Ultra-narrow optical linewidths in rare-earth molecular crystals.

Rare-earth ions (REIs) are promising solid-state systems for building light-matter interfaces at the quantum level1,2. This relies on their potential to show narrow optical and spin homogeneous linewidths, or, equivalently, long-lived quantum states. This enables the use of REIs for photonic quantum technologies such as memories for light, optical-microwave transduction and computing3-5. However, so far, few crystalline materials have shown an environment quiet enough to fully exploit REI properties. This hinders further progress, in particular towards REI-containing integrated nanophotonics devices6,7. Molecular systems can provide such capability but generally lack spin states. If, however, molecular systems do have spin states, they show broad optical lines that severely limit optical-to-spin coherent interfacing8-10. Here we report on europium molecular crystals that exhibit linewidths in the tens of kilohertz range, orders of magnitude narrower than those of other molecular systems. We harness this property to demonstrate efficient optical spin initialization, coherent storage of light using an atomic frequency comb, and optical control of ion-ion interactions towards implementation of quantum gates. These results illustrate the utility of rare-earth molecular crystals as a new platform for photonic quantum technologies that combines highly coherent emitters with the unmatched versatility in composition, structure and integration capability of molecular materials.

Synthesis and Crystal Structure of the Europium(II) Hydride Oxide Iodide Eu5H2O2I4 Showing Blue-Green Luminescence.

As the first europium(II) hydride oxide iodide, dark red single crystals of Eu5H2O2I4 could be synthesized from oxygen-contaminated mixtures of EuH2 and EuI2. Its orthorhombic crystal structure (a = 1636.97(9) pm, b = 1369.54(8) pm, c = 604.36(4) pm, Z = 4) was determined via single-crystal X-ray diffraction in the space group Cmcm. Anion-centred tetrahedra [HEu4]7+ and [OEu4]6+ serve as central building blocks interconnected via common edges to infinite ribbons parallel to the c axis. These ribbons consist of four trans-edge connected (Eu2+)4 tetrahedra as repetition unit, two H--centred ones in the inner part, and two O2--centred ones representing the outer sides. They are positively charged, according to ∞1{[Eu5H2O2]4+}, to become interconnected and charge-balanced by iodide anions. Upon excitation with UV light, the compound shows blue-green luminescence with the shortest Eu2+ emission wavelength ever observed for a hydride derivative, peaking at 463 nm. The magnetic susceptibility of Eu5H2O2I4 follows the Curie-Weiss law down to 100 K, and exhibits a ferromagnetic ordering transition at about 10 K.

A Frequency-Multiplexed Coherent Electro-optic Memory in Rare Earth Doped Nanoparticles.

Quantum memories for light are essential components in quantum technologies like long-distance quantum communication and distributed quantum computing. Recent studies have shown that long optical and spin coherence lifetimes can be observed in rare earth doped nanoparticles, opening exciting possibilities over bulk materials, e.g., for enhancing coupling to light and other quantum systems, and material design. Here, we report on coherent light storage in Eu3+:Y2O3 nanoparticles using the Stark echo modulation memory (SEMM) quantum protocol. We first measure a nearly constant Stark coefficient of 50 kHz/(V/cm) across a bandwidth of 15 GHz, which is promising for broadband operation. Storage of light is then demonstrated with an effective coherence lifetime of 5 µs. Pulses with two different frequencies are also stored, confirming frequency-multiplexing capability, and are used to demonstrate the memory high phase fidelity. These results open the way to nanoscale optical quantum memories with increased efficiency, bandwidth, and processing capabilities.

Simultaneous coherence enhancement of optical and microwave transitions in solid-state electronic spins.

Solid-state electronic spins are extensively studied in quantum information science, as their large magnetic moments offer fast operations for computing1 and communication2-4, and high sensitivity for sensing5. However, electronic spins are more sensitive to magnetic noise, but engineering of their spectroscopic properties, for example, using clock transitions and isotopic engineering, can yield remarkable spin coherence times, as for electronic spins in GaAs6, donors in silicon7-11 and vacancy centres in diamond12,13. Here we demonstrate simultaneously induced clock transitions for both microwave and optical domains in an isotopically purified 171Yb3+:Y2SiO5 crystal, reaching coherence times of greater than 100 µs and 1 ms in the optical and microwave domains, respectively. This effect is due to the highly anisotropic hyperfine interaction, which makes each electronic-nuclear state an entangled Bell state. Our results underline the potential of 171Yb3+:Y2SiO5 for quantum processing applications relying on both optical and spin manipulation, such as optical quantum memories4,14, microwave-to-optical quantum transducers15,16, and single-spin detection17, while they should also be observable in a range of different materials with anisotropic hyperfine interactions.

Electron Spin Coherence in Optically Excited States of Rare-Earth Ions for Microwave to Optical Quantum Transducers.

Efficient and reversible optical to microwave transducers are required for entanglement transfer between superconducting qubits and light in quantum networks. Rare-earth-doped crystals with narrow optical and spin transitions are a promising system for enabling these devices. Current resonant transduction approaches use ground-state electron spin transitions that have coherence lifetimes often limited by spin flip-flop processes and spectral diffusion, even at very low temperatures. We investigate spin coherence in an optically excited state of an Er^{3+}: Y_{2}SiO_{5} crystal at temperatures from 1.6 to 3.5 K for a low 8.7 mT magnetic field compatible with superconducting resonators. Spin coherence and population lifetimes of up to 1.6 µs and 1.2 ms, respectively, are measured by optically detected spin echo experiments. Analysis of decoherence processes suggest that ms coherence can be reached at lower temperatures for the excited-state spins, whereas ground-state spin coherence would be limited to a few µs due to resonant interactions with other Er^{3+} spins in the lattice and greater instantaneous spectral diffusion from the radio-frequency control pulses. We propose a quantum transducer scheme with potential for close to unity efficiency that exploits the advantages offered by spin states of the optically excited electronic energy levels.

Polarized Luminescence of Anisotropic LaPO4:Eu Nanocrystal Polymorphs.

Lanthanide elements exhibit highly appealing spectroscopic properties that are extensively used for phosphor applications. Their luminescence contains precise information on the internal structure of the host materials. Especially, the polarization behavior of the transition sublevel peaks is a fingerprint of the crystal phase, symmetry, and defects. However, this unique feature is poorly explored in current research on lanthanide nanophosphors. We here report on a detailed investigation of the evolution of Eu3+ luminescence during the thermally induced phase transition of LaPO4 nanocrystal hosts. By means of c-axis-aligned nanocrystal assemblies, we demonstrate a dramatic change of the emission polarization feature corresponding to the distinct Eu3+ site symmetries in different LaPO4 polymorphs. We also show that changes of the nanocrystal structure can be identified by this spectroscopic method, with a much higher sensitivity than the X-ray diffraction analysis. This new insight into the nanostructure-luminescence relationship, associated with the unprecedented polarization characterizations, provides a new methodology to investigate phase transitions in nanomaterials. It also suggests a novel function of lanthanide emitters as orientation-sensing nanoprobes for innovative applications such as in bioimaging or microfluidics.

Optical Line Width Broadening Mechanisms at the 10 kHz Level in Eu3+:Y2O3 Nanoparticles.

We identify the physical mechanisms responsible for the optical homogeneous broadening in Eu3+:Y2O3 nanoparticles to determine whether rare-earth crystals can be miniaturized to volumes less than λ3 while preserving their appeal for quantum technology hardware. By studying how the homogeneous line width depends on temperature, applied magnetic field, and measurement time scale, the dominant broadening interactions for various temperature ranges above 3 K were characterized. Below 3 K the homogeneous line width is dominated by an interaction not observed in bulk crystal studies. These measurements demonstrate that broadening due to size-dependent phonon interactions is not a significant contributor to the homogeneous line width, which contrasts previous studies in rare-earth ion nanocrystals. Importantly, the results provide strong evidence that for the 400 nm diameter nanoparticles under study the minimum line width achieved (45 ± 1 kHz at 1.3 K) is not fundamentally limited. In addition, we highlight that the expected broadening caused by electric field fluctuations arising from surface charges is comparable to the observed broadening. Under the assumption that such Stark broadening is a significant contribution to the homogeneous line width, several strategies for reducing this line width to below 10 kHz are discussed. Furthermore, it is demonstrated that the Eu3+ hyperfine state lifetime is sufficiently long to preserve spectral features for time scales up to 1 s. These results allow integrated rare-earth ion quantum optics to be pursued at a submicron scale and, hence, open up directions for greater scaling of rare-earth quantum technology.

High-Precision Measurement of the Dzyaloshinsky-Moriya Interaction between Two Rare-Earth Ions in a Solid.

We report on a direct measurement of the pairwise antisymmetric exchange interaction, known as the Dzyaloshinsky-Moriya interaction (DMI), in a Nd^{3+}-doped YVO_{4} crystal. To this end, we introduce a broadband electron spin resonance technique coupled with an optical detection scheme which selectively detects only one Nd^{3+}-Nd^{3+} pair. Using this technique we can fully measure the spin-spin coupling tensor, allowing us to experimentally determine both the strength and direction of the DMI vector. We believe that this ability to fully determine the interaction Hamiltonian is of interest for studying the numerous magnetic phenomena where the DMI interaction is of fundamental importance, including multiferroics. We also detect a singlet-triplet transition within the pair, with a highly suppressed magnetic-field dependence, which suggests that such systems could form singlet-triplet qubits with long coherence times for quantum information applications.

Impact of rare earth element clusters on the excited state lifetime evolution under irradiation in oxide glasses.

Rare earth doped active glasses and fibers can be exposed to ionizing radiations in space and nuclear applications. In this work, we analyze the evolution of (2)F(5/2) excited state lifetime in Yb(3+) ions in irradiated aluminosilicate glasses by electrons and γ rays. It is found that the variation of lifetimes depends on the Yb(3+) clusters content of the glasses for irradiation doses in the 10(2)- 1.5∙10(9) Gy range. In particular, glasses with high clustering show a smaller decrease in lifetime with increasing radiation dose. This behavior is well correlated to the variation in paramagnetic defects concentration determined by electron paramagnetic resonance. This effect is also observed in Yb(3+) doped phosphate and Er(3+) doped aluminosilicate glasses, inferring that clustering plays an important role in irradiation induced quenching.

Coherent storage of microwave excitations in rare-earth nuclear spins.

Interfacing between various elements of a computer--from memory to processors to long range communication--will be as critical for quantum computers as it is for classical computers today. Paramagnetic rare-earth doped crystals, such as Nd(3+):Y2SiO5(YSO), are excellent candidates for such a quantum interface: they are known to exhibit long optical coherence lifetimes (for communication via optical photons), possess a nuclear spin (memory), and have in addition an electron spin that can offer hybrid coupling with superconducting qubits (processing). Here we study two of these three elements, demonstrating coherent storage and retrieval between electron and (145)Nd nuclear spin states in Nd(3+):YSO. We find nuclear spin coherence times can reach 9 ms at ∼5 K, about 2 orders of magnitude longer than the electron spin coherence, while quantum state and process tomography of the storage or retrieval operation between the electron and nuclear spin reveal an average state fidelity of 0.86. The times and fidelities are expected to further improve at lower temperatures and with more homogeneous radio-frequency excitation.

Coherent Spin Control at the Quantum Level in an Ensemble-Based Optical Memory.

Long-lived quantum memories are essential components of a long-standing goal of remote distribution of entanglement in quantum networks. These can be realized by storing the quantum states of light as single-spin excitations in atomic ensembles. However, spin states are often subjected to different dephasing processes that limit the storage time, which in principle could be overcome using spin-echo techniques. Theoretical studies suggest this to be challenging due to unavoidable spontaneous emission noise in ensemble-based quantum memories. Here, we demonstrate spin-echo manipulation of a mean spin excitation of 1 in a large solid-state ensemble, generated through storage of a weak optical pulse. After a storage time of about 1 ms we optically read-out the spin excitation with a high signal-to-noise ratio. Our results pave the way for long-duration optical quantum storage using spin-echo techniques for any ensemble-based memory.

Faithful solid state optical memory with dynamically decoupled spin wave storage.

We report a high fidelity optical memory in which dynamical decoupling is used to extend the storage time. This is demonstrated in a rare-earth doped crystal in which optical coherences were transferred to nuclear spin coherences and then protected against environmental noise by dynamical decoupling, leading to storage times of up to 4.2 ms. An interference experiment shows that relative phases of input pulses are preserved through the whole storage and retrieval process with a visibility ≈1, demonstrating the usefulness of dynamical decoupling for extending the storage time of quantum memories. We also show that dynamical decoupling sequences insensitive to initial spin coherence increase retrieval efficiency.

Diode-pumped Pr:BaY2F8 continuous-wave orange laser.

We report the realization of the continuous wave laser emission in the orange at 607 nm from a Pr:BaY(2)F(8) (Pr:BYF) crystal pumped by a blue GaN laser diode. A maximal output power of 78 mW is obtained in a quasi-single transverse mode beam. The effect of reabsorption losses at the laser wavelength is also evidenced.

Optical spin-state polarization in a binuclear europium complex towards molecule-based coherent light-spin interfaces.

The success of the emerging field of solid-state optical quantum information processing (QIP) critically depends on the access to resonant optical materials. Rare-earth ion (REI)-based molecular systems, whose quantum properties could be tuned taking advantage of molecular engineering strategies, are one of the systems actively pursued for the implementation of QIP schemes. Herein, we demonstrate the efficient polarization of ground-state nuclear spins-a fundamental requirement for all-optical spin initialization and addressing-in a binuclear Eu(III) complex, featuring inhomogeneously broadened 5D0 → 7F0 optical transition. At 1.4 K, long-lived spectral holes have been burnt in the transition: homogeneous linewidth (Γh) = 22 ± 1 MHz, which translates as optical coherence lifetime (T2opt) = 14.5 ± 0.7 ns, and ground-state spin population lifetime (T1spin) = 1.6 ± 0.4 s have been obtained. The results presented in this study could be a progressive step towards the realization of molecule-based coherent light-spin QIP interfaces.

Dynamic control of Purcell enhanced emission of erbium ions in nanoparticles.

The interaction of single quantum emitters with an optical cavity enables the realization of efficient spin-photon interfaces, an essential resource for quantum networks. The dynamical control of the spontaneous emission rate of quantum emitters in cavities has important implications in quantum technologies, e.g., for shaping the emitted photons' waveform or for driving coherently the optical transition while preventing photon emission. Here we demonstrate the dynamical control of the Purcell enhanced emission of a small ensemble of erbium ions doped into a nanoparticle. By embedding the nanoparticles into a fully tunable high finesse fiber based optical microcavity, we demonstrate a median Purcell factor of 15 for the ensemble of ions. We also show that we can dynamically control the Purcell enhanced emission by tuning the cavity on and out of resonance, by controlling its length with sub-nanometer precision on a time scale more than two orders of magnitude faster than the natural lifetime of the erbium ions. This capability opens prospects for the realization of efficient nanoscale quantum interfaces between solid-state spins and single telecom photons with controllable waveform, for non-destructive detection of photonic qubits, and for the realization of quantum gates between rare-earth ion qubits coupled to an optical cavity.

Twenty-three-millisecond electron spin coherence of erbium ions in a natural-abundance crystal.

Erbium ions embedded in crystals have unique properties for quantum information processing, because of their optical transition at 1.5 µm and of the large magnetic moment of their effective spin-1/2 electronic ground state. Most applications of erbium require, however, long electron spin coherence times, and this has so far been missing. Here, by selecting a host matrix with a low nuclear-spin density (CaWO4) and by quenching the spectral diffusion due to residual paramagnetic impurities at millikelvin temperatures, we obtain a 23-ms coherence time on the Er3+ electron spin transition. This is the longest Hahn echo electron spin coherence time measured in a material with a natural abundance of nuclear spins and on a magnetically sensitive transition. Our results establish Er3+:CaWO4 as a potential platform for quantum networks.

Defect Engineering for Quantum Grade Rare-Earth Nanocrystals.

Nanostructured systems that combine optical and spin transitions offer new functionalities for quantum technologies by providing efficient quantum light-matter interfaces. Rare-earth (RE) ion-doped nanoparticles are promising in this field as they show long-lived optical and spin quantum states. However, further development of their use in highly demanding applications, such as scalable single-ion-based quantum processors, requires controlling defects that currently limit coherence lifetimes. In this work, we show that a post-treatment process that includes multistep high-temperature annealing followed by high-power microwave oxygen plasma processing advantageously improves key properties for quantum technologies. We obtain single crystalline Eu3+:Y2O3 nanoparticles (NPs) of 100 nm diameter, presenting bulk-like inhomogeneous line widths (Γinh) and population lifetimes (T1). Furthermore, a significant coherence lifetime (T2) extension, up to a factor of 5, is successfully achieved by modifying the oxygen-related point defects in the NPs by the oxygen plasma treatment. These promising results confirm the potential of engineered RE NPs to integrate devices such as cavity-based single-photon sources, quantum memories, and processors. In addition, our strategy could be applied to a large variety of oxides to obtain outstanding crystalline quality NPs for a broad range of applications.

Hyperfine spectroscopy in a quantum-limited spectrometer.

We report measurements of electron-spin-echo envelope modulation (ESEEM) performed at millikelvin temperatures in a custom-built high-sensitivity spectrometer based on superconducting micro-resonators. The high quality factor and small mode volume (down to 0.2 pL) of the resonator allow us to probe a small number of spins, down to 5×102. We measure two-pulse ESEEM on two systems: erbium ions coupled to 183W nuclei in a natural-abundance CaWO4 crystal and bismuth donors coupled to residual 29Si nuclei in a silicon substrate that was isotopically enriched in the 28Si isotope. We also measure three- and five-pulse ESEEM for the bismuth donors in silicon. Quantitative agreement is obtained for both the hyperfine coupling strength of proximal nuclei and the nuclear-spin concentration.

Fast electrical modulation of strong near-field interactions between erbium emitters and graphene.

Combining the quantum optical properties of single-photon emitters with the strong near-field interactions available in nanophotonic and plasmonic systems is a powerful way of creating quantum manipulation and metrological functionalities. The ability to actively and dynamically modulate emitter-environment interactions is of particular interest in this regard. While thermal, mechanical and optical modulation have been demonstrated, electrical modulation has remained an outstanding challenge. Here we realize fast, all-electrical modulation of the near-field interactions between a nanolayer of erbium emitters and graphene, by in-situ tuning the Fermi energy of graphene. We demonstrate strong interactions with a  >1000-fold increased decay rate for  ~25% of the emitters, and electrically modulate these interactions with frequencies up to 300 kHz - orders of magnitude faster than the emitter's radiative decay (~100 Hz). This constitutes an enabling platform for integrated quantum technologies, opening routes to quantum entanglement generation by collective plasmon emission or photon emission with controlled waveform.

Systematic investigation of the antiproliferative activity of a series of ruthenium terpyridine complexes.

Due to acquired resistance or limitations of the currently approved drugs against cancer, there is an urgent need for the development of new classes of compounds. Among others, there is an increasing attention towards the use of Ru(II) polypyridyl complexes. Most studies in the literature were made on complexes based on the coordination of N-donating bidentate ligands to the ruthenium core whereas studies on 2,2':6', 2″-terpyridine (terpy) coordinating ligands are relatively scare. However, several studies have shown that [Ru(terpy)2]2+ derivatives are able bind to DNA through various binding modes making these compounds potentially suitable as chemotherapeutic agents. Additionally, light irradiation of these compounds was shown to enable DNA cleavage, highlighting their potential use as photosensitizers (PSs) for photodynamic therapy (PDT). In this work, we present the systematic investigation of the potential of 7 complexes of the type [Ru(terpy)(terpy-X)]2+ (X = H (1), Cl (2), Br (3), OMe (4), COOH (5), COOMe (6), NMe2 (7)) as potential chemotherapeutic agents and PDT PSs. Importantly, six of the seven complexes were found to be stable in human plasma as well as photostable in acetonitrile upon continuous light irradiation (480 nm). The determination of the distribution coefficient logP values for the 7 complexes revealed their good water solubility. Complex 7 was found to be cytotoxic in the micromolar range in the dark as well as to have some phototoxicity upon light exposure at 480 nm in non-cancerous retinal pigment epithelium (RPE-1) and cancerous human cervical carcinoma (HeLa) cells. SYNOPSIS: The systematic investigation of the potential of 7 complexes of the type [Ru(terpy)(terpy-X)]2+ (terpy: 2,2':6', 2″-terpyridine; X = H (1), Cl (2), Br (3), OMe (4), COOH (5), COOMe (6), NMe2 (7)) as potential chemotherapeutic agents and photosensitizers for photodynamic therapy is presented.