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In situ ATR - FTIR spectroscopy of Hf(IV) tert butoxide adsorption on Si and Ge

Published online by Cambridge University Press:  01 February 2011

Shilpa Dubey ,
Keijing Li ,
Harish Bhandari ,
Zheng Hu ,
C. Heath Turner  and
Tonya M. Klein
Shilpa Dubey
Affiliation:
[email protected], The University of Alabama, Chemical Engineering, A127, Bevill Building, Chemical Engineering, The University of Alabama, Tuscaloosa, Alabama, 35487, United States, 205-348-5425, 205-348-6579
Keijing Li
Affiliation:
[email protected], The University of Alabama, Department of Chemical Engineering, A127, Bevill Building, Tuscaloosa, Alabama, 35487, United States
Harish Bhandari
Affiliation:
[email protected], The University of Alabama, Department of Chemical Engineering, A127, Bevill Building, Tuscaloosa, Alabama, 35487, United States
Zheng Hu
Affiliation:
[email protected], The University of Alabama, Department of Chemical Engineering, A127, Bevill Building, Tuscaloosa, Alabama, 35487, United States
C. Heath Turner
Affiliation:
[email protected], The University of Alabama, Department of Chemical Engineering, A127, Bevill Building, Tuscaloosa, Alabama, 35487, United States
Tonya M. Klein
Affiliation:
[email protected], The University of Alabama, Department of Chemical Engineering, A127, Bevill Building, Tuscaloosa, Alabama, 35487, United States
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Abstract

Hafnium oxide ultra thin films on Si (100) are being developed to replace thermally grown SiO2 gates in CMOS devices. In this work, a specially designed Attenuated Total Reflectance - Fourier Transform Infra Red Spectroscopy (ATR-FTIR) reaction cell has been developed to observe chemisorption of hafnium (IV) t-butoxide onto a Si and Ge ATR crystal heated up to 250°C and under 1 torr of vacuum to observe the initial reaction pathways and species on the substrate surface in real time and under typical process conditions. Chemisorption spectra were compared to spectra of the liquid precursor and to spectra generated by density functional theory (DFT) calculations of liquid, monodentate and bidentate absorbed precursor. An asymmetric stretching mode located at ~1017 cm-1 present in the chemisorbed spectra but not in the liquid spectra indicates that the adsorbed hafnium containing group is prevalent as a bidentate ligand according to calculations. Surface concentration of the chemisorbed species was dependant on the substrate temperature and precursor partial pressure allowing for determination of heats of adsorption which was 26.5 kJ/mol on Si.

Keywords

SiHfadsorption
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 917: Symposium E – Gate Stack Scaling – Materials Selection, Role of Interfaces, and Reliability Implications , 2006 , 0917-E09-03
Copyright
Copyright © Materials Research Society 2006

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