Large Second Harmonic Generation Research Articles

Switchable Photovoltaic Effect and Robust Nonlinear Optical Response in a High-Temperature Molecular Ferroelectric [C8N2H22][PbI4

Hybrid organic-inorganic molecular ferroelectrics (HOIMFs) have garnered significant attention for their potential applications in nonvolatile memory and spintronic devices. However, few efforts have been devoted to the photoelectric properties of lead halide molecular ferroelectrics, despite the fact that robust ferroelectricity and flexibility are desirable for thin-film photoelectric devices. Herein, we present a novel lead halide molecular ferroelectric [C8N2H22][PbI4] (1) synthesized hydrothermally. A polar monoclinic structure of 1 was solved by single-crystal X-ray diffraction and second-harmonic generation (SHG) tests. A direct band gap of 2.36 eV was confirmed by UV-vis spectrum and theoretical calculation. Hysteresis measurements demonstrated inherent room-temperature (RT) ferroelectricity in 1 with a spontaneous polarization (Ps) of 3.2 μC/cm2. The 1-based photoelectric device shows a notable photovoltaic (PV) effect with Voc ∼ 0.27 V, Jsc ∼ 38 nA/cm2 under AM 1.5 G illumination, and a rapid response time of ∼1.5 ms. A considerable enhancement in PV performance has been achieved by adjusting the ferroelectric polarization, resulting in a maximum Voc ∼ 0.75 V, Jsc ∼ 2.28 μA/cm2. Notably, 1 exhibits a rather large SHG signal, which is approximately 2.61-fold higher than that of KH2PO4 (KDP) upon a 1064 nm laser radiation. This study offers a bright avenue for lead halide molecular ferroelectrics as promising optoelectronic devices and SHG materials.

An Unprecedented [BO2]-Based Deep-Ultraviolet Transparent Nonlinear Optical Crystal by Superhalogen Substitution.

Solid-state structures with the superhalogen [BO2]- have thus far only been observed with a few compounds whose syntheses require high reaction temperatures and complicated procedures, while their optical properties remain almost completely unexplored. Herein, we report a facile, energy-efficient synthesis of the first [BO2]-based deep-ultraviolet (deep-UV) transparent oxide K9[B4O5(OH)4]3(CO3)(BO2) ⋅ 7H2O (KBCOB). Detailed structural characterization and analysis confirm that KBCOB possesses a rare four-in-one three-dimensional quasi-honeycomb framework, with three π-conjugated anions ([BO2]-, [BO3]3-, and [CO3]2-) and one non-π-conjugated anion ([BO4]5-) in the one crystal. The evolution from the traditional halogenated nonlinear optical (NLO) analogues to KBCOB by superhalogen [BO2]- substitution confers deep-UV transparency (<190 nm), a large second-harmonic generation response (1.0×KH2PO4 @ 1064 nm), and a 15-fold increase in birefringence. This study affords a new route to the facile synthesis of functional [BO2]-based oxides, paving the way for the development of next-generation high-performing deep-UV NLO materials.

Vacancy‐Induced Extraordinary Second Harmonic Generation Response for Diamond‐Like Cu3PS4

AbstractImproving polarizability is an important strategy for designing high‐performance mid‐infrared (mid‐IR) nonlinear optical (NLO) materials. The substitution of equivalent or aliovalent atoms can manipulate the polarizability by adjusting the symmetry of the polyhedron. Herein, the Li+ and Cd2+ are introduced into the Cu3PS4 as the equivalent and aliovalent dopants for the Cu site. As a result, Li+ can significantly improve the bandgap (Eg) of LixCu3−xPS4 from 2.38 to 2.88 eV, leading to a higher laser‐induced damage threshold (LIDT) of 4.9 times than AgGaS2 (AGS) with a comparable second harmonic generation (SHG) response of AGS (26−45 µm). Interestingly, Cd2+ can improve the SHG response and enlarge the Eg simultaneously. As a result, Cd0.4Cu2.2PS4 has a large SHG response of 10 × AGS at 2050 nm (26−45 µm) and a LIDT of 2.6 × AGS. Theoretical calculations reveal that lattice vacancies induced by Cd2+ significantly boost polarizability compared to LixCu3−xPS4 with no vacancy, leading to a strong NLO response.

Cadmium Hydroxyl Chloride with Balanced Band Gap and Second-Harmonic-Generation Response.

Ultraviolet (UV) nonlinear-optical (NLO) materials are crucial in laser technology due to their ability to modulate light frequency. In this work, when d10 cations, hydroxyl groups, and Cl atoms were combined, a cadmium double salt, Cd(OH)Cl, was synthesized by a simple hydrothermal method. It has a large phase-matched second-harmonic-generation (SHG) response at 1064 nm (2.5 × KDP) with a short UV-cutoff edge (260 nm), which can be applied in a solar-blind UV band. Theoretical calculations suggest that [Cd(OH)3Cl3] groups lead to a large SHG response. Our work may shed light on the exploration of new NLO materials in metal hydroxyl chlorides.

Anhydrous Aluminum Iodate: Strong Second Harmonic Generation Effect Contributed by Unbonded and Antibonding Orbitals.

Exploring materials that balance the second harmonic generation (SHG) effect and laser-induced damage threshold (LIDT) is the frontier of nonlinear optical (NLO) crystal research at present. In this work, the NLO property of anhydrous aluminum iodate is extensively explored and discussed first. It exhibits a strong SHG intensity of 18.3 × KH2PO4 (KDP) and a high-powder LIDT of 1.4 × KDP at 1064 nm. Combining experimental and theoretical studies at the atomic level and electronic levels, it is found that the cations in the structure are replaced by cations with small radius and high valence, enabling the production of materials with large SHG responses. Unbonded and antibonding orbitals play a crucial positive role in the SHG response of the structure, whereas bonding orbitals produce a large negative contribution. This provides a scarce example of materials in which bonding orbitals make significant negative contributions.

Molecular Crystals Constructed by Polar Molecular Cages: A Promising System for Exploring High-performance Infrared Nonlinear Optical Crystals.

Polar molecular crystals, with their densely stacked polar nonlinear optical (NLO) active units, are favored for their large second harmonic generation (SHG) responses and birefringence. However, their potential for practical applications as Infrared (IR) NLO materials has historically been underappreciated due to the weak inter-molecular interaction forces that may compromise their physicochemical properties. In this study, we propose molecular crystals with polar molecular cages as a treasure-house for the development of superior IR NLO materials and a representative system, binary chalcogenide molecular crystals, composed of [P4 Sn ] (n=3-9) polar molecular cages, is introduced. These crystals may not only achieve wide band gap, large SHG response, and birefringence in a single structure, but also exhibit favorable physicochemical properties. We subsequently obtained a polar molecular crystal, α-P4 S5 , which demonstrated exceptional IR optical properties, including a strong SHG response (1.1×AGS), wide band gap (3.02 eV), large birefringence (0.134@2050 nm), and a broad transmission range (0.41-14.7 μm). Moreover, it showed excellent water resistance and hardness. These findings highlight the potential of polar molecular crystals as a promising platform for the development of high-performance IR NLO materials.

Molecular Crystals Constructed by Polar Molecular Cages: A Promising System for Exploring High‐performance Infrared Nonlinear Optical Crystals

AbstractPolar molecular crystals, with their densely stacked polar nonlinear optical (NLO) active units, are favored for their large second harmonic generation (SHG) responses and birefringence. However, their potential for practical applications as Infrared (IR) NLO materials has historically been underappreciated due to the weak inter‐molecular interaction forces that may compromise their physicochemical properties. In this study, we propose molecular crystals with polar molecular cages as a treasure‐house for the development of superior IR NLO materials and a representative system, binary chalcogenide molecular crystals, composed of [P4Sn] (n=3–9) polar molecular cages, is introduced. These crystals may not only achieve wide band gap, large SHG response, and birefringence in a single structure, but also exhibit favorable physicochemical properties. We subsequently obtained a polar molecular crystal, α‐P4S5, which demonstrated exceptional IR optical properties, including a strong SHG response (1.1×AGS), wide band gap (3.02 eV), large birefringence (0.134@2050 nm), and a broad transmission range (0.41–14.7 μm). Moreover, it showed excellent water resistance and hardness. These findings highlight the potential of polar molecular crystals as a promising platform for the development of high‐performance IR NLO materials.

Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence

AbstractConsiderable effort has been invested in the development of non‐centrosymmetric (NCS) inorganic solids for ferroelectricity‐, piezoelectricity‐ and, particularly, optical nonlinearity‐related applications. While great progress has been made, a persistent problem is the difficulty in constructing NCS materials, which probably stems from non‐directionality and unsaturation of the ionic bonds between metal counter‐cations and covalent anionic modules. We report herein a secondary‐bond‐driven approach that circumvents the cancellation of dipole moments between adjacent anionic modules that has plagued second‐harmonic generation (SHG) material design, and which thereby affords a polar structure with strong SHG properties. The resultant first NCS counter‐cation‐free iodate, VO2(H2O)(IO3) (VIO), a new class of iodate, crystallizes in a polar lattice with VO2(H2O)(IO3)] zigzag chains connected by weak hydrogen bonds and intermolecular forces. VIO exhibits very large SHG responses (18 × KH2PO4 @ 1200 nm, 1.5 × KTiOPO4 @ 2100 nm) and sufficient birefringence (0.184 @ 546 nm). Calculations and crystal structure analysis attribute the large SHG responses to consistent polarization orientations of the VO2(H2O)(IO3)] chains controlled by secondary bonds. This study highlights the advantages of manipulating the secondary bonds in inorganic solids to control NCS structure and optical nonlinearity, affording a new perspective in the development of high‐performance NLO materials.

Secondary-Bond-Driven Construction of a Polar Material Exhibiting Strong Broad-Spectrum Second-Harmonic Generation and Large Birefringence.

Considerable effort has been invested in the development of non-centrosymmetric (NCS) inorganic solids for ferroelectricity-, piezoelectricity- and, particularly, optical nonlinearity-related applications. While great progress has been made, a persistent problem is the difficulty in constructing NCS materials, which probably stems from non-directionality and unsaturation of the ionic bonds between metal counter-cations and covalent anionic modules. We report herein a secondary-bond-driven approach that circumvents the cancellation of dipole moments between adjacent anionic modules that has plagued second-harmonic generation (SHG) material design, and which thereby affords a polar structure with strong SHG properties. The resultant first NCS counter-cation-free iodate, VO2 (H2 O)(IO3 ) (VIO), a new class of iodate, crystallizes in a polar lattice with VO2 (H2 O)(IO3 )] zigzag chains connected by weak hydrogen bonds and intermolecular forces. VIO exhibits very large SHG responses (18 × KH2 PO4 @ 1200 nm, 1.5 × KTiOPO4 @ 2100 nm) and sufficient birefringence (0.184 @ 546 nm). Calculations and crystal structure analysis attribute the large SHG responses to consistent polarization orientations of the VO2 (H2 O)(IO3 )] chains controlled by secondary bonds. This study highlights the advantages of manipulating the secondary bonds in inorganic solids to control NCS structure and optical nonlinearity, affording a new perspective in the development of high-performance NLO materials.

Three in one: a cadmium bismuth vanadate NLO crystal exhibiting a large second-harmonic generation response and enhanced birefringence

A novel vanadate NLO crystal Cd2BiVO6 was synthesized through spontaneous crystallization, exhibiting a large SHG response, an enhanced birefringence and a wide transmittance range.

Hydrogen bonding bolstered head-to-tail ligation of functional chromophores in a 0D SbF3·glycine adduct for a short-wave ultraviolet nonlinear optical material.

The key properties of nonlinear optical (NLO) materials highly rely on the quality of functional chromophores (FCs) and their optimized interarrangement in the lattice. Despite the screening of various FCs, significant challenges persist in optimizing their arrangement within specific structures. Generally, FC alignment is achieved by designing negatively charged 2D layers or 3D frameworks, further regulated by templating cations. In this study, a novel 0D adduct NLO material, SbF3·glycine, is reported. Neutrally charged 0D [SbF3C2H5NO2] FCs, comprising [SbF3] pyramids and zwitterionic glycine, are well-aligned in the structure. The alignment is facilitated by the hydrogen bonding, reinforcing a 'head-to-tail' ligation of [SbF3C2H5NO2] FCs. Consequently, the title compound exhibits favorable NLO properties, including a large second-harmonic generation efficiency (3.6 × KDP) and suitable birefringence (cal. 0.057 @ 1064 nm). Additionally, its short absorption cut-off edge (231 nm) positions it as a promising short-wave ultraviolet NLO material. Importantly, the binary SbF3-amino acid system is expected to serve as a new resource for exploring ultraviolet NLO crystals, owing to the abundance of the amino acid family.

Ag2[TeO2(OH)4]: a nonlinear optical tellurate with balanced comprehensive performance

A single crystal of Ag2[TeO2(OH)4] with size of 8 × 4 × 4 mm3 was obtained, which exhibits balanced comprehensive performances, including a large second-harmonic generation response of 0.84 × AgGaS2 and large birefringence of 0.106@1064 nm.

ZnGa2S4: an infrared nonlinear optical material with large second-harmonic generation response and wide band gap

ZnGa2S4: an infrared nonlinear optical material with large second-harmonic generation response and wide band gap

Two UV organic-inorganic hybrid antimony-based materials with superior optical performance derived from cation-anion synergetic interactions

Finding suitable strategies to effectively enhance the optical properties of materials are the goal being pursued by researchers. Herein, cation-anion synergetic interactions strategy was proposed to develop two novel organic-inorganic hybrid antimony-based optical materials, (C3H5N2)SbF2SO4 (I) and (C5H6N)SbF2SO4 (II), which were obtained by introducing Sb3+cation containing stereochemically active lone-pair (SCALP) and organic π-conjugated cations into sulphate system. The synergistic interactions of the organic π-conjugated cations, the inorganic [SbO2F2]3− seesaw anions and the [SO4]2− distorted tetrahedra anions make their ultraviolet (UV) absorption edges approach 297 and 283 nm, respectively, and raise their birefringence up to 0.193@546 nm and 0.179@546 nm, respectively. Interestingly, although the two compounds have the same stoichiometric ratio and similar one-dimensional (1D) chain structure, they show opposite macroscopic symmetry, where the NCS compound (II) exhibits a large second-harmonic generation (SHG) response (1.6 times that of KH2PO4). The two reported compounds are found to be promising UV optical materials in the experimental tests.

AllHgMIVS4 (All = Sr, Ba, MIV = Si, Ge): A Series of Materials with Large Second Harmonic Generation Response and Wide Band Gaps

AbstractWide band gaps and large second harmonic generation (SHG) response are two crucial yet contradictory parameters for nonlinear optical (NLO) crystals. Herein, through exploring the influence of anion groups on structural crystallization dimension and space group, a series of new NLO Hg‐based chalcogenides AIIHgMIVS4 (AII = Sr, Ba, MIV = Si, Ge) with wide band gaps and large SHG responses have been successfully designed and synthesized. The structures of these compounds consist of 2D [HgMS4]2− (M = Si and Ge) layers composed of distorted (HgS4 and MS4) tetrahedra arranged alternately, and the layers are separated by eight‐coordinated A2+ (A = Sr and Ba) cations. Their band gaps and SHG responses meet the basic requirements (SHG &gt; 1 × AgGaS2; Eg &gt; 2.33 eV). Especially, SrHgSiS4 and SrHgGeS4 exhibit both large SHG effects (2 and 2.4 × AgGaS2) and wide band gaps (3.06 and 2.97 eV), respectively, indicating they are promising IR NLO crystals. This work opens a new avenue for new NLO material design to achieve the balance between strong SHG response and large band gaps.

Manipulation of nonlinear optical responses in layered ferroelectric niobium oxide dihalides

Realization of highly tunable second-order nonlinear optical responses, e.g., second-harmonic generation and bulk photovoltaic effect, is critical for developing modern optical and optoelectronic devices. Recently, the van der Waals niobium oxide dihalides are discovered to exhibit unusually large second-harmonic generation. However, the physical origin and possible tunability of nonlinear optical responses in these materials remain to be unclear. In this article, we reveal that the large second-harmonic generation in NbOX2 (X = Cl, Br, and I) may be partially contributed by the large band nesting effect in different Brillouin zone. Interestingly, the NbOCl2 can exhibit dramatically different strain-dependent bulk photovoltaic effect under different polarized light, originating from the light-polarization-dependent orbital transitions. Importantly, we achieve a reversible ferroelectric-to-antiferroelectric phase transition in NbOCl2 and a reversible ferroelectric-to-paraelectric phase transition in NbOI2 under a certain region of external pressure, accompanied by the greatly tunable nonlinear optical responses but with different microscopic mechanisms. Our study establishes the interesting external-field tunability of NbOX2 for nonlinear optical device applications.

A Non-π-Conjugated Molecular Crystal with Balanced Second-Harmonic Generation, Bandgap, and Birefringence.

Traditional nonlinear optical (NLO) crystals are exclusively limited to ionic crystals with π-conjugated groups and it is a great challenge to achieve a subtle balance between second-harmonic generation, bandgap, and birefringence for them, especially in the deep-UV spectrum region (Eg >6.20eV). Herein, a non-π-conjugated molecular crystal, NH3 BH3 , which realizes such balance with a large second-harmonic generation response (2.0× KH2 PO4 at 1064nm, and 0.45 × β-BaB2 O4 at 532nm), deep-UV transparency (Eg > 6.53eV), and moderate birefringence (Δn = 0.056@550nm) is reported. As a result, NH3 BH3 exhibits a large quality factor of 0.32, which is evidently larger than those of non-π-conjugated sulfate and phosphate ionic crystals. Using an unpolished NH3 BH3 crystal, effective second-harmonic generation outputs are observed at different wavelengths. These attributes indicate that NH3 BH3 is a promising candidate for deep-UV NLO applications. This work opens up a new door for developing high-performance deep-UV NLO crystals.

LiGa(IO3 )4 : An Excellent NLO Material with Unprecedented 2D [Ga(IO3 )4 ]∞ - Layer Synthesized by Aliovalent Substitution.

Nonlinear optical (NLO) crystals are indispensable for the solid-state lasers for their ability to expand wavelength spectral to the regions where the directing lasing is difficult or even impossible, yet the rational design of a high-performance NLO crystal remains a great challenge owing to the severe structural and properties' requirements. Herein, a new noncentrosymmetric (NCS) and polar gallium iodate, LiGa(IO3 )4 , with a novel 2D anionic layer, is successfully designed and synthesized by the aliovalent substitution strategy based on classic α-LiIO3 . The 2D [Ga(IO3 )4 ]∞ - layer in LiGa(IO3 )4 is built from the GaO6 octahedra and highly polarizable units IO3 . Compared with its parent compound, the partial replacement of A-site Li+ cation with main group Ga3+ cation facilitates LiGa(IO3 )4 to possess excellent NLO properties, including the large second-harmonic generation (SHG) response (14 × KH2 PO4 (KDP) @ 1064nm), wide bandgap (4.25eV), large birefringence (0.23 @ 1064nm), and wide optical transparency from UV to mid-IR. These reveal that LiGa(IO3 )4 will be a promising NLO crystal.

Giant Mid‐Infrared Second‐Harmonic Generation Response in a Densely‐Stacked Van Der Waals Transition‐Metal Oxychloride

AbstractSecond‐harmonic generation (SHG) is a fundamental optical property of nonlinear optical (NLO) crystals. Thus far, it has proved difficult to engineer large SHG responses, particularly in the mid‐infrared region, owing to the difficulty in simultaneously controlling the arrangement and density of functional NLO‐active units. Herein, a new assembly strategy employing functional modules only, and aimed at maximizing the density and optimizing the spatial arrangement of highly efficient functional modules, has been applied to the preparation of NLO crystals, affording the van der Waals crystal MoO2Cl2. This exhibits the strongest powder SHG response (2.1×KTiOPO4 (KTP) @ 2100 nm) for a transition‐metal oxyhalide, a wide optical transparency window, and a sufficient birefringence. MoO2Cl2 is the first SHG‐active transition‐metal oxyhalide effective in the infrared region. Theoretical studies and crystal structure analysis suggest that the densely packed, optimally‐aligned [MoO4Cl2] modules within the two‐dimensional van der Waals layers are responsible for the giant SHG response.

Giant Mid-Infrared Second-Harmonic Generation Response in a Densely-Stacked Van Der Waals Transition-Metal Oxychloride.

Second-harmonic generation (SHG) is a fundamental optical property of nonlinear optical (NLO) crystals. Thus far, it has proved difficult to engineer large SHG responses, particularly in the mid-infrared region, owing to the difficulty in simultaneously controlling the arrangement and density of functional NLO-active units. Herein, a new assembly strategy employing functional modules only, and aimed at maximizing the density and optimizing the spatial arrangement of highly efficient functional modules, has been applied to the preparation of NLO crystals, affording the van der Waals crystal MoO2 Cl2 . This exhibits the strongest powder SHG response (2.1×KTiOPO4 (KTP) @ 2100 nm) for a transition-metal oxyhalide, a wide optical transparency window, and a sufficient birefringence. MoO2 Cl2 is the first SHG-active transition-metal oxyhalide effective in the infrared region. Theoretical studies and crystal structure analysis suggest that the densely packed, optimally-aligned [MoO4 Cl2 ] modules within the two-dimensional van der Waals layers are responsible for the giant SHG response.