Self-Trapped Exciton Emission in Highly Polar 0D Hybrid Ammonium/Hydronium-Based Perovskites Triggered by Antimony Doping.

Various monovalent cations are employed to construct metal halide perovskites with various structures and functionalities. However, perovskites based on highly polar A-site cations have seldom been reported. Here, a novel hybrid 0D (NH4)x(OH3)3-xInCl6 perovskite with highly polar hydronium OH3+ cations is introduced in this study. Upon doping with Sb3+, hybrid 0D (NH4)x(OH3)3-xInCl6 single crystals exhibited highly efficient broadband yellowish-green (550 nm) and red (630 nm) dual emissions with a PLQY of 86%. The dual emission arises due to Sb3+ occupying two sites within the crystal lattice that possess different polarization environments, leading to distinct Stokes shift energies. The study revealed that lattice polarity plays a significant role in the self-trapped exciton emission of Sb3+-doped perovskites, contributing up to 25% of the Stokes shift energy for hybrid 0D (NH4)x(OH3)3-xInCl6:Sb3+ as a secondary source, in addition to the Jahn-Teller deformation. These findings highlight the potential of Sb3+-doped perovskites for achieving tunable broadband emission and underscore the importance of lattice polarity in determining the emission properties of perovskite materials.

Toward an Ideal Light Source for Indoor Photosynthesis: Broadband Red Emission in Zero-Dimensional Hafnium-Based Metal Halide (TPP)2HfCl6·4C2H3N:Sb3.

With suitable electron-phonon coupling strength, a near-unity broadband photoluminescence quantum yield (PLQY) can be achieved in organic-inorganic hybrid metal halides (OIHMHs) via self-trapped exciton (STE) emission. However, it is still challenging to obtain high-quality red emission from OIHMHs with a desirable emission wavelength and high chemical stability, which hinders their practical application in high-performance displays, plant-growth lighting, and biomedical imaging. Herein, a series of hafnium-based zero-dimensional (TPP)2HfCl6·4C2H3N (TPP: tetraphenylphosphonium) single crystals with different Sb3+ doping levels are synthesized. The Sb3+-doped (TPP)2HfCl6·4C2H3N shows dual-band red emission with a full width at half-maximum of 178 nm and a high PLQY of 91.09%. This broad dual-band emission originates from dopant-induced extrinsic free excitons and STEs. Furthermore, (TPP)2HfCl6·4C2H3N:Sb3+ was employed as a luminescence converter in a light-emitting diode (LED) for plant growth regulation. A correlated color temperature of 4055 K and a color rendering index of 82.13 were achieved upon excitation of the LED at 365 nm. These results provide fundamental perspectives on the emission behavior of Sb3+-doped OIHMHs and illustrate their promise for use in plant-growth lighting.

Enhance terahertz radiation and its polarization- control with two paralleled filaments pumped by two-color femtosecond laser fields.

We present experimentally an obvious enhancement of the terahertz (THz) radiation with two paralleled filaments pumped by two-color laser fields for a full use of a high laser power, compared with single filament. By mapping the 3-dimensional electric trajectories of generated THz fields with a (111) ZnTe crystal, we observe that the total THz polarization from two filaments can be manipulated by varying the time delay between the two orthogonally polarized pumps, which agrees well with the simulations under the photocurrent model. Notably, the power and spectrum of the THz field almost keep unchanged while manipulating the ellipticity of the THz polarization, which is important for a polarization-controllable THz source.

Temperature-insensitive broadband optical parametric chirped pulse amplification based on a tilted noncollinear QPM design.

Ultrafast pulsed laser of high intensity and high repetition rate is the combined requisite for advancing strong-field physics experiments and calls for the development of thermal-stable ultrafast laser systems. Noncollinear phasing matching (PM) is an effective solution of optimizing the properties of optical parametric chirped pulse amplification (OPCPA) to achieve broadband amplification or to be temperature-insensitive. But as a cost, distinct noncollinear geometries have to be respectively satisfied. In this paper, a noncollinear quasi-phase-matching (QPM) scheme of both temperature- and wavelength-insensitive is presented. With the assistance of the design freedom of grating wave vector, the independent noncollinear-angle requirements can be simultaneously realized in a tilted QPM crystal, and the temperature-insensitive broadband amplification is achieved. Full-dimensional spatial-temporal simulations for a typical 1064 nm pumped mid-IR OPCPA at 3.4 µm are presented in detail. Compared with a mono-functional temperature-insensitive or broadband QPM scheme, the presented QPM configuration shows a common characteristic that simultaneously optimizes the thermal stability and the gain spectrum. Broadband parametric amplification of a ∼40 fs (FWHM) pulsed laser is achieved with no signs of gain-narrowing. Both of the beam profiles and the amplified spectra stay constant while the temperature is elevated by ∼100°C. Finally, influence of the QPM grating errors on the gain spectrum is discussed.

Comprehensive analyses of the thermal insensitive noncollinear phase-matching for power scalable parametric amplifications.

Thermal-induced phase-mismatch distortion, which will dramatically deteriorate the efficient energy transfer, has become a critical obstacle to power scaling of optical parametric amplifiers. To ease this efficiency deterioration, the noncollinear optical parametric amplification (OPA) configuration widely employed to achieve broadband phase-matching (PM) may also serve as a promising approach to optimize the temperature acceptance. In this paper, starting from the noncollinear wave-vector equations, a required thermo- and angle-relationship analogous to that of noncollinear broadband PM is firstly inferred. Based on the presented mathematical criterion, we have explored the potential spectral boundaries of this ingenious temperature insensitive OPA scheme. Full-dimensional simulations of two types of typical OPA processes were quantitatively discussed. Compared with traditional collinear PM designs, the presented noncollinear PM configurations show significant common characteristics on improving the temperature acceptance and subsequently the overall amplification efficiency. For a typical high power parametric process of the 532 nm pumped near-IR OPA at 800 nm especially, incredible temperature bandwidth exceeding 8000 °C was obtained while a YCOB (xz plane) crystal is adopted. What is more, it can also be applied to ameliorate the gain-spectrum thermo-instability of OPA.

Degeneracy-analogous femtosecond dual-wavelength optical parametric oscillator at non-degenerate wavelengths.

Synchronously pumped optical parametric oscillator (OPO) at degeneracy is ideal for generating ultrafast laser pulses. Normally, however, group velocity mismatch (GVM) is ubiquitous among the interacting pulses at widely separated wavelengths. A versatile quasi-phase-matching (QPM) technique is proposed for temporal synchronizing of the signal and idler pulses relied on a less common Type-II QPM (oe-o interaction). The proposed group-velocity regulation technology is advantageous to constructing a degeneracy-analogous femtosecond OPO for dual-wavelength operation. Qualitative prediction for the proposed design is conducted based on a commercial femtosecond pump source at 1064 nm while the signal/idler wavelengths are 3.2 µm and 1.59 µm respectively. Compared with the conventional Type-0 QPM based counterpart (ee-e interaction), the uncompensated temporal distortion caused by temporal walk-off is strongly suppressed while the idler spectrum gets significantly broader. The versatility of the proposed scheme is also clearly demonstrated by its fairly stable performance within a broad tuning range of 2.9-3.5 µm and 1.68-1.53 µm. The demonstrated configuration might be promising for synchronously obtaining dual-wavelength ultrafast pulses with higher spectral and temporal qualities.

Versatile backconversion-inhibited broadband optical parametric amplification based on an idler-separated QPM configuration.

Conversion efficiency and phase-matching (PM) bandwidth are both critical issues for broadband parametric processes. In some sense, they determine the highest peak power achieved via the optical parametric amplification. In this Letter, a versatile idler-separated quasi-phase matching scheme capable of both backconversion circumvention and ultra-broadband PM is presented. Full-dimensional spatial-temporal simulations for the typical optical parametric chirped pulse amplification processes at 800 nm and 3.4 µm were presented in detail. By virtue of the broad PM bandwidth on account of the non-collinear PM configuration, the backconversion circumvention on account of the idler-separated design, and the walk-off self-compensation on account of the symmetrical tilting grating patterns, significantly improved gain bandwidth, extremely high conversion efficiency, and a well-preserved beam profile are simultaneously achieved. Compared with the collinear configuration, the peak power can be potentially enhanced by 5-10 times under the same operation circumstances.

Propagation dynamics of super-Gaussian beams in fractional Schrödinger equation: from linear to nonlinear regimes.

We have investigated the propagation dynamics of super-Gaussian optical beams in fractional Schrödinger equation. We have identified the difference between the propagation dynamics of super-Gaussian beams and that of Gaussian beams. We show that, the linear propagation dynamics of the super-Gaussian beams with order m > 1 undergo an initial compression phase before they split into two sub-beams. The sub-beams with saddle shape separate each other and their interval increases linearly with propagation distance. In the nonlinear regime, the super-Gaussian beams evolve to become a single soliton, breathing soliton or soliton pair depending on the order of super-Gaussian beams, nonlinearity, as well as the Lévy index. In two dimensions, the linear evolution of super-Gaussian beams is similar to that for one dimension case, but the initial compression of the input super-Gaussian beams and the diffraction of the splitting beams are much stronger than that for one dimension case. While the nonlinear propagation of the super-Gaussian beams becomes much more unstable compared with that for the case of one dimension. Our results show the nonlinear effects can be tuned by varying the Lévy index in the fractional Schrödinger equation for a fixed input power.

Spectrum regulation for mid-infrared ultrafast pulses via a time-synchronization aperiodically poled LiNbO3.

Restricted to temporal separation during the coupled-waves interaction, aperiodically quasi-phase-matching (QPM) nonlinear crystals are primarily implemented for prechirped pulses, showing limited applications in ultrafast temporal scale. Under the proposed time-synchronization framework, pump and signal waves travel with identical group-velocity, which permits sustaining energy transfer in long aperiodically poled LiNbO3 crystals (APPLN) even with ultrafast pulse duration. With the help of this structure, adiabatic frequency conversion shows extra advantages compared with the common cases, which enables lower stretching ratio and smoother gain spectrum. Focusing on the typical mid-infrared wavelength of ~3 µm, we numerically study the potential performance of APPLN with chirp-free ultrabroad interacting waves. In contrast to the spectral shift and conversion efficiency degradation presented by its traditional Type-0 QPM counterpart, the proposed design demonstrated impressive ability to obtain arbitrary spectrum via a simple femtosecond OPA/OPO. Peculiarly, the QPM chirp rate sign plays a significant role to the output spectrum, and a positive chirp rate is preferential in delivering a bandwidth-controllable spectrum. The proposed design provides a promising technical route to achieve spectrum manipulation in ultrafast temporal scale.

Effect of initial frequency chirp on Airy pulse propagation in an optical fiber.

We study both analytically and numerically the propagation dynamics of an initially chirped Airy pulse in an optical fiber. It is found that the linear propagation of an initially chirped Airy pulse depends considerably on whether the second-order dispersion parameter ß(2) and chirp C have the same or opposite signs. For ß(2)C<0, the chirped Airy pulse first undergoes an initial compression phase, then reaches a breakup area as depending on the values of C, and then experiences a lossy inversion transformation such that it continues to propagate with an opposite acceleration. The chirped Airy pulse is always dispersed during propagation in the case of ß(2)C>0. The impact of truncation coefficient and Kerr nonlinearity on the chirped Airy pulse propagation is also disclosed separately.

Modulation instability of finite energy Airy pulse in optical fiber.

We have investigated and analyzed the modulation instability (MI) of finite energy Airy pulse (FEAP) in an optical fiber in order to reveal the impact of truncation coefficient on the nonlinear propagation dynamics of FEAP with or without amplitude perturbation. We have also characterized the difference between the propagation process of smooth FEAP and that of modulated FEAP. It is shown that, for a smooth FEAP, the side lobes prior to the main lobe first undergo compression and then break up into multiple sub-pulses during propagation in the case of small truncation coefficient; while the opposite occurs in the case of large truncation coefficient. For a FEAP with amplitude modulation, the breakup of the main lobe induced by MI precedes that of side lobes for arbitrary values of truncation coefficients; but the evolution of secondary lobes is made by a transition from splitting process to a simple compression process with increasing truncation coefficient. The propagation dynamics of secondary lobes with number symbol larger 2, marked the secondary lobes starting number 1 from near to far according the distance between itself and the main lobe, is insensitive to the truncation coefficients variation in both cases. Finally, the MI gain spectra of FEAP with different truncation coefficients are obtained by numerically solving the nonlinear Schrödinger equation and the results have been compared with the theoretical predictions.

Manipulation of Raman-induced frequency shift by use of asymmetric self-accelerating Airy pulse.

We investigate the evolution of asymmetric self-accelerating finite energy Airy pulses (FEAP) in optical fibers with emphasis on the role of Raman scattering. We show that the Raman-induced frequency shift (RIFS) of soliton initiated by an asymmetric self-accelerating FEAP depends not only on the launched peak power but also on the truncation coefficient imposed on the asymmetric self-accelerating FEAP. We find that the RIFS of asymmetric self-accelerating FEAP increases with a decrease in the truncation coefficient, while the peak power and spectrum width of the outermost red shift of the shedding soliton spectrum are almost unchanged. The time and frequency shifts of the shedding soliton are found to be sensitive to the truncation coefficient when the truncation coefficient is in the range of 0 to 0.1. These excellent features would lead to the realization of a RIFS-based tunable light source by launching self-accelerating FEAP with different truncation coefficient into an optical fiber.

Temperature-insensitive frequency tripling for generating high-average power UV lasers.

Aimed for generating high-average power ultraviolet (UV) lasers via third-harmonic generation (THG) consisting of frequency doubling and tripling stages, we numerically and experimentally demonstrate a novel frequency tripling scheme capable of supporting temperature-insensitive phase-matching (PM). Two cascaded tripling crystals, with opposite signs of the temperature derivation of phase-mismatch, are proposed and theoretically studied for improving the temperature-acceptance of PM. The proof-of-principle tripling experiment using two crystals of LBO and BBO shows that the temperature acceptance can be ~1.5 times larger than that of using a single tripling crystal. In addition, the phase shift caused by air dispersion, along with its influence on the temperature-insensitive PM, are also discussed. To illustrate the potential applications of proposed two-crystal tripling design in the high-average-power regime, full numerical simulations for the tripling process, are implemented based on the realistic crystals. The demonstrated two-crystal tripling scheme may provide a promising route to high-average-power THG in the UV region.

Generation of 120 GW mid-infrared pulses from a widely tunable noncollinear optical parametric amplifier.

We demonstrate a noncollinear optical parametric chirped-pulse amplification scheme for generating high-peak-power tunable mid-infrared (IR) pulses. The high-gain LiNbO(3)-based noncollinear parametric amplifier, seeded by a tunable femtosecond optical parametric amplifier, provides a wide wavelength tuning range from 3.3 to 3.95 µm and a large saturated gain of over 4000 in a single-stage amplifier. The compressed mid-IR pulse has a pulse energy of 13.3 mJ and pulse duration of 111 fs, with a peak power as high as 120 GW. To the best of our knowledge, this is the highest peak power ever reported for 3-5 µm tunable mid-IR lasers.

Modulation of the Excitation States in All-Inorganic Halide Perovskites via Sb3+ and Bi3+ Codoping.

Sb3+-doped halide perovskites are promising candidates for solid-state lighting due to their diverse fluorescent colors and high efficiency. However, the mismatched high excitation energy with commercial UV chips is one of the critical issues to be addressed. Herein, a Bi3+ codoping strategy was established as a general and efficient approach to modulate the excitation spectrum from the Sb3+-doping center in all-inorganic perovskites of Cs2InCl5·H2O, Cs2NaInCl6, and Rb3InCl6. The incorporated Bi3+ greatly enhanced the splitting of the A band (1S0-3P1 transition) and boosts the enormous redshift of the low-energy branch in all these systems. The interactions persist strongly even at extremely low doping concentrations, suggesting a dipole-based long-range interaction. The results provide an in-depth insight into the contribution mechanism of Bi3+ to Sb3+ in all-inorganic perovskites, which throws light upon tuning the excitation spectrum of broadband emission from the extrinsic self-trapped exciton (STE).

Zero-Dimensional Tellurium-Based Organic-Inorganic Hybrid Halide Single Crystal with Yellow-Orange Emission from Self-Trapped Excitons.

Organic-inorganic hybrid halides and their analogs that exhibit efficient broadband emission from self-trapped excitons (STEs) offers an unique pathway towards realization of highly efficient white light sources for lighting applications. An appropriate dilution of ns2 ions into a halide host is essential to produce auxiliary emissions. However, the realization of ns2 cation-based halides phosphor that can be excited by blue light-emitting diode (LED) is still rarely reported. In this study, a zero-dimensional Te-based single crystal (C8H20N)2TeCl6 was synthesized, which exhibits a yellow-orange emission centered at 600 nm with a full width at half maximum of 130 nm upon excitation under 437 nm. Intense electron-phonon coupling was confirmed in the (C8H20N)2TeCl6 single crystal and the light emitting mechanism is comprehensively discussed. The results of this study are pertinent to the emissive mechanism of Te-based hybrid halides and can facilitate discovery of unidentified metal halides with broadband excitation features.

Achieving Tunable Cold/Warm White-Light Emission in a Single Perovskite Material with Near-Unity Photoluminescence Quantum Yield.

Single materials that exhibit efficient and stable white-light emission are highly desirable for lighting applications. This paper reports a novel zero-dimensional perovskite, Rb4CdCl6:Sn2+, Mn2+, which demonstrates exceptional white-light properties including adjustable correlated color temperature, high color rendering index of up to 85, and near-unity photoluminescence quantum yield of 99%. Using a co-doping strategy involving Sn2+ and Mn2+, cyan-orange dual-band emission with complementary spectral ranges is activated by the self-trapped excitons and d-d transitions of the Sn2+ and Mn2+ centers in the Rb4CdCl6 host, respectively. Intriguingly, although Mn2+ ions doped in Rb4CdCl6 are difficult to excite, efficient Mn2+ emission can be realized through an ultra-high-efficient energy transfer between Sn2+ and Mn2+ via the formation of adjacent exchange-coupled Sn-Mn pairs. Benefiting from this efficient Dexter energy transfer process, the dual emission shares the same optimal excitation wavelengths of the Sn2+ centers and suppresses the non-radiative vibration relaxation significantly. Moreover, the relative intensities of the dual-emission components can be modulated flexibly by adjusting the fraction of the Sn2+ ions to the Sn-Mn pairs. This co-doping approach involving short-range energy transfer represents a promising avenue for achieving high-quality white light within a single material.

Emission Mechanism of Self-Trapped Excitons in Sb3+-Doped All-Inorganic Metal-Halide Perovskites.

Sb3+ doping confers highly efficient and color-diverse broadband light emission to all-inorganic metal-halide perovskites. However, the emission mechanism is still under debate. Herein, a trace amount of Sb3+ ions (<0.1% atomic percentage) doping in the typical all-inorganic perovskites Cs2NaInCl6, Rb3InCl6, and Cs2InCl5·H2O allows universal observation of the fine structure in the photoluminescence excitation spectrum of the ns2 electron. A lifetime mapping method was utilized to reveal the origin of broadband emission triggered by Sb3+ doping, by which various fluorescence components can be differentiated. In particular, free-exciton emission was identified at the high-energy end of the broadband emission for all three doped systems. The excitation-energy- and temperature-dependent fluorescence decay further indicates the existence and origin of self-trapped states. The observed structural and vibrational symmetry-dependent emission behaviors suggest dipole interactions can dramatically alter Stokes-shift energy and modulate the light-emitting wavelength.

A Novel 4,4'-Bipiperidine-Based Organic Salt for Efficient and Stable 2D-3D Perovskite Solar Cells.

The efficiency of metal halide perovskite solar cells (PSCs) has dramatically increased over the past decade (formerly 3.8%, now 25.5%). It has been widely demonstrated that the defects passivation of perovskite photo-active layer plays a vital role in increasing the efficiency and improving the stability of PSCs. In this study, we developed a novel 4,4'-bipiperidine (BiPi)-based organic salt with good stability and successfully introduced this ligand into perovskite for the first time. The embedded BiPi-based organic salt in the 3D perovskites facilitated the formation of two-dimensional-three-dimensional (2D-3D) perovskite materials that passivated the perovskite layer, with a constructive consequence in both photovoltaic performance and device stability. Incorporating this ligand improved the crystallinity of the perovskite materials with reduced defect states, prolonged resolved carrier lifetime, and improved stability. An optimized PSC device exhibited substantially improved device stability and an outstanding power conversion efficiency of 20.03%, with the aid of the BiPi-based organic salt [open-circuit voltage (VOC), 1.10 V; current density (JSC), 23.51 mA/cm2; and fill factor (FF), 0.77], which are 13.0% higher than the original device. Our study provides a ligand design protocol for developing next-generation, highly efficient, stable PSCs.

High-contrast near-IR short pulses generated by a mid-IR optical parametric chirped-pulse amplifier with frequency doubling.

We demonstrate the generation of high-contrast 1054nm short pulses based on a mid-IR optical parametric chirped-pulse amplifier with frequency doubling. Measurement-limited contrast higher than 10(9) is obtained over a large temporal range from approximately 100 ps to 3ps before the peak of the main pulse. With the potential of pulse-energy scalability, the demonstrated scheme incorporating further chirped-pulse amplification in the near-IR range is applicable to petawatt power-level laser systems.