Flexible Anionic Groups-Activated Structure Dissymmetry for Strong Nonlinearity in Ln2 Ae3 MIV 3 S12 Family.

Structural dissymmetry and strong second-harmonic generation (SHG) responses are key conditions for nonlinear optical (NLO) crystals, and targeted combinatorial screening of suitable anionic groups has become extremely effective. Herein, optimal combination of flexible SnSn (n = 5, 6) groups and highly electropositive cations (lanthanides (Ln3+ ) and alkaline earth (Ae2+ : Sr, Ca) metals) affords the successful synthesis of 12 NLO thiostannates including Ln2 Sr3 Sn3 S12 (Pmc21 ) and Ln2 Ca3 Sn3 S12 (P-62m); whereas 17 rigid GeS4 or SiS4 tetrahedra-constructed Ln2 Ae3 Ge3 S12 and Ln2 Ae3 Si3 S12 crystallize in the centrosymmetric (CS) Pnma. This unprecedented CS to noncentrosymmetric (NCS) structural transformation (Pnma to P-62m to Pmc21 ) in the Ln2 Ae3 MIV 3 S12 family indicates that chemical substitution of the tetrahedral GeS4 /SiS4 units with SnSn breaks the original symmetry to form the requisite NCS structures. Remarkably, strong polarization anisotropy and hyperpolarizability of the Sn(4+) S5 unit afford huge performance improvement from the nonphase-matching (NPM) SHG response (1.4 × AgGaS2 and Δn = 0.008) of La2 Ca3 Sn3 S12 to the strong phase-matching (PM) SHG effect (3.0 × AgGaS2 and Δn = 0.086) of La2 Sr3 Sn3 S12 . Therefore, Sn(4+) S5 is proven to be a promising "NLO-active unit." This study verifies that the coupling of flexible SnSn building blocks into structures opens a feasible path for designing targeted NCS crystals with strong nonlinearity and optical anisotropy.

Modulating the d-Band Center of RuO2 via Ni Incorporation for Efficient and Durable Li-O2 batteries.

Rechargeable Li-O2 batteries (LOBs) are considered as one of the most promising candidates for new-generation energy storage devices. One of major impediments is the poor cycle stability derived from the sluggish reaction kinetics of unreliable cathode catalysts, hindering the commercial application of LOBs. Therefore, the rational design of efficient and durable catalysts is critical for LOBs. Optimizing surface electron structure via the negative shift of the d-band center offers a reasonable descriptor for enhancing the electrocatalytic activity. In this study, the construction of Ni-incorporating RuO2 porous nanospheres is proposed as the cathode catalyst to demonstrate the hypothesis. Density functional theory calculations reveal that the introduction of Ni atoms can effectively modulate the surface electron structure of RuO2 and the adsorption capacities of oxygen-containing intermediates, accelerating charge transfer between them and optimizing the growth pathway of discharge products. Resultantly, the LOBs exhibit a large discharge specific capacity of 19658 mA h g-1 at 200 mA g-1 and extraordinary cycle life of 791 cycles. This study confers the concept of d-band center modulation for efficient and durable cathode catalysts of LOBs.

7.56-W continuous-wave Pr3+-based green laser via managing thermally induced effects.

Blue-laser-diode-pumped Pr3+-based continuous-wave (CW) green lasers have aroused growing research interest in developing optoelectronic applications and deep ultraviolet laser sources due to their simple and compact structural design. However, the obstacle of thermally induced effects limits the available output power of Pr3+-based green lasers. Herein, combined with the theoretical analysis and experimental feedback, we effectively adjust the heat distribution inside the Pr3+:LiYF4 gain crystal by optimizing the crystal dimension and doping concentration. The excellent mode matching between the pump and green lasers is achieved under the consideration of thermally induced effects, yielding a maximum CW output power of 7.56 W. To the best of our knowledge, this is the largest output power of Pr3+-based CW green lasers so far. Moreover, the obtained green laser demonstrates excellent output stability (RMS = 1.27%) and beam quality (M2 = 1.30 × 1.12) under the lasing operation state with the maximum output power. We hope that this study can provide a feasible paradigm for developing blue-laser-diode-pumped visible lasers, especially for high-power lasers.

Multiphonon-coupling yellow laser in Yb:La2CaB10O19 crystal.

Yellow lasers at 590 nm have many extensive applications in our daily life, but extremely difficult to attain by traditional solid-state laser technology, owing to the absence of highly-efficient transition channels at this spectral range. In this work, we proposed a cooperative lasing mechanism to obtain the yellow light emission, with multiphonon-assisted electronic transitions and phase-matched frequency-doubling. Based on the predictable configurational coordinate model, we can calculate the multiphonon-assisted emission step-by-step. Using Yb3+-doped La2CaB10O19 crystal as an example, it is capable of producing yellow laser at 581-590 nm, with a maximum output power of 4.83 W and a high slope efficiency of 31.6%. To the best of our knowledge, it represents the highest power of solid-state yellow laser realized in one single crystal pumped by a laser diode. This power scaling can be assigned to the amplified phonon-assisted emission beyond the fluorescence spectrum, and optimized crystal angle for phase-matching condition. Such a compact, low-cost, and high-power laser device, provides an alternative candidate for the spectral "yellow-gap" where no practical solid-state laser exists at present.

Intracavity frequency-doubled yellow laser in an electron-phonon-coupled Nd:YVO4 crystal.

An approach to obtain a yellow laser is demonstrated for the first time to our knowledge by the employment of an Nd3+-doped YVO4 crystal and a LBO frequency-doubling crystal. Differing from the previous stimulated self-Raman radiation of Nd:YVO4, a direct 1176 nm lasing, without a high-intensity intracavity 1064 nm laser, was realized by utilizing an electron-phonon coupling effect and amplifying the thermally activated vibronic transitions. Combining with intracavity frequency-doubling, a yellow laser at 588 nm was obtained. At the pump power of 14.3 W, the output power of the yellow laser was 1.17 W, corresponding to a diode-to-visible efficiency of 8.2%. Moreover, for the first time, the yellow laser at 584 nm with output power of 164 mW was realized by tuning the filter, indicating the great potential of such an electron-phonon coupling laser for a wavelength extension in the yellow regime.

Realizing high-efficiency third harmonic generation via accidental bound states in the continuum.

The bound states in the continuum (BICs) have attracted much attention in designing metasurface due to their high Q-factor and effectiveness in suppressing radiational loss. Here we report on the realization of the third harmonic generation (THG) at a near-ultraviolet wavelength (343 nm) via accidental BICs in a metasurface. The absolute conversion efficiency of the THG reaches 1.13 × 10-5 at a lower peak pump intensity of 0.7 GW/cm2. This approach allows the generation of an unprecedentedly high nonlinear conversion efficiency with simple structures.

Influence of Cation-Size Effects of Alkaline Earth (Ae) Metals on Dimensionality and Optical Anisotropy Regulation in K4AeP2S8 Thiophosphates.

Cationic substitution demonstrates significant potential for regulating structural dimensionality and physicochemical performance owing to the cation-size effect. Leveraging this characteristic, this study synthesized a new family of K4AeP2S8 (Ae = alkaline earth elements: Mg, Ca, Sr, and Ba) thiophosphates, involving the substitution of Ae2+ cations. The synthesized compounds crystallized in distinct space groups, monoclinic P2/c (Ae = Mg) versus orthorhombic Ibam (Ae = Ca, Sr, and Ba), exhibiting intriguing dimensionality transformations from zero-dimensional (0D) [Mg2P4S16]8- clusters in K4MgP2S8 to 1D ∞[AeP2S8]4- chains in other K4AeP2S8 thiophosphates owing to the varying ionic radii of Ae2+ cations, Ae-S bond lengths, and coordination numbers of AeSn (Mg: n = 6 versus other: n = 8). Experimental investigations revealed that K4AeP2S8 thiophosphates featured wide optical bandgaps (3.37-3.64 eV), and their optical absorptions were predominantly influenced by the S 3p and P 3s orbitals, with negligible contributions from the K and Ae cations. Notably, within the K4AeP2S8 series, birefringence (Δn) increased from K4MgP2S8 (Δn = 0.034) to other K4AeP2S8 (Δn = 0.050-0.079) compounds, suggesting that infinite 1D chains more significantly influence Δn origins than 0D clusters, thus offering a feasible approach for enhancing optical anisotropy and exploring potential new birefringent materials.

Strong, anisotropic, layer-independent second harmonic generation in multilayer SnS film.

Materials based on group IV chalcogenides exhibit extensive technologically important properties. Its unusual chemical bonding and off-centering of in-layer sublattices could cause chemical polarity and weakly broken symmetry, making optical field controlling feasible. Here, we fabricated large-area SnS multilayer films and observed unexpected strong SHG response at 1030 nm. The appreciable SHG intensities were obtained with an independence on layer, which is opposite to the generation principle of overall nonzero dipole moment only in odd-layer material. Taking GaAs for reference, the second-order susceptibility was estimated to be 7.25 pm/V enhanced by mixed-chemical bonding polarity. Further polarization-dependent SHG intensity confirmed the crystalline orientation of SnS films. The results imply surface inversion symmetry broken and nonzero polarization field modified by metavalent bonding should be the origin of SHG responses. Our observations establish multilayer SnS as a promising nonlinear material, and will guide in design of IV chalcogenides with improved optics and photonics properties for the potential applications.

Deciphering the vibronic lasing performances in an electron-phonon-photon coupling system.

Coupling between electronic motions and the lattice vibrations, phonons could broaden the spectral bandwidth of the fluorescence spectroscopy by the energy transferring, which was recognized from the beginning of last century and successfully applied in many vibronic lasers. However, the laser performances under electron-phonon coupling were mainly prejudged by the experimental spectroscopy. The multiphonon participated lasing mechanism is still elusive and should be in-depth investigated. Here, a direct quantitative relationship between the laser performance and phonon participating dynamic process was derived in theory. With a transition metal doped alexandrite (Cr3+:BeAl2O4) crystal, the multiphonon coupled laser performance was manifested in experiments. Associated with the Huang-Rhys factor calculations and hypothesis, the multiphonon participated lasing mechanism with phonon numbers from 2 to 5 was discovered and identified. This work provides not only a credible model for understanding the multiphonon participated lasing, but should also boost the study of laser physics in the electron-phonon-photon coupled systems.

Kerr-lens mode-locking of an Yb:CLNGG laser.

We report on a Kerr-lens mode-locked laser based on an Yb3+-doped disordered calcium lithium niobium gallium garnet (Yb:CLNGG) crystal. Pumping by a spatially single-mode Yb fiber laser at 976 nm, the Yb:CLNGG laser delivers soliton pulses as short as 31 fs at 1056.8 nm with an average output power of 66 mW and a pulse repetition rate of ∼77.6 MHz via soft-aperture Kerr-lens mode-locking. The maximum output power of the Kerr-lens mode-locked laser amounted to 203 mW for slightly longer pulses of 37 fs at an absorbed pump power of 0.74 W, which corresponds to a peak power of 62.2 kW and an optical efficiency of 20.3%.

Efficient passively Q switched lasers with a large-energy stored Yb:LuScO3 crystal.

Ytterbium (Yb)-ions-doped sesquioxide crystal is an attractive gain medium for a tunable and pulsed laser owing to its high thermal conductivity. In particular, it has been identified that Yb:LuScO3 has the largest energy storage property compared with other sesquioxide crystals, which is favorable for passive Q switching. In this Letter, continuous wave (CW) and the first, to the best of our knowledge, passively Q switched laser operations were demonstrated with a Yb:LuScO3 crystal. For CW laser operation, it generated the maximum output power of 8.68 W, corresponding to a slope efficiency up to 78.3%. Using Cr:YAG crystals as saturable absorbers, stable passive Q switching lasers were obtained with the Yb:LuScO3 crystal. Both the CW and Q switched lasers operate on the strongest fluorescence emission peak of 1038 nm. With Cr:YAG as the saturable absorber, efficient passively Q switched lasers with a slope efficiency of 45% were obtained with the pulse width, pulse energy, and peak power of 5.9 ns, 116 µJ, and 18.5 kW, respectively.

Actively Q-switched self-frequency-doubled Yb:YCOB green laser with output power of a dozen watts.

A diode laser (LD) end-pumped acousto-optic Q-switched self-frequency-doubled (SFD) Yb:YCa4O(BO3)3 (Yb:YCOB) pulsed green laser was realized for the first time (to our knowledge), with a maximum average output power of 11.6 W and an optical conversion efficiency of 30.0% from the LD to SFD lasers. The wavelength of the SFD lasers was controlled to be 507 nm for improving quantum efficiency up to 96% and reducing thermal effects. The repetition rates ranged from 20 to 500 kHz, and the maximum pulse energy was 312.0 µJ with a peak power of 4.78 kW at a repetition rate of 20 kHz. This work represents the highest output power in the SFD pulsed lasers and provides an efficient and compact way to generate high-power pulsed green lasers that should have important applications in many aspects, such as ultraviolet (UV) laser generation, laser display, and medical, military, and scientific research.

Monolithic 591-nm laser with cooperative multiphonon-coupling and nonlinear frequency-doubling.

Stable and miniaturized orange lasers at 591 nm are in urgent demand for ophthalmology and dermatological treatment. However, at present, traditional dye lasers and nonlinear sum-frequency lasers are limited by their complex setup and high cost, whereas semiconductor laser diodes (LDs) emitting in the yellow-orange range suffer from low output power. Here, we propose a new, to the best of our knowledge, route to create self-frequency-doubling (SFD) orange laser with a combination of multiphonon-assisted lasing and nonlinear frequency-doubling in one crystal. Using Yb3+-doped YCa4O(BO3)3 (Yb:YCOB) crystal, we first realize a widely tunable laser beyond the fluorescence spectrum in the wavelength range of 1175-1248 nm. Then, by selecting the laser polarization and crystal angle to satisfy phase-matching conditions, we obtained a directly diode-pumped orange laser at 591.8 nm with 3.07-W output power and an optical-to-optical conversion efficiency of 13%. This work represents a new step forward for portable high-power solid-state orange lasers and provides an intriguing platform for electron-phonon coupled lasing.

Noncentrosymmetric Na6Pb3P4S16 and Centrosymmetric K2MIIP2S6 (MII = Mg and Zn) Displaying Multiple Membered-Ring Configurations and Strong Optical Anisotropy.

Three thiophosphates including noncentrosymmetric Na6Pb3P4S16 and centrosymmetric K2MIIP2S6 (MII = Mg and Zn) were successfully synthesized in vacuum-sealed silica tubes. Note that interesting multiple six membered-rings (6-MRs) including 6-NaS6-MRs and 6-KSn-MRs (n = 6 and 7) formed by A+-centered polyhedra were discovered in the structures of title thiophosphates and these MR-composed three-dimensional (3D) tunnels show great possibility to facilitate the filling of various structural blocks (such as zero-dimensional (0D) Pb3S10 trimers or one-dimensional (1D) (MIISn)n chains). Na6Pb3P4S16 exhibits the strongest nonlinear optical (NLO) response (5.4 × AgGaS2) with phase-matching (PM) behavior among the known Pb-based PM NLO sulfides, which is much larger than that of Pb3P2S8 (3.5 × AgGaS2); it was verified that such large second harmonic generation (SHG) response in Na6Pb3P4S16 can be attributed to the huge contribution of stereochemically active PbS4 units based on the SHG-density and dipole-moment calculations. Moreover, title thiophosphates show large birefringences (Δn = 0.102-0.21), which indicates that incorporation of [P2S6] dimers or polarized PbS4 units into structures provides positive benefits for the onset of strong optical anisotropy.

Insight into Eu3+-Doped Phase-Change K3Lu(PO4)2 Phosphate toward Data Encryption.

Adjusting the local coordination environment of lanthanide luminescent ions can modulate their crystal-field splittings and broaden their applications in the relevant optical fields. Here, we introduced Eu3+ ions into the phase-change K3Lu(PO4)2 phosphate and found that the temperature-induced reversible phase transitions of K3Lu(PO4)2 (phase I ⇆ phase II and phase II ⇆ phase III, below room temperature) give rise to an obvious photoluminescence (PL) difference of Eu3+ ions. The Eu3+ emission mainly focused on the 5D0 → 7F1 transition in phase III but manifested comparable 5D0 → 7F1,2 transitions in the two low-temperature phases. On this basis, the change of Eu3+-doped concentration led to the phase evolution in Eu3+:K3Lu(PO4)2, which could stabilize two types of low-temperature polymorphs to the specific temperature by controlling the doping content. Finally, we proposed a feasible information encryption strategy based on the PL modulation of Eu3+:K3Lu(PO4)2 phosphors, which was caused by the temperature hysteresis of the relevant phase transition, exhibiting good stability and reproducibility. Our findings pave an avenue for exploring the optical application of lanthanide-based luminescent materials by introducing phase-change hosts.

Compact acousto-optical Q-switched Yb:ScBO3 laser with giant pulse energy.

In this Letter, a continuous-wave Yb:ScBO3 laser was enhanced with a maximum output power of 1.63 W and a slope efficiency of 48.97%, pumped by a continuous-wave 965 nm diode laser. Subsequently, the first, to the best of our knowledge, acousto-optically Q-switched Yb:ScBO3 laser was realized with an output wavelength of 1022 nm and repetition rates ranging from 0.04 to 1 kHz. The characteristics of pulsed lasers modulated by a commercial acousto-optic Q switcher were comprehensively demonstrated. With a low repetition rate of 0.05 kHz, the pulsed laser was generated under an absorbed pump power of 2.62 W, having an average output power of 0.44 W and giant pulse energy of 8.80 mJ. The pulse width and peak power were 80.71 ns and 109 kW, respectively. The findings manifest that the Yb:ScBO3 crystal is a gain medium with great potential for Q-switched laser generation with high pulse energy.

High-power continuous-wave self-frequency-doubled monolithic laser.

We report a high-power self-frequency-doubled (SFD) Yb:YCa4O(BO3)3 laser by employing a simple and high-integration monolithic configuration with an oscillator length of 6 mm. By reducing the reabsorption and increasing the quantum efficiency, the continuous-wave output power of 21.6 W was obtained with an optical conversion efficiency of 19.0% at the wavelength of about 510 nm. To our knowledge, the results represent the highest output power of a SFD laser. We believe that the high-power SFD laser with a highly compact structure will have broad and promising application prospects in laser display, medical treatment, spectral analysis, scientific research, and other fields.

Diode-pumped continuous-wave laser of a self-frequency-doubling Yb:La2CaB10O19 crystal.

We report the first, to the best of our knowledge, laser operation of acentric Yb3+-doped La2CaB10O19 (Yb:LCB) crystal since its discovery in 1998. The polarized absorption and emission cross-section spectra of Yb:LCB were calculated at room temperature. Using a fiber-coupled 976 nm laser diode (LD) as the pump source, we realized effective dual-wavelength laser generation at around 1030 and 1040 nm. The highest slope efficiency of 50.1% was obtained in the Y-cut Yb:LCB crystal. In addition, via resonant cavity design on a phase-matching crystal, a compact self-frequency-doubling (SFD) green laser at 521 nm was also realized in a single Yb:LCB crystal with an output power of 152 mW. These results promote Yb:LCB as a competitive multifunctional laser crystal, especially for highly integrated microchip laser devices ranging from the visible to the near-infrared regime.

Enhanced Electron-Phonon Coupling Effect in Rare-Earth Borate Crystals Containing a "Quasi-Free-Oxygen" Motif.

Revealing the interaction between electrons and phonons, e.g., electron-phonon coupling or decoupling, is a great challenge for physics and functional material communities. For rare-earth single crystals, the electron-phonon coupling and fluorescence behaviors strongly depend on the crystal structure and constituent motifs. Here, we proposed a universal "quasi-free O" as an effective structural motif to enhance phonon-assisted electronic transitions and photoluminescence. Using Gd3+ ion as a probe, we studied Gd:La2CaB10O19 (Gd:LCB) and GdMgB5O10 (GdMB) crystals composed of double B-O layers and dangling "quasi-free O", respectively, which enable strengthened phonon-involved luminescence. Especially, a GdMB crystal features an infinite [O-Gd-O-Gd-O] chain (O represents quasi-free oxygen), thus greatly promoting the energy transfer and electron-phonon coupling effect. As a result, its Huang-Rhys S factor is two times larger than that of a Gd:LCB crystal under room temperature. These results put forward "quasi-free O" to improve the electron-phonon coupling intensity and allow LCB and GdMB crystals to serve as potential hosts for phonon-terminated vibronic lasers.

Anion-Centered Polyhedron Strategy for Strengthening Photon Emission Induced by Electron-Phonon Coupling.

Electron-phonon coupling emerges as a growing frontier in the heart of condensed matter from physical symmetry to the electronic quantum state, but its quantitative strength dependence on the chemical structure has not been assessed. Here, we originally proposed the anion-centered polyhedron (ACP) strategy for elaborating the electron-phonon coupling interaction in rare-earth (RE) materials comprising three chemical factors, RE-O bond length, the effective charge of the coordinated atom, and structural dimensionality. Using Gd3+ cation with 4f7 configuration as a fluorescence probe, we found that the "free-O"-centered polyhedron is the most crucial motif in strengthening the phonon-assisted energy transfer and photon emission. The temperature-dependent Huang-Rhys S factors were calculated to identify the electron-phonon coupling intensity based on the fluorescence spectrum quantitatively. Finally, beyond conventional wisdom, a series of structural criteria were presented, serving as useful guidelines for discovering strongly coupled rare-earth optical materials. Our study breaks the long-time "blind"-searching diagram and provides reliable principles for many functional materials associated with electron-phonon coupling, such as superconductors, multiferroics, and phosphors.