• Bulletin of the Korean Chemical Society
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• v.27 no.2
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• pp.219-223
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• 2006

The thermal decomposition of tetrakis(ethylmethylamido) titanium (TEMAT) has been investigated in Ar and $H_2$ gas atmospheres at gas temperatures of 100-400 ${^{\circ}C}$ by using Fourier Transform infrared spectroscopy (FTIR) as a fundamental study for the chemical vapor deposition (CVD) of titanium nitride (TiN) thin film. The activation energy for the decomposition of TEMAT was estimated to be 10.92 kcal/mol and the reaction order was determined to be the first order. The decomposition behavior of TEMAT was affected by ambient gases. TEMAT was decomposed into the intermediate forms of imine (C=N) compounds in Ar and $H_2$ atmosphere, but additional nitrile (RC$\equiv$N) compound was observed only in $H_2$ atmosphere. The decomposition rate of TEMAT under $H_2$ atmosphere was slower than that in Ar atmosphere, which resulted in the extension of the regime of the surface reaction control in the CVD TiN process.

• Korean Journal of Materials Research
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• v.10 no.11
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• pp.732-737
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• 2000

Plasma enhanced chemical vapor deposition of $TiO_{2$\pm}{\delta}$ has been carried out using TEMAT [tetrakis(ethylmethylamido) titanium] and $H_2$. Increasing the power from 300 W to 500 W produced the high density plasma, leading to the formation of TiO$_2$films with an increased ratio of Ti to O and a negligible amount of C and N. Applying the bias of 30W to the substrate in creased the growth rate of the film with a slightly increased content of Ti in the film. In addition, $H_2O$ was from either the residual gas in the gase pressure or $H_2(/He)$ gas and actively participated in the formation of $TiO_2$ films. Consequently, Ti ions created in the plasma could be a main contributor to $TiO_2$ formation with a slight amount of $H_2O(~10^{-4}Toor)$ in the ambient, which provided the dissociation of TEMAT.

• Proceedings of the IEEK Conference
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• 1998.10a
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• pp.581-584
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• 1998

TiN thin films were grown on (100) Si substrate by atomic layer epitaxy at 130 - $240^{\circ}C$ using TEMAT and NH3 as precursors. Reactants were injected into the reactor in sequence of TEMAT precursor vapor pulse, N2 purging gas pulse, NH3 gas pulse and N2 purging gas pulse so that gas-phase reactions could be removed. The films were characterized by means of x-ray diffraction(XRD), 4-point probe, atomic force microscopy(AFM) and auger electron spectroscopy(AES).

• Korean Journal of Materials Research
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• v.8 no.5
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• pp.377-382
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• 1998

Atomic layer deposition(ALD) of amorphous TiN films on $SiO_2$ between 17$0^{\circ}C$ and 21O$^{\circ}C$ has been investigated by alternate supply of reactant sources, Ti[N($C_2,H_5,CH_3)_2]_4$ [tetrakis(ethylmethylamminoltitanium: TEMAT] and $NH_3$. Reactant sources were injected into the reactor in the order of TEMAT vapor pulse, Ar gas pulse, $NH_3$. gas pulse and Ar gas pulse. Film thickness per cycle was saturated at around 1.6 monolayer(MU per cycle with sufficient pulse times of reactant sources at 20$0^{\circ}C$. The results suggest that film thickness per cycle could be beyond 1 MLicycie in ALD, which were explained by rechemisorption mechanisms of reactant sources. The ideal linear relationship be¬tween number of cycles and film thickness is confirmed. As a results of surface limited reactions of ALD, step cover¬age was excellent. Particles caused by the gas phase reactions between TEMAT and NH3 were almost free because TEMAT was seperated from $NH_3$ by the Ar pulse. In spite of relatively low substrate temperature, carbon impurity was incorporated below 4 at%.

• Korean Journal of Materials Research
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• v.9 no.3
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• pp.244-250
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• 1999

MOCVD TiN films were prepared from a new TiN precursor, tetrakis(etylmethylamino)titanium (TEMAT) and ammonia. Deposition of TiN films from a single precursor, TEMA T yielded the growth rates of $70 to 1050\AA$/min, depending on the deposition temperature. Furthermore, the excellent bottom coverage of -90% over $0.35\mu\textrm{m}$ contacts was obtained at $275^{\circ}C$. The addition of ammonia to TEMA T lowered the resistivity of as- deposited TiN film to ~ $800\mu\omega-cm$ from $3500~6000\mu\omega-cm$ and improved the stability of TiN film in air. Examination of the films by Auger electron spectroscopy(AES) showed that the oxygen and carbon contents decreased with the addition of ammonia. However, increasing ammonia flow rate decreased the bottom coverage of TiN films over $0.5\mu\textrm{m}$ contacts, probably due to the high sticking coefficient of intermediate species produced from the gas phase reaction of TEMA T and ammonia. Based on the byproduct gases detected by the quadrupole mass spectrometer (QMS), the transammination reaction was proposed to be responsible for TiN deposition. In addition, XPS analysis revealed that the carbon in the films made from TEMA T and ammonia was metallic carbon, suggesting that $\beta$-hydrogen activation process occurs competitively with the transammination reaction.

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.37 no.6
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• pp.43-49
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• 2000

The TiN thin films were deposited by ALE(atomic layer epitaxy) on (100) silicon substrate. The TiN thin films were characterized by means of XRD, 4-point probe, AFM, AES and SEM. TEMAT(terakis(ethyl methy lamino)titanium) and $NH_3$ were injected into the reactor in sequence of TEMAT-$N_2-NH_3-N_2$ to ensure a saturated surface reaction. As a result, the depostion rate of the TiN film was controlled by self-limiting growth mechanism at temperature range form 150 to 220 $^{\circ}C$. Deposited TiN films, all of which show amorphous structure, had a fixed deposition rate of 4.5 ${\AA}$/cycle. The resistivity of 210 ~ 230 ${\mu}{\Omega}{\cdot}$cm and the surface r.m.s. roughness of 7.9 ~ 9.3 ${\AA}$ were measured. When TiN film of 2000 ${\AA}$ were deposited, a excellent step coverage were observed in a trench structure of 0.43${\mu}m$ contacts with 6:1 aspect ratio.

• Korean Journal of Materials Research
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• v.9 no.11
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• pp.1129-1136
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• 1999

TIN films were prepared on Si(100) substrate by ICP-CVD(inductive1y coupled plasma enhanced chemical vapor deposition) using TEMAT(tetrakis ethylmethamido titanium : Ti$[\textrm{N}\textrm{(CH)}_{3}\textrm{C}_{2}\textrm{H}_{5}]_{4}$) precursor at various deposition conditions. Phase, microstructure, and the electrical properties of TIN films were characterized by x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM) and electrical measurements. Polycrystalline TiN films with B1 structure were grown at temperatures over $200^{\circ}C$. Preferentially oriented along TiN(111) films were obtained at temperatures over $300^{\circ}C$ with the flow rates of 10, 5, and 5 sccm for TEMAT, $\textrm{N}_{2}$ and Ar gas. The TiN/Si(100) interface was flat and no chemical reaction between TIN and $\textrm{SiO}_2$ was found. The resistivity, carrier concentration and the carrier mobility for the TiN sample prepared at $500^{\circ}C$ are 21 $\mu\Omega$cm, 9.5$\times\textrm{10}^{18}\textrm{cm}^{-3}$ and $462.6\textrm{cm}^{2}$/Vs, respectively.

• Proceedings of the Korean Vacuum Society Conference
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• 1999.07a
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• pp.118-118
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• 1999

CVD방법에 의한 TiN 박막 형성에 있어서 ICP-CVD 방법이 대두되고 있다. 이것은 precursor에 대한 radical 형성, 식각된 패턴에서 양 벽의 self-shadowing 효과, 낮은 tress등으로 dense 한 박막을 얻을 수 있기 때문이다. TiN 박막은 Si 기판의 온도를 상온에서 50$0^{\circ}C$까지 유지하면서 TEMAT의 유량을 5-20sccm으로 변화시키면서 증착하였다. 증착 후 TiN 박막의 결정화에 따른 열처리는 Ar과 N2-가스분위기에서 in-situ로 증착하였다. 증착 후 TiN 박막증착 조건수립에 따른 플라즈마 특성진단은 전자의 온도와 밀도, 평균 전자밀도, 이온 에너지 분포, radical 분포, negative 이온분포 등으로 측정하였다. 플라즈마 변수에 따른 TiN 박막의 결정성과 상 변화는 XRD로 분석하였고, 조성비 및 TiN 박막의 원소화학적 상태, 결합에너지, 각 상에 따른 결합 에너지 천이정도, 초기 형성과정 및 반응기구 등은 RBS와 XPS로 조사하였다. TiN 박막의 표면상태, morphology 거칠기, TiN/Si(100)구조에서 계면상태 등은 SEM, AFM, 그리고 HRTEM으로 분석하였다. TiN 구조 박막의 비저항, carrier concentration 그리고 mobility 측정은 박막의 표면이 균일하고 bls-홀이 없는 것으로 하여 4-point probe 방법으로 측정하였다. 이들 분석으로부터 ICP-CVD 방법에 의하여 형성된 TiN 박막이 초고집적 반도체 소자의 contact barrier layer로서의 적용 가능성을 평가하였다.