신규의 몰리브데넘과 텅스텐 전구체의 합성 및 특성 연구 = Synthesis and Characterization of Novel Molybdenum and Tungsten Precursors

다국어 초록 (Multilingual Abstract)

The present studies reported synthesis and characterization of novel molybdenum and tungsten precursors suitable for CVD/ALD process. The novel precursors, Mo(NtBu)2(dmampS)2 (1), Mo(NtBu)2(dmampS)Cl (2), Mo(NtBu)2(StBu)(dmampS) (3), W(NtBu)2(dmampS)2 (4), W(NtBu)2(dmampS)Cl (5), W(NtBu)2(StBu)(dmampS) (6), W(NtBu)2(dmamp)2 (7), W(NtBu)2(dmamb)2 (8) and W(NtBu)2(btsa)2 (9), were synthesized by metathesis reaction of Mo(NtBu)2Cl2(dme) and W(NtBu)2Cl2Py2 with lithium 1-(dimethylamino)-2-methylpropane-2-thiolate [Li(dmampS)], sodium1-(dimethylamino)-2-methylpropan-2-olate [Na(dmamp)], sodium1-(dimethylamino)-2-methylbutan-2-olate [Na(dmamb)], and lithium-bis(trimethylsilyl)amide [Li(btsa)], respectively. The compounds have been characterized by IR, 1H NMR, 13C NMR spectroscopy, microanalytical data, and mass spectrometry. The molecular structures of 1, 3, 4, and 6, obtained by X-ray single crystallography, reveal distorted trigonal bipyramidal geometry. Optimized geometries of 7 and 8 were calculated by density functional theory (DFT). The calculated geometry of 7 is similar to the experimental molecular geometry. Thermal properties of the all precursors were analyzed by thermogravimetric analysis (TGA). In TGA, the residues of 1 and 3, 4 and 6, and 7 and 8 are calculated to MoS2, WS2, and WO2, respectively. TGA of 9 exhibits smaller residue than the calculated values for tungsten nitrides due to volatilization before decomposition. Thermal decomposition of 7 under nitrogen atmosphere was confirmed to form WO2 by X-ray powder diffraction (XRD).

목차 (Table of Contents)

• I. 서 론
• I.1. CVD/ALD 공정에 적합한 전구체 13
• I.2. MoS2, WS2 전구체의 연구배경 14
• I.3. WOx 전구체의 연구배경 15
• I.4. WxNy 전구체의 연구배경 16
• II. 실 험
• II.1. 시약 및 기기 18
• II.2. 리간드 합성 19
• II.2.1. Li(dmampS) 19
• II.2.2. Na(dmamp) 19
• II.2.3. Na(dmamb) 19
• II.2.4. Li(btsa) 20
• II.3. 전구체 합성 20
• II.3.1. Mo(NtBu)2(dmampS)2 (1) 20
• II.3.2. Mo(NtBu)2Cl(dmampS) (2) 20
• II.3.3. Mo(NtBu)2(StBu)(dmampS) (3) 21
• II.3.4. W(NtBu)2(dmampS)2 (4) 21
• II.3.5. W(NtBu)2Cl(dmampS) (5) 22
• II.3.6. W(NtBu)2(StBu)(dmampS) (6) 22
• II.3.7. W(NtBu)2(dmamp)2 (7) 23
• II.3.8. W(NtBu) 2(dmamb)2 (8) 23
• II.3.9. W(NtBu) 2(btsa)2 (9) 24
• III. 결과 및 고찰
• III.1. 전구체 합성 25
• III.2. 전구체 1H NMR 분석 28
• III.3. 전구체 TGA 분석 30
• III.3.1. 몰리브데넘 황화물 전구체의 TGA 30
• III.3.2. 텅스텐 황화물 전구체의 TGA 31
• III.3.3. 텅스텐 산화물 전구체의 TGA 32
• III.3.4. 텅스텐 질화물 전구체의 TGA 33
• III.4. 전구체 결정구조 분석 34
• III.4.1. 몰리브데넘 및 텅스텐 황화물 전구체들(1,3,4,6)의 결정구조 34
• III.4.2. 텅스텐 산화물 전구체 (7)의 결정구조 및 (7), (8)의 DFT 계산 42
• III.5. 텅스텐 산화물 전구체 (7)의 열분해 46
• IV. 결 론 48
• V. 참고문헌 49