KR102443313B1 - Insulation layer etchant composition comprising the silane compound and method of forming pattern using the same - Google Patents

Abstract

Embodiments of the present invention provide an insulating film etchant composition including phosphoric acid and a silane compound including a hydroxyalkyl group, and a pattern forming method using the same. When the silane compound according to embodiments of the present invention contains a hydroxyalkyl group, gelation or aggregation phenomenon may be suppressed when added to an aqueous solution.

Description

Insulation layer etchant composition containing silane compound and pattern formation method using the same

The present invention relates to an insulating film etchant composition including phosphoric acid and a silane compound including a hydroxyalkyl group, 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 diode (OLED) display device. and insulating layers such as an interlayer insulating layer, a gate insulating layer, and a via insulating layer that insulate the conductive structures are formed.

Also, in a semiconductor device such as a memory device, insulating films such as an element isolation film, an interlayer insulating film, and a gate insulating film are formed on, for example, a silicon or germanium substrate.

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

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

Accordingly, an additional component may be included in the etchant composition to protect the silicon oxide layer. However, when the additional component has poor compatibility with an acid acting as an etching component, uniform etching characteristics may not be realized due to agglomeration, gelation, etc. as the etching process progresses.

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.

Korean Patent Publication No. 10-0823461

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

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 a pattern forming method using the insulating film etchant composition.

1. Phosphoric acid; And an insulating film etchant composition comprising a silane compound represented by the following Chemical Formula 1:

[Formula 1]

(In Formula 1, R ¹¹ to R ¹³ are each independently an alkoxy group having 1 to 4 carbon atoms, and R ¹⁴ is a hydroxyalkyl group having 1 to 4 carbon atoms)

2. The insulating film etchant composition according to 1 above, wherein the silane compound further comprises a compound represented by the following Chemical Formula 2:

[Formula 2]

(In Formula 2, R ²¹ to R ²⁵ are each independently an alkoxy group having 1 to 4 carbon atoms, R ²⁶ is a hydroxyalkyl group having 1 to 4 carbon atoms, and R ²⁷ is an alkanediyl group having 1 to 4 carbon atoms)

3. The insulating film etchant composition according to the above 1, wherein the silane compound further comprises a compound represented by the following Chemical Formula 3:

[Formula 3]

(In Formula 3, R ³¹ to R ³⁴ are each independently a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms)

4. The insulating film etchant composition of 2 above, wherein the silane compound further comprises a compound represented by the following Chemical Formula 3:

[Formula 3]

(In Formula 3, R ³¹ to R ³⁴ are each independently a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms)

5. In the above 4, the weight ratio of the sum of the weight of the compound represented by Formula 1 and the compound represented by Formula 2 to the weight of the compound represented by Formula 3 is 5:1 to 1:5, insulating film etchant composition .

6. The insulating film etchant composition according to the above 1, wherein the content of the silane compound is 0.0001 to 5% by weight based on the total weight of the composition.

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

Including the step of selectively etching the nitride film using the insulating film etchant composition of any one of 1 to 6 above, the pattern forming method.

8. The method according to 7 above, wherein the oxide layer includes silicon oxide, and the nitride layer includes silicon nitride.

The insulating film etchant composition according to the embodiments of the present invention contains a silane compound including an alkoxy and a hydroxyalkyl group to perform a passivation function on a silicon oxide, for example, a silicon oxide film, thereby exhibiting improved etch selectivity and etch uniformity. can

Since the insulating film etchant composition according to embodiments of the present invention contains a silane compound including a hydroxyalkyl group, gelation or aggregation phenomenon may be suppressed when added to an aqueous solution.

The insulating film etchant composition according to the exemplary embodiments may be effectively used in a selective etching process of the nitride film, in which the silicon nitride film is etched while suppressing the etching of the silicon oxide film.

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

Embodiments of the present invention provide an insulating film etchant composition including phosphoric acid and a silane compound including a hydroxyalkyl group, and a pattern forming method using the same. When the silane compound according to embodiments of the present invention contains a hydroxyalkyl group, gelation or aggregation phenomenon may be suppressed when added to an aqueous solution.

In the present specification, the 'alkoxy group' refers to a monovalent atomic group in which an alkyl group is bonded to oxygen, and may be represented by -OR (R is alkyl). The number of carbon atoms in the alkoxy group is used to refer to the number of carbon atoms in the alkyl group in the alkoxy group, and the alkyl group in the alkoxy group includes straight or branched chains unless otherwise specified.

In the present specification, the 'hydroxyalkyl group' means a monovalent atomic group in a form in which a hydroxyl group is bonded to an alkyl group, for example, one hydrogen in the alkyl group is substituted with a hydroxyl group, and may be represented by -ROH (R silver alkyl). The number of carbon atoms in the hydroxyalkyl group is used to refer to the number of carbon atoms in the alkyl group in the hydroxyalkyl group, and the alkyl group in the hydroxyalkyl group includes straight or branched chains unless otherwise specified. The position of the hydroxy group in the hydroxyalkyl group is not particularly limited.

In the present specification, the 'alkanediyl group' refers to a divalent atomic group in which two hydrogen atoms are removed from an alkane, and may be represented by -C _n H _2n -. Unless otherwise specified, the alkanediyl group includes a straight chain or a branched chain. The alkanediyl group is used to include all cases in which one or more hydrogen atoms are substituted or unsubstituted with other substituents.

In the present specification, regrowth is used to refer to a phenomenon in which etching by-products are aggregated or accumulated on a substrate to be etched, thereby preventing a desired etching shape from being realized.

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

< Insulation film etchant composition>

The insulating film etchant composition according to 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 ¹¹ to R ¹³ may each independently be an alkoxy group having 1 to 4 carbon atoms, and R ¹⁴ may be a hydroxyalkyl group having 1 to 4 carbon atoms.

In an exemplary embodiment, the insulating film etchant composition may be supplied on a structure including an oxide film and a nitride film at the same time to etch only the nitride film with 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 a silicon nitride film in a semiconductor device manufacturing process.

(1) phosphoric acid

Phosphoric acid may be represented by the chemical formula of, for example, H ₃ PO ₄ , and may act as a main etching component for etching the nitride layer. According to exemplary embodiments, the nitride layer etchant composition may include about 80 to about 95 weight % of phosphoric acid, expressed as a weight percent based on the total weight of the composition.

When the content of phosphoric acid is less than about 80% by weight, the overall etching rate may be reduced. When the phosphoric acid content exceeds about 95% by weight, the etching rate for not only the nitride film but also the conductive film such as an oxide film or a metal film may increase, so that the etch selectivity for the nitride film may be lowered.

Preferably, the content of phosphoric acid may be adjusted to about 80 to 90 wt % in consideration of both the etching rate and the selectivity.

(2) silane compound

The insulating film etchant composition may include a silane compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ¹¹ to R ¹³ may each independently be an alkoxy group having 1 to 4 carbon atoms, and R ¹⁴ may be a hydroxyalkyl group having 1 to 4 carbon atoms.

In some embodiments, the alkoxy group may have 1 to 4 carbon atoms. When the number of carbon atoms of the alkoxy group falls within the above range, an oxide film passivation function and a gelation or aggregation prevention function of the insulating film etchant composition may be smoothly performed. Preferably, the carbon number of the alkoxy group may be 1 to 3, more preferably methoxy (-OMe) or ethoxy (-OEt).

In some embodiments, the hydroxyalkyl group may have 1 to 4 carbon atoms. When the number of carbon atoms of the hydroxyalkyl group falls within the above range, the performance of preventing gelation or aggregation of the insulating film etchant composition and the passivation performance of the oxide film may be improved together. In addition, the regrowth inhibitory effect may be enhanced. Preferably, the hydroxyalkyl group may have 1 to 3 carbon atoms, more preferably hydroxymethyl (-Me-OH) or hydroxyethyl (-Et-OH).

In some embodiments, the insulating film etchant composition may further include a silane compound represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2, R ²¹ to R ²⁵ may be each independently an alkoxy group having 1 to 4 carbon atoms, R ²⁶ may be a hydroxyalkyl group having 1 to 4 carbon atoms, and R ²⁷ is an alkanediyl group having 1 to 4 carbon atoms. can

In some embodiments, the alkoxy group may have 1 to 4 carbon atoms. When the number of carbon atoms of the alkoxy group falls within the above range, an oxide film passivation function and a gelation or aggregation prevention function of the insulating film etchant composition may be smoothly performed. Preferably, the carbon number of the alkoxy group may be 1 to 3, more preferably methoxy (-OMe) or ethoxy (-OEt).

In some embodiments, the hydroxyalkyl group may have 1 to 4 carbon atoms. When the number of carbon atoms of the hydroxyalkyl group falls within the above range, the performance of preventing gelation or aggregation of the insulating film etchant composition and the passivation performance of the oxide film may be improved together. In addition, the regrowth inhibitory effect may be enhanced. Preferably, the hydroxyalkyl group may have 1 to 3 carbon atoms, more preferably hydroxymethyl (-Me-OH) or hydroxyethyl (-Et-OH).

In some embodiments, R ²⁷ may be an alkanediyl group having 1 to 4 carbon atoms. Since the two silane-podals are spaced apart through the alkanediyl group having 1 to 4 carbon atoms, the passivation function of the oxide film may be enhanced due to the chelating effect. Preferably, the carbon number of the alkanediyl group may be 1 to 3, more preferably methanediyl or 1,2-ethanediyl.

The silane compound represented by Chemical Formula 1 in the etchant composition may perform a so-called passivation function of protecting the oxide layer while the nitride layer is being etched. The alkoxy group of the silane compound may be substituted with a hydroxyl group through hydrolysis, etc., and the substituted hydroxyl group may form a passivation layer or a barrier to the oxide layer through interaction with silicon oxide. Through the passivation action, the etchant composition may have a high selectivity with respect to the oxide layer.

In addition, the silane compound may suppress the regrowth of silicon oxide by stabilizing the silicon oxide generated during the etching process of the nitride layer.

In some embodiments, an etch by-product may be generated during the silicon nitride layer etching process. When the concentration of the etch by-product in the solution exceeds the solubility, regrowth may occur in which the etch by-product is aggregated or accumulated on the substrate to be etched. In some embodiments, the etching by-product may be silicon oxide.

However, the etchant composition according to an embodiment of the present invention improves the solubility of silicon oxide by stabilizing the silicon oxide in solution through the silane compound represented by Chemical Formula 1, and as a result, suppression of regrowth of silicon oxide and a pattern of a desired shape implementation is possible.

Specifically, the silane compound represented by Formula 1 may form a bond with the silicon oxide through an alkoxy group directly connected to a silicon atom and a hydroxyl group derived from the alkoxy group.

Meanwhile, the silane compound includes a hydroxy group spaced apart from a silicon atom through a hydroxyalkyl group, that is, an alkanediyl group, and thus may exhibit hydrophilicity to water.

As a result, the insulating film etchant composition according to an embodiment of the present invention can improve the solubility of silicon oxide by collecting silicon oxide, which is a by-product of the nitride film etching process, and suppress the regrowth of silicon oxide.

In some embodiments, the insulating film etchant composition may further include a compound represented by Formula 2 above. By simultaneously including the compound represented by Formula 1, which is a single-silanpodal compound, and the compound represented by Formula 2, which is a di-silanpodal compound, the oxide film passivation effect, gelation or aggregation prevention effect, and regrowth inhibitory effect of the insulating film etchant composition are more can be improved

In some embodiments, the insulating film etchant composition may include the compound represented by Formula 1 and the compound represented by Formula 2 in a weight ratio of 10:0 to 1:10. Preferably, the weight ratio of the compound represented by Formula 1 to the compound represented by Formula 2 is 10:1 to 1:10, more preferably 5:1 to 1:5, even more preferably 2:1 to It can be 1:2.

In some embodiments, the insulating film etchant composition may further include a compound represented by Formula 3 below.

[Formula 3]

In Formula 3, R ³¹ to R ³⁴ may be each independently a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms.

In some embodiments, at least one of R ³¹ to R ³⁴ may be an alkoxy group having 1 to 4 carbon atoms. When the number of carbon atoms of the alkoxy group falls within the above range, the oxide film passivation function of the insulating film etchant composition may be smoothly performed. In addition, anti-gelling properties can be improved. Preferably, the alkoxy group may have 1 to 3 carbon atoms, more preferably methoxy (-OMe) or ethoxy (-OEt).

As the insulating film etchant composition further includes the compound represented by Chemical Formula 3, the passivation function for the oxide film, that is, the etch selectivity for the nitride film may be improved.

In some embodiments, the weight ratio of the sum of the weight of the compound represented by Formula 1 and the compound represented by Formula 2 to the weight of the compound represented by Formula 3 ((Formula 1 + Formula 2): (Formula 3) ) may be 5:1 to 1:5. Within the above weight ratio, an oxide film passivation and gelation or aggregation inhibition function of the etchant composition may be uniformly improved.

In some embodiments, the insulating film etchant composition may include about 0.0001 to 5% by weight of the silane compound based on the total weight of the composition. When the content of the silane compound is less than about 0.0001 wt%, the oxide film passivation, that is, the selective etching function may not be substantially implemented. When the content of the silane compound exceeds about 5% by weight, the etching performance of phosphoric acid may be excessively inhibited or stability over time may be deteriorated.

Preferably, in consideration of the oxide film passivation effect and etching uniformity, the content of the silane compound may be adjusted to about 0.01 to 5 wt%, more preferably 0.01 to 1 wt%, based on the total weight of the composition.

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

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 an additional component such as an etch enhancer within a range that does not impair the passivation performance and chronological stability of the silane compound.

In exemplary embodiments, the silane compound represented by Formula 1 may include a compound represented by Formula 4 or 5 below.

[Formula 4]

[Formula 5]

In exemplary embodiments, the silane compound represented by Formula 2 may include a compound represented by Formula 6 or 7 below.

[Formula 6]

[Formula 7]

In exemplary embodiments, the silane compound represented by Formula 3 may include a compound represented by Formula 8 below.

[Formula 8]

<Pattern Forming Method>

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

Referring to FIG. 1 , an oxide layer 110 and a nitride layer 120 may be sequentially formed on a substrate 100 .

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

According to example embodiments, the oxide layer 110 may be formed to include silicon oxide. The oxide layer 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.

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

Referring to FIG. 2 , a photoresist pattern 130 may be formed on the nitride layer 120 . For example, after forming a photoresist layer on the nitride layer 120 , a portion of the photoresist layer 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 layer 120 may be formed.

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

Accordingly, the nitride layer pattern 125 may be formed by removing the exposed portion of the nitride layer 120 . As described above, the insulating film etchant composition according to the exemplary embodiments may stably provide the oxide film passivation significantly improved by the above-described silane compound for a long time. Accordingly, the surface of the oxide layer 110 is not substantially etched or damaged, and only the nitride layer 120 may 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° C. or higher. Thereafter, the photoresist pattern 130 may be removed through a strip process and/or an ashing process.

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

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

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

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

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

Accordingly, the oxide layers 210 may remain on the sidewall of the through pattern 230 , and gaps 240 may be defined by a space from which the nitride layers 220 are removed. A conductive film such as a metal film may be filled in the gaps 240 . The oxide layers 210 may be entirely passivated by the above-described silane compound 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 embodiments of the present invention forms various insulating structures included in a semiconductor device or a display device (eg, a gate insulating film, a barrier film, a device isolation film, etc.) can be applied for

Hereinafter, experimental examples including specific examples and comparative examples are presented to aid understanding of the present invention, but these are merely illustrative of the present invention and do not limit the appended claims, the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope, and it is natural that such variations and modifications fall within the scope of the appended claims.

Example and comparative example

The insulating film etchant compositions of Examples and Comparative Examples were prepared according to the components and contents (parts by weight) of Table 1 below.

silane compound 85% aqueous phosphoric acid solution ingredient content Example 1 A-1 One 100 Example 2 A-1/A-3 0.5/0.5 100 Example 3 A-1/A-5 0.5/0.5 100 Example 4 A-1/A-3/A-5 0.25/0.25/0.5 100 Example 5 A-2/A-4 0.5/0.5 100 Comparative Example 1 A-5 One 100 Comparative Example 2 A'-1 One 100 Comparative Example 3 A'-2 One 100 Comparative Example 4 A'-3 One 100

Specific components listed in Table 1 are as follows. A-1: A silane compound represented by the following formula (4)

[Formula 4]

A-2: a silane compound represented by the following formula (5)

[Formula 5]

A-3: a silane compound represented by the following formula (6)

[Formula 6]

A-4: a silane compound represented by the following formula (7)

[Formula 7]

A-5: a silane compound represented by the following formula (8)

[Formula 8]

A'-1: a silane compound represented by the following formula (9)

[Formula 9]

A'-2: a silane compound represented by the following formula (10)

[Formula 10]

A'-3: a silane compound represented by the following formula (11)

[Formula 11]

Experimental example

(1) Acceptability evaluation

The water solubility of the insulating film etchant composition of Examples and Comparative Examples was evaluated. Specifically, the generation of phase separation was evaluated when 1 g of the insulating film etchant compositions of Examples and Comparative Examples were mixed with 100 g of water at room temperature, stirred at room temperature for 1 minute, and left at room temperature for additional 5 minutes.

<Determination of solubility>

(double-circle): Undissolved polymer was not visually confirmed in the state left at room temperature.

○: Undissolved polymer was not visually confirmed at room temperature, but a small amount of undissolved polymer was visually confirmed when left at room temperature.

×: The undissolved polymer was visually confirmed at room temperature.

(2) Gelation Measurement of prevention properties

The anti-gelling properties of the etchant compositions of Examples and Comparative Examples were evaluated. Specifically, phase separation was evaluated when the insulating film etchant compositions of Examples and Comparative Examples were stirred at room temperature for 1 minute and then left at room temperature for additional 1 minute.

<Determination of solubility>

○: Undissolved polymer was not visually confirmed in a state of being left at room temperature.

△: Undissolved polymer was not visually confirmed at room temperature, but a small amount of undissolved polymer was visually confirmed at room temperature left.

×: The undissolved polymer was visually confirmed at room temperature.

(3) silicone nitride film ( SiN ) Etching rate (Etch Rate: E/R) measurement

A silicon nitride film (SiN) 5000Å thick wafer was cut to a size of 2x2cm ² to prepare a sample, and the sample was immersed in the compositions of Examples and Comparative Examples at a temperature of 160° C. for 3 minutes. Thereafter, after washing and drying with deionized water (DIW), the film thickness was measured with a scanning electron microscope (SEM) to measure the etching rate (Å/min).

(4) silicon oxide film ( SiO ₂ ) Etching rate measurement

A silicon oxide film (SiO ₂ ) A 400 Å-thick wafer was cut to a size of ² ×2 cm 2 to prepare a sample, and the sample was immersed in the compositions of Examples and Comparative Examples described in Table 1 at a temperature of 160° C. for 30 seconds. Thereafter, after washing and drying with deionized water (DIW), the etch rate (Å/min) was measured by measuring the film thickness with an ellipsometer.

(5) According to the number of processed SiO inhibition of regrowth

A SiN substrate was prepared by cutting a silicon nitride film (SiN) 5000 Å thick wafer into a size of 2x5 cm ² , and 5 SiN substrates prepared in each of the compositions of Examples and Comparative Examples were put in 5 sheets each and treated at a temperature of 160° C. for 60 minutes The SiN substrate was removed from each composition. Then, a silicon oxide film (SiO ₂ ) 400Å thick wafer was cut to a size of 2x2cm ² to prepare a specimen, and the sample was immersed in the compositions of Examples and Comparative Examples described in Table 1 at a temperature of 160° C. for 30 seconds. Thereafter, after washing and drying with deionized water (DIW), the film thickness was measured with a scanning electron microscope (SEM) to measure the etching rate (Å/min).

<Regrowth inhibition determination>

SiO ₂ E/R change rate (%) = (SiO ₂ E/R (before processing SiN substrate) - SiO ₂ E/R (after processing SiN substrate)/(SiO ₂ E/R (before processing SiN substrate)) x 100

○: SiO ₂ E/R change rate 30% or less

△: SiO ₂ E/R rate of change greater than 30% and less than or equal to 50%

×: SiO ₂ E/R change rate more than 50%

The evaluation results are shown in Table 2 below.

division receptivity
evaluation gelation
Prevention Selective etching for nitride film according to the number of transactions
SiO regrowth inhibition SiN E/R
(Å/min)
(A) SiO ₂ E/R
(Å/min)
(B) etching
selection fee
(A/B) Example 1 ◎ ○ 117 3.5 34.4 ○ Example 2 ○ ○ 114 2.9 39.3 ○ Example 3 ○ ○ 116 3.0 39.7 ○ Example 4 ○ ○ 112 3.1 38.7 ○ Example 5 ○ ○ 118 3.2 36.9 ○ Comparative Example 1 ○ × 112 0.63 178 △ Comparative Example 2 △ △ 107 4.3 25 △ Comparative Example 3 × × 110 ≤0.1 ≥1000 × Comparative Example 4 ○ × 105 0.7 150 △

Referring to Table 2, in the case of Examples, it can be seen that the gelation prevention performance, the etch selectivity, and the SiO regrowth inhibition performance are generally superior to those of the Comparative Examples.

In the case of Comparative Example 1, the etch selectivity was excellent, but the gelation prevention performance and the SiO regrowth inhibition performance were deteriorated, and in the case of Comparative Example 2, the etch selectivity was very low. In the case of Comparative Example 3, the etching selectivity was excellent, but the water solubility and gelation prevention performance and the SiO regrowth inhibition performance were remarkably low. In the case of Comparative Example 4, water solubility and etch selectivity were excellent, but the gelation prevention performance was remarkably low, and the SiO regrowth inhibition performance was also low.

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

Claims (8)

phosphoric acid; and
An insulating film etchant composition comprising a silane compound represented by the following Chemical Formula 1:
[Formula 1]

(In Formula 1, R ¹¹ to R ¹³ are each independently an alkoxy group having 1 to 4 carbon atoms, and R ¹⁴ is a hydroxyalkyl group having 1 to 4 carbon atoms)
The method according to claim 1, wherein the silane compound further comprises a compound represented by the following formula (2), insulating film etchant composition:
[Formula 2]

(In Formula 2, R ²¹ to R ²⁵ are each independently an alkoxy group having 1 to 4 carbon atoms, R ²⁶ is a hydroxyalkyl group having 1 to 4 carbon atoms, and R ²⁷ is an alkanediyl group having 1 to 4 carbon atoms)
The method according to claim 1, wherein the silane compound further comprises a compound represented by the following formula (3), insulating film etchant composition:
[Formula 3]

(In Formula 3, R ³¹ to R ³⁴ are each independently a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms)
The method according to claim 2, wherein the silane compound further comprises a compound represented by the following formula (3), insulating film etchant composition:
[Formula 3]

(In Formula 3, R ³¹ to R ³⁴ are each independently a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms)
The method according to claim 4, The weight ratio of the sum of the weight of the compound represented by Formula 1 and the compound represented by Formula 2 to the weight of the compound represented by Formula 3 is 5:1 to 1:5, the insulating film etchant composition.
The method according to claim 1, The content of the silane compound is 0.0001 to 5% by weight of the total weight of the composition, the insulating film etchant composition.
forming an oxide film and a nitride film on a substrate; and
Including the step of selectively etching the nitride film using the insulating film etchant composition of any one of claims 1 to 6, a pattern forming method.
The method of claim 7 , wherein the oxide layer includes silicon oxide, and the nitride layer includes silicon nitride.

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