Silicon precursor compound, composition for forming silicon-containing film containing the same, and method for forming silicon-containing film

Abstract

The present application relates to a silicon precursor compound, a method for producing the silicon precursor compound, a precursor composition for forming a silicon-containing film including the silicon precursor compound, and a method for forming a silicon-containing film using the precursor composition.

Description

[Technical field]

[0001] The present application relates to a silicon precursor compound, a method for producing the silicon precursor compound, a precursor composition for forming a silicon-containing film containing the silicon precursor compound, and a method for forming a silicon-containing film using the precursor composition. [Background technology]

[0002] Silicon-containing films, such as silicon oxide, nitride, oxynitride, and carbonitride, are essential thin films for driving microelectronic devices such as semiconductors (DRAM, Flash Memory, ReRAM, PCRAM, etc.) as well as non-semiconductors (Logic). In the display field, silicon-containing films are used in flat panel displays including oxide thin film transistors (OTFTs), solar cells, and organic light emitting diodes (OLEDs). In memory devices, silicon-containing oxide thin films are used for dielectric films, gate insulating films, tunneling oxide films, spacer oxide films, ILD&IMD, passivation oxide films, etc., and silicon-containing nitride thin films are used for diffusion masks, gate spacers, gate dielectric films, etch stoppers, stressors, passivations, etc. In the display field, silicon-containing oxide thin films / nitride thin films are used in various thin film layers such as gate dielectric film, interlayer dielectric film, insulating film, moisture permeation prevention film, etc. In particular, in the case of silicon-containing oxide thin films, the processes for manufacturing such thin films require various silicon-containing oxide films with various film qualities according to various process conditions such as double patterning (DPT), quadruple patterning (QPT), and 3D NAND gate sealing oxide film processes that require extremely low temperatures depending on the application field, gate oxide film that is carried out at high temperatures, and 3D NAND slit oxide film, and various silicon precursors are used for each process depending on their physical and chemical properties.

[0003] Silicon-containing films can be formed with uniform thickness even on uneven surfaces by using atomic layer deposition (ALD), which sequentially supplies silicon compound gas and reactant gas required for film formation. Silicon-containing films can be formed at low temperatures by using plasma-based atomic layer deposition. If a silicon precursor compound with fast film growth per gas supply cycle (growth-per-cycle; GPC) is used in atomic layer deposition, more semiconductor or display substrates can be processed per unit time in ALD equipment, thereby minimizing the number of ALD equipment required. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent Publication No. 2012 / 0085733 Summary of the Invention [Problem to be solved by the invention]

[0005] The present application aims to provide a silicon precursor compound, a method for producing the silicon precursor compound, a precursor composition for forming a silicon-containing film containing the silicon precursor compound, and a method for forming a silicon-containing film using the precursor composition.

[0006] In particular, the present application provides a method for forming a silicon-containing film in which a film is grown rapidly per gas supply cycle in an atomic layer deposition method in which a source material and a reactant gas are sequentially supplied, and also provides a novel silicon compound and a method for producing the same, which are advantageous for use in the method for forming a silicon-containing film according to an embodiment of the present application, and a precursor composition containing the novel silicon compound.

[0007] However, the problems to be solved by the present application are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those of ordinary skill in the art from the following description. [Means for solving the problem]

[0008] A first aspect of the present application provides a silicon precursor compound represented by Formula I: [Chemical formula I] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In said formula I, R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group; or comprises substituted or unsubstituted C4-C8 cyclic alkyl groups linked together; R 1 and R 2 is the cyclic alkyl group, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms, R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C1-C4 alkyl group, or a linear or branched alkenyl group; However, R 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0009] A second aspect of the present invention is a method for producing a compound comprising the steps of: (a) subjecting a compound to a halide amine substitution reaction according to a reaction scheme selected from the following reaction scheme 1-1, the following reaction scheme 1-2, or the following reaction scheme 1-3 to produce a compound having a structure similar to that of the compound shown in FIG. 3 R 4 R 5 )2; and (b) obtaining said XSiH2N(SiR 3 R 4 R 5 The present invention provides a method for preparing a silicon precursor compound according to the following chemical formula I, comprising: subjecting 2 to a halide amine substitution reaction according to a reaction scheme selected from the following reaction schemes 2-1, 2-2, and 2-3 to obtain a silicon precursor compound according to the following chemical formula I: [Reaction Scheme 1-1] H2SiX2+M 1 -N(SiR 3 R 4 R 5 )2→XSiH2N(SiR 3 R 4 R 5 )2+M 1 X; [Reaction Scheme 1-2] H2SiX2+2HN(SiR 3 R 4 R 5 )2→XSiH2N(SiR 3 R 4 R 5 )2+HX·HN(SiR 3 R 4 R 5 )2; [Reaction Scheme 1-3] H2SiX2+HN(SiR 3 R 4 R 5 )2+NEt3→XSiH2N(SiR 3 R 4 R 5 )2+HX·NEt3; [Reaction Scheme 2-1] XSiH2N(SiR 3 R 4 R 5 )2+M 2 -NR 1 R 2 →R 1 R 2 NSiH2N(SiR 3 R 4 R 5 )2+M 2 X; [Reaction Scheme 2-2] XSiH2N(SiR 3 R 4 R 5 )2+2HNR 1 R 2 →R 1 R 2 NSiH2N(SiR 3 R 4 R 5 )2+HX·HNR 1 R 2 ; [Reaction Scheme 2-3] XSiH2N(SiR 3 R 4 R 5 )2+HNR 1 R 2 +NEt3→R 1 R 2 NSiH2N(SiR 3 R 4 R 5 )2+HX·NEt3; [Chemical formula I] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the reaction formulas 1-1 to 1-3, the reaction formulas 2-1 to 2-3, and the chemical formula 1, M 1 and M 2 are each independently Li, Na, or K, X is a halogen element, and R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group; or comprises substituted or unsubstituted C4-C8 cyclic alkyl groups linked together; R 1 and R 2 is the cyclic alkyl group, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms, and R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C1-C4 alkyl group, or a linear or branched alkenyl group, with the proviso that R 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0010] A third aspect of the present application provides a precursor composition for forming a silicon-containing film, comprising the silicon precursor compound according to the first aspect.

[0011] A fourth aspect of the present application provides a method for forming a silicon-containing film, comprising forming a silicon-containing film using a film-forming precursor composition containing the silicon precursor compound according to the first aspect. Effect of the Invention

[0012] By using the silicon precursor compound according to the embodiment of the present application, a silicon-containing film can be formed. In particular, a silicon oxide film can be grown much faster in a plasma atomic layer deposition method using oxygen (O2) gas than when using a conventional silicon compound. By using a silicon precursor compound that has a fast film growth-per-cycle in the atomic layer deposition method, more semiconductor or display substrates can be processed per unit time in the ALD equipment, thereby minimizing the number of ALD equipment required.

[0013] The thin film deposition method using a silicon precursor compound of the present invention is to deposit a silicon-containing oxide thin film or a silicon nitride thin film on a substrate by atomic layer deposition using a silicon precursor compound. By depositing a silicon-containing oxide thin film or a silicon nitride thin film using atomic layer deposition, the process temperature during deposition can be reduced and the thickness and composition of the thin film can be accurately controlled, so that a thin film having excellent coverage can be deposited even on a substrate with a complex shape, and the thickness uniformity and physical properties of the thin film can be improved.

[0014] The thin film deposition method using the silicon precursor compound of the present invention can be used to manufacture memory devices, logic devices, display devices, and OLED devices. [Brief description of the drawings]

[0015] [Figure 1] 1H-NMR spectra of silicon-containing compounds prepared in Examples 1 and 2 of the present invention. [Diagram 2] 1 is an FT-IR spectrum of the silicon-containing compound prepared in Example 1 of the present invention. [Diagram 3] 1 is a TGA graph of silicon-containing compounds prepared according to Examples 1 and 2 of the present invention; [Figure 4] 1 is a graph showing the growth of a silicon oxide film per gas supply cycle in a plasma atomic layer deposition method using oxygen (O2) gas at a substrate temperature range of 125°C to 300°C using the silicon compounds prepared according to Examples 1 and 2 of the present invention, as a function of temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Hereinafter, the present application will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present application. However, the present application may be embodied in various different forms and is not limited to the embodiments and examples described herein. In the drawings, in order to clearly explain the present invention, parts that are not related to the description are omitted, and similar parts are designated by similar reference numerals throughout the specification.

[0017] Throughout the specification of this application, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "electrically connected" with another element therebetween.

[0018] Throughout this specification, when a member is said to be "on" another member, this includes not only when the member is in contact with the other member, but also when there is another member between the two members.

[0019] Throughout the specification of this application, when a part is said to "comprise" a certain element, this means that it may further include other elements, but not to the exclusion of other elements, unless specifically stated to the contrary.

[0020] As used herein, terms of degree such as "about," "substantially," and the like are used to mean a numerical value or close to a numerical value when the manufacturing and material tolerances inherent in the recited value are given, and are used to prevent unscrupulous infringers from unfairly taking advantage of the disclosure in which precise or absolute numerical values ​​are recited to aid in the understanding of the present application.

[0021] As used throughout the specification of this application, the terms "a step of" or "a step of" do not mean "a step for."

[0022] Throughout the specification of this application, the term "combination(s) of" contained in a Markush form expression means a mixture or combination of one or more selected from the group of elements set forth in the Markush form expression, and is meant to include one or more selected from the group of elements set forth above.

[0023] Throughout the specification of this application, the statement "A and / or B" means "A or B, or A and B."

[0024] Throughout this specification, the term "alkyl" or "alkyl group" includes linear or branched alkyl groups having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 5 carbon atoms, and all possible isomers thereof. For example, the above alkyl or alkyl groups include methyl (Me), ethyl (Et), n-propyl (N-propyl) groups, etc. n Pr), iso-propyl group ( i Pr), n-butyl group ( n Bu), iso-butyl group ( i Bu), tert-butyl group (tert-Bu, t Bu), sec-butyl group (sec-Bu, sec Bu), n-pentyl group ( n Pe), iso-pentyl group ( iso Pe), sec-pentyl group ( sec Pe), tert-pentyl group ( tPe), neo-pentyl group ( neo Pe), 3-pentyl, n-hexyl, iso-hexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof.

[0025] Throughout this specification, the term "film" means "membrane" or "thin film."

[0026] Hereinafter, specific examples of the present application will be described in detail, but the present application is not limited thereto.

[0027] A first aspect of the present application provides a silicon precursor compound represented by Formula I: [Chemical formula I] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above formula I, R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group or a substituted or unsubstituted C4-C8 cyclic alkyl group linked together; R 1 and R 2 is the above cyclic alkyl group, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0028] In one embodiment of the present application, R 1 and R 2may each independently comprise, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, or a substituted or unsubstituted C4-C8 cyclic alkyl group linked together.

[0029] In one embodiment of the present application, -NR 1 R 2 may include, but is not limited to, a dimethylamino group (MeN-), an ethylmethylamino group (EtMeN-), a diethylamino group (EtN-), a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

[0030] In one embodiment of the present application, R 3 , R 4 , and R 5 may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0031] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( n Pr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH( n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R5 may be -SiHMe2.

[0032] In an embodiment of the present application, the silicon precursor compound may be represented by the following Formula 1: [Chemical formula 1] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above Chemical Formula 1, R 1 and R 2 are substituted or unsubstituted C4-C8 cyclic alkyl groups linked together, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0033] In one embodiment of the present application, -NR 1 R 2 may be a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

[0034] In one embodiment of the present application, R 3 , R 4 , and R 5 may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0035] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( n Pr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH( n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R 5 may be -SiHMe2.

[0036] In an embodiment of the present application, the silicon precursor compound may be represented by the following Formula 2: [Chemical formula 2] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above Chemical Formula 2, R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0037] In one embodiment of the present application, R 3 , R 4 , and R 5may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0038] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( n Pr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH( n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R 5 may be -SiHMe2.

[0039] In an embodiment of the present application, the silicon precursor compound may include the following compounds: [ka]

[0040] A second aspect of the present invention is a method for producing a compound comprising the steps of: (a) subjecting a compound to a halide amine substitution reaction according to a reaction scheme selected from the following reaction scheme 1-1, the following reaction scheme 1-2, or the following reaction scheme 1-3 to produce a compound having a structure similar to that of the compound shown in FIG. 3 R 4 R 5 )2; and (b) obtaining the above XSiH2N(SiR 3 R 4 R 5 The present invention provides a method for preparing a silicon precursor compound according to the following chemical formula I, comprising: subjecting 2 to a halide amine substitution reaction according to a reaction scheme selected from the following reaction schemes 2-1, 2-2, and 2-3 to obtain a silicon precursor compound according to the following chemical formula I: [Reaction Scheme 1-1] H2SiX2+M 1 -N(SiR 3 R 4 R 5 )2→XSiH2N(SiR 3 R 4 R 5 )2+M 1 X; [Reaction Scheme 1-2] H2SiX2+2HN(SiR 3 R 4 R 5 )2→XSiH2N(SiR 3 R 4 R 5 )2+HX·HN(SiR 3 R 4 R 5 )2; [Reaction Scheme 1-3] H2SiX2+HN(SiR 3 R 4 R 5 )2+NEt3→XSiH2N(SiR 3 R 4 R 5 )2+HX·NEt3; [Reaction Scheme 2-1] XSiH2N(SiR 3 R 4 R 5 )2+M 2 -NR 1 R 2 →R 1 R 2 NSiH2N(SiR 3 R 4 R 5 )2+M 2 X; [Reaction Scheme 2-2] XSiH2N(SiR 3 R 4 R 5 )2+2HNR 1 R 2 →R 1 R 2 NSiH2N(SiR 3 R 4 R 5 )2+HX·HNR 1 R 2 ; [Reaction Scheme 2-3] XSiH2N(SiR 3 R 4 R 5 )2+HNR 1 R 2 +NEt3→R 1 R 2 NSiH2N(SiR 3 R 4 R 5 )2+HX·NEt3; [Chemical formula I] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above-mentioned reaction formulas 1-1 to 1-3, the above-mentioned reaction formulas 2-1 to 2-3, and the above-mentioned chemical formula 1, M 1 and M 2 are each independently Li, Na, or K, X is a halogen element, and R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group; or comprises substituted or unsubstituted C4-C8 cyclic alkyl groups linked together; R 1 and R 2 is the above cyclic alkyl group, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0041] Detailed descriptions of parts that overlap with the first aspect of the present application are omitted, but the contents described with respect to the first aspect of the present application may be similarly applied even if the description is omitted in the second aspect of the present application.

[0042] In one embodiment of the present application, R 1 and R2 may each independently include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or a substituted or unsubstituted C4-C8 cyclic alkyl group linked together. 1 and R 2 may contain substituted or unsubstituted C4-C8 cyclic alkyl groups linked together.

[0043] In one embodiment of the present application, -NR 1 R 2 may include, but is not limited to, a dimethylamino group (MeN-), an ethylmethylamino group (EtMeN-), a diethylamino group (EtN-), a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group. 1 R 2 may be a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

[0044] In one embodiment of the present application, -SiR 3 R 4 R 5 may include, but is not limited to, -SiHMe2, -SiHMeEt, -SiHMe(n-Pr), -SiHMe(iso-Pr), -SiHEt2, -SiHEt(n-Pr), -SiHEt(iso-Pr), -SiH(n-Pr)2, -SiH(n-Pr)(iso-Pr), or -SiH(iso-Pr). 3 R 4 R 5may be -SiHMe2.

[0045] In an embodiment of the present application, the silicon precursor compound may include the following compounds: [ka]

[0046] In one embodiment of the present application, the silicon precursor compound represented by the above formula I is prepared by reacting dichlorosilane (H2SiCl2) compound with about 1 equivalent of metal silylamine salt (M) at low temperature in a first reaction when X=Cl as shown in the above reaction formula 1-1. 1 -N(SiR 3 R 4 R 5 ), M 1 After adding metal halide salt (Li, Na, or K), the halide and amine are subjected to a substitution reaction while maintaining room temperature. Then, the reaction by-product is removed through a filter in the form of a metal halide salt. As shown in Reaction Scheme 2-1 above, the secondary reaction is carried out at a low temperature with about 1 equivalent of a metal amine salt (M 2 -NR 1 R 2 , M: Li, Na, or K), and then the halide and amine are subjected to a substitution reaction while maintaining room temperature, and then the reaction by-product is removed through a filter in the form of a metal halide salt, and the synthesis may be performed, but is not limited thereto.

[0047] In an embodiment of the present application, instead of the alkali metal salt of the amino group, an excess amount of amine may be used, or a tertiary amine such as triethylamine (NEt3) may be used. Specifically, the silicon precursor compound may be prepared according to Reaction Scheme 1-2 or 1-2 instead of Reaction Scheme 1-1, and the silicon precursor compound may be prepared according to Reaction Scheme 2-2 or 2-3 instead of Reaction Scheme 2-1. However, the present invention is not limited thereto.

[0048] In one embodiment of the present application, the solvent used in the reaction (a) may be an alkane having 5 to 8 carbon atoms, such as pentane, hexane, or octane, which has non-polarity, or toluene, which has weak polarity. It is preferable to use hexane, since it has a boiling point of 78° C. and is stable.

[0049] In one embodiment of the present application, the compound represented by the following formula 4 is prepared by reacting dichlorosilane (SiH2Cl2) with lithium (tetramethyldisilyl)amine salt at low temperature in a non-polar solvent, hexane, as a first reaction to cause a substitution reaction between Cl and amine, and then reacting with lithium piperidine salt at low temperature in a second reaction to cause another Cl to be substituted with amine, followed by filtration and distillation under reduced pressure to produce silicon precursor (tetramethyldisilyl)aminopiperidinylsilane represented by the following formula 4, as shown in the following reaction formula A. Lithium (tetramethyldisilyl)amine salt and lithium piperidine salt are prepared by reacting n-BuLi with tetramethyldisilazane and n-BuLi with piperidine, respectively, in a non-polar solvent, hexane, at low temperature. It is preferable to carry out the reaction under a nitrogen (N2) or argon (Ar) stream in order to safely remove salt (LiCl) and unreacted SiH2Cl2, which are products of the first and second reactions of reaction formula A, and to suppress decomposition reactions due to moisture or oxygen during the reaction. However, this is not limited to this. [ka]

[0050] A third aspect of the present application provides a precursor composition for forming a silicon-containing film, comprising the silicon precursor compound according to the first aspect.

[0051] Detailed descriptions of parts that overlap with the first and second aspects of the present application are omitted, but the contents described for the first and second aspects of the present application may be similarly applied even if the description is omitted in the third aspect of the present application.

[0052] In one embodiment of the present application, the silicon precursor compound may be represented by the following formula I: [Chemical formula I] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above formula I, R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group or a substituted or unsubstituted C4-C8 cyclic alkyl group linked together; R 1 and R 2 is the above cyclic alkyl group, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0053] In one embodiment of the present application, R 1 and R 2 may each independently comprise, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, or a substituted or unsubstituted C4-C8 cyclic alkyl group linked together.

[0054] In one embodiment of the present application, -NR 1 R 2may include, but is not limited to, a dimethylamino group (MeN-), an ethylmethylamino group (EtMeN-), a diethylamino group (EtN-), a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

[0055] In one embodiment of the present application, R 3 , R 4 , and R 5 may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0056] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( n Pr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH( n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R 5 may be -SiHMe2.

[0057] In an embodiment of the present application, the silicon precursor compound may be represented by the following Formula 1: [Chemical formula 1] R 1 R 2 N-SiH2-N(SiR 3 R 4 R5 )2; In the above Chemical Formula 1, R 1 and R 2 are substituted or unsubstituted C4-C8 cyclic alkyl groups linked together, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0058] In one embodiment of the present application, -NR 1 R 2 may be a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

[0059] In one embodiment of the present application, R 3 , R 4 , and R 5 may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0060] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( n Pr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH(n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R 5 may be -SiHMe2.

[0061] In an embodiment of the present application, the silicon precursor compound may be represented by the following Formula 2: [Chemical formula 2] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above Chemical Formula 2, R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0062] In one embodiment of the present application, R 3 , R 4 , and R 5 may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0063] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( nPr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH( n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R 5 may be -SiHMe2.

[0064] In an embodiment of the present application, the precursor composition for forming a silicon-containing film may include one or more selected from the following silicon precursor compounds: [ka]

[0065] In an embodiment of the present application, the film may be one or more selected from, but not limited to, a silicon-containing oxide film or thin film, a silicon-containing nitride film or thin film, a silicon-containing carbide film or thin film, a silicon-containing oxynitride film or thin film, and a silicon-containing carbonitride film or thin film. In an embodiment of the present application, the film may be a silicon oxide film. In particular, in an embodiment of the present application, when a silicon-containing film is formed using a film-forming precursor composition including a silicon precursor compound represented by Chemical Formula 2, a silicon oxide film may be formed.

[0066] In an embodiment of the present application, the film-forming precursor composition may further include one or more nitrogen sources selected from the group consisting of ammonia, nitrogen, hydrazine, and dimethylhydrazine, but is not limited thereto.

[0067] In an embodiment of the present application, the film-forming precursor composition may further include one or more oxygen sources selected from the group consisting of water vapor, oxygen, and ozone, but is not limited thereto.

[0068] A fourth aspect of the present application provides a method for forming a silicon-containing film, comprising forming a silicon-containing film using a film-forming precursor composition containing the silicon precursor compound according to the first aspect.

[0069] Detailed descriptions of parts that overlap with the first to third aspects of the present application are omitted, but the contents described for the first to third aspects of the present application may be similarly applied even if the description is omitted in the fourth aspect of the present application.

[0070] In one embodiment of the present application, the silicon precursor compound may be represented by the following formula I: [Chemical formula I] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above formula I, R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group or a substituted or unsubstituted C4-C8 cyclic alkyl group linked together; R 1 and R 2 is the above cyclic alkyl group, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0071] In one embodiment of the present application, R 1 and R 2may each independently comprise, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, or a substituted or unsubstituted C4-C8 cyclic alkyl group linked together.

[0072] In one embodiment of the present application, -NR 1 R 2 may include, but is not limited to, a dimethylamino group (MeN-), an ethylmethylamino group (EtMeN-), a diethylamino group (EtN-), a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

[0073] In one embodiment of the present application, R 3 , R 4 , and R 5 may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0074] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( n Pr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH( n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R5 may be -SiHMe2.

[0075] In an embodiment of the present application, the silicon precursor compound may be represented by the following Formula 1: [Chemical formula 1] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above Chemical Formula 1, R 1 and R 2 are substituted or unsubstituted C4-C8 cyclic alkyl groups linked together, -NR 1 R 2 contains a cyclic amino group containing one or more nitrogen atoms; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0076] In one embodiment of the present application, -NR 1 R 2 may be a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

[0077] In one embodiment of the present application, R 3 , R 4 , and R 5 may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0078] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( n Pr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH( n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R 5 may be -SiHMe2.

[0079] In an embodiment of the present application, the silicon precursor compound may be represented by the following Formula 2: [Chemical formula 2] R 1 R 2 N-SiH2-N(SiR 3 R 4 R 5 )2; In the above Chemical Formula 2, R 1 and R 2 each independently comprises a linear or branched C1-C4 alkyl group; R 3 , R 4 , and R 5 each independently comprises hydrogen, a linear or branched C-C alkyl group, or a linear or branched alkenyl group; 3 , R 4 , and R 5 The case where all are hydrogen is excluded.

[0080] In one embodiment of the present application, R 3 , R 4 , and R 5may each independently be, but is not limited to, hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group.

[0081] In one embodiment of the present application, -SiR 3 R 4 R 5 -SiHMe2, -SiHMeEt, -SiHMe( n Pr), -SiHMe( iso Pr), -SiHEt2, -SiHEt( n Pr), -SiHEt( iso Pr), -SiH( n Pr)2, -SiH( n Pr)( iso Pr), or -SiH( iso In one embodiment of the present application, the compound may include, but is not limited to, -SiR 3 R 4 R 5 may be -SiHMe2.

[0082] In an embodiment of the present application, the silicon precursor compound included in the precursor composition for forming a silicon-containing film may include one or more selected from the following compounds: [ka]

[0083] In an embodiment of the present application, the silicon-containing film may be one or more selected from, but is not limited to, a silicon-containing oxide film or thin film, a silicon-containing nitride film or thin film, a silicon-containing carbide film or thin film, a silicon-containing oxynitride film or thin film, and a silicon-containing carbonitride film or thin film. In an embodiment of the present application, the silicon-containing film may be a silicon oxide film. In particular, in an embodiment of the present application, when a silicon-containing film is formed using a film-forming precursor composition including a silicon precursor compound represented by Chemical Formula 2, a silicon oxide film may be formed.

[0084] In an embodiment of the present application, the method for forming a silicon-containing film can achieve a film growth rate (GPC) per gas supply cycle of about 1.8 Å / cycle or more. For example, the method for forming a silicon-containing film can achieve a film growth rate of about 1.8 Å / cycle or more, about 1.9 Å / cycle or more, or about 2 Å / cycle or more.

[0085] In the embodiment of the present application, the silicon-containing oxide film or thin film, the silicon-containing nitride film or thin film, and / or the silicon-containing carbide film or thin film may be used in various ways depending on the application, such as a dielectric film, a gate insulating film, a tunneling oxide film, a spacer oxide film, an ILD&IMD, and / or a passivation oxide film, and a diffusion mask, a gate spacer, a gate dielectric film, an etch stopper, a stressor, and / or a passivation film, and the like, but is not limited thereto.

[0086] In an embodiment of the present application, the silicon-containing film may be deposited by, but is not limited to, chemical vapor deposition (CVD) or atomic layer deposition (ALD). The silicon-containing film may be deposited by, but is not limited to, metalorganic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD). The chemical vapor deposition or atomic layer deposition may be performed using a deposition apparatus, deposition conditions, and additional reaction gases known in the art, but is not limited to the above.

[0087] In one embodiment of the present application, when depositing the film, it is preferable to use one or more of water vapor (HO), oxygen (O), oxygen plasma (O2 plasma), nitrogen oxide (NO, NO), nitrogen oxide plasma (NO plasma), oxygen nitride (NO2), hydrogen peroxide (HO2), and ozone (O3) as a reactive gas to form a silicon-containing oxide film or a composite metal silicon-containing oxide film (HfSiOx, ZrSiOx, TiSiOx, HfAlOx, ZrAlSiOx, TiAlSiOx, ZrHfSiOx, ZrHfAlSiOx, SiC, SiCO, or SiON, etc.).

[0088] In one embodiment of the present application, when depositing the above-mentioned film, it is preferable to use one or more of ammonia (NH3), ammonia plasma (NH3 Plasma), hydrazine (N2H4), and nitrogen plasma (N2 Plasma) as a reactive gas to deposit a silicon-containing nitride film (SiN) or a composite metal nitride film (HfSiNx, ZrSiNx, TiSiNx, AlSiNx, HfAlSiNx, ZrAlSiNx, TiAlSiNx, HfZrAlSiNx, HfZrTiSiNx, TiAlSiNx, SiCN, SiOCN, or SiBN, etc.).

[0089] In an embodiment of the present application, the silicon-containing film may be formed at a temperature range of, but is not limited to, about 100° C. to about 300° C., about 100° C. to about 250° C., about 100° C. to about 200° C., about 100° C. to about 150° C., about 100° C. to about 125° C., about 125° C. to about 300° C., about 125° C. to about 250° C., about 125° C. to about 200° C., about 125° C. to about 150° C., about 150° C. to about 300° C., about 150° C. to about 250° C., about 150° C. to about 200° C., about 200° C. to about 300° C., about 200° C. to about 250° C., or about 250° C. to about 300° C., but is not limited thereto. In an embodiment of the present application, the silicon-containing film may be formed at a temperature range of about 100°C to about 300°C, or about 100°C to about 250°C.

[0090] In one embodiment of the present application, the silicon-containing film may be formed to a thickness range of about 1 nm to about 500 nm, but may be applied in various ways depending on the application, and is not limited thereto. For example, the silicon-containing film may be formed to a thickness range of about 1 nm to about 500 nm, about 1 nm to about 400 nm, about 1 nm to about 300 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 50 nm, about 1 nm to about 40 nm, about 1 nm to about 30 nm, about 1 nm to about 20 nm, about 1 nm to about 10 nm, about 10 nm to about 500 nm, about 10 nm to about 400 nm, about 10 nm to about 300 nm, about 10 nm to about 20 ...500 nm, about 10 nm to about 500 nm, about 10 nm to about 500 nm, about 10 nm to about 200 nm, about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 500 nm, about 10 nm to about 200 nm, about 10 nm to about 500 nm, about 10 nm to about 300 nm, about 1 m ~ about 100nm, about 10nm - about 50nm, about 10nm - about 40nm, about 10nm - about 30nm, about 10nm - about 20nm, about 20nm - about 500nm, about 20nm - about 400nm, about 20nm - about 300 nm, approximately 20 nm to approximately 200 nm, approximately 20 nm to approximately 100 nm, approximately 20 nm to approximately 50 nm, approximately 20 nm to approximately 40 nm, approximately 20 nm to approximately 30 nm, approximately 30 nm to approximately 500 nm, approximately 30 nm to approximately 400 nm, approximately 30 nm~about 300nm, about 30nm~about 200nm, about 30nm~about 100nm, about 30nm~about 50nm, about 30nm~about 40nm, about 40nm~about 500nm, about 40nm~about 400nm, about 40nm~about 300nm, about 40nm to about 200nm, about 40nm to about 100nm, about 40nm to about 50nm, about 50nm to about 500nm, about 50nm to about 400nm, about 50nm to about 300nm, about 50nm to about 200 The film may be formed to a thickness range of, but is not limited to, about 50 nm to about 100 nm, about 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, about 100 nm to about 200 nm, about 200 nm to about 500 nm, about 200 nm to about 400 nm, about 200 nm to about 300 nm, about 300 nm to about 500 nm, about 300 nm to about 400 nm, or about 400 nm to about 500 nm.

[0091] In one embodiment of the present application, the silicon-containing film may be formed on one or more substrates selected from, but not limited to, a typical silicon semiconductor wafer, a compound semiconductor wafer, and a plastic substrate (PI, PET, PES, and PEN). A substrate having holes or grooves, or a porous substrate having a large surface area may be used, but is not limited to these. Furthermore, the silicon-containing film may be formed on the whole or part of a substrate simultaneously or sequentially in a substrate in which two or more different substrates are in contact or connected with each other, but is not limited to these.

[0092] In an embodiment of the present application, the silicon-containing film may be formed on a substrate including one or more irregularities having an aspect ratio of about 1 or more and a width of about 1 μm or less, but is not limited thereto. In an embodiment of the present application, the silicon-containing film may be formed on a substrate including one or more irregularities having an aspect ratio of about 1 to about 80 and a width of about 1 nm to about 1 μm, but is not limited thereto. For example, the aspect ratio is about 1 or more, about 5 or more, about 10 or more, about 20 or more, about 30 or more, about 40 or more, about 50 or more, about 60 or more, about 70 or more, or about 1 to about 80, about 1 to about 70, about 1 to about 60, about 1 to about 50, about 1 to about 40, about 1 to about 30, about 1 to about 20, about 1 to about 10, about 10 to about 80, about 10 to about 70, about 10 to about 60, about 10 to about 50, about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 80, It may be about 20 to about 70, about 20 to about 60, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 80, about 30 to about 70, about 30 to about 60, about 30 to about 50, about 30 to about 40, about 40 to about 80, about 40 to about 70, about 40 to about 60, about 40 to about 50, about 50 to about 80, about 50 to about 70, about 50 to about 60, about 60 to about 80, about 60 to about 70, or about 70 to about 80, but is not limited thereto. For example, the width is from about 1 nm to about 1 μm, from about 1 nm to about 900 nm, from about 1 nm to about 800 nm, from about 1 nm to about 700 nm, from about 1 nm to about 600 nm, from about 1 nm to about 500 nm, from about 1 nm to about 400 nm, from about 1 nm to about 300 nm, from about 1 nm to about 200 nm, from about 1 nm to about 100 nm, from about 1 nm to about 90 nm, from about 1 nm to about 80 nm, from about 1 nm to about 70 nm, from about 1 nm to about 60 nm, from about 1 to about 50 nm, from about 1 nm to about 40 nm, from about 1 nm to about 30 nm, from about 1 nm to about 20 nm, from about 1 nm to about 10 nm, nm ~ about 1μm, about 10nm - about 900nm, about 10nm - about 800nm, about 10nm - about 700nm, about 10nm - about 600nm, about 10nm - about 500nm, about 10nm - about 400nm, about 10nm - about 300nm, about 10nm - about 200nm, about 10 nm to about 100nm, about 10nm to about 90nm, about 10nm to about 80nm, about 10nm to about 70nm, about 10nm to about 60nm, about 10 to about 50nm, about 10nm to about 40nm, about 10nm to about 30nm, about 10nm to about 20nm, about 20nm to about 1μm,about 20 nm to about 900 nm, about 20 nm to about 800 nm, about 20 nm to about 700 nm, about 20 nm to about 600 nm, about 20 nm to about 500 nm, about 20 nm to about 400 nm, about 20 nm to about 300 nm, about 20 nm to about 200 nm, about 20 nm to about 100 nm, about 20 nm to about 90 nm, about 20 nm to about 80 nm, about 20 nm to about 70 nm, about 20 nm to about 60 nm, about 20 to about 50 nm, about 20 nm to about 40 nm, about 20 nm to about 30 nm, about 30 nm to about 1 μm, about 30 nm to about 900 nm, about 30 nm to about 800 nm, about 30 nm to about 700 nm , about 30nm to about 600nm, about 30nm to about 500nm, about 30nm to about 400nm, about 30nm to about 300nm, about 30nm to about 200nm, about 30nm to about 100nm, about 30nm to about 90nm, about 30nm to about 80nm, about 30nm to about 70nm, about 30nm to about 60nm, about 30 to about 50nm, about 30nm to about 40nm, about 40nm to about 1μm, about 40nm to about 900nm, about 40nm to about 800nm, about 40nm to about 700nm, about 40nm to about 600nm, about 40nm to about 500nm, about 40nm to about 400nm, about 40nm to about 300 nm, about 40 nm to about 200 nm, about 40 nm to about 100 nm, about 40 nm to about 90 nm, about 40 nm to about 80 nm, about 40 nm to about 70 nm, about 40 nm to about 60 nm, about 40 to about 50 nm, about 50 nm to about 1 μm, about 50 nm to about 900 nm, about 50 nm to about 800 nm, about 50 nm to about 700 nm, about 50 nm to about 600 nm, about 50 nm to about 500 nm, about 50 nm to about 400 nm, about 50 nm to about 300 nm, about 50 nm to about 200 nm, about 50 nm to about 100 nm, about 50 nm to about 90 nm, about 50 nm to about 80 nm, about 50 nm to about 70 nm, about 50 nm to about 60 nm, about 100 nm to about 1 μm, about 100 nm to about 900 nm, about 100 nm to about 800 nm, about 100 nm to about 700 nm, about 100 nm to about 600 nm, about 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, about 100 nm to about 200 nm, about 200 nm to about 1 μm, about 200 nm to about 900 nm, about 200 nm to about 800 nm, about 200 nm to about 700 nm, about 200 nm to about 600 nm, about 200 nm to about 500 nm, about 200 nm to about 400 nm, about 200 nm to about 300 nm,Approximately 300nm to approximately 1μm, approximately 300nm to approximately 900nm, approximately 300nm to approximately 800nm, approximately 300nm to approximately 700nm, approximately 300nm to approximately 600nm, approximately 300nm to approximately 500nm, approximately 300nm to approximately 400nm, approximately 400nm nm ~ approx. 1 μm, approx. 400 nm ~ approx. 900 nm, approx. 400 nm ~ approx. 800 nm, approx. 400 nm ~ approx. 700 nm, approx. 400 nm ~ approx. 600 nm, approx. nm, about 500 nm to about 800 nm, about 500 nm to about 700 nm, about 500 nm to about 600 nm, about 600 nm to about 1 μm, about 600 nm to about 900 nm, about 600 nm to about 800 nm, about 600 nm to about 700 nm, about 700 nm to about 1 μm, about 700 nm to about 900 nm, about 700 nm to about 800 nm, about 800 nm to about 1 μm, about 800 nm to about 900 nm, or about 900 nm to about 1 μm, but is not limited thereto.

[0093] In one embodiment of the present application, the method for forming a silicon-containing film includes, but is not limited to, supplying a precursor composition for forming a silicon-containing oxide thin film or a nitride thin film in a gaseous state to a substrate located in a deposition chamber to form a silicon-containing oxide film or thin film, or a nitride film or thin film, etc. The method for depositing the film may use a method, apparatus, etc. known in the technical field of the present application, and may be performed together with one or more additional reaction gases as necessary.

[0094] In an embodiment of the present application, the silicon precursor compound of the present application contained in the precursor composition for forming a film has a high vapor pressure, a low density, and a high thermal stability, and can be used as a precursor for an atomic layer deposition method or a chemical vapor deposition method to form a silicon-containing film. In particular, it has an excellent effect of being able to uniformly form a silicon-containing oxide film or thin film, or a nitride film or thin film having a thickness of several nm to several tens of μm, or about 1 nm to about 500 nm, even on a substrate having a pattern (groove) on the surface, a porous substrate, or a plastic substrate, in a wide temperature range of about 100° C. to about 300° C.

[0095] In one embodiment of the present application, the silicon-containing film forming method preferably includes placing a substrate in a reaction chamber, transporting the silicon precursor compound onto the substrate using a carrier gas or dilution gas, and depositing a silicon-containing oxide thin film or nitride thin film at a wide deposition temperature range of about 100°C to about 300°C. Here, the ability to form the silicon-containing film at the wide deposition temperature range broadens the process temperatures applicable to memory devices, logic devices, and display devices, and has high applicability to various fields. In addition, since the film characteristics of silicon-containing oxide films, nitride films, and carbide films are different, a silicon precursor compound that can be used in a wide temperature range is required, and therefore deposition is preferably performed at a wide deposition temperature range of about 100°C to about 300°C. However, the present invention is not limited thereto.

[0096] In one embodiment of the present application, the silicon-containing film forming method preferably uses one or more mixed gases selected from argon (Ar), nitrogen (N2), helium (He), and hydrogen (H2) as the carrier gas or dilution gas. In addition, the silicon precursor compound may be delivered to the substrate by various supply methods including a bubbling method in which the precursor is forcibly vaporized using a carrier gas, a liquid delivery system (LDS) method in which the precursor is supplied in liquid form at room temperature and vaporized through a vaporizer, and a vapor flow controller (VFC) method in which the precursor is directly supplied using the vapor pressure of the precursor. Most preferably, when the vapor pressure of the silicon precursor compound is high, the VFC method may be used, and when the vapor pressure of the silicon precursor compound is high, the LDS method may be used in which the silicon precursor compound is supplied in liquid form and vaporized in a vaporizer and supplied into a chamber, and when the vapor pressure of the silicon precursor is low, the VFC method may be used in which the container is heated to vaporize the silicon precursor. Most preferably, the silicon precursor compound may be placed in a bubbler container, an LDS container, or a VFC container, and transported into the chamber using a high vapor pressure such as bubbling, LDS, or VFC, using a carrier gas at a pressure range of about 0.1 torr to about 10 torr and a temperature range of room temperature to about 100° C. However, the present invention is not limited thereto.

[0097] In an embodiment of the present disclosure, the silicon precursor compound may be vaporized by, but is not limited to, transporting it with argon (Ar) or nitrogen (N2) gas, using thermal energy or plasma, or applying a bias to the substrate.

[0098] In one embodiment of the present application, a silicon-containing oxide film can be grown much faster by atomic layer deposition, particularly by plasma-enhanced atomic layer deposition using oxygen (O2) gas, using a film-forming precursor composition containing the silicon compound. EXAMPLES

[0099] Hereinafter, the present application will be described in more detail with reference to examples. However, the following examples are merely illustrative to aid in understanding the present application, and the contents of the present application are not limited to the following examples.

[0100] Example 1: Preparation of pyrrolidinyl(tetramethyldisilyl)aminosilane: [(CH2CH2CH2CH2N)SiH2{N(SiHMe2)2}] In a 5L round-bottom flask, 358.49g (2.5M, 1.287mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with 3,000mL of anhydrous hexane. 171.62g (1.287mol) of 1,1,3,3-tetramethyldisilazane was added at around -20℃, and the temperature was gradually raised to room temperature while stirring and stirred for 4 hours. 130g (1.287mol) of dichlorosilane was added to the formed lithium (tetramethyldisilylamine) salt solution at -30℃ to -20℃ for 30 minutes, and the temperature was gradually raised while stirring and stirred for 17 hours. After the reaction was completed, the LiCl salt produced during the reaction was removed by filtration, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 168 g (yield: 66%) of the colorless liquid compound (tetramethyldisilyl)aminochlorosilane [ClSiH2{N(SiHMe2)2}].

[0101] In a 1L round-bottom flask, 77.414g (2.5M, 0.278mol) of normal butyl lithium hexane solution (n-BuLi in n-hexane) was mixed with 500mL of anhydrous hexane. 19.77g (0.278mol) of pyrrolidine was added at around -20℃, and the temperature was gradually raised to room temperature while stirring and stirred for 4 hours. 50g (0.252mol) of (tetramethyldisilyl)aminochlorosilane [ClSiH2{N(SiHMe2)2}] recovered in the above process was added to the lithium pyrrolidine salt solution formed at -30℃ to -20℃ for 30 minutes, and the temperature was gradually raised while stirring and stirred for 17 hours. After the reaction was completed, the salt produced during the reaction was removed by filtration, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 38 g (yield: 65%) of pyrrolidinyl(tetramethyldisilyl)aminosilane [(CH2CH2CH2CH2N)SiH2{N(SiHMe2)2}], a colorless liquid compound represented by the following chemical formula 3.

[0102] bp:32℃ at 0.3torr(210.3℃ at 760mmHg) 1 H-NMR(C6D6): δ0.265, 0.273(N-Si-C H 3, d, 12H), δ1.502(N-CH2-C H 2, m, 4H), δ2.973(NC H 2, m, 4H), δ4.827(H3C-Si- H , m, 2H), δ 4.981 (Si- H , s, 2H)

[0103] [ka]

[0104] Example 2: Preparation of piperidinyl(tetramethyldisilyl)aminosilane: [(CH2CH2CH2CH2CH2N)SiH2{N(SiHMe2)2}] In a 1L round-bottom flask, 77.414g (2.5M, 0.278mol) of normal butyl lithium hexane solution (n-BuLi in n-hexane) was mixed with 500mL of anhydrous hexane. 23.66g (0.278mol) of piperidine was added at around -20℃, and the temperature was gradually raised to room temperature while stirring and stirred for 4 hours. 50g (0.252mol) of (tetramethyldisilyl)aminochlorosilane [ClSiH2{N(SiHMe2)2}] synthesized in the same manner as in Example 1 was added to the formed lithium piperidine salt solution at -30℃ to -20℃ for 30 minutes, and the temperature was gradually raised while stirring and stirred for 17 hours. After the reaction was completed, the LiCl salt produced during the reaction was removed by filtration, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 47 g (yield: 75%) of piperidinyl(tetramethyldisilyl)aminosilane [(CH2CH2CH2CH2CH2N)SiH2{N(SiHMe2)2}], a colorless liquid compound represented by the following chemical formula 4.

[0105] bp:36℃ at 0.3torr(221.2℃ at 760mmHg) 1 H-NMR(C6D6):δ0.264, 0.272(N-Si-C H 3, d, 12H), δ1.335(N-CH2-C H 2, m, 4H), δ1.424(N-CH2-CH2-C H 2, m, 2H), δ2.876(NC H 2, m, 4H), δ4.819(H3C-Si- H , m, 2H), δ 4.867 (Si- H , s, 2H)

[0106] [ka]

[0107] Example 3: Preparation of 2,6-dimethylpiperidinyl(tetramethyldisilyl)aminosilane: [{CH(CH3)CH2CH2CH2CH(CH3)N}SiH2{N(SiHMe2)2}] In a 1L round-bottom flask, 77.414g (2.5M, 0.278mol) of normal butyl lithium hexane solution (n-BuLi in n-hexane) was mixed with 500mL of anhydrous hexane. 31.45g (0.278mol) of 2,6-dimethylpiperidine was added at around -20℃, and the temperature was gradually raised to room temperature while stirring and stirred for 4 hours. 50g (0.252mol) of (tetramethyldisilyl)aminochlorosilane [ClSiH2{N(SiHMe2)2}] synthesized in the same manner as in Example 1 was added to the formed lithium 2,6-dimethylpiperidine salt solution at -30℃ to -20℃ for 30 minutes, and the temperature was gradually raised while stirring and stirred for 17 hours. After the reaction was completed, the LiCl salt produced during the reaction was removed by filtration, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 46 g (yield: 66%) of 2,6-dimethylpiperidinyl(tetramethyldisilyl)aminosilane [{CH(CH3)CH2CH2CH2CH(CH3)N}}SiH2{N(SiHMe2)2}], a colorless liquid compound represented by the following chemical formula 5.

[0108] bp:55℃ at 0.3torr(244.5℃ at 760mmHg) 1 H-NMR(C6D6): δ0.282, 0.290(N-Si-C H 3, d, 12H), δ1.220,1.238(N-CH-C H 3, d, 6H), δ1.292, 1.329(N-CH-C H 2, m, 4H), δ1.515(N-CH-CH2-C H 2, m, 2H), δ3.365(NC H , m, 2H), δ4.833(HC-Si- H , m, 2H), δ 4.902 (Si- H , s, 2H)

[0109] [ka]

[0110] Example 4: Preparation of 4-methylpiperazinyl(tetramethyldisilyl)aminosilane: [{CH2CH2N(CH3)CH2CH2N}SiH2{N(SiHMe2)2}] In a 1L round-bottom flask, 77.414g (2.5M, 0.278mol) of n-butyllithium hexane solution (n-BuLi in n-hexane) was mixed with 500mL of anhydrous hexane. 27.84g (0.278mol) of 4-methylpiperazine was added at around -20℃, and the temperature was gradually raised to room temperature while stirring and stirred for 4 hours. 50g (0.252mol) of (tetramethyldisilyl)aminochlorosilane [ClSiH2{N(SiHMe2)2}] synthesized in the same manner as in Example 1 was added to the formed lithium 4-methylpiperazine salt solution at -30℃ to -20℃ for 30 minutes, and the temperature was gradually raised while stirring and stirred for 17 hours. After the reaction was completed, the salt produced during the reaction was removed by filtration, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 46 g (yield: 70%) of 4-methylpiperazinyl(tetramethyldisilyl)aminosilane [{CH2CH2N(CH3)CH2CH2N}}SiH2{N(SiHMe2)2}], a colorless liquid compound represented by the following chemical formula 6.

[0111] bp:45℃ at 0.3torr(230.4℃ at 760mmHg) 1 H-NMR(C6D6): δ0.250, 0.259(N-Si-C H 3, d, 12H), δ2.092(NC H 3, s, 3H), δ2.132 (H3C-NC H 2, m, 4H), δ2.985(Si-NC H 2, t, 2H), δ4.804(H3C-Si- H , m, 4H), δ 4.858 (Si- H , s, 2H)

[0112] [ka]

[0113] Example 5: Preparation of morpholino(tetramethyldisilyl)aminosilane: [(CH2CH2OCH2CH2N)SiH2{N(SiHMe2)2}] In a 1L round-bottom flask, 77.414g (2.5M, 0.278mol) of normal butyl lithium hexane solution (n-BuLi in n-hexane) was mixed with 500mL of anhydrous hexane. 24g (0.278mol) of morpholine was added at around -20℃, and the temperature was gradually raised to room temperature while stirring and stirred for 4 hours. 50g (0.252mol) of (tetramethyldisilyl)aminochlorosilane [ClSiH2{N(SiHMe2)2}] synthesized in the same manner as in Example 1 was added to the formed lithium morpholine salt solution at -30℃ to -20℃ for 30 minutes, and the temperature was gradually raised while stirring and stirred for 17 hours. After the reaction was completed, the salt produced during the reaction was removed by filtration, and the solvent and volatile by-products were removed by distillation under reduced pressure to obtain 24 g (yield: 35%) of the colorless liquid compound morpholino(tetramethyldisilyl)aminosilane [(CH2CH2OCH2CH2N)SiH2{N(SiHMe2)2}] represented by the following chemical formula 7.

[0114] bp:45℃ at 0.3torr(230.4℃ at 760mmHg) 1 H-NMR(C6D6):δ0.212, 0.221(N-Si-C H 3, d, 12H), δ2.779(NC H 2, t, 4H), δ3.434(OC H 2, t, 4H), δ4.754(H3C-Si- H , m, 2H), δ4.767(Si- H , s, 2H)

[0115] [ka]

[0116] Example 6: Preparation of MeNSiHN(SiHMe)(TMDMS) Me2NSiH2N(SiHMe2)2(TMDMS) represented by the following formula was prepared in the same manner as in Example 1, except that dimethylamine was used instead of pyrrolidine. [ka]

[0117] Example 7: Preparation of EtMeNSiH2N(SiHMe2)2 (TMEMS) EtMeNSiH2N(SiHMe2)2(TMEMS) represented by the following formula was prepared in the same manner as in Example 1, except that ethylmethylamine was used instead of pyrrolidine. [ka]

[0118] <Experimental Example 1> Structural analysis of silicon precursor compound In order to analyze the structures of the silicon precursor compounds prepared in Examples 1 and 2 of the above examples, 1 H-NMR and FT-IR analyses were carried out, and the results are shown in Figures 1 and 2.

[0119] As can be seen from FIG. 1, the silicon precursor compound produced in Example 1 has 1 As a result of H-NMR analysis, it was confirmed that Si-H peaks appeared at 4.827 ppm and 4.981 ppm. As can be seen from Figure 2, the RF-IR analysis showed that the peak of Si-H in the molecule was strong at 2158 cm -1 It was confirmed that the above 1 The results of H-NMR and FT-IR analysis confirmed that it was the material of Example 1, and the structure of the material confirmed that it is an excellent precursor capable of forming silicon-containing oxide thin films and nitride thin films in a variety of temperature ranges.

[0120] <Experimental Example 2> Thermal property analysis of silicon precursor compound In order to analyze the basic thermal properties of the silicon precursor compounds produced in Examples 1 and 2 among the above-mentioned Examples, TG analysis was carried out, and the results are shown in FIG.

[0121] As can be seen from Fig. 3, the silicon precursor compounds prepared in Examples 1 and 2 all have sufficient volatility to be applied to atomic layer deposition. In addition, it was confirmed that the silicon precursor compounds of the present invention have various volatilities and are excellent precursors capable of forming silicon-containing oxide thin films and nitride thin films in various temperature ranges, such as below 150°C, between 150°C and 500°C, and above 500°C.

[0122] Example 8: Plasma atomic layer deposition using silicon compounds of the present invention as precursors Silicon oxide films were formed by plasma-enhanced ALD using the silicon precursor compounds prepared by the methods of Examples 1 and 2 and the TMDMS and TMEMS prepared by Examples 6 and 7. O2 plasma was generated by applying 200W RF power when oxygen O2 gas was supplied during the ALD gas supply cycle. Silicon wafer pieces were immersed in a piranha solution of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2) mixed at a ratio of 4:1 for 10 minutes, removed, and then immersed in a dilute HF aqueous solution for 2 minutes to remove the native oxide, and then heated to a substrate temperature of 125°C to 300°C. The silicon precursor compounds were placed in a stainless steel container, and the silicon compound of Example 1 was heated to a container temperature of 50°C, and the silicon compound of Example 2 was heated to a container temperature of 60°C, while argon (Ar) gas with a flow rate of 200sccm was used as a carrier gas for the precursor compounds to vaporize them. The TMDMS and TMEMS prepared in Examples 6 and 7 were vaporized using Ar carrier gas at the same flow rate while maintaining the stainless steel container at room temperature. The process pressure of the ALD reaction chamber was maintained at 1 torr, and an ALD gas supply cycle consisting of silicon compound gas supply for 3 seconds - Ar purge for 10 seconds - O2 plasma for 3 seconds - Ar purge for 10 seconds was repeated 100 times. The thickness of the silicon oxide film thus formed was measured using an ellipsometer, and the growth of the silicon oxide film per ALD gas supply cycle as a function of temperature is shown in FIG. 4.

[0123] In addition, the existing silicon precursor compound for ALD, diisopropylaminosilane (DIPAS, H3SiN i Pr2), bis(diethylamino)silane [BDEAS, H2Si(NEt2)2], bis(t-butylamino)silane [BTBAS, H2Si(NH t Silicon oxide films were formed using the same plasma-based ALD method, except that [Bu)2] was vaporized at room temperature. Figure 4 shows the growth of silicon oxide films per ALD gas supply cycle as a function of temperature.

[0124] It was confirmed from FIG. 4 that the film growth per ALD gas supply cycle using the silicon compound of the present invention as a precursor was much greater than when the conventional silicon precursors DIPAS, BTBAS, and BDEAS were used. From FIG. 4, it can be seen that the GPCs were 1.8 Å / cycle or more, 1.9 Å / cycle or more, and 2 Å / cycle or more, which could not be achieved when using the conventional DIPAS, BTBAS, and BDEAS. If the film growth per ALD gas supply cycle is large, more semiconductor or display substrates can be processed per unit time in the ALD equipment, and therefore the number of ALD equipment required can be minimized, and therefore the manufacturing cost of semiconductor or display devices can be reduced by using the silicon compound of the present invention.

[0125] The above description of the present application is for illustrative purposes only, and a person having ordinary skill in the art to which the present application pertains should understand that the present application can be easily modified into other specific forms without changing the technical idea or essential features of the present application. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and are not limiting. For example, each component described as a single type may be implemented in a distributed form, and similarly, each component described as a distributed type may be implemented in a combined form.

[0126] The scope of the present application is indicated by the claims set forth below rather than by the above detailed description, and all modifications and variations derived from the meaning and scope of the claims, as well as their equivalent concepts, should be construed as being included within the scope of the present application.

Claims

1. A precursor compound for forming a silicon-containing film represented by the following chemical formula 1: [Chemical formula 1] R １ R ２ N-SiH ２ -N(SiR ３ R ４ R ５ ) ２ ; In the above Chemical Formula 1, R １ and R ２ are substituted or unsubstituted C ４ -C ８ is a cyclic alkyl group, -NR １ R ２ contains a cyclic amino group containing one or more nitrogen atoms; R 3 is hydrogen, a linear or branched C 1 -C 4 alkyl group, or a linear or branched alkenyl group; R ４ , and R ５ each independently represents a linear or branched C １ -C ４ It is an alkyl group, or a linear or branched alkenyl group.

2. -NR １ R ２ The precursor compound for forming a silicon-containing film according to claim 1, wherein the precursor compound for forming a silicon-containing film according to claim 1 comprises a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

3. -SiR ３ R ４ R ５ is -SiHMe ２ , -SiHMeEt, -SiHMe( ｎ Pr), -SiHMe( ｉｓｏ Pr), -SiHEt ２ , -SiHEt ( ｎ Pr), -SiHEt( ｉｓｏ Pr), -SiH( ｎ Pro) ２ , -SiH( ｎ P) ( ｉｓｏ Pr), or -SiH( ｉｓｏ Pro) ２ The precursor compound for forming a silicon-containing film according to claim 1 ,

4. The precursor compound for forming a silicon-containing film according to claim 1 , comprising the following compound: 【Chemistry 1】

5. A precursor composition for forming a silicon-containing film, comprising the precursor compound for forming a silicon-containing film according to any one of claims 1 to 4.

6. The precursor compound for forming a silicon-containing film according to claim 5, comprising one or more compounds selected from the following compounds: 【Chemistry 2】

7. The silicon-containing film-forming precursor composition according to claim 5 , wherein the film is one or more selected from a silicon-containing oxide film, a silicon-containing nitride film, and a silicon-containing carbide film.

8. 6. The silicon-containing film-forming precursor composition of claim 5, further comprising one or more nitrogen sources selected from ammonia, nitrogen, hydrazine, and dimethylhydrazine.

9. 6. The silicon-containing film-forming precursor composition of claim 5, further comprising one or more oxygen sources selected from water vapor, oxygen, and ozone.

10. A method for forming a silicon-containing film, comprising forming a silicon-containing film using a precursor composition for film formation, the precursor composition including a precursor compound for forming a silicon-containing film represented by the following Chemical Formula 1: [Chemical formula 1] R １ R ２ N-SiH ２ -N(SiR ３ R ４ R ５ ) ２ ; In the above Chemical Formula 1, R １ and R ２ are substituted or unsubstituted C ４ -C ８ is a cyclic alkyl group, -NR １ R ２ contains a cyclic amino group containing one or more nitrogen atoms; R 3 is hydrogen, a linear or branched C 1 -C 4 alkyl group, or a linear or branched alkenyl group; R ４ , and R ５ each independently represents a linear or branched C １ -C ４ It is an alkyl group, or a linear or branched alkenyl group.

11. -NR １ R ２ The silicon-containing film forming method according to claim 10, wherein the aryl group includes a pyrrolidine group, a piperidine group, a 2,6-dimethylpiperidine group, a 4-methylpiperazine group, or a morpholine group.

12. -SiR ３ R ４ R ５ is -SiHMe ２ , -SiHMeEt, -SiHMe( ｎ Pr), -SiHMe( ｉｓｏ Pr), -SiHEt ２ , -SiHEt ( ｎ Pr), -SiHEt( ｉｓｏ Pr), -SiH( ｎ Pro) ２ , -SiH( ｎ P) ( ｉｓｏ Pr), or -SiH( ｉｓｏ Pro) ２ The method for forming a silicon-containing film according to claim 10 , comprising:

13. The method for forming a silicon-containing film according to claim 10, wherein the precursor compound for forming a silicon-containing film contained in the precursor composition for forming a film includes one or more compounds selected from the following compounds: 【Chemistry 3】

14. The silicon-containing film forming method according to claim 10 , wherein the silicon-containing film is one or more selected from a silicon-containing oxide film, a silicon-containing nitride film, and a silicon-containing carbide film.

15. A method for forming a silicon-containing film, comprising forming a silicon-containing film using a precursor composition for film formation, the precursor composition including a precursor compound for forming a silicon-containing film represented by the following chemical formula 2: The silicon-containing film forming method, wherein the silicon-containing film is a silicon oxide film. [Chemical formula 2] R １ R ２ N-SiH ２ -N(SiR ３ R ４ R ５ ) ２ ; In the above Chemical Formula 2, R １ and R ２ each independently represents a linear or branched C １ -C ４ Contains an alkyl group; -SiR 3 R 4 R 5 is -SiHMe 2 , -SiHMeEt, -SiHMe (n Pr), -SiHMe (iso Pr), -SiHEt 2 , -SiHEt (n Pr), -SiHEt (iso Pr), -SiH (n Pr) 2 , -SiH( n Pr) ( iso Pr), or -SiH( iso Pr) 2 .

16. The method for forming a silicon-containing film according to claim 15, wherein the precursor compound for forming a silicon-containing film contained in the precursor composition for forming a film includes one or more compounds selected from the following compounds: 【Chemistry 4】

17. The method of claim 10 or 15, wherein the silicon-containing film is deposited by chemical vapor deposition or atomic layer deposition.

18. The silicon-containing film forming method according to claim 10 or 15, wherein the silicon-containing film is formed at a temperature in the range of 100°C to 300°C.

19. The silicon-containing film forming method according to claim 10 or 15, wherein the silicon-containing film is formed to a thickness in the range of 1 nm to 500 nm.

20. The silicon-containing film forming method according to claim 10 or 15, wherein the silicon-containing film is formed on a substrate including one or more irregularities having an aspect ratio of 1 or more and a width of 1 μm or less.

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