Harmonic Generation Response Research Articles

BaF2TeF2(OH)2: A UV Nonlinear Optical Fluorotellurite Material Designed by Band-Gap Engineering.

Balancing the wide band gap, large second harmonic generation (SHG) response, and moderate birefringence are significant but addressable challenges for designing nonlinear optical (NLO) materials. Based on the band-gap engineering in perovskite solar cell materials, we have successfully synthesized a new fluorotellurite, BaF2TeF2(OH)2, which exhibits a pseudo-Aurivillius structure and crystallizes in a noncentrosymmetric and polar space group Pmn21. The physical property measurements show that this material can effectively balance the requirements among the short UV absorption edge (∼205 nm), large SHG response (∼3 × KDP) and moderate birefringence (∼0.078@350-700 nm) and is a promising ultraviolet NLO crystal.

Pb6O5(NO3)2: A Nonlinear Optical Oxynitrate Structurally Based on Lead Oxide Framework.

A high second harmonic generation response is demonstrated by a Pb6O5(NO3)2 lead oxynitrate whose identity was verified upon reinvestigation of the PbO-Pb(NO3)2 system. Its crystal structure exhibits a unique cationic [Pb6O5]2+ framework hosting orientationally ordered NO3- triangles in the channels. Easy preparation and high thermal stability (until ∼500 °C in air) suggest it to be a new promising NLO material.

Effects of P2O7 clusters arrangement on second harmonic generation responses of pyrophosphates

Phosphates with rich structural diversities and novel physicochemical properties can be regarded as the indispensible sources of optical functional materials. Therefore, the extensive research has been performed to search the suitable nonlinear optical (NLO) materials and unveil the relationship among the crystal structures, properties and functions of phosphates system. Herein, two pyrophosphates, namely, Na4P2O7 and β-Ca2P2O7 have been obtained and characterized. Results show that the two title compounds can achieve the coexistence of deep-ultraviolet (UV) cutoff edges (<190 nm) and observable second harmonic generation (SHG) effects (0.2 × and 0.5 × KH2PO4 (KDP)). Besides, the positive roles of alkaline and alkaline earth metals with larger radii or higher ratios of M/P2O7 on SHG effects of pyrophosphates can be concluded. Theoretical analysis reveals that their NLO effects mainly originate from O-2p and P-2p orbitals near to the Fermi level. In addition, their thermal properties, infrared spectra and elemental analysis were also discussed.

The inflation response of the human lamina cribrosa and sclera: Analysis of deformation and interaction

This study investigated the inflation response of the lamina cribrosa (LC) and adjacent peripapillary sclera (PPS) in post-mortem human eyes with no history of glaucoma. The posterior sclera of 13 human eyes from 7 donors was subjected to controlled pressurization between 5–45 mmHg. A laser-scanning microscope (LSM) was used to image the second harmonic generation (SHG) response of collagen and the two-photon fluorescent (TPF) response of elastin within the volume of the LC and PPS at each pressure. Image volumes were analyzed using digital volume correlation (DVC) to calculate the three-dimensional (3D) deformation field between pressures. The LC exhibited larger radial strain, Err, and maximum principal strain, Emax, (p < 0.0001) and greater posterior displacement (p=0.0007) compared to the PPS between 5–45 mmHg, but had similar average circumferential strain, Eθθ, and maximum shear strain, Γmax. The Emax and Γmax were highest near the LC-PPS interface and lowest in the nasal quadrant of both tissues. Larger LC area was associated with smaller Emax in the peripheral LC and larger Emax in the central LC (p ≤ 0.01). The Emax, Γmax, and Eθθ in the inner PPS increased with increasing strain in adjacent LC regions (p ≤ 0.001). Smaller strains in the PPS were associated with a larger difference in the posterior displacement between the PPS and central LC (p < 0.0001 for Emax and Err), indicating that a stiffer pressure-strain response of the PPS is associated with greater posterior bowing of the LC. Statement of SignificanceGlaucoma causes vision loss through progressive damage of the retinal ganglion axons at the lamina cribrosa (LC), a connective tissue structure that supports the axons as they pass through the eye wall. It is hypothesized that strains caused by intraocular pressure may initiate this damage and that these strains are modulated by the combined deformation of the LC and adjacent peripapillary sclera (PPS). In this study we present a method to measure the pressure-induced 3D displacement and strain field in the LC and PPS simultaneously. Regional strain variation in the LC and PPS was investigated and compared and strains were analyzed for associations with age, LC area, LC strain magnitude, and LC posterior motion relative to the PPS.

Key Factors Controlling the Large Second Harmonic Generation in Nonlinear Optical Materials.

The second harmonic generation (SHG) responses of nonisostructural nonlinear optical (NLO) compounds, β-BaB2O4, LiB3O5, CsB3O5, CsLiB6O10, KBe2BO3F2, and LiCs2PO4, were examined by density functional theory (DFT) calculations, and the contributions of their individual cations and anions were determined by performing atomic response theory analyses. In all of these compounds, the contribution of all metal cations lies in the range of ∼9.3 to ∼29.7% of the total SHG responses, and that of all anions lies between ∼57.4 and ∼72.3%. However, in terms of individual atom contribution, a large metal cation can contribute more than does an anion to the total SHG response. Our work shows that the SHG contribution of an individual anion (e.g., O2-) is weakened when it forms covalent bonds with its surrounding cations (e.g., O-B). The contribution of an individual cation is further affected by the homogeneity of its surrounding anion distribution and also by how strongly the polarizabilities of its surrounding anions are weakened by covalent bonding with other cations. The SHG response increases with αsum/(NEg), an important parameter useful in searching for new NLO materials, where αsum is the sum of the polarizabilities of all of the ions in the primitive unit cell, N is the total number of atoms per primitive cell, and Eg is the band gap.

(NH4 )Bi2 (IO3 )2 F5 : An Unusual Ammonium-Containing Metal Iodate Fluoride Showing Strong Second Harmonic Generation Response and Thermochromic Behavior.

An ammonium-containing metal iodate fluoride compound, (NH4 )Bi2 (IO3 )2 F5 , featuring a two-dimensional double-layered framework constructed by [BiO2 F5 ]6- and [BiO4 F4 ]9- polyhedra, as well as [IO3 ]- groups, was successfully synthesized. The well-ordered alignment of these SHG-active units leads to an extraordinary strong SHG response of 9.2 times that of KDP. Moreover, this compound possesses a large birefringence (Δn=0.0690 at 589.3 nm), a wide energy band gap (Eg =3.88 eV), and a high laser damage threshold (LDT; 40.2×AgGaS2 ). In particular, thermochromic behavior was observed for the first time in this type of compound. Such multifunctional crystals will expand the application of nonlinear optical materials.

PbSrSiO4: a new ultraviolet nonlinear optical material with a strong second harmonic generation response and moderate birefringence.

Introduction of Pb2+ cations in silicate systems generates a new compound, PbSrSiO4, which exhibits excellent properties, including a strong second harmonic generation response (∼5.8 × KDP), a short UV cut-off edge (240 nm) and moderate birefringence (0.053@1064 nm). These results suggest that PbSrSiO4 is a promising UV NLO material.

Polar polymorphism: α- and β-KCsWP2O9nonlinear optical materials with a strong second harmonic generation response

Two polymorphs of KCsWP2O9exhibit a large SHG response due to non-bonding O-2p orbitals and strong orbital interactions of W-5d orbitals and O-2p orbitals, the orientations of the dipole moments of WO6are also beneficial for the large SHG response.

RbNa(HC3N3O3)·2H2O exhibiting a strong second harmonic generation response and large birefringence as a new potential UV nonlinear optical material

A new hydro-isocyanurate, RbNa(HC3N3O3)·2H2O, with a strong SHG response and large birefringence, has been successfully grown by a hydrothermal method.

NLO-active Y-shaped ferrocene conjugated imidazole chromophores as precursors for SHG polymeric films.

New Y-shaped ferrocene conjugated imidazole chromophores were prepared and fully characterized. The Y-shaped structure was confirmed by the single crystal X-ray diffraction technique. The chromophores show interesting second-order nonlinear optical (NLO) properties in solution, as determined by the Electric-Field Induced Second Harmonic generation (EFISH) technique. Remarkably, the trifluoro substituted compound 3 is characterized by a high μβEFISH value and has good potential as a molecular building block for composite films with Second Harmonic Generation (SHG) properties. For all compounds, the dipole moments and frontier orbital energies were calculated by the Density Functional Theoretical method.

Selenite bromide nonlinear optical materials Pb2GaF2(SeO3)2Br and Pb2NbO2(SeO3)2Br: synthesis and characterization.

Two new isomorphic selenite bromides, namely Pb2GaF2(SeO3)2Br (1) and Pb2NbO2(SeO3)2Br (2), were synthesized by mild hydrothermal reactions. These two compounds crystallize in the noncentrosymmertric space group P21 and feature 3D structures consisting of 1D (Pb2Br)3+ cationic chains and 2D [Ga2F4(SeO3)4]6-/[Nb2O4(SeO3)4]6- anonic chains. As measured, 1 and 2 are phase-matchable and exhibit excellent second harmonic generation (SHG) responses of 4.5 and 1.4 times that of KDP, respectively. Moreover, these two compounds possess wide bandgaps (>3.17 eV) and high thermal stabilities (>425 °C), indicating their suitable performances as potential nonlinear optical materials. First-principle density functional theory (DFT) calculations were also performed to explicate the structure-property relationship.

Synthesis of the perovskite-type oxyfluoride AgTiO2F: an approach adopting the HSAB principle.

A synthetic approach for oxyfluorides involving the hard and soft acids and bases (HSAB) principle was examined. Using AgF composed of the Ag+ ion as a soft acid and F- as a hard base, we attempted to synthesize an oxyfluoride, AgTiO2F, that included the O2- ion as a softer base than the F- ion and the Ti4+ ion as a harder acid than the Ag+ ion. Consequently, a perovskite (Pv)-type oxyfluoride AgTiO2F was synthesized by a solid-state reaction under ambient pressure and under high pressure, and a heat treatment at 1000 °C for 30 min under a pressure of 4 GPa produced the Pv-type phase with minimal impurity phases. The lack of an optical second harmonic generation (SHG) response and the result of Rietveld refinement indicated that the compound is centro-symmetric and shows the anti-phase tilt of Ti(O, F)6 octahedra along the c-axis on the basis of the space group I4/mcm. O/F ordering on the anion site was not clarified. The phase stability of a Pv-type AgTiO2F is discussed in terms of the HSAB principle and the thermodynamics in the formation of the Pv-type phase by comparing KTiO2F and NaTiO2F. AgTiO2F has a light yellow color and a band gap energy of 2.8 eV in the visible region, which originates from the covalent bonding between the soft cation Ag+ and O2- as a softer anion than F-. We propose that the HSAB principle is useful for selecting a cation for the synthesis of oxyfluorides.

Second harmonic generation responses of KH2PO4: importance of K and breaking down of Kleinman symmetry.

The second harmonic generation (SHG) responses of the paraelectric and ferroelectric phases of KH2PO4 (KDP) were calculated by first-principles density functional theory (DFT) calculations, and the individual atom contributions to the SHG responses were analyzed by the atom response theory (ART). We show that the occurrence of static polarization does not enhance the SHG responses of the ferroelectric KDP, and that the Kleinman symmetry is reasonably well obeyed for the paraelectric phase, but not for the ferroelectric phase despite that the latter has a larger bandgap. This is caused most likely by the fact that the ferroelectric phase has lower-symmetry local structures than does the paraelectric phase. The contribution to the SHG response of an individual K+ ion is comparable to that of an individual O2− ion. The contributions of the O2− and K+ ions arise overwhelmingly from the polarizable parts of the electronic structure, namely, from the valence bands of the O-2p nonbonding states and from the conduction bands of the K-3d states.

NaRb3B6O9(OH)3(HCO3): A Borate-Bicarbonate Nonlinear Optical Material.

A noncentrosymmetric mixed alkali metal borate-bicarbonate, NaRb3B6O9(OH)3(HCO3), was synthesized and characterized. The compound crystallizes in the monoclinic space group P21 (No. 4) with a = 8.988(3) Å, b = 8.889(2) Å, c = 10.068(4) Å, and β = 114.6(4)°. The structure features a combination of chains of boron-oxygen [B6O9 (OH)3]3- groups and isolated HCO3- groups, with charge compensation provided by Rb+ and Na+ cations. It exhibits a second harmonic generation response of about 0.5 × KDP. The UV-vis-NIR absorption spectrum indicated a transparency of about 40% at 200 nm. The IR spectrum confirms the coordination environments of anionic groups, and thermogravimetric measurements indicate the material is thermally stable up to approximately 320 °C. Additionally, first-principles calculations were performed in order to gain insight into the role of boron-oxygen and HCO3- groups with respect to the band structure and NLO properties.

Circular dichroism of second harmonic generation response

Polarization-dependent photon spectroscopy (dichroism) of the second-harmonic generation (SHG) response is shown to reveal chiral and magnetic properties of a sample. Two dichroic signals are allowed with electric-dipole (E1) and electric-quadrupole (E2) scattering events, and both require circular polarization in the primary beam. Explicit expressions for electronic multipoles, which benefit from equivalent electronic operators, in NCD and MCD of the SHG response are derived using theoretical techniques from atomic physics.

Li[LiCs2 Cl][Ga3 S6 ]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance.

A large nonlinear optical (NLO) coefficient and a wide band gap are two crucial but contradictory parameters that are difficult to achieve simultaneously in a single infrared (IR) NLO compound. A salt-inclusion chalcogenide (SIC), Li[LiCs2 Cl][Ga3 S6 ] (1), was prepared that presents a nanosized tunnel framework constructed from monotype chalcogenide tetrahedra. Highly oriented covalent GaS4 tetrahedra in the host lead to a moderate second harmonic generation response (0.7 AgGaS2 ), and ionic guests effectively broaden the band gap to the widest value (4.18 eV) among all IR NLO chalcogenides, thereby achieving a remarkable balance between NLO efficiency and band gap.

Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance

AbstractA large nonlinear optical (NLO) coefficient and a wide band gap are two crucial but contradictory parameters that are difficult to achieve simultaneously in a single infrared (IR) NLO compound. A salt‐inclusion chalcogenide (SIC), Li[LiCs2Cl][Ga3S6] (1), was prepared that presents a nanosized tunnel framework constructed from monotype chalcogenide tetrahedra. Highly oriented covalent GaS4 tetrahedra in the host lead to a moderate second harmonic generation response (0.7 AgGaS2), and ionic guests effectively broaden the band gap to the widest value (4.18 eV) among all IR NLO chalcogenides, thereby achieving a remarkable balance between NLO efficiency and band gap.

Rb10Zn4Sn4S17: A Chalcogenide with Large Laser Damage Threshold Improved from the Mn-Based Analogue.

In the military and civilian fields, with the development of new technologies, high-powered nonlinear optical (NLO) crystals demonstrate broad application prospects. In this work, for purposes of designing a better NLO material, a new chalcogenide Rb10Zn4Sn4S17 was successfully designed with a high temperature solid-state method on the basis of previously reported compound Sr3MnSn2S8. The experimental results indicate that Rb10Zn4Sn4S17 possesses a prominent band gap of 3.59 eV, compared with the laser damage threshold (LDT) of Sr3MnSn2S8 (3 times that of AgGaS2); Rb10Zn4Sn4S17 shows an outstanding LDT about 5 times that of AgGaS2. Meanwhile, it has an ideal second harmonic generation (SHG) response approximately 0.7 times that of AgGaS2.

Nontoxic KBBF Family Member Zn2BO3(OH): Balance between Beneficial Layered Structure and Layer Tendency.

The conflict between beneficial layered structure for performances and layered growth habits in KBe2BO3F2 (KBBF) always restricts its practical applications. A beryllium‐free KBBF family member, Zn2BO3(OH), is explored to feature the same topological layer with KBBF by replacing [BeO3F]5− with [ZnO3(OH)]5− and excellent UV performances. It exhibits a second harmonic generation response of about 1.5 × KH2PO4 with the UV cutoff edge of 204 nm. The birefringence of Zn2BO3(OH) in the visible region is about 0.067, which is larger than those of commercial UV crystals LiB3O5, CsB3O5, and CsLiB6O10. Additionally, it has excellent thermal and water‐resistant stabilities. Owing to the removal of interlayer cations, Zn2BO3(OH) shows better growth habits than KBBF while achieving the balance between beneficial layered structure and layer tendency.

Cs2Bi2O(Ge2O7) (CBGO): A Larger SHG Effect Induced by Synergistic Polarizations of BiO5 Polyhedra and GeO4 Tetrahedra

AbstractA cesium bismuth germanate, Cs2Bi2O(Ge2O7) (CBGO), was synthesized by a traditional high‐temperature solid‐state reaction. Its structure features a 3D network composed of a 1D chains composed of Bi2O8 dimers that are further bridged by Ge2O7 dimers, forming tunnels of seven member rings (MRs) that are filled by the Cs+ cations. CBGO exhibits extraordinary larger second harmonic generation (SHG) response of about 13.7 times that of KDP (KH2PO4) under 1064 nm laser radiation and 1.1 times that of KTP (KTiOPO4) under 2.05 μm laser radiation, which is the highest among all of the metal germanates reported so far. CBGO possesses a moderate birefringence (0.073 at 1064 nm) and is phase matchable. Furthermore, CBGO melts congruently and exhibits high thermal stability.