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D7.2.1

Nitrogen Distribution and Oxidation of HfOxNy Gate Dielectrics Deposited by MOCVD using [(C2H5)2N]4Hf with NO and O2 Minsoo Lee1, Dolf Landheer2, Xiaohua Wu2, Martin Couillard3, Zhenghong Lu1, Wai T. Ng4, Jianhao Chen5, Tiensheng Chao6, and Tanfu Lei5 1 Department of Materials Science and Engineering, University of Toronto, Toronto, ON, Canada M5S 3E4 2 Institute for Microstructural Sciences, National Research Council of Canada, Ottawa, ON, Canada K1A 0R6 3 Brockhouse Institute for Materials Research, McMaster University, Hamilton, ON, Canada L8S 4L7 4 Department of Electrical and Computer Engineering, University of Toronto, Toronto, ON, Canada M5S 3G4 5 Department of Electronics Engineering, National Chiao-Tung University, Hsinchu 300, Taiwan 6 Department of Electrophysics, National Chiao-Tung University, Hsinchu 300, Taiwan ABSTRACT Ultra-thin HfOxNy gate dielectric films were deposited by pulse-mode metalorganic chemical vapor deposition (MOCVD) with [(C2H5)2N]4Hf (TDEAH) and either NO or O2 as oxidants. Nitrogen incorporation was studied by x-ray photoelectron spectroscopy (XPS) and spatially-resolved elemental profiles were obtained by scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) and energy dispersive x-ray spectroscopy (EDS). The results indicate that nitrogen is incorporated throughout the high-k film with a higher concentration in the interface layer between the deposited layer and the Si(100) substrate. The concentration of nitrogen is increased in both layers by using NO instead of O2 as the oxidant. The N in the deposited and interface layers can be replaced by oxygen during oxygen ambient annealing at temperatures above 500 °C. Films with 8 at.% nitrogen remain amorphous following vacuum annealing at temperatures up to 800 °C. By encapsulating vacuum-annealed films with amorphous Si from an e-beam evaporator prior to removal from the cluster tool, it was possible to reduce the thickness of the interface layer upon air exposure to the 0.5 nm range. INTRODUCTION A number of materials are being considered as a replacement for silicon oxynitride gate dielectrics in future generations of metal oxide semiconductor field effect transistors. Of the transition-metal oxides, HfO2 has been regarded as the most desirable because it combines a high dielectric constant with the highest thermodynamic stability [1,2]. However, low crystallization temperatures, < 500ºC, and high impurity diffusion rates are causing concerns about the reliability of pure HfO2 [3]. Nitrogen incorporation, investigated with sputtered films [4], has been shown to reduce these drawbacks. This paper describes the deposition and characterization of HfOxNy gate dielectric films deposited by MOCVD using an oxygen-free, nitrogen-based precursor, [(C2H5)2N]4Hf (tetrakis diethylamido hafnium or TDEAH), with oxidants NO or O2. The thermal stability of these films was investigated by analyzing the compositional and

D7.2.2

structural changes accompanying in-situ vacuum annealing and o

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