Sequential Two-photon Absorption Research Articles

Experimental demonstration of energy-transfer ratchet intermediate-band solar cell

A detailed balance calculation reveals an extremely high efficiency of 63.2% for intermediate-band solar cells (IBSCs) under maximum sunlight concentration. However, an actual IBSC device with an efficiency larger than the Shockley-Queisser (SQ) limit has so far not been reported. The main difficulties lie in realizing an efficient sequential two-photon absorption (STPA) which requires a sufficiently long lifetime intermediate state or intermediate band. In this article, we propose the concept of a ratchet type IBSC, utilizing a long lifetime of rare-earth ion luminescence centers in Erbium-doped GaAs. The temperature dependent differential external quantum efficiency reveals a significant STPA contribution originating from the Er3+ luminescence center. All the results were modeled and interpreted by integrating the ratchet effect with up-conversion along with a density functional theory (DFT) simulation. Our work demonstrates that the long lifetime energy-transfer mechanism in Er3+ centers contributes directly to the formation of a ratchet type IB.

Intensity-dependent two-photon absorption and its saturation in 2-methyl 4-nitroaniline nanofibers

The Nonlinear absorption and its optical limiting properties of 2-methyl 4-nitroaniline-polymethylmethacrylate (2M4NA-PMMA) electro-spun nanofibers are investigated by Z-scan technique using Q switched Nd:YAG laser as an excitation source (532 nm, 5 ns, 10 Hz). Open-aperture measurements show that 2M4NA-PMMA nanofibers exhibit reverse saturable absorption. Intensity-dependent two-photon absorption coefficient demonstrates the presence of sequential two-photon absorption process involving real resonant intermediate states. The incorporation and orientation of 2M4NA in PMMA nanofibers are analyzed by XRD and it is found to range from 38 nm to 43 nm of crystallite size. SEM images illustrate the formation of smooth fibers using electrospinning by applying different voltages (12, 14, 17 kV). Ground-state absorption analysis shows that the nanofibers possess maximum absorption around 400 nm with a optical transmittance window (410–1200 nm) in the wide range of entire visible and NIR region. Lower optical limiting threshold (0.97 to 1.79 × 1012 W/m2) of 2M4NA-PMMA nanofibers ensures the suitability of optical fibers as optical limiters towards the development of laser goggles for pulsed green laser.

Three-dimensional view of ultrafast dynamics in photoexcited bacteriorhodopsin

Bacteriorhodopsin (bR) is a light-driven proton pump. The primary photochemical event upon light absorption is isomerization of the retinal chromophore. Here we used time-resolved crystallography at an X-ray free-electron laser to follow the structural changes in multiphoton-excited bR from 250 femtoseconds to 10 picoseconds. Quantum chemistry and ultrafast spectroscopy were used to identify a sequential two-photon absorption process, leading to excitation of a tryptophan residue flanking the retinal chromophore, as a first manifestation of multiphoton effects. We resolve distinct stages in the structural dynamics of the all-trans retinal in photoexcited bR to a highly twisted 13-cis conformation. Other active site sub-picosecond rearrangements include correlated vibrational motions of the electronically excited retinal chromophore, the surrounding amino acids and water molecules as well as their hydrogen bonding network. These results show that this extended photo-active network forms an electronically and vibrationally coupled system in bR, and most likely in all retinal proteins.

A hot-carrier assisted InAs/AlGaAs quantum-dot intermediate-band solar cell

The intermediate-band assisted hot-carrier solar cell (IB-HCSC) concept has been proposed in order to assist the extraction of hot carriers from an absorber that has an intermediate band (IB). In this study, we used a heterostructure based on ten layers of In(Ga)As quantum dots (QDs) embedded in an Al0.2Ga0.8As single-junction solar cell designed for an intermediate band solar cell (IBSC). QD-IBSCs have proven to be limited by the thermal escape of photo-carriers from QDs at room temperature. In such cases, fundamental improvements in conversion efficiency are only possible if carriers in the IB are not in thermal equilibrium with either conduction or valence bands. Additionally, the IB-HCSC concept provides a high-efficiency limit and enables us to work with all relaxation mechanisms (thermalization, carrier-carrier scattering, and thermal radiation). Under high irradiation, we confirmed the emergence of a hot carrier population in the QDs, limited mostly by thermionic emission, which assists the IBSC by providing a thermoelectric gain in voltage without hindering the possibility of sequential two-photon absorption. Absolute intensity calibrated photoluminescence spectroscopy indicated that the triggering mechanism happens when the QD ensemble is estimated to have a high carrier concentration that behaves as a metal-like IB. Experimental results suggested that the hot carrier effect also occurred in other solar cells based on quantum heterostructures and directions for improvements of hot-carrier assisted QD-IBSCs are proposed for further efficiency gain in optimized device architectures.

Cross-section determination for one- and two-photon absorption of cobalt at hard-x-ray energies

For incident x-ray energies below the core level ionization threshold, one-photon absorption (OPA) leads to off-resonant x-ray excitations that are mediated by a virtual intermediate electronic state. In the linear regime of x-ray interaction, this intermediate state may decay radiatively and the maximum energy of the emitted photon is given by the initial and final atomic state as well as the energy of the incident photon. In the nonlinear excitation regime, however, this intermediate state may be depleted by a second x-ray absorption process as described in the sequential two-photon absorption (TPA) mechanism. Since the same intermediate state is involved in the OPA and TPA processes, the cross-section values for OPA and TPA are interconnected. We report on the determination of cross-section values for off-resonant excitation conditions, and show how the data can be used for estimating the TPA cross section in the sequential absorption mechanism. The determined off-resonant cross sections for cobalt exhibit a Lorentz-like energy-dependent behavior allowing for an energy-dependent description of the OPA and TPA cross sections with semiempirical models. The dependence of TPA cross sections on atomic number is discussed and different scaling laws are investigated. The effect of the lifetimes of a virtual intermediate state is also studied in relation to the incidence x-ray energy.

Photoreleasable Protecting Groups Triggered by Sequential Two-Photon Absorption of Visible Light: Release of Carboxylic Acids from a Linked Anthraquinone- N-Alkylpicolinium Ester Molecule.

A photoreleasable protecting group activated by sequential absorption of two visible photons is designed, synthesized, and tested. Specifically, an anthraquinone-based chromophore is covalently attached to an N-alkylpicolinium ester. Photolysis of this linked system results in the clean release of a corresponding carboxylic acid. Through product analysis, laser flash photolysis, and steady-state UV-vis spectroscopy, it is demonstrated that carboxylate ion release is affected by sequential absorption of two photons. The initial photochemical step results in reduction of an anthraquinone chromophore to the corresponding hydroquinone. The latter either reacts with O2 to regenerate the starting material, or absorption of a second photon causes an electron transfer to the picolinium group triggering C-O bond scission and release of the carboxylate.

Analysis of the intermediate-band absorption properties of type-II GaSb/GaAs quantum-dot photovoltaics

Quantum-dot (QD) intermediate-band (IB) materials are regarded as promising candidates for high-efficiency photovoltaics. The sequential two-step two-photon absorption processes that take place in these materials have been proposed to develop high-efficiency solar cells and infrared (IR) photodetectors. In this work, we experimentally and theoretically study the interrelation of the absorptivity with transitions of carriers to and from the IB in type-II GaSb/GaAs QD devices. Our devices exhibit three optical band gaps with: ${E}_{\mathrm{L}}=0.49\phantom{\rule{0.16em}{0ex}}\mathrm{eV},{E}_{\mathrm{H}}=1.02\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$, and ${E}_{\mathrm{G}}=1.52\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$, with the IB located 0.49 eV above the valence band. These values are well supported by semiempirical calculations of the QDs electronic structure. Through intensity-dependent two-photon photocurrent experiments, we are able to vary the filling state of the IB, thus modifying the absorptivity of the transitions to and from this band. By filling the IB with holes via $E=1.32\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$ or $E=1.93\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$ monochromatic illumination, we demonstrate an increase in the ${E}_{\mathrm{L}}$-related absorptivity of more than two orders of magnitude and a decrease in the ${E}_{\mathrm{H}}$-related absorptivity of one order of magnitude. The antisymmetrical evolution of those absorptivities is quantitatively explained by a photoinduced shift of the quasi-Fermi level of the IB. Furthermore, we report the observation of a two-photon photovoltage, i.e., the contribution of subband gap two-photon absorption to increase the open-circuit voltage of solar cells. We find that the generation of the two-photon photovoltage is related, in general, to the production of a two-photon photocurrent. However, while photons with energy close to ${E}_{\mathrm{L}}$ participate in the production of the two-photon photocurrent, they are not effective in the production of a two-photon photovoltage. We also report the responsivity of GaSb/GaAs QD devices performing as optically triggered photodetectors. These devices exhibit an amplification factor of almost 400 in the IR spectral region. This high value is achieved by minimizing---via doping---the absorptivity in the IR range of the QDs under equilibrium conditions.

Photoluminescence upconversion atGaAs/InGaP2interfaces driven by a sequential two-photon absorption mechanism

This paper reports on the results of an investigation into the nature of photoluminescence upconversion at GaAs/InGaP2 interfaces. Using a dual-beam excitation experiment, we demonstrate that the upconversion in our sample proceeds via a sequential two-photon optical absorption mechanism. Measurements of photoluminescence and upconversion photoluminescence revealed evidence of the spatial localization of carriers in the InGaP2 material, arising from partial ordering of the InGaP2. We also observed the excitation of a two-dimensional electron gas at the GaAs/InGaP2 heterojunction that manifests as a high-energy shoulder in the GaAs photoluminescence spectrum. Furthermore, the results of upconversion photoluminescence excitation spectroscopy demonstrate that the photon energy onset of upconversion luminescence coincides with the energy of the two-dimensional electron gas at the GaAs/InGaP2 interface, suggesting that charge accumulation at the interface can play a crucial role in the upconversion process.

Terahertz-visible two-photon rotational spectroscopy of coldOD−

We present a method to measure rotational transitions of molecular anions in the terahertz domain by sequential two-photon absorption. Ion excitation by bound-bound terahertz absorption is probed by absorption in the visible on a bound-free transition. The visible frequency is tuned to a state-selective photodetachment transition of the excited anions. This provides a terahertz action spectrum for just few hundred molecular ions. To demonstrate this we measure the two lowest rotational transitions, J=1<-0 and J =2<-1 of OD- anions in a cryogenic 22-pole trap. We obtain rotational transition frequencies of 598596.08(19) MHz for J=1<-0 and 1196791.57(27) MHz for J=2<-1 of OD-, in good agreement with their only previous measurement. This two-photon scheme opens up terahertz rovibrational spectroscopy for a range of molecular anions, in particular for polyatomic and cluster anions.

Insights on proximity effect and multiphoton induced luminescence from gold nanospheres in far field optical microscopy

Gold nanoparticles can be visualized in far-field multiphoton laser-scanning microscopy (MPM) based on the phenomena of multiphoton induced luminescence (MIL). This is of interest for biomedical applications, e.g., for cancer diagnostics, as MPM allows for working in the near-infrared (NIR) optical window of tissue. It is well known that the aggregation of particles causes a redshift of the plasmon resonance, but its implications for MIL applying far-field MPM should be further exploited. Here, we explore MIL from 10 nm gold nanospheres that are chemically deposited on glass substrates in controlled coverage gradients using MPM operating in NIR range. The substrates enable studies of MIL as a function of inter-particle distance and clustering. It was shown that MIL was only detected from areas on the substrates where the particle spacing was less than one particle diameter, or where the particles have aggregated. The results are interpreted in the context that the underlying physical phenomenon of MIL is a sequential two-photon absorption process, where the first event is driven by the plasmon resonance. It is evident that gold nanospheres in this size range have to be closely spaced or clustered to exhibit detectable MIL using far-field MPM operating in the NIR region.

Establishing the Two-Photon Linkage Isomerization Mechanism in the Nitrosyl Complex trans-[RuCl(NO)(py)4](2+) by DFT and TDDFT.

The density functional theory calculations presented in this work allow the first rationalization of the full linkage photoisomerization mechanism of trans-[RuCl(NO)(py)4](2+), in both the forward and reverse directions. These mechanisms are consistent with the experimental data establishing that blue-light irradiation triggers the forward process, while red or IR photons trigger the reverse process. Characterization of the singlet and lowest triplet potential energy surfaces shows that, despite the unfavorable thermodynamic character of the forward process, the topologies of the surfaces and particularly some crucial surface crossings enable the isomerization. In the forward Ru-NO → Ru-ON direction, a sequential two-photon absorption mechanism is unraveled that involves a sideways-bonded metastable state. In contrast, in the reverse reaction, two mechanisms are proposed involving either one or two photons.

Molecular interferometer using XUV attosecond pulses to unravel electron and nuclear dynamics

SynopsisTwo identical XUV attosecond pulses interact with the hydrogen molecule creating an interferometer resulting from the direct and sequential two-photon absorption paths reaching the same final ionized states. The dependence of the ionization yields with the time delay between the pulses allows to reconstruct the pumped vibronic (electronic and vibrational) wave packet created in the singly excited states of the molecule. The use of XUV pulses avoids a laser-induced distortion of the molecular potential, ensuring the characterization of the intrinsic behaviour of the system.

Photoelectron angular distributions for the two-photon sequential double ionization of xenon by ultrashort extreme ultraviolet free electron laser pulses

Xenon atoms are double-ionized by sequential two-photon absorption by ultrashort extreme ultraviolet free-electron laser pulses with a photon energy of 23.0 and 24.3 eV, produced by the SPring-8 Compact SASE Source test accelerator. The angular distributions of photoelectrons generated by two-photon double ionization are obtained using velocity map imaging. The results are reproduced reasonably well by the present theoretical calculations within the multi-configurational Dirac–Fock approach.

Homogeneous broadening effect on temperature dependence of green upconversion luminescence in erbium doped fibers

We study the green upconversion luminescence of Er3+ ions in an aluminosilicate optical fiber upon near infrared excitation at 787nm. The dependence of the upconversion luminescence on temperature has been determined. As temperature drops from room to cryogenic temperatures, the upconversion green emission reaches a maximum around 40K, and then decreases. A nearly quadratic dependence of the upconversion luminescence with excitation power is found, which is consistent with a sequential stepwise two-photon absorption process. These results have been explained with a semiclassical model that considers the inhomogeneous broadening of the optical transitions due to glass imperfections, and the dependence of the homogeneous linewidth broadening on temperature.

X-Ray FEL-induced Double Core-Hole Formation in Polyatomic Molecules

We use extremely intense, ultrashort soft X-Ray pulses generated by the LCLS X-Ray Free Electron Laser to investigate the production of molecular double core-hole states by sequential two-photon X-Ray absorption. The effect of critical LCLS parameters such as the number of photons per pulse, the pulse duration, and the focal spot size on the photoelectron and Auger spectra is modeled in detail and the results of these simulations are used as an aid in the interpretation of the experimental spectra obtained. The emphasis is on double core-hole formation in small polyatomic molecules such as CO2.

Synthesis of TiO2 nanoparticles and spectroscopic upconversion luminescence of Nd3+-doped TiO2–SiO2 composite glass

Nd3+-doped TiO2–SiO2 composites were prepared by sol–gel method. Optical properties such as radiative life-time (τ), stimulated emission cross-section (σp) and branching ratio (β) were calculated using Judd–Ofelt theory. Violet to blue upconversion emissions at 380nm (4D3/2→4I11/2), 399nm (2P3/2→4I11/2), 420nm (2D5/2→4I9/2) and 452nm (2P3/2→4I13/2) were obtained under 578nm xenon-lamp excitation. The choice of 578nm is justified by the absorption spectra of the same samples, which shows a strong absorption peak at 578nm. This 578nm excitation pump produces upconversion in Nd3+ by a sequential two-photon absorption process.

Interpretation of the photoelectron spectra of superalkali species: Li3O and Li3O−

The present paper deals with the interpretation of the photoelectron spectrum of the Li(3)O(-). After several failed attempts to attribute all of the observed peaks in the experimental spectrum to anionic species, neutral species were considered assuming a sequential two-photon absorption mechanism. We find that only two of the six observed peaks can be attributed to photodetachments and that all other observed features can be assigned to ionizations from the ground and excited states of the neutral. Nuclear distributions other than three lithium atoms surrounding the oxygen are not likely to be stable. The interpretation of the experimental peak located at about 1.2 eV remains challenging. It can either be attributed to the second electron detachment (involving the HOMO -1 orbital) energy from the anion's triplet C(2v) state or to higher excited states (involving HOMO +10, 11, 12... orbitals) of the neutral species. Furthermore, we have examined the influence of vibrational displacements on the location of the observed peaks. We find that this effect is smaller than 0.05 eV and, therefore, must be considered as negligible.

Double-core-hole spectroscopy for chemical analysis with an intense X-ray femtosecond laser

Theory predicts that double-core-hole (DCH) spectroscopy can provide a new powerful means of differentiating between similar chemical systems with a sensitivity not hitherto possible. Although DCH ionization on a single site in molecules was recently measured with double- and single-photon absorption, double-core holes with single vacancies on two different sites, allowing unambiguous chemical analysis, have remained elusive. Here we report that direct observation of double-core holes with single vacancies on two different sites produced via sequential two-photon absorption, using short, intense X-ray pulses from the Linac Coherent Light Source free-electron laser and compare it with theoretical modeling. The observation of DCH states, which exhibit a unique signature, and agreement with theory proves the feasibility of the method. Our findings exploit the ultrashort pulse duration of the free-electron laser to eject two core electrons on a time scale comparable to that of Auger decay and demonstrate possible future X-ray control of physical inner-shell processes.

Transient Absorption for Characterization of Quantum Dot Intermediate Band Solar Cells

ABSTRACTWe use transient absorption methods to characterize the sequential two-photon absorption in a quantum-dot super-lattice based intermediate band solar cell (QD-IBSC). Using collinear, orthogonally polarized beams generated from an Optical Parametric Oscillator (OPO) at varying time delay, tuned stepwise from 1050nm to 1250nm, we use the solar cell photocurrent as a direct measure of the transient absorption by measuring the differential photo-current as a function of time delay between two energetically degenerate, 100fs pulses. For comparison, we measure the pulse autocorrelation in the same geometry using a GaAsP photodiode, where all observed photocurrent is derived from instantaneous two-photon absorption. Our measurements show that at high intensity, the measurement is dominated by instantaneous two photon absorption, with a simultaneous sequential two-photon photocurrent which persists beyond the pulse overlap. Our measurements demonstrate the method can reveal carrier dynamics in a working QD-IBSC, and their dependence on energy. The method could potentially give details of the band structure formed in the QD-IBSC. Such knowledge may benefit device development and future designs of IBSCs based on QD superlattices or alternative intermediate band materials or device structures.

The use of the green emission inEr3+-dopedCaF2 crystals for thermometry application

We report here the use of the green upconversion emissions originating from the thermally coupledlevels 2H11/2 and 4S3/2 of the Er3+ ion in CaF2:Er (0.01 at.%) for thermometry application in the range 303–423 K. The mechanismresponsible for excitation of the green emitting levels is a sequential two-photonabsorption process. The fluorescence intensity ratio (FIR) of the green upconversionemissions at wavelengths of about 519 and 551 nm is studied as a function oftemperature in the range 303–423 K using a 634 nm tunable dye laser as anexcitation source. It is found that the logarithm of the FIR varies linearly withthe inverse of temperature. The gap between the two thermally coupled levels 4S3/2 and 2H11/2 was determinedto be about 721 cm−1. This value is in good agreement with that found by spectroscopic investigations. Thecalibration curve is established, and the temperature is calculated.