We demonstrate an efficient ENZ response in the visible spectral range using organic
molecular ultrathin films possessing a Lorentz-type dispersion. For this purpose, two
polymethine dyes: sodium [5,6-dichloro-2-[[5,6-dichloro-1-ethyl-3-(4-sulphobutyl)-
benzimidazol-2-ylidene]-propenyl]-1-ethyl-3-(4-sulphobutyl)-benzimidazolium hydroxide]
(TDBC), and [2,4-bis[8-hydroxy-1,1,7,7-tetramethyljulolidin-9-yl]squaraine]
(HTJSq) were used in spin-coated polymer films at different doping concentrations.
By varying the doping concentration in thin films, the real part of highly dispersive permittivity
ε1 can be manipulated and tuned such that the spectral width of ENZ region -1 < ε1 <1 resides
in the visible spectral range. These results are not only extremely relevant for applications
requiring a custom-tailored ENZ region in the visible but also provide important novel
information on how molecular aggregation affects the ENZ properties. In particular, based on our findings, we stress that J-aggregate is not always a mandatory molecular assembly for
obtaining a strong ENZ response. Instead, molecular aggregates with the size of a few
nanometers resulting in strong molecular interactions (i.e. Davydov splitting of the lowest
transition in energy) are required to achieve a strong ENZ response. The ENZ-enhanced optical
Kerr nonlinearity is then investigated in the optimum concentration films of TDBC and HTJSq.
Both nonlinear refractive index and nonlinear absorption coefficient are found to be strongly
enhanced in the ENZ region originating from the coupling of excitonic transition dipoles
associated with large molecular aggregates.
The two-photon absorption properties of brunched π-conjugated hydrocarbons at visible wavelengths, up to 400 nm measured by using the femtosecond open-aperture Z-scan method are presented. The hydrocarbons, phenylethynylsubstituted benzenes, shows moderate (several hundreds GM) or very large (~20,000 GM) two-photon absorption cross sections, suggesting such a hydrocarbons can be efficient two-photon absorption chromophores in the wavelength region.
KEYWORDS: Absorption, Telecommunications, Optical limiting, Chromophores, Nonlinear optics, Near infrared, Molecules, Americium, System on a chip, Pulsed laser operation
The rapid development of frequency-tunable pulsed lasers up to telecommunication wavelengths (1400-1600
nm) led to the design of new materials for nonlinear absorption in this spectral range. In this context, two
families of near infra-red (NIR) chromophores, namely heptamethine cyanine and aza-borondipyrromethene
(aza-bodipy) dyes were studied. In both cases, they show significant two-photon absorption (TPA) cross-sections
in the 1400-1600 nm spectral range and display good optical power limiting (OPL) properties. OPL curves were
interpreted on the basis of TPA followed by excited state absorption (ESA) phenomena. Finally these systems
have several relevant properties like nonlinear absorption properties, gram scale synthesis and high solubility. In
addition, they could be functionalized on several sites which open the way to numerous practical applications in
biology, solid-state optical limiting and signal processing.
A selection rule for two-photon transition is considered based on the alternancy symmetry and the result is adopted to
explain the experimental and calculation results of two-photon absorption (TPA) properties of two diacetylene
derivatives with neutral and charged peripheral groups. The discussion successfully explains the difference in strength
of the TPA bands and the existence of the higher-lying TPA states that is strongly allowed and plays a main role to the
resonance enhancement of TPA.
Differential optical Kerr effect (DOKE) detection is a powerful tool for studying the ultrafast time-resolved dynamics of 3rd-order nonlinear processes. In this study, DOKE was used to measure the nonlinear absorption properties of tetraethynylphenylene (TEP) solutions in THF using 800 nm, 80 fs laser pulses. These two-dimensional, highly-conjugated chromophores (also known as TPEBs) show high instantaneous two-photon absorption (TPA) for relatively small chromophores. The TPA cross section is strongly dependent on the donor-acceptor geometry in these materials: a quadrupolar, all-donor TEP shows the smallest TPA, with a cross-section of σ(2)= 90 ± 15 GM. ortho-TEP, for which the donors (and acceptors) are conjugated via the ortho position across the central phenyl ring, is dipolar and displays the largest cross-section, of σ(2)= 260 ± 30 GM. para-TEP, which is quadrupolar, and meta-TEP, which is dipolar, display similar cross-sections of σ(2)= 160 ± 10 GM and σ(2)= 150 ± 10 GM, respectively. In addition to an instantaneous TPA response, these isomers show unique two-photon assisted excited-state absorption (ESA), with the ortho- and meta-TEP displaying a clear 3-10 ps rise to an ESA peak, and subsequent decay. The differences in the nonlinear absorption behaviour of these materials may be partially explained by selection rules and UV-vis spectroscopy. In addition, the polar geometries, coupled to the various in-plane conjugation paths, may further influence their optical nonlinearities. Understanding these trends impacts both the design of materials with desirable nonlinear absorption properties and our understanding of the electronic landscape in functionalized organic materials.
Two-photon absorption (TPA) cross section of some previously reported compounds is reexamined by the femtosecond open-aperture Z-scan method and the comparison among cross-section values measured by different measurement techniques is discussed. Also a TPA spectrum of a diacetylene derivative measured by the Z-scan method is presented. Drastic enhancement has been observed in the visible wavelength region of the spectrum, which is interpreted in terms of resonance enhancement of simultaneous TPA process. Contribution of stepwise TPA process to the observed enhancement is estimated by simulation for the dynamics.
The elementary processes contributing to the ultrafast change of refractive index were studied for organic molecular system. The ultrafast change was measured by optical heterodyne detected optical Kerr effect with femtosecond laser pulses. The observed responses were separated into the electronic and nuclear nonlinearities by an analytical method based on the Fourier transform. Second hyperpolarizability γ was determined from the separated electronic contribution, and is discussed in terms of the structure-property relationship for four thiophene homologues. The γ value was found to increase systematically, which is explained with change of the energy levels of the excited states affected by the hetero atom in their aromatic rings. The structure-property relationship of the nuclear nonlinearity was also discussed for CS2 and CCl4. Their pulse width dependences of the nonlinear optical response were demonstrated, which brings the problems of CS2 as a standard material of femtosecond χ(3) measurement to light. Also accumulated thermal effect, which can be a measurement artifact, is demonstrated for femtosecond closed-aperture Z-scan measurements of dye solution. The thermal effect was found to appear at the laser repetition rate as low as 1 kHz and gave apparent large nonlinearity with negative sign.
The crystal growth of Tb-Fe giant magnetostrictive materials under microgravity (μG) and terrestrial gravity (1G) was investigated. The microgravity conditions were obtained by free fall in drop tower facility at the Japan Microgravity Center (JAMIC). TbFe1.83 alloy with 1 gram and cubic form was prepared for unidirectional solidification under microgravity environment. The samples were melted just before drop and solidified by contact chill against a sample at the period of microgravity after dropping. The microstructure of μG sample was columnar structure and growth direction was aligned in thermal gradient. In 1G sample, the microstructure was weak aligned in thermal gradient. The composition was measured by EDX. The TbFe3 phase was observed in 1G sample, and no TbFe3 phase was observed in μG sample, caused by reduction of thermal convection in microgravity environment. In μG sample, the columnar structure that aligned thermal gradient was oriented orientation. The magnetostriction of parallel direction to the thermal gradient was larger than perpendicular direction in μG and 1G. The magnetostriction of μG sample, the measurement direction was parallel to the thermal gradient, was larger than 1G sample caused by microstructure.
Machining properties of Ag containing glasses (ACG) using KrF excimer laser and femtosecond laser are reported. Ag ions in the ACG are effective to prevent cracking and chipping during the laser machining. A 4x4 hole array fabricated by KrF excimer laser onto an ACG has good uniformity of hole diameter, d(ave) equals 129.9um and (sigma) equals 0.8um. V- and U- grooves are fabricated on ACG using a Ti:Al2O3 laser irradiation. The cross- sectional shape is controlled by Ag ion concentration in ACG.
We report the observation of high light-induced change in refractive index (recognizable by observation in conventional microscope) in PMMA film doped with an optically non-linear dye 2-nitroaniline (NO2(C6H4)NH2 abbreviated as 2NA). The optically altered micrometer-sized regions were fabricated by single-shot radiation of 120 fs laser pulses into doped PMMA film using high numerical aperture 1.3 and high magnification x100 objective lens. The doping of films can be achieved in a wide range of 2NA concentrations (up to 40 wt%) without precipitation. This allows to control a storage time of an optically altered region up to one month by the adjusting the energy of the femtosecond (fs) recording pulse at 800 nm. Typical recording energy was 10-80 nJ/pulse at the point of irradiation. Total recovery of transmission of the PMMA2NA film was confirmed by optical transmission measurements in a microscope. The light induced damage threshold (LIDT) (for permanent damage) was increased more than by four times (up to 40 nJ/pulse) when 2NA doping were ca.1e wt%. While the LIDT for transient damage was decreased by 1.5-2 times. Total optical recovery was observed single exponential with decay time of ca. 0.5-1 minute for moderate irradiation intensities (0.1xLIDT of permanent damage). The damage induced with at the higher intensities lasts up to a month, but the recovery was not total (residual transmission changes were observable). The phenomenon can be applied for the optical memory, photonic crystal, and micro-mechanical applications. The underlying mechanism of the phenomenon is discussed in terms of anelastic (alpha) and (beta) -relaxation (polymer backbone and side chain relaxation, respectively).
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