KR20190142010A - Compositions comprising polysiloxane-based compounds, and etching compositions comprising same - Google Patents

Abstract

The present invention relates to a silicon nitride film etching composition, which selectively etches a silicon nitride film compared to a silicon oxide film, has excellent etch selectivity, and has little change in the etching rate and the etching selectivity for the silicon nitride film even if the use time of the composition is increased or the composition is repetitively used.

Description

Composition comprising a polysiloxane compound and an etching composition comprising the same {COMPOSITIONS COMPRISING POLYSILOXANE-BASED COMPOUNDS, AND ETCHING COMPOSITIONS COMPRISING SAME}

The present invention relates to a composition comprising a polysiloxane compound, a selective etching composition for a silicon nitride film comprising the same, and a method of manufacturing a semiconductor device including the same. More particularly, the present invention relates to a composition comprising a polysiloxane compound having a high etching selectivity by selectively etching a silicon nitride film with respect to a silicon oxide film, an etching composition including the same, and a method of manufacturing a semiconductor device including the same.

Silicon oxide film (SiO ₂ ) and silicon nitride film (SiN _x ) are representative insulating films used in semiconductor manufacturing processes. The double silicon nitride film is a silicon nitride used as a cap layer, spacer layer or hard mask layer in semiconductor devices. The silicon oxide film and the silicon nitride film may be used alone, or one or more layers of silicon oxide film and one or more layers of silicon nitride film may be alternately stacked.

The silicon nitride film is etched using a mixture of high purity phosphoric acid and deionized water at a high temperature of about 160 ° C. However, high-purity phosphoric acid has a problem that the etching selectivity of the silicon nitride film to the silicon oxide film is low, and thus it is difficult to apply to the laminated structure of the silicon nitride film and the silicon oxide film. In addition, the silicon nitride etching composition containing phosphoric acid must be continuously supplied with deionized water because the silicon nitride film etching composition is concentrated by evaporation of moisture continuously at a high temperature, thereby affecting the etching rate of the nitride film and the oxide film. However, even a slight change in the amount of pure water supplied may cause defects in the removal of the silicon nitride film, and phosphoric acid itself has a problem of being corrosive with strong acid, making it difficult to handle.

In order to solve the above problems and to improve the etching selectivity of the silicon nitride film to the silicon oxide film, a silicon nitride film etching composition in which silicic acid is dissolved in phosphoric acid may be used. However, the silicon nitride film etching composition has a problem that it is difficult to apply to the process due to the abnormal growth (anomalous growth) problem that the precipitate is generated during the etching process, the thickness of the silicon oxide film is rather increased.

In addition, a method of controlling an etch selectivity using a silicon compound containing an oxygen atom directly bonded to silicon may be used. However, the selectivity of the silicon nitride film is not high compared to the silicon oxide film, and the silicic acid generated by etching the silicon nitride film It still causes abnormal growth and causes various problems in the later process.

The present invention is to solve the above problems, a composition comprising a polysiloxane compound, an etching additive comprising the same, the silicon nitride film etching composition with improved etching selectivity to the silicon nitride film comprising the same and a method of manufacturing a semiconductor device comprising the same To provide.

Specifically, an object of the present invention is to provide a composition comprising a polysiloxane compound that can be added to an etchant.

Still another object of the present invention is to provide an etching additive including a polysiloxane composition and capable of selectively etching a silicon nitride film relative to a silicon oxide film.

Another object of the present invention is to provide a silicon nitride film etching composition which can selectively etch a silicon nitride film compared to a silicon oxide film, and the etching selectivity is significantly improved.

It is still another object of the present invention to provide a stable silicon nitride film etching composition having a small change in the etching rate and the etching selectivity with respect to the silicon nitride film even when the etching process time is increased or repeatedly used.

One aspect of the present invention for achieving the above object may be a composition comprising a compound represented by the following formula (1) and (2).

[Formula 1]

In Formula 1, R ¹ is selected from hydrogen, hydroxy, (C ¹ -C 20) alkoxy, halogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ and amino (C 1 -C 20) alkyl. ; One of R ² and R ³ is amino (C 1 -C 20) alkyl, the other is hydrogen, hydroxy, (C 1 -C 20) alkoxy, halogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ and amino (C1-C20) alkyl; R ⁴ is selected from hydrogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ , —P (═O) (OH) ₂ , —P (═O) (OH) R ¹¹⁰ ; R ¹¹⁰ is (C1-C20) alkyl; n is an integer from 1 to 100; a is 1-4.

[Formula 2]

In Formula 2, R ⁵ is hydrogen, hydroxy, (C 1 -C 20) alkoxy, halogen, (C 1 -C 20) alkyl, -L-SO ₃ H, -OP (= O) (OH) ₂ , -L- OP (= O) (OH) _2, -LP (= O) (OH) ₂ , -OP (= O) (OH) R ¹¹⁰ , -LP (= O) (OH) R ¹²⁰ And -L-OP (= 0) (OH) R ¹⁰⁰ ; One of R ⁶ and R ⁷ is —L—SO ₃ H, —L—OP (═O) (OH) ₂ , —LP (═O) (OH) ₂ , -LP (= O) (OH) R ¹²⁰ And -L-OP (= 0) (OH) R ¹⁰⁰ , the other is hydrogen, hydroxy, (C1-C20) alkoxy, halogen, (C1-C20) alkyl, -L-SO ₃ H,- OP (= O) (OH) ₂ , -L-OP (= O) (OH) _2, -LP (= O) (OH) ₂ , -OP (= O) (OH) R ¹¹⁰ , -LP (= O) (OH) R ¹²⁰ And -L-OP (= 0) (OH) R ¹⁰⁰ ; R ⁸ is selected from hydrogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ , —P (═O) (OH) ₂ and —P (═O) (OH) R ¹¹⁰ ; R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ (C1-C20) alkyl; L is (C1-C20) alkylene; m is an integer from 1 to 100; b is 1-4.

In one embodiment of the present invention, R ¹ in Formula 1 is selected from hydroxy, (C ¹ -C 20) alkyl and amino (C 1 -C 20) alkyl; One of R ² and R ³ is amino (C 1 -C 20) alkyl, the other is selected from hydroxy, (C 1 -C 7) alkoxy and amino (C 1 -C 20) alkyl; R ⁴ is selected from hydrogen, (C 1 -C 20) alkyl and —P (═O) (OH) ₂ ; n is an integer from 1 to 50; a is 1 to 4; R ⁵ in Formula 2 is selected from hydroxy, (C1-C20) alkyl and -L-SO ₃ H; One of R ⁶ and R ⁷ is -L-SO ₃ H, and the other is selected from hydroxy, (C1-C20) alkoxy and -L-SO ₃ H; R ⁸ is selected from hydrogen and (C 1 -C 20) alkyl; L is (C1-C20) alkylene; m is an integer from 1 to 50; b may be a polysiloxane composition of 1 to 4.

In one embodiment of the present invention, R ¹ of Formula 1 is selected from hydroxy, (C ¹ -C 7) alkyl and amino (C 1 -C 7) alkyl; One of R ² and R ³ is amino (C 1 -C 7) alkyl and the other is selected from hydroxy, (C 1 -C 7) alkoxy and amino (C 1 -C 7) alkyl; R ⁴ is selected from hydrogen, (C 1 -C 7) alkyl and —P (═O) (OH) ₂ ; n is an integer from 2 to 20; a is 2 to 4; R ⁵ in Formula 2 is selected from hydroxy, (C1-C7) alkyl and -L-SO ₃ H; One of R ⁶ and R ⁷ is -L-SO ₃ H, and the other is selected from hydroxy, (C1-C7) alkoxy and -L-SO ₃ H; R ⁸ is selected from hydrogen and (C 1 -C ⁷ ) alkyl; L is (C1-C7) alkylene; m is an integer from 2 to 20; b may be a polysiloxane composition of 2 to 4.

In one embodiment of the present invention, the polysiloxane compound represented by Formula 1 may be selected from the following Structural Formula 1, the polysiloxane compound represented by Formula 2 may be a composition selected from the compound represented by the following Structural Formula 2 have.

[Formula 1]

  [Formula 2]

In one embodiment of the present invention, Formula 1 and Formula 2 may be a composition comprising a weight ratio of 1: 99 to 99: 1.

In addition, another aspect of the present invention may be an etchant including the polysiloxane composition.

In addition, another aspect of the present invention may be a silicon nitride film etching composition comprising the polysiloxane-based composition, phosphoric acid and water.

In one embodiment of the present invention, the silicon nitride film etching composition comprising 0.005 to 10% by weight of the polysiloxane composition, 60 to 90% by weight of phosphoric acid and the balance of water based on the total weight of the etching composition.

In one embodiment of the present invention, it may be a silicon nitride film etching composition that satisfies the etching selectivity of the following relation 1.

[Relationship 1]

500 ≤ E _SiNx / E _SiO2

In Equation 1, E _SiNx is an etching rate of a silicon nitride film, and E _SiO2 is an etching rate of a silicon oxide film.

In one embodiment of the present invention, the etching rate reduction rate of the silicon nitride film after the repeated etching process may be a silicon nitride film etching composition satisfying the following relation 2.

[Relationship 2]

△ ERD _SiNx ≤ 1%

In Equation 2, ΔERD _SiNx is an etching rate reduction rate relative to the initial etching rate for the silicon nitride film.

In one embodiment of the present invention, the silicon nitride film etching composition may further include an alcohol solvent.

In one embodiment of the present invention, the silicon nitride film etching composition may further include a fluorine-based compound.

In addition, another aspect of the present invention is a method of manufacturing a semiconductor device including an etching step using the silicon nitride film etching composition.

In the silicon nitride film etching composition according to the present invention, a composition containing a polysiloxane compound may be used to selectively etch the silicon nitride film compared to the silicon oxide film, and the etching selectivity may be remarkably excellent.

In addition, the silicon nitride film etching composition according to the present invention has a small effect of changing the etching rate and the etching selectivity with respect to the silicon nitride film even if the etching process time is increased or repeated use, ultimately manufacturing a semiconductor for selectively etching the silicon nitride film Productivity in the process can be improved.

In addition, the silicon nitride film etching composition according to the present invention is excellent in storage stability, and can maintain a constant etching rate and etching selectivity with respect to the silicon nitride film despite long-term use or storage.

In addition, when the silicon nitride film etching composition of the present invention is used in a semiconductor manufacturing process, there is an effect of reducing the abnormal growth of other films existing around the silicon oxide film.

DETAILED DESCRIPTION Hereinafter, the present invention will be described in more detail with reference to the accompanying examples or embodiments. However, the following specific examples or examples are only one reference for describing the present invention in detail, but the present invention is not limited thereto and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description in the present invention are only for effectively describing specific embodiments and are not intended to limit the present invention.

Also, the singular forms used in the specification and the appended claims may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

As used herein, the term 'etch selectivity (E _SiNx / E _SiO2 )' means a ratio of an etching rate (E _SiNx ) of a silicon nitride film to an etching rate (E _SiO2 ) of a silicon oxide film. In addition, when the etching rate of the silicon oxide film approaches zero or the value of the etching selectivity is large, it means that the silicon nitride film can be selectively etched.

As used herein, the term “change in etching selectivity” refers to an absolute value for a difference in etching selectivity compared to an initial etching selectivity when the etching process is repeatedly performed two or more times using the same silicon nitride etching composition.

As used herein, the term “etch rate drift (ΔERD)” refers to the rate of change of the etching rate relative to the initial etching rate when the etching process is repeatedly performed two or more times using the same silicon nitride film etching composition. In general, as the etching process is repeatedly performed, the etching ability, that is, the etching rate tends to decrease and is defined as a reduction rate, and the change rate is of course interpreted as the same meaning.

The unit of% used without particular mention in the present invention means weight%.

Silicon nitride films and silicon oxide films are representative insulating films used in semiconductor manufacturing processes. In the semiconductor process, the silicon nitride film is in contact with a silicon oxide film, a poly silicon film, a silicon wafer surface, and the like, and is mainly deposited through a chemical vapor deposition (CVD) process, which is removed by etching.

Conventional wet etching has a problem that the selectivity of the silicon nitride film to the silicon oxide film is lowered and the etching selectivity is changed when the etching solution is used several times. In addition, a precipitate is generated during the etching process has a problem that the thickness of the silicon oxide film is increased.

Accordingly, the present inventors have solved the above-described problems, and have deepened research on silicon nitride film etching compositions having improved selectivity. As a result, when the specific polysiloxane-based etching additive is treated, it was found that the selectivity of the silicon nitride film to the silicon oxide film is excellent and the abnormal growth is reduced.

In addition, the silicon nitride film etching composition according to the present invention exhibits excellent etching selectivity for the silicon nitride film compared to the silicon oxide film, and despite the increase in the treatment time and the number of treatments with high stability, the etching rate and the etching selectivity for the silicon nitride film are long maintained. The maintenance was found and the present invention was completed.

The silicon nitride film referred to in the present invention may be various silicon nitride films such as a SiN film, a SiON film, and a doped SiN film. The silicon nitride film is a concept including such a silicon nitride film. As a specific example, the silicon nitride film is mainly used as an insulating film when a gate electrode is formed. It can mean the film quality. However, the technical field having the purpose of selectively etching the silicon nitride film relative to the silicon oxide film may be used without limitation.

In addition, the 'silicon oxide film' referred to in the present invention is not limited as long as it is a silicon oxide film commonly used in the art. For example, a spin on dielectric (SOD) film, a high density plasma film (HDP) film, and a thermal oxide film. , BPSG (Borophosphate Silicate Glass), PSG (Phospho Silicate Glass), BSG (Boro Silicate Glass), PSZ (Polysilazane), FSG (Fluorinated Silicate Glass), LP-TEOS (Low Pressure Tetra Ethyl Ortho Silicate) Film, PETEOS (Plasma Enhanced Tetra Ethyl Ortho Silicate), HTO (High Temperature Oxide), MTO (Medium Temperature Oxide), USG (Undopped Silicate Glass), SOG (Spin On Glass), APL (Advanced Planarization Layer) ) Film, ALD (Atomic Layer Deposition) film, PE-Plasma Enhanced oxide (PE-Plasma Enhanced oxide) and at least one film selected from the group consisting of O ₃ -TEOS (O ₃ -Tetra Ethyl Ortho Silicate). However, this is only a specific example and is not limited thereto.

Hereinafter, a polysiloxane composition according to the present invention, an etching additive including the same, a selective etching composition for the silicon nitride film including the same, and a method of manufacturing the semiconductor device will be described in more detail.

The composition according to the present invention may include a polysiloxane compound represented by the following Chemical Formula 1 and Chemical Formula 2.

[Formula 1]

In Formula 1, R ¹ is selected from hydrogen, hydroxy, (C ¹ -C 20) alkoxy, halogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ and amino (C 1 -C 20) alkyl. ; One of R ² and R ³ is amino (C 1 -C 20) alkyl, the other is hydrogen, hydroxy, (C 1 -C 20) alkoxy, halogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ and amino (C1-C20) alkyl; R ⁴ is selected from hydrogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ , —P (═O) (OH) ₂ , —P (═O) (OH) R ¹¹⁰ ; R ¹¹⁰ is (C1-C20) alkyl; n is an integer from 1 to 100; a is 1-4.

[Formula 2]

In Formula 2, R ⁵ is hydrogen, hydroxy, (C 1 -C 20) alkoxy, halogen, (C 1 -C 20) alkyl, -L-SO ₃ H, -OP (= O) (OH) ₂ , -L- OP (= O) (OH) _2, -LP (= O) (OH) ₂ , -OP (= O) (OH) R ¹¹⁰ , -LP (= O) (OH) R ¹²⁰ and -L-OP (= 0) (OH) R ¹⁰⁰ ; One of R ⁶ and R ⁷ is -L-SO ₃ H, -L-OP (= O) (OH) ₂ , -LP (= O) (OH) _2, -LP (= O) (OH) R ¹²⁰ And -L-OP (= 0) (OH) R ¹⁰⁰ , the other is hydrogen, hydroxy, (C1-C20) alkoxy, halogen, (C1-C20) alkyl, -L-SO ₃ H,- OP (= O) (OH) ₂ , -L-OP (= O) (OH) _2, -LP (= O) (OH) _2, -OP (= O) (OH) R ¹¹⁰ , -LP (= O) (OH) R ¹²⁰ And -L-OP (= 0) (OH) R ¹⁰⁰ ; R ⁸ is selected from hydrogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ , —P (═O) (OH) ₂ and —P (═O) (OH) R ¹¹⁰ ; R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ (C1-C20) alkyl; L is (C1-C20) alkylene; m is an integer from 1 to 100; b is 1-4.

When the composition is used as an etch additive, the Si-O bonds present in the additive and the Si-O bonds formed upon hydrolysis protect the silicon oxide film and thus have a high selectivity.

'Alkoxy' of R ¹ to R ³ and R ⁵ to R ⁷ means what is represented by the following functional group.

R of the alkoxy group means a hydrocarbon chain including carbon and hydrogen, and may be branched or straight chain, and more specifically, may be straight chain, but is not limited thereto. In addition, R in the alkoxy group may be (C1-C20) alkyl, preferably (C1-C7) alkyl, more preferably (C1-C5) alkyl. Examples of non-limiting alkoxy include -OCH ₃ , -OC ₂ H ₅ , -OC ₃ H ₇ , -OCH (CH ₃ ) ₂ , -OC ₄ H ₉ , -OCH ₂ -CH (CH ₃ ) ₂ , -OCH (CH ₃ ) -C ₂ H ₅ , -OC (CH ₃ ) ₃ , -OC ₅ H ₁₁ , -OCH (CH ₃ ) -C ₃ H ₇ , -OCH ₂ -CH (CH ₃ ) -C ₂ H ₅ , -OCH (CH ₃ ) -CH (CH ₃ ) ₂ , -OC (CH ₃ ) ₂ -C ₂ H ₅ , -OCH ₂ -C (CH ₃ ) ₃ , -OCH (C ₂ H ₅ ) ₂ ,- OC ₂ H ₄ -CH (CH ₃ ) ₂ , -OC ₆ H ₁₃ , -OC ₃ H ₆ -CH (CH ₃ ) ₂ , -OC ₂ H ₄ -CH (CH ₃ ) -C ₂ H ₅ , -OCH (CH ₃ ) -C ₄ H ₉ , -OCH ₂ -CH (CH ₃ ) -C ₃ H ₇ , -OCH (CH ₃ ) -CH ₂ -CH (CH ₃ ) ₂ , -OCH (CH ₃ ) -CH (CH ₃ ) -C ₂ H ₅ , -OCH ₂ -CH (CH ₃ ) -CH (CH ₃ ) ₂ , -OCH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , -OC (CH ₃ ) ₂ -C ₃ H ₇ , -OC (CH ₃ ) ₂ -CH (CH ₃ ) ₂ , -OC ₂ H ₄ -C (CH ₃ ) ₃ , -OCH ₂ -CH (C ₂ H ₅ ) ₂ and -OCH ( CH ₃ ) -C (CH ₃ ) ₃ , and the like, and preferably, -OC ₂ H ₅ , but is not limited thereto.

'Halogen' of R ¹ to R ³ and R ⁵ to R ⁷ means fluorine, chlorine, bromine and iodine atoms.

'Alkyl' of R ¹ to R ⁸ means a hydrocarbon chain containing carbon and hydrogen. Such hydrocarbon chains may be branched or straight chain, and more particularly, may be straight chain, but is not limited thereto. Carbon number of the alkyl group is C1 to C20, preferably C1 to C7, more preferably C1 to C5. Examples of non-limiting alkyl include -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , -CH (CH ₃ ) ₂ , -C ₄ H ₉ , -CH ₂ -CH (CH ₃ ) ₂ , -CH (CH ₃ ) -C ₂ H ₅ , -C (CH ₃ ) ₃ , -C ₅ H ₁₁ , -CH (CH ₃ ) -C ₃ H ₇ , -CH ₂ -CH (CH ₃ ) -C ₂ H ₅ , -CH (CH ₃ ) -CH (CH ₃ ) ₂ , -C (CH ₃ ) ₂ -C ₂ H ₅ , -CH ₂ -C (CH ₃ ) ₃ , -CH (C ₂ H ₅ ) ₂ ,- C ₂ H ₄ -CH (CH ₃ ) ₂ , -C ₆ H ₁₃ , -C ₃ H ₆ -CH (CH ₃ ) ₂ , -C ₂ H ₄ -CH (CH ₃ ) -C ₂ H ₅ , -CH (CH ₃ ) -C ₄ H ₉ , -CH ₂ -CH (CH ₃ ) -C ₃ H ₇ , -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) ₂ , -CH (CH ₃ ) -CH (CH ₃ ) -C ₂ H ₅ , -CH ₂ -CH (CH ₃ ) -CH (CH ₃ ) ₂ , -CH ₂ -C (CH ₃ ) ₂ -C ₂ H ₅ , -C (CH ₃ ) ₂ -C ₃ H ₇ , -C (CH ₃ ) ₂ -CH (CH ₃ ) ₂ , -C ₂ H ₄ -C (CH ₃ ) ₃ , -CH ₂ -CH (C ₂ H ₅ ) ₂ and -CH ( CH ₃ ) -C (CH ₃ ) ₃ etc. But may not be limited thereto.

"Aminoalkyl" of the above R ¹ to R ³ means represented by the following functional group.

L of the aminoalkyl group may be (C1-C20) alkylene, preferably (C1-C7) alkylene, more preferably (C1-C5) alkylene.

Non-limiting examples of aminoalkyl include NH ₂ -CH _2- , NH ₂ -CH ₂ -CH _2- , NH ₂ -CH (CH ₃ ) -CH _2- , NH ₂ -CH ₂ -CH (CH ₃ )- , NH ₂ -CH ₂ -CH ₂ -CH ₂ -CH _2- , NH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ -CH _2- , NH ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ -, NH ₂ -CH ₂ -CH ₂ -CH (CH ₃ )-, NH ₂ -CH ₂ -CH ₂ -CH ₂ -and the like, preferably NH ₂ -CH ₂ -CH ₂ -CH _2- But may not be limited thereto.

R ⁵ to R ⁷ may be a functional group represented by '* -L-SO ₃ H'.

L may be (C1-C20) alkylene, preferably (C1-C7) alkylene, more preferably (C1-C5) alkylene.

R ⁵ to R ⁷ may be a functional group represented by '* -L-OP (= O) (OH) ₂ '.

L means a hydrocarbon chain including carbon and hydrogen, and may be branched or straight chain, and more specifically, straight chain. In addition, L may be (C 1 -C 20) alkylene, preferably (C 1 -C 7) alkylene, more preferably (C 1 -C 5) alkylene.

R ⁵ to R ⁷ represents '* -LP (= O) (OH) ₂ ' or It may be a functional group represented by '* -L-OP (= O) (OH) R ¹⁰⁰ '. R ¹⁰⁰ and L refer to a hydrocarbon chain including carbon and hydrogen, and may be branched or straight chain, and more specifically, straight chain. In addition, L may be (C 1 -C 20) alkylene, preferably (C 1 -C 7) alkylene, more preferably (C 1 -C 5) alkylene. In addition, R ¹⁰⁰ may be (C 1 -C 20) alkyl, preferably (C 1 -C 7) alkyl, more preferably (C 1 -C 5) alkyl.

R ⁴ and R ⁸ may be a functional group represented by '* -P (= O) (OH) R ¹¹⁰ '. R ¹¹⁰ refers to a hydrocarbon chain including carbon and hydrogen, and may be branched or straight chain, and more specifically, straight chain. In addition, R ¹¹⁰ may be (C 1 -C 20) alkyl, preferably (C 1 -C 7) alkyl, more preferably (C 1 -C 5) alkyl.

R ⁵ to R ⁷ may be a functional group represented by '* -OP (= O) (OH) R ¹¹⁰ '. R ¹¹⁰ refers to a hydrocarbon chain including carbon and hydrogen, and may be branched or straight chain, and more specifically, straight chain. In addition, R ¹¹⁰ may be (C 1 -C 20) alkyl, preferably (C 1 -C 7) alkyl, more preferably (C 1 -C 5) alkyl.

R ⁵ to R ⁷ may be a functional group represented by '-LP (= O) (OH) R ¹²⁰ '.

L and R ¹²⁰ refer to a hydrocarbon chain including carbon and hydrogen, and may be branched or straight chain, and more specifically, straight chain. In addition, L may be (C 1 -C 20) alkylene, preferably (C 1 -C 7) alkylene, more preferably (C 1 -C 5) alkylene. In addition, R ¹²⁰ may be (C 1 -C 20) alkyl, preferably (C 1 -C 7) alkyl, more preferably (C 1 -C 5) alkyl.

In a preferred embodiment of the present invention, the substituent R ² in the siloxane repeating unit included in the compound represented by the formula (1) and One of R ³ is amino (C 1 -C 20) alkyl and a substituent R ⁶ in the siloxane repeating unit included in the compound represented by the formula (2); One of R ⁷ is at -L-SO ₃ H, -L-OP (= 0) (OH) ₂ , -LP (= 0) (OH) ₂ and -L-OP (= 0) (OH) R ¹⁰⁰ . Having one or two functional groups selected. The inclusion of acidic polysiloxane-based compounds and basic polysiloxane-based compounds in the polysiloxane-based composition provides an appropriate acid-base balance, resulting in a stable etching characteristic regardless of treatment time and number of times, along with better etching ratio. can do.

In one embodiment of the present invention, the n and m may be 1 to 100 independently from each other, but may be from 1 to 50 to facilitate the adjustment of the etching selectivity and the etching rate as an etching additive, preferably 2 to May be 20.

In one embodiment of the present invention, the a and b may be 1 to 4, preferably 2 to 4 for the high selectivity as an etching additive, but is not limited thereto.

The polysiloxane compound represented by Formula 1 and Formula 2 according to an embodiment of the present invention may be water-soluble, and may be stably included in the aqueous silicon nitride film etching composition as it has water-soluble properties. In addition, the polysiloxane compound according to an aspect of the present invention may be mixed in a substantially homogeneous form in an aqueous etchant composition containing phosphoric acid.

In one embodiment of the present invention, R ¹ in Formula 1 is selected from hydroxy, (C ¹ -C 7) alkyl and amino (C 1 -C 7) alkyl; One of R ² and R ³ is amino (C 1 -C 7) alkyl and the other is selected from hydroxy, (C 1 -C 7) alkoxy and amino (C 1 -C 7) alkyl; R ⁴ is selected from hydrogen, (C 1 -C 7) alkyl and —P (═O) (OH) ₂ ; n is an integer from 2 to 20; a is 2 to 4; R ⁵ in Formula 2 is selected from hydroxy, (C1-C7) alkyl and -L-SO ₃ H; One of R ⁶ and R ⁷ is -L-SO ₃ H, and the other is selected from hydroxy, (C1-C7) alkoxy and -L-SO ₃ H; R ⁸ is selected from hydrogen and (C 1 -C ⁷ ) alkyl; L is (C1-C7) alkylene; m is an integer from 2 to 20; b may be a polysiloxane composition of 2 to 4.

As R ¹ to R ⁸ has a carbon number of 7 or less, it may be preferably included in the aqueous etchant composition and may have high water solubility. In addition, since R ¹ to R ⁸ contain heteroatoms such as oxygen, sulfur, phosphorus, and nitrogen as substituents, they may exhibit high polarity and selectively interact with the silicon oxide film with excellent water solubility to protect the silicon oxide film. It may be desirable because it can exhibit an excellent etching selectivity.

In one embodiment of the present invention, the compound represented by Formula 1 may be selected from the following Structural Formula 1. In addition, the compound represented by Formula 2 may be selected from the following Structural Formula 2.

[Formula 1]

[Formula 2]

In the polysiloxane composition according to one embodiment of the present invention, the compounds represented by Formula 1 and Formula 2 may be included in a weight ratio of 1:99 to 99: 1. Preferably it may be included in the weight ratio of 40: 60 to 99: 1, more preferably 50: 50 to 95: 5. As two different compounds are included within the above ranges, the silicon oxide film may be effectively protected to etch the silicon nitride film at a higher selectivity.

In the polysiloxane composition according to an aspect of the present invention, each compound represented by Formula 1 or Formula 2 may further include any repeating unit represented by -Si (R ⁹ ) (R ¹⁰ ) O-. . R ⁹ and R ¹⁰ may be each independently selected from hydroxy, (C 1 -C 20) alkoxy, halogen, amine, —OP (═O) (OH) ₂ and (C 1 -C 20) alkyl. More specifically, the number of repeating units represented by -Si (R ⁹ ) (R ¹⁰ ) O- in the polysiloxane single substituent chain bonded to Si, which is a central element of the polysiloxane compound, may be included as 0 to 20, Preferably it may be 0 to 10, more preferably 0 to 5 but it is not limited to the numerical range because it is only an optional element. As a non-limiting example, when a and b are 3, the repeating unit represented by -Si (R ⁹ ) (R ¹⁰ ) O- is included in only one polysiloxane substituent chain and not in the other two polysiloxane substituent chains. You may not. However, this is only one example, and various modifications are also included in the scope of the present invention.

Another aspect of the present invention may be an etchant including the polysiloxane composition.

The etch additive imparts a high selectivity to the silicon nitride film due to the Si-O bond and the new Si-O bond formed during hydrolysis, and reduces the abnormal growth of the thickness of the silicon oxide film and the like besides the silicon nitride film. In addition, the etching additive improves the etching rate of the silicon nitride film, and has an effect of reducing the change in the etching rate even when using the etching solution several times.

Silicon nitride film etching composition according to an aspect of the present invention comprises the polysiloxane-based composition, phosphoric acid and water. Specifically, based on the total weight of the etching composition, the polysiloxane composition may include 0.005 to 10 wt%, the phosphoric acid may include 60 to 90 wt%, and a balance of water. When the above range is satisfied, precipitates can be significantly reduced, more effective in preventing abnormal growth of silicon oxide films other than silicon nitride film, and the etching composition has excellent stability during high temperature semiconductor etching process. Therefore, when the silicon nitride film etching composition according to an aspect of the present invention is used in an etching process, the silicon nitride film can be etched with high etching selectivity, and the etching rate and high etching selectivity for the silicon nitride film can be maintained even after repeated etching processes. It may be desirable. Preferably the polysiloxane composition based on the total weight of the etching composition may comprise 0.005 to 8% by weight, the phosphoric acid may include 75% to 90% by weight and the balance of water, more preferably based on the total weight of the etching composition As the polysiloxane composition is 0.005 to 5% by weight, the phosphoric acid may include 80 to 90% by weight and the balance of water. However, this is merely to indicate a preferred embodiment, the present invention is not limited to the above numerical range.

The water is not particularly limited, but is preferably deionized water, and more preferably deionized water for a semiconductor process, but may have a specific resistance value of 18 Pa · cm or more, but is not limited thereto.

The silicon nitride film etching composition according to an aspect of the present invention may further include any additive commonly used in the art. The optional additive may include any one or two or more selected from surfactants, antioxidants, corrosion inhibitors, and the like, and various additives may be used. At this time, any additive may be used in 0.01 to 2% by weight based on the total weight of the etching composition, but is not limited thereto.

In one embodiment of the present invention, the silicon nitride film etching composition may satisfy the etching selectivity of the following relation 1.

[Relationship 1]

500 ≤ E _SiNx / E _SiO2

In Equation 1, E _SiNx is an etching rate of a silicon nitride film, and E _SiO2 is an etching rate of a silicon oxide film.

 Preferably, the etching selectivity may satisfy the following Equation 1-1, and more preferably satisfy the following Equation 1-2.

[Relationship 1-1]

1,000 ≤ E _SiNx / E _SiO2 ≤ 10,000

[Relationship 1-2]

1,000 ≤ E _SiNx / E _SiO2 ≤ 7,000

The etch selectivity (E _SiNx / E _SiO2 ) referred to in the present invention refers to the ratio of the etching rate (E _SiNx ) of the silicon nitride film to the etching rate (E _SiO2 ) of the silicon oxide film. In addition, when the etching rate of the silicon oxide film is near zero or the value of the etching selectivity is large, it means that the silicon nitride film can be selectively etched.

In one embodiment of the present invention, the etching rate reduction rate of the silicon nitride film etching composition after the repeated etching process may satisfy the following equation 2.

[Relationship 2]

△ ERD _SiNx ≤ 1%

When satisfying the relation 2, it is possible to maintain a high etching selectivity and etching rate when the silicon nitride film etching composition is used repeatedly, there is an advantage of excellent process efficiency.

Preferably, the etching rate reduction rate may satisfy the following Equation 2-1, and more preferably satisfy the following Equation 2-2.

[Relationship 2-1]

△ ERD _SiNx ≤ 0.8%

[Relationship 2-2]

△ ERD _SiNx ≤ 0.6%

In Equations 2, 2-1, and 2-2, ΔERD _SiNx is an etching rate reduction rate relative to an initial etching rate for the silicon nitride film.

'Etch rate drift (ΔERD)' referred to in the present invention means the rate of change of the etching rate compared to the initial etching rate when the etching process is repeated (two or more times) using the same silicon nitride film etching composition. do. Specifically, the etching rate reduction rate ΔERD is calculated by Equation 1 below. In Equation 1 below, n is a natural number of 2 or more.

[Equation 1]

△ ERD (%) = [1-{(etching speed over n times) / (etching speed over one time)}] Х100

In general, as the etching rate tends to decrease as the etching process is repeatedly performed, the reduction rate is defined as a measure thereof, and the change rate is also interpreted as the same meaning.

In one aspect of the invention, the silicon nitride film composition may further include an alcohol solvent. The alcohol solvent may be 0.05 to 10% by weight, preferably 0.05 to 5% by weight, and more preferably 0.05 to 3% by weight, based on the total weight of the etching composition. When the above range is satisfied, a stable effect may be obtained even at a high temperature of the semiconductor manufacturing process due to the viscosity control of the silicon nitride film etching composition. In addition, even when the composition is used several times, the rate of change of the etching rate for the silicon nitride film is low, and thus the process efficiency is good.

The alcohol solvent may be one or more mixtures of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol and tetrahydrofurfuryl alcohol (THFA) It is not limited thereto.

In one aspect of the present invention, the silicon nitride film composition may further include an ammonium compound. The ammonium compound may be 0.05 to 1 wt% based on the total weight of the etching composition. When the ammonium compound is added, the decrease in the etching rate and the change in the selection ratio are small even during long-term use, and the etching rate can be kept constant.

The ammonium compound may be one or a mixture of two or more selected from ammonia water, ammonium chloride, ammonium acetate, ammonium phosphate, ammonium and oxydisulfate, ammonium sulfate and ammonium fluorate, but is not limited thereto.

In one aspect of the invention, the silicon nitride film composition may further include a fluorine-based compound. The fluorine-based compound may be 0.001 to 2% by weight based on the total weight of the etching composition. When the fluorine-based compound is added, it is possible to increase the speed of the silicon nitride film and the change of the etching rate and the etching selectivity with respect to the silicon nitride film may be small even when used repeatedly. The fluorine-based compound may be one or a mixture of two or more selected from hydrogen fluoride, ammonium fluoride, ammonium bifluoride and tetrafluoroboric acid, but is not limited thereto. no.

As the silicon nitride film etching composition according to the present invention includes the compound described above, when the silicon nitride film and the silicon oxide film are mixed, only the silicon nitride film may be selectively etched with respect to the silicon oxide film, the etching rate is high, and the silicon nitride film after etching Since other films do not grow abnormally, defects in manufacturing a semiconductor device can be minimized.

In addition, since the silicon nitride film etching composition according to the present invention has high temperature stability, phosphoric acid heated to a high temperature effectively suppresses the problem of etching the silicon oxide film, and thus, abnormal growth of the silicon oxide film does not occur, thereby preventing substrate defects. The silicon nitride film may be selectively etched to implement excellent semiconductor device characteristics.

In still another aspect of the present invention, a method of selectively etching a silicon nitride film relative to a silicon oxide film using the silicon nitride film etching composition described above is also provided. In this case, the etching method may be performed according to a method commonly used in the art, and for example, may be selected from a method of immersion, spraying, and the like. At this time, the etching method may be carried out at a process temperature of 100 ℃ or more, preferably 100 to 500 ℃, more preferably at a process temperature of 100 to 300 ℃, the appropriate temperature may be other processes and other factors. Of course, it can be changed as needed in consideration.

In this case, the silicon oxide film, the silicon nitride film, the photoresist film, etc. formed on the substrate may be formed as a single film, a double film, or a multilayer film (multilayer film), respectively, and the stacking order of the double film or the multilayer film is not limited. .

In addition, the substrate may be a variety of materials, for example, silicon, quartz, glass, silicon wafers, polymers, metals and metal oxides may be used, but is not limited thereto. As an example of the polymer substrate, a film substrate such as polyethylene terephthalate, polycarbonate, polyimide, polyethylene naphthalate, cycloolefin polymer, or the like may be used. It is not limited to this.

The silicon nitride film etching composition according to the present invention may also be used in a method of manufacturing a semiconductor device. Specifically, according to the method for manufacturing a semiconductor device using the silicon nitride film etching composition according to the present invention, in a semiconductor device in which the silicon nitride film and the silicon oxide film are alternately stacked or mixed, selective etching of the silicon nitride film is possible, and the silicon oxide film By effectively suppressing the damage of the silicon oxide film, the damage of the silicon oxide film due to the etching can be minimized, thereby greatly improving the stability, efficiency and reliability of the semiconductor device manufacturing process. At this time, the type of the semiconductor device is not particularly limited in the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for explaining the present invention in more detail, the present invention is not limited by the following Examples and Comparative Examples. Unless stated otherwise in the invention, the temperature means all units in degrees Celsius, and unless otherwise indicated, the amount of use of the composition means units by weight.

[Measurement Method]

1) Etch Speed Measurement

Specifically, a silicon nitride film (SiN film) wafer and a silicon oxide wafer were prepared by chemical vapor deposition (CVD) in the same manner as in the semiconductor manufacturing process. PETEOS film (Plasma Enhanced Tetra Ethyl Ortho Silicate) was used as the silicon oxide wafer.

The thickness before etching of the composition was measured using an ellipsometer (M-2000U, J.A WOOLLAM, Inc.), which is a thin film thickness measuring instrument. The etching process was performed by immersing the wafer for 10 minutes in a composition maintained at an etching temperature of 163 ° C. in a quartz bath. After the etching was completed, the resultant was washed with ultrapure water, and the etching rate was measured by completely drying the remaining etchant and moisture using a drying apparatus.

The etching rate was calculated by dividing the difference between the thickness before etching and the thickness after etching by using an ellipsometer (J.A WOOLLAM, M-2000U).

2) Etch rate reduction rate measurement

The nitride film etching rate of the composition was measured by the etching rate measuring method.

The etching process was performed in one batch, and ten batches were performed in a method of repeatedly using the silicon nitride film etching composition without exchanging the etching rate of the etching rate.

Etch rate reduction rate (ΔERD (%)) was calculated by the following equation (1).

[Equation 1]

△ ERD (%) = [1-{(etching speed with 10 times) / (etching speed with 1 time)}] Х100

[Production Example 1]

[Formula 1]

In order to prepare a polysiloxane compound of Formula 1 wherein R ¹ = hydroxy, R ² = aminopropyl, R ³ = hydroxy, R ⁴ = hydrogen, n = 3, a = 3, a cooling tube and a stirrer are provided. Triethoxysilane was added to the flask, and allylamine was added at a molar ratio of 1: 1 with triethoxysilane. Ethyl acetate as a solvent was added at 500 parts by weight based on 100 parts by weight of triethoxysilane.

The reaction mixture was heated to 50 ° C., and then Karstedt's catalyst was added at 0.004 parts by weight based on 100 parts by weight of triethoxysilane, and ethylacetate was obtained after hydrosilylation at 80 ° C. for 3 hours. Removal gave a synthetic intermediate.

40 weight part of the said synthetic intermediates were added with respect to 100 weight part of water which is a solvent, and it stirred at 60 degreeC and 500 rpm for 1 hour. Thereafter, tetraethyl orthosilicate was added dropwise at a rate of 3 mL / min to 1/3 mole of triethoxysilane while maintaining stirring at 30 ° C.

The result of EA analysis showed that the structure of each compound was as follows: C = 27.85%, H = 6.96% N = 11.51% O = 29.39% Si = 24.29%.

[Production Example 2]

In order to prepare a polysiloxane compound having R ¹ = methyl, R ² = aminopropyl, R ³ = hydroxy, R ⁴ = hydrogen, n = 3, a = 3 in Formula 1, triethoxy instead of tetraethyl orthosilicate It carried out similarly to the manufacture example 1 except having changed to methylsilane.

As a result of EA analysis, the compound's structure was confirmed as the ratio of each element mass was C = 29.61%, H = 8.27% N = 10.93% O = 27.65% Si = 23.54%.

[Production Example 3]

In order to prepare a polysiloxane compound of Formula 1, R ¹ = methyl, R ² = aminopropyl, R ³ = hydroxy, R ⁴ = hydrogen, n = 10, a = 3, stirred at 60 ° C. and 500 rpm for 1 hour. Instead it was carried out in the same manner as in Preparation Example 2 except changing to 3 hours at 60 ℃, 500rpm.

As a result of the elemental analyzer, the mass structure of each element was C = 28.78%, H = 8.15% N = 10.35% O = 26.89% Si = 25.83% to confirm the structure of the compound.

[Production Example 4]

In order to prepare a polysiloxane compound of Formula 1, R ¹ = methyl, R ² = aminopropyl, R ³ = ethoxy, R ⁴ = ethyl, n = 10, a = 3, ethanol instead of 100 parts by weight of a solvent It carried out similarly to the manufacture example 3 except having used the solvent which mixed 1 weight part of water with respect to 100 weight part.

As a result of EA analysis, the structure of the compound was confirmed as the ratio of each element mass was C = 40.87%, H = 8.04% N = 10.12% O = 22.87% Si = 18.10%.

Production Example 5

In order to prepare a polysiloxane compound of Formula 1 wherein R ¹ = aminopropyl, R ² = aminopropyl, R ³ = hydroxy, R ⁴ = hydrogen, n = 10, a = 3, triethoxymethylsilane was added. The same procedure as in Preparation Example 3 was carried out except for omission.

The result of EA analysis (Elemental analyzer) confirmed the structure of the compound as the ratio of each element mass is C = 30.01%, H = 8.11% N = 12.15% O = 27.10% Si = 22.63%.

[Manufacture example 6]

In order to prepare a polysiloxane compound of Formula 1, R ¹ = aminopropyl, R ² = aminopropyl, R ³ = ethoxy, R ⁴ = ethyl, n = 10, a = 3, instead of 100 parts by weight of water as a solvent The same procedure as in Preparation Example 5 was carried out except that a solvent in which 1 part by weight of water was mixed with respect to 100 parts by weight of ethanol was used. The result of EA analysis (Elemental analyzer) confirmed the structure of the compound as the ratio of each element mass is C = 40.37%, H = 9.30% N = 0.011% O = 20.85% Si = 19.47%.

[Manufacture example 7]

[Formula 2]

In order to prepare a polysiloxane compound of Formula 2, R ⁵ = hydroxy, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = hydroxy, R ⁸ = hydrogen, m = 3, b = 3 Into the flask equipped with a cooling tube and a stirrer, triethoxysilane was added, and allyl chloride was added at a molar ratio of 1: 1 with triethoxysilane. Ethyl acetate as a solvent was added at 500 parts by weight based on 100 parts by weight of triethoxysilane.

The reaction mixture was heated to 50 ° C., and then Karlstedt's catalyst (0.004 parts by weight) was added thereto, followed by hydrosilylation at 80 ° C. for 3 hours. Thereafter, sodium sulfite was added with 2 equivalents of allyl chloride together with a small amount of water at room temperature, stirred for 15 hours, and ethyl acetate was removed to obtain a synthetic intermediate.

40 parts by weight of the synthetic intermediate was added to 100 parts by weight of water, which was a solvent, and stirred at 60 ° C. and 500 rpm for 1 hour. Thereafter, tetraethyl orthosilicate was added dropwise at a rate of 3 mL / min to 1/3 mole of triethoxysilane while maintaining stirring at 30 ° C.

As a result of EA analysis, the structure of each compound was confirmed as C = 19.11%, H = 4.89%, O = 45.87%, S = 15.79%, and Si = 14.34%.

[Manufacture example 8]

In order to prepare a polysiloxane compound of Formula 2, R ⁵ = methyl, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = hydroxy, R ⁸ = hydrogen, m = 3, b = 3, The same procedure as in Preparation Example 7 was repeated except that triethoxymethylsilane was used instead of tetraethyl orthosilicate.

The result of EA analysis (Elemental analyzer) confirmed the structure of the compound as the ratio of each element mass is C = 20.11%, H = 5.85%, O = 44.78%, S = 14.87%, Si = 14.39%.

[Manufacture example 9]

In order to prepare a polysiloxane compound of Formula 2, R ⁵ = methyl, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = hydroxy, R ⁸ = hydrogen, m = 10, b = 3, Instead of stirring at 60 ° C and 500rpm for 1 hour, it was carried out in the same manner as in Preparation Example 8 except for changing to 60 ° C and 500rpm for 3 hours.

The result of EA analysis (Elemental analyzer) confirmed the structure of the compound as the ratio of each element mass is C = 20.85%, H = 4.93%, O = 42.51%, S = 15.84%, Si = 15.87%.

[Production Example 10]

In order to prepare a polysiloxane compound of Formula 2, R ⁵ = methyl, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = ethoxy, R ⁸ = ethyl, m = 10, b = 3, The same procedure as in Preparation Example 9 was carried out except that a solvent in which 1 part by weight of water was mixed with respect to 100 parts by weight of ethanol instead of 100 parts by weight of water as a solvent was used.

As a result of EA analysis, the compound structure of the compound was confirmed to be C = 29.51%, H = 4.93%, O = 38.14%, S = 13.96%, and Si = 13.46%.

[Production Example 11]

In Formula 2, R ⁵ =-(CH ₂ ) ₃ -SO ₃ H, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = hydroxy, R ⁸ = hydrogen, m = 10, b = 3 In order to prepare a phosphorus polysiloxane compound, it was carried out in the same manner as in Preparation Example 9 except that the addition of triethoxymethylsilane was omitted.

As a result of EA analysis, the compound's structure was confirmed as the ratio of each element mass was C = 20.31%, H = 4.89%, O = 44.10%, S = 16.46%, and Si = 14.24%.

[Manufacture example 12]

In Formula 2, R ⁵ =-(CH ₂ ) ₃ -SO ₃ H, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = ethoxy, R ⁸ = ethyl, m = 10, b = 3 In order to prepare a phosphorus polysiloxane compound, it was carried out in the same manner as in Preparation Example 11 except that a solvent in which 1 part by weight of water was mixed with respect to 100 parts by weight of ethanol instead of 100 parts by weight of water as a solvent.

The result of EA analysis (Elemental analyzer) confirmed the structure of the compound as the ratio of each element mass is C = 27.46%, H = 6.44%, O = 36.97%, S = 15.23%, Si = 14.10%.

Example 1

0.1 wt% of A-1 prepared in Preparation Example 1 and 0.1 wt% of B-1 compound prepared in Preparation Example 8, 85 wt% of phosphoric acid, and 14.8 wt% of water were mixed, and then, at a speed of 500 rpm for 5 minutes at room temperature. By stirring, a silicon nitride film etching composition was prepared.

[Examples 2 to 8 and Comparative Examples 1 to 6]

As shown in Table 1, except that the compound represented by the formula (1), the compound represented by the formula (2) and the content of each component was changed in the same manner as in Example 1 to prepare a silicon nitride film etching composition.

Phosphoric Acid
(weight%) To Formula 1
Compound displayed   Compound represented by formula (2) Other additives water
(weight%) ingredient content
(weight%) ingredient content
(weight%) ingredient content
(weight%) Example 1 85.00 A-1 0.10 B-1 0.10 - - 14.80 Example 2 85.00 A-2 0.10 B-2 0.10 - - 14.80 Example 3 85.00 A-3 0.10 B-3 0.10 - - 14.80 Example 4 85.00 A-4 0.10 B-4 0.10 - - 14.80 Example 5 85.00 A-5 0.10 B-5 0.10 - - 14.80 Example 6 85.00 A-5 0.50 B-5 0.10 - - 14.40 Example 7 85.00 A-5 1.00 B-5 0.10 - - 13.90 Example 8 85.00 A-6 0.10 B-6 0.10 - - 14.80 Example 9 85.00 A-1 0.10 B-5 0.10 - - 14.80 Example 10 85.00 A-5 0.66 B-5 0.10 D1 0.04 14.20 Comparative Example 1 85.00 - - - - - - 15.00 Comparative Example 2 85.00 C-1 0.10 - - - - 14.90 Comparative Example 3 85.00 C-2 0.10 - - - - 14.90 Comparative Example 4 85.00 C-3 0.10 - - - - 14.90 Comparative Example 5 85.00 A-1 0.10 - - - - 14.90 Comparative Example 6 85.00 - - B-1 0.10 - - 14.90 A-1: R ¹ = hydroxy, R ² = aminopropyl, R ³ = hydroxy, R ⁴ = hydrogen, n = 3, a = 3
A-2: R ¹ = methyl, R ² = aminopropyl, R ³ = hydroxy, R ⁴ = hydrogen, n = 3, a = 3
A-3: R ¹ = methyl, R ² = aminopropyl, R ³ = hydroxy, R ⁴ = hydrogen, n = 10, a = 3
A-4: R ¹ = methyl, R ² = aminopropyl, R ³ = ethoxy, R ⁴ = ethyl, n = 10, a = 3
A-5: R ¹ = aminopropyl, R ² = aminopropyl, R ³ = hydroxy, R ⁴ = hydrogen, n = 10, a = 3
A-6: R ¹ = aminopropyl, R ² = aminopropyl, R ³ = ethoxy, R ⁴ = ethyl, n = 10, a = 3
B-1: R ⁵ = hydroxy, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = hydroxy, R ⁸ = hydrogen, m = 3, b = 3
B-2: R ⁵ = methyl, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = hydroxy, R ⁸ = hydrogen, m = 3, b = 3
B-3: R ⁵ = methyl, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = hydroxy, R ⁸ = hydrogen, m = 10, b = 3
B-4: R ⁵ = methyl, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = ethoxy, R ⁸ = ethyl, m = 10, b = 3
B-5: R ⁵ =-(CH ₂ ) ₃ -SO ₃ H, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = hydroxy, R ⁸ = hydrogen, m = 10, b = 3
B-6: R ⁵ =-(CH ₂ ) ₃ -SO ₃ H, R ⁶ =-(CH ₂ ) ₃ -SO ₃ H, R ⁷ = ethoxy, R ⁸ = ethyl, m = 10, b = 3
C-1: Tetraethylorthosilicate
C-2: 3-aminopropylsilane triol (3-Aminopropylsilantriol)
C-3: 3-trihydroxysilyl-1-propanesulfonic acid
D-1: Ammonium fluoride

  Etching Speed (Å / min) Selectivity
(E _SiNx / E _SiO2 ) Nitride film
(E _SiNx ) Oxide film
(E _SiO2 ) Example 1 166.30 0.11 1512 Example 2 164.70 0.13 1267 Example 3 164.20 0.03 5473 Example 4 163.30 0.04 4083 Example 5 162.70 0.08 2034 Example 6 164.80 0.07 2354 Example 7 164.90 0.05 3298 Example 8 165.10 0.09 1834 Example 9 165.70 0.12 1381 Example 10 186.30 0.18 1035 Comparative Example 1 170.20 2.98 57 Comparative Example 2 166.00 0.32 494 Comparative Example 3 165.30 1.94 86 Comparative Example 4 165.30 0.86 190 Comparative Example 5 168.20 2.23 75 Comparative Example 6 165.80 0.79 213

Batch count Nitride Etching
Speed (Å / min) Nitride Etching
Rate of Decrease (%) Occurrence of abnormal growth of oxide film Example 1 One 166.30 - 0 10 165.60 0.42 0 Example 2 One 164.70 - 0 10 164.20 0.30 0 Example 3 One 164.20 - 0 10 163.80 0.24 0 Example 4 One 163.30 - 0 10 162.90 0.24 0 Example 5 One 162.70 - 0 10 162.40 0.18 0 Example 6 One 164.80 - 0 10 164.40 0.24 0 Example 7 One 164.90 - 0 10 164.70 0.12 0 Example 8 One 165.10 - 0 10 164.60 0.30 0 Example 9 One 165.70 - 0 10 165.00 0.42 0 Example 10 One 186.30 - 0 10 185.50 0.43 0 Comparative Example 1 One 170.10 - 0 10 160.90 5.41 50 Comparative Example 2 One 158.20 - 0 10 149.50 5.50 80 Comparative Example 3 One 167.40 - 0 10 162.20 3.11 30 Comparative Example 4 One 163.50 - 0 10 157.90 3.42 40 Comparative Example 5 One 167.80 - 0 10 165.60 1.31 5 Comparative Example 6 One 168.10 - 0 10 163.10 2.97 10

First, the etching selectivity of the silicon nitride film compared to the silicon oxide film, as shown in Table 2 and Table 3, in the case of each of the silicon nitride film etching compositions of Examples 1 to 10, the etching selectivity was all excellent as 1000 or more. In addition, the etching process was repeatedly performed, and even though the silicon nitride film etching composition was reused several times, it was confirmed that the reduction rate of the etching rate for the silicon nitride film was significantly low.

On the other hand, in the case of each of the silicon nitride film etching compositions of Comparative Examples 1 to 6, the etching selectivity was significantly lower than that of the examples below 500.

Looking at the etching selectivity for each of Examples 1 to 10, compared with Example 2 was confirmed that the higher the etching selectivity as the number of repeat units of n and m of the compound in Example 3.

R ¹ and R ⁵ of Example 1 is increased the more hydrophilic group is hydroxyl group is bonded to the embodiments, R ¹ and R ⁵ than Example 2 coupled to, and the number of Si-O bond As more selective etching of the silicon nitride film It was found that the rain was higher.

In addition, R ³ and R ⁷ hydroxyl group on, R ⁴ and R ⁶ a third embodiment is an ethoxy group in R ³ and R ⁷ hydrogen is bonded to, R ⁴ and R ⁶ the ethyl group is bonded exemplary silicon than Example 4 The etching selectivity with respect to the nitride film was higher, which confirmed that the etching selectivity was increased due to the increased hydrophilicity due to the hydroxyl group of Example 3.

Also, in R ¹ to aminopropyl _{^{group, R 5 - (CH 2)}} 3 -SO 3 H groups, unlike the fifth embodiment combining R ¹ and R ^5, the embodiment of Example 3 was higher etching selection ratio of a methyl group is bonded to. For this reason, it was confirmed that the effect of the methyl group was higher in the R ¹ and R ⁵ substituents except for the repeating unit than the amino (C ¹ -C 20) alkyl group and the-(CH ₂ ) ₃ -SO ₃ H group.

In addition, as shown in Examples 6 to 7, when the content of the compound represented by the formula (1) increased, it was confirmed that the selectivity is significantly increased.

In addition, R ³ and ethoxy group in R ^7, R ⁴ and R ⁸ an exemplary hydroxy group in R ³ and R ^7, unlike Example 8, ethyl group are bonded to, R ⁴ and the R ⁸ in Example 5, the hydrogen bond It was confirmed that the etching selectivity is high because it is included in the aqueous silicon nitride film etching composition.

In addition, the ^{_{R 5 - (CH 2) 3}} -SO 3 H group is bonded, was higher in the practice of the repeating unit of m-hydroxy group is bonded in many embodiments R 9 than ⁵ Example 1 etch selectivity. For this reason, it was confirmed that the effect of the hydroxyl group was higher in the substituent R ⁵ except for the repeating unit than the-(CH ₂ ) ₃ -SO ₃ H group.

In addition, in Example 10, when the content ratio of A-5 including the fluorine-based compound was increased compared to B-5, it was confirmed that the etching selectivity was higher than that of the comparative example.

Next, looking at the etching rate reduction rate of the silicon nitride film, it was confirmed that in each of the silicon nitride film etching compositions of Examples 1 to 10, the silicon nitride film etching rate reduction rate is significantly lower when the number of steps is increased.

In addition, in Examples 1 to 10, abnormal growth of the silicon oxide film did not occur, and it was found that the failure rate of the manufactured semiconductor device could be minimized.

As described above, in the case of the embodiments, the selectivity of the etching rate of the silicon nitride film to the silicon nitride film, the etching rate reduction rate due to repeated use, and the silicon oxide abnormal growth rate were significantly superior to those of the comparative examples. .

In Comparative Examples 1 to 6, the number of repetitions of the Si-O bonds and the number of specific substituents is small, and only the acidic polysiloxane compound and the basic polysiloxane compound have low etching selectivity and high silicon nitride etching rate reduction rate. Or, it was confirmed that abnormal growth of the oxide film occurred.

Therefore, the silicon nitride film etching composition including the polysiloxane compound represented by Chemical Formulas 1 and 2 according to the present invention enables selective etching of the silicon nitride film with an excellent etching selectivity. In addition, even when used several times, the rate of decrease in the etching rate is low, thereby maintaining the initial etching ability to significantly increase the production efficiency. In addition, it is possible to minimize the damage of the silicon oxide film during the etching process and to effectively suppress abnormal growth of the silicon oxide film, thereby providing a high quality semiconductor device.

Claims (13)

Polysiloxane-based composition comprising a compound represented by the formula (1) and formula (2).
[Formula 1]

(In Formula 1, R ¹ is selected from hydrogen, hydroxy, (C1-C20) alkoxy, halogen, (C1-C20) alkyl, -OP (= O) (OH) ₂ and amino (C1-C20) alkyl. Become;
One of R ² and R ³ is amino (C 1 -C 20) alkyl, the other is hydrogen, hydroxy, (C 1 -C 20) alkoxy, halogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ and amino (C1-C20) alkyl;
R ⁴ is selected from hydrogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ , —P (═O) (OH) ₂ , —P (═O) (OH) R ¹¹⁰ ;
R ¹¹⁰ is (C1-C20) alkyl;
n is an integer from 1 to 100;
a is 1-4.

[Formula 2]

(In Formula 2, R ⁵ is hydrogen, hydroxy, (C 1 -C 20) alkoxy, halogen, (C 1 -C 20) alkyl, -L-SO ₃ H, -OP (= O) (OH) ₂ , -L -OP (= O) (OH) _2, -LP (= O) (OH) ₂ , -OP (= O) (OH) R ¹¹⁰ , -LP (= O) (OH) R ¹²⁰ and -L-OP (= 0) (OH) R ¹⁰⁰ ;
One of R ⁶ and R ⁷ is -L-SO ₃ H, -L-OP (= O) (OH) ₂ , -LP (= O) (OH) _2, -LP (= O) (OH) R ¹²⁰ And -L-OP (= 0) (OH) R ¹⁰⁰ , the other is hydrogen, hydroxy, (C1-C20) alkoxy, halogen, (C1-C20) alkyl, -L-SO ₃ H,- OP (= O) (OH) ₂ , -L-OP (= O) (OH) _2, -LP (= O) (OH) _2, -OP (= O) (OH) R ¹¹⁰ , -LP (= O) (OH) R ¹²⁰ And -L-OP (= 0) (OH) R ¹⁰⁰ ;
R ⁸ is selected from hydrogen, (C 1 -C 20) alkyl, —OP (═O) (OH) ₂ , —P (═O) (OH) ₂ and —P (═O) (OH) R ¹¹⁰ ;
R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ (C1-C20) alkyl;
L is (C1-C20) alkylene;
m is an integer from 1 to 100;
b is 1-4. The method of claim 1,
R ¹ in Formula 1 is selected from hydroxy, (C1-C20) alkyl and amino (C1-C20) alkyl;
One of R ² and R ³ is amino (C 1 -C 20) alkyl, the other is selected from hydroxy, (C 1 -C 7) alkoxy and amino (C 1 -C 20) alkyl;
R ⁴ is selected from hydrogen, (C 1 -C 20) alkyl and —P (═O) (OH) ₂ ;
n is an integer from 1 to 50;
a is 1 to 4;
R ⁵ in Formula 2 is selected from hydroxy, (C1-C20) alkyl and -L-SO ₃ H;
One of R ⁶ and R ⁷ is -L-SO ₃ H, and the other is selected from hydroxy, (C1-C20) alkoxy and -L-SO ₃ H;
R ⁸ is selected from hydrogen and (C 1 -C 20) alkyl;
L is (C1-C20) alkylene;
m is an integer from 1 to 50;
b is 1 to 4 polysiloxane composition. The method of claim 1,
R ¹ in Formula 1 is selected from hydroxy, (C1-C7) alkyl and amino (C1-C7) alkyl;
One of R ² and R ³ is amino (C 1 -C 7) alkyl and the other is selected from hydroxy, (C 1 -C 7) alkoxy and amino (C 1 -C 7) alkyl;
R ⁴ is selected from hydrogen, (C 1 -C 7) alkyl and —P (═O) (OH) ₂ ;
n is an integer from 2 to 20;
a is 2 to 4;
R ⁵ in Formula 2 is selected from hydroxy, (C1-C7) alkyl and -L-SO ₃ H;
One of R ⁶ and R ⁷ is -L-SO ₃ H, and the other is selected from hydroxy, (C1-C7) alkoxy and -L-SO ₃ H;
R ⁸ is selected from hydrogen and (C 1 -C ⁷ ) alkyl;
L is (C1-C7) alkylene;
m is an integer from 2 to 20;
b is 2 to 4 polysiloxane composition. The method of claim 1,
Formula 1 is selected from compounds represented by the following structural formula 1,
Formula 2 is selected from the compound represented by the following structural formula 2.
[Formula 1]

[Formula 2]

The method according to any one of claims 1 to 4,
The compound of Formula 1 and Formula 2 is a polysiloxane composition comprising a weight ratio of 1:99 to 99: 1. An etching additive comprising the polysiloxane composition according to any one of claims 1 to 5. A silicon nitride film etching composition comprising the polysiloxane composition, phosphoric acid and water according to any one of claims 1 to 5. The method of claim 7, wherein
Silicon nitride film etching composition comprising 0.005 to 10% by weight of the polysiloxane composition, 60 to 90% by weight of the phosphoric acid and the balance of water based on the total weight of the etching composition. The method of claim 7, wherein
The silicon nitride film etching composition satisfying the etching selectivity of the following relation 1.
[Relationship 1]
500 ≤ E _SiNx / E _SiO2
In Equation 1, E _SiNx is an etching rate of a silicon nitride film, and E _SiO2 is an etching rate of a silicon oxide film. The method of claim 7, wherein
The silicon nitride film etching composition of the etching rate reduction rate of the silicon nitride film after the repeated etching process satisfies the following relation 2.
[Relationship 2]
△ ERD _SiNx ≤ 1%
In Equation 2, ΔERD _SiNx is an etching rate reduction rate relative to the initial etching rate for the silicon nitride film. The method of claim 7, wherein
Silicon nitride film etching composition further comprising an alcohol solvent. The method of claim 7, wherein
Silicon nitride film etching composition further comprising a fluorine-based compound. The method of manufacturing a semiconductor device comprising etching using the silicon nitride film etching composition of any one of claims 7 to 12.