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result(s) for
"Diroll, Benjamin T."
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High-efficiency stretchable light-emitting polymers from thermally activated delayed fluorescence
2023
Stretchable light-emitting materials are the key components for realizing skin-like displays and optical biostimulation. All the stretchable emitters reported to date, to the best of our knowledge, have been based on electroluminescent polymers that only harness singlet excitons, limiting their theoretical quantum yield to 25%. Here we present a design concept for imparting stretchability onto electroluminescent polymers that can harness all the excitons through thermally activated delayed fluorescence, thereby reaching a near-unity theoretical quantum yield. We show that our design strategy of inserting flexible, linear units into a polymer backbone can substantially increase the mechanical stretchability without affecting the underlying electroluminescent processes. As a result, our synthesized polymer achieves a stretchability of 125%, with an external quantum efficiency of 10%. Furthermore, we demonstrate a fully stretchable organic light-emitting diode, confirming that the proposed stretchable thermally activated delayed fluorescence polymers provide a path towards simultaneously achieving desirable electroluminescent and mechanical characteristics, including high efficiency, brightness, switching speed and stretchability as well as low driving voltage.We synthesized stretchable electroluminescent polymers capable of reaching a near-unity theoretical quantum yield through thermally activated delayed fluorescence. Their polymers show 125% stretchability with 10% external quantum efficiency and demonstrate a fully stretchable organic light-emitting diode.
Journal Article
Exploiting the colloidal nanocrystal library to construct electronic devices
2016
Synthetic methods produce libraries of colloidal nanocrystals with tunable physical properties by tailoring the nanocrystal size, shape, and composition. Here, we exploit colloidal nanocrystal diversity and design the materials, interfaces, and processes to construct all-nanocrystal electronic devices using solution-based processes. Metallic silver and semiconducting cadmium selenide nanocrystals are deposited to form high-conductivity and high-mobility thin-film electrodes and channel layers of field-effect transistors. Insulating aluminum oxide nanocrystals are assembled layer by layer with polyelectrolytes to form high—dielectric constant gate insulator layers for low-voltage device operation. Metallic indium nanocrystals are codispersed with silver nanocrystals to integrate an indium supply in the deposited electrodes that serves to passivate and dope the cadmium selenide nanocrystal channel layer. We fabricate all-nanocrystal field-effect transistors on flexible plastics with electron mobilities of 21.7 square centimeters per volt-second.
Journal Article
Spin-exchange carrier multiplication in manganese-doped colloidal quantum dots
by
Kim, Whi Dong
,
Livache, Clément
,
Diroll, Benjamin T
in
Cadmium selenides
,
Colloiding
,
Conduction bands
2023
Carrier multiplication is a process whereby a kinetic energy of a carrier relaxes via generation of additional electron–hole pairs (excitons). This effect has been extensively studied in the context of advanced photoconversion as it could boost the yield of generated excitons. Carrier multiplication is driven by carrier–carrier interactions that lead to excitation of a valence-band electron to the conduction band. Normally, the rate of phonon-assisted relaxation exceeds that of Coulombic collisions, which limits the carrier multiplication yield. Here we show that this limitation can be overcome by exploiting not ‘direct’ but ‘spin-exchange’ Coulomb interactions in manganese-doped core/shell PbSe/CdSe quantum dots. In these structures, carrier multiplication occurs via two spin-exchange steps. First, an exciton generated in the CdSe shell is rapidly transferred to a Mn dopant. Then, the excited Mn ion undergoes spin-flip relaxation via a spin-conserving pathway, which creates two excitons in the PbSe core. Due to the extremely fast, subpicosecond timescales of spin-exchange interactions, the Mn-doped quantum dots exhibit an up-to-threefold enhancement of the multiexciton yield versus the undoped samples, which points towards the considerable potential of spin-exchange carrier multiplication in advanced photoconversion.Carrier multiplication generates multiple excitons for each absorbed photon but is normally limited by fast phonon-assisted relaxation. Here the authors achieve a threefold enhancement in multiexciton yields in Mn-doped PbSe/CdSe quantum dots, due to very fast spin-exchange interactions between Mn ions and the quantum dots that outpace energy losses arising from phonon emission.
Journal Article
Bright and durable scintillation from colloidal quantum shells
by
Cassidy, James P.
,
Harankahage, Dulanjan
,
Schaller, Richard D.
in
140/125
,
147/143
,
639/624/1020
2024
Efficient, fast, and robust scintillators for ionizing radiation detection are crucial in various fields, including medical diagnostics, defense, and particle physics. However, traditional scintillator technologies face challenges in simultaneously achieving optimal performance and high-speed operation. Herein we introduce colloidal quantum shell heterostructures as X-ray and electron scintillators, combining efficiency, speed, and durability. Quantum shells exhibit light yields up to 70,000 photons MeV
−1
at room temperature, enabled by their high multiexciton radiative efficiency thanks to long Auger-Meitner lifetimes (>10 ns). Radioluminescence is fast, with lifetimes of 2.5 ns and sub-100 ps rise times. Additionally, quantum shells do not exhibit afterglow and maintain stable scintillation even under high X-ray doses (>10
9
Gy). Furthermore, we showcase quantum shells for X-ray imaging achieving a spatial resolution as high as 28 line pairs per millimeter. Overall, efficient, fast, and durable scintillation make quantum shells appealing in applications ranging from ultrafast radiation detection to high-resolution imaging.
Traditional scintillators face challenges in achieving fast response and avoiding afterglow. Guzelturk et al. report colloidal quantum shell heterostructures with bright multiexciton emission, enabling efficient, fast, and robust scintillation for high-resolution and high-speed X-ray imaging.
Journal Article
Photoinduced, reversible phase transitions in all-inorganic perovskite nanocrystals
by
Brumberg, Alexandra
,
Wasielewski, Michael R.
,
Schaller, Richard D.
in
639/301/357/354
,
639/766/119/1000
,
Cesium
2019
Significant interest exists in lead trihalides that present the perovskite structure owing to their demonstrated potential in photovoltaic, lasing, and display applications. These materials are also notable for their unusual phase behavior often displaying easily accessible phase transitions. In this work, time-resolved X-ray diffraction, performed on perovskite cesium lead bromide nanocrystals, maps the lattice response to controlled excitation fluence. These nanocrystals undergo a reversible, photoinduced orthorhombic-to-cubic phase transition which is discernible at fluences greater than 0.34 mJ cm
−2
through the loss of orthorhombic features and shifting of high-symmetry peaks. This transition recovers on the timescale of 510 ± 100 ps. A reversible crystalline-to-amorphous transition, observable through loss of Bragg diffraction intensity, occurs at higher fluences (greater than 2.5 mJ cm
−2
). These results demonstrate that light-driven phase transitions occur in perovskite materials, which will impact optoelectronic applications and enable the manipulation of non-equilibrium phase characteristics of the broad perovskite material class.
Lead trihalide perovskites are notable for their excellent optoelectronic properties and uncommon phase behavior. Here, Kirschner et al. show that cesium lead bromide nanocrystals experience a reversible orthorhombic-to-cubic phase transition at moderate excitation fluences and become amorphous at higher fluences.
Journal Article
Flexible and low-voltage integrated circuits constructed from high-performance nanocrystal transistors
by
Murray, Christopher B.
,
Kim, David K.
,
Lai, Yuming
in
639/301/357/995
,
639/925/357
,
Humanities and Social Sciences
2012
Colloidal semiconductor nanocrystals are emerging as a new class of solution-processable materials for low-cost, flexible, thin-film electronics. Although these colloidal inks have been shown to form single, thin-film field-effect transistors with impressive characteristics, the use of multiple high-performance nanocrystal field-effect transistors in large-area integrated circuits has not been shown. This is needed to understand and demonstrate the applicability of these discrete nanocrystal field-effect transistors for advanced electronic technologies. Here we report solution-deposited nanocrystal integrated circuits, showing nanocrystal integrated circuit inverters, amplifiers and ring oscillators, constructed from high-performance, low-voltage, low-hysteresis CdSe nanocrystal field-effect transistors with electron mobilities of up to 22 cm
2
V
−1
s
−1
, current modulation >10
6
and subthreshold swing of 0.28 V dec
−1
. We fabricated the nanocrystal field-effect transistors and nanocrystal integrated circuits from colloidal inks on flexible plastic substrates and scaled the devices to operate at low voltages. We demonstrate that colloidal nanocrystal field-effect transistors can be used as building blocks to construct complex integrated circuits, promising a viable material for low-cost, flexible, large-area electronics.
Field-effect transistors based on semiconductor nanocrystals are promising candidates for low-cost, flexible electronics. This work demonstrates fabrication on flexible substrates and low-voltage operations of integrated circuits based on nanocrystal transistors, including amplifiers and ring oscillators.
Journal Article
Large optical nonlinearity of ITO nanorods for sub-picosecond all-optical modulation of the full-visible spectrum
2016
Nonlinear optical responses of materials play a vital role for the development of active nanophotonic and plasmonic devices. Optical nonlinearity induced by intense optical excitation of mobile electrons in metallic nanostructures can provide large-amplitude, dynamic tuning of their electromagnetic response, which is potentially useful for all-optical processing of information and dynamic beam control. Here we report on the sub-picosecond optical nonlinearity of indium tin oxide nanorod arrays (ITO-NRAs) following intraband, on-plasmon-resonance optical pumping, which enables modulation of the full-visible spectrum with large absolute change of transmission, favourable spectral tunability and beam-steering capability. Furthermore, we observe a transient response in the microsecond regime associated with slow lattice cooling, which arises from the large aspect-ratio and low thermal conductivity of ITO-NRAs. Our results demonstrate that all-optical control of light can be achieved by using heavily doped wide-bandgap semiconductors in their transparent regime with speed faster than that of noble metals.
Optical nonlinearity in metallic nanostructures has been exploited for all-optical signal switching. Here, Guo
et al
. report on the optical nonlinearity of indium tin oxide nanorod arrays in the dielectric range induced by pumping in the metallic range, enabling modulation of the full-visible spectrum.
Journal Article
Engineering the temporal dynamics of all-optical switching with fast and slow materials
by
Boltasseva, Alexandra
,
Schaller, Richard D.
,
Ozlu, Mustafa Goksu
in
132/122
,
140/125
,
639/301/1019/1021
2023
All-optical switches control the amplitude, phase, and polarization of light using optical control pulses. They can operate at ultrafast timescales – essential for technology-driven applications like optical computing, and fundamental studies like time-reflection. Conventional all-optical switches have a fixed switching time, but this work demonstrates that the response-time can be controlled by selectively controlling the light-matter-interaction in so-called fast and slow materials. The bi-material switch has a nanosecond response when the probe interacts strongly with titanium nitride near its epsilon-near-zero (ENZ) wavelength. The response-time speeds up over two orders of magnitude with increasing probe-wavelength, as light’s interaction with the faster Aluminum-doped zinc oxide (AZO) increases, eventually reaching the picosecond-scale near AZO’s ENZ-regime. This scheme provides several additional degrees of freedom for switching time control, such as probe-polarization and incident angle, and the pump-wavelength. This approach could lead to new functionalities within key applications in multiband transmission, optical computing, and nonlinear optics.
Here the authors demonstrate the active control of an all-optical switch harnessing the interaction of light with the constituent materials. The response speeds up by two orders of magnitude and scales accordingly with the strength of the light matter interaction.
Journal Article
Double-crowned 2D semiconductor nanoplatelets with bicolor power-tunable emission
by
Xu, Xiang Zhen
,
Climente, Juan I.
,
Barisien, Thierry
in
140/146
,
639/301/357/1017
,
639/925/357/1017
2022
Nanocrystals (NCs) are now established building blocks for optoelectronics and their use as down converters for large gamut displays has been their first mass market. NC integration relies on a combination of green and red NCs into a blend, which rises post-growth formulation issues. A careful engineering of the NCs may enable dual emissions from a single NC population which violates Kasha’s rule, which stipulates that emission should occur at the band edge. Thus, in addition to an attentive control of band alignment to obtain green and red signals, non-radiative decay paths also have to be carefully slowed down to enable emission away from the ground state. Here, we demonstrate that core/crown/crown 2D nanoplatelets (NPLs), made of CdSe/CdTe/CdSe, can combine a large volume and a type-II band alignment enabling simultaneously red and narrow green emissions. Moreover, we demonstrate that the ratio of the two emissions can be tuned by the incident power, which results in a saturation of the red emission due to non-radiative Auger recombination that affects this emission much stronger than the green one. Finally, we also show that dual-color, power tunable, emission can be obtained through an electrical excitation.
Nanocrystals are desirable light sources for advanced display technologies. Here, the authors report on double-crowned 2D semiconductor nanoplatelets as light downconverters that offer both green and red emissions to achieve a wide color gamut.
Journal Article
Gain roll-off in cadmium selenide colloidal quantum wells under intense optical excitation
by
Brumberg, Alexandra
,
Diroll, Benjamin T.
,
Schaller, Richard D.
in
639/301/1019
,
639/301/119
,
639/301/357
2022
Colloidal quantum wells, or nanoplatelets, show among the lowest thresholds for amplified spontaneous emission and lasing among solution-cast materials and among the highest modal gains of any known materials. Using solution measurements of colloidal quantum wells, this work shows that under photoexcitation, optical gain increases with pump fluence before rolling off due to broad photoinduced absorption at energies lower than the band gap. Despite the common occurrence of gain induced by an electron–hole plasma found in bulk materials and epitaxial quantum wells, under no measurement conditions was the excitonic absorption of the colloidal quantum wells extinguished and gain arising from a plasma observed. Instead, like gain, excitonic absorption reaches a minimum intensity near a photoinduced carrier sheet density of 2 × 10
13
cm
−2
above which the absorption peak begins to recover. To understand the origins of these saturation and reversal effects, measurements were performed with different excitation energies, which deposit differing amounts of excess energy above the band gap. Across many samples, it was consistently observed that less energetic excitation results in stronger excitonic bleaching and gain for a given carrier density. Transient and static optical measurements at elevated temperatures, as well as transient X-ray diffraction of the samples, suggest that the origin of gain saturation and reversal is a heating and disordering of the colloidal quantum wells which produces sub-gap photoinduced absorption.
Journal Article