Atomic Layer Deposition of AlF3 Using Trimethylaluminum and Hydrogen Fluoride

The atomic layer deposition (ALD) of AlF3 was demonstrated using trimethylaluminum (TMA) and hydrogen fluoride (HF). The HF source was HF-pyridine. In situ quartz crystal microbalance (QCM), quadrupole mass spectrometer (QMS), and Fourier transform infrared (FTIR) spectroscopy measurements were used to study AlF3 ALD. The AlF3 ALD film growth was examined at temperatures from 75 to 300 °C. Both the TMA and HF reactions displayed self-limiting behavior. The maximum mass gain per cycle (MGPC) of 44 ng/(cm2 cycle) for AlF3 ALD occurred at 100 °C. The MGPC values decreased at higher temperatures. The MGPC values were negative at T > 250 °C when TMA and HF were able to etch the AlF3 films. Film thicknesses were also determined using ex situ X-ray reflectivity (XRR) and spectroscopic ellipsometry (SE) measurements. The AlF3 ALD growth rate determined by the ex situ analysis was 1.43 A/cycle at 100 °C. These ex situ measurements were in excellent agreement with the in situ QCM measurements. FTIR analysis monitor...

[1]  Akira Tanaka,et al.  Optical properties of fluoride thin films deposited by RF magnetron sputtering. , 2006, Applied optics.

[2]  N. I. Giricheva,et al.  Structure and vibrational frequencies of aluminum trifluoride and gallium trifluoride , 1986 .

[3]  G. Scholz,et al.  Spectroscopic characterization of crystalline AlF3 phases , 2010 .

[4]  G. Olah,et al.  SYNTHETIC METHODS AND REACTIONS PART 2, HYDROFLUORINATION OF ALKENES, CYCLOPROPANE AND ALKYNES WITH POLY‐HYDROGEN FLUORIDE/PYRIDINE (TRIALKYLAMINE) REAGENTS , 1973 .

[5]  S. George,et al.  Atomic layer etching of Al2O3 using sequential, self-limiting thermal reactions with Sn(acac)2 and hydrogen fluoride. , 2015, ACS nano.

[6]  J. Yates,et al.  Transmission infrared spectroscopy of high area solid surfaces. A useful method for sample preparation , 1992 .

[7]  H. Macleod,et al.  Densification of aluminum fluoride thin films by ion-assisted deposition , 1988 .

[8]  P. Ayotte,et al.  Why is hydrofluoric acid a weak acid? , 2005, The Journal of chemical physics.

[9]  Cheng-Chung Lee,et al.  Characterization of AlF3 thin films at 193 nm by thermal evaporation. , 2005, Applied optics.

[10]  S. George,et al.  Pyrolysis of Alucone Molecular Layer Deposition Films Studied Using In Situ Transmission Fourier Transform Infrared Spectroscopy , 2015 .

[11]  Bruno Scrosati,et al.  The Role of AlF3 Coatings in Improving Electrochemical Cycling of Li‐Enriched Nickel‐Manganese Oxide Electrodes for Li‐Ion Batteries , 2012, Advanced materials.

[12]  A. Barrière,et al.  Optical transitions in disordered thin films of the ionic compounds MgF(2) and AIF(3) as a function of their conditions of preparation. , 1977, Applied optics.

[13]  S. George.  Atomic layer deposition: an overview. , 2010, Chemical reviews.

[14]  Alexander Gottwald,et al.  Experimental determination of optical constants of MgF2 and AlF3 thin films in the vacuum ultra-violet wavelength region (60-124 nm), and its application to optical designs , 2010 .

[15]  Yong Yang,et al.  The Effects of AlF3 Coating on the Performance of Li [ Li0.2Mn0.54Ni0.13Co0.13 ] O2 Positive Electrode Material for Lithium-Ion Battery , 2008 .

[16]  S. George,et al.  Molecular layer deposition of aluminum alkoxide polymer films using trimethylaluminum and glycidol. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[17]  Mikko Heikkilä,et al.  Atomic Layer Deposition of AlF3 Thin Films Using Halide Precursors , 2015 .

[18]  W. Heitmann.  Vacuum evaporated films of aluminum fluoride , 1970 .

[19]  J. Hennessy,et al.  Atomic layer deposition of magnesium fluoride via bis(ethylcyclopentadienyl)magnesium and anhydrous hydrogen fluoride , 2015 .

[20]  Ding Shi-jin,et al.  FTIR Characterization of Fluorine Doped Silicon Dioxide Thin Films Deposited by Plasma Enhanced Chemical Vapor Deposition , 2000 .

[21]  Steven M. George,et al.  Al3O3 thin film growth on Si(100) using binary reaction sequence chemistry , 1997 .

[22]  R. Staley,et al.  Reactions of titanium tetrachloride and trimethylaluminum at silica surfaces studied by using infrared photoacoustic spectroscopy , 1983 .

[23]  K. Amine,et al.  Effect of AlF3 Coating on Thermal Behavior of Chemically Delithiated Li0.35[Ni1/3Co1/3Mn1/3]O2 , 2010 .

[24]  Steven M. George,et al.  Viscous flow reactor with quartz crystal microbalance for thin film growth by atomic layer deposition , 2002 .

[25]  Ji‐Guang Zhang,et al.  Enhanced performance of graphite anode materials by AlF3 coating for lithium-ion batteries , 2012 .

[26]  P. A. Giguère,et al.  SPECTRE INFRAROUGE DE HF À L'ÉTAT CRISTALLIN , 1958 .

[27]  S. F. Pellicori,et al.  Fluoride compounds for IR coatings , 1992 .

[28]  Steven M. George,et al.  Atomic Layer Deposition of Al 2 O 3 Films on Polyethylene Particles , 2004 .

[29]  D. Zahn,et al.  Band diagram of the AlF3/SiO2/Si system , 2005 .

[30]  Yusuke Taki,et al.  Film structure and optical constants of magnetron-sputtered fluoride films for deep ultraviolet lithography , 2004 .

[31]  W. Farneth,et al.  The design and synthesis of Heterogeneous Catalyst Systems , 1996 .

[32]  H. Pulker,et al.  Characterization of optical thin films. , 1979, Applied optics.

[33]  Masanobu Hasegawa,et al.  Development of optical coatings for 157-nm lithography. I. Coating materials. , 2002, Applied optics.

[34]  J. Weidlein,et al.  Die schwingungsspektren von dimethyl- und diäthylaluminiumfluorid , 1968 .

[35]  Steven M. George,et al.  Atomic Layer Etching of HfO2 Using Sequential, Self-Limiting Thermal Reactions with Sn(acac)2 and HF , 2015 .

[36]  E. Kemnitz,et al.  Fluorinated metal oxides and metal fluorides as heterogeneous catalysts , 1998 .

[37]  N. Harrison,et al.  Adsorption of HF and HCl on the beta-AlF3 (100) surface. , 2008, Physical chemistry chemical physics : PCCP.

[38]  Robert D. Shannon,et al.  Refractive Index and Dispersion of Fluorides and Oxides , 2002 .

[39]  E. Kemnitz,et al.  Amorphous metal fluorides with extraordinary high surface areas. , 2003, Angewandte Chemie.

[40]  E. Kemnitz,et al.  Vibrational Analysis Study of Aluminum Trifluoride Phases , 2007 .