Electronic Transitions Research Articles

DFT and TD‐DFT Study of Many‐Body and Hydrogen Bonding Interactions: Nitrosamine Oligomers

AbstractThis study focuses on the properties and intermolecular interactions of nitrosamine oligomers, which are important in both semiconductor manufacturing and nuclear waste management. The study explores various configurations of nitrosamine oligomers, ranging from monomers to pentamers in linear, ladder, and cyclic clusters, with the finding that dimer cyclic forms and hexamers and above are unstable. Many‐body analysis revealed that two‐body interaction energies made remarkable contributions to the binding energy, while the sum of 3‐, 4‐, and 5‐body energy contributed less, indicating the decrease in stability of nitrosamine from dimer to pentamer clusters. Using advanced computational techniques, such as dispersion‐corrected B3LYP‐D3 and TD‐DFT, the study investigates the vibrational modes and electronic absorption spectra of nitrosamine oligomers. The results reveal that different configurations can significantly affect the vibrational modes and electronic properties of nitrosamine oligomers. The NH2 symmetric and asymmetric modes were particularly intense in various forms of nitrosamine oligomers. The wavelengths of electronic transition, oscillator strength, and HOMO to LUMO gap were reported. Additionally, the study reports on nitrosamine oligomers’ hydrogen‐bonded cooperativity and binding energy contributions. Overall, these findings offer valuable insights into the stability and properties of nitrosamine oligomers, with potential applications in materials science and chemical engineering.

Rare-Earth-Ion (RE3+)-Doped Aluminum and Lanthanum Borates for Mobile-Phone-Interrogated Luminescent Markers

In this paper, we present the synthesis and luminescent spectra of rare-earth (RE)-doped aluminum and lanthanum borates intended to serve as narrow excitation–emission band fluorescent markers. We perform a detailed 3D excitation–emission matrix (EEM) analysis of their spectra, compare the measurements from both standard and mobile phone spectrometers, and outline the basic differences and advantages of each method. While smartphones have a different and non-uniform spectral response compared to standard spectrometers, it is shown that they offer a number of advantages such as contactless interrogation, efficient suppression of the UV excitation light, and simultaneous spectral analysis of spatially arranged arrays of fluorescent markers. The basic emission peaks have been observed and their corresponding electronic transitions identified. The obtained results show that the rare-earth-doped La and Al borates feature excitation–emission bandwidths as low 15 nm/12 nm, which makes them particularly appropriate for use as luminescent markers with UV LED excitation and smartphone interrogation.

Optoelectronic Response to the Fluor Ion Bond on 4-(4,4,5,5-Tetramethyl-1,3,2-dioxoborolan-2-yl)benzaldehyde.

Boronate esters are a class of compounds containing a boron atom bonded to two oxygen atoms in an ester group, often being used as precursors in the synthesis of other materials. The characterization of the structure and properties of esters is usually carried out by UV-visible, infrared, and nuclear magnetic resonance (NMR) spectroscopic techniques. With the aim to better understand our experimental data, in this article, the density functional theory (DFT) is used to analyze the UV-visible and infrared spectra, as well as the isotropic shielding and chemical shifts of the hydrogen atoms 1H, carbon 13C and boron 11B in the compound 4-(4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl)benzaldehyde. Furthermore, this study considers the change in its electronic and spectroscopic properties of this particular ester, when its boron atom is coordinated with a fluoride anion. The calculations were carried out using the LSDA and B3LYP functionals in Gaussian-16, and PBE in CASTEP. The results show that the B3LYP functional gives the best approximation to the experimental data. The formation of a coordinated covalent B-F bond highlights the remarkable sensitivity of the NMR chemical shifts of carbon, oxygen, and boron atoms and their surroundings. Furthermore, this bond also highlights the changes in the electron transitions bands n → π* and π → π* during the absorption and emission of a photon in the UV-vis, and in the stretching bands of the C=C bonds, and bending of BO2 in the infrared spectrum. This study not only contributes to the understanding of the properties of boronate esters but also provides important information on the interactions and responses optoelectronic of the compound when is bonded to a fluorine atom.

Highly active ZnO/Fe3+-TiO2 photocatalysts for visible-light photodegradation application and its colour change behaviour by d-d transition

Highly active novel ZnO/Fe-TiO2 composite catalysts with p-n junction heterostructure have been fabricated by adding commercial ZnO and sol–gel derived Fe-TiO2 nano-powders controlled by grinding and drying. This work reported that doped Fe (III) with TiO2 form a p-type semiconductor and whereas ZnO is an n-type semiconductor. The slight variation of electronegativity between ZnO and TiO2 causes a strong rectifying action for the formation of an interface between ZnO and Fe-TiO2. The occurrence of red shift phenomenon in absorption spectrum of the samples suggest the outcome of d-d transition of Fe3+ (2T2g → 2A2g, 2T1g) and the charge transfer transition between interacting Fe3+ ions (Fe3+ + Fe3+ → Fe4+ + Fe2+). These Fe3+ 3d states in addition to oxygen vacancies and Ti3+ centers create band states, thereby favouring the electronic transition to these levels and resulting in narrowing of TiO2 band gap. A direct confirmation is the increase of Urbach energy with the lowering in the band gap of ZnO/Fe-TiO2.The crystal field splitting of d orbitals (5 degenerate orbitals) of Fe3+ and the approach of free ligand ions which split into two sets and Fe3+ ligand field transition is discussed schematically. The photocatalytic activities of these heterostructure photocatalysts were evaluated by degrading toxic cationic organic dyes such as Methylene Blue (MB) and Malachite Green Oxalate (MG) under visible light. The mechanism of photocatalysis has been recommended which is based on the relative band structure of the semiconductor and integrated heterostructure. The formation of a spike barrier in the CB at the interface gives rise to trap sites that capture the migration of charge carriers and occurs recombination of electron-hole pair at higher Fe(III) doping concentration. The dark adsorption property of the catalysts sample has been also studied.

Aero-ZnS prepared by physical vapor transport on three-dimensional networks of sacrificial ZnO microtetrapods.

Aeromaterials represent a class of increasingly attractive materials for various applications. Among them, aero-ZnS has been produced by hydride vapor phase epitaxy on sacrificial ZnO templates consisting of networks of microtetrapods and has been proposed for microfluidic applications. In this paper, a cost-effective technological approach is proposed for the fabrication of aero-ZnS by using physical vapor transport with Sn2S3 crystals and networks of ZnO microtetrapods as precursors. The morphology of the produced material is investigated by scanning electron microscopy (SEM), while its crystalline and optical qualities are assessed by X-ray diffraction (XRD) analysis and photoluminescence (PL) spectroscopy, respectively. We demonstrate possibilities for controlling the composition and the crystallographic phase content of the prepared aerogels by the duration of the technological procedure. A scheme of deep energy levels and electronic transitions in the ZnS skeleton of the aeromaterial was deduced from the PL analysis, suggesting that the produced aerogel is a potential candidate for photocatalytic and sensor applications.

Ciprofloxacin Metal Complexes–Silica Nanoparticles: Characterization, Spectroscopic Study, DNA Interaction and Biological Activity

Ciprofloxacin (CIPH) was classified as one of the most effective quinolone antibiotics, which is commonly used to cure a wide range of infections resulting from Gram-negative and Gram-positive microorganisms. The complexes which formed due to the interaction of Ni(II), Zn(II), Cu(II), Gd(III) and Sm(III) with ciprofloxacin were characterized by CHN% analysis, conductivity, FTIR, electronic spectra, fluorescence measurements, and magnetic susceptibility, besides studying the complex–DNA interaction. Meanwhile, the molar conductance values (0.001 mol·L−1 in DMSO) revealed the electrolytic behavior of the complexes and could be designated with the A−B+ formula. In addition, the geometry of the compounds was confirmed from the electronic transitions as well as the μeff values as octahedral for all complexes. The postulated formula could be generally assigned as [M(CIP)a(CIPH)b(H2O)c](NO3)(H2O)n(C2H5OH)m. Moreover, the interaction between metal complexes and DNA revealed that the Cu complex had the highest binding constant. Nanotechnology was applied to synthesized compounds using silica nanoparticles (SiNPs), which were prepared using a sol–gel process. The silica nanoparticles were chemically functionalized for binding the ligand and its metal complexes; this enables the as-prepared compounds to enhance their features as a drug delivery platform. Meanwhile, the antimicrobial activity was tested for the free complexes and SiNPs composites. Collectively, Sm complex gave the largest zone of inhibition, while the Cu(II)–SiNPs composite showed the strongest potential to reduce the bacterial activity. Furthermore, the fluorescence data of CIPH, ligand–metal mixture and the effect of silica nanoparticles on them were studied.

State-to-state dynamics and machine learning predictions of inelastic and reactive O(3P) + CO(1∑+) collisions relevant to hypersonic flows.

The state-to-state (STS) inelastic energy transfer and O-atom exchange reaction between O and CO(v), as two fundamental processes in non-equilibrium air flow around spacecraft entering Mars' atmosphere, yield the same products and both make significant contributions to the O + CO(v) → O + CO(v') collisions. The inelastic energy transfer competes with the O-atom exchange reaction. The detailed reaction mechanisms of these two elementary processes and their specific contributions to the CO relaxation process are still unclear. To address these concerns, we performed systematic investigations on the 3A' and 3A″ potential energy surfaces (PESs) of CO2 using quasi-classical trajectory (QCT) calculations. Analysis of the collision mechanisms reveals that inelastic collisions have an apparent PES preference (i.e., they tend to occur on the 3A' PES), while reactive collisions do not. Reactive rates decrease significantly when the total collision energy approaches dissociation energy, which differs from the inelastic process. Inelastic rates are generally lower than the reactive rates below ∼10 000K, except for single quantum jumps, whereas the reverse is observed above ∼10 000K. In addition, by combining QCT with convolutional neural networks, we have established neural network (NN)-STS1 (inelastic) and NN-STS2 (reactive) models to generate all possible STS cross sections. The NN-based models accurately reproduce the results calculated from QCT calculations. In this study, all calculations have been focused on analyzing collisions at the ground rotational level.

Semiclassical approaches to perturbative time-convolution and time-convolutionless quantum master equations for electronic transitions in multistate systems.

Understanding the dynamics of photoinduced processes in complex systems is crucial for the development of advanced energy-conversion materials. In this study, we investigate the nonadiabatic dynamics using time-convolution (TC) and time-convolutionless (TCL) quantum master equations (QMEs) based on treating electronic couplings as perturbation within the framework of multistate harmonic (MSH) models. The MSH model Hamiltonians are mapped from all-atom simulations such that all pairwise reorganization energies are consistently incorporated, leading to a heterogeneous environment that couples to the multiple electronic states differently. Our exploration encompasses the photoinduced charge transfer dynamics in organic photovoltaic carotenoid-porphyrin-C60 triad dissolved in liquid solution and the excitation energy transfer (EET) dynamics in photosynthetic Fenna-Matthews-Olson complexes. By systematically comparing the perturbative TC and TCL QME approaches with exact quantum-mechanical and various semiclassical approximate kernels, we demonstrate their efficacy and accuracy in capturing the essential features of photoinduced dynamics. Our calculations show that TC QMEs generally yield more accurate results than TCL QMEs, especially in EET, although both methods offer versatile approaches adaptable across different systems. In addition, we investigate various semiclassical approximations featuring the Wigner-transformed and classical nuclear densities as well as the governing dynamics during the quantum coherence period, highlighting the trade-off between accuracy and computational cost. This work provides valuable insights into the applicability and performance of TC and TCL QME approaches via the MSH model, offering guidance for realistic applications to condensed-phase systems on the atomistic level.

Boosting persulfate activation through efficient π → π* transition activated by Cu ion anchored porphyrin-based metal–organic framework

Photocatalytic persulfate activation provides a promising approach for the elimination of persistent organic pollutants from water. This has been exemplified in porphyrin-based metal organic frameworks (PMOFs), which however come with ineffective electron transition within the porphyrin ligand. Herein, we present a Cu ion modification strategy capable of boosting electron transition by inducing electron delocalization under visible light. The introduction of Cu ions increased the degradation rate constant of ciprofloxacin (CIP) by nearly 44 times, surpassing most state-of-the-art photocatalysts. The in-situ characterizations and theoretical calculations suggest that π-electron localization constitutes the origin of ineffective electron transition in PMOFs. The introduction of Cu ions induces π-electron delocalization to intensify the π → π* transition, forming electron-rich centers of Cu to lower the energy barrier for O-O bond cleavage. This work offers fundamental insights into the electron transition within PMOFs, upon which the universal strategy is proposed for improved water decontamination performance via persulfate activation.

Structural and Quantum chemical insights into the atomic orbitals of 2-benzoylbenzoic acid: Density functional theory approach

Abstract The present work aims to explore the structural insights and the molecular orbitals associated with 2-benzoylbenzoic acid through density functional theory approach. The geometrical parameters of the optimized structure of 2-benzoylbenzoic acid were obtained at B3LYP/6-311++G basis set. The atomic sites which are prone to electrophilic/nucleophilic attack were identified from molecular electrostatic potential (MEP) surface analysis. The molecular orbitals (lone pair, bonding and anti-bonding) which are favorable to the charge delocalization within the system and stabilize the molecule were studied. Besides, the vibrational assignments of the characteristic group frequencies and coupled modes vibrations were made using Cartesian coordinate displacement analysis. Moreover, the electronic transitions between the filled and unfilled molecular orbitals of 2-benzoylbenzoic acid were investigated.

Exploration of rice husk ash as a green corrosion inhibitor immersed in NH4Cl 7.5 % solution

The study reports the development of a liquid smoke solution of rice husk ash (RHA) as a green corrosion inhibitor in NH4Cl solution in approaching corrosion protection for refinery facilities. The recent utilization of RHA has a partial solution to address the possible chemical to form a filming layer to disconnect bare metal and their environment. This work prepared the RHA solution by condensing the RHA vapor before adding it to various concentrations. The corrosion test of potentiodynamic and electrochemicals intends to discover the inhibitor's corrosion resistance before examining the electronic transition corresponding to the contribution of several functional groups using Ultraviolet Visible (UV–Vis) and Fourier-Transform Infrared Spectroscopy (FTIR). Surface evaluation intends to unveil the nature of the corrosion by utilizing the Scanning Electronic and Atomic Force Microscope. The corrosion test result shows the depression of corrosion rate to 0.120 mmpy with high efficiency beyond 96 % in the addition of 7.5 ppm RHA inhibitor. The greater Nyquist semicircle diameter at high concentrations increases the adsorption of the RHA on the surface of C1018. The electronic transition of n–π* and π –π* shows an extensive contribution of CC, CO, and –OH based on the UV–Vis and FTIR test. The formation of a complex compound of Fe-(NH4Cl-RHA)n blocks the corrosion active sites to reduce the corrosion. This study paves the way for using RHA as an organic compound under NH4Cl conditions, such as in a refinery process facility.

Probing single electrons across 300-mm spin qubit wafers

Building a fault-tolerant quantum computer will require vast numbers of physical qubits. For qubit technologies based on solid-state electronic devices1–3, integrating millions of qubits in a single processor will require device fabrication to reach a scale comparable to that of the modern complementary metal–oxide–semiconductor (CMOS) industry. Equally important, the scale of cryogenic device testing must keep pace to enable efficient device screening and to improve statistical metrics such as qubit yield and voltage variation. Spin qubits1,4,5 based on electrons in Si have shown impressive control fidelities6–9 but have historically been challenged by yield and process variation10–12. Here we present a testing process using a cryogenic 300-mm wafer prober13 to collect high-volume data on the performance of hundreds of industry-manufactured spin qubit devices at 1.6 K. This testing method provides fast feedback to enable optimization of the CMOS-compatible fabrication process, leading to high yield and low process variation. Using this system, we automate measurements of the operating point of spin qubits and investigate the transitions of single electrons across full wafers. We analyse the random variation in single-electron operating voltages and find that the optimized fabrication process leads to low levels of disorder at the 300-mm scale. Together, these results demonstrate the advances that can be achieved through the application of CMOS-industry techniques to the fabrication and measurement of spin qubit devices.

DFT study of rare-earth ferromagnetic spinels HgNd2Z4 (Z = S, Se) for spintronics applications

Spintronic technology and energy applications benefit greatly from the exceptional characteristics of rare-earth-based spinel chalcogenides. Examining the electrical, magnetic and thermoelectric properties of HgNd2Z4 (Z = S, Se) in a systematic manner is essential for the strategic advancement of spin polarized current in a spintronic device. In this recent study, the WIEN2K code was employed to comprehensively analyze these properties. The calculated lattice constants, obtained using the generalized gradient approximation (GGAsol-PBE), closely match experimental findings of the similar family compounds. The examination of the stability of ferromagnetic states in the ground state involves comparing energies between anti-ferromagnetic and ferromagnetic states. Moreover, an assessment of the stability of the cubic phase in both spinels was conducted using analyses of the phonon dispersion curve, formation energy and Born stability criteria. The ductility characteristics were examined through the calculation of Poisson's and Pugh's ratios. Furthermore, details regarding the density of states, spin polarization, exchange coupling and Curie temperature were provided to explore the characteristics associated with ferromagnetism. Potential optoelectronic applications were proposed, leveraging the direct band gaps of 1.4 and 1.0 eV for HgNd2Z4 (Z = S, Se) respectively, within the visible spectrum. Particularly noteworthy is the effective light absorption of HgNd2Se4 in the visible range, characterized by prominent peaks that facilitate the transition of electrons from the valence band (VB) to the conduction band (CB). Additionally, the study extends to thermoelectric characteristics, determining various factors such as Seebeck coefficient (S), figure of merit (ZT), electrical and thermal conductivities of the evaluated spinels.

Improved stability of aluminum surface plasmon resonance sensor by protective gold layer

The surface plasmon resonance (SPR) sensing in the ultraviolet (UV) region, achieved through the optimization of aluminum (Al) film conditions, has attracted attention due to its heightened energy levels and more plentiful molecular electronic transitions compared to the visible region. In this research, the stability of the UV-SPR sensor is improved by applying a protective thin layer of gold (Au) onto the Al film. This reduces spectral alterations observed when the Al film was uncoated in water pre and post flow system measurements. This exploration presents the initial experimental confirmation of the reliability of Al-Au bilayer coatings as SPR sensors in the UV region, highlighting advancements in UV-SPR sensor technology.

Super long ultraviolet-A persistent luminescence and photo-stimulated luminescence from CaMgGeO4: Bi3+

Here, we have developed a novel ultra long ultraviolet-A afterglow material CaMgGeO4: Bi3+, which shows more than 24 h UVA afterglow emission peaked at 346 nm. The crystal structure shows that the prepared sample is a pure phase with an orthogonal system of Pmnb space group. The composition of valence band and conduction band was analyzed by the density of states, which reveals that the bandgap of the CaMgGeO4 matrix is 3.69 eV. The photoluminescence spectrum of the sample consists of a broadband in the 320–400 nm UVA region, which belongs to the 3P1 → 1S0 electron transition of Bi3+. More importantly, under the excitation of ultraviolet lamp for 3 min, CaMgGeO4: Bi3+ exhibited an UVA ultra long persistent luminescence (LPL) with a duration of more than 24 h, which afterglow emission intensity still reaches 1500 cps and is about 6 times of the background intensity. In addition, the UVA emission of CaMgGeO4: Bi3+ after 13 h day can be repeatedly by short periods of low-energy light sources stimulation. The thermoluminescence analysis indicates that the presence of shallow and deep traps is responsible for excellent UVA-LPL and photo-stimulate luminescence (PSL). The excellent LPL and PSL properties can prompt CaMgGeO4: Bi3+ phosphor to be widely used in the field of photodynamic therapy.

The coupled WO3-AgBr nanocatalyst, part II: Synthesis, characterization, and the boosted photocatalytic activity towards metronidazole in an aqueous solution

The AgBr and WO3 nanoparticles (NPs) were synthesized and coupled, and the coupled AgBr-WO3 binary catalyst, as well as the individual AgBr and WO3 NPs, were then characterized by XRD, FTIR, DRS, and SEM-EDX. XRD results showed the formation of orthorhombic WO3 cubic AgBr crystals. The crystallite sizes of 45, 28, and 45 nm were estimated by the Scherrer formula for the as-prepared AgBr, WO3, and AgBr-WO3 catalysts, respectively. The DRS study estimated band gap energies using both absorption edge wavelengths and the Kubelka-Munk model. The band gap energies of 2.72, 3.06, and 2.92 eV were obtained for the direct electronic transitions of AgBr, WO3, and AgBr-WO3. The ECB (potential position) of AgBr and WO3 were estimated to be 0.01 and 0.52 V, while their EVB values were 2.60 and 3.55 V, respectively. Typical FTIR absorption bands of W‒OH, the W‒O‒W, and AgBr bonds have appeared at 1637 cm−1, 823 (and 766) cm−1, and 1384 cm−1, respectively. The pHpzc of 4 was estimated for the individual and coupled catalysts. In studying the photocatalytic activity of the catalysts in the photodegradation of metronidazole (MNZ) a boosted activity was achieved for the coupled system. This increased activity depends on the maximum AgBr:WO3 mole ratio in a 1:3 mol ratio. Grinding time applied to prepare the coupled catalyst has also varied the photocatalytic activity.

Spectroscopic studies of Eu doped CaF2 single crystal

The Eu-doped CaF2 crystal is investigated for potential use in visible-region solid-state lasers. The single-crystal Eu: CaF2 has an FCC crystal structure and belongs to the space group Fm-3 m, as confirmed by single-crystal X-ray diffraction. A Raman shift of 324 cm−1 has been observed in a single crystal of Eu: CaF2. The vibrational mode at low frequency is suitable for minimizing non-radiative emissions and increasing radiative emissions. Eu: CaF2 crystal has two absorption bands, at 399 nm and 415 nm, corresponding to the 7F0→5L6 and 7F0→5D3 transitions, respectively. The strongest absorption peak (399 nm) is associated with the 7F0→5L6 electronic transition. The orange-red emission was observed at 588 nm (5D0→7F1), 612 nm (5D0→7F2), 648 (5D0→7F3), and 685(5D0→7F4) when excited at 399 nm. Measurements of the luminescence intensity ratio (R) between the 5D0→7F2 (electric dipole) transition and the 5D0→7F1 (magnetic dipole) transition predict that Eu3+ ions are situated at the symmetric sites in CaF2. The radiative parameters for the Eu: CaF2 crystal are calculated using the JOES code using the Judd-Ofelt theory. The calculated total radiative transition probability (AR) is 64.54 s−1, and the radiative lifetime (τR) is 15.57 ms. Radiative transition probabilities are 43.41,7.02 and 14.10, and branching ratios are 67.26 %,10.88 % and 21.85 % for 5D0→7F1, 5D0→7F25D0→7F4 transitions respectively.

Red Shift in the Absorption Spectrum of Phototropin LOV1 upon the Formation of a Semiquinone Radical: Reconstructing the Orbital Architecture.

Flavin mononucleotide (FMN) is a ubiquitous blue-light pigment due to its ability to drive one- and two-electron transfer reactions. In both light-oxygen-voltage (LOV) domains of phototropin from the green algae Chlamydomonas reinhardtii, FMN is noncovalently bound. In the LOV1 cysteine-to-serine mutant (C57S), light-induced electron transfer from a nearby tryptophan occurs, and a transient spin-correlated radical pair (SCRP) is formed. Within this photocycle, nuclear hyperpolarization is created by the solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) effect. In a side reaction, a stable protonated semiquinone radical (FMNH·) forms undergoing a significant bathochromic shift of the first electronic transition from 445 to 591 nm. The incorporation of phototropin LOV1-C57S into an amorphous trehalose matrix, stabilizing the radical, allows for application of various magnetic resonance experiments at ambient temperatures, which are combined with quantum-chemical calculations. As a result, the bathochromic shift of the first absorption band is explained by lifting the degeneracy of the molecular orbital energy levels for electrons with alpha and beta spins in FMNH· due to the additional electron.

Charge density waves tuned by biaxial tensile stress.

The precise arrangement and nature of atoms drive electronic phase transitions in condensed matter. To explore this tenuous link, we developed a true biaxial mechanical deformation device working at cryogenic temperatures, compatible with x-ray diffraction and transport measurements, well adapted to layered samples. Here we show that a slight deformation of TbTe3 can have a dramatic influence on its Charge Density Wave (CDW), with an orientational transition from c to a driven by the a/c parameter, a tiny coexistence region near a = c, and without space group change. The CDW transition temperature Tc displays a linear dependence with while the gap saturates out of the coexistence region. This behaviour is well accounted for within a tight-binding model. Our results question the relationship between gap and Tc in RTe3 systems. This method opens a new route towards the study of coexisting or competing electronic orders in condensed matter.

Microwave-assisted solvothermal synthesis of Eu3+-doped CsY2F7 and RbY2F7 phosphorescent nanoparticles

We synthesized Eu3+-doped CsY2F7 and RbY2F7 nanoparticles (orthorhombic crystal structure, Pnna space group, No. 52) by the microwave-assisted solvothermal technique and investigated the influence of reaction temperature and fluoride ion concentration on the particles’ phase and crystal structure. Fluoride ions were added in excess of the stoichiometric amount to achieve the orthorhombic phase for CsY2F7 and to convert the cubic RbY3F10 to the orthorhombic RbY2F7. Mild synthesis conditions yielded nanoparticles with crystallites ranging in size from 19 to 37 nm and a combination of spherical, rod-like, and hexagonal shapes. Nanoparticles emit a strong orange and red light when excited into the Eu3+5L6 level, which is centered around 390 nm. The strongest emission peak is around 612 nm, which comes from the 5D0→7F2 electronic transitions. Emission intensity dependence on Eu3+ concentration revealed that nanoparticles can be heavily doped with Eu3+, up to 25 % with respect to Y3+. Emission decay measurements provided values of excited state lifetimes of 6.2 ms for the Cs(Y0.75Eu0.25)2F7 and 6.0 ms for the Rb(Y0.75Eu0.25)2F7.