KR20200006874A - Etching composition for silicon nitride layer and etching process of silicon nitride layer using the same - Google Patents

Abstract

The present invention relates to a composition for etching a silicon nitride film, which comprises: inorganic acids or salts thereof; water; a compound represented by chemical formula 1; a compound represented by chemical formula 2; and at least one of reaction products of the compound of represented by the chemical formula 1 or the compound represented by the chemical formula 2, and to a silicon nitride film etching method using the same.

Description

Composition for Silicon Nitride Etching and Silicon Nitride Etching Method Using the Same {Etching COMPOSITION FOR SILICON NITRIDE LAYER AND ETCHING PROCESS OF SILICON NITRIDE LAYER USING THE SAME}

The present invention relates to a silicon nitride film etching composition and a silicon nitride film etching method using the same. More specifically, the present invention is a silane-based compound; A compound of formula 2; And at least one of the reaction products of the compound of Formula 1 or the compound of Formula 2, thereby significantly increasing the etching selectivity of the silicon nitride film to the silicon oxide film, and increasing the thickness of the silicon oxide film or during and / or during etching. The present invention relates to a silicon nitride film etching composition and a silicon nitride film etching method using the same, which can prevent precipitation due to self-reaction of a silane compound after etching.

The silicon nitride film is present above or below the silicon oxide film or alternately stacked.

An etching method using a phosphoric acid solution heated to a high temperature is known to remove a silicon nitride film pattern formed on a substrate during a semiconductor manufacturing process. However, the phosphoric acid solution has a limit in increasing the etching selectivity of the silicon nitride film to the silicon oxide film. In order to increase the etching selectivity, a method of including a silane compound is considered.

Tetraethoxysilane can be used as a silane type compound. However, tetraethoxysilane still has limitations in improving the etching selectivity, and there is a problem in that the thickness of the silicon oxide film is increased due to the accumulation of tetraethoxysilane on the surface of the silicon oxide film (ideal growth problem) or the tetraethoxysilane reacts itself There was a problem of precipitation during or after etching.

The object of the present invention is It is to provide a silicon nitride film etching composition that can significantly increase the etching selectivity of the silicon nitride film to the silicon oxide film.

Another object of the present invention is to provide a silicon nitride film etching composition capable of increasing the thickness of the silicon oxide film or preventing precipitation due to self-reaction of the silane compound during and / or after etching.

It is still another object of the present invention to provide a silicon nitride film etching method capable of improving the etching selectivity of the silicon nitride film with respect to the silicon oxide film and preventing the silicon oxide film from increasing in thickness or precipitation due to self reaction of the silane compound. will be.

The silicon nitride film etching composition of the present invention is an inorganic acid or a salt thereof; water; And a compound of Formula 1; A compound of Formula 2; And a reaction product of a compound of Formula 1 or a compound of Formula 2:

<Formula 1>

(In Formula 1, R ₁ , R ₂ , R ₃ , R ₆ are as defined in the description of the following invention)

<Formula 2>

(In Formula 2, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ are as defined in the following description of the invention)

The silicon nitride film etching method of the present invention may include etching the silicon nitride film by using the silicon nitride film etching composition of the present invention.

The present invention Provided is a silicon nitride film etching composition capable of significantly increasing the etching selectivity of the silicon nitride film with respect to the silicon oxide film.

The present invention provides a silicon nitride film etching composition capable of increasing the thickness of the silicon oxide film or preventing precipitation due to self-reaction of the silane compound.

The present invention provides a silicon nitride film etching method that can significantly increase the etching selectivity of the silicon nitride film with respect to the silicon oxide film and prevent the precipitation of the silicon oxide film from increasing due to the increase of the thickness or the self-reaction of the silane compound.

Where numerical ranges are given herein (eg, C ₁ -C ₁₀ alkyl groups), each range within this range, as well as all ranges in between, may be included. For example, "C ₁ -C ₁₀ alkyl group" means C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C _2-10 , C _{3 -10} , or C _1-2 alkyl.

 "Alkyl" means a saturated straight or branched carbon chain having the indicated number of carbon atoms.

 "Alkenyl" means an unsaturated straight or branched chain alkyl group having the indicated number of carbon atoms and having at least one carbon-carbon double bond derived from the removal of one molecule of hydrogen from the neighboring carbon atoms of the corresponding alkyl group. do.

"Alkynyl" means an unsaturated straight or branched chain alkyl group having the indicated number of carbon atoms and having at least one carbon-carbon triple bond derived from the removal of two molecules of hydrogen from the neighboring carbon atoms of the corresponding alkyl group. do.

"Cycloalkyl" means a non-aromatic, fully saturated carbonated ring having the ring carbon atoms of the indicated number of carbon atoms. Cycloalkyls can be monocyclic or polycyclic (eg bicyclic or tricyclic).

"Cycloalkenyl" refers to a non-aromatic carbocyclic ring containing at least one carbon-carbon double bond derived from the removal of one molecule of hydrogen from the neighboring carbon atoms of the corresponding cycloalkyl containing the indicated number of carbon atoms. it means. Cycloalkenyl groups may be monocyclic or polycyclic (eg bicyclic or tricyclic).

"Aryl" means an aromatic carbon ring having the indicated number of carbon atoms. The aryl group can be monocyclic or polycyclic (eg bicyclic or tricyclic).

"Arylalkyl" means a moiety having the indicated number of carbon atoms to which the aryl moiety is attached to the parent structure through an alkyl moiety. The alkyl moiety can be straight or branched.

"Hetero" in "heterocycloalkyl", "heterocycloalkenyl", "heteroaryl" and "heteroarylalkyl" means a functional group in which the carbon atom of the functional group is substituted with an atom selected from N, O, and S.

"Halogen" means F, Cl, Br or I.

"Substituted" in "substituted or unsubstituted" means that at least one hydrogen atom of the corresponding functional group is halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C (= O) (R ₄ ), * -C (= O) -N (R ₄ ) (R ₅ ), * -C (= O) -OC (= O) (R ₄ ), C _1- C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ It means substituted by one of a cycloalkenyl group, a C ₁ -C ₁₀ heterocycloalkenyl group, a C ₆ -C ₂₀ aryl group, and a C ₁ -C ₂₀ heteroaryl group.

In the composition for etching silicon nitride film comprising an inorganic acid or a salt thereof and water, the present invention comprises a compound of the formula (1) as a silane-based compound; A compound of Formula 2; And at least one of a reaction product of the compound of Formula 1 or the compound of Formula 2 below, the ratio (etch selectivity) of the silicon nitride film to the etching rate of the silicon oxide film can be significantly increased, and the silicon A compound of formula 1 below on an oxide film surface; A compound of Formula 2; Or there is no problem of increasing the thickness of the silicon oxide film (abnormal growth problem) because the reaction product of the compound of formula (1) or compound of formula (2) does not accumulate, and after etching or during etching, the compound of formula (1), compound of formula (2) ; Or it was confirmed that the reaction product of the compound of formula (1) or the compound of formula (2) does not react by itself to precipitate and completed the present invention.

Hereinafter, the component of the silicon nitride film etching composition of this invention is demonstrated in detail.

The inorganic acid or a salt thereof is not particularly limited as long as it can accelerate the etching by providing hydrogen ions in the silicon nitride film etching composition. For example, inorganic acids are sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, hydrofluoric acid, boric acid, phosphoric acid (H ₃ PO ₄ ), phosphorous acid (H ₃ PO ₃ ), hypophosphoric acid (H ₃ PO ₂ ), hypophosphoric acid (H ₄ P ₂ O ₆ ), one or more of tripolyphosphoric acid (H ₅ P ₃ O ₁₀ ), pyrophosphoric acid (H ₄ P ₂ O ₇ ). Preferably, phosphoric acid may be used as the inorganic acid.

The inorganic acid or a salt thereof may be included in 60 to 99.99% by weight of the silicon nitride film etching composition. In the above range, the ratio (etch selectivity) of the etching rate of the silicon nitride film to the etching rate of the silicon oxide film may be increased. For example, the inorganic acid or a salt thereof may be included in 60 to 95% by weight, 80 to 90% by weight of the silicon nitride film etching composition.

Water may be, for example, but not limited to semiconductor grade water or ultrapure water. Water may be included in the remaining amount of the silicon nitride film etching composition.

As the silane-based compound, the compound of Formula 1 may be included:

<Formula 1>

(In Formula 1,

R ₁ , R ₂ , and R ₃ are each independently hydrogen, halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C (= O) (R ₄ ), * -C (= O) -N (R ₄ ) (R ₅ ), * -C (= O) -OC (= O) (R ₄ ), C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heterocycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group, wherein R ₄ and R ₅ are independently of each other, hydrogen, halogen, C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heterocycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group,

At least one of R ₁ , R ₂ and R ₃ is halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C (= O) (R ₄ ), * -C (= 0) -N (R ₄ ) (R ₅ ), * -C (= 0) -OC (= 0) (R ₄ ) and a C ₁ -C ₁₀ alkoxy group,

R ₆ is the following Chemical Formula 1-1 or the following Chemical Formula 1-2;

<Formula 1-1>

R ₈ -AR _7- *

(In Chemical Formula 1-1,

* Is a binding site to Si in Formula 1,

A is *-(C = O) -O- * or * -O- (C = O)-*, where * is the linking site,

R ₇ is a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ -C ₂₀ arylene group, substituted or unsubstituted C ₃ -C ₂₀ heteroarylene group, substituted or unsubstituted C ₇ -C ₂₀ arylalkylene group or substituted or unsubstituted C ₃ -C ₂₀ heteroarylalkylene group ego,

R ₈ is a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkyl group, a substituted or unsubstituted C _6- A C ₂₀ aryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaryl group, a substituted or unsubstituted C ₇ -C ₂₀ arylalkyl group, or a substituted or unsubstituted C ₃ -C ₂₀ heteroarylalkyl group)

<Formula 1-2>

R ₁₄ -BR _13- *

(In Chemical Formula 1-2,

* Is a binding site to Si in Formula 1,

B is * -O- *, where * is the linking site,

R ₁₃ is a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ -C ₂₀ arylene group, substituted or unsubstituted C ₃ -C ₂₀ heteroarylene group, substituted or unsubstituted C ₇ -C ₂₀ arylalkylene group or substituted or unsubstituted C ₃ -C ₂₀ heteroarylalkylene group ego,

R ₁₄ is H, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkyl group, a substituted or unsubstituted C _{A 6} -C ₂₀ aryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaryl group, a substituted or unsubstituted C ₇ -C ₂₀ arylalkyl group or a substituted or unsubstituted C ₃ -C ₂₀ heteroarylalkyl group,

R ₁₄ is H, or

At least one of R ₁₃ and R ₁₄ is substituted with a hydroxy group).

In one embodiment, one of R ₁ , R ₂ , R ₃ may be a C ₁ -C ₁₀ alkoxy group. In one embodiment, _{two of} R ₁ , R ₂ , R ₃ may be C ₁ -C ₁₀ alkoxy groups. In one embodiment, R ₁ , R ₂ , R ₃ can be a C ₁ -C ₁₀ alkoxy group.

In one embodiment, A can be *-(C = 0) -0- *. In this case, R ₇ may be a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkylene group, or a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkylene group. In one embodiment, R ₇ can be a substituted or unsubstituted C ₁ -C ₁₀ alkylene group. In one embodiment, R ₇ can be a substituted or unsubstituted C ₁ -C ₅ alkylene group.

In one embodiment, A can be *-(C = 0) -0- *. In this case, R ₈ may be a substituted or unsubstituted C ₁ -C ₁₀ alkyl group or a substituted or unsubstituted C ₆ -C ₂₀ aryl group. In one embodiment, R ₈ can be a substituted or unsubstituted C ₁ -C ₅ alkyl group or a substituted or unsubstituted C ₆ -C ₁₀ aryl group.

In one embodiment, A can be * -O- (C = 0)-*. In this case, R ₇ may be a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkylene group, or a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkylene group. In one embodiment, R ⁷ can be a substituted or unsubstituted C ₁ -C ₁₀ alkylene group. In one embodiment, R ⁷ can be a substituted or unsubstituted C ₁ -C ₅ alkylene group.

In one embodiment, A can be * -O- (C = 0)-*. In this case, R ₈ may be a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, or a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkyl group. In one embodiment, R ₈ can be a substituted or unsubstituted C ₁ -C ₁₀ alkyl group. In one embodiment, R ₈ can be a substituted or unsubstituted C ₁ -C ₅ alkyl group.

In one embodiment, R ₁₃ in Formula 1-2 is a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, and R ₁₄ is H.

In one embodiment, the compound of formula 1 is acetoxyalkyltrialkoxysilane, including acetoxymethyltrialkoxysilane, acetoxyethyltrialkoxysilane, acetoxypropyltrialkoxysilane, and the like; Benzoyloxyalkyl trialkoxysilanes including benzoyloxypropyl trialkoxysilane and the like; (Carboalkoxy) alkyltrialkoxysilanes including 2- (carbomethoxy) ethyltrialkoxysilane and the like; It may contain one or more of hydroxyalkyltrialkoxysilanes including hydroxypropyltrimethoxysilane and the like.

As the silane-based compound, the compound of Formula 2 may be included:

<Formula 2>

(In Formula 2,

R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen, halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C (= O) (R ₄ ), * -C (= O) -N (R ₄ ) (R ₅ ), * -C (= O) -OC (= O) (R ₄ ), C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heterocycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group, wherein R ₄ and R ₅ are independently of each other, hydrogen, halogen, C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heterocycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group,

R ₁₂ is a substituted or unsubstituted, epoxidized aliphatic hydrocarbon group or epoxidized alicyclic hydrocarbon group and is a C ₁ -C ₁₀ alkylene group with or without one or more oxygens in the alkylene chain).

The "epoxylated aliphatic hydrocarbon group" and "epoxylated alicyclic hydrocarbon group" described in R ₁₂ in Formula 2 may be located in the alkylene chain of the C ₁ -C ₁₀ alkylene group or at the end of the alkylene chain. .

"Epoxylated aliphatic hydrocarbon group" described in R ₁₂ in Formula 2 means a functional group epoxidized carbon-carbon constituting aliphatic hydrocarbon. For example, the epoxidized aliphatic hydrocarbon group may be a glycidoxy group, but is not limited thereto.

"Epoxylated alicyclic hydrocarbon group" described in R ₁₂ in Chemical Formula 2 means a functional group epoxidized by carbon-carbon constituting the alicyclic hydrocarbon. For example, the epoxidized cycloaliphatic hydrocarbon group can be an epoxidized C ₅ -C ₁₀ cycloaliphatic hydrocarbon group. For example, the epoxidized alicyclic hydrocarbon group may be an epoxycyclohexyl group, an epoxycycloheptyl group, or an epoxycyclopentyl group, but is not limited thereto.

In the C ₁ -C ₁₀ alkylene group described in R ₁₂ in Formula 2, "C ₁ -C ₁₀ " is the number of carbon atoms excluding carbon atoms included in the epoxidized aliphatic hydrocarbon group and the epoxidized alicyclic hydrocarbon group. It means 1 to 10.

In one embodiment, at least one of R ₁₁ , R ₁₂ , R ₁₃ is halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C ( = O) (R ₄ ), * -C (= O) -N (R ₄ ) (R ₅ ), * -C (= O) -OC (= O) (R ₄ ) and C ₁ -C ₁₀ alkoxy It may be selected from the group.

In one embodiment one of R ₉ , R ₁₀ , R ₁₁ may be a C ₁ -C ₁₀ alkoxy group. In one embodiment, two of R ₉ , R ₁₀ , R ₁₁ may be C ₁ -C ₁₀ alkoxy groups. In one embodiment, R ₉ , R ₁₀ , R ₁₁ can be a C ₁ -C ₁₀ alkoxy group.

In one embodiment, the compound of formula 2 is a glycidoxyalkyltrialkoxysilane, including (3-glycidoxypropyl) trialkoxysilane and the like; (Glycidoxyalkyl) alkyl dialkoxysilanes including (3-glycidoxypropyl) methyl dialkoxysilane and the like; It may contain one or more of epoxycyclohexylalkyltrialkoxysilanes including 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane and the like.

The reaction product of the compound of Formula 1 or the compound of Formula 2 means a component derived from the compound of Formula 1 or the compound of Formula 2. The reaction product may be, for example, a reaction product of each of the compound of Formula 1 or the compound of Formula 2; A reaction product of the compound of Formula 1 or the compound of Formula 2 with the inorganic acid or a salt thereof; A reaction product of the compound of Formula 1 or the compound of Formula 2 with the water; It may be a compound of formula (1) or a compound of formula (2), the inorganic acid or a salt thereof and the reaction product with the water. The compound of Formula 1 or the compound of Formula 2 is halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C (= O) (R ₄ ), * -C (= O) -N (R ₄ ) (R ₅ ), * -C (= O) -OC (= O) (R ₄ ) and C ₁ -C ₁₀ alkoxy groups And a compound of formula 1 or a compound of formula 2, an inorganic acid or a salt thereof, and / or water. For example, when the compound of Formula 1 or the compound of Formula 2 includes a hydroxyl group, the compound of Formula 1 or the compound of Formula 1 or the compound of Formula 2 and an inorganic acid or a salt thereof are adjacent to each other. The dehydration reaction may proceed in between to form a reaction product including an ether bond. For example, when the compound of Formula 1 or the compound of Formula 2 includes a halogen group or an alkoxy group, the compound of Formula 1 or the compound of Formula 2 due to the reaction of the compound of Formula 1 or the compound of Formula 2 with water A reaction product can be formed in which a halogen group or an alkoxy group of is converted to a hydroxy group. In addition, the compound of formula (1) or compound of formula (2) including the hydroxy group produced by the reaction with water includes an ether bond through a dehydration reaction with a compound of formula (1) or a compound of formula (2) or an inorganic acid or a salt thereof. The reaction product can be formed. In addition, various reaction products may be formed, and one of ordinary skill in the art may readily prepare the reaction product from the functional group of the compound of Formula 1 or the compound of Formula 2, the inorganic acid or salt thereof, and / or water. I can think of it.

The compound of Formula 1, the compound of Formula 2, and the reaction product of the compound of Formula 1 or the compound of Formula 2 may be included in 0.1 ppm to 25% by weight of the silicon nitride film etching composition. Etch selectivity in the content range can be significantly higher, there is no abnormal growth problem, there can be no precipitation due to self reaction. For example, at least one of the reaction products of the compound of Formula 1, the compound of Formula 2, and the compound of Formula 1 or the compound of Formula 2 is 0.001 to 10% by weight, 0.01 to 10% by weight of the silicon nitride film etching composition 5 wt%, 0.1 to 3 wt% may be included.

The silicon nitride film etching composition may further include at least one of an organic solvent and an inorganic solvent to increase the solubility of the reaction product of the compound of Formula 1 and / or the compound of Formula 2 and / or the compound of Formula 1 or the compound of Formula 2. It may include. The organic solvent and the inorganic solvent are not particularly limited as long as they are commonly used in the art, and may be, for example, 1-methoxy-2-propanol, propylene glycol methyl ether acetate, or the like. According to one embodiment, the organic solvent and the inorganic solvent may have a boiling point of 100 ° C. or more, for example, 100 ° C. to 150 ° C. at 1 atmosphere, but is not limited thereto.

The silicon nitride film etching composition may further include any additive commonly used in the art to improve etching performance. For example, a corrosion inhibitor, a surfactant, a dispersant, an etching rate control agent, etc. may be further included, but are not limited thereto.

The silicon nitride film etching method of the present invention may include etching the silicon nitride film by using the silicon nitride film etching composition of the present invention.

The etching method may include, for example, forming a silicon nitride film or the silicon oxide film on a substrate; Etching by adding the silicon nitride film etching composition to the silicon nitride film or the silicon oxide film; And removing the silicon nitride film etching composition after etching.

The substrate is not particularly limited as long as it is commonly used in the art, and may be, for example, a semiconductor wafer.

The etching of the silicon nitride film etching composition by adding the silicon nitride film or the silicon oxide film to the silicon nitride film may include, for example, immersing the silicon nitride film or the silicon oxide film in an etching bath including the silicon nitride film etching composition, or etching the silicon nitride film. Spraying a composition on the silicon nitride film or the silicon oxide film, but is not limited thereto.

Before the etching by adding the silicon nitride film etching composition to the silicon nitride film or the silicon oxide film, the silicon nitride film etching composition may further comprise a step, wherein the silicon nitride film etching composition is 100 ℃ or more, For example, it may be heated to 100 ℃ to 500 ℃. According to one embodiment, the silicon nitride film etching composition may be heated to 150 ℃ to 300 ℃, but is not limited thereto.

Removing the silicon nitride film etching composition after the etching may include, for example, washing the etching composition with ultrapure water, and then drying the silicon oxide film or the silicon nitride film, but is not limited thereto. no.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, it is presented as a preferred example of the present invention and should not be construed as limiting the present invention by any means.

Example  One

A silicon nitride film etching composition including 85% by weight of phosphoric acid, 0.5% by weight of acetoxymethyltrimethoxysilane as a silane compound, and a residual amount of water was prepared.

Example  2 to Example  8

In Example 1, a silicon nitride film etching composition was prepared in the same manner as in Example 1, except that the type and / or content of the silane compound was changed as in Table 1 below.

Example  9 to Example  14

In Example 1, a silicon nitride film etching composition was prepared in the same manner as in Example 1, except that the type and / or content of the silane compound was changed as in Table 2 below.

Comparative example  1 to Comparative example  8

In Example 1, a silicon nitride film etching composition was prepared in the same manner as in Example 1, except that the type and / or content of the silane compound was changed as in Table 1 and Table 2 below.

The physical properties described in Tables 1 and 2 below were evaluated for the silicon nitride film etching compositions prepared in Examples and Comparative Examples.

After the silicon nitride film etching composition prepared in Examples and Comparative Examples was heated to 160 ° C., an LP-SiN film or a PE-SiO film was added thereto and then etched for 5 minutes. After measuring the thickness of the LP-SiN film or PE-SiO film before and after etching using an ellipsometer, the etching rate (A) of the silicon nitride film and the etching rate (B) of the silicon oxide film were calculated and The etching selectivity was calculated and the results are shown in Table 1 and Table 2.

[Equation 1]

Etch selectivity = A / B

(In Formula 1, A is the etching rate (unit: dl / min) with respect to the silicon nitride film per unit time of a composition, B is the etching rate (unit: dl / min) with respect to the silicon oxide film per unit time of a composition.)

After the silicon nitride film etching composition prepared in Examples and Comparative Examples was heated to 160 ° C., an LP-SiN film or a PE-SiO film was added thereto and then etched for 5 minutes. The composition after etching was put into a vial, and the transmittance was measured at a wavelength of 880 nm using a Turbiscan to confirm the presence of precipitates in the composition, and the results are shown in Table 1 and Table 2.

Phosphoric Acid
(weight%) Silane compound
(weight%) A
(Å / min) B
(Å / min) Etch selectivity Precipitate
The presence or absence Example 1 85 Acetoxymethyltrimethoxysilane (0.5 wt%) 59.3 0.98 60.5 radish Example 2 85 Acetoxymethyltriethoxysilane (0.5 wt%) 56.5 1.10 51.4 radish Example 3 85 Acetoxyethyltrimethoxysilane (0.5 wt%) 58.9 0.62 95.0 radish Example 4 85 3-acetoxypropyltrimethoxysilane (0.5 wt%) 57.2 0.25 228.8 radish Example 5 85 Benzoyloxypropyltrimethoxysilane (0.5 wt%) 58.5 0.15 390.0 radish Example 6 85 2- (carbomethoxy) ethyltrimethoxysilane (0.5 wt%) 57.4 0.84 68.3 radish Example 7 85 Acetoxymethyltrimethoxysilane (3% by weight) 58.1 0.03 1936.7 radish Example 8 85 3-hydroxypropyltrimethoxysilane (0.5 wt%) 57.9 0.28 206.8 radish Comparative Example 1 85 - 60.4 4.3 14.0 U Comparative Example 2 85 Tetraethoxysilane (0.5% by weight) 59.6 More than
growth N / A U Comparative Example 3 85 3-chloropropyltrimethoxysilane (0.5 wt%) 58.0 More than
growth N / A U Comparative Example 4 85 Octyltrimethoxysilane (0.5 wt%) 57.7 More than
growth N / A U Comparative Example 5 85 Benzyltrimethoxysilane (0.5% by weight) 56.3 More than
growth N / A U Comparative Example 6 85 Trimethylsilyl acetic acid (0.5% by weight) 59.5 4.1 14.5 radish Comparative Example 7 85 Methyltrimethylsilyl acetate (0.5 wt%) 59.7 4.2 14.2 radish

Phosphoric Acid
(weight%) Silane compound
(weight%) A
(Å / min) B
(Å / min) Etch selectivity Precipitate
The presence or absence Example 9 85 (3-Glycidoxypropyl) trimethoxysilane (0.5 wt%) 56.4 0.10 564.0 radish Example 10 85 (3-Glycidoxypropyl) triethoxysilane (0.5 wt%) 59.2 0.20 296.0 radish Example 11 85 (3-Glycidoxypropyl) ethyltrimethoxysilane (0.5 wt%) 59.0 2.90 20.3 radish Example 12 85 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
(0.5 wt%) 58.4 0.15 389.3 radish Example 13 85 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane
(0.5 wt%) 56.2 0.23 244.3 radish Example 14 85 (3-Glycidoxypropyl) trimethoxysilane (3% by weight) 55.6 0.04 1390 radish Comparative Example 1 85 - 60.4 4.3 14.0 U Comparative Example 2 85 Tetraethoxysilane (0.5% by weight) 59.6 Growth over N / A U Comparative Example 3 85 3-chloropropyltrimethoxysilane (0.5 wt%) 58.0 Growth over N / A U Comparative Example 4 85 Octyltrimethoxysilane (0.5 wt%) 57.7 Growth over N / A U Comparative Example 8 85 Cyclohexyltrimethoxysilane (0.5% by weight) 58.5 Growth over N / A U

* In Table 1 and Table 2, "N / A" means that the etching selectivity could not be measured.

As shown in Table 1 and Table 2, the silicon nitride film etching composition of the present invention can increase the etching selectivity of the silicon nitride film to the silicon oxide film, the thickness of the silicon oxide film is increased or precipitated due to the self-reaction of the silane compound This can be done.

On the other hand, the silicon nitride film etching composition of the comparative example, which does not include the silane compound of the present invention, has a problem that the etch selectivity is not improved, the thickness of the silicon oxide film is increased, or precipitation due to the self-reaction of the silane compound.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (9)

Inorganic acids or salts thereof;
water; And
A compound of Formula 1; A compound of Formula 2; And at least one of a reaction product of a compound of Formula 1 or a compound of Formula 2:
<Formula 1>

(In Formula 1,
R ₁ , R ₂ , and R ₃ are each independently hydrogen, halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C (= O) (R ₄ ), * -C (= O) -N (R ₄ ) (R ₅ ), * -C (= O) -OC (= O) (R ₄ ), C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heterocycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group, wherein R ₄ and R ₅ are independently of each other, hydrogen, halogen, C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heterocycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group,
At least one of R ₁ , R ₂ and R ₃ is halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C (= O) (R ₄ ), * -C (= 0) -N (R ₄ ) (R ₅ ), * -C (= 0) -OC (= 0) (R ₄ ) and a C ₁ -C ₁₀ alkoxy group,
R ₆ is the following Formula 1-1 or the following Formula 1-2;
<Formula 1-1>
R ₈ -AR _7- *
(In Chemical Formula 1-1,
* Is a binding site to Si in Formula 1,
A is *-(C = O) -O- * or * -O- (C = O)-*, where * is the linking site,
R ₇ is a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ -C ₂₀ arylene group, substituted or unsubstituted C ₃ -C ₂₀ heteroarylene group, substituted or unsubstituted C ₇ -C ₂₀ arylalkylene group or substituted or unsubstituted C ₃ -C ₂₀ heteroarylalkylene group ego,
R ₈ is a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkyl group, a substituted or unsubstituted C _6- A C ₂₀ aryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaryl group, a substituted or unsubstituted C ₇ -C ₂₀ arylalkyl group, or a substituted or unsubstituted C ₃ -C ₂₀ heteroarylalkyl group)
<Formula 1-2>
R ₁₄ -BR _13- *
(In Chemical Formula 1-2,
* Is a binding site to Si in Formula 1,
B is * -O- *, where * is the linking site,
R ₁₃ is a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkylene group, a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ -C ₂₀ arylene group, substituted or unsubstituted C ₃ -C ₂₀ heteroarylene group, substituted or unsubstituted C ₇ -C ₂₀ arylalkylene group or substituted or unsubstituted C ₃ -C ₂₀ heteroarylalkylene group ego,
R ₁₄ is H, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted C ₃ -C ₁₀ cycloalkyl group, a substituted or unsubstituted C ₂ -C ₁₀ heterocycloalkyl group, a substituted or unsubstituted C _{A 6} -C ₂₀ aryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaryl group, a substituted or unsubstituted C ₇ -C ₂₀ arylalkyl group or a substituted or unsubstituted C ₃ -C ₂₀ heteroarylalkyl group,
R ₁₄ is H, or
At least one of R ₁₃ and R ₁₄ is substituted with a hydroxy group)),
<Formula 2>

(In Formula 2,
R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen, halogen, hydroxy group, thiol group, cyano group, amino group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, * -C (= O) (R ₄ ), * -C (= O) -N (R ₄ ) (R ₅ ), * -C (= O) -OC (= O) (R ₄ ), C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heterocycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group, wherein R ₄ and R ₅ are independently of each other, hydrogen, halogen, C ₁ -C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀ alkynyl group, C ₁ -C ₁₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heterocycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group,
R ₁₂ is a substituted or unsubstituted, epoxidized aliphatic hydrocarbon group or epoxidized alicyclic hydrocarbon group and is a C ₁ -C ₁₀ alkylene group with or without one or more oxygens in the alkylene chain).
The composition of claim 1, wherein in Formula 1, R ₁ , R ₂ , and R ₃ are C ₁ -C ₁₀ alkoxy groups.
According to claim 1, wherein the compound of formula (1) comprises at least one of acetoxyalkyl trialkoxysilane, benzoyloxyalkyl trialkoxysilane, (carboalkoxy) alkyl trialkoxysilane, hydroxyalkyl trialkoxysilane Phosphorus, silicon nitride film etching composition.
The composition of claim 1, wherein in Formula 2, R ₉ , R ₁₀ and R ₁₁ are C ₁ -C ₁₀ alkoxy groups.
The composition of claim 1, wherein the epoxidized aliphatic hydrocarbon group is a glycidoxy group and the epoxidized alicyclic hydrocarbon group is an epoxycyclohexyl group.
The silicon nitride film according to claim 1, wherein the compound of Formula 2 comprises at least one of glycidoxyalkyltrialkoxysilane, (glycidoxyalkyl) alkyldialkoxysilane, and epoxycyclohexylalkyltrialkoxysilane. Etching composition.
According to claim 1, wherein the compound of Formula 1; A compound of Formula 2; And at least one of the reaction product of the compound of Formula 1 or the compound of Formula 2 is 0.1 ppm to 25% by weight of the silicon nitride film etching composition.
The composition of claim 1, wherein the inorganic acid is phosphoric acid.
The silicon nitride film etching method comprising etching the silicon nitride film using the composition for etching silicon nitride film of any one of claims 1 to 8.