Effective Two-photon Absorption Cross-section Research Articles

Linear and nonlinear absorption properties of hemicyanine dyes containing 5-(4H)-oxazolone as heterocyclic ring

A series of dyes containing electron-donating (D) and electron-accepting (A) groups connected through a π-conjugated linker were designed and their linear and nonlinear absorption properties were studied. The dyes combined 1,3-oxazol-5(4H)-one core with methoxy, methyl, phenyl, cyano, and nitro group in the para-position of a phenyl ring. Spectrally resolved two-photon absorption cross-section measurements carried out by the femtosecond Z-scan technique showed wide wavelength regions of nonlinear optical absorption. The studied compound containing the phenyl ring exhibits relatively high effective two-photon absorption cross-section equal to 772 ± 100 GM at 600 nm. The experimental optical characterization is supported by the results of electronic-structure calculations.

Two quinoline-based two-photon fluorescent probes for imaging of viscosity in subcellular organelles of living HeLa cells

Two viscosity-sensitive two-photon fluorescent probes (QL and QLS) were designed and synthesized, which can be localized in lysosome and mitochondria in living HeLa cells, respectively. As the increases of viscosity from 2.55 to 1150 cP, the fluorescence quantum yield (Φ) of QL and QLS was increased by 28-fold and 37-fold, respectively. At the same time, its effective two-photon absorption cross section (ΦδTPA) was enhanced by 15-fold and 16-fold, respectively. Fluorescence lifetime imaging (FLIM) of living HeLa cells stained with QL and QLS, revealed that lysosomal viscosity ranged from 100.76 to 254.74 cP and mitochondrial viscosity ranged from 92.21 to 286.79 cP. This type of fluorescent probe is helpful in the design and application of materials for monitoring diseases associated with abnormal viscosity.

Strong increase in the effective two-photon absorption cross-section of excitons in quantum dots due to the nonlinear interaction with localized plasmons in gold nanorods.

Excitons in semiconductor quantum dots (QDs) feature high values of the two-photon absorption cross-sections (TPACSs), enabling applications of two-photon-excited photoluminescence (TPE PL) of QDs in biosensing and nonlinear optoelectronics. However, efficient TPE PL of QDs requires high-intensity laser fields, which limits these applications. There are two possible ways to increase the TPE PL of QDs: by increasing their photoluminescence quantum yield (PLQY) or by further increasing the TPACS. Plasmonic nanoparticles (PNPs) may act as open nanocavities for increasing the PLQY via the Purcell effect, but this enhancement is strictly limited by the maximum possible PLQY value of 100%. Here we directly investigated the effect of PNPs on the effective TPACS of excitons in QDs. We have found that effective TPACS of excitons in a QD-PMMA thin film can be increased by a factor of up to 12 near the linearly excited gold nanorods (GNRs). Using gold nanospheres (GNSs), in which plasmons cannot be excited in the infrared range, as a control system, we have shown that, although both GNSs and GNRs increase the recombination rate of excitons, the TPACS is increased only in the case of GNRs. We believe that the observed effect of TPACS enhancement is a result of the nonlinear interaction of the plasmons in GNRs with excitons in QDs, which we have supported by numerical simulations. The results show the way to the rational design of the spectral features of plasmon-exciton hybrids for using them in biosensing and nonlinear optoelectronics.

Synthesis and Linear and Nonlinear Optical Properties of Three Push-Pull Oxazol-5(4H)-one Compounds.

Three uncharged push-pull oxazol-5(4H)-ones were synthesized and thoroughly characterized. The examined molecules contained electron-donor and electron-acceptor groups interacting via a π-conjugated bridge. Spectral properties of the oxazol-5(4H)-ones were studied in detail in three solvents of different polarities. The results indicate a solvatochromic shift toward lower energy for the charge-transfer state. The compounds are weakly fluorescent in polar solvents, but they have high fluorescence quantum yields in nonpolar solvents. Their two-photon absorption (2PA) properties were characterized by the open- and closed-aperture Z-scan technique, by the pump-probe technique, and by the two-photon excited fluorescence method. The dyes exhibit relatively high effective two-photon absorption cross sections ranging from 490 to 2600 GM at ~100 GW/cm(2), according to the Z-scan results, which are found, however, to contain significant contribution from higher-order absorption processes. In addition, these compounds display good photostability.

Nonlinear Optical Switching and Enhanced Nonlinear Optical Response of Au–CdSe Heteronanostructures

The metal–semiconductor heterostructures have recently emerged as a new class of functional materials for their potential applications due to plasmon-exciton interactions. Here, we demonstrate the nonlinear optical switching and enhanced nonlinear optical response of Au–CdSe heterostructures. The nonlinear optical properties of CdSe quantum dots and Au–CdSe heteronanostructures are investigated by using a Z-scan technique at 532 nm picosecond laser pulses, and 800 nm femtosecond laser pulses. Interestingly, we observe switching behavior from saturable absorption (SA) to reverse saturable absorption (RSA) with increasing laser intensity. The effective two-photon absorption cross section (σeff) of Au–CdSe heteronanostructures is greatly enhanced which is attributed to charge transfer between CdSe and Au nanoparticles. The nonlinear refraction changes its sign from positive to negative nonlinearity at higher intensities for Au–CdSe heterostructures. Third order nonlinear optical susceptibility is being measu...

Morphology- and size-dependent spectroscopic properties of Eu3+-doped Gd2O3 colloidal nanocrystals.

The synthesis, morphological characterization, and optical properties of colloidal, Eu(III) doped Gd2O3 nanoparticles with different sizes and shapes are presented. Utilizing wet chemical techniques and various synthesis routes, we were able to obtain spherical, nanodisk, nanotripod, and nanotriangle-like morphology of Gd2O3:Eu3+ nanoparticles. Various concentrations of Eu3+ ions in the crystal matrix of the nanoparticles were tested in order to establish the levels at which the concentration quenching effect is negligible. Based on the luminescence spectra, luminescence lifetimes and optical parameters, which were calculated using the simplified Judd–Ofelt theory, correlations between the Gd2O3 nanoparticles morphology and Eu3+ ions luminescence were established, and allowed to predict the theoretical maximum quantum efficiency to reach from 61 to 98 %. We have also discussed the impact of the crystal structure of Gd2O3 nanoparticles, as well as coordinating environment of luminescent ions located at the surface, on the emission spectra. With the use of a tunable femtosecond laser system and the Z-scan measurement technique, the values of the effective two-photon absorption cross-section in the wavelength range from 550 to 1,200 nm were also calculated. The nonlinear optical measurements revealed maximum multi-photon absorption in the wavelength range from 600 to 750 nm.

Nanoplasmonic Array Enhancement of Two-Photon Absorption in a Dye Film

We investigate the enhancement of the effective two-photon absorption cross section of a film of an organic dye by a plasmonic triangular prism array through finite element calculations and experim...

Synthesis, Structural Characterization, Photophysics, and Broadband Nonlinear Absorption of a Platinum(II) Complex with the 6-(7-Benzothiazol-2′-yl-9,9-diethyl-9 H-fluoren-2-yl)-2,2′-bipyridinyl Ligand

A platinum complex with the 6-(7-benzothiazol-2'-yl-9,9-diethyl-9H-fluoren-2-yl)-2,2'-bipyridinyl ligand (1) was synthesized and the crystal structure was determined. UV/Vis absorption, emission, and transient difference absorption of 1 were systematically investigated. DFT calculations were carried out on 1 to characterize the electronic ground state and aid in the understanding of the nature of low-lying excited electronic states. Complex 1 exhibits intense structured (1)π-π* absorption at λ(abs)<440 nm, and a broad, moderate (1)MLCT/(1)LLCT transition at 440-520 nm in CH(2)Cl(2) solution. A structured (3)π-π*/(3)MLCT emission at about 590 nm was observed at room temperature and at 77 K. Complex 1 exhibits both singlet and triplet excited-state absorption from 450 nm to 750 nm, which are tentatively attributed to the (1)π-π* and (3)π-π* excited states of the 6-(7-benzothiazol-2'-yl-9,9-diethyl-9H-fluoren-2-yl)-2,2'-bipyridine ligand, respectively. Z-scan experiments were conducted by using ns and ps pulses at 532 nm, and ps pulses at a variety of visible and near-IR wavelengths. The experimental data were fitted by a five-level model by using the excited-state parameters obtained from the photophysical study to deduce the effective singlet and triplet excited-state absorption cross sections in the visible spectral region and the effective two-photon absorption cross sections in the near-IR region. Our results demonstrate that 1 possesses large ratios of excited-state absorption cross sections relative to that of the ground-state in the visible spectral region; this results in a remarkable degree of reverse saturable absorption from 1 in CH(2)Cl(2) solution illuminated by ns laser pulses at 532 nm. The two-photon absorption cross sections in the near-IR region for 1 are among the largest values reported for platinum complexes. Therefore, 1 is an excellent, broadband, nonlinear absorbing material that exhibits strong reverse saturable absorption in the visible spectral region and large two-photon-assisted excited-state absorption in the near-IR region.

Organometallic Complexes for Non-Linear Optics. 51. Second- and Third-Order Non-Linear Optical Properties of Alkynylgold Complexes

The alkynes HC≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2 (4) and HC≡CC6H4-4-C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2 (6) and gold alkynyl complexes Au{C≡CC6H2-2,5-(OEt)2-4-C≡CC6H4-4-NO2}(PPh3) (7), Au(C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2)(PPh3) (8), and Au(C≡CC6H4-4-C≡CC6H2-2,6-Et2-4-C≡CC6H4-4-NO2)(PPh3) (9) have been synthesized. The linear optical properties and quadratic optical non-linearities of 7–9 have been measured, the latter by hyper-Rayleigh scattering at 1064 nm, and compared with data for the previously reported complexes Au(C≡CC6H4-4-NO2)(PPh3) (10) and Au(C≡CC6H4-4-C≡CC6H4-4-NO2)(PPh3) (11). The optical absorption maximum red-shifts and the first hyperpolarizabilities increase on π-system lengthening and on introduction of electron-releasing substituents on the π-bridge ring adjacent to the metal centre. The cubic non-linear optical properties of 1,4-{(PCy3)Au(C≡C)}2C6H4 (12) and {(PCy3)Au(C≡C-4-C6H4C≡C)}6C6 (13) have been assessed by wide spectroscopic range femtosecond Z-scan studies; the maximal values of the imaginary component and the effective two-photon absorption cross-section increase markedly on proceeding from linear complex 12 to 6-fold-symmetric complex 13, an increase that is maintained when data are scaled by relative molecular weight.

60]Fullerene metal complexes with large effective two-photon absorption cross-section

Fourteen novel complexes of fullerene C(60) with metal dialkyldithiophosphate, {[(RO)(2)PS(2)](2)M}·2C(60) (R = Me and Et; M = Mn, Fe, Co, Ni, Cu, Zn and Pd), can be obtained in high yield by the reaction of metal(II) dialkyldithiophosphate complexes with C(60) fullerene. Their structures are determined by (1)H, (13)C, and (31)P NMR spectroscopy, elemental analysis, FT-IR and UV-vis, and are supplied by single crystal X-ray data. The compound {[(EtO)(2)PS(2)](2)Pd}·2C(60) was also studied by the HRTEM image and SAED patterns. Studies of the optical properties of the complexes of fullerene C(60) with metal dialkyldithiophosphate show that these compounds all have very strong nonlinear optical absorption effects. The nonlinear absorption of fourteen complexes of fullerene C(60) with metal dialkyldithiophosphate (in o-dichlorobenzene and in the solid state) was measured by the open-aperture Z-scan technique at a wavelength of 532 nm. DFT calculations are also used to discuss the stability of these complexes and to confirm the structural assignments.

The third-order nonlinear optical properties of novel styryl dyes

The third-order nonlinear optical properties of two novel styryl dyes, namely, 1,3-diethyl-5-(4-methoxybenzylidene)-2-thioxodihydropyrimidine-4,6(1 H,5 H)-dione and 5-(3,4-dimethoxybenzylidene)-1,3-diethyl-2-thioxodihydropyrimidine-4,6(1 H,5 H)-dione were studied using the Z-scan technique employing 7 ns laser pulses at 532 nm. The nonlinear refractive index, nonlinear absorption coefficient, magnitude of effective third-order susceptibility and coupling factor were determined. The optical power limiting behavior of the colorants was ascribed to two-photon absorption phenomenon. Nonlinear absorption cross-section increased with increase in π electron density and the effective two-photon absorption cross-section was two orders of magnitude larger than those of commercially available azo compounds. The results suggest that these colorants offer promise as nonlinear optical materials for device applications.

Platinum Acetylide Two-Photon Chromophores

To explore the photophysics of platinum acetylide chromophores with strong two-photon absorption cross-sections, we have investigated the synthesis and spectroscopic characterization of a series of platinum acetylide complexes that feature highly pi-conjugated ligands substituted with pi-donor or -acceptor moieties. The molecules (numbered 1-4) considered in the present work are analogs of bis(phenylethynyl)bis(tributylphosphine)platinum(II) complexes. Molecule 1 carries two alkynyl-benzothiazolylfluorene ligands, and molecule 2 has two alkynyl-diphenylaminofluorene ligands bound to the central platinum atom. Compounds 3 and 4 possess two dihexylaminophenyl substituents at their ends and differ by the number of platinum atoms in the oligomer "core" (one vs two in 3 and 4, respectively). The ligands have strong effective two-photon absorption cross-sections, while the heavy metal platinum centers give rise to efficient intersystem crossing to long-lived triplet states. Ultrafast transient absorption and emission spectra demonstrate that one-photon excitation of the chromophores produces an S1 state delocalized across the two conjugated ligands, with weak (excitonic) coupling through the platinum centers. Intersystem crossing occurs rapidly (Kisc approximately 1011 s-1) to produce the T1 state, which is possibly localized on a single conjugated fluorenyl ligand. The triplet state is strongly absorbing (epsilonTT > 5 x 104 M-1 cm-1), and it is very long-lived (tau > 100 micro s). Femtosecond pulses were used to characterize the two-photon absorption properties of the complexes, and all of the chromophores are relatively efficient two-photon absorbers in the visible and near-infrared region of the spectrum (600-800 nm). The complexes exhibit maximum two-photon absorption at a shorter wavelength than 2lambda for the one-photon band, consistent with the dominant two-photon transition arising from a two-photon-allowed gerade-gerade transition. Nanosecond transient absorption experiments carried out on several of the complexes with excitation at 803 nm confirm that the long-lived triplet state can be produced efficiently via a sequence involving two-photon excitation to produce S1, followed by intersystem crossing to produce T1.

Syntheses and properties of acetylene-linked bis- and trisporphyrins toward two-photon photodynamic therapy

Acetylene-bridged bisporphyrins and trisporphyrins having branched bulky bis(carboxylethyl)methyl meso-substituents were synthesized. These compounds showed large effective two-photon absorption cross-section values at 890 nm measured by using a nanosecond Z-scan method. Sodium salt of hydrolyzed trisporphyrins showed broad and red-shifted Q-bands over 900 nm. Two-photon absorption cross-section values of water-soluble dimers in water were similar to, or slightly larger than, those of ester forms evaluated in toluene. Furthermore, the generation of singlet oxygen upon one-photon irradiation for dimers in water was confirmed.

Syntheses and nonlinear absorption properties of conjugated porphyrin supramolecules

Self-assemblies consisting of acetylene-linked bisporphyrins with a 4-nitrophenylethynyl substituent and with a phenylethynyl substituent were synthesized. The Q-band of the phenylethynyl-substituted compound appears at 762 nm whereas that of the 4-nitrophenylethynyl-substituted one was red-shifted to 784 nm and intensified. This may be attributed to the participation of the nitro group in the π-electronic communication system. HOMOs and LUMOs were calculated for these compounds using an INDO/S-CI method. The effective two-photon absorption cross-section values of these self-assemblies were measured by using a nanosecond open aperture Z-scan method. The maximum effective two-photon absorption cross-section values of 4-nitrophenylethynyl- and phenylethynyl-substituted bisporphyrins were obtained as 1.2 × 105 GM and 8.1 × 104 GM , respectively, at 890 nm. A 1.5 enhancement factor was obtained by introducing nitro groups, which was similar to the value previously reported for ferrocene- and fullerene-connected supramolecular porphyrin.

Effect of the concentration of organic dyes on their surface plasmon enhanced two-photon absorption cross section using activated Au nanoparticles

In this article we present the study of the surface plasmon enhanced two-photon absorption of a hydrophilic stilbene derivative (trans-4,4’-diaminostilbene) in aqueous solution at different concentrations. The observed exponential growth of the effective two-photon absorption cross section [σ2′(Au)] is attributed to the electric-field augmentation via surface plasmon resonance between nanoparticles, i.e., hot spots, and the molecular density on Au nanospheres. An unprecedented σ2′(Au)=550 000 GM has been measured. This result opens a new universe of applications in multiphoton imaging, photodynamic therapy, telecommunications, optical limiting, and multidimensional data storage using hybrid systems.

Ab initio studies of two-photon absorption of some stilbenoid chromophores

Two-photon absorption of a series of donor-acceptor trans-stilbene derivatives is studied by means of density functional theory applied to second-order response function. Several important issues in modeling are highlighted which must be addressed for a reliable reproduction of the experimental results. It is evident that the correct order of magnitude of calculated two-photon absorption cross sections can only be obtained if proper account is taken of vibrational broadening of the absorption profiles. A comparison of the theoretical results with the experimental ones indicates that the computed two-photon absorption cross sections are in rough agreement with our previous report, although the observed systematic increase of the cross sections with the electron acceptor strength is not well reproduced. It is suggested that this disagreement may be due not only to the deficiencies of the computations but also to a variety of factors contributing to the experimental value of the effective two-photon absorption cross section, which are not taken into account in the ab initio calculations.

One- and two-photon absorption of three-coordinate compounds with different centers (B,Al,N) and a 2,2′-dipyridylnitrogen functional group

A series of three-coordinate octupolar compounds with varied centers (boron, aluminum, and nitrogen), which exhibit very large effective two-photon absorption cross sections have been theoretically studied. The ground state geometries and electronic structures are obtained using the density functional theory with the B3LYP functional and 6-31G(d) basis set, and the results are comparable to the available experimental determinations. Based on the correct geometrical and electronic structures, the one- and two-photon absorptions are predicted by the ZINDO-SOS method. Among these compounds, the boron (B) and aluminum (Al) centers act as acceptors, while the nitrogen center acts as donor according to the net charge changes during the excitation. It is found that (i) the compounds with boron and aluminum centers show two large two-photon absorption peaks, while the molecule with nitrogen center show only one two-photon absorption peak; (ii) the cross sections of the molecules with B or Al as centers are larger than that of the molecule with nitrogen as center; furthermore, the two-photon absorption cross section of the molecule with Al center is larger than that of the molecule with B center, from this point of view, our theoretical prediction provides for the experiment a good new candidate with large two-photon absorption cross section for further research; (iii) lengthening the conjugation bridge by inserting a benzene ring on the organoborane compounds (forming the investigated molecule B-2) enhances the two-photon absorption cross section, and keeping good transparency at the same time.

Understanding the One-Photon Photophysical Properties of a Two-Photon Absorbing Chromophore

A comprehensive one-photon photophysical study has been carried out on AF455, a known two-photon absorbing dye. AF455 is composed of an electron-accepting center with three arms that consist of a π-conjugated group with an electron-donating group at the terminal end of each arm. The objective of this work is to understand the one-photon excitation photophysical properties so that this knowledge will be carried into understanding the two-photon absorption properties. This was done by utilizing steady-state absorption, steady-state and time-resolved emission, femtosecond pump−probe, and nanosecond laser flash photolysis techniques. Through this study it was determined that AF455 undergoes an excited-state intramolecular charge transfer (ICT) upon absorption of a single photon. The extent of ICT stabilization is dependent on the solvent polarity, with increasing ICT stabilization in more polar solvents. The formation of the triplet excited state is small (<8%) and is effected only slightly by a change in the solvent polarity. With an increase in polarity the fluorescence quantum yield decreased and internal conversion was found to become more competitive. On the basis of a two-photon assisted excited-state absorption model we tied in the measured one-photon photophysical properties to understand why the nanosecond effective two-photon absorption cross section is much larger than the femtosecond intrinsic two-photon absorption cross section. We found that AF455 exhibits triplet excited-state absorption in the region of 800 nm that leads to enhancement of the nanosecond effective two-photon absorption cross section.

Two-Photon Absorption and Optical Limiting Properties of Organic Salt trans-4-[p-(N-hydroxyethyl-N-methylamino)styryl]-N-methylpyridinium Iodide in Various Solvents

The absorption spectra, single-photon induced fluorescence spectra, two-photon absorption (TPA) and optical limiting behaviors of organic dye trans-4-[p-(N-hydroxyethyl-N-methylamino)styryl]-N-methylpyridinium iodide (abbreviated as ASPI) have been studied in three solvents [chloroform, benzyl alcohol, dimethyl formamide (DMF)] with different polarities. The optical properties of ASPI were found to be strongly influenced by the solvents used. With increasing polarity of the solvents, the absorption and fluorescence peaks of ASPI solutions exhibit marked blue and red shifts, respectively, and the effective TPA cross sections and the optical limiting effects decrease. The TPA cross sections of ASPI measured in the three solvents are 3.41×10-47 (chloroform), 1.86×10-48 (benzyl alcohol) and 1.05×10-48 (DMF) cm4·s·photon-1.

Synthesis and nonlinear optical properties of new symmetrically substituted stilbenes

Three new chromophores and trans-4-( N-(ethyl 4″-nitrobenzoate)- N-ethyl amino)-4′-(dimethyl amino) stilbene (DMANHAS) have been synthesized and whose chemical structures have been characterized by 1H NMR, IR, and elemental analyses. Linear absorption, single-photon-induced fluorescence and two-photon-induced fluorescence are experimentally studied. Trans-4-( N-2-hydroxyethyl- N-ethyl amino)-4′-(dimethyl amino)stilbene (DMAHAS) and trans-4-( N-2-hydroxyethyl- N-ethyl amino)-4′-(diethyl amino)stilbene (DEAHAS) have effective two-photon absorption cross-sections of σ 2=0.91×10 −46 cm 4 s/photon and σ 2=1.19×10 −46 cm 4 s/photon at 532 nm by using an open aperture Z-scan technique, respectively. When pumped with 800 nm laser irradiation, DMAHAS and DEAHAS indicate strong two-photon-induced blue fluorescence of 436 and 440 nm, respectively, while trans-4-( N-(ethyl 4″-nitrobenzoate)- N-ethyl amino)-4′-(diethyl amino) stilbene (DEANHAS) and DMANHAS exhibit no fluorescence.