Diamondoids are molecular versions of diamond.
The yellow cage embedded in the blue diamond lattice is the smallest
diamondoid, adamantane.
Materials for electron emitters have long been sought because
electrons emitted into vacuum can be precisely controlled and easily
integrated into elaborate devices. They lie at the heart of a number
of modern technologies, such as field-emission flat-screen displays,
electron microscopes, electron lithography, and next-generation
free-electron lasers. For electron emitters, one of the biggest
challenges is to develop large, uniform surfaces that emit electrons
with a sharp energy distribution.
In the late 1970s, scientists found that hydrogen-terminated diamond
surfaces are characterized by negative electron affinity (NEA),
meaning for electrons, the energy level of the vacuum is lower
than that of the diamond conduction bands. At surfaces with NEA,
electrons excited into the conduction band will spontaneously fall
out into vacuum even at low temperature. Thus, NEA-based electron
emitters have several advantages over conventional emitters. They
exhibit electron emission at extremely low bias voltage (zero in
the ideal case), and the energy distribution of the emitted electron
is extremely narrow. However, two critical issues prevented NEA
semiconductors from being used in commercialized products. One
is the nonuniform emission normally observed on diamond surfaces.
The other is the difficulty of supplying electrons to the emission
surface, because diamond and other NEA semiconductors are wide-gap
materials with low electron conductivity.
Diamondoids, being diamond-like nanoclusters, provide us with
the opportunity to sustain the NEA feature of diamond while avoiding
the conventional problems of bulk NEA materials. Toward this end,
the collaborators replaced one of the hydrogen atoms on the surface
of tetramantane (four-cage diamondoids) with a thiol group (hydrogen
+ sulfur). This substitution chemically "functionalizes" the
tetramantane, i.e., it promotes bonding with other molecules, enabling
it to form more complex structures, like nanosized tinker toys.
The researchers found that these diamondoid–thiol complexes
would then self-assemble into a uniform monolayer on metal surfaces
such as silver or gold.
Tetramantane (inset) consists of four diamond cages fused together
and terminated with hydrogen. After being functionalized by the
replacement of one of the hydrogen atoms by a thiol group (yellow
tip), the molecules will self-assemble into large-area monolayers
on metal surfaces (purple).
Photoelectron spectroscopy was then performed on the tetramantane–thiol
monolayers at Beamline 10.0.1, where a strong, sharp peak was detected.
The outstanding peak observed in the spectra is a strong indication
of NEA. Furthermore, up to 68% of all the emitted electrons were
within this single energy peak, with a width of less than 0.5 eV.
This is several times as strong as the same measurement for bulk
diamond. Technologically, this means most electrons are emitted
from the diamondoid monolayer at the same energy, i.e., speed.
Photoelectron spectrum of tetramantane–thiol
self-assembled monolayers grown on a silver substrate. The intensity
of the emission peak at about 1 eV exceeds all valence-band features
and includes 68% of the total electron yield. Even with a logarithmic
plot (inset), one can still see a sharp feature rather than the
typical exponential decay of secondary electrons in this energy
range.
The result directly shows that diamondoid monolayers can be superior
to conventional materials as electron emitters. The molecules can
be purified and functionalized under precise control. They can
be inexpensively self-assembled into large-area, uniform monolayers.
More importantly, they perform better than previous materials in
terms of the energy distribution of the emitted electrons. Further
investigations are under way to fully understand this striking
phenomenon, as well as to make real devices based on diamondoids.
Research conducted by W.L. Yang, N. Mannella, K. Tanaka, and X.J.
Zhou (Stanford University and ALS); J.D. Fabbri, W. Meevasana,
M.A. Kelly, N.A. Melosh, and Z.-X. Shen (Stanford University);
T.M. Willey, J.R.I. Lee, and T. van Buuren (Lawrence Livermore
National Laboratory); J.E. Dahl and R.M.K. Carlson (MolecularDiamond
Technologies, Chevron Technology Ventures); P.R. Schreiner, B.A.
Tkachenko, and N.A. Fokina (Justus-Liebig University, Germany);
A.A. Fokin (Justus-Liebig University, Germany, and Kiev Polytechnic
Institute, Ukraine); and Z. Hussain (ALS).
Research funding: U.S. Department of Energy, Office of Basic Energy
Sciences (BES). Operation of the ALS is supported by BES.
Publication about this research: W.L. Yang, J.D. Fabbri, T.M.
Willey, J.R.I. Lee, J.E. Dahl, R.M.K. Carlson, P.R. Schreiner,
A.A. Fokin, B.A. Tkachenko, N.A. Fokina, W. Meevasana, N. Mannella,
K. Tanaka, X.J. Zhou, T. van Buuren, M.A. Kelly, Z. Hussain, N.A.
Melosh, and Z.-X. Shen, "Monochromatic electron photoemission
from diamondoid monolayers," Science 316,
1460 (2007). |