TWI691582B - Composition for etching - Google Patents

Abstract

The disclosure is related to a composition for etching, a method for manufacturing the composition, and a method for fabricating a semiconductor using the same. The composition may include a first inorganic acid, at least one of silane inorganic acid salts produced by reaction between a second inorganic acid and a silane compound, and a solvent. The second inorganic acid may be at least one selected from the group consisting of a sulfuric acid, a fuming sulfuric acid, a nitric acid, a phosphoric acid, and a combination thereof.

Description

Etching composition

The present invention relates to a composition for an etching process, and more specifically, to a highly selective etching composition and a method for preparing a semiconductor using the etching composition, the composition can selectively remove a nitride layer while enabling an oxide layer The etching speed is minimized.

In preparing semiconductors, oxide layers and nitride layers have been used as insulating layers. The oxide layer may include a silicon dioxide (SiO ₂ ) layer, and the nitride layer may include a silicon nitride (SiN ₂ ) layer. The silicon dioxide layer and the silicon nitride (SiN ₂ ) layer are used independently or alternately stacked on top of each other as an insulating layer. In addition, the oxide layer and the nitride layer can be used as a hard mask for forming conductive patterns of metal interconnections.

A wet etching process can be performed to remove this nitride layer. Generally, as an etching composition, a mixture of phosphoric acid and deionized water is used to remove the nitride layer. Deionized water can be added to prevent the deterioration of etching speed and the change of etching selectivity. However, even a small change in the amount of deionized water supplied may cause defects in the etching process to remove the nitride layer. In addition, because phosphoric acid is strongly acidic and corrosive or caustic, it is difficult to handle phosphoric acid.

In order to overcome this defect of the conventional etching composition, an etching composition containing phosphoric acid (H ₃ PO ₄ ) mixed with one of hydrofluoric acid (HF) and nitric acid (HNO ₃ ) is proposed. However, this etching composition deteriorates the etching selectivity of the nitride layer and the oxide layer. Another etching composition containing phosphoric acid and one of silicate and silicic acid is proposed. However, silicate and silicic acid produce particles that seriously affect the substrate.

This overview is provided for the selection of concepts in a simplified form, which is further described in the detailed description below. The purpose of this summary is not to determine the key or essential characteristics of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

The embodiments of the present invention overcome the disadvantages described above and other disadvantages not described above. In addition, the embodiment of the present invention does not need to overcome the disadvantages described above, and the embodiment of the present invention may not overcome any of the problems described above.

According to one of the present embodiments, there is provided an etching composition which selectively removes the nitride layer and minimizes the etching rate of the oxide layer.

According to one of the embodiments, there is provided an etching composition with high selectivity, which is used to prevent the generation of particles during the etching process.

According to one of the present embodiments, there is provided a semiconductor preparation method using a highly selective etching composition having selective removal of a nitride layer while minimizing the etching rate of an oxide layer.

其中，R¹至R⁴中的每一個選自氫、鹵素、(C₁-C₁₀)烷基、(C₁-C₁₀)烷氧基和(C₆-C₃₀)芳基，並且R¹至R⁴中的至少一個為鹵素和(C₁-C₁₀)烷基中的一種。 According to at least one embodiment, the composition may include a first inorganic acid, at least one silicate inorganic acid salt generated by a reaction between the second inorganic acid and the silane compound, and a solvent. The second inorganic acid may be at least one selected from sulfuric acid, fuming sulfuric acid, nitric acid, phosphoric acid, anhydrous phosphoric acid, and combinations thereof. The silane compound may be a compound represented by the first chemical formula:

Wherein each of R ¹ to R ⁴ is selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl, and R At least one of ¹ to R ⁴ is one of halogen and (C ₁ -C ₁₀ ) alkyl.

According to another embodiment, the composition may include a first inorganic acid, at least one silicate inorganic acid salt generated by a reaction between polyphosphoric acid and a silane compound, and a solvent.

According to another embodiment, the composition may include a first inorganic acid, at least one silicate inorganic acid salt generated by a reaction between the second inorganic acid and the siloxane compound, and a solvent. The second inorganic acid may be one selected from phosphoric acid, anhydrous phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof.

According to another embodiment, the composition may include a first inorganic acid, at least one silicate inorganic acid salt generated by a reaction between the second inorganic acid and the siloxane compound, and a solvent. The second inorganic acid may be one selected from sulfuric acid, fuming sulfuric acid, and combinations thereof.

According to another embodiment, the composition may include a first inorganic acid, at least one silicate inorganic acid salt generated by a reaction induced between a second inorganic acid including nitric acid and a siloxane compound, and a solvent.

，以及其中，第十一化學式為：

According to another embodiment, the composition may include a first inorganic acid, at least one silicate mineral acid salt generated by a reaction induced between the second inorganic acid and the first silane compound, a second silane compound, and a solvent. The second inorganic acid may be one selected from sulfuric acid, fuming sulfuric acid, nitric acid, phosphoric acid, anhydrous phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof. The first silane compound and the second silane compound may be one selected from the compound represented by the tenth chemical formula, the compound represented by the eleventh chemical formula, and combinations thereof. The tenth chemical formula is:

, And among them, the eleventh chemical formula is:

Wherein, i) each of R ¹ to R ¹⁰ is selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl, ii) at least one of R ¹ to R ⁴ is one of halogen and (C ₁ -C ₁₀ ) alkoxy, iii) at least one of R ⁵ to R ¹⁰ is halogen and (C ₁ -C ₁₀ ) alkane One of the oxygen groups, iv) n is an integer from 1 to 10.

According to another embodiment, a method for manufacturing a semiconductor device is provided. The method may include performing an etching process using the etching composition.

10‧‧‧ base

11‧‧‧ Tunnel oxide column

12‧‧‧polysilicon layer

13‧‧‧buffer oxide layer

14‧‧‧Nitride pad

15‧‧‧SOD oxide layer

15A‧‧‧Component isolation layer

20‧‧‧ base

21‧‧‧Tunnel oxide layer

22‧‧‧polysilicon layer

23‧‧‧buffer oxide layer

24‧‧‧Nitride pad

25‧‧‧groove

26‧‧‧ oxide layer

26A‧‧‧Isolation layer

30‧‧‧ base

31‧‧‧Tube gate electrode layer

31A‧‧‧The first conductive layer

31B‧‧‧Second conductive layer

32‧‧‧Nitride layer

33‧‧‧ First interlayer insulating layer

34‧‧‧ First gate electrode layer

35‧‧‧Nitride layer

36‧‧‧Sacrifice

37‧‧‧Second interlayer insulating layer

38‧‧‧Second gate electrode layer

40‧‧‧ base

41‧‧‧conductive area

42‧‧‧polysilicon layer

43‧‧‧Titanium silicide layer

44‧‧‧Titanium nitride layer

45‧‧‧Nitride layer

46‧‧‧Oxide layer

H1~H4‧‧‧First hole

H2‧‧‧Second hole

H3‧‧‧The third hole

H4‧‧‧Fourth hole

H5, H6‧‧‧ Tunnel hole

H7‧‧‧Tunnel hole

CGS‧‧‧unit gate structure

SGS‧‧‧Select gate structure

S‧‧‧Groove

The above and/or other aspects of the invention will become apparent and easier to understand from the following description of the embodiments in conjunction with the drawings.

1A and 1B show the device isolation process of the flash memory device.

2A to 2C are cross-sectional views illustrating a device isolation process of a flash memory device according to at least one embodiment.

3A to 3F are cross-sectional views illustrating a process of forming a channel of a flash memory device according to at least one embodiment.

4A and 4B are cross-sectional views illustrating a process of forming a diode of a phase change memory device according to at least one embodiment.

5 is an image showing nuclear magnetic resonance (NMR) data of the silane inorganic acid salt prepared according to the first embodiment A.

The embodiments of the present invention will now be described in detail. The embodiments of the present invention are illustrated in the drawings, in which the same drawing symbols refer to the same elements throughout. In order to explain the present invention with reference to the drawings, the embodiments will be described below.

The drawings need not be to scale, and in some cases, the scale may have been enlarged to clearly illustrate the features of the embodiment. When referring to the first layer being "on" the second layer or "on" the substrate, it does not only mean that the first layer is formed directly on the second layer or substrate, but also means that the third layer is present on the first Between the layer and the second layer or substrate.

In the specification, the term "(C ₁ -C ₁₀ )alkyl" refers to a linear or branched acyclic saturated hydrocarbon having 1 to 10 carbon atoms, and the term "(C ₁ -C ₁₀ )alkoxy" refers to Straight-chain or branched non-cyclic hydrocarbons having more than one ether group and 1 to 10 carbon atoms.

According to at least one embodiment, the etching composition may include the first Organic acid, at least one silane inorganic acid salt and solvent. The at least one silane inorganic acid salt may be generated by the reaction between the second inorganic acid and the silane compound.

In preparing a semiconductor device according to at least one embodiment, the at least one silane inorganic acid salt contained in the etching composition can easily and effectively control the etching rate of the oxide layer, and can also easily control the effective field oxide height (EFH).

Hereinafter, such an etching composition according to at least one embodiment will be described with reference to the drawings. Before describing the etching composition according to at least one embodiment, the conventional use of the etching composition in preparing a semiconductor device will be described with reference to FIGS. 1A to 1B.

1A and 1B show the device isolation process of the flash memory device. Referring to FIG. 1A, a tunnel oxide file 11 (tunnel oxide file 11 ), a polysilicon layer 12, a buffer oxide layer 13 and a nitride pad layer 14 are sequentially formed on the substrate 10. At least one trench is formed by selectively etching the polysilicon layer 12, the buffer oxide layer 13, and the nitride pad layer 14. A gap filling process for filling at least one trench is performed by forming an SOD (Spin-on Dielectric; Dielectric Spin On) oxide layer 15. Then, a chemical mechanical polishing (CMP) process may be performed using the nitride pad layer 14 as a polishing stop layer.

Referring to FIG. 1B, the nitride pad layer 14 is removed by performing a wet etching process using a phosphoric acid solution. The buffer oxide layer 13 is removed through the cleaning process. Therefore, the element isolation layer 15A is formed. However, when a phosphoric acid solution is used in the wet etching process, the etching selectivity of the nitride layer and the oxide layer decreases. Due to this reduction, the SOD oxide layer 15 will be together with the nitride pad layer 14 Remove, and it is difficult to control the effective field oxide height (EFH). Therefore, due to the phosphoric acid solution, it is difficult to i) ensure sufficient time for the wet etching to remove the nitride pad layer 14, ii) an additional process may be required, and iii) the phosphoric acid solution causes fluctuations that seriously affect device performance.

Therefore, in order to selectively etch the nitride layer with respect to the oxide layer without generating particles, a highly selective etching composition is required.

In order to overcome the defects of the conventional etching composition and meet the needs, according to at least one embodiment, a highly selective etching composition is provided that selectively removes the nitride layer while minimizing the etching rate of the oxide layer . The etching composition may include a first inorganic acid, at least one silane inorganic acid salt, and a solvent. According to at least one embodiment, the at least one silane inorganic acid salt can be generated by the reaction between the second inorganic acid and the silane compound.

Due to the at least one silane inorganic acid salt contained in the etching composition, the etching rate of the oxide layer can be easily and effectively controlled. Therefore, in manufacturing a semiconductor device according to at least one embodiment, the effective field oxide height (EFH) can be easily and effectively controlled.

As described above, the at least one silane inorganic acid salt may be generated by repeated and continuous reactions between the second inorganic acid and the silane compound. Therefore, the at least one silane inorganic acid salt may include various chemical formulas instead of having a single chemical formula.

The second inorganic acid may be one selected from sulfuric acid, fuming sulfuric acid, nitric acid, phosphoric acid, anhydrous phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof. Preferably, the second inorganic acid may be sulfuric acid, nitric acid and phosphoric acid Kind of.

The silane compound may be one selected from compounds represented by the following chemical formulas A1 to A2 and combinations thereof.

In the chemical formula A1, each of R ¹ to R ⁴ may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl base. In addition, at least one of R ¹ to R ⁴ may be one of halogen and (C ₁ -C ₁₀ )alkyl.

The halogen may include fluorine, chlorine, bromine and iodine. Preferably, the halogen may be one of fluorine and chlorine.

Specifically, the silane compound represented by the chemical formula A1 may include a halosilane compound and an alkoxysilane compound.

The halogenated silane compound may be selected from trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, trimethylfluorosilane, triethylfluorosilane, tripropylfluorosilane, dimethyldichlorosilane , Diethyldichlorosilane, dipropyldichlorosilane, dimethyldifluorosilane, diethyldifluorosilane, dipropyldifluorosilane, ethyltrichlorosilane, propyltrichlorosilane, methyl Trifluorosilane, ethyl trifluorosilane, propyl trifluorosilane, and combinations thereof.

The alkoxysilane compound may be selected from tetramethoxysilane, tetrapropoxysilane, methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), methyltripropoxysilane , Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, propyltrimethoxysilane (PrTMOS), propyltriethoxysilane (PrTEOS), propyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, Diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropylene Oxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane Silane, tripropylmethoxysilane, tripropylethoxysilane, tripropylpropoxysilane, 3-chloropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, [3-(2-aminoethyl)aminopropyl]trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-propenyl propyl propyl trimethoxy silane and their combination.

In the chemical formula A2, each of R ⁵ to R ¹⁰ may be selected from hydrogen, halogen, (C ₁ -C ₁₀ ) alkyl, (C ₁ -C ₁₀ ) alkoxy, and (C ₆ -C ₃₀ ) aryl base. In addition, at least one of R ⁵ to R ¹⁰ may be one of halogen and (C ₁ -C ₁₀ ) alkoxy, and n is an integer of 1 to 10.

The halogen may include fluorine, chlorine, bromine and iodine. Preferably, the halogen may be one of fluorine and chlorine.

Specifically, the compound represented by Chemical Formula A2 may include chlorodimethylsiloxy-chlorodimethylsilane, chlorodiethylsiloxy-chlorodimethylsilane, dichloromethylsiloxy-chlorodimethyl Silane, dichloroethylsiloxy-chlorine Dimethylsilane, trichlorosiloxy-chlorodimethylsilane, fluorodimethylsiloxy-chlorodimethylsilane, difluoromethylsiloxy-chlorodimethylsilane, trifluorosiloxy -Chlorodimethylsilane, methoxydimethylsilyloxy-chlorodimethylsilane, dimethoxydimethylsilyloxy-chlorodimethylsilane, trimethoxysilyloxy-chlorodimethyl Silane, ethoxydimethylsiloxy-chlorodimethylsilane, diethoxymethylsiloxy-chlorodimethylsilane, triethoxysiloxy-chlorodimethylsilane, chlorine Dimethylsiloxy-dichloromethylsilane, trichlorosiloxy-dichloromethylsilane, chlorodimethylsiloxy-trichlorosilane, dichloromethylsiloxy-trichlorosilane and trichlorosilane Chlorosiloxy-trichlorosilane.

The silane inorganic acid salt can be added by i) a silane compound to the second inorganic acid, and ii) within a temperature range of about 20°C to about 300°C, preferably, about 50°C to about 200°C The reaction is generated within the temperature range. This process is carried out while removing air and moisture. When the reaction temperature is lower than about 20°C, the silane compound will crystallize or evaporate due to the relatively low reaction rate. When the reaction temperature is higher than about 300°C, the second inorganic acid evaporates.

For example, about 100 parts by weight of the second inorganic acid may be reacted with about 0.001 to about 50 parts by weight of the silane compound. Preferably, about 0.01 to about 30 parts by weight of the silane compound can be reacted with about 100 parts by weight of the second inorganic acid. When the content of the silane compound is less than about 0.01 parts by weight, it is difficult to obtain desired selectivity. When the content of the silane compound is greater than about 50 parts by weight, the silane compound may crystallize and form an irregular structure.

During the reaction, volatile by-products are produced. This volatile by-product can be removed by distillation under reduced pressure. The reaction product can be distilled and Separate the silane inorganic acid salt from it. The separated silicate inorganic acid salt is added to the etching composition. However, this embodiment is not limited to this. For example, the reaction product may be added to the etching composition without distillation.

This reaction can be carried out with or without an aprotic solvent. When an aprotic solvent is used, it is preferred to use a solvent or solvent mixture having a boiling point of up to 120°C at 10013 mbar. This solvent may include: i) dioxane, tetrahydrofuran, diethyl ether, diisopropyl ether, diethylene glycol monomethyl ether; ii) chlorinated hydrocarbons, such as dichloromethane, chloroform, tetrachloromethane, 1, 2-dichloroethane and trichloroethylene; iii) hydrocarbons such as pentane, n-hexane, hexane isomer mixtures, heptane, octane, benzene, petroleum ether, benzene, toluene and xylene; iv ) Ketones, such as acetone, methyl ethyl ketone, diisopropyl ketone, and methyl isobutyl ketone (MIBK); v) esters, such as ethyl acetate, butyl acetate, propyl propionate, ethyl butyrate, Ethyl isobutyrate, carbon disulfide, and nitrobenzene; and combinations thereof.

As described above, the silane inorganic acid salt is generated by inducing a reaction between the second inorganic acid and the silane compound. Therefore, according to at least one embodiment, the silane inorganic acid salt has a different chemical formula. That is, the silane inorganic acid salt may be generated by repeated and continuous reaction between the second inorganic acid and the silane compound. Depending on the number of halogen atoms and the position of the halogen atoms, the silane inorganic acid salt may have a plurality of linear or branched chemical formula structures that can react.

This silane inorganic acid salt can be exemplified by the following chemical formula. However, this embodiment is not limited to this.

In the chemical formulas A3-1 to A3-7, A4-1 to A4-7 and A5-1 to A5-7, each of R ^1-1 to R ^1-8 may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl. The halogen may include fluorine, chlorine, bromine and iodine. Preferably, the halogen may be one of fluorine and chlorine.

Based on the total weight of the etching composition, the content of the silane inorganic acid salt is about 0.01 to about 15 wt%, more preferably about 0.05 to about 15 wt%, even more preferably about 1 to about 15 wt%, even more preferably about 3 to about 7 wt% %.

When the content of the silane inorganic acid salt is less than about 0.01 wt%, a high etching selectivity of the nitride layer cannot be achieved. When the content of the silane inorganic acid salt is higher than about 15 wt%, the increase in the content does not cause a further increase in etching selectivity and causes problems such as generation of particles.

For example, when the content of the silicate inorganic acid salt is higher than about 0.7 wt%, the selectivity between the nitride etching rate and the oxide etching rate of the etching composition Above about 200:1 (for example, nitride etching rate Å/min: oxide etching rate Å/min). For example, the selectivity of the etching composition may be about 200:1, about 200:5, and about 200:10.

For example, when the content of the silane inorganic acid salt is higher than about 1.4 wt%, the selectivity between the nitride etching speed and the oxide etching speed of the silane inorganic acid salt may be about 200: infinity (nitride etching speed: oxide Etching speed). As described above, the etching composition according to at least one embodiment has a high selectivity of the nitride layer relative to the oxide layer. Therefore, the etching composition can easily control the etching rate of the oxide layer and easily control the EFH.

According to at least one embodiment, the silane inorganic acid salt can be generated by the reaction of polyphosphoric acid and a silane compound. This silane inorganic acid salt can be represented by the following chemical formula B1.

In the chemical formula B1, R ¹ may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl. The halogen may include fluorine, chlorine, bromine and iodine. Preferably, the halogen may be one of fluorine and chlorine. n ₁ is an integer from 1 to 4, and m ₁ is an integer from 1 to 10. Each of R ² to R ⁴ may be hydrogen. Alternatively, at least one hydrogen selected from R ² to R ⁴ may be substituted with a substituent represented by the following Chemical Formula B2.

In the chemical formula B2, one R ⁵ of the R ⁵ may be connected to the chemical formula B1 and the other R ⁵ may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl. For example, when there are four R ⁵ , one R ^{5 is} connected to the chemical formula B1, and each of the remaining three R ⁵ may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ ) Alkoxy and (C ₆ -C ₃₀ ) aryl. As another example, when there is an R ⁵ , it is connected to the chemical formula B1. n ₂ is an integer from 0 to 3, and m ₂ is an integer from 1 to 10.

In Chemical Formula B2, each of R ² to R ⁴ may be hydrogen or substituted with a substituent represented by Chemical Formula B2. That is, one of R ² to R ⁴ may be substituted with a substituent represented by Chemical Formula B2. In addition, one of R ² to R ⁴ of the substituent represented by the second chemical formula B2 may be substituted with the substituent represented by the third chemical formula B2.

This is because silane inorganic acid salts are generated by the reaction between polyphosphoric acid and silane compounds. For example, the composition represented by the chemical formula B1 is generated by the reaction between the polyphosphoric acid and the silane compound. In the resulting composition represented by the chemical formula B1, the hydroxyl group can react with the silane compound again. Here, the hydroxyl group is located at one of R ² to R ⁴ from the portion of the polyphosphoric acid, and the silane compound is a reactant that initiates this repeated reaction. Continuously, the reacted silane compound and polyphosphoric acid react again. This reaction can be repeated and continued.

Due to the repeated and continuous reaction, the following composition of silane inorganic acid salts can be produced.

In the chemical formula B1, n ₁ is 1, m ₁ is 1, and R ² to R ⁴ are all hydrogen. At this time, a silane inorganic acid salt represented by the following chemical formula B3-1 can be generated. The definition of R ^1-1 to R ^{1-3 is} the same as the definition of R ¹ .

Except that m ₁ is 2, the compound represented by the following chemical formula B3-2 is substantially the same as the compound represented by the chemical formula B3-1.

The following chemical formula B3-3 exemplarily represents a compound when chemical formula B1 has the following conditions: i) n ₁ is 2, ii) m ₁ is 1, iii) each of R ² to R ⁴ is hydrogen. The definition of R ^1-1 to R ^{1-2 is} the same as the definition of R ¹ .

The following chemical formula B3-4 exemplarily shows that when the chemical formula B1 has the following conditions: i) n ₁ is 1, ii) m ₁ is 1, iii) all R ² to R ³ are hydrogen, iv) R ⁴ is used as the chemical formula B2 The compound when the indicated substituent is substituted. In the substituent of the chemical formula B2, n ₂ is 0, and at least one R ^{5 is} connected to the chemical formula B1. Here, the definition of R ^1-1 to R ^{1-6 is} the same as the definition of R ¹ .

This compound represented by the following Chemical Formula B3-4 is generated by a repeated reaction between i) a portion derived from polyphosphoric acid having an R ⁴ substituent of the compound represented by Chemical Formula B1 and ii) a silane compound. Here, the silane compound is a reactant that initiates repeated reactions.

The following chemical formula B3-5 exemplarily shows that when chemical formula B1 has the following conditions: i) n ₁ is 1, ii) m ₁ is 1, iii) R ³ to R ⁴ are hydrogen, and iv) R ² is substituted by chemical formula B2 compound of. Here, the chemical formula B2 has the following conditions: i) n ₂ is 1, ii) m ₂ is 1, iii) at least one R ^{5 is} connected to the chemical formula B1, and iv) all the compounds when R ² to R ⁴ are hydrogen. Here, the definition of R ^1-1 to R ^{1-5 is} the same as the definition of R ¹ .

This compound represented by the following chemical formula B3-5 is formed by repeated and continuous reactions. For example, i) the hydroxyl group, located at the R ⁴ position of the portion derived from polyphosphoric acid in the compound represented by the chemical formula B1, reacts with the silane compound again. Here, the silane compound is a reactant that initiates this repeated reaction. Then, ii) the silane compound continuously reacted with the compound represented by the chemical formula B1 and the polyphosphoric acid are continuously reacted. Here, the polyphosphoric acid is the reactant that initiates this continuous reaction.

The following Chemical Formula B3-6 and Chemical Formula B3-7 exemplarily represent compounds that are substantially the same as the compound represented by Chemical Formula B3-5 except that the positions of the substituents represented by Chemical Formula B2 are different. In Chemical Formula B3-6, the substituent represented by Chemical Formula B2 is located at the R ³ position of Chemical Formula B1. In the chemical formula B3-7, the substituent represented by the chemical formula B2 is located at the R ⁴ position of the chemical formula B1.

The following chemical formula B3-8 exemplarily shows that when chemical formula B1 has the following conditions: i) n ₁ is 1, ii) m ₁ is 1, iii) R ² to R ³ are hydrogen, iv) R ^{4 of} chemical formula B1 is used The compound substituted by the first substituent represented by the chemical formula B2, v) when the R ⁴ of the substituent represented by the chemical formula B2 is substituted by the second substituent represented by the chemical formula B2. Here, the chemical formula B2 has the following conditions: i) n ₂ is 1, ii) m ₂ is 1, iii) at least one R ^{5 is} connected to the chemical formula B1, and iv) at least one of R ² and R ³ is hydrogen. Here, the definition of R ^1-1 to R ^{1-7 is} the same as the definition of R ¹ .

This compound represented by the following chemical formula B3-8 is formed by repeated and continuous reactions. For example, i) the hydroxyl group reacts with the silane compound again. Here, the hydroxyl group after the reaction is located at a portion derived from polyphosphoric acid at the right end of the compound represented by Chemical Formula B3-7, and the silane compound is a reactant that initiates this repeated reaction. Then, ii) the silane compound reacted with the compound represented by the chemical formula B3-7 is continuously reacted with the polyphosphoric acid. Here, polyphosphoric acid is the reactant that initiates this continuous reaction.

As described above, according to at least one embodiment, different compositions represented by chemical formulas B3-1 to B3-8 can be produced. However, the embodiment is not limited to this.

As described above, the silane compound can react with polyphosphoric acid and generate a silane inorganic acid salt represented by the chemical formula B1 due to the reaction. The silane compound may be a compound represented by Chemical Formula A1. Since the compound represented by the chemical formula A1 has been described, its detailed description is omitted here.

The polyphosphoric acid may be pyrophosphoric acid containing two phosphoric acid atoms or polyphosphoric acid containing three or more phosphoric acid atoms.

Except for using polyphosphoric acid instead of the second inorganic acid, the method of generating the silicate inorganic acid salt from the reaction of the polyphosphoric acid and the silane compound can be basically the same as the method of generating the silane inorganic acid salt from the reaction of the second inorganic acid and the silane compound.

According to at least one embodiment, the silicate inorganic acid salt may be a siloxane inorganic acid salt represented by the following chemical formula C1. The inorganic acid salt of siloxane can be generated by the reaction of the second inorganic acid and the siloxane compound. Here, the second inorganic acid may be selected from phosphoric acid, anhydrous phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof.

In the chemical formula C1, each of R ¹ to R ² may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl base. The halogen may include fluorine, chlorine, bromine and iodine. Preferably, the halogen may be one of fluorine and chlorine.

1)。例如，化學式C1可以包括至少一個來自第二無機酸例如磷酸的原子基團。 In the chemical formula C1, n ₁ is an integer from 0 to 3, n ₂ is an integer from 0 to 2, and m ₁ is _one of integers 0 and 1, wherein the sum of n ₁ , n ₂ and m ₁ is equal to or Greater than 1 (for example, n ₁ +n ₂ +m ₁

1). For example, the chemical formula C1 may include at least one atomic group from a second inorganic acid such as phosphoric acid.

In the chemical formula C1, l ₁ is an integer of 1 to 10 and each of O ₁ to O ₃ is an integer of 0 to 10.

In the chemical formula C1, each of R ³ to R ¹¹ is hydrogen. Alternatively, at least one hydrogen selected from R ³ to R ¹¹ may be substituted with a substituent represented by the following chemical formula C2.

In the chemical formula C2, one of R ¹² and R ¹³ may be connected to the chemical formula C1 and the other may be independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy And (C ₆ -C ₃₀ )aryl. For example, when there are two R ¹² and one R ¹³ , one of them may be connected to the chemical formula C1, and each of the remaining two may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl. For another example, when there is one R ¹² and no R ¹³ , R ^{12 is} connected to the chemical formula C1.

n ₃ is an integer from 0 to 3, n ₄ is an integer from 0 to 2, and m ₁ is an integer from 0 to 1. l ₁ is an integer from 1 to 10, and each of O ₁ to O ₃ is an integer from 0 to 10.

In the chemical formula C2, R ³ to R ¹¹ may be hydrogen or may be substituted with a substituent represented by the chemical formula C2 (referred to as a second chemical formula C2). That is, at least one of R ³ to R ¹¹ of the chemical formula C2 may be substituted with the substituent represented by the second chemical formula C2, and at least one of the R ³ to R ¹¹ of the second chemical formula C2 may be substituted by the substituent represented by the chemical formula C2 (Referred to as the third chemical formula C2) substituted again.

This is because the inorganic acid salt of siloxane is generated by the repeated and continuous reaction of the second inorganic acid and the siloxane compound. For example, the compound represented by the chemical formula C1 is generated by the reaction between the second inorganic acid and the siloxane compound. In the generated compound represented by the chemical formula C1, the hydroxyl group can react with the siloxane compound again. Here, the siloxane compound is a reactant that initiates this repeated reaction, and the hydroxyl group that reacts with the siloxane is located at the position of R ³ to R ¹¹ from the portion of the second inorganic acid. Continuously, the siloxane compound that has reacted with the generated compound represented by the chemical formula C1 reacts again with the second inorganic acid. Here, the second inorganic acid is a reactant that initiates this continuous reaction. This reaction can be repeated and continued.

The following chemical formula exemplarily represents the silicate inorganic acid salt produced by this repeated and continuous reaction.

The following chemical formula C1-1 exemplarily shows that when the chemical formula C1 has the following conditions: i) n ₁ is 1, ii) n ₂ is 0, iii) m ₁ is 0, iv) l ₁ is 1, v) O ₁ When O ₃ is 0, vi) all the compounds when R ³ to R ¹¹ are hydrogen. Here, the definition of R ^1-1 to R ^{1-2 is} the same as the definition of R ¹ , and the definition of R ^2-1 to R ^{2-2 is} the same as the definition of R ² .

The following Chemical Formula C1-2 represents a compound that is substantially the same as the compound represented by Chemical Formula C1-1 except when n ₂ is 1.

The following chemical formula C1-3 represents a compound that is substantially the same as the compound represented by the chemical formula C1-1 except when O ₂ and O ₃ are 1.

The following chemical formula C1-4 represents a compound that is substantially the same as the compound represented by the chemical formula C1-2 except when l ₁ is 2.

The following chemical formula C1-5 exemplarily shows that when the chemical formula C1 has the following conditions: i) n ₁ is 2, ii) n ₂ is 2, iii) m ₁ is 0, iv) l ₁ is 1, v) O ₁ to At least one of O ₃ is 0, vi) a compound in which all R ³ to R ¹¹ are hydrogen.

The following chemical formula C1-6 exemplarily shows that when the chemical formula C1 has the following conditions: i) n ₁ is 1, ii) n ₂ is 1, iii) m ₁ is 0, iv) l ₁ is 1, v) O ₁ to At least one of O ₃ is 0, vi) R ⁶ , R ⁹ and R ¹¹ are hydrogen, and vii) R ⁸ is a compound when a substituent represented by the chemical formula C2 is substituted. Here, in the chemical formula C2 of the substituent, i) n ₃ and n ₄ are 0, ii) m ₁ is 0, iii) l ₁ is 1, and iv) at least one of R ¹² is connected to the chemical formula C1.

Here, the definition of R ^1-1 to R ^{1-7 is} the same as the definition of R ¹ , and the definition of R ^{2-1 is} the same as the definition of R ² . This compound represented by the following chemical formula C1-6 is generated by the repeated reaction between i) a hydroxyl group and ii) a siloxane compound. The hydroxyl group after the reaction is located at the R ⁸ position of the portion derived from the second inorganic acid in the compound represented by the chemical formula C1, and the siloxane compound is a reactant that initiates this repeated reaction.

The following chemical formula C1-7 exemplarily shows that when the chemical formula C1 has the following conditions: i) n ₁ is 1, ii) n ₂ is 1, iii) m ₁ is 0, iv) l ₁ is 1, v) O ₁ to At least one of O ₃ is 0, vi) R ⁶ , R ⁹ and R ¹¹ are hydrogen, and vii) R ⁸ is a compound when a substituent represented by the chemical formula C2 is substituted. Here, in the chemical formula C2 of the substituent, i) n ₃ and n ₄ are 1, ii) m ₁ is 0, iii) O ₂ and O ₃ are 0, iv) at least one of R ¹² is connected to the chemical formula C1 , V) R ⁶ , R ⁸ , R ⁹ and R ¹¹ are hydrogen. Here, the definitions of R ^1-1 to R ^1-3 , R ^2-1 , R ^2-2 , R ^3-1 and R ^3-2 are the same as the definitions of R ¹ , R ² and R ³ , respectively.

This compound represented by the chemical formula C1-7 is formed by repeated and continuous reactions. For example, the hydroxyl group reacts with the siloxane compound again. Here, the reacted hydroxyl group is the hydroxyl group located at R ⁸ in the portion derived from the second inorganic acid in the compound represented by Chemical Formula C1. Then, the reacted siloxane compound continuously reacts with the second inorganic acid. Here, the second inorganic acid is a reactant that initiates this continuous reaction.

Except that the substituent represented by the chemical formula C2 is located at the R ^1-3 position of the chemical formula C1-7 and is connected to the chemical formula C1, the following chemical formula C1-8 represents a compound substantially the same as the compound represented by the chemical formula C1-7.

The following chemical formula C1-9 exemplarily shows that when the chemical formula C1 has the following conditions: i) n ₁ is 1, ii) n ₂ is 1, iii) m ₁ is 0, iv) l ₁ is 1, v) O ₁ to At least one of O ₃ is 0, vi) R ³ , R ⁶ , R ⁹ and R ¹¹ are hydrogen, vii) R ^{8 of the} chemical formula C1 is the first substituent represented by the chemical formula C2 (referred to as the first chemical formula C2) Substitution, viii) The compound when the first substituent R ⁸ (for example, the first chemical formula C2) is substituted with the second substituent represented by the chemical formula C2 (referred to as the second chemical formula C2). Here, in the first chemical formula C2 of the first substituent, i) n ₃ and n ₄ are 1, ii) m ₁ is 0, iii) l ₁ is 1, iv) O ₂ and O ₃ are 0, v ) At least one of R ¹² is connected to the chemical formula C1, v) R ⁶ , R ⁹ and R ¹¹ are hydrogen, vi) R ⁸ is the second substituent represented by the second chemical formula C2. In the second chemical formula C2 of the second substituent, i) n ₃ and n ₄ are 1, ii) m ₁ is 0, iii) l ₁ is 1, iv) O ₂ and O ₃ are 0, v) R ¹² At least one of them is connected to the first chemical formula C2, and v) R ⁶ , R ⁸ , R ⁹ and R ¹¹ are hydrogen. Here, the definitions of R ^1-1 to R ^1-4 , R ^2-1 to R ^2-3 and R ^3-1 to R ^3-3 are the same as the definitions of R ¹ , R ² and R ³ , respectively.

This compound represented by the following chemical formula C1-9 is formed by repeated and continuous reactions. For example, the part derived from the second inorganic acid at the right end of the compound represented by Chemical Formula B1-7 reacts again with the siloxane compound. Then, the reacted siloxane compound continuously reacts with the second inorganic acid. Here, the second inorganic acid is a reactant that initiates this continuous reaction.

Except that the substituent represented by the chemical formula C2 is located at the R ^1-4 position of the chemical formula C1-9 and is connected to the chemical formula C1, the following chemical formula C1-10 represents a compound substantially the same as the compound represented by the chemical formula C1-9.

The compound according to the embodiment is not limited to the compounds represented by Chemical Formulas C1-1 to C1-10.

For example, according to at least one embodiment, the silane compound may be a silicate inorganic acid salt represented by the following chemical formula C3 and generated by the reaction of a second inorganic acid and a siloxane compound. Here, the second inorganic acid may be selected from sulfuric acid, fuming sulfuric acid, and combinations thereof.

In the chemical formula C3, each of R ²¹ and R ²² may be independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )Aryl. The halogen may include fluorine, chlorine, bromine and iodine. Preferably, the halogen may be one of fluorine and chlorine.

1)。例如，化學式C3可以包括至少一個來自所述第二無機酸例如硫酸的原子基團。 In the chemical formula C3, n ₁ is an integer from 0 to 3, n ₂ is an integer from 0 to 2, and m ₁ is _one of integers 0 and 1, wherein the sum of n ₁ , n ₂ and m ₁ is equal to or Greater than 1 (for example, n ₁ +n ₂ +m ₁

1). For example, the chemical formula C3 may include at least one atomic group from the second inorganic acid such as sulfuric acid.

In Chemical Formula C3, l ₁ is an integer from 1 to 10.

In the chemical formula C3, each of R ²³ to R ²⁵ is hydrogen. Alternatively, at least one hydrogen selected from R ²³ to R ²⁵ may be substituted with a substituent represented by the following chemical formula C4.

In the chemical formula C4, one of R ²⁶ and R ²⁷ may be connected to the chemical formula C3 and the other may be independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy And (C ₆ -C ₃₀ )aryl. For example, when there are two R ²⁶ and one R ²⁷ , one of them is connected to the chemical formula C3, and each of the remaining two may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C _1- C ₁₀ ) alkoxy and (C ₆ -C ₃₀ ) aryl. For another example, when there is one R ²⁶ and no R ²⁷ , R ^{26 is} connected to the chemical formula C3.

In the chemical formula C4, n ₃ is an integer from 0 to 3, n ₄ is an integer from 0 to 2, m ₁ is an integer from 0 to 1, and l ₁ is an integer from 1 to 10.

In the chemical formula C4, R ²³ to R ²⁵ may independently be hydrogen. R ²³ to R ²⁵ may be substituted with a substituent represented by a chemical formula C4 (referred to as a second chemical formula C4). That is, at least one of R ²³ to R ²⁵ in Chemical Formula C4 may be substituted with a substituent represented by second chemical formula C2, and at least one of R ²³ to R ²⁵ of Second Chemical Formula C4 may be substituted by chemical formula C4 (referred to as The substituent represented by the third chemical formula C4) is substituted again.

The following chemical formulas C3-1 to C3-9 exemplarily represent siloxane inorganic acid salts generated by the above-mentioned repeated and continuous reactions, which are similar to the chemical formulas C1-1 to C1-10. In the chemical formulas C3-1 to C3-9, the definitions of R ^11-1 to R ^11-7 , R ^12-1 to R ^12-3 and R ^13-1 to R ^13-3 are the same as R ¹¹ , R ¹² and R ^{13 has} the same definition.

The compound according to at least one embodiment is not limited to the chemical formula Compounds represented by C3-1 to C3-9.

According to at least one embodiment, the silane inorganic acid salt may be a silane inorganic acid salt generated by reacting a second inorganic acid such as nitric acid with a siloxane compound. This silane inorganic acid salt can be represented by the following chemical formula C5.

In the chemical formula C5, each of R ³¹ and R ³² may be independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )Aryl. The halogen may include fluorine, chlorine, bromine and iodine. Preferably, the halogen may be one of fluorine and chlorine.

1)。例如，化學式C5可以包括至少一個來自所述第二無機酸例如硝酸的原子基團。 In the chemical formula C5, n ₁ is an integer from 0 to 3, n ₂ is an integer from 0 to 2, and m ₁ is _one of integers 0 and 1, wherein the sum of n ₁ , n ₂ and m ₁ is equal to or Greater than 1 (for example, n ₁ +n ₂ +m ₁

1). For example, the chemical formula C5 may include at least one atomic group from the second inorganic acid such as nitric acid.

In the chemical formula C5, l ₁ is an integer of 1 to 10.

In the chemical formula C5, each of R ³³ to R ³⁵ is hydrogen. Alternatively, at least one hydrogen selected from R ³³ to R ³⁵ may be substituted with a substituent represented by the following chemical formula C6.

In the chemical formula C6, one of R ³⁶ and R ³⁷ may be connected to the chemical formula C5 and the other may be independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy And (C ₆ -C ₃₀ )aryl. For example, when there are two R ³⁶ and one R ³⁷ , one of them may be connected to the chemical formula C5, and each of the remaining two may be selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl. For another example, when there is one R ³⁶ and no R ³⁷ , R ^{36 is} connected to the chemical formula C5.

In the chemical formula C6, n ₃ is an integer from 0 to 3, n ₄ is an integer from 0 to 2, m ₁ is an integer from 0 to 1, and l ₁ is an integer from 1 to 10.

In the chemical formula C6, R ³³ to R ³⁵ may independently be hydrogen. R ³³ to R ³⁵ may be substituted with a substituent represented by chemical formula C6 (referred to as a second chemical formula C6). That is, at least one of R ³³ to R ³⁵ of Chemical Formula C6 may be substituted with a substituent represented by second chemical formula C6, and at least one of R ³³ to R ³⁵ of Second Chemical Formula C6 may be substituted by chemical formula C6 (referred to as The substituent represented by the third chemical formula C6) is substituted again.

The following chemical formulas C5-1 to C5-9 exemplarily represent siloxane inorganic acid salts generated by the above-mentioned repeated and continuous reactions, similar to the chemical formulas C1-1 to C1-10. In the chemical formulas C5-1 to C5-9, the definitions of R ^21-1 to R ^21-7 , R ^22-1 to R ^22-3 and R ^23-1 to R ^23-3 are the same as R ²¹ , R ²² and R The definition of ^{23 is} the same.

As described above, the embodiments are not limited to the compositions exemplarily represented by the chemical formulas C5-1 to C5-9.

As described above, according to at least one embodiment, the siloxane inorganic acid salt represented by the chemical formula C1 can be generated by the reaction between the second inorganic acid and the siloxane compound. The siloxane compound may be a compound represented by Chemical Formula A2. Since the compound represented by the chemical formula A2 has been described previously, its detailed description is omitted here.

In addition to using a siloxane compound instead of a silane compound, the method of generating a silicate inorganic acid salt from the reaction of the second inorganic acid and the siloxane compound can be combined with the reaction of the second inorganic acid and the silane compound to produce the silicate inorganic acid salt The method is basically the same.

According to another embodiment, the etching composition may include a first inorganic acid, at least one silane inorganic acid salt, and a solvent. The at least one silane inorganic acid salt may be generated by reacting a second inorganic acid with a second silane compound.

As described above, the etching composition may additionally include the second silane compound and the silane inorganic acid salt. During the etching process using the etching composition, this additional second silane compound can react with the first inorganic acid and generate additional silane inorganic acid salt. Therefore, the additional second silane compound can also improve the selectivity of the selective removal of the nitride layer, while minimizing the etching rate of the oxide layer and preventing the generation of particles that seriously affect the performance of the device. In addition, the additional second silane compound can additionally provide the silicate inorganic acid salt consumed in the etching process.

As the second silane compound, the silane compound described above can be used. Preferably, the same silane compound used to generate the silane inorganic acid salt can be used as the second silane compound. At this time, the composition of the second silane compound will be similar to the composition of the silane inorganic acid salt. Therefore, the effect of adding the second silane compound can be further improved. In addition, it is permissible to add a reaction liquid that generates a silane inorganic acid salt to the etching composition without a purification process. That is, the unreacted second silane compound can be effectively added to the etching composition.

Based on the total weight of the etching composition, the content of the second silane compound may be about 0.001 to about 15 wt%, preferably about 0.005 to about 10 wt%, more preferably about 0.01 to about 5 wt%. When the amount of the second silane compound added is less than about 0.001 wt%, it is difficult to control the selectivity because the content of the second silane compound is small. When the addition amount of the second silane compound is higher than about 15%, it causes crystallization or the generation of by-products.

The first inorganic acid is added as an etchant for etching the nitride layer. Therefore, the first inorganic acid may include any inorganic acid capable of etching the nitride layer. example For example, the first inorganic acid may be selected from sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrochloric acid, chloric acid, and combinations thereof.

Preferably, in order to obtain the etching selectivity of the nitride layer relative to the oxide layer, phosphoric acid may be used as the first inorganic acid. By supplying hydrogen ions to the etching composition, phosphoric acid can accelerate etching. When phosphoric acid is used as the first inorganic acid, the etching composition may further include sulfuric acid as an additive. Sulfuric acid can increase the boiling point of the etching composition containing phosphoric acid as the first inorganic acid, thereby promoting the etching of the nitride layer.

The content of the first inorganic acid may be about 70 to 99 wt%, preferably about 70 to 90 wt%, more preferably about 57 to about 85 wt%. When the content of the first inorganic acid is less than about 70 wt%, it is difficult to effectively remove the nitride layer and the generation of particles. When the content of the first inorganic acid is higher than about 99 wt%, it is difficult to obtain a high selectivity of the nitride layer.

As described above, the etching composition may contain a solvent. Specifically, the solvent may include water and deionized water.

The etching composition may further contain an ammonium compound. The content of the ammonium compound may be about 0.01 to about 20 wt%. Even if the etching composition is used for a relatively long time, the ammonium compound contained in the etching composition can prevent a decrease in etching rate and a change in selectivity. In addition, the ammonium compound can maintain the etching rate constantly.

When the content of the ammonium compound is less than about 0.01 wt%, the advantageous effect of maintaining selectivity deteriorates. When the content of the ammonium compound is higher than about 20 wt%, the etching rate between the nitride layer and the silicon oxide layer changes. Therefore, the selectivity will change.

The ammonium compound may be selected from ammonium hydroxide, ammonium chloride, ammonium acetate, ammonium phosphate, ammonium peroxodisulfate, ammonium sulfate, ammonium hydrofluorate, and combinations thereof. However, ammonium compounds are not limited to this. For example, the ammonium compound may include a compound containing ammonium ions. For example, the ammonium compound may include NH4 and HCl.

The etching composition may further contain a fluorine-based compound. The content of the fluorine-based compound may be about 0.01 to about 1 wt%. When the content of the fluorine-based compound is less than about 0.01% by weight, the etching rate of the nitride layer is reduced. Therefore, it is difficult to remove the nitride layer. When the content of the fluorine-based compound is higher than about 1 wt%, the etching rate of the nitride layer will be significantly increased. However, the oxide layer can be accidentally etched.

The fluorine compound may be selected from hydrogen fluoride, ammonium fluoride, ammonium hydrogen fluoride, and combinations thereof. Preferably, ammonium bifluoride may be used because it can improve the selectivity of maintenance when the etching composition is used for a relatively long time.

In addition, in order to improve the etching performance, the etching composition of the present embodiment may further contain additives commonly used in the art. Examples of additives that can be used in the present embodiment include surfactants, chelating agents, corrosion inhibitors, and the like.

The etching composition containing a silane inorganic acid salt of the present embodiment exhibits a remarkably high etching selectivity of the nitride layer relative to the oxide layer, so it can be used in the process of etching the nitride layer.

Therefore, in the nitride film etching process using the etching composition of the present embodiment, by minimizing the etching rate of the nitride film, it is possible to easily Control EFH. In addition, in the process of selectively etching and removing the nitride film using the etching composition, it is possible to avoid deterioration of electrical properties caused by destruction of the oxide film or etching of the oxide film, and no particles are generated, This will improve device performance.

According to another aspect of the embodiment, a method for manufacturing a semiconductor device may be provided, the method including an etching process using the etching composition of the embodiment.

In an exemplary embodiment, this etching process may include etching a nitride layer. Specifically, the etching process may include selectively etching the nitride film with respect to the oxide film.

The nitride layer may include a SiN film, a SiON film, and the like.

In addition, the oxide film may be at least one film selected from silicon oxide films, for example, SOD (dielectric spin coating) film, HDP (high density plasma) film, thermal oxide film, BPSG (borophosphosilicate glass) ) Film, PSG (phosphosilicate glass) film, BSG (borosilicate glass) film, PSZ (polysilazane) film, FSG (fluorinated silicate glass) film, LPTEOS (low pressure orthosilicate four) Ethyl) film, PETEOS (plasma-reinforced tetraethyl orthosilicate) film, HTO (high temperature oxide) film, MTO (medium temperature oxide) film, USG (undoped silicate glass) film, SOG ( Glass spin coating) film, APL (Advanced Flat Layer) film, ALD (Atomic Layer Deposition) film, plasma enhanced oxide film, O3-TEOS (O3-tetraethyl orthosilicate) film, and combinations thereof.

The etching process using the etching composition of this embodiment can be performed by a wet etching method known in the art, for example, a dipping method or a spray method.

The etching process may be between about 50°C and about 300°C and preferably about The temperature range is between 100°C and about 200°C. In view of other processes and other factors, the temperature of the etching process can be appropriately changed.

In the method of manufacturing a semiconductor device including an etching process using the etching composition of the present embodiment, the nitride film can be selectively etched from a structure in which nitride films and oxide films are alternately stacked or exist together. In addition, the problem of particles generated in the conventional etching process can be avoided, thereby ensuring the stability and reliability of the process.

Therefore, this method can be effectively used in various semiconductor manufacturing processes in which the nitride film needs to be selectively etched relative to the oxide film.

2A to 2C are cross-sectional views illustrating a device isolation process of a flash memory device according to at least one embodiment. Here, the device isolation process may include an etching process using the etching composition (for example, a highly selective etching composition) according to this embodiment.

2A, in at least one embodiment, a tunnel oxide layer 21, a polysilicon layer 22, a buffer oxide layer 23, and/or a nitride pad layer 24 may be formed on the substrate 20. For example, in some embodiments, a tunnel oxide layer 21, a polysilicon layer 22, a buffer oxide layer 23, and/or a nitride pad layer 24 may be sequentially formed on the substrate 20.

The nitride pad layer 24, the buffer oxide layer 23, the polysilicon layer 22, and/or the tunnel oxide layer 21 may be selectively etched through the lithography and etching processes to expose the device isolation region of the substrate 20. Then, the nitride pad layer 24 may be used as a mask to selectively etch the exposed regions of the substrate 20 to form at least one trench 25 having a predetermined depth on the surface of the substrate 20.

2B, an oxide may be formed on the entire surface of the substrate 20 The purpose of the layer 26 is to fill at least one trench 25 with a gap. For example, the oxide layer 26 may be formed by chemical vapor deposition (CVD).

A chemical mechanical polishing (CMP) process may be performed on the oxide layer 26 using the nitride pad layer 24 as a polishing stop layer. Then, dry etching can be used for the cleaning process.

2C, the etching composition according to the present embodiment may be used to selectively remove the nitride pad layer 24 through a wet etching process, and then the buffer oxide layer 23 may be removed through a cleaning process to form a device isolation layer in the field region 26A.

As shown in FIG. 2C, in at least one embodiment, a highly selective etching composition having a high etching selectivity for the nitride layer relative to the oxide layer can be used. When a highly selective etching composition is used, the nitride layer can be selectively removed in sufficient time, while the etching of the oxide layer filled in the STI pattern is minimized. At this time, the selective removal of the nitride layer can be sufficiently performed. Therefore, in this embodiment using a highly selective etching composition, the effective field oxide height (EFH) can be easily controlled. In addition, in the present embodiment using a highly selective etching composition, it is possible to prevent deterioration of electrical characteristics and generation of particles caused by damage to the oxide layer and etching of the oxide layer, thereby improving device characteristics.

As described above, the highly selective etching composition according to the present embodiment can be used in the device isolation process of flash memory devices. For example, the highly selective etching composition according to the present embodiment can be used in the device isolation process of DRAM (kinetic energy random access memory) devices.

3A to 3F are diagrams showing the formation of flash memory according to at least one embodiment A cross-sectional view of the manufacturing process of the memory device tunnel. Here, the tunnel formation process may include an etching process using the etching composition (for example, a highly selective etching composition) according to the present embodiment.

Referring to FIG. 3A, in at least one embodiment, a tube gate electrode layer 31 may be formed on the substrate 30. At this time, the nitride layer 32 forming the tube channel may be buried in the tube gate electrode layer 31. Here, the tube gate electrode layer 31 includes a first conductive layer 31A and/or a second conductive layer 31B. For example, at least one of the first conductive layer 31A and the second conductive layer 31B may include polysilicon doped with impurities.

More specifically, a first conductive layer 31A is formed on the substrate 30, and a nitride layer is deposited and patterned on the first conductive layer 31A to form a nitride layer 32 for forming at least one tube channel. Next, a second conductive layer 31B is formed on the first conductive layer 31A exposed through the nitride layer 32. The first conductive layer 31A and/or the second conductive layer 31B form the tube gate electrode layer 31.

In order to form a plurality of vertically stacked memory cells, at least one first interlayer insulating layer 33 and at least one first gate electrode layer 34 may be alternately stacked as shown in FIG. 3A. Hereinafter, for convenience of description, the alternating stack structure of at least one first interlayer insulating layer 33 and at least one first gate electrode layer 34 will be referred to as a “cell gate structure (CGS)”.

Here, at least one first interlayer insulating layer 33 can achieve the function of isolating the storage unit through a plurality of layers. For example, in at least one embodiment, at least one first interlayer insulating layer 33 may include an oxide layer, and at least one first gate electrode layer 34 may include polysilicon doped with impurities. As shown in FIG. 3A, at least one first interlayer insulating layer 33 and/or at least one The first gate electrode layer 34 includes six layers, but is not limited thereto.

The cell gate structure (CGS) may be selectively etched to form at least one hole exposing the nitride layer 32. For example, the cell gate structure (CGS) may be selectively etched to form a pair of first holes H1 and second holes H2 exposing the nitride layer 32. Here, the first hole H1 and the second hole H2 may be regions of a tunnel forming a storage unit.

Referring to FIG. 3B, at least one nitride layer buried in the first hole H1 and the second hole H2 may be formed. At this time, when at least one first gate electrode layer 34 is exposed through the first hole H1 and the second hole H2, at least one nitride layer 35 can be prevented from occurring in the trench formation process (described later in FIG. 3C) Damaged effect.

Referring to FIG. 3C, in order to divide the at least one first gate electrode layer 34 into a portion corresponding to each of the first hole H1 and the second hole H2, it is possible to select between a pair of the first hole H1 and the second hole H2 The cell gate structure (CGS) is etched to form a trench "S".

Referring to FIG. 3D, a sacrificial layer 36 buried in the trench "S" may be formed.

Referring to FIG. 3E, in at least one embodiment, in order to form a selective transistor, a structure (for example, the structure shown in FIG. 3D may be obtained after undergoing the above process (for example, the process described in relation to FIGS. 3A to 3D) ) At least one second interlayer insulating layer 37 and at least one second gate electrode layer 38 formed in this order. For example, as shown in FIG. 3E, a second interlayer insulating layer 37, a second gate electrode layer 38, and another second interlayer insulating layer 37 may be sequentially formed. Hereinafter, for convenience of description, the stacked structure of at least one second interlayer insulating layer 37 and at least one second gate electrode layer 38 will be referred to as “select Gate Structure (SGS)".

For example, in at least one embodiment, the at least one second interlayer insulating layer 37 may include an oxide layer, but it is not limited thereto. The at least one second gate electrode layer 38 may include polysilicon doped with impurities, but is not limited thereto.

The selective gate structure (SGS) may be selectively etched to form at least one hole exposing the nitride layer 35 buried in the pair of first holes H1 and second holes H2. For example, a selective gate structure (SGS) may be selectively etched to form a third hole H3 and a fourth hole H4 that expose the nitride layer 35 buried in the pair of first holes H1 and second holes H2. Here, the third hole H3 and the fourth hole H4 may be regions where the selective transistor tunnel is formed.

Referring to FIG. 3F, the nitride layer 35 exposed through the third hole H3 and the fourth hole H4 and (ii) provided on the nitride can be selectively removed through the wet etching process using the etching composition according to the present embodiment The nitride layer 32 below the layer 35.

When a tunneling process (including an etching process) for forming a flash memory is performed according to this embodiment, at least one tunnel hole (for example, a pair of tunnel holes H5 and H6) for forming a tunnel layer of a memory cell may be formed. In addition, at least one pipe tunnel hole (for example, H7) may be formed under the tunnel holes H5 and H6, so the tunnel holes H5 and H6 may be connected to each other. In the process (including the etching process) of forming the flash memory tunnel according to the present embodiment, using a highly selective etching composition can allow sufficient time to selectively remove the nitride layer without loss of the oxide layer, Therefore, tube tunnels can be formed accurately without loss of profile. At this time, you can thoroughly This selective removal of the nitride layer is carried out. In addition, in the process of forming the channel of the flash memory according to the present embodiment (including the etching process), typical problems such as the generation of particles can be prevented, so the stability and reliability of the process can be ensured.

Then, subsequent processes such as a process of forming a floating gate electrode and a process of forming a control gate may be performed, thereby forming a flash memory device.

4A and 4B are cross-sectional views illustrating a process of forming a diode of a phase change memory device according to at least one embodiment. Here, the diode forming process may include an etching process using the etching composition (for example, a highly selective etching composition) according to this embodiment.

Referring to FIG. 4A, in at least one embodiment, an insulating structure may be provided on the substrate 40. Here, the insulating structure may include a hole exposing the conductive region 41. For example, the conductive region 41 may be an n+ impurity region, but it is not limited thereto.

A polysilicon layer 42 may be formed for the purpose of filling the hole area, and then ion implantation of impurities to form a diode.

A titanium silicide layer 43 may be formed on the polysilicon layer 42. For example, the titanium silicide layer 43 can be formed by forming a titanium layer and heat-treating the formed titanium layer to react with the polycrystalline silicon layer 42.

A titanium nitride layer 44 and a nitride layer 45 may be sequentially formed on the titanium silicide layer 43. For example, a titanium nitride layer 44 may be formed on the titanium silicide layer 43, and then a nitride layer 45 may be formed on the titanium nitride layer 44.

The oxide layer 46 may be formed in an isolation space between diodes, which is formed by a dry etching process using a hard mask. then, A chemical mechanical polishing (CMP) process can be performed to form the basic structure of the bottom electrodes isolated from each other.

Referring to FIG. 4B, the nitride layer 45 can be selectively removed by performing a wet etching process on the structure generated through the above-described process described in relation to FIG. 4A. Here, the wet etching process may be performed using the etching composition according to the present embodiment (for example, a highly selective etching composition). In at least one embodiment, a highly selective etching composition can be used to remove the nitride layer. At this time, the nitride layer can be selectively removed with sufficient time without damaging the oxide layer. This selective removal of the nitride layer can be carried out thoroughly. In addition, in the present embodiment using a highly selective etching composition, it is possible to prevent deterioration of electrical properties and generation of particles caused by damage to the oxide layer or etching of the oxide layer, thereby improving electrical characteristics. Titanium may be deposited in the remaining space after removing the nitride layer 45, thereby forming a bottom electrode.

As described above, the etching process using the highly selective etching composition according to this embodiment can be used for various semiconductor device manufacturing methods. For example, the etching process according to the present embodiment can be used in a process that requires selective removal of the nitride layer. More specifically, the etching process according to the present embodiment can be used in a process that requires selective etching of a nitride layer from a structure in which nitride layers and oxide layers are alternately stacked or coexist.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples and comparative examples. However, it should be understood that these embodiments are for exemplary purposes and are not intended to limit the scope of the embodiments of the present invention.

[First Embodiment A: Preparation of etching composition]

In the first embodiment A, it can be determined by the following table 1A The predetermined weight ratio shown is a mixture of at least one silane inorganic acid salt and phosphoric acid to produce an etching composition. As the first inorganic acid, an 85% aqueous solution was used.

1) 1st IA: the first inorganic acid

2) 2nd IA: second inorganic acid

3) PA: phosphoric acid

5 is an image showing nuclear magnetic resonance (NMR) data of the silane inorganic acid salt generated according to the first embodiment A. FIG.

Referring to FIG. 5, the image shows at least one silane inorganic acid salt in the etching composition according to at least one embodiment. That is, the compound represented by the chemical formula A1 in which R ¹ is a methyl group and R ² to R ⁴ is chlorine reacts with phosphoric acid (for example, a second inorganic acid). Therefore, at least one silicate inorganic acid salt can be produced. That is, the image of FIG. 5 includes broad peaks at about 11.1364 ppm and about 11.4053, which are different from the sharp peaks representing a single compound. Therefore, this broad peak indicates that the etching composition includes a plurality of silane inorganic acid salts having different chemical formulas.

[Experimental Example A1: Measuring the selectivity of the etching composition]

Using the etching composition of this embodiment, the nitride layer and the oxide layer are etched at a process temperature of 157°C. The ellipsometer (NANO VIEW, SEMG-1000) of the film thickness measurement system was used to measure the etching rate and selectivity of the nitride layer and the oxide layer. The measurement results are shown in Table A2 below. The etching rate is determined by etching each layer for about 300 seconds and measuring the difference between the thickness of each layer before etching and the layer thickness of each layer after etching. Therefore, the etching rate is obtained by dividing the thickness difference by the etching time (minutes). The etching selectivity is expressed as the ratio of the etching rate of the nitride layer to the etching rate of the oxide layer.

1) ThO: thermal oxide layer

2) LP-TEOS: low-pressure tetraethyl orthosilicate layer

3) BPSG: Borophosphate silicate glass layer

[Comparative Examples A1 to A3: Preparation of etching composition]

In Comparative Example A1, phosphoric acid was used for etching at a process temperature of 157°C. The etching speed and etching selectivity were measured in the same manner as the above embodiment. In Comparative Example 2, a mixture of 0.05% hydrofluoric acid and phosphoric acid mixed at a low temperature of 130° C. was used for etching. In Comparative Example A3, the same mixture as Comparative Example A2 was used for etching at a process temperature of 157°C. In Comparative Examples A2 and A3, the etching speed and selectivity were measured in the same manner as in the above examples. The phosphoric acid used in Comparative Examples A1 to A3 was an 85% aqueous solution of phosphoric acid. The measurement results of Comparative Examples A1 to A3 are shown in Table A3 below.

As can be seen from Tables 2 and 3, the etching composition shows a significantly higher etching selectivity of the nitride layer relative to the oxide layer compared to the etching selectivities of Comparative Examples A1 to A3. Therefore, when the highly selective etching composition of the present embodiment is used, the EEH can be easily controlled by controlling the etching rate of the oxide layer, and damage to the oxide layer can be prevented. In addition, the generation of problematic particles can be prevented, thus ensuring the stability and reliability of the etching process.

[Experimental Example A2: Measurement of changes over time]

The etching composition produced in Examples A1 and A2 was mixed with phosphoric acid. Immediately after mixing (0 hours) and at 8 hours after mixing, the nitride layer and the oxide layer were etched using each mixture. The nitride layer and oxide layer etching rate and selectivity were measured. In Comparative Example 4 (Basic PA), phosphoric acid was used to evaluate the etching rate and selectivity of the nitride layer and the oxide layer in the same manner as in the above example.

The evaluation was performed at a process temperature of 160°C. The etching rate is determined by etching each layer for about 300 seconds and measuring the difference between the thickness of each layer before etching and the layer thickness of each layer after etching. Therefore, the etching rate is obtained by dividing the thickness difference by the etching time (minutes). The etching selectivity is expressed as the ratio of the etching rate of the nitride film to the etching rate of the PSZ film. The evaluation results are shown in Table A4 below.

1) PSZ: polysilazane layer

As can be seen from Table A4, the etching composition of the present embodiment exhibits a very high nitride layer etching selectivity compared to the conventional etching composition containing phosphoric acid. Therefore, when the nitride layer is removed using the highly selective etching composition of the present embodiment, the nitride layer can be etched selectively, and at the same time, damage to the oxide layer or electrical properties caused by etching of the oxide layer can be prevented Deterioration or prevention of particle generation will improve device performance.

[Second Embodiment B: Preparation of etching composition]

According to the second embodiment B, the etching composition is prepared by mixing the silane inorganic acid salt and phosphoric acid in the weight ratio shown in Table B1 below. As the first inorganic acid, an 85% aqueous solution was used.

1) 1st IA: the first inorganic acid

2) 2nd IA: second inorganic acid

3) PT: process temperature

[Experimental Example B1: Measuring the selectivity of the etching composition]

Using the etching composition of the second embodiment B1, the nitride layer and the oxide layer are etched at a process temperature of 157°C. The ellipsometer (NANO VIEW, SEMG-1000) of the film thickness measurement system was used to measure the etching rate and selectivity of the nitride layer and the oxide layer. The measurement results are shown in Table B2 below. The etching rate is determined by etching each layer for about 300 seconds and measuring the difference between the thickness of each layer before etching and the layer thickness of each layer after etching. Therefore, the etching rate is obtained by dividing the thickness difference by the etching time (minutes). The etching selectivity is expressed as the ratio of the etching rate of the nitride layer to the etching rate of the oxide layer.

1) ThO: thermal oxide layer

2) LP-TEOS: low-pressure tetraethyl orthosilicate layer

3) BPSG: Borophosphate silicate glass layer

[Comparative Examples B1 to B3: Preparation of etching composition]

In Comparative Example B1, phosphoric acid was used for etching at a process temperature of 157°C. The etching speed and etching selectivity were measured in the same manner as the above embodiment. In Comparative Example B2, a mixture of 0.05% hydrofluoric acid and phosphoric acid mixed at a low temperature of 130° C. was used for etching. The etching speed and etching selectivity were measured in the same manner as the above embodiment. In Comparative Example B3, the same mixture as Comparative Example B2 was used for etching at a process temperature of 157°C. The etching speed and selectivity were measured in the same manner as the above embodiment. The phosphoric acid used in Comparative Examples B1 to B3 was an 85% aqueous solution of phosphoric acid. The measurement results of Comparative Examples B1 to B3 are shown in Table B3 below.

As can be seen from Table B2 and Table B3, the etching composition shows a significantly higher etching selectivity of the nitride layer relative to the oxide layer compared to the etching selectivities of Comparative Examples B1 to B3. Therefore, when the highly selective etching composition of the present embodiment is used, EEH can be easily controlled by controlling the etching rate of the oxide layer, and damage to the oxide layer can be prevented. In addition, the generation of problematic particles can be prevented, thus ensuring the stability and reliability of the etching process.

[Third Embodiment C: Preparation of etching composition]

According to the third embodiment C, the etching composition is prepared by mixing the silane inorganic acid salt and phosphoric acid in the weight ratio shown in Table C1 below. As the first inorganic acid, an 85% aqueous solution was used.

1st IA: the first inorganic acid

2nd IA: second inorganic acid

PT: process temperature

[Experimental Example C1: measuring the selectivity of the prepared etching composition]

Using the etching composition of the third embodiment C1, the nitride layer and the oxide layer are etched at a process temperature of 157°C. The ellipsometer (NANO VIEW, SEMG-1000) of the film thickness measurement system was used to measure the etching rate and selectivity of the nitride layer and the oxide layer. The measurement results are shown in Table B2 below. The etching rate is determined by etching each layer for about 300 seconds and measuring the difference between the thickness of each layer before etching and the layer thickness of each layer after etching. Therefore, the etching rate is obtained by dividing the thickness difference by the etching time (minutes). The etching selectivity is expressed as the ratio of the etching rate of the nitride layer to the etching rate of the oxide layer.

1) ThO: thermal oxide layer

2) LP-TEOS: low-pressure orthosilicate layer

3) BPSG: Borophosphate silicate glass layer

[Comparative Examples C1 to C3: Preparation of etching composition]

In Comparative Example C1, phosphoric acid was used for etching at a process temperature of 157°C. The etching speed and etching selectivity were measured in the same manner as the above embodiment. In Comparative Example C2, a mixture of 0.05% hydrofluoric acid and phosphoric acid mixed at a low temperature of 130° C. was used for etching. The etching speed and etching selectivity were measured in the same manner as the above embodiment. In Comparative Example C3, the same mixture as Comparative Example C2 was used for etching at a process temperature of 157°C. The etching speed and etching selectivity were measured in the same manner as the above embodiment. The phosphoric acid used in Comparative Examples C1 to C3 was an 85% aqueous solution of phosphoric acid. The measurement results of Comparative Examples C1 to C3 are shown in Table C3 below.

As can be seen from Table C2 and Table C3, the etching composition shows a significantly higher etching selectivity of the nitride layer relative to the oxide layer compared to the etching selectivities of Comparative Examples C1 to C3. Therefore, when the highly selective etching composition of the present embodiment is used, EEH can be easily controlled by controlling the etching rate of the oxide layer, and damage to the oxide layer can be prevented. In addition, the generation of problematic particles can be prevented, thus ensuring the stability and reliability of the etching process.

[Experimental Example C2: Measurement of change with time]

Using the etching composition produced in Example C1, the nitride layer and the oxide layer were etched immediately (0 hours) after mixing with phosphoric acid and 8 hours after mixing with phosphoric acid. The nitride layer and oxide layer etching rate and selectivity were measured. In Comparative Example C4, phosphoric acid was used to evaluate the etching rate and selectivity of the nitride layer and the oxide layer in the same manner as in the above example.

The evaluation was performed at a process temperature of 160°C. The etching rate is determined by etching each layer for about 300 seconds and measuring the difference between the thickness of each layer before etching and the layer thickness of each layer after etching. Therefore, the etching rate is obtained by dividing the thickness difference by the etching time (minutes). The etching selectivity is expressed as the ratio of the etching rate of the nitride film to the etching rate of the PSZ film. The evaluation results are shown in Table C4 below.

1) PSZ: polysilazane layer

As can be seen from Table C4, the etching composition of Example C1 exhibits a very high nitride layer etching selectivity compared to the conventional etching composition containing phosphoric acid. Therefore, when the nitride layer is removed using the highly selective etching composition of this embodiment, the nitride layer can be etched selectively, and at the same time, the deterioration of the electrical properties or the oxide caused by the damage to the oxide layer can be prevented The etching of the layer will improve the device performance.

[Fourth Embodiment D: Preparation of Etching Composition]

According to the fourth embodiment D, the etching composition is prepared by mixing the silane inorganic acid salt and phosphoric acid in the weight ratio shown in Table D1 below. As phosphoric acid, an 85% aqueous solution was used.

[Experimental Example D1: measuring the selectivity of the prepared etching composition]

Using the etching composition prepared in the fourth embodiment, the nitride layer and the oxide layer are etched at a process temperature of 157°C. The ellipsometer (NANO VIEW, SEMG-1000) of the film thickness measurement system was used to measure the etching rate and selectivity of the nitride layer and the oxide layer. The measurement results are shown in Table D2 below. The etching rate is determined by etching each layer for about 300 seconds and measuring the difference between the thickness of each layer before etching and the layer thickness of each layer after etching. Therefore, the etching rate is obtained by dividing the thickness difference by the etching time (minutes). The etching selectivity is expressed as the ratio of the etching rate of the nitride layer to the etching rate of the oxide layer.

1) ThO: thermal oxide layer

2) LP-TEOS: low-pressure tetraethyl orthosilicate layer

3) BPSG: Borophosphate silicate glass layer

[Comparative Examples D1 to D3: Preparation of etching composition]

In Comparative Example D1, phosphoric acid was used for etching at a process temperature of 157°C. The etching speed and etching selectivity were measured in the same manner as the above embodiment. In Comparative Example D2, a mixture of 0.05% hydrofluoric acid and phosphoric acid mixed at a low temperature of 130° C. was used for etching. In Comparative Example D3, the same mixture as Comparative Example D2 was used for etching at a process temperature of 157°C. In Comparative Examples D2 and D3, the etching speed and selectivity were measured in the same manner as in the above examples. The phosphoric acid used in Comparative Examples D1 to D3 was an 85% aqueous solution of phosphoric acid. The measurement results of Comparative Examples D1 to D3 are shown in Table D3 below.

As can be seen from Table D2 and Table D3, the etching composition shows a significantly higher etching selectivity of the nitride layer relative to the oxide layer compared to the etching selectivities of Comparative Examples A1 to A3. Therefore, when the highly selective etching composition of the present embodiment is used, EFH can be easily controlled by controlling the etching rate of the oxide layer, and damage to the oxide layer can be prevented. In addition, the generation of problematic particles can be prevented, thus ensuring the stability and reliability of the etching process.

The "one embodiment" or "embodiment" referred to herein means that specific features, structures, or features described in relation to the embodiment can be included in at least one embodiment of the present invention. The expression "in one embodiment" appearing in different places in the specification does not necessarily refer to the same embodiment, nor does it necessarily mean separate or alternative embodiments that exclude other embodiments from each other. The same principle applies to the term "implementation".

As used in this application, the word "exemplary" as used herein refers to achieving an embodiment, example, or explanatory role. Any aspect or design described herein as "exemplary" is not necessarily understood to be better or advantageous than other aspects or designs. Rather, the use of the word "exemplary" is intended to illustrate the concept in a specific way.

In addition, the term "or" means an inclusive "or" rather than an exclusive "or". That is, unless otherwise specified, or as is clear from the text, "X uses A or B" means any naturally inclusive substitution. That is, if X uses A; X uses B; or X uses A and B, then "X uses A or B" is satisfied in any of the foregoing cases. In addition, the articles “一” and “一” used in the scope of the patents of the application and the attached applications shall This is generally understood to mean "more than one" unless specified otherwise or it is clear from the context to refer to the singular form.

In addition, the terms "system", "component", "module", "interface", "model", etc. generally refer to computer-related concepts, hardware, a combination of hardware and software, software or executed software. For example, the component may be, but not limited to, a process, a processor, an object, an execution block, an execution thread, a program, and/or a computer that runs a processor. By way of explanation, applications and controllers running on the processor can be components. More than one component may be located in a program and/or thread of execution and the component may be located on one computer and/or distributed between more than two computers.

The present invention can be embodied in terms of methods and apparatuses for implementing those methods. The present invention can also be embodied in the form of program code, which can be embodied in touchable media and non-touch media, such as magnetic recording media, optical recording media, solid-state memory, floppy disks, CD-ROM (read only disc), In a hard disk drive, or any other machine-readable storage medium, when the program code is loaded and executed by a machine, such as a computer, the machine becomes a device embodying the present invention. The invention can also be embodied in the form of program code, for example, whether it is stored in a storage medium, loaded and/or executed by a machine, or propagated through some propagation medium or carrier, such as through wires or cables, through optical fibers, or through Electromagnetic radiation, where, when the program code is loaded and executed by a machine, such as a computer, the machine becomes a device embodying the present invention. When executed on a general-purpose processor, the code snippets are combined with the processor to provide a unique component that executes similar to a specific logic circuit. The present invention can also be produced using the method and/or device of the present invention to pass the medium, electrical or The form of the optically transmitted bit stream or other signal value sequence and the storage magnetic field change in the magnetic recording medium is embodied.

It should be understood that the steps of the exemplary method proposed herein do not necessarily need to be performed in the order described, and the order of the steps of this method should be understood to be merely exemplary. Similarly, in methods consistent with different embodiments of the present invention, these methods may include additional steps, and some steps may be omitted or combined.

As used herein for elements and standards, the term "compatible" means that an element communicates with other elements in a manner specified in whole or in part by the standard, and can be recognized by other elements as being sufficiently capable of communicating with other elements in a manner specified by the standard. Compatible components do not need to be internally operated in the manner specified by the standard.

The elements of the patent-pending scope are not interpreted in accordance with 35 U.S.C. § 112, paragraph 6, unless the elements are clearly stated in the terms "means" or "means".

Although the embodiments of the present invention have been described here, it should be understood that the foregoing embodiments and advantages are only examples and should not be construed as limiting the scope of the present invention or patent application. Those with ordinary knowledge in the technical field can design many other changes and implementations, which fall within the scope of the spirit and principles of this application, and the provisions can also be easily applied to other types of devices, more specifically Therefore, within the scope of the present application, drawings, and appended patent applications, various changes and changes can be made in the arrangement and/or arrangement of element parts in the subject arrangement. In addition to changes and improvements in component parts and/or arrangements, alternatives The use is also obvious to those with ordinary knowledge in the technical field to which they belong.

20‧‧‧ base

21‧‧‧Tunnel oxide layer

22‧‧‧polysilicon layer

23‧‧‧buffer oxide layer

24‧‧‧Nitride pad

25‧‧‧groove

Claims (18)

A composition comprising: a first inorganic acid; at least one silane inorganic acid salt generated by a reaction between a second inorganic acid and a silane compound; and a solvent; wherein the second inorganic acid is selected from sulfuric acid and fuming sulfuric acid , Nitric acid, phosphoric acid, and at least one of their combinations; the aforementioned silane compound is a compound represented by the first chemical formula:

Wherein each of R ¹ to R ⁴ is selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl, and R At least one of ¹ to R ⁴ is one of halogen and (C ₁ -C ₁₀ ) alkyl; and wherein, with respect to the total weight of the aforementioned composition, the aforementioned composition further contains 0.01 to 20% by weight of an ammonium compound. The composition according to claim 1, wherein the aforementioned composition contains 0.01 to 15 wt% of at least one silane inorganic acid salt, 70 to 99 wt% of the first inorganic acid, and the balance of the solvent. The composition according to claim 1, wherein the first inorganic acid is selected from sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, At least one of boric acid, hydrochloric acid, perchloric acid, and combinations thereof. The composition according to claim 1, wherein the composition further contains 0.01 to 1 wt% of a fluorine-based compound relative to the total weight of the composition. A composition comprising: a first inorganic acid; at least one silicate inorganic acid salt produced by a reaction between polyphosphoric acid and a silane compound; and a solvent; wherein the aforementioned composition further comprises 0.01 relative to the total weight of the aforementioned composition Up to 20wt% ammonium compounds. The composition according to claim 5, wherein the at least one silane inorganic acid salt includes a compound represented by the second chemical formula:

Wherein, i) R ^{1 is} selected from hydrogen, halogen, (C ₁ -C ₁₀ ) alkyl, (C ₁ -C ₁₀ ) alkoxy, and (C ₆ -C ₃₀ ) aryl; ii) n ₁ is 1 to An integer of 4; iii) m ₁ is an integer of 1 to 10; iv) each of R ² to R ⁴ is hydrogen. The composition according to claim 6, wherein in the aforementioned at least one silane inorganic acid salt represented by the second chemical formula, one hydrogen atom selected from R ² to R ⁴ is substituted with a substituent represented by the third chemical formula :

Wherein, i) one R ^{5 is} connected to the second chemical formula; ii) the other R ^{5 is} selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C _6- C ₃₀ ) aryl; iii) each of R ² to R ⁴ is hydrogen or substituted by a substituent represented by the third chemical formula; iv) n ₂ is an integer of 0 to 3; v) m ₂ is 1 to An integer of 10. A composition comprising: a first inorganic acid; at least one silicate inorganic acid salt formed by a reaction between a second inorganic acid and a siloxane compound; and a solvent; wherein the second inorganic acid is selected from phosphoric acid , Pyrophosphoric acid, polyphosphoric acid, and combinations thereof; wherein, the aforementioned at least one inorganic acid salt of siloxane includes a compound represented by the fourth chemical formula:

Wherein, i) each of R ¹ to R ² is selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy, and (C ₆ -C ₃₀ )aryl; ii) n ₁ is an integer from 0 to 3; iii) n ₂ is an integer from 0 to 2; iv) m ₁ is _one of the integers 0 and 1; v) the sum of n ₁ , n ₂ and m ₁ is equal to Or more than 1; vii) l ₁ is an integer of 1 to 10; vii) each of O ₁ to O ₃ is an integer of 0 to 10; viii) each of R ³ to R ¹¹ is hydrogen. The composition according to claim 8, wherein in the aforementioned at least one siloxane mineral acid salt represented by the fourth chemical formula, at least one hydrogen selected from R ³ to R ¹¹ is substituted by the fifth chemical formula Substitution:

Where i) one of R ¹² and R ¹³ is connected to the fourth chemical formula; ii) the other R ¹² and R ^{13 are} independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ ) alkoxy and (C ₆ -C ₃₀ ) aryl; iii) each of R ³ to R ¹¹ is hydrogen or substituted by a substituent represented by the fifth chemical formula; iv) n ₃ is 0 to 3 An integer; v) n ₄ is an integer from 0 to 2; vi) m ₁ is an integer from 0 to 1; vii) l ₁ is an integer from 1 to 10; vii) each of O ₁ to O ₃ An integer from 0 to 10. A composition comprising: a first inorganic acid; At least one siloxane inorganic acid salt generated by a reaction between a second inorganic acid and a siloxane compound; and a solvent; wherein the aforementioned second inorganic acid is one selected from sulfuric acid, fuming sulfuric acid, and combinations thereof , Wherein, relative to the total weight of the aforementioned composition, the aforementioned composition further comprises 0.01 to 20% by weight of an ammonium compound. The composition according to claim 10, wherein the aforementioned at least one siloxane inorganic acid salt includes a compound represented by the sixth chemical formula:

Wherein each of R ²¹ and R ²² is independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl; ii) n ₁ is an integer from 0 to 3; iii) n ₂ is an integer from 0 to 2; iv) m ₁ is _one of the integers 0 and 1; v) the sum of n ₁ , n ₂ and m ₁ is equal to Or greater than 1; vi) l ₁ is an integer from 1 to 10; vii) each of R ²³ to R ²⁵ is hydrogen. The composition according to claim 11, wherein in the aforementioned at least one siloxane inorganic acid salt, at least one hydrogen atom selected from R ²³ to R ²⁵ is substituted with a substituent represented by the seventh chemical formula:

Where one of R ²⁶ and R ²⁷ is connected to the sixth chemical formula; ii) the other R ²⁶ and R ^{27 are} independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ ) Alkoxy and (C ₆ -C ₃₀ ) aryl; iii) each of R ²³ to R ²⁵ is hydrogen or substituted by a substituent represented by the seventh chemical formula; iv) n ₃ is an integer of 0 to 3 ; V) n ₄ is an integer from 0 to 2; vi) m ₁ is an integer from 0 to 1; vii) l ₁ is an integer from 1 to 10. A composition comprising: a first inorganic acid; at least one siloxane inorganic acid salt generated by a reaction induced between a second inorganic acid including nitric acid and a siloxane compound; and a solvent; wherein, relative to the aforementioned composition The total weight of the aforementioned composition also contains 0.01 to 20% by weight of ammonium compounds. The composition according to claim 13, wherein the aforementioned at least one siloxane inorganic acid salt includes a compound represented by the eighth chemical formula:

Where i) one of R ³¹ and R ³² is independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy and (C ₆ -C ₃₀ )aryl Ii) n ₁ is an integer from 0 to 3; iii) n ₂ is an integer from 0 to 2; iv) m ₁ is _one of the integers 0 and 1; v) the sum of n ₁ , n ₂ and m ₁ Equal to or greater than 1; vi) l ₁ is an integer from 1 to 10; vii) each of R ³³ to R ³⁵ is hydrogen. The composition according to claim 14, wherein, in the aforementioned at least one siloxane inorganic acid salt, at least one hydrogen selected from R ³³ to R ³⁵ is substituted with a substituent represented by the ninth chemical formula:

Wherein, i) one of R ³⁶ and R ³⁷ is connected to the eighth chemical formula; ii) the other R ³⁶ and R ^{37 are} independently selected from hydrogen, halogen, (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ ) alkoxy and (C ₆ -C ₃₀ ) aryl; iii) each of R ³³ to R ³⁵ is hydrogen or substituted by a substituent represented by the ninth chemical formula; iv) n ₃ is 0 to 3 An integer; v) n ₄ is an integer from 0 to 2; vi) m ₁ is an integer from 0 to 1; vii) l ₁ is an integer from 1 to 10. A composition comprising: a first inorganic acid; at least one silane inorganic acid salt generated by a reaction induced between a second inorganic acid and a first silane compound; a second silane compound; and a solvent; wherein, the aforementioned second inorganic acid Is one selected from sulfuric acid, fuming sulfuric acid, nitric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof; wherein the first silane compound and the second silane compound are selected from the compound represented by the tenth chemical formula, One of the compounds represented by the eleventh chemical formula and their combinations; wherein, the aforementioned tenth chemical formula is:

; And wherein the aforementioned eleventh chemical formula is:

Wherein, i) each of R ¹ to R ¹⁰ is selected from hydrogen, halogen, (C ₁ -C ₁₀ ) alkyl, (C ₁ -C ₁₀ ) alkoxy, and (C ₆ -C ₃₀ ) aryl; ii) at least one of R ¹ to R ⁴ is one of halogen and (C ₁ -C ₁₀ ) alkoxy; iii) at least one of R ⁵ to R ¹⁰ is halogen and (C ₁ -C ₁₀ ) alkane One of the oxygen groups; iv) n is an integer from 1 to 10. The composition according to claim 16, wherein the aforementioned composition contains 0.01 to 15 wt% of at least one silane inorganic acid salt, 70 to 99 wt% of the first inorganic acid, 0.001 to 15 wt% of the second silane compound, and the balance Of solvent. A preparation method of a semiconductor device, the preparation method comprising a process of etching using the composition described in claim 1.

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