S0 Transition Research Articles

Resonance Effect in Brunel Harmonic Generation in Thin Film Organic Semiconductors

AbstractNonlinear optical properties of organic semiconductors (OSCs) have been extensively investigated in the perturbative regime, while strong light induced high‐order processes in solid‐state OSCs are less studied. Here, below‐threshold harmonic generation is examined, both experimentally and theoretically, in two solid‐state thin film OSCs, that is, tetraphenylporphyrin and zinc tetraphenylporphyrin. Results show that the π–π* excitations of the porphyrin ring system generate the harmonic emission. The contribution of the Brunel harmonic to the 5th harmonic emission is uncovered, where the resonant 5‐photon transition (S0 → S2 transition) is found to lead to an early onset of non‐perturbative behavior. A similar resonance effect is expected in Brunel harmonic generation in other organic materials.

Dual-emitting from Bi[formula omitted], Ln[formula omitted] (Ln [formula omitted] Eu, Sm) co-activated Ca[formula omitted]Sb[formula omitted]O[formula omitted] phosphor for optical temperature measurement

In this paper, a series of Ca(2−x−y) Sb2O7: xBi3+, yLn3+ (Ln = Eu, Sm) fluorescent powder samples were successfully obtained, which used the traditional high-temperature solid-phase synthesis method in the preparation process. Samples of Ca2Sb2O7: Bi3+, Ln3+ (Ln = Eu, Sm) fluorescent powder samples were structurally and optically characterized​ using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), photoluminescence excitation spectroscopy and emission spectroscopy, and fluorescence decay measurements. The results show that the prepared Ca(2−x−y) Sb2O7: xBi3+, yLn3+ (Ln = Eu, Sm) samples have an orthogonal spider web structure, which remains unchanged whether Bi3+ is single doped or Bi3+ is co-doped with Ln3+ (Ln = Eu, Sm). Under ultraviolet lamp (λex=340nm) irradiation, Bi3+ doped Ca2Sb2O7 powder shows a wide emission band centered at 435 nm, which is owing to the 3P1→1S0 transition of Bi3+ ion. Therefore, the effect of Bi3+ and Ln3+ (Ln = Eu, Sm) co-doped Ca2Sb2O7 samples on the luminescence intensity of the samples at different concentrations was studied. When the temperature was varied from 293 K to 483 K, the absolute temperature sensitivity (Sa) of doped Bi3+/Eu3+ and Bi3+/Sm3+ phosphors is 0.001K−1 (at 483 K) and 0.02K−1 (at 293 K), respectively, and the relative temperature sensitivity (Sr) is 1.03% K−1 (at 343 K) and 1.19% K−1 (at 293 K), respectively. These results demonstrate that Ca(2−x−y) Sb2O7: xBi3+, yLn3+(Ln = Eu, Sm) phosphors are prospective double emission thermal thermometers.

An X-ray spectroscopy study of structural stability of superhydrogenated pyrene derivatives

ABSTRACT The stability of polycyclic aromatic hydrocarbons (PAHs) upon soft X-ray absorption is of crucial relevance for PAH survival in X-ray dominated regions. PAH stability depends on molecular size but also on the degree of hydrogenation that is related to H2 formation in the interstellar medium. In this project, we intend to reveal the changes of electronic structure caused by hydrogenation and the impact of hydrogenation on the stability of the carbon backbone for cationic pyrene and its hydrogenated derivatives by analysis of near C K-edge soft X-ray photoions. In our experiments, the PAH cations were trapped in a cryogenic radiofrequency linear ion trap and exposed to monochromatic X-rays with energies from 279 to 300 eV. The photoproducts were mass-analysed by means of time-of-flight spectroscopy. Partial ion yields were then studied as a function of photon energy. X-ray absorption spectra computed by time-dependent density functional theory (TD-DFT) aided the interpretation of the experimental results. A very good agreement between experimental data and TD-DFT with short-range corrected functionals for all PAH ions was reached. The near-edge X-ray absorption mass spectra exhibit clear peaks due to C 1s transitions to singly occupied molecular orbitals and to low-lying unoccupied molecular orbitals. In contrast to coronene cations, where hydrogen attachment drastically increases photostability of coronene, the influence of hydrogenation on photostability is substantially weaker for pyrene cations. Here, hydrogen attachment even destabilizes the molecular structure. An astrophysical model describes the half-life of PAH ions in interstellar environments.

Accurate Vertical Electron Detachment Energies and Multiphoton Resonant Photoelectron Spectra of Biochromophore Anions in Aqueous Solution.

We introduce a new methodology for calculating vertical electron detachment energies (VDEs) of biologically relevant chromophores in their deprotonated anionic forms in aqueous solution. It combines a large-scale mixed DFT/EFP/MD approach with the high-level multireference perturbation theory XMCQDPT2 and the Effective Fragment Potential (EFP) method. The methodology includes a multiscale flexible treatment of inner (∼1000 water molecules) and outer (∼18000 water molecules) water shells around a charged solute, capturing both the effects of specific solvation and the properties of bulk water. VDEs are calculated as a function of system size for getting a converged value at the DFT/EFP level of theory. The XMCQDPT2/EFP approach, adapted for calculating VDEs, supports the DFT/EFP results. When corrected for a solvent polarization contribution, the XMCQDPT2/EFP method yields the most accurate estimate to date of the first VDE for aqueous phenolate (7.3 ± 0.1 eV), which agrees well with liquid-jet X-ray photoelectron spectroscopy data (7.1 ± 0.1 eV). We show that the geometry of the water shell and its size are essential for accurate VDE calculations of aqueous phenolate and its biologically relevant derivatives. By simulating photoelectron spectra of aqueous phenolate upon two-photon excitation at wavelengths resonant with the S0 → S1 transition, we also provide interpretation of recent multiphoton UV liquid-microjet photoelectron spectroscopy experiments. We show that its first VDE is consistent with our estimate of 7.3 eV, when experimental two-photon binding energies are corrected for the resonant contribution.

Modulating Nonluminous 0D (NH4)2SnCl6 Perovskites by Metal Ion Doping

Metal halide perovskite materials have highly attracted wide attention for lighting applications because of their unique optoelectronic properties. However, the complex preparation processes and the toxicity of lead have limited their practical applications. There are few reports on zero-dimensional (0D) organic/inorganic tin-based perovskites with both good stability and a high photoluminescence quantum yield (PLQY). Here, Sb3+ doping and Bi3+ doping of 0D (NH4)2SnCl6 perovskite powders are reported. Sb3+ doping of 0D (NH4)2SnCl6 perovskites shows wide emission peaks at 530 and 640 nm with a PLQY of up to 17.03%, while Bi3+ doping of 0D (NH4)2SnCl6 perovskites exhibits a broad blue emission at 460 nm with a PLQY of 4.40%. Combining experimental results and theoretical calculations, we propose that the mechanism of Sb3+ ion doping of 0D (NH4)2SnCl6 perovskites is a P1 → 1S0 transition (singlet) at 530 nm and a 3P1 → 1S0 transition (triplet) at 640 nm. However, the mechanism of Bi3+ ion doping of 0D (NH4)2SnCl6 perovskites is a 3P1 → 1S0 transition at 460 nm. In addition, both metal ion dopings of 0D (NH4)2SnCl6 perovskites have good air and thermal stability. We demonstrate that the Sb3+ doping and Bi3+ doping of 0D (NH4)2SnCl6 perovskite phosphors have great potential for solid-state lighting.

Structural evidence for intermediates during O2 formation in photosystem II

In natural photosynthesis, the light-driven splitting of water into electrons, protons and molecular oxygen forms the first step of the solar-to-chemical energy conversion process. The reaction takes place in photosystem II, where the Mn4CaO5 cluster first stores four oxidizing equivalents, the S0 to S4 intermediate states in the Kok cycle, sequentially generated by photochemical charge separations in the reaction center and then catalyzes the O–O bond formation chemistry1–3. Here, we report room temperature snapshots by serial femtosecond X-ray crystallography to provide structural insights into the final reaction step of Kok’s photosynthetic water oxidation cycle, the S3→[S4]→S0 transition where O2 is formed and Kok’s water oxidation clock is reset. Our data reveal a complex sequence of events, which occur over micro- to milliseconds, comprising changes at the Mn4CaO5 cluster, its ligands and water pathways as well as controlled proton release through the hydrogen-bonding network of the Cl1 channel. Importantly, the extra O atom Ox, which was introduced as a bridging ligand between Ca and Mn1 during the S2→S3 transition4–6, disappears or relocates in parallel with Yz reduction starting at approximately 700 μs after the third flash. The onset of O2 evolution, as indicated by the shortening of the Mn1–Mn4 distance, occurs at around 1,200 μs, signifying the presence of a reduced intermediate, possibly a bound peroxide.

Does Serial Femtosecond Crystallography Depict State-Specific Catalytic Intermediates of the Oxygen-Evolving Complex?

Recent advances in serial femtosecond crystallography (SFX) of photosystem II (PSII), enabled by X-ray free electron lasers (XFEL), provided the first geometric models of distinct intermediates in the catalytic S-state cycle of the oxygen-evolving complex (OEC). These models are obtained by flash-advancing the OEC from the dark-stable state (S1) to more oxidized intermediates (S2 and S3), eventually cycling back to the most reduced S0. However, the interpretation of these models is controversial because geometric parameters within the Mn4CaO5 cluster of the OEC do not exactly match those expected from coordination chemistry for the spectroscopically verified manganese oxidation states of the distinct S-state intermediates. Here we focus on the first catalytic transition, S1 → S2, which represents a one-electron oxidation of the OEC. Combining geometric and electronic structure criteria, including a novel effective oxidation state approach, we analyze existing 1-flash (1F) SFX-XFEL crystallographic models that should depict the S2 state of the OEC. We show that the 1F/S2 equivalence is not obvious, because the Mn oxidation states and total unpaired electron counts encoded in these models are not fully consistent with those of a pure S2 state and with the nature of the S1 → S2 transition. Furthermore, the oxidation state definition in two-flashed (2F) structural models is practically impossible to elucidate. Our results advise caution in the extraction of electronic structure information solely from the literal interpretation of crystallographic models and call for re-evaluation of structural and mechanistic interpretations that presume exact correspondence of such models to specific catalytic intermediates of the OEC.

VIS-VUV spectroscopy of heavily Tb and Eu doped gadolinium aluminum borate (GAB) crystal

GdAl3(BO3)4 (GAB) compound doped with Tb3+ and Eu3+ was synthetized. The excited states of these lanthanide ions were analyzed up to VUV range 125 000 cm-1 (80 nm). VUV multiplets of Tb3+ and Eu3+ has been determined. The Eg has been estimated to be 7.15 eV and it was assigned to the O 2p → B 2p, 2s transitions within the isolated BO3− groups. The strong and effective coupling between terbium and europium was observed and examined. The efficient impact of temperature on inter-ionic energy transfer was found and examined. The yields of energy transfer (η) at room temperature were determined to be: ca. 20% and 60% for GAB: 20 at.%Tb, 3 at.%Eu and GAB: 20 at.%Tb, 20 at.%Eu, respectively. When the europium 5D0 multiplet is excited via terbium multiplets, the decay curve becomes non-exponential with build-up part maximum situated at ca. 0.7 ms after initial pulses. Based on the low- and room temperature excitation and luminescence spectra, experimental free-ion levels, located between 0 and 35 000 cm-1, were determined and used for the free-ion analysis.

Dynamics of Electronically Excited Metal Atoms (Zn and Cd) in Rare Gas Matrices: Simulation of Multiple-band Emission using Molecular Dynamics with Quantum Transitions.

Molecular dynamics with quantum transitions approach is employed to simulate the spectroscopic characteristics of the 1 P1 ↔1 S0 transitions in atomic zinc and cadmium in order to gain insight into the excited state behavior of these atoms isolated in solid rare gases neon, argon, and krypton. The absorption and emission spectra are simulated. Non-radiative processes play a fundamental role in the transfer of population among the three electronic states initially accessed in absorption. Three distinct relaxation pathways were identified. Two of these are related to the dynamical modes described in previous works [McCaffrey and Kerins, J. Chem. Phys. 106, 7885 (1997); Kerins and McCaffrey, J. Chem. Phys. 109, 3131 (1998)] in which the system evolves to form a square planar configuration around the metal atom. The third distinct pathway involves motion on a hexagonal close packed plane. The temperature dependence of complex formation was also determined for the three relaxation pathways.

Engineering of Cyano Functionalized Benzo[d]imidazol-2-ylidene Ir(III) Phosphors for Blue Organic Light-Emitting Diodes

In this study, we designed and synthesized three series of blue emitting homoleptic iridium(III) phosphors bearing 4-cyano-3-methyl-1-phenyl-6-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (mfcp), 5-cyano-1-methyl-3-phenyl-6-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (ofcp), and 1-(3-(tert-butyl)phenyl)-6-cyano-3-methyl-4-(trifluoromethyl)-benzo[d]imidazol-2-ylidene (5-mfcp) cyclometalates, respectively. These iridium complexes exhibit intense phosphorescence in the high energy region of 435-513 nm in the solution state at RT, to which the relatively large T1 → S0 transition dipole moment is beneficial for serving as a pure emitter and an energy donor to the multiresonance thermally activated delayed fluorescence (MR-TADF) terminal emitters via Förster resonance energy transfer (FRET). The resulting OLEDs achieved true blue, narrow bandwidth EL with a max EQE of 16-19% and great suppression of efficiency roll-off with ν-DABNA and t-DABNA. We obtained the FRET efficiency up to 85% using titled Ir(III) phosphors f-Ir(mfcp)3 and f-Ir(5-mfcp)3 to achieve true blue narrow bandwidth emission. Importantly, we also provide analysis on the kinetic parameters involved in the energy transfer processes and, accordingly, propose feasible ways to improve the efficiency roll-off caused by the shortened radiative lifetime of hyperphosphorescence.

Bending Effect on the Electronic Properties and Nonlinear Optical Responses of Linear Porphyrin Oligomer

AbstractPhysical bending provides a more stable and controllable method to modify the electronic properties and device applications compared to chemical doping/surface modification in traditional optoelectronic materials. The bending effect on the electronic properties and nonlinear optical (NLO) responses of linear porphyrin oligomer is explored using quantum chemistry methods by designing a series of curved structures with different bending degrees. The highest occupied molecular orbital−lowest unoccupied molecular orbital energy gap (Egap) of the linear porphyrin oligomer decreases after being bended to form the curved structures, and the Egap values and orbital distributions show independent behavior on bending degree. In the electronic absorption spectra, the maximum absorptions mainly come from the S0 → S1/S0 → S2 transitions with the characteristic of local excitation. The NLO response presents a tendency to increase and then decrease with decreasing the bending degree, which is in good accordance with the widely used two‐level model. The curved frameworks as well as the results offer guidelines for novel organic NLO device design and fabrication.

Pterin interactions with gold clusters: A theoretical study

Gold (Au) nanoclusters (NCs) are novel materials with low cytotoxicity and high chemical stability. These properties are in high demand during the bioimaging. Moreover, the optical properties of gold clusters allow to use them as colorimetric and luminescent bionanosensors. Pterins are low molecular weight organic compounds, which are used in medicine as biomarkers of phenylketonuria, vitiligo, inflammation and immune system activation, cancer, COVID-19, etc. We have investigated the possibility of gold nanosensors usage to detect pterin (Ptr). Ptr-Aunq structures (n = 1–6; q = 0–2) Gibbs energy of complexation (Eb) have been obtained using density functional theory. The highest Eb was determined for the complexes of Au62+ and Au32+ in acidic and alkaline aqueous solution, respectively. The detection of pterin with gold clusters seems to be prospective using both colorimetric and fluorescent detection because of the intense S0→S1 transition in the absorption spectrum of the Au5+ complex. Raman detection of pterin should be performed at alkaline pH because of the dramatic changes in the spectrum of Ptr−1 upon the addition of Au clusters. We believe that these tunable changes of the pterin spectra due to Au clusters and nanoparticles attachment could be exploited in further studies on nanosensor design.

Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening.

The results of electronic and vibrational structure simulations are an invaluable support for interpreting experimental absorption/emission spectra, which stimulates the development of reliable and cost-effective computational protocols. In this work, we contribute to these efforts and propose an efficient first-principle protocol for simulating vibrationally-resolved absorption spectra, including nonempirical estimations of the inhomogeneous broadening. To this end, we analyze three key aspects: (i) a metric-based selection of density functional approximation (DFA) so to benefit from the computational efficiency of time-dependent density function theory (TD-DFT) while safeguarding the accuracy of the vibrationally-resolved spectra, (ii) an assessment of two vibrational structure schemes (vertical gradient and adiabatic Hessian) to compute the Franck-Condon factors, and (iii) the use of machine learning to speed up nonempirical estimations of the inhomogeneous broadening. In more detail, we predict the absorption band shapes for a set of 20 medium-sized fluorescent dyes, focusing on the bright ππ★ S0 → S1 transition and using experimental results as references. We demonstrate that, for the studied 20-dye set which includes structures with large structural variability, the preselection of DFAs based on an easily accessible metric ensures accurate band shapes with respect to the reference approach and that range-separated functionals show the best performance when combined with the vertical gradient model. As far as band widths are concerned, we propose a new machine-learning-based approach for determining the inhomogeneous broadening induced by the solvent microenvironment. This approach is shown to be very robust offering inhomogeneous broadenings with errors as small as 2 cm-1 with respect to genuine electronic-structure calculations, with a total CPU time reduced by 98%.

Update of Muonium 1S–2S transition frequency

We present an updated value of the Muonium 1S–2S transition frequency, highlighting contributions from different QED corrections as well as the large uncertainty in the Dirac contribution, stemming from the uncertainty of the electron to muon mass ratio. Improving the measurement of this spectral line would allow to extract a more accurate determination of fundamental constants, such as the electron to muon mass ratio or, combined with the Muonium hyperfine splitting, an independent value of the Rydberg constant. Furthermore, we report on the current status of the Mu-MASS experiment, which aims at measuring the Muonium 1S–2S transition frequency at a 10hbox {kHz} uncertainty level.Graphic abstract

Natural line profile asymmetry

The paper discusses the line profile asymmetry of the photon scattering process that arises naturally in quantum electrodynamics (QED). Based on precision spectroscopic experiments conducted on hydrogen atoms, we focus our attention on the two-photon 1s − 2s transition. As one of the most precisely determined transition frequencies, it is a key pillar of optical frequency standards and is used in determining fundamental physical constants, testing physical principles, and searching constraints on new fundamental interactions. The results obtained in this work show the need to take into account the natural line profile asymmetry in precision spectroscopic experiments.

Molecular modification effects on the electrochromic and photochromic properties of diarylethene with intramolecular isomerization behavior.

Diarylethene (DAE) is one of the most widely used functional units for electrochromic or photochromic materials. To better understand the molecular modification effects on the electrochromic and photochromic properties of DAE, two modification strategies, substitution with functional groups or heteroatoms, were investigated theoretically by density functional theory calculations. It is found that red-shifted absorption spectra caused by a decreased highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap and S0 → S1 transition energy during the ring-closing reaction become more significant by adding different functional substituents. In addition, for two isomers, the energy gap and S0 → S1 transition energy decreased by heteroatom substitution of S atoms with O or NH, while they increased by replacing two S atoms with CH2. For intramolecular isomerization, one-electron excitation is the most effective way to trigger the closed-ring (O → C) reaction, while the open-ring (C → O) reaction occurs most readily in the presence of one-electron reduction. Moreover, it is confirmed that substitution with strong electron donating groups (-OCH3/-NH2) or with one O/two CH2 heteroatoms leads to a more favorable closed-ring (O → C) reaction. Functionalized with strong electron-withdrawing groups (-NO2 and -COOH) or one/two NH heteroatom substitutions, the open-ring (C → O) reaction is easier. Our results confirmed that the photochromic and electrochromic properties of DAE can be tuned effectively by molecular modifications, which provides theoretical guidance for the design of new DAE-based photochromic/electrochromic materials.

DFT and TD-DFT study of hydrogen bonded complexes of aspartic acid and n water (n = 1 and 2)

Hydrogen bonds (HB) influence the conformational preferences of biomolecules and their optical and electronic properties. The directional interaction of molecules of water can be a prototype to understand the effects of HBs on biomolecules. Among the neurotransmitters (NT), L-aspartic acid (ASP) stands out due to its importance in health and as a precursor of several biomolecules. As it presents different functional groups and readily forms inter- and intramolecular HBs, ASP can be considered a prototype for understanding the behavior of NTs when interacting by HB with other substances. Although several theoretical studies have been performed in the past on isolated ASP and its formed complexes with water, both in gas and liquid phases, using DFT and TD-DFT formalisms, these works did not perform large basis set calculations or study electronic transitions of ASP-water complexes. We investigated the HB interactions in complexes of ASP and water molecules. The results show that the interactions between the carboxylic groups of ASP with water molecules, forming cyclic structures with two HBs, lead to more stable and less polar complexes than other conformers formed between water and the NH2 group. It was observed that there is a relationship between the deviation in the UV-Vis absorption band of the ASP and the interactions of water with the HOMO and LUMO orbitals with the stabilization/destabilization of the S1 state to the S0 of the complexes. However, in some cases, such as 1:1 complex ASP-W2, this analysis may be inaccurate due to small changes in ΔE. We studied the landscapes of the ground state surface of different conformers of isolated L-ASP and the L-ASP-(H2O)n complexes (n = 1 and 2) using the DFT formalism, with the B3LYP functional, and six different basis sets: 6-31 + + G(d,p), 6-311 + + G(d,p), D95 + + (d,p), D95V + + (d,p), cc-pVDZ, and, cc-pVTZ basis sets. The cc-pVTZ basis set provides the minimum energy of all conformers, and therefore, we performed the analysis with this basis set. We evaluated the stabilization of the ASP and complexes using the minimum ground state energy, corrected by the zero point energy and the interaction energy between the ASP and the water molecules. We also calculated the vertical electronic transitions S1 ← S0, and their properties using the TD-DFT formalism at B3LYP/cc-pVTZ level with the optimized geometries for S0 state with the same basis set. For the analysis of the vertical transitions of isolated ASP and the ASP-(H2O)n complexes, we calculated the electrostatic energy in the S0 and S1 states. We performed the calculations with the Gaussian 09 software package. We used the VMD software package to visualize the geometries and shapes of the molecule and complexes.

Gas phase electronic spectra of xylene-water aggregates

Using a jet spectroscopy molecular beam setup, gas phase electronic spectra of three xylene isomers (para, meta and ortho) have been collected for the neutral monomer species as well as for their clusters with one and two water molecules. Scans at a resolution of ±0.02 nm showed a clear 0–0 transition for each xylene isomer as well as the vibronic progression. The spectra were assigned with the help of Franck–Condon factor PGOPHER simulations from theoretical studies at the CAM-B3LYP/aug-cc-pVDZ level of theory. The vibronic spectra of the xylene⋅H2O and xylene⋅(H2O)2 clusters showed broad features between 36800–38400 cm−1 (260–272 nm) for p- and m-xylene, while the water clusters of o-xylene gave more defined bands. The separation of the vibronic bands in the clusters mirrors the progression of the neutral monomers implying that, for the S1← S0 transition, it is the same vibrational modes that are involved in the monomer as in the clusters with water. Both the separation and the spectral width of the bands can be explained by the calculated differences in geometries of the clusters in the ground and first electronic excited states.

Improved quantum yield of thermally activated delayed fluorescence by nanoconfinement in organophilic octosilicate

A hybrid of a thermally activated delayed fluorescent dye (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, designated as 4CzIPN) and an organophilic layered silicate (dioleyldimethylammonium-octosilicate) was synthesized to achieve high photoluminescence quantum yield (0.71) of the dye, which is the critical factor in device application. Absorption, photoexcitation, and luminescence spectra suggested that the molecular conformation of 4CzIPN in the organophilic silicate enabled the utilization of the S0 → S1 transition efficiently. Furthermore, thanks to the flexible assembly of the dioleyldimethylammonium moieties, 4CzIPN was dispersed in the hybrid to suppress concentration quenching. Emission spectra and photoluminescence lifetimes in ambient and N2 atmosphere revealed that the photoluminescence quantum yield increased by the utilization of transition to a lower vibrational state and protection of a triplet state of 4CzIPN from oxygen in air in the organophilic silicate.

Luminescence properties, tunable emission and energy transfer of Na3Sc2(PO4)3: Sm3+, Bi3+ phosphors

Na3Sc2(PO4)3:R (R = Bi3+, Sm3+, and Sm3+/Bi3+) are successfully synthesized in air atmosphere. The high-temperature solid-state reaction method is used in this work. The X-ray diffractometer patterns confirm that all samples have the single pure phase Na3Sc2(PO4)3. Na3Sc2(PO4)3:Bi3+ displays blue emission because of the Bi3+ - Sc3+ metal-to-metal charge-transfer and the 3P1 → 1S0 transition of Bi3+. Na3Sc2(PO4)3:Sm3+ shows red-orange emission with four emission bands derived from the 4G5/2 → 6H5/2 (550 - 582 nm), 6H7/2 (582–625 nm), 6H9/2 (625–675 nm), and 6H11/2 (675–750 nm) transitions of Sm3+. The optimal Sm3+ concentration in Na3Sc2(PO4)3:Sm3+ is ∼8mol%. An adjustable color emission from blue to red-orange of Na3Sc2(PO4)3:Sm3+, Bi3+ with excitation at 345 nm can be observed when the ratio between Sm3+ and Bi3+ ions is changed. Na3Sc2(PO4)3:Sm3+, Bi3+ emits red–orange light under excitation 406 nm. The optimal Bi3+ concentration in Na3Sc2(PO4)3:8mol%Sm3+, Bi3+ is ∼ 6mol%. The energy transfer from Bi3+ to Sm3+ in Na3Sc2(PO4)3:Sm3+, Bi3+ is verified by the spectral properties of samples. We discuss the influences of Bi3+ or Sm3+ concentration on luminescence properties of samples and analyze their luminous mechanism by energy level diagram. The experimental results of paper are useful for the research of new Bi3+ and Sm3+ doped phosphors.