Silicon etching solution composition and pattern formation method using the same

Abstract

To provide a silicon etching solution composition that offers improved etching selectivity, and a pattern formation method using the silicon etching solution composition. [Solution] The silicon etching solution composition according to the embodiment of the present disclosure comprises an amine compound, a pyrazine compound, an alkaline compound, and a solvent. According to the pattern forming method according to the embodiment of the present disclosure, a silicon-containing film is formed on a substrate. A silicon protective film containing silicon and germanium is formed on a portion of the silicon-containing film. The silicon-containing film is etched with the silicon etching solution composition.

Description

[Technical Field]

[0001] The present invention relates to a silicon etching solution composition and a pattern forming method using the same. [Background technology]

[0002] In thin-film transistors for display devices such as liquid crystal displays (LCDs) and organic light-emitting diodes (OLEDs), as well as in semiconductor devices such as memory elements, silicon-containing substrates or silicon films manufactured from silicon wafers, polysilicon, amorphous silicon, etc., are used.

[0003] To achieve highly reliable semiconductor device manufacturing processes, fast etching rates and selective etching of the material to be removed are required. For example, a selective etching process can be performed on a silicon film. For instance, a protective film can be formed on the silicon film, allowing for selective etching of only the silicon film while adequately protecting the area where the protective film is formed.

[0004] For example, additional components may be included in the etching solution composition to selectively etch only the silicon layer. However, if components such as halides are included, the etching rate of silicon-containing insulating films such as silicon oxide films and silicon-germanium films, or silicon-containing semiconductor films that combine elements other than silicon, will also increase, potentially reducing the etching selectivity ratio for silicon films. [Overview of the project] [Problems that the invention aims to solve]

[0005] One objective of the present invention is to provide a silicon etching solution composition that offers improved etching selectivity.

[0006] One objective of the present invention is to provide a pattern formation method using the silicon etching solution composition. [Means for solving the problem]

[0007] 1. A silicon etching solution composition comprising an amine compound, a pyrazine compound, an alkaline compound containing one or more organic hydroxides and inorganic hydroxides, and a solvent.

[0008] 2. In item 1 above, the pyrazine compound is a silicon etching solution composition containing a carbonyl group.

[0009] 3. In item 1 above, the pyrazine compound is a silicon etching solution composition comprising a compound represented by the following chemical formula 1. [ka] (In Chemical Formula 1, R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C2-C5 alkenyl groups, substituted or unsubstituted C1-C5 alkylcarbonyl groups, substituted or unsubstituted amide groups, C1-C5 alkoxy groups, amine groups, hydroxyl groups, and carboxyl groups.)

[0010] 4. A silicon etching solution composition in which, in item 3 above, at least one of R1 to R4 in chemical formula 1 is hydrogen.

[0011] 5. A silicon etching solution composition in which, in item 3 above, at least one of R1 to R4 in chemical formula 1 is selected from the group consisting of halogen, C1 to C3 alkyl group, C1 to C3 alkoxy group, amide group, amide group substituted with amine group, amine group, hydroxyl group, and carboxyl group.

[0012] 6. A silicon etching solution composition in which, in item 3 above, at least one of R1 to R4 is selected from the group consisting of an amide group, an amide group substituted with an amine group, and a carboxyl group.

[0013] 7. The silicon etching solution composition according to item 3 above, wherein the halogen is selected from the group consisting of Cl, Br, and I.

[0014] 8. The silicon etching solution composition according to item 1 above, wherein the content of the amine compound is 0.01% by weight to 40% by weight based on the total weight of the silicon etching solution composition. [[ID=⑥]]

[0015] 9. The silicon etching solution composition according to item 1 above, wherein the content of the pyrazine compound is 0.01% by weight to 20% by weight based on the total weight of the silicon etching solution composition.

[0016] 10. The silicon etching solution composition according to item 1 above, wherein the content of the alkaline compound is 0.01% by weight to 40% by weight based on the total weight of the silicon etching solution composition.

[0017] 11. The silicon etching solution composition according to item 1 above, wherein the number of amine groups in the molecule of the amine compound is 3 or more.

[0018] 12. The silicon etching solution composition according to item 1 above, which does not contain a fluorine salt-containing compound.

[0019] 13. A patterning method comprising: a step of forming a silicon-containing film on a substrate; a step of forming a silicon protective film containing silicon and germanium partially on a part of the silicon-containing film; and a step of etching the silicon-containing film with the silicon etching solution composition according to item 1 above.

[0020] 14. The patterning method according to item 13 above, wherein the silicon protective film is used as an etching mask.

[0021] 15. The patterning method according to item 13 above, wherein the step of etching the silicon-containing film includes etching the silicon-containing film to form a gate pattern.

Advantages of the Invention

[0022] By using a silicon etching solution composition according to an exemplary embodiment of the present invention, the etching selectivity for silicon films can be improved. By including a pyrazine compound in the silicon etching solution composition, the etching rate and etching selectivity for silicon films can be enhanced.

[0023] According to exemplary embodiments, by using a pyrazine compound containing a carbonyl group, it is possible to suppress etching of the silicon-germanium film while improving the etching properties of the silicon film. This provides high etching selectivity for the silicon film. [Brief explanation of the drawing]

[0024] [Figure 1] Figure 1 is a schematic cross-sectional view illustrating a pattern formation method according to an exemplary embodiment. [Figure 2] Figure 2 is a schematic cross-sectional view illustrating a pattern formation method according to an exemplary embodiment. [Figure 3] Figure 3 is a schematic cross-sectional view illustrating a pattern formation method according to an exemplary embodiment. [Figure 4] Figure 4 is a schematic cross-sectional view illustrating a pattern formation method according to an exemplary embodiment. [Figure 5] Figure 5 is a schematic cross-sectional view illustrating a pattern formation method according to an exemplary embodiment. [Figure 6] Figure 6 is a schematic cross-sectional view illustrating a pattern formation method according to an exemplary embodiment. [Figure 7] Figure 7 is a schematic cross-sectional view illustrating a pattern formation method according to an exemplary embodiment. [Modes for carrying out the invention]

[0025] Embodiments of this disclosure provide a silicon etching solution composition containing a pyrazine-based compound (hereinafter sometimes abbreviated as "etching solution composition"). Furthermore, a pattern formation method using the silicon etching solution composition is also provided.

[0026] The present disclosure will be described in detail below. However, these embodiments are illustrative and do not limit the invention.

[0027] As used herein, the term "Ca~Cb Y group" refers to a Y group having a number of carbon atoms a~b. For example, Ca~Cb refers to the number of carbon atoms of an unsubstituted Y group, and the Y group may have additional substituents attached.

[0028] According to exemplary embodiments, the silicon etching solution composition may include an amine compound, a pyrazine compound, an alkaline compound, and a solvent.

[0029] The aforementioned amine-based compounds can etch silicon films. Furthermore, the etching of silicon can be accelerated by adjusting or maintaining the pH of the etching solution composition. As used herein, the term "silicon film" may encompass wafers, substrates, thin films (e.g., silicon films formed by a vapor deposition process), etc., that are substantially composed of silicon.

[0030] For example, the amine compound may or may not contain a hydroxyl group. For instance, if the amine compound contains a hydroxyl group, the concentration of hydroxide ions in the etching solution composition may increase, potentially improving the etching rate. For instance, if it does not contain a hydroxyl group, the silicon in the silicon film may react with the amine compound and be etched.

[0031] For example, amine compounds containing a hydroxyl group include 1-amino-2-propanol, 2-amino-1-butanol, 3-amino-1-propanol, 3-amino-1,2-propanediol, methyldiethanolamine, propanolamine, ethanolamine, diethanolamine, N-methylethanolamine, N-methyldiethanolamine, 2-amino-3-methyl-1-butanol, 3-amino-2,2-dimethyl-1-propanol, tris(hydroxymethyl)aminomethane, 2-amino-2-methyl-1,3-propanediol, 3-methylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-dimethylamino-1-propanol, 2-diethylamino-1-propanol, 2-diethylamino-1-ethanol, 2- Examples include ethylamino-1-ethanol, 1-(dimethylamino)2-propanol, N-propyldiethanolamine, N-isopropyldiethanolamine, N-(2-methylpropyl)diethanolamine, Nn-butyldiethanolamine, Nt-butylethanolamine, N-cyclohexyldiethanolamine, 2-(dimethylamino)ethanol, 2-diethylaminoethanol, 2-dipropylaminoethanol, 2-butylaminoethanol, 2-t-butylaminoethanol, 2-cycloaminoethanol, 2-amino-2-pentanol, 2-[bis(2-hydroxyethyl)amino]-2-methyl-1-propanol, 2-[bis(2-hydroxyethyl)amino]-2-propanol, N,N-bis(2-hydroxypropyl)ethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, etc. These can be used individually or in combination of two or more.

[0032] For example, amine compounds that do not contain a hydroxyl group include 1,2-diaminopropane, diethylenetriamine, isopropylamine, triethylamine, trimethylamine, methylamine, ethylamine, aniline (aminobenzene), 2-aminopentane, diethylamine, and N-dodecyldiethylamine. These can be used individually or in combination of two or more.

[0033] For example, the amine compound may include a linear amine compound or a cyclic amine compound.

[0034] For example, linear amine compounds may include the aforementioned compounds.

[0035] For example, the cyclic amine compounds include monoazabicyclo compounds such as 8-azabicyclo[3.2.1]octane, 11-azabicyclo[4.4.1]undecane-1,3,5,7,9-pentene; 1,8-diazabicyclo[6.3.2]tridecane, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 2,8-diazabicyclo[4.3.0]nonane, and 1,4-diazabicyclo[4 Examples include diazabicyclo compounds such as [3.0]nonane, 1,4-diazabicyclo[3.2.2]nonane, 1,4-diazabicyclo[2.2.2]octane, 1,4-diazabicyclo[3.2.1]octane, and 3-benzyl-3,8-diazabicyclo[3.2.1]octane; and triazabicyclo compounds such as 1,5,7-triazabicyclo[4.4.0]deca-5-ene and 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene. These can be used individually or in combination of two or more.

[0036] According to exemplary embodiments, the amine compound may include an alkylamine.

[0037] The alkylamine may represent a compound comprising one or more alkyl groups and alkylene groups, and an amine group. The amine group may include one or more primary amine groups, secondary amine groups, and tertiary amine groups. The secondary amine group and / or tertiary amine group may be bonded to one or more alkyl groups and / or alkylene groups.

[0038] For example, the alkylamine is C x N y H z It can be expressed as (x, y, and z are integers greater than or equal to 1). The value of z can be determined by considering the number of carbon atoms x and nitrogen atoms y of the alkylamine.

[0039] For example, the alkylamines include 1,2-diaminopropane, isopropylamine, methylamine, ethylamine, trimethylamine, 2-aminopentane, diethylamine, triethylamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexaamine, 1,3-propylenediamine, dipropylenetriamine, 1,4-butadiamine, pentamethylenehexaamine, trimethylenediamine, and N,N-dimethylethylenediamine. These can be used individually or in combination of two or more.

[0040] According to exemplary embodiments, the number of amines in the alkylamine molecule may be three or more. For example, the number of nitrogen atoms in the alkylamine may be three or more. This improves the contact efficiency between the alkylamine and silicon, thereby improving the silicon etching properties of the etching solution composition.

[0041] According to exemplary embodiments, the content of the amine compound may be 0.01% to 40% by weight, 0.03% to 37% by weight, 0.05% to 35% by weight, 0.08% to 32% by weight, 0.1% to 30% by weight, 0.3% to 28% by weight, 0.5% to 26% by weight, 0.7% to 25% by weight, 0.8% to 23% by weight, 0.9% to 22% by weight, 0.95% to 21% by weight, or 1% to 20% by weight, based on the total weight of the etching solution composition.

[0042] In one embodiment, the content of the amine compound may be 1% by weight or more and less than 30% by weight, 1% by weight to 20% by weight, 1% by weight to 15% by weight, or 1% by weight to 10% by weight, based on the total weight of the etching solution composition.

[0043] Within the aforementioned range, the etching solution composition can suppress excessive etching of the silicon-germanium film and improve the silicon etching rate. For example, if the content is below the aforementioned range, the etching selectivity may decrease due to excessive etching of the silicon-germanium film. For example, if the content exceeds the aforementioned range, the amine compound may remain on the silicon surface, reducing the silicon etching rate and thus degrading the etching performance.

[0044] The pyrazine compound can form a protective film on the silicon-germanium film, thereby preventing corrosion of the silicon-germanium film (e.g., inhibiting etching). For example, the pyrazine compound can remain on the surface of the silicon-germanium film through hydrogen bonding, thereby reducing the etching rate of the silicon-germanium film surface.

[0045] The aforementioned pyrazine compound may refer to a compound containing a pyrazine structure (an aromatic heterocyclic compound represented by C4H4N2). For example, one or more hydrogen atoms bonded to carbon in the pyrazine structure may be substituted.

[0046] For example, the pyrazine compounds include pyrazine, pyrazineamide, methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, trimethylpyrazine, tetramethylpyrazine, ethylpyrazine, propylpyrazine, isopropylpyrazine, sec-butylpyrazine, methoxypyrazine, ethoxypyrazine, chloropyrazine, bromopyrazine, 2-methoxypyrazine-3-(1-methylpropyl)pyrazine, 3-isobutyl-2-methoxypyrazine, 2-ethoxy-3-methylpyrazine, 2 Examples include -ethoxy-6-methylpyrazine, 3-hydroxypyrazine-2-carboxamide, pyrazine-2-carbhydrazide, pyrazine carboxylic acid, 5-methylpyrazine-2-carboxylic acid, 3-aminopyrazine-2-carboxylic acid, 5-methoxypyrazine-2-carboxylic acid, 6-chloropyrazine-2-carboxylic acid, 2,3-pyrazinedicarboxylic acid, pyrazine-2,5-dicarboxylic acid, 2,6-bis(1,1-dimethylethoxy)pyrazine, and 2-2-(aziridin-1-yl)ethoxy)pyrazine. These can be used individually or in combination of two or more.

[0047] According to exemplary embodiments, the pyrazine compound may contain a carbonyl group. This can further reduce the etching rate of the silicon-germanium film and improve silicon etching selectivity.

[0048] For example, the carbonyl group can be represented as -C(=O)R. For example, R can include hydrogen, an amine group, a hydroxyl group, an alkyl group, an alkylene group, and the like.

[0049] According to exemplary embodiments, the pyrazine compound may include a compound represented by the following chemical formula 1.

[0050] [ka]

[0051] In Chemical Formula 1, R1, R2, R3, and R4 may each independently be selected from the group consisting of hydrogen, halogen, a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C2-C5 alkenyl group, a C1-C5 alkylcarbonyl group, a substituted or unsubstituted amide group, a C1-C5 alkoxy group, an amine group, a hydroxy group, and a carboxy group.

[0052] The alkyl group and the alkenyl group may exhibit a linear or branched structure. For example, a C3 alkyl group may include an n-propyl group, an iso-propyl group, etc.

[0053] For example, the alkylcarbonyl group in Chemical Formula 1 can be represented by -C(=O)R5.

[0054] For example, the alkoxy group in Chemical Formula 1 can be represented by -OR6.

[0055] For example, the amide group in Chemical Formula 1 can be represented by -C(=O)NR a R b as can be represented by.

[0056] For example, R5 may be a C2-C4 alkyl group. R6 may be a C1-C5 alkyl group. R a and R b may each independently be hydrogen or a C1-C5 alkyl group.

[0057] As used herein, the term "substituted" means that any hydrogen in a hydrocarbon group is replaced by a halogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 alkoxy group, a C1-C6 acetyl group, a C6-C12 phenoxy group, a C6-C12 aryl group, a C1-C6 alkylsulfonyl group, a sulfonic acid group, a hydroxy group, a nitro group, an amine group, an amide group, -NR c R d Re(R c 、R d and R eEach of these is independently hydrogen or a C1-C6 alkyl group. This may mean that each is substituted with at least one selected from the group consisting of alkylamine groups and cyano groups.

[0058] According to an exemplary embodiment, at least one of R1 to R4 in the chemical formula 1 may be hydrogen. For example, two or more of R1 to R4 in the chemical formula 1 may be hydrogen.

[0059] According to exemplary embodiments, at least one of R1 to R4 in Chemical Formula 1 may be selected from the group consisting of halogens, C1 to C3 alkyl groups, C1 to C3 alkoxy groups, amide groups, amide groups substituted with amine groups, amine groups, hydroxyl groups, and carboxyl groups.

[0060] In some embodiments, the amide group substituted with the amine group can be represented as -C(=O)NH-NH2.

[0061] In some embodiments, two or more of R1 to R4 in Chemical Formula 1 may be selected from the group consisting of amide groups substituted with amine groups, amine groups, hydroxyl groups, and carboxyl groups.

[0062] In some embodiments, at least one of R1 to R4 in Chemical Formula 1 may be selected from the group consisting of a hydroxyl group, a carboxyl group, and an amide group.

[0063] According to an exemplary embodiment, the compound represented by chemical formula 1 may include the compound represented by the following chemical formula 1-1.

[0064] [ka]

[0065] In chemical formula 1-1, R2, R3, and R4 may each be independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C2-C5 alkenyl groups, substituted or unsubstituted C1-C5 alkylcarbonyl groups, substituted or unsubstituted amide groups, C1-C5 alkoxy groups, amine groups, hydroxyl groups, and carboxyl groups.

[0066] In chemical formula 1-1, R X The group may be selected from the group consisting of hydrogen, amine groups, hydroxyl groups, and C1-C3 alkyl groups.

[0067] According to an exemplary embodiment, in the chemical formula 1-1, R X This may be hydrogen, an amine group, or a hydroxyl group.

[0068] According to exemplary embodiments, in the chemical formula 1-1, at least one of R2 to R4 may be selected from the group consisting of hydrogen, halogen, C1 to C3 alkyl group, C1 to C3 alkoxy group, amide group, amide group substituted with amine group, amine group, hydroxyl group, and carboxyl group.

[0069] According to exemplary embodiments, in the chemical formula 1-1, at least one of R2 to R4 may be selected from the group consisting of hydrogen, halogen, C1 to C3 alkyl group, C1 to C3 alkoxy group, amide group, and carboxyl group.

[0070] According to exemplary embodiments, the halogens in the compounds represented by chemical formula 1 and chemical formula 1-1 may be selected from the group consisting of Cl, Br, and I. For example, the compounds represented by chemical formula 1 and chemical formula 1-1 do not have to contain fluorine atoms. Fluorine atoms in the compounds may increase the etching rate of the silicon-germanium film, which may reduce the etching selectivity.

[0071] According to exemplary embodiments, the pyrazine compound may contain one or more of the following: pyrazineamide, 3-hydroxypyrazine-2-carboxamide, pyrazine-2-carbozide, pyrazinecarboxylic acid, 5-methylpyrazine-2-carboxylic acid, 3-aminopyrazine-2-carboxylic acid, 5-methoxypyrazine-2-carboxylic acid, 6-chloropyrazine-2-carboxylic acid, 2,3-pyrazinedicarboxylic acid, and pyrazine-2,5-dicarboxylic acid.

[0072] According to exemplary embodiments, the content of the pyrazine compound may be 0.01% to 20% by weight, 0.03% to 18% by weight, 0.05% to 17% by weight, 0.1% to 15% by weight, 0.3% to 12% by weight, 0.5% to 10% by weight, 0.7% to 8% by weight, 0.9% to 6% by weight, 1% to 4% by weight, or 1% to 3% by weight, based on the total weight of the etching solution composition.

[0073] In one embodiment, the content of the pyrazine compound may be 1% to 10% by weight, 1% or more and less than 10% by weight, 1% to 5% by weight, or 1% to 3% by weight, based on the total weight of the etching solution composition.

[0074] Within the aforementioned content range, the surface corrosion protection performance of the etching solution composition on silicon-germanium films can be further improved. For example, if the content of the pyrazine compound is excessively low, almost no corrosion protection effect on silicon-germanium films can be obtained, and silicon selectivity may decrease. For example, if the content of the pyrazine compound is excessively high, the silicon solubility of the etching solution composition may decrease due to the pyrazine compound, and etching performance may decrease.

[0075] The alkaline compound can function as a main etching agent for removing the film to be etched (e.g., a silicon film) during the etching process. For example, the alkaline compound can dissociate in solution to generate hydroxide ions, thereby increasing the pH of the etching solution composition and dissolving the silicon in the silicon film.

[0076] According to exemplary embodiments, the alkaline compound may include one or more organic hydroxides and inorganic hydroxides.

[0077] For example, the alkaline compound may contain an inorganic cation or an organic cation as a cation and a hydroxide ion as an anion.

[0078] For example, the organic hydroxides include quaternary alkylammonium hydroxides such as ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, benzyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, methyltributylammonium hydroxide, etc.; azabicyclo-type, diazabicyclo-type, and triazabicyclo-type, which contain nitric acid in the carbon bicyclo structure. Examples include compounds containing one of the triazabicyclo-) type structures and one of the following depending on the number of carbon atoms and bonds: butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, nonene, decene, and undecene; and so on.

[0079] For example, the inorganic hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, and the like.

[0080] According to exemplary embodiments, the organic hydroxide may include a quaternary alkylammonium hydroxide.

[0081] According to exemplary embodiments, the quaternary alkylammonium hydroxide may include a compound represented by the following chemical formula 2.

[0082] [ka]

[0083] In chemical formula 2, R 1 , R 2 , R 3 and R 4 Each of these is independently a C1-C8 alkyl group or aryl group.

[0084] According to an exemplary embodiment, in the chemical formula 2, R 1 ~R 4 At least one of them may be a C1-C4 alkyl group.

[0085] According to an exemplary embodiment, in the chemical formula 2, R 1 ~R 4 Each of these may independently be a C1-C4 alkyl group.

[0086] R 1 , R 2 , R 3 and R 4 When the number of carbon atoms in each atom falls within the aforementioned range, the dissociation activity of hydroxide ions in quaternary alkylammonium hydroxide increases, thereby improving etching performance.

[0087] In exemplary embodiments, the content of the alkaline compound may be 0.01% to 40% by weight, 0.03% to 37% by weight, 0.05% to 35% by weight, 0.08% to 32% by weight, 0.1% to 30% by weight, 0.3% to 28% by weight, 0.5% to 26% by weight, 0.7% to 25% by weight, 0.8% to 23% by weight, 0.9% to 22% by weight, 0.95% to 21% by weight, or 1% to 20% by weight, based on the total weight of the etching solution composition.

[0088] Within the aforementioned range, the degree of dissociation of hydroxide ions or the amount dissociated from the composition is ensured, and sufficient etching performance can be achieved.

[0089] The etching solution composition may contain an excess or residual amount of solvent. As used in this application, the terms “excess” or “residual” may refer to a variable amount that changes with the addition of components or formulations. For example, it may mean the amount remaining after removing the aforementioned amine compounds, pyrazine compounds and alkaline compounds, or the amount remaining after removing the aforementioned amine compounds, pyrazine compounds, alkaline compounds and other additives.

[0090] According to exemplary embodiments, the solvent may include water. For example, the water may include distilled water, deionized water, and the like.

[0091] In some embodiments, the water may be deionized water used in semiconductor processes.

[0092] In some embodiments, the water content relative to the total weight of the etching solution composition may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 75% by weight or more, or 80% by weight or more. The upper limit of the water content can be variably adjusted by the content of the aforementioned amine compounds, pyrazine compounds, alkaline compounds and additives. For example, the water content may be less than 99% by weight, 98% by weight or less, 96% by weight or less, 95% by weight or less, 90% by weight or less, or 85% by weight or less.

[0093] The etching solution composition may further contain other additives, provided that they do not impair the etching performance, corrosion protection performance, etc., of each of the aforementioned amine compounds, pyrazine compounds, and alkaline compounds. Examples of such additives include etching accelerators, corrosion inhibitors, and pH adjusters.

[0094] In some embodiments, the pH of the etching solution composition can be adjusted to a range of about 11 to 14. Within this pH range, damage to other insulating structures, semiconductor patterns, substrates, etc., during etching of the silicon film can be suppressed.

[0095] According to exemplary embodiments, the etching solution composition does not need to contain a fluoride-containing compound. This improves corrosion protection of the silicon-germanium film and etching selectivity for the silicon film. For example, if the fluoride-containing compound is included, the etching rate for the silicon-germanium film increases, and corrosion protection of the silicon-germanium film may not be achieved.

[0096] For example, the fluoride-containing compound is a compound containing fluoride ions (F - This can refer to compounds containing fluoride. For example, examples of fluoride-containing compounds include tetramethylammonium fluoride, tetraethylammonium fluoride, and diethyldimethylammonium fluoride.

[0097] In some embodiments, the etching solution composition does not need to contain a thickening agent such as a carboxymethylcellulose compound. This prevents etching non-uniformity caused by an increase in the viscosity of the etching solution composition.

[0098] According to exemplary embodiments, the etching rate of the etching solution composition with respect to the silicon film may be 3000 Å / min or more, 3500 Å / min or more, 4000 Å / min or more, 4500 Å / min or more, or 5000 Å / min or more. Within this range, a selective etching effect on silicon can be effectively achieved, and the efficiency of the etching process can be improved.

[0099] According to exemplary embodiments, the etching rate of the etching solution composition with respect to the silicon-germanium film may be less than 35 Å / min, 30 Å / min or less, 25 Å / min or less, or 20 Å / min or less. The lower limit of the etching rate of the etching solution composition with respect to the silicon-germanium film is not limited, but may be, for example, 0.1 Å / min or more, or 0.5 Å / min or more. Within this range, the protective film of the insulating film is maintained during the etching process, and patterns and the like can be efficiently formed.

[0100] The silicon etching method using the etching solution composition can be carried out by methods commonly known in the art. For example, a batch-type etching apparatus or a single-wafer etching apparatus can be used, and methods such as immersion, spraying, or a combination of immersion and spraying can be used. However, these conditions are not strictly applicable, and those skilled in the art may select conditions that are easily or suitably chosen.

[0101] In some embodiments, the etching solution composition can selectively etch a silicon film while suppressing the etching of the silicon oxide film and / or silicon nitride film.

[0102] Figures 1 to 7 are schematic cross-sectional views illustrating a pattern formation method according to an exemplary embodiment.

[0103] However, the etching solution compositions according to the exemplary embodiments are not limited to use in the processes shown in Figures 1 to 7, and can be used in the process of forming various structures or patterns such as wiring, contacts, and gates within the concept and technical scope of the present invention.

[0104] For example, Figures 1 to 3 are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an exemplary embodiment.

[0105] Referring to Figure 1, an insulating film 110 can be formed on the substrate 100, and a silicon-containing film 120 can be formed on the insulating film 110.

[0106] The substrate 100 contains semiconductor materials such as single-crystal silicon and single-crystal germanium, and may also contain polysilicon.

[0107] The insulating film 110 can be formed to include insulating materials such as silicon oxide, silicon nitride, silicon oxynitride, and polysiloxane. For example, the insulating film 110 can be formed by chemical vapor deposition (CVD), sputtering, physical vapor deposition (PVD), atomic layer deposition (ALD), and the like.

[0108] The silicon-containing film 120 may include one or more of single-crystal silicon, polysilicon, and amorphous silicon.

[0109] Referring to Figure 2, a silicon protective film 130 can be formed on the silicon-containing film 120. The silicon protective film 130 can be formed to include a film containing silicon and germanium. For example, it can be formed to include a silicon-germanium film. For example, the silicon protective film 130 can be formed by a CVD process, a sputtering process, a PVD process, an ALD process, etc.

[0110] The silicon protective film 130 can be partially etched to form a mask pattern 132. For example, a portion of the silicon protective film 130 may be partially etched until a portion of the upper surface of the silicon-containing film 120 is exposed.

[0111] Referring to Figure 3, the silicon-containing film 120 can be partially removed using the etching solution composition according to the exemplary embodiment described above. This allows the gate pattern 122 to be formed from the silicon-containing film 120.

[0112] As described above, since the etching solution composition contains a pyrazine compound, it can enhance the etching performance on silicon and the corrosion protection effect on the silicon protective film. This makes it possible to selectively etch only the silicon-containing film 220 while effectively preventing etching of the mask pattern 132, thereby forming a highly reliable gate pattern 122.

[0113] Figures 4 to 7 are schematic cross-sectional views illustrating a pattern formation method according to an exemplary embodiment. Specifically, Figures 4 to 7 illustrate an exemplary embodiment of STI (shallow pattern formation). This is a schematic cross-sectional view illustrating the method of forming a trench isolation.

[0114] Referring to Figure 4, a silicon protective film 210 can be formed on the substrate 200.

[0115] The substrate 200 may be a silicon substrate containing single-crystal silicon, polysilicon, or amorphous silicon.

[0116] The silicon protective film 210 may contain silicon and germanium. In this case, the silicon protective film 210 can be formed by chemical vapor deposition (CVD), sputtering, physical vapor deposition (PVD), atomic layer deposition (ALD), etc., so as to cover the upper surface of the substrate 200.

[0117] Referring to Figure 5, the mask pattern 215 can be formed by partially etching the silicon protective film 210. For example, a portion of the silicon protective film 210 may be etched until a portion of the upper surface of the substrate 200 is exposed.

[0118] Referring to Figure 6, the upper part of the substrate 200 can be partially etched using the etching solution composition according to the exemplary embodiment described above. This allows trenches 220 to be formed inside the substrate 200.

[0119] As described above, by using the etching solution composition, etching of the mask pattern 215 can be prevented, and only the upper part of the substrate 200 can be selectively etched. This makes it possible to remove the upper part of the substrate 200 without generating etching defects, for example, in a nanoscale micro-etching process, and to perform a highly reliable etching process.

[0120] Referring to Figure 7, an insulating pattern 230 can be formed inside the trench 220.

[0121] The insulating pattern 230 can be formed to include an insulating material such as silicon oxide, silicon nitride, silicon oxynitride, or polysiloxane. For example, the insulating material can be formed by a CVD process, sputtering process, PVD process, ALD process, etc., so as to fill the inside of the trench 220.

[0122] The embodiments of the present invention will be further described below with reference to specific experimental examples. The examples and comparative examples included in the experimental examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be obvious to those skilled in the art that various changes and modifications to the examples are possible within the scope of the present invention and the technical concept, and that such variations and modifications naturally fall within the scope of the appended claims.

[0123] Examples and Comparative Examples As shown in Tables 1 and 2 below, silicon etching solution compositions were prepared. Water was added as the remainder to produce a total of 100 parts by weight of the composition.

[0124] [Table 1] JPEG2026116752000007.jpg80161

[0125] Amine compounds A-1: Triethylenetetramine A-2: Diethylenetriamine A-3: Tetraethylenepentamine A-4: Tripropylenetetramine A-5: Ethylenediamine Cyclic compounds B-1: Pyrazinamide B-2: 3-Hydroxypyrazine-2-carboxamide B-3: Pyrazine-2-carbohydrazide B-4: Pyrazinecarboxylic acid B-5: 5-Methylpyrazine-2-carboxylic acid B-6: 3-Aminopyrazine-2-carboxylic acid B-7: 5-Methoxypyrazine-2-carboxylic acid B-8: 6-Chloropyrazine-2-carboxylic acid B-9: 2,3-Pyrazinedicarboxylic acid B-10: Pyrazine-2,5-dicarboxylic acid B-11: Pyrazine C-1: Piperazine C-2: Pyridine C-3: Pyridine-2-carboxylic acid Alkaline compounds D-1: Tetramethylammonium hydroxide D-2: Ammonium hydroxide D-3: Potassium hydroxide Fluoride F-1: Tetramethylammonium fluoride water ultra pure water

[0126] Experimental example Experimental Example 1: Evaluation of silicon etching performance A silicon wafer was cut into 1.5 cm x 1.5 cm pieces to prepare test specimens. The test specimens were immersed in each of the etching solution compositions described in the above examples and comparative examples. The temperature of the etching solution composition was maintained at 70°C, and the test specimens were immersed while being stirred at a speed of 400 rpm for 5 minutes. The test specimens were then removed, washed with water, and dried using air. The etching rate of the silicon film was calculated from the change in film thickness before and after immersion using SEM analysis. The etching performance was evaluated according to the following criteria. <Evaluation Criteria> ◎: Etching speed of 4000 Å / min or higher ○: Etching rate less than 4000 Å / min to 3500 Å / min or more △: Etching rate less than 3500 Å / min to 3000 Å / min or more ×: Etching rate less than 3000 Å / min

[0127] Experimental Example 2. Evaluation of the corrosion protection performance of silicon-germanium films. A silicon-germanium film was cut into 1.5 cm x 1.5 cm pieces to prepare test specimens. The test specimens were immersed in the etching solution compositions of the examples and comparative examples. The temperature of the etching solution composition was maintained at 70°C, and the test specimens were immersed while being stirred at a speed of 400 rpm for 1 minute. The test specimens were then removed, washed with water, and dried using air. An ellipsometer was used to calculate the etching rate of the silicon-germanium film from the change in film thickness before and after immersion. The etching rate was evaluated according to the following criteria. <Evaluation Criteria> ◎: Etching rate 25 Å / min or less ○: Etching rate exceeding 25 Å / min to 30 Å / min or less △: Etching rate exceeding 30 Å / min to 35 Å / min or less ×: Etching rate exceeding 35 Å / min The evaluation results of the aforementioned experimental example are shown in Table 2 below.

[0128] [Table 2] JPEG2026116752000009.jpg65151

[0129] Referring to Table 2 above, in the examples containing amine compounds, pyrazine compounds in cyclic compounds, alkaline compounds, and solvents, silicon etching performance and corrosion protection performance of silicon-germanium films were improved compared to the comparative examples.

[0130] In Example 1, where the amine compound content was relatively low, the corrosion protection performance of the silicon-germanium film was relatively reduced.

[0131] In Example 7, where the content of amine compounds was relatively high, the corrosion protection performance of the silicon-germanium film was relatively reduced.

[0132] In Example 8, where the pyrazine compound content was relatively low, the corrosion protection performance of the silicon-germanium film was relatively reduced.

[0133] In Example 13, which had a relatively high pyrazine compound content, the silicon etching performance was relatively reduced.

[0134] In Example 14, where the alkaline compound content was relatively low, the silicon etching performance was relatively reduced.

[0135] In Example 19, which had a relatively high content of alkaline compounds, the corrosion protection performance of the silicon-germanium film was relatively reduced.

[0136] In Example 27, which included a pyrazine compound that does not contain a carbonyl group, the corrosion protection performance of the silicon-germanium film was relatively reduced.

[0137] In Examples 30 and 33, where the number of amine groups in the amine compounds was relatively small, the corrosion protection performance of the silicon-germanium film was relatively reduced.

[0138] In Comparative Example 10, which contained fluoride, the silicon etching performance and the corrosion protection performance of the silicon-germanium film were significantly reduced.

Claims

1. Amine compounds and, Pyrazine compounds and Alkaline compounds containing one or more organic hydroxides and inorganic hydroxides, A silicon etching solution composition comprising a solvent.

2. The silicon etching solution composition according to claim 1, wherein the pyrazine compound contains a carbonyl group.

3. The silicon etching solution composition according to claim 1, wherein the pyrazine compound comprises a compound represented by the following chemical formula 1. 【Chemistry 1】 (In chemical formula 1, R １ , R ２ , R ３ and R ４ Each of these is independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C2-C5 alkenyl groups, substituted or unsubstituted C1-C5 alkylcarbonyl groups, substituted or unsubstituted amide groups, C1-C5 alkoxy groups, amine groups, hydroxyl groups, and carboxyl groups.

4. In the above chemical formula 1, R １ ~R ４ The silicon etching solution composition according to claim 3, wherein at least one of the elements is hydrogen.

5. In the above chemical formula 1, R １ ~R ４ The silicon etching solution composition according to claim 3, wherein at least one of is selected from the group consisting of halogens, C1-C3 alkyl groups, C1-C3 alkoxy groups, amide groups substituted with amine groups, amide groups, amine groups, hydroxyl groups, and carboxyl groups.

6. The above R １ ~R ４ At least one of which is selected from the group consisting of an amide group, an amide group substituted with an amine group, and a carboxy group, the silicon etching liquid composition according to claim 3.

7. The silicon etching solution composition according to claim 3, wherein the halogen is selected from the group consisting of Cl, Br, and I.

8. The silicon etching solution composition according to claim 1, wherein the content of the amine compound is 0.01% by weight to 40% by weight based on the total weight of the silicon etching solution composition.

9. The silicon etching solution composition according to claim 1, wherein the content of the pyrazine compound is 0.01% to 20% by weight relative to the total weight of the silicon etching solution composition.

10. The silicon etching solution composition according to claim 1, wherein the content of the alkaline compound is 0.01% by weight to 40% by weight based on the total weight of the silicon etching solution composition.

11. The silicon etching solution composition according to claim 1, wherein the number of amine groups in the molecule of the amine compound is three or more.

12. The silicon etching solution composition according to claim 1, which does not contain a fluoride-containing compound.

13. The steps include forming a silicon-containing film on a substrate, The steps include forming a silicon protective film partially containing silicon and germanium on a portion of the silicon-containing film, A method for forming a pattern, comprising the step of etching the silicon-containing film with the silicon etching solution composition described in claim 1.

14. The pattern forming method according to claim 13, wherein the silicon protective film is used as an etching mask.

15. The pattern forming method according to claim 13, wherein the step of etching the silicon-containing film includes etching the silicon-containing film to form a gate pattern.

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