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Graduate Exam Abstract


Ilya Kuznetsov

Ph.D. Final
March 2, 2018, 3:00 pm - 5:00 pm
ERC Electronic Classroom A210
Extreme Ultraviolet Laser Ablation Mass Spectrometer for Molecular Imaging at the Nanoscale

Abstract: The demand for high-precision
analytical instrumentation in modern
science and technology is exploding.
The quality of questions to be
answered sets the requirements for a
given piece of technology. The type of
analytical instrumentation that enables
users to unambiguously identify,
quantify, and map the chemical
structure of a solid is imaging mass
spectrometry (IMS). Most common
commercially available instruments
include desorption electrospray
ionization (DESI), matrix-assisted laser
desorption and ionization (MALDI),
and secondary ion mass spectrometry
(SIMS) as well as their derivatives.
Each of these instruments possesses
a set of capabilities that define its use
for one or another research task. None
of them, however, enables scientists to
map a solid’s molecular composition in
three dimensions at the nanoscale.
We have developed an extreme
ultraviolet laser ablation time-of-flight
mass spectrometer (EUV TOF) that
relies on sample probing by a 46.9 nm
laser. In this work, the unique
interaction of EUV light with matter
was experimentally assessed and
compared to SIMS TOF. It was found
that the spatial resolution can be as
small as 80 nm in molecular and
atomic analysis in organic and
inorganic materials respectively. Depth
resolution is as high as 20 nm as
measured on an organic bilayer.
Sensitivity of the EUV TOF reaches
~0.02 amol, which is estimated to be
20× better than that of SIMS TOF in
the sample of the amino acid alanine.
Sensitivity in other units—sample
utilization efficiency—was found to be
similar to SIMS TOF when assessed
by means of detecting trace actinides
in a glass matrix. It was shown that it
can be further improved by means of
post-ablation ionization (PI) with a
secondary UV laser source. Using
vacuum ultraviolet (VUV) laser light
can increase the mass range of
molecular detection. For instance, an
intact cholesterol molecule was first
detected by the EUV TOF instrument
operating in VUV PI mode. This
approach opens a range of
opportunities to use the technique for
biological studies.
EUV TOF is capable to image
chemical composition. This capability
is demonstrated by imaging the 3D
nanoscale spatial distribution of low
mass fragments in a single
mycobacterium. With additional
instrumental modifications, it will be
possible to achieve sub-cellular
imaging of the molecular structure of a
single microorganism without the need
for using a matrix. Such capabilities
may also help to steer the
development of new drugs in
pharmacology and identify the
signature isotope pattern of the
miniscule bits of material examined by
nuclear scientists.


Adviser: Carmen Menoni
Co-Adviser: NA
Non-ECE Member: Elliot Bernstein, Chemistry
Member 3: Dean Crick, Microbiology, Immunology and Pathology
Addional Members: Diego Krapf, Electrical and Computer Engineering; Jorge Rocca, Physics

Publications:
Kuznetsov, I., Filevich, J., Dong, F., Woolston, M., Chao, W. L., Anderson, E. H., Bernstein, E. R., Crick, D. C., Rocca, J. J. and Menoni, C. S., “Three-dimensional nanoscale molecular imaging by extreme ultraviolet laser ablation mass spectrometry,” Nature Communications, 6, 2015
Green, T., Kuznetsov, I., Willingham, D., Naes, B. E., Eiden, G. C., Zhu, Z., Chao, W., Rocca, J. J., Menoni, C. S., Duffin, A. M., “Characterization of extreme ultraviolet laser ablation mass spectrometry for actinide trace analysis and nanoscale isotopic imaging,” J. Anal. At. Spectrom., 2017
Kuznetsov, I., Filevich, J., Dong, F., Woolston, M., Chao, W. L., Anderson, E. H., Bernstein, E. R., Crick, D. C., Rocca, J. J. and Menoni, C. S., “Nanoscale Mass-Spectral Imaging in 3-D,” OPN 2015
Aslanyan, V., Kuznetsov, I., Bravo, H., Woolston, M., Rossall, A. K., Menoni, C. S., Rocca, J. J. and Tallents, G. J., “Ablation and transmission of thin solid targets irradiated by intense extreme ultraviolet laser radiation,” APL Photonics 1, 066101, 2016
Rossall, A. K., Aslanyan, V., Tallents, G. J., Kuznetsov, I., Rocca, J. J. and Menoni, C. S., “Ablation of Submicrometer Holes Using an Extreme-Ultraviolet Laser,” Physical Review Applied, 3(6), 2015
Kuznetsov, I., Burian, T., Juha, L., Soufli, R., Filevich, J., Woolston, M., Bernstein, E. R., Crick, D. C., Carlton, D., Chao, W., Anderson, E. H., Rocca, J. J. and Menoni, C. S., “Soft X-Ray Laser Ablation Mass Spectrometry for Materials Study and Nanoscale Chemical Imaging,” Proc. of SPIE, 958905-1, 2015
Kuznetsov, I., Filevich, J., Woolston, M., Bernstein, E. R., Crick, D. C., Carlton, D., Chao, W., Anderson, E. H., Rocca, J. J. and Menoni, C. S., “Volumetric Composition Imaging at the Nanoscale by Soft X-Ray Laser Ablation Mass Spectrometry,” ICXRL, Springer Proceedings in Physics 169, 2014
Kuznetsov, I., Filevich, J., Woolston, M., Bernstein, E. R., Crick, D. C., Carlton, D., Chao, W., Anderson, E. H., Rocca, J. J. and Menoni, C. S., “Composition Depth Profiling by Soft X-Ray Laser-Ablation Mass Spectrometry,” Proc. of SPIE, 8849, 88490G, 2013


Program of Study:
ECE 504
ECE 506
ECE 526
ECE 574
ECE 650
ECE 673
NA
NA