Giant Third-Order Nonlinear Response of Mixed Perovskite Nanocrystals

Mixed (FAPbI3)₀.₉₂(MAPbBr3)₀.₀₈ perovskite thin films exhibit strong nonlinear optical responses, rendering them promising candidates for applications in photonics and optical communications. In this work, we present a systematic study on the ultrafast third-order nonlinear optical processes in mixed perovskite nanocrystals (NCs) by exploring the generation of third harmonic radiation and giant two-photon absorption-based photoluminescence (PL) when excited by femtosecond laser pulses of a 1030 nm central wavelength. A comparative analysis of the coherent third harmonic generation in the thin-film-containing perovskite nanocrystals has shown a 40× enhancement of the third harmonic signal compared to the signal generated in the pure quartz substrate. The cubic dependence of the third-nonlinear optical response of the (FAPbI₃)₀.₉₂(MAPbBr₃)₀.₀₈ perovskites on the intensity of the driving radiation was identified using broadband 38 femtosecond driving pulses. The positive nonlinear refractive index (γ = +1.4 × 10⁻¹² cm²·W⁻¹) is found to play an important role in improving the phase-matching conditions of the interacting pulses by generating a strong third order harmonic. The giant two-photon absorption (TPA)-assisted PL peak was monitored and a blue shift of the PL was obtained in the higher intensity range of the laser pulses, with the absorption coefficient β estimated to be~+7.0 cm·MW⁻¹ at a 1030 nm laser wavelength.     

Phase matching of high harmonic generation in the soft and hard X-ray regions of the spectrum

We show how bright, tabletop, fully coherent hard X-ray beams can be generated through nonlinear upconversion of femtosecond laser light. By driving the high-order harmonic generation process using longer-wavelength midinfrared light, we show that, in theory, fully phase-matched frequency upconversion can extend into the hard X-ray region of the spectrum. We verify our scaling predictions experimentally by demonstrating phase matching in the soft X-ray region of the spectrum around 330 eV, using ultrafast driving laser pulses at 1.3-μm wavelength, in an extended, high-pressure, weakly ionized gas medium. We also show through calculations that scaling of the overall conversion efficiency is surprisingly favorable as the wavelength of the driving laser is increased, making tabletop, fully coherent, multi-keV X-ray sources feasible. The rapidly decreasing microscopic single-atom yield, predicted for harmonics driven by longer-wavelength lasers, is compensated macroscopically by an increased optimal pressure for phase matching and a rapidly decreasing reabsorption of the generated X-rays.     

Single-electron pulses for ultrafast diffraction

Visualization of atomic-scale structural motion by ultrafast electron diffraction and microscopy requires electron packets of shortest duration and highest coherence. We report on the generation and application of single-electron pulses for this purpose. Photoelectric emission from metal surfaces is studied with tunable ultraviolet pulses in the femtosecond regime. The bandwidth, efficiency, coherence, and electron pulse duration are investigated in dependence on excitation wavelength, intensity, and laser bandwidth. At photon energies close to the cathode's work function, the electron pulse duration shortens significantly and approaches a threshold that is determined by interplay of the optical pulse width and the acceleration field. An optimized choice of laser wavelength and bandwidth results in sub-100-fs electron pulses. We demonstrate single-electron diffraction from polycrystalline diamond films and reveal the favorable influences of matched photon energies on the coherence volume of single-electron wave packets. We discuss the consequences of our findings for the physics of the photoelectric effect and for applications of single-electron pulses in ultrafast 4D imaging of structural dynamics.     

Coherent Fano resonances in a plasmonic nanocluster enhance optical four-wave mixing

Plasmonic nanoclusters, an ordered assembly of coupled metallic nanoparticles, support unique spectral features known as Fano resonances due to the coupling between their subradiant and superradiant plasmon modes. Within the Fano resonance, absorption is significantly enhanced, giving rise to highly localized, intense near fields with the potential to enhance nonlinear optical processes. Here, we report a structure supporting the coherent oscillation of two distinct Fano resonances within an individual plasmonic nanocluster. We show how this coherence enhances the optical four-wave mixing process in comparison with other double-resonant plasmonic clusters that lack this property. A model that explains the observed four-wave mixing features is proposed, which is generally applicable to any third-order process in plasmonic nanostructures. With a larger effective susceptibility χ⁽³⁾ relative to existing nonlinear optical materials, this coherent double-resonant nanocluster offers a strategy for designing high-performance third-order nonlinear optical media.     

Generation of ultra-intense single-cycle laser pulses by using photon deceleration

A scheme to generate single-cycle laser pulses is presented based on photon deceleration in underdense plasmas. This robust and tunable process is ideally suited for lasers above critical power because it takes advantage of the relativistic self-focusing of these lasers and the nonlinear features of the plasma wake. The mechanism is demonstrated by particle-in-cell simulations in three and 2(1/2) dimensions, resulting in pulse shortening up to a factor of 4, thus making it feasible to generate few-femtosecond single-cycle pulses in the optical to IR domain with intensities I > 10(20) W/cm(2) by using present-day laser technology.     

Coherence brightened laser source for atmospheric remote sensing

We have studied coherent emission from ambient air and demonstrated efficient generation of laser-like beams directed both forward and backward with respect to a nanosecond ultraviolet pumping laser beam. The generated optical gain is a result of two-photon photolysis of atmospheric O₂, followed by two-photon excitation of atomic oxygen. We have analyzed the temporal shapes of the emitted pulses and have observed very short duration intensity spikes as well as a large Rabi frequency that corresponds to the emitted field. Our results suggest that the emission process exhibits nonadiabatic atomic coherence, which is similar in nature to Dicke superradiance where atomic coherence is large and can be contrasted with ordinary lasing where atomic coherence is negligible. This atomic coherence in oxygen adds insight to the optical emission physics and holds promise for remote sensing techniques employing nonlinear spectroscopy.     

Attosecond electron pulses for 4D diffraction and microscopy

In this contribution, we consider the advancement of ultrafast electron diffraction and microscopy to cover the attosecond time domain. The concept is centered on the compression of femtosecond electron packets to trains of 15-attosecond pulses by the use of the ponderomotive force in synthesized gratings of optical fields. Such attosecond electron pulses are significantly shorter than those achievable with extreme UV light sources near 25 nm ( approximately 50 eV) and have the potential for applications in the visualization of ultrafast electron dynamics, especially of atomic structures, clusters of atoms, and some materials.     

Structural Analysis of Low Defect Ammonothermally Grown GaN Wafers by Borrmann Effect X-ray Topography

X-ray topography defect analysis of entire 1.8-inch GaN substrates, using the Borrmann effect, is presented in this paper. The GaN wafers were grown by the ammonothermal method. Borrmann effect topography of anomalous transmission could be applied due to the low defect density of the substrates. It was possible to trace the process and growth history of the GaN crystals in detail from their defect pattern imaged. Microscopic defects such as threading dislocations, but also macroscopic defects, for example dislocation clusters due to preparation insufficiency, traces of facet formation, growth bands, dislocation walls and dislocation bundles, were detected. Influences of seed crystal preparation and process parameters of crystal growth on the formation of the defects are discussed.     

The Characterization of Fatigue Damage of 316L Stainless Steel Parts Formed by Selective Laser Melting with Harmonic Generation Technique

Fatigue damage is the main reason for the failure of parts formed by selective laser melting (SLM) technology. This paper presents a high-order, harmonic, and nonlinear ultrasonic testing system for monitoring the generation and evolution of fatigue damage in SLM 316L stainless steel parts. The results demonstrate that the normalized ultrasonic, nonlinear coefficients show a significant dependence on the degree of fatigue damage of the tested specimen and that the normalized, ultrasonic, and nonlinear coefficients are effective in characterizing the degree of fatigue damage in SLM 316L stainless steel parts. Transmission electron microscope (TEM) and scanning electron microscope (SEM) analyses show that the variation in the normalized, ultrasonic, nonlinear coefficients reflect the generation and evolution process of dislocation and crack in the fatigue process of SLM 316L stainless steel specimens, and reveal the fatigue damage mechanism of SLM 316L stainless steel parts.     

Label-free live brain imaging and targeted patching with third-harmonic generation microscopy

The ability to visualize neurons inside living brain tissue is a fundamental requirement in neuroscience and neurosurgery. Especially the development of a noninvasive probe of brain morphology with micrometer-scale resolution is highly desirable, as it would provide a noninvasive approach to optical biopsies in diagnostic medicine. Two-photon laser-scanning microscopy (2PLSM) is a powerful tool in this regard, and has become the standard for minimally invasive high-resolution imaging of living biological samples. However, while 2PLSM-based optical methods provide sufficient resolution, they have been hampered by the requirement for fluorescent dyes to provide image contrast. Here we demonstrate high-contrast imaging of live brain tissue at cellular resolution, without the need for fluorescent probes, using optical third-harmonic generation (THG). We exploit the specific geometry and lipid content of brain tissue at the cellular level to achieve partial phase matching of THG, providing an alternative contrast mechanism to fluorescence. We find that THG brain imaging allows rapid, noninvasive label-free imaging of neurons, white-matter structures, and blood vessels simultaneously. Furthermore, we exploit THG-based imaging to guide micropipettes towards designated neurons inside live tissue. This work is a major step towards label-free microscopic live brain imaging, and opens up possibilities for the development of laser-guided microsurgery techniques in the living brain.     

Monitoring molecular dynamics using coherent electrons from high harmonic generation

We report a previously undescribed spectroscopic probe that makes use of electrons rescattered during the process of high-order harmonic generation. We excite coherent vibrations in SF(6) using impulsive stimulated Raman scattering with a short laser pulse. A second, more intense laser pulse generates high-order harmonics of the fundamental laser, at wavelengths of approximately 20-50 nm. The high-order harmonic yield is observed to oscillate, at frequencies corresponding to all of the Raman-active modes of SF(6), with an asymmetric mode most visible. The data also show evidence of relaxation dynamics after impulsive excitation of the molecule. Theoretical modeling indicates that the high harmonic yield should be modulated by both Raman and infrared-active vibrational modes. Our results indicate that high harmonic generation is a very sensitive probe of vibrational dynamics and may yield more information simultaneously than conventional ultrafast spectroscopic techniques. Because the de Broglie wavelength of the recolliding electron is on the order of interatomic distances, i.e., approximately 1.5 A, small changes in the shape of the molecule lead to large changes in the high harmonic yield. This work therefore demonstrates a previously undescribed spectroscopic technique for probing ultrafast internal dynamics in molecules and, in particular, on the chemically important ground-state potential surface.     

Temporal lenses for attosecond and femtosecond electron pulses

Here, we describe the “temporal lens” concept that can be used for the focus and magnification of ultrashort electron packets in the time domain. The temporal lenses are created by appropriately synthesizing optical pulses that interact with electrons through the ponderomotive force. With such an arrangement, a temporal lens equation with a form identical to that of conventional light optics is derived. The analog of ray diagrams, but for electrons, are constructed to help the visualization of the process of compressing electron packets. It is shown that such temporal lenses not only compensate for electron pulse broadening due to velocity dispersion but also allow compression of the packets to durations much shorter than their initial widths. With these capabilities, ultrafast electron diffraction and microscopy can be extended to new domains,and, just as importantly, electron pulses can be delivered directly on an ultrafast techniques target specimen.     

Aggregation Induced Emission and Nonlinear Optical Properties of an Intramolecular Charge-Transfer Compound

Intramolecular charge transfer (ICT) compounds have attracted wide attention for their potential applications in optoelectronic materials and devices such as fluorescent sensors, dye-sensitized solar cells, organic light emitting diodes and nonlinear optics. In this work, we have synthesized a new ICT compound, dimethyl-[4-(7-nitro-benzo[1,2,5]thiadiazol-4-yl)-phenyl]-amine (BTN), and have fabricated it into low dimensional micro/nano structures with well-defined morphologies. These self-assembled nanostructures exhibit high efficiency solid state fluorescence via an aggregation induced emission mechanism, which overcomes the defect of fluorescence quenching caused by aggregation in the solid state of traditional luminescent materials. We also explored and studied the nonlinear optical properties of this material through the Z-scan method, and found that this material exhibits large third-order nonlinear absorption and refraction coefficients, which promises applications of the materials in the fields of nonlinear optics and optoelectronics.     

Strained Silicon Photonics

A review of recent progress in the field of strained silicon photonics is presented. The application of strain to waveguide and photonic crystal structures can be used to alter the linear and nonlinear optical properties of these devices. Here, methods for the fabrication of strained devices are summarized and recent examples of linear and nonlinear optical devices are discussed. Furthermore, the relation between strain and the enhancement of the second order nonlinear susceptibility is investigated, which may enable the construction of optically active photonic devices made of silicon.     

Breaking resolution limits in ultrafast electron diffraction and microscopy

Ultrafast electron microscopy and diffraction are powerful techniques for the study of the time-resolved structures of molecules, materials, and biological systems. Central to these approaches is the use of ultrafast coherent electron packets. The electron pulses typically have an energy of 30 keV for diffraction and 100-200 keV for microscopy, corresponding to speeds of 33-70% of the speed of light. Although the spatial resolution can reach the atomic scale, the temporal resolution is limited by the pulse width and by the difference in group velocities of electrons and the light used to initiate the dynamical change. In this contribution, we introduce the concept of tilted optical pulses into diffraction and imaging techniques and demonstrate the methodology experimentally. These advances allow us to reach limits of time resolution down to regimes of a few femtoseconds and, possibly, attoseconds. With tilted pulses, every part of the sample is excited at precisely the same time as when the electrons arrive at the specimen. Here, this approach is demonstrated for the most unfavorable case of ultrafast crystallography. We also present a method for measuring the duration of electron packets by autocorrelating electron pulses in free space and without streaking, and we discuss the potential of tilting the electron pulses themselves for applications in domains involving nuclear and electron motions.     

Generation of bright isolated attosecond soft X-ray pulses driven by multicycle midinfrared lasers

High harmonic generation driven by femtosecond lasers makes it possible to capture the fastest dynamics in molecules and materials. However, to date the shortest subfemtosecond (attosecond, 10⁻¹⁸ s) pulses have been produced only in the extreme UV region of the spectrum below 100 eV, which limits the range of materials and molecular systems that can be explored. Here we experimentally demonstrate a remarkable convergence of physics: when midinfrared lasers are used to drive high harmonic generation, the conditions for optimal bright, soft X-ray generation naturally coincide with the generation of isolated attosecond pulses. The temporal window over which phase matching occurs shrinks rapidly with increasing driving laser wavelength, to the extent that bright isolated attosecond pulses are the norm for 2-µm driving lasers. Harnessing this realization, we experimentally demonstrate the generation of isolated soft X-ray attosecond pulses at photon energies up to 180 eV for the first time, to our knowledge, with a transform limit of 35 attoseconds (as), and a predicted linear chirp of 300 as. Most surprisingly, advanced theory shows that in contrast with as pulse generation in the extreme UV, long-duration, 10-cycle, driving laser pulses are required to generate isolated soft X-ray bursts efficiently, to mitigate group velocity walk-off between the laser and the X-ray fields that otherwise limit the conversion efficiency. Our work demonstrates a clear and straightforward approach for robustly generating bright isolated attosecond pulses of electromagnetic radiation throughout the soft X-ray region of the spectrum.High-order harmonic generation (HHG) is the most extreme nonlinear optical process in nature, making it possible to coherently upconvert intense femtosecond laser light to much shorter wavelengths (1, 2). High harmonics are radiated as a result of a coherent electron recollision process that occurs each half-cycle of the driving laser field while an atom is undergoing strong-field ionization. The short pulse duration of HHG (which must be shorter than the driving laser pulse) has made it possible to directly access the fastest timescales relevant to electron dynamics in atoms, molecules, and materials. The unique properties of attosecond HHG in the extreme UV (EUV) have uncovered new understanding of fundamental processes in atoms, molecules, plasmas, and materials, including the timescales on which electrons are emitted from atoms (3), the timescale for spin–spin and electron–electron interactions (4, 5), the timescale that determines molecular dissociation and electron localization (6–9), the timescale and mechanisms for spin and energy transport in nanosystems (10–12), as well as new capabilities to implement EUV microscopes with wavelength-limited spatial resolution (13).The temporal structure of HHG is related to the number of times a high-energy electron undergoes a coherent recollision process, as well as the time window over which bright harmonics emerge. Using multicycle 0.8-µm driving lasers, HHG generally emerges as a train of attosecond (as) pulses (14, 15) corresponding to a series of harmonic peaks in frequency space. This emission can narrow to a single isolated as burst when the driving laser field is a few optical cycles (∼5 fs) in duration (16, 17), with an associated broad continuous spectrum. Other techniques can isolate a single burst using a combination of multicolor fields and polarization control (18–26) or spatial lighthouse gating of the driving laser pulses (27, 28). Phase matching can also result in bright isolated as pulse generation for short driving laser pulses (29, 30). To obtain bright, phase-matched, high harmonic beams, the laser and HHG fields must both propagate at the speed of light c so that emission from many atoms interferes constructively. Above a critical ionization level, the phase velocity of the laser exceeds c, which terminates the HHG temporal emission. The chirp present on attosecond bursts can be compensated by using thin materials, gases, or chirped mirrors (31–33). To date, however, most schemes for creating isolated attosecond pulses require either very short-duration few-cycle 0.8-µm driving laser pulses that are difficult to reliably generate, or complex polarization modulation schemes. In addition, the carrier envelope phase (CEP) of the driving laser pulse must be stabilized.A more general understanding of how to efficiently sculpt the temporal, spatial, and spectral characteristics of HHG emission over an extremely broad photon energy range (from the EUV to the keV and higher) has emerged in recent years (34–39). This understanding is critical both for a fundamental understanding of strong-field quantum physics, as well as for applications which have fundamentally different needs in terms of the HHG pulse duration, spectral bandwidth, and flux. By considering both the microscopic single-atom response as well as the macroscopic coherent buildup of HHG, efficient phase-matched HHG can now be implemented from the EUV to >keV photon energies, simply by driving HHG with midinfrared (mid-IR) femtosecond driving lasers. This advance represents, to our knowledge, the first general-purpose, tabletop, coherent soft X-ray light source (39). Furthermore, theory suggested that bright isolated attosecond X-ray bursts would be achievable using multicycle mid-IR driving lasers in a phase-matched geometry (35). However, the low repetition rate of the driving lasers precluded experimental testing of these predictions. Moreover, formidable computation requirements meant that advanced simulations could not be fully extended into the mid-IR region at 2–4 µm.In this paper, we experimentally demonstrate a beautiful convergence of physics for mid-IR (2-µm) driving lasers by showing that the conditions for optimal bright, soft X-ray generation naturally coincide with the generation of bright isolated attosecond soft X-ray bursts. We combine advanced theory with a novel experimental method equivalent to high-resolution Fourier transform spectroscopy to measure bright, attosecond soft X-ray pulses for the first time, to our knowledge. Specifically, we measure a field autocorrelation pulse width of 70 as, corresponding to a transform-limited 35-as pulse, that is supported by a coherent supercontinuum spectrum extending to photon energies around 180 eV. We also validate experimentally, for the first time, to our knowledge, the most intuitive dynamic picture of phase matching of HHG in the time domain by clearly demonstrating that the temporal window during which phase matching occurs shrinks rapidly with increasing driving laser wavelength. Finally, we show through advanced theory that the isolated attosecond pulse is chirped to 300 as. Most surprisingly, we find that bright attosecond pulse generation in the soft X-ray region requires the use of longer-duration, multicycle, mid-IR driving lasers to mitigate group velocity walk-off issues that would otherwise reduce the conversion efficiency. By harnessing the beautiful physics of phase matching, this work represents the simplest and most robust scheme for attosecond soft X-ray pulse generation, and will make attosecond science and technology accessible to a broader community.     

Stimulated Raman photoacoustic imaging

Achieving label-free, molecular-specific imaging with high spatial resolution in deep tissue is often considered the grand challenge of optical imaging. To accomplish this goal, significant optical scattering in tissues has to be overcome while achieving molecular specificity without resorting to extrinsic labeling. We demonstrate the feasibility of developing such an optical imaging modality by combining the molecularly specific stimulated Raman excitation with the photoacoustic detection. By employing two ultrashort excitation laser pulses, separated in frequency by the vibrational frequency of a targeted molecule, only the specific vibrational level of the target molecules in the illuminated tissue volume is excited. This targeted optical absorption generates ultrasonic waves (referred to as stimulated Raman photoacoustic waves) which are detected using a traditional ultrasonic transducer to form an image following the design of the established photoacoustic microscopy.     

Nonexponential fluorescence decay of aqueous tryptophan and two related peptides by picosecond spectroscopy

Time-resolved fluorescence spectroscopy of tryptophan and two related dipeptides, tryptophylalanine and alanyltryptophan, has been carried out on the subnanosecond time scale by using picosecond exciting pulses at a wavelength of 264 nm. Detection was with an ultrafast streak camera coupled to an optical multichannel analyzer. The zwitterions of these molecules show a definite nonexponential fluorescence decay which can be analyzed in terms of two exponentials. The two decay rates increase strongly with increasing temperature, as does the weight of the faster component. In tryptophan at pH 11, where the amino group is deprotonated, there remains only a single temperature-dependent exponential. The results are interpreted in terms of two kinds of trapped conformers in the excited state that interconvert no quicker than the time scale of the fluorescence. A model is suggested in which the nonradiative processes in one conformer approximate those in the bare indole moiety. The nonradiative decay rate of the other conformer is substantially faster. It is believed that the process responsible for this fast decay is intramolecular electron transfer from the indole to the amino acid side chain. The predilection for this electron transfer depends on steric relationships as well as on the electron-attracting power of the carbonyl group. This picture is consistent with earlier fluorescence quantum yield results. In fact, a self-consistent picture emerges from the temporal and yield data that quantitatively explains most important facets of tryptophan photochemistry in aqueous solution.     

Standoff spectroscopy via remote generation of a backward-propagating laser beam

In an earlier publication we demonstrated that by using pairs of pulses of different colors (e.g., red and blue) it is possible to excite a dilute ensemble of molecules such that lasing and/or gain-swept superradiance is realized in a direction toward the observer. This approach is a conceptual step toward spectroscopic probing at a distance, also known as standoff spectroscopy. In the present paper, we propose a related but simpler approach on the basis of the backward-directed lasing in optically excited dominant constituents of plain air, N(2) and O(2). This technique relies on the remote generation of a weakly ionized plasma channel through filamentation of an ultraintense femtosecond laser pulse. Subsequent application of an energetic nanosecond pulse or series of pulses boosts the plasma density in the seed channel via avalanche ionization. Depending on the spectral and temporal content of the driving pulses, a transient population inversion is established in either nitrogen- or oxygen-ionized molecules, thus enabling a transient gain for an optical field propagating toward the observer. This technique results in the generation of a strong, coherent, counterpropagating optical probe pulse. Such a probe, combined with a wavelength-tunable laser signal(s) propagating in the forward direction, provides a tool for various remote-sensing applications. The proposed technique can be enhanced by combining it with the gain-swept excitation approach as well as with beam shaping and adaptive optics techniques.