% to about 15% by weight. In certain preferred compositions, the quaternary ammonium hydroxide is present at about 0.1% to about 1% by weight. In certain preferred compositions, the quaternary ammonium hydroxide is present at about 0.4% to about 2% by weight. In certain preferred compositions, the quaternary ammonium hydroxide is present at about 0.4% to about 1% by weight. In certain preferred compositions, the quaternary ammonium hydroxide is present at about 0.1% to about 0.5% by weight.

[0071] In one embodiment, the solution comprises about 0.5% to about 5% by weight of neat TEAH. In a further aspect of this embodiment, the solution comprises about 1% to about 4% by weight of neat TEAH. In another aspect of this embodiment, the solution comprises about 1.5% to about 3.5% by weight of neat TEAH. In another aspect of this embodiment, the solution comprises about 2% to about 3% by weight of neat TEAH. In another aspect of this embodiment, the solution comprises about 0.5% by weight of neat TEAH. In another aspect of this embodiment, the solution comprises about 1% by weight of neat TEAH. In another aspect of this embodiment, the solution comprises about 1.5% by weight of neat TEAH. In another aspect of this embodiment, the solution comprises about 2% by weight of neat TEAH. In another aspect of this embodiment, the solution comprises about 2.5% by weight of neat TEAH. In another aspect of this embodiment, the solution comprises about 3% by weight neat TEAH. In another aspect of this embodiment, the solution comprises about 3.5% by weight neat TEAH. In another aspect of this embodiment, the solution comprises about 4% by weight neat TEAH. In another aspect of this embodiment, the solution comprises about 5% by weight neat TEAH.

[0072] In one embodiment, the solution comprises about 1% to about 5% by weight of neat DMDPAH. In a further aspect of this embodiment, the solution comprises about 1% to about 4.5% by weight of neat DMDPAH. In another aspect of this embodiment, the solution comprises about 1.5% to about 4% by weight of neat DMDPAH. In another aspect of this embodiment, the solution comprises about 2% to about 3.5% by weight of neat DMDPAH. In another aspect of this embodiment, the solution comprises about 2% to about 3% by weight of neat DMDPAH. In another aspect of this embodiment, the solution comprises about 2.1% by weight of neat DMDPAH. In another aspect of this embodiment, the solution comprises about 2.2% by weight of neat DMDPAH. In another aspect of this embodiment, the solution comprises about 2.3% by weight of neat DMDPAH. In another aspect of this embodiment, the solution comprises about 2.4% by weight of neat DMDPAH. In another aspect of this embodiment, the solution comprises about 2.6% by weight neat DMDPAH. In another aspect of this embodiment, the solution comprises about 2.8% by weight neat DMDPAH. In another aspect of this embodiment, the solution comprises about 3% by weight neat DMDPAH.

[0073] In one embodiment, the solution comprises about 0.5% to 5% by weight of neat choline hydroxide. In a further aspect of this embodiment, the solution comprises about 1% to about 4% by weight of neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 1.5% to about 3.5% by weight of neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 2% to about 3% by weight of neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 0.5% by weight of neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 1% by weight of neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 1.5% by weight of neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 2% by weight of neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 2.5% by weight of neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 3% by weight neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 3.5% by weight neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 4% by weight neat choline hydroxide. In another aspect of this embodiment, the solution comprises about 5% by weight neat choline hydroxide.

[0074] In one embodiment, the solution comprises about 0.1% to about 3% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.1% to about 2.5% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.1% to about 2% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.1% to about 1.5% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.1% to about 1% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.1% to about 0.5% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.2% to about 2% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.2% to about 1.5% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.2% to about 1% by weight of neat ETMAH. In one embodiment, the solution comprises about 0.2% to about 0.5% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.1% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.2% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.3% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.4% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.5% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.6% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.7% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.8% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.9% by weight of neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.0% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.1% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.2% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.3% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.4% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.5% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.6% by weight neat ETMAH.In another aspect of this embodiment, the solution comprises about 1.7% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.8% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.9% by weight neat ETMAH. In another aspect of this embodiment, the solution comprises about 2.0% by weight neat ETMAH.

[0075] In one embodiment, the solution comprises about 0.1% to about 3% by weight of neat TMAH. In one embodiment, the solution comprises about 0.1% to about 2.5% by weight of neat TMAH. In one embodiment, the solution comprises about 0.1% to about 2% by weight of neat TMAH. In one embodiment, the solution comprises about 0.1% to about 1.5% by weight of neat TMAH. In one embodiment, the solution comprises about 0.1% to about 1% by weight of neat TMAH. In one embodiment, the solution comprises about 0.1% to about 0.5% by weight of neat TMAH. In one embodiment, the solution comprises about 0.2% to about 2% by weight of neat TMAH. In one embodiment, the solution comprises about 0.2% to about 1.5% by weight of neat TMAH. In one embodiment, the solution comprises about 0.2% to about 1% by weight of neat TMAH. In one embodiment, the solution comprises about 0.2% to about 0.5% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.1% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.2% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.3% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.4% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.5% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.6% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.7% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.8% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 0.9% by weight of neat TMAH. In another aspect of this embodiment, the solution comprises about 1.0% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 1.1% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 1.2% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 1.3% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 1.4% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 1.5% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 1.6% by weight neat TMAH.In another aspect of this embodiment, the solution comprises about 1.7% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 1.8% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 1.9% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 2.0% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 2.1% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 2.2% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 2.3% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 2.4% by weight neat TMAH. In another aspect of this embodiment, the solution comprises about 2.5% by weight neat TMAH. In one embodiment, the solution is substantially free of neat TMAH. In one embodiment, the solution is free of neat TMAH.

[0076] Component D: Silicon-containing compounds

[0077] As noted above, the silicon-containing compound has the formula II: [ka] During the ceremony, (i) m = 0 to 20; (ii)R 1 , R 2 , R 3 , R 4 and R 5 each independently represents hydrogen, C 1 ~C 10 C substituted with linear alkyl groups, fluorine, nitrogen-containing groups, and oxygen-containing groups 1 ~C 10 Straight chain alkyl group, C 3 ~C 10 Branched chain alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 5 ~C 12 Aryl group, C 2 ~C 10 Linear or branched alkenyl groups and C 2 ~C 10 A straight or branched chain alkynyl group, [ka] is selected from the group (iii)R a and R b Each of the following may be independently selected: C 1 ~C 10 Straight chain alkyl group, C 3 ~C 10 Branched chain alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 5 ~C 12 Aryl group, C 2 ~C 10 Linear or branched alkenyl groups and C 2 ~C 10 A straight or branched chain alkynyl group, [ka] [ka] C replaced with 1 ~C 10 is selected from alkyl.

[0078] In some embodiments of the etching composition comprising the silicon-containing compound of formula I, R 1 , R 2 , R 3 , R 4 and R 5 are the same. In a further aspect of this embodiment, R 1 , R 2 , R 3 , R 4 and R 5 Each of is hydrogen.

[0079] In some embodiments of the etching composition comprising the silicon-containing compound of formula I, R 1 , R 2 , R 3 , R 4 and R 5 At least one of is other than hydrogen.

[0080] In some embodiments of the etching composition comprising a silicon-containing compound of Formula I, m=0-20. In a further aspect of this embodiment, m is 0. In a further aspect of this embodiment, m is 1. In a further aspect of this embodiment, m is 2. In a further aspect of this embodiment, m is 3. In a further aspect of this embodiment, m is 4. In a further aspect of this embodiment, m is 5. In a further aspect of this embodiment, m is 6. In a further aspect of this embodiment, m is 7. In a further aspect of this embodiment, m is 8. In a further aspect of this embodiment, m is 9. In a further aspect of this embodiment, m is 10. In a further aspect of this embodiment, m is 11. In a further aspect of this embodiment, m is 12. In a further aspect of this embodiment, m is 13. In a further aspect of this embodiment, m is 14. In a further aspect of this embodiment, m is 15. In a further aspect of this embodiment, m is 16. In a further aspect of this embodiment, m is 17. In a further aspect of this embodiment, m is 18. In a further aspect of this embodiment, m is 19. In a further aspect of this embodiment, m is 20.

[0081] In one embodiment, the solution comprises about 0.15% to about 2% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.2% to about 1.75% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.25% to about 1.5% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.3% to about 1.25% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.35% to about 1.0% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.4% to about 0.95% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.45% to about 0.9% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises from about 0.5% to about 0.85% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises from about 0.55% to about 0.8% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises from about 0.6% to about 0.75% by weight of one or more neat silicon-containing compounds of formula I.

[0082] In one embodiment, the solution comprises about 0.15 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.25 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.325 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.4875 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.5 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.65 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.75 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.8 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.9 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.0 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.1 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.2 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.3 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.4 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.5 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.6 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.7 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.8 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.9 wt% of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 2.0 wt% of one or more neat silicon-containing compounds of formula I.

[0083] In some embodiments, the etching composition comprises a silicon-containing compound of formula I, a and R b Each of [ka] and (ii)R 1 , R 2 , R 4 and R 5 Each of [ka] and (iii) m = 0.

[0084] In some embodiments, the etching composition comprises a silicon-containing compound of formula I, a and R b Each of [ka] and (ii) R 1 , R 2 , R 4 and R 5 Each of [ka] (iii) m = 0; and (iv) [ka] It is.

[0085] In some embodiments, the etching composition comprises a silicon-containing compound of formula I, a and R b Each of [ka] and (ii) R 1 , R 2 , R 3 , R 4 and R 5 Each of [ka] and (iii) m = 0.

[0086] In some embodiments, the etching composition has the structure: [ka] (hereinafter, "Si Compound 1"),

[0087] In one embodiment, the solution contains about 0.15 wt% to about 2.0 wt% of the neat Si compound 1. In one embodiment, the solution contains about 0.2 wt% to about 1.75 wt% of the neat Si compound 1. In one embodiment, the solution contains about 0.25 wt% to about 1.5 wt% of the neat Si compound 1. In one embodiment, the solution contains about 0.3 wt% to about 1.25 wt% of the neat Si compound 1. In one embodiment, the solution contains about 0.35 wt% to about 1.0 wt% of the neat Si compound 1. In one embodiment, the solution contains about 0.4 wt% to about 0.95 wt% of the neat Si compound 1. In one embodiment, the solution contains about 0.05 wt% to about 0.9 wt% of the neat Si compound 1. In one embodiment, the solution contains about 0.5 wt% to about 0.85 wt% of the neat Si compound 1. In one embodiment, the solution contains about 0.55% to about 0.8% by weight of neat Si compound 1. In one embodiment, the solution contains about 0.6% to about 0.75% by weight of neat Si compound 1.

[0088] In one embodiment, the solution contains about 0.15 wt% of neat Si compound 1. In one embodiment, the solution contains about 0.25 wt% of neat Si compound 1. In one embodiment, the solution contains about 0.325 wt% of neat Si compound 1. In one embodiment, the solution contains about 0.5 wt% of neat Si compound 1. In one embodiment, the solution contains about 0.65 wt% of neat Si compound 1. In one embodiment, the solution contains about 0.75 wt% of neat Si compound 1. In one embodiment, the solution contains about 0.8 wt% of neat Si compound 1. In one embodiment, the solution contains about 0.9 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.0 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.1 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.2 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.3 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.4 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.5 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.6 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.7 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.8 wt% of neat Si compound 1. In one embodiment, the solution contains about 1.9 wt% of neat Si compound 1. In one embodiment, the solution contains about 2.0 wt% of neat Si compound 1.

[0089] Exemplary embodiments of etching compositions

[0090] The following are exemplary embodiments of etching compositions suitable for selectively removing silicon relative to silicon oxide from microelectronic devices: A. one or more aqueous solvents; B. one or more alkanolamines; C. one or more quaternary ammonium hydroxides, and D. Contains one or more silicon-containing compounds.

[0091] In one embodiment, the etching composition comprises: A. Water, B. One or more alkanolamines of formula I, [ka] In the formula, R 1 , R 2 and R 3 However, each independently, (a) hydrogen, (b1)C 1 ~C 20 Straight chain alkyl groups, (b2)C 4 ~C 20 Branched chain alkyl groups, (b3)C 3 ~C 20 Cyclic alkyl groups, (c) Unsubstituted C 2 ~C 20 Alkyl ether groups, (d) C 1 ~C 20 Alkanol groups, (e) C substituted with -OH group 2 ~C 20 alkyl ether groups; R 1 , R 2 and R 3 one or more alkanolamines of formula I, at least one of which is (d) or (e); C. one or more quaternary ammonium hydroxides, and D. One or more silicon-containing compounds of formula II, [ka] During the ceremony, (i) m = 0 to 20; (ii)R 1 , R 2 , R 3 , R 4 and R 5 each independently represents hydrogen, C 1 ~C 10 C substituted with linear alkyl groups, fluorine, nitrogen-containing groups, and oxygen-containing groups 1 ~C 10 Straight chain alkyl group, C3 ~C 10 Branched chain alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 5 ~C 12 Aryl group, C 2 ~C 10 Linear or branched alkenyl groups and C 2 ~C 10 A straight or branched chain alkynyl group, [ka] is selected from the group (iii)R a and R b Each of the following may be independently selected: C 1 ~C 10 Straight chain alkyl group, C 3 ~C 10 Branched chain alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 5 ~C 12 Aryl group, C 2 ~C 10 Linear or branched alkenyl groups and C 2 ~C 10 A straight or branched chain alkynyl group, [ka] [ka] C replaced with 1 ~C 10 The silicon-containing compound of formula II is selected from the group consisting of alkyl, aryl, arylalkyl, arylsulfuric acid ...

[0092] In one embodiment, the etching composition comprises: A. Water, B. Monoethanolamine (MEA), C. Ethyltrimethylammonium hydroxide (ETMAH), and D. Contains Si compound 1.

[0093] In one embodiment, the etching composition comprises: A. about 35% to about 60% by weight of water; B. about 20.0 to about 70.0% by weight monoethanolamine (MEA); C. about 0.1% to about 3% by weight of ethyltrimethylammonium hydroxide (ETMAH), and D. containing about 0.15 wt % to about 2.0 wt % of neat Si compound 1.

[0094] Other Ingredients

[0095] The etching compositions, including those exemplified above, may contain other optional components, as described below.

[0096] Additional Silicon-Containing Compounds

[0097] In some embodiments, the mixture can include additional silicon-containing compound(s) other than those of Formula 1. Such additional silicon-containing compound(s) can be one or more of alkyl silsesquioxanes, vinyl silsesquioxanes, carboxylic acid alkyl silsesquioxanes, and alkylene glycol alkyl silsesquioxanes.

[0098] Hydroxyl-containing water-miscible solvents

[0099] In some embodiments, the mixture can include a hydroxyl-containing water-miscible solvent that functions primarily to protect the silicon oxide so that silicon is preferentially and selectively etched.

[0100] Classes of suitable hydroxyl-containing water-miscible solvents include, but are not limited to, alkanediols and polyols (including, but not limited to, alkylene glycols), glycols, alkoxyalcohols (including, but not limited to, glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and low molecular weight alcohols containing a ring structure.

[0101] (C 2 ~C 20 ) alkanediols and (C 3 ~C 20 ) Examples of suitable water-soluble alkanediols and polyols, such as alkanetriols, include, but are not limited to, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, and pinacol.

[0102] Examples of suitable water soluble alkylene glycols include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

[0103] Examples of suitable water-soluble alkoxy alcohols include, but are not limited to, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and water-soluble glycol monoethers.

[0104] Examples of suitable water-soluble glycol monoethers include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether and ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, and mixtures thereof.

[0105] Examples of suitable water-soluble saturated aliphatic monohydric alcohols include, but are not limited to, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, 1-hexanol, and mixtures thereof.

[0106] Examples of suitable water soluble unsaturated non-aromatic monohydric alcohols include, but are not limited to, allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, 4-penten-2-ol, and mixtures thereof.

[0107] Examples of suitable water-soluble low molecular weight alcohols containing a ring structure include, but are not limited to, alpha-terpineol, tetrahydrofurfuryl alcohol, furfuryl alcohol, 1,3-cyclopentanediol, and mixtures thereof.

[0108] In some embodiments, the amount of hydroxyl-containing water-miscible solvent comprises from about 1.0% to about 30% by weight of the composition. Preferably, the hydroxyl-containing water-miscible solvent, if used, comprises from about 5% to about 15% by weight of the composition.

[0109] In some embodiments, the compositions of the disclosed and claimed subject matter are free or substantially free of hydroxyl-containing water-miscible solvents or any or all of the hydroxyl-containing water-miscible solvents listed above.

[0110] Silicic acid

[0111] In some embodiments, the mixture can include silicic acid, which, when used, helps protect the silicon oxide and increase silicon etch selectivity.

[0112] In some embodiments, the amount of silicic acid comprises from about 0.001% to about 5.0% by weight of the composition, preferably from about 0.01% to about 2.0% by weight, while in other embodiments, the silicic acid comprises from about 0.02% to about 0.08% by weight of the composition.

[0113] In some embodiments, the compositions of the disclosed and claimed subject matter are free or substantially free of added silicic acid.

[0114] Surfactants

[0115] In some embodiments, the mixture can include at least one water-soluble non-ionic surfactant, which serves to aid in the removal of residues.

[0116] Examples of the water-soluble nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene derivatives, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitotetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, alkyl alkanolamide, and mixtures thereof.

[0117] In some embodiments, the amount of surfactant comprises from about 0.001% to about 5% by weight of the composition, preferably from about 0.01% to about 2.5% by weight, and most preferably from about 0.1% to about 1.0% by weight of the composition.

[0118] In some embodiments, the compositions of the disclosed and claimed subject matter are free or substantially free of surfactants.

[0119] In some embodiments, the compositions are substantially free or free of metal hydroxides, added metals, halide-containing compounds, TEOS, silyl phosphate compounds, and silanes and silanols that do not contain repeating monomers.

[0120] Manufacturing method

[0121] The disclosed and claimed subject matter further includes methods of making the etching compositions described and claimed herein.

[0122] In one embodiment, a method for forming an etching composition includes: A. one or more aqueous solvents; B. one or more alkanolamines; C. one or more quaternary ammonium hydroxides, and D. Combining one or more silicon-containing compounds.

[0123] In one embodiment, a method for forming an etching composition includes: A. Water B. One or more alkanolamines of formula I, [ka] In the formula, R 1 , R 2 and R 3 However, each independently, (a) hydrogen, (b1)C 1 ~C 20 Straight chain alkyl groups, (b2)C 4 ~C 20 Branched chain alkyl groups, (b3)C 3 ~C 20 Cyclic alkyl groups, (c) Unsubstituted C 2 ~C 20 Alkyl ether groups, (d) C 1 ~C 20 Alkanol groups, (e) C substituted with -OH group 2 ~C 20 alkyl ether groups; R 1 , R 2 and R 3 one or more alkanolamines of formula I, at least one of which is (d) or (e); C. one or more quaternary ammonium hydroxides, and D. One or more silicon-containing compounds of formula II, [ka] During the ceremony, (i) m = 0 to 20; (ii)R 1 , R 2 , R 3 , R 4 and R 5 each independently represents hydrogen, C 1 ~C 10 C substituted with linear alkyl groups, fluorine, nitrogen-containing groups, and oxygen-containing groups 1 ~C 10 Straight chain alkyl group, C 3 ~C 10 Branched chain alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 5 ~C 12 Aryl group, C 2 ~C 10 Linear or branched alkenyl groups and C 2 ~C 10 A straight or branched chain alkynyl group, [ka] is selected from the group (iii)R a and R b Each of the following may be independently selected: C 1 ~C 10 Straight chain alkyl group, C 3 ~C 10 Branched chain alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 5 ~C 12 Aryl group, C 2 ~C 10 Linear or branched alkenyl groups and C 2 ~C 10 A straight or branched chain alkynyl group, [ka] [ka] C replaced with 1 ~C 10The present invention includes combining one or more silicon-containing compounds of formula II selected from the group consisting of alkyl, aryl, arylalkyl ...

[0124] In one embodiment, the method for forming the etching composition comprises: A. water. B. Monoethanolamine (MEA), C. Ethyltrimethylammonium hydroxide (ETMAH), and D.Si Compound 1 is combined.

[0125] In one embodiment, a method for forming an etching composition includes: A. about 35% to about 60% by weight water; B. about 20.0 to about 70.0% by weight monoethanolamine (MEA); C. about 0.1% to about 3% by weight of ethyltrimethylammonium hydroxide (ETMAH), and D. Combining about 0.015 wt % to about 0.2 wt % of neat Si compound 1.

[0126] How to use

[0127] The disclosed and claimed subject matter further includes methods for selectively removing silicon films while minimizing the etch rate of oxide films using the disclosed and claimed etching compositions, and methods for manufacturing semiconductors that include etching processes using the disclosed and claimed etching compositions.

[0128] In one embodiment, the method comprises: a. contacting a composite semiconductor device comprising a silicon film with one or more of the etching compositions disclosed and / or claimed herein; b. cleaning the semiconductor device complex after the silicon film has been at least partially removed. In a further aspect of this embodiment, the contacting step is carried out at a temperature of from about 25°C to about 90°C.

[0129] In a further embodiment, the method may include a drying step c.

[0130] In the described method, "at least partially removed" means at least 90% removal of the material, preferably at least 95% removal. Most preferably, at least 99% is removed using the compositions of the present development. "Si-oxide compatible" means less than 10% film loss.

[0131] In a further embodiment, the method can include a pretreatment step that includes contacting the substrate with dilute hydrofluoric acid ("DHF") (1:100 HF:water) (e.g., by immersion or spraying). Further damage resulting from the dHF pretreatment step can be minimized by reducing agitation when treating with the compositions of the disclosed and claimed subject matter, and by reducing the time between pretreatment and contact with the compositions of the disclosed and claimed subject matter.

[0132] In some embodiments, the contacting step can be performed by any suitable means, such as, for example, dipping, spraying, or via a single wafer process.

[0133] In some embodiments, the temperature of the composition during the contacting step is preferably from about 25° C. to about 90° C. In further aspects, the temperature is from about 40° C. to about 80° C. In further aspects, the temperature of the composition during the contacting step is about 75° C.

[0134] In some embodiments, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide of about 300 to about 5000. In some embodiments, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide of about 500 to about 4000. In some embodiments, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide of about 1000 to about 3000. In some embodiments, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide of about 1000 to about 2000. In some embodiments, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide of about 1000 to about 1500. In some embodiments, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide of about 500 to about 1500. In some embodiments, the etching compositions of the disclosed and claimed subject matter have an etch selectivity of silicon over silicon oxide of from about 500 to about 2000.

[0135] In some embodiments, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide greater than about 300. In further aspects, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide greater than about 500. In further aspects, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide greater than about 1000. In further aspects, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide greater than about 1250. In further aspects, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide greater than about 1500. In further aspects, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide greater than about 2000. In further aspects, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon to silicon oxide greater than about 2500. In further embodiments, the etching compositions of the disclosed and claimed subject matter have an etch selectivity of silicon to silicon oxide greater than about 3000. In further embodiments, the etching compositions of the disclosed and claimed subject matter have an etch selectivity of silicon to silicon oxide greater than about 3500. In further embodiments, the etching compositions of the disclosed and claimed subject matter have an etch selectivity of silicon to silicon oxide greater than about 4000. In further embodiments, the etching compositions of the disclosed and claimed subject matter have an etch selectivity of silicon to silicon oxide greater than about 4500. In further embodiments, the etching compositions of the disclosed and claimed subject matter have an etch selectivity of silicon to silicon oxide greater than about 5000.

[0136] In some embodiments, the silicon oxide etches at less than 1 Å / min. In further aspects, the silicon oxide etches at less than 0.5 Å / min. In further aspects, the silicon oxide etches at less than 0.01 Å / min.

[0137] In some embodiments, the cleaning step c. is performed by washing the substrate with deionized water by any suitable means, such as immersion or spraying techniques. In another aspect, the rinsing step is performed with a mixture of deionized water and a water-miscible organic solvent (e.g., isopropyl alcohol).

[0138] In some embodiments, the drying step is performed by any suitable means, for example, isopropyl alcohol (IPA) vapor drying, heat, or centripetal force. EXAMPLES

[0139] Reference is now made to more specific embodiments of the present disclosure, as well as experimental results supporting such embodiments. The examples are provided below to more fully explain the disclosed subject matter, and should not be construed as limiting the disclosed subject matter in any way.

[0140] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and the specific examples provided herein without departing from the spirit and scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the description provided by the following examples, is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claims and their equivalents.

[0141] Materials and Methods:

[0142] All components used herein are commercially available.

[0143] In the examples, the following silicon-containing compounds were used: [Table 1]

[0144] General Procedure for Preparing the Etching Composition

[0145] All compositions described in the examples were prepared by mixing the ingredients in a 250 mL beaker with a 1 inch Teflon coated stir bar. Typically, the first material added to the beaker was deionized (DI) water.

[0146] Substrate Composition

[0147] The test coupons used in the examples included a 20 mm x 20 mm polysilicon wafer, an alpha silicon wafer, and a TEOS oxide wafer.

[0148] Processing conditions

[0149] Etching tests were conducted using 100 g of the etching composition in a 250 mL beaker with a 1 inch Teflon coated stir bar set at 500 rpm. The etching composition was heated on a hot plate to a temperature of about 25°C to about 90°C. Polysilicon and patterned test substrate coupons (test coupons) were treated with DHF (1:100 HF:DI water) for about 3 minutes prior to testing; SiOx coupons were not pretreated with DHF. The test coupons were immersed in the composition with stirring for about 1 minute (for silicon substrates) to about 90 minutes (for SiOx substrates).

[0150] The segments were then rinsed in a DI water bath or spray for approximately 3 minutes before drying using filtered nitrogen. Silicon and silicon oxide etch rates were estimated from the change in thickness before and after etching and measured by spectroscopic ellipsometry (FilmTek™ 2000 PAR-SE, Scientific Computing International).

[0151] The following series of tables show the evaluation results of several embodiments of the disclosed and claimed etching compositions. All example values ​​are reported as "neat" values ​​unless otherwise noted. Additionally, performance wafer testing was not performed on samples that did not meet the selectivity or etch rate requirements. [Table 2]

[0152] Table 1 shows the NH 4 It is shown that by adding the Si-containing compound of formula II and fluorosilicic acid in the OH solution, the silicon oxide etch rate can be suppressed while maintaining the silicon etch rate at the same level. [Table 3]

[0153] Table 2 shows that the silicon oxide etching rate can be suppressed by adding the Si-containing compound of formula II and fluorosilicic acid in the QAH solution. As can be seen, the Si-containing compound exhibited better protection ability. Furthermore, the silicon etching rate is much higher by using QAH as the alkali source, and is maintained at the same level by adding the Si-containing compound and fluorosilicic acid. [Table 4]

[0154] Table 3 further shows that the silicon etch rate can be promoted while introducing a higher content of QAH, but the selectivity of Si to SiOx becomes lower. [Table 5]

[0155] Table 4 shows the effect on the formulation of Example 10 when used to etch at various temperatures. As seen in Table 4, the silicon etch rate can be accelerated by increasing the process temperature, but the selectivity of Si to SiOx becomes lower. Furthermore, silicon residue still cannot be removed with such a high etch rate at 75°C. [Table 6]

[0156] Table 5 shows that the silicon oxide etch rate is high during processing at 75° C. As can be seen, the silicon oxide etch rate is suppressed by adding more Si-containing compounds. [Table 7]

[0157] Table 6 shows the ability of some of the disclosed and claimed formulations to remove silicon residues on patterned structures by introducing various levels of alkanolamine. Note that residual material remained on the wafer surface even when the solvent to water ratio was too high (e.g., greater than about 2.4, see Example 18). [Table 8]

[0158] Table 7 shows that the silicon oxide etch rate can also be suppressed by adding more Si-containing compounds while introducing alkanolamines. [Table 9]

[0159] Table 8 shows that the polysilicon etch rate can be increased by increasing the QAH content. [Table 10]

[0160] Table 9 shows the compositions using TMAH as the QAH. [Table 11]

[0161] Table 10 provides a comparative formulation using about 2.4 wt% TMAH. As can be seen, the TMAH formulations in Table 9 show better Si to SiOx selectivity and residue removal than the TMAH only composition.

[0162] summary

[0163] The disclosed and claimed subject matter relates to semi-aqueous etching compositions for polysilicon etching applications. Compared to conventional alkaline solutions, the formulated chemistry can completely remove polysilicon without residue by processing at comparable process times, and no damage to SiOx was observed. Importantly, the disclosed and claimed compositions contain Si-containing oxide inhibitors that suppress the oxide etch rate and promote the selectivity of Si to SiOx in alkaline chemistry. Furthermore, the cleaning performance of the disclosed and claimed compositions can be "tuned" to specific applications by controlling the water-to-solvent ratio.

[0164] The foregoing description has been primarily for purposes of illustration. While the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in form and detail thereof may be made without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A. about 20% to about 65% by weight of water; B. One or more alkanolamines of formula I, 【Chemistry 1】 wherein R 1 , R 2 and R 3 are each independently (a) hydrogen, (b1) a C 1 to C 20 linear alkyl group; (b2) a C 4 to C 20 branched alkyl group; (b3) a C 3 -C 20 cyclic alkyl group; (c) an unsubstituted C 2 -C 20 alkyl ether group; (d) a C 1 -C 20 alkanol group; (e) C 2 -C 20 alkyl ether groups substituted with —OH groups; one or more alkanolamines of formula I, wherein at least one of R 1 , R 2 and R 3 is (d) or (e); C. about 0.1% to about 3% by weight of one or more quaternary ammonium hydroxides, and D. 0.15% to about 2.0% by weight of neat one or more silicon-containing compounds of Formula II, 【Chemistry 2】 During the ceremony, (i) m=0 to 20; (ii) R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen, a C 1 to C 10 straight chain alkyl group, a C 1 to C 10 straight chain alkyl group substituted with fluorine, a nitrogen-containing group, an oxygen-containing group, a C 3 to C 10 branched chain alkyl group, a C 3 to C 10 cyclic alkyl group, a C 5 to C 12 aryl group, a C 2 to C 10 straight chain or branched chain alkenyl group and a C 2 to C 10 straight chain or branched chain alkynyl group; 【Transformation 3】 is selected from the group (iii) each of R a and R b is independently a C 1 to C 10 straight chain alkyl group, a C 3 to C 10 branched chain alkyl group, a C 3 to C 10 cyclic alkyl group, a C 5 to C 12 aryl group, a C 2 to C 10 straight chain or branched chain alkenyl group, and a C 2 to C 10 straight chain or branched chain alkynyl group; 【Chemistry 4】 【Transformation 5】 one or more silicon-containing compounds of formula II selected from C 1 -C 10 alkyl substituted with 1. An etching composition comprising:

2. 10. The etching composition of claim 1, wherein the one or more alkanolamines of Formula I comprise monoethanolamine (MEA).

3. 10. The etching composition of claim 1, wherein the one or more quaternary ammonium hydroxides comprise one or more of ETMAH and TMAH.

4. The one or more silicon-containing compounds of formula II are 【Transformation 6】 The composition of claim 1 comprising:

5. A. about 35% to about 60% by weight of water; B. about 20.0 to about 70.0 wt. % monoethanolamine (MEA); C. about 0.1% to about 3% by weight of neat ethyltrimethylammonium hydroxide (ETMAH) or neat tetramethylammonium hydroxide (TMAH), and D. From about 0.15% to about 2.0% by weight neat 【Transformation 7】 The etching composition of claim 1 comprising:

6. 10. The composition of claim 1, wherein the composition further comprises one or more additional silicon-containing compounds selected from alkyl silsesquioxanes, vinyl silsesquioxanes, carboxylic acid alkyl silsesquioxanes, and alkylene glycol alkyl silsesquioxanes.

7. 2. The composition of claim 1, wherein the composition further comprises one or more hydroxyl-containing water-miscible solvents selected from the group consisting of alkanediols, polyols, glycols, alkoxyalcohols, saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and low molecular weight alcohols containing a ring structure.

8. The composition of claim 1 , wherein the composition further comprises one or more silicic acids.

9. The composition of claim 1 , wherein the composition further comprises one or more surfactants.

10. A. about 20% to about 55% by weight of water; B. about 20% to about 70% by weight monoethanolamine (MEA); C. about 0.1% to about 2.5% by weight of neat ethyltrimethylammonium hydroxide (ETMAH), and D. about 0.3% to about 1.25% by weight neat 【Transformation 8】 The etching composition of claim 1 comprising:

11. A. about 52.6% by weight water; B. about 46.5 wt. % monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH), and D. About 0.5% by weight neat 【Chemistry 9】 The etching composition of claim 1 comprising:

12. A. about 39% by weight water; B. about 60% by weight monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH), and D. About 0.5% by weight neat 【Chemistry 10】 The etching composition of claim 1 comprising:

13. A. about 29% by weight water; B. about 70% by weight monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH), and D. About 0.5% by weight neat 【Chemistry 11】 The etching composition of claim 1 comprising:

14. A. about 53% by weight water; B. about 46% by weight of monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH), and D. About 0.6% by weight neat 【Chemistry 12】 The etching composition of claim 1 comprising:

15. A. about 53.6% by weight water; B. about 45% by weight of monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH), and D. About 1% by weight neat 【Chemistry 13】 The etching composition of claim 1 comprising:

16. A. about 52% by weight water; B. about 46.5 wt. % monoethanolamine (MEA); C. about 1% by weight of neat ethyltrimethylammonium hydroxide (ETMAH), and D. About 0.5% by weight neat 【Chemistry 14】 The etching composition of claim 1 comprising:

17. A. about 51% by weight water; B. about 46.5 wt. % monoethanolamine (MEA); C. about 2% by weight of neat ethyltrimethylammonium hydroxide (ETMAH), and D. About 0.5% by weight neat 【Chemistry 15】 The etching composition of claim 1 comprising:

18. A. about 45% to about 55% by weight of water; B. about 40% to about 55% by weight of monoethanolamine (MEA); C. about 0.1% to about 2.5% by weight of neat tetramethylammonium hydroxide (TMAH), and D. From about 0.4% to about 0.95% by weight of neat 【Chemistry 16】 The etching composition of claim 1 comprising:

19. A. about 52.5% by weight water; B. about 45% by weight of monoethanolamine (MEA); C. about 2% by weight of neat tetramethylammonium hydroxide (TMAH), and D. About 0.5% by weight neat 【Chemistry 17】 The etching composition of claim 1 comprising:

20. A. about 47.5% by weight water; B. about 50% by weight monoethanolamine (MEA); C. about 2% by weight of neat tetramethylammonium hydroxide (TMAH), and D. About 0.5% by weight neat [Chemistry 18] The etching composition of claim 1 comprising:

21. A. about 47.514% by weight water; B. about 50% by weight monoethanolamine (MEA); C. about 2% by weight of neat tetramethylammonium hydroxide (TMAH), and D. About 0.5% by weight neat 【Chemistry 19】 The etching composition of claim 1 comprising:

22. A. about 42.5% by weight water; B. about 55% by weight of monoethanolamine (MEA); C. about 2% by weight of neat tetramethylammonium hydroxide (TMAH), and D. About 0.5% by weight neat 【Chemistry 20】 The etching composition of claim 1 comprising:

23. A. about 42.514% by weight water; B. about 55% by weight of monoethanolamine (MEA); C. about 2% by weight of neat tetramethylammonium hydroxide (TMAH), and D. about 0.486% by weight neat 【Chemistry 21】 The etching composition of claim 1 comprising:

24. A. about 37.5% by weight water; B. about 60% by weight monoethanolamine (MEA); C. about 2% by weight of neat tetramethylammonium hydroxide (TMAH), and D. About 0.5% by weight neat 【Chemistry 22】 The etching composition of claim 1 comprising:

25. A. about 37.514% by weight water; B. about 60% by weight monoethanolamine (MEA); C. about 2% by weight of neat tetramethylammonium hydroxide (TMAH), and D. about 0.486% by weight neat 【Chemistry 23】 The etching composition of claim 1 comprising:

26. 1. A method for selectively enhancing the etch rate of silicon relative to silicon dioxide on a semiconductor substrate comprising silicon and silicon dioxide, comprising: a. contacting the semiconductor substrate comprising silicon and silicon dioxide with the composition of claim 1; b) cleaning the semiconductor device after the silicon has been at least partially removed.

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