Persistence of Spin Coherence in a Crystalline Environment.

We analyze quantum interference in the triplet-exciton pair generated by singlet exciton fission in a molecular crystal and introduce transport-induced dephasing (TID) as a key effect that can suppress the expected fluorescence quantum beats when the triplet-exciton wave function can localize on inequivalent sites. TID depends on the triplet-exciton hopping rate between inequivalent sites and on the energy shifts among the stationary states of the entangled triplet pair in different spatial configurations. The theoretical model is confirmed by experiments in rubrene single crystals, where triplet pairs remain entangled for more than 50 ns but quantum beats are suppressed by TID within a few nanoseconds when the magnetic field is misaligned by just a few degrees from specific symmetric directions. Our experiments deliver the zero-field parameters for the rubrene molecule in its orthorhombic lattice and information on triplet-exciton transport, in particular, the triplet-exciton hopping rate between inequivalent sites, which we evaluate to be of the order of 150 ps in rubrene.

Electrically poled vapor-deposited organic glasses for integrated electro-optics.

We introduce electrically poled small molecule assemblies that can serve as the active electro-optic material in nano-scale guided-wave circuits such as those of the silicon photonics platform. These monolithic organic materials can be vacuum-deposited to homogeneously fill nanometer-size integrated-optics structures, and electrically poled at higher temperatures to impart an orientational non-centrosymmetric order that remains stable at room temperature. An initial demonstration using the DDMEBT molecule and corona poling delivered a material with the required high optical quality, an effective glass transition temperature of the order of ∼80°C, and an electro-optic coefficient of 20 pm/V.

The Appeal of Small Molecules for Practical Nonlinear Optics.

Small organic molecules with a π-conjugated system that consists of only a few double or triple bonds can have significantly smaller optical excitation energies when equipped with donor and acceptor groups, which raises the quantum limits to the molecular polarizabilities. As a consequence, third-order nonlinear optical polarizabilities become orders of magnitude larger than those of molecules of similar size without donor-acceptor substitution. This enables strong third-order nonlinear optical effects (as high as 1000 times those of silica glass) in dense, amorphous monolithic assemblies. These properties, accompanied by the possibility of deposition from the vapor phase and of electric-field poling at higher temperatures, make the resulting materials competitive towards adding an active nonlinear optical or electro-optic functionality to state-of-the-art integrated photonics platforms.

Dielectrophoresis and colloidal phase transitions for ultra-broadband optical limiting.

We demonstrate wavelength-independent optical limiting based on colloidal phase transitions induced by the dielectrophoretic force from focused electromagnetic radiation. The focused radiation acts as an optical trap that increases the particle density. The increased density then leads to a colloidal gas-solid phase transition and an aggregate that effectively blocks the incoming radiation when it passes a threshold power. The process is reversible, with the colloidal particles returning to a homogenous distribution after the incoming radiation is removed. We demonstrate the effect using polystyrene nanoparticles mixed with pluronics and polyethylene glycol polymers in low-concentration KCl salt solutions. We observe the light-induced phase separation under confocal fluorescent microscope, and we provide a proof-of-principle demonstration of optical limiting using a 100 µm thick colloid cell.

Introduction: Nonlinear Optics (NLO) 2017 feature issue.

The editors introduce the feature issue on "Nonlinear Optics 2017," based on the topics presented at the NLO 2017 conference, which was held in Waikoloa, Hawaii, USA from July 17-21, 2017. This feature issue is jointly published by Optics Express and Optical Materials Express.

Formation and dynamics of "waterproof" photoluminescent complexes of rare earth ions in crowded environment.

Understanding behavior of rare-earth ions (REI) in crowded environments is crucial for several nano- and bio-technological applications. Evolution of REI photoluminescence (PL) in small compartments inside a silica hydrogel, mimic to a soft matter bio-environment, has been studied and explained within a solvation model. The model uncovered the origin of high PL efficiency to be the formation of REI complexes, surrounded by bile salt (DOC) molecules. Comparative study of these REI-DOC complexes in bulk water solution and those enclosed inside the hydrogel revealed a strong correlation between an up to 5×-longer lifetime of REIs and appearance of the DOC ordered phase, further confirmed by dynamics of REI solvation shells, REI diffusion experiments and morphological characterization of microstructure of the hydrogel.

Noncollinear third-harmonic Maker fringes for the determination of third-order nonlinear optical susceptibilities.

We describe noncollinear third-harmonic Maker fringes for the determination of third-order optical nonlinearities. This method builds on the same principles as conventional Maker fringes experiments, but thanks to the limited interaction length of two intersecting beams, it allows to eliminate the requirement of taking into account the contribution of air to the third-harmonic signal. Thus, third-order susceptibilities can be accurately determined without the need for a vacuum chamber. We review the theoretical underpinnings of the method, and discuss the dependence of the coherence length for harmonic generation on the intersection angle between the beams and the sample orientation, and the effect this has on the Maker fringes pattern.

Donor-acceptor (D-A)-substituted polyyne chromophores: modulation of their optoelectronic properties by varying the length of the acetylene spacer.

A series of donor-acceptor-substituted alkynes, 2 a-f, was synthesized in which the length of the π-conjugated polyyne spacer between the N,N-diisopropylanilino donor and the 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) acceptor was systematically changed. The effect of this structural change on the optoelectronic properties of the molecules and, ultimately, their third-order optical nonlinearity was comprehensively investigated. The branched N,N-diisopropyl groups on the anilino donor moieties combined with the nonplanar geometry of 2 a-f imparted exceptionally high solubility to these chromophores. This important property allowed for performing INADEQUATE NMR measurements without (13) C labeling, which, in turn, resulted in a complete assignment of the carbon skeleton in chromophores 2 a-f and the determination of the (13) C-(13) C coupling constants. This body of data provided unprecedented insight into characteristic (13) C chemical shift patterns in push-pull-substituted polyynes. Electrochemical and UV/Vis spectroscopic studies showed that the HOMO-LUMO energy gap decreases with increasing length of the polyyne spacer, while this effect levels off for spacers with more than four acetylene units. The third-order optical nonlinearity of this series of molecules was determined by measuring the rotational averages of the third-order polarizabilities (γrot ) by degenerate four-wave mixing (DFWM). These latter studies revealed high third-order optical nonlinearities for the new chromophores; most importantly, they provided fundamental insight into the effect of the conjugated spacer length in D-A polyynes, that can be exploited in the future design of suitable charge-transfer chromophores for applications in optoelectronic devices.

Direct imaging of anisotropic exciton diffusion and triplet diffusion length in rubrene single crystals.

We visualize exciton diffusion in rubrene single crystals using localized photoexcitation and spatially resolved detection of excitonic luminescence. We show that the exciton mobility in this material is strongly anisotropic with long-range diffusion by several micrometers associated only with the direction of molecular stacking in the crystal, along the b axis. We determine a triplet exciton diffusion length of 4.0 ± 0.4 µm from the spatial exponential decay of the photoluminescence that originates from singlet excitons formed by triplet-triplet fusion.

Nonplanar push-pull chromophores for opto-electronic applications.

Donor-substituted cyanoethynylethenes (CEEs) are planar push-pull chromophores featuring intense intramolecular charge-transfer (CT) interactions and high third-order optical nonlinearities. Their thermal stability allows for the formation of crystalline thin films by vapor-phase deposition. On the other hand, high-quality amorphous thin films are preferred for opto-electronic applications and such films can be prepared using nonplanar push-pull chromophores with a less pronounced propensity to crystallize. By taking advantage of a versatile, atom-economic 'click-chemistry'-type transformation, involving a formal [2 + 2] cycloaddition of tetracyanoethene (TCNE) to electron-rich alkynes, followed by cycloreversion, stable donor-substituted 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) are obtained in high yield and large quantities. These nonplanar push-pull chromophores also feature intense intramolecular CT and, in many cases, high third-order optical nonlinearities. Some of these compounds form high-optical-quality amorphous thin films by vapor-phase deposition, and first applications in next-generation opto-electronic devices have already been demonstrated. Chiral derivatives display high helical twisting power and are efficient dopants to translate molecular into macroscopic chirality, by switching nematic into cholesteric liquid crystalline phases.

Optical properties of highly nonlinear silicon-organic hybrid (SOH) waveguide geometries.

Geometry, nonlinearity, dispersion and two-photon absorption figure of merit of three basic silicon-organic hybrid waveguide designs are compared. Four-wave mixing and heterodyne pump-probe measurements show that all designs achieve high nonlinearities. The fundamental limitation of two-photon absorption in silicon is overcome using silicon-organic hybrid integration, with a five-fold improvement for the figure of merit (FOM). The value of FOM = 2.19 measured for silicon-compatible nonlinear slot waveguides is the highest value published.

A new class of organic donor-acceptor molecules with large third-order optical nonlinearities.

Donor-acceptor molecules with 4-(dimethylamino)phenyl donor and 1,1,4,4-tetracyanobuta-1,3-diene acceptor moieties are readily prepared by short, high-yielding routes. The quite small chromophores are characterised by X-ray crystallography and feature intense intramolecular charge-transfer bands, substantial quinoid character in the donor rings, reversible electrochemical reductions and oxidations and powerful third-order optical nonlinearities.

N,N'-Dicyanoquinone diimide-derived donor-acceptor chromophores: conformational analysis and optoelectronic properties.

A formal [2 + 2] cycloaddition-cycloreversion (CA-CR) between N,N'-dicyanoquinone diimides (DCNQIs) and electron-rich alkynes was explored, providing a new class of π-conjugated donor-acceptor chromophores. These DCNQI adducts exist in the solid state as single diastereoisomers, but as two interconverting diastereoisomers in solution. Solid- and solution-state evidence for intramolecular charge transfer (CT) was obtained; additionally, the DCNQI adducts exhibit positive solvatochromism and significant solution-state third-order polarizabilities.

Significant FRET between SWNT/DNA and rare earth ions: a signature of their spatial correlations.

Significant acceleration of the photoluminescence (PL) decay rate was observed in water solutions of two rare earth ions (REIs), Tb and Eu. We propose that the time-resolved PL spectroscopy data are explained by a fluorescence resonance energy transfer (FRET) between the REIs. FRET was directly confirmed by detecting the induced PL of the energy acceptor, Eu ion, under the PL excitation of the donor ion, Tb, with FRET efficiency reaching 7% in the most saturated solution, where the distance between the unlike REIs is the shortest. Using this as a calibration experiment, a comparable FRET was measured in the mixed solution of REIs with single-wall nanotubes (SWNTs) wrapped with DNA. From the FRET efficiency of 10% and 7% for Tb and Eu, respectively, the characteristic distance between the REI and SWNT/DNA was obtained as 15.9 ± 1.3 Å, suggesting that the complexes are formed because of Coulomb attraction between the REI and the ionized phosphate groups of the DNA.

Ab initio study of linear and nonlinear optical properties of mixed tellurite-chalcogenide glasses.

We discuss the potential functionalities of a mixed tellurite-chalcogenide glass where alternate oxygen atoms in a TeO(2) vitreous network are substituted with either sulfur or selenium atoms. We calculate the microscopic linear and nonlinear polarizabilities of chains with a finite number (n) of TeOX (X = S or Se) units from ab initio quantum chemistry computations and apply rotational averaging to the results. We find that the rotationally averaged linear polarizability, α(av), increases linearly with the number of units, while the second hyper-polarizability, γ(av), grows as a power law with an exponent that changes from 1.2 to 1.9 and 2.4 when going from pure tellurite to S substitution and Se substitution, respectively. We then estimate the density of the resulting glass and local field corrections to obtain the macroscopic linear and nonlinear susceptibilities for a glass made from chains of n = 5. We find that the extra Te-S (or Te-Se) bonds in the mixed tellurite-chalcogenide system enhance the linear refractive index n(0) and the third-order susceptibility χ((3)) by factors of ∼ 1.3 (or 1.4) and ∼ 8 (or 14), respectively, over the base tellurite glasses (X = O).

Property tuning in charge-transfer chromophores by systematic modulation of the spacer between donor and acceptor.

A series of donor-acceptor chromophores was prepared in which the spacer separating 4-dimethylanilino (DMA) donor and C(CN)(2) acceptor moieties is systematically varied. All of the new push-pull systems, except 4 b, are thermally stable molecules. In series a, the DMA rings are directly attached to the central spacer, whereas in series b additional acetylene moieties are inserted. X-ray crystal structures were obtained for seven of the new, intensely colored target compounds. In series a, the DMA rings are sterically forced out of the mean plane of the residual pi system, whereas the entire conjugated pi system in series b is nearly planar. Support for strong donor-acceptor interactions was obtained through evaluation of the quinoid character of the DMA ring and by NMR and IR spectroscopy. The UV/Vis spectra feature bathochromically shifted, intense charge-transfer bands, with the lowest energy transitions and the smallest optical gap being measured for the two-dimensionally extended chromophores 6 a and 6 b. The redox behavior of the push-pull molecules was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). In the series 1 b, 2 b, 4 b, 5 b, in which the spacer between donor and acceptor moieties is systematically enlarged, the electrochemical gap decreases steadily from 1.94 V (1 b) to 1.53 V (5 b). This decrease is shown to be a consequence of a reduction in the D-A conjugation with increasing spacer length. Degenerate four-wave mixing experiments reveal high third-order optical nonlinearities, pointing to potentially interesting applications of some of the new chromophores in optoelectronic devices.

Primary photoexcitations and the origin of the photocurrent in rubrene single crystals.

By simultaneously measuring the excitation spectra of transient luminescence and transient photoconductivity after picosecond pulsed excitation in rubrene single crystals, we show that free excitons are photoexcited starting at photon energies above 2.0 eV. We observe a competition between photoexcitation of free excitons and photoexcitation into vibronic states that subsequently decays into free carriers, while molecular excitons are instead formed predominantly through the free exciton. At photon energies below 2.25 eV, free charge carriers are created only through a long-lived intermediate state with a lifetime of up to 0.1 ms and no free carriers appear during the exciton lifetime.

Highly efficient third-order optical nonlinearities in donor-substituted cyanoethynylethene molecules.

We investigated the third-order nonlinear optical properties of several donor-substituted cyanoethynylethene molecules in the zero-frequency limit. We observed nonlinearities that are extraordinarily large relative to the small molecular mass of these molecules and that are within a factor of 50 from the fundamental limit. At a wavelength of 1.5 microm, the rotational average of the third-order molecular polarizability is 53 +/- 13 x 10(-48) m5 V(-2) (3.8 x 10(-33) esu) for the best molecule, which corresponds to 1.7 x 10(-48) m5 V(-2) per delocalized electron. The high nonlinear efficiency of these molecules is due to the compact two-dimensional conjugated system and the effective donor-acceptor substitution patterns.

Method for generating solitons sustained by competing nonlinearities by use of optical rectification.

We put forward a method for generating engineerable competing quadratic and cubic nonlinearities in suitable settings in which frequency generation is accompanied by optical rectification. The novel scheme is based on the full exploitation of the geometrical conditions that determine the magnitude of the rectified fields and translates the different orientations of an elliptical pump beam into tunable nonlinearities, which can be used to act on the spectral composition and overall features of optical solitons.