KR20200137502A - Etching solution for silicon substrate and method for preparing semiconductor device using the same - Google Patents

Abstract

The present invention relates to a silicon substrate etching solution and to a production method of a semiconductor device using the same. More specifically, the present invention relates to: a silicon substrate etching solution capable of improving etching selectivity for a silicon nitride film compared to a silicon oxide film when etching the silicon nitride film by increasing distribution of a silane compound in the silicon substrate etching solution; and a production method of a semiconductor device comprising an etching process performed by using the same.

Description

A silicon substrate etching solution and a method of manufacturing a semiconductor device using the same {ETCHING SOLUTION FOR SILICON SUBSTRATE AND METHOD FOR PREPARING SEMICONDUCTOR DEVICE USING THE SAME}

The present invention relates to a silicon substrate etching solution and a method of manufacturing a semiconductor device using the same, and more particularly, an etching selectivity for a silicon nitride layer compared to a silicon oxide layer when etching a silicon nitride layer by increasing the distribution of a silane compound in the silicon substrate etching solution. The present invention relates to a method of manufacturing a semiconductor device including an etching solution capable of improving the silicon substrate and an etching process performed using the same.

Currently, there are various methods of etching the silicon nitride layer and the silicon oxide layer, and the dry etching method and the wet etching method are mainly used.

The dry etching method is an etching method using a gas, and has the advantage that isotropy is superior to the wet etching method, but the wet etching method is widely used in that the productivity is much lower than the wet etching method and is an expensive method.

In general, as a wet etching method, a method of using phosphoric acid as an etching solution is well known. In this case, if only pure phosphoric acid is used for etching the silicon nitride film, problems such as various defects and pattern abnormalities may occur as the device is refined, and as the silicon nitride film as well as the silicon oxide film is etched, a protective film is formed on the silicon oxide film. It is necessary to further lower the etching rate of the silicon oxide film.

An object of the present invention is to provide a silicon substrate etching solution capable of improving an etching selectivity for a silicon nitride layer compared to a silicon oxide layer by increasing the distribution of a silane compound in a silicon substrate etching solution to lower an etching rate for a silicon oxide layer.

In addition, an object of the present invention is to provide an etching solution for a silicon substrate in which an etching rate is stably maintained in an etching process performed at a high temperature and an etching selectivity for a silicon nitride layer compared to a silicon oxide layer is not lowered.

In addition, an object of the present invention is to provide a method of manufacturing a semiconductor device including an etching process performed using the silicon substrate etching solution described above.

In order to solve the above-described technical problem, according to an aspect of the present invention, a silicon substrate etching solution including a phosphoric acid aqueous solution, a silicon additive, and a compound represented by Formula 1 below is provided.

[Formula 1]

Wherein X ₁ and X ₂ are each independently oxygen, sulfur, or phosphorus, Y ₁ and Y ₂ are each independently oxygen or sulfur, and R ₁ and R ₂ are each independently alkyl, cycloalkyl, at least one It is selected from heteroalkyl containing hetero atoms, haloalkyl, aminoalkyl, aryl, heteroaryl, aralkyl, benzyl.

In addition, according to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device including an etching process performed using the silicon substrate etching solution described above.

In the silicon substrate etching solution according to the present invention, the compound represented by Formula 1 may decrease the etching rate of the silicon oxide layer by increasing the distribution of the silane compound under the etching conditions of the silicon substrate.

In this case, the compound represented by Formula 1 used herein can increase the distribution of the silane compound in the etching solution of the silicon substrate by preventing the silane compound from being changed to the siloxane compound at high temperature.

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, only these embodiments make the disclosure of the present invention complete, and common knowledge in the technical field to which the present invention pertains. It is provided to completely inform the scope of the invention to those who have, and the invention is only defined by the scope of the claims.

Hereinafter, a silicon substrate etching solution according to the present invention will be described in detail.

According to an aspect of the present invention, there is provided a silicon substrate etching solution comprising a phosphoric acid aqueous solution, a silicon additive, and a compound represented by Formula 1 below.

The silicon substrate, which is a target for etching the silicon substrate etching solution according to the present invention, preferably includes at least a silicon oxide film (SiO _x ), and simultaneously includes a silicon oxide film and a silicon nitride film (Si _x N _y , SI _x O _y N _z ). I can. In addition. In the case of a silicon substrate including a silicon oxide layer and a silicon nitride layer at the same time, a silicon oxide layer and a silicon nitride layer may be alternately stacked or stacked in different regions.

Here, the silicon oxide film is SOD (Spin On Dielectric) film, HDP (High Density Plasma) film, thermal oxide film, BPSG (Borophosphate Silicate Glass) film, PSG (Phospho Silicate Glass) film depending on the use and type of material. , BSG (BoroSilicate Glass) film, PSZ (Polysilazane) film, FSG (Fluorinated Silicate Glass) film, LP-TEOS (Low Pressure TetraEthyl Ortho Silicate) film, PETEOS (Plasma Enhanced Tetra Ethyl Ortho Silicate) film, HTO (High Temperature Oxide) Film, MTO (Medium Temperature Oxide) film, USG (Undopped Silicate Glass) film, SOG (Spin On Glass) film, APL (Advanced Planarization Layer) film, ALD (Atomic Layer Deposition) film, PE-Oxide film (Plasma Enhanced oxide) Or it may be mentioned as O ₃ -TEOS (O ₃ -Tetra Ethyl Ortho Silicate).

Here, the phosphoric acid aqueous solution is a component that inhibits the conversion of various types of silane compounds present in the etching solution into silicon-based particles by maintaining the pH of the etching solution while etching the silicon nitride layer.

In one embodiment, the phosphoric acid aqueous solution is preferably contained in an amount of 60 to 90 parts by weight based on 100 parts by weight of the silicon substrate etching solution.

When the amount of the phosphoric acid aqueous solution is less than 60 parts by weight based on 100 parts by weight of the silicon substrate etching solution, the etching rate of the silicon nitride layer is lowered, so that the silicon nitride layer may not be sufficiently etched, or the process efficiency of etching the silicon nitride layer may decrease.

On the other hand, when the amount of the phosphoric acid aqueous solution exceeds 90 parts by weight based on 100 parts by weight of the silicon substrate etching solution, not only the etching rate of the silicon nitride layer increases excessively, but also the silicon oxide layer is rapidly etched. An etch selectivity may be lowered, and a silicon substrate may be defective due to the etching of the silicon oxide layer.

The silicon substrate etching solution according to an embodiment of the present invention contains a silicon additive to increase an etching selectivity for a silicon nitride layer compared to a silicon oxide layer.

Here, the silicone additive may include a silane compound, and specifically, the silicone additive may include a compound represented by Formula 2 below.

[Formula 2]

Wherein R ₁ to R ₄ are each independently hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ heteroalkyl containing at least one hetero atom, aryl, heteroaryl, are Alkyl, halogen, alkoxy and hydrophilic functional groups.

Herein, the C _a -C _b functional group means a functional group having a to b carbon atoms. For example, C _a -C _b alkyl means saturated aliphatic groups including straight chain alkyl and branched alkyl and the like having a to b carbon atoms. Linear or branched alkyl is 10 or less in its main chain (e.g., C ₁ -C ₁₀ straight chain, C ₃ -C ₁₀ pulverized), preferably 4 or less, more preferably 3 or less carbon atoms Have.

Specifically, alkyl is methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, pent-1-yl, pent-2-yl, pent-3-yl , 3-methylbut-1-yl, 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2,2-trimethyleth-1-yl, n-hexyl, n-heptyl and n -May be octyl.

Cycloalkyl or heterocycloalkyl including a hetero atom herein may be understood as a cyclic structure of alkyl or heteroalkyl, respectively, unless otherwise defined.

Non-limiting examples of cycloalkyls include cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl and cycloheptyl, and the like.

Non-limiting examples of cycloalkyl containing hetero atoms include 1-(1,2,5,6-tetrahydropyridyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4- Morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-piperazinyl and 2 -Piperazinyl, etc.

In addition, cycloalkyl or cycloalkyl including a hetero atom may have a form in which cycloalkyl, cycloalkyl including hetero atom, aryl or heteroaryl are fused or covalently linked thereto.

As used herein, aryl refers to an unsaturated aromatic ring comprising a single ring or multiple rings (preferably 1 to 4 rings) linked by conjugation or covalent bond to each other, unless otherwise defined. Non-limiting examples of aryl include phenyl, biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2- Anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3--phenanthrenyl, 4--phenanthrenyl, 9-phenanthrenyl, 1-pyrenyl, 2- Pyrenyl and 4-pyrenyl.

Heteroaryl herein refers to a functional group in which at least one carbon atom in the aryl as defined above is substituted with a non-carbon atom such as nitrogen, oxygen or sulfur.

Aralkyl herein is a functional group in which aryl is substituted with carbon of alkyl, and is a generic term for -(CH ₂ ) _n Ar. Examples of aralkyl include benzyl (-CH ₂ C ₆ H ₅ ) or phenethyl (-CH ₂ CH ₂ C ₆ H ₅ ).

As used herein, halogen means fluoro (-F), chloro (-Cl), bromo (-Br) or iodo (-I), and haloalkyl means alkyl substituted with the aforementioned halogen. For example, halomethyl means methyl (-CH ₂ X, -CHX ₂ or -CX ₃ ) in which at least one of the hydrogens of methyl is replaced by halogen.

In addition, alkoxy herein refers to both an -O-(alkyl) group and an -O-(unsubstituted cycloalkyl) group, and is a straight or branched hydrocarbon having at least one ether group and 1 to 10 carbon atoms.

Specifically, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, Cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like, but are not limited thereto.

The hydrophilic functional group herein refers to a hydroxyl group or a functional group that can be substituted with a hydroxyl group under the pH condition of an aqueous phosphoric acid solution.

Here, non-limiting examples of functional groups that can be substituted with hydroxy groups under the pH condition of aqueous phosphoric acid solution include amino, sulfone, phosphonic, phosphoric, thiol, amide, ester, acid anhydride, acyl halide, cyano, carboxyl and azole, , It should be understood that it is not necessarily limited to the functional groups described above, and includes any functional groups that can be substituted with hydroxy groups under the pH condition of the aqueous phosphoric acid solution.

The above-described silicon additive is preferably present in an amount of 100 to 10,000 ppm in the silicon substrate etching solution. Here, the content of the silicon additive is the amount of the silicon additive dissolved in the silicon substrate etching solution, and is expressed in ppm.

For example, the presence of 100 ppm of the silicon additive in the silicon substrate etching solution will mean that the dissolved silicon additive is 100 ppm in the silicon substrate etching solution.

If the silicon additive is present in the silicon substrate etching solution at less than 100 ppm, the amount of the silane compound decomposed from the silicon additive and released under the etching conditions is excessively small, so the effect of increasing the etching selectivity for the silicon nitride layer compared to the silicon oxide layer may be insufficient. have.

On the other hand, when the silicon additive in the silicon substrate etching solution exceeds 10,000 ppm, the amount of the silane compound decomposed from the silicon additive and released under etching conditions is excessively increased, resulting in a problem of lowering the etching rate of the silicon nitride layer as well as the silicon oxide layer. Can occur. In addition, the silane compound in the etching solution can itself act as a source of silicon-based particles.

The silicon substrate etching solution according to an exemplary embodiment of the present invention includes a compound represented by Formula 1 below to increase the etch selectivity for the silicon nitride layer compared to the silicon oxide layer by increasing the distribution of the silane compound.

In general, a silane compound used as a silicone additive can be converted into a siloxane compound by bonding itself at high temperature. The siloxane compound may grow into silicon-based particles and may contaminate the silicon substrate. In addition, since the siloxane compound does not function as a passivation layer of a silicon substrate, there may be a problem that an etching selectivity for a silicon nitride layer compared to a silicon oxide layer is lowered.

Here, the compound represented by Formula 1 of the present invention may convert the siloxane compound into a silane compound. Accordingly, the ratio of the siloxane compound may be reduced, and the distribution of the silane compound in the silicon substrate etching solution may be increased.

That is, the silicon substrate etching solution according to the present invention includes not only the silicon additive but also the compound represented by Formula 1, thereby increasing the distribution of the silane compound under the etching conditions of the silicon substrate, thereby lowering the etching rate for the silicon oxide layer. In addition, contamination of the silicon substrate and generation of silicon-based particles can be prevented.

[Formula 1]

Wherein X ₁ and X ₂ are each independently oxygen, sulfur, or phosphorus, Y ₁ and Y ₂ are each independently oxygen or sulfur, and R ₁ and R ₂ are each independently alkyl, cycloalkyl, at least one It is selected from heteroalkyl containing hetero atoms, haloalkyl, aminoalkyl, aryl, heteroaryl, aralkyl, benzyl.

Specifically, the compound represented by Formula 1 may convert a siloxane compound into a silane compound by radical reaction under etching conditions of a silicon substrate.

Here, the polarity of the order for a smooth-radical reaction with the compound and the siloxane compound represented by Formula 1 and Y ₁ Y ₂ Y ₁ and Y ₂ coupled to a number of easily broken is preferably smaller. In addition, the electronegativity of Y ₁ and Y and Y ₁ Y ₂ to a stable radical of ₂ to be formed is preferably high. Therefore, it is preferable that Y ₁ and Y ₂ are oxygen or sulfur, and that Y ₁ and Y ₂ are the same.

In addition, in order to smoothly perform a radical reaction between the compound represented by Formula 1 and the siloxane compound, it is preferable to form a radical structure in which Y ₁ and Y ₂ are delocalized.

[Formula 2]

Specifically, the compound represented by Formula 2 represents a radical structure in which the bonds of Y ₁ and Y ₂ of the compound represented by Formula 1 are separated.

[Formula 3]

Here, the radical structure in which the bonds of Y ₁ and Y ₂ are separated may represent a resonance structure represented by Chemical Formula 3 above. The resonance structure represented by Formula 3 may exhibit a stable radical structure due to radical delocalization.

In order to represent the resonance structure represented by Chemical Formula 3, it is preferable that X ₁ and Y ₁ are the same, and X ₂ and Y ₂ are the same. Further, X ₁ and it is preferred that X ₁ and X ₂ is also high in electronegativity so that the stable radicals of X ₂ may be formed. Therefore, X ₁ and X ₂ are oxygen, sulfur or phosphorus, and it is preferable that X ₁ , X ₂ , Y ₁ and Y ₂ are the same.

As an example, when X ₁ , X ₂ , Y ₁ and Y _2- of the compound represented by Formula 1 are oxygen, they may exhibit high electronegativity and resonance structures, and thus radical reaction with the siloxane compound under the etching conditions of the silicon substrate. This can be done smoothly. Accordingly, the siloxane compound is changed to a silane compound, so that the distribution of the silane compound in the etching solution of the silicon substrate is increased, and accordingly, the etching rate of the silicon oxide layer may be lowered.

In addition, R ₁ and R ₂ of the compound represented by Formula 1 herein are each independently alkyl, cycloalkyl, heteroalkyl containing at least one hetero atom, haloalkyl, aminoalkyl, aryl, heteroaryl, aralkyl, Is selected from benzyl. In order for the compound represented by Formula 1 to form a stable radical structure, it is preferable that R ₁ and R ₂ are each independently selected from C ₁ -C ₂₀ alkyl, CF ₃ , CCl ₃ , CBr ₃ , and CI ₃ .

When R ₁ and R ₂ are C ₁ -C ₂₀ alkyl, a stable radical structure may be formed by hyperconjugation of R ₁ and R ₂ with a radical. When R ₁ and R ₂ are CF ₃ , CCl ₃ , CBr ₃ , or CI ₃ , a stable radical structure may be formed by an electron withdrawing inductive effect of R ₁ and R ₂ and a radical.

[Formula 4-1]

[Formula 4-2]

As an example, the compounds represented by Chemical Formulas 4-1 and 4-2 may form a stable radical structure, and thus the siloxane compound may be converted into a silane compound under etching conditions of a silicon substrate. Accordingly, by increasing the distribution of the silane compound in the silicon substrate etching solution, the etching rate for the silicon oxide layer may be reduced, and the etching selectivity for the silicon nitride layer compared to the silicon oxide layer may be improved.

It is preferable that the compound represented by Formula 1 is present in an amount of 100 to 400,000 ppm in the silicon substrate etching solution. Here, the content of the compound represented by Formula 1 is the amount of the compound represented by Formula 1 dissolved in the etching solution of the silicon substrate, and is expressed in ppm.

For example, the presence of 5,000 ppm of the compound represented by Formula 1 in the etching solution of the silicon substrate will mean 5,000 ppm of the compound represented by Formula 1 dissolved in the etching solution of the silicon substrate.

When the compound represented by Formula 1 is present in an amount of less than 100 ppm in the etching solution of the silicon substrate, the distribution of the silane compound is lowered under etching conditions, so that the effect of increasing the etching selectivity for the silicon nitride layer compared to the silicon oxide layer may be insufficient.

On the other hand, when the compound represented by Formula 1 in the silicon substrate etching solution exceeds 400,000 ppm, the ratio of water contained in the phosphoric acid solution in the silicon substrate etching solution is reduced under the etching conditions, resulting in a decrease in the etching selectivity for the silicon nitride layer compared to the silicon oxide layer. Problems may occur.

The silicon substrate etching solution according to an embodiment of the present invention may further include a fluorine-containing compound to compensate for the etching rate of the silicon nitride film that is degraded by the use of the silicon additive and to improve the efficiency of the overall etching process. .

As used herein, fluorine-containing compounds refer to any type of compound capable of dissociating fluorine ions.

In one embodiment, the fluorine-containing compound is at least one selected from hydrogen fluoride, ammonium fluoride, ammonium bifluoride and ammonium hydrogen fluoride.

In addition, in another embodiment, the fluorine-containing compound may be a compound in which an organic cation and a fluorine-based anion are ionically bonded.

For example, the fluorine-containing compound may be a compound in which an alkyl ammonium and a fluorine-based anion are ionically bonded. Here, the alkyl ammonium is ammonium having at least one alkyl group and may have up to four alkyl groups. The definition of the alkyl group has been described above.

In another example, the fluorine-containing compound is alkylpyrrolium, alkylimidazolium, alkylpyrazolium, alkyloxazolium, alkylthiazolium, alkylpyridinium, alkylpyrimidinium, alkylpyridazinium, alkylpyra Organic cations and fluorophosphates selected from genium, alkylpyrrolidinium, alkylphosphonium, alkylmorpholinium and alkylpiperidinium, fluoroalkyl-fluorophosphate, fluoroborate and fluoroalkyl-fluoro It may be an ionic liquid in which a fluorine-based anion selected from roborate is ionically bonded.

Compared to hydrogen fluoride or ammonium fluoride commonly used as fluorine-containing compounds in silicon substrate etching solutions, fluorine-containing compounds, which are provided in ionic liquid form, have a high boiling point and decomposition temperature, and are decomposed during etching processes performed at high temperatures. Accordingly, there is an advantage in that there is little fear of changing the composition of the etching solution.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device including an etching process performed using the above-described silicon substrate etching solution.

According to the present manufacturing method, it is possible to manufacture a semiconductor device by performing a selective etching process on the silicon nitride layer using the above-described etching solution on a silicon substrate including at least a silicon nitride layer (SI _x O _y N _z ).

A silicon substrate used for manufacturing a semiconductor device may include a silicon nitride film (SI _x O _y N _z ) or a silicon oxide film and a silicon nitride film (Si _x N _y , SI _x O _y N _z ) at the same time. In addition. In the case of a silicon substrate including a silicon oxide layer and a silicon nitride layer at the same time, a silicon oxide layer and a silicon nitride layer may be alternately stacked or stacked in different regions.

The method of manufacturing a semiconductor device according to the present invention requires selective removal of the silicon nitride film without loss of the silicon oxide film during the device separation process of the flash memory device, the device separation process of the DRAM device, or the diode formation process in the phase change memory device. It can be performed by using the silicon substrate etching solution described above in the process step.

Hereinafter, specific embodiments of the present invention are presented. However, the examples described below are merely for illustrating or explaining the present invention in detail, and the present invention is not limited thereto.

Silicon substrate Etching Composition of the solution

Example One

A silicon substrate etching solution was prepared by mixing 85% by weight of phosphoric acid, 100 ppm of fumed silica, 5,000 ppm of a compound represented by the following Chemical Formula 5, and the remaining amount of water.

[Formula 5]

Example 2

A silicon substrate etching solution was prepared in the same manner as in Example 1, except that the compound represented by Formula 6 was used.

[Formula 6]

Example 3

A silicon substrate etching solution was prepared in the same manner as in Example 1, except that the compound represented by the following Formula 7 was used.

[Formula 7]

Example 4

A silicon substrate etching solution was prepared in the same manner as in Example 1, except that the compound represented by Formula 8 was used.

[Formula 8]

Comparative example One

A silicon substrate etching solution was prepared in the same manner as in Example 1 except that the compound represented by Chemical Formula 5 of Example 1 was not used.

Experimental example

A silicon substrate etching solution having a composition according to each Example and Comparative Example was immersed in a 500 Å-thick silicon oxide layer and a silicon nitride layer in a heated etching solution at 175°C and etched for 10 minutes.

The thickness of the silicon oxide layer and the silicon nitride layer before and after etching was measured using an ellipsometric tree (Nano-View, SE MG-1000; Ellipsometery), and the etching rate was the difference between the thickness of the silicon oxide layer and the silicon nitride layer before and after etching. Is a value calculated by dividing by the etching time (10 minutes).

Etching rates measured using the silicon substrate etching solution with different heating times are shown in Table 1 below.

/min)Silicon oxide film
Etch rate(

/min) Silicon nitride film
Etch rate(

/min) Etch selectivity
(Silicone nitride film etch rate/ Silicon oxide film etch rate) Example 1 1.33 74.11 55.72 Example 2 1.12 67.12 59.93 Example 3 1.34 69.92 52.18 Example 4 1.33 68.98 51.86 Comparative Example 1 2.78 76.91 27.67

As shown in Table 1, the silicon substrate etching solutions of Examples 1 to 4 can lower the etching rate of the silicon oxide layer compared to the silicon substrate etching solution of Comparative Example 1, and thus, the etching of the silicon nitride layer compared to the silicon oxide layer. It can be seen that the selection ratio is improved.

As described above, one embodiment of the present invention has been described, but those of ordinary skill in the relevant technical field add, change, delete or add components within the scope not departing from the spirit of the present invention described in the claims. Various modifications and changes can be made to the present invention by means of the like, and this will also be said to be included within the scope of the present invention.

Claims (10)

Phosphoric acid aqueous solution;
Silicone additives; And
A compound represented by the following formula (1);
Containing,
Silicon substrate etching solution:
[Formula 1]

here,
X ₁ and X ₂ are each independently oxygen, sulfur, or phosphorus,
Y ₁ and Y ₂ are each independently oxygen or sulfur,
R ₁ and R ₂ are each independently selected from alkyl, cycloalkyl, heteroalkyl containing at least one hetero atom, haloalkyl, aminoalkyl, aryl, heteroaryl, aralkyl, benzyl.
The method of claim 1,
The Y ₁ and Y ₂ are characterized in that the same,
Silicon substrate etching solution.
The method of claim 1,
The X ₁ , X ₂ , Y ₁ and Y ₂ are characterized in that the same,
Silicon substrate etching solution.
The method of claim 1,
The X ₁ , X ₂ , Y ₁ and Y ₂ are characterized in that oxygen,
Silicon substrate etching solution.
The method of claim 1,
The R ₁ and R ₂ are each independently selected from C ₁ -C ₂₀ alkyl, CF ₃ , CCl ₃ , CBr ₃ , CI ₃ ,
Silicon substrate etching solution.
The method of claim 1,
The silicone additive is represented by the following formula (2),
Silicon substrate etching solution:
[Formula 2]

here,
R ₁ to R ₄ are each independently hydrogen, C ₁ -C ₁₀ alkyl, C ₆ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ heteroalkyl containing at least one hetero atom, aryl, heteroaryl, aralkyl, Selected from halogen, alkoxy and hydrophilic functional groups.
The method of claim 1,
In the silicon substrate etching solution, the compound is contained in an amount of 100 to 400,000 ppm,
Silicon substrate etching solution.
The method of claim 1,
The silicon substrate etching solution further comprises at least one fluorine-containing compound selected from hydrogen fluoride, ammonium fluoride, ammonium bifluoride, and ammonium hydrogen fluoride,
Silicon substrate etching solution.
The method of claim 1,
The silicon substrate etching solution further comprises a fluorine-containing compound having an ion bonded form of an organic cation and a fluorine anion,
Silicon substrate etching solution.
A method of manufacturing a semiconductor device including an etching process performed using the etching composition according to claim 1.