Electrical, structural, and chemical properties of HfO2 films formed by electron beam evaporation

High dielectric constant hafnium oxide films were formed by electron beam (e-beam) evaporation on HF last terminated silicon (100) wafers. We report on the influence of low energy argon plasma ( ∼ 70 eV) and oxygen flow rate on the electrical, chemical, and structural properties of metal-insulator-silicon structures incorporating these e-beam deposited HfO2 films. The use of the film-densifying low energy argon plasma during the deposition results in an increase in the equivalent oxide thickness (EOT) values. We employ high resolution transmission electron microscopy (HRTEM), x-ray photoelectron spectroscopy (XPS), and medium energy ion scattering experiments to investigate and understand the mechanisms leading to the EOT increase. We demonstrate very good agreement between the interfacial silicon oxide thicknesses derived independently from XPS and HRTEM measurements. We find that the e-beam evaporation technique enabled us to control the SiOx interfacial layer thickness down to ∼ 6 A. Very low leakage current density (<10−4 A/cm2) is measured at flatband voltage +1 V into accumulation for an estimated EOT of 10.9±0.1 A. Based on a combined HRTEM and capacitance-voltage (CV) analysis, employing a quantum-mechanical CV fitting procedure, we determine the dielectric constant (k) of HfO2 films, and associated interfacial SiOx layers, formed under various processing conditions. The k values are found to be 21.2 for HfO2 and 6.3 for the thinnest ( ∼ 6 A) SiOx interfacial layer. The cross-wafer variations in the physical and electrical properties of the HfO2 films are presented.

[1]  H. Ohta,et al.  Thin-Film Transistor Fabricated in Single-Crystalline Transparent Oxide Semiconductor , 2003, Science.

[2]  Ming-Fu Li,et al.  A high performance MIM capacitor using HfO2 dielectrics , 2002, IEEE Electron Device Letters.

[3]  H. Bender,et al.  X-ray photoelectron spectroscopy characterisation of high-k dielectric Al2O3 and HfO2 layers deposited on SiO2/Si surface , 2004 .

[4]  B. Tsui,et al.  Formation of interfacial layer during reactive sputtering of hafnium oxide , 2003 .

[5]  W. Stickle,et al.  Handbook of X-Ray Photoelectron Spectroscopy , 1992 .

[6]  Defects at the interface of ultra-thin VUV-grown oxide on Si studied by electron spin resonance , 2000 .

[7]  Max C. Lemme,et al.  Interface defects in HfO2, LaSiOx and Gd2O3 high-k/metal gate structures on silicon: Energy distribution and passivation , 2008 .

[8]  Si(100)–SiO2 interface properties following rapid thermal processing , 2001 .

[9]  J. Zhang,et al.  A review of the plasma oxidation of silicon and its applications , 1993 .

[10]  M. White,et al.  Initial growth of interfacial oxide during deposition of HfO2 on silicon , 2004 .

[11]  S. Gangopadhyay,et al.  HfO2 gate dielectric with 0.5 nm equivalent oxide thickness , 2002 .

[12]  B. O’Sullivan,et al.  Interface states and Pb defects at the Si(100)/HfO2 interface , 2005 .

[13]  H. A. Macleod,et al.  Optical and microstructural properties of hafnium dioxide thin films , 1991 .

[14]  S. Hayashi,et al.  Effect of Hf metal predeposition on the properties of sputtered HfO2/Hf stacked gate dielectrics , 2002 .

[15]  Max C. Lemme,et al.  Impact of H 2 /N 2 annealing on interface defect densities in Si(100)/SiO 2 /HfO 2 /TiN gate stacks , 2005 .

[16]  Hiroshi Iwai,et al.  On the scaling issues and high-κ replacement of ultrathin gate dielectrics for nanoscale MOS transistors , 2006 .

[17]  F. J. Himpsel,et al.  Microscopic structure of the SiO 2 /Si interface , 1988 .

[18]  Martin P. Seah,et al.  Ultrathin SiO2 on Si IV. Intensity measurement in XPS and deduced thickness linearity , 2003 .

[19]  E. Vogel,et al.  A comparison of quantum-mechanical capacitance-voltage simulators , 2001, IEEE Electron Device Letters.

[20]  J. Robertson High dielectric constant gate oxides for metal oxide Si transistors , 2006 .

[21]  Je-Hun Lee,et al.  Thermal stability and structural characteristics of HfO2 films on Si (100) grown by atomic-layer deposition , 2002 .

[22]  Y. Taur,et al.  Quantum-mechanical modeling of electron tunneling current from the inversion layer of ultra-thin-oxide nMOSFET's , 1997, IEEE Electron Device Letters.

[23]  Jane P. Chang,et al.  Infrared spectroscopic analysis of the Si/SiO2 interface structure of thermally oxidized silicon , 2000 .

[24]  M. Harada,et al.  Significant enhancement of Si oxidation rate at low temperatures by atmospheric pressure Ar/O2 plasma , 2007 .

[25]  Norbert Kaiser,et al.  A comparative study of the UV optical and structural properties of SiO2, Al2O3, and HfO2 single layers deposited by reactive evaporation, ion-assisted deposition and plasma ion-assisted deposition , 2002 .

[26]  D. P. Woodruff,et al.  A medium energy ion scattering study of the structure of Sb overlayers on Cu(111) , 1999 .

[27]  Eduard A. Cartier,et al.  Physical and electrical characterization of Hafnium oxide and Hafnium silicate sputtered films , 2001 .

[28]  F. Giustino,et al.  Infrared properties of ultrathin oxides on Si(100) , 2005 .

[29]  D. G. Armour,et al.  Radiation damage in silicon (001) due to low energy (60–510 eV) argon ion bombardment , 1990 .

[30]  V. Afanas’ev,et al.  Electrical activity of interfacial paramagnetic defects in thermal (100) Si/SiO2 , 1998 .

[31]  N. Johnson,et al.  Interface traps and Pb centers in oxidized (100) silicon wafers , 1986 .