Characterization of HafSOx inorganic photoresists using electron stimulated desorption

Inorganic resists are of interest for nanomanufacturing due to the potential for high resolution, low line width roughness, and high sensitivity. The combination of high absorption coefficient elements and radiation sensitive ligands can improve inorganic resist sensitivity while still allowing high contrast for extreme ultraviolet (EUV) lithography. A prototypical resist is Hf(OH)4-2x-2y(O2)x(SO4)y·qH2O (HafSOx), which has both high absorption coefficient elements (Hf) and radiation sensitive ligands (peroxides). Herein, we evaluate the use of electron stimulated desorption (ESD) to characterize HafSOx. These results indicate that the peroxo species are extremely radiation sensitive, even for low kinetic energy electrons that approximate the range of electron energies expected during EUV exposures. The primary desorption products from HafSOx are O2 and H2O, where the time evolution suggest much faster desorption kinetics for O2. These data provide insight into the radiation-induced changes responsible for the solubility transition upon exposure and dissolution during development, and the role of low kinetic energy electrons in these processes. The following describes our experimental methodology for the ESD studies, and the specific kinetic model used to extract total desorption cross sections from the ESD data.

[1]  Douglas A. Keszler,et al.  Patterning chemistry of HafSOx resist , 2014, Advanced Lithography.

[2]  R. Gomer,et al.  Desorption from Metal Surfaces by Low‐Energy Electrons , 1964 .

[3]  P. Redhead INTERACTION OF SLOW ELECTRONS WITH CHEMISORBED OXYGEN , 1964 .

[4]  W. Casey,et al.  Hafnium sulfate prenucleation clusters and the Hf(18) polyoxometalate red herring. , 2014, Inorganic chemistry.

[5]  J. Stowers,et al.  High resolution, high sensitivity inorganic resists , 2009 .

[6]  G. Kimmel,et al.  Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO2(110) , 2015 .

[7]  W. A. Dench,et al.  Quantitative electron spectroscopy of surfaces: A standard data base for electron inelastic mean free paths in solids , 1979 .

[8]  T. Orlando,et al.  Electron-Stimulated Oxidation of Thin Water Films Adsorbed on TiO2(110) , 2007 .

[9]  D. Lichtman,et al.  Electron stimulated desorption: A critical review , 1977 .

[10]  Characterization of Electron Beams in Multiple Welders Using the Enhanced Modified Faraday Cup , 2006 .

[11]  Alan J. Telecky,et al.  In‐situ characterization of aqueous‐based hafnium oxide hydroxide sulfate thin films , 2014 .

[12]  Feixiang Luo,et al.  Chemical and structural investigation of high-resolution patterning with HafSO(x). , 2014, ACS applied materials & interfaces.

[13]  Y. Ekinci,et al.  Beyond EUV lithography: a comparative study of efficient photoresists' performance , 2015, Scientific Reports.

[14]  R. D. Ramsier,et al.  Electron-stimulated desorption: Principles and applications , 1991 .