Isotopic Purification Research Articles

Influence of interstitial cluster families on post-synthesis defect manipulation and purification of oxides using submerged surfaces.

Injection of interstitial atoms by specially prepared surfaces submerged in liquid water near room temperature offers an attractive approach for post-synthesis defect manipulation and isotopic purification in device structures. However, this approach can be limited by trapping reactions that form small defect clusters. The compositions and dissociation barriers of such clusters remain mostly unknown. This communication seeks to address this gap by measuring the dissociation energies of oxygen interstitial traps in rutile TiO2 and wurtzite ZnO exposed to liquid water. Isotopic self-diffusion measurements using 18O, combined with progressive annealing protocols, suggest the traps are small interstitial clusters with dissociation energies ranging from 1.3 to 1.9eV. These clusters may comprise a family incorporating various numbers, compositions, and configurations of O and H atoms; however, in TiO2, native interstitial clusters left over from initial synthesis may also play a role. Families of small clusters are probably common in semiconducting oxides and have several consequences for post-synthesis defect manipulation and purification of semiconductors using submerged surfaces.

A rapid procedure for isotopic purification of copper and nickel from seawater using an automated chromatography system

BackgroundTrace metals such as iron, nickel, copper, zinc, and cadmium (Fe, Ni, Cu, Zn, and Cd) are essential micronutrients (and sometimes toxins) for phytoplankton, and the analysis of trace-metal stable isotopes in seawater is a valuable tool for exploring the biogeochemical cycling of these elements in the ocean. However, the complex and often time-consuming chromatography process required to purify these elements from seawater has limited the number of trace-metal isotope samples which can be easily processed in biogeochemical studies. To facilitate the trace-metal stable isotope analysis, here, we describe a new rapid procedure that utilizes automated chromatography for extracting and purifying Ni and Cu from seawater for isotope analysis using a prepFAST-MC™ system (Elemental Scientific Inc.). ResultsWe have tested the matrix removal effectiveness, recoveries, and procedural blanks of the new purification procedure with satisfactory results. A nearly complete recovery of Ni and a quantitative recovery of Cu are achieved. The total procedural blanks are 0.33 ± 0.24 ng for Ni and 0.42 ± 0.18 ng for Cu, which is negligible for natural seawater samples. The new procedure cleanly separates Ni and Cu from key seawater matrix elements that may cause interferences during mass spectrometry analysis. When the new procedure was used to purify seawater samples for Ni and Cu stable isotope analysis by multi-collector ICP-MS, we achieved an overall uncertainty of 0.07 ‰ for δ60Ni and 0.09 ‰ for δ65Cu (2 SD). The new purification procedure was also tested using natural seawater samples from the South Pacific, for comparison of δ60Ni and δ65Cu achieved in the same samples purified by traditional hand columns. Both methods produced similar results, and the results from both methods are consistent with analyses of δ60Ni and δ65Cu from other ocean locations as reported by other laboratories. SignificanceThis study presents a new rapid procedure for seawater stable-metal isotope analysis by automating the chromatography step. We anticipate that the automated chromatography described here will facilitate the rapid and accurate analysis of seawater δ60Ni and δ65Cu in future studies, and may be adapted in the future to automate chromatographic purification of Fe, Zn, and Cd isotopes from seawater.

Boron and Nitrogen Isotope Effects on Hexagonal Boron Nitride Properties.

The unique physical, mechanical, chemical, optical, and electronic properties of hexagonal boron nitride (hBN) make it a promising 2D material for electronic, optoelectronic, nanophotonic, and quantum devices. Here, the changes in hBN's properties induced by isotopic purification in both boron and nitrogen are reported. Previous studies on isotopically pure hBN have focused on purifying the boron isotope concentration in hBN from its natural concentration (≈20 at% 10 B, 80 at% 11 B) while using naturally abundant nitrogen (99.6 at% 14 N, 0.4 at% 15 N), that is, almost pure 14 N. In this study, the class of isotopically purified hBN crystals to 15 N is extended. Crystals in the four configurations, namely h10 B14 N, h11 B14 N, h10 B15 N, and h11 B15 N, are grown by the metal flux method using boron and nitrogen single isotope (> 99%) enriched sources, with nickel plus chromium as the solvent. In-depth Raman and photoluminescence spectroscopies demonstrate the high quality of the monoisotopic hBN crystals with vibrational and optical properties of the 15 N-purified crystals at the state-of-the-art of currently available 14 N-purified hBN. The growth of high-quality h10 B14 N, h11 B14 N, h10 B15 N, and h11 B15 N opens exciting perspectives for thermal conductivity control in heat management, as well as for advanced functionalities in quantum technologies.

Isotopic Control of the Boron-Vacancy Spin Defect in Hexagonal Boron Nitride.

We report on electron spin resonance (ESR) spectroscopy of boron-vacancy (V_{B}^{-}) centers hosted in isotopically engineered hexagonal boron nitride (hBN) crystals. We first show that isotopic purification of hBN with ^{15}N yields a simplified and well-resolved hyperfine structure of V_{B}^{-} centers, while purification with ^{10}B leads to narrower ESR linewidths. These results establish isotopically purified h^{10}B^{15}N crystals as the optimal host material for future use of V_{B}^{-} spin defects in quantum technologies. Capitalizing on these findings, we then demonstrate optically induced polarization of ^{15}N nuclei in h^{10}B^{15}N, whose mechanism relies on electron-nuclear spin mixing in the V_{B}^{-} ground state. This work opens up new prospects for future developments of spin-based quantum sensors and simulators on a two-dimensional material platform.

Magnetometry Based on Silicon-Vacancy Centers in Isotopically Purified 4H - SiC

Point defects in solid-state materials are promising systems in the fields of quantum information, communications, and sensing. Particular to sensing, defects with coherent spin states are used for high-sensitivity room-temperature sensing under ambient conditions. Applications involving magnetic sensing with point defects are mostly dominated by the nitrogen-vacancy center in diamond, which possesses an attractive combination of spin coherence at room temperature as well as spin initialization and read-out. However, spin defects in other materials are explored as alternatives, especially in industrially mature materials, such as silicon carbide. Here, we report on the improved sensitivity of a magnetic sensor system utilizing an ensemble of silicon vacancies in silicon carbide due to isotopic purification of the host crystal. A maximum sensitivity of 4.0 nT/\ensuremath{\surd}Hz is reported, representing an order of magnitude improvement from the best previously reported sensitivity. Additional sensing modalities, such as angle-resolved magnetic imaging and highly broadband ac field sensing, are also demonstrated.

Non-Covalent Isotope Effects.

In this Perspective, we present examples of isotope effects that originate from noncovalent interactions, mainly hydrogen bonding, electrostatics, and confinement. They are traditionally widely used in isotopic enrichment processes, as well as in studies of mechanisms of different (bio)chemical and physical phenomena. We then show the emerging areas of their applications, mainly medical and material sciences. We stress that these emerging applications require either high enrichment or isotopic substitution, which requires the development of new effective techniques of isotopic purification.

Orders of Magnitude Improvement in Coherence of Silicon-Vacancy Ensembles in Isotopically Purified 4H - SiC

For solid-state spin systems, unwanted interactions with surrounding spin baths and inhomogeneity are ubiquitous challenges. In defect spin systems, part of this challenge is that the process of generating the desired defect often involves creating numerous unwanted defects that induce dephasing. Here we show that many of these issues can be alleviated with the silicon vacancy in silicon carbide (SiC), which is a simple defect to produce as it does not require the introduction of impurity atoms into the crystal. Previous measurements of the inhomogeneous dephasing time T2∗ of silicon-vacancy ensembles have thus far been limited to a few 100 ns due to the nuclear spin bath. We perform isotopic purification to minimize the influence of nuclear spins, leading to an order of magnitude improvement in the T2∗ at room temperature. Further improvements emerge by suppressing the effects of strain inhomogeneity via an informed choice of basis in the spin quartet. Combining these techniques leads to about a factor 50 improvement in the T2∗ of the defect ensemble even at high defect densities.Received 31 August 2021Accepted 18 February 2022DOI:https://doi.org/10.1103/PRXQuantum.3.010343Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.Published by the American Physical SocietyPhysics Subject Headings (PhySH)Research AreasCoherent controlColor centersQuantum optics with artificial atomsSpin dynamicsVacanciesAtomic, Molecular & OpticalCondensed Matter, Materials & Applied Physics

Extended spin coherence of the zinc-vacancy centers in ZnSe with fast optical access

Qubits based on crystal defect centers have been shown to exhibit long spin coherence times, up to seconds at room temperature. However, they are typically characterized by a comparatively slow initialization timescale. Here, fluorine implantation into ZnSe epilayers is used to induce defect states that are identified as zinc vacancies. We study the carrier spin relaxation in these samples using various pump-probe measurement methods, assessing phenomena such as resonant spin amplification, polarization recovery, and spin inertia in transverse or longitudinal magnetic field. The spin dynamics in isotopically natural ZnSe show a significant influence of the nuclear spin bath. Removing this source of relaxation by using isotopic purification, we isolate the anisotropic exchange interaction as the main spin dephasing mechanism and find spin coherence times of 100 ns at room temperature, with the possibility of fast optical access on the picosecond time scales through excitonic transitions of ZnSe.

High-purity solid parahydrogen.

Alkali atoms trapped in solid hydrogen matrices have demonstrated ultralong electron spin coherence times and are promising as quantum sensors. Their spin coherence is limited by magnetic noise from naturally occurring orthohydrogen molecules in the parahydrogen matrix. In the gas phase, the orthohydrogen component of hydrogen can be converted to parahydrogen by flowing it over a catalyst held at cryogenic temperatures, with lower temperatures giving a lower orthohydrogen fraction. In this work, we use a single cryostat to reduce the orthohydrogen fraction of hydrogen gas and grow a solid matrix from the resulting high-purity parahydrogen. We demonstrate the operation of the catalyst down to a temperature of 8K, and we spectroscopically verify that orthohydrogen impurities in the resulting solid are at a level <10-6. We also find that, at sufficiently low temperatures, the cryogenic catalyst provides isotopic purification, reducing the HD fraction.

Large substitutional impurity isotope shift in infrared spectra of boron-doped diamond

Isotopic enrichment offers cutting-edge properties of materials opening exciting research and development opportunities. In semiconductors, reached progress of ultimate control in growth and doping techniques follows nowadays the high level isotopic purification. This requires deep understanding of isotopic disorder effects and techniques of their effective determination. Isotopic content of both crystal lattice and impurity centers cause the effects, which can be examined by different optical techniques. While disorder in the host lattice can be straight forward evaluated by inelastic light scattering or by SIMS measurements, determination of isotopic contributions of many orders less presented impurities remains challenging and usually observed in high-resolution photoluminescence or optical absorption spectra. Boron-doped diamonds exhibit complex infrared absorption spectra while boron-related luminescence remains unobserved. Boron, as a most light element acting as a hydrogen-like dopant in elemental semiconductors, has a largest relative difference in its isotope masses, and by this, cause the largest isotopic disorder in semiconductors, including diamond, an elemental semiconductor with the lightest atomic mass of a host lattice. This enables an access to the isotopic constitution of boron in diamond by infrared absorption spectroscopy. By comparison of low-temperature absorption spectra of a natural (20% of 10B and 80% of 11B isotopes) and 11B enriched (up to 99%) doped diamonds we differentiate the intracenter transitions related to 10B and to 11B isotopes. We have found that the isotopic spectral lines of the same boron intracenter transition are separated with the energy of about 0.7 meV. This is the largest impurity isotopic shift ever observed in semiconductors doped by hydrogen-like impurity centers.

Entanglement and control of single nuclear spins in isotopically engineered silicon carbide.

Nuclear spins in the solid state are both a cause of decoherence and a valuable resource for spin qubits. In this work, we demonstrate control of isolated 29Si nuclear spins in silicon carbide (SiC) to create an entangled state between an optically active divacancy spin and a strongly coupled nuclear register. We then show how isotopic engineering of SiC unlocks control of single weakly coupled nuclear spins and present an ab initio method to predict the optimal isotopic fraction that maximizes the number of usable nuclear memories. We bolster these results by reporting high-fidelity electron spin control (F = 99.984(1)%), alongside extended coherence times (Hahn-echo T2 = 2.3 ms, dynamical decoupling T2DD > 14.5 ms), and a >40-fold increase in Ramsey spin dephasing time (T2*) from isotopic purification. Overall, this work underlines the importance of controlling the nuclear environment in solid-state systems and links single photon emitters with nuclear registers in an industrially scalable material.

Spin coherence in two-dimensional materials

Spin defects in semiconducting solids are promising platforms for the realization of quantum bits. At low temperature and in the presence of a large magnetic field, the central spin decoherence is mainly due to the fluctuating magnetic field induced by nuclear spin flip-flop transitions. Using spin Hamiltonians and a cluster expansion method, we investigate the electron spin coherence of defects in two-dimensional (2D) materials, including delta-doped diamond layers, thin Si films, MoS2, and h-BN. We show that isotopic purification is much more effective in 2D than in three-dimensional materials, leading to an exceptionally long spin coherence time of more than 30 ms in an isotopically pure monolayer of MoS2.

28Si+ ion beams from Penning ion source based implanter systems for near-surface isotopic purification of silicon.

Modern computing technology is based on silicon. To date, a cost-effective and easy to implement method to obtain isotopically pure silicon is highly desirable for attaining efficient heat dissipation in microelectronic devices and for hosting spin qubits in quantum computing. We propose that it is possible to use a 28Si+ ion beam to obtain an isotopically pure near-surface region in wafer silicon. However, this requires a highly stable, high current, and isotopically pure 28Si ion beam. This work presents and discusses the instrumentation details and experimental parameters involved in generating this required ion beam. Silane is used as the precursor gas and is decomposed in a Penning ion source to generate a 28Si+ ion beam. The influence of key ion source parameters such as the gas flow rate, magnetic field strength, and anode voltage is presented. An isotopically pure 28Si+ ion beam with 10 ± 0.5 μA current on the target is obtained at the GNS Science 40 kV ion implanter. The beam was observed to be stable for at least 8 h and contains less than 700 ppm of other Si isotopes. This high current and high purity provides opportunities to explore efficient modification of the isotopic distribution in a native Si substrate at ambient temperature. The results highlight opportunities offered by using Penning ion source based low energy ion implanters for the synthesis of isotopically modified Si surface regions-a technique also applicable to other materials such as diamonds and diamond-like carbon.

Effect of isotopic purification on spectral-hole narrowing in 167Er3+ hyperfine transitions

We investigated spectral-hole narrowing in optical transitions between hyperfine sublevels in isotopically purified erbium ions (167Er3+). The homogeneous broadening Γh of the optical transition was measured in purified and non-purified Er3+-doped crystals via spectral-hole burning. The measured Γh in the purified 167Er3+ exhibited a significant reduction of the hole width because the fluctuation of the local magnetic field induced by the electron spins of the surrounding Er3+ ions was eliminated. Because the narrowing of the Γh is equivalent to the prolongation of the coherence time, the isotopic purification is effective for the coherent manipulation of quantum states.

Gate fidelity and coherence of an electron spin in an Si/SiGe quantum dot with micromagnet

The gate fidelity and the coherence time of a quantum bit (qubit) are important benchmarks for quantum computation. We construct a qubit using a single electron spin in an Si/SiGe quantum dot and control it electrically via an artificial spin-orbit field from a micromagnet. We measure an average single-qubit gate fidelity of ∼99% using randomized benchmarking, which is consistent with dephasing from the slowly evolving nuclear spins in the substrate. The coherence time measured using dynamical decoupling extends up to ∼400 μs for 128 decoupling pulses, with no sign of saturation. We find evidence that the coherence time is limited by noise in the 10-kHz to 1-MHz range, possibly because charge noise affects the spin via the micromagnet gradient. This work shows that an electron spin in an Si/SiGe quantum dot is a good candidate for quantum information processing as well as for a quantum memory, even without isotopic purification.

Cryogenic distillation facility for isotopic purification of protium and deuterium.

Isotopic purification of the protium and deuterium is an important requirement of many physics experiments. A cryogenic facility for high-efficiency separation of hydrogen isotopes with a cryogenic distillation column as the main element is described. The instrument is portable, so that it can be used at the experimental site. It was designed and built at the Petersburg Nuclear Physics Institute, Gatchina, Russia. Fundamental operating parameters have been measured including a liquid holdup in the column packing, the pressure drops across the column and the purity of the product at different operating modes. A mathematical model describes expected profiles of hydrogen isotope concentration along the distillation column. An analysis of ortho-parahydrogen isomeric composition by gas chromatography was used for evaluation of the column performance during the tuning operations. The protium content during deuterium purification (≤100 ppb) was measured using gas chromatography with accumulation of the protium in the distillation column. A high precision isotopic measurement at the Institute of Particle Physics, ETH-Zurich, Switzerland, provided an upper bound of the deuterium content in protium (≤6 ppb), which exceeds all commercially available products.

A new bench-top approach to the isotopic purification of 244Pu

A new approach to isotopic purification has been developed and applied to the production of a small quantity of 244Pu with an isotopic purity >99.996 %, as compared against the standard 244Pu available that displays an isotopic purity of 97.87 %. The presence of Pu isotopes 239Pu, 240Pu, 241Pu and 242Pu have been greatly reduced, allowing for higher spiking levels of the isotopically purified 244Pu tracer to be used in environmental level sample analysis. Details of the isotopic purification process will be described along with the effect this improved Pu tracer could have on analytical Pu mass spectrometry measurements.

Production, characterization and operation of $$^{76}$$ 76 Ge enriched BEGe detectors in GERDA

The GERmanium Detector Array (GERDA) at the Gran Sasso Underground Laboratory (LNGS) searches for the neutrinoless double beta decay (0{\nu}{\beta}{\beta}) of $^{76}$Ge. Germanium detectors made of material with an enriched $^{76}$Ge fraction act simultaneously as sources and detectors for this decay. During Phase I of the experiment mainly refurbished semi-coaxial Ge detectors from former experiments were used. For the upcoming Phase II, 30 new $^{76}$Ge enriched detectors of broad energy germanium (BEGe)-type were produced. A subgroup of these detectors has already been deployed in GERDA during Phase I. The present paper reviews the complete production chain of these BEGe detectors including isotopic enrichment, purification, crystal growth and diode production. The efforts in optimizing the mass yield and in minimizing the exposure of the $^{76}$Ge enriched germanium to cosmic radiation during processing are described. Furthermore, characterization measurements in vacuum cryostats of the first subgroup of seven BEGe detectors and their long-term behavior in liquid argon are discussed. The detector performance fulfills the requirements needed for the physics goals of GERDA Phase~II.

Phonon thermal transport in strained and unstrained graphene from first principles

A rigorous first principles Boltzmann-Peierls equation (BPE) for phonon transport approach is employed to examine the lattice thermal conductivity, ${\ensuremath{\kappa}}_{L}$, of strained and unstrained graphene. First principles calculations show that the out-of-plane, flexural acoustic phonons provide the dominant contribution to ${\ensuremath{\kappa}}_{L}$ of graphene for all strains, temperatures, and system sizes considered, supporting a previous prediction that used an optimized Tersoff empirical interatomic potential. For the range of finite system sizes considered, we show that the ${\ensuremath{\kappa}}_{L}$ of graphene is relatively insensitive to strain. This provides validation for use of the BPE approach to calculate ${\ensuremath{\kappa}}_{L}$ for unstrained graphene, which has recently been called into question. The temperature and system size dependence of the calculated ${\ensuremath{\kappa}}_{L}$ of graphene is in good agreement with experimental data. The enhancement of ${\ensuremath{\kappa}}_{L}$ with isotopic purification is found to be relatively small due to strong anharmonic phonon-phonon scattering. This work provides insight into the nature of phonon thermal transport in graphene, and it demonstrates the power of first principles thermal transport techniques.

Phonon-isotope scattering and thermal conductivity in materials with a large isotope effect: A first-principles study

The interplay between phonon-isotope and phonon-phonon scattering in determining lattice thermal conductivities in semiconductors and insulators is examined using an ab initio Boltzmann transport equation approach. We identify materials with large enhancements to their thermal conductivities with isotopic purification, known as the isotope effect, and we focus in particular on results for beryllium-VI compounds and cubic germanium carbide. We find that germanium carbide and beryllium selenide have very large room temperature isotope effects of 450$%$, far larger than in any other material. Thus, isotopic purification in these materials gives surprisingly high intrinsic room temperature thermal conductivities, over 1500 Wm${}^{\ensuremath{-}1}$ K${}^{\ensuremath{-}1}$ for germanium carbide and over 600 Wm${}^{\ensuremath{-}1}$ K${}^{\ensuremath{-}1}$ for beryllium selenide, well above those of the best metals. In compound semiconductors, a large mass ratio of the constituent atoms and large isotope mixture for the heavier atom gives enhanced isotope scattering. A frequency gap between acoustic and optic phonons (also due to a large mass ratio) and bunching of the acoustic phonon branches give weak anharmonic scattering. Combined, weak anharmonic phonon scattering and strong isotope scattering give a large isotope effect in the materials examined here. The physical insights discussed in this work will help guide the efficient manipulation of thermal transport properties of compound semiconductors through isotopic modification.