KR20190127049A - Silane compound, insulation layer etchant composition comprising the same and method of forming pattern using the same - Google Patents

Abstract

Embodiments of the present invention provide a silane compound having a specific structure, an etchant composition comprising the same, and a pattern forming method using the same. The silane compound having the specific structure according to embodiments of the present invention can be water-soluble to suppress gelation or aggregation when added to an aqueous solution.

Description

Silane compound, insulating film etching liquid composition comprising the same and pattern formation method using the same {SILANE COMPOUND, INSULATION LAYER ETCHANT COMPOSITION COMPRISING THE SAME AND METHOD OF FORMING PATTERN USING THE SAME}

The present invention relates to a silane compound having a specific structure, an insulating film etchant composition comprising the same, and a pattern forming method using the same. More specifically, the present invention relates to a die-podal silane compound including a hydrophilic group, an inorganic acid-based insulating film etchant composition, and a pattern forming method using the same.

For example, a thin film transistor (TFT) and various pixel circuits are arranged on a back-plane substrate of an image display device such as a liquid crystal display (LCD) device or an organic light emitting display (OLED) display device. Insulating layers, such as an interlayer insulating film, a gate insulating film, a via insulating film, and the like, are formed to insulate the conductive structures.

Also in semiconductor devices such as memory devices, insulating films such as device isolation films, interlayer insulating films, gate insulating films and the like are formed on silicon or germanium substrates, for example.

For example, the insulating layers may be deposited to include silicon oxide or silicon nitride to include a silicon oxide layer and a silicon nitride layer.

When the insulating layer is etched to form an insulation pattern, etching may be selectively performed on a specific layer. For example, a selective etching process for the silicon nitride film may be required. In this case, an etchant composition for etching only the silicon nitride film may be used while sufficiently protecting the silicon oxide film.

Accordingly, additional components may be included in the etchant composition to protect the silicon oxide layer. However, when the additional component is incompatible with the acid acting as an etching component, as the etching process proceeds, uniform etching characteristics may not be realized due to coagulation and gelation.

For example, Korean Patent Publication No. 10-0823461 discloses a composition capable of etching a silicon oxide film and a silicon nitride film together. It is difficult to implement the above-described selective etching process.

Korea Patent Publication No. 10-0823461

One object of the present invention is to provide a silane compound in which gelation or aggregation phenomenon is suppressed when added to an aqueous solution.

One object of the present invention is to provide an insulating film etching liquid composition having improved etching selectivity and etching uniformity.

One object of the present invention is to provide a pattern forming method using the insulating film etching solution composition.

1. Silane compound represented by the following formula (1):

[Formula 1]

(In formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ are each independently an alkanediyl group having 1 to 4 carbon atoms, X , Y are each independently NH, O or S, Z is C, S or P-OR ₅ , R ₅ is an alkyl group having 1 to 4 carbon atoms)

2. In the above 1, wherein the silane compound represented by Formula 1 comprises a compound represented by the following formula 2 to 6, silane compound:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

3. The silane compound according to the above 1, wherein the silane compound is a water-soluble silane compound.

4. The silane compound according to the above 1, wherein the silane compound is mixed with 100 g of water at room temperature at 1 g, and stirred at room temperature for 1 minute, and then left at room temperature for an additional 1 minute.

5. phosphoric acid; And an insulating film etchant composition comprising a silane compound represented by Formula 1 below:

[Formula 1]

(In formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ are each independently an alkanediyl group having 1 to 4 carbon atoms, X , Y are each independently NH, O, or S, Z is C, S or P-OR ₅ , R ₅ is an alkyl group having 1 to 4 carbon atoms)

6. In the above 5, wherein the silane compound represented by Formula 1 comprises a compound represented by the following formula 2 to 6, insulating film etching solution composition:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

7. In the above 5, wherein the content of the silane compound is 0.0001 to 1% by weight of the total weight of the composition, the insulating film etching liquid composition.

8. forming an oxide film and a nitride film on the substrate; And

Selectively etching the nitride film using the insulating film etchant composition of any one of 5 to 7, above, a pattern forming method.

9. The method of claim 8, wherein the oxide film includes silicon oxide and the nitride film includes silicon nitride.

The silane compound having a specific structure according to embodiments of the present invention includes a hydrophilic group, and thus gelation or aggregation may be suppressed when added to an aqueous solution.

The silane compound having a specific structure according to embodiments of the present invention may include a trialkoxysilyl group to perform a passivation function for silicon oxide, for example, silicon oxide film.

The insulating film etchant composition according to the embodiments of the present invention may include a silane compound having a specific structure, thereby improving etching stability while maintaining oxide passivation.

The insulating film etchant composition according to the exemplary embodiments may be effectively used for the selective etching process of the nitride film to etch the silicon nitride film while suppressing the etching of the silicon oxide film.

1 to 3 are schematic cross-sectional views for describing a method of forming a pattern according to example embodiments.
4 through 6 are schematic cross-sectional views for describing a method of forming a pattern according to example embodiments.

Embodiments of the present invention provide silane compounds of specific chemical structures. The silane compound having a specific structure according to the embodiments of the present invention may be water-soluble so that gelation or agglomeration may be suppressed when added to an aqueous solution.

As used herein, the term "Et" is used to mean an ethyl group.

Hereinafter, embodiments of the present invention will be described in detail.

< Silane compound>

The silane compound according to the embodiments of the present invention may include a silane compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ may each independently be an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ may each independently be an alkanediyl group having 1 to 4 carbon atoms. X, Y may be each independently NH, O or S. Z may be C, S or P-OR ₅ , and R ₅ may be an alkyl group having 1 to 4 carbon atoms.

(1-1) trialkoxysilyl group (T-silyl)

The silane compound may include a silyl group including a trialkoxy group (hereinafter referred to as 'T-silyl'). The alkoxy group included in the T-silyl may be substituted with a hydroxy (-OH) group through hydrolysis in an aqueous solution. For example, the substituted hydroxy group may react with the silicon oxide film or the silicon oxide in the solution to form a bond.

Due to the T-silyl, the silane compound according to an embodiment of the present invention may perform a passivation function for protecting an oxide film in a selective etching process for a nitride film described later, and a silicon oxide which is a by-product of the selective etching process for the nitride film. It can also perform a function to stabilize.

In some embodiments, R ₁ and R ₂ may be an alkyl group having 1 to 4 carbon atoms. For example, R ₁ and R ₂ may be each independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl, preferably R At least one of ₁ and R ₂ may be ethyl or propyl, and more preferably both R ₁ and R ₂ may be ethyl.

(1-2) Linker Machine

In some embodiments, the T-silyl may be spaced apart from each other through a linker represented by R ₃ and R ₄ of Formula 1. By the linker, the chelating effect of substantially protecting the silicon oxide layer may be implemented, and thus the silicon oxide layer protection effect may be further increased. In addition, even in high temperature phosphoric acid, decomposition of the silane groups may be suppressed to maintain a uniform etching performance for a long time.

In some embodiments, R ₃ and R ₄ can each independently be an alkanediyl group having 1 to 4 carbon atoms. For example, R ₃ and R ₄ may be each independently selected from the group consisting of methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene and t-butylene, Preferably at least one of R ₁ and R ₂ may be ethylene, propylene or n-butylene, and more preferably both R ₁ and R ₂ may be propylene.

(1-3) hydrophilic group

The silane compound may include a hydrophilic group in the center portion. For example, -XZOY- of Formula 1 may be a hydrophilic group. When the silane compound contains a hydrophilic group in the center, when the silane compound is added to an aqueous solution, gelation or aggregation may be suppressed and water may be provided.

For example, the T-silyl may be substituted with an alkoxy group to a hydroxy group through hydrolysis, and the substituted hydroxy group may exhibit a bond with a silicon oxide, for example, a silicon oxide film. The problem is that the hydroxy group directly connected with the silicon atom may react with other silane compounds, which may cause gelation or aggregation phenomenon, in which the silane compound is not dissolved but aggregates.

However, as the silane compound according to an embodiment of the present invention includes a hydrophilic group, the silane compound may be rapidly dispersed before gelation or aggregation occurs, thereby preventing gelation or aggregation. Therefore, there is an advantage that can be added to a larger amount faster than using a conventional silane compound.

In an exemplary embodiment, the hydrophilic group represented by -XZOY- may include a hydrophilic group represented by the following Chemical Formulas 1-1 to 1-5.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In exemplary embodiments, the silane compound represented by Chemical Formula 1 may include a compound represented by the following Chemical Formulas 2 to 6.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In some embodiments, the silane compound may be selected from water soluble silane compounds. In the present specification, the "water-soluble silane compound" means a silane compound which is mixed with 100 g of water at room temperature by an amount of 1 g of the silane compound, stirred for 1 minute at room temperature, and left for 5 minutes at room temperature, and then no phase separation or particles are observed. . As described above, the silane compound according to the embodiments of the present invention may be water soluble by including a hydrophilic group.

< Insulator etching solution composition>

The insulating film etchant composition according to the embodiments of the present invention may include phosphoric acid and a silane compound represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₂ may each independently be an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ may each independently be an alkanediyl group having 1 to 4 carbon atoms. X, Y may be each independently NH, O or S. Z is C, S or P-OR ₅ , R ₅ may be an alkyl group having 1 to 4 carbon atoms.

For example, R ₁ and R ₂ may be each independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl, preferably R At least one of ₁ and R ₂ may be ethyl or propyl, and more preferably both R ₁ and R ₂ may be ethyl.

For example, R ₃ and R ₄ may be each independently selected from the group consisting of methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene and t-butylene, Preferably at least one of R ₁ and R ₂ may be ethylene, propylene or n-butylene, and more preferably both R ₁ and R ₂ may be propylene.

In an exemplary embodiment, the insulating film etchant composition may be supplied onto a structure including an oxide film and a nitride film at the same time to be used to etch only the nitride film at a high selectivity without substantially damaging the oxide film. For example, the oxide layer may be a silicon oxide layer, and the nitride layer may be a silicon nitride layer.

For example, the insulating film etchant composition may be used to selectively etch the silicon nitride film in the manufacturing process of the semiconductor device.

Phosphoric acid may be represented, for example, by the chemical formula of H ₃ PO ₄ , and may serve as a main etching component for nitride film etching. In example embodiments, the nitride film etchant composition may include about 80 to about 95 wt% of phosphoric acid in terms of weight percent based on the total weight of the composition.

If the content of phosphoric acid is less than about 80% by weight, the overall etching rate may be lowered. When the content of phosphoric acid exceeds about 95% by weight, the etching rate of not only the nitride film but also the conductive film such as the oxide film or the metal film may increase together, thereby reducing the etching selectivity of the nitride film.

Preferably, considering the etching rate and the selection ratio together, the content of phosphoric acid may be adjusted to about 80 to 90% by weight.

The silane compound represented by Chemical Formula 1 in the insulating film etchant composition may perform a so-called passivation function to protect the oxide film while the nitride film is etched. The silane compound contains T-silyl at both ends. The alkoxy group included in the T-silyl may be substituted with a hydroxy (-OH) group through hydrolysis and the like, and the substituted hydroxy group may then form a passivation layer or barrier for the oxide layer through interaction with silicon oxide. have. Through the passivation action, the insulating film etchant composition may have a high selectivity with respect to the oxide film.

In addition, the silane compound may also play a role of encapsulating and stabilizing silicon oxide, which is a nitride film etching product. Silicon oxide may be generated as an etching byproduct of the silicon nitride layer. When the concentration of the silicon oxide in the solution is increased, the reaction of the reaction may be suppressed by the Le Chatelier's Principle or the Equilibrium Law, and the number of sheets of silicon nitride may be reduced. However, the insulating film etchant composition according to the embodiment of the present invention can stabilize the silicon oxide in the solution through the silane compound represented by Chemical Formula 1, thereby maintaining a high number of treatments for the silicon nitride film.

Specifically, the silane compound of Formula 1 may surround silicon oxide through T-silyl at both ends. On the other hand, the silane compound may contain a hydrophilic group and can exhibit water solubility. In this case, as the silicon oxide is collected by the silane compound, the concentration of the free silicon compound in the solution decreases, thereby maintaining a high number of treated sheets for the nitride film.

In addition, the silane compound according to the embodiments of the present invention, the gelation and aggregation phenomenon is suppressed, including the T-silyl at both ends has excellent bonding strength with the oxide film by the chelate effect, high etching selectivity even with a small amount of use You can get it.

In some embodiments, the insulating film etchant composition may include about 0.0001 to 1% by weight of the silane compound in the total weight of the composition. When the content of the silane compound is less than about 0.0001 wt%, oxide passivation may not be substantially implemented. When the content of the silane compound exceeds about 1% by weight, rather, the etching performance of phosphoric acid may be excessively inhibited or the stability over time may deteriorate.

Preferably, in consideration of the oxide passivation effect and etching uniformity, the content of the silane compound may be adjusted to about 0.001 to 1% by weight, more preferably 0.001 to 0.1% by weight of the total weight of the composition.

The insulating film etchant composition may include excess water (eg, deionized water). For example, the phosphoric acid may be provided in the form of an aqueous solution (eg, 85% by weight phosphoric acid), and the silane compound may be mixed in the amount described above with respect to 100 parts by weight of the aqueous solution of phosphoric acid.

In some embodiments, the insulating film etchant composition may be substantially composed of the above-described phosphoric acid, the silane compound, and excess water. In some embodiments, the insulating film etchant composition may include additional components such as an etching enhancer within a range that does not impair passivation performance and stability over time of the silane compound.

<Pattern forming method>

1 to 3 are schematic cross-sectional views for describing a method of forming a pattern according to example embodiments.

Referring to FIG. 1, the oxide film 110 and the nitride film 120 may be sequentially formed on the substrate 100.

The substrate 100 may include a semiconductor material such as monocrystalline silicon, single crystal germanium, or may be formed to include polysilicon.

In example embodiments, the oxide layer 110 may be formed to include silicon oxide. The oxide film 110 may be formed through a chemical vapor deposition (CVD) process, a sputtering process, a physical vapor deposition (PVD) process, an atomic layer deposition (ALD) process, or the like.

The nitride film 130 may be formed on the oxide film 110. In example embodiments, the nitride layer 130 may be formed through a CVD process, a PVD process, a sputtering process, an ALD process, and the like to include silicon nitride.

Referring to FIG. 2, a photoresist pattern 130 may be formed on the nitride film 120. For example, after the photoresist film is formed on the nitride film 120, a portion of the photoresist film may be removed through a selective exposure process and a developing process.

Accordingly, the photoresist pattern 130 exposing a portion of the upper surface of the nitride film 120 may be formed.

Referring to FIG. 3, a wet etching process using the photoresist pattern 130 as an etching mask and using an insulating film etchant composition according to the exemplary embodiments described above may be performed.

Accordingly, the exposed nitride layer 120 may be removed to form the nitride layer pattern 125. As described above, the insulating film etchant composition according to the exemplary embodiments may stably provide the oxide passivation significantly improved by the silane compound described above for a long time. Therefore, the surface of the oxide film 110 is not substantially etched or damaged, and only the nitride film 120 can be selectively etched.

For the efficiency of the etching process, the temperature of the etchant composition may be heated to a temperature of about 150 ℃ or more. The photoresist pattern 130 may then be removed through a strip process and / or an ashing process.

1 to 3, the nitride film 120 may be partially etched, but the nitride film 120 may be entirely removed using the etchant composition. Even in this case, the entire upper surface of the oxide film 110 may be passivated entirely by the silane compound described above to be protected from etching damage.

4 through 6 are schematic cross-sectional views for describing a method of forming a pattern according to example embodiments.

Referring to FIG. 4, a plurality of oxide layers 210 and a plurality of nitride layers 220 may be alternately repeatedly stacked on the substrate 200.

Referring to FIG. 5, a through pattern 230 penetrating the oxide films 210 and the nitride films 220 may be formed. For example, after the oxide layers 210 and the nitride layers 220 are etched together through dry etching to form an opening, a through pattern 230 may be formed by filling a filling material in the openings. The through pattern 230 may include a semiconductor material such as polysilicon or a conductive material such as a metal.

Referring to FIG. 6, the nitride layers 220 may be selectively removed using the etchant composition according to the exemplary embodiments described above.

Accordingly, the oxide layers 210 may remain on the sidewall of the through pattern 230, and the gaps 240 may be defined by the space from which the nitride layers 220 are removed. The gaps 240 may be filled with a conductive film, for example, a metal film. The oxide layers 210 may be passivated entirely by the silane compound described above during the etching process to be protected from etching damage.

The above-described pattern forming method is exemplary, and the insulating film etchant composition according to the embodiments of the present invention may be used to form various insulating structures (eg, gate insulating film, barrier film, device isolation film, etc.) included in a semiconductor device or a display device. Can be applied for

Hereinafter, an experimental example including specific examples and comparative examples is provided to help understanding of the present invention, which is intended to illustrate the present invention, but not to limit the appended claims, and the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications to the embodiments can be made within the scope, and such variations and modifications are within the scope of the appended claims.

<Production of Silane Compound>

Synthesis Example 1

20.0 g of (triethoxysilyl) methyl carbamate and 16.4 g of (triethoxysilyl) methanol were added to a three neck wide bottom flask. The mixture was purified by distillation under reduced pressure to obtain 0.3 g of bis ((triethoxysilyl) methyl) carbonate of the following Chemical Formula 2.

[Formula 2]

1H-NMR analysis was performed on Chemical Formula 2. NMR analysis results are shown in Table 1 below. In Table 1 below, the number means the carbon atom marked with the corresponding number of the formula (2).

The same NMR analysis was performed in Synthesis Examples 1 to 5 below.

number ppm Hydrogen count offshoot One 1.21 18 t 2 3.78 12 q 3 3.25 4 s

Synthesis Example  2

20.0 g of 3- (triethoxysilyl) propan-1-amine, 17.6 g of (triethoxysilyl) methanol, 10.5 g of urea, and 52.0 g of Potassium carbonate were added to a three neck wide bottom flask, and the reaction mixture was stirred for 24 hours, and the reaction was terminated. . The mixture was purified by distillation under reduced pressure to obtain 0.3 g of (triethoxysilyl) methyl (3- (triethoxysilyl) propyl) carbamate of Chemical Formula 3 below.

[Formula 3]

The NMR analysis of the compound is shown in Table 2 below.

number ppm Hydrogen count offshoot One 1.21 18 t 2 3.78 12 q 3 0.59 2 t 4 1.58 2 m 5 2.94 2 m 6 3.41 2 s 7 7.55 One s

Synthesis Example  3

20.0 g of 3- (triethoxysilyl) propan-1-amine and 100 g of dichloromethane were added to a three neck wide bottom flask and cooled to 0 ° C. 22.4 g of triethoxy (3-isocyanatopropyl) silane and 100 g of dichloromethane were slowly added dropwise to the cooled flask. After the addition, the mixture was stirred under reflux for 8 hours and the reaction was terminated. The mixture was concentrated under reduced pressure to give 39.9 g of the title compound 1,3-bis (3- (triethoxysilyl) propyl) urea.

[Formula 4]

The NMR analysis of the compound is shown in Table 3 below.

number ppm Hydrogen count offshoot One 1.21 18 t 2 3.78 12 q 3 0.59 4 t 4 1.58 4 m 5 2.88 4 m 6 6.00 2 s

Synthesis Example  4

Into a three neck wide bottom flask, 8.4 g of ethyl phosphorodichloridate, 60 g of dichloromethane, and 9.4 g of triethylamine were added and cooled to 0 ° C. 20.0 g of triethoxysilyl methanol and 100 g of dichloromethane were slowly added dropwise to the cooled flask. After dropping, the mixture was stirred for 5 hours at room temperature and the reaction was terminated. The mixture was washed with distilled water and concentrated under reduced pressure to obtain 44.3 g of the title compound ethyl bis ((triethoxysilyl) methyl) phosphate.

[Formula 5]

The NMR analysis of the compound is shown in Table 4 below.

number ppm Hydrogen count offshoot One 1.22 18 t 2 3.75 12 q 3 3.33 4 d 4 3.89 2 q 5 1.25 3 t

Synthesis Example  5

7.4 g of ethyl phosphorodichloridate, 60 g of dichloromethane, and 8.3 g of triethylamine were added to a three neck wide bottom flask and cooled to 0 ° C. 20.0 g of 3- (triethoxysilyl) propan-1-amine and 60 g of dichloromethane were slowly added dropwise to the cooled flask. After dropping, the mixture was stirred for 5 hours at room temperature and the reaction was terminated. The mixture was washed with distilled water, and then concentrated under reduced pressure to obtain 46.1 g of the compound represented by Chemical Formula 6.

[Formula 6]

The NMR analysis of the compound is shown in Table 5 below.

number ppm Hydrogen count offshoot One 1.21 18 t 2 3.78 12 q 3 0.59 4 m 4 1.58 4 m 5 2.89 4 m 6 3.98 2 m 7 1.27 3 q 8 2.52 2 q

Example  And Comparative example (One)

Example  1, manufacture

The insulating film etchant composition of Example 1 was prepared by mixing 0.05 parts by weight of the compound of Synthesis Example 1 with respect to 100 parts by weight of an aqueous solution of 85% by weight phosphoric acid.

(2) Preparation of Example 2

The insulating film etchant composition of Example 2 was prepared by mixing 0.05 parts by weight of the compound of Synthesis Example 2 with respect to 100 parts by weight of an aqueous 85% by weight phosphoric acid solution.

(3) Preparation of Example 3

The insulating film etchant composition of Example 3 was prepared by mixing 0.05 parts by weight of the compound of Synthesis Example 3 with respect to 100 parts by weight of an aqueous 85% by weight phosphoric acid solution.

(4) Preparation of Example 4

The insulating film etchant composition of Example 4 was prepared by mixing 0.05 parts by weight of the compound of Synthesis Example 4 with respect to 100 parts by weight of an aqueous solution of 85 wt% phosphoric acid.

(5) Preparation of Example 5

An insulating film etchant composition of Example 5 was prepared by mixing 0.05 parts by weight of the compound of Synthesis Example 5 with 100 parts by weight of an aqueous solution of 85 wt% phosphoric acid.

(6) Preparation of Comparative Example 1

An insulating film etchant composition of Comparative Example 1 was prepared by mixing 1 part by weight of a compound represented by the following Formula 7 with respect to 100 parts by weight of an 85% by weight aqueous solution of phosphoric acid.

[Formula 7]

(7) Preparation of Comparative Example 2

An insulating film etchant composition of Comparative Example 2 was prepared by mixing 0.05 parts by weight of a compound represented by the following Formula 8 with respect to 100 parts by weight of an aqueous 85% by weight phosphoric acid solution.

[Formula 8]

(8) Preparation of Comparative Example 3

An insulating film etchant composition of Comparative Example 3 was prepared by mixing 1 part by weight of a compound represented by the following Formula 9 with respect to 100 parts by weight of an 85% by weight aqueous solution of phosphoric acid.

[Formula 15]

Experimental Example

(1) Water solubility evaluation

The water solubility of the insulating film etching liquid composition of an Example and a comparative example was evaluated. Specifically, 1 g of the insulating film etchant composition of Examples and Comparative Examples was mixed with 100 g of water at room temperature, and stirred for 1 minute at room temperature, and then left for 5 minutes at room temperature to evaluate whether phase separation was generated.

Solubility determination

(Double-circle): Undissolved polymer is not visually recognized in the state of normal temperature standing.

(Circle): Undissolved polymer is not visually recognized at room temperature, but a small amount of undissolved polymer is visually confirmed at room temperature.

(Triangle | delta): A small amount of undissolved polymer is visually recognized in a normal temperature state.

X: Undissolved at normal temperature, the polymer is visually confirmed.

(2) Evaluation of gelation prevention property (phosphate compatibility)

The gelation prevention properties of the etching liquid compositions of Examples and Comparative Examples were evaluated. Specifically, when the insulating film etchant composition of the Examples and Comparative Examples were stirred at room temperature for 1 minute, and then left at room temperature for 1 minute, the separation of the phases was evaluated.

Solubility determination

(Double-circle): Undissolved polymer is not visually recognized in the state of normal temperature standing.

(Circle): Undissolved polymer is not visually recognized at room temperature, but a small amount of undissolved polymer is visually confirmed at room temperature.

(Triangle | delta): A small amount of undissolved polymer is visually recognized in a normal temperature state.

X: Undissolved at normal temperature, the polymer is visually confirmed.

(3) Silicon Nitride (SiN) Etch Rate (E / R) Measurement

A sample was prepared by cutting a silicon nitride film (SiN) 5000 mm thick wafer into a size of ² × ² cm ² , and the sample was immersed in the compositions of Examples and Comparative Examples at a temperature of 160 ° C. for 3 minutes. Then, after washing and drying with deionized water (DIW), the film thickness was measured by scanning electron microscope (SEM) to measure the etching rate (Å / min).

(4) silicon oxide film (SiO ₂ ) Etch Speed Measurement

A silicon oxide film (SiO ₂ ) 400 mm thick wafer was cut into a size of ² × ² cm ² , and a sample was prepared. Then, after washing and drying with deionized water (DIW), the film thickness was measured with an ellipsometer to measure the etching rate (속도 / min).

The evaluation results are shown in Table 6 below.

division Water solubility evaluation Gel
Prevention SiN E / R
(Å / min)
(A) SiO ₂ E / R
(Å / min)
(B) Etching
Selectivity
(A / B) Example 1 △ ○ 113 ≤0.1 ≥1000 Example 2 △ ○ 117 ≤0.1 ≥1000 Example 3 △ ○ 114 ≤0.1 ≥1000 Example 4 ○ ○ 115 ≤0.1 ≥1000 Example 5 ○ ○ 113 ≤0.1 ≥1000 Comparative Example 1 ○ × 112 0.63 178 Comparative Example 2 × × 110 ≤0.1 ≥1000 Comparative Example 3 ○ △ 107 4.3 25

Referring to Table 6, in the case of using the silane compound containing a di-silane ford and a hydrophilic group, the gelation or aggregation phenomenon was suppressed, it was possible to obtain an experimental result of maintaining a high level of etching selectivity for the nitride film In Comparative Example 1 in which tetraethoxysilane, a mono-silanepodal, was used, a low etching selectivity for the nitride film was measured because it did not exhibit sufficient passivation effect on the oxide film.

In Comparative Example 2 in which a di-podalsilane compound containing no hydrophilic group was used, the etching selectivity with respect to the nitride film was excellent, but a problem in which gelation or aggregation occurred was observed.

In Comparative Example 3 including a single-podal and an amine group, the gelation or aggregation phenomenon including the hydrophilic group was suppressed, but it did not form a sufficient passivation layer for the oxide film, resulting in a low etching selectivity for the nitride film.

100, 200: substrate 110, 210: oxide film
120 and 220: nitride film 130: photoresist pattern
230: through pattern

Claims (9)

Silane compounds represented by the following formula (1):
[Formula 1]

(In formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ are each independently an alkanediyl group having 1 to 4 carbon atoms, X , Y are each independently NH, O or S, Z is C, S or P-OR ₅ , R ₅ is an alkyl group having 1 to 4 carbon atoms) The silane compound of claim 1, wherein the silane compound represented by Chemical Formula 1 comprises a compound represented by the following Chemical Formulas 2 to 6.
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

The silane compound of claim 1, wherein the silane compound is a water-soluble silane compound. The silane compound according to claim 1, wherein the silane compound is selected from compounds having no phase separation when 1 g is mixed with 100 g of water at room temperature, and stirred at room temperature for 1 minute and then left at room temperature for 1 minute. Phosphoric acid; And
An insulating film etching liquid composition comprising a silane compound represented by Formula 1 below:
[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ are each independently an alkanediyl group having 1 to 4 carbon atoms, X , Y are each independently NH, O, or S, Z is C, S or P-OR ₅ , R ₅ is an alkyl group having 1 to 4 carbon atoms) The method of claim 5, wherein the silane compound represented by Formula 1 comprises a compound represented by the following formula 2 to 6, insulating film etching solution composition:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

The method of claim 5, wherein the content of the silane compound is 0.0001 to 1% by weight of the total weight of the composition, the insulating film etching liquid composition. Forming an oxide film and a nitride film on the substrate; And
Selectively etching the nitride film using the insulating film etchant composition according to any one of claims 5 to 7. The method of claim 8, wherein the oxide film comprises silicon oxide and the nitride film comprises silicon nitride.

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