Harmonic Generation Measurements Research Articles

Flexible epitaxial LiNbO3 thin film with ferroelectricity and nonlinear optical response

Flexible or wearable devices are of great interests in the modern technologies, and oxide thin films are critical components for such applications. In this work, epitaxial LiNbO3 (LNO) thin film integrated on flexible mica substrate has been achieved. Al-doped ZnO (AZO) layer has been first deposited as buffer layer to obtain the epitaxial LNO film, furthermore AZO serves as bottom electrode for electrical measurement. The as-deposited LNO film exhibits high epitaxial quality with c-direction growth. The transmittance measurement indicates the high transparency of the film, ～85 % in visible range and ～90 % in near infrared region up to 1500 nm. The second harmonic generation (SHG) measurement confirms the nonlinearity of the flexible LNO film. The LNO/AZO/mica film also presents apparent ferroelectric response. Overall, the high-quality LNO integrated on flexible mica could be potentially applied in wearable optical and electrical devices.

Micrometric patterning of a borogermanate glass containing terbium by thermal poling to manage luminescence and second order optical properties

Borogermanate glasses containing terbium ions are interesting materials due to their luminescent and magnetic properties. Terbium can present two different oxidation states and the thermal poling technique can be a pertinent way to modulate spatially the oxidation state of these ions. In this work, we demonstrate using a thermo-electrical imprinting process the transfer of micro scaled motifs on the surface of a borogermanate glass containing Tb3+ resulting in a micrometric structuring of the oxidation state of Tb3+/Tb4+ ions. A large change in absorption and luminescence optical properties is observed, arising from the distinct properties of trivalent and tetravalent terbium ions. Correlative micro luminescence, Raman and second harmonic generation measurements were carried out on the patterned poled glass surface. This has demonstrated an accurate concomitant modification of the glass structure accompanying large luminescence changes and the appearance of a second order optical response which could be attributed to a localized space charge implantation. These original results demonstrate how a simple electrical process allows managing multi optical properties but also paves the way to induce static electrical functionalities in a magnetic optical glassy system.

Out-of-Plane Ferroelectricity in Two-Dimensional 1T‴-MoS2 Above Room Temperature.

Two-dimensional (2D) molybdenum disulfide (MoS2), one of the most extensively studied van der Waals (vdW) materials, is a significant candidate for electronic materials in the post-Moore era. MoS2 exhibits various phases, among which the 1T‴ phase possesses noncentrosymmetry. 1T‴-MoS2 was theoretically predicted to be ferroelectric a decade ago, but this has not been experimentally confirmed until now. Here, we have prepared high-purity 2D 1T‴-MoS2 crystals and experimentally confirmed the room-temperature out-of-plane ferroelectricity. The noncentrosymmetric crystal structure in 2D 1T‴-MoS2 was convinced by atomically resolved transmission electron microscopic imaging and second harmonic generation (SHG) measurements. Further, the ferroelectric polarization states in 2D 1T‴-MoS2 can be switched using piezoresponse force microscopy (PFM) and electrical gating in field-effect transistors (FETs). The ferroelectric-to-paraelectric transition temperature is measured to be about 350 K. Theoretical calculations have revealed that the ferroelectricity of 2D 1T‴-MoS2 originates from the intralayer charge transfer of S atoms within the layer. The discovery of intrinsic ferroelectricity in the 1T‴ phase of MoS2 further enriches the properties of this important vdW material, providing more possibilities for its application in the field of next-generation electronic devices.

Three-State Dielectric Switching within a Narrow Temperature Range in Isopropylammonium Lead Iodide, a One-Dimensional Perovskite with Polar Phase.

The phenomenon of dielectric switching has garnered considerable attention due to its potential applications in electronic and photonic devices. Typically, hybrid organic-inorganic perovskites, HOIPs, exhibit a binary (low-high) dielectric state transition, which, while useful, represents only the tip of the iceberg in terms of functional relevance. One way to boost the versatility of applications is the discovery of materials capable of nonbinary switching schemes, such as three-state dielectric switching. The ideal candidate for that task would exhibit a trio of attributes: two reversible, first-order phase transitions across three distinct crystal phases, minimal thermal hysteresis, and pronounced, step-like variations in dielectric permittivity, with a substantial change in its real part. Here, we demonstrate a one-dimensional lead halide perovskite with the formula (CH3)2C(H)NH3)PbI3, abbreviated as ISOPrPbI3, that fulfills these criteria and demonstrates three-state dielectric switching within a narrow temperature range of ca. 45 K. Studies on ISOPrPbI3 also revealed the polar nature of the low-temperature phase III below 266 K through pyrocurrent experiments, and the noncentrosymmetric character of the intermediate phase II and low-temperature phase III is confirmed via second harmonic generation measurements. Additionally, luminescence studies of ISOPrPbI3 have demonstrated combined broadband and narrow emission properties. The introduction of ISOPrPbI3 as a three-state dielectric switch not only addresses the limitations posed by the wide thermal gap between dielectric states in previous materials but also opens new avenues for the development of nonbinary dielectric switchable materials.

Chiral Stacking Identification of Two-Dimensional Triclinic Crystals Enabled by Machine Learning.

Chiral materials possess broken inversion and mirror symmetry and show great potential in the application of next-generation optic, electronic, and spintronic devices. Two-dimensional (2D) chiral crystals have planar chirality, which is nonsuperimposable on their 2D enantiomers by any rotation about the axis perpendicular to the substrate. The degree of freedom to construct vertical stacking of 2D monolayer enantiomers offers the possibility of chiral manipulation for designed properties by creating multilayers with either a racemic or enantiomerically pure stacking order. However, the rapid recognition of the relative proportion of two enantiomers becomes demanding due to the complexity of stacking orders of 2D chiral crystals. Here, we report the unambiguous identification of racemic and enantiomerically pure stackings for layered ReSe2 and ReS2 using circular polarized Raman spectroscopy. The chiral Raman response is successfully manipulated by the enantiomer proportion, and the stacking orders of multilayer ReSe2 and ReS2 can be completely clarified with the help of second harmonic generation and scanning transmission electron microscopy measurements. Finally, we trained an artificial intelligent Spectra Classification Assistant to predict the chirality and the complete crystallographic structures of multilayer ReSe2 from a single circular polarized Raman spectrum with the accuracy reaching 0.9417 ± 0.0059.

A Lead-Free Ferroelectric 2D Dion-Jacobson Tin Iodide Perovskite.

2D hybrid organic-inorganic halide perovskites emerge as a new class of 2D semiconductors with the potential to combine excellent optoelectronic properties with symmetry-enabled properties such as ferroelectricity. Although many lead-based ferroelectric 2D halide perovskites are reported, there is yet to be a conclusive report of ferroelectricity in tin-based 2D perovskites. Here, the structures and properties of a new series of 2D Dion-Jacobson (DJ) Sn perovskites: (4AMP)SnI4, (4AMP)(MA)Sn2I7, and (4AMP)(FA)Sn2I7 (4AMP = 4-(aminomethyl)piperidinium, MA = methylammonium, and FA = formamidinium), are reported. Structural characterization reveals that (4AMP)SnI4 is polar with in-plane spontaneous polarization whereas (4AMP)(MA)Sn2I7 and (4AMP)(FA)Sn2I7 are centrosymmetric. Further, (4AMP)SnI4 displays second harmonic generation (SHG) and polarization-electric field hysteresis measurements confirm it is ferroelectric with a spontaneous polarization of 10.0 µC cm-2 at room temperature. (4AMP)SnI4 transitions into a centrosymmetric structure above 367 K. As the first direct experimental observation of the spontaneous ferroelectric polarization of a Sn-based 2D hybrid perovskite, this work opens up environmentally friendly 2D tin halide perovskites for ferroelectricity and other physical property studies.

Photon-pair generation using inverse-designed thin-film lithium niobate mode converters

Spontaneous parametric down-conversion (SPDC) has become a key method for generating entangled photon pairs. Periodically poled thin-film lithium niobate (TFLN) waveguides induce strong SPDC but require complex fabrication processes. In this work, we experimentally demonstrate efficient SPDC and second harmonic generation using modal phase matching methods. This is achieved with inverse-designed optical mode converters and low-loss optical waveguides in a single nanofabrication process. Inverse design methods provide enhanced functionalities and compact footprints for the converter. Despite the extensive achievements in inverse-designed photonic integrated circuits, the potential of inverse-designed TFLN quantum photonic devices has been seldom explored. The device shows an on-chip conversion efficiency of 3.95% W−1 cm−2 in second harmonic generation measurements and a coincidence count rate up to 21.2 kHz in SPDC experiments. This work highlights the potential of the inverse-designed TFLN photonic devices and paves the way for their applications in on-chip nonlinear or quantum optics.

Terahertz-triggered ultrafast nonlinear optical activities in two-dimensional centrosymmetric PtSe2.

The nonlinear mechanisms of polarization and optical fields can induce extensive responses in materials. In this study, we report on two kinds of nonlinear mechanisms in the topological semimetal PtSe2 crystal under the excitation of intense terahertz (THz) pulses, which are manipulated by the real and imaginary parts of the nonlinear susceptibility of PtSe2. Regarding the real part, the broken inversion symmetry of PtSe2 is achieved through a THz-electric-field polarization approach, which is characterized by second harmonic generation (SHG) measurements. The transient THz-laser-induced SHG signal occurs within 100 fs and recombines to the equilibrium state within 1 ps, along with a high signal-to-noise ratio (∼51 dB) and a high on/off ratio (∼102). Regarding the imaginary part, a nonlinear absorption change can be generated in the media. We reveal a THz-induced absorption enhancement in PtSe2 via nonlinear transmittance measurements, and the sheet conductivity can be modulated up to 42% by THz electric fields in our experiment. Therefore, the THz-induced ultrafast nonlinear photoresponse reveals the application potential of PtSe2 in photonic and optoelectronic devices in the THz technology.

High-pressure synthesis of acentric sodium pyrocarbonate, Na2[C2O5

The inorganic pyrocarbonate salt Na2[C2O5] crystallizes in the acentric, monoclinic space group P21 with Z = 2. It contains monovalent alkali metal cations together with isolated pyrocarbonate anions. The [C2O5]2--groups consist of two planar [CO3]2--groups which are slightly tilted with respect to each other around the bridging oxygen atom. Na2[C2O5] was synthesized in a laser-heated diamond anvil cell at 20(2) GPa by heating a mixture of Na2[CO3] + CO2 to ≈800(200) K. Its crystal structure was obtained by single crystal synchrotron X-ray diffraction and confirmed by density functional theory-based calculations in combination with Raman spectroscopy. Second harmonic generation measurements verified the acentric space group symmetry. The crystal structure is characterized by alternating layers of Na+-cations and [C2O5]2--complex anions.

Lipid content evaluation of Drosophila tumour associated haemocytes through Third Harmonic Generation measurements.

Non-linear microscopy is a powerful imaging tool to examine structural properties and subcellular processes of various biological samples. The competence of Third Harmonic Generation (THG) includes the label free imaging with diffraction-limited resolution and three-dimensional visualization with negligible phototoxicity effects. In this study, THG records and quantifies the lipid content of Drosophila haemocytes, upon encountering normal or tumorigenic neural cells, in correlation with their shape or their state. We show that the lipid accumulations of adult haemocytes are similar before and after encountering normal cells. In contrast, adult haemocytes prior to their interaction with cancer cells have a low lipid index, which increases while they are actively engaged in phagocytosis only to decrease again when haemocytes become exhausted. This dynamic change in the lipid accrual of haemocytes upon encountering tumour cells could potentially be a useful tool to assess the phagocytic capacity or activation state of tumour-associated haemocytes.

Molecular Structure, Computational Studies and Nonlinear Optical properties of a New Organic Chalcone Crystal

A new conjugated chalcone compound (Z)-2-(1-(1-(2,4-dimethylphenyl)-3-oxo-3-phenylprop-1-en-2-yl)pyridin-2(1H)ylidene) malononitrile was prepared and structurally analyzed using single-crystal X-ray diffraction. This new compound's quadratic and cubic susceptibilities at 1064 nm were analyzed and evaluated using the second and third harmonic generation methods after deposition in PMMA polymer thin films. These films have been used for the induced second harmonic generation measurements achieved using the corona poling technique. Complementary information on electric dipole moment, static dipole polarizability, and initial hyperpolarizability of this compound were obtained from the density functional theory (DFT) calculation performed at the DFT/B3LYP/6-311G++ (d, p) and Gaussian 09 software. The findings demonstrate that when compared to previous chalcone NLO crystals that have been published, the synthesized crystals had greater crystal transparency, polarizability, and π-conjugation. In particular, the (Z)-2-(1-(1-(2,4-dimethylphenyl)-3-oxo-3-phenylprop-1-en-2-yl)pyridin-2(1H)ylidene) malononitrile crystal's SHG and THG susceptibility are 0. 243 [pmV−1] and 41.13 10−22 [m2V−2], respectively. The combined findings demonstrate that the NLO properties depend only on the steric hindrance and the chemical structure, that is, the system of π-conjugated electrons.

Giant room-temperature nonlinearities in a monolayer Janus topological semiconductor

Nonlinear optical materials possess wide applications, ranging from terahertz and mid-infrared detection to energy harvesting. Recently, the correlations between nonlinear optical responses and certain topological properties, such as the Berry curvature and the quantum metric tensor, have attracted considerable interest. Here, we report giant room-temperature nonlinearities in non-centrosymmetric two-dimensional topological materials—the Janus transition metal dichalcogenides in the 1 T’ phase, synthesized by an advanced atomic-layer substitution method. High harmonic generation, terahertz emission spectroscopy, and second harmonic generation measurements consistently show orders-of-the-magnitude enhancement in terahertz-frequency nonlinearities in 1 T’ MoSSe (e.g., > 50 times higher than 2H MoS2 for 18th order harmonic generation; > 20 times higher than 2H MoS2 for terahertz emission). We link this giant nonlinear optical response to topological band mixing and strong inversion symmetry breaking due to the Janus structure. Our work defines general protocols for designing materials with large nonlinearities and heralds the applications of topological materials in optoelectronics down to the monolayer limit.

Experimental and Computational studies on Intramolecular charge transfer, Terahertz and Two photon absorption of 3-[(4-Nitrophenyl Azo)]-9H-Carbazole-9-Ethanol (NPACE) from their Vibrational spectra for Optical limiting and NLO applications

Non-linear optical (NLO) features of 3-[(4-Nitrophenyl Azo)]-9H-Carbazole-9-Ethanol (NPACE) chromophore were investigated by FT-IR, FT-Raman, and UV–visible spectra aided by Density Functional Theory (DFT) using the B3LYP/6–311++G(d,p) basis set of Gaussian 16 W package. It is observed from the DFT calculation that the slight increase in the endocyclic angle of C13 -C14 -C15 and the reduction in exocyclic angle of N40 –N39 -C14 and C15 -C14 –N39 ascertained by experimental XRD values indicating the intramolecular charge-transfer interaction between the carbazole and nitrophenyl group through the diazo bridge. The vibrational contribution to the linear electro-optic effect is 15% of the total hyperpolarizability being calculated at B3LYP/6–311++G (d, p) for the NPACE molecule. It is also observed that the 8a, 19a, and 19b modes of the carbazole ring and the 8a, 8b, and 19b modes of the phenyl ring are found to be simultaneously and intensely active in IR and Raman spectra explaining the charge transfer interactions throughout the molecule. The low value of the HOMO- LUMO energy gap (2.5843 eV) and the deviation between the measured absorption wavelength (3.36 eV) from the computed (3.87 eV), both these facts substantiate the intramolecular charge transfer. The polarizability and first-order hyperpolarizability were calculated as 6.48 × 10-24 and 3.8 × 10-29 esu, respectively. The second harmonic generation (SHG) measurement experiment of NPACE was carried out using the powder method. The SHG efficiency is measured in comparison with the urea standard. The calculated torsional mode at 20 cm−1 is in excellent quantitative agreement with the experimentally determined terahertz absorption peak. The two-photon absorption coefficient of NPACE was estimated to be 0.9 × 10-11 mW−1, which is mainly due to the D-π-A type of molecular structure, and the optical limiting threshold for NPACE was estimated to be 1.52 × 1013 Wm−2 enabling this material as a potential candidate for optical limiting applications.

Synthesis, Spectroscopic, Optical, and Thermal Characterizations of Zinc (Tris)-Thiourea Sulfate: A Metal-Organic Crystal.

In the current research, Zinc (tris)-thiourea sulfate (ZTTS), a metal-organic crystal, has been synthesized using the slow solvent evaporation technique. Powder-X-ray diffraction (PXRD) analysis, Fourier transform infrared (FT-IR) spectroscopy, UV-Vis spectroscopy, photoluminescence (PL) spectroscopy, and thermal, and second harmonic generation measurements have all been applied to describe the as-synthesized ZTTS crystals. The synthesized samples crystallized in an orthorhombic structure, based on XRD analysis. The functional groups of ZTTS samples were validated by FT-IR analysis. The extensive transparency of ZTTS over the UV-visible spectral region has been confirmed by UV-Vis analysis and the band gap has been estimated as 4.43eV. The photoluminescence spectra exhibit a prominent emission peak around the wavelength of 484nm and significant emission peaks at 444 and 513nm with an excitation wavelength of 250nm. The SHG test illustrates the creation of second harmonic signals from the ZTTS samples. The thermal response of the as-synthesized ZTTS was shown by the TG/DTA measurements. The results suggest that as-synthesized ZTTS crystals could be used as a possible nonlinear optical substance.

Optical and structural characterization of femtosecond laser written micro-structures in germanate glass

We report on direct femtosecond laser writing in zinc barium gallo-germanate glasses. A combination of spectroscopic techniques allows to progress in the understanding of the mechanisms taking place depending on the energy. In the first regime (type I, isotropic local index change) up to 0.5 µJ, the main occurrence is the generation of charge traps inspected by luminescence, together with separation of charges detected by polarized second harmonic generation measurements. At higher pulse energies notably at the threshold corresponding to 0.8 µJ or in the second regime (type II modifications corresponding to nanograting formation energy domain), the main occurrence is a chemical change and re-organization of the network evidenced by the appearance of molecular O2 seen in the Raman spectra. In addition, the polarization dependence of the second harmonic generation in type II indicates that the organization of nanogratings may be perturbed by the laser-imprinted electric field.

Application of Odd Harmonic Resonances of a Single Crystal to Generation and Reception of Superharmonic Waves for Sensitive Monitoring of Heat-Treated Materials.

In nonlinear ultrasonic testing, the quadratic and more recently cubic nonlinearity parameters are frequently measured as a quantitative indicator of damaged material state. Application of higher-order harmonics can improve the sensitivity of detection and monitoring for damages and microstructures due to their higher values of nonlinearity parameters. The excitation and reception of higher-order harmonics, so-called superharmonics, which use the third to fifth harmonics arising from nonlinear wave propagation, is not sufficiently investigated and applied. The purpose of this communication is to develop a highly sensitive superharmonic nondestructive technique that efficiently generates and receives third- and fifth-order harmonics using the odd harmonic resonances of a single piezoelectric crystal. The method focuses on the measurement of fifth harmonic generation and reception, and the calculation of the relative quintic nonlinearity parameter (δ'). The method also addresses the issue of source nonlinearity that may be contained in the measured fifth harmonic amplitude. The measurement results of δ' for a series of precipitation heat-treated samples clearly show a much better sensitivity than the results of the cubic nonlinearity parameter (γ'). The proposed method enables a highly sensitive and true pulse-echo mode nonlinear ultrasound testing.

Highly Sensitive Detection of Microstructure Variation Using a Thickness Resonant Transducer and Pulse-Echo Third Harmonic Generation.

In nonlinear ultrasound testing, the relative nonlinear parameter is conveniently measured as a sensitive means of detecting and imaging overall variation of microstructures and damages. Compared to the quadratic nonlinear parameter (β'), the cubic nonlinear parameter (γ'), calculated as the third harmonic amplitude divided by the cube of the fundamental amplitude, has generally a higher value, providing better sensitivity in nonlinear parameter mapping. Since the third harmonic amplitude is about two orders of magnitude lower than the fundamental amplitude, efficient excitation and highly sensitive reception of third harmonic is very important. In this paper, we explore an odd harmonic thickness resonant transducer that meets the requirements for pulse-echo third harmonic generation (THG) measurements. We also address the problem of source nonlinearity that may be present in the measured amplitude of the third harmonic and propose a method to properly correct it. First, we measure γ' for a series of aluminum specimens using the through-transmission method to observe the behavior of γ' as a function of specimen thickness and input voltage, and examine the effects of various corrections such as attenuation, diffraction and source nonlinearity. Next, we apply the odd harmonic resonant transducer to pulse-echo THG measurements of precipitation heat-treated specimens. It is shown that such transducer is very effective in generation and detection of fundamental and third harmonics under finite amplitude toneburst excitation. The highly sensitive detectability of γ' are presented as a function of aging time, and the sensitivity of γ' is compared with that of β' and β'2.

High-pressure synthesis, crystal structure, and characterization of the new non-centrosymmetric terbium borate Tb3B10O17(OH)5

Herein, the high-pressure/high-temperature synthesis (11 GPa, 650 °C) of Tb3B10O17(OH)5 in a modified Walker-type multianvil device is presented. The structure of this rare-earth borate was determined by single-crystal X-ray diffraction methods and was found to crystallize orthorhombically in the space group Pmn21 (no. 31) with the unit cell parameters a = 16.2527(4), b = 4.4373(1), and c = 8.8174(2) Å. The new compound was further characterized using infrared spectroscopy, energy-dispersive X-ray spectroscopy, second harmonic generation (SHG) measurements, and temperature-dependent X-ray powder diffraction. Tb3B10O17(OH)5 decomposes to β-Tb(BO2)3 at temperatures higher than 460 °C. With increasing temperatures, the formation of μ-TbBO3 was observed, which transforms to π-TbBO3 upon cooling.

Measurement and In-Depth Analysis of Higher Harmonic Generation in Aluminum Alloys with Consideration of Source Nonlinearity.

Harmonic generation measurement is recognized as a promising tool for inspecting material state or micro-damage and is an ongoing research topic. Second harmonic generation is most frequently employed and provides the quadratic nonlinearity parameter (β) that is calculated by the measurement of fundamental and second harmonic amplitudes. The cubic nonlinearity parameter (β2), which dominates the third harmonic amplitude and is obtained by third harmonic generation, is often used as a more sensitive parameter in many applications. This paper presents a detailed procedure for determining the correct β2 of ductile polycrystalline metal samples such as aluminum alloys when there exists source nonlinearity. The procedure includes receiver calibration, diffraction, and attenuation correction and, more importantly, source nonlinearity correction for third harmonic amplitudes. The effect of these corrections on the measurement of β2 is presented for aluminum specimens of various thicknesses at various input power levels. By correcting the source nonlinearity of the third harmonic and further verifying the approximate relationship between the cubic nonlinearity parameter and the square of the quadratic nonlinearity parameter (β∗β), β2≈β∗β, the cubic nonlinearity parameters could be accurately determined even with thinner samples and lower input voltages.

Growth and phase transition of Sr3Zr2O7 single crystals

The melting behavior of Ruddlesden-Popper type hybrid improper ferroelectric Sr3Zr2O7 phase in the ZrO2–SrO pseudo-binary system was investigated, and its single crystals were successfully grown. A series of the slow-cooling floating zone experiments revealed that Sr3Zr2O7 melts incongruently into SrZrO3 phase and a liquid and that the compositional range where Sr3Zr2O7 and a liquid coexist is located around 70 mol% SrO composition. Based on the results, we attempted to grow Sr3Zr2O7 single crystals by the traveling solvent floating zone method using SrO-excess solvent and feed. Consequently, many small single crystals of Sr3Zr2O7 phase with several millimeters in size were discovered in the as-grown boules covered with SrO phase. The phase transition behavior of the grown crystals was investigated by differential thermal analysis with polarizing optical microscopy as well as by optical second harmonic generation measurements. We directly observed a reconstruction of orthorhombic twin domains in Sr3Zr2O7 single crystals accompanied by the first-order ferroelectric transition at about 410 °C.