Influence of carrier gas pressure and flow rate on atomic layer deposition of HfO2 and ZrO2 thin films

Abstract Influence of the carrier gas on HfCl4–H2O and ZrCl4–H2O atomic layer processes was investigated. The growth rates of HfO2 and ZrO2 decreased with increasing flow rate and pressure of the N2 carrier gas. Data of real-time quartz crystal microbalance measurements demonstrated that the effect observed was mainly due to influence of carrier gas on surface reactions and the role of overlapping the precursor pulses was negligible. At the same increase of the carrier gas mass flow, the increase of the linear flow rate led to more significant changes of thin-film properties than the increase of the carrier gas pressure did. Thin films with higher density, higher refractive index and, particularly, lower concentration of residual chlorine were obtained at higher carrier gas flow rates. Increase of the carrier gas flow rate also resulted in a higher concentration of a metastable phase in HfO2 thin films deposited at 300 °C.

[1]  D. Aspnes Reflectance-difference spectroscopy: a new probe of crystal growth by MBE and OMCVD , 1989 .

[2]  I. D. Brown,et al.  INORGANIC CRYSTAL STRUCTURE DATABASE , 1981 .

[3]  K. Kukli,et al.  Effect of selected atomic layer deposition parameters on the structure and dielectric properties of hafnium oxide films , 2004 .

[4]  Mikko Ritala,et al.  Zirconium dioxide thin films deposited by ALE using zirconium tetrachloride as precursor , 1994 .

[5]  Jaan Aarik,et al.  Atomic layer deposition of polycrystalline HfO2 films by the HfI4–O2 precursor combination , 2003 .

[6]  K. Hashimoto,et al.  TiO2 Thin Films Prepared by Pulsed Beam Chemical Vapor Deposition from Titanium Tetraisopropoxide and Water , 1992 .

[7]  D. Choi,et al.  Characterization of Ultra-Thin HfO$_2$ Gate Oxide Prepared by Using Atomic Layer Deposition , 2003 .

[8]  Mikko Ritala,et al.  Comparison of hafnium oxide films grown by atomic layer deposition from iodide and chloride precursors , 2002 .

[9]  Mikko Ritala,et al.  Effect of water dose on the atomic layer deposition rate of oxide thin films , 2000 .

[10]  M. Ritala,et al.  Reaction mechanism studies on the zirconium chloride–water atomic layer deposition process , 2002 .

[11]  C. Musgrave,et al.  A quantum chemical study of ZrO2 atomic layer deposition growth reactions on the SiO2 surface , 2004 .

[12]  I. Ibrahim,et al.  Polymorphic Behavior of Thin Evaporated Films of Zirconium and Hafnium Oxides , 1970 .

[13]  J. Aarik,et al.  Texture development in nanocrystalline hafnium dioxide thin films grown by atomic layer deposition , 2000 .

[14]  K. Kukli,et al.  Dielectric Permittivity and Intercalation Parameters of Li Ion Intercalated Atomic Layer Deposited ZrO2 , 2004 .

[15]  S.-L. Zhang,et al.  Influence of surface treatment prior to ALD high-/spl kappa/ dielectrics on the performance of SiGe surface-channel pMOSFETs , 2004, IEEE Electron Device Letters.

[16]  J. Bartlett,et al.  IR Spectroscopy of Surface Water and Hydroxyl Species on Nanocrystalline TiO2 Films , 2001 .

[17]  D. Estève,et al.  DFT investigation of HfCl4 decomposition on hydroxylated SiO2: first stage of HfO2 atomic layer deposition , 2003 .

[18]  J. Aarik,et al.  Influence of substrate temperature on atomic layer growth and properties of HfO2 thin films , 1999 .

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

[20]  Krishna C. Saraswat,et al.  Atomic layer deposition of ZrO2 on W for metal-insulator-metal capacitor application , 2003 .

[21]  M. Ritala,et al.  Development of crystallinity and morphology in hafnium dioxide thin films grown by atomic layer epitaxy , 1994 .

[22]  A. Nakajima,et al.  Growth and electrical properties of atomic-layer deposited ZrO2 /Si-nitride stack gate dielectrics , 2004 .

[23]  A. Chin,et al.  A high-density MIM capacitor (13 fF/μm/sup 2/) using ALD HfO2 dielectrics , 2003, IEEE Electron Device Letters.

[24]  S. Ferrari,et al.  Combining grazing incidence X-ray diffraction and X-ray reflectivity for the evaluation of the structural evolution of HfO2 thin films with annealing , 2004 .

[25]  Mikko Ritala,et al.  Atomic layer deposition of HfO2 thin films and nanolayered HfO2–Al2O3–Nb2O5 dielectrics , 2003 .

[26]  Cheol Seong Hwang,et al.  Chemical interaction between atomic-layer-deposited HfO2 thin films and the Si substrate , 2002 .

[27]  M. Ritala,et al.  Titanium isopropoxide as a precursor in atomic layer epitaxy of titanium dioxide thin films , 1993 .

[28]  Thomas E. Seidel,et al.  Thin film atomic layer deposition equipment for semiconductor processing , 2002 .

[29]  Riikka L. Puurunen,et al.  Analysis of hydroxyl group controlled atomic layer deposition of hafnium dioxide from hafnium tetrachloride and water , 2004 .

[30]  Ho-Kyu Kang,et al.  Atomic layer deposition of zirconium silicate films using zirconium tetrachloride and tetra-n-butyl orthosilicate , 2002 .

[31]  J. Aarik,et al.  Growth kinetics and structure formation of ZrO2 thin films in chloride-based atomic layer deposition process , 2002 .

[32]  Wilfried Vandervorst,et al.  Nucleation and growth of atomic layer deposited HfO2 gate dielectric layers on chemical oxide (Si–O–H) and thermal oxide (SiO2 or Si–O–N) underlayers , 2002 .

[33]  M. Leskelä,et al.  In situ study of a strontium β-diketonate precursor for thin-film growth by atomic layer epitaxy , 1994 .

[34]  H. Brongersma,et al.  Sequential saturating reactions of ZrCl4 and H2O vapors in the modifications of silica and g-Alumina with ZrO2 , 1997 .

[35]  A. Root,et al.  Controlled Formation of ZrO2 in the Reaction of ZrCl4 Vapor with Porous Silica and γ-Alumina Surfaces , 1996 .

[36]  R. Kuse,et al.  Effect of precursor concentration in atomic layer deposition of Al2O3 , 2003 .

[37]  D. Lincot,et al.  Synthesis of ZrO2 thin films by atomic layer deposition: growth kinetics, structural and electrical properties , 2002 .