Etching composition and method for manufacturing semiconductor device by using same

Abstract

The present invention relates to an etching composition and a method for manufacturing a semiconductor device by using same, the etching composition comprises: an inorganic acid; a first etching inhibitor; and a remainder of solvent, wherein the first etching inhibitor includes at least two nitrogen atoms while including a heterocyclic structure containing at least one nitrogen atom.

Description

Etching composition and method for manufacturing semiconductor devices using the same

[0001] The present invention relates to an etching composition and a method for manufacturing a semiconductor device using the same, and more particularly, to an etching composition for etching a nitride film and a method for manufacturing a semiconductor device using the same.

[0002]

[0003] Recently, with the increasing multi-functionality of information and communication devices, semiconductor devices including memory elements are required to have larger capacities and higher integration. As the memory cell size is reduced for higher integration, the operating circuits and wiring structures included in the memory devices for the operation and electrical connection of the memory devices are also becoming more complex. In the manufacturing process of highly downscaled semiconductor devices, representative insulating films such as oxide films and nitride films may be used individually or in an alternating layer. In order to form electronic devices with complex and miniaturized structures, such as three-dimensional structures, a selective etching process of the nitride film formed in a pattern of various shapes may be required. In particular, an etching composition that can secure sufficient etching selectivity of the nitride film without causing problems such as unnecessary particle generation or undesirable abnormal growth of byproducts on the oxide film surface during the nitride film etching process is required.

[0004] In integrated circuit (semiconductor) devices, oxide films such as silicon oxide (SiO2) and nitride films such as silicon nitride (SiNx) are representative insulating films, each of which can be formed singly or in alternating layers of one or more layers. These oxide and nitride films are also used as hard masks to form conductive patterns such as metal wiring.

[0005] In the wet etching process for removing the above nitride film, an etching composition mixed with phosphoric acid and deionized water is generally used. At this time, the deionized water is added to prevent a decrease in the etching rate and a change in the etching selectivity for the oxide film. However, there was a problem in that defects occurred due to slight changes in the amount of deionized water when removing the nitride film through the wet etching process, and this limited the ability to etch the nitride film to the required level.

[0006] In addition, in the case of recent logic semiconductors, attention is being paid to forming elements with a three-dimensional stacked structure in a vertical structure in order to increase integration in a horizontal manner, and in this case, a germanium-containing film is included, such as silicon-germanium (Ge).

[0007] Therefore, in the case of the etching process of logic semiconductors, there is a need for an etching composition that increases the etching rate of the silicon nitride film while maintaining a low etching rate of the germanium-containing film within the process conditions. In particular, the etching process is sometimes performed at a high temperature in the range of 130°C to 170°C. In this case as well, in order to have a high etching selectivity of the nitride film compared to the germanium-containing film, selection of an additive material within a certain range is a very important task and research is ongoing.

[0008] In addition, when an additive is included in the nitride film etchant, there are problems such as the occurrence of bubbles due to gases such as H2 in the etchant itself, which are adsorbed on the surface of the silicon wafer and cause side effects such as hindering the selective etching of the nitride film, and there is a need for additional means to solve this problem.

[0009]

[0010] The present invention has been devised to solve the above-mentioned problem, and one embodiment of the present invention provides an etching composition capable of securing sufficient etching selectivity of a nitride film compared to a germanium-containing film without causing problems such as the generation of bubbles in an etchant.

[0011] In addition, another embodiment of the present invention provides a method for manufacturing a semiconductor device, which can secure a sufficient etching selectivity of a nitride film compared to an optimized germanium-containing film in a predetermined temperature range while etching a nitride film of various shapes for implementing an electronic device having a complex and miniaturized, particularly three-dimensional, layered structure, thereby ensuring stability and reliability of the nitride film etching process and improving productivity of the semiconductor device manufacturing process.

[0012] In addition, another embodiment of the present invention provides a method for manufacturing an integrated circuit device.

[0013] In addition, another embodiment of the present invention provides an integrated circuit device.

[0014] The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0015]

[0016] As a technical means for achieving the aforementioned technical task, one aspect of the present invention is,

[0017] An etching composition is provided, comprising: an inorganic acid; a first etching inhibitor; and a residual amount of a solvent, wherein the first etching inhibitor comprises at least two nitrogen atoms and comprises a heterocyclic structure containing at least one nitrogen atom.

[0018] A second etching inhibitor is further included, wherein the first etching inhibitor can inhibit etching of a germanium-containing film, and the second etching inhibitor can inhibit etching of a silicon oxide film.

[0019] The above first etching inhibitor may be represented by the following chemical formula 1 or chemical formula 2.

[0020] [Chemical Formula 1]

[0021]

[0022] [Chemical Formula 2]

[0023]

[0024] In the above chemical formula 1 or chemical formula 2, A1 to A9 are each independently carbon or nitrogen, and R 21 Inland R 24 and R 31 Inland R 35 are each independently hydrogen, halogen, amino group, amide group, hydroxyl group, thiol group (-SH or =S), -NO2, -NHCOR 41 (R 41 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 42 (R 42 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -OCOR 43 (R 43 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and when all of A1 to A4 in the above chemical formula 1 are carbon, the R 21 Inland R 24 At least one of them is an amino group, an amide group, -NO2, -NHCOR 51 (R 51is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 52 (R 52 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, or when all of A5 to A9 in the above chemical formula 2 are carbon, the above R 31 Inland R 35 At least one of them is an amino group, an amide group, -NO2, -NHCOR 61 (R 61 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 62 (R 62 It may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms.

[0025] The first etch inhibitor may be nicotinamide, pyrimidine, or imidazole.

[0026] The above second etching inhibitor may be represented by any one selected from the following chemical formulas 3 to 5.

[0027] [Chemical Formula 3]

[0028]

[0029] In the above chemical formula 3, R1 is selected from the group consisting of a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetyloxy group, and a substituted or unsubstituted haloalkylacetyloxy group having 1 to 20 carbon atoms, and R2 and R3 may be a hydroxy group.

[0030] [Chemical Formula 4]

[0031]

[0032] In the above chemical formula 4, R4 is hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted amino (C1-C) group having 1 to 20 carbon atoms 10 )alkylamino(C1-C 10 )alkyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylcarbonyloxy group having 1 to 20 carbon atoms, and cyano (C1-C 10 ) is selected from the group consisting of alkyl groups, R5 to R 11 are each independently hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted amino (C1-C 10 )alkylamino(C1-C 10 )alkyl group, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano (C1-C 10 ) is selected from the group consisting of alkyl groups, m is an integer from 1 to 10, and when m is 2 or more, each of a plurality of R4, R 10 , and R 11 may all be the same or at least some may be different.

[0033] [Chemical Formula 5]

[0034]

[0035] In the above chemical formula 5, R 12 is hydrogen, an alkyl group, an aminoalkyl group or an aminoalkoxy group, and R 13 , R 14 and R 15 At least one of them is an amino alkyl group or an amino alkoxy group, and l can be 2 or 3.

[0036] The second etching inhibitor is represented by the above chemical formula 4, and in the chemical formula 4, R4 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 4 carbon atoms, and R 5, R 6, R 10 and R 11 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 5 carbon atoms, R7 to R9 are each independently selected from the group consisting of hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 5 carbon atoms, and m may be an integer of 1 to 5.

[0037] The second etching inhibitor may be represented by the following chemical formula 6:

[0038] [Chemical Formula 6]

[0039]

[0040] In the above chemical formula 6, the R 16 is a methyl group, an ethyl group, or a propyl group, and n is an integer from 1 to 5, and when n is 2 or more, multiple R 16 may all be the same or at least some may be different.

[0041] The etching composition may include 7 to 85 wt% of the inorganic acid, 0.1 to 10 wt% of the first etching inhibitor, 0.1 to 10 wt% of the second etching inhibitor, and the remaining amount of a solvent, based on the entire etching composition.

[0042] The first etching inhibitor may be present in an amount of more than 0.1 wt% to 2 wt% relative to the total weight of the etching composition.

[0043] The second etching inhibitor may be present in an amount of more than 0.1 wt% to 3 wt% relative to the total weight of the etching composition.

[0044] The above inorganic acid may include at least one selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrochloric acid, and perchloric acid.

[0045] The above etching composition may further include an ammonium compound.

[0046] The above ammonium compound may include at least one of ammonium chloride, ammonium phosphate, ammonium acetate, ammonium sulfate, ammonium formate, and a metal amine complex salt.

[0047] The etching selectivity of the silicon nitride film / germanium-containing material film of the above etching composition may be characterized by being 50 or more.

[0048] It may be characterized in that the bubble height on the surface immediately after formation of the above etching composition is 0.9 cm or less.

[0049] The above etching composition may be used for an integrated circuit element including a silicon oxide film, a silicon nitride film, and a germanium-containing film, to suppress etching of the germanium-containing film and to etch the silicon oxide film and the silicon nitride film.

[0050] The above etching composition may be used for an integrated circuit element including a silicon oxide film, a silicon nitride film, and a germanium-containing film, to suppress etching of the germanium-containing film and the silicon oxide film, and to etch the silicon nitride film.

[0051]

[0052] Another aspect of the present invention is:

[0053] A method for manufacturing an integrated circuit device is provided, comprising: a step of forming a structure by stacking a plurality of insulating films and a plurality of sacrificial films on a substrate; and a step of performing an etching process using the etching composition to remove the sacrificial films and form a space region.

[0054] The sacrificial film may include silicon nitride, and the insulating film may include a germanium-containing material or silicon oxide.

[0055] In the above etching process, the sacrificial film may be characterized by having a higher etching rate than the insulating film.

[0056] In the step of performing the above etching process to remove the sacrificial film and form a space region, the space region may be characterized by including a gate region formed between the insulating films and a trench connected to the gate region.

[0057] Further comprising forming openings penetrating the laminated structure; and forming an integrated circuit pattern within the openings and spaced apart from the trenches, wherein forming the integrated circuit pattern may be performed prior to forming the trenches.

[0058]

[0059] Another aspect of the present invention is:

[0060] The present invention provides an integrated circuit device comprising: a structure formed by stacking an insulating film and a sacrificial film; a space formed by etching the sacrificial film in the structure by an etching composition; and a deposition portion formed by depositing a conductive material or an insulating material in the space; wherein the etching composition comprises an inorganic acid, a first etching inhibitor, a second etching inhibitor, and a remaining amount of a solvent, wherein the first etching inhibitor comprises at least two nitrogen atoms, and the device comprises a heterocyclic structure containing at least one nitrogen atom.

[0061]

[0062] According to one embodiment of the present invention, since the etching selectivity of the nitride film is high, the etching rate of the germanium-containing film can be controlled, thereby easily controlling the effective oxide height (EFH). In addition, the etching composition of the present invention can prevent damage to the film quality of the germanium-containing film when removing the nitride film, deterioration of electrical characteristics due to etching of the germanium-containing film, and particle generation, thereby improving the reliability of semiconductor devices.

[0063] In addition, when etching a nitride film, even when the nitride film and the germanium-containing film or oxide film are alternately laminated or mixed, only the nitride film can be selectively etched with a relatively high etching selectivity between the nitride film and the germanium-containing film or oxide film. Therefore, in order to construct an electronic device having a complex and miniaturized structure, while etching a nitride film formed of patterns of various shapes, sufficient etching selectivity of the nitride film compared to the oxide film or germanium-containing film can be secured without causing the above-mentioned problems, thereby ensuring the stability and reliability of the nitride film etching process, and by preventing damage to the germanium-containing film or oxide film exposed to the etching composition together with the nitride film or deterioration of the electrical characteristics of the germanium-containing film or oxide film, the productivity of the semiconductor device manufacturing process can be improved, and the reliability of the semiconductor device can be improved.

[0064] Therefore, the etching composition of the present invention can be usefully used in a semiconductor device manufacturing process requiring selective removal of a nitride film with respect to a germanium-containing film or oxide film (e.g., a micro-etching process for devices such as logic semiconductor devices and image sensors, a device separation process for flash memory devices, a pipe channel formation process for 3D flash memory devices, a diode formation process for phase change memory devices, etc.), thereby contributing to improving the efficiency of the semiconductor device manufacturing process.

[0065] In addition, by containing an additive material that can obtain both the characteristics of improving the etching selectivity of the etchant and exhibiting an optimized effect in a predetermined temperature range, an etching composition having high process usability can be provided.

[0066] In addition, it is possible to suppress the occurrence of bubbles due to gases such as H2 that may be generated during the process in the etchant itself and the phenomenon of these bubbles being adsorbed on the surface of a silicon wafer and interfering with the selective etching of the nitride film.

[0067] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the composition of the invention described in the claims.

[0068]

[0069] FIG. 1 illustrates a plan view of a semiconductor device according to embodiments of the present invention.

[0070] FIGS. 2 to 8 are drawings for explaining a method for manufacturing a semiconductor device according to embodiments of the present invention.

[0071] Figure 9 is an enlarged view of area A of Figure 8.

[0072]

[0073] Hereinafter, the present invention will be described in more detail. However, the present invention may be implemented in various different forms, and the present invention is not limited to the embodiments described herein, but is defined only by the claims set forth below.

[0074] Additionally, the terminology used herein is solely for the purpose of describing specific embodiments and is not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. Throughout the specification of the present invention, the term "including" or "comprising" a component does not exclude other components, but rather implies the inclusion of other components, unless specifically stated otherwise.

[0075] As used herein, “silicon nitride film”, “silicon nitride” and “Si x N y "is applicable not only to pure silicon nitride but also to impure silicon nitride containing hydrogen, carbon and / or oxygen impurities in the crystal structure (wherein, x and y are each independently positive integers).

[0076] As used herein, “silicon oxide film” and “silicon oxide” refer to silicon oxide (SiO x ), for example, SiO2, "thermal oxide" (ThOx), etc. Silicon oxide may be deposited on a substrate by any method, such as thermal deposition or deposition via chemical vapor deposition from TEOS or other sources. Silicon oxide may generally contain low levels of other materials or impurities that are commercially useful. Silicon oxide may be present as a feature of a microelectronic device, for example, as an insulating layer.

[0077] As used herein, "at least partial removal of silicon nitride material" corresponds to removal of at least a portion of an exposed silicon nitride layer. For example, partial removal of silicon nitride includes anisotropic removal of silicon nitride covering / protecting a gate electrode to form Si3N4. It is contemplated that the compositions of the present invention may be more generally used to substantially remove silicon nitride compared to polysilicon and / or silicon oxide films. In this context, "substantially removing" may mean that in one embodiment of the present invention, at least 90%, in another embodiment at least 95%, and in another embodiment at least 99% of the silicon nitride material is removed using the compositions of the present invention.

[0078] In this specification, “substituted or unsubstituted” may mean substituted or unsubstituted with one or more substituents selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a silyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, a carboxyl group, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group. Specifically, “substituted or unsubstituted” may mean substituted or unsubstituted with one or more substituents selected from the group consisting of a hydrogen atom, a deuterium atom, an alkyl group, an amino group, a silyl group, and an alkoxy group. In addition, each of the above-mentioned substituents may be substituted or unsubstituted. For example, a methyl amino group and an aminoalkyl amino group may be interpreted as an amino group.

[0079] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms.

[0080] In this specification, the alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, i-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, Examples thereof include, but are not limited to, t-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyloctyl group, 3,7-dimethyloctyl group, cyclooctyl group, n-nonyl group, and n-decyl group.

[0081] For example, the term "C1-C20 alkyl group" as used in the specification refers to a straight-chain or branched non-cyclic saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. The term "C2-C20 alkenyl group" refers to a straight-chain or branched non-cyclic unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms and having at least one double bond between adjacent carbon atoms. The term "C2-C20 alkynyl group" may refer to a straight-chain or branched non-cyclic unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms and having at least one triple bond between adjacent carbon atoms. The term "C1-C20 alkoxy group" may refer to a straight-chain or branched non-cyclic saturated or unsaturated aliphatic hydrocarbon group having one or more ether groups and 1 to 20 carbon atoms.

[0082] In the present specification, the amino group may include an alkyl amino group and an aryl amino group. Examples of amino groups include, but are not limited to, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, and / or an ethylmethylamino group.

[0083] In the present specification, the alkoxy group may include an alkyl alkoxy group and an aryl alkoxy group. Examples of the alkoxy group include, but are not limited to, a methyl alkoxy group, an ethyl alkoxy group, a propyl alkoxy group, a butyl alkoxy group, a pentyl alkoxy group, a hexyl alkoxy group, a heptyl alkoxy group, an octyl alkoxy group, a nonyl alkoxy group, and a decyl alkoxy group.

[0084] As used herein, “%” may mean “weight%” or “wt%” in terms of content, unless otherwise specified.

[0085]

[0086] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0087]

[0088] Examples 1 to 6 and Comparative Examples 1 to 10. Preparation of etching compositions

[0089] As a compound contained in the additive, the first etching inhibitor was added according to the type and content according to Table 1 below, and the second etching inhibitor was R of the chemical formula 6 above. 16 The type and content range were varied according to Table 1 below (n in Chemical Formula 6 was 1), and the remaining amount of phosphoric acid was included.

[0090] Inorganic acid (type / content) 1st etching inhibitor (germanium-containing film etching inhibitor) 2nd etching inhibitor (silicon oxide film etching inhibitor) 85 wt% phosphoric acid aqueous solution Content (weight%) Type Content (weight%) Type (substituent type of R16) Content (weight%) Example 1 Phosphoric acid residue Nicotine amide 0.3 Methyl 0.3 Example 2 Phosphoric acid residue Pyrimidine 0.5 Ethyl 0.5 Example 3 Phosphoric acid residue Imidazole 0.8 Propyl 1 Example 4 Phosphoric acid residue Nicotine amide 1 Methyl 2 Example 5 Phosphoric acid residue Pyrimidine 1 Ethyl 3 Example 6 Phosphoric acid residue Imidazole 2 Propyl 1 Comparative example 1 Phosphoric acid residue Nicotine amide 0.1 Methyl 0.3 Comparative example 2 Phosphoric acid residue Nicotine amide 3 Methyl 0.3 Comparative example 3 Phosphate residue Pyrimidine 0.1 Ethyl 0.5 Comparative example 4 Phosphate residue Pyrimidine 2.5 Ethyl 0.5 Comparative example 5 Phosphate residue Nicotine amide 0.3 Butyl 0.3 Comparative example 6 Phosphate residue Pyrimidine 0.5 Octhyl 0.5 Comparative example 7 Phosphate residue Imidazole 0.8 TEOS 1 Comparative example 8 Phosphate residue 1, 3-Diaminopropane 0.3 Methyl 0.3 Comparative example 9 Phosphate residue Propyl amine 0.5 Ethyl 0.5 Comparative example 10 Phosphate residue 4-Methylpiperidine 0.8 Propyl 1

[0091]

[0092] Experimental Example 1: Analysis of Bubble Generation Level in Etching Composition

[0093] The bubble pour method was used to determine the extent of bubble formation. The flow was N2 [0.5 L / min], and immediately after the etching composition was formed, the bubble height was measured (cm). After 60 seconds, the bubble height after foaming was measured to determine the foaming characteristics. The results are shown in Table 2 below.

[0094] ClassificationBubble Height (cm)Example 10.5Example 20.6Example 30.5Example 40.6Example 50.6Example 60.7Comparative Example 10.5Comparative Example 210Comparative Example 30.5Comparative Example 43.8Comparative Example 56Comparative Example 615Comparative Example 78Comparative Example 85Comparative Example 915Comparative Example 1012

[0095]

[0096] According to Table 2, it was confirmed that the etching compositions according to the embodiments of the present invention formed low bubbles with a height of less than 1.0 cm immediately after the composition was formed. On the other hand, in the case of the comparative example compound, the bubbles were formed high immediately after the etching composition was formed, so it could be seen that the amount of bubbles was large, and it could be confirmed that the bubbles were removed very slowly over time. In the case of comparative examples 1 and 3, it can be seen that the bubble generation itself was at a similar level to the embodiments, but as described below, it may be necessary to reconsider the basic performance aspect such as the etching selectivity. As described above, such bubbles can be a factor that reduces the efficiency in the overall etching process, and the etching composition according to an embodiment of the present invention can be seen as an invention that solves this problem by including a second etching inhibitor compound. This bubble removal effect is because the etching composition has a relatively lower surface tension than the single layer in which the bubble liquid is generated by controlling the surface tension of the surface, so that the bubbles easily spread to the surroundings and become thinner. For this reason, it was confirmed that the bubble generation was suppressed in the etching composition itself. By suppressing the generation of bubbles in this way, it was confirmed that the factor that interferes with the nitride film etching can be removed.

[0097]

[0098] Experimental Example 2. Measurement of etching rate and selectivity

[0099] Using the etching compositions manufactured in each of the examples and comparative examples, etching of nitride films and oxide films was performed at a process temperature of 165°C. The etching rates for nitride films, oxide films, doped silicon films (doped-Si), and germanium films were measured using an ellipsometer (NANO VIEW, SEMG-1000), a thin film thickness measuring device, and the results are shown in Table 3 below. Specifically, the etching rates in Table 3 below are values ​​calculated by dividing the difference between the film thickness before and after etching of each film by the etching time (minutes) after etching each film for 300 seconds.

[0100] SiN etch rate (Å / min) Oxide etch rate (Å / min) Nitride / oxide SiGe etch rate (Å / min) Nitride / SiGe doped Si etch rate (Å / min) Nitride / doped Si Example 1 39.2 0.15 26 1.33 0.66 59.39 1.16 33.79 Example 2 37.9 0.12 315.8 30.66 3.17 1.03 36.80 Example 3 390.1 390.00 0.55 70.91 0.84 8.75 Example 4 39.4 0.08 492.50 0.57 8.80 0.72 54.72 Example 538.50.05770.000.4389.530.7452.03 Example 639.10.09434.440.6263.060.4390.93 Comparative Example 1390.15260.001.5824.681.9719.80 Comparative Example 238.70.13297.690.5866.720.8545.53 Comparative Example 339.40.11358.181.3229.852.0119.60 Comparative Example 441.80.12348.330.5576.000.6762.39 Comparative Example 542.60.1426.000.5676.070.8848.41Comparative example 643.10.12359.170.671.830.7458.24Comparative example 741.20.25164.801.0340.002.5815.97Comparative example 840.60.16253.752.5615.869.864.12Comparative example 939.80.12331.671.7822.365.517.22Comparative example 1039.50.09438.891.3229.923.1412.58

[0101]

[0102] According to Table 3 above, it can be confirmed that the nitride film:oxide film etching rate selectivity of the examples corresponding to the etching composition of the present invention is at a relatively high level, but is generally at a level similar to that of the comparative examples.

[0103] Specifically, in the case of Comparative Examples 1 and 3, where the content of the first etching inhibitor was insufficient compared to the embodiment, it was confirmed that the etching speed of the germanium film was not sufficiently suppressed, and accordingly, the nitride film / germanium film selectivity was less than 30. On the other hand, in the case of Comparative Examples 2 and 4, where the content of the first etching inhibitor was relatively excessive, the overall selectivity pattern showed a similar level compared to the embodiment, but as mentioned above, it was confirmed that there was a factor that hindered the processability due to bubble formation.

[0104] In addition, in the case of the example composition satisfying the structure of the second etching inhibitor, it was confirmed that the etching selectivity of the nitride film was high compared to the oxide film, the germanium film, and the doped silicon film. In addition, as described above, it was confirmed that bubble generation immediately after the etching composition was formed could also be suppressed.

[0105] Looking into more detail, in the case of Comparative Examples 5 and 6, it was confirmed that the effect of suppressing bubble generation in Experimental Example 1 was inhibited when the number of carbon atoms in the alkyl group of the chemical formula 6 exceeded 3, and therefore, it was confirmed that there was a problem with the fairness. In addition, in the case of Comparative Example 7, since the basic structure of the second etching inhibitor compound was different, the effect was different from that of the Examples in that a sufficient nitride film / oxide film etching selectivity was not observed.

[0106] Meanwhile, as in Comparative Examples 8 to 10, when the type of the first etching inhibitor was different from the scope of the present invention, it was confirmed that a sufficient nitride film / germanium film selectivity was not secured, and as confirmed in Experimental Example 1, it was found that the height of the bubbles was formed high immediately after the formation of the etching composition, which included a factor that inhibited the process.

[0107] Before explaining the first aspect of the present invention, the concept of an etching composition is explained.

[0108] The etching composition can be used to etch a silicon-containing material. For example, the etching composition can be used to etch a silicon nitride film, a germanium-containing film, or a silicon oxide film, which are insulating films. Etching of a silicon nitride film using the etching composition can proceed as shown in Scheme 1 below. Etching of a silicon oxide film using the silicon composition can proceed as shown in Scheme 2 below. Etching of a germanium-containing film can include oxidizing silicon-germanium to form a semiconductor oxide, reacting the semiconductor oxide to form a water-soluble product, and removing the water-soluble product.

[0109] However, in the etching process using the etching composition, the etching rate of the silicon nitride film, which is the first insulating film, may be greater than the etching rates of the silicon oxide film, which is the second insulating film, and the germanium-containing film, which is the third insulating film. In the present specification, etching of the silicon nitride film may mean that silicon nitride is removed, and etching of the silicon oxide film or the germanium-containing film may mean that silicon oxide or the germanium-containing material is removed. Silicon nitride may be Si x N y can be represented as Si. Silicon oxide is Si x O y Or it may include germanium oxide (e.g., GeOy). (Here, x and y may each be independent positive rational numbers. For example, x may be 2 and y may be 2.) The germanium-containing material may include silicon-germanium (SiGe).

[0110]

[0111] [Reaction Formula 1]

[0112] 3Si3N4+ 4H3PO4+ 27H2O →4(NH4)3PO4+ 9SiO2H2O

[0113] [Reaction Formula 2]

[0114] SiO2+4H + + 4e- →Si + 2H2O

[0115]

[0116] Referring to the above reaction formula 1, phosphoric acid can react with silicon nitride to remove the silicon nitride. At this time, the composition ratio of phosphoric acid as an inorganic acid may be 70 to 99 parts by weight. In the present specification, the composition ratio means the composition ratio with respect to the composition. When phosphoric acid is less than 70 parts by weight of the etching composition, it may be difficult to easily remove the silicon nitride film. Alternatively, etching byproducts may be formed during the etching process. In one embodiment of the present invention, the composition ratio of phosphoric acid may mean the composition ratio of an 85% phosphoric acid aqueous solution. That is, a composition ratio of 65% of phosphoric acid may mean that the 85% phosphoric acid aqueous solution is 65% of the etching composition.

[0117] Referring to Reaction Scheme 2, phosphoric acid can react with silicon oxide by providing hydrogen ions. If phosphoric acid exceeds 99 parts by weight of the etching composition, the reaction rate between phosphoric acid and silicon oxide may increase. Accordingly, in the etching process, the silicon nitride film may have difficulty achieving a sufficiently high etching selectivity with respect to the silicon oxide film.

[0118] Hereinafter, the etching composition according to the first aspect of the present invention will be described in detail.

[0119]

[0120] The first aspect of this article is,

[0121] An etching composition is provided, comprising: an inorganic acid; a first etching inhibitor; and a residual amount of a solvent, wherein the first etching inhibitor comprises at least two nitrogen atoms and comprises a heterocyclic structure containing at least one nitrogen atom.

[0122]

[0123] In one embodiment of the present invention, the first etching inhibitor may be represented by the following chemical formula 1 or chemical formula 2.

[0124] [Chemical Formula 1]

[0125]

[0126] [Chemical Formula 2]

[0127]

[0128] In the above chemical formula 1 or chemical formula 2, A1 to A9 are each independently carbon or nitrogen, and R 21 Inland R 24 and R 31 Inland R 35 are each independently hydrogen, halogen, amino group, amide group, hydroxyl group, thiol group (-SH or =S), -NO2, -NHCOR 41 (R 41 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 42 (R 42 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -OCOR 43 (R 43 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, and when all of A1 to A4 in the above chemical formula 1 are carbon, the R 21 Inland R 24 At least one of them is an amino group, an amide group, -NO2, -NHCOR 51 (R 51 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 52 (R 52is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, or when all of A5 to A9 in the above chemical formula 2 are carbon, the above R 31 Inland R 35 At least one of them is an amino group, an amide group, -NO2, -NHCOR 61 (R 61 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 62 (R 62 It may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms.

[0129] In one embodiment of the present invention, preferably, the first etching inhibitor may be nicotinamide, pyrimidine, or imidazole.

[0130] In one embodiment of the present invention, the first etch inhibitor can act as an etch inhibitor for a germanium-containing film. For example, the first etch inhibitor can increase the etch selectivity of a silicon nitride film with respect to a germanium-containing film. The first etch inhibitor can be adsorbed on germanium oxide formed during the etching process. Since the germanium oxide adsorbed with the first etch inhibitor can function as a passivation film, the first etch inhibitor can suppress the removal of the germanium oxide.

[0131] In one embodiment of the present invention, the first etching inhibitor may be present in an amount of 0.01 wt% to 15 wt%, preferably 0.1 wt% to 10 wt%, and more preferably more than 0.1 wt% to 2 wt%, based on the total weight of the etching composition. If the content of the first etching inhibitor is less than the above-mentioned range, the amine compound may be insufficient to adsorb germanium oxide and further inhibit etching of the germanium-containing film. If the content of the first etching inhibitor exceeds the above-mentioned range, the etching rate of the silicon oxide film may unnecessarily increase, or the etching rates of the nitride film, the oxide film, and the germanium-containing film may all decrease overall, and above all, it may become impossible to suppress the generation of bubbles that occur immediately after the formation of the etching composition.

[0132] In one embodiment of the present invention, a second etching inhibitor may be further included. The second etching inhibitor may be represented by any one selected from the following chemical formulas 3 to 5.

[0133] [Chemical Formula 3]

[0134]

[0135] In the above chemical formula 3, R1 is selected from the group consisting of a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetyloxy group, and a substituted or unsubstituted haloalkylacetyloxy group having 1 to 20 carbon atoms, and R2 and R3 may be a hydroxy group.

[0136] [Chemical Formula 4]

[0137]

[0138] In the above chemical formula 4, R4 is hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted amino (C1-C) group having 1 to 20 carbon atoms 10 )alkylamino(C1-C 10 )alkyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylcarbonyloxy group having 1 to 20 carbon atoms, and cyano (C1-C 10 ) is selected from the group consisting of alkyl groups, R5 to R 11 are each independently hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted amino (C1-C 10 )alkylamino(C1-C 10 )alkyl group, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano (C1-C 10 ) is selected from the group consisting of alkyl groups, m is an integer from 1 to 10, and when m is 2 or more, each of a plurality of R4, R 10 , and R 11 may all be the same or at least some may be different.

[0139] Preferably, the second etching inhibitor is represented by the above chemical formula 4, and in the chemical formula 4, R4 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 4 carbon atoms, and R 5, R 6, R 10 and R 11 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 5 carbon atoms, R7 to R9 are each independently selected from the group consisting of hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 5 carbon atoms, and m may be an integer of 1 to 5.

[0140] In a preferred embodiment, the second etching inhibitor may be represented by the following chemical formula 6:

[0141] [Chemical Formula 6]

[0142]

[0143] In the above chemical formula 6, the R 16 is a methyl group, an ethyl group, or a propyl group, and n is an integer from 1 to 5, and when n is 2 or more, multiple R 16 may all be the same or at least some may be different.

[0144] [Chemical Formula 5]

[0145]

[0146] In the above chemical formula 5, R 12 is hydrogen, an alkyl group, an aminoalkyl group or an aminoalkoxy group, and R 13 , R 14 and R 15At least one of them is an amino alkyl group or an amino alkoxy group, and l can be 2 or 3.

[0147] In one embodiment of the present invention, the second etching inhibitor may be present in an amount of 0.01 wt% to 15 wt%, preferably 0.1 wt% to 10 wt%, and more preferably more than 0.1 wt% to 3 wt%, based on the total weight of the etching composition. If it exceeds the above-mentioned range, it may act as an impurity itself, which may adversely affect the overall etching rate regardless of the film type, and if it is less than the above-mentioned range, it may be difficult to utilize the etching composition in a process in the temperature range described below, and it may be difficult to secure a sufficient nitride film etching selectivity.

[0148] In addition, in one embodiment of the present invention, the etching composition may include a solvent. Specifically, the solvent may be water or deionized water (DIW). The content of the solvent may be the remaining weight portion (remainder) after excluding the above components based on 7 to 85 wt% of the inorganic acid, 0.1 to 10 wt% of the second etching inhibitor, and 0.1 to 10 wt% of the first etching inhibitor, based on 100 wt% of the total etching composition.

[0149] In one embodiment of the present invention, the inorganic acid included in the etching composition enables the etching composition to have an acidic pH (e.g., pH 2 to 6) so as to etch an etching target (e.g., an insulating film).

[0150] The inorganic acid is not particularly limited, but may be at least one selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrochloric acid, and perchloric acid. Specifically, the inorganic acid may be phosphoric acid. When phosphoric acid is used as the inorganic acid and the etching target is an oxide film and a nitride film, the etching selectivity of the nitride film over the oxide film can be increased. In addition, when phosphoric acid is used as the inorganic acid, hydrogen ions are provided in the etching composition, thereby promoting etching.

[0151] Additionally, when the inorganic acid is phosphoric acid, the etching composition according to one embodiment of the present disclosure may further include sulfuric acid as an additive. The sulfuric acid may increase the boiling point of the etching composition containing phosphoric acid as the inorganic acid, thereby assisting in the etching of the nitride film.

[0152] In one embodiment of the present invention, the etching composition may contain 70 to 99 parts by weight of the inorganic acid. Specifically, the etching composition may contain 70 to 90 parts by weight of the inorganic acid, and more specifically, the etching composition may contain 75 to 85 parts by weight of the inorganic acid. When the content of the inorganic acid is less than 70 parts by weight, etching (removal) of the nitride film is not easy or the usability is low under a predetermined temperature condition described below, and when it exceeds 99 parts by weight, it is difficult to obtain a high etching selectivity for the nitride film.

[0153] In one embodiment of the present invention, the etching composition may further include an ammonium compound. The ammonium compound is, in an aqueous solution condition, ammonium (NH 4+) may mean a compound forming a silicon oxide film. The ammonium-based compound may include, for example, at least one of ammonia, ammonium chloride, ammonium phosphate, ammonium acetate, ammonium sulfate, ammonium formate, and a metal amine complex. The metal amine complex may be a metal complex including at least one ammonia (NH3) ligand. If the etching process of the silicon nitride film is performed for a long time, the concentration of silicon ions may increase. For example, the silicon ions may be formed by SiO2H2O, which is a product of the above reaction formula 1. Abnormal growth of the silicon oxide film may occur due to the silicon ions. According to embodiments, in the etching process, the ammonium-based compound may be dissociated to form ammonium (NH 4+ ) can be formed. Ammonium can react with a precursor of silicon ions (e.g., SiO2) and remove the precursor of silicon ions. Accordingly, abnormal growth of the silicon oxide film can be prevented. Ammonium-based compounds can maintain a constant etching rate according to the etching time.

[0154] If the ammonium-based compound is less than 0.01 wt% of the etching composition, it may be difficult to prevent abnormal growth of the silicon oxide film or changes in the etching selectivity of the silicon nitride film over the silicon oxide film over time. If the ammonium-based compound is more than 10 wt% of the etching composition, the etching rates of the silicon nitride film and the silicon oxide film may change over time. In an embodiment, the composition ratio of the ammonium-based compound may be 0.01 wt% to 10 wt%.

[0155] In addition, in one embodiment of the present invention, the etching composition may further include any additive commonly known to improve etching performance. The additive may be a surfactant, a metal ion sequestering agent, or a corrosion inhibitor.

[0156] As described above, the etching composition of the present invention can exhibit a remarkably high etching selectivity of a nitride film with respect to an oxide film or a germanium-containing film by selectively further including an additive, an ammonium-based compound, in addition to an inorganic acid, a second etching inhibitor, and a first etching inhibitor. In addition, the etching composition can prevent damage to the film quality of an oxide film or a germanium-containing film during the etching process of a nitride film, or deterioration of electrical characteristics due to etching of a germanium-containing film or an oxide film, and can minimize particle generation. Therefore, the etching composition of the present invention can be usefully used in an etching process during the manufacture of a semiconductor device.

[0157] In one embodiment of the present invention, the etching composition may be characterized as being used for etching a silicon nitride film. As a preferred range, in this case, the etching selectivity of the silicon nitride film / oxide film may be characterized as being 250 or more, and the etching selectivity of the silicon nitride film / germanium-containing film of the etching composition may be 50 or more. In addition, the etching selectivity of the silicon nitride film / doped silicon film of the etching composition may be 30 or more.

[0158] In one embodiment of the present invention, the second etching inhibitor may be characterized by suppressing bubble generation of the etching composition during the etching process. Specifically, in terms of preventing adsorption of gas bubbles such as H2 on the silicon surface, the second etching inhibitor may have a hydrophobic interaction with the nonpolar silicon surface and may prevent the generation and adsorption of bubbles by imparting polarity to the silicon surface. As described above, in one embodiment of the present invention, the etching composition may be characterized by having a bubble generation rate of less than 1 cm. According to one embodiment of the present application, the bubble height on the surface immediately after formation of the etching composition may be characterized by being 0.9 cm or less. According to another embodiment of the present application, the bubble height on the surface may be characterized by being 0.9 cm or less after 60 seconds from formation of the etching composition. According to another embodiment of the present invention, the bubble height of the surface immediately after formation of the etching composition may be 0.1 to 1.0 cm, and the rate of change in the bubble height of the surface after 60 seconds may be 50% or more.

[0159] In one embodiment of the present invention, the etching composition may suppress etching of the germanium-containing film and etch the silicon oxide film and the silicon nitride film in an integrated circuit device including a silicon oxide film, a silicon nitride film, and a germanium-containing film. This may be an effect of the first etching inhibitor.

[0160] In one embodiment of the present invention, the etching composition may suppress etching of the germanium-containing film and the silicon oxide film, and etch the silicon nitride film, in an integrated circuit device including a silicon oxide film, a silicon nitride film, and a germanium-containing film. The above-described effect may be an effect due to the first and second etching inhibitors.

[0161]

[0162] Manufacturing method of semiconductor devices

[0163] The second aspect of this article is,

[0164] A method for manufacturing an integrated circuit device is provided, comprising: a step of forming a structure by laminating an insulating film and a sacrificial film on a substrate; and a step of performing an etching process using the etching composition to remove the sacrificial film and form a space region.

[0165]

[0166] Detailed explanations of parts that overlap with the first aspect of the present application have been omitted, but the explanations of the first aspect of the present application may be applied equally even if the explanations are omitted in the second aspect.

[0167]

[0168] Hereinafter, a method for manufacturing a semiconductor device according to the second aspect of the present invention will be described in detail.

[0169]

[0170] As used herein, the term “space region” or “space portion” refers to a space formed by removing a sacrificial film during an etching process of a semiconductor device, and may include, as non-limiting examples, trenches, channels, gates, spacers, etc.

[0171] In addition, the “deposition portion” used in this specification means a portion formed by depositing a conductive material or an insulating material in the above-described space area or space portion, and may be configured in a patterned manner.

[0172] FIG. 1 of the present application is a plan view of a semiconductor device according to embodiments. FIGS. 2 to 8 are drawings for explaining a method of manufacturing a semiconductor device according to embodiments, and correspond to cross-sections taken along line II' of FIG. 1. Hereinafter, any content that overlaps with what has been previously described will be omitted.

[0173] Referring to FIGS. 1 and 2 of the present application, a laminated structure (200) may be formed on a substrate (100). The substrate (100) may be a bulk silicon substrate, a silicon-on-insulator (SOI) substrate, a germanium substrate, a germanium-on-insulator (GOI) substrate, a silicon-germanium substrate, or a substrate of an epitaxial thin film obtained by performing selective epitaxial growth (SEG). A first direction (D1) and a second direction (D2) may be parallel to an upper surface (100a) of the substrate (100). The second direction (D2) may intersect the first direction (D1). A third direction (D3) may be perpendicular to the upper surface (100a) of the substrate (100).

[0174] In one embodiment of the present invention, the laminated structure (200) may include sacrificial films (SC) and insulating films (IL). Formation of the laminated structure (200) may include alternately and repeatedly forming sacrificial films (SC) and insulating films (IL) on a substrate (100). The sacrificial films (SC) may be formed between the insulating films (IL). The sacrificial films (SC) may have etch selectivity with respect to the insulating films (IL). The sacrificial films (SC) may be formed of, for example, silicon nitride (e.g., Si x N y ) may be included. The insulating films (IL) may be germanium-containing films (e.g., SiGe), or silicon oxide (e.g., Si x O y ) may be included. The insulating films (IL) may be formed using tetraethoxysilane (TEOS), and tetraethoxysilane may be represented as (C2H5O)4Si.

[0175] In embodiments of the present invention, the sacrificial films (SC) may have substantially the same thicknesses. Alternatively, the sacrificial film (SC) of the lowest layer and the sacrificial film (SC) of the highest layer among the sacrificial films (SC) may be formed thicker than the sacrificial films (SC) positioned therebetween. In addition, the insulating films (IL) may have the same thicknesses, or the thicknesses of at least two of the insulating films (IL) may be different from each other. The lowest layer among the insulating films (IL) may have a thickness thinner than the sacrificial films (SC) and the insulating films (IL) formed thereon. The lowest layer among the insulating films (IL) may be a silicon oxide film formed through a thermal oxidation process. In the present specification, the thickness of a component may mean a distance of the component in a third direction (D3).

[0176] Referring to FIGS. 1 and 3 of the present invention, openings (210) and vertical structures (300) can be formed within a laminated structure (200). Forming the openings (210) can include forming a mask pattern (not shown) defining the planar positions of the openings (210) on the laminated structure (200) and etching the laminated structure (200) using the mask pattern as an etching mask. The etching of the laminated structure (200) can be performed by an anisotropic etching process.

[0177] In one embodiment of the present invention, the openings (210) can penetrate the laminated structure (200). The sidewalls of the openings (210) can expose the sacrificial films (SC) and the insulating films (IL). The openings (210) can expose the substrate (100). During the formation of the openings (210), the upper surface (100a) of the substrate (100) can be over-etched. In this case, the upper surface (100a) of the substrate (100) exposed to the openings (210) can be recessed to a predetermined depth.

[0178] In one embodiment of the present invention, each of the openings (210) may be formed in the shape of a cylindrical or rectangular parallelepiped hole. The lower portions of the openings (210) may have smaller widths than their upper portions. As shown in FIG. 1, the openings (210) may form rows parallel to the second direction (D2) in a plan view. The openings (210) between two adjacent rows may be arranged in a zigzag shape in the second direction (D2). Unlike FIG. 1, the openings (210) may form an array aligned along the first direction (D1) and the second direction (D2). For example, the openings (210) of two adjacent rows may be aligned in the first direction (D1) to form an array.

[0179] In one embodiment of the present invention, first dielectric patterns (310) may be formed within the openings (210). The first dielectric patterns (310) may cover sidewalls of the openings (210). The first dielectric patterns (310) may expose the upper surface (100a) of the substrate (100). The first dielectric pattern (310) may include a single-layer insulating layer or multiple insulating layers. The first dielectric pattern (310) may function as a part of a data storage film of a charge trapping type flash memory transistor. Exemplary embodiments of the first dielectric pattern (310) are described below in the description with respect to FIG. 9.

[0180] In one embodiment of the present invention, semiconductor patterns (320) may be formed within the openings (210). The semiconductor patterns (320) may include, for example, silicon (Si), germanium (Ge), or a mixture thereof. The semiconductor patterns (320) may have a crystal structure including at least one of single crystal, amorphous, and polycrystalline. The semiconductor patterns (320) may further include doped impurities. As another example, the semiconductor patterns (320) may be an intrinsic semiconductor in an undoped state. The semiconductor patterns (320) may be formed using thermal chemical vapor deposition (CVD), plasma enhanced CVD, or atomic layer deposition (ALD) techniques.

[0181] In one embodiment of the present invention, semiconductor patterns (320) may be formed on sidewalls of the openings (210) to cover the first dielectric patterns (310). The semiconductor patterns (320) may extend onto the substrate (100) to contact a portion of the upper surface (100a) of the substrate (100) exposed by the openings (210). Each of the semiconductor patterns (320) may be formed in a pipe-shaped, hollow cylindrical shape, or cup-shaped shape within the corresponding openings (210). The semiconductor patterns (320) may define empty areas (321) in the central portions of the openings (210).

[0182] In one embodiment of the present invention, buried insulating patterns (330) may be respectively filled in the empty areas (321). The buried insulating patterns (330) may be formed of an insulating material having excellent gap-fill characteristics. The buried insulating patterns (330) may be formed of, for example, a high-density plasma oxide film, a SOG (Spin On Glass layer), an ALD oxide film, and / or a CVD oxide film.

[0183] In one embodiment of the present invention, pads (340) may be formed on vertical structures (300). The pads (340) may be made of a conductive material such as a semiconductor material or metal doped with impurities. The lower surface of the pads (340) may be positioned at a level higher than the upper surface of the uppermost sacrificial film (SC). A lower capping film (510) may be formed on the upper surfaces of the vertical structures (300) and the stacked structure (200). The lower capping film (510) may include an insulating material such as silicon oxide, silicon nitride, and / or silicon oxynitride.

[0184] Referring to FIG. 4 of the present invention, trenches (600) may be formed to penetrate the laminated structure (200) and the lower capping film (510). Forming the trenches (600) may include forming a mask pattern (not shown) defining the planar positions of the trenches (600) on the lower capping film (510) and etching the laminated structure (200) using the mask pattern as an etching mask. Etching the laminated structure (200) may be performed by an anisotropic etching process.

[0185] In one embodiment of the present invention, trenches (600) may be formed between adjacent vertical structures (300). The trenches (600) may be spaced apart from the vertical structures (300) to expose sidewalls of the sacrificial films (SC) and sidewalls of the insulating films (IL). Upper portions of the trenches (600) may have larger widths than lower portions thereof. The trenches (600) may expose an upper surface (100a) of the substrate (100). During the formation of the trenches (600), the upper surface (100a) of the substrate (100) exposed to the trenches (600) may be recessed to a predetermined depth by over-etching. As shown in FIG. 1, the trenches (600) may have long axes parallel to the second direction (D2) in a plan view. The trenches (600) can be spaced apart from each other in the first direction (D1).

[0186] Referring to FIG. 5 of the present invention, sacrificial films (SC) may be etched to form gate regions (250). The gate regions (250) may be pores and may be regions where gate electrode patterns (450) are formed in FIG. 7. The gate regions (250) are formed between insulating films (IL) and may be connected to trenches (600). The gate regions (250) may expose portions of sidewalls (300c) of the vertical structures (300). The thicknesses of the gate regions (250) may be substantially the same as the thicknesses of the removed sacrificial films (SC). The etching of the sacrificial films (SC) may be performed by an etching process using an etching composition. The etching process may be a wet etching process.

[0187] In one embodiment of the present invention, the etching composition may include a first inorganic acid such as phosphoric acid, an ammonium compound, and a compound represented by the first or chemical formula 1. Since the sacrificial films (SC) include silicon nitride, they can be etched by phosphoric acid as in Reaction Scheme 1.

[0188] In one embodiment of the present invention, for example, an etching composition of 130°C to 170°C may be supplied onto the substrate (100). At temperatures below 130°C, the etching speed of the silicon nitride film is too low to be applied, and at temperatures exceeding 170°C, uniform etching may not be achieved due to an etching speed that is too fast.

[0189] Under the above temperature conditions, phosphoric acid can further etch not only the sacrificial films (SC), but also the silicon oxide or germanium-containing films. The insulating films (IL) may include silicon oxide or germanium-containing films. According to embodiments, the etching composition may include an oxide film etching inhibitor and an amine-based compound as additives, so that etching of the insulating films (IL) by phosphoric acid may be prevented / reduced. For example, in the etching process, oxygen of the silicon-containing compound may be bonded to the surface of the insulating films (IL) to protect the insulating films (IL). Accordingly, the insulating films (IL) may exhibit a low etching rate during the etching process. The oxygen atoms of the silicon-containing compound may not interact (e.g., hydrogen bond) with the surface of the sacrificial films (SC). Accordingly, the etching selectivity of the sacrificial films (SC) with respect to the insulating films (IL) may be increased. If the silicon-containing compound is unstable, by-products may be formed, and the by-products may form particles. Byproducts and / or particles can cause defects during the manufacturing process of semiconductor devices. For example, byproducts and / or particles can be adsorbed on insulating films (IL). Since the bonding between silicon atoms and oxygen atoms of a silicon-containing compound is stable, the formation of byproducts can be prevented during the etching process. The sacrificial films (SC) can be etched to form silicon ions (e.g., SiO2H2O). The ammonium-based compound can remove the silicon ions generated during the etching of the sacrificial films (SC). Accordingly, abnormal growth of the insulating films (IL) caused by the silicon ions can be prevented / reduced.

[0190] In one embodiment of the present invention, in the etching process, the etching composition may be applied onto the substrate (100) by a method of coating, dipping, spraying, or injecting. If the etching composition is applied by a dipping method, a batch type device may be used in the etching process. If the etching composition is sprayed onto the substrate (100), a single wafer type device may be used in the etching process. After the etching process, a cleaning process and a drying process using ultrapure water or the like may be performed on the substrate (100). Ultrapure water may mean water having an impurity content of 100 ppb or less.

[0191] Referring to FIG. 6 of the present invention, a second dielectric pattern (410) and a gate conductive film (451) may be formed on the laminated structure (200) and within the trenches (600). The second dielectric pattern (410) may be substantially conformally formed on the laminated structure (200) and within the trenches (600). The second dielectric pattern (410) may extend into the trenches (600) and the gate regions (250). The second dielectric pattern (410) can substantially conformally cover the upper surface of the uppermost insulating film (IL) among the insulating films (IL), the sidewalls of the insulating films (IL) exposed by the trenches (600), the upper and lower surfaces of the insulating films (IL) exposed by the gate regions (250), the sidewalls (300c) of the vertical structures (300) exposed by the gate regions (250), and the upper surface (100a) of the substrate (100). The second dielectric pattern (410) can be formed by a deposition process. The deposition method and deposition conditions can be controlled so that the second dielectric pattern (410) can be formed to have good step coverage. For example, the deposition process of the second dielectric pattern (410) can be performed by chemical vapor deposition or atomic layer deposition. The second dielectric pattern (410) can include a single layer or a plurality of layers. The second dielectric pattern (410) may be a part of a data storage film (DS) of a charge trap type flash memory transistor. Exemplary embodiments of the second dielectric pattern (410) are described later in the description with respect to FIG. 9. A gate conductive film (451) may be formed on the second dielectric pattern (410). The gate conductive film (451) may fill at least a portion of each of the trenches (600) and the gate regions (250). Unlike the illustration, the gate conductive film (451) may completely fill each of the trenches (600). Although not illustrated, a barrier metal film and a metal film may be sequentially deposited to form the gate conductive film (451).The barrier metal film may include a metal nitride, such as, for example, titanium nitride (TiN), tantalum nitride (TaN), or tungsten nitride (WN). The metal film may include, for example, tungsten (W), aluminum (Al), titanium (Ti), tantalum (Ta), cobalt (Co), or copper (Cu).

[0192] Referring to FIGS. 1 and 7 of the present invention, a gate conductive film (451) may be patterned, so that gate electrode patterns (450) may be formed within each of the gate regions (250). The patterning of the gate conductive film (451) may be performed by an etching process. At this time, the second dielectric pattern (410) may be further etched. In the etching process of the gate conductive film (451), the gate conductive film (451) on the substrate (100) may be removed. The etching of the gate conductive film (451) may be performed until the insulating films (IL) on the sidewalls of the insulating films (IL) are removed and the sidewalls of the insulating films (IL) are exposed. Accordingly, the gate electrode patterns (450) and the second dielectric pattern (410) may be localized in the gate regions (250), and gate structures (400) may be formed. Each of the gate structures (400) may be formed between two adjacent trenches (600). Sidewalls of the gate structures (400) may be exposed to the trenches (600). The gate structures (400) may expose an upper surface (100a) of the substrate (100) within the trenches (600). The exposed upper surface (100a) of the substrate (100) may be further etched. As shown in FIG. 1, the gate structures (400) may have long axes that are parallel to the second direction (D2) in a plan view. The gate structures (400) may be spaced apart from each other in the first direction (D1).

[0193] In one embodiment of the present invention, each of the gate structures (400) may include stacked gate electrode patterns (450), a second dielectric pattern (410), and insulating films (IL). In each of the gate structures (400), the gate electrode patterns (450) may be interposed between the insulating films (IL). The gate electrode patterns (450) may be used as string selection lines, ground selection lines, and word lines. For example, the uppermost and lowermost of the stacked gate electrode patterns (450) may be used as string selection lines and ground selection lines, respectively. The gate electrode patterns (450) between the uppermost and lowermost gate electrode patterns (450) may be used as word lines.

[0194] In one embodiment of the present invention, in the gate structures (400), the second dielectric pattern (410) may be interposed between the gate electrode patterns (450) and the insulating films (IL) and between the vertical structure (300) and the insulating films (IL).

[0195] In one embodiment of the present invention, common source regions (CSR) may be formed within the substrate (100) exposed by trenches (600). The common source regions (CSR) may be spaced apart from each other in a second direction (D2). The common source regions (CSR) may be formed through an ion implantation process using the gate structures (400) as an ion mask. The common source regions (CSR) may overlap a portion of the lower portion of the gate structures (400) in a plan view due to diffusion of impurities. The common source regions (CSR) may have a different conductivity type from that of the substrate (100). As another example, the common source regions (CSR) may be performed after the formation of the trenches (600) of FIG. 4.

[0196] Referring to FIGS. 1 and 8 of the present invention, spacers (550) and common source plugs (CSPs) may be formed within trenches (600), respectively. The spacers (550) may cover sidewalls of the gate structures (400). The spacers (550) may include an insulating material. The spacers (550) may be formed of, for example, silicon oxide, silicon nitride, silicon oxynitride, or a low-k material. Forming the spacers (550) may include depositing a spacer film (not shown) on a substrate (100) to a uniform thickness to cover the gate structures (400) and performing an etch-back process on the spacer film to expose the common source regions (CSR).

[0197] In one embodiment of the present invention, common source plugs (CSPs) may be formed on spacers (550) to fill trenches (600). The common source plugs (CSPs) may be connected to common source regions (CSRs), respectively. Forming the common source plugs (CSPs) may include depositing a barrier metal film (not shown) covering sidewalls of the spacers (550) and depositing a metal film (not shown) on the barrier metal film. The barrier metal film may include at least one of, for example, tantalum (Ta), tantalum nitride (TaN), titanium (Ti), titanium nitride (TiN), tungsten (W), tungsten nitride (WN), and combinations thereof. The metal film may include tungsten (W), aluminum (Al), titanium (Ti), tantalum (Ta), cobalt (Co), or copper (Cu). As shown in Fig. 1, in a planar view, the major axes of the common source plugs (CSPs) can extend parallel to the second direction (D2).

[0198] In one embodiment of the present invention, an upper capping film (520) may be formed on a lower capping film (510) to cover the upper surfaces of a common source plug (CSP). The upper capping film (520) may include an insulating material.

[0199] In one embodiment of the present invention, bit line contact plugs (530) may be formed in the upper capping film (520). The bit line contact plugs (530) may penetrate the upper capping film (520) and the lower capping film (510) and may be connected to the pads (340), respectively. The bit line contact plugs (530) may be electrically connected to the vertical structures (300) (e.g., the semiconductor patterns (320)) through the pads (340), respectively. Bit lines (BL) may be formed on the upper capping film (520) and may be connected to the bit line contact plugs (530). As shown in FIG. 1, the bit lines (BL) may extend in a first direction (D1) in a plan view. The bit line contact plugs (530) and the bit lines (BL) may include a conductive material such as a metal. Accordingly, the manufacturing of the semiconductor device (1) can be completed. The semiconductor device (1) may be a three-dimensional memory device.

[0200] FIG. 9 of the present application is a drawing for explaining insulating patterns of semiconductor devices according to embodiments, and is an enlarged view of area A of FIG. 8. Hereinafter, in the description of FIG. 9, a single insulating film, a single gate electrode pattern, and a single vertical structure are described for simplicity of explanation.

[0201] Referring to FIGS. 8 and 9 of the present invention, the first dielectric pattern (310) may include a tunnel insulating film (311), a charge storage film (312), and a first blocking insulating film (313). The tunnel insulating film (311) may extend along the vertical structure. The charge storage film (312) and the first blocking insulating film (313) may be laminated on the tunnel insulating film (311). The tunnel insulating film (311) may be formed of a material having a lower dielectric constant than the first blocking insulating film (313). The tunnel insulating film (311) may include, for example, at least one selected from an oxide, a nitride, or an oxynitride. Alternatively, the tunnel insulating film (311) may include a high-k material. The high-k material refers to an insulating material having a higher dielectric constant than silicon oxide, and may include zirconium oxide, aluminum oxide, and / or hafnium oxide. A charge storage film (312) may be interposed between a tunnel insulating film (311) and a first blocking insulating film (313). The charge storage film (312) may include at least one of a charge trap insulating film, a floating gate electrode, or conductive nano dots. The first blocking insulating film (313) may include a high-k material.

[0202] In one embodiment of the present invention, the second dielectric pattern (410) may include a second blocking insulating film. The second blocking insulating film may be interposed between the gate electrode pattern (450) and the first dielectric pattern (310) and between the gate electrode pattern (450) and the insulating film (IL). The second blocking insulating film may include a high-k dielectric material. For example, the first blocking insulating film (313) may include a high-k dielectric material, and the second blocking insulating film may be a material having a lower dielectric constant than the first blocking insulating film (313). For another example, the second blocking insulating film may be one of the high-k dielectric materials, and the first blocking insulating film (313) may be a material having a lower dielectric constant than the second blocking insulating film.

[0203] In one embodiment of the present invention, the first dielectric pattern (310) and the second dielectric pattern (410) can function as a data storage film. Data stored in the data storage film can be changed using Fowler-Northernheim tunneling, which can be induced by a voltage difference between the vertical structure (300) and the gate electrode pattern (450).

[0204] In one embodiment of the present invention, unlike as shown, the second dielectric pattern (410) may not be formed. As another example, the first blocking insulating film (313) may not be formed.

[0205]

[0206] integrated circuit components

[0207] The third aspect of this foundation is,

[0208] The present invention provides an integrated circuit device comprising: a structure formed by stacking an insulating film and a sacrificial film; a space formed by etching the sacrificial film in the structure by an etching composition; and a deposition portion formed by depositing a conductive material or an insulating material in the space; wherein the etching composition comprises an inorganic acid, a first etching inhibitor, a second etching inhibitor, and a remaining amount of a solvent, wherein the first etching inhibitor comprises at least two nitrogen atoms, and the device comprises a heterocyclic structure containing at least one nitrogen atom.

[0209]

[0210] Detailed descriptions of overlapping parts with the first and second aspects of the present application have been omitted, but the contents described with respect to the first and second aspects of the present application may be equally applied even if the description is omitted with respect to the third aspect.

[0211]

[0212] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0213]

[0214] According to one embodiment of the present invention, since the etching selectivity of the nitride film is high, the etching rate of the germanium-containing film can be controlled, thereby easily controlling the effective oxide height (EFH). In addition, the etching composition of the present invention can prevent damage to the film quality of the germanium-containing film when removing the nitride film, deterioration of electrical characteristics due to etching of the germanium-containing film, and particle generation, thereby improving the reliability of semiconductor devices.

[0215] In addition, when etching a nitride film, even when the nitride film and the germanium-containing film or oxide film are alternately laminated or mixed, only the nitride film can be selectively etched with a relatively high etching selectivity between the nitride film and the germanium-containing film or oxide film. Therefore, in order to construct an electronic device having a complex and miniaturized structure, while etching a nitride film formed of patterns of various shapes, sufficient etching selectivity of the nitride film compared to the oxide film or germanium-containing film can be secured without causing the above-mentioned problems, thereby ensuring the stability and reliability of the nitride film etching process, and by preventing damage to the germanium-containing film or oxide film exposed to the etching composition together with the nitride film or deterioration of the electrical characteristics of the germanium-containing film or oxide film, the productivity of the semiconductor device manufacturing process can be improved, and the reliability of the semiconductor device can be improved.

[0216] Therefore, the etching composition of the present invention can be usefully used in a semiconductor device manufacturing process requiring selective removal of a nitride film with respect to a germanium-containing film or oxide film (e.g., a micro-etching process for devices such as logic semiconductor devices and image sensors, a device separation process for flash memory devices, a pipe channel formation process for 3D flash memory devices, a diode formation process for phase change memory devices, etc.), thereby contributing to improving the efficiency of the semiconductor device manufacturing process.

[0217] In addition, by containing an additive material that can obtain both the characteristics of improving the etching selectivity of the etchant and exhibiting an optimized effect in a predetermined temperature range, an etching composition having high process usability can be provided.

[0218] In addition, it is possible to suppress the occurrence of bubbles due to gases such as H2 that may be generated during the process in the etchant itself and the phenomenon of these bubbles being adsorbed on the surface of a silicon wafer and interfering with the selective etching of the nitride film.

[0219] For the reasons described above, the etching composition according to one embodiment of the present invention, the method for manufacturing an integrated circuit device including performing an etching process using the same, and the integrated circuit device manufactured thereby can be considered to be industrially applicable.

Claims

1. Weapon Mountain; First etch inhibitor; and Contains the remaining solvent, An etching composition wherein the first etching inhibitor comprises at least two nitrogen atoms and comprises a heterocyclic structure containing at least one nitrogen atom.

2. In paragraph 1, further comprising a second etch inhibitor; The above first etching inhibitor inhibits the etching of the germanium-containing film, The above second etching inhibitor is an etching composition that inhibits etching of a silicon oxide film.

3. In paragraph 1, The above first etching inhibitor is an etching composition represented by the following chemical formula 1 or chemical formula 2. [Chemical Formula 1] [Chemical Formula 2] (In the above chemical formula 1 or chemical formula 2, The above A1 to A9 are each independently carbon or nitrogen. The above R 21 Inland R 24 and R 31 Inland R 35 are each independently hydrogen, halogen, amino group, amide group, hydroxyl group, thiol group (-SH or =S), -NO2, -NHCOR 41 (R 41 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 42 (R 42 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -OCOR 43 (R 43 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, and a substituted or unsubstituted heteroaryl group having 5 to 20 carbon atoms, When A1 to A4 in the above chemical formula 1 are all carbon, the above R 21 Inland R 24 At least one of them is an amino group, an amide group, -NO2, -NHCOR 51 (R 51 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 52 (R 52 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms, or When A5 to A9 in the above chemical formula 2 are all carbon, the above R 31 Inland R 35 At least one of them is an amino group, an amide group, -NO2, -NHCOR 61 (R 61 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), -CONHR 62 (R 62 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms), a substituted or unsubstituted aminoalkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms) 4. In paragraph 1, An etching composition wherein the first etching inhibitor is nicotinamide, pyrimidine, or imidazole.

5. In paragraph 2, An etching composition wherein the second etching inhibitor is represented by any one selected from the following chemical formulas 3 to 5. [Chemical Formula 3] (In the above chemical formula 3, The above R1 is selected from the group consisting of a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted acetyloxy group, and a substituted or unsubstituted haloalkylacetyloxy group having 1 to 20 carbon atoms, and R2 and R3 are hydroxy groups. [Chemical Formula 4] (In the above chemical formula 4, R4 is hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted amino (C1-C) group having 1 to 20 carbon atoms 10 )alkylamino(C1-C 10 )alkyl group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylcarbonyloxy group having 1 to 20 carbon atoms, and cyano (C1-C 10 ) is selected from the group consisting of alkyl groups, R5 to R 11 are each independently hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aminoalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted amino (C1-C 10 )alkylamino(C1-C 10 )alkyl group, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano (C1-C 10 ) is selected from the group consisting of alkyl groups, m is an integer from 1 to 10, When the above m is 2 or more, each of the plurality of R4, R 10 , and R 11 are all the same or at least some are different) [Chemical Formula 5] (In the above chemical formula 5, R 12 is hydrogen, an alkyl group, an aminoalkyl group or an aminoalkoxy group, R 13 , R 14 and R 15 At least one of them is an amino alkyl group or an amino alkoxy group, l is 2 or 3) 6. In paragraph 5, The above second etching inhibitor is represented by the above chemical formula 4, In the above chemical formula 4, R4 is selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 3 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 4 carbon atoms, R 5, R 6, R 10 and R 11 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 5 carbon atoms, R7 to R9 are each independently selected from the group consisting of hydrogen, OH, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a substituted or unsubstituted aminoalkyl group having 1 to 5 carbon atoms, An etching composition wherein m is an integer from 1 to 5.

7. In paragraph 5, The second etching inhibitor is an etching composition represented by the following chemical formula 6. [Chemical Formula 6] (In the above chemical formula 6, the R 16 is a methyl group, an ethyl group, or a propyl group, The above n is an integer from 1 to 5, When the above n is 2 or more, multiple R 16 are all the same or at least some are different) 8. In paragraph 2, The etching composition comprises 7 to 85 wt% of the inorganic acid, 0.1 to 10 wt% of the first etching inhibitor, 0.1 to 10 wt% of the second etching inhibitor, and the remaining amount of a solvent, based on the entire etching composition.

9. In paragraph 2, An etching composition, characterized in that the first etching inhibitor is greater than 0.1% by weight and 2% by weight relative to the total weight of the etching composition.

10. In paragraph 2, An etching composition, characterized in that the second etching inhibitor is more than 0.1% by weight and 3% by weight based on the total weight of the etching composition.

11. In paragraph 1, An etching composition comprising at least one inorganic acid selected from the group consisting of sulfuric acid, nitric acid, phosphoric acid, silicic acid, hydrofluoric acid, boric acid, hydrochloric acid, and perchloric acid.

12. In paragraph 1, The above etching composition further comprises an ammonium compound.

13. In paragraph 8, An etching composition wherein the ammonium compound comprises at least one of ammonium chloride, ammonium phosphate, ammonium acetate, ammonium sulfate, ammonium formate, and a metal amine complex salt.

14. In paragraph 1, The above etching composition is characterized in that it is used for etching a silicon nitride film.

15. In paragraph 1, An etching composition characterized in that the etching selectivity of the silicon nitride film / germanium-containing material film of the above etching composition is 50 or more.

16. In paragraph 1, An etching composition characterized in that the bubble height on the surface immediately after formation of the etching composition is 0.9 cm or less.

17. A step of forming a structure by laminating an insulating film and a sacrificial film on a substrate; and A method for manufacturing an integrated circuit element, comprising: performing an etching process using an etching composition according to claim 1 to remove a sacrificial film and form a space region; 18. In paragraph 17, A method for manufacturing an integrated circuit element, wherein the sacrificial film comprises silicon nitride and the insulating film comprises a germanium-containing material or silicon oxide.

19. In paragraph 17, A method for manufacturing an integrated circuit element, characterized in that in the above etching process, the sacrificial film has a higher etching rate than the insulating film.

20. In paragraph 17, A method for manufacturing an integrated circuit element, characterized in that in the step of performing the above etching process to remove the sacrificial film and form a space region, the space region includes a gate region formed between the insulating films and a trench connected to the gate region.

21. In paragraph 17, forming openings penetrating the laminated structure; and Further comprising forming a semiconductor pattern spaced apart from the trench within the above openings, A method for manufacturing an integrated circuit element, wherein forming the semiconductor pattern is performed before forming the trench.

22. A structure formed by laminating an insulating film and a sacrificial film; A space formed by etching a sacrificial film in the above structure by an etching composition; and It includes a deposition part formed by depositing a conductive material or an insulating material in the above space; An integrated circuit element, wherein the etching composition comprises an inorganic acid, a first etching inhibitor, a second etching inhibitor, and a remaining amount of a solvent, wherein the first etching inhibitor comprises at least two nitrogen atoms and comprises a heterocyclic structure containing at least one nitrogen atom.

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