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Quantitative Energy Dispersive X-ray Microanalysis of Electron Beam-Sensitive Alloyed Nanoparticles

Published online by Cambridge University Press:  03 March 2008

Nadi Braidy ,
Zygmunt J. Jakubek ,
Benoit Simard  and
Gianluigi A. Botton
Nadi Braidy
Affiliation:
Department of Materials Science and Engineering, McMaster University and the Brockhouse Institute for Materials Research, Hamilton, ON L8S 4L7, Canada
Zygmunt J. Jakubek
Affiliation:
National Research Council of Canada, Steacie Institute for Molecular Sciences, Ottawa, ON K1A 0R6, Canada
Benoit Simard
Affiliation:
National Research Council of Canada, Steacie Institute for Molecular Sciences, Ottawa, ON K1A 0R6, Canada
Gianluigi A. Botton
Affiliation:
Department of Materials Science and Engineering, McMaster University and the Brockhouse Institute for Materials Research, Hamilton, ON L8S 4L7, Canada
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Abstract

An energy dispersive X-ray spectrometry (EDXS) method is developed to evaluate the composition of alloyed nanoparticles (NPs) where one of the alloying elements is removed under the electron beam during microanalysis with a transmission electron microscope (TEM). The method is demonstrated for alloyed Au-Ag NPs of a diameter ranging from 6 to 20 nm produced by laser evaporation of a water-suspended Ag-Au powder mixture of varying composition. Series of EDXS spectra are recorded for 30 NPs from samples with five different Ag:Au ratios revealing Ag depletion from NPs during electron irradiation. By studying the evolution of NPs composition as a function of dose, the initial Ag content for each NP is extrapolated. The rate of Ag depletion is discussed in terms of sputtering and knock-on damage. On average, approximately one Ag atom is lost from the NP for each Ag L X-ray detected. To assess the limitations of microanalysis in these sensitive nanoscale structures, the concept of detectability limit is adapted to our method. This benchmark is then evaluated for Ag in Au-Ag NPs of various sizes and acquisition times. This study should be regarded as a guide for the design of analytical TEM measurements of beam-sensitive NPs.

Keywords

nanoparticlesanalytical TEMenergy dispersive X-ray spectrometryelectron-beam damagesilvergold
Type
Research Article
Information
Microscopy and Microanalysis , Volume 14 , Issue 2 , April 2008 , pp. 166 - 175
Copyright
© 2008 Microscopy Society of America

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References

REFERENCES

Arepalli, S. (2004). Laser ablation process for single-walled carbon nanotube production. J Nanosci Nanotechnol 4, 317–325.Google Scholar
Chadderton, L.T. (1965). Radiation Damage in Crystals. London: Methuen, and New York: Wiley.
Cliff, G. & Lorimer, G.W. (1975). The quantitative analysis of thin specimens. J Microsc 103, 203–207.Google Scholar
Egerton, R.F., Li, P. & Malac, M. (2004). Radiation damage in the TEM and SEM. Micron 35, 399–409.Google Scholar
Egerton, R.F. & Rauf, I. (1999). Dose-rate dependence of electron-induced mass loss from organic specimens. Ultramicroscopy 80, 247–254.Google Scholar
Egerton, R.F. & Rossouw, C.J. (1976). Direct measurement of contamination and etching rates in an electron-beam. J Phys D: Appl Phys 9, 659–663.Google Scholar
Elghanian, R., Storhoff, J.J., Mucic, R.C., Letsinger, R.L. & Mirkin, C.A. (1997). Selective colorimetric detection of polynucleotides based on the distance-dependent optical properties of gold nanoparticles. Science 277, 1078–1081.Google Scholar
Feldheim, D.L. & Foss, C.A. (Eds.). (2001). Metal Nanoparticles: Synthesis Characterization & Applications. New York: Marcel Dekker.
Fiori, C.E., Swyt-Thomas, C. & Myklebust, B. (2003). Desktop Spectrum Analyzer (DTSA) 3.0.1. Gaithersburg, MD: National Institute of Standards and Technology. Available at http://www.cstl.nist.gov/div837/Division/outputs/DTSA/DTSA.htm. Accessed March 2006.
Goldstein, J.I., Costley, J.L., Lorimer, G.W. & Reed, S.J.B. (1977). SEM/77. Chicago: IITRI.
Goldstein, J.I., Williams, D.B. & Cliff, G. (1986). Quantitative x-ray analysis. In Principles of Analytical Electron Microscopy, Joy, D.C., Romig, A.D.J. & Goldstein, J.I. (Eds.), pp. 156–217. New York and London: Plenum Press.
Horita, Z., Sano, T. & Nemoto, M. (1987). Simplification of x-ray absorption correction in thin-sample quantitative microanalysis. Ultramicroscopy 21, 271–276.Google Scholar
Howitt, D.G. (1986). Radiation effects encountered by inorganic materials in analytical electron microscopy. In Principles of Analytical Electron Microscopy, Joy, D.C., Romig, A.D.J. & Goldstein, J.I. (Eds.), pp. 375–392. New York and London: Plenum Press.
Hren, J.J. (1986). Barriers to AEM: Contamination and etching. In Principles of Analytical Electron Microscopy, Joy, D.C., Romig, A.D.J. & Goldstein, J.I. (Eds.), pp. 353–374. New York and London: Plenum Press.
Jin, R., Cao, Y., Mirkin, C.A., Kelly, K.L., Schatz, G.C. & Zheng, J.G. (2001). Photoinduced conversion of silver nanospheres to nanoprisms. Science 294, 1901–1903.Google Scholar
Kelly, T.F. (1987). An experimental x-ray-detector efficiency function determined using pure submicron spheres—An approach to quantification. Ultramicroscopy 22, 175–189.Google Scholar
Kim, Y., Johnson, R.C. & Hupp, J.T. (2001). Gold nanoparticle-based sensing of “spectroscopically silent” heavy metal ions. Nano Lett 1, 165–167.Google Scholar
Kingston, C.T. & Simard, B. (2003). Fabrication of carbon nanotubes. Anal Lett 36, 3119–3145.Google Scholar
Leapman, R.D. & Hunt, J.A. (1991). Comparison of detection limits for EELS and EDXS. Microsc Microanal Microstruct 2, 231–244.Google Scholar
Liebhafsky, A.H., Pfeiffer, G.H. & Zemany, D.P. (1960). Reliability of trace determination by x-ray emission spectrography. In X-Ray Microscopy and X-Ray Microanalysis, Engström, A., Cosslett, V. & Pattee, H. (Eds.), pp. 321–330. Amsterdam, London, New York, Princeton: Elsevier Publishing Company.
Lyman, C.E., Hepburn, J.S. & Stenger, H.G. (1990). Quantitative Pt and Rh distributions in pollution-control catalysts. Ultramicroscopy 34, 73–80.Google Scholar
Oen, O.S. (1973). Cross-section for atomic displacements in solids by fast electrons. Report #TM-4897. Oak Ridge, TN: Oak Ridge National Laboratory.
Park, S.-J., Taton, T.A. & Mirkin, C.A. (2002). Array-based electrical detection of DNA with nanoparticle probes. Science 295, 1503–1506.Google Scholar
Romig, A.D.J. & Goldstein, J.I. (1979). Detectability limit and spatial resolution in STEM X-ray analysis: Application to Fe-Ni alloys. In Microbeam Analysis 1979, Newbury, D.E. (Ed.), pp. 124–128. San Francisco: San Francisco Press.
Sharma, A.K. & Gupta, B.D. (2006). Fibre-optic sensor based on surface plasmon resonance with Ag-Au alloy nanoparticle films. Nanotechnology 17, 124–131.Google Scholar
Shuman, H., Somlyo, A.V. & Somlyo, A.P. (1976). Quantitative electron-probe microanalysis of biological thin-sections—methods and validity. Ultramicroscopy 1, 317–339.Google Scholar
Storhoff, J.J., Elghanian, R., Mucic, R.C., Mirkin, C.A. & Letsinger, R.L. (1998). One-pot colorimetric differentiation of polynucleotides with single base imperfections using gold nanoparticle probes. J Am Chem Soc 120, 1959–1964.Google Scholar
Storhoff, J.J., Lazarides, A.A., Mirkin, C.A., Letsinger, R.L., Mucic, R.C. & Schatz, G.C. (2000). What controls the optical properties of DNA-linked gold nanoparticle assemblies? J Am Chem Soc 122, 4640–4650.Google Scholar
Taton, T.A., Mirkin, C.A. & Letsinger, R.L. (2000). Scanometric DNA array detection with nanoparticle probes. Science 289, 1757–1760.Google Scholar
Williams, D.B. & Carter, C.C. (1996). Spectrometry IV. In Transmission Electron Microscopy, pp. 632–633. New York: Plenum Press.
Wonnacott, H.T. & Wonnacott, J.R. (1981). Time series. In Regression: A Second Course in Statistics, pp. 208–277. New York, Chichester, Brisbane, Toronto: John Wiley & Sons.
Yudasaka, M., Kasuya, Y., Kokai, F., Takahashi, K., Takizawa, M., Bandow, S. & Iijima, S. (2002). Causes of different catalytic activities of metals in formation of single-wall carbon nanotubes. Appl Phys A: Mater Sci Process 74, 377–385.Google Scholar
Zhang, J., Worley, J., Dénommée, S., Kingston, C., Jakubek, Z.J., Deslandes, Y., Post, M., Simard, B., Braidy, N. & Botton, G.A. (2003). Synthesis of metal alloy nanoparticles in solution by laser irradiation of a metal powder suspension. J Phys Chem B 107, 6920–6923.Google Scholar
Ziebold, T.O. (1967). Precision and sensitivity in electron microprobe analysis. Anal Chem 39, 858–861.Google Scholar
Zreiba, N.A. & Kelly, T.F. (1988). Absorption and fluorescence corrections of characteristic X-rays from thin spheres. X-Ray Spectrom 17, 229–238.Google Scholar