KR20220073813A - Etching composition and method for selectively removing silicon nitride during fabrication of semiconductor devices - Google Patents

Abstract

The subject matter disclosed and claimed herein relates to an etching composition comprising a mixture comprising (A) phosphoric acid and (B) (i) a silicon-containing compound and (ii) an aqueous solvent. In some embodiments, the etching composition comprises additional components. The etching composition is useful for selectively removing silicon nitride versus silicon oxide from microelectronic devices having such material(s) during manufacture thereof.

Description

Etching composition and method for selectively removing silicon nitride during fabrication of semiconductor devices

The subject matter disclosed and claimed herein relates to an etching composition, and more particularly a high selectivity etching composition capable of selectively removing a nitride film while minimizing the etch rate of the oxide film, and a method of fabricating a semiconductor comprising an etching process using the etching composition. it's about

Selective silicon nitride (SiN _x ) sacrificial removal is one of the important steps for 3D NAND memory device fabrication. After the etching process, the SiN _x is removed and the silicon oxide (SiO _x ) core along with the SiO _x fins remains unchanged. Traditionally, SiN _x etching could be achieved by high temperature phosphoric acid at 160 °C, but the selectivity of SiN _x etching to silicon or silicon oxide materials is generally low compared to advanced 3D NAND memory technology.

As semiconductor devices become more highly integrated, reliability and electrical characteristics of semiconductor devices are more susceptible to damage or deformation of layers constituting the semiconductor device. Therefore, when an etching process for selectively removing a specific material layer is performed using an etching agent, the etching agent must have a higher etching selectivity compared to other material layers, and the etching process generates fewer byproducts to cause process defects It is desirable to reduce

Thus, with such high integration, material selectivity requirements for selective SiN _x sacrificial removal in 3D NAND fabrication become even more important to the point that it is desirable to effectively leave the SiO _x layer unchanged while etching the SiN _x layer. Therefore, there is a need in the art to further suppress the SiO _x etch rate to achieve a much higher SiN _x to SiO _x selectivity.

In one aspect, the disclosed and claimed subject matter is an etching composition suitable for selectively removing silicon nitride versus silicon oxide from a microelectronic device, comprising:

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)

It provides an etching composition comprising a.

In some embodiments, the silicon-containing compound has Formula I:

In the above formula,

(i) m = 0 to 20,

OH의 군으로부터 선택되고,(ii) each R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently hydrogen, a C ₁ to C ₁₀ linear alkyl group, a C ₁ to C ₁₀ linear alkyl group substituted with fluorine, a 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 group alkynyl group,

selected from the group of OH,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택된다.(iii) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH.

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

In the above formula,

(i) m = 0 to 20,

(ii) n = 0 to 20;

OH, Z¹ 및 Z²의 군으로부터 선택되고,(iii) R ³ is hydrogen, C ₁ to C ₁₀ linear alkyl group, C ₁ to C ₁₀ linear alkyl group substituted with fluorine, 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,

selected from the group of OH, Z ¹ and Z ² ,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택되고,(iv) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH,

(v) Z ¹ and Z ² are each independently

, a.

,

, b.

,

N⁺(CH₃)₃Cl^-, 및c.

N ⁺ (CH ₃ ) ₃ Cl ⁻ , and

CH(OH)CH₂OH로부터 선택된다.d.

CH(OH)CH ₂ OH.

In some embodiments, the silicon-containing compound has Formula III:

In the above formula,

(i) m1 and m2 are each 0 to 10, provided that at least one of m1 and m2 is ≥ 1,

(ii) n = 0 or 1,

O-C₁ 내지 C₆ 선형 알킬기의 군으로부터 선택되고,(iii) each R ¹ , R ² and R ³ is independently hydrogen, a C ₁ to C ₆ linear alkyl group, a C ₃ to C ₆ branched alkyl group, and

OC ₁ to C ₆ selected from the group of linear alkyl groups,

(iv) A is

, a.

,

(여기서, R^a는 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), b.

(wherein R ^a is selected from hydrogen, C ₁ to C ₆ linear alkyl group, C ₃ to C ₆ branched alkyl group),

(여기서, R^a 및 R^b는 각각 독립적으로 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), 및c.

(wherein R ^a and R ^b are each independently selected from hydrogen, a C ₁ to C ₆ linear alkyl group, and a C ₃ to C ₆ branched alkyl group), and

로부터 선택되고,d.

is selected from

(v) L is

, a.

,

,b.

,

, c.

,

, d.

,

(여기서, 각각의 X¹, X² 및 X³는 독립적으로 Cl, Br, F 또는 I로부터 선택됨),e.

(wherein each of X ¹ , X ² and X ³ is independently selected from Cl, Br, F or I),

,f.

,

,g.

,

,h.

,

, 및i.

, and

로부터 선택된다.j.

is selected from

In some embodiments, the etching composition comprises up to about 70% by weight pure phosphoric acid. In a further aspect of this embodiment, the etching composition comprises no more than approximately 60 weight percent pure phosphoric acid. In a further aspect of this embodiment, the etching composition comprises at least about 30% by weight of the mixture. In a further aspect of this embodiment, the etching composition comprises at least about 40% by weight of the mixture. In a further aspect of this embodiment, pure phosphoric acid and the mixture are combined to constitute approximately 100% by weight of the etching composition.

In some embodiments, the etching composition comprises greater than approximately 70 weight percent pure phosphoric acid. In a further aspect of this embodiment, the etching composition comprises greater than approximately 75 weight percent pure phosphoric acid. In a further aspect of this embodiment, the etching composition comprises no more than about 30% by weight of the mixture. In a further aspect of this embodiment, the etching composition comprises at least about 25% by weight of the mixture. In a further aspect of this embodiment, pure phosphoric acid and the mixture are combined to constitute approximately 100% by weight of the etching composition.

In some embodiments, the mixture further comprises at least one additional acid other than phosphoric acid. In one aspect of this embodiment, the at least one additional acid is in nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl) and sulfonic acid (eg, methane sulfuric acid (CH ₃ SO ₃ H)). one In a further aspect, the at least one additional acid comprises sulfuric acid.

In another aspect, disclosed and claimed subject matter herein is a method for selectively improving the etch rate of silicon nitride compared to silicon dioxide in a composite semiconductor device comprising silicon nitride and silicon dioxide, said method comprising a composite comprising silicon nitride and silicon dioxide and contacting the semiconductor device with the etching composition.

In some embodiments, the compound of Formula I, Formula II, and/or Formula III contains an epoxy group, a styryl group, a metasiloxy group, an acryloxy group, a urea group, an isocyanate group, an isocyanurate group and It may include any group such as a mercapto group.

Embodiments of the subject matter disclosed and claimed herein may be used alone or in combination with one another.

details

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

The use of the singular and the like in the context of describing the subject matter disclosed and claimed herein (especially in the context of the following claims) includes both the singular and the plural unless otherwise indicated herein or otherwise clearly contradicted by context. should be interpreted as The terms “comprising,” “having,” “including,” and “containing,” are open-ended terms (i.e., “including but not limited to”) unless stated otherwise. meaning) should be interpreted as Recitation of ranges of values herein, unless otherwise indicated herein, are merely intended to serve as a shorthand way of referring individually to each separate value falling within that range, and each discrete value is incorporated herein as if individually recited in All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples or illustrative language (eg, “such as”) provided herein is merely intended to better illuminate the subject matter disclosed and claimed herein, unless otherwise claimed. In so far, no limitations are placed on the scope of the subject matter disclosed and claimed herein. No language in this specification should be construed as indicating any non-claimed element as essential to the practice of this disclosed and claimed subject matter.

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

The subject matter disclosed and claimed herein relates generally to compositions useful for the selective removal of silicon nitride versus silicon oxide from microelectronic devices having such material(s) thereon during manufacture.

For convenience of reference, "microelectronic device" or "semiconductor substrate" refers to semiconductor wafers, flat panel displays, phase change memory devices, solar panels, and manufactured for use in microelectronic, integrated circuit, or computer chip applications. photovoltaic substrates, photovoltaic cells, and other products including microelectromechanical systems (MEMS). 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 on gallium. The solar substrate may be doped or undoped. The term “microelectronic device” is not meant to be limited in any way and is to be understood to include any substrate that will eventually become a microelectronic device or microelectronic assembly. The microelectronic device or semiconductor substrate may include low-k dielectric materials, barrier materials, and metals such as AlCu alloys, W, Ti, TiN, as well as other materials thereon.

As defined herein, “low-k dielectric material” corresponds to any material used as a dielectric material in a stacked microelectronic device, wherein the material has a dielectric constant less than about 3.5. have Preferably, the low-k dielectric material is a low polarity material such as a silicon-containing organic polymer, a silicon-containing hybrid organic/inorganic material, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG). silicate glass), silicon dioxide, and carbon-doped oxide (CDO) glass. It should be understood that the low-k dielectric material may have a variety of densities and a variety of porosity.

As defined herein, the term “barrier material” is used in the art to seal a metal wire, eg, a copper interconnect, to minimize diffusion of the metal, eg, copper, into a dielectric material. Any material used in Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

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

As used herein, the terms “about” and “approximately” are each intended to correspond to ±5% of the stated value.

As used herein, "neat" refers to the weight percent amount of an undiluted acid or other substance. For example, the inclusion of 100 g of 85% phosphoric acid consists of 85 g of acid and 15 g of diluent.

"는 또한 공유 결합의 부착점을 지정하기 위해 의도된 것이다.In addition to the known and understood expressions for the points of attachment of covalent bonds, the notation "

" is also intended to designate the point of attachment of a covalent bond.

In all such compositions, specific components of the composition are discussed with reference to weight percentage ranges inclusive of the lower zero limit, which components may or may not be present in various specific embodiments of the composition, and when such components are present, they are , it will be understood that these components may be present in concentrations as low as 0.001 weight percent, based on the total weight of the composition in which they are employed. It is noted that, unless otherwise indicated, all defined weight percentages of ingredients are based on the total weight of the composition. Additionally, unless otherwise indicated, all weight percentages are "pure", meaning that they do not include aqueous compositions present when added to the compositions. Any reference to “at least one” may be replaced by “one or more”. “At least one” and/or “one or more” includes “at least two” or “two or more” and “at least three” and “three or more”, and the like.

In the broad practice of the subject matter disclosed and claimed herein, the aforementioned etching composition comprising, consisting essentially of, or consisting of (A) phosphoric acid and (B) a mixture of an aqueous solvent and a silicon-containing compound as disclosed herein. is about

In some embodiments, the etching compositions disclosed herein are 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.

In a further embodiment, the etching composition consists essentially of (i) phosphoric acid and (ii) a mixture of a silicon-containing compound as disclosed herein with an aqueous solvent. In such embodiments, the combined amount of (i) and (ii) is not 100% by weight, and may include other ingredients that do not substantially change the effectiveness of the etching composition.

In another embodiment, the etching composition consists of varying concentrations of (i) phosphoric acid and (ii) a silicon-containing compound as disclosed herein and an aqueous solvent. In such embodiments, the combined amount of (i) and (ii) is approximately 100% by weight, but may include other minor and/or trace impurities present in minor amounts that do not substantially alter the effectiveness of the composition. For example, in one such embodiment, the etching composition may contain up to 2 weight percent impurities. In another embodiment, the etching composition may contain up to 1% by weight impurities. In a further embodiment, the etching composition may contain up to 0.05% by weight impurities.

When referring to the composition of the compositions of the present invention described herein in terms of weight percent, it is understood that the weight percent of all components, including non-essential components such as impurities, do not add more than 100%. In compositions "consisting essentially of" the stated ingredients, these ingredients may be added up to 100% by weight of the composition, or may be added to less than 100% by weight of the composition. When components are added up to less than 100% by weight, such compositions may contain some minor amounts of non-essential contaminants or impurities. For example, in one such embodiment, the etching composition may contain up to 2% by weight impurities. In another embodiment, the etching composition may contain up to 1% by weight impurities. In a further embodiment, the etching composition may contain up to 0.05% by weight impurities. In other such embodiments, the components form at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight, even more preferably at least 99.5% by weight, most preferably at least 99.9% by weight. and may include other components that do not substantially affect the performance of the etching composition. Alternatively, if no significant non-essential impurity components are present, it is understood that combinations of all essential components will be added up to essentially 100% by weight.

composition

As mentioned above, the subject matter disclosed and claimed herein is an etching composition comprising, consisting essentially of, or consisting of (A) phosphoric acid and (B) a mixture of an aqueous solvent and a silicon-containing compound as disclosed herein. is about In some embodiments, the etching composition may include other components.

ingredient

A. phosphoric acid

The etching composition of the subject matter disclosed and claimed herein comprises phosphoric acid. Commercial grade phosphoric acid may be used. Typically commercially available phosphoric acid is available in 80% to 85% aqueous solutions. In a preferred embodiment an electronic grade phosphoric acid solution is employed wherein such electronic grade compositions typically have a particle count of less than 100 particles/ml, the particle size being 0.5 microns or less and metal ions as low as ppm to ppb per liter. exists in the mountains. In certain embodiments, no other mineral acid is added to the compositions of the subject matter disclosed and claimed herein, such as, for example, hydrofluoric acid, nitric acid or mixtures thereof.

Phosphoric acid (on a pure basis) is included in an amount ranging from about 40% to about 95%, 45% to about 90% or 50% to about 90% or 55% of the composition having a starting point and an endpoint selected from the list of weight percentages. to about 85% by weight. Phosphoric acid may also be present in an amount defined by the following list of weight percentages: 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.

In some embodiments, the content of pure phosphoric acid is approximately 70% by weight or less. In a further aspect of this embodiment, the content of pure phosphoric acid is approximately 60% by weight or less.

In some embodiments, the content of pure phosphoric acid is greater than approximately 70% by weight. In a further aspect of this embodiment, the content of pure phosphoric acid is greater than approximately 75% by weight.

B. mixture

As mentioned above, the etching composition comprises a mixture of (I) a silicon-containing compound as disclosed herein and (II) an aqueous solvent.

I. Silicon-containing compounds

The amount of silicon-containing compound will range from about 0.001% to about 15% by weight of the etching composition. Preferably, the silicon-containing compound constitutes from about 0.1% to about 10% by weight of the etching composition. Unless otherwise indicated, the weight-percentages, including the weight percentages just before, of the silicon-containing compound added to the composition are on a pure basis. In alternative embodiments, the silicon-containing compound may be present in an amount within a range having starting and ending points defined by the following list of weight percentages: 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.

In some embodiments, the silicon-containing compound has Formula I:

In the above formula,

(i) m = 0 to 20,

OH의 군으로부터 선택되고,(ii) each R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently hydrogen, a C ₁ to C ₁₀ linear alkyl group, a C ₁ to C ₁₀ linear alkyl group substituted with fluorine, a 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 group alkynyl group,

selected from the group of OH,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택된다.(iii) each R ^a and R ^b is independently a 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 groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH.

In some embodiments of an etching composition comprising a silicon-containing compound of Formula (I), each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is the same. In a further aspect of this embodiment, each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is hydrogen.

In some embodiments of etching compositions comprising a 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.

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

In some embodiments of the etching composition, the content of the silicon-containing compound of formula (I) is approximately 5% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (I) is approximately 4% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (I) is approximately 3% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (I) is approximately 2% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (I) is approximately 1% by weight or less.

C₃H₆

이고, (ii) 각각의 R¹, R², R⁴ 및 R⁵가

H이고, (iii) m = 0인 화학식 I의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises: (i) each of R ^a and R ^b is

C ₃ H ₆

and (ii) each of R ¹ , R ² , R ⁴ and R ⁵ is

H, and (iii) m=0.

C₃H₆

이고, (ii) 각각의 R¹, R², R⁴ 및 R⁵가

H이고, (iii) m = 0이고, (iv) R³ =

C₃H₆NH₂인 화학식 I의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ^a and R ^b is

C ₃ H ₆

and (ii) each of R ¹ , R ² , R ⁴ and R ⁵ is

H, (iii) m = 0, and (iv) R ³ =

C ₃ H ₆ NH ₂ .

NH-C₂H₄

이고, (ii) 각각의 R¹, R², R³, R⁴ 및 R⁵가

H이고, (iii) m = 0인 화학식 I의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ^a and R ^b is

NH-C ₂ H ₄

and (ii) each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is

H, and (iii) m=0.

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

In the above formula,

(i) m = 0 to 20,

(ii) n = 0 to 20;

OH, Z¹ 및 Z²의 군으로부터 선택되고,(iii) R ³ is hydrogen, C ₁ to C ₁₀ linear alkyl group, C ₁ to C ₁₀ linear alkyl group substituted with fluorine, 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,

selected from the group of OH, Z ¹ and Z ² ,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택되고, (iv) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH,

(v) Z ¹ and Z ² are each independently

, a.

,

, b.

,

N⁺(CH₃)₃Cl^-, 및c.

N ⁺ (CH ₃ ) ₃ Cl ⁻ , and

CH(OH)CH₂OH로부터 선택된다.d.

CH(OH)CH ₂ OH.

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

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

In some embodiments of the etching composition, the content of the silicon-containing compound of formula (II) is approximately 5% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (II) is approximately 4% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (II) is approximately 3% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (II) is approximately 2% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (II) is approximately 1% by weight or less.

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

인 화학식 II의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) m = 0 and (ii) each of Z ¹ and Z ² is

silicon-containing compounds of formula (II).

인 화학식 II의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) m = 0, (ii) n = 0, and (iii) each of Z ¹ and Z ² is

silicon-containing compounds of formula (II).

N⁺(CH₃)₃Cl^-인 화학식 II의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) m = 0, (ii) n = 0, and (iii) each of Z ¹ and Z ² is

N ⁺ (CH ₃ ) ₃ Cl ⁻ .

CH(OH)CH₂OH인 화학식 II의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) m = 0, (ii) n = 0, and (iii) each of Z ¹ and Z ² is

CH(OH)CH ₂ OH.

In some embodiments, the silicon-containing compound has Formula III:

In the above formula,

(i) m1 and m2 are each 0 to 10, provided that at least one of m1 and m2 is ≥ 1,

(ii) n = 0 or 1,

O-C₁ 내지 C₆ 선형 알킬기의 군으로부터 선택되고,(iii) each R ¹ , R ² and R ³ is independently hydrogen, hydroxyl, a C ₁ to C ₆ linear alkyl group, a C ₃ to C ₆ branched alkyl group, and

OC ₁ to C ₆ selected from the group of linear alkyl groups,

(iv) A is

, a.

,

(여기서, R^a는 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), b.

(wherein R ^a is selected from hydrogen, C ₁ to C ₆ linear alkyl group, C ₃ to C ₆ branched alkyl group),

(여기서, R^a 및 R^b는 각각 독립적으로 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), 및 c.

(wherein R ^a and R ^b are each independently selected from hydrogen, a C ₁ to C ₆ linear alkyl group, and a C ₃ to C ₆ branched alkyl group), and

로부터 선택되고,d.

is selected from

(v) L is

, a.

,

,b.

,

, c.

,

, d.

,

(여기서, 각각의 X¹, X² 및 X³는 독립적으로 Cl, Br, F 또는 I로부터 선택됨),e.

(wherein each of X ¹ , X ² and X ³ is independently selected from Cl, Br, F or I),

,f.

,

,g.

,

,h.

,

, 및i.

, and

로부터 선택된다.j.

is selected from

In some embodiments of the etching composition, the content of the silicon-containing compound of formula (III) is approximately 5% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (III) is approximately 4% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (III) is approximately 3% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (III) is approximately 2% by weight or less. In a further aspect of this embodiment, the content of the silicon-containing compound of formula (III) is approximately 1% by weight or less.

OCH₃이고, (ii) L이

이고, (iii) m1과 m2의 합이 = 1 내지 5이고, (iv) n = 0인 화학식 III의 규소-함유 화합물을 포함한다. 이러한 실시양태의 추가 양태에서, m1과 m2의 합 = 1이다. 이러한 실시양태의 추가 양태에서, m1과 m2의 합 = 2이다. 이러한 실시양태의 추가 양태에서, m1과 m2의 합 = 3이다. 이러한 실시양태의 추가 양태에서, m1과 m2의 합 = 4이다. 이러한 실시양태의 추가 양태에서, m1과 m2의 합 = 5이다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OCH ₃ , and (ii) L is

, (iii) the sum of m1 and m2 = 1 to 5, and (iv) n = 0. In a further aspect of this embodiment, the sum of m1 and m2=1. In a further aspect of this embodiment, the sum of m1 and m2=2. In a further aspect of this embodiment, the sum of m1 and m2=3. In a further aspect of this embodiment, the sum of m1 and m2=4. In a further aspect of this embodiment, the sum of m1 and m2 = 5.

OH이고, (ii) m1과 m2의 합 = 3이고, (iii) n = 0이고, (iv) L이

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OH, (ii) the sum of m1 and m2 = 3, (iii) n = 0, (iv) L is

silicon-containing compounds of formula (III).

OCH₃이고, (ii) m2 = 3이고, (iii) n = 1이고, (iv) A가

(여기서, R^a =

H임)이고, (v) m1 = 0이고, (vi) L

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) m2 = 3, (iii) n = 1, and (iv) A is

(where R ^a =

H), (v) m1 = 0, and (vi) L

silicon-containing compounds of formula (III).

OH이고, (ii) m2 = 3이고, (iii) n = 1이고, (iv) A가

이고, (v) m1 = 0이고, (vi) L이

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OH, (ii) m2 = 3, (iii) n = 1, and (iv) A is

, (v) m1 = 0, and (vi) L is

silicon-containing compounds of formula (III).

OCH₃이고, (ii) m2 = 3이고, (iii) n = 1이고, (iv) A가

(여기서, R^a =

H임)이고, (v) m1 = 0이고, (vi) L가

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) m2 = 3, (iii) n = 1, and (iv) A is

(where R ^a =

H), (v) m1 = 0, and (vi) L is

silicon-containing compounds of formula (III).

(여기서, 각각의 X¹, X² 및 X³는 F임)인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is —OCH ₃ , (ii) sum of m1 and m2=2, (iii) n=0, (iv) L is

wherein each of X ¹ , X ² and X ³ is F.

OCH₃이고, (ii) m2 = 3이고, (iii) n = 1이고, (iv) A가

(여기서, R^a =

H임)이고, (v) m1 = 0이고, (vi) L이

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) m2 = 3, (iii) n = 1, and (iv) A is

(where R ^a =

H), (v) m1 = 0, and (vi) L

silicon-containing compounds of formula (III).

OH이고, (ii) m2 = 2이고, (iii) n = 1이고, (iv) A가

이고, (v) m1 = 0이고, (vi) L이

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OH, (ii) m2 = 2, (iii) n = 1, and (iv) A is

, (v) m1 = 0, and (vi) L is

silicon-containing compounds of formula (III).

OCH₃이고, (ii) m2 = 3이고, (iii) n = 1이고, (iv) A가

(여기서, R^a 및 R^b는 -CH₃임)이고, (v) m1 = 3이고, (vi) L이

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) m2 = 3, (iii) n = 1, and (iv) A is

(wherein R ^a and R ^b are -CH ₃ ), (v) m1 = 3, (vi) L is

silicon-containing compounds of formula (III).

OCH₃이고, (ii) m1과 m2의 합 = 2이고, (iii) n = 0이고, (iv) L이

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) sum of m1 and m2 = 2, (iii) n = 0, (iv) L is

silicon-containing compounds of formula (III).

OCH₂CH₃이고, (ii) m1과 m2의 합이 = 3이고, (iii) n = 0이고, (iv) L이

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OCH ₂ CH ₃ , (ii) the sum of m1 and m2 = 3, (iii) n = 0, (iv) L is

silicon-containing compounds of formula (III).

OCH₂CH₃이고, (ii) m1과 m2 = 1이고, (iii) n = 0이고, (iv) L이

인 화학식 III의 규소-함유 화합물을 포함한다.In some embodiments, the etching composition comprises (i) each of R ¹ , R ² and R ³ is

OCH ₂ CH ₃ , (ii) m1 and m2 = 1, (iii) n = 0, (iv) L is

silicon-containing compounds of formula (III).

In some embodiments, the etching composition comprises a silicon-containing compound of Formula III having the structure:

(CH₂)_x

이고, x = 1 내지 5이다. 이러한 실시양태의 추가 양태에서, x = 1이다. 이러한 실시양태의 추가 양태에서, x = 2이다. 이러한 실시양태의 추가 양태에서, x = 3이다. 이러한 실시양태의 추가 양태에서, x = 4이다. 이러한 실시양태의 추가 양태에서, x = 5이다.where R =

(CH ₂ ) _x

, and x = 1 to 5. In a further aspect of this embodiment, x=1. In a further aspect of this embodiment, x=2. In a further aspect of this embodiment, x=3. In a further aspect of this embodiment, x=4. In a further aspect of this embodiment, x = 5.

In some embodiments, the one or more silicon-containing compound(s) comprises a combination of one or more silicon-containing compound(s) having Formula I, Formula II, and/or Formula III.

II. aqueous solvent

The etching composition of the present invention is aqueous and contains water. In the subject matter disclosed and claimed herein, water is used for dissolving one or more components of a composition in various ways, for example, as a carrier of the component, as an aid in the removal of residues, as a viscosity modifier of the composition, and as a diluent. function. Preferably, the water used in the etching composition is deionized (DI) water.

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

Water is included in an amount in a range having a starting point and an endpoint selected from the following list of weight percentages: from about 1% to about 50% by weight of the etching composition. Another preferred embodiment of the subject matter disclosed and claimed herein comprises from about 5.0% to about 35% by weight, or from 10% to 30% by weight of water. Water may be present in an amount defined by the following weight percent list: 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 subject matter disclosed and claimed herein may include water in an amount to achieve a desired weight percent of the other ingredients.

Exemplary Embodiments of Etching Compositions

The following is an exemplary embodiment of an etching composition comprising (A) pure phosphoric acid and (B) a mixture of (I) a silicon-containing compound as disclosed herein and (II) an aqueous solvent.

In one embodiment, the etching composition comprises

A. up to about 70% by weight of pure phosphoric acid;

B. I. a compound of formula (I); and

II. aqueous solvent

About 30% by weight or more of a mixture comprising

includes:

In the above formula,

(i) m = 0 to 20,

OH의 군으로부터 선택되고,(ii) each R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently hydrogen, a C ₁ to C ₁₀ linear alkyl group, a C ₁ to C ₁₀ linear alkyl group substituted with fluorine, a 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 group alkynyl group,

selected from the group of OH,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택된다.(iii) each R ^a and R ^b is independently a 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 groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH.

In a further aspect of this embodiment, the etching composition consists essentially of A and B. In a further aspect of this embodiment, the etching composition consists of A and B.

In one embodiment, the etching composition comprises

A. up to about 70% by weight of pure phosphoric acid;

B. I. a compound of formula II; and

II. aqueous solvent

About 30% by weight or more of a mixture comprising

includes:

In the above formula,

(i) m = 0 to 20,

(ii) n = 0 to 20;

OH, Z¹ 및 Z²의 군으로부터 선택되고,(iii) R ³ is hydrogen, C ₁ to C ₁₀ linear alkyl group, C ₁ to C ₁₀ linear alkyl group substituted with fluorine, 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,

selected from the group of OH, Z ¹ and Z ² ,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택되고,(iv) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH,

(v) Z ¹ and Z ² are each independently

, a.

,

, b.

,

N⁺(CH₃)₃Cl^-, 및c.

N ⁺ (CH ₃ ) ₃ Cl ⁻ , and

CH(OH)CH₂OH로부터 선택된다. d.

CH(OH)CH ₂ OH.

In a further aspect of this embodiment, the etching composition consists essentially of A and B. In a further aspect of this embodiment, the etching composition consists of A and B.

In one embodiment, the etching composition comprises

A. up to about 70% by weight of pure phosphoric acid;

B. I. a compound of formula III; and

II. aqueous solvent

About 30% by weight or more of a mixture comprising

includes:

In the above formula,

(i) m1 and m2 are each 0 to 10, provided that at least one of m1 and m2 is ≥ 1,

(ii) n = 0 or 1,

O-C₁ 내지 C₆ 선형 알킬기의 군으로부터 선택되고,(iii) each R ¹ , R ² and R ³ is independently hydrogen, a C ₁ to C ₆ linear alkyl group, a C ₃ to C ₆ branched alkyl group, and

OC ₁ to C ₆ selected from the group of linear alkyl groups,

(iv) A is

, a.

,

(여기서, R^a는 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), b.

(wherein R ^a is selected from hydrogen, C ₁ to C ₆ linear alkyl group, C ₃ to C ₆ branched alkyl group),

(여기서, R^a 및 R^b는 각각 독립적으로 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), c.

(wherein R ^a and R ^b are each independently selected from hydrogen, C ₁ to C ₆ linear alkyl group, C ₃ to C ₆ branched alkyl group),

로부터 선택되고,d.

is selected from

(v) L is

, a.

,

,b.

,

, c.

,

, d.

,

(여기서, 각각의 X¹, X² 및 X³는 독립적으로 Cl, Br, F 또는 I로부터 선택됨),e.

(wherein each of X ¹ , X ² and X ³ is independently selected from Cl, Br, F or I),

,f.

,

,g.

,

,h.

,

, 및i.

, and

로부터 선택된다.j.

is selected from

In a further aspect of this embodiment, the etching composition consists essentially of A and B. In a further aspect of this embodiment, the etching composition consists of A and B.

In one embodiment, the etching composition comprises

A. greater than about 70 weight percent pure phosphoric acid;

B. I. a compound of formula (I); and

II. aqueous solvent

less than about 30% by weight of a mixture comprising

includes:

In the above formula,

(i) m = 0 to 20,

OH의 군으로부터 선택되고,(ii) each R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently hydrogen, a C ₁ to C ₁₀ linear alkyl group, a C ₁ to C ₁₀ linear alkyl group substituted with fluorine, a 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 group alkynyl group,

selected from the group of OH,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택된다.(iii) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH.

In a further aspect of this embodiment, the etching composition consists essentially of A and B. In a further aspect of this embodiment, the etching composition consists of A and B. In a further aspect of this embodiment, the etching composition comprises (i) greater than about 75 weight percent pure phosphoric acid and (ii) less than about 25 weight percent mixture.

In one embodiment, the etching composition comprises

A. greater than about 70 weight percent pure phosphoric acid;

B. I. a compound of formula II; and

II. aqueous solvent

less than about 30% by weight of a mixture comprising

includes:

In the above formula,

(i) m = 0 to 20,

(ii) n = 0 to 20;

OH, Z¹ 및 Z²의 군으로부터 선택되고,(iii) R ³ is hydrogen, C ₁ to C ₁₀ linear alkyl group, C ₁ to C ₁₀ linear alkyl group substituted with fluorine, 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,

selected from the group of OH, Z ¹ and Z ² ,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택되고,(iv) each R ^a and R ^b is independently a 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 groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH,

(v) Z ¹ and Z ² are each independently

, a.

,

, b.

,

N⁺(CH₃)₃Cl^-, 및c.

N ⁺ (CH ₃ ) ₃ Cl ⁻ , and

CH(OH)CH₂OH로부터 선택된다.d.

CH(OH)CH ₂ OH.

In a further aspect of this embodiment, the etching composition consists essentially of A and B. In a further aspect of this embodiment, the etching composition consists of A and B. In a further aspect of this embodiment, the etching composition comprises (i) greater than about 75 weight percent pure phosphoric acid and (ii) less than about 25 weight percent mixture.

In one embodiment, the etching composition comprises

A. greater than about 70 weight percent pure phosphoric acid;

B. I. a compound of formula III; and

II. aqueous solvent

less than about 30% by weight of a mixture comprising

includes:

In the above formula,

(i) m1 and m2 are each 0 to 10, provided that at least one of m1 and m2 is ≥ 1,

(ii) n = 0 or 1,

O-C₁ 내지 C₆ 선형 알킬기의 군으로부터 선택되고,(iii) each R ¹ , R ² and R ³ is independently hydrogen, a C ₁ to C ₆ linear alkyl group, a C ₃ to C ₆ branched alkyl group, and

OC ₁ to C ₆ selected from the group of linear alkyl groups,

(iv) A is

, a.

,

(여기서, R^a는 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), b.

(wherein R ^a is selected from hydrogen, C ₁ to C ₆ linear alkyl group, C ₃ to C ₆ branched alkyl group),

(여기서, R^a 및 R^b는 각각 독립적으로 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), 및 c.

(wherein R ^a and R ^b are each independently selected from hydrogen, a C ₁ to C ₆ linear alkyl group, and a C ₃ to C ₆ branched alkyl group), and

로부터 선택되고,d.

is selected from

(v) L is

, a.

,

,b.

,

, c.

,

, d.

,

(여기서, 각각의 X¹, X² 및 X³는 독립적으로 Cl, Br, F 또는 I로부터 선택됨),e.

(wherein each of X ¹ , X ² and X ³ is independently selected from Cl, Br, F or I),

,f.

,

,g.

,

,h.

,

, 및i.

, and

로부터 선택된다. j.

is selected from

In a further aspect of this embodiment, the etching composition consists essentially of A and B. In a further aspect of this embodiment, the etching composition consists of A and B. In a further aspect of this embodiment, the etching composition comprises (i) greater than about 75 weight percent pure phosphoric acid and (ii) less than about 25 weight percent mixture.

C. other ingredients

Etching compositions, including those exemplified above, may include other components as described below.

I. additional acid

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

a. sulfuric acid

In some embodiments, the at least one additional acid included in the mixture is sulfuric acid. In one aspect of this embodiment, the at least one additional acid comprises up to about 25 wt. % pure sulfuric acid. In a further aspect of this embodiment, the at least one further acid consists of sulfuric acid. In some embodiments, the at least one additional acid consists of no more than about 25% by weight pure sulfuric acid.

In some embodiments of the etching composition, the mixture comprises pure sulfuric acid, wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. In a further aspect of this embodiment, the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

In some embodiments of the etching composition, the mixture further comprises pure sulfuric acid, wherein there is from about 2.0 parts by weight to about 7.0 parts by weight pure phosphoric acid per 1 part by weight pure sulfuric acid. In a further aspect of this embodiment, there is from about 2.0 parts by weight to about 6.0 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid. In a further aspect of this embodiment, there is from about 2.0 parts by weight to about 5.0 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid. In a further aspect of this embodiment, there is from about 2.0 parts by weight to about 4.0 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid. In a further aspect of this embodiment, there is from about 2.0 parts by weight to about 3.0 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid. In a further aspect of this embodiment, there is from about 2.0 parts by weight to about 2.5 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid. In a further aspect of this embodiment, there is approximately 3.0 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid. In a further aspect of this embodiment, there is approximately 2.25 parts by weight of pure phosphoric acid per part by weight of pure sulfuric acid. In a further aspect of this embodiment, there is approximately 2.5 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid. In a further aspect of this embodiment, there is approximately 2.75 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid.

In some embodiments of the etching composition, the mixture further comprises pure sulfuric acid, wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. In a further aspect of this embodiment, the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

Various non-limiting embodiments of etching compositions comprising sulfuric acid are illustrated below.

i. Exemplary Embodiments: Compositions Having a Silicon-Containing Compound of Formula I and Sulfuric Acid

이고, ii) 혼합물은 추가로 순수 황산을 포함한다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

and ii) the mixture further comprises pure sulfuric acid.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 80 중량% 내지 대략 85 중량%이다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.5 중량%이다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

이고, 및 (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.83 중량%이다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

and (ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.83% by weight of the composition.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.94 중량%이다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.94% by weight of the composition.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 84.27 중량%이다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 84.27% by weight of the composition.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 84.6 중량%이다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 84.6% by weight of the composition.

이고, (ii) 혼합물은 순수 황산을 추가로 포함한다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

and (ii) the mixture further comprises pure sulfuric acid.

이고, (ii) 혼합물은 순수 황산을 추가로 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 80 중량% 내지 대략 85 중량%이다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition.

이고, (ii) 혼합물은 순수 황산을 추가로 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.5 중량%이다.In some embodiments of the etching composition, (i) the compound of formula (I) comprises:

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

, (ii) 대략 24 중량% 이하의 순수 황산 및 (iii) 물을 포함하는 수성 용매를 포함하는 대략 40 중량% 이상의 혼합물을 포함한다.In some embodiments, the etching composition comprises A. up to about 60 wt% pure phosphoric acid and B. (i) up to about 5 wt%

, (ii) up to about 24 weight percent pure sulfuric acid and (iii) at least about 40 weight percent of an aqueous solvent comprising water.

, (ii) 대략 24 중량% 이하의 순수 황산; 및 (iii) 물로 필수적으로 이루어지는 수성 용매를 포함하는 대략 40 중량% 이상의 혼합물로 필수적으로 이루어진다.In some embodiments, the etching composition comprises A. up to about 60 wt% pure phosphoric acid and B. (i) up to about 5 wt%

, (ii) up to about 24% by weight of pure sulfuric acid; and (iii) at least about 40% by weight of an aqueous solvent consisting essentially of water.

, (ii) 대략 24 중량% 이하의 순수 황산 및 (iii) 물로 이루어지는 수성 용매로 이루어진 대략 40 중량% 이상의 혼합물로 이루어진다.In some embodiments, the etching composition comprises A. up to about 60 wt% pure phosphoric acid and B. (i) up to about 5 wt%

, (ii) up to about 24 wt. % of pure sulfuric acid and (iii) at least about 40 wt. % of an aqueous solvent consisting of water.

ii. Exemplary Embodiments: Compositions Having a Silicon-Containing Compound of Formula II and Sulfuric Acid

이고, (ii) 혼합물은 순수 황산을 추가로 포함한다.In some embodiments of the etching composition, (i) the compound of Formula II is

and (ii) the mixture further comprises pure sulfuric acid.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 80 중량% 내지 대략 85 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula II is

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition.

이고, (ii) 혼합물은 추가로 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.5 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula II is

(ii) the mixture further comprises sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

이고, (II) 혼합물은 추가로 순수 황산을 포함한다.In some embodiments of the etching composition, (i) the compound of Formula II is

and (II) the mixture further comprises pure sulfuric acid.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 80 중량% 내지 대략 85 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula II is

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition.

이고, (ii) 혼합물은 추가로 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.5 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula II is

(ii) the mixture further comprises sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

iii. Exemplary embodiments: A composition having a silicon-containing compound of formula III and sulfuric acid

이고, 여기서 R =

(CH₂)_x

이고, x = 1 내지 5이고, (ii) 혼합물은 추가로 순수 황산을 포함한다. 이러한 실시양태의 추가 양태에서, x = 1이다. 이러한 실시양태의 추가 양태에서, x = 2이다. 이러한 실시양태의 추가 양태에서, x = 3이다. 이러한 실시양태의 추가 양태에서, x = 4이다. 이러한 실시양태의 추가 양태에서, x = 5이다.In some embodiments of the etching composition, (i) the compound of Formula III is

, where R =

(CH ₂ ) _x

, x = 1 to 5, and (ii) the mixture further comprises pure sulfuric acid. In a further aspect of this embodiment, x=1. In a further aspect of this embodiment, x=2. In a further aspect of this embodiment, x=3. In a further aspect of this embodiment, x=4. In a further aspect of this embodiment, x = 5.

이고, 여기서 R =

(CH₂)_x

이고, x = 1 내지 5이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 80 중량% 내지 대략 85 중량%이다. 이러한 실시양태의 추가 양태에서, x = 1이다. 이러한 실시양태의 추가 양태에서, x = 2이다. 이러한 실시양태의 추가 양태에서, x = 3이다. 이러한 실시양태의 추가 양태에서, x = 4이다. 이러한 실시양태의 추가 양태에서, x = 5이다.In some embodiments of the etching composition, (i) the compound of Formula III is

, where R =

(CH ₂ ) _x

, x = 1 to 5, (ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. In a further aspect of this embodiment, x=1. In a further aspect of this embodiment, x=2. In a further aspect of this embodiment, x=3. In a further aspect of this embodiment, x=4. In a further aspect of this embodiment, x = 5.

이고, 여기서 R =

(CH₂)_x

이고, x = 1 내지 5이고, (ii) 혼합물은 추가로 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.5 중량%이다. 이러한 실시양태의 추가 양태에서, x = 1이다. 이러한 실시양태의 추가 양태에서, x = 2이다. 이러한 실시양태의 추가 양태에서, x = 3이다. 이러한 실시양태의 추가 양태에서, x = 4이다. 이러한 실시양태의 추가 양태에서, x = 5이다.In some embodiments of the etching composition, (i) the compound of Formula III is

, where R =

(CH ₂ ) _x

, x = 1 to 5, (ii) the mixture further comprises sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. In a further aspect of this embodiment, x=1. In a further aspect of this embodiment, x=2. In a further aspect of this embodiment, x=3. In a further aspect of this embodiment, x=4. In a further aspect of this embodiment, x = 5.

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 comprises pure sulfuric acid.

In some embodiments of the etching composition, (i) the compound of Formula III is Si(OCH ₃ ) ₃ (CH ₂ CH ₂ CF ₃ ), (ii) the mixture further comprises pure sulfuric acid, (iii) pure phosphoric acid The combined content of and pure sulfuric acid is from about 80% to about 85% by weight of the composition.

In some embodiments of the etching composition, (i) the compound of Formula III is Si(OCH ₃ ) ₃ (CH ₂ CH ₂ CF ₃ ), (ii) the mixture further comprises sulfuric acid, (iii) pure phosphoric acid and The combined content of pure sulfuric acid is approximately 83.5% by weight of the composition.

이고, (ii) 혼합물은 추가로 순수 황산을 포함한다.In some embodiments of the etching composition, (i) the compound of Formula III is

and (ii) the mixture further comprises pure sulfuric acid.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 80 중량% 내지 대략 85 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula III is

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition.

이고, (ii) 혼합물은 추가로 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.5 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula III is

(ii) the mixture further comprises sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

이고, (ii) 혼합물은 추가로 순수 황산을 포함한다.In some embodiments of the etching composition, (i) the compound of Formula III is

and (ii) the mixture further comprises pure sulfuric acid.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 80 중량% 내지 대략 85 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula III is

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.5 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula III is

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

이고, (ii) 혼합물은 추가로 순수 황산을 포함한다.In some embodiments of the etching composition, (i) the compound of Formula III is

and (ii) the mixture further comprises pure sulfuric acid.

이고, (ii) 혼합물은 추가로 순수 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 80 중량% 내지 대략 85 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula III is

(ii) the mixture further comprises pure sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition.

이고, (ii) 혼합물은 추가로 황산을 포함하고, (iii) 순수 인산과 순수 황산의 합한 함량은 조성물의 대략 83.5 중량%이다.In some embodiments of the etching composition, (i) the compound of Formula III is

(ii) the mixture further comprises sulfuric acid, and (iii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition.

b. sulfonic acid

In some embodiments, the at least one additional acid included in the mixture is a sulfonic acid. The sulfonic acid is typically an alkyl or aryl sulfonic acid. Sulfonic acids have the general structure R'-S(O)(O)-OH. In one aspect of this embodiment, R′ is 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 group. or a branched alkenyl group, a C ₂ to C ₁₀ linear or branched alkynyl group. In another aspect of this embodiment, R' is selected from a C ₁ to C ₁₀ linear alkyl group or a C ₃ to C ₁₀ branched alkyl group. In another embodiment, the mixture is ethanesulfonic acid, 3-hydroxypropane-1-sulfonic acid, 3-amino-1-propanesulfonic acid, sulfoacetic acid, nonafluorobutane-1-sulfonic acid, benzenesulfonic acid, 3 - at least one sulfonic acid selected from aminobenzenesulfonic acid, p-toluenesulfonic acid monohydrate and methane sulfonic acid. In one aspect of this embodiment, the sulfonic acid is methane sulfuric acid (CH ₃ SO ₃ H).

c. other acids

In some embodiments, the at least one additional acid comprised in the mixture is sulfuric acid and is one or more of nitric acid (HNO ₃ ) and hydrochloric acid (HCl).

The total amount of at least one additional acid (eg, sulfonic acid and/or sulfuric acid) is from about 0.1% to about 60%, from about 0.2% to about 40%, or from about 0.5% to about 35% by weight of the etching composition. to be. Preferably, the at least one additional acid, if used, comprises from about 1% to about 30% by weight of the composition. In alternative embodiments, the total amount of the at least one additional acid is an amount within a range having starting and ending points defined by the following list of weight percentages: 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 weight percentages are “pure” weight percent values.

In alternative embodiments, the compositions of the subject matter disclosed and claimed herein will be free or substantially free of at least one additional acid (eg, added sulfuric and/or sulfonic acid).

II. Additional silicon-containing compounds

In some embodiments, the mixture may include additional silicon-containing compound(s) other than those of Formula I, Formula II, or Formula III. Such additional silicon-containing compound(s) may be one or more of alkylsilsesquioxane, vinylsilsesquioxane, carboxylic acid alkylsilsesquioxane and alkyleneglycol alkylsilsesquioxane.

III. Hydroxyl group-containing water-miscible solvent

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

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

Examples of suitable water-soluble alkane diols and polyols such as (C ₂ -C ₂₀ ) alkanediols and (C ₃ -C ₂₀ ) 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.

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.

Examples of suitable water-soluble alkoxyalcohols 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. includes

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

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

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

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

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

In some embodiments, the compositions of the subject matter disclosed and claimed herein are free or substantially free of any or all of the hydroxyl group-containing water-miscible solvents or the hydroxyl group-containing water-miscible solvents enumerated above. will be.

IV. silicic acid

In some embodiments, the mixture may include silicic acid. Silicic acid, if used, helps protect the silicon oxide and increase the selectivity of the silicon nitride etch.

In some embodiments, the amount of silicic acid will constitute from about 0.001% to about 5.0%, and preferably from about 0.01% to about 2.0%, by weight of the composition. In another embodiment, the silicic acid constitutes from about 0.02% to about 0.08% by weight of the composition.

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

V. phosphate compound

In some embodiments, the mixture may include phosphate compounds such as, for example, triethyl phosphate (TEPO) and/or trimethyl phosphate (TMPO). Phosphate compounds, when used, act as co-solvents.

In some embodiments, the amount of phosphate compound (eg, TMPO) will constitute from about 0.05% to about 15%, and preferably from about 0.1% to about 5%, by weight of the composition. In other embodiments, the phosphate compound (eg, TMPO), when used, constitutes about 2% by weight of the composition.

In some embodiments, the compositions of the subject matter disclosed and claimed herein are free or substantially free of added phosphate compounds.

VI. Surfactants

In some embodiments, the mixture may include at least one water-soluble nonionic surfactant. Surfactants serve to aid in the removal of residues.

Examples of water-soluble nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, poly Oxyethylene nonyl phenyl ether, polyoxyethylene derivatives, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene Sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbit tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxy ethylene alkylamines, polyoxyethylene hydrogenated castor oil, alkylalkanolamides, and mixtures thereof.

In some embodiments, the amount of surfactant is from about 0.001% to about 5% by weight of the composition, preferably from about 0.01% to about 2.5% by weight, and most preferably from about 0.1% to about 1.0% by weight of the composition. will include

In some embodiments, compositions of the subject matter disclosed and claimed herein will be free or substantially free of surfactants.

VII. chelating agent

In some embodiments, the mixture may include at least one metal chelating agent. The metal chelating agent may function to increase the ability of the composition to retain metals in the composition and enhance dissolution of metal moieties.

Examples of suitable chelating agents include, but are not limited to, the following organic acids and isomers and salts thereof: 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 (mepylene phosphonic acid) ) acid (EDTMP), triethylenetetraminehexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (DHPTA), methyliminodiacetic acid, Propylenediaminetetraacetic acid, nitrotriacetic 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. Preferred chelating agents are aminocarboxylic acids such as EDTA, CyDTA and aminophosphonic acids such as EDTMP.

In some embodiments, the amount of chelating agent will constitute from about 0.1% to about 10%, and preferably from about 0.5% to about 5%, by weight of the composition.

In some embodiments, compositions of the subject matter disclosed and claimed herein will be free or substantially free of chelating agents.

In some embodiments, the composition is free or substantially free of metal hydroxides, additive metals, halide containing compounds, TEOS, silyl phosphate compounds, and silanes and silanols free of repeating monomers.

manufacturing method

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

In one embodiment, the method of forming the etching composition comprises:

A. up to about 70% by weight of pure phosphoric acid; and

B. I. a compound of formula (I); and

II. aqueous solvent

About 30% by weight or more of a mixture comprising

It comprises the steps of combining:

In the above formula,

(i) m = 0 to 20,

OH의 군으로부터 선택되고,(ii) each R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently hydrogen, a C ₁ to C ₁₀ linear alkyl group, a C ₁ to C ₁₀ linear alkyl group substituted with fluorine, a 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 group alkynyl group,

selected from the group of OH,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택된다.(iii) each R ^a and R ^b is independently a 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 groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH.

In one embodiment, the method of forming the etching composition comprises:

A. up to about 70% by weight of pure phosphoric acid;

B. I. a compound of formula II; and

II. aqueous solvent

About 30% by weight or more of a mixture comprising

It comprises the steps of combining:

In the above formula,

(i) m = 0 to 20,

(ii) n = 0 to 20;

OH, Z¹ 및 Z²의 군으로부터 선택되고,(iii) R ³ is hydrogen, C ₁ to C ₁₀ linear alkyl group, C ₁ to C ₁₀ linear alkyl group substituted with fluorine, 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,

selected from the group of OH, Z ¹ and Z ² ,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택되고,(iv) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH,

(v) Z ¹ and Z ² are each independently

, a.

,

, b.

,

N⁺(CH₃)₃Cl^-, 및c.

N ⁺ (CH ₃ ) ₃ Cl ⁻ , and

CH(OH)CH₂OH로부터 선택된다.d.

CH(OH)CH ₂ OH.

In one embodiment, a method for forming an etching composition comprises:

A. up to about 70% by weight of pure phosphoric acid;

B. I. a compound of formula III; and

II. aqueous solvent

About 30% by weight or more of a mixture comprising

It comprises the steps of combining:

In the above formula,

(i) m1 and m2 are each 0 to 10, provided that at least one of m1 and m2 is ≥ 1,

(ii) n = 0 or 1,

O-C₁ 내지 C₆ 선형 알킬기의 군으로부터 선택되고,(iii) each R ¹ , R ² and R ³ is independently hydrogen, a C ₁ to C ₆ linear alkyl group, a C ₃ to C ₆ branched alkyl group, and

OC ₁ to C ₆ selected from the group of linear alkyl groups,

(iv) A is

, a.

,

(여기서, R^a는 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), b.

(wherein R ^a is selected from hydrogen, C ₁ to C ₆ linear alkyl group, C ₃ to C ₆ branched alkyl group),

(여기서, R^a 및 R^b는 각각 독립적으로 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), 및 c.

(wherein R ^a and R ^b are each independently selected from hydrogen, a C ₁ to C ₆ linear alkyl group, and a C ₃ to C ₆ branched alkyl group), and

로부터 선택되고,d.

is selected from

(v) L is

, a.

,

,b.

,

, c.

,

, d.

,

(여기서, 각각의 X¹, X² 및 X³는 독립적으로 Cl, Br, F 또는 I로부터 선택됨),e.

(wherein each of X ¹ , X ² and X ³ is independently selected from Cl, Br, F or I),

,f.

,

,g.

,

,h.

,

, 및i.

, and

로부터 선택된다.j.

is selected from

In one embodiment, a method for forming an etching composition comprises:

A. greater than about 70 weight percent pure phosphoric acid;

B. I. a compound of formula (I); and

II. aqueous solvent

less than about 30% by weight of a mixture comprising

It comprises the steps of combining:

In the above formula,

(i) m = 0 to 20,

OH의 군으로부터 선택되고,(ii) each R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently hydrogen, a C ₁ to C ₁₀ linear alkyl group, a C ₁ to C ₁₀ linear alkyl group substituted with fluorine, a 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 group alkynyl group,

selected from the group of OH,

NH-C₁-C₁₀알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택된다.(iii) each R ^a and R ^b is independently a 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 groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH.

In one embodiment, a method for forming an etching composition comprises:

A. greater than about 70 weight percent pure phosphoric acid;

B. I. a compound of formula II; and

II. aqueous solvent

less than about 30% by weight of a mixture comprising

It comprises the steps of combining:

In the above formula,

(i) m = 0 to 20,

(ii) n = 0 to 20;

OH, Z¹ 및 Z²의 군으로부터 선택되고,(iii) R ³ is hydrogen, C ₁ to C ₁₀ linear alkyl group, C ₁ to C ₁₀ linear alkyl group substituted with fluorine, 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,

selected from the group of OH, Z ¹ and Z ² ,

NH-C₁-C₁₀ 알킬,

OH로 치환된 C₁-C₁₀ 알킬로부터 선택되고,(iv) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH,

(v) Z ¹ and Z ² are each independently

, a.

,

, b.

,

N⁺(CH₃)₃Cl^-, 및c.

N ⁺ (CH ₃ ) ₃ Cl ⁻ , and

CH(OH)CH₂OH로부터 선택된다.d.

CH(OH)CH ₂ OH.

In one embodiment, a method for forming an etching composition comprises:

A. greater than about 70 weight percent pure phosphoric acid;

B. I. a compound of formula III; and

II. aqueous solvent

less than about 30% by weight of a mixture comprising

It comprises the steps of combining:

In the above formula,

(i) m1 and m2 are each 0 to 10, provided that at least one of m1 and m2 is ≥ 1,

(ii) n = 0 or 1,

O-C₁ 내지 C₆ 선형 알킬기의 군으로부터 선택되고,(iii) each R ¹ , R ² and R ³ is independently hydrogen, a C ₁ to C ₆ linear alkyl group, a C ₃ to C ₆ branched alkyl group, and

OC ₁ to C ₆ selected from the group of linear alkyl groups,

(iv) A is

, a.

,

(여기서, R^a는 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), b.

(wherein R ^a is selected from hydrogen, C ₁ to C ₆ linear alkyl group, C ₃ to C ₆ branched alkyl group),

(여기서, R^a 및 R^b는 각각 독립적으로 수소, C₁ 내지 C₆ 선형 알킬기, C₃ 내지 C₆ 분지형 알킬기로부터 선택됨), 및c.

(wherein R ^a and R ^b are each independently selected from hydrogen, a C ₁ to C ₆ linear alkyl group, and a C ₃ to C ₆ branched alkyl group), and

로부터 선택되고,d.

is selected from

(v) L is

, a.

,

,b.

,

, c.

,

, d.

,

(여기서, 각각의 X¹, X² 및 X³는 독립적으로 Cl, Br, F 또는 I로부터 선택됨),e.

(wherein each of X ¹ , X ² and X ³ is independently selected from Cl, Br, F or I),

,f.

,

,g.

,

,h.

,

, 및i.

, and

로부터 선택된다.j.

is selected from

How to use

The subject matter disclosed and claimed herein further includes a method for selectively improving the etch rate of silicon nitride relative to silicon dioxide on a composite semiconductor device comprising silicon nitride and silicon dioxide.

In one embodiment, the method

a. contacting a composite semiconductor device comprising silicon nitride and silicon dioxide with one or more of the etching compositions disclosed and/or claimed herein; and

b. cleaning the composite semiconductor device after the silicon nitride is at least partially removed.

includes

In a further aspect of this embodiment, the contacting step is performed at a temperature of about 160°C.

In a further embodiment, the method comprises c. A drying step may be included.

In the method described above, "at least partially removed" means at least 90% removal, preferably at least 95% removal, and most preferably at least 99% removal of material using the composition of the present invention.

In a further embodiment, the method can include a pretreatment step comprising contacting (eg, by immersion or spraying) the substrate with dilute hydrofluoric acid (dHF) (1:100 HF:water). It has been observed that there may be no dHF pretreatment step and that high relative etch rates may still be achieved using such compositions of the disclosed and claimed subject matter herein. Additionally, it was determined that the compositions of the subject matter disclosed and claimed herein provided less damage to the substrate when a pretreatment dHF step was used, compared to the phosphoric acid composition alone. Additional damage due to the dHF pretreatment step can be minimized by reducing agitation when treating with the compositions of the disclosed and claimed subject matter herein and reducing the time between the pretreatment and contact with the compositions of the disclosed and claimed subject matter.

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

In some embodiments, the temperature of the composition during the contacting step is preferably between about 100°C and 200°C. In a further aspect, the temperature is between about 140°C and 180°C. In a further aspect, the temperature of the composition during the contacting step is about 160°C.

In some embodiments, the etching selectivity of silicon nitride to silicon oxide of the disclosed and claimed subject matter is at least about 300. In a further aspect, the etching composition of the disclosed and claimed subject matter has an etch selectivity of silicon nitride to silicon oxide of at least about 500. In a further aspect, the etching selectivity of silicon nitride to silicon oxide of the disclosed and claimed inventive etching compositions is at least about 1000. In a further aspect, the disclosed and claimed inventive etching compositions have an etch selectivity of silicon nitride to silicon oxide of at least about 1250. In a further aspect, the etching selectivity of silicon nitride to silicon oxide of the disclosed and claimed inventive etching compositions is at least about 1500. In a further aspect, the disclosed and claimed inventive etching compositions have an etch selectivity of silicon nitride to silicon oxide of at least about 2000. In a further aspect, the etching selectivity of silicon nitride to silicon oxide of the disclosed and claimed inventive etching compositions is at least about 2500. In a further aspect, the etch selectivity of silicon nitride to silicon oxide of the disclosed and claimed inventive etching compositions is at least about 3000. In a further aspect, the disclosed and claimed inventive etching compositions have an etch selectivity of silicon nitride to silicon oxide of at least about 3500. In a further aspect, the etch selectivity of silicon nitride to silicon oxide of the disclosed and claimed inventive etching compositions is at least about 4000. In a further aspect, the etch selectivity of silicon nitride to silicon oxide of the disclosed and claimed inventive etching compositions is at least about 4500. In a further aspect, the disclosed and claimed inventive etching compositions have an etch selectivity of silicon nitride to silicon oxide of at least about 5000.

In some embodiments, the silicon oxide etch is less than 1 Å/min. In a further aspect, the silicon oxide etch is less than 0.5 Å/min. In a further aspect, the silicon oxide etch is less than 0.01 Å/min.

In some embodiments, cleaning step c is performed by any suitable means of cleaning the substrate with deionized water, for example, by dipping or spraying techniques. In another embodiment, the washing step is performed using a mixture of deionized water and a water-miscible organic solvent such as, for example, isopropyl alcohol.

In some embodiments, the drying step is performed by any suitable means, such as isopropyl alcohol (IPA) vapor drying, heat, or centripetal force.

Example

Reference will now be made to more specific embodiments of the present disclosure and to experimental results providing support for such embodiments. The examples are provided below to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

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

Materials and Methods:

All ingredients used herein are commercially available.

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

General Procedure for Preparing Etching Compositions

All compositions described in this example were prepared by mixing the ingredients with a 1" Teflon coated stir bar in a 250 mL beaker. Typically, the first material added to the beaker was deionized (DI) water. Phosphoric acid is typically Next is added followed by addition of the silicon-containing compound, after which the remaining ingredients (if present) are added.

composition of the substrate

Each test 20 mm x 20 mm coupon used in this example included a layer of silicon nitride SiN _x on a silicon substrate. The comparative example included a layer of silicon oxide, SiO _x on a silicon substrate.

processing conditions

Etching tests were performed using 100 g of the etching composition in a 250 mL beaker with a ½" round Teflon stir bar set at 300 rpm. The etching composition was heated on a hot plate to a temperature of about 160° C. SiN _x , polysilicon and A piece of patterned test substrate (test coupon) was treated with DHF (1:100 HF:DI water) for about 3 minutes before testing.Si0 _x test coupon was not pretreated with DHF.With stirring test coupon, about 3 minutes (SiN _x for substrates) to about 60 minutes (for SiO _x substrates).

Next, the segments were rinsed in a DI water bath or spray for about 3 minutes and subsequently dried using filtered nitrogen. The silicon nitride and silicon oxide etch rates were estimated from the thickness changes before and after etching, and were measured by spectroscopic ellipticity (FilmTek™ 2000 PAR-SE, Scientific Computing International). Typical starting layer thicknesses were 4395 Å for SiN _x and 229 Å for SiO _x .

The following series of tables presents the results of evaluation of various embodiments of the etching compositions disclosed and claimed herein.

Table 1: H ₂ SO ₄ SiO in the presence of ₂ Contrast SiN _x Influence of Si compounds on the selectivity of

Table 2: H ₂ SO ₄ SiO in the absence of ₂ Contrast SiN _x Influence of Si compounds on the selectivity of

Tables 1 and 2 show that the addition of silicon-containing oligomers increased the etch selectivity of SiN _x relative to SiO ₂ by suppressing the SiO _x etch rate. Table 1 further shows that the addition of sulfuric acid further reduced the SiO ₂ etch rate and thus increased the selectivity.

Table 3: SiO ₂ Contrast SiN _x H for the selectivity of ₂ SO ₄ Influence of concentration

Table 3 further shows the significant effect of sulfuric acid concentration on the selectivity of SiN _x versus SiO ₂ .

Table 4: SiO ₂ Contrast SiN _x Influence of Si compound 1 concentration on the selectivity of

Table 4 shows that increasing the Si compound 1 concentration clearly increased the selectivity of SiN _x relative to SiO ₂ by decreasing the SiO ₂ etch rate.

Table 5: Evaluation of sulfonic acids

Table 6: SiO in the presence of methanesulfonic acid ₂ Contrast SiN _x Influence of Si compound 1 concentration on the selectivity of

Tables 5 and 6 show that methanesulfonic acid also plays the same role as sulfuric acid, and the addition of methanesulfonic acid can also reduce the SiO ₂ etch rate and increase the selectivity.

Table 7: SiO in the presence of methane sulfonic acid ₂ Contrast SiN _x The effect of sulfuric acid concentration on the selectivity of

Table 7 shows the increase in relative removal rates when adding alkylsulfonic acid and sulfuric acid to the compositions of the subject matter disclosed and claimed herein.

Table 8: SiO as Si compound 1 ₂ Contrast SiN _x Influence of organic solvents and surfactants on the selectivity of

Table 9: SiO ₂ Contrast SiN _x Influence of Si compound 2 on the selectivity of

The above detailed description is intended primarily for purposes of illustration. Although the subject matter disclosed and claimed herein has been shown and described with respect to such exemplary embodiments, those skilled in the art will appreciate the above-mentioned forms and details of the subject matter disclosed and claimed herein without departing from the spirit and scope of the subject matter disclosed and claimed herein. and that various other changes, omissions, and additions may be made.

Claims (181)

A. up to approximately 70% by weight of pure phosphoric acid;
BI a compound of formula (I); and
II. aqueous solvent
About 30% by weight or more of a mixture comprising
A composition comprising:

In the above formula,
(i) m = 0 to 20;
(ii) each R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently hydrogen, a C ₁ to C ₁₀ linear alkyl group, a C ₁ to C ₁₀ linear alkyl group substituted with fluorine, a 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 group alkynyl group,

selected from the group of OH,
(iii) each R ^a and R ^b is independently a 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 groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH. A. up to approximately 70% by weight of pure phosphoric acid;
BI a compound of formula II; and
II. aqueous solvent
About 30% by weight or more of a mixture comprising
A composition comprising:

In the above formula,
(i) m = 0 to 20;
(ii) n = 0 to 20;
(iii) R ³ is hydrogen, C ₁ to C ₁₀ linear alkyl group, C ₁ to C ₁₀ linear alkyl group substituted with fluorine, 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,

selected from the group of OH, Z ¹ and Z ² ,
(iv) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH,
(v) Z ¹ and Z ² are each independently
a.

,
b.

,
c.

N ⁺ (CH ₃ ) ₃ Cl ⁻ , and
d.

CH(OH)CH ₂ OH. A. up to approximately 70% by weight of pure phosphoric acid;
BI a compound of formula III; and
II. aqueous solvent
About 30% by weight or more of a mixture comprising
A composition comprising:

In the above formula,
(i) m1 and m2 are each from 0 to 10, provided that at least one of m1 and m2 is ≥ 1,
(ii) n = 0 or 1,
(iii) each R ¹ , R ² and R ³ is independently hydrogen, a C ₁ to C ₆ linear alkyl group, a C ₃ to C ₆ branched alkyl group, and

OC ₁ to C ₆ selected from the group of linear alkyl groups,
(iv) A is
a.

,
b.

,
c.

,
d.

is selected from, and in b, R ^a is selected from hydrogen, a C ₁ to C ₆ linear alkyl group, and a C ₃ to C ₆ branched alkyl group, wherein R ^a and R ^b are each independently hydrogen, C ₁ to C ₆ linear alkyl groups, C ₃ to C ₆ selected from branched alkyl groups,
(v) L is
a.

,
b.

,
c.

,
d.

,
e.

,
f.

,
g.

,
h.

,
i.

, and
j.

and each of X ¹ , X ² and X ³ in e is independently selected from Cl, Br, F or I. 4. The composition according to any one of claims 1 to 3, wherein the mixture further comprises at least one additional acid other than pure phosphoric acid. 4 . The composition according to claim 1 , 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 methane sulfuric acid. 4. The composition of any one of claims 1 to 3, wherein the mixture further comprises pure sulfuric acid. 4. The composition of any one of claims 1 to 3, wherein the mixture further comprises up to approximately 25% by weight of pure sulfuric acid. 4. The composition of any one of claims 1 to 3, wherein the mixture further comprises pure methane sulfuric acid. 4. The composition of any one of claims 1 to 3, wherein the mixture further comprises a sulfonic acid. 4. The composition of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. phosphorus composition. 4. The composition of any one of claims 1 to 3, wherein (i) the mixture further comprises sulfuric acid, and (ii) the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 4. The method of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) between about 2.0 parts by weight to about 7.0 parts by weight of pure phosphoric acid is present per 1 part by weight pure sulfuric acid. composition. 4. The method of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) between about 2.0 parts by weight to about 6.0 parts by weight of pure phosphoric acid is present per 1 part by weight pure sulfuric acid. composition. 4. The method of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is between about 2.0 parts by weight to about 5.0 parts by weight of pure phosphoric acid per 1 part by weight pure sulfuric acid. composition. 4. The method of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) between about 2.0 parts by weight to about 4.0 parts by weight of pure phosphoric acid is present per 1 part by weight pure sulfuric acid. composition. 4. The method of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) between about 2.0 parts by weight to about 3.0 parts by weight of pure phosphoric acid is present per 1 part by weight pure sulfuric acid. composition. 4. The method of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) between about 2.0 parts by weight to about 2.5 parts by weight of pure phosphoric acid is present per 1 part by weight pure sulfuric acid. composition. 4. The composition of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is approximately 3.0 parts by weight of pure phosphoric acid present per 1 part by weight of pure sulfuric acid. 4. The composition of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is approximately 2.25 parts by weight of pure phosphoric acid present per 1 part by weight of pure sulfuric acid. 4. The composition of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is approximately 2.5 parts by weight of pure phosphoric acid present per 1 part by weight of pure sulfuric acid. 4. The composition of any one of claims 1 to 3, wherein (i) the mixture further comprises pure sulfuric acid, and (ii) there is approximately 2.75 parts by weight of pure phosphoric acid per 1 part by weight of pure sulfuric acid. 4. The composition of any one of claims 1 to 3, wherein the aqueous solvent comprises water. 4. A composition according to any one of claims 1 to 3, wherein the aqueous solvent consists essentially of water. The composition according to any one of claims 1 to 3, wherein the aqueous solvent consists of water. 4. The method according to any one of claims 1 to 3, wherein the mixture comprises at least one further selected from alkylsilsesquioxane, vinylsilsesquioxane, carboxylic acid alkylsilsesquioxane and alkyleneglycol alkylsilsesquioxane. The composition further comprising a silicon-containing compound. 4. The composition of any one of claims 1 to 3, wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 4. The composition according to any one of claims 1 to 3, wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 4. A composition according to any one of claims 1 to 3, wherein the formula consists essentially of pure phosphoric acid and a mixture. The composition according to any one of claims 1 to 3, wherein the formula consists of pure phosphoric acid and a mixture. The composition of claim 1 , wherein the formula consists essentially of pure phosphoric acid and the mixture consists essentially of the compound of formula (I) and an aqueous solvent. The composition according to claim 1, wherein the formula consists of pure phosphoric acid and the mixture consists of the compound of formula (I) and an aqueous solvent. 3. The composition of claim 2, wherein the formula consists essentially of pure phosphoric acid and the mixture consists essentially of the compound of formula II and an aqueous solvent. 3. The composition of claim 2, wherein the formula consists of pure phosphoric acid and the mixture consists of a compound of formula II and an aqueous solvent. 4. The composition of claim 3, wherein the formula consists essentially of pure phosphoric acid and the mixture consists essentially of the compound of formula III and an aqueous solvent. 4. The composition of claim 3, wherein the formula consists of pure phosphoric acid and the mixture consists of a compound of formula III and an aqueous solvent. The composition of claim 1 , wherein m is zero. The composition according to claim 1, wherein the content of the compound of formula (I) is approximately 5% by weight or less. The composition according to claim 1, wherein the content of the compound of formula (I) is approximately 4% by weight or less. The composition according to claim 1, wherein the content of the compound of formula (I) is approximately 3% by weight or less. The composition according to claim 1, wherein the content of the compound of formula (I) is approximately 2% by weight or less. The composition according to claim 1, wherein the content of the compound of formula (I) is approximately 1% by weight or less. The composition of claim 1 , wherein each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is the same. The composition of claim 1 , wherein each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is hydrogen. The composition of claim 1 , wherein at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is other than hydrogen. The method of claim 1 , wherein (i) each of R ^a and R ^b is

C ₃ H ₆

and (ii) each of R ¹ , R ² , R ⁴ and R ⁵ is

H, and (iii) m = 0. The method of claim 1 , wherein (i) each of R ^a and R ^b is

C ₃ H ₆

and (ii) each of R ¹ , R ² , R ⁴ and R ⁵ is

H, and (iii) m = 0. The method of claim 1 , wherein (i) each of R ^a and R ^b is

NH-C ₂ H ₄ -, and (ii) each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is

H, and (iii) m = 0. According to claim 1,
(i) the compound of formula I

phosphorus composition. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises pure sulfuric acid. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.83% by weight of the composition. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.94% by weight of the composition. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 84.27% by weight of the composition. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 84.6% by weight of the composition. According to claim 1,
(i) the compound of formula I

phosphorus composition. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises pure sulfuric acid. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. According to claim 1,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. A. up to approximately 60% by weight of pure phosphoric acid;
B. (i) about 5% by weight or less

, and
(ii) up to about 24 weight percent pure sulfuric acid; and
(iii) an aqueous solvent comprising water;
About 40% by weight or more of a mixture comprising
A composition comprising a. A. up to approximately 60% by weight of pure phosphoric acid;
B. (i) about 5% by weight or less

, and
(ii) up to about 24 weight percent pure sulfuric acid; and
(iii) an aqueous solvent consisting essentially of water
About 40% by weight or more of a mixture consisting essentially of
A composition consisting essentially of A. up to approximately 60% by weight of pure phosphoric acid;
B. (i) about 5% by weight or less

, and
(ii) up to about 24 weight percent pure sulfuric acid; and
(iii) an aqueous solvent consisting of water
About 40% by weight or more of a mixture consisting of
A composition comprising. 3. The composition of claim 2, wherein m is 0. 3. The composition of claim 2, wherein n is zero. 3. The composition of claim 2, wherein m is 0 and n is 0. 3. The composition of claim 2, wherein the content of the compound of formula (II) is approximately 5% by weight or less. The composition according to claim 2, wherein the content of the compound of formula (II) is approximately 4% by weight or less. 3. The composition of claim 2, wherein the content of the compound of formula (II) is approximately 3% by weight or less. 3. The composition of claim 2, wherein the content of the compound of formula (II) is approximately 2% by weight or less. 3. The composition according to claim 2, wherein the content of the compound of formula (II) is approximately 1% by weight or less. 3. The method of claim 2, wherein (i) m = 0, n = 3, and (ii) each of Z ¹ and Z ² is

phosphorus composition. 3. The method of claim 2, wherein (i) m = 0, (ii) n = 3, and (iii) each of Z ¹ and Z ² is

phosphorus composition. 3. The method of claim 2, wherein (i) m = 0, (ii) n = 3, and (II) each of Z ¹ and Z ² is

N ⁺ (CH ₃ ) ₃ Cl ^- phosphorous composition. 3. The method of claim 2, wherein (i) m = 0, (ii) n = 3, and (iii) each of Z ¹ and Z ² is

CH(OH)CH ₂ OH. 3. The method of claim 2,
(i) the compound of formula II

ego,
(ii) the mixture further comprises pure sulfuric acid. 3. The method of claim 2,
(i) the compound of formula II

ego,
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 3. The method of claim 2,
(i) the compound of formula II

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 3. The method of claim 2,
(i) the compound of formula II

ego,
(ii) the mixture further comprises pure sulfuric acid. 3. The method of claim 2,
(i) the compound of formula II

ego,
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 3. The method of claim 2,
(i) the compound of formula II

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 4. The composition of claim 3, wherein the content of the compound of formula (III) is approximately 5% by weight or less. 4. The composition of claim 3, wherein the content of the compound of formula (III) is approximately 4% by weight or less. 4. The composition according to claim 3, wherein the content of the compound of formula (III) is approximately 3% by weight or less. 4. The composition of claim 3, wherein the content of the compound of formula (III) is approximately 2% by weight or less. 4. The composition of claim 3, wherein the content of the compound of formula (III) is approximately 1% by weight or less. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₃ , and (ii) L is

(iii) n = 0, and (iv) the sum of m1 and m2 = 1 to 5. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OH, (ii) the sum of m1 and m2 = 3, (iii) n = 0, (iv) L is

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) m2 = 3, (iii) n = 1, and (iv) A is

, where Ra = H, (v) m1 = 0, and (vi) L is

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OH, (ii) m2 = 3, (iii) n = 1, and (iv) A is

, (v) m1 = 0, and (vi) L is

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) m2 = 3, (iii) n = 1, and (iv) A is

, where Ra =

H, (v) m1 = 0, and (vi) L

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) sum of m1 and m2 = 2, (iii) n = 0, (iv) L is

, wherein each of X ¹ , X ² and X ³ is

F. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) m2 = 3, (iii) n = 1, and (iv) A is

, where Ra =

H, (v) m1 = 0, and (vi) L

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OH, (ii) m2 = 2, (iii) n = 1, and (iv) A is

, (v) m1 = 0, and (vi) L is

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) m2 = 3, (iii) n = 1, and (iv) A is

, wherein R ^a and R ^b are

CH ₃ , (v) m1 = 3, and (vi) L

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₃ , (ii) the sum of m1 and m2 = 2, (iii) n = 0, (iv) L is

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₂ CH ₃ , (ii) sum of m1 and m2 = 3, (iii) n = 0, (iv) L is

phosphorus composition. 4. The method of claim 3, wherein (i) each of R ¹ , R ² and R ³ is

OCH ₂ CH ₃ , (ii) the sum of m1 and m2 = 1, (iii) n = 0, (iv) L is

phosphorus composition. 4. The method of claim 3,
(i) the compound of formula III

, where R =

(CH ₂ ) _x

, and x = 1 to 5,
(ii) the mixture further comprises pure sulfuric acid. 4. The method of claim 3,
(i) the compound of formula III

, where R =

(CH ₂ ) _x

and x = 1 to 5),
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III

, where R =

(CH ₂ ) _x

, and x = 1 to 5,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III is Si(OCH ₃ ) ₃ (CH ₂ CH ₂ CF ₃ ),
(ii) the mixture further comprises pure sulfuric acid. 4. The method of claim 3,
(i) the compound of formula III is Si(OCH ₃ ) ₃ (CH ₂ CH ₂ CF ₃ ),
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III is Si(OCH ₃ ) ₃ (CH ₂ CH ₂ CF ₃ ),
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises pure sulfuric acid. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises pure sulfuric acid. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises pure sulfuric acid. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 4. The method of claim 3,
(i) the compound of formula III

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.5% by weight of the composition. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of approximately 2700. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of at least about 2500. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of at least about 2250. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of at least about 2000. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of at least about 1500. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of at least about 1250. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of at least about 1000. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of at least about 500. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of at least about 300. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride relative to silicon oxide of from about 1500 to about 2700. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride relative to silicon oxide of from about 2000 to about 2700. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride relative to silicon oxide of from about 2250 to about 2700. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride relative to silicon oxide of from about 2500 to about 2700. 4. The composition of any one of claims 1 to 3, wherein the composition has a selectivity of etching to silicon nitride versus silicon oxide of between about 2600 and about 2700. A. greater than approximately 70% by weight pure phosphoric acid;
BI a compound of formula (I); and
II. aqueous solvent
less than about 30% by weight of a mixture comprising
A composition comprising:

In the above formula,
(i) m = 0 to 20;
(ii) each R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently hydrogen, a C ₁ to C ₁₀ linear alkyl group, a C ₁ to C ₁₀ linear alkyl group substituted with fluorine, a 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 group alkynyl group,

selected from the group of OH,
(iii) each R ^a and R ^b is independently 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, C ₂ to C ₁₀ linear or branched alkenyl groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH. A. greater than approximately 70% by weight pure phosphoric acid;
BI a compound of formula II; and
II. aqueous solvent
less than about 30% by weight of a mixture comprising
A composition comprising:

In the above formula,
(i) m = 0 to 20;
(ii) n = 0 to 20;
(iii) R ³ is hydrogen, C ₁ to C ₁₀ linear alkyl group, C ₁ to C ₁₀ linear alkyl group substituted with fluorine, 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,

selected from the group of OH, Z ¹ and Z ² ,
(iv) each R ^a and R ^b is independently a 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 groups and C ₂ to C ₁₀ linear or branched alkynyl groups,

NH-C ₁ -C ₁₀ alkyl,

C ₁ -C ₁₀ alkyl substituted with OH,
(v) Z ¹ and Z ² are each independently
a.

,
b.

,
c.

N ⁺ (CH ₃ ) ₃ Cl ⁻ , and
d.

CH(OH)CH ₂ OH. A. greater than approximately 70% by weight pure phosphoric acid;
BI a compound of formula III; and
II. aqueous solvent
less than about 30% by weight of a mixture comprising
A composition comprising:

In the above formula,
(i) m1 and m2 are each from 0 to 10, provided that at least one of m1 and m2 is ≥ 1,
(ii) n = 0 or 1,
(iii) each R ¹ , R ² and R ³ is independently hydrogen, a C ₁ to C ₆ linear alkyl group, a C ₃ to C ₆ branched alkyl group, and

OC ₁ to C ₆ selected from the group of linear alkyl groups,
(iv) A is
a.

,
b.

,
c.

, and
d.

is selected from, and in b, R ^a is selected from hydrogen, a C ₁ to C ₆ linear alkyl group, and a C ₃ to C ₆ branched alkyl group, wherein R ^a and R ^b are each independently hydrogen, C ₁ to C ₆ linear alkyl groups, C ₃ to C ₆ selected from branched alkyl groups,
(v) L is
a.

,
b.

,
c.

,
d.

,
e.

,
f.

,
g.

,
h.

,
i.

, and
j.

and each of X ¹ , X ² and X ³ in e is independently selected from Cl, Br, F or I. 131. The composition of any one of claims 127-129, wherein (i) the composition comprises greater than about 75 weight percent pure phosphoric acid, and (ii) less than about 25 weight percent of the mixture. 131. The composition of any one of claims 127-129, wherein the mixture further comprises at least one additional acid other than pure phosphoric acid. 131. The composition of any one of claims 127-129, 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 methane sulfuric acid. 130. The composition of any one of claims 127-129, wherein the mixture further comprises pure sulfuric acid. 131. The composition of any one of claims 127-129, wherein the mixture further comprises up to approximately 10% by weight pure sulfuric acid. 130. The composition of any one of claims 127-129, wherein the mixture further comprises pure methane sulfuric acid. 130. The composition of any one of claims 127-129, wherein the mixture further comprises a sulfonic acid. 130. The composition of any one of claims 127-129, wherein the aqueous solvent comprises water. 131. The composition of any one of claims 127-129, wherein the aqueous solvent consists essentially of water. 131. The composition of any one of claims 127-129, wherein the aqueous solvent consists of water. 130. The method according to any one of claims 127 to 129, wherein the mixture comprises at least one additional selected from alkylsilsesquioxane, vinylsilsesquioxane, carboxylic acid alkylsilsesquioxane and alkyleneglycol alkylsilsesquioxane. The composition further comprising a silicon-containing compound. 131. The composition of any one of claims 127-129, wherein the formula consists essentially of pure phosphoric acid and the mixture. 131. The composition of any one of claims 127-129, wherein the formula consists of pure phosphoric acid and a mixture. 127. The composition of claim 127, wherein the formula consists essentially of pure phosphoric acid and the mixture consists essentially of the compound of formula (I) and an aqueous solvent. 128. The composition of claim 127, wherein the formula consists of pure phosphoric acid and a mixture, and wherein the mixture consists of a compound of formula (I) and an aqueous solvent. 129. The composition of claim 128, wherein the formula consists essentially of pure phosphoric acid and the mixture consists essentially of the compound of formula II and an aqueous solvent. 129. The composition of claim 128, wherein the formula consists of pure phosphoric acid and a mixture, and wherein the mixture consists of a compound of formula II and an aqueous solvent. 130. The composition of claim 129, wherein the formula consists essentially of pure phosphoric acid and the mixture consists essentially of the compound of formula III and an aqueous solvent. 130. The composition of claim 129, wherein the formula consists of pure phosphoric acid and a mixture, and wherein the mixture consists of a compound of formula III and an aqueous solvent. 127. The composition of claim 127, wherein each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is the same. 127. The composition of claim 127, wherein each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is hydrogen. 127. The composition of claim 127, wherein at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is other than hydrogen. 127. The composition of claim 127, wherein the content of the compound of formula (I) is approximately 5% by weight or less. 127. The composition of claim 127, wherein the content of the compound of formula (I) is approximately 4% by weight or less. 127. The composition of claim 127, wherein the content of the compound of formula (I) is approximately 3% by weight or less. 127. The composition of claim 127, wherein the content of the compound of formula (I) is approximately 2% by weight or less. 127. The composition of claim 127, wherein the content of the compound of formula (I) is approximately 1% by weight or less. 127. The method of claim 127, wherein (i) each of R ^a and R ^b is

C ₃ H ₆

and (ii) each of R ¹ , R ² , R ⁴ and R ⁵ is

H, and (iii) m = 0. 127. The method of claim 127, wherein (i) each of R ^a and R ^b is

C ₃ H ₆

and (ii) each of R ¹ , R ² , R ⁴ and R ⁵ is

H, (iii) m = 0, and (iv) R ³ = —C ₃ H ₆ NH ₂ . 131. The method of claim 128, wherein (i) each of R ^a and R ^b is

NH-C ₂ H ₄

and (ii) each of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is hydrogen, and (iii) m = 0. 129. The method of claim 128,
(i) the compound of formula I

phosphorus composition. 127. The method of claim 127,
(i) the compound of formula I

ego,
(ii) a composition wherein the content of pure phosphoric acid is approximately 80.75% by weight of the composition. 127. The method of claim 127,
(i) the compound of formula I

ego,
(ii) the mixture further comprises pure sulfuric acid. 127. The method of claim 127,
(i) the compound of formula I

ego,
(ii) the mixture further comprises pure sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is from about 80% to about 85% by weight of the composition. 127. The method of claim 127,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 81.85% by weight of the composition. 127. The method of claim 127,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 82.4% by weight of the composition. 127. The method of claim 127,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 82.95% by weight of the composition. 127. The method of claim 127,
(i) the compound of formula I

ego,
(ii) the mixture further comprises sulfuric acid;
(iii) a composition wherein the combined content of pure phosphoric acid and pure sulfuric acid is approximately 83.23% by weight of the composition. 127. The method of claim 127,
(i) the compound of formula I

phosphorus composition. 127. The method of claim 127,
(i) the compound of formula I

ego,
(ii) a composition wherein the content of pure phosphoric acid is approximately 80.75% by weight of the composition. 129. The method of claim 128,
(i) the compound of formula II

phosphorus composition. 129. The method of claim 128,
(i) the compound of formula II

ego,
(ii) a composition wherein the content of pure phosphoric acid is approximately 80.75% by weight of the composition. 129. The method of claim 128,
(i) the compound of formula II

phosphorus composition. 129. The method of claim 128,
(i) the compound of formula II

ego,
(ii) a composition wherein the content of pure phosphoric acid is approximately 80.75% by weight of the composition. 130. The method of claim 129,
(i) the compound of formula III

phosphorus composition. 130. The method of claim 129,
(i) the compound of formula III

ego,
(ii) a composition wherein the content of pure phosphoric acid is approximately 80.75% by weight of the composition. 130. The method of claim 129,
(i) the compound of formula III

phosphorus composition. 130. The method of claim 129,
(i) the compound of formula III

ego,
(ii) a composition wherein the content of pure phosphoric acid is approximately 80.75% by weight of the composition. A method for selectively improving the etching rate of silicon nitride compared to silicon dioxide on a semiconductor substrate comprising silicon nitride and silicon dioxide,
a. 178. A method comprising: contacting a semiconductor substrate comprising silicon nitride and silicon dioxide with the composition of any one of claims 1-177; and
b. cleaning the semiconductor device after the silicon nitride is at least partially removed.
How to include. 179. The method of any one of claims 178, further comprising drying the semiconductor device. 179. The method of any one of claims 178, wherein the selectivity of the etch to silicon nitride relative to silicon oxide is at least about 300. 179. The method of claim 178, wherein the contacting step is performed at a temperature of about 160°C.