WO2014196827A2 - Novel amino-silyl amine compound, method for perparing the 'same and silicon-containing thin-film using the same - Google Patents

Novel amino-silyl amine compound, method for perparing the 'same and silicon-containing thin-film using the same Download PDF

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Publication number
WO2014196827A2
WO2014196827A2 PCT/KR2014/005006 KR2014005006W WO2014196827A2 WO 2014196827 A2 WO2014196827 A2 WO 2014196827A2 KR 2014005006 W KR2014005006 W KR 2014005006W WO 2014196827 A2 WO2014196827 A2 WO 2014196827A2
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Prior art keywords
chemical formula
alkyl
compound represented
following chemical
aryl
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PCT/KR2014/005006
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French (fr)
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WO2014196827A3 (en
Inventor
Se Jin Jang
Sang-Do Lee
Jun Hee Cho
Sung Gi Kim
Jong Hyun Kim
Byeong-Il Yang
Jang Hyeon Seok
Sang Ick Lee
Myong Woon Kim
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Dnf Co., Ltd.
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Priority claimed from KR1020130159399A external-priority patent/KR101600337B1/en
Application filed by Dnf Co., Ltd. filed Critical Dnf Co., Ltd.
Priority to CN201480032373.5A priority Critical patent/CN105377860B/en
Priority to JP2016518275A priority patent/JP6366698B2/en
Priority to US14/896,156 priority patent/US9586979B2/en
Publication of WO2014196827A2 publication Critical patent/WO2014196827A2/en
Publication of WO2014196827A3 publication Critical patent/WO2014196827A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C23C16/402—Silicon dioxide

Definitions

  • the present invention relates to novel .a orsiiyl amine compound, ai method for preparing the same, and a si 1 icon-containing thin-f i lni using the sane , and more par icularly, to a novel ami o-si lyl amine compound having thermal stability a d in & 1 iquid state at room temperature and under ar pressure ; ⁇ whe e ihahdiing is easy, a method for preparing the same, and p i 1 icon-containing thin-f i lm us i ng he same .
  • a silicon-containing thin-film is manufactured in various shapes , includi g i 1 icon, silicon oxide,, s i 1 i con nit ide, si 1 icon eafbonit ide, s i 1 : con oxyni tride, and the 1 ike, by various deposition processes in a semieonrluetor field, and the apjli cation field is wide.
  • s i 1 i con oxide -and S;i ticoii, nitride function as an insulating film, ia 'diffusion " i reve pn: f i .,. a hard mask, a etching stop 1 aye , a seed layer, a spacer , t rench isolation, intermetal lie dielectric mate ial and a protect ive layer in -manufacturing a device, due to significantly excellent block property and oxidation resis ance.
  • a representati e technology knoyn for manufacturing a s i 1 i con- containing thin-f i lir. there are metal organic chemical vapor depos i t i on (MQCVD) form i eg a fi lm on a surface of a substrate by reacting a silicon: precursor in a mixed gas form and a reactive gas, or formi g a f i lm by direct reaction on a surface, and atomic l yer deposition (ALD) forming a film by physical or chemical ladsorptioji of a ⁇ si ijaon, -piedurspr in a gas form on a surface of substrate, followed by sequential :ihtrodiiciiph of react ive gas.
  • MQCVD metal organic chemical vapor depos i t i on
  • various techhoiogieg; f b -( n :f ;e;tur g 3 ⁇ 4 thin-f i lm such as low pressure chemical vapor deposition (LPCVD) using the method, plasma enhanced chemical vapor deposition (PECVD), plasma enhanced atomic layer deposition (PEALD) using plasma capable of being deposited at a low temperature, and the like, are applied to next-generation semiconductor and a display device manufacturing process, thereby being used to form ultra-fine patterns and deposit ultra-thin-film having uniform nano-sized thickness and excellent properties.
  • LPCVD low pressure chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • PEALD plasma enhanced atomic layer deposition
  • a precursor used in forming a silicon- containing thin-film as described in Korean Patent Laid-Open Publication No. KR 2007-0055898 include si lanes, silane chlorides, amino si lanes and alkoxysi lanes , and more specifically, silane chlorides such as dichlorosilane (SiH2Cl2) and hexachlorodisi lane (Cl3SiSiCl 3 ) and trisi lylamine (N(SiH 3 ) 3 )), bis-diethylaminosi lane (H 2 Si ( ⁇ ((3 ⁇ 4(3 ⁇ 4)2)2)) and di-isopropylaminosi lane
  • silane chlorides such as dichlorosilane (SiH2Cl2) and hexachlorodisi lane (Cl3SiSiCl 3 ) and trisi lylamine (N(SiH 3 ) 3 )
  • bis-diethylaminosi lane
  • An object of the present invention is to provide a novel amino-silyl amine compound.
  • Another object of the present invention is to provide a novel amino- silyl amine compound which is a precursor compound for thin-film deposition.
  • Another object of the present invention is to provide a method for preparing an amino-silyl amine compound.
  • Another object of the present invention is to provide a silicon- containing composition for thin-film deposition containing the amino-silyl amine compound of the present invention, a method for manufacturing a thin- film using the same, and a silicon-containing thin-film manufactured by containing the amino-silyl amine compound of the present invention.
  • the present invention provides a novel amino- silyl amine compound capable of forming a silicon thin-film having excellent cohesion, high deposition rate, and superior physical and electrical properties even at a low temperature.
  • the novel amino-silyl amine compound of the present invention is represented by the following Chemical Formula 1:.
  • ⁇ i7> to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
  • R 5 to R 8 are each independently hydrogen, (Cl-C7)alkyl , (C2-C7)alkenyl ,
  • ⁇ i9 > the alkyl, alkenyj, alkynyl, cycloalkyl, and aryl of R to R , and the
  • alkyl, alkenyl , alkynyl, cycloalkyl, and aryl of R to R can further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy.
  • the amino-silyl amine compound of the present invention has high volatility to easily form a thin-film.
  • the amino-silyl amine compound of the present invention has high thermal stability and low activation energy to thereby have excellent reactivity, and does not produce non-volatile by-product to be capable of easily forming a silicon-containing thin-film having high purity.
  • R or R 6 is each independently (C2-C7) alkyl, (C2-C7) alkenyl, (C2-C7) alkynyl, (C3-C10) cycloalkyl or (C6-C12) aryl , or both may be lined to form 5- to 7-
  • R or R is (C2-C7) , the compound is maintained in a liquid state at room temperature and under atmospheric pressure to have significantly high volatility, thereby being easy to form a thin-film, and
  • R or R is C2-C5.
  • the amino-silyl amine compound of the present invention is a liquid- state compound at room temperature and under atmospheric pressure to have superior volatility, thereby being easy to form a thin-film.
  • the amino-silyl amine compound of the present invention has high thermal stability and low activation energy to thereby have excellent reactivity, and does not produce non-volatile by-product to be capable of easily forming a silicon-containing thin-film having high purity.
  • R to R may be each independently hydrogen, halogen, (Cl-C5)alkyl , (C2-C5)alkehyl , (C2-
  • R 5 to R 8 may be each independently hydrogen, (Cl-C5)alkyl , (C2-C5) alkenyl , (C2-C5) alkynyl , (C3- C5)cycloalkyl or (C6-C10)aryl .
  • R to R may be each independently hydrogen or (Cl-C5)alkyl
  • R to R may be each independently hydrogen or (Cl-C5)alkyl .
  • the Chemical Formula 1 may be selected from the following compounds, but the present invention is not limited thereto ' .
  • part described in the present invention may include all linear or branched types.
  • aryl which is an organic radical derived from aromatic hydrocarbon by removal of one hydrogen, may include single or fused ring system including ring atoms of 4 to 7 in each ring, preferably, 5 or 6, and may include a plurality of aryls linked with a single bond. Specific examples of aryl may include phenyl, naphthyl , biphenyl, anthryl, indenyl, fluorenyl, and the like, but the present invention is not limited thereto.
  • alkenyl of the present invention which is linear or branched hydrocarbon including at least one double bond, may include vinyl, prop-l-en, buta-l,3-diene, and the like, but the present invention is not limited thereto, and "alkynyl” of the present invention may include linear or branched hydrocarbon including at least one triple bond.
  • the amino-silyl amine compound represented by the Chemical Formula 1 above of the present inventio may be preferably a silicon-containing precursor compound for thin-film deposition.
  • the present invention provides a method for preparing an amino-silyl amine compound represented by the Chemical Formula 1 above, the method including:
  • R to R are each independently (Cl-C7)alkyl ;
  • R to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
  • R 5 to R 8 are each independently hydrogen, (Cl-C7)alkyl , (Q2-C7)alkenyl ,
  • (C2-C7)alkynyl , (C3-C10)cycloalkyl or (C6-C12)aryl ,. or subst ituents adjacent to each other may be linked to form 5- to 7-membered alicyclic ring;
  • alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl ⁇ C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy;
  • ⁇ 60> M is an alkali metal;
  • the compound represented by Chemical Formula 6 may be prepared by reacting (Cl-C7)alkylmetal (wherein the metal is an. alkali metal) and a compound represented by the following Chemical Formula 7:
  • R or R is each independently hydrogen, (Cl-C7)alkyl , (C2-C7) alkenyl ,
  • the alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R or R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy or (CI- C7)aryloxy .
  • the present invention provides a method for preparing an amino-silyl amine compound represented by the Chemical Formula 1 above, the method including:
  • R to R are each independently hydrogen, halogen, (Cl ⁇ C7)alkyl , (C2- C7)alkenyl, (C2-C7)alkynyl , (C3-C7)cycloalkyl or (C6-C12)aryl ,
  • R to R are each independently hydrogen, (Cl-C7)a Iky 1, (C2-C7)alkenyl ,
  • (C2-C7)alkynyl , (C3-Cl0)cycloalkyl or (C6-C12)aryl , or substituents adjacent to each other may be linked to form 5- to 7-membered alicyclic ring;
  • the alkyl, alkenyl , alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy; and
  • X or X is halogen.
  • the present invention provides a method for preparing an amino-si lyl amine compound represented by the Chemical Formula 1 above, the method including ' .
  • R to R are each independently (Cl-C7)alkyl ;
  • R to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
  • R to R are each independently. hydrogen, (Cl-C7)alkyl , (C2-C7)alkenyl ,
  • alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy; and
  • alkyl lithium according an exemplary embodiment of the present invention is a compound where lithium is bonded to alkyl having carbon atoms of 1 to 7, for example, methyl lithium, n-butyl lithium, and the like, and preferably, n-butyl lithium.
  • alkyl metal is a compound where a metal is bonded to alkyl having carbon atoms of 1 to 7, wherein the metal is an alkali metal, for example, Li, Na, K, and the like, and preferably, Li.
  • the method may further include ' ⁇ ⁇
  • M is B, Al or Sn; .
  • R to R are each independently (Cl-C7)alkyl ;
  • R and R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
  • R and R are each independently hydrogen, (Cl-C7)alkyl , (C2-
  • X and X are each independently halogen.
  • the Chemical Formula 11 according to an exemplary embodiment of the present invention is a halogenated metal, wherein the metal is B, Al or Sn, preferably, Al .
  • the solvent used in the preparing method of the present invention is not limited if a solvent is not reacted with the starting material among general organic solvents, for example, may be at least one kind selected from a group consisting of normal hexane (n-hexane), cyclohexane, normal pentane (n-pentane), diethyl ether, toluene, tetrahydrofuran (THF), dichloromethane (DCM) , and tr ichloromethane (chloroform).
  • the reaction temperature in the preparing method of the present invention is not limited if temperature is used in general organic synthesis; however, may be varied depending on the reaction time, the reaction material, and an amount of the starting material, wherein the reaction needs to be finished after confirming that the starting material is completely consumed by M , GC, and the like.
  • a solvent may be removed by filtration, followed by simple distillation, under reduced pressure, to thereby separate and refine a desired material by general, methods such as fractional distillation, distillation under reduced pressure, and the like.
  • the present invention provides a silicon- containing composition for thin-film deposition including the amino-silyl amine compound as described above, and a method for manufacturing a silicon- containing thin-film including the same.
  • the si 1 icon-contai ing composition for thin-film deposition may contain the amino-silyl amine compound as a precursor for thin-film deposition, and the amino-silyl amine compound in the composition may have a content within the range recognized by a person skilled in the art in consideration of film forming conditions, or thickness, properties, and the like, of the thin-film.
  • the present invention provides a silicon- containing thin-film manufactured by containing the amino-silyl amine compound as described above.
  • the silicon-containing thin-film of the . present invention may be manufactured by general methods, for example, metal organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), plasma enhanced atomic layer deposition (PEALD), and the like.
  • MOCVD metal organic chemical vapor deposition
  • ALD atomic layer deposition
  • LPCVD low pressure chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • PEALD plasma enhanced atomic layer deposition
  • the amino-silyl amine compound of the present invention has low activation energy, high reactivity and little non-volatile by-products, such that the silicon-containing thin-film manufactured by using the amino-silyl amine compound as a precursor may have high purity and excellent physical and electrical properties.
  • the amino-silyl amine compound of the present invention has excellent thermal stability and high reactivity, such that the silicon-containing thin- film manufactured by using the amino-silyl amine compound as a precursor may have high purity and significantly excellent physical and electrical properties.
  • the amino-silyl amine compound of the present invention may have high content of silicon and be maintained in a liquid state at room temperature and under atmospheric pressure to thereby be easily stored and handled and have high volatility to be rapidly and easily deposited, and it is possible to deposit a thin-film having excellent cohesion and step coverage.
  • FIG. 1 shows a result obtained by measuring vapor pressure of alkylaminosi lane prepared by Example 2;
  • FIG. 2 shows a result obtained by analyzing thermogravimetry of alkylaminosi lane prepared by Examples 3 and 4;
  • FIG. 3 shows a result obtained by measuring vapor pressure of alkylaminosi lane prepared by Examples 3 and 4;
  • FIG. 4 shows a result obtained by analyzing thermogravimetry of alkylaminosi lane prepared by Example 6;
  • FIG. 5 shows a result obtained by measuring vapor pressure of alkylaminosi lane prepared by Example 6;
  • FIG. 6 shows a silicon-containing thin-film deposition method practiced by Examples 7 and 8, and Comparative Example
  • FIG. 7 shows a result showing a thickness of the film by Ellipsometer analysis of the silicon-containing thin-film manufactured by Example 7 and Comparative Example " ,
  • FIG. 8 shows a result obtained by infrared spectroscopy analysis of the deposited silicon-containing thin-film manufactured by Example 7 and Comparative Example ' ,
  • FIG. 9 shows a result showing a thickness of the film by Ellipsometer analysis of the silicon-containing thin-films manufactured by Example 8 and Comparative Example! and
  • FIG. 10 shows a result obtained by infrared spectroscopy analysis of the deposited silicon-containing thin-film manufactured by Example 8.
  • FIG. 7 shows a thickness of the film by Ellipsometer analysis. It was shown that the thicknesses of thin-films ranging 98 to 112A are different from each other depending on the kind or the number of substituents, and it is determined that the thin-film is useful in all silicon oxide thin-film application fields requiring high deposition rate.
  • FIG. 8 shows a result obtained by infrared spectroscopy analysis of the deposited film. It was shown that all of the silicon oxide thin-films were formed, and impurities peak such as OH, Si -OH was not observed.
  • the novel amino-silyl amine compound prepared by the present invention is capable of forming silicon oxide thin- film having high purity, and high deposition rate by PEALD, which has high value.
  • FIG. 6 and Table 2 specifically show a method for depositing the silicon oxide thin-film.
  • Example 8 Deposition of Si 1 icon . Nitride Film by Plasma Enhanced Atomic Layer Deposition (PEALD) Using Amino-silyl Amine Compound of Present Invention
  • FIG. 6 and Table 3 specifically show a method for depositing the silicon nitride thin-film.
  • FIG. 9 shows a thickness of the film by Ellipsometer analysis. It was shown that the thicknesses of thin-films ranging 65 to 72A are different from each other depending on the kind or the number of subst ituents, and it is determined that the thin-film is useful in all silicon nitride thin-film application fields.
  • FIG. 10 shows infrared spectroscopy analysis of the deposited thin-film.
  • novel amino-silyl amine compound prepared by the present invention has high value in forming a high purity silicon nitride thin-film capable of being deposited at a low temperature by plasma enhanced chemical vapor deposition (PECVD).
  • PECVD plasma enhanced chemical vapor deposition

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Abstract

Provided are a novel amino-silyl amine compound, a method for preparing the same, and a silicon-containing thin-film using the same, wherein the amino-silyl amine compound has thermal stability and high volatility and is maintained in a liquid state at room temperature and under a pressure where handling is easy to thereby form a silicon-containing thin-film haying high purity and excellent physical and electrical properties by various deposition methods.

Description

I Invention Title]
NOVEL AMIMO-SILYL AMINE COMPOUND, METHOD FOR RERPARING THE ;S¾ME AND [Technical Field]
<t> The present invention relates to novel .a orsiiyl amine compound, ai method for preparing the same, and a si 1 icon-containing thin-f i lni using the sane , and more par icularly, to a novel ami o-si lyl amine compound having thermal stability a d
Figure imgf000002_0001
in & 1 iquid state at room temperature and under ar pressure; ^whe e ihahdiing is easy, a method for preparing the same, and p i 1 icon-containing thin-f i lm us i ng he same .
[Background Art]
<2> A silicon-containing thin-film is manufactured in various shapes , includi g i 1 icon, silicon oxide,, s i 1 i con nit ide, si 1 icon eafbonit ide, s i 1 : con oxyni tride, and the 1 ike, by various deposition processes in a semieonrluetor field, and the apjli cation field is wide.
<3> $fc particular, s i 1 i con oxide -and S;i ticoii, nitride function as an insulating film, ia 'diffusion" i reve pn: f i .,. a hard mask, a etching stop 1 aye , a seed layer, a spacer , t rench isolation, intermetal lie dielectric mate ial and a protect ive layer in -manufacturing a device, due to significantly excellent block property and oxidation resis ance.
<4> Recent ly, polycrystalline s i 1 i con thin-f i !m has been used to a thi - film transistor (TFT) , a solar eel , and the l ke,, and- the : applicafion field becomes various.
<5> As a representati e technology knoyn for manufacturing a s i 1 i con- containing thin-f i lir., there are metal organic chemical vapor depos i t i on (MQCVD) form i eg a fi lm on a surface of a substrate by reacting a silicon: precursor in a mixed gas form and a reactive gas, or formi g a f i lm by direct reaction on a surface, and atomic l yer deposition (ALD) forming a film by physical or chemical ladsorptioji of a ^si ijaon, -piedurspr in a gas form on a surface of substrate, followed by sequential :ihtrodiiciiph of react ive gas. In addition, various techhoiogieg; f b -( n :f ;e;tur g ¾ thin-f i lm such as low pressure chemical vapor deposition (LPCVD) using the method, plasma enhanced chemical vapor deposition (PECVD), plasma enhanced atomic layer deposition (PEALD) using plasma capable of being deposited at a low temperature, and the like, are applied to next-generation semiconductor and a display device manufacturing process, thereby being used to form ultra-fine patterns and deposit ultra-thin-film having uniform nano-sized thickness and excellent properties.
<6> Representative examples of a precursor used in forming a silicon- containing thin-film as described in Korean Patent Laid-Open Publication No. KR 2007-0055898 include si lanes, silane chlorides, amino si lanes and alkoxysi lanes , and more specifically, silane chlorides such as dichlorosilane (SiH2Cl2) and hexachlorodisi lane (Cl3SiSiCl3) and trisi lylamine (N(SiH3)3)), bis-diethylaminosi lane (H2Si (Ν((¾(¾)2)2)) and di-isopropylaminosi lane
(H3SiN( i -C3H7)2) ) , and the like, and used in a mass production of a semiconductor and a dis lay.
<7> However, a technology of forming a ultra-fine thin-film having a uniform and thin thickness and excellent electrical properties at a desired low temperature according to miniaturization of devices caused by ultra high integration of the devices, an increase in an aspect ratio, and diversification of device material has been demanded, and thus, high temperature process at 600°C or more, step coverage, etching property, and physical and electrical properties of a thin-film at the time of using the existing silicon precursor are emerging as an issue, and accordingly, excellent novel silicon precursor has been demanded to be developed.
[Disclosure]
[Technical Problem]
<8> An object of the present invention is to provide a novel amino-silyl amine compound.
<9> Another object of the present invention is to provide a novel amino- silyl amine compound which is a precursor compound for thin-film deposition. <io> Another object of the present invention is to provide a method for preparing an amino-silyl amine compound.
<ii> Another object of the present invention is to provide a silicon- containing composition for thin-film deposition containing the amino-silyl amine compound of the present invention, a method for manufacturing a thin- film using the same, and a silicon-containing thin-film manufactured by containing the amino-silyl amine compound of the present invention.
[Technical Solution]
<|2> In one general aspect, the present invention provides a novel amino- silyl amine compound capable of forming a silicon thin-film having excellent cohesion, high deposition rate, and superior physical and electrical properties even at a low temperature.
<i3> The novel amino-silyl amine compound of the present invention is represented by the following Chemical Formula 1:.
Figure imgf000004_0001
<i6> in Chemical Formula 1,
1 4
<i7> to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C7)cycloalkyl or (C6-C12)aryl ,
<i8> R5 to R8 are each independently hydrogen, (Cl-C7)alkyl , (C2-C7)alkenyl ,
(C2-C7) alkynyl , (C3-Cl0)cycloalkyl or (C6-C12)aryl , or substituents adjacent to each other are linked to form 5- to 7-membered a 1 i eye lie ring;
1 4
<i9> the alkyl, alkenyj, alkynyl, cycloalkyl, and aryl of R to R , and the
5 8
alkyl, alkenyl , alkynyl, cycloalkyl, and aryl of R to R can further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy.
<20> The amino-silyl amine compound of the present invention has high volatility to easily form a thin-film. In addition, due to Si3N trigonal planar molecular structure having three silicon atoms bonded to central nitrogen atom, the amino-silyl amine compound of the present invention has high thermal stability and low activation energy to thereby have excellent reactivity, and does not produce non-volatile by-product to be capable of easily forming a silicon-containing thin-film having high purity.
<2i> In order to provide excellent volatility, in the Chemical Formula 1
5 above representing the amino-silyl amine compound of the present invention, R or R6 is each independently (C2-C7) alkyl, (C2-C7) alkenyl, (C2-C7) alkynyl, (C3-C10) cycloalkyl or (C6-C12) aryl , or both may be lined to form 5- to 7-
5 6
member ed ali cyclic ring, and if R or R is hydrogen or methyl, the compound
5 6 .
is solid, whereas if R or R is (C2-C7) , the compound is maintained in a liquid state at room temperature and under atmospheric pressure to have significantly high volatility, thereby being easy to form a thin-film, and
5 6
more preferably, R or R is C2-C5.
<22> The amino-silyl amine compound of the present invention is a liquid- state compound at room temperature and under atmospheric pressure to have superior volatility, thereby being easy to form a thin-film.
<23> In addition, due to S13N trigonal planar molecular structure having three silicon atoms bonded to central nitrogen atom, the amino-silyl amine compound of the present invention has high thermal stability and low activation energy to thereby have excellent reactivity, and does not produce non-volatile by-product to be capable of easily forming a silicon-containing thin-film having high purity.
<24> In order for the amino-silyl amine compound represented by the Chemical
Formula 1 above according to an exemplary embodiment of the present invention to form a thin-film having high thermal stability and reactivity, and high
1 4
purity, it is preferred that in the Chemical Formula 1 above, R to R may be each independently hydrogen, halogen, (Cl-C5)alkyl , (C2-C5)alkehyl , (C2-
C5)alkynyl, (C3-C6) cycloalkyl or (C6-Cl0)aryl , and R5 to R8 may be each independently hydrogen, (Cl-C5)alkyl , (C2-C5) alkenyl , (C2-C5) alkynyl , (C3- C5)cycloalkyl or (C6-C10)aryl .
1 4
<25> More preferably, in the Chemical Formula 1 above, R to R may be each independently hydrogen or (Cl-C5)alkyl , and R to R may be each independently hydrogen or (Cl-C5)alkyl .
The Chemical Formula 1 may be selected from the following compounds, but the present invention is not limited thereto'.
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000007_0001
Figure imgf000008_0001
Figure imgf000008_0002
<40> The term: "alkyl" "alkoxy" and other substituents including "alkyl
" part described in the present invention may include all linear or branched types. In addition, "aryl" described in the present invention, which is an organic radical derived from aromatic hydrocarbon by removal of one hydrogen, may include single or fused ring system including ring atoms of 4 to 7 in each ring, preferably, 5 or 6, and may include a plurality of aryls linked with a single bond. Specific examples of aryl may include phenyl, naphthyl , biphenyl, anthryl, indenyl, fluorenyl, and the like, but the present invention is not limited thereto. Further, "alkenyl" of the present invention, which is linear or branched hydrocarbon including at least one double bond, may include vinyl, prop-l-en, buta-l,3-diene, and the like, but the present invention is not limited thereto, and "alkynyl" of the present invention may include linear or branched hydrocarbon including at least one triple bond.
<4i> The amino-silyl amine compound represented by the Chemical Formula 1 above of the present inventio may be preferably a silicon-containing precursor compound for thin-film deposition.
<42> In another general aspect, the present invention provides a method for preparing an amino-silyl amine compound represented by the Chemical Formula 1 above, the method including:
<43> preparing a compound represented by the following Chemical Formula 5 by reacting a compound represented by the following Chemical Formula 3 with a compound represented by the following Chemical Formula 4 in the presence of a base represented by the following Chemical Formula 2 or (Cl-C7)alkyl 1 ithium; and
<44> preparing a compound represented by the following Chemical Formula 1 by reacting the compound represented by the following Chemical Formula 5 with a compound represented by the following Chemical Formula 6:
<45> Chemical Formula 2
, U . 12^ . 13.
<46> NCR )(R )(R )
<47> Chemical Formula 3
Figure imgf000009_0001
<49> Chemical Formula 4
R3
R4-Si-X1
<50> X 2
<5i> Chemical Formula 5
Figure imgf000009_0002
<53> Chemical Formula 6 R7
/
MN
\ .
<54> ^
<55> in Chemical Formulas 2 to 6,
11 13
<56> R to R are each independently (Cl-C7)alkyl ;
1 4
<57> R to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C7) cycloalkyl or (C6-C12)aryl ;
<58> R5 to R8 are each independently hydrogen, (Cl-C7)alkyl , (Q2-C7)alkenyl ,
(C2-C7)alkynyl , (C3-C10)cycloalkyl or (C6-C12)aryl ,. or subst ituents adjacent to each other may be linked to form 5- to 7-membered alicyclic ring;
1 4
<59> the alkyl , alkenyl , alkynyl, cycloalkyl, and aryl of R to R , and the
5 8
alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl~C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy; <60> M is an alkali metal; and
<6i> X or X is halogen.
<62 The compound represented by Chemical Formula 6 may be prepared by reacting (Cl-C7)alkylmetal (wherein the metal is an. alkali metal) and a compound represented by the following Chemical Formula 7:
<63> Chemical Formula 7
R7
/
HN
<64> R8
<65>
<66> in Chemical Formula 7,
7 8
<67> R or R is each independently hydrogen, (Cl-C7)alkyl , (C2-C7) alkenyl ,
(C2-C7) alkynyl, (C3-C10)cycloalkyl or (C6-C12)aryl ; and
7 8
<68> the alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R or R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy or (CI- C7)aryloxy .
<69> In another general aspect, the present invention provides a method for preparing an amino-silyl amine compound represented by the Chemical Formula 1 above, the method including:
preparing a compound represented by the following Chemical Formula 8 by reacting the compound represented by the following Chemical Formula 4 with the compound represented by the following Chemical Formula 6; and
preparing the compound represented by the Chemical Formula 1 above by reacting the compound represented by the following Chemical Formula 8 with the compound represented by the following Chemical Formula 3 in the presence of (Cl-C7)alkyl lithium:
Chemical Formula 3
Figure imgf000011_0001
Chemical Formula 4 .
R3
R4-Si-X1
I
Chemical Formula 6
R7
/
MN
R8
Chemical Formula 8
Figure imgf000011_0002
in Chemical Formulas 3, 4, 6, and 8,
1
R to R are each independently hydrogen, halogen, (Cl~C7)alkyl , (C2- C7)alkenyl, (C2-C7)alkynyl , (C3-C7)cycloalkyl or (C6-C12)aryl ,
5 8
R to R are each independently hydrogen, (Cl-C7)a Iky 1, (C2-C7)alkenyl ,
(C2-C7)alkynyl , (C3-Cl0)cycloalkyl or (C6-C12)aryl , or substituents adjacent to each other may be linked to form 5- to 7-membered alicyclic ring;
1 4
the alkyl, alkenyl , alkynyl, cycloalkyl, and aryl of R to R , and the 5 8 alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy; and
1 2
X or X is halogen.
In another general aspect, the present invention provides a method for preparing an amino-si lyl amine compound represented by the Chemical Formula 1 above, the method including'.
preparing a compound represented by the following Chemical Formula 5 by reacting the compound represented by the following Chemical Formula 3 with the compound represented by the following Chemical Formula 4 in the presence of a base represented by the following Chemical Formula 2 or (Cl- C7)alkyl lithium; and
preparing a compound represented by the following Chemical Formula 1 by reacting the compound represented by the following Chemical Formula 5 with a compound represented by the following Chemical Formula 7 in the presence of the base represented by the following Chemical Formula 2."
Chemical Formula 2
. 11. . 12, , 13,
NCR )(R )(R )
Chemical Formula 3
Figure imgf000012_0001
Chemic l Formula 4
R -Si-X1
I
Chemical Formula 5
Figure imgf000012_0002
<96> Chemical Formula 7
R7
/
HN
V 8
<97> > R
<98> in Chemical Formulas 2 to 5 and 7,
11 13
<99> R to R are each independently (Cl-C7)alkyl ;
1
<ioo> R to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C7) cycloalkyl , or (C6-C12)aryl ;
<ioi> R to R are each independently. hydrogen, (Cl-C7)alkyl , (C2-C7)alkenyl ,
(C2-C7) alkynyl , (C3-C10)cycloalkyl or (C6-C12)aryl , or substituents adjacent to each other may be linked to form 5- to 7-membered alicyclic ring!
1 4
<102> the alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R , and the
5 ■ 8
alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy; and
1 2
<i03> X or X is halogen.
<i04> (C1-C7) alkyl lithium according an exemplary embodiment of the present invention is a compound where lithium is bonded to alkyl having carbon atoms of 1 to 7, for example, methyl lithium, n-butyl lithium, and the like, and preferably, n-butyl lithium.
<i05> (C1-C7) alkyl metal according an exemplary embodiment of the present invention is a compound where a metal is bonded to alkyl having carbon atoms of 1 to 7, wherein the metal is an alkali metal, for example, Li, Na, K, and the like, and preferably, Li.
r
<i06> The method may further include '· ·
<i07> preparing a compound represented by the following Chemical Formula 14 by reacting the compound represented by the following Chemical Formula 12 with the compound represented by the following Chemical Formula 13 in the presence of the compound represented by the following Chemical Formula 11; and
<i08> preparing the compound represented by the Chemical Formula 3 above by reacting the compound represented by the following Chemical Formula 14 with the compound represented by the following Chemical Formula 15:
<109> ChemicaT Formula 11
11
<no> MX
<ni> Chemical Formula 12
R21
HN-(si— R22 )2
p23
<112> K
<H3> Chemical Formula 13
R2
R1-Si-X12
I
X12
<114>
<ii5> Chemical Formula 14
Figure imgf000014_0001
<ii7> Chemical Formula 15
<ii8> HN(R5)(R6)
<ii9> in Chemical Formula 11 to 15,
<120> M is B, Al or Sn; .
21 23
<i2i> R to R are each independently (Cl-C7)alkyl ;
1 2
<i22> R and R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C7)cycloalkyl , or (C6-C12)aryl ;
5 6
<i23> R and R are each independently hydrogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C10)cycloalkyl or (C6-C12)aryl , or may be linked to form 5- to 7-membered alicyclic ring; and
11 12
<i24> X and X are each independently halogen.
<i25> The Chemical Formula 11 according to an exemplary embodiment of the present invention is a halogenated metal, wherein the metal is B, Al or Sn, preferably, Al . <126> The solvent used in the preparing method of the present invention is not limited if a solvent is not reacted with the starting material among general organic solvents, for example, may be at least one kind selected from a group consisting of normal hexane (n-hexane), cyclohexane, normal pentane (n-pentane), diethyl ether, toluene, tetrahydrofuran (THF), dichloromethane (DCM) , and tr ichloromethane (chloroform).
<i27> The reaction temperature in the preparing method of the present invention is not limited if temperature is used in general organic synthesis; however, may be varied depending on the reaction time, the reaction material, and an amount of the starting material, wherein the reaction needs to be finished after confirming that the starting material is completely consumed by M , GC, and the like. When the reaction is finished, a solvent may be removed by filtration, followed by simple distillation, under reduced pressure, to thereby separate and refine a desired material by general, methods such as fractional distillation, distillation under reduced pressure, and the like.
<i28> In another general aspect, the present invention provides a silicon- containing composition for thin-film deposition including the amino-silyl amine compound as described above, and a method for manufacturing a silicon- containing thin-film including the same.
<i29> The si 1 icon-contai ing composition for thin-film deposition may contain the amino-silyl amine compound as a precursor for thin-film deposition, and the amino-silyl amine compound in the composition may have a content within the range recognized by a person skilled in the art in consideration of film forming conditions, or thickness, properties, and the like, of the thin-film.
<i3o> In another general aspect, the present invention provides a silicon- containing thin-film manufactured by containing the amino-silyl amine compound as described above.
<i3i> The silicon-containing thin-film of the . present invention may be manufactured by general methods, for example, metal organic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), plasma enhanced atomic layer deposition (PEALD), and the like.
The amino-silyl amine compound of the present invention has low activation energy, high reactivity and little non-volatile by-products, such that the silicon-containing thin-film manufactured by using the amino-silyl amine compound as a precursor may have high purity and excellent physical and electrical properties.
[Advantageous Effects]
<134> The amino-silyl amine compound of the present invention has excellent thermal stability and high reactivity, such that the silicon-containing thin- film manufactured by using the amino-silyl amine compound as a precursor may have high purity and significantly excellent physical and electrical properties.
<135> In addition, the amino-silyl amine compound of the present invention may have high content of silicon and be maintained in a liquid state at room temperature and under atmospheric pressure to thereby be easily stored and handled and have high volatility to be rapidly and easily deposited, and it is possible to deposit a thin-film having excellent cohesion and step coverage.
[Description of Drawings]
<136> The above and other objects, features and advantages of the present invention will become apparent from the following description of preferred embodiments given in conjunction with the accompanying drawings, in which'-
<137> FIG. 1 shows a result obtained by measuring vapor pressure of alkylaminosi lane prepared by Example 2;
<138> FIG. 2 shows a result obtained by analyzing thermogravimetry of alkylaminosi lane prepared by Examples 3 and 4;
<i39> FIG. 3 shows a result obtained by measuring vapor pressure of alkylaminosi lane prepared by Examples 3 and 4;
<i40> FIG. 4 shows a result obtained by analyzing thermogravimetry of alkylaminosi lane prepared by Example 6;
<i4i> FIG. 5 shows a result obtained by measuring vapor pressure of alkylaminosi lane prepared by Example 6;
<142> FIG. 6 shows a silicon-containing thin-film deposition method practiced by Examples 7 and 8, and Comparative Example;
ii43 FIG. 7 shows a result showing a thickness of the film by Ellipsometer analysis of the silicon-containing thin-film manufactured by Example 7 and Comparative Example",
:i44> FIG. 8 shows a result obtained by infrared spectroscopy analysis of the deposited silicon-containing thin-film manufactured by Example 7 and Comparative Example',
<145> FIG. 9 shows a result showing a thickness of the film by Ellipsometer analysis of the silicon-containing thin-films manufactured by Example 8 and Comparative Example! and
<i46> FIG. 10 shows a result obtained by infrared spectroscopy analysis of the deposited silicon-containing thin-film manufactured by Example 8. [Mode for Invention]
<i47> Hereinafter, the present invention will be described in more detail with reference to the following exemplary embodiments. However, the following exemplary embodiments describe the present invention by way of example only but are not limited thereto.
<i48> The following Examples of all compounds were practiced under anhydrous and inert atmosphere using a' glovebox or a Schlenk pipe, products were analyzed by H Nuclear Magnetic Resonance (NMR), thermogravimetric analysis (TGA) and gas chromatography (GC), a thickness of deposited thin-film were measured by Ellipsometer, and components of the films were analyzed by infrared spectroscopy.
<i49> [Example 1] Synthesis of Diethylamino Dimethyl Disilazane
<i50> 250g. (1.55mol) of hexamethyldisi lazane (((CH3)3Si)2NH) and lOg
(0.075mol) of aluminum chloride (A1C13) were, put into 2000 mL of flame-dried
Schlenk flask under anhydrous and inert atmosphere while stirring, 499.80g (3.87mol) of dichloro dimethylsi lane ( (CH3)2SiCl2) was slowly added thereto while maintaining temperature of 25°C , and a temperature of the reaction solution was slowly raised to 40°C . The mixed reaction solution was stirred for 3 hours and the produced chlorotr imethylsi lane ((C¾)3SiCl) and the excessively added dichloro dimethylsi lane ((CH3)2SiCl2) were removed therefrom by simple distillation or distillation under reduced pressure. The recovered chloro dimethyl disilazane ( ( (CH3)2SiCl )2NH)) solution was stirred and then
475.45g (6.5mol) of diethylamine ((CH3C¾)2NH) was slowly added thereto while maintaining temperature of -15 "C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 6 hours. After the white solid obtained by filtration was removed to obtain filtrate, solvent was removed from the filtrate under reduced pressure, and 319.90g (1.16mol) of diethylamino dimethyl disilazane ((CH3)2SiN(CH2CH3)2)2NH) was obtained by reduced pressure distillation with a yield of 75%.
<i5i> H NMR(inC6D6) δ 0.14(s, 12H, HNSi (Ctf3)2N) , 0.97(t, 12H, Si (NCH2Ctf3)2) ,
3.42(q, 8H, Si (NC½CH3)2) , Boiling Point 238
<152>
<153> [Example 2] Synthesis of Bis-Diethylamino Dimethylsi lyl Tr imethylsi lyl
Amine
<154> 180g (0.65mol) of diethylamino dimethyl disilazane
( ( CH3)2SiN(CH2CH3)2)2 H) synthesized by Example 1 above and 200ml of n-hexane organic solvent were added to 2000 mL of a flame-dried flask under anhydrous and inert atmosphere while stirring, and 202.16g (0.65mol) of 2.29M normal butyl lithium (n-CjHgLi ) ■ hexane (CeHu) solution was slowly added while maintaining a temperature of -15°C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred for 12 hours and 200ml of tetrahydrofuran (0(02Η2)2) was added thereto. 70.94g (0.65mol) of chlorotr imethylsi lane (C I Si (CH3)3) ) was slowly added to the reaction solution while maintaining a temperature of -20°C . After the addition was completed, a temperature of the reaction solution was slowly raised to 65°C and the reaction solution was stirred for 12 hours whi le maintaining the temperature. After the white solid obtained by filtration was removed to obtain filtrate, solvent was removed from the filtrate under reduced pressure, and 159g (0.46mol) of bis-diethylaminosi lyl tr imethylsi lyl amine
( (CH3)3SiN(Si(CH3)2N(CH2CH3)2)2) was obtained by reduced pressure distillation with a yield of 70%. <i55> ¾ NMR(inCeD6)6 0.30(s, 12H, NSi(C//3)2N) , 0.32(s,'9H, Si(C 3)3), 0.99(t,
12H, Si(NC 2CH3)2), 2.82(q, 8H, Si (NC¾CH3)2) ; Boiling Point.279; GC Analysis Result > 99.85%.
<156>
<i57> [Example 3] Synthesis of Tris-cli ethyl amino dimethylsi lyl Amine
<i58> 180g (0.65mol) of diethylamino dimethyl disilazane
((CH3)2SiN(CH£H3)2)2 H) synthesized by Example 1 above and 200ml of n-hexane organic solvent were added to 2000 mL of a flame-dried flask under anhydrous and inert atmosphere while stirring, and 202.16g (0.65mol) of 2.29M normal butyl lithium (n-CALi ) · hexane (CeHu) solution was slowly added while maintaining a temperature of -15°C . After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred for 12 hours and 200ml of tetrahydrofuran (0(C2H2)2) was added thereto. 108.25g (0.65mol) of chloro- dimethyl diethylamino si lane synthesized by reacting dichloro dimethylsi lane (Cl2Si (CH3)2) and 2 equivalents of dimethylamine in a quantitative scheme was slowly added to the reaction solution while maintaining a temperature of -20 °C . After the addition was completed, a temperature of the reaction solution was slowly raised to 65°C and the reaction solution was stirred for 12 hours while maintaining the temperature. After the reaction was completed, the reaction mixture was filtrated and the produced white solid was removed from the reaction mixture to obtain a filtrate'. Solvent of the filtrate was removed under reduced pressure, and 119. OOg (0.29mol) of tris- diethylaminosi lyl amine (N(Si (CH3)2N(CH2CH3)2)3) was obtained by reduced pressure distillation with a yield of 45%.
:i59> ¾ NMR(inC6D6) δ 0.37(s, 18H, NSi (C//3)2N) , 1.02(t, 18H, Si (NCH2<¾)2) ,
2.86(q, 12H, Si (NC 2CH3)2) ; Boiling Point 311; GC Analysis Result > 99.27%.
I60>
i6i> [Example 4] Synthesis of Tris-diethylamino dimethylsi lyl Amine <i62> 180g (0.65mol) of diethylamino dimethyl disilazane
((CH3)2SiN(CH2CH3)2)2NH) synthesized by Example 1 above and 200ml of n-hexane organic solvent were added to 2000 mL of a flame-dried flask under anhydrous and inert atmosphere while stirring, and 202.16g (0.65mol) of 2.29M normal butyl lithium (n-C4H9Li ) · hexane (ΟβΗΉ) solution was slowly added while maintaining a temperature of -15°C . After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred for 12 hours and 200ml of tetrahydrofuran (0(C2H2)2) was added thereto. 84.30g (0.65mol) of dichloro dimethyl si lane was slowly added to the reaction solution while maintaining a temperature of -20°C. After the addition was completed, a temperature of the reaction solution was slowly raised to 65°C and the reaction solution was stirred for 12 hours while maintaining the temperature. After the reaction mixture was filtrated and the obtained white solid was removed from the reaction mixture to obtain a filtrate, 51.65g (0.65mol) of lithium diethylamine salt (LiN^Hs^) obtained by reacting diethylamine (HN^Hs^) and
2.29M normal butyl lithium (n-C4H9Li ) · hexane ( ^u solution i a quantitative scheme was slowly added thereto while stirring the filtrate and maintaining a temperature of -20°C. After the addition was completed, a temperature of the reaction solution was slowly raised to 65°C and the reaction solution was stirred for 12 hours while maintaining the temperature. After the white solid obtained by filtration was removed to obtain filtrate, solvent was removed from the filtrate under reduced pressure, and 171.88g (0.42mol) of tris-cliethylaminosilyl amine (N(Si (CHs^ CC^CHa^s) was obtained by reduced pressure distillation with a yield of 65%.
<i63> H NMR(inC6D6) 5 0.37(s, 18H, HNSi(C½)2N), 1.02(t, 18H, Si (NCH2(%)2) ,
2.86(q, 12H, Si(NC½CH3)2); Boiling Point 311; GC Analysis Result > 99.27%.
<164>
<i65> [Example 5] Synthesis of Dimethyl ami no Methyl Disilazane <166> 250g (1.55mol) of hexamethyldisi lazane (((CH3)3Si )2NH) and lOg
(0.075mol) of aluminum chloride (AICI3) were put into 2000 niL of flame-dried
Schlenk flask under anhydrous and inert atmosphere while stirring, 713.19g (3.87mol) of dichloro dimethylsi lane ((CH3)2SiCl2) was slowly added thereto while maintaining temperature of 25°C , and a temperature of the reaction solution was slowly raised to 40°C . The mixed reaction solution was stirred for 3 hours and the produced chlorotr imethylsi lane ((CH3)3SiCl) and the excessively added dichloro dimethylsi lane ((CH3)2SiCl2) were removed therefrom by simple distillation or distillation under reduced pressure. The recovered chloro methyl disilazane ( (CH3S1HCI )2NH) ) solution was stirred , and then
293.47g (4.2mol) of diethylamine ((CH3)2NH) was slowly added thereto while maintaining temperature of -15°C . After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 6 hours. The white solid obtained by filtration was removed to obtain filtrate. Solvent of the filtrate was removed under reduced pressure, and 222.54g (1.16mol) of dimethylamino methyl disilazane ((CH3SiHN(CH3)2)2NH) was obtained by reduced pressure distillation with a yield of 75%.
<i67> H-NMRUnCeDe) δ 0.19(t, 6H, (((CH3)2)2N(¾>HSi )2NH) , 2.46(s, 12H,
(((C/ WCH3)HSi)2NH), 4.71(m, 2H, NSitf).
<168>
<169> [Example 6] Synthesis of Tr is-dimethylaminomethylsi lyl Amine
<i70> 191.43g (l.OOmol) of dimethylamino methyl disilazane
((CH3SiHN(CrI3)2)2NH) synthesized by Example 5 above and 200ml of n-hexane organic solvent were added to 2000 mL of a flame-dried flask under anhydrous and inert atmosphere while stirring, and 303.32g (l.OOmol) of 2.29M normal butyl lithium (n-C4H9Li )■ hexane (CeHu) solution was slowly added while maintaining a temperature of -15°C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred for 12 hours and 300ml of tetrahydrofuran (0(C2H2)2) was added thereto. 123g (l.OOmol) of chloro-methyl chloro dimethyl ami no si lane synthesized by reacting dichloro methylsi lane (CI2S1HCH3) and 2 equivalents of dimethylamine in a quantitative scheme was slowly added to the reaction solution while maintaining a temperature of -20 °C . After the addition was completed, a temperature of the reaction solution was slowly raised to 65°C and the react ion' solut ion was stirred for 12 hours while maintaining the temperature. After the white solid obtained by filtration of the completely reacted reaction mixture was removed to obtain filtrate, solvent was removed from the filtrate under reduced pressure, and 195.03g (0.70mol) of tris-dimethylaminomethylsilyl amine ((CH3SiHN(CH3)2)3N) was obtained by reduced pressure distillation with a yield of 70%.
<!7i> H-NMR(inC6D6) δ 0.28(m, 9H, NSiCft) 2.46(m, 18H, SiN(C%)2), 4.81(m, 3H,
NSi/0; Boiling Point 237; GC Analysis Result > 99.5%.
<!72>
<i73> [Example 7] Deposition of Silicon Oxide Film by Plasma Enhanced Atomic
Layer Deposition (PEALD) Using Amino-silyl Amine Compound of Present Invention
<i74> Film forming evaluation was conducted with the amino-silyl amine compounds of Examples 2, 3, and 6 according to the present invention as the composition for forming the silicon oxide film in the general plasma enhanced atomic Layer deposition (PEALD) apparatus using the known PEALD method. Oxygen together with plasma was used as the reaction gas, and argon being an inert gas was used as purge gas. Hereinafter, FIG. 6 and Table 1 specifically show a method for depositing the silicon oxide thin-film.
ii75> [Table 1]
ii 6> Silicone Oxide Thin-Film Deposition Conditions
Figure imgf000024_0001
A thickness of each deposited thin-film was measured by Ellipsometer, and formation of Si02 thin-film was analyzed by infrared spectroscopy. FIG. 7 shows a thickness of the film by Ellipsometer analysis. It was shown that the thicknesses of thin-films ranging 98 to 112A are different from each other depending on the kind or the number of substituents, and it is determined that the thin-film is useful in all silicon oxide thin-film application fields requiring high deposition rate. FIG. 8 shows a result obtained by infrared spectroscopy analysis of the deposited film. It was shown that all of the silicon oxide thin-films were formed, and impurities peak such as OH, Si -OH was not observed.
<i89> That is, it was confirmed that the novel amino-silyl amine compound prepared by the present invention is capable of forming silicon oxide thin- film having high purity, and high deposition rate by PEALD, which has high value.
<190>
<i9i> [Comparative Example] Deposition of Silicon Oxide Film by Plasma
Enhanced Atomic Layer Deposition (PEALD) Using Known Amino-silyl Amine Compound
<i92> Film forming evaluation of Comparative Example was conducted by known
PEALD under the same deposition conditions as practiced by Example 7 above except for using known amino-silyl amine compound as shown in the following Table 2 instead of using the amino-silyl amine compound of the present invention, and the deposited thin-film was analyzed by the same analysis method and conditions as practiced by Example 7 above and the analysis result thereof was obtained. Hereinafter, FIG. 6 and Table 2 specifically show a method for depositing the silicon oxide thin-film.
<i93> It was shown that the thicknesses of thin-films had a range of 21 to 60
A having a low deposition rate as compared to the amino-silyl amine compounds of Examples 3, 4 and 6, and all of the silicon oxide thin-films were formed.
<194> [Table 2]
<195> Silicon Oxide Thin-Film Deposition Conditions
Figure imgf000026_0001
[Example 8] Deposition of Si 1 icon . Nitride Film by Plasma Enhanced Atomic Layer Deposition (PEALD) Using Amino-silyl Amine Compound of Present Invention
Film forming evaluation was conducted with the amino-silyl amine compounds of Examples 2, and 4 according to the present invention as the composition for forming the silicon nitride film in the general plasma enhanced atomic Layer deposition (PEALD) apparatus using the known PEALD method. Nitrogen (N2) and ammonia (N¾) together with plasma were used as the reaction gas, and argon being an inert gas was used as purge gas. Hereinafter, FIG. 6 and Table 3 specifically show a method for depositing the silicon nitride thin-film.
[Table 3]
Silicon Nitride Thin-Film Deposition Conditions
Figure imgf000027_0001
El 1 ipsometer , and formation of silicon nitride thin-film was analyzed by infrared spectroscopy. FIG. 9 shows a thickness of the film by Ellipsometer analysis. It was shown that the thicknesses of thin-films ranging 65 to 72A are different from each other depending on the kind or the number of subst ituents, and it is determined that the thin-film is useful in all silicon nitride thin-film application fields. FIG. 10 shows infrared spectroscopy analysis of the deposited thin-film.
That is, it was confirmed that the novel amino-silyl amine compound prepared by the present invention has high value in forming a high purity silicon nitride thin-film capable of being deposited at a low temperature by plasma enhanced chemical vapor deposition (PECVD).

Claims

[CLAIMS]
[Claim 1]
<227> An amino-silyl amine compound represented by the following Chemical
Formula 1:
<228> Ch mical Formul 1
Figure imgf000029_0001
<230> in Chemical Formula 1,
1
<23 i > R to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C7)cycloalkyl or (C6-C12)aryl ,
<232> R to R are each independently hydrogen, (Cl-C7)alkyl , (C2-C7)alkenyl ,
(C2-C7)alkynyl, (C3-C10)cycloalkyl or (C6-C12)aryl , or are linked to form 5- to 7-membered alicyclic ring;
1 4
<233> the alkyl, alkenyl, alkynyl , cycloalkyl, and aryl of R to R , and the
5 8
alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R can further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy. [Claim 2]
<234> The amino-silyl amine compound of claim 1, wherein
1 4
<235> R to R are each independently hydrogen, halogen, (Cl-C5)alkyl, (C2-
C5)alkenyl, (C2-C5)alkynyl , (C3-C6)cycloalkyl . or (C6-C10)aryl, and ■
<236> R5 to R8 are each independent ly hydrogen, (Cl-C5)alkyl , . (C2-C5)alkenyl ,
(C2-C5)alkynyl, (C3-C5)cycloal.kyl or (C6-C10)aryl .
[Claim 3]
<237> The amino-silyl amine compound of claim 2, wherein
1 4
<238> R to R are each independently hydrogen or (Cl-C5)alkyl , and
5 8
<239> R to R are each independently hydrogen or (Cl-C5)alkyl .
[Claim 4]
<240> The amino-silyl amine compound of claim 1, wherein
<24i> the Chemical Formula 1 is selected from the following compounds:
Figure imgf000030_0001
6Z
900£00/H0Zi I/I3d /.Ζ896Ϊ/Η0Ζ OAV
Figure imgf000031_0001
Figure imgf000031_0002
Figure imgf000031_0003
Figure imgf000031_0004
Figure imgf000032_0001
[Claim 5]
A method for preparing an amino-silyl amine compound represented by the following Chemical Formula 1, the method comprising:
preparing a compound represented by the following Chemical Formula 5 by reacting a compound represented by the following Chemical Formula 3 with a compound represented by the following Chemical Formula 4 in the presence of a base represented by the following Chemical Formula 2 or (Cl~C7)alkyl lithium; and
preparing a compound represented by the following Chemical Formula 1 by reacting- the compound represented by the following Chemical Formula 5 with a compound represented by the following Chemical Formula 6:
Chemical Formula 1
Figure imgf000032_0002
Chemical Formula 2
, 11, , 12,„ 13,
N(R )(R )(R )
Chemical Formula 3
Figure imgf000032_0003
Chemical Formula 4 R3
R4-Si-X1
I
<265> x Λ2
<266> rmula 5
Figure imgf000033_0001
<268> Chemical Formula 6
R7
/
N
<269> R ^8
<27o> in Chemical Formulas 1 to 6,
11 13
<27i> R to R are each independent ly (C1-C7) alky 1 ;
1 4
<272> R to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C7)cycloalkyl or (C6-C12)aryl ;
5 8
<273> R to R are each independently hydrogen, (Cl~C7)alkyl , (C2-C7)alkenyl ,
(C2-C7)alkynyl , (C3-C10)cycloalkyl or (C6-C12)aryl , or substituents adjacent to each other may be linked to form 5- to 7-membered alicyclic ring;
. 1 4
<274> the alkyl, alkenyl, alkynyl , cycloalkyl, and aryl of R to R , and the
5 . 8
alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy-' <275> M is an alkali metal; and
1 2
<276> X or X is halogen.
[Claim 6]
<277> The method of claim 5, wherein
<278> the compound represented by Chemical Formula 6 is prepared by reacting
(Cl-C7)alkylmetal (wherein the metal is an alkali metal) and a compound represented by the following Chemical Formula 7' .
<279> Chemical Formula 7 R7
/
HIM
<280> R
<28i in Chemical Formula 7,
7 8
<282> R or R is each independently hydrogen, (Cl-C7)alkyl , (C2-C7) alkenyl ,
(C2-C7)alkynyl , (C3-C10) cycloalkyl or (C6-C12)aryl ; and
7 8
<283> the alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R or R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy or (Cl- C7)aryloxy.
[Claim 7]
<284> A method for preparing an amino-silyl amine compound represented by the following Chemical Formula 1, the method comprising:
<285> preparing a compound represented by the following Chemical Formula 8 by reacting the compound represented by the following Chemical Formula 4 with the compound represented by the following Chemical Formula 6; and
<286> preparing the compound represented by the following Chemical Formula 1 by reacting the compound represented by the following Chemical Formula 8 with the compound represented by the following Chemical Formula 3 in the presence
Figure imgf000034_0001
<289> Chemical Formula 3
Figure imgf000034_0002
<29i> Chemical Formula 4
R3
R4-Si-X1
I
<292> Λ
<293> Chemical Formula 6
Figure imgf000035_0001
Chemical F rmula 8
Figure imgf000035_0002
in Chemical Formulas 1, 3, 4, 6 and 8,
1 4
R to R are each independently hydrogen, halogen, (Cl-C7)alkyl , (C2- C7)alkenyl, (C2-C7)alkynyl , (C3-C7)cycloalkyl or (C6-Cl2)aryl ,
5 8
R to R are each independently hydrogen, (Cl-C7)alkyl , (C2-C7)alkenyl ,
(C2-C7)alkynyl , (C3-C10)cycloalkyl or (C6-C12)aryl , or substituents adjacent to each other may be linked to form 5- to 7-membered alicyclic ring;
1 4
the alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R , and the
5 8
alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl-C7)alkyl, (Cl-C7)alkoxy, or (Cl-C7)aryloxy; and
1 2
X or X is halogen.
[Claim 8]
A method for preparing an amino-silyl amine compound represented by the following Chemical Formula 1, the method comprising:
preparing a compound represented by the following Chemical Formula 5 by reacting the compound represented by the following Chemical Formula 3 with the compound represented by the following Chemical Formula 4 in the presence of a base represented by the following Chemical Formula 2 or (Cl- C7)alkyl 1 ithium; and
preparing a compound represented by the following Chemical Formula 1 by reacting the compound represented by the following Chemical Formula 5 with a compound represented by the following Chemical Formula 7 in the presence of the base represented by the following Chemical Formula 2:
Chemical Formula 1
Figure imgf000036_0001
<307> Chemical Formula 2
.' 11,„ 12, , 13,
<308> N(R )(R )(R )
3
Figure imgf000036_0002
<3ii> Chemical Formula 4
R3
R4-Si-X1
I
<3l2> χ2
<3i3> Chemical Formula 5
Figure imgf000036_0003
<3i5> Chemical Formula 7
R7
/
HN
<316> R
<3i7> in Chemical Formulas 1 to 5 and 7,
11 13
<3i8> R to R are each independently (Cl-C7)alkyl ;
1 4'
<3i9> R to R are each independen ly hydrogen, halogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C7)cycloalkyl, or (C6-C12)aryl ;
5 8
<320> R to R are each independently hydrogen, (Cl-C7)alkyl, (C2-C7)alkenyl,
(C2-C7)alkynyl , (C3-C10)cycloalkyl or (C6-C12)aryl , or substituents adjacent to each other may be linked to form 5- to 7-membered alicyclic ring;
1
<32i> the alkyl, alkenyl , alkynyl, cycloalkyl, and aryl of R to R , and the
5 8
■ alkyl, alkenyl, alkynyl, cycloalkyl, and aryl of R to R may be further substituted with halogen, (Cl-C7)alkyl , (Cl-C7)alkoxy, or (Cl-C7)aryloxy; and
1 2
<322> X or X is halogen.
[Claim 9]
<323> The method of any one of claims 5 to 8, further comprising'.
<324> preparing a compound represented by the following Chemical Formula 14 by reacting the compound represented by the following Chemical Formula 12 with the compound represented by the following Chemical Formula 13 in the presence of the compound represented by the following Chemical Formula 11; and
<32s> preparing the compound represented by the Chemical Formula 3 above by reacting the compound represented by the following Chemical Formula 14 with the compound represented by the following Chemical Formula 15:
<326> Chemical Formula 11
11
<327> MX
<328> Chemical Formula 12
R21
HN-(si— R22)2
D23
<329>
<330> Chemical Formula 13
R2
R -Si-X12
I
y12
<331> Λ
<332> Chemical Formula 14
Figure imgf000037_0001
<334> Chemical Formula 15
<335> HN(R5)(R6)
<336> in Chemical Formula 11 to 15,
<337> M is B, Al or Sn;
21 23
<338> R to R are each independently (Cl-C7)alkyl ; I 2
<339> R and R are each independently hydrogen, halogen, (Cl-C7)alkyl, (C2-
C7)alkeny], (C2-C7)alkynyl, (C3-C7)cycloalkyl, or (C6-Cl2)aryl;
5 6
<340> R and R are each independently hydrogen, (Cl-C7)alkyl , (C2-
C7)alkenyl, (C2-C7)alkynyl , (C3-C10)cycloalkyl or■ (C6-C12)aryl , or may be linked to form 5- to 7-membered alicyclic ring; and
II 12
<34i> X and X are each independently halogen.
[Claim 10]
<342> A silicon-containing composition for thin-film deposition comprising the amino-silyl amine compound of any one of claims 1 to 4.
[Claim 11]
<343> A method for manufacturing a silicon-containing thin-film comprising the tr i -si lyl amine compound of any one of claims 1 to 4.
[Claim 12]
<344> A silicon-containing thin-film manufactured by using the amino-silyl amine compound of any one of claims 1 to 4.
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US9777025B2 (en) 2015-03-30 2017-10-03 L'Air Liquide, Société pour l'Etude et l'Exploitation des Procédés Georges Claude Si-containing film forming precursors and methods of using the same
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US10403494B2 (en) 2015-03-30 2019-09-03 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Si-containing film forming precursors and methods of using the same
WO2018182305A1 (en) * 2017-03-29 2018-10-04 Dnf Co., Ltd. Silylamine compound, composition for depositing silicon-containing thin film containing the same, and method for manufacturing silicon-containing thin film using the composition
US11358974B2 (en) 2017-03-29 2022-06-14 Dnf Co., Ltd. Silylamine compound, composition for depositing silicon-containing thin film containing the same, and method for manufacturing silicon-containing thin film using the composition
US11393676B2 (en) 2017-03-29 2022-07-19 Dnf Co., Ltd. Composition for depositing silicon-containing thin film containing bis(aminosilyl)alkylamine compound and method for manufacturing silicon-containing thin film using the same
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