Precursorchemie von HfN, TaN, WNx und ähnlichen Metallnitriden in MOCVD und ALD-Prozessen für Gate-Metallisierungs- und Diffusions-Grenzschichten für CMOS-Bauteile

• Applicant: Professor Dr. Roland A. Fischer
• Subject Area: Chemical and Thermal Process Engineering
• Term: from 2005 to 2008
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 5449780

• Final Report Year: 2008

Final Report Abstract

The synthesis of the tungsten and molybdenum guanidinato complexes was elucidated to a satisfying extent, and the synthesis can be easily scaled up to a multi gram scale. But the mechanistic pathways of the decomposition of the precursor could only be clarified to a small extent. The different mechanisms of the two tungsten precursors could not be resolved fully. Further experiments are required, for a proper identification of the decomposition pathways. A suitable experiment for this purpose would be a direct coupling of a MOCVD reactor to an analytical method such as El-mass spectroscopy or FT-IR for direct identification of the decomposition products. Especially the tungsten precursor W(Nt-Bu)2(NMe2){(i-PrN)2-CNMe2}, which was identified to be the most promising of all studied compounds is worth further studies. By variation of the parameters of the MOCVD experiment it might be possible to avoid the particle formation that was observed in deposition experiments using three dimensional substrates. Also the application of this compound in ALD experiments should be taken into consideration. While very promising results were obtained in tungsten nitride depositions, a scale up of the molybdenum nitride depositions was not promising, due the properties of the precursor. A possible application for this compound might be the production of nanoparticles or several sol-gel applications.

Publications

• "Metal Organic Chemical Vapor Deposition of Conductive and Crystalline Hafnium Nitride Films". Chem. Vap. Dep. 2005, 11, 294-297
  Y. Kim, A. Baunemann, H. Parala, A. Devi, R. A. Fischer
  
• "MOCVD of Conductive Cubic HfN Thin Films from Hf(NR2)4 and N,N-Dimethylhydrazine". Electrochemical Society Proceedings 2005,9,762-765
  Y. Kim, H. Parala, A. Bauer, M. Lemberger, A. Baunemann, R. A. Fischer
  
• "Selective Growth of Tantalum Nitride and hafnium Nitride Thin Films on OTS Patterned Si(100) Substrates by MOCVD Method". Electrochemical Society Proceedings 2005, 9, 326-332
  B.-C. Kang, A. Baunemann, Y. Kim, J.-H. Lee, D.-Y. Jung, H. Parala, A. Devi, R. A. Fischer, J.-H. Boo
  
• "Tantalum complexes with all nitrogen coordination sphere: Mixed amido-, imido-, guanidinato complexes of tantalum and their thermal behaviour". J. Chem. Soc. Dalton Trans., 2005, 3051-3055
  A. Baunemann, A. Milanov, D. Rische, C. Gemel, M. Winter, Y. Kim, R. A. Fischer
  
• "Mixed Amido/Imido/Guanidinato complexes of tantalum: Effects of ligand substitution on thermal properties". Eur. J. Inorg. Chem. 2006, 4665-4672
  A. Baunemann, M. Winter, K. Csapek, C. Gemel, R. A. Fischer
  
• "Mixed guanidinato/alkylimido/azido tungsten(VI) complexes: Synthesis and structural characterization". Inorg. Chem. 2006, 45, 269-277
  D. Rische, A. Baunemann, M. Winter, R. A. Fischer
  
• "Mixed hydrazido amido/imido complexes of tantalum, hafnium and zirconium: potential precursors for metal nitride MOCVD". Dalton Trans. 2006, 121-128
  A. Baunemann, Y. Kim, M. Winter, R. A. Fischer
  
• "New Tungsten(VI) Guanidinato Complexes: Synthesis, Characterization, and Application in Metal-Organic Chemical Vapor Deposition of Tungsten Nitride Thin Films". Chem. Mater. 2006, 18, 6075 - 6082
  D. Rische, H. Parala, E. Gemel, M. Winter, R. A. Fischer
  
• "Guanidinato based precursors for MOCVD of metal nitrides (MxN; M = Ta, W)". Surface Coatings and Technology 2007,201,9125-9130
  D. Rische, H. Parala, A. Baunemann, T. Thiede and R. A. Fischer
  
• "MOCVD of TaN using the all nitrogen coordinated precursors: [Ta(NEtMe)3(N-t-Bu)], [Ta(NEtMe)(N-t-Bu){C(N-i-Pr)2(NEtMe)}2] and [Ta(NMeEt)2(N-t-Bu){Me2N-N(SiMe3)}". Chem. Vap. Depos. 2007, 2-3, 78-83
  A. Baunemann, M. Lemberger, A. J. Bauer, H. Parala and R. A. Fischer
  
• "MOCVD of tantalum nitride thin films from TBTEMT single source precursor as metal electrodes in CMOS applications". Surface Coatings and Technology 2007,201,9154-9158
  M. Lemberger, S. Thiemann, A. Baunemann, H. Parala, R. A. Fischer, J. Hinz, A. J. Bauer and H. Ryssel