KR102415960B1 - Etching solution composition for a silicon nitride layer and method for manufacturing a semiconductor device and a TFT array substrate using the same - Google Patents

Abstract

[화학식 2]

The present invention relates to a silicon nitride etchant composition comprising (a) an inorganic acid, (b) a fluorine-containing compound, (c) at least one silane compound represented by the following Chemical Formulas 1 and 2, and (d) water, and the etchant composition It provides a method of manufacturing a semiconductor device or TFT array substrate comprising a process of etching a silicon nitride film using:
[Formula 1]

[Formula 2]

Description

Etching solution composition for a silicon nitride layer and a method for manufacturing a semiconductor device and a TFT array substrate using the same

The present invention relates to an etchant composition for a silicon nitride film that selectively removes a silicon nitride film used as a switching film for a semiconductor device or a flat panel display, and has a high selectivity to a silicon oxide film, and a method for manufacturing a semiconductor device and a TFT array substrate using the same will be.

In general, a silicon nitride film is present above or below a silicon oxide film layer, or is alternately laminated. In addition, a silicon nitride film is used as a hard mask when forming an element insulating film on a wafer.

An etching method using a phosphoric acid solution heated to a high temperature to remove a silicon nitride layer (SiNx) pattern formed on a substrate during a semiconductor manufacturing process is known. This method generally involves the process of removing the silicon compound precipitated while removing other impurities contained in the etchant by filtering and circulating the etchant to keep the etchant clean.

In addition, a method of selectively removing the silicon nitride layer through a low-temperature process by adding a fluorine compound to the etchant has also been proposed. However, this method is not only difficult to secure the stability of the process due to the low boiling point of the fluorine compound, but also is currently being avoided because the fluorine compound is harmful to the human body and the environment.

In addition, although a technique using phosphoric acid and silicate and a method using silicic acid are known, there is a problem in that silicic acid and silicate cause particles that may affect the substrate, and thus are not suitable for semiconductor processing.

Korean Patent No. 10-1320416 discloses a wet etchant composition for a silicon nitride film containing phosphoric acid and a silyl sulfate compound. In this invention, it is described that the silicon nitride film wet etchant can selectively etch the silicon oxide film and the silicon nitride film, and since particles are not generated, the stability and reliability of the process can be secured.

However, the etchant composition does not seem to satisfy the etch selectivity of the silicon nitride film to the silicon oxide film required in this field.

Republic of Korea Patent Registration No. 10-1320416

The present invention has been devised to solve the above problems of the prior art, and has excellent etching selectivity of the silicon nitride film to the silicon oxide film, so that the silicon nitride film can be effectively etched while minimizing the attack of the silicon oxide film when the silicon nitride film is etched. An object of the present invention is to provide an etchant composition that can be used.

In addition, an object of the present invention is to provide an etchant composition exhibiting excellent etching characteristics as described above even at low temperatures.

Another object of the present invention is to provide a method of manufacturing a semiconductor device and a method of manufacturing a TFT array substrate, which includes a process of etching a silicon nitride layer using the etchant composition.

the present invention

(a) inorganic acids;

(b) fluorinated compounds;

(c) at least one silane compound represented by the following Chemical Formulas 1 and 2, and

(d) provides a silicon nitride etchant composition comprising water:

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X is a carbon atom, a sulfur atom, or a phosphorus atom;

Y is selected from the group consisting of Na, K, and NH ₄ ;

m and n are 1 or 2; o is 0 or 1; p and Q are integers from 0 to 3; In the above, when o is 0, hydrogen (H) is absent, oxygen (O) adjacent thereto exists as an anion, and Y ⁺ has a relationship between it and a counter ion, and when n is 2, each o is independently 0 or 1;

R1, R2, and R3 are each independently hydrogen, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms , an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a heteroarylalkyl group having 4 to 30 carbon atoms, an amino group, an aminoalkyl group having 1 to 4 carbon atoms, a vinyl group, an epoxy group, and a thiol group;

R4 is unsubstituted or substituted with one or more selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a carboxylate group, and the group consisting of N, O and S or a hydrocarbon chain having 1 to 10 carbon atoms with or without one or more heteroatoms selected from;

A cycloalkylene group having 3 to 20 carbon atoms, unsubstituted or substituted with one or more selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a carboxylate group It is an arylene group of ~ 30, or a heteroarylene group of 3 ~ 20 carbon atoms;

R5 is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a methylene group unsubstituted or substituted with one or more selected from the group consisting of a carboxylate group, an amine group, an amine group, 6 to carbon atoms an arylene group of 20, a heteroarylene group having 3 to 20 carbon atoms, an oxygen atom, and a sulfur atom;

When R4 and R5 include at least one carboxylate group, at least one counter ion selected from the group consisting of Na, K, and NH ₄ corresponding thereto is further included, wherein the hetero compound is composed of N, O and S one or more heteroatoms selected from the group.

Also, the present invention

Provided are a method of manufacturing a semiconductor device and a method of manufacturing a TFT array substrate including a step of etching a silicon nitride layer using the etchant composition.

The silicon nitride etchant composition of the present invention has excellent etch selectivity of the silicon nitride film to the silicon oxide film, so that it is possible to effectively etch the silicon nitride film while minimizing the attack of the silicon oxide film when the silicon nitride film is etched.

In addition, the silicon nitride film etchant composition of the present invention provides excellent etching properties as described above even at low temperatures.

In addition, the method for manufacturing a semiconductor device and a TFT array substrate of the present invention makes it possible to efficiently manufacture a semiconductor device and a TFT array substrate.

The present invention relates to a silicon nitride etchant composition comprising (a) an inorganic acid, (b) a fluorine-containing compound, (c) at least one silane compound represented by the following Chemical Formulas 1 and 2, and (d) water:

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X is a carbon atom, a sulfur atom, or a phosphorus atom;

Y is selected from the group consisting of Na, K, and NH ₄ ;

m and n are 1 or 2; o is 0 or 1; p and Q are integers from 0 to 3; In the above, when o is 0, hydrogen (H) is absent, oxygen (O) adjacent thereto exists as an anion, and Y ⁺ has a relationship between it and a counter ion, and when n is 2, each o is independently 0 or 1;

R1, R2, and R3 are each independently hydrogen, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms , an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a heteroarylalkyl group having 4 to 30 carbon atoms, an amino group, an aminoalkyl group having 1 to 4 carbon atoms, a vinyl group, an epoxy group, and a thiol group;

R4 is unsubstituted or substituted with one or more selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a carboxylate group, and the group consisting of N, O and S or a hydrocarbon chain having 1 to 10 carbon atoms with or without one or more heteroatoms selected from;

A cycloalkylene group having 3 to 20 carbon atoms, unsubstituted or substituted with one or more selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a carboxylate group It is an arylene group of ~ 30, or a heteroarylene group of 3 ~ 20 carbon atoms;

R5 is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a methylene group unsubstituted or substituted with one or more selected from the group consisting of a carboxylate group, an amine group, an amine group, 6 to carbon atoms an arylene group of 20, a heteroarylene group having 3 to 20 carbon atoms, an oxygen atom, and a sulfur atom;

When R4 and R5 include at least one carboxylate group, at least one counter ion selected from the group consisting of Na, K, and NH ₄ corresponding thereto is further included, wherein the hetero compound is composed of N, O and S one or more heteroatoms selected from the group.

In the above formulas 1 and 2, more preferably

X is a carbon atom, a sulfur atom, or a phosphorus atom;

Y is selected from the group consisting of Na, K, and NH ₄ ;

m and n are 1 or 2; o is 0 or 1; p and Q are integers from 0 to 3; In the above, when o is 0, hydrogen (H) is absent, oxygen (O) adjacent thereto exists as an anion, and Y ⁺ has a relationship between it and a counter ion, and when n is 2, each o is independently 0 or 1;

R1, R2, and R3 are each independently a hydroxyl group or an alkoxy group having 1 to 5 carbon atoms;

R4 is a hydrocarbon chain having 1 to 5 carbon atoms, which is unsubstituted or substituted with one or more selected from an oxo group and a carboxylate group, and with or without one or more heteroatoms selected from the group consisting of N, O and S; ;

R5 is a methylene group, an amine group, or a phenylene group unsubstituted or substituted with a carboxylate group;

When R4 and R5 include at least one carboxylate group, at least one counter ion selected from the group consisting of Na, K, and NH ₄ corresponding thereto is further included, wherein the hetero compound is composed of N, O and S one or more heteroatoms selected from the group.

The (a) inorganic acid serves to etch the silicon nitride layer. The inorganic acid is preferably included in an amount of 60-83% by weight based on the total weight of the composition. When the inorganic acid is included in an amount of less than 60% by weight, the etching rate of the silicon nitride film is reduced, which is not preferable, and when it exceeds 83% by weight, the content of water becomes insufficient and the etching rate is slowed, so it is not preferable.

Since the etching rate of the silicon oxide film is increased too much, it is difficult to selectively etch the silicon oxide film.

At least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid may be used as the inorganic acid. Among these, phosphoric acid and sulfuric acid can be preferably used.

The (b) fluorine-containing compound serves to etch the silicon nitride layer. The fluorine-containing compound is preferably included in an amount of 0.01-10% by weight based on the total weight of the composition. When the fluorine-containing compound is included in an amount of less than 0.01 wt%, the etching rate of the silicon nitride film is decreased, which is not preferable, and when it exceeds 10 wt%, the etching rate of the silicon oxide film is increased too much, making it difficult to selectively etch the silicon oxide film.

As the fluorine-containing compound, at least one selected from the group consisting of hydrofluoric acid, fluoroboric acid, and an ammonium fluoride salt represented by the following formula (3) may be used:

[Formula 3]

In the above formula (3)

R is each independently hydrogen, a linear or branched chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms.

Examples of the ammonium fluoride salt represented by Formula 3 include Ammonium Fluoride, Tetramethylammonium Fluoride, Tetraethylammonium Fluoride, Tetrabuthylammonium Fluoride, and the like. can

(c) The silane-based compound represented by Chemical Formulas 1 and 2 serves to protect the silicon oxide film by forming a protective layer on the silicon oxide film. The silane-based compound is preferably included in an amount of 0.01-3 wt%, more preferably 0.5-3 wt%, based on the total weight of the composition.

When the silane-based compound is included in an amount of less than 0.01% by weight, it is difficult to obtain the desired effect, and when it is included in an amount exceeding 3% by weight, contamination such as a surface stain occurs on the surface of the object to be etched, which is not preferable.

As the silane compound, triethoxysilylpropylmaleamic acid, 3-(trimethoxysilyl)propyl succinic anhydride (3-(Trimethoxysilyl)propylsuccinic anhydride), 3-(triethoxysilyl)propyl succinic anhydride Acid anhydride (3-(Triethoxysilyl)propylsuccinic anhydride), N-(trimethoxysilylpropyl)ethylenediamine triacetic acid trisodium salt (N-(Trimethoxysilylpropyl)ethylenediamine triacetic acid trisodium salt), Carboxyethylsilanetriol sodium salt), 3-(trihydroxysilyl)-1-propanesulfonic acid (3-(Trihydroxysilyl)-1-propanesulfonic acid), 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane (2-(4 -Chlorosulfonylphenyl)ethyltrimethoxysilane), diethylphosphatoethyltriethoxysilane, 3-trihydroxysilylpropylmethylphosphate sodium salt (3-Trihydroxysilylpropylmethylphosphonate sodium salt), and the like.

The silicon nitride etchant composition of the present invention may further include (d) water. The water may be included in the remaining amount to make the composition 100% by weight in consideration of the content of other components. Deionized water may be preferably used as the water.

The silicon nitride film etchant composition of the present invention may further include conventional additives in addition to the above-described components, and the additives include corrosion inhibitors and the like. In addition, the additive is not limited thereto, and in order to further improve the effect of the present invention, various other additives known in the art may be selected and added.

The silicon nitride etchant composition of the present invention can be prepared by a conventionally known method, and it is preferable to have a purity for semiconductor processing.

Also, the present invention

It relates to a method of manufacturing a semiconductor device and a TFT array substrate comprising the step of etching a silicon nitride film using the etchant composition of the present invention described above.

The above manufacturing method makes it possible to efficiently manufacture a semiconductor device and a TFT array substrate. In addition, the semiconductor device and TFT array substrate manufactured by the above method have very excellent performance since the silicon nitride film is etched to be clear in the manufacturing process and the silicon oxide film is hardly damaged.

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples and may be variously modified and changed.

Example : silicon nitride film etchant preparation of the composition and Etching Characteristics evaluation

The etchant compositions of Examples and Comparative Examples were prepared by mixing the components shown in Tables 1 and 2 according to their contents, and the etch rate of the silicon nitride film, the etch rate of the silicon oxide film, and the surface stain of the oxide film were evaluated. 2 is shown.

(1) silicone of nitride film etch rate measurement

A sample was prepared by cutting a wafer on which a silicon nitride film was deposited to a thickness of 800 Å to a size of 2 X 2 cm 2 . After heating the etchant compositions of the prepared Examples and Comparative Examples to 100 °C, the specimens prepared in the etchant compositions of Examples and Comparative Examples were immersed for 5 minutes. The specimen was removed, washed with water for 30 seconds, dried, and the thickness of the residual nitride film was measured by SEM.

(2) of the silicon oxide film etch rate Measure and check surface stains

A specimen was prepared by cutting a wafer on which a silicon oxide film was deposited to a thickness of 1000 Å to a size of 2 X 2 cm 2 . After heating the etchant compositions of the prepared Examples and Comparative Examples to 100 °C, the specimens prepared in the etchant compositions of Examples and Comparative Examples were immersed for 5 minutes. The specimen was taken out, washed with water for 30 seconds, dried, and the thickness of the residual oxide film was measured by SEM, and surface stains were confirmed. In the following Examples and Comparative Examples, the content of each component is a Net content that does not include water.

sulfuric acid phosphoric acid Foshan AF TBAF TMSPSA THSPSA TESPSA DEPTES DIW Silicon Nitride Etching Rate
(Å/min) Silicon oxide film etch rate
(Å/min) oxide film
surface stain Example 1 80 0.01 One 18.99 52.2 1.6 doesn't exist Example 2 83 0.05 2 14.95 178.5 1.4 doesn't exist Example 3 80 0.1 0.1 19.8 63.5 1.5 doesn't exist Example 4 80 0.5 One 18.5 142.6 1.2 doesn't exist Example 5 80 1.5 2 16.5 233.5 2.0 doesn't exist Example 6 80 0.01 One 18.99 64.3 2.2 doesn't exist Example 7 80 0.05 2 17.95 190.3 2.0 doesn't exist Example 8 80 0.05 2 17.95 182.3 1.6 doesn't exist Example 9 80 0.05 2 17.95 178.5 1.5 doesn't exist Example 10 80 0.1 0.1 19.8 70.6 1.2 doesn't exist Example 11 80 0.5 One 18.5 158.5 1.0 doesn't exist Example 12 80 1.5 2 16.5 247.6 2.3 doesn't exist Example 13 70 0.7 0.1 29.2 55.6 0.5 doesn't exist Example 14 70 3 0.5 26.5 161.5 1.7 doesn't exist Example 15 70 3 One 26 153.0 0.8 doesn't exist Example 16 70 10 3 17 214.5 1.5 doesn't exist Example 17 60 2 2 35 245.7 1.6 doesn't exist Example 18 70 1.5 1.5 26.5 205.5 1.6 doesn't exist Example 19 70 0.05 2 27.95 183.5 1.8 doesn't exist Example 20 70 2 2 26 247.5 2.0 doesn't exist Example 21 70 10 3 17 250.2 1.8 doesn't exist Example 22 70 2 2 26 215.0 1.5 doesn't exist Example 23 70 2 2 26 201.5 1.5 doesn't exist Example 24 10 70 0.05 One 18.95 180.6 1.6 doesn't exist Example 25 10 70 0.5 One 18.5 158.2 1.5 doesn't exist Example 26 10 60 10 3 17 178.5 0.6 doesn't exist Example 27 5 55 2.5 3 34.5 143.6 2.6 doesn't exist

(content unit: weight %)

sulfuric acid phosphoric acid Foshan AF TBAF TMSPSA THSPSA BTMSS sci-fi DIW Silicon Nitride Etching Rate
(Å/min) Silicon oxide film etch rate
(Å/min) oxide film
surface stain Comparative Example 1 85 15 2.5 8.2 doesn't exist Comparative Example 2 80 0.05 19.95 203.5 2485.0 doesn't exist Comparative Example 3 80 1.5 18.5 287.0 3024.5 doesn't exist Comparative Example 4 70 10 20 301.5 2830.0 doesn't exist Comparative Example 5 70 1.5 29.5 265.2 2505.3 doesn't exist Comparative Example 6 10 70 0.05 19.95 227.3 2175.5 doesn't exist Comparative Example 7 5 55 10 30 58.8 153.1 doesn't exist Comparative Example 8 80 0.05 4 15.95 120.3 1.5 has exist Comparative Example 9 80 1.5 4 14.5 174.5 1.0 has exist Comparative Example 10 10 70 0.05 4 15.95 180.0 0.5 has exist Comparative Example 11 5 55 10 4 26 134.3 0.5 has exist Comparative Example 12 85 0.01 One 13.99 34.3 2.0 doesn't exist Comparative Example 13 5 50 2.5 3 39.5 51.3 2.7 doesn't exist Comparative Example 14 70 0.05 11 18.95 143.3 0.2 has exist Comparative Example 15 84.5 0.5 15 54.3 8.2 doesn't exist Comparative Example 16 84 One 15 44.2 6.0 doesn't exist Comparative Example 17 84.5 0.5 15 52.5 7.0 doesn't exist Comparative Example 18 84 One 15 43.4 5.7 doesn't exist

(content unit: weight %)

main)

- AF: Ammonium fluoride

- TBAF: Tetrabutylammonium fluoride

- TMSPSA: 3-(Trimethoxysilyl)propylsuccinic anhydride

- THSPSA: 3-(Trihydroxysilyl)-1-propanesulfonic acid

- TESPSA: 3-(Triethoxysilyl)propylsuccinic anhydride

- DEPTES: Diethylphosphatoethyltriethoxysilane

- BTMSS: Bis (trimethylsilyl) sulfate

- SF: Silicon fluoride

As can be seen from Tables 1 and 2, the etchant compositions of Examples 1 to 27 of the present invention were very excellent with an etch selectivity ratio of the silicon nitride film to the silicon oxide film of at least 1:29.2 (Example 6), and the surface of the oxide film There was no staining. In particular, in Examples 2, 4, 5, 11 to 13, and 15 to 26, the etch selectivity of the silicon nitride film to the silicon oxide film was greater than at least 1:100, indicating a remarkably excellent selectivity.

On the other hand, in the etchant compositions of Comparative Examples 1 to 7, which did not contain the silicon compound of the present invention, the etch selectivity of the silicon nitride film to the silicon oxide film was at most 1: -2.6 (Comparative Example 7), so that the silicon oxide film was etched more. Confirmed.

In addition, the etchant compositions of Comparative Examples 15 to 18 containing a silicon compound other than the silicon compound of the present invention have an etch selectivity of a silicon nitride film to a silicon oxide film of at most 1: 7.6 (Comparative Example 18), compared to the etchant composition of Examples. It showed a significantly low selectivity ratio.

On the other hand, in Comparative Examples 8 and 11 containing an excessive amount of the silicon compound, the etch selectivity was very high, but it was judged that it was difficult to use it because stains were generated on the surface of the oxide film.

Claims (7)

(a) inorganic acids;
(b) fluorinated compounds;
(c) at least one silane compound represented by the following Chemical Formulas 1 and 2, and
(d) a silicon nitride etchant composition comprising water:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
X is a carbon atom, a sulfur atom, or a phosphorus atom;
Y is selected from the group consisting of Na, K, and NH ₄ ;
m and n are 1 or 2; o is 0 or 1; p and Q are integers from 0 to 3; In the above, when o is 0, hydrogen (H) is absent, oxygen (O) adjacent thereto exists as an anion, and Y ⁺ has a relationship between it and a counter ion, and when n is 2, each o is independently 0 or 1;
R1, R2, and R3 are each independently hydrogen, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms , an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a heteroarylalkyl group having 4 to 30 carbon atoms, an amino group, an aminoalkyl group having 1 to 4 carbon atoms, a vinyl group, an epoxy group, and a thiol group;
R4 is unsubstituted or substituted with one or more selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a carboxylate group, and the group consisting of N, O and S or a hydrocarbon chain having 1 to 10 carbon atoms with or without one or more heteroatoms selected from;
A cycloalkylene group having 3 to 20 carbon atoms, unsubstituted or substituted with one or more selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a carboxylate group It is an arylene group of ~ 30, or a heteroarylene group of 3 ~ 20 carbon atoms;
R5 is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen group, an oxo group, and a methylene group unsubstituted or substituted with one or more selected from the group consisting of a carboxylate group, an amine group, an amine group, 6 to carbon atoms an arylene group of 20, a heteroarylene group having 3 to 20 carbon atoms, an oxygen atom, and a sulfur atom;
When R4 and R5 include at least one carboxylate group, at least one counter ion selected from the group consisting of Na, K, and NH ₄ corresponding thereto is further included, wherein the hetero compound is composed of N, O and S one or more heteroatoms selected from the group. The method according to claim 1,
Based on the total weight of the composition, 60-80% by weight of an inorganic acid, 0.01-10% by weight of a fluorine compound, and 0.01-3% by weight of a silane-based compound, and the remaining amount of water, the silicon nitride film etchant composition comprising. The method according to claim 1,
The inorganic acid is a silicon nitride film etchant composition comprising at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. The method according to claim 1,
The fluorine-containing compound is a silicon nitride film etchant composition comprising at least one selected from the group consisting of hydrofluoric acid, fluoroboric acid, and an ammonium fluoride salt represented by the following formula (3):
[Formula 3]

In the above formula (3)
R is each independently hydrogen, a linear or branched chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. The method according to claim 1,
The silane compounds represented by Chemical Formulas 1 and 2 are triethoxysilylpropylmaleamic acid, 3-(trimethoxysilyl)propyl succinic anhydride (3-(Trimethoxysilyl)propylsuccinic anhydride), 3-( Triethoxysilyl)propyl succinic anhydride (3-(Triethoxysilyl)propylsuccinic anhydride), N-(trimethoxysilylpropyl)ethylenediamine triacetic acid trisodium salt (N-(Trimethoxysilylpropyl)ethylenediamine triacetic acid trisodium salt), carboxyethyl Carboxyethylsilanetriol sodium salt, 3-(trihydroxysilyl)-1-propanesulfonic acid (3-(Trihydroxysilyl)-1-propanesulfonic acid), 2-(4-chlorosulfonylphenyl)ethyl trime Tooxysilane (2- (4-Chlorosulfonylphenyl) ethyltrimethoxysilane), diethylphosphatoethyltriethoxysilane (Diethylphosphatoethyltriethoxysilane), or 3-trihydroxysilylpropylmethyl phosphate sodium salt (3-Trihydroxysilylpropylmethylphosphonate sodium salt) A silicon nitride film etchant composition comprising a. A method of manufacturing a semiconductor device comprising the step of etching a silicon nitride layer using the etchant composition of claim 1 . A method of manufacturing a TFT array substrate comprising the step of etching a silicon nitride film using the etchant composition of claim 1 .