Atomic Layer Deposition of Metal Fluorides Using HF–Pyridine as the Fluorine Precursor

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• 作者：Younghee Lee ; Huaxing Sun ; Matthias J. Young ; Steven M. George
• 刊名：Chemistry of Materials
• 出版年：2016
• 出版时间：April 12, 2016
• 年：2016
• 卷：28
• 期：7
• 页码：2022-2032
• 全文大小：687K
• 年卷期：0
• ISSN：1520-5002

文摘

The atomic layer deposition (ALD) of a variety of metal fluorides including ZrF₄, MnF₂, HfF₄, MgF₂, and ZnF₂ was demonstrated using HF from a HF–pyridine solution. In situ quartz crystal microbalance (QCM) studies were utilized to examine the growth of these metal fluorides. ZrF₄ ALD using tetrakis(ethylmethylamido) zirconium and HF as the reactants was studied as a model system. The QCM measurements determined a mass gain per cycle (MGPC) of 35.5 ng/(cm² cycle) for ZrF₄ ALD at 150 °C. This MGPC was equivalent to a growth rate of 0.9 Å/cycle at 150 °C. MnF₂, HfF₄, MgF₂, ZnF₂, and additional ZrF₄ were also grown using bis(ethylcyclopentadienyl) manganese, tetrakis(dimethylamido) hafnium, bis(ethylcyclopentadienyl) magnesium, diethylzinc, and zirconium tetra-tert-butoxide as the metal precursors, respectively. The growth rates for MnF₂, HfF₄, MgF₂, ZnF₂, and ZrF₄ ALD were 0.4, 0.8, 0.4, 0.7, and 0.6 Å/cycle, respectively, at 150 °C. All of these metal fluoride ALD systems displayed self-limiting reactions. Ex situ measurements of the growth rates using X-ray reflectivity and spectroscopic ellipsometry analysis agreed with the in situ QCM measurements. Analysis of the QCM mass changes after the individual metal precursor and HF exposures quantified HF adsorption after the HF reaction. The ZrF₄ and HfF₄ films acted as strong Lewis acids and adsorbed an average of two HF per deposited MF_y species after the HF reaction. In contrast, the MnF₂, MgF₂, and ZnF₂ films all behaved as weak Lewis acids and did not adsorb HF after the HF reaction. The refractive indices of the metal fluoride films were in agreement with previous optical measurements. Most of the metal fluoride films were crystalline as measured by X-ray diffraction studies. The majority of the metal fluoride films also had high purity as established by X-ray photoelectron spectroscopy studies. This pathway for metal fluoride ALD using HF–pyridine as the fluorine precursor will be useful for many applications of metal fluoride films such as optical coatings in the ultraviolet wavelength region.