KR100684993B1 - Novel neodymium(iii) complexes and preparation method thereof - Google Patents

Novel neodymium(iii) complexes and preparation method thereof Download PDF

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KR100684993B1
KR100684993B1 KR1020060031579A KR20060031579A KR100684993B1 KR 100684993 B1 KR100684993 B1 KR 100684993B1 KR 1020060031579 A KR1020060031579 A KR 1020060031579A KR 20060031579 A KR20060031579 A KR 20060031579A KR 100684993 B1 KR100684993 B1 KR 100684993B1
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neodymium
neodymium oxide
branched alkyl
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이영국
김창균
정택모
안기석
이선숙
박미현
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한국화학연구원
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    • 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
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    • C23C16/409—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
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    • 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
    • C23C16/44—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 method of coating
    • 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
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    • 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
    • C23C16/44—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 method of coating
    • C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]

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Abstract

A neodymium complex represented by specific formula as precursor of neodymium oxide thin film is provided to show thermal stability and increased volatile property advantageous to form the thin film of neodymium oxide with high quality by reacting neodymium compound with alkali metal salt compound then substitution reacting the reactive product with alcohol compound. The neodymium oxide precursor is represented by a formula of Nd[O-A-N(R^3)-B-NR(^1)R(^2)]3 wherein A is C2 to C5 alkylene; B is C1-C4 alkylene; A and B are substituted by at least one of linear or branched alkyl group; and R^1, R^2 and R^3 are independently H or C1 to C5 linear or branched alkyl group. More particularly, the neodymium oxide precursor is represented by a formula of Nd[OCR(^4)R(^5)(CH2)mN(R(^3))-(CH2)nNR(^1)R(^2)]3 wherein R^1,R^2,R^3,R^4 and R^5 are independently H or C1 to C5 linear or branched alkyl group, and m and n are integer of 1 to 4. The neodymium oxide precursor is grown into neodymium oxide by MOCVD or ALD.

Description

신규의 네오디뮴 화합물 및 그 제조 방법{NOVEL NEODYMIUM(III) COMPLEXES AND PREPARATION METHOD THEREOF}Novel neodymium compound and its manufacturing method {NOVEL NEODYMIUM (III) COMPLEXES AND PREPARATION METHOD THEREOF}

도 1은 실시예 1에서 제조한 Nd(demamp)3 화합물의 푸리에 변환 적외선 분광 (FT-IR) 분석 결과이고,1 is a result of Fourier transform infrared spectroscopy (FT-IR) analysis of an Nd (demamp) 3 compound prepared in Example 1,

도 2는 실시예 1에서 제조한 Nd(demamp)3 화합물의 열중량 분석 (TGA) 및 시차 열분석 (DTA) 결과를 나타내는 그래프이고,2 is a graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the Nd (demamp) 3 compound prepared in Example 1,

도 3은 실시예 2에서 제조한 Nd(demae)3 화합물의 푸리에 변환 적외선 분광 (FT-IR) 분석 결과이고,3 is a result of Fourier transform infrared spectroscopy (FT-IR) analysis of the Nd (demae) 3 compound prepared in Example 2,

도 4는 실시예 2에서 제조한 Nd(demae)3 화합물의 열중량 분석 (TGA) 및 시차 열분석 (DTA) 결과를 나타내는 그래프이다.Figure 4 is a graph showing the results of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of the Nd (demae) 3 compound prepared in Example 2.

본 발명은 신규의 네오디뮴 화합물에 관한 것으로서, 네오디뮴 산화물 박막의 선구 물질로서 유용한 화합물의 제조 방법에 관한 것이다.The present invention relates to novel neodymium compounds, and to methods for preparing compounds useful as precursors of neodymium oxide thin films.

산화규소는 안정하고 높은 질의 규소-산화규소 계면과 뛰어난 전기적 절연 성질 때문에 절연체로 많이 사용되었다. 그러나 최근 반도체 업계에서는 0.1 미크론 이하의 반도체 공정 기술을 도입함에 있어서 채널 길이나 게이트 유전 두께 또한 급격히 축소되어지고 있다. 따라서 얇아진 산화규소 게이트 절연체의 직접 터널링(direct tunneling) 현상에 의한 누설 전류 문제를 해결하기 위해 적합한 대체 박막 재료 및 공정 기술에 관한 연구를 활발히 진행하고 있다.Silicon oxide has been widely used as an insulator because of its stable and high quality silicon-silicon oxide interface and excellent electrical insulation properties. In recent years, however, the channel length and gate dielectric thickness have also been dramatically reduced in the semiconductor process technology of 0.1 micron or less. Therefore, research is being actively conducted on suitable thin film materials and process technologies to solve the leakage current problem caused by the direct tunneling phenomenon of the thinned silicon oxide gate insulator.

상기 문제를 해결하기 위해서는 절연성이 뛰어나고 유전율이 높으며 유전 손실이 적은 고 유전 물질의 개발이 필요한데, 예를 들면 산화규소(SiO2)의 대체 물질로서, 이산화규소보다 유전 상수 값이 큰 오산화탄탈럼(Ta2O5), BST{(Ba,Sr)TiO3}, PZT{Pb(Zr,Ti)O3}; 및 공정 안정성의 관점에서 유리한 산화알루미늄(Al2O3), 산화하프늄(HfO2), 산화지르코늄(ZrO2), 산화란탄(La2O3), 산화프라세오디뮴(Pr2O3), 산화가돌리늄(Gd2O3), 산화네오디뮴(Nd2O3) 등을 예로 들 수 있다.In order to solve the problem, it is necessary to develop a high dielectric material having excellent insulation, high dielectric constant, and low dielectric loss. For example, as a substitute for silicon oxide (SiO 2 ), tantalum pentoxide having a higher dielectric constant value than silicon dioxide ( Ta 2 O 5 ), BST {(Ba, Sr) TiO 3 }, PZT {Pb (Zr, Ti) O 3 }; And aluminum oxide (Al 2 O 3 ), hafnium oxide (HfO 2 ), zirconium oxide (ZrO 2 ), lanthanum oxide (La 2 O 3 ), praseodymium oxide (Pr 2 O 3 ), and gadolinium oxide, which are advantageous in terms of process stability. (Gd 2 O 3 ), neodymium oxide (Nd 2 O 3 ), and the like.

특히, 란탄계열 산화물은 큰 밴드갭(bandgaps)(Eg(Pr2O3) = 3.9 eV, Eg(Gd2O3) = 5.6 eV)을 가지고, 비교적 높은 유전상수(κ(Gd2O3) = 16, κ(La2O3) = 27, κ(Pr2O3) = 26-30)를 가지며, 실리콘 위에서 산화지르코늄과 산화하프늄보다 높은 열역학적 안정성을 가지므로 차세대 high-κ gate insulator로 유망한 물질이다. 게다가 몇몇 란탄계열 산화물은 실리콘과 격자 매개변수가 상대적으로 매우 유사하여 박막의 에피택셜(epitaxial) 성장을 가능케 한다.In particular, lanthanide oxides have a large bandgaps (E g (Pr 2 O 3 ) = 3.9 eV, E g (Gd 2 O 3 ) = 5.6 eV), and have a relatively high dielectric constant (κ (Gd 2 O) 3 ) = 16, κ (La 2 O 3 ) = 27, κ (Pr 2 O 3 ) = 26-30), and have higher thermodynamic stability than zirconium oxide and hafnium oxide on silicon. As a promising substance. In addition, some lanthanide-based oxides have relatively similar lattice parameters to silicon, allowing epitaxial growth of thin films.

그 중에서 산화네오디뮴(Nd2O3)는 0.40-14 μFcm-2의 capacitance 밀도, 높은 유전상수(κ = 12.64), 높은 breakdown field strength, 낮은 dissipation factor (대략 0.0045), 그리고 낮은 capacitance의 온도계수 (대략 350 ppmK-1) 등의 많은 성질들로 인해 게이트 유전물질로 유망하다.Among them, neodymium oxide (Nd 2 O 3 ) has a capacitance density of 0.40-14 μFcm -2 , high dielectric constant (κ = 12.64), high breakdown field strength, low dissipation factor (approximately 0.0045), and low capacitance temperature coefficient ( Many properties, such as approximately 350 ppmK- 1 ), are promising gate dielectrics.

박막 제조 기술 중 다양한 산화물 박막 제조에 사용되고 있는 방법에는 유기금속 화학기상 증착(metal organic chemical vapor deposition, 이하 ‘MOCVD’라 한다) 공정이나 원자층 증착 (Atomic Layer Deposition, 이하 ‘ALD’라 한다) 공정이 있는데, MOCVD는 장치가 비교적 간단하고 층 덮임이 균일하며, 성분 조절이 쉽고, 대량 생산으로 전환하기에 무리가 없다는 장점이 있고, ALD는 사이클을 조절하여 박막의 두께 조절이 용이하다는 장점이 있다.Among the thin film manufacturing techniques, the method used for manufacturing various oxide thin films includes a metal organic chemical vapor deposition (MOCVD) process or an atomic layer deposition (ALD) process. MOCVD has the advantages of relatively simple device, uniform layer covering, easy control of components, and no difficulty in switching to mass production, and ALD has advantages in controlling the thickness of thin films by controlling cycles. .

이러한 MOCVD 공정이나 ALD 공정을 이용하여 박막을 제조하기 위해서는, 이 공정에 사용되는 선구 물질의 개발과 그 특성의 이해가 필수적이다. MOCVD용 선구 물질은 200 ℃ 이하에서 충분히 높은 증기압을 가져야 하고, 기화시키기 위해 가열하는 동안 열적으로 충분히 안정해야 하며, 350 내지 500 ℃의 기질 온도에서 유기 물질 등의 분해 없이 신속히 분해되어야 하며, 저장 기간 동안 공기 및 습기에 충분히 안정해야 한다. 또한, 선구 물질 자체에 또는 분해 생성 물질에 독성이 없거나 적어야 하며, 합성법이 간단하고 원재료 단가가 저렴해야 한다. 그러나 이런 유기금속 화학기상 증착(MOCVD) 공정이나 원자층 증착(ALD) 공정의 다수의 장점에도 불구하고 적당히 안정하고 휘발성이 좋은 선구물질이 없어 이 기술을 통한 높은 질 의 Nd2O3나 NdSixOy 박막의 연구가 드문 실정이다.In order to manufacture a thin film using such a MOCVD process or ALD process, it is essential to develop a precursor material and to understand its characteristics. The precursors for MOCVD must have a sufficiently high vapor pressure below 200 ° C, be thermally stable enough for heating to vaporize, and decompose rapidly at the substrate temperature of 350 to 500 ° C without decomposition of organic materials, etc. Should be stable enough to air and moisture while. In addition, it should be non-toxic or less toxic to the precursor itself or to the decomposition products, the synthesis method should be simple and the raw material cost should be low. However, despite the many advantages of such organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) processes, there are no suitable stable and volatile precursors, so high quality Nd 2 O 3 or NdSi x O y thin films are rarely studied.

네오디뮴 산화물을 박막으로 만들기 위해 사용되어 온 선구 물질은 크게 네 가지로 구분되며, 염화네오디뮴 또는 질산네오디뮴 등과 같은 무기염, 알콕사이드 화합물, 디알킬아미도 화합물 및 β-디케토네이트를 포함하는 화합물 등이 있다. The precursors that have been used to make neodymium oxide into thin films are classified into four types, including inorganic salts such as neodymium chloride or neodymium nitrate, alkoxide compounds, dialkylamido compounds, and compounds including β-diketonate. have.

최근엔 MOCVD 공정에 의해서 [Nd(tmhd)3] (tmhd = 2,2,6,6-tetramethylheptane-3,5-dionate)를 이용하여 Nd2O3 박막을 제조하였으나, 심각한 탄소오염을 보였다(S. Chavalier, G. Bonnet. J. P. Larpin, Appl. Surf. Sci. 2000, 167, 125).Recently, Nd 2 O 3 thin films were prepared using [Nd (tmhd) 3 ] (tmhd = 2,2,6,6-tetramethylheptane-3,5-dionate) by MOCVD process, but showed serious carbon contamination (S Chavalier, G. Bonnet.JP Larpin, Appl.Surf.Sci. 2000, 167, 125).

란탄계열 알콕사이드 화합물은 Ln3 + 의 크기가 큰 이온 반지름을 가지고 있기 때문에 간단한 알콕사이드 화합물 대부분이 고분자나 저중합체를 형성하여 휘발성이 좋지 않아 MOCVD용 선구 물질로 용이하지 않았다. 그러나 최근, 알콕사이드 선구 물질로써 Nd(mmp)3 [mmp = OCMe2CH2OMe]는 donor 작용기인 알콕사이드 리간드 mmp의 α-탄소 원자에 두 개의 메틸기가 금속 중심에 가까이 접근하고 있어 단일 금속 알콕사이드의 화합물을 가능하게 하고 있다. 따라서 [Nd(mmp)3]는 탄소의 오염이 없는 란탄계열 알콕사이드 박막을 산소 가스의 존재 하에 용액 상태로 사용하는 액체 주입 MOCVD(liquid injection MOCVD, LI-MOCVD)에 의해 250 내지 550 ℃의 온도에서 증착되었다. 그 중에서 실리콘 기판 온도가 450 ℃ 이상에서 C-타입의 큐빅 구조를 나타내었지만, 낮은 성장온도에서는 비결정질을 나타내었다(Y. F. Loo, R. J. Potter, A. C. Jones, H. C. Aspinall, J. Gaskell, P. R. Chalker, L. M. Smith, and G. W. Critchlow, Chem. Vap. Deposition, 2004, 10, 306).Lanthanide alkoxide compound is most simple alkoxide compound due to the magnitude of Ln + 3 it has a large ion radius are not volatile good to form a polymer or oligomer was not easy as a precursor for the MOCVD. Recently, however, as an alkoxide precursor, Nd (mmp) 3 [mmp = OCMe 2 CH 2 OMe] is a compound of a single metal alkoxide because two methyl groups near the metal center of the α-carbon atom of the alkoxide ligand mmp, a donor functional group Is making it possible. Therefore, [Nd (mmp) 3 ] is a liquid injection MOCVD (LI-MOCVD) using a lanthanum-based alkoxide thin film free of carbon contamination in the presence of oxygen gas at a temperature of 250 to 550 ° C. Deposited. Among them, the silicon substrate showed C-type cubic structure above 450 ℃, but it showed amorphous at low growth temperature (YF Loo, RJ Potter, AC Jones, HC Aspinall, J. Gaskell, PR Chalker, LM Smith). , and GW Critchlow, Chem.Vap.Deposition, 2004, 10, 306).

본 발명자들은 β-디케토네이트 화합물들이 갖는 문제점들을 해결하기 위해 새로운 리간드를 합성하여 네오디뮴에 산소와 질소 원자 리간드만 배위하도록 하여 탄소나 할로겐의 오염을 일으키지 않으며, 열적 안정성과 휘발성이 개선된 신규한 네오디뮴 산화물 선구 물질을 개발하기에 이르렀다.In order to solve the problems of β-diketonate compounds, the present inventors have synthesized a new ligand so that only oxygen and nitrogen atom ligands are coordinated to neodymium, which does not cause carbon or halogen contamination, and improves thermal stability and volatility. Neodymium oxide precursors have been developed.

본 발명의 목적은 양질의 네오디뮴 산화막을 형성하기 위해 열적으로 안정하고 휘발성이 증가된 네오디뮴 산화물 선구 물질 및 그의 제조방법을 제공하는 데 있다.It is an object of the present invention to provide a neodymium oxide precursor which is thermally stable and has increased volatility in order to form a good quality neodymium oxide film and a method of manufacturing the same.

본 발명은 상기 목적을 달성하기 위하여, 하기 화학식 1로 표시되는 신규한 네오디뮴 산화물 선구 물질을 제공한다:The present invention provides a novel neodymium oxide precursor represented by the following general formula (1) to achieve the above object:

[화학식 1][Formula 1]

Nd[O-A-N(R3)-B-NR1R2]3 Nd [OAN (R 3 ) -B-NR 1 R 2 ] 3

[상기 식에서 A는 C2-C5의 알킬렌이고; B는 C1-C4의 알킬렌이고; 상기 A 및 B는 하나 이상의 C1-C5의 직쇄 또는 분지쇄의 알킬기로 더 치환될 수 있고; R1, R2 및 R3는 서로 독립적으로 H 또는 C1-C5의 선형 또는 분지형 알킬기이다.][Wherein A is alkylene of C 2 -C 5 ; B is alkylene of C 1 -C 4 ; A and B may be further substituted with one or more C 1 -C 5 straight or branched alkyl groups; R 1 , R 2 and R 3 independently of one another are H or C 1 -C 5 linear or branched alkyl groups.]

더 상세하게는 상기 화학식 1의 네오디뮴 산화물 선구 물질은 하기 화학식 2로 표시되는 네오디뮴 산화물 선구 물질을 포함한다.More specifically, the neodymium oxide precursor of Formula 1 includes a neodymium oxide precursor represented by Formula 2 below.

[화학식 2][Formula 2]

Nd[OCR4R5(CH2)mN(R3)-(CH2)nNR1R2]3 Nd [OCR 4 R 5 (CH 2 ) m N (R 3 )-(CH 2 ) n NR 1 R 2 ] 3

[상기 식에서 R1, R2, R3, R4 및 R5는 서로 독립적으로 H 또는 C1-C5의 선형 또는 분지형 알킬기이고, m 및 n은 1 내지 4의 정수이다.][Wherein R 1 , R 2 , R 3 , R 4 And R 5 is independently of each other H or a C 1 -C 5 linear or branched alkyl group, m and n are integers from 1 to 4.]

보다 바람직하게는 상기 화학식 2에서 R1, R2, R3, R4 및 R5는 서로 독립적으로 H, CH3, C2H5, CH(CH3)2 또는 C(CH3)3로부터 선택되는 네오디뮴 산화물 선구 물질이 예시된다.More preferably in Formula 2 R 1 , R 2 , R 3 , R 4 And R 5 independently of one another are exemplified neodymium oxide precursors selected from H, CH 3 , C 2 H 5 , CH (CH 3 ) 2 or C (CH 3 ) 3 .

이하, 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명에 따른 화학식 1의 네오디뮴 산화물 선구 물질은 하기 화학식 3의 네오디뮴 화합물과 3당량의 하기 화학식 4의 알칼리 금속 염 화합물을 반응시켜 얻어진 하기 화학식 5의 화합물 1당량과 하기 화학식 6의 알코올 화합물 3당량을 치환 반응시켜 제조할 수 있으며, 상기 화학식 1의 네오디뮴 산화물 선구 물질을 제조하기 위한 반응식은 하기 반응식 1로 나타낼 수 있다.The neodymium oxide precursor of Chemical Formula 1 according to the present invention may be obtained by reacting a neodymium compound represented by Chemical Formula 3 with three equivalents of an alkali metal salt compound represented by Chemical Formula 4 below, and one equivalent of the compound represented by Chemical Formula 5 and an alcohol compound of Chemical Formula 6 May be prepared by substitution reaction, and a reaction scheme for preparing the neodymium oxide precursor of Chemical Formula 1 may be represented by the following Scheme 1.

한편, 하기 화학식 6의 알코올 화합물은 디아민 화합물과 1-위치에 두 치환체가 붙은 에틸렌 산화물 유도체(1,1-disubstituted ethylene oxide)를 수용액 중에서 반응시켜 제조할 수 있다.Meanwhile, the alcohol compound of Formula 6 may be prepared by reacting a diamine compound with an ethylene oxide derivative (1,1-disubstituted ethylene oxide) having two substituents in 1-position in an aqueous solution.

[화학식 1][Formula 1]

Nd[O-A-N(R3)-B-NR1R2]3 Nd [OAN (R 3 ) -B-NR 1 R 2 ] 3

[화학식 3][Formula 3]

NdCl3 NdCl 3

[화학식 4][Formula 4]

M[N(Si(CH3)3)2]M [N (Si (CH 3 ) 3 ) 2 ]

[화학식 5][Formula 5]

Nd[N(Si(CH3)3)2]3 Nd [N (Si (CH 3 ) 3 ) 2 ] 3

[화학식 6][Formula 6]

HO-A-N(R3)-B-NR1R2 HO-AN (R 3 ) -B-NR 1 R 2

[상기 화학식 1, 화학식 4 및 화학식 6에서, M은 Li, Na 또는 K이며; A는 C2-C5의 알킬렌이고; B는 C1-C4의 알킬렌이고; 상기 A 및 B는 하나 이상의 C1-C5의 직쇄 또는 분지쇄의 알킬기로 더 치환될 수 있고; R1, R2 및 R3는 서로 독립적으로 H 또는 C1-C5의 선형 또는 분지형 알킬기이다.][In Formula 1, Formula 4 and Formula 6, M is Li, Na or K; A is alkylene of C 2 -C 5 ; B is alkylene of C 1 -C 4 ; A and B may be further substituted with one or more C 1 -C 5 straight or branched alkyl groups; R 1 , R 2 and R 3 independently of one another are H or C 1 -C 5 linear or branched alkyl groups.]

[반응식 1]Scheme 1

NdCl3 + 3 M[N(Si(CH3)3)2] → Nd[N(Si(CH3)3)2]3 + 3 MClNdCl 3 + 3 M [N (Si (CH 3 ) 3 ) 2 ] → Nd [N (Si (CH 3 ) 3 ) 2 ] 3 + 3 MCl

Nd[N(Si(CH3)3)2]3 + 3 HO-A-N(R3)-B-NR1R2 → Nd[O-A-N(R3)-B-NR1R2]3 + 3 HN(Si(CH3)3)2 Nd [N (Si (CH 3 ) 3 ) 2 ] 3 + 3 HO-AN (R 3 ) -B-NR 1 R 2 → Nd [OAN (R 3 ) -B-NR 1 R 2 ] 3 + 3 HN (Si (CH 3 ) 3 ) 2

상기 화학식 1의 신규한 네오디뮴 산화물 선구 물질은 안정한 착화합물이고, 금속과 결합하는 알콕사이드의 산소에 대하여 α-탄소 위치에 비극성 알킬기가 결합해 있어 유기 용매에 대한 친화성이 높고, 중심 금속이 이웃한 리간드의 산소와 분자간 상호 작용을 일으키지 못하도록 입체 장애를 주기 때문에 단위체로 존재할 수 있다. 이러한 구조적 특성으로 인하여 상기 화학식 1의 네오디뮴 산화물용 선구 물질은 상온에서 안정한 액체로서 유기 용매, 예를 들면 펜탄, 헥산, 디에틸에테르, 테트라하이드로퓨란, 톨루엔 등에 대한 용해도가 높고, 휘발성이 뛰어날 뿐만 아니라, 할로겐 원소를 포함하지 않아 보관에 유리하기 때문에, 이들을 사용하여 질이 더 우수한 네오디뮴 산화물 박막을 얻을 수 있다.The novel neodymium oxide precursor of Formula 1 is a stable complex compound, a non-polar alkyl group is bonded at the α-carbon position to the oxygen of the alkoxide to bond with the metal, high affinity for the organic solvent, a ligand adjacent to the central metal It can exist as a monomer because it gives steric hindrance to prevent intermolecular interaction with oxygen. Due to these structural characteristics, the precursor material for neodymium oxide of Chemical Formula 1 is a stable liquid at room temperature and has high solubility in organic solvents such as pentane, hexane, diethyl ether, tetrahydrofuran, toluene, etc. Since it does not contain a halogen element and is convenient for storage, these can be used to obtain a neodymium oxide thin film of better quality.

이와 같이 제조한 3가 네오디뮴 화합물은 상온에서 점성이 있는 액체로 얻어진다.The trivalent neodymium compound thus prepared is obtained as a viscous liquid at room temperature.

반응 생성물인 화학식 1의 네오디뮴 산화물 선구 물질은 푸리에 변환 적외선 분광법 (Fourier transform infrared spectroscopy, FTIR) (도 1 및 도 3 참조)을 이용하여 확인하였으며, 본 발명에서 합성한 란타늄 산화물 선구 물질의 열적 안정성 및 휘발성 그리고 분해 온도는 열중량 분석법/시차 열분석법(thermogravimetric analysis/differential thermal analysis, TGA/DTA) (도 2 및 도 4참조)을 이용하여 분석하였다. The reaction product of neodymium oxide precursor of Formula 1 was confirmed by Fourier transform infrared spectroscopy (FTIR) (see Figs. 1 and 3), and the thermal stability and the thermal stability of the lanthanum oxide precursor synthesized in the present invention Volatility and decomposition temperature were analyzed using thermogravimetric analysis / differential thermal analysis (TGA / DTA) (see FIGS. 2 and 4).

도 2에서 나타낸 바와 같이 트리스(1-(N-(2-디메틸아미노)에틸)-N-메틸아미 노)-2-메틸-2-프로폭시)네오디뮴 (Nd(demamp)3) 화합물의 경우에는 110 ℃와 250 ℃ 부근에서는 약한 질량감소를 보이다가 320 ℃ 부근까지 급격한 질량 감소가 일어남을 확인하였고, 잔류량은 28.98 %이었다. 또한 도 4에 나타낸 바와 같이 트리스[2-(N-(2-(디메틸아미노)에틸)-N-메틸아미노)에폭시]네오디뮴(Nd(demae)3) 화합물의 경우 130 ℃ 부근에서 천천히 질량이 감소하다가 350 ℃ 부근에서 급격하게 떨어져 390 ℃ 부근에서 완료되고 그 잔류량은 35.19 %이었다.In the case of the tris (1- (N- (2-dimethylamino) ethyl) -N-methylamino) -2-methyl-2-propoxy) neodymium (Nd (demamp) 3 ) compound as shown in FIG. At 110 ℃ and 250 ℃ showed a weak mass loss, but a sudden mass loss occurred to around 320 ℃, the residual amount was 28.98%. In addition, in the case of the tris [2- (N- (2- (dimethylamino) ethyl) -N-methylamino) epoxy] neodymium (Nd (demae) 3 ) compound as shown in FIG. It suddenly fell near 350 ° C and was completed near 390 ° C, and the residual amount was 35.19%.

상기 결과로부터 본 발명에서 합성한 네오디뮴 산화물 선구 물질은 분해 온도 이전에 충분한 휘발성을 보일 뿐만 아니라 유기 용매에 대해 용해도가 높기 때문에 반도체 제조 공정에 널리 이용하는 금속 유기물 화학 증착(MOCVD) 공정 또는 원자층 증착법(ALD)에 바람직하게 적용할 수 있다.From the above results, the neodymium oxide precursor synthesized in the present invention not only exhibits sufficient volatility before decomposition temperature but also has high solubility in organic solvents, so it is widely used in the semiconductor organic chemical vapor deposition (MOCVD) process or atomic layer deposition method ( ALD) is preferably applied.

본 발명은 하기의 실시예에 의하여 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부한 특허 청구 범위에 의하여 한정되는 보호 범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

모든 실험은 장갑 상자 또는 슐렝크 관(Schlenk line)을 이용하여 비활성 아르곤 또는 질소 분위기에서 수행하였다. 실시예 1 및 2에서 얻은 각각의 반응 생성물의 구조는 푸리에 변환 적외선 분광 (FT-IR) 분석 및 원소 분석법 (elemental analysis, EA), 열무게 분석법/시차 열분석법 (thermogravimetric analysis/differential thermal analysis, TGA/DTA)을 이용하여 분석하였다. All experiments were performed in an inert argon or nitrogen atmosphere using a glove box or Schlenk line. The structure of each reaction product obtained in Examples 1 and 2 was Fourier transform infrared spectroscopy (FT-IR) analysis and elemental analysis (EA), thermogravimetric analysis / differential thermal analysis, TGA / DTA).

네오디뮴Neodymium 산화물의 제조 Preparation of Oxide

[실시예 1] 트리스(1-(N-(2-디메틸아미노)에틸)-N-메틸아미노)-2-메틸-2-프로폭시)네오디뮴 [Nd(demamp)3]의 합성Example 1 Synthesis of Tris (1- (N- (2-dimethylamino) ethyl) -N-methylamino) -2-methyl-2-propoxy) neodymium [Nd (demamp) 3 ]

테트라하이드로퓨란(70 mL)이 들어 있는 125 mL 슐렝크 플라스크에 비스(트리메틸실릴)아미도 리튬 1.86 g (11.12 mmol)을 넣고 용해시킨 후 1.0 g 의 염화네오디뮴 (3.99 mmol)을 넣고 상온에서 약 24시간 동안 교반하였다. 상기 반응물을 감압 하에서 용매를 제거하여 화학식 5로 나타낸 파란색 고체의 화합물 2.08 g(수율 83.87 %)을 얻었다.1.86 g (11.12 mmol) of bis (trimethylsilyl) amido lithium was dissolved in a 125 mL Schlenk flask containing tetrahydrofuran (70 mL), followed by 1.0 g of neodymium chloride (3.99 mmol). Stir for hours. The reaction product was removed under reduced pressure to obtain 2.08 g (yield 83.87%) of a compound of a blue solid represented by Chemical Formula 5.

톨루엔(70 mL)이 들어 있는 125 mL 슐렝크 플라스크에 화학식 5의 화합물 3.12 g (4.99 mmol)을 넣고 용해시키고, 여기에 1-[N-{2-(디메틸아미노)에틸}-N-메틸아미노]-2-메틸프로판-2-올(demampH, 1-(N-(2-(dimethylamino)ethyl)-N-methylamino)-2-methylpropan-2-ol, 2.61 g, 14.98 mmol)를 첨가한 후 3일 동안 교반하였다. 상기 반응용액을 감압 하에서 용매를 제거하여 파란색 액체의 표제 화합물 1.95 g을 얻었다(수율: 58.85 %).3.12 g (4.99 mmol) of the compound of formula 5 were dissolved in a 125 mL Schlenk flask containing toluene (70 mL), which was dissolved in 1- [N- {2- (dimethylamino) ethyl} -N-methylamino. ] -2-methylpropan-2-ol (demampH, 1- (N- (2- (dimethylamino) ethyl) -N-methylamino) -2-methylpropan-2-ol, 2.61 g, 14.98 mmol) Stir for 3 days. The solvent was removed under reduced pressure to give 1.95 g of the title compound as a blue liquid (yield: 58.85%).

원소 분석 C27H63N6O3Nd {계산치 (실측치)}: C, 48.83 (47.96); H, 9.56 (10.02); N, 12.66 (11.81)Elemental Analysis C 27 H 63 N 6 O 3 Nd {calculated (calculated)}: C, 48.83 (47.96); H, 9.56 (10.02); N, 12.66 (11.81)

FT-IR (cm-1, KBr pellet) : υ 2960, 2760, 1460, 1360, 1160, 1030, 787, 584, 471, 424 cm-1.FT-IR (cm -1 , KBr pellet): υ 2960, 2760, 1460, 1360, 1160, 1030, 787, 584, 471, 424 cm -1 .

[실시예 2] 트리스[2-(N-(2-(디메틸아미노)에틸)-N-메틸아미노)에폭시]네오디뮴, [Nd(demae)3]의 합성Example 2 Synthesis of Tris [2- (N- (2- (dimethylamino) ethyl) -N-methylamino) epoxy] neodymium, [Nd (demae) 3 ]

톨루엔(70 mL)이 들어 있는 125 mL 슐렝크 플라스크에 화학식 5의 화합물 3.0 g (4.80 mmol)을 넣고 용해시키고, 여기에 2-(N-(2-디메틸아미노)에틸)-N-메틸아미노]에탄올(demaeH, (2-(N-(2-(dimethylamino)ethyl)-N-methylamino)ethanol, 2.10 g, 14.36 mmol)를 첨가한 후 3일 동안 교반하였다. 상기 반응용액을 감압 하에서 용매를 제거하여 파란색 액체의 표제 화합물 1.68 g을 얻었다(수율: 60.39 %).3.0 g (4.80 mmol) of the compound of formula 5 were dissolved in a 125 mL Schlenk flask containing toluene (70 mL), and 2- (N- (2-dimethylamino) ethyl) -N-methylamino] was added thereto. Ethanol (demaeH, (2- (N- (2- (dimethylamino) ethyl) -N-methylamino) ethanol, 2.10 g, 14.36 mmol) was added and stirred for 3 days.The reaction solution was removed under reduced pressure. This gave 1.68 g of the title compound as a blue liquid (yield: 60.39%).

원소 분석 C21H51N6O3Nd {계산치 (실측치)}: C, 43.49 (41.97); H, 8.86 (10.08); N, 14.49 (13.45)Elemental Analysis C 21 H 51 N 6 O 3 Nd {calculated (calculated)}: C, 43.49 (41.97); H, 8.86 (10.08); N, 14.49 (13.45)

FT-IR (cm-1, KBr pellet) : υ 2940, 2770, 1460, 1270, 1110, 1030, 889, 731,607, 465 cm-1.FT-IR (cm -1 , KBr pellet): υ 2940, 2770, 1460, 1270, 1110, 1030, 889, 731,607, 465 cm -1 .

상술한 바와 같이, 본 발명에 따른 네오디뮴 산화물 선구 물질은 네오디뮴에 산소 원자와 질소 원자 리간드만 배위됨으로써 열안정성 및 휘발성이 우수할 뿐만 아니라, 수분에 덜 민감하고 보관이 유리하여 특히 질이 우수한 산화막을 제조해야 하는 금속 유기물 화학 증착법 (MOCVD) 또는 원자층 증착법(ALD) 용의 새로운 리간드를 갖는 네오디뮴 선구 물질로서 유용하게 사용할 수 있다.As described above, the neodymium oxide precursor according to the present invention is not only excellent in thermal stability and volatility by coordinating an oxygen atom and a nitrogen atom ligand to neodymium, but also less sensitive to moisture and advantageous in storage, thus providing an excellent oxide film. It can be usefully used as a neodymium precursor having a novel ligand for metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) to be produced.

Claims (6)

하기 화학식 1로 표시되는 네오디뮴 산화물 선구 물질:Neodymium oxide precursors represented by Formula 1: [화학식 1][Formula 1] Nd[O-A-N(R3)-B-NR1R2]3 Nd [OAN (R 3 ) -B-NR 1 R 2 ] 3 [상기 식에서 A는 C2-C5의 알킬렌이고; B는 C1-C4의 알킬렌이고; 상기 A 및 B는 하나 이상의 C1-C5의 직쇄 또는 분지쇄의 알킬기로 더 치환될 수 있고; R1, R2 및 R3는 서로 독립적으로 H 또는 C1-C5의 선형 또는 분지형 알킬기이다.][Wherein A is alkylene of C 2 -C 5 ; B is alkylene of C 1 -C 4 ; A and B may be further substituted with one or more C 1 -C 5 straight or branched alkyl groups; R 1 , R 2 and R 3 independently of one another are H or C 1 -C 5 linear or branched alkyl groups.] 제 1항에 있어서,The method of claim 1, 하기 화학식 2로 표시되는 네오디뮴 산화물 선구 물질.Neodymium oxide precursor represented by the following formula (2). [화학식 2][Formula 2] Nd[OCR4R5(CH2)mN(R3)-(CH2)nNR1R2]3 Nd [OCR 4 R 5 (CH 2 ) m N (R 3 )-(CH 2 ) n NR 1 R 2 ] 3 [상기 식에서 R1, R2, R3, R4 및 R5는 서로 독립적으로 H 또는 C1-C5의 선형 또는 분지형 알킬기이고, m 및 n은 1 내지 4의 정수이다.][Wherein R 1 , R 2 , R 3 , R 4 And R 5 is independently of each other H or a C 1 -C 5 linear or branched alkyl group, m and n are integers from 1 to 4.] 제 2항에 있어서,The method of claim 2, 상기 식에서 R1, R2, R3, R4 및 R5는 서로 독립적으로 H, CH3, C2H5, CH(CH3)2 또는 C(CH3)3로부터 선택되는 것을 특징으로 하는 네오디뮴 산화물 선구 물질.Wherein R 1 , R 2 , R 3 , R 4 And R 5 is independently of each other H, CH 3 , C 2 H 5 , CH (CH 3 ) 2 or C (CH 3 ) 3 neodymium oxide precursor. 하기 화학식 3의 네오디뮴 화합물과 하기 화학식 4의 알칼리 금속 염 화합물을 반응시켜 얻어진 하기 화학식 5의 화합물을 하기 화학식 6의 알코올 화합물과 반응시키는 것을 특징으로 하는 화학식 1의 네오디뮴 산화물 선구 물질의 제조방법.A process for producing the neodymium oxide precursor of formula (1), comprising reacting a compound of formula (5) obtained by reacting a neodymium compound of formula (3) with an alkali metal salt compound of formula (4): [화학식 1][Formula 1] Nd[O-A-N(R3)-B-NR1R2]3 Nd [OAN (R 3 ) -B-NR 1 R 2 ] 3 [화학식 3][Formula 3] NdCl3 NdCl 3 [화학식 4][Formula 4] M[N(Si(CH3)3)2]M [N (Si (CH 3 ) 3 ) 2 ] [화학식 5][Formula 5] Nd[N(Si(CH3)3)2]3 Nd [N (Si (CH 3 ) 3 ) 2 ] 3 [화학식 6][Formula 6] HO-A-N(R3)-B-NR1R2 HO-AN (R 3 ) -B-NR 1 R 2 [상기 화학식 1, 화학식 4 및 화학식 6에서, M은 Li, Na 또는 K이며; A는 C2-C5의 알킬렌이고; B는 C1-C4의 알킬렌이고; 상기 A 및 B는 하나 이상의 C1-C5의 직쇄 또는 분지쇄의 알킬기로 더 치환될 수 있고; R1, R2 및 R3는 서로 독립적으로 H 또는 C1-C5의 선형 또는 분지형 알킬기이다.][In Formula 1, Formula 4 and Formula 6, M is Li, Na or K; A is alkylene of C 2 -C 5 ; B is alkylene of C 1 -C 4 ; A and B may be further substituted with one or more C 1 -C 5 straight or branched alkyl groups; R 1 , R 2 and R 3 independently of one another are H or C 1 -C 5 linear or branched alkyl groups.] 제 1항에 따른 네오디뮴 산화물 선구 물질을 사용하여 네오디뮴 산화물을 성장시키는 방법.A method of growing neodymium oxide using the neodymium oxide precursor according to claim 1. 제 5항에 있어서,The method of claim 5, 네오디뮴 산화물을 유기금속 화학기상 증착법(MOCVD) 또는 원자층 증착법(ALD)으로 형성하는 것을 특징으로 하는 방법.Neodymium oxide is formed by organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR920000783B1 (en) * 1985-03-01 1992-01-23 롱-쁠랑 스뻬씨알리뜨 쉬미끄 Neodymium titanate and barium neodymium titanate processes for their preparation and thetr applications in ceramic compositions
JPH08325013A (en) * 1995-05-26 1996-12-10 Imura Zairyo Kaihatsu Kenkyusho:Kk Neodymium based oxide superconducting formed body and its manufacture
WO2005082782A2 (en) 2004-02-26 2005-09-09 Rhodia Chimie Composition based on zirconium oxides, de praseodymium, lanthanum or neodymium, method for the preparation and use thereof in a catalytic system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR920000783B1 (en) * 1985-03-01 1992-01-23 롱-쁠랑 스뻬씨알리뜨 쉬미끄 Neodymium titanate and barium neodymium titanate processes for their preparation and thetr applications in ceramic compositions
JPH08325013A (en) * 1995-05-26 1996-12-10 Imura Zairyo Kaihatsu Kenkyusho:Kk Neodymium based oxide superconducting formed body and its manufacture
WO2005082782A2 (en) 2004-02-26 2005-09-09 Rhodia Chimie Composition based on zirconium oxides, de praseodymium, lanthanum or neodymium, method for the preparation and use thereof in a catalytic system

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