K2HgGe3Se8: A Quaternary Hg-Based Selenide with Nonlinear Optical Properties.

A new quaternary Hg-based selenide K2HgGe3Se8 was successfully synthesized and characterized as an engaging infrared (IR) nonlinear optical (NLO) material, which crystallizes in the P21 space group of the noncentrosymmetric monoclinic crystal system. The crystal structure of K2HgGe3Se8 is characterized by the stacking of countless [HgGe3Se8]2-∞2 layers with K+ cations filling the interlayers. The UV-vis-NIR diffuse reflectance spectrum shows that K2HgGe3Se8 possesses an indirect band gap of 2.13 eV. The second harmonic generation (SHG) response of K2HgGe3Se8 is approximately 1.1 times that of AgGaS2 (AGS) within the particle size of 20-50 µm along with a nonphase-matching (NPM) behavior at 2090 nm, as indicated by the SHG test. K2HgGe3Se8 also has a large powder laser-induced damage threshold (∼ 2.3 × AGS). As revealed by theoretical calculations, the optical properties of K2HgGe3Se8 are predominantly determined by [HgSe4] and [GeSe4] tetrahedra, and K2HgGe3Se8 possesses a calculated optical band gap of 1.44 eV together with a maximum SHG coefficient d22 of -7.70 pm V-1.

Narrowband mid-infrared optical parametric generator based on a type-II BaGa4Se7 crystal.

In this Letter, we first reported on a mid-infrared double-pass optical parametric generator (OPG) based on a single type-II phase-matching BaGa4Se7 (BGSe) crystal, pumped at 2.1 µm. The OPG achieved a maximum pulse energy of 55 µJ for generating narrowband mid-infrared laser pulses. The signal and idler lights exhibited center wavelengths of 4.04 and 4.33 µm, respectively, with bandwidths of 18.6 nm (11.4 cm-1) and 20.4 nm (10.9 cm-1). To improve the output performance, we utilized a cascaded scheme of type-I ZnGeP2 (ZGP) and type-II BGSe crystals. The spectral bandwidths of the signal and idler lights, nearing 4 µm, were narrower than 170 nm (90 cm-1), representing a significant improvement over the ZGP OPG. The cascaded OPG achieved a remarkable total optical-to-optical conversion efficiency (OOCE) of 14.9% and a maximum pulse energy of 0.329 mJ.

High-peak-power long-wave infrared BaGa4Se7 optical parametric oscillator with 6.7-13.9†µm widely tunable range.

A high-peak-power, widely tunable range long-wave infrared optical parametric oscillator (OPO) based on the BaGa4Se7 (BGSe) crystal is demonstrated in this Letter. Pumped by a 1064 nm Nd:YAG laser, a high-peak-power of 0.15 MW was achieved at 9.8 µm with a pulse width of 5.0 ns. At 11.0 µm, a high beam quality of M2x = 4.1 and M2y = 3.3 was achieved. By rotating the BGSe crystal, a broad tuning range of 6.7-13.9 µm was realized. Furthermore, a theoretical analysis was conducted to elucidate the reasons behind the improvement in beam quality in the x-direction as the wavelength of the idler wave increases.

Advancing nonlinear optics: discovery and characterization of new non-centrosymmetric phenazine-based halides.

Organic-inorganic metal halides (OIMHs) have drawn considerable attention due to their remarkable optoelectronic properties and substantial promise for nonlinear optical applications. In this research, phenazine has been selected as the organic cation because of its π-conjugated feature. Three compounds, (C12H9N2)PbCl3, (C12H9N2)SbCl4, and (C12H9N2)2InBr4·Br, were synthesized. Initial space group assignments were centrosymmetric for (C12H9N2)PbCl3 and (C12H9N2)SbCl4. However, under 1550 nm laser excitation, (C12H9N2)PbCl3 and (C12H9N2)SbCl4 exhibited second harmonic generation intensities ∼1.7 times greater than that of the benchmark KH2PO4. Structural reevaluation ultimately confirmed non-centrosymmetric P1 and P21 space groups for (C12H9N2)PbCl3 and (C12H9N2)SbCl4, respectively. Upon excitation at 335 nm and 470 nm, (C12H9N2)PbCl3, (C12H9N2)SbCl4, and (C12H9N2)2InBr4·Br emit fluorescence at room temperature. (C12H9N2)2InBr4·Br exhibits reversible phase transitions, showing potential for phase change energy storage. Our research underscores the critical role of comprehensive experimental validation in determining the precise crystallographic space groups and reveals the extensive potential of OIMHs as versatile candidates for advanced optoelectronic applications.

Sr2HgGe2OS6: A Hg-Based Oxychalcogenide Infrared Nonlinear Optical Material Exhibiting Favorable Balance between a Large Band Gap and Strong Second Harmonic Generation Response.

Currently, oxychalcogenides with mixed-anion groups that integrate the property advantages of oxides (wide optical band gap) and chalcogenides [strong second harmonic generation (SHG) response] through chemical substitution engineering have attracted widespread interest and are considered to be important candidates for infrared (IR) nonlinear optical (NLO) materials. Herein, the first Hg-based oxychalcogenide Sr2HgGe2OS6 with mixed anion [GeOS3] units has been successfully synthesized through a spontaneous crystallization method, which exhibits a favorable balance between the strong SHG response (0.7 × AgGaS2) and large optical band gap (2.9 eV). In addition, Sr2HgGe2OS6 shows high laser-induced damage threshold (LIDT, 2.1 × AgGaS2) as well as phase-matching (PM) performance. Theoretical calculations indicate that the Sr2HgGe2OS6 encompasses large birefringence of 0.128@2090 nm (3.3 × AgGaS2) and its SHG density mainly comes from [HgS4] tetrahedra and [GeOS3] units. This work not only demonstrates that Sr2HgGe2OS6 is a promising IR NLO material but also provides new ideas for the exploration of Hg-based oxychalcogenide IR NLO materials.

Sub-picosecond tunable mid-infrared light source for driving high-efficiency optical rectification.

Optical rectification (OR) is a popular way to generate coherent terahertz radiation. Here, we develop a sub-picosecond mid-infrared (mid-IR) light source with a tailored wavelength and pulse duration for enhancing the OR efficiency. Numerical simulations for a LiNbO3-based OR with tilted pulse-front excitation are first conducted to determine the optimal parameters of pump wavelength and pulse duration, demonstrating that the OR efficiency pumped by 4-µm sub-picosecond (0.5-0.6 ps) pulses is approximately twice the value with 0.8-µm pump at the same conditions. Guided by the simulation results, we build a BaGa4Se7-based optical parametric chirped-pulse amplification system with 1030-nm thin-disk pump and broadband mid-IR seeds. The output performances of >200-µJ pulse energy, ∼600-fs pulse duration and 1-kHz pulse repetition rate are achieved in a spectral range tunable from 3.5 to 5 µm. The large energy scalability and high parameter tunability make the light source attractive to high-efficiency OR in various materials.

Widely tunable and high resolution mid-infrared laser based on BaGa4Se7 optical parametric oscillator.

The widely tunable and high resolution mid-infrared laser based on a BaGa4Se7 (BGSe) optical parametric oscillator (OPO) was demonstrated. A wavelength tuning range of 2.76-4.64 µm and a wavelength tuning resolution of about 0.3 nm were obtained by a BGSe (56.3°, 0°) OPO, which was pumped by a 1064 nm laser. It is the narrowest reported wavelength tuning resolution for BGSe OPO, and was obtained by simultaneously controlling the angle and temperature of BGSe.

Synthesis and characterization of a new rare earth borate nonlinear optical crystal K7PbLu2B15O30.

A new complex rare earth borate K7PbLu2B15O30 was prepared by the spontaneous crystallization method. K7PbLu2B15O30 is crystallized in the chiral trigonal space group R32 with cell parameters a = b = 13.0893(3) Å, c = 15.2379(6) Å, α = ß = 90°, γ = 120°, and Z = 3. The basic structure of the crystal can be seen as composed of B5O10 groups and LuO6 polyhedra sharing oxygen atoms, while K+ and Pb2+ fill the space to balance the charge. The UV transmission cut-off edge of K7PbLu2B15O30 was less than 300 nm, and the powder SHG response was roughly 1.1 times that of KDP. Furthermore, a first-principles analysis was performed to see more about the relationship between the crystal structure and optical characteristics.

Mixed Alkali Metal and Alkaline Earth Metal Scandium Borate Birefringence Material with Layered Structure and Short Ultraviolet Cutoff Edge.

Birefringent crystals are essential in the domains of linear and nonlinear optics that need light wave polarization control. Rare earth borate has become a popular study material for ultraviolet (UV) birefringence crystals due to its short cutoff edge in the UV area. RbBaScB6O12, a two-dimensional layered structure compound with the B3O6 group, was effectively synthesized through spontaneous crystallization. The UV cutoff edge of RbBaScB6O12 is shorter than 200 nm, and the experimental birefringence is 0.139 @ 550 nm. Theoretical research indicates that the large birefringence originates from the synergistic impact of the B3O6 group and the ScO6 octahedron. RbBaScB6O12 is an outstanding candidate material for birefringence crystals in the UV and even deep UV regions due to its short UV cutoff edge and significant birefringence.

Synthesis, Crystal Structure, and Nonlinear-Optical Properties of a Diamond-Like Chalcogenide Cu2GeS3.

Metal sulfides with diamond-like (DL) structures generally exhibit excellent mid-IR nonlinear-optical (NLO) properties. Here, Cu2GeS3 (CGS) as a member of the DL chalcogenides was synthesized by a high-temperature solid-state method, and the optical properties were carefully studied experimentally and theoretically. The results revealed that CGS has a large second harmonic generation (0.8 × AgGaSe2) and a moderate birefringence of 0.067 at 1064 nm. In addition, the linear and NLO properties of the A2MS3 (A = Cu, Li; M = Ge, Si) series of compounds were evaluated and compared with the help of first-principles calculations.

Structure and Optical Properties of LixAg1-xGaSe2 and LixAg1-xInSe2.

Complete substitution of Li atoms for Ag atoms in AgGaSe2 and AgInSe2 was achieved, resulting in the solid solutions LixAg1-xGaSe2 and LixAg1-xInSe2. The detailed crystal structures were determined by single-crystal X-ray diffraction and solid-state 7Li nuclear magnetic resonance spectroscopy, which confirm that Li atoms occupy unique sites and disorder only with Ag atoms. The tetragonal CuFeS2-type structure (space group I4̅2d) was retained within the entirety of the Ga-containing solid solution LixAg1-xGaSe2, which is noteworthy because the end-member LiGaSe2 normally adopts the orthorhombic ß-NaFeO2-type structure (space group Pna21). These structures are closely related, being superstructures of the cubic sphalerite and hexagonal wurtzite prototypes adopted by diamond-like semiconductors. For the In-containing solid solution LixAg1-xInSe2, the structure transforms from the tetragonal to orthorhombic forms as the Li content increases past x = 0.50. The optical band gaps increase gradually with higher Li content, from 1.8 to 3.4 eV in LixAg1-xGaSe2 and from 1.2 to 2.5 eV in LixAg1-xInSe2, enabling control to desired values, while the second harmonic generation responses become stronger or are similar to those of benchmark infrared nonlinear optical materials such as AgGaS2. All members of these solid solutions remain congruently melting at accessible temperatures between 800 and 900 °C. Electronic structure calculations support the linear trends seen in the optical band gaps and confirm the mostly ionic character present in Li-Se bonds, in contrast to the more covalent character in Ga-Se or In-Se bonds.

The Kurtz-Perry Powder Technique Revisited: A Study of the Effect of Reference Selection on Powder Second-Harmonic Generation Response.

The accurate evaluation of nonlinear optical (NLO) coefficient, the main parameter affecting light conversion efficiency, plays a crucial role in the development of NLO materials. The Kurtz-Perry powder technique can evaluate second-harmonic generation (SHG) intensity in pristine powder form, saving a significant amount of time and energy in the preliminary screening of materials. However, the Kurtz-Perry method has recently been subject to some controversy due to the limitations of the Kurtz-Perry theory and the oversimplified experimental operation. Therefore, it is very meaningful to revisit and develop the Kurtz-Perry technique. In this work, on the basis of introducing the light scattering effect into the original Kurtz-Perry theory, the theoretical expression of second-harmonic generation intensity with respect to band gap and refractive index are analyzed. In addition, the reference-dependent SHG measurements were carried out on polycrystalline LiB3O5 (LBO), AgGaQ2 (Q = S, Se), BaGa4Q7 (Q = S, Se), and ZnGeP2 (ZGP), and the results of SHG response emphasize the importance of using appropriate references to the Kurtz-Perry method. In order to obtain reliable values of nonlinear coefficients, two criteria for selecting a reference compound were proposed: (1) it should possess a band gap close to that of the sample to be measured and (2) it should possess a refractive index close to that of the sample to be measured. This work might shed light on improvements in accuracy that can be made for effective NLO coefficients obtained using the Kurtz-Perry method.

Two non-centrosymmetric mixed alkali metal and alkaline earth metal scandium borate nonlinear optical materials with short ultraviolet cutoff edges.

Rare earth borates, a subset of the essential nonlinear optical (NLO) materials, have sparked a significant amount of attention in recent years. In self-fluxing systems, two non-centrosymmetric scandium borates with classical B5O10 groups, namely Rb7SrSc2B15O30 (I) and Rb7CaSc2B15O30 (II), were successfully discovered. Both I and II exhibit a short ultraviolet (UV) cutoff edge (<200 nm) and appropriate second-harmonic generation efficiency (∼0.76 × KH2PO4, ∼0.88 × KH2PO4 at 1064 nm, respectively). According to theoretical calculations, it is speculated that the band gap and NLO characteristics of these two compounds are mostly derived from the B5O10 group and the ScO6 octahedron. Due to the short cutoff edges of I and II, they may be considered as potential NLO materials in the UV and even deep UV spectral ranges. Furthermore, the advent of I and II adds to the diversity of rare earth borates.

Output characteristics of 3-8 µm mid-infrared source based on BaGa4Se7 crystal.

An optical parametric oscillator based on B a G a 4 S e 7 crystal is constructed for use as a 3-8 µm mid-infrared source. The output characteristics of the light source, including wavelength tuning, beam quality, and energy stability, are studied, which are usually concerned differently in spectral analysis, imaging, and laser processing. When the light source operates far from the threshold, the mid-infrared output is poor in beam quality and good in energy stability, and the contradiction should be addressed in practice. The results provide guidance on the selection of operating parameters and performance optimization for the application of the B a G a 4 S e 7 based mid-infrared source in various settings.

Structure and Characterization of K2Na3B2P3O13, a New Nonlinear Optical Borophosphate with One-Dimensional Chain Structure and Short Ultraviolet Cutoff Edge.

Nonlinear optical (NLO) crystals, being the primary medium for laser wavelength conversion, are crucial in all-solid-state lasers. Borophosphates offer more structural varieties than pure borates and phosphates, and they have become popular as NLO crystal candidates. Through spontaneous crystallization, we acquired a noncentrosymmetric alkali metal borophosphate crystal material, K2Na3B2P3O13 (KNBPO). KNBPO crystallizes in the orthorhombic Cmc21 space group with the following unit cell parameters: a = 13.9238(18) Å, b = 6.7673(8) Å, c = 12.1298(15) Å, and Z = 4, and its structure is characterized by a fundamental building unit 1∞ [B2P3O13] chain structure made up of bridging oxygen linkages between BO4 and PO4 tetrahedra. KNBPO has a short ultraviolet (UV) cut-off edge (<186 nm), a congruent melting characteristic, good thermal stability, and a moderate second harmonic generation response roughly 0.42 times that of KH2PO4. Theoretical calculations reveal that the optical properties of the compound mainly originate from BO4 and PO4 units. Due to the short UV cut-off edge, KNBPO can be used as a potential NLO material in the UV and even deep UV regions, and it enhances the structural variety of borophosphates, which has a reference value for scholars investigating similar materials.

Growth, Structure, and Optical Properties of a Nonlinear Optical Niobium Borate Crystal CsNbOB2O5 with Distorted NbO5 Square Pyramids.

In this paper, a revised structure determination of an already known compound CsNbOB2O5 with new structural insights was performed and the detailed characterization of its optical properties was reported for the first time. CsNbOB2O5 was synthesized by spontaneous crystallization. It crystallizes in the Pmn21 space group, and the unit lattice parameters are a = 7.5220(7) Å, b = 3.9881(4) Å, c = 9.7167(9) Å, and Z = 2. In the structure of CsNbOB2O5, a [NbO5] square pyramid and [B2O5] unit are linked to constitute an infinitely extended two-dimensional ∞2[NbOB2O5] layer via sharing oxygen atoms. Between these two-dimensional layers, there are no covalent bonds perpendicular to their planes based on Mulliken bond order analysis. CsNbOB2O5 has a wide band gap (4.52 eV) and a large second-harmonic-generation (SHG) response (1.2 × KDP) and demonstrates type-I phase-matchable behavior. First-principles simulations reveal that the birefringence is approximately 0.10. Moreover, SHG-weighted charge density analysis shows that the primary source of the nonlinearity of the title compound is the distorted NbO5 square pyramids.

Comparison of a high-power 3.75 µm BaGa4Se7 OPO based on a plane-parallel resonator and an unstable resonator with a Gaussian reflectivity mirror.

Using a homemade Nd:YAG laser with a pulse repetition frequency of 300 Hz as a pump source, we demonstrated a tunable BaGa4Se7 (BGSe) optical parametric oscillator (OPO). Wavelength-tuning ranges of 1.42-1.59 µm and 3.21-4.22 µm were realized, and a maximum average output power of 1.03 W at 3746 nm was achieved in a plane-parallel resonator. To date, this is the highest output power at around 4 µm obtained from a BGSe OPO pumped by a 1 µm laser, to our knowledge. Moreover, the BGSe OPO employing a plano-convex Gaussian reflectivity mirror (GRM) as an output coupler (OC) was demonstrated for the first time, to our knowledge. At the same pump power, the corresponding output power and M2 value of the idler at 3746 nm were 0.86 W and 10.2 (x direction) and 11.6 (y direction), respectively. The results indicate that the beam quality factor M2 of the idler has an over 30% improvement in comparison with the BGSe OPO based on a conventional flat OC of a plane-parallel resonator. Limited by the beam quality of the pump source, there is little room for improvement in the beam quality of the BGSe OPO with a GRM OC, which could be improved in the future by optimizing the pump beam.

Bridging oxygen atoms in trigonal prism units driven strong second-harmonic-generation efficiency in Sr3Ge2O4Te3.

Herein, a novel IR NLO oxytelluride Sr3Ge2O4Te3 was successfully designed and synthesized through a "partial O-to-Te substitution" strategy. Compared with the parent oxide, Sr3Ge2O4Te3 not only successfully achieves a phase-matchability transition (from NPM to PM), but also greatly improves the linear and NLO performances, including a wide band gap (2.26 eV), strong SHG response (1.3 × AgGaSe2) and large optical anisotropy (Δn = 0.152@2090 nm). The analyses of the structure-property relationship and SHG-density indicate that the bridging oxygen in the [O3Ge-O-GeTe3] prism unit plays the most important role in the multiplication SHG effect. This work provides some insights into the design and exploration of novel IR NLO materials.

Second-Harmonic-Generation Effect and Giant Optical Birefringence in the Weyl Material CaAgAs.

Nonlinear-optical (NLO) materials suitable for the "8-14 µm" atmospheric transparent window are in urgent need. Arsenide is one of the most promising material systems for such an application. However, the second-harmonic-generation (SHG) effect of arsenide is difficult to characterize using the conventional powder SHG technique with a 2 µm fundamental laser. To overcome this problem, we focused on a novel arsenide Weyl material, CaAgAs, with a zero band gap and proposed a modified powder SHG measurement method for narrow-band-gap materials. We successfully observed the SHG signal of CaAgAs, which was approximately 0.7 times that of CdGeAs2. Moreover, on the basis of first-principles calculations, the largest SHG coefficient for CaAgAs is equal to 236 pm/V, and the ionic bonds in the [Ca3As13] motif play an indispensable role for the SHG effect because of the distorted Kagome lattice pattern. CaAgAs is predicted to have strong optical anisotropy with a giant optical birefringence of 0.52.

Ultrabroad (3.7-17†µm) tunable femtosecond optical parametric amplifier based on BaGa4Se7 crystal.

We demonstrate the first (to the best of our knowledge) tunable femtosecond (fs) mid-infrared (MIR) optical parametric amplifier (OPA) based on BaGa4Se7 (BGSe) crystal with an ultra-broadband spectral range. Benefiting from the broad transparency range, high nonlinearity, and relatively large bandgap of BGSe, the MIR OPA pumped at 1030 nm with a repetition of 50 kHz has an output spectrum that is tunable across an extremely wide spectral range spanning from 3.7 to 17 µm. The maximum output power of the MIR laser source is measured as 10 mW at a center wavelength of 16 µm, corresponding to a quantum conversion efficiency of 5%. Power scaling is straightforwardly achieved by using a stronger pump in BGSe with an available large aperture size. A pulse width of 290 fs centered at 16 µm is supported by the BGSe OPA. Our experimental result indicates that BGSe crystal could serve as a promising nonlinear crystal for fs MIR generation with an ultra-broadband tuning spectral range via parametric downconversion for applications such as MIR ultrafast spectroscopy.