Etching composition and etching method for selectively removing silicon nitride during semiconductor device fabrication

Abstract

To provide an etching composition containing a mixture of (A) phosphoric acid and (B) a silicon-containing compound (i) and an aqueous solvent (ii).SOLUTION: In some embodiments, this etching composition contains additional components. The etching compositions are useful for selectively removing silicon nitride from a microelectronic element having silicon nitride or silicon oxide rather than silicon oxide during manufacture of the microelectronic element.SELECTED DRAWING: None

Description

[Technical field]

[0001] Field

[0002] The subject matter disclosed and claimed herein relates to etching compositions, and more particularly to highly selective etching compositions capable of selectively removing nitride films while minimizing the etch rate of oxide films, and methods for semiconductor manufacturing that include etching processes using said etching compositions. [Background technology]

[0003] Related Technology

[0004] Sacrificial Silicon Nitride (SiN x ) Selective removal is one of the key steps in the fabrication of 3D-NAND memory devices. After etching, the SiN x is removed and SiO x The fin structure is unchanged. x ) core remains. Traditionally, SiN x Etching can be accomplished with hot phosphoric acid at 160°C, but the SiN etching rate is higher than that of silicon or silicon oxide materials. x Etching selectivity is generally low for advanced 3D-NAND memory technology.

[0005] As semiconductor devices become more highly integrated, their reliability and electrical characteristics become more susceptible to damage or deformation of the layers that make up the semiconductor devices. Therefore, when performing an etching process to selectively remove a particular material layer using an etching solution, it is desirable for the etching solution to have high etching selectivity with respect to other material layers, thereby reducing by-products produced by the etching process and reducing in-process defects. Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, at such high integration density, sacrificial SiN in 3D-NAND manufacturing isx The importance of the material selectivity requirement for selective removal becomes high, and SiN x while etching the layer, it is desirable to effectively keep the SiO x layer unchanged. Therefore, it is required in the art to further suppress the SiO x etching rate to achieve a higher SiN x selectivity. x

Means for Solving the Problem

Means for Solving the Problem

[0007] In one aspect, the subject matter of the present disclosure and the claims is an etching composition suitable for the selective removal of silicon nitride over silicon oxide from a microelectronic device, (A) phosphoric acid, and (B) a mixture comprising an aqueous solvent and a silicon-containing compound (which may also be referred to as an organosilicon compound) is provided.

[0008] In some embodiments, the silicon-containing compound has the formula I,

Chemical formula

Chem.

Chem.

Chem.

[0009] In some embodiments, the silicon-containing compound has Formula II,

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0010] In some embodiments, the silicon-containing compound has Formula III,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0011] In some embodiments, the etching composition comprises up to about 70% by weight of pure phosphoric acid. In other aspects of this embodiment, the etching composition comprises up to about 60% by weight of pure phosphoric acid. In other aspects of this embodiment, the etching composition comprises at least about 30% by weight of the mixture. In other aspects of this embodiment, the etching composition comprises at least about 40% by weight of the mixture. In other aspects of this embodiment, the pure phosphoric acid and the mixture together constitute about 100% by weight of the etching composition.

[0012] In some embodiments, the etching composition comprises more than about 70% by weight of pure phosphoric acid. In other aspects of this embodiment, the etching composition comprises more than about 75% by weight of pure phosphoric acid. In other aspects of this embodiment, the etching composition comprises up to about 30% by weight of the mixture. In other aspects of this embodiment, the etching composition comprises at least about 25% by weight of the mixture. In other aspects of this embodiment, the pure phosphoric acid and the mixture together constitute about 100% by weight of the etching composition.

[0013] In some embodiments, the mixture further comprises at least one additional acid other than phosphoric acid. In one aspect of this embodiment, this at least one additional acid is one of nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), and sulfonic acid (methanesulfonic acid (CH 3 SO 3 H), etc.). In other aspects, this at least one additional acid comprises sulfuric acid.

[0014] In another aspect, the subject matter of the present disclosure and the claims provides a method for selectively improving the etching rate of silicon nitride compared to silicon dioxide on a composite semiconductor device comprising silicon nitride and silicon dioxide, the method comprising contacting the composite semiconductor device comprising silicon nitride and silicon dioxide with the etching composition.

[0015] In some embodiments, the compounds of Formula I, Formula II, and / or Formula III can include additional selectable groups such as epoxy groups, styryl groups, metasiloxy groups, acyloxy groups, ureido groups, isocyanato groups, isocyanurate groups, and mercapto groups at one or more hydrogen positions.

[0016] These embodiments of the present disclosure and the subject matter of the present claims may be used alone or in combination with each other.

Mode for Carrying Out the Invention

[0017] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference in their entirety 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.

[0018] In the context of the present disclosure and the description of the subject matter of the present claims (particularly the following claims), the terms "a," "an," and "the," and similar designators, are to be construed to include both the singular and the plural, unless otherwise indicated herein or clearly contradicted by the context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to") unless otherwise noted. The recitation of a range of values herein is intended merely as a convenient method of referring individually to each separate value falling within the range, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "such as") presented herein is merely intended to better illustrate the present disclosure and the subject matter of the present claims and is not intended to limit the scope of the present disclosure and the subject matter of the present claims, unless otherwise claimed in the claims. There is no representation herein that any element not claimed in the claims is essential to the practice of the subject matter of the present disclosure and the present claims.

[0019] The preferred embodiments of the present disclosure and the subject matter of the present claims are described herein and include the best mode known to the inventors for carrying out the present disclosure and the subject matter of the present claims. Variations of these preferred embodiments may become apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to employ these variations as appropriate, and the inventors intend that the present disclosure and the subject matter of the present claims be practiced in a manner different from that specifically described herein. Accordingly, the present disclosure and the subject matter of the present claims include all modifications and equivalents of the subject matter enumerated in the claims appended hereto as permitted by applicable law. Also, all combinations of those elements in all possible variations thereof are included in the present disclosure and the subject matter of the present claims unless otherwise indicated herein or clearly precluded from the context.

[0020] The present disclosure and the subject matter of the present claims generally relate to compositions useful for selectively removing silicon nitride over silicon oxide from microelectronic devices having silicon nitride and silicon oxide during the manufacture of such microelectronic devices.

[0021] For ease of reference, a "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 power, and microelectromechanical systems (MEMS) manufactured for use in microelectronic applications, integrated circuit applications, or computer chip applications. Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide. The solar substrate may be doped or undoped. It should be understood that the term "microelectronic device" has no limiting meaning whatsoever and includes any substrate that ultimately becomes a microelectronic device or microelectronic assembly. These microelectronic devices or semiconductor substrates may include low dielectric constant (k) dielectric materials, barrier materials, and metals such as AlCu alloys, W, Ti, TiN, and other materials on the microelectronic device or semiconductor substrate.

[0022] As defined herein, a "low dielectric constant (k) dielectric material" corresponds to any material having a dielectric constant of less than about 3.5 used as a dielectric material in a layered microelectronic device. These low dielectric constant (k) dielectric materials preferably include low polarity materials such as silicon-containing organic polymers, silicon-containing organic / inorganic hybrid materials, organosilicate glass (OSG), TEOS, fluorine-doped silicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It should be understood that these low dielectric constant (k) dielectric materials can have various densities and various porosities.

[0023] As defined herein, the term "barrier material" corresponds to any material used in the art to seal a metal wire, such as a copper wiring, in order to minimize the diffusion of a metal, such as copper, into the dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

[0024] As used herein, "substantially free" is defined as less than 2% by mass, preferably less than 1% by mass, more preferably less than 0.5% by mass, and most preferably less than 0.1% by mass. "Substantially free" includes 0.0% by mass. The term "free" means 0.0% by mass.

[0025] As used herein, the terms "about" and "approximately" are each intended to correspond to ±5% of the indicated value.

[0026] As used herein, "pure" refers to the mass percentage amount of an undiluted acid or other material. For example, what is contained in 100 g of 85% phosphoric acid is composed of 85 g of the acid and 15 grams of a diluent.

[0027] In addition to the representations known and understood as covalent bond connection points

Chemical formula

[0028] In all such compositions where a particular component of the composition is discussed with reference to a mass percentage range that includes a zero lower limit, such a component may or may not be present in various specific embodiments of the composition. And in examples where such components are present, it should be understood that those components may be present at a low concentration of as little as 0.001 mass percent relative to the total mass of the composition in which such components are used. It should be noted that all specified mass percentages of these components are based on the total mass of the composition unless otherwise indicated. Further, all mass percentages are "pure" unless otherwise indicated, meaning that aqueous compositions in which these components are added to the composition and in which those components are present are not included. Whenever "at least 1" is referred to, it can always be replaced by "1 or more". "At least 1" or "1 or more" includes "at least 2" or "2 or more" and "at least 3" or "3 or more", etc.

[0029] Broadly speaking, the embodiments of the present disclosure and the subject matter of the claims relate to the above-described etching compositions that comprise, or consist essentially of, or consist of a mixture of (A) phosphoric acid and (B) a silicon-containing compound disclosed herein and an aqueous solvent. In some embodiments, the etching composition can include other components.

[0030] In some embodiments, the etching composition disclosed herein is formulated to be substantially free of at least one of the following compounds: hydrogen peroxide and other peroxides, ammonium ions, fluoride ions, inorganic bases, quaternary ammonium hydroxides, metal-containing compounds, and abrasives.

[0031] In other embodiments, the etching composition consists essentially of (i) phosphoric acid and (ii) the mixture of the silicon-containing compound disclosed herein and the aqueous solvent. In such embodiments, the total amount of (i) and (ii) is not equal to 100 mass%, and other components that do not substantially change the effectiveness of the etching composition can be included.

[0032] In another embodiment, the etching composition consists of (i) phosphoric acid and (ii) the silicon-containing compounds disclosed herein at various concentrations and the aqueous solvent. In such an embodiment, the total amount of (i) and (ii) is equal to 100% by mass, but may contain small amounts and / or trace amounts of other impurities present in such 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 mass or less of impurities. In another embodiment, the etching composition may contain 1% by mass or less of impurities. In other embodiments, the etching composition may contain 0.05% by mass or less of impurities.

[0033] When referring to the composition of the compositions of the present invention described herein in terms of mass%, it is understood that the mass% of all components including non-essential components such as impurities is never added up to exceed 100% by mass. In a composition "consisting essentially of" the recited components, such components may be added up to 100% by mass of the composition or may be added up to less than 100% by mass. When these components are added up to less than 100% by mass, such a composition may contain some small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the etching composition may contain 2% by mass or less of impurities. In another embodiment, the etching composition may contain 1% by mass or less of impurities. In other embodiments, the etching composition may contain 0.05% by mass or less of impurities. In other such embodiments, the components can be at least 90% by mass, more preferably at least 95% by mass, more preferably at least 99% by mass, more preferably at least 99.5% by mass, most preferably at least 99.9% by mass, and can contain other components that do not substantially affect the performance of the etching composition. Alternatively, it is understood that when there are no important non-essential impurity components, the combination of all essential components is basically added up to 100% by mass.

[0034] Composition

[0035] As described above, the subject matter of the present disclosure and claims relates to an etching composition comprising, consisting essentially of, or consisting of a mixture of (A) phosphoric acid and (B) a silicon-containing compound disclosed herein and an aqueous solvent. In some embodiments, the etching composition can include other components.

[0036] Component

[0037] (A) Phosphoric acid

[0038] The etching composition of the subject matter of the present disclosure and claims contains phosphoric acid. Commercially available phosphoric acid can be used. This commercially available phosphoric acid is typically available as an 80% - 85% aqueous composition. In a preferred embodiment, an electronics-grade phosphoric acid composition is used. Such electronics-grade compositions typically have 100 particles / ml or less in terms of particle count, the size of those particles is 0.5 microns or less, and metal ions are present in the acid at low parts per million to low parts per trillion levels per liter. In certain embodiments, other inorganic acids, such as hydrofluoric acid, nitric acid, or mixtures thereof, etc., are not added to the composition of the subject matter of the present disclosure and claims.

[0039] The phosphoric acid is included in an amount within a range having a starting point and an ending point selected from the following list of mass percentages (on a pure basis), i.e., about 40 mass% to about 95 mass%, about 45 mass% to about 90 mass%, or about 50 mass% to about 90 mass%, or about 55 mass% to about 85 mass% of the composition. The phosphoric acid may be present in amounts defined by the following list of mass percentages, i.e., 30%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, and 95%.

[0040] In some embodiments, the content of the pure phosphoric acid is about 70% by mass or less. In other aspects of this embodiment, the content of the pure phosphoric acid is about 60% by mass or less.

[0041] In some embodiments, the content of the pure phosphoric acid is more than about 70% by mass. In other aspects of this embodiment, the content of the pure phosphoric acid is more than about 75% by mass.

[0042] (B) Mixture

[0043] As described above, the etching composition contains a mixture of (I) the silicon-containing compound disclosed herein and (II) an aqueous solvent.

[0044] I. Silicon-containing compound

[0045] The amount of the silicon-containing compound ranges from about 0.001% to about 15% by mass of the etching composition. The silicon-containing compound preferably constitutes about 0.1% to about 10% by mass of the etching composition. These mass percentages, including the stated mass percentage of the silicon-containing compound converted to the composition, are on a pure basis unless otherwise indicated. In alternative embodiments, the silicon-containing compound is present in an amount within a range having start and end points defined by the following list of mass percentages, namely 0.001, 0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.7%, 2%, 2.2%, 2.5%, 2.7%, 3%, 3.2%, 3.5%, 3.7%, 4%, 4.2%, 4.5%, 4.7%, 5%, 5.2%, 5.5%, 5.7%, 6%, 6.2%, 6.5%, 6.8%, 7%, 7.2%, 7.5%, 7.8%, 8%, 8.2%, 8.5%, 8.8%, 9%, 9.2%, 9.5%, 10%, 12%, 15%, 17%, and 20%.

[0046] In some embodiments, the silicon-containing compound has Formula I,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0047] In some embodiments of the etching composition comprising the silicon-containing compound of formula I, R 1 , R 2 , R 3 , R 4 , and R 5 are each the same. In other aspects of this embodiment, R 1 , R 2 , R 3 , R 4 , and R 5 are each hydrogen.

[0048] In some embodiments of the etching composition comprising the silicon-containing compound of formula I, at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is other than hydrogen.

[0049] In some embodiments of the etching composition comprising the silicon-containing compound of formula I, m is from 0 to 20. In other aspects of this embodiment, m is 0. In other aspects of this embodiment, m is 1. In other aspects of this embodiment, m is 2. In other aspects of this embodiment, m is 3. In other aspects of this embodiment, m is 4. In other aspects of this embodiment, m is 5. In other aspects of this embodiment, m is 6. In other aspects of this embodiment, m is 7. In other aspects of this embodiment, m is 8. In other aspects of this embodiment, m is 9. In other aspects of this embodiment, m is 10. In other aspects of this embodiment, m is 11. In other aspects of this embodiment, m is 12. In other aspects of this embodiment, m is 13. In other aspects of this embodiment, m is 14. In other aspects of this embodiment, m is 15. In other aspects of this embodiment, m is 16. In other aspects of this embodiment, m is 17. In other aspects of this embodiment, m is 18. In other aspects of this embodiment, m is 19. In other aspects of this embodiment, m is 20.

[0050] In some embodiments of the etching composition, the content of the silicon-containing compound of Formula I is about 5% by weight or less. In other aspects of this embodiment, the content of the silicon-containing compound of Formula I is about 4% by weight or less. In other aspects of this embodiment, the content of the silicon-containing compound of Formula I is about 3% by weight or less. In other aspects of this embodiment, the content of the silicon-containing compound of Formula I is about 2% by weight or less. In other aspects of this embodiment, the content of the silicon-containing compound of Formula I is about 1% by weight or less.

[0051] In some embodiments, the etching composition is (i) R a and R b each being

Chemical formula

Chemical formula

[0052] In some embodiments, the etching composition is (i) R a and R b each being

Chemical formula

Chemical formula

Chemical formula

[0053] In some embodiments, the etching composition comprises (i) R a and R b each of which is

Chem.

Chem.

[0054] In some embodiments, the silicon-containing compound has Formula II,

Chem.

Chem.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0055] In some embodiments of the etching composition comprising the silicon-containing compound of formula II, m is from 0 to 20. In other aspects of this embodiment, m is 0. In other aspects of this embodiment, m is 1. In other aspects of this embodiment, m is 2. In other aspects of this embodiment, m is 3. In other aspects of this embodiment, m is 4. In other aspects of this embodiment, m is 5. In other aspects of this embodiment, m is 6. In other aspects of this embodiment, m is 7. In other aspects of this embodiment, m is 8. In other aspects of this embodiment, m is 9. In other aspects of this embodiment, m is 10. In other aspects of this embodiment, m is 11. In other aspects of this embodiment, m is 12. In other aspects of this embodiment, m is 13. In other aspects of this embodiment, m is 14. In other aspects of this embodiment, m is 15. In other aspects of this embodiment, m is 16. In other aspects of this embodiment, m is 17. In other aspects of this embodiment, m is 18. In other aspects of this embodiment, m is 19. In other aspects of this embodiment, m is 20.

[0056] In some embodiments of the etching composition comprising the silicon-containing compound of Formula II, n is from 0 to 20. In other aspects of this embodiment, n is 0. In other aspects of this embodiment, n is 1. In other aspects of this embodiment, n is 2. In other aspects of this embodiment, n is 3. In other aspects of this embodiment, n is 4. In other aspects of this embodiment, n is 5. In other aspects of this embodiment, n is 6. In other aspects of this embodiment, n is 7. In other aspects of this embodiment, n is 8. In other aspects of this embodiment, n is 9. In other aspects of this embodiment, n is 10. In other aspects of this embodiment, n is 11. In other aspects of this embodiment, n is 12. In other aspects of this embodiment, n is 13. In other aspects of this embodiment, n is 14. In other aspects of this embodiment, n is 15. In other aspects of this embodiment, n is 16. In other aspects of this embodiment, n is 17. In other aspects of this embodiment, n is 18. In other aspects of this embodiment, n is 19. In other aspects of this embodiment, n is 20.

[0057] In some embodiments of the etching composition, the content of the silicon-containing compound of Formula II is about 5% by mass or less. In other aspects of this embodiment, the content of the silicon-containing compound of Formula II is about 4% by mass or less. In other aspects of this embodiment, the content of the silicon-containing compound of Formula II is about 3% by mass or less. In other aspects of this embodiment, the content of the silicon-containing compound of Formula II is about 2% by mass or less. In other aspects of this embodiment, the content of the silicon-containing compound of Formula II is about 1% by mass or less.

[0058] In some embodiments, the etching composition comprises the silicon-containing compound of Formula II.

[0059] In some embodiments, the etching composition is such that (i) m = 0 and (ii) each of Z 1 and Z 2 is

Chemical formula

[0060] In some embodiments, the etching composition: (i) m = 0; (ii) n = 0; (iii) each of Z 1 and Z 2 is

Chemical formula

[0061] In some embodiments, the etching composition: (i) m = 0; (ii) n = 0; (ii) each of Z 1 and Z 2 is

Chemical formula

[0062] In some embodiments, the etching composition: (i) m = 0; (ii) n = 0; and (iii) each of Z 1 and Z 2 is

Chemical formula

[0063] In some embodiments, the silicon-containing compound has formula III,

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0064] In some embodiments of the etching composition, the content of the silicon-containing compound of formula III is about 5% by mass or less. In other aspects of this embodiment, the content of the silicon-containing compound of formula III is about 4% by mass or less. In other aspects of this embodiment, the content of the silicon-containing compound of formula III is about 3% by mass or less. In other aspects of this embodiment, the content of the silicon-containing compound of formula III is about 2% by mass or less. In other aspects of this embodiment, the content of the silicon-containing compound of formula III is about 1% by mass or less.

[0065] In some embodiments, the etching composition is such that (i) each of R 1 , R 2 , and R 3 is

Chemical formula

Chemical formula

[0066] In some embodiments, the etching composition comprises (i) R 1 , R 2 , and R 3 each being [Chemical formula] and (ii) the sum of m1 and m2 is 3, (iii) n = 0, (iv) L is [Chemical formula] and includes the silicon-containing compound of Formula III.

[0067] In some embodiments, the etching composition comprises (i) R 1 , R 2 , and R 3 each being [Chemical formula] and (ii) m2 = 3, (iii) n = 1, (iv) A is [Chemical formula] wherein Ra is [Chemical formula] and (v) m1 = 0, (vi) L is [Chemical formula] It contains the silicon-containing compound of formula III as described.

[0068] In some embodiments, the etching composition comprises (i) R 1 、R 2 、and R 3 each of which is

Chem.

Chem.

Chem.

[0069] In some embodiments, the etching composition comprises (i) R 1 、R 2 、and R 3 each of which is

Chem.

Chem.

Chem.

Chem.

[0070] In some embodiments, the etching composition comprises (i) R 1 、R 2 、and R3 each of which is -OCH 3 where (ii) the sum of m1 and m2 is 2, (iii) n = 0, (iv) L is

Chemical formula

[0071] In some embodiments, the etching composition is such that (i) R 1 , R 2 , and R 3 each is

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0072] In some embodiments, the etching composition is such that (i) R 1 , R 2 , and R 3 each is

Chemical formula

Chemical formula

[0073] In some embodiments, the etching composition comprises (i) each of R 1 , R 2 , and R 3 is [Chemical formula] as follows, (ii) m2 = 3, (iii) n = 1, (iv) A is [Chemical formula] as follows, wherein R a and R b are -CH 3 , (v) m1 = 3, (vi) L is [Chemical formula] contains the silicon-containing compound of formula III which is as follows.

[0074] In some embodiments, the etching composition comprises (i) each of R 1 , R 2 , and R 3 is [Chemical formula] as follows, (ii) the sum of m1 and m2 is 2, (iii) n = 0, (iv) L is [Chemical formula] contains the silicon-containing compound of formula III which is as follows.

[0075] In some embodiments, the etching composition comprises (i) each of R 1 , R 2 , and R 3 is [Chemical formula] and (ii) the sum of m1 and m2 is 3, (iii) n = 0, and (iv) L is

Chemical formula

[0076] In some embodiments, the etching composition is such that (i) each of R 1 , R 2 , and R 3 is

Chemical formula

Chemical formula

[0077] In some embodiments, the etching composition has the following structure, namely

Chemical formula

Chemical formula

[0078] In some embodiments, the one or more silicon-containing compounds include a combination of one or more silicon-containing compounds having Formula I, Formula II, and / or Formula III.

[0079] II. Aqueous solvent

[0080] The etching composition of the present development is aqueous and contains water. In the context of the present disclosure and claims, water functions in various forms, for example, to dissolve one or more components of the composition, as a carrier for those components, as an aid in removing residues, as a viscosity regulator for the composition, and as a diluent. The water used in the etching composition is preferably deionized (DI) water.

[0081] In some embodiments, the aqueous solvent contains water. In other aspects of this embodiment, the aqueous solvent consists essentially of water. In other aspects of this embodiment, the aqueous solvent consists of water.

[0082] Water is included in an amount within a range having a starting point and an ending point selected from the following list of mass percentages, namely, in the range of about 1 mass% to about 50 mass% of the etching composition. Other preferred embodiments of the present disclosure and claims include about 5.0 mass% to about 35 mass% or 10 mass% to 30 mass% of water. Water may be present in amounts defined by the following list of mass percentages, namely 1%, 5%, 8%, 10%, 12%, 15%, 17%, 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, and 50%. Still other preferred embodiments of the present disclosure and claims can include an amount of water such that the desired mass percentages of these other components are achieved.

[0083] Embodiments of an etching composition

[0084] The following are embodiments that are examples of an etching composition comprising (A) pure phosphoric acid and (B) a mixture of (I) a silicon-containing compound disclosed herein and (II) an aqueous solvent.

[0085] In one embodiment, the etching composition is (A) up to about 70 mass% of pure phosphoric acid, (B) a mixture of at least about 30 mass%, wherein (I) Formula I, namely, [Chemical formula] is a compound, where in the formula, (i) m = 0 to 20, (ii) Each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, a C 1 to C 10 linear alkyl group, a fluorine-substituted C 1 to C 10 linear alkyl group, a nitrogen-containing group, an oxygen-containing group, a C 3 to C 10 branched-chain alkyl group, a C 3 to C 10 cyclic alkyl group, a C 5 to C 12 aryl group, a C 2 to C 10 linear or branched-chain alkenyl group, a C 2 to C 10 linear or branched-chain alkynyl group, and [Chemical formula] is selected from the group consisting of, and (iii) Each of R a and R b is independently a C 1 to C 10 linear alkyl group, a C 3 to C 10 branched-chain alkyl group, a C 3 to C 10 cyclic alkyl group, a C 5 to C 12 aryl group, a C 2 to C 10 linear or branched-chain alkenyl group, a C 2 to C 10 linear or branched-chain alkynyl group, [Chemical formula] and [Chemical formula] C substituted with 1 ~C 10 the compound selected from alkyl, and (II) the mixture containing an aqueous solvent is included. In other aspects of this embodiment, the etching composition consists essentially of A and B. In other aspects of this embodiment, the etching composition consists of A and B.

[0086] In one embodiment, the etching composition is (A) pure phosphoric acid of about 70% by mass or less, (B) a mixture of about 30% by mass or more, which is (I) Formula II, that is, [Chemical formula] a compound of, in the formula, (i) m = 0 to 20, (ii) n = 0 to 20, (iii) R 3 is hydrogen, C 1 ~C 10 linear alkyl group, fluorine-substituted C 1 ~C 10 linear alkyl group, nitrogen-containing group, oxygen-containing group, C 3 ~C 10 branched-chain alkyl group, C 3 ~C 10 cyclic alkyl group, C 5 ~C 12 aryl group, C 2 ~C 10 linear or branched alkenyl group and C 2 ~C 10 linear or branched alkynyl group, [Chemical formula] Z 1 , and Z 2 selected from the group consisting of, and (iv) each of R a and R b is independently C 1 ~C 10 linear alkyl group, C3 ~C 10 Branched-chain alkyl group, C 3 ~C 10 Cyclic alkyl group, C 5 ~C 12 Aryl group, C 2 ~C 10 Straight-chain or branched-chain alkenyl group, C 2 ~C 10 Straight-chain or branched-chain alkynyl group, [Chemical formula] and [Chemical formula] C substituted with 1 ~C 10 selected from alkyl, (v) Z 1 and Z 2 are each independently (a) [Chemical formula] (b) [Chemical formula] (c) [Chemical formula] (d) and [Chemical formula] the compound selected from, and (II) the mixture containing an aqueous solvent is included. In other aspects of this embodiment, the etching composition consists essentially of A and B. In other aspects of this embodiment, the etching composition consists of A and B.

[0087] In one embodiment, the etching composition is, (A) about 70% by mass or less of pure phosphoric acid, (B) a mixture of about 30% by mass or more, (I) Formula III, that is,

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0088] In one embodiment, the etching composition is (A) More than about 70% by mass of pure phosphoric acid, (B) A mixture of less than about 30% by mass, (I) Formula I, that is,

Chemical formula

Chemical formula

Chemical formula

[0089] In one embodiment, the etching composition is (A) more than about 70% by mass of pure phosphoric acid, (B) a mixture of less than about 30% by mass, wherein (I) Formula II, that is, [Chem.] a compound of, wherein in the formula (i) m = 0 to 20, (ii) n = 0 to 20, (iii) R 3 is hydrogen, C 1 ~C 10 linear alkyl group, fluorine-substituted C 1 ~C 10 linear alkyl group, nitrogen-containing group, oxygen-containing group, C 3 ~C 10 branched alkyl group, C 3 ~C 10 cyclic alkyl group, C 5 ~C 12 aryl group, C 2 ~C 10 linear or branched alkenyl group and C 2 ~C 10 linear or branched alkynyl group, [Chem.] Z1 and Z 2 selected from the group consisting of, and (iv) R a and R b each independently being C 1 ~C 10 linear alkyl group, C 3 ~C 10 branched alkyl group, C 3 ~C 10 cyclic alkyl group, C 5 ~C 12 aryl group, C 2 ~C 10 linear or branched alkenyl group, C 2 ~C 10 linear or branched alkynyl group,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0090] In one embodiment, the etching composition is, (A) More than about 70% by mass of pure phosphoric acid, (B) A mixture less than about 30% by mass, (I) Formula III, that is,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0091] C. Other Components

[0092] The etching composition containing the etching composition exemplified above may contain other components as described below.

[0093] I. Additional Acid

[0094] In some embodiments, the mixture further contains at least one additional acid other than phosphoric acid. In one aspect of this embodiment, the at least one additional acid is nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), and sulfonic acid (e.g., methanesulfonic acid (CH 3 SO 3 H)) of which one.

[0095] (a) Sulfuric Acid

[0096] In some embodiments, the at least one additional acid contained in the mixture is sulfuric acid. In one aspect of this embodiment, the at least one additional acid contains about 25% by mass or less of pure sulfuric acid. In other aspects of this embodiment, the at least one additional acid consists of sulfuric acid. In some embodiments, the at least one additional acid consists of about 25% by mass or less of pure sulfuric acid.

[0097] In some embodiments of the etching composition, the mixture contains pure sulfuric acid, and the total content of the pure phosphoric acid and the pure sulfuric acid is between about 80% by mass and about 85% by mass of the composition. In other aspects of this embodiment, the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition.

[0098] In some embodiments of the etching composition, the mixture further contains pure sulfuric acid, and there is about 2.0 parts by mass to about 7.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 2.0 parts by mass to about 6.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 2.0 parts by mass to about 5.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 2.0 parts by mass to about 4.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 2.0 parts by mass to about 3.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 2.0 parts by mass to about 2.5 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 3.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 2.25 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 2.5 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid. In other aspects of this embodiment, there is about 2.75 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

[0099] In some embodiments of the etching composition, the mixture further contains pure sulfuric acid, and the total content of the pure phosphoric acid and the pure sulfuric acid is between about 80% by mass and about 85% by mass of the composition. In other aspects of this embodiment, the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition.

[0100] Various non-limiting embodiments of the etching composition containing sulfuric acid are illustrated below.

[0101] (i) An embodiment that is an example of a composition containing a silicon-containing compound of Formula I and sulfuric acid

[0102] In some embodiments of the etching composition, (i) the compound of Formula I is

Chemical formula

[0103] In some embodiments of the etching composition, (i) the compound of Formula I is

Chemical formula

[0104] In some embodiments of the etching composition, (i) the compound of Formula I is

Chemical formula

[0105] In some embodiments of the etching composition, (i) the compound of Formula I is

Chemical formula

[0106] In some embodiments of the etching composition, (i) the compound of Formula I is

Chemical formula

[0107] In some embodiments of the etching composition, (i) the compound of Formula I is

Chem.

[0108] In some embodiments of the etching composition, (i) the compound of Formula I is

Chem.

[0109] In some embodiments of the etching composition, (i) the compound of Formula I is

Chem.

[0110] In some embodiments of the etching composition, (i) the compound of Formula I is

Chem.

[0111] In some embodiments of the etching composition, (i) the compound of Formula I is

Chem.

[0112] In some embodiments, the etching composition comprises (A) phosphoric acid in an amount of about 60% by weight or less and (B) (i) [Chemical formula] (ii) sulfuric acid in an amount of about 24% by weight or less, and (iii) an aqueous solvent containing water, and comprises a mixture in an amount of about 40% by weight or more.

[0113] In some embodiments, the etching composition comprises (A) phosphoric acid in an amount of about 60% by weight or less and (B) (i) [Chemical formula] and consists essentially of an aqueous solvent consisting essentially of (ii) sulfuric acid in an amount of about 24% by weight or less, and (iii) water, and consists essentially of the mixture in an amount of about 40% by weight or more.

[0114] In some embodiments, the etching composition comprises (A) phosphoric acid in an amount of about 60% by weight or less and (B) (i) [Chemical formula] and consists of a mixture in an amount of about 40% by weight or more consisting of an aqueous solvent consisting of (ii) sulfuric acid in an amount of about 24% by weight or less, and (iii) water.

[0115] (ii) Embodiments that are examples of compositions containing a silicon-containing compound of formula II and sulfuric acid

[0116] In some embodiments of the etching composition, (i) the compound of formula II [Chemical formula] and (ii) the mixture further contains sulfuric acid.

[0117] In some embodiments of the etching composition, (i) the compound of formula II [Chemical formula] and (ii) the mixture further comprises pure sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is between about 80% and about 85% by mass of the composition.

[0118] In some embodiments of the etching composition, (i) the compound of formula II is

Chemical formula

[0119] In some embodiments of the etching composition, (i) the compound of formula II is

Chemical formula

[0120] In some embodiments of the etching composition, (i) the compound of formula II is

Chemical formula

[0121] In some embodiments of the etching composition, (i) the compound of formula II is

Chemical formula

[0122] (iii) Embodiments that are examples of compositions containing a silicon-containing compound of formula III and sulfuric acid

[0123] In some embodiments of the etching composition, (i) the compound of Formula III is

Chemical formula

Chemical formula

[0124] In some embodiments of the etching composition, (i) the compound of Formula III is

Chemical formula

Chemical formula

[0125] In some embodiments of the etching composition, (i) the compound of Formula III is

Chemical formula

Chemical formula

[0126] In some embodiments of the etching composition, (i) the compound of Formula III is Si(OCH 3 ) 3 (CH 2 CH 2 CF 3 ) and (ii) the mixture further contains pure sulfuric acid.

[0127] In some embodiments of the etching composition, (i) the compound of Formula III is Si(OCH 3 ) 3 (CH 2 CH 2 CF 3 ) and (ii) the mixture further contains pure sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is between about 80% and about 85% by mass of the composition.

[0128] In some embodiments of the etching composition, (i) the compound of Formula III is Si(OCH 3 ) 3 (CH 2 CH 2 CF 3 ) and (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition.

[0129] In some embodiments of the etching composition, (i) the compound of Formula III is

Chemical formula

[0130] In some embodiments of the etching composition, (i) the compound of formula III is

Chemical formula

[0131] In some embodiments of the etching composition, (i) the compound of formula III is

Chemical formula

[0132] In some embodiments of the etching composition, (i) the compound of formula III is

Chemical formula

[0133] In some embodiments of the etching composition, (i) the compound of formula III is

Chemical formula

[0134] In some embodiments of the etching composition, (i) the compound of formula III is

Chemical formula

[0135] In some embodiments of the etching composition, (i) the compound of Formula III is

Chemical formula

[0136] In some embodiments of the etching composition, (i) the compound of Formula III is

Chemical formula

[0137] In some embodiments of the etching composition, (i) the compound of Formula III is

Chemical formula

[0138] (b) Sulfonic acid

[0139] In some embodiments, the at least one additional acid contained in the mixture is a sulfonic acid. This sulfonic acid is typically an alkyl sulfonic acid or an aryl sulfonic acid. The sulfonic acid has a general structure of R'-S(O)(O)-OH. In one aspect of this embodiment, R' is C 1 ~C10 linear alkyl group, C 3 ~C 10 branched alkyl group, C 3 ~C 10 cyclic alkyl group, C 5 ~C 12 aryl group, C 2 ~C 10 linear or branched alkenyl group, C 2 ~C 10It is selected from a linear or branched alkynyl group. In another aspect of this embodiment, R' is C 1 ~C10 linear alkyl group or C 3 ~C 10 selected from branched alkyl groups. In another aspect, the mixture contains ethane sulfonic acid, 3-hydroxypropane-1-sulfonic acid, 3-amino-1-propane sulfonic acid, sulfonic acetic acid, nonafluorobutane-1-sulfonic acid, benzene sulfonic acid, 3-aminobenzene sulfonic acid, p-toluenesulfonic acid monohydrate, and one or more sulfonic acids selected from methanesulfonic acid. In one aspect of this embodiment, the sulfonic acid is methanesulfonic acid (CH 3 SO 3 H).

[0140] (c) Other acids

[0141] In some embodiments, the at least one additional acid contained in the mixture is sulfuric acid and is one or more of nitric acid (HNO 3 ).

[0142] The total amount of this at least one additional acid (such as sulfonic acid and / or sulfuric acid) is about 0.1% by mass to about 60%, about 0.2% by mass to about 40%, or about 0.5% by mass to about 35% of the etching composition. When this at least one additional acid is used, it is preferably contained at about 1% by mass to about 30% by mass of the composition. In an alternative embodiment, the total amount of this at least one additional acid is an amount within a range having a starting point and an end point defined by the following list of mass percentages, namely 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7.0%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 27%, 30%, 32%, 35%, 37%, and 40%. These mass percentages are the mass percentage values of "pure" substances.

[0143] In alternative embodiments, the compositions of the present disclosure and the subject of the present claims do not contain, or substantially do not contain, this at least one additional acid (such as the addition of sulfuric acid and / or sulfonic acid).

[0144] II. Additional Silicon-Containing Compounds

[0145] In some embodiments, the mixture can include additional silicon-containing compounds other than the compounds of Formula I, Formula II, or Formula III. Such additional silicon-containing compounds can be one or more of alkylsilsesquioxanes, vinylsilsesquioxane, carboxylic acid alkylsilsesquioxane, and alkylene glycol alkylsilsesquioxane.

[0146] III. Hydroxyl Group-Containing Water-Miscible Solvents

[0147] In some embodiments, the mixture can include a hydroxyl group-containing water-miscible solvent. This hydroxyl group-containing water-miscible solvent mainly functions to protect silicon oxide so that silicon nitride is preferentially and selectively etched.

[0148] Suitable classifications of hydroxyl group-containing water-miscible solvents include, but are not limited to, alkanediols and alkanepolyols (including but not limited to alkylene glycols), glycols, alkoxy alcohols (including but not limited to glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and ring-containing low molecular weight alcohols.

[0149] (C 2 ~C 20 ) alkanediol and (C 3 ~C 20)Examples of suitable water-soluble alkanediols and alkanepolyols such as alkanetriols include, but are not limited to, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, and pinacol.

[0150] 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.

[0151] 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.

[0152] Examples of suitable water-soluble glycol monoethers include 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, but are not limited thereto.

[0153] Examples of suitable water-soluble saturated aliphatic monohydric alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, 1-hexanol, and mixtures thereof, but are not limited thereto.

[0154] Examples of suitable water-soluble unsaturated non-aromatic monohydric alcohols include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, 4-penten-2-ol, and mixtures thereof, but are not limited thereto.

[0155] Examples of suitable water-soluble ring-containing low molecular weight alcohols include α-terpineol, tetrahydrofurfuryl alcohol, furfuryl alcohol, 1,3-cyclopentanediol, and mixtures thereof, but are not limited thereto.

[0156] In some embodiments, the amount of the hydroxyl group-containing water-miscible solvent constitutes about 1.0% to about 30% by weight of the composition. When this hydroxyl group-containing water-miscible solvent is used, it is preferably that this hydroxyl group-containing water-miscible solvent constitutes about 5% to about 15% by weight of the composition.

[0157] In some embodiments, the composition of the present disclosure and the subject of the present claims does not contain or substantially does not contain a hydroxyl group-containing water-miscible solvent, or does not contain or substantially does not contain any or all of the above-mentioned hydroxyl group-containing water-miscible solvents.

[0158] IV. Silicic acid

[0159] In some embodiments, the mixture can include silicic acid. When silicic acid is used, this silicic acid aids in protecting silicon oxide and improving the selectivity of silicon nitride etching.

[0160] In some embodiments, the amount of silicic acid constitutes about 0.001% to about 5.0% by weight of the composition, preferably about 0.01% to about 2.0% by weight. In other embodiments, this silicic acid constitutes about 0.02% to about 0.08% by weight of the composition.

[0161] In some embodiments, the composition of the present disclosure and the subject of the present claims is not added with silicic acid or is substantially not added.

[0162] V. Phosphoric acid compound

[0163] In some embodiments, the mixture can include a phosphoric acid compound, such as triethyl phosphate (TEPO) and / or trimethyl phosphate (TMPO), etc. When a phosphoric acid compound is used, this phosphoric acid compound functions as a supplementary solvent.

[0164] In some embodiments, the amount of the phosphate compound (e.g., TMPO) constitutes about 0.05% to about 15% by weight of the composition, preferably about 0.1% to about 5% by weight. In other embodiments, when a phosphate compound is used, this phosphate compound (e.g., TMPO) constitutes about 2% by weight of the composition.

[0165] In some embodiments, the composition of the present disclosure and the subject of the present claims is not added with a phosphate compound or is substantially not added.

[0166] VI. Surfactant

[0167] In some embodiments, the mixture can include at least one water-soluble nonionic surfactant. The surfactant functions to assist in the removal of residues.

[0168] Examples of these 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 sorbitol tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, alkylalkanolamide, and mixtures thereof.

[0169] In some embodiments, the amount of the surfactant may be from about 0.001% to about 5% by weight of the composition, preferably from about 0.01% to about 2.5% by weight of the composition, and most preferably from about 0.1% to about 1.0% by weight of the composition.

[0170] In some embodiments, the composition of the present disclosure and the subject of the present claims may not contain or may be substantially free of surfactants.

[0171] VII. Chelating Agent

[0172] In some embodiments, the mixture may contain at least one metal chelating agent. The metal chelating agent may function to hold the metal in the composition and enhance the ability of the composition to dissolve metal residues.

[0173] Examples of suitable chelating agents include the following organic acids and their isomers and salts, namely ethylenediaminetetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenediamine) tetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), N,N,N’,N’-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), triethylenetetraminehexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N,N,N’,N’-tetraacetic acid (DHPTA), methyliminodiacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid (NTA), citric acid, tartaric acid, gluconic acid, saccharic acid, glyceric acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, salicylic acid, propyl gallate, pyrogallol, 8-hydroxyquinoline, and cysteine, but are not limited thereto. Preferred chelating agents are aminocarboxylic acids such as EDTA and CyDTA and aminophosphonic acids such as EDTMP.

[0174] In some embodiments, the amount of the chelating agent constitutes from about 0.1% to about 10% by weight of the composition, preferably from about 0.5% to about 5% by weight.

[0175] In some embodiments, the composition of the present disclosure and the subject of the present claims does not contain or substantially does not contain a chelating agent.

[0176] In certain embodiments, the composition is substantially free of or does not contain metal hydroxides, metal additions, halide-containing compounds, TEOS, silyl phosphate compounds, and silanes and silanols that do not contain repeating monomers.

[0177] Manufacturing method

[0178] The subject of the present disclosure and the present claims further includes a method for manufacturing the etching composition described and claimed herein.

[0179] In one embodiment, the method for forming the etching composition is (A) pure phosphoric acid of about 70% by weight or less, and (B) a mixture of about 30% by weight or more, wherein (I) Formula I, namely,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0180] In one embodiment, the method for forming the said etching composition is (A) about 70 mass% or less of pure phosphoric acid, (B) a mixture of about 30 mass% or more, and (I) Formula II, that is,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0181] In one embodiment, the method for forming the said etching composition is (A) pure phosphoric acid of about 70 mass% or less, (B) a mixture of about 30 mass% or more, (I) Formula III, that is, [Chemical formula] a compound of, in the formula, (i) m1 and m2 are each equal to 0 to 10 on condition that at least one of m1 and m2 is 1 or more, (ii) n = 0 or 1, (iii) each of R 1 , R 2 , and R 3 is independently hydrogen, a C 1 ~C 6 linear alkyl group, a C 3 ~C 6 branched alkyl group, and [Chemical formula] selected from the group consisting of (iv) A is (a) [Chemical formula] (b)R a is hydrogen, C 1 ~C 6 linear alkyl group, C 3 ~C 6 selected from branched alkyl groups

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0182] In one embodiment, the method for forming the etching composition is (A) pure phosphoric acid of more than about 70% by mass, (B) a mixture of less than about 30% by mass, which is (I) Formula I, that is, [Chemical formula] a compound of, wherein (i) m = 0 to 20, (ii) each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently hydrogen, C 1 ~C 10 linear alkyl group, fluorine-substituted C 1 ~C 10 linear alkyl group, nitrogen-containing group, oxygen-containing group, C 3 ~C 10 branched alkyl group, C 3 ~C 10 cyclic alkyl group, C 5 ~C 12 aryl group, C 2 ~C 10 linear or branched alkenyl group, C 2 ~C10 a linear or branched alkynyl group, and

Chem.

Chem.

Chem.

[0183] In one embodiment, the method for forming the said etching composition is (A) more than about 70 mass% of pure phosphoric acid, (B) a mixture of less than about 30 mass%, wherein (I) Formula II, namely,

Chem.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0184] In one embodiment, said method for forming said etching composition is (A) more than about 70% by mass of pure phosphoric acid, (B) less than about 30% by mass of a mixture, (I) Formula III, that is, [Chemical formula] a compound of, wherein (i) m1 and m2 are each equal to 0 to 10, provided that at least one of m1 and m2 is 1 or more, (ii) n = 0 or 1, (iii) each of R 1 , R 2 , and R 3 is independently hydrogen, C 1 ~C 6 linear alkyl group, C 3 ~C 6 branched alkyl group, and [Chemical formula] selected from the group consisting of, (iv) A is (a) [Chemical formula] (b) R a is hydrogen, C 1 ~C 6A linear alkyl group, C 3 ~C 6 selected from branched alkyl groups

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0185] Method of use

[0186] The subject matter of the present disclosure and claims further includes a method for selectively improving the etching rate of silicon nitride compared to silicon dioxide on a composite semiconductor device containing silicon nitride and silicon dioxide.

[0187] In one embodiment, the method comprises (a) contacting said composite semiconductor device containing silicon nitride and silicon dioxide with one or more of said etching compositions disclosed and / or claimed herein, and (b) washing said composite semiconductor device after at least partially removing said silicon nitride including. In other aspects of this embodiment, the contacting step is carried out at a temperature of about 160 °C.

[0188] In other embodiments, the method may include (c) a drying step.

[0189] In the method of this description, "at least partially removed" means removal of at least 90% of said material, preferably at least 95% removal. Most preferably, at least 99% is removed using said composition of the present development.

[0190] In other embodiments, the method can include a pretreatment step that includes contacting the substrate with dilute hydrofluoric acid (dHF) (a 1:100 HF / water mixture), for example, by immersion or spraying. The dHF pretreatment step can also be excluded, and it has been recognized that a high relative etching rate can still be achieved using the compositions of the present disclosure and the subject matter of the present claims. It has also been found that when this dHF pretreatment step is used, the compositions of the present disclosure and the subject matter of the present claims cause less damage to the substrate compared to when using only the phosphoric acid composition. The spread of damage caused by this dHF pretreatment step can be minimized by suppressing agitation during treatment using the compositions of the present disclosure and the subject matter of the present claims and shortening the time between the pretreatment and contact with the compositions of the present disclosure and the subject matter of the present claims.

[0191] In some embodiments, the contacting step can be carried out by any suitable means, such as, for example, immersion, spraying, or the intervention of a single-wafer process.

[0192] In some embodiments, the temperature of the composition during the contacting step is preferably about 100°C to 200°C. In other aspects, this temperature is about 140°C to 180°C. In other aspects, the temperature of the composition during the contacting step is about 160°C.

[0193] In some embodiments, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 300 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 500 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 1000 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 1250 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 1500 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 2000 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 2500 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 3000 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 3500 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 4000 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 4500 or greater. In other aspects, the etch selectivity of the disclosed and claimed etching compositions for silicon nitride over silicon oxide is about 5000 or greater.

[0194] In some embodiments, the etching of silicon oxide is less than 1 Å / min. In other aspects, the etching of silicon oxide is less than 0.5 Å / min. In other aspects, the etching of silicon oxide is less than 0.01 Å / min.

[0195] In some embodiments, the cleaning step (c) is carried out by any suitable means, for example, by cleaning the substrate with deionized water by means of a dipping method or a spraying method. In another aspect, the cleaning step is carried out using a mixture of deionized water and a water-miscible organic solvent, such as isopropyl alcohol or the like.

[0196] In some embodiments, the drying step is carried out by any suitable means, for example, by isopropyl alcohol (IPA) vapor drying, heating, or centrifugal force.

Example

[0197] Reference is now made to more specific embodiments of the present disclosure and experimental results supporting such embodiments. These examples are presented below to more fully illustrate the content of the present disclosure and should not be construed as in any way limiting the content of the present disclosure.

[0198] It will be apparent to those skilled in the art that various modifications and variations can be made to the content of the present disclosure and the specific examples presented herein without departing from the spirit or scope of the content of the present disclosure. Accordingly, the content of the present disclosure, including the description provided by the following examples, is intended to embrace modifications and variations of the content of the present disclosure that fall within the scope of any claims and their equivalents.

[0199] Materials and Methods

[0200] All components used herein are commercially available.

[0201] In this example, the following silicon-containing compounds were applied.

Table 1

[0202] General procedure for preparing the etching composition

[0203] All compositions shown in this example were prepared by mixing the components in a 250 mL beaker using a 1-inch (about 2.54 cm) Teflon-coated stir bar. Typically, the first material added to this beaker was deionized (DI) water. Phosphoric acid was then typically added, followed by the silicon-containing compound, and (if any) the remaining components were added thereafter.

[0204] Composition of the substrate

[0205] Each 20 mm × 20 mm coupon used in this example contained a layer of silicon nitride, i.e., SiN, on a silicon substrate. x The comparative example contained a layer of silicon oxide, i.e., SiO, on a silicon substrate. x

[0206] Processing conditions

[0207] A 1 / 2-inch (about 1.27 cm) spherical Teflon stir bar was set at 300 rpm and an etching test was performed using 100 g of the etching composition in a 250 mL beaker. The etching composition was heated to a temperature of about 160 °C on a hot plate. The SiNx substrate pieces, polysilicon substrate pieces, and pattern inspection substrate pieces (test coupons) were treated with DHF (1:100 HF / DI water) for about 3 minutes before the inspection. The SiOx test coupons were not pretreated with DHF. These test coupons were immersed in the composition with stirring for about 3 minutes (SiNx substrate) to about 60 minutes (SiOx substrate).

[0208] These parts were washed for about 3 minutes in a DI water bath or by spraying with DI water, and then dried using filtered nitrogen. The etching rate of silicon nitride and the etching rate of silicon oxide were estimated from the change in thickness before and after etching and measured by spectroscopic ellipsometry (FilmTek (trademark) 2000 PAR-SE, Scientific Computing International). A typical initial layer thickness was SiN xis 4395 Å for, and SiO x was 229 Å for.

[0209] The following series of tables show the evaluation results of several embodiments of the etching compositions of the present disclosure and the present claims. [Table 2] [Table 3]

[0210] Tables 1 and 2 show that the addition of the silicon-containing oligomer suppresses the etching rate of SiO x and increases the selectivity for etching SiN 2 over SiO x Table 1 further shows that the addition of sulfuric acid further reduces the etching rate of SiO 2 and thus increases the selectivity. [Table 4]

[0211] Table 3 further shows a significant effect of sulfuric acid concentration on the selectivity for selecting SiNx over SiO 2 [Table 5]

[0212] Table 4 shows that as the concentration of Si compound 1 increases, the etching rate of SiO 2 decreases, and the selectivity for selecting SiNx over SiO 2 obviously increases. [Table 6] [Table 7]

[0213] Tables 5 and 6 show that methanesulfonic acid plays the same role as sulfuric acid, and the addition of methanesulfonic acid also causes the SiO 2 etching rate to decrease and the selectivity to increase. [Table 8]

[0214] Table 7 shows the increase in the relative removal rate when the alkylsulfonic acid and sulfuric acid are added to the composition of the present disclosure and the present claims. [Table 9] [Table 10]

[0215] The foregoing description has been primarily for purposes of illustration. Although the present disclosure and the subject matter of the present claims have been shown and described with respect to exemplary embodiments thereof, those skilled in the art should understand that various changes, omissions, and additions, as well as other various changes, omissions, and additions, can be made to the present disclosure and the subject matter of the present claims without departing from the spirit and scope of the present disclosure and the subject matter of the present claims.

Claims

1. (A)Pure phosphoric acid at about 70% by mass or less, (B)A mixture at about 30% by mass or more, (I)Formula I, that is, 【Chemical 1】 a compound of, wherein in the formula, (i)m = 0 to 20, (ii) R １ , R ２ , R ３ , R ４ , and R ５ each is independently hydrogen, C １ - C １０ linear alkyl group, fluorine-substituted C １ - C １０ linear alkyl group, nitrogen-containing group, oxygen-containing group, C ３ - C １０ branched-chain alkyl group, C ３ - C １０ cyclic alkyl group, C ５ - C １２ aryl group, C ２ - C １０ linear or branched alkenyl group, C ２ - C １０ linear or branched alkynyl group, and 【Chemical 2】 selected from the group consisting of, and (iii) R ａ and R ｂ each independently is C １ to C １０ linear alkyl group, C ３ to C １０ branched alkyl group, C ３ to C １０ cyclic alkyl group, C ５ to C １２ aryl group, C ２ to C １０ linear or branched alkenyl group, C ２ to C １０ linear or branched alkynyl group, [Chemical Formula 3] and 【Chemical Formula 4】 C replaced by １ ~C １０ said compound selected from alkyl, and (II)An aqueous solvent, said mixture containing a composition containing

2. (A)Pure phosphoric acid at about 70% by mass or less, (B)A mixture at about 30% by mass or more, (I)Formula II, that is, 【Chemical Formula 5】 a compound of, wherein in the formula, (i)m = 0 to 20, (ii)n = 0 to 20, (iii) R ３ is hydrogen, C １ - C １０ linear alkyl group, fluorine-substituted C １ - C １０ linear alkyl group, nitrogen-containing group, oxygen-containing group, C ３ - C １０ branched-chain alkyl group, C ３ - C １０ cyclic alkyl group, C ５ - C １２ aryl group, C ２ - C １０ linear or branched alkenyl group and C ２ - C １０ linear or branched alkynyl group, [Chemical Formula 6] Z １ and Z ２ selected from the group consisting of, and (iv) R ａ and R ｂ each independently represents a C １ to C １０ linear alkyl group, a C ３ to C １０ branched alkyl group, a C ３ to C １０ cyclic alkyl group, a C ５ to C １２ aryl group, a C ２ to C １０ linear or branched alkenyl group, a C ２ to C １０ linear or branched alkynyl group 【Chemical Formula 7】 and 【Chemical 8】 C replaced by １ ~C １０ selected from alkyl, (v) Z １ and Z ２ are each independently (a) 【Chemical Formula 9】 (b) 【Chemical Formula 10】 (c) 【Chemical 11】 (d) and 【Chemical Formula 12】 said compound selected from, and (II)An aqueous solvent, said mixture containing a composition containing

3. (A)Pure phosphoric acid at about 70% by mass or less, (B)A mixture at about 30% by mass or more, (I)Formula III, that is, 【Chemical 13】 a compound of, wherein in the formula, (i)Provided that at least one of m1 and m2 is 1 or more, m1 and m2 are each equal to 0 to 10, (ii)n = 0 or 1, (iii) R １ R ２ and R ３ each independently is hydrogen, C １ to C ６ linear alkyl group, C ３ to C ６ branched alkyl group, and 【Chemical Formula 14】 selected from the group consisting of, (iv)A is (a) 【Chemical Formula 15】 (b) R ａ is hydrogen, C １ ~ C ６ linear alkyl group, C ３ ~ C ６ selected from branched alkyl groups 【Chemical 16】 (c) R ａ and R ｂ are each independently hydrogen, C １ ~ C ６ linear alkyl group, C ３ ~ C ６ selected from branched alkyl groups 【Chemical 17】 (d) 【Chemical Formula 18】 selected from, (v)L is (a) 【Chemical 19】 (b) 【Chemical 20】 (c) 【Chemical 21】 (d) 【Chemical 22】 (e) X １ , X ２ , and X ３ each is independently selected from Cl, Br, F, or I 【Chemical 23】 (f) 【Chemical 24】 (g) 【Chemical 25】 (h) 【Chemical 26】 (i) 【Chemical 27】 (j) 【Chemical 28】 said compound selected from, and (II)An aqueous solvent, said mixture containing a composition containing

4. The composition according to any one of Claims 1 to 3, wherein said mixture further contains at least one additional acid other than pure phosphoric acid.

5. wherein the mixture further comprises at least one additional acid other than pure phosphoric acid selected from HNO ３ , H ２ SO ４ , HCl, and methanesulfonic acid, the composition according to any one of claims 1 to 3.

6. The composition according to any one of Claims 1 to 3, wherein said mixture further contains pure sulfuric acid.

7. The composition according to any one of Claims 1 to 3, wherein said mixture further contains pure sulfuric acid at about 25% by mass or less.

8. The composition according to any one of Claims 1 to 3, wherein said mixture further contains pure methanesulfonic acid.

9. The composition according to any one of Claims 1 to 3, wherein said mixture further contains sulfonic acid.

10. (i)Said mixture further contains pure sulfuric acid, and (ii)The total content of said pure phosphoric acid and said pure sulfuric acid is between about 80% by mass and about 85% by mass of said composition. The composition according to any one of Claims 1 to 3.

11. (i)Said mixture further contains sulfuric acid, and (ii)The total content of said pure phosphoric acid and said pure sulfuric acid is about 83.5% by mass of said composition. The composition according to any one of Claims 1 to 3.

12. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.0 parts by mass to about 7.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

13. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.0 parts by mass to about 6.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

14. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.0 parts by mass to about 5.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

15. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.0 parts by mass to about 4.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

16. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.0 parts by mass to about 3.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

17. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.0 parts by mass to about 2.5 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

18. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 3.0 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

19. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.25 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

20. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.5 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

21. The composition according to any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is about 2.75 parts by mass of pure phosphoric acid per 1 part by mass of pure sulfuric acid.

22. The composition according to any one of claims 1 to 3, wherein the aqueous solvent contains water.

23. The composition according to any one of claims 1 to 3, wherein the aqueous solvent consists essentially of water.

24. The composition according to any one of claims 1 to 3, wherein the aqueous solvent consists of water.

25. The composition according to any one of claims 1 to 3, wherein the mixture further comprises one or more additional silicon-containing compounds selected from alkylsilsesquioxanes, vinylsilsesquioxane, carboxylic acid alkylsilsesquioxane, and alkylene glycol alkylsilsesquioxane.

26. The composition according to any one of claims 1 to 3, wherein the total content of the pure phosphoric acid and the pure sulfuric acid ranges from about 80% to about 85% by mass of the composition.

27. The composition according to any one of claims 1 to 3, wherein the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition.

28. The composition according to any one of claims 1 to 3, wherein the formula consists essentially of the pure phosphoric acid and the mixture.

29. The composition according to any one of claims 1 to 3, wherein the formula consists of the pure phosphoric acid and the mixture.

30. The composition according to claim 1, wherein the formula consists essentially of the pure phosphoric acid and the mixture, and consists essentially of the compound of formula I and the aqueous solvent.

31. The composition according to claim 1, wherein the formula consists of the pure phosphoric acid and the mixture, and the mixture consists of the compound of formula I and the aqueous solvent.

32. The composition according to claim 2, wherein the formula consists essentially of the pure phosphoric acid and the mixture, and consists essentially of the compound of formula II and the aqueous solvent.

33. The composition according to claim 2, wherein the formula consists of the pure phosphoric acid and the mixture, and the mixture consists of the compound of formula II and the aqueous solvent.

34. The composition according to claim 3, wherein the formula consists essentially of the pure phosphoric acid and the mixture, and consists essentially of the compound of formula III and the aqueous solvent.

35. The composition according to claim 3, wherein the formula consists of the pure phosphoric acid and the mixture, and the mixture consists of the compound of formula III and the aqueous solvent.

36. The composition according to claim 1, wherein m is 0.

37. The composition according to claim 1, wherein the content of the compound of formula I is about 5% by mass or less.

38. The composition according to claim 1, wherein the content of the compound of formula I is about 4% by mass or less.

39. The composition according to claim 1, wherein the content of the compound of formula I is about 3% by mass or less.

40. The composition according to claim 1, wherein the content of the compound of formula I is about 2% by mass or less.

41. The composition according to claim 1, wherein the content of the compound of formula I is about 1% by mass or less.

42. R １ 、R ２ 、R ３ 、R ４ 、and R ５ The composition according to claim 1, wherein each of R

43. R １ , R ２ , R ３ , R ４ , and R ５ The composition according to claim 1, wherein each of them is hydrogen.

44. R １ 、R ２ 、R ３ 、R ４ 、and R ５ The composition according to claim 1, wherein at least one of them is other than hydrogen.

45. (i) R ａ and R ｂ each of which 【Chemical Formula 29】 and (ii) R １ R ２ R ４ and R ５ each of which is 【Chemical Formula 30】 and (iii) m = 0, the composition according to claim 1.

46. (i) R ａ and R ｂ each of 【Chemical 31】 and (ii) R １ R ２ R ４ and R ５ each of which is 【Chemical 32】 and (iii) m = 0, the composition according to claim 1.

47. (i) R ａ and R ｂ each of 【Chemical 33】 and (ii) R １ R ２ R ３ R ４ R ５ each of and R 【Chemical 34】 and (iii) m = 0, the composition according to claim 1.

48. (i) The compound of formula I is 【Chemical 35】 the composition according to claim 1.

49. (i) The compound of formula I is 【Chemical Formula 36】 and (ii) the mixture further contains pure sulfuric acid, the composition according to claim 1.

50. (i) The compound of formula I is 【Chemical 37】 and (ii) the mixture further contains pure sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is in the range of about 80% to about 85% by mass of the composition, the composition according to claim 1.

51. (i) The compound of formula I is 【Chemical 38】 and (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition, the composition according to claim 1.

52. (i) The compound of formula I is 【Chemical Formula 39】 and (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.83% by mass of the composition, the composition according to claim 1.

53. (i) The compound of formula I is 【Chemical 40】 and (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.94% by mass of the composition, the composition according to claim 1.

54. (i) The compound of formula I is 【Chemical Formula 41】 and (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 84.27% by mass of the composition, the composition according to claim 1.

55. (i) The compound of formula I is 【Chemical 42】 and (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 84.6% by mass of the composition, the composition according to claim 1.

56. (i) The compound of formula I is 【Chemical Formula 43】 the composition according to claim 1.

57. (i) The compound of formula I is 【Chemical 44】 and (ii) the mixture further contains pure sulfuric acid, the composition according to claim 1.

58. (i) The compound of formula I is 【Chemical 45】 and (ii) the mixture further contains pure sulfuric acid, and (iii) The total content of the pure phosphoric acid and the pure sulfuric acid is in the range of about 80% to about 85% by mass of the composition. The composition according to claim 1.

59. (i) The compound of formula I is 【Chemical 46】 and (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition, The composition according to claim 1.

60. (A) Pure phosphoric acid of about 60% by mass or less, (B) A mixture of about 40% by mass or more, which (i) is about 5% by mass or less of 【Chemical 47】 (ii) pure sulfuric acid of about 24% by mass or less, and (iii) an aqueous solvent containing water The composition comprising the mixture comprising

61. (A) Pure phosphoric acid of about 60% by mass or less, (B) A mixture of about 40% by mass or more, which (i) is about 5% by mass or less of 【Chemical 48】 (ii) pure sulfuric acid of about 24% by mass or less, and (iii) an aqueous solvent consisting essentially of water The mixture consisting essentially of The composition consisting essentially of

62. (A) Pure phosphoric acid of about 60% by mass or less, (B) A mixture of about 40% by mass or more, which (i) is about 5% by mass or less of 【Chemical 49】 (ii) pure sulfuric acid of about 24% by mass or less, and (iii) an aqueous solvent consisting of water The mixture consisting of The composition consisting of

63. The composition according to claim 2, wherein m is 0.

64. The composition according to claim 2, wherein n is 0.

65. The composition according to claim 2, wherein m is 0 and n is 0.

66. The composition according to claim 2, wherein the content of the compound of formula II is about 5% by mass or less.

67. The composition according to claim 2, wherein the content of the compound of formula II is about 4% by mass or less.

68. The composition according to claim 2, wherein the content of the compound of formula II is about 3% by mass or less.

69. The composition according to claim 2, wherein the content of the compound of formula II is about 2% by mass or less.

70. The composition according to claim 2, wherein the content of the compound of formula II is about 1% by mass or less.

71. (i) m = 0 and n = 3, and (ii) Z １ and Z ２ each is 【Chemical Formula 50】 The composition according to claim 2, which is

72. (i) m = 0, (ii) n = 3 and (iii) Z １ and Z ２ each of 【Chemical 51】 The composition according to claim 2, which is

73. (i) m = 0, (ii) n = 3 and (ii) Z １ and Z ２ each of 【Chemical 52】 The composition according to claim 2, which is

74. (i) m = 0, (ii) n = 3 and (iii) Z １ and Z ２ each of 【Chemical 53】 The composition according to claim 2, which is

75. (i) The compound of formula II is 【Chemical 54】 and (ii) the mixture further contains pure sulfuric acid, The composition according to claim 2.

76. (i) The compound of formula II is 【Chemical Formula 55】 and (ii) the mixture further contains pure sulfuric acid, and (iii) The total content of the pure phosphoric acid and the pure sulfuric acid is in the range of about 80% by mass to about 85% by mass of the composition. The composition according to claim 2.

77. (i) The compound of formula II is 【Chemical 56】 and (ii) The mixture further contains sulfuric acid, and (iii) The total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition. The composition according to claim 2.

78. (i) The compound of formula II is 【Chemical 57】 and (ii) The mixture further contains pure sulfuric acid. The composition according to claim 2.

79. (i) The compound of formula II is 【Chemical Formula 58】 and (ii) The mixture further contains pure sulfuric acid, and (iii) The total content of the pure phosphoric acid and the pure sulfuric acid is in the range of about 80% by mass to about 85% by mass of the composition. The composition according to claim 2.

80. (i) The compound of formula II is 【Chemical Formula 59】 and (ii) The mixture further contains sulfuric acid, and (iii) The total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition. The composition according to claim 2.

81. The composition according to claim 3, wherein the content of the compound of formula III is about 5% by mass or less.

82. The composition according to claim 3, wherein the content of the compound of formula III is about 4% by mass or less.

83. The composition according to claim 3, wherein the content of the compound of formula III is about 3% by mass or less.

84. The composition according to claim 3, wherein the content of the compound of formula III is about 2% by mass or less.

85. The composition according to claim 3, wherein the content of the compound of formula III is about 1% by mass or less.

86. (i) R １ , R ２ , and R ３ each is 【Chemical Formula 60】 and (ii) L is 【Chemical Formula 61】 and (iii) n = 0, and (iv) the sum of m1 and m2 is 1 to 5. The composition according to claim 3.

87. (i) R １ , R ２ , and R ３ each is 【Chemical Formula 62】 and (ii) the sum of m1 and m2 is 3, and (iii) n = 0, and (iv) L is 【Chemical Formula 63】 The composition according to claim 3.

88. (i) R １ , R ２ , and R ３ each is 【Chemical Formula 64】 and (ii) m2 = 3, and (iii) n = 1, and (iv) A is 【Chemical Formula 65】 where Ra = H, and (v) m1 = 0, and (vi) L is 【Chemical Formula 66】 The composition according to claim 3.

89. (i) R １ , R ２ , and R ３ each is 【Chemical Formula 67】 and (ii) m2 = 3, and (iii) n = 1, and (iv) A is 【Chemical Formula 68】 and (v) m1 = 0, and (vi) L is 【Chemical Formula 69】 The composition according to claim 3.

90. (i) R １ , R ２ , and R ３ each is 【Chemical Formula 70】 and (ii) m2 = 3, and (iii) n = 1, and (iv) A is where Ra is 【Chemical 71】 and (v) m1 = 0, and (vi) L is 【Chemical Formula 72】 ​ 【Chemical Formula 73】 The composition according to claim 3, which is

91. (i) R １ , R ２ , and R ３ each is 【Chemical 74】 and (ii) the sum of m1 and m2 is = 2, (iii) n = 0, and (iv) L is X １ , X ２ and X ３ each of which is 【Chemical 75】 which is 【Chemical 76】 The composition according to claim 3, which is

92. (i) R １ , R ２ , and R ３ each is 【Chemical 77】 which is, (ii) m2 = 3, (iii) n = 1, (iv) A is Ra where 【Chemical 78】 which is 【Chemical Formula 79】 which is, (v) m1 = 0, (vi) L is 【Chemical 80】 The composition according to claim 3, which is

93. (i) R １ , R ２ , and R ３ each is 【Chemical Formula 81】 which is, (ii) m2 = 2, (iii) n = 1, (iv) A is 【Chemical 82】 which is, (v) m1 = 0 and (vi) L is 【Chemical Formula 83】 The composition according to claim 3, which is

94. (i) R １ , R ２ , and R ３ each is 【Chemical 84】 where (ii) m2 = 3, (iii) n = 1, and (iv) A is R ａ and R ｂ are 【Chemical 85】 which is 【Chemical 86】 which is, (v) m1 = 3, (vi) L is 【Chemical 87】 The composition according to claim 3, which is

95. (i) R １ , R ２ , and R ３ each is 【Chemical 88】 which is, (ii) the sum of m1 and m2 is 2, (iii) n = 0, (iv) L is 【Chemical 89】 The composition according to claim 3, which is

96. (i) R １ , R ２ , and R ３ each is 【Chemical Formula 90】 which is, (ii) the sum of m1 and m2 is 3, (iii) n = 0, (iv) L is 【Chemical Formula 91】 The composition according to claim 3, which is

97. (i) R １ , R ２ , and R ３ each is 【Chemical Formula 92】 which is, (ii) the sum of m1 and m2 is 1, (iii) n = 0, (iv) L is 【Chemical Formula 93】 The composition according to claim 3, which is

98. (i) The compound of formula III is R where 【Chemical Formula 94】 which is, x = 1 to 5 【Chemical Formula 95】 which is, and (ii) the mixture further contains pure sulfuric acid, The composition according to claim 3.

99. (i) The compound of formula III is R where 【Chemical Formula 96】 which is, x = 1 to 5 【Chemical Formula 97】 which is, (ii) the mixture further contains pure sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is in the range of about 80% to about 85% by mass of the composition, The composition according to claim 3.

100. (i) The compound of formula III is R where 【Chemical Formula 98】 which is, x = 1 to 5, 【Chemical Formula 99】 which is, (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition, The composition according to claim 3.

101. (i) the compound of formula III is Si(OCH ３ ) ３ (CH ２ CH ２ CF ３ ) and (ii) the mixture further contains pure sulfuric acid, The composition according to claim 3.

102. (i) the compound of formula III is Si(OCH ３ ) ３ (CH ２ CH ２ CF ３ ), and (ii) the mixture further contains pure sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is in the range of about 80% to about 85% by mass of the composition, The composition according to claim 3.

103. (i) the compound of formula III is Si(OCH ３ ) ３ (CH ２ CH ２ CF ３ ), (ii) the mixture further contains sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition, The composition according to claim 3.

104. (i) The compound of formula III is 【Chemical Formula 100】 which is, and (ii) the mixture further comprises pure sulfuric acid, The composition according to claim 3. **Claim 105** (i) the compound of formula III is 【Chemical 101】 wherein, (ii) the mixture further comprises pure sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid ranges from about 80% to about 85% by mass of the composition, The composition according to claim 3. **Claim 106** (i) the compound of formula III is 【Chemical 102】 wherein, (ii) the mixture further comprises sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition, The composition according to claim 3. **Claim 107** (i) the compound of formula III is 【Chemical 103】 wherein, and (ii) the mixture further comprises pure sulfuric acid, The composition according to claim 3. **Claim 108** (i) the compound of formula III is 【Chemical 104】 wherein, (ii) the mixture further comprises pure sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid ranges from about 80% to about 85% by mass of the composition, The composition according to claim 3. **Claim 109** (i) the compound of formula III is 【Chemical 105】 wherein, (ii) the mixture further comprises sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition, The composition according to claim 3. **Claim 110** (i) the compound of formula III is 【Chemical 106】 wherein, and (ii) the mixture further comprises pure sulfuric acid, The composition according to claim 3. **Claim 111** (i) the compound of formula III is 【Chemical 107】 wherein, (ii) the mixture further comprises pure sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid ranges from about 80% to about 85% by mass of the composition, The composition according to claim 3. **Claim 112** (i) the compound of formula III is 【Chemical 108】 wherein, (ii) the mixture further comprises sulfuric acid, and (iii) the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.5% by mass of the composition, The composition according to claim 3. **Claim 113** The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 2700. **Claim 114** The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 2500 or more. **Claim 115** The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 2250 or more.

116. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 2000 or more.

117. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 1500 or more.

118. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 1250 or more.

119. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 1000 or more.

120. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 500 or more.

121. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide of about 300 or more.

122. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity for silicon nitride between about 1500 and about 2700 that is superior to the etching selectivity for silicon oxide.

123. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity for silicon nitride between about 2000 and about 2700 that is superior to the etching selectivity for silicon oxide.

124. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide in the range of about 2250 to about 2700.

125. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide in the range of about 2500 to about 2700.

126. The composition according to any one of claims 1 to 3, wherein the composition has an etching selectivity of silicon nitride to silicon oxide in the range of about 2600 to about 2700.

127. (A)More than about 70% by mass of pure phosphoric acid, (B)A mixture of less than about 30% by mass, (I)Formula I, that is, 【Chemical 109】 A compound of, wherein in the formula, (i)m = 0 to 20, (ii) R １ , R ２ , R ３ , R ４ , and R ５ each is independently hydrogen, C １ - C １０ linear alkyl group, fluorine-substituted C １ - C １０ linear alkyl group, nitrogen-containing group, oxygen-containing group, C ３ - C １０ branched-chain alkyl group, C ３ - C １０ cyclic alkyl group, C ５ - C １２ aryl group, C ２ - C １０ linear or branched alkenyl group, C ２ - C １０ linear or branched alkynyl group, and 【Chemical 110】 Selected from the group consisting of, and (iii) R ａ and R ｂ each independently is C １ to C １０ linear alkyl group, C ３ to C １０ branched alkyl group, C ３ to C １０ cyclic alkyl group, C ５ to C １２ aryl group, C ２ to C １０ linear or branched alkenyl group, C ２ to C １０ linear or branched alkynyl group 【Chemical 111】 And 【Chemical 112】 C replaced by １ ~C １０ said compound selected from alkyl, and (II)An aqueous solvent, The mixture containing the above, A composition containing the above.

128. (A) More than about 70% by mass of pure phosphoric acid, (B) A mixture of less than about 30% by mass, (I) Formula II, that is, 【Chemical 113】 A compound of, wherein in the formula, (i) m = 0 to 20, (ii) n = 0 to 20, (iii) R ３ is hydrogen, C １ to C １０ linear alkyl group, fluorine-substituted C １ to C １０ linear alkyl group, nitrogen-containing group, oxygen-containing group, C ３ to C １０ branched alkyl group, C ３ to C １０ cyclic alkyl group, C ５ to C １２ aryl group, C ２ to C １０ linear or branched alkenyl group and C ２ to C １０ linear or branched alkynyl group, 【Chemical 114】 Z １ and Z ２ selected from the group consisting of, (iv) R ａ and R ｂ each independently represents a C １ to C １０ linear alkyl group, a C ３ to C １０ branched alkyl group, a C ３ to C １０ cyclic alkyl group, a C ５ to C １２ aryl group, a C ２ to C １０ linear or branched alkenyl group, a C ２ to C １０ linear or branched alkynyl group 【Chemical 115】 and 【Chemical 116】 C replaced by １ ~C １０ selected from alkyl, (v) Z １ and Z ２ are each independently (a) 【Chemical 117】 (b) 【Chemical 118】 (c) 【Chemical 119】 (d) and 【Chemical 120】 The compound selected from, and (II) An aqueous solvent, The mixture containing, A composition containing.

129. (A) More than about 70% by mass of pure phosphoric acid, (B) A mixture of less than about 30% by mass, (I) Formula III, that is, 【Chemical 121】 A compound of, wherein in the formula, (i) Provided that at least one of m1 and m2 is 1 or more, m1 and m2 are each equal to 0 to 10, (ii) n = 0 or 1, (iii) R １ R ２ and R ３ each of which is independently hydrogen, C １ to C ６ linear alkyl group, C ３ to C ６ branched alkyl group, and 【Chemical 122】 Selected from the group consisting of, (iv) A is (a) [Chemical 123] (b) R ａ is hydrogen, C １ ~ C ６ linear alkyl group, C ３ ~ C ６ selected from branched alkyl groups 【Chemical 124】 (c) R ａ and R ｂ each independently is hydrogen, C １ ~ C ６ linear alkyl group, C ３ ~ C ６ selected from branched alkyl groups 【Chemical 125】 (d) 【Chemical 126】 Selected from, (v) L is (a) 【Chemical 127】 (b) 【Chemical 128】 (c) 【Chemical 129】 (d) 【Chemical 130】 (e) X １ , X ２ , and X ３ each of which is independently selected from Cl, Br, F, or I 【Chemical 131】 (f) 【Chemical 132】 (g) 【Chemical 133】 (h) 【Chemical 134】 (i) 【Chemical 135】 (j) 【Chemical 136】 The compound selected from, and (II) An aqueous solvent, The mixture containing, A composition containing.

130. The composition according to any one of claims 127 to 129, wherein the composition contains (i) more than about 75% by mass of pure phosphoric acid and (ii) less than about 25% by mass of a mixture.

131. The composition according to any one of claims 127 to 129, wherein the mixture further contains at least one additional acid other than pure phosphoric acid.

132. wherein the mixture further comprises at least one additional acid other than pure phosphoric acid selected from HNO ３ , H ２ SO ４ , HCl, and methanesulfonic acid; the composition according to any one of claims 127 to 129.

133. The composition according to any one of claims 127 to 129, wherein the mixture further contains pure sulfuric acid.

134. The composition according to any one of claims 127 to 129, wherein the mixture further contains about 10% by mass or less of pure sulfuric acid.

135. The composition according to any one of claims 127 to 129, wherein the mixture further contains pure methanesulfonic acid.

136. The composition according to any one of claims 127 to 129, wherein the mixture further contains sulfonic acid.

137. The composition according to any one of claims 127 to 129, wherein the aqueous solvent contains water.

138. The composition according to any one of claims 127 to 129, wherein the aqueous solvent consists essentially of water.

139. The composition according to any one of claims 127 to 129, wherein the aqueous solvent consists of water.

140. The composition according to any one of claims 127 to 129, wherein the mixture further comprises one or more additional silicon-containing compounds selected from alkylsilsesquioxanes, vinylsilsesquioxane, carboxylic acid alkylsilsesquioxane, and alkylene glycol alkylsilsesquioxane.

141. The composition according to any one of claims 127 to 129, wherein the formula consists essentially of the pure phosphoric acid and the mixture.

142. The composition according to any one of claims 127 to 129, wherein the formula consists of the pure phosphoric acid and the mixture.

143. The composition according to claim 127, wherein the formula consists essentially of the pure phosphoric acid and the mixture, and consists essentially of the compound of formula I and the aqueous solvent.

144. The composition according to claim 127, wherein the formula consists of the pure phosphoric acid and the mixture, and the mixture consists of the compound of formula I and the aqueous solvent.

145. The composition according to claim 128, wherein the formula consists essentially of the pure phosphoric acid and the mixture, and consists essentially of the compound of formula II and the aqueous solvent.

146. The composition according to claim 128, wherein the formula consists of the pure phosphoric acid and the mixture, and the mixture consists of the compound of formula II and the aqueous solvent.

147. The composition according to claim 129, wherein the formula consists essentially of the pure phosphoric acid and the mixture, and consists essentially of the compound of formula III and the aqueous solvent.

148. The composition according to claim 129, wherein the formula consists of the pure phosphoric acid and the mixture, and the mixture consists of the compound of formula III and the aqueous solvent.

149. R １ 、 R ２ 、 R ３ 、 R ４ 、 and R ５ The composition according to claim 127, wherein each of is the same.

150. R １ 、 R ２ 、 R ３ 、 R ４ 、 and R ５ The composition according to claim 127, wherein each of

151. R １ 、R ２ 、R ３ 、R ４ 、and R ５ The composition according to claim 127, wherein at least one of them is other than hydrogen.

152. The composition according to claim 127, wherein the content of the compound of formula I is about 5% by mass or less.

153. The composition according to claim 127, wherein the content of the compound of formula I is about 4% by mass or less.

154. The composition according to claim 127, wherein the content of the compound of formula I is about 3% by mass or less.

155. The composition according to claim 127, wherein the content of the compound of formula I is about 2% by mass or less.

156. The composition according to claim 127, wherein the content of the compound of formula I is about 1% by mass or less.

157. (i) R ａ and R ｂ each of 【Chemical 137】 and (ii) R １ R ２ R ４ and R ５ each of which is 【Chemical 138】 and (iii) m = 0, the composition according to claim 127.

158. (i) R ａ and R ｂ each of 【Chemical 139】 and (ii) R １ R ２ R ４ and R ５ each of 【Chemical 140】 and (iii) m = 0, and (iv) R ３ = -C ３ H ６ NH ２ The composition according to claim 127, wherein it is

159. (i) R ａ and R ｂ each of 【Chemical 141】 and (ii) R １ R ２ R ３ R ４ and R ５ each of which is hydrogen, and (iii) m = 0, the composition according to claim 128.

160. wherein the compound of formula I is 【Chemical 142】 the composition according to claim 128. **Claim 161** wherein the compound of formula I is 【Chemical 143】 and wherein the content of the pure phosphoric acid is about 80.75% by mass of the composition, the composition according to claim 127. **Claim 162** wherein the compound of formula I is 【Chemical 144】 and wherein the mixture further contains pure sulfuric acid, the composition according to claim 127. **Claim 163** wherein the compound of formula I is 【Chemical 145】 and wherein the mixture further contains pure sulfuric acid, and wherein the total content of the pure phosphoric acid and the pure sulfuric acid is in the range of about 80% to about 85% by mass of the composition, the composition according to claim 127. **Claim 164** wherein the compound of formula I is 【Chemical 146】 and wherein the mixture further contains sulfuric acid, and wherein the total content of the pure phosphoric acid and the pure sulfuric acid is about 81.85% by mass of the composition, the composition according to claim 127. **Claim 165** wherein the compound of formula I is 【Chemical 147】 and wherein the mixture further contains sulfuric acid, and wherein the total content of the pure phosphoric acid and the pure sulfuric acid is about 82.4% by mass of the composition, the composition according to claim 127. **Claim 166** wherein the compound of formula I is 【Chemical 148】 and wherein the mixture further contains sulfuric acid, and wherein the total content of the pure phosphoric acid and the pure sulfuric acid is about 82.95% by mass of the composition, the composition according to claim 127. **Claim 167** wherein the compound of formula I is 【Chemical 149】 and wherein the mixture further contains sulfuric acid, and wherein the total content of the pure phosphoric acid and the pure sulfuric acid is about 83.23% by mass of the composition, the composition according to claim 127. **Claim 168** wherein the compound of formula I is 【Chemical 150】 the composition according to claim 127. **Claim 169** wherein the compound of formula I is 【Chemical 151】 and wherein the content of the pure phosphoric acid is about 80.75% by mass of the composition, the composition according to claim 127. **Claim 170** wherein the compound of formula II is 【Chemical 152】 the composition according to claim 128. **Claim 171** wherein the compound of formula II is 【Chemical 153】 and wherein the content of the pure phosphoric acid is about 80.75% by mass of the composition, the composition according to claim 128. **Claim 172** wherein the compound of formula II is 【Chemical 154】 the composition according to claim 128. **Claim 173** wherein the compound of formula II is 【Chemical 155】 and wherein the content of the pure phosphoric acid is about 80.75% by mass of the composition, The composition according to claim 128.

174. (i) the compound of formula III is 【Chemical 156】 the composition according to claim 129.

175. (i) the compound of formula III is 【Chemical 157】 and (ii) the content of the pure phosphoric acid is about 80.75% by mass of the composition, the composition according to claim 129.

176. (i) the compound of formula III is 【Chemical 158】 the composition according to claim 129.

177. (i) the compound of formula III is 【Chemical 159】 and (ii) the content of the pure phosphoric acid is about 80.75% by mass of the composition, the composition according to claim 129.

178. A method for selectively improving the etching rate of silicon nitride with respect to silicon dioxide on a semiconductor substrate containing silicon nitride and silicon dioxide, comprising: (a) contacting the semiconductor substrate containing silicon nitride and silicon dioxide with the composition according to any one of claims 1 to 177, and (b) washing the semiconductor element after at least a part of the silicon nitride is removed the method comprising the above.

179. The method according to claim 178, further comprising a step of drying the semiconductor element.

180. The method according to claim 178, wherein the etching selectivity of silicon nitride with respect to silicon dioxide is more than about 300.

181. The method according to claim 178, wherein the contacting step is carried out at a temperature of about 160 °C.

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