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Reconfiguration of amorphous complex oxides provides a readily controllable source of stress that can be leveraged in nanoscale assembly to access a broad range of 3D geometries and hybrid materials. An amorphous SrTiO 3 layer on a Si:B/Si 1- x Ge x :B heterostructure is reconfigured at the atomic scale upon heating, exhibiting a change in volume of ≈2% and accompanying biaxial stress. The Si:B/Si 1- x Ge x :B bilayer is fabricated by molecular beam epitaxy, followed by sputter deposition of SrTiO 3 at room temperature. The processes yield a hybrid oxide/semiconductor nanomembrane. Upon release from the substrate, the nanomembrane rolls up and has a curvature determined by the stress in the epitaxially grown Si:B/Si 1- x Ge x :B heterostructure. Heating to 600 °C leads to a decrease of the radius of curvature consistent with the development of a large compressive biaxial stress during the reconfiguration of SrTiO 3 . The control of stresses via post-deposition processing provides a new route to the assembly of complex-oxide-based heterostructures in 3D geometry. The reconfiguration of metastable mechanical stressors enables i) synthesis of various types of strained superlattice structures that cannot be fabricated by direct growth and ii) technologies based on strain engineering of complex oxides via highly scalable lithographic processes and on large-area semiconductor substrates., (© 2021 Wiley-VCH GmbH.)

We present a transformative route to obtain mass-producible helical slow-wave structures for operation in beam-wave interaction devices at THz frequencies. The approach relies on guided self-assembly of conductive nanomembranes. Our work coordinates simulations of cold helices (i.e., helices with no electron beam) and hot helices (i.e., helices that interact with an electron beam). The theoretical study determines electromagnetic fields, current distributions, and beam-wave interaction in a parameter space that has not been explored before. These parameters include microscale diameter, pitch, tape width, and nanoscale surface finish. Parametric simulations show that beam-wave interaction devices based on self-assembled and electroplated helices will potentially provide gain-bandwidth products higher than 2 dBTHz at 1 THz. Informed by the simulation results, we fabricate prototype helices for operation as slow-wave structures at THz frequencies, using metal nanomembranes. Single and intertwined double helices, as well as helices with one or two chiralities, are obtained by self-assembly of stressed metal bilayers. The nanomembrane stiffness and built-in stress control the diameter of the helices. The in-plane geometry of the nanomembrane determines the pitch, the chirality, and the formation of single vs intertwined double helices.

Liquid water, despite its simple molecular structure, remains one of the most fascinating and complex substances. Most notably, many questions continue to exist regarding the phase transitions and anomalous properties of water, which are subtle to observe experimentally. Here, we report a sharp transition in water at 330 K unveiled through experimental measurements of the instantaneous Brownian velocity of NaYF 4 :Yb/Er upconversion nanoparticles in water. Our experimental investigations, corroborated by molecular dynamics simulations, elucidate a geometrical phase transition where a low-density liquid (LDL) clusters become percolated below 330 K. Around this critical temperature, we find the sizes of the LDL clusters to be similar to those of the nanoparticles, confirming the role of the upconversion nanoparticle as a powerful ruler for measuring the extensiveness of the LDL hydrogen-bond network and nanometer-scale spatial changes (20-100 nm) in liquids. Additionally, a new order parameter that unequivocally classifies water molecules into two local geometric states is introduced, providing a new tool for understanding and modeling water's many anomalous properties and phase transitions.

The mechanism of upconversion enhancement for Li+-doped materials is still contentious. Attempting to settle the debate, here the upconversion emission enhancement of (Y0.97-xYb0.02Er0.01Lix)2O3, x = 0.000-0.123, nanoparticles is studied. Li+ incorporation in the Y2O3 host lattice is achieved via co-precipitation and solid-state reaction routes. In contrast to numerous reports, elemental analysis reveals that the former method does not afford Li+-bearing nanoparticles. The solid-state reaction route accomplishes an effective Li+ doping, as witnessed by inductively coupled plasma atomic emission spectroscopy and X-ray photoelectron spectroscopy (XPS). Transmission electron microscopy and powder X-ray diffraction showed an increase in nanoparticle size with increasing Li+ concentration. Rietveld refinement of powder X-ray diffraction data shows that the cubic lattice parameter decreases with increasing Li+ content. The emission quantum yield increases tenfold with increasing Li+ content up to x = 0.123, reaching a maximal value of 0.04% at x = 0.031. XPS and infrared spectroscopy show that the carbonate groups increase with increasing Li+ content, thus not supporting the prevailing view that the upconversion luminescence enhancement observed upon Li+ nanoparticle's doping is due to the decrease of the number of quenching carbonate groups present. Rather, the particle size increment and the decrease in the lattice parameter of the host crystals are shown to be the prime sources of quantum yield enhancement.

Brownian motion is one of the most fascinating phenomena in nature. Its conceptual implications have a profound impact in almost every field of science and even economics, from dissipative processes in thermodynamic systems, gene therapy in biomedical research, artificial motors and galaxy formation to the behaviour of stock prices. However, despite extensive experimental investigations, the basic microscopic knowledge of prototypical systems such as colloidal particles in a fluid is still far from being complete. This is particularly the case for the measurement of the particles' instantaneous velocities, elusive due to the rapid random movements on extremely short timescales. Here, we report the measurement of the instantaneous ballistic velocity of Brownian nanocrystals suspended in both aqueous and organic solvents. To achieve this, we develop a technique based on upconversion nanothermometry. We find that the population of excited electronic states in NaYF 4 :Yb/Er nanocrystals at thermal equilibrium can be used for temperature mapping of the nanofluid with great thermal sensitivity (1.15% K -1 at 296 K) and a high spatial resolution (<1 μm). A distinct correlation between the heat flux in the nanofluid and the temporal evolution of Er 3+ emission allows us to measure the instantaneous velocity of nanocrystals with different sizes and shapes.

Luminescence thermal sensing and deep-tissue imaging using nanomaterials operating within the first biological window (ca. 700-980 nm) are of great interest, prompted by the ever-growing demands in the fields of nanotechnology and nanomedicine. Here, we show that (Gd1-xNdx)2O3 (x = 0.009, 0.024 and 0.049) nanorods exhibit one of the highest thermal sensitivity and temperature uncertainty reported so far (1.75 ± 0.04% K(-1) and 0.14 ± 0.05 K, respectively) for a nanothermometer operating in the first transparent near infrared window at temperatures in the physiological range. This sensitivity value is achieved using a common R928 photomultiplier tube that allows defining the thermometric parameter as the integrated intensity ratio between the (4)F5/2 → (4)I9/2 and (4)F3/2 → (4)I9/2 transitions (with an energy difference between the barycentres of the two transitions >1000 cm(-1)). Moreover, the measured sensitivity is one order of magnitude higher than the values reported so far for Nd(3+)-based nanothermometers enlarging, therefore, the potential of using Nd(3+) ions in luminescence thermal sensing and deep-tissue imaging.

The photoluminescence properties of (Gd,Yb,Tb)PO4 nanocrystals synthesized via a hydrothermal route at 150 °C are reported. Energy-transfer from Gd(3+) to Tb(3+) is witnessed by the detailed analyses of excited-state lifetimes, emission quantum yields, and emission and excitation spectra at room temperature, for Tb(3+) concentrations ranging from 0.5 to 5.0 mol%. Absolute-emission quantum yields up to 42% are obtained by exciting within the (6)I7/2-17/2 (Gd(3+)) manifold at 272 nm. The room temperature emission spectrum is dominated by the (5)D4 → (7)F5 (Tb(3+)) transition at 543 nm, with a long decay-time (3.95-6.25 ms) and exhibiting a rise-time component. The (5)D3 → (7)F6 (Tb(3+)) rise-time (0.078 ms) and the (6)P7/2 → (8)S7/2 (Gd(3+)) decay-time (0.103 ms) are of the same order, supporting the Gd(3+) to Tb(3+) energy-transfer process. A remarkably longer lifetime of 2.29 ms was measured at 11 K for the (6)P7/2 → (8)S7/2 (Gd(3+)) emission upon excitation at 272 nm, while the emission spectrum at 11 K is dominated by the (6)P7/2 → (8)S7/2 transition line, showing that the Gd(3+) to Tb(3+) energy-transfer process is mainly phonon-assisted with an efficiency of ~95% at room temperature. The Gd(3+) to Tb(3+) energy transfer is governed by the exchange mechanism with rates between 10(2) and 10(3) s(-1), depending on the energy mismatch conditions between the (6)I7/2 and (6)P7/2 levels of Gd(3+) and the Tb(3+ 5)I7, (5)F2,3 and (5)H5,6,7 manifolds and the radial overlap integral values.

A single nanoplatform integrating laser-induced heat generation by gold nanoparticles and temperature sensing up to 2000 K via (Gd,Yb,Er)2 O3 nanorods is demonstrated, which presents considerable potential for nanoscale photonics and biomedicine. Blackbody emission is ascertained from the temperature increment with AuNP concentration, emission color coordinates as a function of the laser pump power, and Planck's law of blackbody radiation., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Up-conversion (Gd,Yb,Tb)PO(4) materials and their potential for bimodal imaging have received little attention in the literature. Herein, we report the first study on the up-conversion emission of (Gd,Yb,Tb)PO(4) nanocrystals synthesized via a hydrothermal method at 150 °C. These materials exhibit ultraviolet, blue and green up-conversion emissions upon excitation with a 980 nm continuous wave laser diode. The intensity of the blue-emission band at 479 nm, ascribed to the cooperative up-conversion emission of a pair of excited Yb(3+) ions, depends on the Yb(3+)/Tb(3+) concentration ratio, calcination temperature and particle size. Strong green up-conversion emission of Tb(3+) is observed at 543 nm for the (5)D(4)→(7)F(5) transition. Relaxometry measurements reveal that the nanocrystals are efficient T(2)-weighted (negative) contrast agents which, combined with visible-light emission generated by infrared excitation, affords them considerable potential for being used in bimodal, photoluminescence-magnetic resonance, imaging.