Room-temperature Quantum Research Articles

Chemical Modification toward Long Spin Lifetimes in Organic Conjugated Radicals.

Organic semiconductors for spin-based devices require long spin relaxation times. Understanding their spin relaxation mechanisms is critical to organic spintronic devices and applications for quantum information processing. However, reports on the spin relaxation mechanisms of organic conjugated molecules are rare and the research methods are also limited. Herein, we study the molecular design and spin relaxation mechanisms by systematically varying the structure of a conjugated radical. We found that solid-state relaxation times of organic materials are largely different from that in solution state. We demonstrate that substitution of a lower gyromagnetic ratio nucleus (e. g. D, Cl) on the para-position of the aryl rings in the triphenylmethyl (TM) radical can significantly improve their coherence times (Tm ). Flexible thin films based on such radicals exhibit ultra-long spin-lattice relaxation times (T1 ) up to 35.6(6) μs and Tm up to 1.08(4) μs under ambient conditions, which are among the longest values in films. More importantly, using the TM radical derivative (5CM), we observed room-temperature quantum coherence and Rabi cycles in thin film for the first time, suggesting that organic conjugated radicals have great potentials for spin-based information processing.

Polarization-resolved black phosphorus/molybdenum disulfide mid-wave infrared photodiodes with high detectivity at room temperature

Infrared photodetectors are currently subject to a rapidly expanding application space, with an increasing demand for compact, sensitive and inexpensive detectors. Despite continued advancement, technological factors limit the widespread usage of such detectors, specifically, the need for cooling and the high costs associated with processing of iii–v/ii–vi semiconductors. Here, black phosphorous (bP)/MoS2 heterojunction photodiodes are explored as mid-wave infrared (MWIR) detectors. Although previous studies have demonstrated photodiodes using bP, here we significantly improve the performance, showing that such devices can be competitive with conventional MWIR photodetectors. By optimizing the device structure and light management, we demonstrate a two-terminal device that achieves room-temperature external quantum efficiencies (ηe) of 35% and specific detectivities (D*) as high as 1.1 × 1010 cm Hz1/2 W−1 in the MWIR region. Furthermore, by leveraging the anisotropic optical properties of bP we demonstrate the first bias-selectable polarization-resolved photodetector that operates without the need for external optics. Black phosphorus/molybdenum disulfide mid-wave infrared photodiodes with external quantum efficiencies of 35% across 2.5–3.5 μm at room temperature and a peak detectivity of 1.1 × 1010 cm Hz1/2 W–1 at 3.8 μm are demonstrated.

Strong Light-Matter Coupling between Plasmons in Individual Gold Bi-pyramids and Excitons in Mono- and Multilayer WSe2.

Monolayer transition-metal dichalcogenides (TMDCs) have attracted a lot of research attention recently, motivated by their remarkable optical properties and potential for strong light-matter interactions. Realization of strong plasmon-exciton coupling is especially desirable in this context because it holds promise for the enabling of room-temperature quantum and nonlinear optical applications. These efforts naturally require investigations at a single-nanoantenna level, which, in turn, should possess a compact optical mode interacting with a small amount of excitonic material. However, standard plasmonic nanoantenna designs such as nanoparticle dimers or particle-on-film suffer from misalignment of the local electric field in the gap with the in-plane transition dipole moment of monolayer TMDCs. Here, we circumvent this problem by utilizing gold bi-pyramids (BPs) as very efficient plasmonic nanoantennas. We demonstrate strong coupling between individual BPs and tungsten diselenide (WSe2) monolayers at room temperature. We further study the coupling between multilayers of WSe2 and BPs to elucidate the effect of the number of layers on the coupling strength. Importantly, BPs adopt a reduced-symmetry configuration when deposited on WSe2, such that only one sharp antenna tip efficiently interacts with excitons. Despite the small interaction area, we manage to achieve strong coupling, with Rabi splitting exceeding ∼100 meV. Our results suggest a feasible way toward realizing plasmon-exciton polaritons involving nanoscopic areas of TMDCs, thus pointing toward quantum and nonlinear optics applications at ambient conditions.

Controlling the solid-state luminescence of gold(I) N-heterocyclic carbene complexes through changes in the structure of molecular aggregates

Thermally stable, solid-state luminescent organic materials are highly desired for the development of practical applications. Herein we synthesized new gold(I) complexes with N -heterocyclic carbene ligands, which have the ability to form strong metal-organic bond. Consequently, their thermochemical stability is enhanced at temperatures around 300 °C. Precise design of the molecular structure of the ligands, with a focus on ensuring low steric hindrance around Au atoms in order to limit disturbances to Au/Au interactions, provided a complex with a densely packed crystal with a shorter intermolecular Au–Au distance (3.17 A) than the typical distance. In the solid state, this complex exhibited strong aurophilic interactions, which generated intense phosphorescence even in air at room temperature (quantum yield=16%) in spite of absence of any phosphorescence in solution. This behavior is characteristic for solid-state luminescence referred to as aggregation-controlled emission. Furthermore, the gold(I) complex displays capacity for mechano- and vapo-chromism—that is, the ability to change color reversibly in response to the application of external stimuli. We believe that the proposed design framework, which involves controlling thermal stability and luminescence property separately, provides a new opportunity for the development of practical applications using solid-state luminescent organic molecules.

Doping-Enhanced Short-Range Order of Perovskite Nanocrystals for Near-Unity Violet Luminescence Quantum Yield.

All-inorganic perovskite nanocrystals (NCs) have emerged as a new generation of low-cost semiconducting luminescent system for optoelectronic applications. The room-temperature photoluminescence quantum yields (PLQYs) of these NCs in the green and red spectral range approach unity. However, their PLQYs in the violet are much lower, and an insightful understanding of such poor performance remains missing. We report a general strategy for the synthesis of all-inorganic violet-emitting perovskite NCs with near-unity PLQYs through engineering local order of the lattice by nickel ion doping. A broad range of experimental characterizations, including steady-state and time-resolved luminescence spectroscopy, X-ray absorption spectra, and magic angle spinning nuclear magnetic resonance spectra, reveal that the low PLQY in undoped NCs is associated with short-range disorder of the lattice induced by intrinsic defects such as halide vacancies and that Ni doping can substantially eliminate these defects and result in increased short-range order of the lattice. Density functional theory calculations reveal that Ni doping of perovskites causes an increase of defect formation energy and does not introduce deep trap states in the band gap, which is suggested to be the main reason for the improved local structural order and near-unity PLQY. Our ability to obtain violet-emitting perovskite NCs with near-perfect properties opens the door for a range of applications in violet-emitting perovskite-based devices such as light-emitting diodes, single-photon sources, lasers, and beyond.

Simulations point to new materials for room-temperature quantum spin Hall insulators

Predictions show that methyl- and ethyl-functionalized honeycombs of thallium antimonide have large enough band gaps and the robustness needed for a topological insulator at room temperature.

Quantum cascade laser based absorption spectroscopy for direct monitoring of atmospheric N2O isotopes

A compact high-resolution spectroscopic sensor using a thermoelectrically (TE) cooled continuous-wave (CW) room temperature (RT) quantum cascade laser (QCL) operating at 4.6 μm, is employed for simultaneous detection of three main isotopic species (14N15N16O, 15N14N16O and 14N14N16O). To enable a high-precision analysis of N2O isotopic species at ambient mixing ratios, a liquid nitrogen-free preconcentration unit is built to trap and load atmospheric N2O. The absorption spectra of 14N15N16O, 15N14N16O, and 14N14N16O between 2188.6 cm−1 and 2189 cm−1 are measured, and the respective ratios of the rare to the abundant isotopologues abundances are demonstrated. Moreover, spectroscopic parameters of pressure-broadening coefficient for selected absorption lines have been determined, and a good agreement is obtained by comparing with HITRAN database.

Ultrabright Room-Temperature Sub-Nanosecond Emission from Single Nitrogen-Vacancy Centers Coupled to Nanopatch Antennas.

Solid-state quantum emitters are in high demand for emerging technologies such as advanced sensing and quantum information processing. Generally, these emitters are not sufficiently bright for practical applications, and a promising solution consists in coupling them to plasmonic nanostructures. Plasmonic nanostructures support broadband modes, making it possible to speed up the fluorescence emission in room-temperature emitters by several orders of magnitude. However, one has not yet achieved such a fluorescence lifetime shortening without a substantial loss in emission efficiency, largely because of strong absorption in metals and emitter bleaching. Here, we demonstrate ultrabright single-photon emission from photostable nitrogen-vacancy (NV) centers in nanodiamonds coupled to plasmonic nanocavities made of low-loss single-crystalline silver. We observe a 70-fold difference between the average fluorescence lifetimes and a 90-fold increase in the average detected saturated intensity. The nanocavity-coupled NVs produce up to 35 million photon counts per second, several times more than the previously reported rates from room-temperature quantum emitters.

Ba(1-x)SrxMg3SiN4:Eu narrowband red phosphor

A new narrowband red phosphor, Ba0.8Sr0.2Mg3SiN4:Eu, suitable for use in LED lighting, has been identified as the optimal composition from the series of Ba(1-x)SrxMg3SiN4:Eu including x = 0, 0.2, 0.5, 0.8, and 1. Experimental X-ray diffraction measurements and structures calculated via density functional theory reveal that Ba(1-x)SrxMg3SiN4:Eu stabilizes in a tetragonal crystal structure, changing to the triclinic structure for Ba >0.8. Narrow band Eu2+ emission is observed in the tetragonal phase, but as a function of Ba substitution onto the Sr site, several properties change in concert: the emission maximum shifts to longer wavelengths, room temperature quantum efficiency improves, Eu2+ decay time increases and thermal stability of emission improves. Concomitant with the structure change to triclinic, the narrow Eu2+ emission band becomes broadened, the bandgap increases, and decay time slows to a typical Eu2+ decay of ∼1 μs. Although significantly moisture-sensitive, the strong absorption of Ba0.8Sr0.2Mg3SiN4:Eu at 450 nm, its emission peak at 635 nm and width of 51 nm FWHM provide efficient color rendering in the red, potentially achieving CRI and R9 values in excess of 95, along with good efficacy, in combination with other phosphors. Excitation intensity droop is comparable to other similar Eu-doped nitrides, but while thermally induced quenching is reduced with Ba substitution, it is still significant. The measured photoluminescence decay for Ba0.8Sr0.2Mg3SiN4:Eu of ∼200 ns is faster than of related Eu-doped nitrides, and together with a Q.E. of only ∼40% suggests the presence of competing non-radiative decay routes, thought to be due to thermal ionization of the Eu2+ excited state to the conduction band. Improved Q.E. for SrMg3SiN4:Eu partially substituted with Ba is likely due to the cation disorder this introduces, suppressing nonradiative processes correlated with lattice vibrations and increasing the population of shallow traps that release electrons on the emission lifetime timescale, consistent with the emission decay time lengthening and Q.E. improvement as a function of Ba content.

Magnetoluminescence in a Photostable, Brightly Luminescent Organic Radical in a Rigid Environment

We investigated the emission properties of a photostable luminescent organic radical, (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM), doped into host molecular crystals. The 0.05 wt %-doped crystals displayed luminescence attributed to a PyBTM monomer with a room-temperature emission quantum yield of 89 %, which is exceptionally high among organic radicals. The 10 wt %-doped crystals exhibited both PyBTM monomer and excimer-centered emission bands, and the intensity ratio of these two bands was modulated drastically by applying a magnetic field of up to 18 T at 4.2 K. This is the first observation of a magnetic field affecting the luminescence of organic radicals, and we also proposed a mechanism for this effect.

<i>Ab Initio</i> Theory of Si-Vacancy Quantum Bits in 4H and 6H-SiC

Point defects in wide band gap semiconductors have recently shown outstanding potential for implementing room temperature quantum bits and single photon emitters. These atomic scale tools can be used in various quantum information processing, sensing, and imaging applications. Silicon vacancy related photoluminescence centers in 4H, 6H, and 15R-SiC are among the most studied quantum bits that possess a particular spin-3/2 ground and excited state. The microscopic structures of these defects have been recently identified as isolated negatively charged silicon vacancy defects at the symmetrically non-equivalent silicon sites in SiC. Relying on this identification, here we carry out high precision ab initio simulations on negatively charged silicon vacancies in 4H and 6H-SiC and calculate the most important magneto-optical data, such as the zero-phonon photoluminescence energies, the zero-field-splitting, and the hyperfine tensors for the nearest and farther nuclear spins.

Coupling a Single Nitrogen-Vacancy Center in Nanodiamond to Superparamagnetic Nanoparticles

Single nitrogen-vacancy (NV) defect centers in diamond have been exploited as single photon sources and spin qubits due to their room-temperature robust quantum light emission and long electron spin coherence times. They were coupled to a manifold of structures, such as optical cavities, plasmonic waveguides, and even injected into living cells to study fundamental interactions of various nature at the nanoscale. Of particular interest are applications of NVs as quantum sensors for local nanomagnetometry. Here, we employ a nanomanipulation approach to couple a single NV center in a nanodiamond to a single few-nm superparamagnetic iron oxide nanoparticle in a controlled way. After measuring via relaxometry the magnetic particle spin-noise, we take advantage of the crystal strain ms = ± 1 spin level separation to detect the superparamagnetic particle’s effect in presence of a driving AC magnetic field. Our experiments provide detailed insight in the behavior of such particles with respect to high frequency fields. The approach can be extended to the investigation of increasingly complex, but controlled nanomagnetic hybrid particle assemblies. Moreover, our results suggest that superparamagnetic nanoparticles can amplify local magnetic interactions in order to improve the sensitivity of diamond nanosensors for specific measurement scenarios.

Room-temperature quantum cascade superluminescent light emitters with wide bandwidth and high temperature stability.

The realization of room-temperature (RT) mid-infrared (MIR) broadband light sources is fundamentally interesting and highly desirable for a number of applications. Recently, superluminescent light emitters (SLEs) based on quantum cascade (QC) structures have emerged as excellent candidates among mid-infrared broadband light sources. However, it is challenging to achieve RT-QCSLEs due to the very low efficiency of the spontaneous emission in the intersubband transitions. Here, we demonstrate the realization of a set of ~5 μm RT-SLEs under continuous wave (CW) or quasi-CW (10% duty circle) operation by using a two-phonon resonant QC active region and monolithic integrated waveguide structures. In addition, with the design of an inclined tapered cavity, the SLEs exhibit high milliwatt power, large spectral width of more than 200 cm-1 and good temperature characteristic. These demonstrated results are believed to be a big step forward to the applications of broadband MIR semiconductor light sources.

Liquid-Metal Enabled Droplet Circuits.

Conventional electrical circuits are generally rigid in their components and working styles, which are not flexible and stretchable. As an alternative, liquid-metal-based soft electronics offer important opportunities for innovation in modern bioelectronics and electrical engineering. However, their operation in wet environments such as aqueous solution, biological tissue or allied subjects still encounters many technical challenges. Here, we propose a new conceptual electrical circuit, termed as droplet circuit, to fulfill the special needs described above. Such unconventional circuits are immersed in a solution and composed of liquid metal droplets, conductive ions or wires, such as carbon nanotubes. With specifically-designed topological or directional structures/patterns, the liquid-metal droplets composing the circuit can be discrete and disconnected from each other, while achieving the function of electron transport through conductive routes or the quantum tunneling effect. The conductive wires serve as electron transfer stations when the distance between two separate liquid-metal droplets is far beyond that which quantum tunneling effects can support. The unique advantage of the current droplet circuit lies in the fact that it allows parallel electron transport, high flexibility, self-healing, regulation and multi-point connectivity without needing to worry about the circuit break. This would extend the category of classical electrical circuits into newly emerging areas like realizing room temperature quantum computing, making brain-like intelligence or nerve–machine interface electronics, etc. The mechanisms and potential scientific issues of the droplet circuits are interpreted and future prospects in this direction are outlined.

Epitaxial growth of highly strained antimonene on Ag(111)

The synthesis of antimonene, which is a promising group-V 2D material for both fundamental studies and technological applications, remains highly challenging. Thus far, it has been synthesized only by exfoliation or growth on a few substrates. In this study, we show that thin layers of antimonene can be grown on Ag (111) by molecular beam epitaxy. High-resolution scanning tunneling microscopy combined with theoretical calculations revealed that the submonolayer Sb deposited on a Ag (111) surface forms a layer of AgSb2 surface alloy upon annealing. Further deposition of Sb on the AgSb2 surface alloy causes an epitaxial layer of Sb to form, which is identified as antimonene with a buckled honeycomb structure. More interestingly, the lattice constant of the epitaxial antimonene (5 {\AA}) is much larger than that of freestanding antimonene, indicating a high tensile strain of more than 20%. This kind of large strain is expected to make the antimonene a highly promising candidate for room-temperature quantum spin Hall material.

Transient Spectroscopy of Glass-Embedded Perovskite Quantum Dots: Novel Structures in an Old Wrapping

Abstract Semiconductor doped glasses had been used by the research and engineering communities as color filters or saturable absorbers well before it was realized that their optical properties were defined by tiny specs of semiconductor matter known presently as quantum dots (QDs). Nowadays, the preferred type of QD samples are colloidal particles typically fabricated via organometallic chemical routines that allow for exquisite control of QD morphology, composition and surface properties. However, there is still a number of applications that would benefit from the availability of high-quality glass-based QD samples. These prospective applications include fiber optics, optically pumped lasers and amplifiers and luminescent solar concentrators (LSCs). In addition to being perfect optical materials, glass matrices could help enhance stability of QDs by isolating them from the environment and improving heat exchange with the outside medium. Here we conduct optical studies of a new type of all-inorganic CsPbBr3 perovskite QDs fabricated directly in glasses by high-temperature precipitation. These samples are virtually scattering free and exhibit excellent waveguiding properties which makes them well suited for applications in, for example, fiber optics and LSCs. However, the presently existing problem is their fairly low room-temperature emission quantum yields of only ca. 1%–2%. Here we investigate the reasons underlying the limited emissivity of these samples by conducting transient photoluminescence (PL) and absorption measurements across a range of temperatures from 20 to 300K. We observe that the low-temperature PL quantum yield of these samples can be as high as ~25%. However, it quickly drops (in a nearly linear fashion) with increasing temperature. Interestingly, contrary to traditional thermal quenching models, experimental observations cannot be explained in terms of a thermally activated nonradiative rate but rather suggest the existence of two distinct QD sub-ensembles of “emissive” and completely “nonemissive” particles. The temperature-induced variation in the PL efficiency is likely due to a structural transformation of the QD surfaces or interior leading to formation of extremely fast trapping sites or nonemissive phases resulting in conversion of emissive QDs into nonemissive. Thus, future efforts on improving emissivity of glass-based perovskite QD samples might focus on approaches for extending the range of stability of the low-temperature highly emissive structure/phase of the QDs up to room temperature.

Measurements of the intrinsic quantum efficiency and absorption length of tetraphenyl butadiene thin films in the vacuum ultraviolet regime

A key enabling technology for many liquid noble gas (LNG) detectors is the use of the common wavelength shifting medium tetraphenyl butadiene (TPB). TPB thin films are used to shift ultraviolet scintillation light into the visible spectrum for detection and event reconstruction. Understanding the wavelength shifting efficiency and optical properties of these films are critical aspects in detector performance and modeling and hence in the ultimate physics sensitivity of such experiments. This article presents the first measurements of the room-temperature microphysical quantum efficiency for vacuum-deposited TPB thin films – a result that is independent of the optics of the TPB or substrate. Also presented are measurements of the absorption length in the vacuum ultraviolet regime, the secondary re-emission efficiency, and more precise results for the “black-box” efficiency across a broader spectrum of wavelengths than previous results. The low-wavelength sensitivity, in particular, would allow construction of LNG scintillator detectors with lighter elements (Ne, He) to target light mass WIMPs.

Wafer-Scale Fabrication and Room-Temperature Experiments on Graphene-Based Gates for Quantum Computation

We have fabricated at wafer scale graphene-based configurations suitable for implementing at room temperature one-qubit quantum gates and a modified Deutsch-Jozsa algorithm. Our measurements confirmed the (quasi-)ballistic nature of charge carrier propagation through both types of devices, which have dimensions smaller than the room-temperature mean-free-path in graphene. As such, both graphene-based configurations were found to be suitable for quantum computation. These results are encouraging for demonstrating a miniaturized, room-temperature quantum computer based on graphene.

All-optical control and super-resolution imaging of quantum emitters in layered materials

Layered van der Waals materials are emerging as compelling two-dimensional platforms for nanophotonics, polaritonics, valleytronics and spintronics, and have the potential to transform applications in sensing, imaging and quantum information processing. Among these, hexagonal boron nitride (hBN) is known to host ultra-bright, room-temperature quantum emitters, whose nature is yet to be fully understood. Here we present a set of measurements that give unique insight into the photophysical properties and level structure of hBN quantum emitters. Specifically, we report the existence of a class of hBN quantum emitters with a fast-decaying intermediate and a long-lived metastable state accessible from the first excited electronic state. Furthermore, by means of a two-laser repumping scheme, we show an enhanced photoluminescence and emission intensity, which can be utilized to realize a new modality of far-field super-resolution imaging. Our findings expand current understanding of quantum emitters in hBN and show new potential ways of harnessing their nonlinear optical properties in sub-diffraction nanoscopy.

Free-Space Quantum Communication with a Portable Quantum Memory

The realization of an elementary quantum network that is intrinsically secure and operates over long distances requires the interconnection of several quantum modules performing different tasks. In this work we report the interconnection of four different quantum modules: (i) a random polarization qubit generator, (ii) a free-space quantum communication channel, (iii) an ultra-low noise portable quantum memory and (iv) a qubit decoder, in a functional elementary quantum network possessing all capabilities needed for quantum information distribution protocols. We create weak coherent pulses at the single photon level encoding polarization states $|H\rangle, |V\rangle, |D\rangle, |A\rangle$ in a randomized sequence. The random qubits are sent over a free-space link and coupled into a dual rail room temperature quantum memory and after storage and retrieval are analyzed in a four detector polarization analysis akin to the requirements of the BB84 protocol. We also show ultra-low noise and fully-portable operation, paving the way towards memory assisted all-environment free space quantum cryptographic networks.