Quantum Defect Research Articles

Precision Spectroscopy of Radiation Transitions between Singlet Rydberg States of the Group IIb and Yb Atoms

The measurements of microwave (μw) and radio-frequency (RF) radiation quantitative parameters may be based on the quantum–optical approach to determine the spectral characteristics of radiation transitions between the Rydberg states of atoms. Frequencies and matrix elements are calculated for dipole transitions between opposite-parity Rydberg states nL 1L and n′L±1 1L±1 (where n′= n,n±1,n±2) of the singlet series in the alkaline–earth–metal-like atoms of group IIb (Zn, Cd, Hg) and Yb. The matrix elements determine the shifts of Rydberg-state energy levels in the field of resonance μw or RF radiation, splitting the resonance of electromagnetically induced transparency (EIT) for intensely absorbed probe radiation. Numerical computations based on the single-electron quantum defect method (QDM) and the Fues’ model potential (FMP) approach with the use of the most reliable data from the current literature on quantum defect values are performed for frequencies and matrix elements of transitions between singlet Rydberg states of 1S0-, 1P1-, 1D2-, and 1F3-series in Zn, Cd, Hg, and Yb atoms. The calculated data are approximated by polynomials in the powers of the principal quantum numbers. The polynomial coefficients are determined with the use of a standard curve-fitting interpolation polynomial procedure for numerically calculated functions. These approximation expressions provide new possibilities for accurately evaluating the frequencies and matrix elements of dipole transitions between Rydberg states over a wide range of quantum numbers n >> 1, accompanied by the emission and absorption of μw and RF photons.

High-throughput identification of spin-photon interfaces in silicon.

Color centers in host semiconductors are prime candidates as spin-photon interfaces for quantum applications. Finding an optimal spin-photon interface in silicon would move quantum information technologies toward a mature semiconducting host. However, the space of possible charged defects is vast, making the identification of candidates from experiments alone extremely challenging. Here, we use high-throughput first-principles computational screening to identify spin-photon interfaces among more than 1000 charged defects in silicon. The use of a single-shot hybrid functional approach is critical in enabling the screening of many quantum defects with a reasonable accuracy. We identify three promising spin-photon interfaces as potential bright emitters in the telecom band: [Formula: see text], [Formula: see text], and [Formula: see text]. These candidates are excited through defect-bound excitons, stressing the importance of such defects in silicon for telecom band operations. Our work paves the way to further large-scale computational screening for quantum defects in semiconductors.

High repetition rate π-polarized 1084 nm passively Q-switched Nd:MgO:LiNbO3 laser based on 888 nm thermally boosted pumping

We report a high-repetition-rate π-polarized 1084 nm passively Q-switched (PQS) Nd:MgO:LiNbO3 (Nd:MgO:LN) laser under 888 nm thermally boosted pumping. The 888 nm pumping is selected based on Nd:MgO:LN crystal absorption and energy level properties. Under 813 nm pumping, the continuous wave (CW) 1084 nm average output power (AOP) increased to 2.85 W. After that, 1084 nm is suppressed and gradually disappears as the pump power increases. At the same time, the 1093 nm AOP increases, and 4.4 W of 1093 nm laser is obtained. In contrast, under 888 nm pumping, the CW 1084 nm laser AOP of 5.16 W is obtained. The thermally boosted pumping can eliminate quantum defects caused by conventional 813 nm pumping non-radiative transitions and suppress unmatched σ-polarized 1093 nm output. Moreover, the Cr4+: YAG is replaced into the resonant cavity as the output mirror to obtain 1084 nm pulsed laser output. AOP with different initial transmission (T0) on laser output characteristics is measured under the compact resonant cavity structure. Finally, an AOP of 3.52 W pulsed laser with a repetition rate of 24.43 kHz and the highest peak power of 5.26 kW is obtained when T0 = 87 %, and the absorbed pump power is 20.87 W. The optical conversion efficiency is 16.87 %, and the slope efficiency is about 29.38 %.

FDTD modeling of excitation-balanced, mJ-level pulse amplifiers in Yb-doped double-clad optical fibers.

A finite-difference time-domain (FDTD) simulation of Yb-doped cladding-pumped, mJ-level, excitation-balanced fiber pulse amplifiers (EBFAs) is presented. In EBFAs, two pumps, one above (anti-Stokes pump, or ASP) and one below (Stokes pump, or SP) the signal wavelength, are utilized to reduce the net thermal energy generated due to the quantum defect. From the results of the FDTD simulation, detailed analyses on the fiber length optimization, excited Yb3+ population evolution, pump and signal power evolution, optical-to-optical (o-o) conversion efficiency, wall plug efficiency, as well as thermal energy generation are performed. For example, with an ASP at 990 nm and a SP at 975 nm, only 2.3 µJ of thermal energy is produced when generating a 2 mJ output pulse at 985 nm, whereas a pulse amplifier with only SP pumping rendering the same 2 mJ output gives more than 10 times the thermal energy. In the meantime, the system maintains an o-o efficiency of 8.43% and wall plug efficiency of 6.6%. The results here indicate the feasibility of the power-scaling of excitation-balanced laser systems, and the FDTD model will be beneficial for the design and optimization of such systems. The first half of this paper presents the FDTD model and provides an example calculation outlining the modeling procedure. The remaining half details the impact of varying laser parameters on system performance. These include pumping and input signal energies, repetition rates, and selection of the ASP, SP, and signal wavelengths. The results presented herein can also be extended to excitation balancing in other solid-state laser systems, such as Yb:YAG and Tm:YAG lasers.

Mean Lifetimes of ns, np, nd, & nf Levels of N V

Nitrogen is one of the key elements in the evolution and formation of stellar objects. Earth's atmosphere contains 21% oxygen and 78% nitrogen; these two gases give rise to aurora when ions of the solar wind in the ionosphere collide with them. Some aerosols made of nitrogen and oxygen are also found in the atmosphere. Nitrogen, hydrogen, carbon, and oxygen are the main contributors to the origin of life on Earth. The spectrum of nitrogen ion (N V) has been studied using Quantum defect theory (QDT) and Numerical Coulombic approximation (NCA). N V has two electrons in the core, with the nucleus, and one electron outside the core. It makes it hydrogen or lithium-like. In the first part, the energies of the ns, np, nd, and nf up to n < 30 were calculated with the help of QDT. In the second part, the wavelengths were calculated using the energies and line strength parameters using NCA. Very little experimental data on lifetime and transition probability are available; however, Biemont et al. have calculated the lifetime of the 48 levels of N V using coulomb approximation. In this study, we calculated the lifetime of 196 multiplets of N V. The results are compared with the available experimental and theoretical lifetimes; an excellent agreement was found between known lifetimes and calculated in this work. The lifetimes of 100 multiplets are presented for the first time. The lifetimes of each of the Rydberg series of N V were fitted, and a third-degree polynomial represents the lifetimes of each series.

Absorption Line Oscillator Strengths for the C 2Π(0)-A 2Σ+(0) Band of Nitric Oxide

We have determined absorption oscillator strengths for rotational transitions of the C 2Π(0)-A 2Σ+(0) band of NO, which has been detected in the upper atmosphere of Venus. The molecular quantum defect orbital method has been used in the calculation of the electronic transition moment and the Rydberg–valence interaction between the C 2Π(v = 0) and the B 2Π (v = 7) states has been considered. Considerable deviations from normal intensity distribution of the rotational lines have been found at J ≤ 5.5. As far as we know, the present line f-values are reported here for the first time. These data may be useful in the interpretation of the observations obtained by the Visible and Infrared Thermal Imaging Spectrometer instrument on the Venus Express spacecraft.

(Invited) Stochasticity in the Number of Quantum Defects in Fluorescent Carbon Nanotubes

Single wall carbon nanotubes (SWCNTs) display chirality dependent near infrared (NIR) fluorescence. Their optoelectronic properties can be further tuned by incorporating quantum defects/organic color centers (OCC) via reactions with diazonium salts. The absolute number of defects per SWCNT determines the properties but is not exactly known. Measuring it is complicated because typical SWCNT samples contain multiple chiralities, that congest the spectra and prevents to distinguish defects from different chiralities. Aqueous two-phase extraction (APTE) is a powerful technique to isolate specific chiralities. Here, we show that quantum defects do not affect APTE, which indicates that the chemical potential is not substantially affected and pinpoints to low numbers of defects. The purity of (6,5)-SWCNTs allows us to image the NIR fluorescence contributions (E11 below 1050 nm, and E11 * above 1050 nm) on the single SWCNT level and defect incorporation itself on the single molecule level. Interestingly, one observes a stochastic distribution of the numbers of defects, which can be explained by a Poisson distribution. We find a mean number of defects of 0-3 per SWCNT. These results indicate the large variance between ensemble and single particle picture. In summary, we show that single quantum defects can be counted by NIR imaging and that stochasticity plays a crucial role for their optical properties.

(Invited) Quantum Defects as Sensors

Organic color-centers are molecularly tunable quantum defects that can be synthetically introduced into semiconducting carbon nanotube hosts. Charge carriers in the form of electron-hole pairs (or excitons) are efficiently harvested at these atomic defect sites to emit as bright shortwave-infrared photons that carry local chemical information. These intriguing properties open new possibilities of pushing the limits of sensing and imaging. In this talk, we will discuss recent advances as well as the challenges and opportunities at this emerging frontier.

(Invited) Electroluminescence from Single-Walled Carbon Nanotubes with Quantum Defects

Individual single-walled carbon nanotubes with covalent sidewall defects have emerged as a new class of photon sources whose photoluminescence spectra can be tailored by the carbon nanotube chirality and the attached functional group/molecule. Here we present electroluminescence spectroscopy data from single-tube devices based on (7,5) carbon nanotubes, functionalized with dichlorobenzene molecules, and wired to graphene electrodes. We observe electrically generated, defect-induced emissions that are controllable by electrostatic gating and strongly red-shifted compared to emissions from pristine nanotubes. The defect-induced emissions are assigned to excitonic and trionic recombination processes by correlating electroluminescence excitation maps with electrical transport and photoluminescence data. At cryogenic conditions additional, gate-dependent emission lines appear which are assigned to phonon-assisted hot-exciton electroluminescence from quasi-levels. Similar results were obtained with functionalized (6,5) nanotubes. We also compare functionalized (7,5) electroluminescence data with photoluminescence of pristine and functionalized (7,5) nanotubes redox-doped using gold(III) chloride solution. This work shows that electroluminescence excitation is selective toward neutral defect-state configurations with the lowest transition energy, which in combination with gate-control over neutral versus charged defect-state emission leads to high spectral purity.Reference: Min-Ken Li et al., ACS Nano 2022 (doi: 10.1021/acsnano.2c03083) Figure 1

Advanced Data Analytics and Organic Color Centers for Diagnostic Applications

Biofluids, most notably serum, contain many molecules that together may help to define the physiological state of a person. A grand challenge is to use serum to identify a clinical state with a high degree of certainty. Rather than attempting to accomplish biomarker development on a one-to-one recognition basis, it may be more effective to determine a whole clinical state via perception-based platforms due to recent achievements in sensor technologies and computational algorithms. In this talk, we present the development of carbon nanotube-based nanosensor arrays wherein the optical responses of the nanotubes were used to train machine learning models. We introduce the optical and chemical diversity of nanosensor array using molecular masking effects of DNA-wrapping and covalent functionalization of fluorescent quantum defects on nanotube surface. Machine learning can be employed to process the complex spectral responses of nanosensors and recognize spectroscopic fingerprints of certain clinical states from serum. We will discuss how these methods can complement and improve conventional diagnostic assays.

Guanine Functionalization of SWCNTs Using Metalloporphyrin Photosensitizers

Chemical modifications of single-wall carbon nanotubes (SWCNT) have opened new areas in the creation of quantum defects and the tailoring of optical properties for these one-dimensional semiconducting materials. Recent research has revealed a novel and controllable chemical functionalization reaction in which guanine nucleobases of ssDNA coatings react covalently with the SWCNT side wall in the presence of singlet oxygen. Generation of singlet oxygen through photosensitizer optical excitation is a key part of this process. To further explore guanine functionalization of SWCNTs, we have investigated reaction kinetics under various conditions. We replaced the rose bengal photosensitizer by metalloporphyrin dyes. These have greater photostability and more intense and shorter wavelength absorptions, allowing them to be used at micro- to nanomolar concentrations and leaving a wider spectral transparency window for reaction monitoring. Excitation was at 405 nm. Our kinetic studies show that the rates of change of E11 and E22 energies depend linearly on sensitizer concentration, which implies that guanine functionalization is a first order reaction with respect to singlet oxygen. Using a series of oligos with the same length but different guanine contents, we find E11 spectral shifts that increase sub-linearly to an asymptotic value. To help understand the structure of the guanine covalent adduct, we also performed semi-empirical quantum chemistry simulations. These suggest that the lowest energy structure is bonded to two adjacent carbon atoms of the SWCNT sidewall, and that reaction exothermicity is larger for smaller diameter nanotubes. Computations will also be presented for presumed intermediate adducts of guanine peroxide bonded to (6,5) SWCNTs in different orientations relative to the nanotube axis.

A Generic Covalent Functionalization Concept for Near-Infrared Fluorescent Carbon Nanotube Biosensors

Biosensors are powerful tools with wide applications in basic research and biomedical diagnostics. In the last decades, the use of nanomaterials decorated with biological recognition units have attracted significant attention and reformed the field. However, this development requires substantial input from the chemical sciences.In this context, semiconducting single-walled carbon nanotubes (SWCNTs) are versatile near infrared (NIR, 870 – 2400 nm) emitting fluorophores. They have been non-covalently modified to create sensors that change their fluorescence when interacting with biomolecules. However, non-covalent chemistry has several disadvantages and prevents a consistent way to signal transduction and rational design. Here, we introduce a widely applicable covalent approach to create molecular sensors without destroying the fluorescence in the NIR. For this purpose, a new class of quantum defects in the SWCNT lattice is used to bind biomolecules and to guarantee colloidal stability. To showcase the potential of this approach we demonstrate sensing for different classes of biomolecular analytes (nucleic acids, proteins as well as macromolecular complexes). We analyze sensitivity and selectivity of this recognition approach and present a straightforward way for the generation of novel sensors. In summary, we introduce a novel quantum defect-based covalent functionalization approach of fluorescent SWCNTs with great potential for biosensing.

Theoretical Modeling of sp3 Quantum Defects in Boron Nitride

Atomic defects in solids are intensively investigated as promising candidates for use as single photon sources. However, except for several remarkable exceptions, the atomic structures of these defects are largely unknown. We performed density functional theory calculations to predict SP3 quantum defects in boron nitride that can behave as bright emitters. The results point to possible new designs of quantum emitters in low-dimensional BN materials.

Protein Engineering to Modulate Carbon Nanotube Photoluminescence Response

Semiconducting single-walled carbon nanotubes (SWCNTs) have been investigated as a promising nano-biosensor. Chemical functionalization of SWCNTs sensitizes their near-infrared fluorescence to various analytes with environmental responsivity as high as single-molecule levels. Covalent quantum defects on SWCNTs enable a newly developing category of SWCNT-based biosensors with their unique sensitivities and increased quantum yield. In this work, we present the development of a strategy to sensitize and enhance functionality of SWCNT-based biosensors for bioanalytes via protein engineering. We assess the time-resolved protein binding events on the nanotube surface in molecular level. The approach resulted in improved sensor sensitivity and longer shelf life, maintaining high specificity to their targets. The approach to construct robust and sensitive nanosensors could be readily adapted to the detection of many other disease biomarkers and use in technologies such as point-of-care and wearable/implantable devices.

Stochastic Formation of Quantum Defects in Carbon Nanotubes.

Small perturbations in the structure of materials significantly affect their properties. One example is single wall carbon nanotubes (SWCNTs), which exhibit chirality-dependent near-infrared (NIR) fluorescence. They can be modified with quantum defects through the reaction with diazonium salts, and the number or distribution of these defects determines their photophysics. However, the presence of multiple chiralities in typical SWCNT samples complicates the identification of defect-related emission features. Here, we show that quantum defects do not affect aqueous two-phase extraction (ATPE) of different SWCNT chiralities into different phases, which suggests low numbers of defects. For bulk samples, the bandgap emission (E11) of monochiral (6,5)-SWCNTs decreases, and the defect-related emission feature (E11*) increases with diazonium salt concentration and represents a proxy for the defect number. The high purity of monochiral samples from ATPE allows us to image NIR fluorescence contributions (E11 = 986 nm and E11* = 1140 nm) on the single SWCNT level. Interestingly, we observe a stochastic (Poisson) distribution of quantum defects. SWCNTs have most likely one to three defects (for low to high (bulk) quantum defect densities). Additionally, we verify this number by following single reaction events that appear as discrete steps in the temporal fluorescence traces. We thereby count single reactions via NIR imaging and demonstrate that stochasticity plays a crucial role in the optical properties of SWCNTs. These results show that there can be a large discrepancy between ensemble and single particle experiments/properties of nanomaterials.

Coupled quantum vortex kinematics and Berry curvature in real space

The Berry curvature provides a powerful tool to unify several branches of science through their geometrical aspect: topology, energy bands, spin and vector fields. While quantum defects–phase vortices and skyrmions–have been in the spotlight, as rotational entities in condensates, superfluids and optics, their dynamics in multi-component fields remain little explored. Here we use two-component microcavity polaritons to imprint a dynamical pseudospin texture in the form of a double full Bloch beam, a conformal continuous vortex beyond unitary skyrmions. The Berry curvature plays a key role to link various quantum spaces available to describe such textures. It explains for instance the ultrafast spiraling in real space of two singular vortex cores, providing in particular a simple expression–also involving the complex Rabi frequency–for their intricate velocity. Such Berry connections open new perspectives for understanding and controlling highly-structured quantum objects, including strongly asymmetric cases or even higher multi-component fields.

Dissociative recombination of N_2hbox {H}^+: a revisited study

Dissociative recombination of N_2H^+ is explored in a two-step theoretical study. In a first step, a diatomic (1D) rough model with a frozen NN bond and frozen angles is adopted, in the framework of the multichannel quantum defect theory (MQDT). The importance of the indirect mechanism and of the bending mode is revealed, in spite of the disagreement between our cross section and the experimental one. In the second step, we use our recently elaborated 3D approach based on the normal mode approximation combined with R-matrix theory and MQDT. This approach results in satisfactory agreement with storage-ring measurements, significantly better at very low energy than the former calculations.

Ultralow-quantum-defect single-frequency fiber laser.

A single-frequency distributed-Bragg-reflector fiber laser at 980 nm with a quantum defect of less than 0.6% was developed with a 1.5-cm 12 wt% ytterbium-doped phosphate fiber pumped by a 974.5-nm laser diode. Linearly polarized single-longitude-mode laser with a polarization extinction ratio (PER) of nearly 30 dB and spectral linewidth of less than 1.8 kHz was obtained. A maximum output power of 275 mW was measured at a launched pump power of 620 mW. The performance of the single-frequency fiber laser pumped at 909 nm and 976 nm was also characterized. This research demonstrated an approach to high-power single-frequency fiber laser oscillators with mitigated thermal effects.

High-resolution absorption spectroscopy of room-temperature and jet-cooled ammonia between 59,000 and 93,000 cm−1

We present new high-resolution photoabsorption spectra of ammonia spanning the region between 59,000 cm−1 and 93,000 cm−1 that were recorded by using the Fourier Transform Spectrometer at the Synchrotron SOLEIL. This region extends from just above the Franck-Condon envelope for the Ã1A2″ ← X̃1A1′ transition to well above the NH3+X̃+2A2″ ionization threshold. The spectra were recorded at a measured resolution of 0.23 cm−1 in both a room-temperature cell (293 K) and in a slit-jet supersonic expansion (∼70 K). The absolute photoabsorption cross section with an uncertainty of ± 5% is also reported for the room-temperature spectrum. The present resolution is a factor of 10 – 100 times higher than in other recently reported broad band spectra of ammonia, and many of the observed bands show partially resolved rotational structure. We have attempted to assign this structure for a number of these bands. The oscillator strengths extracted from the data are in good agreement with previous measurements but, in the case of structured bands, the present higher resolution measurements return higher peak absorption cross sections, that increase further when the sample is cooled. The present higher resolution spectra suggest that a number of previous vibronic band assignments that were based on quantum defect considerations may require some revision. Finally, we discuss the substantial differences between the photoabsorption and photoionization data just above the first ionization threshold.

Effect of environmental screening and strain on optoelectronic properties of two-dimensional quantum defects

Point defects in hexagonal boron nitride (hBN) are promising candidates as single-photon emitters (SPEs) in nanophotonics and quantum information applications. The precise control of SPEs requires in-depth understanding of their optoelectronic properties. However, how the surrounding environment of host materials, including the number of layers, substrates, and strain, influences SPEs has not been fully understood. In this work, we study the dielectric screening effect due to the number of layers and substrates, and the strain effect on the optical properties of carbon dimer and nitrogen vacancy defects in hBN from first-principles many-body perturbation theory. We report that environmental screening causes a lowering of the quasiparticle gap and exciton binding energy, leading to nearly constant optical excitation energy and exciton radiative lifetime. We explain the results with an analytical model starting from the Bethe–Salpeter equation Hamiltonian with Wannier basis. We also show that optical properties of quantum defects are largely tunable by strain with highly anisotropic response, in good agreement with experimental measurements. Our work clarifies the effect of environmental screening and strain on optoelectronic properties of quantum defects in two-dimensional insulators, facilitating future applications of SPEs and spin qubits in low-dimensional systems.