Optical Materials Research Articles

Systematic long-term investigation on Cu2ZnCdS4 wide band gap semiconducting materials for optics and luminescence applications

Copper Zinc Cadmium Sulfide (Cu2ZnCdS4) semiconducting material compound synthesized using a new economic beneficial route. Copper sulfate, zinc sulfate, cadmium sulfate and thiourea salt solutions were utilized for Cu2ZnCdS4 compound formation. Basic characteristics like pH value, electrical conductivity, concentration measurements were investigated for several hundred samples. Optics transmittance was investigated by UV – Vis spectrophotometer within the 350 to 950 nm range. Photo luminescence measurement was examined by using photo–fluorometer. Optic properties of Cu2ZnCdS4 compound were investigated through photo-calorimeter measurements including mixed wavelength bands. The real time investigated noteworthy results from several hundred samples are presented and discussed.

Synthesis, structural characterization and third-order nonlinear optical study of W/Cu/S cluster-based coordination polymers with thioether-containing ligands

The assembly of [Et4N][Tp*WS3] (Et = ethyl, Tp* = tetrakis(3,5-dimethyl-1-pyrazolyl)borate), Cu(I) with 1,3,5-tri((pyridin-4-ylthio)methyl)benzene (tptmb) or 4,4′-bis((pyridin-4-ylthio)methyl)-1,1′-biphenyl (bptmb) leads to two coordination polymer with the formulae of {[Tp*WS3Cu3(tptmb)(CH3CN)](PF6)2·CHCl3·2CH3CN}n (1·CHCl3·2CH3CN) and {[(Tp*WS3Cu3)2(bptmb)3(CH3CN)](PF6)4·5CH2Cl2·1.5CH3CN}n (2·5CH2Cl2·1.5CH3CN), respectively. Compounds 1 and 2 were characterized by elemental analysis, infrared spectroscopy, UV–vis spectroscopy, high-resolution electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. In 1, each tptmb ligand connects two adjacent cluster nodes by its three coordination arms, forming a cluster-based one-dimensional zigzag chain. In 2, equal amounts of [Tp*WS3Cu3(CH3CN)]2+ and [Tp*WS3Cu3]2+ clusters serve as three-connected nodes and are alternatively bridged by the bptmb ligands, forming a 2D network. Z-scan tests of 1 and 2 in dimethylformamide (DMF) solution reveal they have reverse saturable absorption with effective nonlinear absorption coefficients of 1.50 × 10−11 m/W for 1 and 5.00 × 10−11 m/W for 2. This work could inspire the construction of coordination polymer structures using cluster nodes and flexible thioether-containing ligands, providing a new way for the development of third-order nonlinear optical materials.

Mixed (NH4)2Mn0.47Cu0.53(SO4)2(H2O)6 Tutton salt: A novel optical material for solar-blind technology

In this paper, a novel mixed Tutton salt (NH4)2Mn0.47Cu0.53(SO4)2(H2O)6 obtained in single crystal form is described. Their structural, thermal, electrical, and spectroscopic properties have been examined, and their possible uses are discussed. The salt crystallizes in a monoclinic symmetry (P21/c) and exhibits thermal stability between 300-333 K. Above this temperature, the crystal undergoes phase changes associated with dehydration and crystallization processes. 231 optical phonons distributed between 50 and 4000 cm–1, calculated through density functional perturbation theory, were used to accurately assign vibrational modes in experimental FT-IR and Raman spectra. Additional computational studies using Hirshfeld surfaces have revealed that H···O/O···H and H···H intermolecular contacts are crucial interactions for stabilizing the crystal lattice. Electrical characteristics (resistivity = 1160 MΩ·cm; capacitance = 3.6 pF) and optical data (bandgap = 4.27 eV) depict a typical behavior of nonpolar dielectric materials. UV-Vis-NIR transmittance spectrum has shown deep light blocking in the UV-C and Vis/NIR spectral regions and high transmittance levels (reaching 98.5%) in the UV-B/-A/Vis range. The photoresponse findings point out that (NH4)2Mn0.47Cu0.53(SO4)2(H2O)6 is a promising light-absorbing material for solar-blind photodetection devices operating in the 200-280 nm interval. The crystal as a bandpass filter (280-615 nm) or a cut-off filter (615-1000 nm) are also excellent prospects for application.

Exploiting Deep‐Ultraviolet Nonlinear Optical Material Rb2ScB3O6F2 Originated from Congruously Oriented [B3O6] Groups

AbstractThe exploration and research for deep‐ultraviolet (UV) nonlinear optical (NLO) crystals are of great significance for all‐solid‐state lasers. This work is based on the excellent structural [B3O6] units which manipulate the excellent performances of famous commercial NLO crystal β‐BaB2O4 (β‐BBO) to explore new alternatives of deep‐UV NLO materials. A deep‐UV rare‐earth metal borate fluoride Rb2ScB3O6F2 (RSBF) is successfully designed by combining the heterovalent ions substitution strategy, and fluorination strategy. Expectedly, RSBF exhibits an extremely short cutoff edge below 175 nm (189 nm for β‐BBO), and a moderate birefringence of 0.088 at 1064 nm. The shortest phase‐matching (PM) wavelength of RSBF (λPM=182 nm) is shortened by 23 nm compared with β‐BBO (λPM=205 nm) due to the improvements in the chromatic dispersion and cutoff edge, and an experimental frequency‐doubling effect 1.4×KH2PO4 (KDP) further suggests that RSBF can output a deep‐UV harmonic laser. This work provides new sights from the original influencing factors for the rational and purposeful design of deep‐UV NLO materials.

Nonlinear wave dynamics in ferromagnetic media: A study with the Kuralay-IIA equation

In this research, we delve into the exploration of the Kuralay-IIA equation by employing two power full approaches, namely extended hyperbolic function method (EHFM) and the improved modified Sardar-subequation method (IMSSEM). Applications of the Kuralay-IIA equation can be observed in a variety of physical phenomena, particularly in optical fibers, magnetic materials, and nonlinear optics. This equation performs an essential part in understanding gas behavior. Specifically, it offers an image of the relationship between volume, temperature and pressure in a gas system. We proceed through the matter in detail through the use of space curves which demonstrate integrable motion. Using the proposed techniques, our investigation provides an extensive variety of soliton solutions, such as periodic, dark–bright, bright, dark, solitary, and some other solutions. These solutions are in good alignment with previous study findings in this area. Analytical wave solutions are vital as they provide a basic comprehension of the physics or mathematics at play and establish a framework for further studies. The findings obtained from this study may help design models to come. The techniques used in this study are very effective, straightforward, and capable of handling more nonlinear models with high reliability. We use the Mathematica software to validate the accuracy and reliability of our results. Using carefully constructed 2D and 3D graphs generated, the resulting solutions are visually shown.

LiLnGeS4 (Ln=La-Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through "Band Reformation of AGS".

AgGaS2 (AGS) is the most commonly used commercial infrared nonlinear optical (IR NLO) material. However, AGS has a narrow band gap (Eg=2.58 eV) and a low laser-induced damage threshold (LIDT), primarily attributed to its mobile liquid-like Ag+ constituent and the unstable Ag-S chemical bond. Herein, we propose a "band reformation of AGS" strategy, which leads to the successful syntheses of four lanthanide sulfides, LiLnGeS4 (Ln=La-Nd), crystalizing in an asymmetric Ama2 structure. LiLaGeS4 demonstrates that eliminating the presence of Ag-4d band increases the Eg to 3.32 eV and enhances the LIDT (14-29×AGS, measured by both powder and single crystal); while increasing the nonbonding density of states of the S-3p band enhances the 2nd-nonlinear optical coefficient (1.06×AGS). Besides, the bond length discrepancy between [LiS4], [GeS4] and [LaS8] units leads to a moderate birefringence (Δn=0.052). Such a unique structure further results in extremely small thermal expansion with αL=0.41-1.74×10-5 K-1, along different crystallographic axes. Our theoretical studies indicate that the synergy of the structure building units contribute to the second harmonic generation performance. These results suggest that the "band reformation of AGS" strategy provides effective guidance to discover new NLO crystals with optimized performance.

LiLnGeS4 (Ln=La−Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through “Band Reformation of AGS”

AbstractAgGaS2 (AGS) is the most commonly used commercial infrared nonlinear optical (IR NLO) material. However, AGS has a narrow band gap (Eg=2.58 eV) and a low laser‐induced damage threshold (LIDT), primarily attributed to its mobile liquid‐like Ag+ constituent and the unstable Ag−S chemical bond. Herein, we propose a “band reformation of AGS” strategy, which leads to the successful syntheses of four lanthanide sulfides, LiLnGeS4 (Ln=La−Nd), crystalizing in an asymmetric Ama2 structure. LiLaGeS4 demonstrates that eliminating the presence of Ag‐4d band increases the Eg to 3.32 eV and enhances the LIDT (14–29×AGS, measured by both powder and single crystal); while increasing the nonbonding density of states of the S‐3p band enhances the 2nd‐nonlinear optical coefficient (1.06×AGS). Besides, the bond length discrepancy between [LiS4], [GeS4] and [LaS8] units leads to a moderate birefringence (Δn=0.052). Such a unique structure further results in extremely small thermal expansion with αL=0.41–1.74×10−5 K−1, along different crystallographic axes. Our theoretical studies indicate that the synergy of the structure building units contribute to the second harmonic generation performance. These results suggest that the “band reformation of AGS” strategy provides effective guidance to discover new NLO crystals with optimized performance.

Two-Dimensional MXene Flakes with Large Second Harmonic Generation and Unique Surface Responses.

MXenes are a family of two-dimensional (2D) materials with broad and varied applications in biology, materials science, photonics, and environmental remediation owing to their layered structure and high surface area-to-volume ratio. MXenes have exhibited significant nonlinear optical characteristics, which have been primarily explored in the context of photonics applications, yet the second-harmonic generation (SHG) behavior of MXenes remains an unexplored aspect of their optical properties. Herein, we demonstrate and quantify large second-order responses of 2D Ti3C2Tx MXenes both in aqueous solutions and on a silicon substrate for the first time. MXene flakes showed strong second-harmonic scattering (SHS) in a dilute suspension with a sensitivity of less than 0.1 μg/mL. Angle-dependent SHS experiments further found that the second-order responses originate from coherent 2D dipole radiation. Through confocal and atomic force microscopies, we found that the intense SHG signal from free-standing MXene flakes increases exponentially with decreasing thickness, while two-photon fluorescence increases linearly with thickness. The second-order susceptibility of the MXenes was determined to be 3.6 pm V-1 with a thickness of 10 nm, almost twice of that for an often-used SHG crystal, beta barium borate. We further explored surface properties of the MXene sheets by investigating the SHS responses upon addition of organic dye molecules to the system. It was found that the adsorption of crystal violet (CV) obeys a Langmuir adsorption model while the addition of malachite green (MG) resulted in almost no change in SHG intensity, even though the adsorption capacities for both CV (61.3 ± 1.7 mg/g) and MG (54.8 ± 2.8 mg/g) are similar. Such a stark difference in adsorption characteristics between cationic organic CV and MG dyes is likely due to their distinct orientational orderings on the MXene surfaces. This work opens many possibilities for the further employment of the family of 2D materials in photonics, optics, and surface catalysis applications.

Optomechanical Photonics: feature issue introduction

We introduce the Optical Materials Express feature issue on Optomechanical Photonics. This issue comprises a collection of eight research articles on optomechanical photonics, including studies of new fundamental phenomena, device applications, experimental characterizations, and theoretical models.

Polymerization‐induced Chiral Self‐assembly for the In situ Construction, Modulation, Amplification and Applications of Asymmetric Suprastructures

AbstractIn the polymerization‐induced chiral self‐assembly (PICSA) process, chiral functional monomers undergo spontaneous supramolecular self‐assembly and asymmetric stacking during living polymerization, leading to the in situ generation of chiroptical polymer assemblies characterized by diverse morphologies. The PICSA strategy facilitates precise control and manipulation of both non‐covalent supramolecular helices and covalent macromolecular helices within aggregated cores, thereby driving significant advancements in fields such as chiral recognition materials, asymmetric catalysts, nonlinear optical materials, and ferroelectric liquid crystals (LC). This minireview summarizes recent developments in the in situ chiroptical construction and modulation associated with the PICSA methodology. Furthermore, it seeks to elucidate emerging PICSA systems founded on various living polymerization mechanisms, exploring hierarchical chirality transfer processes and the pathway complexities in both equilibrium and non‐equilibrium conditions. This minireview also presents several illustrative examples that demonstrate the practical applications of chiral polymer materials synthesized through the PICSA approach, thereby illuminating future opportunities in this innovative field.

Synthesis of an Insulated Oligo(phenylene ethynylene) Dimer Through Cyclodextrin-Based [c2]Daisy Chain Rotaxane

Oligo(phenylene ethynylene)s (OPEs) are π-conjugated systems with promising optical, bioactive, and electrical properties, making them valuable candidates for molecular electronics and biosensors. Controlling the arrangement and orientation of π-conjugated systems is crucial in developing molecular devices. Recently, we developed insulated diarylacetylene dimers using a [c2]daisy chain rotaxane strategy, which brings two cores into close proximity without covalent bonding and shields them with permethylated α-cyclodextrins. Here, we synthesized an insulated OPE dimer using a similar rotaxane strategy to investigate its optical properties. The rotaxane structure and optical properties were evaluated using nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization high-resolution mass spectrometry (ESI-HRMS), and absorption and fluorescence spectroscopy. This study is expected to contribute to the development of optical and electronic materials utilizing OPEs.

Theoretical investigation on the surrounding effects of second-order nonlinear properties for (N^C^N)Pt(II)Cl complexes

Pt(II) complexes are widely used as nonlinear optical (NLO) materials. The geometric and electronic structures, second-order NLO property and UV–Vis absorption spectra of (N^C^N)Pt(II)Cl complexes (1–4) N^C^N binding by central benzene and two lateral N-heterocycles) are evaluated by density functional theory (DFT) and time-dependent DFT calculations. The detailed environmental effect of total first hyperpolarizability (βtot) in the solution and crystal phases is simulated by polarized continuum model (PCM) and quantum mechanics/molecular mechanics (QM/MM) method, respectively. The results highlight that the complex 3 exhibits largest βtot value in the gas, solution and crystal phases which can be attributed to the higher electron π-delocalization of ligands. Further, an evident red shift towards longer wavelength is observed for the complex 3. The origin of larger βtot value can be reasonably interpreted by the two-level model. In addition, the surrounding exerts an important influence on modulating second-order NLO properties. The solvent effect results in the larger βtot value than that of gas phase. The intermolecular interaction plays an important role in crystal phase. The formation of dimer can reduce the βtot value in comparison with the βtot value of the monomer in the crystal phase, because the centrosymmetric configuration of dimer implies a decrease of dipole moment (μ) in contrast to the large μ value of monomer. It is expected that this work will provide some guidance for designing Pt(II) NLO materials.

SbO(OH)2(IO3): The First Polar Sb5+-Iodate with a Strong Second-Harmonic Generation Response and a Wide Bandgap.

Widening the bandgaps while maintaining a strong second harmonic generation response has always been a research hotspot in the field of nonlinear optical iodate materials. A strategy involving covalent bonding is proposed that leverages the high valent later main group cation to construct iodates with predominantly covalent interactions. By using BiO(IO3) as a template, the first Sb5+-containing polar iodate, SbO(OH)2(IO3) is successfully isolated. The introduction of the two hydroxide anions led to the reduction of layered BiO(IO3) into 1D SbO(OH)2(IO3) in which two corner-sharing SbO4(OH)2 octahedra are further bridged by an iodate group. The covalently bonded [SbO(OH)2]+ chains and the optimal packing fashion of the asymmetric IO3 - groups generate a very strong second harmonic generation signal of 14 times that of KH2PO4. Furthermore, SbO(OH)2(IO3) exhibits a wide bandgap of 4.14eV and a high laser induced damage threshold [27.9 × AgGaS2, 0.2 × KH2PO4 (10ns, 10Hz)].

Facile fabrication of hemicrystalline bio-based polycarbonate with superhydrophobic and high transmittance

Developing materials that combine superhydrophobic properties with high optical transmittance poses a significant challenge. In this study, hydroxyl-terminated polydimethylsiloxane (HT-PDMS) and isosorbide (ISB) were polymerized in a single step to create a covalently bonded optical polycarbonate material. By inducing the formation of micro-papillary and lotus-shaped nanoscale structures via a solvent-triggered process, we significantly enhanced the “air cushion” effect, achieving a structure scale of approximately 5–7 μm. This resulted in a water contact angle of 157° while maintaining over 90 % optical transmittance. The structures were uniformly distributed throughout the polymer matrix, leading to a 500 % increase in tensile strength at break compared to pure isosorbide polycarbonate, with a maximum strength exceeding 50 MPa. These multifunctional materials show great promise for applications in smart windows, solar panels, camera lenses, and other optoelectronic devices.

Photoelectrodes with Enhanced Carrier Generation and Collection Through Optical Simulation and Materials Engineering

AbstractThe efficiency of solar‐fuel conversion in photoelectrochemical (PEC) systems is hindered by significant losses of photons and photocarriers within the photoelectrodes. This study introduces an innovative ITO@In2S3 core‐shell nanowire structure designed to overcome these challenges through cutting‐edge materials engineering and sophisticated simulation techniques. Optical modeling and finite element simulations highlight the conflict between photocarrier generation and collection in planar In2S3 thin films and demonstrate how the core‐shell nanowire geometry can significantly enhance light absorption. The developed ITO@In2S3 nanowire photoanodes achieve a photocurrent of 11.3 mA cm−2 at 1.23 V versus RHE, which is nearly five times greater than that of planar ITO/In2S3 thin films. Characterization techniques, including UV–vis absorption and charge separation efficiency measurements, confirm the enhanced light absorption and improved carrier collection facilitated by broadening the optical absorption range and reducing carrier transport distances. This research not only deepens the understanding of the dynamics within thin‐film photoelectrodes but also paves the way for the development of more efficient technologies for solar fuel conversion.

Design of an all-optical tunable 2D photonic crystal in As2S3 film

Amorphous arsenic trisulphide (As2S3) chalcogenide glass is widely used in photonics and optoelectronics due to its wide transparency in the infrared spectral range, its high linear refractive index (nAs2S3 = 2.42), which can be significantly modified by light with a suitable wavelength, and its important optical nonlinearity. In this work, we report the design of an all-optical tunable two-dimensional photonic crystal in a geometry which consists in a hexagonal lattice of holes patterned in As2S3 film with the aim to exhibit photonic band gap in the near infrared domain. We numerically investigated the possibility to all-optically tune the photonic band gap of an already patterned photonic crystal in As2S3 modifying only its refractive index by illumination with light of wavelength λ at the band gap energy (λ = 514.5 nm) or shorter, without affecting the lattice geometry. The influence of the variation of As2S3 refractive index (Δn) on the spectral position of the band gap and on its width has been determined for the light-induced modification of Δn up to the value of 0.09. For this value of Δn, a shift of almost 50 nm of the central wavelength of the photonic band gap has been obtained. These results are of great interest in the field of photonics offering a versatile solution to fabricate all-optical tunable photonic crystals in any optical material whose refractive index can be modified by light.

Breaking Symmetry for SHG Response: Lanthanide Acetate Crystals via Water Molecule Regulation Strategy.

In the field of nonlinear optical (NLO) materials research, the design and synthesis of novel materials are crucial for advancing modern scientific and technological development. This study employs an innovative coordination strategy, building upon the existing structure of [Ln2(CH3COO)6(H2O)4]·4H2O (Ln = Tb, Sm), to successfully synthesize a series of acetate rare-earth metal compounds [Ln2(CH3COO)6(H2O)]n [Ln = Tb(1), Er(2), Y(3)] by regulating the number of water molecules. This approach achieved a structural transition from centrosymmetric (CS) to noncentrosymmetric (NCS), endowing these compounds with significant nonlinear optical responses. We discovered that reducing the coordinated water molecules and introducing acetate as a bidentate ligand is an effective method for modulating crystal structure and realizing NLO performance. This finding not only deepens the understanding of the structure of acetate salts but also provides important theoretical and experimental support for the development of materials with potential NLO propeties.

Rational Design of Novel Polar Nonlinear Optical Materials in Alkali Metal Rare Earth Iodates.

Four new potassium rare earth iodates, namely, acentric K2Lu(IO3)5 and KM(IO3)4(HIO3)0.33 (M = Ce/Pr) and centric KLa(IO3)4, were successfully grown by mild hydrothermal reactions. Three of them exhibit polar structures; K2Lu(IO3)5, KCe(IO3)4(HIO3)0.33, and KPr(IO3)4(HIO3)0.33 show second-harmonic generation (SHG) responses of 3.0, 1.0, and 0.8 × KDP, respectively. These three iodates are phase-matchable for second-harmonic generation. The influence of changes in the radius and coordination mode of rare earth ions on the crystal structure and SHG response has been discussed in detail. Our findings suggest that in the alkali metal rare earth iodate, modulating the arrangement of iodate groups by changing the coordination geometry of rare earth ions is an effective strategy for designing polar NLO materials.

Rational Control of Maximum EMI/CPL Intensity and Wavelength of Bora[6]helicene via Polarity and Vibronic Effects.

Solvent polarity control as an efficient methodology to regulate the chiroptical properties, including spectral shape, width, intensity, wavelength, etc., has emerged as a novel frontier in optical materials design. However, the underling relationship connecting polarity to the optical property remains unclear. Herein, using state-of-the-art computations and the FC|VG model, the solvent effect on the chiroptical properties of bora[6]helicene was accurately and systematically computed to shed light on this issue. It is found that the vibronic coupling is crucial in explaining the spectral shape, width, and relative intensity of different peaks. Moreover, the intensity and position of the emission (EMI) and circularly polarized luminescence (CPL) are closely related to the polarity of the solvent. Intriguingly, we got a series of good linear relationships between polarity and EMI|CPL (|r| ≥ 0.95). Thus, this parameter can be used as a potential descriptor to estimate the intensity and position of EMI|CPL, leading to new strategies for designing fully colored fluorescent materials.

Ultrafast Charge Transfer-Induced Unusual Nonlinear Optical Response in ReSe2/ReS2 Heterostructure.

Ultrafast charge transfer in van der Waals heterostructures can effectively engineer the optical and electrical properties of two-dimensional semiconductors for designing photonic and optoelectronic devices. However, the nonlinear absorption conversion dynamics with the pump intensity and the underlying physical mechanisms in a type-II heterostructure remain largely unexplored, yet hold considerable potential for all-optical logic gates. Herein, two-dimensional ReSe2/ReS2 heterostructure is designed to realize an unusual transition from reverse saturable absorption to saturable absorption (SA) with a conversion pump intensity threshold of approximately 170 GW/cm2. Such an intriguing phenomenon is attributed to the decrease of two-photon absorption (TPA) of ReS2 and the increase of SA of ReSe2 with the pump intensity. Based on the characterization results of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, femtosecond transient absorption spectrum, Kelvin probe force microscopy, and density functional theory calculation, a type-II charge-transfer-energy level model is proposed combined with the TPA of ReS2 and SA of ReSe2 processes. The results reveal the critical role of ultrafast interfacial charge transfer in tuning the unusual nonlinear absorption and improving the SA of ReSe2/ReS2 under different excitation wavelengths. Our finding deepens the understanding of nonlinear absorption physical mechanisms in two-dimensional heterostructure materials, which may further diversify the nonlinear optical materials and photonic devices.