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VAN DER WAALS HETEROSTRUCTURES

Rydberg spectroscopy of indirect excitons

Measuring the 1s–2p splitting of direct and indirect excitons in van der Waals heterostructures allows their binding
energy and dynamics to be determined.

Steven T. Cundiff

T
he field of two-dimensional materials a c
e– Energy
was launched by the discovery inter
Mid-infrared
waveform
of graphene and its unique x
WSe2 3s
properties, such as the linear dispersion h+
2p
relation for electrons, which results in WS2 WSe2
them mimicking photons1. However, tpp
the band structure of graphene also 1s

limited its applications in electronics b

NIR
and optoelectronics. This limitation WS2 Near-infrared
MIR
was overcome by the discovery of a new pump
class of two-dimensional materials, the
transition metal dichalcogenides, which
have a bandgap and are semiconductors
that interact strongly with light in the limit
of a single monolayer, especially when a
bound electron–hole pair, known as an Ky Kx
Centre-of-mass
exciton, is created2,3. Heterostructures of teos
momenta
transition metal dichalcogenides can be
made, which enhances their technological Fig. 1 | Excitonic transitions in heterostructures. a, Schematic of the interlayer excitons in a transition
relevance. Recently, heterostructures metal dichalcogenide heterostructure studied by Merkl and colleagues. b, Diagram of the experimental
that display charge separation have been method where the near-infrared (NIR) pulse creates intralayer excitons, where tpp is the time between
realized; however, it has been difficult pump and probe pulses and teos is the time over which electrooptic sampling is performed. c, The
to characterize charge-separated states subsequent mid-infrared (MIR) pulse monitors their conversion to interlayer excitons through the
optically because charge separation internal transitions of the excitons. Panel c courtesy of Philipp Merkl.
weakens their interaction with light.
As reported in Nature Materials, this
challenge has been overcome by P. Merkl
and colleagues4 using mid-infrared but in monolayers it is only ten times characterized the internal states of the
spectroscopy to probe the internal states of weaker due to lack of screening outside excitons by driving transitions between
the interlayer excitons. the monolayer. The binding energy of an them using a mid-infrared pulse (Fig. 1b).
Optical excitation of an undoped exciton in a monolayer of a transition metal This technique was originally pioneered to
semiconductor promotes an electron from dichalcogenide material was the subject of study excitons in gallium arsenide quantum
the valence band to the conduction band, some controversy because it is exquisitely wells where the internal transitions of the
resulting in an electron–hole pair. Since the sensitive to extrinsic influences such as the excitons lie in the terahertz spectral regime10.
electron and hole have opposite charges, they substrate, unintentional doping and the As the initial population of intralayer
can attract, just as an electron and proton excitation level5. excitons converted to interlayer, a new
do, resulting in a bound state of the electron Heterostructures of transition metal resonance appeared, which allowed them to
and hole known as an exciton. The relative dichalcogenides have attracted much both determine the binding energy of the
coordinate for the electron and hole bound attention because of the rich physics they interlayer excitons as well as the dynamics
in an exciton is hydrogenic, having a series can display, such as moiré excitons6–9. of the conversion process. By studying
of levels corresponding to different internal However, one of their more interesting samples with different twist angles between
states that are similar to those of a hydrogen excitations, an indirect exciton (also known the layers, they could determine the effect
atom. The binding energy of the electron and as an interlayer exciton), where the electron of the moiré confinement potential on
hole is much smaller than that of hydrogen and hole are in separate layers (Fig. 1a), has dynamics and binding energies. Comparison
atoms due to their much smaller effective proven hard to characterize due to weak to a detailed model provides evidence that
masses, compared to a bare electron or a interaction of light with both interlayer an intermediate state of unbound interlayer
proton, and the screening of the Coulomb excitons and interlayer unbound electron– electron–hole pairs is not present.
interaction, which is characterized by the hole pairs (the difference in their energies is These results provide important insight
dielectric constant of the host crystal. In the exciton binding energy). To circumvent into the strong Coulomb interactions
traditional semiconductors, such as gallium this, Merkl and colleagues created direct present in monolayers of transition metal
arsenide, the exciton binding energy is a excitons (also known as intralayer excitons) dichalcogenides and how they can be
thousand times weaker than hydrogen, with a near-infrared pump beam and then engineered by using heterostructures

658 Nature Materials | VOL 18 | JULY 2019 | 657–665 | www.nature.com/naturematerials

 news & views

of different materials with varying twist Arbor, MI, USA. 3. Splendiani, A. et al. Nano Lett. 10, 1271–1275
(2010).
angles. From an applied perspective, charge e-mail: [email protected] 4. Merkl, P. et al. Nat. Mater. https://doi.org/10.1038/s41563-019-
separation is a critical first step in converting 0337-0 (2019).
optical excitation into a charge that can Published online: 19 June 2019 5. Qiu, D. Y., da Jornada, F. H. & Louie, S. G. Phys. Rev. Lett. 111,
be read out in a photodetector or light- https://doi.org/10.1038/s41563-019-0410-8 216805 (2013).
6. Tran, K. et al. Nature 567, 71–75 (2019).
harvesting device. ❐
References 7. Seyler, K. L. et al. Nature 567, 66–70 (2019).
1. Geim, A. K. & Novoselov, K. S. Nat. Mater. 6, 183–191 (2007). 8. Jin, C. et al. Nature 567, 76–80 (2019).
Steven T. Cundiff 2. Mak, K. F., Lee, C., Hone, J., Shan, J. & Heinz, T. F. Phys. Rev. Lett. 9. Alexeev, E. M. et al. Nature 567, 81–86 (2019).
Department of Physics, University of Michigan, Ann 105, 136805 (2010). 10. Huber, R. et al. Nature 414, 286–289 (2001).

New dating agency for artists

A
s the arguments over the or a hidden part of the canvas — but
painting Salvator Mundi this would be of no avail against a
demonstrate — is it the work of smart practitioner like van Meegeren.
Leonardo da Vinci himself? — there A more exacting test would carry
is a lot riding on the authentication out dating on the paints themselves,
of art. The painting sold for a record- looking at the organic components
breaking US$450 million on the in individual paint layers — in
strength of its attribution to Leonardo, particular the liquid binder, which
but some say it was made only by his until the advent of modern acrylic
studio, and it has now been excluded resins was typically a drying oil
from a Leonardo exhibition in the such as linseed oil, perhaps mixed Philip Ball
Louvre because of its uncertain status. with natural resins. This level
Verifying authenticity is sometimes of inspection has not previously
no easier for outright fakes. One of the been possible, though, because the mid-twentieth century. Dating
most successful art fakers of all time, tests required too much material. of a tiny amount of the binder
the Dutch painter Han van Meegeren, However, recent developments in (yielding just 19 μg of carbon) has,
went to great lengths to disguise the accelerator mass spectrometry (AMS) however, proved more exacting: the
deception, for example by scraping radiocarbon dating, such as the oil appears to have come from seeds
old canvases clean so that they looked ‘gas ion source’ method, have harvested either in 1958–1961 or
suitably aged. Van Meegeren copied reduced the necessary sample size 1983–1989. (The double date range
the styles of Dutch old masters such down to mere micrograms. comes from the confounding influence
as Frans Hals and Jan Vermeer so This has now enabled Hendriks of nuclear-bomb radiocarbon in
skilfully that some critics hail his et al. to identify a modern faked the 1950s and 1960s.) If we didn’t
work in its own right, and he became painting by radiocarbon microanalysis know already that this was a fake,
a national hero when it emerged after of the materials in the paint1. Their we would now.
World War II that he had sold a fake to sample was purposely chosen to Trotter, incidentally, is still painting
Hermann Göring during the German be a known forgery: made by the in a faux nineteenth-century style after
occupation of the Netherlands. American artist Robert Trotter, who leaving prison — but openly so, selling
Spotting faked paintings usually was convicted in 1990 of producing to buyers of modern folk art. Making a
involves a close inspection of the and selling faked American folk art. living as an artist was, it seems,
materials. Sometimes they come to His Village Scene with Horse and all he had really wanted. ❐
light because of the anachronistic use Honn & Company Factory, signed
of pigments: a ‘modern’ pigment such ‘1866’ by the ‘artist’ Sarah Honn, isn’t
as chrome yellow could not possibly a very sophisticated deception — Published online: 19 June 2019
feature in a genuine Rembrandt. But conventional spectroscopic pigment https://doi.org/10.1038/s41563-019-0417-1
the canny forger will use period- analyses have already revealed telltale
appropriate paints. Another option anachronisms, such as the total References
1. Hendriks, L. et al. Proc. Natl Acad. Sci. USA https://doi.
is to use radiocarbon dating, but this absence of lead white2. org/10.1073/pnas.1901540116 (2019).
has traditionally involved destructive But Trotter did use an old canvas, 2. Smith, G. D., Hamm, J. F., Kushel, D. A. &
Rogge, C. E. in Collaborative Endeavors in the Chemical
testing of a significant amount of and radiocarbon dating of that is Analysis of Art and Cultural Heritage Materials
material — perhaps a few grams. inconclusive, spanning from the (eds Lang, P. L. & Armitage, R. A.) 1–21 (American
Those might be taken from the frame late seventeenth century to the Chemical Society, 2012).

Nature Materials | VOL 18 | JULY 2019 | 657–665 | www.nature.com/naturematerials 659