Probing substrate binding inside a paramagnetic cavity: a NMR spectroscopy toolbox for combined experimental and theoretical investigation.

Protein cavities often rely on the paramagnetic metal present in their active site in order to catalyse various chemical transformations in biology. The selective detection and identification of the substrate is of fundamental importance in environmental monitoring and biological studies. Herein, a covalently linked Fe(iii)porphyrin dimer-based paramagnetic sensory cavity has been devised for the accurate detection and simultaneous identification of phenol (substrate) binding within the cavity that provides a unique spectroscopic signature with valuable structural and environmental information. These substrates within the paramagnetic cavity leave the fingerprints of the specific binding modes (exo vs. endo) which are well distinguished with the help of various spectroscopic studies viz. UV-vis, 1H, and 19F NMR and in their respective crystal structures also. The theoretical 19F NMR analysis plays a pivotal role in replicating the observed NMR trends with large chemical shifts of the phenolato species which in turn helps in deciphering the selective binding modes of the phenols and thereby recognizing the chemical environment within the cavity. These findings will help develop an excellent diagnostic tool for in situ monitoring of subtle conformational changes and transient interactions.

High-Performance Visible-to-SWIR Photodetector Based on the Layered WS2 Heterojunction with Light-Trapping Pyramidal Black Germanium.

This study presents a layered transition metal dichalcogenide/black germanium (b-Ge) heterojunction photodetector that exhibits superior performance across a broad spectrum of wavelengths spanning from visible (vis) to shortwave infrared (SWIR). The photodetector includes a thin layer of b-Ge, which is created by wet etching of germanium (Ge) wafer to form submicrometer pyramidal structures. On top of this b-Ge layer, the WS2 thin film is deposited using pulsed laser deposition. In comparison to conventional germanium, b-Ge absorbs about 25% more light between 850 and 1750 nm wavelengths. The WS2/b-Ge photodetector has a peak photoresponsivity of 0.65 A/W, which is more than twice the photoresponsivity of the WS2/Ge photodetector at 1540 nm. Additionally, it shows better responsivity and response speed compared with other similar state-of-the-art photodetectors. Such an improvement in the performance of the device is credited to the light-trapping effect enabled by the germanium pyramids. Theoretical simulations employing the finite-difference time-domain technique help validate the concept. This novel photodetector holds promise for efficient detection of light across the vis to SWIR spectrum.

A source of entangled photons based on a cavity-enhanced and strain-tuned GaAs quantum dot.

A quantum-light source that delivers photons with a high brightness and a high degree of entanglement is fundamental for the development of efficient entanglement-based quantum-key distribution systems. Among all possible candidates, epitaxial quantum dots are currently emerging as one of the brightest sources of highly entangled photons. However, the optimization of both brightness and entanglement currently requires different technologies that are difficult to combine in a scalable manner. In this work, we overcome this challenge by developing a novel device consisting of a quantum dot embedded in a circular Bragg resonator, in turn, integrated onto a micromachined piezoelectric actuator. The resonator engineers the light-matter interaction to empower extraction efficiencies up to 0.69(4). Simultaneously, the actuator manipulates strain fields that tune the quantum dot for the generation of entangled photons with corrected fidelities to a maximally entangled state up to 0.96(1). This hybrid technology has the potential to overcome the limitations of the key rates that plague QD-based entangled sources for entanglement-based quantum key distribution and entanglement-based quantum networks. Supplementary Information: The online version contains supplementary material available at 10.1186/s43593-024-00072-8.

Is Wave Function Collapse Necessary? Explaining Quantum Nondemolition Measurement of a Spin Qubit within Linear Evolution.

The measurement problem dates back to the dawn of quantum mechanics. Here, we measure a quantum dot electron spin qubit through off-resonant coupling with a highly redundant ancilla, consisting of thousands of nuclear spins. Large redundancy allows for single-shot measurement with high fidelity ≈99.85%. Repeated measurements enable heralded initialization of the qubit and backaction-free detection of electron spin quantum jumps, attributed to burstlike fluctuations in a thermally populated phonon bath. Based on these results we argue that the measurement, linking quantum states to classical observables, can be made without any "wave function collapse" in agreement with the Quantum Darwinism concept.

Approaching a fully-polarized state of nuclear spins in a solid.

Magnetic noise of atomic nuclear spins is a major source of decoherence in solid-state spin qubits. In theory, near-unity nuclear spin polarization can eliminate decoherence of the electron spin qubit, while turning the nuclei into a useful quantum information resource. However, achieving sufficiently high nuclear polarizations has remained an evasive goal. Here we implement a nuclear spin polarization protocol which combines strong optical pumping and fast electron tunneling. Nuclear polarizations well above 95% are generated in GaAs semiconductor quantum dots on a timescale of 1 minute. The technique is compatible with standard quantum dot device designs, where highly-polarized nuclear spins can simplify implementations of qubits and quantum memories, as well as offer a testbed for studies of many-body quantum dynamics and magnetism.

Nuclear spin diffusion in the central spin system of a GaAs/AlGaAs quantum dot.

The spin diffusion concept provides a classical description of a purely quantum-mechanical evolution in inhomogeneously polarized many-body systems such as nuclear spin lattices. The central spin of a localized electron alters nuclear spin diffusion in a way that is still poorly understood. Here, spin diffusion in a single GaAs/AlGaAs quantum dot is witnessed in the most direct manner from oscillatory spin relaxation dynamics. Electron spin is found to accelerate nuclear spin relaxation, from which we conclude that the long-discussed concept of a Knight-field-gradient diffusion barrier does not apply to GaAs epitaxial quantum dots. Our experiments distinguish between non-diffusion relaxation and spin diffusion, allowing us to conclude that diffusion is accelerated by the central electron spin. Such acceleration is observed up to unexpectedly high magnetic fields - we propose electron spin-flip fluctuations as an explanation. Diffusion-limited nuclear spin lifetimes range between 1 and 10 s, which is sufficiently long for quantum information storage and processing.

Beyond the Four-Level Model: Dark and Hot States in Quantum Dots Degrade Photonic Entanglement.

Entangled photon pairs are essential for a multitude of quantum photonic applications. To date, the best performing solid-state quantum emitters of entangled photons are semiconductor quantum dots operated around liquid-helium temperatures. To favor the widespread deployment of these sources, it is important to explore and understand their behavior at temperatures accessible with compact Stirling coolers. Here we study the polarization entanglement among photon pairs from the biexciton-exciton cascade in GaAs quantum dots at temperatures up to ∼65 K. We observe entanglement degradation accompanied by changes in decay dynamics, which we ascribe to thermal population and depopulation of hot and dark states in addition to the four levels relevant for photon pair generation. Detailed calculations considering the presence and characteristics of the additional states and phonon-assisted transitions support the interpretation. We expect these results to guide the optimization of quantum dots as sources of highly entangled photons at elevated temperatures.

Ideal refocusing of an optically active spin qubit under strong hyperfine interactions.

Combining highly coherent spin control with efficient light-matter coupling offers great opportunities for quantum communication and computing. Optically active semiconductor quantum dots have unparalleled photonic properties but also modest spin coherence limited by their resident nuclei. The nuclear inhomogeneity has thus far bound all dynamical decoupling measurements to a few microseconds. Here, we eliminate this inhomogeneity using lattice-matched GaAs-AlGaAs quantum dot devices and demonstrate dynamical decoupling of the electron spin qubit beyond 0.113(3) ms. Leveraging the 99.30(5)% visibility of our optical π-pulse gates, we use up to Nπ = 81 decoupling pulses and find a coherence time scaling of [Formula: see text]. This scaling manifests an ideal refocusing of strong interactions between the electron and the nuclear spin ensemble, free of extrinsic noise, which holds the promise of lifetime-limited spin coherence. Our findings demonstrate that the most punishing material science challenge for such quantum dot devices has a remedy and constitute the basis for highly coherent spin-photon interfaces.

Quantum cryptography with highly entangled photons from semiconductor quantum dots.

Semiconductor quantum dots are capable of emitting polarization entangled photon pairs with ultralow multipair emission probability even at maximum brightness. Using a quantum dot source with a fidelity as high as 0.987(8), we implement here quantum key distribution with an average quantum bit error rate as low as 1.9% over a time span of 13 hours. For a proof of principle, the key generation is performed with the BBM92 protocol between two buildings, connected by a 350-m-long fiber, resulting in an average raw (secure) key rate of 135 bits/s (86 bits/s) for a pumping rate of 80 MHz, without resorting to time- or frequency-filtering techniques. Our work demonstrates the viability of quantum dots as light sources for entanglement-based quantum key distribution and quantum networks. By increasing the excitation rate and embedding the dots in state-of-the-art photonic structures, key generation rates in the gigabits per second range are in principle at reach.

Multifunctional Au-ZnO plasmonic nanostructures for enhanced UV photodetector and room temperature NO sensing devices.

In this study we report the enhancement of UV photodetection and wavelength tunable light induced NO gas sensing at room temperature using Au-ZnO nanocomposites synthesized by a simple photochemical process. Plasmonic Au-ZnO nanostructures with a size less than the incident wavelength have been found to exhibit a localized surface plasmon resonance (LSPR) that leads to a strong absorption, scattering and local field enhancement. The photoresponse of Au-ZnO nanocomposite can be effectively enhanced by 80 times at 335 nm over control ZnO. We also demonstrated Au-ZnO nanocomposite's application to wavelength tunable gas sensor operating at room temperature. The sensing response of Au-ZnO nancomposite is enhanced both in UV and visible region, as compared to control ZnO. The sensitivity is observed to be higher in the visible region due to the LSPR effect of Au NPs. The selectivity is found to be higher for NO gas over CO and some other volatile organic compounds (VOCs), with a minimum detection limit of 0.1 ppb for Au-ZnO sensor at 335 nm.

Fabrication of Si/ZnS radial nanowire heterojunction arrays for white light emitting devices on Si substrates.

Well-separated Si/ZnS radial nanowire heterojunction-based light-emitting devices have been fabricated on large-area substrates by depositing n-ZnS film on p-type nanoporous Si nanowire templates. Vertically oriented porous Si nanowires on p-Si substrates have been grown by metal-assisted chemical etching catalyzed using Au nanoparticles. Isolated Si nanowires with needle-shaped arrays have been made by KOH treatment before ZnS deposition. Electrically driven efficient white light emission from radial heterojunction arrays has been achieved under a low forward bias condition. The observed white light emission is attributed to blue and green emission from the defect-related radiative transition of ZnS and Si/ZnS interface, respectively, while the red arises from the porous surface of the Si nanowire core. The observed white light emission from the Si/ZnS nanowire heterojunction could open up the new possibility to integrate Si-based optical sources on a large scale.

Optical photoresponse of CuS-n-Si radial heterojunction with Si nanocone arrays fabricated by chemical etching.

The paper deals with the fabrication of a p-CuS-n-Si nanocone heterojunction based highly sensitive broad band photodetector. Cone-like one dimensional Si nanostructures formed by metal assisted chemical etching, with superior antireflection characteristics have been used as templates for fabrication of the heterojunction. Covellite CuS material was synthesized by a simple chemical reaction for used as target material for the fabrication of p-CuS-n-Si nanocone heterojunctions via pulsed laser ablation. The effect of surface texturing of Si (cone like nanostructure vs. planar) on spectral photoresponse and detection is reported.

Broadband photoresponse and rectification of novel graphene oxide/n-Si heterojunctions.

We report a novel graphene oxide (GO) based p-n heterojunction on n-Si. The fabricated vertical GO/n-Si heterojunction diode shows a very low leakage current density of 0.25 µA/cm(2) and excellent rectification characteristics upto 1 MHz. The device on illumination shows a broadband (300-1100 nm) spectral response with a characteristic peak at ~700 nm, in agreement with the photoluminescence emission from GO. Very high photo-to-dark current ratio (>10(5)) is observed upon illumination of UV light. The transient photocurrent measurements indicate that the GO based heterojunction diodes can be useful for UV and broadband photodetectors, compatible with silicon device technology.

Resistive switching memory characteristics of Ge/GeOx nanowires and evidence of oxygen ion migration.

The resistive switching memory of Ge nanowires (NWs) in an IrOx/Al2O3/Ge NWs/SiO2/p-Si structure is investigated. Ge NWs with an average diameter of approximately 100 nm are grown by the vapor-liquid-solid technique. The core-shell structure of the Ge/GeOx NWs is confirmed by both scanning electron microscopy and high-resolution transmission electron microscopy. Defects in the Ge/GeOx NWs are observed by X-ray photoelectron spectroscopy. Broad photoluminescence spectra from 10 to 300 K are observed because of defects in the Ge/GeOx NWs, which are also useful for nanoscale resistive switching memory. The resistive switching mechanism in an IrOx/GeOx/W structure involves migration of oxygen ions under external bias, which is also confirmed by real-time observation of the surface of the device. The porous IrOx top electrode readily allows the evolved O2 gas to escape from the device. The annealed device has a low operating voltage (<4 V), low RESET current (approximately 22 µA), large resistance ratio (>103), long pulse read endurance of >105 cycles, and good data retention of >104 s. Its performance is better than that of the as-deposited device because the GeOx film in the annealed device contains more oxygen vacancies. Under SET operation, Ge/GeOx nanofilaments (or NWs) form in the GeOx film. The diameter of the conducting nanofilament is approximately 40 nm, which is calculated using a new method.

Electroluminescence from metal-insulator-semiconductor tunneling diodes using compressively strained Ge on Si0.5Ge0.5 virtual substrates.

Direct band gap optical transition in compressively strained Ge film is demonstrated for the first time under current injection through a metal-insulator-semiconductor diode structure. The compressively strained Ge layer is grown on the relaxed Si0.5Ge0.5 substrate by solid source molecular beam epitaxy. The electroluminescence of direct band gap emission from strained Ge film and TO phonon assisted transition in Si and SiGe from the virtual substrate is observed under different current injections. The signature of heavy hole and light hole splitting in valence band is observed in the electroluminescence spectra from strained Ge layer. The temperature dependent electroluminescence characteristics have been studied over a temperature range of 10-300 K. AC frequency modulation for the Ge direct band electroluminescence has been studied to improve the emission efficiency over the DC bias.

Optical and electrical properties of undoped and doped Ge nanocrystals.

Size-dependent photoluminescence characteristics from Ge nanocrystals embedded in different oxide matrices have been studied to demonstrate the light emission in the visible wavelength from quantum-confined charge carriers. On the other hand, the energy transfer mechanism between Er ions and Ge nanocrystals has been exploited to exhibit the emission in the optical fiber communication wavelength range. A broad visible electroluminescence, attributed to electron hole recombination of injected carriers in Ge nanocrystals, has been achieved. Nonvolatile flash-memory devices using Ge nanocrystal floating gates with different tunneling oxides including SiO2, Al2O3, HfO2, and variable oxide thickness [VARIOT] tunnel barrier have been fabricated. An improved charge storage characteristic with enhanced retention time has been achieved for the devices using VARIOT oxide floating gate.

Structural and optical properties of germanium nanostructures on Si(100) and embedded in high-k oxides.

The structural and optical properties of Ge quantum dots (QDs) grown on Si(001) for mid-infrared photodetector and Ge nanocrystals embedded in oxide matrices for floating gate memory devices are presented. The infrared photoluminescence (PL) signal from Ge islands has been studied at a low temperature. The temperature- and bias-dependent photocurrent spectra of a capped Si/SiGe/Si(001) QDs infrared photodetector device are presented. The properties of Ge nanocrystals of different size and density embedded in high-k matrices grown using radio frequency magnetron sputtering have been studied. Transmission electron micrographs have revealed the formation of isolated spherical Ge nanocrystals in high-k oxide matrix of sizes ranging from 4 to 18 nm. Embedded nanocrystals in high band gap oxides have been found to act as discrete trapping sites for exchanging charge carriers with the conduction channel by direct tunneling that is desired for applications in floating gate memory devices.

Improved infrared photoluminescence characteristics from circularly ordered self-assembled Ge islands.

The formation of circularly ordered Ge-islands on Si(001) has been achieved because of nonuniform strain field around the periphery of the holes patterned by focused ion beam in combination with a self-assembled growth using molecular beam epitaxy. The photoluminescence (PL) spectra obtained from patterned areas (i.e., ordered islands) show a significant signal enhancement, which sustained till 200 K, without any vertical stacking of islands. The origin of two activation energies in temperature-dependent PL spectra of the ordered islands has been explained in detail.