새로운 증착원으로 형성된 MOCVD TiN 에 관한 연구

최정환; 이재갑; 김지용; 이은구; 홍해남; 신현국; J.H. Choi; J.G. Lee; J.Y. Kim; E.G. Lee; H.N. Hong; H.K. Shin

Korean Journal of Materials Research, Vol.9, No.3, 244-250, March, 1999

Export Citation

새로운 증착원으로 형성된 MOCVD TiN 에 관한 연구

Formation of MOCVD TiN from a New Precursor

최정환, 이재갑, 김지용, 이은구¹, 홍해남², 신현국³

국민대학교 금속재료공학부
¹조선대학교 재료공학과
²국방과학연구소
³U.P.Cæm

J.H. Choi, J.G. Lee, J.Y. Kim, E.G. Lee¹, H.N. Hong², and H.K. Shin³

Dept. of Metallurgical Engineering, Kookmin University, Seoul 136-702, Korea
¹Dept. of Materials Science & Engineering, Chosun University, Kwangju 501-759, Korea
²Agency for Defeπse Development, Taejon 305-600, Korea
³Ultra Pure Chemical Inc., Suwon 442-070, Korea

초록

새로운 TiN 선구체인 TEMAT(tertrakis etylmethylamino titanium) 과 암모니아를 이용하여 TiN 박막을 형성하였다. 단일 증착원으로 증착시킨 경우에는 70~1050Å/min의 증착률을 얻을 수 있었으며 증착온도에 지배를 받았다. 275℃의 증착온도에서 0.35 um의 접촉장에서 약 90%의 도포성을 얻을 수 있었다. TEMAT에 암모니아를 첨가하였을 때 단일증착원에서 3500~6000μΩ-cm정도의 값을 나타내던 비저항이 ~800μΩ-cm 정도로 낮아졌으며 대기중 막의 안전성도 향상되었다. AES의 분석결과에서도 암모니아의 첨가로 현저한 산소와 탄소 함량의 감소를 나타내었다. 그러나 암모니아의 유량을 증가시킬수록 0.5um접촉창에서 나타난 TiN 박막의 도포성은 감소하였고 이는 TEMAT와 암모니아의 기상 반응에 의한 높은 접착계수를 가진 중간 생성물의 형성에 의한 것으로 생각된다. 반응 부산물에 대한 분석은 QMS에 의해 이루어 졌으며 transamination 반응에 의한 TiN 증착기구를 제시하였다. 추가적으로 XPS분석으로 TEMAT와 암모니아의 반응에 의해 만들어지는 탄소는 금소기 탄소였으며 β-수소 반응이 transamination 반응과 경쟁적으로 일어남을 나타내었다.

MOCVD TiN films were prepared from a new TiN precursor, tetrakis(etylmethylamino)titanium (TEMAT) and ammonia. Deposition of TiN films from a single precursor, TEMAT yielded the growth rates of 70 to 1050 Å/min, depending on the deposition temperature. Furthermore, the excellent bottom coverage of -90% over 0.35um contacts was obtained at 275℃. The addition of ammonia to TEMA T lowered the resistivity of as- deposited TiN film to ~800μΩ-cm from 3500~6000μΩ-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 0.5um contacts, probably due to the high sticking coefficient of intermediate species produced from the gas phase reaction of TEMAT 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 β- hydrogen activation process occurs competitively with the transammination reaction.

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[1] Eizenberg M, Littau K, Ghanayem S, Mak A, Maeda Y, Chang M, Shinha AK, Appl. Phys. Lett., 65, 7 (1994)

[2] Hegde R, Fiordalice R, Travis E, Tobin P, J. Vac. Sci. Technol. B, 11, 1287 (1993)

[3] Faltermeier CG, Goldberg C, Jones M, Upham A, Knorr A, Ivanova A, Peterson G, Kaloyeros AE, Arkles B, J. Electrochem. Soc., 145(2), 676 (1998)

[4] Lee JG, Kim JH, Shin HK, Park SJ, Yun SJ, Kim GH, 1996 MRS. Symp. Proc. 427, Spring Meeting, San Francisco, CA, 371, 1996.

[5] 김지용, 이재갑, 박상준, 신현국, 한국재료학회지, 7(7), 576 (1997).

[6] Raaijmaaker IJ, Ellwanger RC in Advanced Metallization for ULSI Applications, edited by Cale TS, Pintchovski FB (Mater. Res. Soc., Pittsburg, 1993), 325 (1993).

[7] Hillman JT, Rice MJ, Studiner DW, Foster RF, Fiordalice RW, in the Proceedings of the Ninth International VLSI Multilevel Interconnection Conference., 246-252 (1992).

[8] Shin HK, Shin HJ, Lee JG, Kang SW, Ahn BT, Chem. Mater., 9, 76 (1997)

[9] Weiller BH, J. Am. Chem. Soc., 118(21), 4975 (1996)

[10] Weiller BH, in the Proceedings ofthe thirteenth international conference on Chemical Vapor Deposition, edited by Besmann TM, Allendorf MD, Robinson M, Ulrich RK, published by THE ELECTROCHEMICAL SOCIETY, INC, 10 South Main St., Pennington, NJ 08534-2896, 231-237 (1996).

[11] Raaijamakers IJ, Yang J, Appl. Surf. Sci., 73, 31 (1993)