Optical Properties and Application of Uranium-based Thin-Films for the Extreme Ultraviolet and Soft X-ray Region Richard L. Sandberg, David D. Allred, Marie K. Urry, Shannon Lunt, R. Steven Turley Thanks to Fellow EUV Members: Jed E. Johnson, Winston Larson, Kristi R. Adamson, Nikki Farnsworth, William R. Evans, and others from EUV Group, Andy Aguila & Eric Gullickson at ALS/CXRO Funding: SPIE Scholarship, BYU Physics Dept. Funding, BYU ORCA Scholarship BYU EUV Optics August 4, 2004 Why Extreme Ultraviolet (EUV) and Soft X-Rays? Thin Film or Multilayer Mirrors EUV Lithography (making really small computer chips) EUV Astronomy Soft X-Ray Microscopes BYU EUV Optics The Earth’s magnetosphere in the EUV Images from www.schott.com/magazine/english/info99/ and www.lbl.gov/Science-Articles/Archive/xray-inside-cells.html. August 4, 2004 Why Uranium? • • • • BYU EUV Optics August 4, 2004 Pros: high density and many electrons (92) for absorption, high theoretical reflectivity: low absorption and high index of refraction Con: chemically reactive (oxidizes in air to most abundant natural oxide UO2 at STP) We study different compounds of uranium, such as uranium dioxide (UO2) and uranium mononitride (UN), in search of compounds with the highest reflectance and most chemical stability. Previous Success: IMAGE Satellite Mirror Project—BYU uranium based mirrors (Launched March 25, 2000) Delta vs. beta plot for several elements at 4.48 nm 4.48nm Note: Nickel and its neighboring 3d elements are the nearest to uranium in this area. BYU EUV Optics ~ n ik 1 i n r 1 n, August 4, 2004 k Computed Reflectance at 10 degrees of various materials 0.9 0.8 Reflectance 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 2 4 6 8 Au 10 12 Wavelength (nm) Ni UO2 14 U 16 Ir BYU EUV Optics Reflectance computed using the CXRO Website: http://www-cxro.lbl.gov/optical_constants/mirror2.html August 4, 2004 18 20 Sample Preparation The UO, UN, Ni, and Au samples were deposited on pieces polished silicon test wafers (100 orientation). Quartz crystal monitors were used to measure the sputtering and evaporation rates. •U DC Magnetron/RF Sputtering The uranium sputter targets used here were of depleted uranium metal (less than 0.2% U-235). UO2 deposited in two ways. Reactively sputtered (DC) in oxygen partial pressure (Lunt at oxygen partial pressure of 3x10-4 torr) or as pure uranium (RF) and then allowed to oxidize in ambient air. Uranium nitride was reactively sputtered (RF) in nitrogen partial pressure of about 10-5 torr. Schematic of DC magnetron sputtering system at BYU. BYU EUV Optics August 4, 2004 •Ni/Au Resistive Thermal Evaporation Evaporated Ni wire/Au beads from a resistively heated tungsten boat (RD Mathis Co.) in a large, cryopumped, stainless steel “bell jar” coater. •Ir Sample Prepared at Goddard Space Flight Center on Glass Slides Thickness Determined by XRD Film thickness (nm) 50 y = 40.398x2 - 116.4x + 109.12 R2 = 0.9995 45 40 35 UN (Dens.=14.3) 30 Poly. (UN (Dens.=14.3)) 25 0.6 BYU EUV Optics August 4, 2004 m λ = 2d sin θ 0.8 1 1.2 Theta (for 4 peaks) 1.4 •XRD Sample Thickness -UO2 30.0 nm (ρ=10.97 g/cm3) -UN 38.0 nm (ρ=10. g/cm3) -NiO on Ni 49.7 nm (ρ=6.67 g/cm3) -Au 29.5 nm (ρ=19.3 g/cm3) -Ir ?? (ρ=22.42 g/cm3) Oxidation of a UN Thin Film Percent change in thickness 115 110 105 IMD data Fit 100 95 BYU EUV Optics 1 August 4, 2004 10 Time (hrS.) 100 1000 Studying Our Samples Ellipsometry Scanning/Transmission Electron Microscopes (SEM/TEM) X-ray Photoelectron Spectroscope (XPS) Atomic Force Microscopy (AFM) BYU EUV Optics August 4, 2004 Images courtesy of www.weizmann.ac.il/surflab/peter/afmworks, www.mos.org/sln/SEM/works/ 5 Taking Reflectance Measurements at the ALS (Advance Light Source) BYU EUV Optics August 4, 2004 • Small Discrepancies arise from one region to another with the use of different filters. •XANES Capability • Normalization given by R=(Idetector-Idark)/(Ibeam-Idark) Reflectance Beamline 6.3.2 Reflectometer • Bright synchrotron radiation • 1-24.8 nm range • High spectral purity • Energy/wavelength or θ-2θ scan capability Sample of Data from the ALS 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 2.5 Inage courtesy of http://www.lbl.gov/ 4.5 6.5 8.5 Wavelength (nm) 10.5 12.5 ALS Measured Reflectance Comparison at 5 deg 0.9 0.8 0.7 Reflectance 0.6 0.5 0.4 UO2 UN NiO on Ni Ir Au 0.3 0.2 0.1 0 2 BYU EUV Optics August 4, 2004 3 4 5 6 7 Wavelength (nm) 8 9 10 11 12 ALS Measured Reflectance Comparison at 10 deg 0.7 0.6 UO2 UN NiO on Ni Ir Au Reflectance 0.5 0.4 0.3 0.2 0.1 0 2 BYU EUV Optics August 4, 2004 4 6 8 Wavelength (nm) 10 12 ALS Measured Reflectance Comparison @ 15 deg 0.5 UO2 UN NiO on Ni Ir Au 0.45 0.4 Reflectance 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 BYU EUV Optics 4 5 6 7 8 Wavelength (nm) August 4, 2004 9 10 11 12 Calculating Optical Properties of Uranium Oxide and Uranium Nitride from Reflectance Lunt and Urry both used Kohn and Parratt’s equations to calculate reflectance from previously published value of δ and β. The values of δ and β were then adjusted until the difference between the measured reflectance and calculated reflectance were minimized. The measured reflectance scans were angle scans from the ALS. Urry studied uranium nitride and Lunt studied uranium oxide. rs ,m C 4 m f s ,m rs ,m 1 1 f s ,m rs ,m 1 rp ,m C 4 m f p ,m rp ,m 1 1 f p ,m rp ,m 1 where f s ,m qm qm1 qm qm1 qm N m2 cos 2 i f p ,m N m2 1qm N m2 qm1 2 N m1qm N m2 qm1 C m e iqm Dm / V.G. Kohn. Phys. Stat. Sol. 185(61), 61-70 (1995), L.G. Parratt. Physical Review 95 (2), 359-369 (1954). Optical Properties of Uranium Oxide and Uranium Nitride δ and β of UN from M. Urry λ (nm) 13 0.01152 0.0595 14 0.0138 0.0416 Lunt found that her samples were mostly UO2 with a top layer of an slightly higher oxidation state. δ and β of UO2 obtained from S. Lunt’s Thesis CXRO Calculated ALS Measured λ (nm) β δ δ and β of UOx Top layer obtained from Lunt β δ ALS Measured λ (nm) β δ 4.6 0.0065 8.09E-04 0.0116 0.0011 4.6 0.0065 0.0011 5.6 0.0103 0.0012 0.0187 0.0025 5.6 0.0103 0.0016 6.8 0.0173 0.004 0.0302 0.0065 6.8 0.0161 0.0031 8.5 0.0298 0.0151 0.0491 0.0271 8.5 0.0295 0.0134 10 0.0344 0.0458 0.0674 0.0693 10 0.0398 0.0269 12.5 -0.0038 0.0129 0.0057 0.0399 12.5 0.0206 0.0091 14 0.0229 0.0103 0.0509 0.017 14 0.0360 0.0151 15.5 0.0362 0.0158 0.0782 0.0281 15.5 0.0495 0.0216 17.5 0.0547 0.0246 0.1058 0.0464 17.5 0.0639 0.0338 Reflectance Measured Data compared with CXRO Previously Published Constants 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 UOx Comp UO2 Comp UO2 with C cap 2.5 3 3.5 Wavelength (nm) 4 4.5 5 1 0.9 Measured reflectance features do not agree with CXRO published constants. More work need to be done on measuring uranium’s optical constants. Reflectance 0.8 0.7 0.6 0.5 0.4 Measured UO2 Computed UO2 (d=30 nm) Computed UO2 with 0.5 nm C on top Computed UO2 with C(density=1.5g/cc) 3 nm 0.3 0.2 0.1 0 BYU EUV Optics August 4, 2004 2.5 4.5 6.5 8.5 Wavelength (nm) 10.5 12.5 XANES (X-Ray Absorption Near Edge Spectroscopy) XANES at ALS show additional absorption resonances not accounted for in Published Data at CXRO. Relative XANES Scans of UO2 and ThO2 Relative Intensity 1.8 U NVIOIV @ 286.3 eV * 1.6 ThO2 1.4 UO2 1.2 1 0.8 0.6 0.4 280 285 295 290 300 Energy (eV) BYU EUV Optics August 4, 2004 *D. R. Lide (ed.), CRC Handbook of Chemistry and Physics, 71st edition, CRC Press, Boca Raton, 1990-91, p.10-256. 305 Conclusions • • • UO2 and UN reflect significantly more • than Ni, Ir, and Au, the current materials with highest reflectance, between 4 and 9 nm. • U reflectance differs from the reflectance predicted by the previously published uranium optical properties. Current preparation of UN is not stable in ambient air (oxidizes to UO2). Need to test oxidation of heated UN sample BYU EUV Optics August 4, 2004 Goals Determine the optical properties of UO2 below Shannon’s data (4.5 nm) and fill out UN optical properties data. Work with CXRO to amend the current uranium optical properties. Questions? EUV Group Contact Dr. David Allred allred@byu.edu (801) 422-3489 THANK YOU!!