KR101017897B1 - Siliconiv complexes alkoxyalkoxide and preparation method thereof - Google Patents
Siliconiv complexes alkoxyalkoxide and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000010409 thin film Substances 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 12
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 9
- -1 Alkoxy Alkoxides Chemical class 0.000 claims abstract description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 150000002367 halogens Chemical class 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- 238000001228 spectrum Methods 0.000 description 16
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 11
- 238000000231 atomic layer deposition Methods 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 238000004455 differential thermal analysis Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- RWMKKWXZFRMVPB-UHFFFAOYSA-N silicon(4+) Chemical compound [Si+4] RWMKKWXZFRMVPB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- FXLWDDPGTDBNDP-UHFFFAOYSA-N sodium;1-methoxy-2-methylpropan-2-olate Chemical compound COCC(C)(C)O[Na] FXLWDDPGTDBNDP-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- RJCRUVXAWQRZKQ-UHFFFAOYSA-N oxosilicon;silicon Chemical compound [Si].[Si]=O RJCRUVXAWQRZKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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Abstract
본 발명은 하기 화학식 1로 표시되는 새로운 실리콘 착화합물 및 이의 제조 방법에 관한 것으로, 본 발명에 따라 실리콘에 알킬옥사이드가 배위된 착화합물은 열적으로 안정하고 공기 중에서도 안정하며 휘발성이 높고 화학기상증착(CVD, Chemical Vapor Deposition)에 의한 박막 형성시 탄소나 할로겐 오염을 일으키지 않아 양질의 실리콘 또는 실리콘 산화물 박막을 제조하는데 유리하게 이용될 수 있다.The present invention relates to a new silicon complex compound represented by the following formula (1) and a method for preparing the same, wherein the complex compound in which the alkyl oxide is coordinated in silicon is thermally stable, stable in air, high in volatility, and chemical vapor deposition (CVD, Chemical Vapor Deposition) does not cause carbon or halogen contamination when forming a thin film can be advantageously used to produce a high quality silicon or silicon oxide thin film.
[화학식 1][Formula 1]
Si(R1)n{OCR2R3(CH2)mOR4}4-n Si (R 1 ) n {OCR 2 R 3 (CH 2 ) m OR 4 } 4-n
[상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 선형 또는 분지형의 (C1-C4)알킬이고; m은 1내지 3의 정수이며; n은 0 내지 3의 정수이다.][In Formula 1, R 1 , R 2 , R 3 And R 4 is each independently linear or branched (C 1 -C 4) alkyl; m is an integer of 1 to 3; n is an integer of 0 to 3.]
실리콘 착화합물, 실리콘알콕시알콕사이드 Silicone Complexes, Silicone Alkoxy Alkoxides
Description
본 발명은 신규의 실리콘 착화합물에 관한 것으로서, 실리콘 또는 실리콘 산화물 박막의 화학증착용 전구체로서 유용한 화합물 및 이의 제조 방법에 관한 것이다.The present invention relates to a novel silicon complex, to a compound useful as a precursor for chemical vapor deposition of a silicon or silicon oxide thin film and a method for producing the same.
산화규소는 안정하고 양질의 규소-산화규소 계면과 뛰어난 전기적 절연 성질 때문에 절연체로 많이 사용되었다. 최근에는 다결정 실리콘 박막을 박막 트랜지스터(thin film transistor, TFT), 태양전지 등에 이용하고 있다.Silicon oxide has been widely used as an insulator because of its stable, high quality silicon-silicon oxide interface and excellent electrical insulation properties. Recently, polycrystalline silicon thin films are used for thin film transistors (TFTs), solar cells, and the like.
박막 제조 기술 중 다양한 산화물 박막 제조에 사용되고 있는 금속 유기물 화학 증착(metal organic chemical vapor deposition, MOCVD) 공정은 장치가 비교적 간단하고 층 덮힘이 균일하며, 성분 조절이 쉽고, 대량 생산으로 전환하기에 무리가 없다는 장점이 있다. 이러한 MOCVD 공정을 이용하여 박막을 제조하기 위해서는 이 공정에 사용되는 전구체의 개발과 그 특성의 이해가 필수적이다. MOCVD용 전구체는 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, 전구체 자체에 또는 분해 생성 물질에 독성이 없거나 적어야 하며, 합성법이 간단하고 원재료 단가가 저렴해야 한다.The metal organic chemical vapor deposition (MOCVD) process, which is used to manufacture various oxide thin films among thin film manufacturing techniques, is relatively simple in equipment, uniform in layer covering, easy to control ingredients, and difficult to convert to mass production. There is no advantage. In order to manufacture a thin film using the MOCVD process, development of precursors used in this process and understanding of its characteristics are essential. The precursor for MOCVD must have a sufficiently high vapor pressure below 200 ° C., thermally stable enough for heating to vaporize, decompose rapidly without decomposition of organic matters at substrate temperatures of 350 to 500 ° C., and during storage It must be stable enough to air and moisture. In addition, the precursor itself or the decomposition product should be non-toxic or low, the synthesis method should be simple and the raw material cost should be low.
실리콘 화합물을 박막으로 만들기 위해 사용되어 온 전구체는 크게 네 가지로, 실란, 염화실란, 알콕사이드 화합물 및 β-디케토네이트(β-diketonate)를 포함하는 화합물로 구분된다.Is used to make the silicon compound into a thin film on the precursor is largely into four, silane, chlorosilane, an alkoxide compound and a β - be divided into compounds containing diketonates (β-diketonate).
실란은 실온에서 기체이고, 높은 압력과 충격에도 안정하나 산소와 섞일 때 타거나 폭발한다. 또한 수분과 반응하여 가루나 입자를 형성하므로 주의하여 다뤄야 한다. 사염화실란(SiCl4)은 H2O와 함께 원자층 침착법(Atomic Layer Deposition, ALD)의 전구체로, 반응물 압력이 1-10 Torr이고, 온도는 600-800°K에서 실리콘 산화물 박막을 제조할 수 있다고 개시되어 있으며(문헌[J. W. Klaus, A. W. Ott, J. M. Johnson, and S. M. George, Appl . Phys . Lett . 1997, 70, 1092] 참조), 실란과 마찬가지로 수분에 민감하게 반응하고, 박막을 제조하는 동안 표면을 염화물로 오염시킬 수 있다. 또한 이염화실란(SiH2Cl2)은 O2 또는 O3와 함께 원자층 침착법을 이용하여 300℃에서 실리콘 산화물 박막을 제조하는데 사용되기도 한다(문헌[Japanese Journal of Applied Physics , Part 2: Letters & Express Letters 2004, 43(3A), L328-L33]참조).Silane is a gas at room temperature, stable to high pressures and impacts, but burns or explodes when mixed with oxygen. It should also be handled with care as it reacts with moisture to form powder or particles. Silane tetrachloride (SiCl4) Is H2A precursor of atomic layer deposition (ALD) with O, it is disclosed that a silicon oxide thin film can be produced at a reactant pressure of 1-10 Torr and a temperature of 600-800 ° K (JW Klaus, AW Ott, JM Johnson, and SM George,Appl . Phys . Lett . 1997,70, As with silanes, can be sensitive to moisture and contaminate surfaces with chlorides during the manufacture of thin films. In addition, silane dichloride (SiH2Cl2) Is O2 Or O3It is also used to prepare a silicon oxide thin film at 300 ° C. using atomic layer deposition.Japanese Journal of Applied Physics , Part 2: Letters & Express Letters 2004,43 (3A), L328-L33].
알콕사이드계 전구체 중 실리콘 산화물 박막의 전구체로 가장 많이 사용되는 테트라에틸오르소실리케이트 (TEOS)는 실온에서 액체이고 다루기가 쉽지만, 수분과 반응하여 SiO2와 에탄올로 가수분해하는 반응이 느리다. 이 전구체는 LPCVD (Low-Pressure Chemical Vapor Deposition)이나 APCVD (Atmospheric Pressure Chemical Vapor Deposition)에 의해 400-900 ℃ 정도의 높은 온도에서 박막을 형성한다 (문헌[J. Crowell 등, J. Vac . Sci . Technol . A 1990, 8, 1864]; [L. Tedder 등, J. Appl. Phys . 1991, 69, 7037]; [M. IslamRaja 등, J. Vac . Sci . Technol . B 1993, 11, 720]; 및 [D. Williams 등, J. Electrochem . Soc . 1988, 134, 657] 참조).Among the alkoxide precursors, tetraethylorthosilicate (TEOS), which is most commonly used as a precursor for silicon oxide thin films, is liquid at room temperature and is easy to handle, but it reacts slowly with hydrolysis to SiO 2 and ethanol. These precursors form thin films at temperatures as high as 400-900 ° C. by LPCVD (Low-Pressure Chemical Vapor Deposition) or APCVD (Atmospheric Pressure Chemical Vapor Deposition) (J. Crowell et al . , J. Vac . Sci . . Technol A 1990, 8, 1864 ];.. [L. Tedder , etc., J. Appl Phys 1991, 69, 7037];... [M. IslamRaja such as, J. Vac Sci Technol B 1993, 11, 720] And D. Williams et al . , J. Electrochem . Soc . 1988 , 134 , 657).
또한, β-디케토네이트를 포함하는 화합물로는 SiClMe(acac)2, SiClPh(acac)2, SiMe2(acac)2 (acac = 아세틸아세토네이트) 등이 있는데, 이들은 매우 불안정하고 수율이 떨어지는 단점이 있다. Si(OAc)2(acac)2와 SiX2(thd)2 (X = Me, OtBu, OtAm, thd = 2,2,6,6-테트라메틸-3,5-헵탄디온)는 좀 더 안정하지만, β-디케토네이트를 포함하는 화합물은 높은 열적 안정성 때문에 MOCVD 과정에서 증착 온도가 높다는 단점이 있다(문헌[C. Xu, 등, Inorg . Chem . 2004, 43, 1568]; [R. West, J. Am . Chem. Soc . 1958, 80, 3246]; [R. M. Pike 등, J. Am . Chem . Soc . 1966, 88, 2972]; [D.W. Thompson, Inorg . Chem . 1969, 8, 2015]; 및 [K. M. Taba 등, J. Organomet . Chem . 1985, 280, 27] 참조).In addition, compounds containing β -diketonate include SiClMe (acac) 2 , SiClPh (acac) 2 , SiMe 2 (acac) 2 (acac = acetylacetonate), which are very unstable and have low yields. There is this. Si (OAc) 2 (acac) 2 and SiX 2 (thd) 2 (X = Me, O t Bu, O t Am, thd = 2,2,6,6-tetramethyl-3,5-heptanedion) Although more stable, compounds containing β -diketonate have the disadvantage of high deposition temperature during the MOCVD process due to high thermal stability (C. Xu, et al . , Inorg . Chem . 2004 , 43 , 1568); [ R. West, J. Am . Chem. Soc . 1958 , 80 , 3246; RM Pike et al . , J. Am . Chem . Soc . 1966 , 88 , 2972; DW Thompson, Inorg . Chem . 1969 , 8 , 2015] and KM Taba et al . , J. Organomet . Chem . 1985 , 280 , 27).
본 발명자들은 상기 화합물들이 갖는 문제점들을 해결할 수 있는 새로운 리간드를 도입하여 열적 안정성과 휘발성이 개선된 신규의 실리콘 또는 실리콘 산화물 박막 증착용 전구체를 개발하기에 이르렀다.The present inventors have introduced a new ligand that can solve the problems of the compounds to develop a novel precursor for deposition of silicon or silicon oxide thin film with improved thermal stability and volatility.
본 발명의 목적은 양질의 실리콘 또는 실리콘 산화물 박막을 형성할 수 있는, 열적으로 안정하고 휘발성이 증가된 실리콘 화합물 전구체를 제공하는 데 있다.It is an object of the present invention to provide a thermally stable and increased volatility silicon compound precursor capable of forming a high quality silicon or silicon oxide thin film.
상기 목적을 달성하기 위하여, 본 발명에서는 하기 화학식 1로 표시되는, 실리콘에 알콕시알콕사이드가 결합된, 신규의 실리콘 화합물 전구체를 제공한다.In order to achieve the above object, the present invention provides a novel silicon compound precursor, alkoxyalkoxide is bonded to the silicon represented by the formula (1).
[화학식 1][Formula 1]
Si(R1)n{OCR2R3(CH2)mOR4}4-n Si (R 1 ) n {OCR 2 R 3 (CH 2 ) m OR 4 } 4-n
상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 선형 또는 분지형의 (C1-C4)알킬, 바람직하게는 CH3, C2H5 또는 CH(CH3)2이고; m은 1내지 3의 정수이고; n은 0내지 3의 정수이다.In
이하, 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 상기 화학식 1로 표시되는 착화합물은, 출발 물질로서 하기 화학식 2로 표시되는 실리콘 화합물과 화학식 3으로 표시되는 알코올의 알칼리금속염과 극성 유기용매 중에서 치환반응시켜 염 제거 반응을 통해 제조할 수 있다:The complex compound represented by Chemical Formula 1 according to the present invention may be prepared through a salt removal reaction by performing a substitution reaction in an alkali metal salt of a silicon compound represented by Chemical Formula 2 and an alcohol represented by Chemical Formula 3 with a polar organic solvent as a starting material. have:
[화학식 2][Formula 2]
Si(R1)nX4-n Si (R 1 ) n X 4-n
[화학식 3](3)
MOCR2R3(CH2)mOR4 MOCR 2 R 3 (CH 2 ) m OR 4
상기 화학식 2 또는 화학식3에서, R1, R2, R3 및 R4는 각각 독립적으로 선형 또는 분지형의 (C1-C4)알킬이고; m은 1내지 3의 정수이며; n은 0 내지 3의 정수이다. 또한, M은 Li, Na 및 K로 이루어진 군으로부터 선택되는 알칼리 금속이고, X는 Cl, Br 및 I로 이루어진 군으로부터 선택되는 할로겐 원소이다.In
본 발명의 상기 화학식 1의 실리콘 착화합물을 제조하기 위해, 상기 화학식 2로 표시되는 실리콘 화합물을 출발 물질로 하여 화학식 3으로 표시되는 화합물을 알코올의 알칼리금속염과 반응시키는 공정은 하기 반응식 1로 나타낼 수 있다. In order to prepare the silicone complex compound of Formula 1, the process of reacting a compound represented by Formula 3 with an alkali metal salt of alcohol using the silicone compound represented by Formula 2 as a starting material may be represented by
[반응식 1]
Si(R1)nX4-n + (4-n) MOCR2R3(CH2)mOR4 → Si(R1)n{OCR2R3(CH2)mOR4}4-n + (4-n) MXSi (R 1 ) n X 4-n + (4-n) MOCR 2 R 3 (CH 2 ) m OR 4 → Si (R 1 ) n {OCR 2 R 3 (CH 2 ) m OR 4 } 4-n + (4-n) MX
상기 반응식에서, R1, R2, R3 및 R4는 각각 독립적으로 선형 또는 분지형의 (C1-C4)알킬이고; m은 1내지 3의 정수이며; n은 0 내지 3의 정수이다. 또한, M은 Li, Na 및 K로 이루어진 군으로부터 선택되는 알칼리 금속이고, X는 Cl, Br 및 I로 이루어진 군으로부터 선택되는 할로겐 원소이다.In the above scheme, R 1 , R 2 , R 3 And R 4 is each independently linear or branched (C 1 -C 4) alkyl; m is an integer of 1 to 3; n is an integer of 0-3. In addition, M is an alkali metal selected from the group consisting of Li, Na and K, and X is a halogen element selected from the group consisting of Cl, Br and I.
구체적으로는, 본 발명에 따른 상기 화학식 1 화합물은 화학식 2의 화합물 1 당량, 화학식 3의 화합물 (4-n) 당량을 테트라하이드로퓨란과 같은 유기 용매, 예를 들어 펜탄, 헥산, 디에틸에테르, 테트라하이드로퓨란, 톨루엔, 바람직하게는 테트라하이드로퓨란, 에 녹인 뒤, 실온에서 6시간 내지 24시간, 바람직하게는 12시간 동안 치환 반응을 진행한 뒤, 감압 하에서 여과하고, 생성된 여과액으로부터 용매를 감압 제거하여 수득될 수 있다.Specifically, the compound of Formula 1 according to the present invention may be used in an organic solvent such as tetrahydrofuran, for example, 1 equivalent of
상기 반응에서 사용되는 출발 물질인 상기 화학식 2의 화합물 Si(R1)nX4-n는 할로겐 이온을 포함하고 있어 알칼리 금속 염인 상기 화학식 3의 화합물 MOCR2R3(CH2)mOR4와 반응하여 화학식 1의 화합물인 Si(R1)n{OCR2R3(CH2)mOR4}4-n와 (4-n) 당량의 MX을 생성하였다.Compound Si (R 1 ) n X 4-n of Chemical Formula 2, which is a starting material used in the reaction, includes a halogen ion, which is an alkali metal salt of MOCR 2 R 3 (CH 2 ) m OR 4 . Reaction gave Si (R 1 ) n {OCR 2 R 3 (CH 2 ) m OR 4 } 4-n and (4-n) equivalents of MX of the compound of Formula 1.
상기 화학식 1로 표시되는 신규의 실리콘 또는 실리콘 산화물 박막의 전구체인 화합물 Si(R1)n{OCR2R3(CH2)mOR4}4-n은 안정한 킬레이트 화합물이고, 금속과 결합하는 알콕사이드의 산소에 대하여 α-탄소 위치에 비극성 알킬기가 결합되어 있어 유기 용매에 대한 친화성이 높고, 알콕사이드의 산소와 결합한 중심 금속이 이웃한 리간드의 산소 분자간 상호 작용을 막아 주도록 입체 장애를 주기 때문에 단위체로 존재할 수 있다. 이러한 구조적 특성으로 인하여 상기 화학식 1로 표시되는 실리콘 화합물은 상온에서 안정한 액체로서 유기 용매, 예를 들면 펜탄, 헥산, 디에틸에테르, 테트라하이드로퓨란, 톨루엔 등에 높은 용해도를 갖고, 휘발성이 뛰어날 뿐만 아니라, 할로겐 원소를 포함하지 않고, 상온에서 안정하고 공기 중에서도 특히 안정하여 보관상 유리하며 이들을 사용하여 보다 양질의 실리콘 또는 실리콘 산화물 박막을 얻을 수 있다.Compound Si (R 1 ) n {OCR 2 R 3 (CH 2 ) m OR 4 } 4-n, which is a precursor of the novel silicon or silicon oxide thin film represented by Chemical Formula 1, is a stable chelate compound and an alkoxide that bonds with a metal The non-polar alkyl group is bonded to the α-carbon position with respect to the oxygen, so it has a high affinity for organic solvents. May exist. Due to such structural properties, the silicone compound represented by Chemical Formula 1 is a stable liquid at room temperature, has high solubility in organic solvents such as pentane, hexane, diethyl ether, tetrahydrofuran, toluene, etc., and has excellent volatility. It does not contain halogen elements, is stable at room temperature and is particularly stable in air, which is advantageous for storage and can be used to obtain better silicon or silicon oxide thin films.
본 발명의 실리콘 알콕시알콕사이드 화합물은 실리콘 또는 실리콘 산화물 박막 제조용 전구체로서, 특히 반도체 제조 공정에 널리 사용되고 있는 금속 유기물 화학 증착(MOCVD) 또는 원자층 침착(ALD) 공정에 바람직하게 적용될 수 있다.The silicon alkoxyalkoxide compound of the present invention is a precursor for producing a silicon or silicon oxide thin film, and may be preferably applied to a metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) process, which is widely used in the semiconductor manufacturing process.
본 발명의 실리콘 착화합물은 할로겐 성분을 함유하지 않고 실리콘에 알콕시알콕사이드기가 배위된 착화합물로서 수분에 민감하지 않고 보관이 유리하며, 특히 산화막의 우수한 질을 요구하는 금속 유기물 화학 증착법(MOCVD) 또는 원자층 침착법(ALD)에 사용되는 실리콘의 전구체로서 손색이 없으며, 이에 따라 실리콘을 포함 하는 산화물 박막 제조용 전구체로서 유용하게 사용할 수 있다.The silicon complex of the present invention is a complex compound containing no halogen and alkoxyalkoxide group coordinated in silicon, which is not sensitive to moisture and is advantageous in storage, and in particular, metal organic chemical vapor deposition (MOCVD) or atomic layer deposition which requires excellent quality of oxide film. There is no inferiority as a precursor of silicon used for the method (ALD), and thus it can be usefully used as a precursor for producing an oxide thin film containing silicon.
본 발명은 하기의 실시 예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시 예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허 청구범위에 의하여 한정되는 보호 범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose 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 1에서 각각 얻은 반응 생성물의 구조는 수소 원자 핵자기 공명법(1H nuclear magnetic resonance, NMR), 탄소 원자 핵자기 공명법(13C NMR), 푸리에 변환 적외선 분광 (FTIR) 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. Embodiment, each structure of the obtained reaction product in Example 1 is hydrogen nuclear magnetic resonance (1 H nuclear magnetic resonance, NMR ), the carbon atom nuclear magnetic resonance (13 C NMR), Fourier transform infrared spectroscopy (FTIR) analysis and elemental analysis (elemental analysis, EA), thermogravimetric analysis / differential thermal analysis (TGA / DTA).
[실리콘 착화합물의 제조] [Production of Silicon Complex]
실시예Example 1: One: 트리메틸Trimethyl -(1--(One- 메톡시Methoxy -2--2- 메틸methyl -2--2- 프로폭시Propoxy )실리콘()silicon( IVIV ) [) [ SiSi (( CHCH 33 )) 33 (mmp)]의 제조(mmp)]
(CH3)3SiCl + NaOC(CH3)2CH2OCH3 → (CH3)3SiOC(CH3)2CH2OCH3 + NaCl (CH 3 ) 3 SiCl + NaOC (CH 3 ) 2 CH 2 OCH 3 → (CH 3 ) 3 SiOC (CH 3 ) 2 CH 2 OCH 3 + NaCl
테트라하이드로퓨란(50 mL)이 들어있는 250 mL 슐렝크 플라스크에 실리콘(IV) 트리메틸클로라이드(1.72 g, 16 mmol)를 넣고 용해시켰다. 여기에 1 당량의 Na(mmp) (1-메톡시-2-메틸-2-프로폭시 나트륨, 2 g, 16 mmol)을 테트라하이드로퓨란(50 mL)에 용해시켜 천천히 첨가하고, 이 혼합액을 12 시간 동안 교반하였다. 이용액을 여과하여 여과액을 감압 하에서 용매를 제거하여 무색의 액체의 표제 화합물(2.1 g)을 얻었다 (수율: 71.0 %).Silicon (IV) trimethylchloride (1.72 g, 16 mmol) was added to a 250 mL Schlenk flask containing tetrahydrofuran (50 mL) and dissolved. To this was added 1 equivalent of Na (mmp) (1-methoxy-2-methyl-2-propoxy sodium, 2 g, 16 mmol) in tetrahydrofuran (50 mL) and slowly added. Stir for hours. The filtrate was filtered to remove the solvent under reduced pressure to obtain the title compound (2.1 g) as a colorless liquid (yield: 71.0%).
1H NMR (C6D6, 300.13 MHz): δ 0.21 (s, 9 H (CH3)3Si), 1.27 (s, 6 H, OC(CH3)2), 3.07 (s, 2 H, OCH2C), 3.10 (s, 3 H CH3O). 1 H NMR (C 6 D 6 , 300.13 MHz): δ 0.21 (s, 9 H (CH 3 ) 3 Si), 1.27 (s, 6 H, OC (CH 3 ) 2 ), 3.07 (s, 2 H, OCH 2 C), 3.10 (s, 3 H CH 3 O).
13C NMR (C6D6, 75.04 MHz): δ 82.5, 68.2, 59.2, 28.0, 26.2, 3.06. 13 C NMR (C 6 D 6 , 75.04 MHz): δ 82.5, 68.2, 59.2, 28.0, 26.2, 3.06.
원소 분석 C8H20O2Si {계산치(실측치)}: C, 54.49 (58.08); H, 11.43 (11.53).Elemental Analysis C 8 H 20 O 2 Si {calculated (calculated)}: C, 54.49 (58.08); H, 11.43 (11.53).
상기 화합물의 수소 원자핵 자기 공명(1H NMR) 스펙트럼, 탄소 원자핵 자기 공명(13C NMR) 스펙트럼, 및 푸리에 변환 적외선 분광(FTIR) 스펙트럼을 각각 도 1 내지 3에 나타내었다.Hydrogen nuclear magnetic resonance ( 1 H NMR) spectra, carbon atom magnetic resonance ( 13 C NMR) spectra, and Fourier transform infrared spectroscopy (FTIR) spectra of the compounds are shown in FIGS.
실시예Example 2: 디메틸- 2: dimethyl- 비스Vis -(1--(One- 메톡시Methoxy -2--2- 메틸methyl -2--2- 프로폭시Propoxy )실리콘()silicon( IVIV ) [) [ SiSi (( CHCH 33 )) 22 (mmp)(mmp) 22 ]의 제조Manufacture of
(CH3)2SiCl2 + 2 NaOC(CH3)2CH2OCH3 → (CH3)2Si{OC(CH3)2CH2OCH3}2 + 2 NaCl (CH 3 ) 2 SiCl 2 + 2 NaOC (CH 3 ) 2 CH 2 OCH 3 → (CH 3 ) 2 Si {OC (CH 3 ) 2 CH 2 OCH 3 } 2 + 2 NaCl
테트라하이드로퓨란(50 mL)이 들어있는 250 mL 슐렝크 플라스크에 실리콘(IV) 다이메틸다이클로라이드 (1.02 g, 8 mmol)를 넣고 용해시켰다. 여기에 2 당량의 Na(mmp) (1-메톡시-2-메틸-2-프로폭시 나트륨, 2 g, 16 mmol)을 테트라하이드로퓨란(50 mL)에 용해시켜 천천히 첨가하고, 이 혼합액을 12시간 동안 교반하였다. 이용액을 여과하여 여과액을 감압 하에서 용매를 제거하여 무색의 액체의 표제 화합물(1.00 g)을 얻었다 (수율: 47.7 %).Silicon (IV) dimethyldichloride (1.02 g, 8 mmol) was added to a 250 mL Schlenk flask containing tetrahydrofuran (50 mL) and dissolved. To this was added 2 equivalents of Na (mmp) (1-methoxy-2-methyl-2-propoxy sodium, 2 g, 16 mmol) in tetrahydrofuran (50 mL) and slowly added, this mixture was added 12 Stir for hours. The filtrate was filtered and the filtrate was removed under reduced pressure to give the title compound (1.00 g) as a colorless liquid (yield: 47.7%).
1H NMR (C6D6, 300.13 MHz): δ 0.28 (s, 6 H (CH3)3Si), 1.39 (s, 12 H, OC(CH3)2), 3.14 (s, 6 H CH3O), 3.20 (s, 4 H, OCH2C). 1 H NMR (C 6 D 6 , 300.13 MHz): δ 0.28 (s, 6 H (CH 3 ) 3 Si), 1.39 (s, 12 H, OC (CH 3 ) 2 ), 3.14 (s, 6 H CH 3 O), 3.20 (s, 4H, OCH 2 C).
13C NMR (C6D6, 75.04 MHz): δ 82.5, 74.5, 59.2, 27.9, 3.37, 2.58. 13 C NMR (C 6 D 6 , 75.04 MHz): δ 82.5, 74.5, 59.2, 27.9, 3.37, 2.58.
원소 분석 C12H36O4Si {계산치(실측치)}: C, 54.50 (53.19); H, 10.67 (10.59).Elemental Analysis C 12 H 36 O 4 Si {calculated (calculated)}: C, 54.50 (53.19); H, 10.67 (10.59).
상기 화합물의 수소 원자핵 자기 공명(1H NMR) 스펙트럼, 탄소 원자핵 자기 공명(13C NMR) 스펙트럼, 및 푸리에 변환 적외선 분광(FTIR) 스펙트럼을 각각 도 4 내지 6에 나타내었다.Hydrogen nuclear magnetic resonance ( 1 H NMR) spectra, carbon atom magnetic resonance ( 13 C NMR) spectra, and Fourier transform infrared spectroscopy (FTIR) spectra of the compounds are shown in FIGS. 4 to 6, respectively.
실시예Example 3: 3: 메틸methyl -- 트리스Tris (1-(One- 메톡시Methoxy -2--2- 메틸methyl -2--2- 프로폭시Propoxy )실리콘(IV) [Si(CH) Silicon (IV) [Si (CH 33 )(mmp)) (mmp) 33 ]의 제조Manufacture of
(CH3)SiCl3 + 3 NaOC(CH3)2CH2OCH3 → (CH3)Si{OC(CH3)2CH2OCH3}3 + 3 NaCl (CH 3 ) SiCl 3 + 3 NaOC (CH 3 ) 2 CH 2 OCH 3 → (CH 3 ) Si {OC (CH 3 ) 2 CH 2 OCH 3 } 3 + 3 NaCl
테트라하이드로퓨란(50mL)이 들어있는 250 mL 슐렝크 플라스크에 실리콘(IV) 트리메틸클로라이드 (0.79 g, 5 mmol)를 넣고 용해시켰다. 여기에 3 당량의 Na(mmp) (1-메톡시-2-메틸-2-프로폭시 나트륨, 1.875 g, 15 mmol)을 테트라하이드로퓨란(50mL)에 용해시켜 천천히 첨가하고, 이 혼합액을 12시간 동안 교반하였다. 이용액을 여과하여 여과액을 감압 하에서 용매를 제거하여 무색의 액체의 표제 화합물(0.20 g)을 얻었다 (수율: 10.8 %).Silicon (IV) trimethylchloride (0.79 g, 5 mmol) was added to a 250 mL Schlenk flask containing tetrahydrofuran (50 mL) and dissolved. To this was added 3 equivalents of Na (mmp) (1-methoxy-2-methyl-2-propoxy sodium, 1.875 g, 15 mmol) in tetrahydrofuran (50 mL) and slowly added, and the mixture was added for 12 hours. Was stirred. The filtrate was filtered to remove the solvent under reduced pressure to give the title compound (0.20 g) as a colorless liquid (yield: 10.8%).
1H NMR (C6D6, 300.13 MHz): δ 0.36 (s, 3 H (CH3)3Si), 1.47 (s, 18 H, OC(CH3)2), 3.18 (s, 9 H CH3O), 3.30 (s, 6 H, OCH2C). 1 H NMR (C 6 D 6 , 300.13 MHz): δ 0.36 (s, 3 H (CH 3 ) 3 Si), 1.47 (s, 18 H, OC (CH 3 ) 2 ), 3.18 (s, 9 H CH 3 O), 3.30 (s, 6 H, OCH 2 C).
13C NMR (C6D6, 75.04 MHz): δ 82.4, 74.7, 59.3, 27.7. 13 C NMR (C 6 D 6 , 75.04 MHz): δ 82.4, 74.7, 59.3, 27.7.
원소 분석 C16H36O6Si {계산치(실측치)}: C, 54.51 (55.07); H, 10.29 (10.48).Elemental Analysis C 16 H 36 O 6 Si {calculated (calculated)}: C, 54.51 (55.07); H, 10.29 (10.48).
상기 화합물의 수소 원자핵 자기 공명(1H NMR) 스펙트럼, 탄소 원자핵 자기 공명(13C NMR) 스펙트럼, 및 푸리에 변환 적외선 분광(FTIR) 스펙트럼을 각각 도 8 내지 10에 나타내었다.Hydrogen atomic magnetic resonance ( 1 H NMR) spectra, carbon atom magnetic resonance ( 13 C NMR) spectra, and Fourier transform infrared spectroscopy (FTIR) spectra of the compounds are shown in FIGS. 8 to 10, respectively.
상기 실시예 2 내지 3에서 합성한 실리콘 화합물 각각의 열중량 분석(TGA) 및 시차 열분석(DTA) 결과를 도 7 및 11에 나타내었다. 실시예 1의 Si(CH3)3(mmp)는 열중량 분석 과정에서 휘발되어 측정할 수 없었다. 도 7로부터, 실시예 2의 Si(CH3)2(mmp)2는 100 ℃ 근처에서 급격히 휘발하여 157 ℃ 부근에서 휘발이 완료되고 1.40 %의 잔류분이 남는 것을 알 수 있다. 또한, 도 11로부터, 실시예 3의 Si(CH3)(mmp)3는 100 ℃ 근처에서 급격히 휘발하여 169 ℃ 부근에서 휘발이 완료되고 5.52 %의 잔류분이 남는 것을 알 수 있다.The thermogravimetric analysis (TGA) and differential thermal analysis (DTA) of each of the silicon compounds synthesized in Examples 2 to 3 are shown in FIGS. 7 and 11. Si (CH 3 ) 3 (mmp) of Example 1 was volatilized during thermogravimetric analysis and could not be measured. It can be seen from FIG. 7 that the Si (CH 3 ) 2 (mmp) 2 of Example 2 volatilized rapidly near 100 ° C., and volatilization was completed near 157 ° C., and 1.40% of residue remained. 11, it can be seen that Si (CH 3 ) (mmp) 3 of Example 3 volatilized rapidly at around 100 ° C., and volatilization was completed at around 169 ° C., leaving a residual of 5.52%.
도 1 내지 도 3은 각각 본 발명에 따른 실시예 1에서 제조한 Si(CH3)3(mmp)의 수소 원자핵 자기 공명 (1H NMR) 스펙트럼, 탄소 원자핵 자기 공명 (13C NMR) 스펙트럼, 푸리에 변환 적외선 분광 (FTIR) 스펙트럼이고,1 to 3 show hydrogen atom magnetic resonance ( 1 H NMR) spectra, carbon atom magnetic resonance ( 13 C NMR) spectra, and Fourier of Si (CH 3 ) 3 (mmp) prepared in Example 1 according to the present invention, respectively. Transform infrared spectroscopy (FTIR) spectrum,
도 4 내지 도 7은 각각 본 발명에 따른 실시예 2에서 제조한 Si(CH3)2(mmp)2의 수소 원자핵 자기 공명 스펙트럼, 탄소 원자핵 자기 공명 스펙트럼, 푸리에 변환 적외선 분광 스펙트럼, 및 열중량 분석 및 시차 열분석 결과를 나타내는 그래프이고,4 to 7 are respectively hydrogen hydrogen nuclear magnetic resonance spectrum, carbon atomic magnetic resonance spectrum, Fourier transform infrared spectroscopy, and thermogravimetric analysis of Si (CH 3 ) 2 (mmp) 2 prepared in Example 2 according to the present invention And a graph showing the results of differential thermal analysis,
도 8 내지 도 11은 각각 본 발명에 따른 실시예 3에서 제조한 Si(CH3)(mmp)3의 수소 원자핵 자기 공명 스펙트럼, 탄소 원자핵 자기 공명 스펙트럼, 푸리에 변환 적외선 분광 스펙트럼, 및 열중량 분석 및 시차 열분석 결과를 나타내는 그래프이다.8 to 11 show hydrogen atom nuclear resonance spectra, carbon atom nuclear resonance spectra, Fourier transform infrared spectroscopy spectra, and thermogravimetric analysis of Si (CH 3 ) (mmp) 3 prepared in Example 3 according to the present invention, respectively. A graph showing the results of differential thermal analysis.
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