Noncentrosymmetric (NCS) silicon phosphides have recently shown promise as nonlinear optical materials due to the balance of strong second harmonic generation (SHG) activity and large laser damage threshold (LDT) values. While arsenides of electropositive metals, such as Ba, Mg, Zn, and Cd were explored, no NLO properties for transition metal tetrel arsenides have yet been reported. IrSi 3 As 3 is a novel compound, isostructural to IrSi 3 P 3 , which allows a direct investigation on the impact of the heavier pnictogen on structural and optical properties. The direct bandgap is reduced from 1.8 eV for IrSi 3 P 3 to 1.55 eV for IrSi 3 As 3 . Unlike many NLO chalcogenides, IrSi 3 As 3 has a small bandgap without compromising the balance between SHG signal and high LDT values. IrSi 3 As 3 was found to outperform both its phosphide analogue IrSi 3 P 3 , as well as the state-of-the-art infrared SHG standard AgGaS 2 (AGS) in SHG activity and the LDT.
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Prediction of Large Second Harmonic Generation in the Metal-Oxide/Organic Hybrid Compound CuMoO3(p2c)
Noncentrosymmetric hybrid framework (HF) materials are an important system in discovering new practical second-order nonlinear optical materials. We calculated the second harmonic generation (SHG) response of a noncentrosymmetric (NCS) organic–inorganic HF compound, CuMoO3(p2c) (p2c = pyrazine-2-carboxylate) to find that it exhibits the largest SHG response among all known NCS HF materials with one-dimensional helical chains. Further atom response theory analysis revealed that the metal atoms Cu and Mo contribute much more strongly than do nonmetal atoms in determining the strength of the SHG response, which is a novel example in nonlinear optical materials known to date.
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- Award ID(s):
- 2004455
- NSF-PAR ID:
- 10322572
- Date Published:
- Journal Name:
- Symmetry
- Volume:
- 14
- Issue:
- 4
- ISSN:
- 2073-8994
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Noncentrosymmetric (NCS) materials feature an exciting array of functionalities such as nonlinear optical (NLO) responses and topological spin textures (skyrmions). While NLO materials and magnetic skyrmions display two different sets of physical properties, their design strategies are deeply connected in terms of atomic-scale precision, structural customization, and electronic tunability. Despite impressive progress in studying these systems separately, a joint road map for navigating the chemical principles for NCS materials remains elusive. This review unites two subtopics of NCS systems, NLO materials and magnetic skyrmions, offering a multifaceted narrative of how to translate the often-abstract fundamentals to the targeted functionalities while inviting innovative approaches from the community. We outline the design principles central to the desired properties by exemplifying relevant examples in the field. We supplement materials chemistry with pertinent electronic structures to demonstrate the power of the fundamentals to create systems integration relevant to foreseeable societal impacts in frequency-doubling instrumentation and spin-based electronics.
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Abstract Atomically thin transition metal dichalcogenides (TMDs) in their excited states can serve as exceptionally small building blocks for active optical platforms. In this scheme, optical excitation provides a practical approach to control light‐TMD interactions via the photocarrier generation, in an ultrafast manner. Here, it is demonstrated that via a controlled generation of photocarriers the second‐harmonic generation (SHG) from a monolayer MoS2crystal can be substantially modulated up to ≈55% within a timeframe of ≈250 fs, a set of performance characteristics that showcases the promise of low‐dimensional materials for all‐optical nonlinear data processing. The combined experimental and theoretical study suggests that the large SHG modulation stems from the correlation between the second‐order dielectric susceptibility χ(2)and the density of photoexcited carriers in MoS2. Indeed, the depopulation of the conduction band electrons, at the vicinity of the high‐symmetry
K/K′ points of MoS2, suppresses the contribution of interband electronic transitions in the effective χ(2)of the monolayer crystal, enabling the all‐optical modulation of the SHG signal. The strong dependence of the second‐order optical response on the density of photocarriers reveals the promise of time‐resolved nonlinear characterization as an alternative route to monitoring carrier dynamics in excited states of TMDs. -
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Abstract Optical second harmonic generation (SHG) is a nonlinear optical effect widely used for nonlinear optical microscopy and laser frequency conversion. Closed-form analytical solution of the nonlinear optical responses is essential for evaluating materials whose optical properties are unknown a priori. A recent open-source code, ♯SHAARP.
si , can provide such closed form solutions for crystals with arbitrary symmetries, orientations, and anisotropic properties at asingle interface. However, optical components are often in the form of slabs, thin films on substrates, and multilayer heterostructures with multiple reflections of both the fundamental and up to ten different SHG waves at each interface, adding significant complexity. Many approximations have therefore been employed in the existing analytical approaches, such as slowly varying approximation, weak reflection of the nonlinear polarization, transparent medium, high crystallographic symmetry, Kleinman symmetry, easy crystal orientation along a high-symmetry direction, phase matching conditions and negligible interference among nonlinear waves, which may lead to large errors in the reported material properties. To avoid these approximations, we have developed an open-source package named Second Harmonic Analysis of Anisotropic Rotational Polarimetry in Multilayers (♯SHAARP.ml ). The reliability and accuracy are established by experimentally benchmarking with both the SHG polarimetry and Maker fringes using standard and commonly used nonlinear optical materials as well as twisted 2-dimensional heterostructures. -
The new, quaternary diamond-like semiconductor (DLS) Cu 4 MnGe 2 S 7 was prepared at high-temperature from a stoichiometric reaction of the elements under vacuum. Single crystal X-ray diffraction data were used to solve and refine the structure in the polar space group Cc. Cu 4 MnGe 2 S 7 features [Ge 2 S 7 ] 6− units and adopts the Cu 5 Si 2 S 7 structure type that can be considered a derivative of the hexagonal diamond structure. The DLS Cu 2 MnGeS 4 with the wurtz-stannite structure was similarly prepared at a lower temperature. The achievement of relatively phase-pure samples, confirmed by X-ray powder diffraction data, was nontrival as differential thermal analysis shows an incongruent melting behaviour for both compounds at relatively high temperature. The dark red Cu 2 MnGeS 4 and Cu 4 MnGe 2 S 7 compounds exhibit direct optical bandgaps of 2.21 and 1.98 eV, respectively. The infrared (IR) spectra indicate potentially wide windows of optical transparency up to 25 μm for both materials. Using the Kurtz–Perry powder method, the second-order nonlinear optical susceptibility, χ (2) , values for Cu 2 MnGeS 4 and Cu 4 MnGe 2 S 7 were estimated to be 16.9 ± 2.0 pm V −1 and 2.33 ± 0.86 pm V −1 , respectively, by comparing with an optical-quality standard reference material, AgGaSe 2 (AGSe). Cu 2 MnGeS 4 was found to be phase matchable at λ = 3100 nm, whereas Cu 4 MnGe 2 S 7 was determined to be non-phase matchable at λ = 1600 nm. The weak SHG response of Cu 4 MnGe 2 S 7 precluded phase-matching studies at longer wavelengths. The laser-induced damage threshold (LIDT) for Cu 2 MnGeS 4 was estimated to be ∼0.1 GW cm −2 at λ = 1064 nm (pulse width: τ = 30 ps), while the LIDT for Cu 4 MnGe 2 S 7 could not be ascertained due to its weak response. The significant variance in NLO properties can be reasoned using the results from electronic structure calculations.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/sym14040824
