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Understanding and exploiting material flexibility through phenomena such as the bending and twisting of molecular crystals has been a subject of increased interest owing to the number of applications that benefit from these properties, such as optoelectronics, mechanophotonics, soft robotics, and smart sensors. Here, we report the growth of spontaneously bent and twisted ammonium urate crystals induced by the keto–enol tautomerism of the urate molecule. The major tautomer is native to biogenic crystals, whereas the minor tautomer functions as an effective crystal growth modifier to induce naturally bent and twisted ammonium urate crystals. We show that the degree of curvature can be tailored based on the judicious selection of growth conditions. A combination of state-of-the-art microscopy and spectroscopy techniques are used to characterize the origin of bending. Spatially resolved nano-electron diffraction and high-resolution electron microscopy of naturally bent crystals show nearly single crystallinity with local lattice deformations generated by a combination of screw and edge dislocations. These observations are consistent with photoinduced force microscopy and contact resonance atomic force microscopy, which confirmed spatially resolved changes in the intermolecular interactions and the mechanical properties throughout the cross-sectional and axial regions of bent crystals. A mechanism of bending involving the generation of regionally specific dislocations is proposed as an alternative to more commonly reported models. These findings highlight a unique characteristic of tautomeric crystals that may have broader implications for other biogenic materials. 

Nanohybrids of graphene and colloidal semiconductor quantum dots (QDs/Gr) provide a promising quantum sensing scheme for photodetection. Despite exciting progress made in QDs/Gr photodetectors in broadband from ultraviolet to short-wave infrared, the device performance is limited in middle-wave infrared (MWIR) detection. A fundamental question arises as to whether the thermal noiseinduced dark current and hence poor signal-to-noise ratio in conventional uncooled MWIR photodetectors persist in QDs/ Gr nanohybrids. Herein, we investigated noise, responsivity (R*), and specific detectivity (D*) in HgTe QDs/Gr nanohybrids, revealing that the noise and R* are decoupled in nanohybrids and each can be optimized independently toward its theoretical limit. Specifically, the noise in the QDs/Gr nanohybrids is dominated by that of graphene with a negligible effect from the dark current in HgTe QDs and can be optimized to its intrinsic limit by removing charge doping of adsorbed polar molecules on graphene. Furthermore, the R* is proportional to the photoconductive gain enabled by the strong quantum confinement in QDs and Gr. Achieving high gain in the MWIR spectrum, however, is challenging and requires elimination of charge traps primarily from the surface states of the narrow-bandgap semiconductor HgTe QDs. Using grain-rotation-induced grain-coalescence growth of single-layer and core/shell HgTe QDs, we show the that HgTe QDs surface states caused by Te deficiency can be dramatically suppressed, resulting in high gain up to 4.0 × 107 in the MWIR spectrum. The optimized noise and R* have led to high uncooled MWIR D* up to 2.4 × 1011 Jones, making nanohybrids promising to surpass the fundamental dark-current limit in conventional photodetectors. 

Colloidal quantum dots/graphene (QD/Gr) nanohybrids have been studied intensively for photodetection in a broadband spectrum including ultraviolet, visible, near-infrared, and shortwave infrared (UV−vis-NIR-SWIR). Since the optoelectronic process in the QD/Gr nanohybrid relies on the photogenerated charge carrier transfer from QDs to graphene, understanding the role of the QD−QD and QD−Gr interfaces is imperative to the QD/Gr nanohybrid photodetection. Herein, a systematic study is carried out to probe the effect of these interfaces on the noise, photoresponse, and specific detectivity in the UV−vis-NIR-SWIR spectrum. Interestingly, the photoresponse has been found to be negligible without a 3-mercaptopropionic acid (MPA) ligand exchange, moderate with a single ligand exchange after all QD layers are deposited on graphene, and maximum if it is performed after each QD layer deposition up to five layers of total QD thickness of 260−280 nm. Furthermore, exposure of graphene to C-band UV (UVC) for a short period of 4−5 min before QD deposition leads to improved photoresponse via removal of polar molecules at the QD/Gr interface. With the combination of the MPA ligand exchange and UVC exposure, optimal optoelectronic properties can be obtained on the PbS QD/Gr nanohybrids with high specific detectivity up to 2.6 × 1011, 1.5 × 1011, 5 × 1010, and 1.9 × 109 Jones at 400, 550, 1000, and 1700 nm, respectively, making the nanohybrids promising for broadband photodetection.