Electric Field-induced Second Harmonic Generation Research Articles

Synthesis and Optical Characterization of Hydrazone-Substituted Push-Pull-Type NLOphores.

Two distinct families of NLOphores featuring hydrazone donors were synthesized using click-type [2 + 2] cycloaddition retroelectrocyclizations (CA-RE). Despite the limitations in the substrate scope, it was shown for the first time that hydrazone-activated alkynes could undergo reactions with TCNE/TCNQ. The electrochemical, photophysical, and second-order nonlinear optical (NLO) characteristics of the chromophores were analyzed utilizing experimental and computational approaches. Chromophores 17-21 and 23-27 exhibited two reduction waves, along with one oxidation wave that can be attributed to the hydrazone moiety. All chromophores exhibit charge-transfer bands extending from the visible to the near-infrared region. The λmax of hydrazone-based chromophores falls within the range of 473 to 725 nm. Additionally, all chromophores exhibited positive solvatochromism. Computational studies have been performed to elucidate the origin of the low-energy absorption bands. Parameters such as dipole moment, band gaps, electronegativity, global chemical hardness/softness, average polarizability, and first hyperpolarizability were calculated to obtain information about NLO properties of the target structures. The thermal stabilities of the NLOphores were assessed through TGA. Experimental NLO measurements were conducted using the electric field-induced second harmonic generation (EFISHG) technique. The studied structures demonstrated NLO responses, with μβ values between 520 × 10-48 esu and 5300 × 10-48 esu.

Characterizing electric fields in semiconductor devices: effect of second-harmonic light interference.

Characterizing electric fields in semiconductor devices using electric field-induced second-harmonic generation (EFISHG) has opened new opportunities for an advanced device design. However, this new technique still has challenges due to the interference between background second-harmonic generation (SHG) and EFISHG generated light. We demonstrate that interference effects can effectively be eliminated during EFISHG measurements by focusing the laser from the transparent substrate side of a GaN PN diode, enabling straightforward quantitative electric field analysis, in contrast to PN junction interface side measurements. A model based on wave generation and propagation is proposed and highlights the incoherence between background SHG and EFISHG light. This incoherence may be attributed to the depth of focus of the incident laser and phase mismatch between incident and SHG light.

Electric field measurement in DC corona discharge in atmospheric pressure air using E-FISHG and laser-triggering methods

Electric field measurement using electric-field-induced second-harmonic generation (E-FISHG) draws attention because of its non-invasiveness and is increasingly being applied to various discharge plasmas. However, measurement accuracy of previous studies is unclear since approximations in calibration are inadequate. Therefore, we have developed a measurement and analysis method that does not require approximations and can furthermore obtain the distribution of the electric field. To demonstrate the applicability of the proposed method to discharge plasmas, in this paper, we measure the electric field as a result of the space charge generated by DC corona discharge in atmospheric pressure air and validate the results by comparing them with those obtained using the laser-triggering method. We demonstrate that the electrostatic field and electric field resulting from the space charge can be measured with a difference of about 10% between the results obtained from the laser triggering method and E-FISHG method. The proposed method holds potential for applications in discharge plasmas.

Adequate laser focusing and signal acquisition conditions for 3D measurement of electric-field distribution by the E-FISHG method

Electric field measurement using electric-field-induced second-harmonic generation (E-FISHG) has attracted attention because of its non-invasiveness and high spatiotemporal resolution. In the electric field measurement by the E-FISHG method, the applied electric-field profile along the laser path outside the focal spot affects the second-harmonic generation (SHG) signal. We have proposed a method of calibrating and inferring the applied electric-field profile from the SHG distribution along the laser path. In our previous research, the successful inference of a relatively simple electric-field profile from a series of SHG signals was demonstrated. To measure more complex electric-field profiles, we apply our method to three cases of electric-field profiles: (1) the profile with different sharpness, (2) the profile with two peaks, and (3) the profile with noise superimposed on the SHG signal. The applied electric-field distribution can be inferred within 10% error by adequately choosing the confocal parameter. We also provide guidelines for the required signal acquisition region and measurement pitch when the approximate shape of the applied electric field is known, which are important for actual measurement.

Measurement of inhomogeneous electric field based on electric field-induced second-harmonic generation

The electric field-induced second-harmonic generation (E-FISH) method can offer high spatiotemporal resolution in electric field measurement, but faces challenge in reconstructing the inhomogeneous electric field along the probing laser. This paper presents an inversion method to reconstruct the electric field profile by using E-FISH signals measured from multiple points along the probing laser. The relationship between the condition number of the inversion coefficient matrix and the parameters of E-FISH measurement system is clarified. The inversion method is validated through experimental investigations conducted in three different electrode configurations, namely the plate-to-plate gap, the rod-to-rod gap, and the rod-plate gap. With the inhomogeneity coefficient varies from 1 to 10.7, the maximum deviation between the measured electric field and the finite element simulation is less than 6%. This method does not rely on priori assumptions and electrode configurations, and exhibits good robustness in resisting the effect of measurement noise on the inversion accuracy.

Optical Setup for Investigating the Hyperpolarizability of Organic Nanostructure Materials in Solutions Using Electric Field Induced Second Harmonic Generation

Abstract: In this paper, an optical setup for electric field-induced second-harmonic generation (EFISH) at 1.9 μm experiment was arranged and used to investigate and determine the hyperpolarizability of some nanostructure organic components in two different solutions. First, a laser beam at 1.9 μm was generated by pumping a hydrogen Raman cell pressurized to 55 bar with 10 Hz Q-switched Nd: YAG nanosecond laser operating at λ = 1.064 μm. Next, the generated laser beam was aligned with all optical components within the assembly. The final step was to optimize the beam’s power and polarization at the center of the EFSH cell. Different nanostructure organic samples in solutions were prepared with nearly the same standard concentration of about 5 mmol/L to be investigated under the optimized system. Two solvents were used in this work, dichloromethane, or DCM (CH2Cl2), and chloroform, or trichloromethane (CHCl3). First, the harmonic order hyperpolarizability of five organic molecules in solutions with different chemical components such as quinolinium groups and organic boron complexes (supplied by the Chemistry Department at Catania University, Italy) were experimentally investigated experimentally. Only component (2-(2-[5′-(N,N-dimethylamino)-(2,2′-bithiophen)-5-yl]vinyl)-1-methyquinolin-1-ium iodide) in chloroform showed a significant difference in Maker fringes amplitude of the applied electrical field in comparison with fringes of its pure solvent. The value ofμfor this component has been calculated as 1320 x 10-48 esu. This value indicates that the component is a suitable candidate for use in second-harmonic generation imaging for biological applications. Keywords: Electric field-induced second-harmonic generation (EFISH), Harmonic light, Organic materials, hyperpolarizability. PACS: Nonlinear optics, 42.65.-k, Electric fields, instrumentation for measurement, 07.50.-e, Organic-inorganic hybrid nanostructures, 81.07.Pr, Organic materials optical materials, 42.70.Jk

Nonlinear Optical Imaging of Carrier Transport at the Semiconductor-Insulator Interface in Organic Field-Effect Transistors

Organic field-effect transistors (FETs) are witnessing a revolution in their performance, in part, due to a reduction in contact resistance, and through controlled morphology of the organic semiconducting film. Another major consideration is the role of the dielectric layer in dictating transport properties. The transient electric-field-induced second-harmonic generation (EFISHG) technique allows visualization of carrier dynamics in the channel region of a FET by capturing the movement of the induced dielectric polarization. A microscopic imaging system using a broadband femtosecond laser and a pulse compensation arrangement is constructed for imaging transient EFISHG from organic FETs by synchronized laser and voltage pulses. By varying the dielectric layer in organic FETs comprising pentacene and a donor-acceptor conjugated polymer as semiconducting layers, we show that EFISHG images provide an accurate estimate of the carrier mobility along with providing insights into channel formation and the electric field distribution within the channel region. We further correlate the interface charging effects observed in EFISHG to the interface trap density obtained by capacitance-voltage and conductance-voltage from metal-insulator-semiconductor diodes.

Monitoring interfacial electric fields at a hematite electrode during water oxidation.

To understand the mechanisms of water oxidation on materials such as hematite it is important that accurate measurements and models of the interfacial fields at the semiconductor liquid junction are developed. Here we demonstrate how electric field induced second harmonic generation (EFISHG) spectroscopy can be used to monitor the electric field across the space-charge and Helmholtz layers in a hematite electrode during water oxidation. We are able to identify the occurrence of Fermi level pinning at specific applied potentials which lead to a change in the Helmholtz potential. Through combined electrochemical and optical measurements we correlate these to the presence of surface trap states and the accumulation of holes (h+) during electrocatalysis. Despite the change in Helmholtz potential as h+ accumulate we find that a population model can be used to fit the electrocatalytic water oxidation kinetics with a transition between a first and third order regime with respect to hole concentration. Within these two regimes there are no changes in the rate constants for water oxidation, indicating that the rate determining step under these conditions does not involve electron/ion transfer, in-line with it being O-O bond formation.

Hyperpolarizabilities of Push-Pull Chromophores in Solution: Interplay between Electronic and Vibrational Contributions.

Contemporary design of new organic non-linear optical (NLO) materials relies to a large extent on the understanding of molecular and electronic structure-property relationships revealed during the years by available computational approaches. The progress in theory-hand-in-hand with experiment-has enabled us to identify and analyze various physical aspects affecting the NLO responses, such as the environmental effects, molecular vibrations, frequency dispersion, and system dynamics. Although it is nowadays possible to reliably address these effects separately, the studies analyzing their mutual interplay are still very limited. Here, we employ density functional theory (DFT) methods in combination with an implicit solvent model to examine the solvent effects on the electronic and harmonic as well as anharmonic vibrational contributions to the static first hyperpolarizability of a series of push-pull α,ω-diphenylpolyene oligomers, which were experimentally shown to exhibit notable second-order NLO responses. We demonstrate that the magnitudes of both vibrational and electronic contributions being comparable in the gas phase significantly increase in solvents, and the enhancement can be, in some cases, as large as three- or even four-fold. The electrical and mechanical anharmonic contributions are not negligible but cancel each other out to a large extent. The computed dynamic solute NLO properties of the studied systems are shown to be in a fair agreement with those derived from experimentally measured electric-field-induced second-harmonic generation (EFISHG) signals. Our results substantiate the necessity to consider concomitantly both solvation and vibrational effects in modeling static NLO properties of solvated systems.

Predicting the Second-Order Nonlinear Optical Responses of Organic Materials: The Role of Dynamics.

The last 30 years have witnessed an ever-growing application of computational chemistry for rationalizing the nonlinear optical (NLO) responses of organic chromophores. More specifically, quantum chemical calculations proved highly helpful in gaining fundamental insights into the factors governing the magnitude and character of molecular first hyperpolarizabilities (β), be they either intrinsic to the chromophore molecular structure and arising from symmetry, chemical substitution, or π-electron delocalization, or induced by external contributions such as the laser probe or solvation and polarization effects. Most theoretical reports assumed a rigid picture of the investigated systems, the NLO responses being computed solely at the most stable geometry of the chromophores. Yet, recent developments combining classical molecular dynamics (MD) simulations and DFT calculations have evidenced the significant role of structural fluctuations, which may induce broad distributions of NLO responses, and even generate them in some instances.This Account presents recent case studies in which theoretical simulations have highlighted these effects. The discussion specifically focuses on the simulation of the second-order NLO properties that can be measured experimentally either from Hyper-Rayleigh Scattering (HRS) or Electric-Field Induced Second Harmonic Generation (EFISHG). More general but technical topics concerning several aspects of the calculations of hyperpolarizabilities are instead discussed in the Supporting Information.Selected examples include organic chromophores, photochromic systems, and ionic complexes in the liquid phase, for which the effects of explicit solvation, concentration, and chromophore aggregation are emphasized, as well as large flexible systems such as peptide chains and pyrimidine-based helical polymers, in which the relative variations of the responses were shown to be several times larger than their average values. The impact of geometrical fluctuations is also illustrated for supramolecular architectures with the examples of nanoparticles formed by organic dipolar dyes in water solution, whose soft nature allows for large shape variations translating into huge fluctuations in time of their NLO response, and of self-assembled monolayers (SAMs) based on indolino-oxazolidine or azobenzene switches, in which the geometrical distortions of the photochromic molecules, as well as their orientational and positional disorder within the SAMs, highly impact their NLO response and contrast upon switching. Finally, the effects of the rigidity and fluidity of the surrounding are evidenced for NLO dyes inserted in phospholipid bilayers.

Optimization of beam shaping and error quantification of calibration approach using E-FISHG based electric field measurements

Electric-field measurement based on the electric-field-induced second-harmonic generation (E-FISHG) method is a promising tool for a noncontact field measurement in plasmas and gases. For the E-FISHG method, a probing laser beam is focused at the measurement target by a lens, and the signals integrated along the laser path are acquired. Although the signal is frequently calibrated under uniform electric fields, the yielded value is erroneous if one does not consider the difference in the electric-field-profiles between the calibration and measurement. In this paper, we review the calibration and measurement targets of relevant studies, assess the error in the conventional method for the streamer discharge measurement, and give guidelines on which calibration approach to use depending on the electric field profile to be measured. Our approach uses cylindrical-to-cylindrical electrodes and multipoint measurement corresponding to the target length along the optical path, gas, and pressure.

Excitonic effects on the linear and nonlinear optical properties of solid C60 fullerene, insights from many-body first-principles calculations

We perform the many-body Bethe-Salpeter equation eigenstates based sum-over-states calculations for the linear and nonlinear optical properties of solid C60 fullerene. Excitonic and local field effects are included in the calculations. We calculate the one-photon absorption (OPA), third harmonic generation (THG), degenerate four-wave mixing (DFWM), and electric-field-induced second harmonic generation (ESHG) spectra of solid C60 fullerene. The overall agreement between the theoretical and experimental results is good for all calculated spectra. The OPA spectrum shows that the solid C60 fullerene has a large excitonic binding energy of 0.35 eV. The position and intensity of spectral peaks are modified significantly. By tracing the sum-over-states progress, we determine the type of nonlinear polarization resonances for the characteristic peaks of the THG process, which may clear up a discrepancy in two experimental results. The calculated DFWM spectrum is in excellent agreement with the available experimental results in terms of line shape and peak positions, and thus the two-photon absorption peaks can be well understood on the basis of the excitonic states of solid C60 fullerene. The dynamic ESHG spectrum is given as a reference for the future experiment.

Electric-field-profile measurement along a probing laser path based on electric-field-induced second-harmonic generation

Electric field measurement based on electric-field-induced second-harmonic generation (E-FISHG) of gas molecules is a promising method that enables noninvasive field measurement in gases. Although the probing laser beam is focused on the target area by a lens, the signal detected by the E-FISHG method is affected by the electric field along the probing laser path. The influencing path spans many tens of times the Rayleigh length of the front and rear of the focused spot. The E-FISHG signal has been frequently calibrated under uniform electric fields. However, this can yield a significantly incorrect calibrated value if the difference between the electric-field profiles in the measurement and calibration is not considered. In this paper, we propose a method to calibrate and furthermore restore the electric-field profile along a probing optical path by measuring a series of E-FISHG signals by changing the focusing spot position. The electric-field profile along the probing laser path is successfully restored from the measured E-FISHG signal sequence, which is verified by an experiment.

Recent Advances in Optics (RAO): Contribution of D. Narayana Rao in Optics and Photonics research in India

The fist documented speculations on light were found in oriental and Greek schools of philosophy. The investigations on the light in India were rooted way back to the ancient era. The Indian Samkhya, Nyaya, and Vaisheshika identified light or fie (Tejas) as one of the key elements among the fie elementary things of the universe. The pioneering results of optics and spectroscopy were witnessed in the era of stellar people like Sir Jagadish Chandra Bose and Sir C V Raman. The research has then taken a new directive into the development of nonlinear optics and photonics after the invention of the laser. The present article reviews the past few decades pioneering works of Prof. D Narayana Rao, an experimental physicist, in the context of optics and photonics in India. The most notable contributions of Prof Rao, introduced in India for the fist time, are white-light interferometry, degenerate four-wave mixing (DFWM), electric field induced second harmonic generation (EFISHG), incoherent laser spectroscopy (using dye laser), and femtosecond lasers for creating nano/microstructures.

Influence of the spatial extent of the space-charge region in c-Si on the electric-field-induced second-harmonic-generation effect

Second-harmonic-generation (SHG) spectroscopy can be used as an all-optical probe of space-charge regions (SCR) in semiconductors such as c - S i by exploiting the electric-field-induced second-harmonic-generation (EFISH) effect. To do so accurately, a thorough understanding of the EFISH effect is needed, and here a detailed model is presented, taking into account the so-far neglected spatial extent of the SCR on the spectral shape of the EFISH contribution. This shows that the spatial extent causes a significant phase shift in the EFISH contribution ranging from 0.1 π r a d to 0.4 π r a d with decreasing SCR strength. This predicted phase shift was verified by dedicated measurements of the spectral SHG phase and intensity of a series of samples covering the typical range of SCR strengths. The spectral SHG response of these samples indeed showed the predicted phase shift in the EFISH contribution and demonstrated that the extent of the SCR cannot be neglected. The obtained insights can result in improved accuracy in the determination of built-in charges near a c - S i interface, which is of interest in the context of semiconductor devices using SHG spectroscopy. Moreover, this refined understanding of the EFISH effect is beneficial in SHG experiments on 2D materials with c - S i serving as a substrate of Si-based photonic devices.

Consequence of aging at Au/HTM/perovskite interface in triple cation 3D and 2D/3D hybrid perovskite solar cells

Perovskite solar cells (PSCs) expressed great potentials for offering a feasible alternative to conventional photovoltaic technologies. 2D/3D hybrid PSCs, where a 2D capping layer is used over the 3D film to avoid the instability issues associated with perovskite film, have been reported with improved stabilities and high power conversion efficiencies (PCE). However, the profound analysis of the PSCs with prolonged operational lifetime still needs to be described further. Heading towards efficient and long-life PSCs, in-depth insight into the complicated degradation processes and charge dynamics occurring at PSCs' interfaces is vital. In particular, the Au/HTM/perovskite interface got a substantial consideration due to the quest for better charge transfer; and this interface is debatably the trickiest to explain and analyze. In this study, multiple characterization techniques were put together to understand thoroughly the processes that occur at the Au/HTM/perovskite interface. Inquest analysis using current–voltage (I–V), electric field induced second harmonic generation (EFISHG), and impedance spectroscopy (IS) was performed. These techniques showed that the degradation at the Au/HTM/perovskite interface significantly contribute to the increase of charge accumulation and change in impedance value of the PSCs, hence resulting in efficiency fading. The 3D and 2D/3D hybrid cells, with PCEs of 18.87% and 20.21%, respectively, were used in this study, and the analysis was performed over the aging time of 5000 h. Our findings propose that the Au/HTM/perovskite interface engineering is exclusively essential for attaining a reliable performance of the PSCs and provides a new perspective towards the stability enhancement for the perovskite-based future emerging photovoltaic technology.

Electric-field-induced second-harmonic generation using high-intensity femtosecond laser pulses over the observable optical breakdown threshold.

We investigated the performance of electric-field-induced second-harmonic generation (E-FISHG) by spectroscopic measurement using high-intensity femtosecond laser pulses. The second-harmonic intensity increased quadratically versus the applied electric field, as expected from the theory, up to 15 kV/cm with the laser energy up to 2.5 mJ, which is ∼5 times higher than the observable optical breakdown threshold. In addition, when the laser energy was 2.8 mJ, ∼80 times signal intensity at 0.23 mJ was obtained. These results suggest that the electric-field measurement by E-FISHG with high-intensity second harmonics is expected by using high-intensity laser pulses above the observable optical breakdown threshold. Spectroscopic measurement shows no E-FISHG of white light generated by self-phase modulation in laser-induced filament.

Excitonic Effects on the Linear and Nonlinear Optical Properties of Solid C60 Fullerene, Insights from Many-Body First-Principles Calculations

We perform the many-body Bethe-Salpeter equation eigenstates based sum-over-states calculations for the linear and nonlinear optical properties of solid C 60 fullerene. Excitonic and local field effects are included in the calculations. We calculate the one-photon absorption (OPA), third harmonic generation (THG), degenerate four-wave mixing (DFWM), and electric-field-induced second harmonic generation (ESHG) spectra of solid C 60 fullerene. The overall agreement between the theoretical and experimental results is good for all calculated spectra. The OPA spectrum shows that the solid C 60 fullerene has a large excitonic binding energy of 0.35 eV. The position and intensity of spectral peaks are modified significantly. By tracing the sum-over-states progress, we determine the type of nonlinear polarization resonances for the characteristic peaks of the THG process, which may clear up a discrepancy in two experimental results. The calculated DFWM spectrum is in excellent agreement with the available experimental results in terms of line shape and peak positions, and thus the two-photon absorption peaks can be well understood on the basis of the excitonic states of solid C 60 fullerene. The dynamic ESHG spectrum is given as a reference for the future experiment.

Unraveling the Electric Field-Induced Second Harmonic Generation Responses of Stilbazolium Ion Pairs Complexes in Solution Using a Multiscale Simulation Method.

The electric field-induced second harmonic generation (EFISHG) response has been largely used to describe the first β and the second γ hyperpolarizabilities in solution. Although the EFISHG technique cannot be applied to charged compounds (due to the external static electric field), it can be used to describe ion pairs as neutral complexes. A multiscale computational approach is required to generate representative geometrical configurations of such kinds of complexes (using classical force fields), to compute the electronic structure of each configuration (using quantum mechanics methods), and to perform statistical analyses describing the behavior of the nonlinear optical properties. In this work, we target solvated neutral ion pairs complexes, of which the cation is an organic chromophore, and we estimate their EFISHG and hyper-Rayleigh scattering responses. It is shown that the anion-cation relative spatial distribution determines the permanent dipole moment of the complexes, and therefore the relative distance controls the EFISHG response. On the other hand, the β tensor is independent of the dipole moment and it shows a weak linear correlation with the π-electron conjugation length of the cations. The γ contributions in the global EFISHG response range from 5% to 15%, which is mostly due to the variations of amplitude of the μβ∥ contribution, which results from differences in the μ and β vectors' orientations. The applied multiscale approach provides reasonable results compared with experimental ones, although additional efforts are still required to improve such comparison mainly to consider the possible dissociation effects.

Detection of voltage pulse width effect on charge accumulation in PSCs using EFISHG measurement

We report the effect of applied pulse width on charge accumulation in triple cation perovskite solar cells (PSCs) during the Electric Field Induced Second Harmonic Generation (EFISHG) measurements. The PSCs were prepared in the n-i-p structure using the layer-by-layer deposition technique. The triple cation perovskite precursor containing FAPbI3, MAPbBr3, and CsPbI3 was used to make the perovskite layer on the FTO/c-TiO2/mTiO2 substrates. Spiro OMeTAD was used as a hole transport material over the perovskite active layer, followed by the deposition of Au electrodes. The average power conversion efficiency (PCE) of the fabricated PSCs was 19.17 ± 0.02%. The electric field in the PSCs was selectively probed by the fundamental laser beam wavelength of 960 nm during the EFISHG measurements. Two different pulse widths (100 µs and 50 ms) of the applied potential were used in this study, with consideration of electrode charging and interface charging of PSCs. It has been observed that the pulse width of the applied electric field has a significant effect on the charge accumulation in the PSCs. Using the transient EFISHG measurements, it has also been found that the charging & discharging processes reversibly happen. However, the charging & discharging processes are influenced by remained charges at the interface in PSCs in the investigated triple cations PSCs. The EFISHG results can be well explained by using the Maxwell–Wagner model.