Research and development of nanoscale luminescent and laser materials are part of the rapidly advancing nanoscience and nanotechnology. Because of unique spectroscopic properties and luminescent dynamics of f-electron states, doping luminescent rare earth ions into nano-hosts has been demonstrated as an optimistic approach to developing highly efficient and stable nanophosphors for various applications. In this article, we review the most recent progress in spectroscopic measurements of rare earth ion-activated low-dimensional nanostructures including nanolayers, core-shells, nanowires, nanotubes, and nanodisks. Among a large volume of work reported in the literature on many members of the rare earth series including Ce3+, Pr3+, Nd3+, Eu3+, and Er3+, we focus on recent findings in the spectroscopic and luminescence properties of Eu3+ doped nanolayers, core-shells, and nanotubes, because Eu3+ ions have been extensively studied and widely used as an ideal probe for fundamental understanding of nano-phenomena. Specifically, the dependence of the optical properties of rare earth ions on nanostructures is discussed in detail.
Research and development of nanoscale luminescent and laser materials are part of the rapidly advancing nanoscience and nanotechnology. Because of unique spectroscopic properties and luminescent dynamics of f-electron states, doping luminescent rare earth ions into nano-hosts has been demonstrated as an optimistic approach to developing highly efficient and stable nanophosphors for various applications. In this article, we review the most recent progress in spectroscopic measurements of rare earth ion-activated low-dimensional nanostructures including nanolayers, core-shells, nanowires, nanotubes, and nanodisks. Among a large volume of work reported in the literature on many members of the rare earth series including Ce3+, Pr3+, Nd3+, Eu3+, and Er3+, we focus on recent findings in the spectroscopic and luminescence properties of Eu3+ doped nanolayers, core-shells, and nanotubes, because Eu3+ ions have been extensively studied and widely used as an ideal probe for fundamental understanding of nano-phenomena. Specifically, the dependence of the optical properties of rare earth ions on nanostructures is discussed in detail.
Rare-earth ion doped crystals possess stable solid state physicochemical properties and long optical coherence time and spin coherence time, thus showing important development prospect in quantum information science and technology area. Investigations on macroscopic bulk rare-earth single crystals have obtained many promising results, especially in the field of optical quantum memory. With the rapid development of quantum information science, a variety of new functions or multifunctional integrations are found in rare earth crystal systems, such as on chip quantum storage, microwave to optical frequency conversion, scalable quantum single photon sources, and quantum logic gates. As a result, beyond the macroscopic bulk rare-earth single crystals, micro/nano-scale rare-earth crystals have received much attention in recent years and they are regarded as promising candidates in highly integrated hybrid quantum systems and miniaturized quantum devices. Moreover, wet chemical method synthesized micro/nano-scale rare-earth crystals have lower growth difficulty and more flexible manipulation in volume, shape and composition. Therefore, exploring high-performance micro/nano-scale rare-earth crystals and precisely manipulating their quantum states have become one of the important directions in today’s quantum information science and technology research. In this review, we first briefly introduce the basic concepts and high resolution spectroscopic techniques that are commonly used in rare earth ion doped crystals for quantum information science and technologies, such as hole burning technique and photon echo technique. Then we summarize comprehensively recent research status and development trends of rare earth ion doped polycrystalline nanoparticles, thin films, single crystal based micro systems, and some other micro/nano-scale rare earth platforms in terms of material fabrication, quantum coherence property, dephasing mechanisms, and also quantum device explorations. The latest research advances in quantum information applications such as quantum storage, quantum frequency conversion, quantum single photon sources and quantum logic gates are given. Finally, we discuss the possible optimization directions and strategies to improve the component design, material synthesis and quantum performance of micro/nano-scale rare earth crystals and their related quantum devices. This review highlights that the micro/nano-scale rare earth crystals may offer many new possibilities for designing quantum light-matter interfaces, thus are promising quantum systems to develop scalable and integrated quantum devices in the future.
Without using any trapping lasers, rare-earth (RE) ions can be doped into some nanofabricated materials in form of nanocrystals in a solid state matrix, thus rendering a natural trap for potential application as a quantum computing device. In particular, passive nuclear spin states of RE ions can be utilized as (i) optical quantum memory (with huge density as yielded from nanocrystals), (ii) qubits by encoding in ground hyperfine states and operated as (iii) two-qubit gate when transferring them to active magnetized electronic states. A feasible implementation of qubits is realised by using those doped RE ions whose open-shell (for inner highly shielded 4f shell electrons) energy levels and statevectors are well described by the crystal field (CF) interaction and hyperfine coupling in which the Hamiltonian is composed of various freeion interactions, the CF potential, electronic and nuclear Zeeman effects as well as the hyperfine interaction. For those qubit encoded in the two ground hyperfine states of RE ions, they can have fairly long lifetimes of days and coherence times (from 1.3s for Er3+ to 6 hours for Eu3+) due to the unique spectroscopic properties of RE ions. Because of the recent progress in optical single-ion detection for addressing individual qubits with a specific frequency channel, RE ions could be packed in a solid state 3D matrix at nanometer spacing, hence rendering very high qubit densities for quantum memories. Meanwhile, this configure also leads to strong dipole-dipole interactions (or high connectivity) between qubits which are not nearest neighbors. In this study, Kramers ions like 167Er and 171Yb doped in yttrium orthosilicate Y2SiO5 (YSO) nanocrystals will be investigated as a promising system for quantum computing because of their weak spin bath and possibility for being directly milled in single nanocrystals as nano-resonators. By using the famous Wien2k package to carry out the first-principles calculations, we can obtain the CF parameters and hyperfine constants as well as various electronic properties like energy gap and band structure for those Kramers RE ions doped in YSO. We shall present some essential findings from first-principles calculations to obtain various properties of the ground and excited CF and hyperfine states for those RE ions with an aim to optimize RE ions doping in YSO nanocrystals for quantum memories and qubits, contributing to scalable quantum computing architectures.
Rare-earth ions play an important role in modern technology as optically active elements in solid-state luminescent materials. In many of these materials, interactions between the electronic band states of the host crystal and the rare-earth ion's localized 4f N and 4f N−1 5d states influence the material's optical properties. The importance of these interactions is discussed for material applications in photon-gated hole burning, quantum information and phosphors. Material dependent trends in the relative binding energies of the 4f N states and the host bands have been observed and are summarized. An empirical model for the ion dependence of the 4f electron binding energies is formulated in terms of atomic number and compared with previous models. These models are extended to describe the 4f N−1 5d states with one additional parameter. Improved estimates for the free-ion ionization potentials used in the model are also presented and discussed.
Light-matter interaction at single quantum object level is a long-lived challenge and dream of physicists. From the 1970s, the development of single ion spectroscopy and the observation of single photon states pave a way to a new era of detecting, and coherently manipulating quantum objects with electromagnetic field at single-ion levels. Later on, the invention of single molecular spectroscopy offers a new approach to investigate single quantum objects in condensed matter, where the sophisticated trapping systems like in ions and cold atoms are not needed, resulting in the discovery of various of single photon emitters embedded in solids. Among all, single quantum dots and single negatively charged nitrogen-vacancy centers in diamond attract most attentions, since their single spins can be coherently manipulated and entangled by the light field giving rise to numerous applications from nanoscale sensing to quantum computing. They are intensively studied as the most promising candidates for the realization of solid-state quantum bits. However, these systems coupled to a complex environment which can result in rapid loss of spin coherence or optical instability. Finding an alternative solid-state single system with remarkable optical and spin properties is the motivation of this dissertation. Rare earth ions doped in inorganic crystal hosts provide promises not only by the high quality factor 4f-4f optical transitions but also by the well preserved and long-lived spin states, with the applications from solid-state laser spectroscopy to quantum information processing. However, for almost three decades, not being able to identify single rare earth elements in solids is the obstacle to achieve their full potential functionality. We demonstrated the first direct optical detection of single rare earth ions (praseodymium) in solids in 2012. This research was covered in my Master Degree Thesis. This dissertation presents experimental progress in optically detecting other single rare earth species in crystals, understanding their fundamental spectroscopy properties and coherently controlling them, which is mainly focused on single trivalent cerium ions in different host materials. Following the optical detection of single cerium ions in yttrium aluminum garnet (YAG), the optical and spin properties of single Ce ions are investigated. Single Ce ions show good photostability under the pulsed laser excitation. Still, like in other solid emitters, photo-induced dynamics of single Ce ions is observed, however, in a counterintuitive way under the continuous laser irradiation. To understand this behavior, we proposed a charge dynamics model, and developed a novel method to suppress this undesired charge dynamics. With this approach, we obtain the photoluminescence excitation spectrum of single Ce ions in YAG under a CW laser excitation. Narrow (~80 MHz) and spectrally stable optical transitions between the lowest Kramers doublets of the ground and the excited states are observed. In comparison with the large inhomogeneous broadening (500 GHz), narrow resonant transitions provide the good selectivity in the spectral domain. Moreover, the single Ce ground spin state presents a spin 1/2 system with anisotropy g factor. It results in the optical selection rules dependent on the directions of the external magnetic field. Under parallel external magnetic field with respect to the quantization axis, only the spin-flip transitions are allowed with high transition contrast. It gives the opportunity to optically initialize the ground spin state of single Ce ions with 97.5% fidelity. The coherent spin properties of single Ce ions can be investigated, after the successful optical initialization. By scanning the microwave frequency, we obtain the electron spin resonance of single Ce spin transitions. We show the spin state has a coherence time of 290 ns, which is dominated by the surrounding aluminum nuclear spin bath and impurities induced electron spin bath. The coherence time can be extended to 2 ms through dynamical decoupling method, which approaches closely to the upper limit 4.5 ms due to spin-lattice relaxation. This result indicates single Ce electron spin can be a good solid-state qubit. With the combination of optical and spin manipulations of single Ce ions, a quantum interface between a single spin and a single photon is observed by monitoring the temporal behavior of circularly polarized emission photons from the ion. We obtain the Larmor precession of the excited spin state, indicating the direct mapping of the excited spin states of single Ce ions onto the polarization states of the fluorescence photons. Furthermore, with both optical and spin access, we all-optically demonstrate coherent population trapping of a single Ce spin qubit. To scale up the system for further applications, we present the nano-scale engineering of rare earth species in YAG crystal, with the acquirement of the production yield of Ce and Pr implantation (53 and 91% respectively). The optical and spin properties of single implanted Ce ions show fairly good performance, which paves the way towards coherent coupling of single rare earth qubits in a small volume. Besides the study of single Ce ions, the spectroscopy properties of single praseodymium ions in YAG crystal are investigated. We obtain the photoluminescence excitation spectrum and the hyperfine splitting of a single praseodymium ion. All-optical control of a single praseodymium ion is achieved. In this dissertation, we solve the key problem of optically detecting, spectrally studying and coherently manipulating single rare earth ions in solids. The developed methods including optical detection, initialization, readout, coherent control and nanoscale production of single rare earth elements in crystals offer novel and powerful tools for understanding and exploring the fundamental spectroscopy properties of single rare earth elements in solids. It paves a way towards constructing scalable quantum network based on single rare earth solid-state qubits.
Abstract Rare‐earth dopants are arguably one of the most studied optical centers in solids, with applications spanning from laser optoelectronics, biosensing, lighting to displays. Nevertheless, harnessing rare‐earth dopants’ extraordinary coherence properties for quantum information technologies is a relatively new endeavor, and has been rapidly advancing in recent years. Leveraging the state‐of‐the‐art photonic technologies, on‐chip rare‐earth quantum devices functioning as quantum memories, single photon sources and transducers have emerged, often with potential performances unrivaled by other solid‐state quantum technologies. These existing quantum devices, however, nearly exclusively rely on macroscopic bulk materials as substrates, which may limit future scalability and functionalities of such quantum systems. Thus, the development of new platforms beyond single crystal bulk materials has become an interesting approach. In this review article, we summarize the latest progress towards nanoscale, low‐dimensional rare‐earth doped materials for enabling next generation rare‐earth quantum devices. Different platforms with a variety of synthesis methods are surveyed. Their key metrics measured to date are presented and compared. Special attention is placed on the connection between the topology of each platform to its target device applications. Lastly, an outlook for near term prospects of these platforms are given, with a hope to spur broader interests in rare‐earth doped materials as a promising candidate for quantum information technologies.
Since quantum information technologies are expected to offer communication security and high computational capacities, research in the field is currently attracting a lot of attention. Among the materials studied so far, rare earth doped inorganic insulators are one of the most promising. With the different available trivalent rare earth ions, the visible and the IR range including the telecom wavelength at 1.5 μm can be covered. Transitions are usually narrow, and at low temperatures, long optical and spin coherence times can often be observed. Investigations using bulk single crystals have already led to many promising results. Recently, spectroscopic studies have been extended to other forms of inorganic materials, such as transparent ceramics, thin films, and nanoparticles for single rare‐earth qubits. Progress in these areas is expected to offer many new possibilities for the design of quantum light‐matter interfaces and scalable quantum memories and processors.