Formulated alkali chemicals for polycrystalline silicon excavation

Abstract

The disclosed and claimed subject matter relates to an etching composition capable of selectively removing a silicon film while minimizing the etch rate of an oxide film, and a method of manufacturing a semiconductor device using the composition.

Description

background Technical Field

[0002] The disclosed and claimed subject matter relates to etching compositions, and more particularly, to highly selective etching compositions capable of selectively removing silicon films while minimizing the etching rate of oxide films, and to methods of manufacturing semiconductors including etching processes using the etching compositions. Background Art

[0003] As semiconductor devices become more highly integrated, the reliability and electrical characteristics of semiconductor devices are more susceptible to damage or deformation of the layers constituting the semiconductor devices. Therefore, when an etchant is used to selectively perform an etching process to remove a specific material layer, it is desirable that the etchant should have a higher etching selectivity relative to other material layers and that the etching process produces fewer byproducts to reduce process defects.

[0004] In 3D NAND flash memory device manufacturing, as the number of nitride / oxide alternating layers increases, high aspect ratio (HAR) channel etching challenges the physical limitations of current plasma etching technology. To overcome these challenges, the process flow has been transformed from a single stack to multiple stacks (e.g., 2 layers of 64 layers to provide an equivalent 128-layer array). Figure 1 A dual stack process is shown. After the HAR channel etch of level 1, the vertical channels are filled with sacrificial material. Level 2 processes are performed on top of level 1, namely nitride / oxide deposition and channel etch. Finally, the fill material is removed so that a 2X layer of HAR channel etch can be achieved. The disclosed and claimed subject matter can be used as a wet etchant for polysilicon removal in these processes.

[0005] Wet etchant compositions for eliminating pyramidal Si etching residues produced after etching processes with high silicon to silicon oxide selectivity are known. For example, U.S. Patent Application Publication No. 2017 / 0145311 describes etching compositions that can selectively etch certain crystal planes or perform crystal orientation selective wet etching and provide a flat bottom. U.S. Patent Application Publication No. 2020 / 0157422 describes various oxide inhibitors that can significantly inhibit oxide etching rates in alkaline wet chemical etching formulations and exhibit high silicon to silicon oxide selectivity.

[0006] Despite these known materials, and with such high integration density, the material selectivity requirements for selective sacrificial silicon removal in 3D NAND manufacturing become more critical—to the point where it is desired to effectively retain the SiO x Therefore, there is a need in the art to further inhibit the SiO x Etch rates to achieve even higher Si to SiO xselectivity. Summary of the invention

[0007] 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:

[0008] A. one or more aqueous solvents;

[0009] B. one or more alkanolamines;

[0010] C. one or more quaternary ammonium hydroxides ("QAH"); and

[0011] D. One or more silicon-containing compounds (which may also be referred to herein as organosilicon compounds).

[0012] The alkanolamines useful for the disclosed and claimed subject matter include one or more alkanol groups and one or more amine groups. The structure of the alkanolamines useful for the disclosed and claimed subject matter has Formula I:

[0013]

[0014] Where R 1 , R 2 and R 3 Each independently selected from:

[0015] (a) hydrogen,

[0016] (b1)C1-C 20 Straight chain alkyl groups,

[0017] (b2)C4-C 20 Branched alkyl groups,

[0018] (b3)C3-C 20 Cycloalkyl groups;

[0019] (c) Unsubstituted C2-C 20 Alkyl ether groups;

[0020] (d)C1-C 20 Alkanol group;

[0021] (e) C2-C substituted with -OH group 20 an alkyl ether group; and

[0022] Where R 1 , R 2 and R 3 At least one of the following must be (d) or (e).

[0023] 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, 2-amino-2-ethoxyethanol.

[0024] In some embodiments, the silicon-containing compound has Formula II:

[0025]

[0026] in:

[0027] (i) m = 0-20,

[0028] (ii) R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl groups, fluorine-substituted C1 to C 10 Straight chain alkyl groups, nitrogen-containing groups, oxygen-containing groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, and

[0029] (iii) R a and R b Each independently selected from C1 to C 10 Straight chain alkyl groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, alkyl, Substituted C1-C 10 alkyl.

[0030] Embodiments of the disclosed and claimed subject matter can be used alone or in combination with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0032] Figure 1 Figure 3 shows the 3D NAND process flow using double-stacked HAR vertical channel etch. DETAILED DESCRIPTION

[0033] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0034] Unless otherwise specified herein or clearly contradictory to the context, in the context of describing the disclosed and claimed subject matter (especially in the context of the following claims), the use of the terms "one" and "an" and "the" and similar references should be interpreted as covering the singular and plural. Unless otherwise specified, the terms "comprising", "having", "including" and "containing" should be interpreted as open terms (i.e., meaning "including but not limited to"). Unless otherwise specified herein, the description of the numerical range herein is intended only to be used as a shorthand method for individually referring to each individual value falling within the range, and each individual value is incorporated into this specification as if it is individually described herein. Unless otherwise specified herein or clearly contradictory to the context, all methods described herein can be performed in any suitable order. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the disclosed and claimed subject matter, and does not limit the scope of the disclosed and claimed subject matter, unless otherwise required. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential to the practice of the disclosed and claimed subject matter.

[0035] Preferred embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventor for implementing the disclosed and claimed subject matter. After reading the foregoing description, changes in those preferred embodiments may become apparent to those of ordinary skill in the art. The inventor expects those skilled in the art to appropriately adopt these changes, and the inventor intends to practice the disclosed and claimed subject matter in a manner different from that specifically described herein. Therefore, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter described in the attached claims as permitted by applicable law. In addition, unless otherwise stated herein or clearly contradictory to the context, the disclosed and claimed subject matter covers any combination of the above-mentioned elements in all possible variations thereof.

[0036] The disclosed and claimed subject matter generally relates to compositions useful for selectively removing silicon relative to silicon oxide from microelectronic devices having silicon and silicon oxide materials thereon during their fabrication.

[0037] For ease of reference, "microelectronic device" or "semiconductor substrate" corresponds to semiconductor wafers, flat panel displays, phase change memory devices, solar panels and other products, including solar substrates, photovoltaic devices and microelectromechanical systems (MEMS), which are manufactured for microelectronics, integrated circuit 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 can be doped or undoped. It should be understood that the term "microelectronic device" is not meant to be limiting in any way and includes any substrate that will eventually become a microelectronic device or microelectronic assembly. The microelectronic device or semiconductor substrate may include low-k dielectric materials, barrier materials and metals (such as AlCu alloys, W, Ti, TiN), as well as other materials thereon.

[0038] As defined herein, "low-k dielectric material" corresponds to any material used as a dielectric material in a layered microelectronic device, wherein the material has a dielectric constant of 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 should be understood that the low-k dielectric material can have varying densities and varying porosities.

[0039] As defined herein, the term "barrier material" corresponds to any material used in the art to seal 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.

[0040] "Substantially free" is defined herein as less than 2 weight percent, preferably less than 1 weight percent, more preferably less than 0.5 weight percent, and most preferably less than 0.1 weight percent. "Substantially free" also includes 0.0 weight percent. The term "free" means 0.0 weight percent.

[0041] As used herein, the terms "about" and "approximately" are each intended to correspond to ±5% of the stated value.

[0042] As used herein, "neat" refers to the amount by weight % of the undiluted acid or other material. For example, 100 g of 85% phosphoric acid comprises 85 g of acid and 15 g of diluent.

[0043] In addition to the known and understood representation of the point of attachment of a covalent bond, the symbol It is also intended to represent the point of attachment of a covalent bond.

[0044] In all such compositions (wherein the specific components of the composition are discussed with reference to a weight percentage range including a zero lower limit), it should be understood that such components may or may not be present in various embodiments of the composition, and in the case where such components are present, they may be present in a concentration as low as 0.001% by weight, based on the gross weight of the composition in which such components are used. It should be noted that, unless otherwise stated, all defined weight percentages of components are based on the gross weight of the composition. In addition, unless otherwise stated, all weight percentages are "net", which means that they do not include the aqueous composition in which they are present when added to the composition. Any reference to "at least one" may be replaced by "one or more". "At least one" and / or "one or more" include "at least two" or "two or more" and "at least three" and "three or more" etc.

[0045] In the broad practice of the disclosed and claimed subject matter, the above-mentioned etching composition is related, which includes components (A), (B), (C) and (D), or consists essentially of components (A), (B), (C) and (D), or consists of components (A), (B), (C) and (D). In some aspects, the etching composition may include other ingredients. In some embodiments, the etching composition disclosed herein is formulated to be free of or substantially free of at least one of the following chemical compounds: acids (inorganic and organic), oxidants, hydrogen peroxide and other peroxides, ammonium ions, halides (e.g., fluoride ions, chloride ions), inorganic bases, metal-containing chemicals, reducing agents, hydroxylamine, hydroxylamine derivatives, amidoxime compounds and abrasives.

[0046] In further embodiments, the etching composition consists essentially of (A), (B), (C), and (D) in varying concentrations. In such embodiments, the combined amounts of (A), (B), (C), and (D) do not equal 100 wt %, and may include other ingredients that do not substantially change the effectiveness of the etching composition.

[0047] In another embodiment, the etching composition is composed of (A), (B), (C) and (D) in different concentrations. In such an embodiment, the combined amount of (A), (B), (C) and (D) is equal to or approximately equal to 100% by weight, but may include other small amounts and / or trace amounts of impurities, which are present in small amounts that do not substantially change the effectiveness of the composition. For example, in one such embodiment, the etching composition may contain 2% by weight or less impurities. In another embodiment, the etching composition may contain 1% by weight or less impurities. In a further embodiment, the etching composition may contain 0.05% by weight or less impurities.

[0048] When referring to the composition of the composition of the present invention as described herein in % by weight, it should be understood that in any case, the % by weight of all components including non-essential components (such as impurities) should not be accumulated to more than 100 % by weight. In the composition "essentially composed of the components", such components can add up to 100 % by weight of the composition or can add up to less than 100 % by weight. When the components add up to less than 100 % by weight, such a composition may include some small amounts of non-essential pollutants or impurities. For example, in one such embodiment, the etching composition may contain 2 % by weight or less impurities. In another embodiment, the etching composition may contain 1 % by weight or less impurities. In a further embodiment, the etching composition may contain 0.05 % by weight or less impurities. In other such embodiments, the composition may account for at least 90 % by weight, more preferably at least 95 % by weight, more preferably at least 99 % by weight, more preferably at least 99.5 % by weight, most preferably at least 99.9 % by weight, and may include other components that do not substantially affect the performance of the etching composition. Otherwise, if there is no significant non-essential impurity component, it should be understood that the combination of all necessary components will essentially add up to 100 % by weight.

[0049] Composition

[0050] As described above, the disclosed and claimed subject matter relates to etching compositions comprising, or consisting essentially of, or consisting of (A), (B), (C), and (D). In some aspects, the etching composition may include other ingredients.

[0051] Component A: Aqueous solvent

[0052] The etching compositions of the present invention are water-based and include water. In the disclosed and claimed subject matter, water functions in various ways, such as, for example, dissolving one or more 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 composition is deionized (DI) water.

[0053] 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.

[0054] Water is included in an amount within a range having a starting point and an end point selected from the following weight percentage list: 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.

[0055] In one embodiment, the composition includes about 1% to about 55% by weight of water. In one embodiment, the composition includes about 5% to about 55% by weight of water. In one embodiment, the composition includes about 10% to about 55% by weight of water. In one embodiment, the composition includes about 15% to about 55% by weight of water. In one embodiment, the composition includes about 20% to about 55% by weight of water. In one embodiment, the composition includes about 25% to about 55% by weight of water. In one embodiment, the composition includes about 30% to about 55% by weight of water. In one embodiment, the composition includes about 35% to about 55% by weight of water. In one embodiment, the composition includes about 40% to about 55% by weight of water. In one embodiment, the composition includes about 45% to about 55% by weight of water.

[0056] In one embodiment, the composition includes about 30% by weight of water. In one embodiment, the composition includes about 35% by weight of water. In one embodiment, the composition includes about 40% by weight of water. In one embodiment, the composition includes about 45% by weight of water. In one embodiment, the composition includes about 50% by weight of water. In one embodiment, the composition includes about 51% by weight of water. In one embodiment, the composition includes about 52% by weight of water. In one embodiment, the composition includes about 53% by weight of water. In one embodiment, the composition includes about 54% by weight of water. In one embodiment, the composition includes about 55% by weight of water. In one embodiment, the composition includes about 56% by weight of water. In one embodiment, the composition includes about 57% by weight of water. In one embodiment, the composition includes about 58% by weight of water. In one embodiment, the composition includes about 59% by weight of water. In one embodiment, the composition includes about 60% by weight of water.

[0057] In other embodiments, water can be present in amounts defined by the following weight ratio list: 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 can include water in amounts to achieve the desired weight percentages of the other ingredients.

[0058] Component B: Alkanolamine

[0059] As described above, the disclosed and claimed compositions include one or more alkanolamines, which include one or more alkanol groups and one or more amine groups. The structure of the alkanolamines useful for the disclosed and claimed subject matter has Formula I:

[0060]

[0061] Where R 1 , R 2 and R 3 Each independently selected from:

[0062] (a) hydrogen,

[0063] (b1)C1-C 20 Straight chain alkyl groups,

[0064] (b2)C4-C 20 Branched alkyl groups,

[0065] (b3)C3-C 20 Cycloalkyl groups;

[0066] (c) Unsubstituted C2-C20 Alkyl ether groups;

[0067] (d)C1-C 20 Alkanol group;

[0068] (e) C2-C substituted with -OH group 20 an alkyl ether group; and

[0069] Where R 1 , R 2 and R 3 At least one of the following must be (d) or (e).

[0070] In one embodiment, the one or more alkanolamines include a mixture of two or more alkanolamines. In a further aspect of this embodiment, the one or more alkanolamines include a mixture of three or more alkanolamines. In a further aspect of this embodiment, the one or more alkanolamines, two or more alkanolamines, or three or more alkanolamines include one or more ether-containing alkanolamines. In a further aspect of this embodiment, the one or more alkanolamines consist of a mixture of two alkanolamines. In a further aspect of this embodiment, the one or more alkanolamines consist of a mixture of three alkanolamines.

[0071] In one embodiment, (b1) is C1-C 15 In another embodiment, (b1) is a C1-C 10 In another embodiment, (b1) is a C1-C7 straight chain alkyl group. In another embodiment, (b1) is a C1-C5 straight chain alkyl group. In another embodiment, (b1) is a C1-C4 straight chain alkyl group. In another embodiment, (b1) is a C1-C3 straight chain alkyl group. In another embodiment, (b1) is a C1-C2 straight chain alkyl group. In another embodiment, (b1) is a C5 straight chain alkyl group. In another embodiment, (b1) is a C4 straight chain alkyl group. In another embodiment, (b1) is a C3 straight chain alkyl group. In another embodiment, (b1) is a C2 straight chain alkyl group. In another embodiment, (b1) is a C1 straight chain alkyl group.

[0072] In one embodiment, (b2) is C4-C 15 In another embodiment, (b2) is C4-C 10In another embodiment, (b2) is a C4-C7 branched alkyl group. In another embodiment, (b2) is a C4-C5 branched alkyl group. In another embodiment, (b2) is a C8 branched alkyl group. In another embodiment, (b2) is a C7 branched alkyl group. In another embodiment, (b2) is a C6 branched alkyl group. In another embodiment, (b2) is a C5 branched alkyl group. In another embodiment, (b2) is a C4 branched alkyl group.

[0073] In one embodiment, (b3) is C3-C 15 In another embodiment, (b3) is C3-C 10 In another embodiment, (b3) is a C3-C7 cycloalkyl group. In another embodiment, (b3) is a C3-C5 cycloalkyl group. In another embodiment, (b3) is a C3-C4 cycloalkyl group. In another embodiment, (b3) is a C6 cycloalkyl group. In another embodiment, (b3) is a C5 cycloalkyl group. In another embodiment, (b3) is a C4 cycloalkyl group. In another embodiment, (b3) is a C3 cycloalkyl group.

[0074] The alkyl ether group (c) includes (i) C2-C 20 Straight chain alkyl group, (ii) C4-C 20 Branched alkyl groups and (iii) C3-C 20 Cycloalkyl groups wherein (i), (ii) and (iii) have oxygen atoms (attached between carbons) within the corresponding alkyl groups. 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 carbon atoms.

[0075] The alkanol group (d) includes (i) C1-C 20 Straight chain alkyl group, (ii) C4-C 20 Branched alkyl groups and (iii) C3-C 20 Cycloalkyl groups. In (i), (ii) and (iii), where the structure is appropriate, 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, and further has at least one -(R)(R)-OH attached to a carbon in the alkyl group, wherein each R is independently H or an alkyl group (as just defined, having a carbonyl residue greater than the R of which it is a part) 1 , R 2 or R 3 less carbon).

[0076] The alkyl ether groups (e) substituted with -OH groups include (i) C2-C 20 Straight chain alkyl group, (ii) C4-C 20 Branched alkyl groups and (iii) C3-C 20 Cycloalkyl groups wherein (i), (ii) and (iii) have oxygen atoms (attached between carbons) within 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 having at least one -(R)(R)-OH attached to a carbon in the alkyl group, wherein each R is independently H or an alkyl group (as just defined, having an R greater than that of which it is a part) 1 , R 2 or R 3 less carbon).

[0077] The alkanolamines containing (c) or (e) are referred to as "ether-containing alkanolamines". Preferred ether-containing alkanolamines have (e) an alkyl ether group further having an -OH group. For both (d) and (e), the -(R)(R)-OH attached to the carbon is preferably a cappable group, i.e. both R groups are H.

[0078] In one embodiment, the composition includes an alkanolamine of Formula II, wherein R 1 and R 2 is hydrogen and R 3 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 In a further aspect of this embodiment, the alkanolamine consists of an alkanolamine of formula II, wherein R 1 and R 2 is hydrogen and R 3 Selected from (d) and (e).

[0079] In another embodiment, the composition includes an alkanolamine of Formula II, wherein R 1 Yes (a), R 2 is (b1), (b2) or (b3) and R 3 In a further aspect of this embodiment, the alkanolamine consists essentially of an alkanolamine of Formula II, wherein R 1 Yes (a), R 2 is (b1), (b2) or (b3) and R 3 In a further aspect of this embodiment, the alkanolamine consists of an alkanolamine of formula II, wherein R1 Yes (a), R 2 is (b1), (b2) or (b3) and R 3 Selected from (d) and (e).

[0080] In another embodiment, the composition includes an alkanolamine of Formula II, wherein R 1 and R 2 are the same or different (b1), (b2) or (b3), and R 3 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 In a further aspect of this embodiment, the alkanolamine consists of an alkanolamine of formula II, wherein R 1 and R 2 are the same or different (b1), (b2) or (b3), and R 3 Selected from (d) and (e).

[0081] In another embodiment, the composition includes an alkanolamine of Formula II, wherein R 1 , R 2 and R 3 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 In a further aspect of this embodiment, the alkanolamine consists of an alkanolamine of formula II, wherein R 1 , R 2 and R 3 All are the same or different (d).

[0082] In another embodiment, the composition includes an alkanolamine of Formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3), and R 2 and R 3 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), and R 2 and R 3 In a further aspect of this embodiment, the alkanolamine consists of an alkanolamine of formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3), and R2 and R 3 are the same or different (d).

[0083] In another embodiment, the composition includes an alkanolamine of Formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3), and R 2 and R 3 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), and R 2 and R 3 In a further aspect of this embodiment, the alkanolamine consists of an alkanolamine of formula II, wherein R 1 is selected from (a), (b1), (b2) or (b3), and R 2 and R 3 are the same or different (e).

[0084] As shown in the above structure, in some embodiments, the alkanolamines useful in the compositions of the disclosed and claimed subject matter include two or more identical or different (preferably identical) alkanol groups. In some embodiments, the alkanolamines include three or more identical or different (preferably identical) alkanol groups.

[0085] Examples of alkanolamines useful for 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), tert-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.

[0086] Monoethanolamine (MEA), methanolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol, isobutanolamine and isopropanolamine are R 1 and R 2 is hydrogen and R 3 are examples of alkanolamines of (d). N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine are examples of alkanolamines of (d). 1 and R 2 is H or b1 or b2, R 3is (d). Aminoethoxyethanol, 2-amino-2-ethoxypropanol and 2-amino-2-ethoxyethanol are wherein R 1 and R 2 is hydrogen and R 3 are examples of alkanolamines of (e). N-methyldiethanolamine, N-ethyldiethanolamine, diethanolamine, triethanolamine (TEA), tert-butyldiethanolamine are examples of alkanolamines comprising two or more 1 , R 2 and / or R 3 Those alkanolamines having the same or different (preferably the same) alkanol groups (d). 1 and R 2 When the alkanol groups are the same, R 3 Typically selected from hydrogen or straight chain, branched chain or cyclic alkyl.

[0087] In one embodiment, the one or more alkanolamines include 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).

[0088] As described 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.

[0089] As described above, in some embodiments, a mixture of three or more alkanolamines is used. Therefore, 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.

[0090] In another embodiment, the (i) at least one alkanolamine, (ii) two or more alkanolamines, or (iii) three or more alkanolamines include at least one ether-containing alkanolamine.

[0091] In one embodiment, (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.

[0092] In another embodiment, (i) at least one alkanolamine, (ii) at least two alkanolamines, and (iii) at least three alkanolamines include 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.

[0093] 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, wherein R 1 and R 2 is hydrogen and R 3 Yes(d).

[0094] In one embodiment, the composition includes about 20% to about 70% by weight of one or more alkanolamines. In one embodiment, the composition includes about 20% to about 65% by weight of one or more alkanolamines. In one embodiment, the composition includes about 35% to about 60% by weight of one or more alkanolamines. In one embodiment, the composition includes about 40% to about 55% by weight of one or more alkanolamines. In one embodiment, the composition includes about 45% to about 50% by weight of one or more alkanolamines. In one embodiment, the composition includes about 43% to about 47% by weight of one or more alkanolamines.

[0095] In one embodiment, the composition includes about 20% by weight of one or more alkanolamines. In one embodiment, the composition includes about 25% by weight of one or more alkanolamines. In one embodiment, the composition includes about 30% by weight of one or more alkanolamines. In one embodiment, the composition includes about 35% by weight of one or more alkanolamines. In one embodiment, the composition includes about 40% by weight of one or more alkanolamines. In one embodiment, the composition includes about 41% by weight of one or more alkanolamines. In one embodiment, the composition includes about 42% by weight of one or more alkanolamines. In one embodiment, the composition includes about 43% by weight of one or more alkanolamines. In one embodiment, the composition includes about 44% by weight of one or more alkanolamines. In one embodiment, the composition includes about 45% by weight of one or more alkanolamines. In one embodiment, the composition includes about 46% by weight of one or more alkanolamines. In one embodiment, the composition includes about 47% by weight of one or more alkanolamines. In one embodiment, the composition includes about 48% by weight of one or more alkanolamines. In one embodiment, the composition includes about 49% by weight of one or more alkanolamines. In one embodiment, the composition includes about 50% by weight of one or more alkanolamines.

[0096] Component C: Quaternary ammonium hydroxide

[0097] As mentioned above, one or more alkali components may 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, tri-(hydroxyethyl)methylammonium hydroxide and dimethyldipropylammonium hydroxide (DMDPAH). In some embodiments, TEAH is preferably included. In such an embodiment, TEAH is used as an aqueous solution, such as a 35 wt % aqueous solution. In other embodiments, DMDPAH is preferentially included. In such an embodiment, DMDPAH is used as a 20 wt % solution in propylene glycol. In some embodiments, ETMAH is preferentially included. In such an embodiment, ETMAH is used as an aqueous solution, such as a 20 wt % aqueous solution. In some embodiments, TMAH is preferentially included. In such an embodiment, TMAH is used as an aqueous solution, such as a 25 wt % aqueous solution. In some embodiments, the solution does not contain TMAH.

[0098] Quaternary ammonium hydroxide can be with about 0.1 % by weight to about 20 % by weight of composition, 1 % by weight to about 15 % by weight, or about 1 % by weight to about 14 % by weight, or about 1 % by weight to about 13 % by weight, or about 1 % by weight to about 12 % by weight, or about 1 % by weight to about 11 % by weight, or about 1 % by weight to about 10 % by weight, or about 1 % by weight to about 9 % by weight, or about 1 % by weight to about 8 % by weight, or about 1 % by weight to about 7 % by weight, or about 1 % by weight to about 6 % by weight, or about 1 % by weight to about 5 % by weight, or about 1 % by weight to about 4 % by weight, or about 1 % by weight to about 3 % by weight, or about 1 % by weight to about 2 % by weight, or about 0.1 % by weight to about 0.9 % by weight, or about 0.4 % by weight to about 0.5 % by weight, or about 0.1 % by weight to about any net amount of 0.2 % by weight scope exists. More preferably, there is quaternary ammonium hydroxide, but its amount is not more than about 20 % by weight. In some preferred compositions, quaternary ammonium hydroxide exists with about 8 % by weight to 15 % by weight. In some preferred compositions, the quaternary ammonium hydroxide is present in about 8% by weight to about 13% by weight. In some preferred compositions, the quaternary ammonium hydroxide is present in about 10% by weight to about 15% by weight. In some preferred compositions, the quaternary ammonium hydroxide is present in about 0.1% by weight to about 1% by weight. In some preferred compositions, the quaternary ammonium hydroxide is present in about 0.4% by weight to about 2% by weight. In some preferred compositions, the quaternary ammonium hydroxide is present in about 0.4% by weight to about 1% by weight. In some preferred compositions, the quaternary ammonium hydroxide is present in about 0.1% by weight to about 0.5% by weight.

[0099] In one embodiment, the solution includes about 0.5% to 5% by weight of clean TEAH. In a further aspect of the embodiment, the solution includes about 1% to about 4% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 1.5% to about 3.5% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 2% to about 3% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 0.5% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 1% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 1.5% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 2% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 2.5% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 3% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 3.5% by weight of clean TEAH. In another aspect of the embodiment, the solution includes about 4% by weight of clean TEAH. In another aspect of this embodiment, the solution comprises about 5 wt % neat TEAH.

[0100] In one embodiment, the solution includes about 1% to 5% by weight of neat DMDPAH. In a further aspect of this embodiment, the solution includes about 1% to about 4.5% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes 1.5% to about 4% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 2% to about 3.5% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 2% to about 3% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 2.1% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 2.2% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 2.3% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 2.4% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 2.6% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 2.8% by weight of neat DMDPAH. In another aspect of this embodiment, the solution includes about 3 wt % neat DMDPAH.

[0101] In one embodiment, the solution includes about 0.5% to 5% by weight of clean choline hydroxide. In a further aspect of this embodiment, the solution includes about 1% to about 4% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 1.5% to about 3.5% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 2% to about 3% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 0.5% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 1% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 1.5% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 2% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 2.5% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 3% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 3.5% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution includes about 4% by weight of clean choline hydroxide. In another aspect of this embodiment, the solution comprises about 5 wt % neat choline hydroxide.

[0102] In one embodiment, the solution comprises about 0.1 wt % to about 3 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.1 wt % to about 2.5 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.1 wt % to about 2 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.1 wt % to about 1.5 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.1 wt % to about 1 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.1 wt % to about 0.5 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.2 wt % to about 2 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.2 wt % to about 1.5 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.2 wt % to about 1 wt % of neat ETMAH. In one embodiment, the solution comprises about 0.2 wt % to about 0.5 wt % of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.1 wt % of neat ETMAH. In another aspect of this embodiment, the solution comprises about 0.2% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 0.3% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 0.4% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 0.5% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 0.6% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 0.7% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 0.8% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 0.9% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 1.0% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 1.1% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 1.2% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 1.3% by weight of neat ETMAAH. In another aspect of this embodiment, the solution comprises about 1.4 wt % neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.5 wt % neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.6 wt % neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.7 wt % neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.8 wt % neat ETMAH. In another aspect of this embodiment, the solution comprises about 1.9 wt % neat ETMAH. In another aspect of this embodiment, the solution comprises about 2.0 wt % neat ETMAH.

[0103] In one embodiment, the solution includes about 0.1 wt % to about 3 wt % of neat TMAH. In one embodiment, the solution includes about 0.1 wt % to about 2.5 wt % of neat TMAH. In one embodiment, the solution includes about 0.1 wt % to about 2 wt % of neat TMAH. In one embodiment, the solution includes about 0.1 wt % to about 1.5 wt % of neat TMAH. In one embodiment, the solution includes about 0.1 wt % to about 1 wt % of neat TMAH. In one embodiment, the solution includes about 0.1 wt % to about 0.5 wt % of neat TMAH. In one embodiment, the solution includes about 0.2 wt % to about 2 wt % of neat TMAH. In one embodiment, the solution includes about 0.2 wt % to about 1.5 wt % of neat TMAH. In one embodiment, the solution includes about 0.2 wt % to about 1 wt % of neat TMAH. In one embodiment, the solution includes about 0.2 wt % to about 0.5 wt % of neat TMAH. In another aspect of this embodiment, the solution includes about 0.1 wt % of neat TMAH. In another aspect of this embodiment, the solution includes about 0.2% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 0.3% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 0.4% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 0.5% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 0.6% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 0.7% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 0.8% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 0.9% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.0% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.1% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.2% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.3% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.4% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.5% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.6% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.7% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.8% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 1.9% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 2.0% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 2.1% by weight of neat TMAH. In another aspect of this embodiment, the solution includes about 2.2% by weight of neat TMAH.In another aspect of this embodiment, the solution includes about 2.3% by weight of clean TMAH. In another aspect of this embodiment, the solution includes about 2.4% by weight of clean TMAH. In another aspect of this embodiment, the solution includes about 2.5% by weight of clean TMAH. In one embodiment, the solution is substantially free of clean TMAH. In one embodiment, the solution does not contain clean TMAH.

[0104] Component D: Silicon-containing compounds

[0105] As described above, the silicon-containing compound has the formula II:

[0106]

[0107] in:

[0108] (i) m = 0-20,

[0109] (ii) R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl groups, fluorine-substituted C1 to C 10 Straight chain alkyl groups, nitrogen-containing groups, oxygen-containing groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, and

[0110] (iii) R a and R b Each independently selected from C1 to C 10 Straight chain alkyl groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, alkyl, Substituted C1-C 10 alkyl.

[0111] In some embodiments of the etching composition including the silicon-containing compound of Formula I, R 1 , R 2 , R 3 , R 4and R 5 In a further aspect of this embodiment, R 1 , R 2 , R 3 , R 4 and R 5 Each of them is hydrogen.

[0112] In some embodiments of the etching composition including the silicon-containing compound of Formula I, R 1 , R 2 , R 3 , R 4 and R 5 At least one of them is a group other than hydrogen.

[0113] In some embodiments of the etching compositions comprising the silicon-containing compound of Formula I, m=0-20. In a further aspect of this embodiment, m is 0. In another 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.

[0114] In one embodiment, the solution includes about 0.15 wt % to about 2 wt % of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution includes about 0.2 wt % to about 1.75 wt % of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution includes about 0.25 wt % to about 1.5 wt % of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution includes about 0.3 wt % to about 1.25 wt % of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution includes about 0.35 wt % to about 1.0 wt % of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution includes about 0.4 wt % to about 0.95 wt % of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution includes about 0.45 wt % to about 0.9 wt % of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution includes about 0.5 wt % to about 0.85 wt % of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises from about 0.55 wt % to about 0.8 wt % of one or more neat silicon-containing compounds of Formula I. In one embodiment, the solution comprises from about 0.6 wt % to about 0.75 wt % of one or more neat silicon-containing compounds of Formula I.

[0115] In one embodiment, the solution comprises about 0.15% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.25% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.325% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.4875% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.5% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.65% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.75% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.8% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 0.9% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.0% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.1% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.2% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.3% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.4% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.5% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.6% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.7% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.8% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 1.9% by weight of one or more neat silicon-containing compounds of formula I. In one embodiment, the solution comprises about 2.0% by weight of one or more neat silicon-containing compounds of formula I.

[0116] In some embodiments, the etching composition includes a silicon-containing compound of Formula I, wherein (i) R a and R b Each of (ii) R 1 , R 2 , R 4 and R 5 Each of and (iii) m=0.

[0117] In some embodiments, the etching composition includes a silicon-containing compound of Formula I, wherein (i) R a and R b Each of (ii) R 1 , R 2 , R 4 and R 5 Each of (iii) m = 0 and (iv)

[0118] In some embodiments, the etching composition includes a silicon-containing compound of Formula I, wherein (i) R a and R b Each of (ii) R 1 , R 2 , R 3 , R 4 and R 5 Each of and (iii) m=0.

[0119] In some embodiments, the etching composition includes a silicon-containing compound of Formula I having the following structure: (hereinafter referred to as "Si compound 1").

[0120] In one embodiment, the solution comprises about 0.15 wt % to about 2.0 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.2 wt % to about 1.75 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.25 wt % to about 1.5 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.3 wt % to about 1.25 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.35 wt % to about 1.0 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.4 wt % to about 0.95 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.05 wt % to about 0.9 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.5 wt % to about 0.85 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.55 wt % to about 0.8 wt % of the neat Si compound 1. In one embodiment, the solution comprises about 0.6 wt % to about 0.75 wt % of the neat Si compound 1.

[0121] In one embodiment, the solution comprises about 0.15 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 0.25 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 0.325 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 0.5 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 0.65 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 0.75 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 0.8 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 0.9 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 1.0 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 1.1 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 1.2 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 1.3 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 1.4 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 1.5 wt% of the neat Si compound 1. In one embodiment, the solution comprises about 1.6 wt% of neat Si compound 1. In one embodiment, the solution comprises about 1.7 wt% of neat Si compound 1. In one embodiment, the solution comprises about 1.8 wt% of neat Si compound 1. In one embodiment, the solution comprises about 1.9 wt% of neat Si compound 1. In one embodiment, the solution comprises about 2.0 wt% of neat Si compound 1.

[0122] Exemplary Embodiments of Etching Compositions

[0123] The following is an exemplary embodiment of an etching composition suitable for selectively removing silicon relative to silicon oxide from a microelectronic device, comprising:

[0124] A. one or more aqueous solvents;

[0125] B. one or more alkanolamines;

[0126] C. one or more quaternary ammonium hydroxides; and

[0127] D. One or more silicon-containing compounds.

[0128] In one embodiment, the etching composition comprises:

[0129] A.Water;

[0130] B. one or more alkanolamines of formula I:

[0131]

[0132] Where R 1 , R 2 and R 3 Each independently selected from:

[0133] (a) hydrogen,

[0134] (b1)C1-C 20 Straight chain alkyl groups,

[0135] (b2)C4-C 20 Branched alkyl groups,

[0136] (b3)C3-C 20 Cycloalkyl groups;

[0137] (c) Unsubstituted C2-C 20 Alkyl ether groups;

[0138] (d)C1-C 20 Alkanol group

[0139] (e) C2-C substituted with -OH group 20 an alkyl ether group; and

[0140] Where R 1 , R 2 and R 3 At least one of the following must be (d) or (e);

[0141] C. one or more quaternary ammonium hydroxides; and

[0142] D. one or more silicon-containing compounds of formula II:

[0143]

[0144] in:

[0145] (i) m = 0-20,

[0146] (ii) R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl groups, fluorine-substituted C1 to C 10 Straight chain alkyl groups, nitrogen-containing groups, oxygen-containing groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, and

[0147] (iii) R a and R b Each independently selected from C1 to C 10 Straight chain alkyl groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, alkyl, Substituted C1-C 10 alkyl.

[0148] In one embodiment, the etching composition comprises:

[0149] A.Water;

[0150] B. Monoethanolamine (MEA);

[0151] C. Ethyltrimethylammonium hydroxide (ETMAH; and

[0152] D.Si compound 1.

[0153] In one embodiment, the etching composition comprises:

[0154] A. about 35% to about 60% by weight water;

[0155] B. about 20.0 wt % to about 70.0 wt % monoethanolamine (MEA);

[0156] C. about 0.1 wt % to about 3 wt % ethyltrimethylammonium hydroxide (ETMAH); and

[0157] D. About 0.15 wt % to about 2.0 wt % of neat Si compound 1.

[0158] Other ingredients

[0159] Etching compositions, including those exemplified above, may include other optional components as described below.

[0160] Other silicon-containing compounds

[0161] In some embodiments, the mixture may include additional silicon-containing compounds other than those of Formula 1. Such additional silicon-containing compounds may be one or more of alkyl silsesquioxanes, vinyl silsesquioxanes, carboxylic acid alkyl silsesquioxanes, and alkylene glycol alkyl silsesquioxanes.

[0162] Hydroxyl-containing water-miscible solvents

[0163] In some embodiments, the mixture may include a hydroxyl-containing water-miscible solvent. The hydroxyl-containing water-miscible solvent primarily functions to protect silicon oxide so that silicon is preferentially and selectively etched.

[0164] Classes of suitable hydroxyl-containing water-miscible solvents include, but are not limited to, alkane diols and polyols (including, but not limited to, alkylene glycols), diols, alkoxy alcohols (including, but not limited to, glycol monoethers), saturated aliphatic monools, unsaturated non-aromatic monools, and low molecular weight alcohols containing ring structures.

[0165] Suitable water-soluble alkanediols and polyols (such as (C2-C 20 ) alkanediol and (C3-C 20 Examples of 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] Examples of suitable water-soluble saturated aliphatic monohydric alcohols include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 2-pentanol, tert-pentanol, 1-hexanol, and mixtures thereof.

[0170] Examples of suitable water-soluble unsaturated non-aromatic monohydric alcohols include, but are not limited to, allyl alcohol, propargyl alcohol, 2-butenol, 3-butenol, 4-penten-2-ol, and mixtures thereof.

[0171] Examples of suitable water-soluble low molecular weight alcohols containing a ring structure include, but are not limited to, α-terpineol, tetrahydrofurfuryl alcohol, furfuryl alcohol, 1,3-cyclopentanediol, and mixtures thereof.

[0172] In some embodiments, the amount of hydroxyl-containing water-miscible solvent is from about 1.0% to about 30% by weight of the composition. Preferably, when used, the hydroxyl-containing water-miscible solvent is from about 5% to about 15% by weight of the composition.

[0173] 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.

[0174] Silicic acid

[0175] In some embodiments, the mixture may include silicic acid. If used, silicic acid helps protect silicon oxide and increases the selectivity of silicon etching.

[0176] In some embodiments, the amount of silicic acid is about 0.001% to about 5.0% by weight of the composition, and preferably about 0.01% to about 2.0% by weight. In other embodiments, silicic acid is about 0.02% to about 0.08% by weight of the composition.

[0177] In some embodiments, the compositions of the disclosed and claimed subject matter are free or substantially free of added silicic acid.

[0178] Surfactants

[0179] In some embodiments, the mixture may include at least one water-soluble nonionic surfactant. The surfactant is used to aid in the removal of residues.

[0180] Examples of water-soluble nonionic surfactants 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 sorbitan tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamines, polyoxyethylene hardened castor oil, alkyl alkanolamides, and mixtures thereof.

[0181] In some embodiments, the amount of surfactant is from about 0.001 wt % to about 5 wt %, preferably from about 0.01 wt % to about 2.5 wt %, and most preferably from about 0.1 wt % to about 1.0 wt % of the composition.

[0182] In some embodiments, the compositions of the disclosed and claimed subject matter are free or substantially free of surfactants.

[0183] In some embodiments, the composition is substantially free or free of metal hydroxides, added metals, halogen-containing compounds, TEOS, silyl phosphate compounds, and silanes and silanols excluding repeating monomers.

[0184] Manufacturing method

[0185] The disclosed and claimed subject matter also includes methods of making the etching compositions described and claimed herein.

[0186] In one embodiment, a method for forming an etching composition comprises combining:

[0187] A. one or more aqueous solvents;

[0188] B. one or more alkanolamines;

[0189] C. one or more quaternary ammonium hydroxides; and

[0190] D. One or more silicon-containing compounds.

[0191] In one embodiment, a method for forming an etching composition comprises combining:

[0192] A.Water;

[0193] B. one or more alkanolamines of formula I:

[0194]

[0195] Where R 1 , R 2 and R 3 Each independently selected from:

[0196] (a) hydrogen,

[0197] (b1)C1-C 20 Straight chain alkyl groups,

[0198] (b2)C4-C 20 Branched alkyl groups,

[0199] (b3)C3-C 20 Cycloalkyl groups;

[0200] (c) Unsubstituted C2-C 20 Alkyl ether groups;

[0201] (d)C1-C 20 Alkanol group

[0202] (e) C2-C substituted with -OH group 20 an alkyl ether group; and

[0203] Where R 1 , R 2 and R 3 At least one of the following must be (d) or (e);

[0204] C. one or more quaternary ammonium hydroxides; and

[0205] D. one or more silicon-containing compounds of formula II:

[0206]

[0207] in:

[0208] (i) m = 0-20,

[0209] (ii) R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl groups, fluorine-substituted C1 to C 10 Straight chain alkyl groups, nitrogen-containing groups, oxygen-containing groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, and

[0210] (iii) R a and R b Each independently selected from C1 to C 10 Straight chain alkyl groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, alkyl, Substituted C1-C 10 alkyl.

[0211] In one embodiment, a method for forming an etching composition comprises combining:

[0212] A.Water;

[0213] B. Monoethanolamine (MEA);

[0214] C. ethyltrimethylammonium hydroxide (ETMAH); and

[0215] D.SI compound 1.

[0216] In one embodiment, a method for forming an etching composition comprises combining:

[0217] A. about 35% to about 60% by weight water;

[0218] B. about 20.0 wt % to about 70.0 wt % monoethanolamine (MEA);

[0219] C. about 0.1 wt % to about 3 wt % ethyltrimethylammonium hydroxide (ETMAH); and

[0220] D. About 0.015 wt % to about 0.2 wt % of neat Si compound 1.

[0221] How to use

[0222] The disclosed and claimed subject matter also includes methods of using the disclosed and claimed etching compositions to selectively remove silicon films while minimizing the etch rate of oxide films, and methods for fabricating semiconductors that include etching processes using the disclosed and claimed etching compositions.

[0223] In one embodiment, the method comprises the following steps:

[0224] a. contacting a composite semiconductor device comprising a silicon film with one or more etching compositions disclosed and / or claimed herein, and

[0225] b. Rinsing the composite semiconductor device after at least partially removing the silicon film.

[0226] In a further aspect of this embodiment, the contacting step is performed at a temperature of about 25°C to about 90°C.

[0227] In a further embodiment, the method may include c. a drying step.

[0228] In the described methods, "at least partially removed" means at least 90% of the material is removed using the composition of the present invention, preferably at least 95% removal. Most preferably, at least 99% removal. "Si oxide compatible" means less than 10% film loss.

[0229] In a further embodiment, the method may include a pretreatment step comprising contacting the substrate with dilute hydrofluoric acid ("DHF") (1:100 HF:water) (e.g., by immersion or spraying). Further damage due to the dHF pretreatment step may be minimized by reducing agitation when treating with the composition of the disclosed and claimed subject matter and by reducing the time between pretreatment and contact with the disclosed and claimed composition.

[0230] In some embodiments, the contacting step can be performed by any suitable means, such as immersion, spraying, or via a single wafer process.

[0231] In some embodiments, the temperature of the composition during the contacting step is preferably from about 25° C. to about 90° C. In a further aspect, the temperature is from about 40° C. to about 80° C. In a further aspect, the temperature of the composition during the contacting step is about 75° C.

[0232] In some embodiments, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide of about 300 to about 5000. In some embodiments, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide of about 500 to about 4000. In some embodiments, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide of about 1000 to about 3000. In some embodiments, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide of about 1000 to about 2000. In some embodiments, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide of about 1000 to about 1500. In some embodiments, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide of about 500 to about 1500. In some embodiments, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide of about 500 to about 2000.

[0233] In some embodiments, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide exceeding about 300. In a further aspect, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide exceeding about 500. In another aspect, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide exceeding about 1000. In a further aspect, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide exceeding about 1250. In a further aspect, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide exceeding about 1500. In a further aspect, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide exceeding about 2000. In a further aspect, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide exceeding about 2500. In a further aspect, the disclosed and claimed subject etching compositions have an etch selectivity of silicon relative to silicon oxide exceeding about 3000. In a further aspect, the disclosed and claimed subject etching composition has an etch selectivity of silicon to silicon oxide in excess of about 3500. In a further aspect, the disclosed and claimed subject etching composition has an etch selectivity of silicon to silicon oxide in excess of about 4000. In a further aspect, the disclosed and claimed subject etching composition has an etch selectivity of silicon to silicon oxide in excess of about 4500. In a further aspect, the disclosed and claimed subject etching composition has an etch selectivity of silicon to silicon oxide in excess of about 5000.

[0234] In some embodiments, the silicon oxide etch is less than In a further aspect, the silicon oxide etch is less than In a further aspect, the silicon oxide etch is less than

[0235] In some embodiments, the rinsing step c. is performed by any suitable means, such as rinsing the substrate with deionized water by immersion or spraying techniques. In another aspect, the rinsing step is performed using a mixture of deionized water and a water-miscible organic solvent such as, for example, isopropyl alcohol.

[0236] In some embodiments, the drying step is performed by any suitable means, such as isopropyl alcohol (IPA) vapor drying, heating, or by centrifugal force.

[0237] Example

[0238] Reference will now be made to more specific embodiments of the present disclosure and to experimental results that provide support for these embodiments.Examples are given below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0239] It is obvious to those skilled in the art that various modifications and variations may be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, the disclosed subject matter (including the description provided by the following embodiments) is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claims and their equivalents.

[0240] Materials and methods:

[0241] All ingredients used herein are commercially available.

[0242] In the examples, the following silicon-containing compounds were used:

[0243]

[0244]

[0245] General Procedure for Preparing Etching Compositions

[0246] All compositions presented in the examples were prepared by mixing the components in a 250 mL beaker with a 1" Teflon coated stir bar. Typically, the first material added to the beaker was deionized (DI) water.

[0247] Substrate composition

[0248] Each of the test samples used in the examples includes a 20 mm×20 mm polysilicon wafer, an α-silicon wafer, and a TEOS oxide wafer.

[0249] Processing conditions

[0250] Etching tests were conducted using 100 g of the etching composition in a 250 mL beaker with a 1 "Teflon coated stirring 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. Prior to testing, polysilicon and patterned test substrate pieces (test coupons) were treated with DHF (1:100 HF:DI water) for about 3 minutes, and SiOx test coupons were not pre-treated with DHF. The test coupons were immersed in the composition for about 1 minute (for silicon substrates) to about 90 minutes (for SiOx substrates) while stirring.

[0251] The segments were then rinsed in a deionized water bath or spray for approximately 3 minutes and subsequently dried using filtered nitrogen. The silicon and silicon oxide etch rates were estimated from the change in thickness before and after etching and were measured by spectroscopic ellipsometer (FilmTek TM 2000PAR-SE, Scientific Computing International) measurement.

[0252] The following series of tables show the evaluation results of several embodiments of the disclosed and claimed etching compositions. Unless otherwise stated, all example values ​​are reported as "net" values. In addition, performance wafer testing was not performed for samples that did not meet the selectivity or etching rate requirements.

[0253]

[0254]

[0255] Table 1: Effect of different Si-containing oxide inhibitors in NH4OH

[0256] Table 1 demonstrates that the silicon oxide etching rate can be suppressed by adding the Si-containing compound of formula II and fluorosilicic acid to the NH4OH solution, while the silicon etching rate remains at the same level.

[0257]

[0258] Table 2: Effect of different Si-containing oxide inhibitors in QAH (ETMAH)

[0259] Table 2 demonstrates that the silicon oxide etching rate can be suppressed by adding the Si-containing compound of formula II and fluorosilicic acid to the QAH solution. It can be seen that the Si-containing compound shows better protection ability. In addition, by using QAH as the alkaline source, the silicon etching rate is much higher and remains at the same level when adding the Si-containing compound and fluorosilicic acid.

[0260]

[0261]

[0262] Table 3: Effects of different concentrations of ETMAH

[0263] Table 3 further shows that the silicon etching rate can be improved when a higher content of QAH is introduced, but the selectivity of Si to SiOx becomes lower.

[0264]

[0265] Table 4: Effect of temperature

[0266] Table 4 shows the effect on the formulation of Example 10 when used for etching at different temperatures. As shown in Table 4, the silicon etching rate can be promoted by increasing the process temperature, but the selectivity of Si to SiOx becomes lower. In addition, the silicon residue cannot be removed with such a high etching rate at 75°C.

[0267]

[0268]

[0269] Table 5: Evaluation of Si compound 1 at different concentrations

[0270] Table 5 shows that the silicon oxide etch rate is high when processed at 75° C. It can be seen that the silicon oxide etch rate is suppressed by adding more Si-containing compound.

[0271]

[0272] Table 6: Different ratios of water to solvent (MEA) (QAH = ETMAH)

[0273] Table 6 shows the ability of several disclosed and claimed formulations to remove silicon residues on patterned structures by incorporating different levels of alkanolamine. It should be noted that when the solvent to water ratio is too high (e.g., greater than about 2.4; see Example 18), residual material also remains on the wafer surface.

[0274]

[0275]

[0276] Table 7: Evaluation of Si compound 1 at different concentrations

[0277] Table 7 shows that the silicon oxide etch rate can also be suppressed by adding more Si-containing compound at the same time as the introduction of the alkanolamine.

[0278]

[0279] Table 8: Effects of different concentrations of ETMAH

[0280] Table 8 demonstrates that the polysilicon etching rate can be increased by increasing the QAH content.

[0281]

[0282]

[0283] Table 9: Different water to solvent (MEA) ratios (QAH = TMAH)

[0284] Table 9 demonstrates the composition using TMAH as the QAH.

[0285]

[0286] Table 10: Impact of 2.38% TMAH (net)

[0287] Table 10 provides a comparative formulation using about 2.4 wt % TMAH. As can be seen, the TMAH formulation of Table 9 exhibits superior Si to SiOx selectivity and residue removal over the TMAH-only composition.

[0288] Summarize

[0289] The disclosed and claimed subject matter relates to semi-aqueous etching compositions for polysilicon exhume applications. The formulated chemistry can completely remove polysilicon without residues and without observed damage to SiOx by treating with comparable treatment times compared to conventional alkaline solutions. Significantly, the disclosed and claimed compositions include Si-containing oxide inhibitors that inhibit oxide etching rates and promote selectivity of Si relative to SiOx in alkaline chemistries. In addition, the cleaning performance of the disclosed and claimed compositions can be "tuned" for specific applications by controlling the ratio of water to solvent.

[0290] The foregoing description is primarily for illustrative purposes. Although the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments of the disclosed and claimed subject matter, it will be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions may be made in form and detail without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. An etching composition comprising: A. one or more aqueous solvents; B. one or more alkanolamines; C. one or more quaternary ammonium hydroxides; and D. One or more silicon-containing compounds.

2. The etching composition of claim 1, wherein the one or more aqueous solvents comprises water.

3. The etching composition of claim 1, wherein the one or more aqueous solvents comprise about 35 wt % to about 65 wt % water.

4. The etching composition of claim 1, wherein the one or more aqueous solvents consist of water.

5. The etching composition of claim 1, wherein the one or more aqueous solvents consist essentially of water.

6. The etching composition of claim 1, wherein the one or more alkanolamines comprise an alkanolamine of Formula I: Where R 1 , R 2 and R 3 Each independently selected from: (a) hydrogen, (b1)C1-C 20 Straight chain alkyl groups, (b2)C4-C 20 Branched alkyl groups, (b3)C3-C 20 Cycloalkyl groups; (c) Unsubstituted C2-C 20 Alkyl ether groups; (d)C1-C 20 Alkanol group; (e) C2-C substituted with -OH group 20 an alkyl ether group, and Where R 1 , R 2 and R 3 At least one of the following must be (d) or (e).

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

8. The etching composition of claim 1, wherein the one or more alkanolamines of Formula I comprise about 20.0 wt% to about 70.0 wt% monoethanolamine (MEA).

9. The etching composition of claim 1, wherein the one or more alkanolamines of Formula I consist essentially of monoethanolamine (MEA).

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

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

12. The etching composition of claim 1, wherein the one or more quaternary ammonium hydroxides comprise from about 0.1 wt% to about 3 wt% neat ETMAH.

13. The etching composition of claim 1, wherein the one or more quaternary ammonium hydroxides consists essentially of ETMAH.

14. The etching composition of claim 1, wherein the one or more quaternary ammonium hydroxides consist of ETMAH.

15. The etching composition of claim 1, wherein the one or more quaternary ammonium hydroxides comprise from about 0.1 wt% to about 3 wt% neat TMAH.

16. The etching composition of claim 1, wherein the one or more quaternary ammonium hydroxides consists essentially of TMAH.

17. The etching composition of claim 1, wherein the one or more quaternary ammonium hydroxides consist of TMAH.

18. The etching composition of claim 1, wherein the one or more silicon-containing compounds comprise a compound of Formula II: in: (i) m = 0-20, (ii) R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl groups, fluorine-substituted C1 to C 10 Straight chain alkyl groups, nitrogen-containing groups, oxygen-containing groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, and (iii) R a and R b Each independently selected from C1 to C 10 Straight chain alkyl groups, C3 to C 10 Branched alkyl groups, C3 to C 10 Cycloalkyl groups, C5 to C 12 Aryl group, C2 to C 10 A straight chain or branched alkenyl group and a C2 to C 10 a straight-chain or branched alkynyl group, alkyl, Substituted C1-C 10 alkyl.

19. The composition of claim 1, wherein in the compound of formula II, R 1 , R 2 , R 3 , R 4 and R 5 Each of them is identical.

20. The composition of claim 1, wherein in the compound of formula II, R 1 , R 2 , R 3 , R 4 and R 5 Each of them is hydrogen.

21. The composition of claim 1, wherein in the compound of formula II, R 1 , R 2 , R 3 , R 4 and R 5 At least one of them is a group other than hydrogen.

22. The composition of claim 1, wherein in the compound of formula II, m is 0.

23. The composition of claim 1, wherein the composition comprises from about 0.15 wt. % to about 2.0 wt. % neat of the one or more compounds of Formula II.

24. The composition of claim 1, wherein the composition comprises from about 0.25 wt. % to about 1.5 wt. % neat of the one or more compounds of Formula II.

25. The composition of claim 1, wherein the composition comprises about 0.325 wt. % neat of the one or more compounds of Formula II.

26. The composition of claim 1, wherein the composition comprises about 0.65% by weight neat of the one or more compounds of Formula II.

27. The composition of claim 1, wherein the composition comprises about 1.0 wt. % neat of the one or more compounds of Formula II.

28. The composition of claim 1, wherein the composition comprises from about 0.15% to about 2.0% by weight of neat 29. The composition of claim 1, wherein the composition comprises from about 0.25% to about 1.5% by weight of neat 30. The composition of claim 1, wherein the composition comprises about 0.325% by weight of neat 31. The composition of claim 1, wherein the composition comprises about 0.65% by weight of neat 32. The composition of claim 1, wherein the composition comprises about 1.0% by weight of neat 33. The etching composition of claim 1, comprising: A.Water; B. Monoethanolamine (MEA); C. ethyltrimethylammonium hydroxide (ETMAH); and D.

34. The etching composition of claim 1, comprising: A. about 35% to about 60% by weight water; B. about 20.0 wt % to about 70.0 wt % monoethanolamine (MEA); C. about 0.1 wt % to about 3 wt % ethyltrimethylammonium hydroxide (ETMAH); and D. About 0.15 wt % to about 2.0 wt % of the net 35. The composition of claim 1, wherein the composition further comprises one or more additional silicon-containing compounds selected from the group consisting of alkyl silsesquioxanes, vinyl silsesquioxanes, carboxylic acid alkyl silsesquioxanes, and alkylene glycol alkyl silsesquioxanes.

36. The composition of claim 1, wherein the composition further comprises one or more hydroxyl-containing water-miscible solvents selected from alkanediols, polyols, diols, alkoxy alcohols, saturated aliphatic monoalcohols, unsaturated non-aromatic monoalcohols, and low molecular weight alcohols containing ring structures.

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

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

39. The etching composition of claim 1, comprising: A. about 52.6% by weight of water; B. about 46.5 weight percent monoethanolamine (MEA); C. about 0.4 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. About 0.5% by weight of net 40. The etching composition of claim 1, comprising: A. about 52.6125% by weight of water; B. about 46.5 weight percent monoethanolamine (MEA); C. about 0.4 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. About 0.4875% by weight of net 41. The etching composition of claim 1, comprising: A. about 39% by weight of water; B. about 60% by weight of monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.5 wt. % neat 42. The etching composition of claim 1, comprising: A. about 39.1125% by weight of water; B. about 60% by weight of monoethanolamine (MEA); C. about 0.4 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.4875 weight percent neat 43. The etching composition of claim 1, comprising: A. about 29% by weight of water; B. about 70% by weight of monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.5 wt. % neat 44. The etching composition of claim 1, comprising: A. about 29.1125% by weight of water; B. about 70% by weight of monoethanolamine (MEA); C. about 0.4 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.4875 weight percent neat 45. The etching composition of claim 1, comprising: A. about 22.6% by weight of water; B. about 76.5 wt. % monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.5 wt. % neat 46. ​​The etching composition of claim 1, comprising: A. about 22.6125% by weight of water; B. about 76.5 wt. % monoethanolamine (MEA); C. about 0.4 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.4875 weight percent neat 47. The etching composition of claim 1, comprising: A. about 53% by weight of water; B. about 46% by weight of monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.6 wt. % neat 48. The etching composition of claim 1, comprising: A. about 52.95% by weight of water; B. about 46% by weight of monoethanolamine (MEA); C. about 0.4 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.65 weight percent neat 49. The etching composition of claim 1, comprising: A. about 53.6% by weight of water; B. about 45% by weight of monoethanolamine (MEA); C. about 0.4 wt. % neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 1 wt. % neat 50. The etching composition of claim 1, comprising: A. about 53.625% by weight of water; B. about 45% by weight of monoethanolamine (MEA); C. about 0.4 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.975 weight percent neat 51. The etching composition of claim 1, comprising: A. about 52% by weight of water; B. about 46.5 weight percent monoethanolamine (MEA); C. about 1 wt % neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.5 wt % neat 52. The etching composition of claim 1, comprising: A. about 52.0125% by weight of water; B. about 46.5 weight percent monoethanolamine (MEA); C. about 1 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.4875 weight percent neat 53. The etching composition of claim 1, comprising: A. about 51% by weight of water; B. about 46.5 weight percent monoethanolamine (MEA); C. about 2 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.5 weight percent neat 54. The etching composition of claim 1, comprising: A. about 51.0125% by weight of water; B. about 46.5 weight percent monoethanolamine (MEA); C. about 2 weight percent neat ethyltrimethylammonium hydroxide (ETMAH); and D. about 0.4875 weight percent neat 55. The etching composition of claim 1, comprising: A. about 52.5% by weight of water; B. about 45% by weight of monoethanolamine (MEA); C. about 2 wt % neat tetramethylammonium hydroxide (TMAH); and D. About 0.5% by weight of net 56. The etching composition of claim 1, comprising: A. about 52.514% by weight of water; B. about 45% by weight of monoethanolamine (MEA); C. about 2 wt % neat tetramethylammonium hydroxide (TMAH); and D. about 0.486 wt % neat 57. The etching composition of claim 1, comprising: A. about 47.5% by weight of water; B. about 50 wt. % monoethanolamine (MEA); C. about 2 wt % neat tetramethylammonium hydroxide (TMAH); and D. about 0.5 wt % neat 58. The etching composition of claim 1, comprising: A. about 47.514% by weight of water; B. about 50 wt. % monoethanolamine (MEA); C. about 2 wt % neat tetramethylammonium hydroxide (TMAH); and D. about 0.5 wt % neat 59. The etching composition of claim 1, comprising: A. about 42.5% by weight of water; B. about 55% by weight of monoethanolamine (MEA); C. about 2 wt % neat tetramethylammonium hydroxide (TMAH); and D. about 0.486 wt % neat 60. The etching composition of claim 1, comprising: A. about 42.514% by weight of water; B. about 55% by weight of monoethanolamine (MEA); C. about 2 wt % neat tetramethylammonium hydroxide (TMAH); and D. about 0.486 wt % neat 61. The etching composition of claim 1, comprising: A. about 37.5% by weight of water; B. about 60% by weight of monoethanolamine (MEA); C. about 2 wt % neat tetramethylammonium hydroxide (TMAH); and D. About 0.5% by weight of net 62. The etching composition of claim 1, comprising: A. about 37.514% by weight of water; B. about 60% by weight of monoethanolamine (MEA); C. about 2 wt % neat tetramethylammonium hydroxide (TMAH); and D. About 0.486% by weight of net 63. The composition of any one of claims 1-61, wherein the composition has an etch selectivity of silicon to silicon oxide of about 2700.

64. The composition of any one of claims 1-61, wherein the composition has an etch selectivity of silicon to silicon oxide of about 2500 or more.

65. The composition of any one of claims 1-61, wherein the composition has an etch selectivity of silicon to silicon oxide of about 2250 or more.

66. The composition of any one of claims 1-61, wherein the composition has an etch selectivity of silicon to silicon oxide of about 2000 or more.

67. The composition of any one of claims 1-61, wherein the composition has an etch selectivity of silicon to silicon oxide of about 1500 or more.

68. The composition of any one of claims 1-61, wherein the composition has an etch selectivity of silicon to silicon oxide of about 1250 or more.

69. The composition of any one of claims 1-61, wherein the composition has an etch selectivity of silicon to silicon oxide of about 1000 or more.

70. The composition of any one of claims 1-3, wherein the composition has an etch selectivity of silicon to silicon oxide of about 500 or more.

71. The composition of any one of claims 1-3, wherein the composition has an etch selectivity of silicon to silicon oxide of about 300 or more.

72. A method for selectively increasing the etch rate of silicon relative to silicon dioxide on a semiconductor substrate comprising silicon and silicon dioxide, the method comprising the steps of: a. contacting the semiconductor substrate comprising silicon and silicon dioxide with a composition as described in any one of claims 1-70; and b. Rinsing the semiconductor device after at least partially removing the silicon.

73. The method of claim 71 further comprising the step of drying the semiconductor device.

74. The method of claim 71, wherein the contacting step is performed at a temperature of about 25°C to about 90°C.

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