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This PDF file contains the front matter associated with SPIE Proceedings Volume 7487, including the Title Page, Copyright information, Table of Contents, aand the Conference Committee listing.
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Molecular Based Devices: Materials and Architectures I
In this paper we report on the use of two solution-processable polymeric and molecular n-channel semiconductors for the
fabrication of transistors and CMOS inverters by gravure printing and inkjet printing. Furthermore, the injket-printed
TFT/invertor stability characteristics are analyzed and discussed.
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We report on the characteristics of a host-guest lasing system obtained by co-evaporation of an oligo(9,9-diarylfluorene)
derivative named T3 with the red-emitter
4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran dye
(DCM). We demonstrate that the ambipolar semiconductor T3 can be implemented as active matrix in the realization of a
host-guest system in which an efficient energy transfer takes place from T3 matrix to the lasing DCM molecules. We
performed a spectroscopic study on the system by systematically varying the DCM concentration in the T3 matrix.
Measurements of steady-state photoluminescence (PL), PL quantum yield (PLQY) and amplified spontaneous emission
(ASE) threshold are used to optimize the acceptor concentration at which the ASE from DCM molecules takes place
with the lowest threshold.
Organic light-emitting diodes (OLEDs) implementing the DCM:T3
host-guest system as recombination layer are
fabricated for verifying the optical properties of the optimised blend in real working devices.
Indeed, the very low ASE threshold of T3:DCM makes the investigated blend an appealing system for use as active layer
in lasing devices. In particular, the ambipolar charge transport properties of the T3 matrix and its field-effect
characteristics make the host-guest system presented here an ideal candidate for the realization of electrically-pumped
organic lasers.
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Molecular Based Devices: Materials and Architectures II
Several applications of the thermoluminescence (TL) technique for investigations of mechanisms of charge carrier
trapping and recombination in electroluminescent polymers which are used for construction of various opto-electronic
devices are described. The presented TL studies were focused on polymers emitting blue light, because such emissive
materials are requested to realize the white-light-emitting OLEDs or RGB-displays. We have investigated wide band-gap
conjugated polymers and also non-conjugated polymers: series of polyfluorenes (homo- and copolymers) and poly(9-
vinylcarbazole), neat and doped with low-molecular-weight dopants. The dopants were introduced in order to improve
the charge carrier transport and also the to modify the recombination processes.
It is shown, that the spectrally resolved thermoluminescence studies, especially when performed in a broad
temperature range allow to characterise the nature of the trapping sites and of the recombination centres and to identify
the mechanisms responsible for transfer of energy in the investigated materials.
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Laue diffraction with x-rays is common to determine symmetry and crystal structure of natural crystals.
Extension of the method towards visible light failed so far due to lack of crystals in nature with lattice
parameters in the range of visible light. Nowadays artificially three-dimensional crystals known as photonic
crystals (PCs) are available. However, in contrast to x-rays diffraction from small crystals described by the
kinematic scattering approach, scattering of visible light from PCs suffers from the large contrast and the tensor
character of refractive index originating multiple scattering of probing light. In this paper we show the Laue
scattering with visible light at PCs with internal refractive index contrast less then 1%. The Laue pattern shows
colour separation and displays the crystal symmetry. Scattering curves of individual Laue spots taken with
monochromatic light can be well described by kinematic scattering. Both results demonstrate the applicability of
such crystals for spectral filtering.
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In the large family of polymers, the azobenzene derivatives represent one fascinating materials class, along with
stylbene and azomethinic derivatives. This interest is explained by combination of the properties of anisotropy with the
photoinduced behaviors. The photoinduced birefringence, relief grating, the high optical nonlinearity resulted from the
sin-anti isomerism, molecular reorientation, the exceptional stability to writing and erasing by laser radiation, are just the
most important arguments for their usage of these polymeric architectures in the NLO field as: LCD, chemical sensing,
devices for storage and transmission of information .
This presentation covers the development and characterization a new series of materials from viewpoint of:
-Modification of the polymer materials by the chemical transformation of the "common" polymer support an
underlining: photorefractivity, NLO properties
-Utilization of these polymers as components in guest-host materials preparation.
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We propose a microscopic theory of light-induced deformation of side-chain azobenzene polymers using a statistical
model which takes the chemical architecture of azobenzene macromolecules explicitly into account. The theory provides
the values of the light-induced stress larger than the yield stress. This result explains a possibility for the inscription of
surface relief gratings in glassy side-chain azobenzene polymers. We show that the photo-elastic behavior of azobenzene
polymers is very sensitive to their chemical structure. Depending on the chemical structure, a sample can be either
stretched or uniaxially compressed along the polarization direction of the linearly polarized light. For some chemical
structures, elongation of a sample demonstrates non-monotonic behavior with the light intensity and can even change its
sign (a stretched sample starts to be uniaxially compressed). These results are in agreement with experiments and recent
computer simulations.
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As size requirements and pixel viabilities for mid-wavelength infrared (MWIR) focal plane arrays (FPAs)
continue to increase, larger InSb substrate diameters are of significant interest. To improve resolution and
sensitivity requirements for high performance infrared focal plane array (IRFPA) imaging systems in the 1-5.4 μm
region (77°K), the surface of new larger diameter (150mm) InSb substrates must meet or surpass stringent
demands. The scale-up to 150mm InSb has necessitated changes in processing and finishing parameters, as device
layer growth by epitaxy or other means often requires a surface roughness average (Ra)~0.1 nm. This study
compares two different CMP finishes for new 150mm diameter InSb wafers and examines their suitability for
IRFPA applications. InSb surface quality was examined by molecular beam epitaxy (MBE), reflective high energy
electron diffraction (RHEED), atomic force microscopy (AFM), thermal X-ray spectroscopy (TXPS), and
multiple crystal x-ray diffraction (XRD) for two distinct CMP finishes on InSb(111)B substrates from the same
crystal boule. This study has shown that differences result in thermal desorption properties with the CMP process,
consistent with differences in surface smoothness and oxide composition. Better surface composition and
crystallinity were produced with a modified CMP process for the 150mm diameter crystals. We conclude that the
differential ratio between the pH, the oxidizer percentage, and the buffering percentage of the modified CMP
process is a benefit to larger diameter InSb IRFPA applications.
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We have performed Hyper-Rayleigh Scattering (HRS) experiments to measure the quadratic hyperpolarizability of
several natural amino acids, in particular tryptophan and tyrosine. Values of (29.6+/-0.4)x10-30 esu for tryptophan and
(25.7+/-0.03)x10-30 esu for tyrosine have been found. We have then investigated the dependence of the quadratic
hyperpolarizability of tryptophan-rich short peptides as a function of the number of tryptophans in the sequence. The
experimental findings indicate that the resulting quadratic hyperpolarizability in these peptides cannot be assumed as the
mere coherent superposition of the hyperpolarizabilities of the tryptophans contained in the peptide. Our results
unambiguously demonstrate that there must be strong interactions between the tryptophans contained in these short
peptides. We have also investigated the case of the collagen triple helix. A second order hyperpolarizability of (1.25+/-
0.05)x10-27 esu for rat-tail type I collagen has been measured. In this case, we have been able to model this effective
quadratic hyperpolarizability by summing coherently the nonlinear response of elementary moieties forming the triple
helix, as opposed to the previous case of the tryptophan-rich peptides.
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Collagen is a major protein of the extracellular matrix that is characterized by triple helical domains. It plays a
central role in the formation of fibrillar and microfibrillar networks, basement membranes, as well as other structures of
the connective tissue. Remarkably, fibrillar collagen exhibits efficient Second Harmonic Generation (SHG) so that SHG
microscopy proved to be a sensitive tool to probe the
three-dimensional architecture of fibrillar collagen and to assess
the progression of fibrotic pathologies. We obtained sensitive and reproducible measurements of the fibrosis extent, but
we needed quantitative data at the molecular level to further process SHG images. We therefore performed Hyper-
Rayleigh Scattering (HRS) experiments and measured a second order hyperpolarisability of 1.25 10-27 esu for rat-tail
type I collagen. This value is surprisingly large considering that collagen presents no strong harmonophore in its aminoacid
sequence. In order to get insight into the physical origin of this nonlinear process, we performed HRS
measurements after denaturation of the collagen triple helix and for a collagen-like short model peptide [(Pro-Pro-
Gly)10]3. It showed that the collagen large nonlinear response originates in the tight alignment of a large number of
weakly efficient harmonophores, presumably the peptide bonds, resulting in a coherent amplification of the nonlinear
signal along the triple helix. To illustrate this mechanism, we successfully recorded SHG images in collagenous
biomimetic matrices.
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LiInSe2 is one of the few (in the meanwhile 6) non-oxide nonlinear crystals whose band-gap (2.86 eV) and transparency
enabled in the past nanosecond optical parametric oscillation in the mid-IR without two-photon absorption for a pump
wavelength of 1064 nm. However, the first such demonstration was limited to the 3.34-3.82 μm spectral range with a
maximum idler energy of 92 μJ at 3.457 μm for a repetition rate of 10 Hz. Now we achieved broadly tunable operation,
from 4.65 to 7.5 μm, with a single crystal, reaching maximum idler pulse energy of 282 μJ at 6.514 μm, at a repetition
rate of 100 Hz (~28 mW of average power).
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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.
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We present here novel easily processible organic-inorganic nanocomposites suitable for holographic fabrication of
diffraction optical elements (DOE). The nanocomposites are based on photocurable acrylate monomers and inorganic
nanoparticles (NP). The compatibility of inorganic NP with monomers was achieved by capping the NP surface with
proper organic shells. Surface modification allows to introduce up to 50wt.% of inorganic NP in organic media.
Depending on the NP nature (metal oxides, phosphates, semiconductors, noble metals) and their properties, the materials
for both efficient DOE and multifunctional elements can be designed. Organic-inorganic composites prepared have been
successfully used for the effective inscription of periodic volume refractive index structures using the holographic
photopolymerization method. The nanocomposite preparation procedure, their properties and optical performance of
holographic gratings are reported. The use of functional NP makes it possible to obtain effective holographic gratings
having additional physical properties such as light-emission or NLO. Some examples of such functional polymer-NP
structures and their possible application fields are presented. The combination of easy photo-patterning of soft organic
compounds with physical properties of inorganic materials in new nanocomposites and the flexibility of the holographic
patterning method allow the fabrication of mono- and multifunctional one- and multi-dimensional passive or active
optical and photonic elements.
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We report on ZnGeP2 and AgGaS2 crystal growth and improvement of optical transparency by annealing. Good optical
quality single-crystal samples with size up to 5×5×20 mm3 were cut from our ingots, allowing to demonstrate efficient
optical parametric oscillation with ZnGeP2 and to carry out first difference-frequency generation experiments with
AgGaS2.
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Gelatin and DNA are abundant natural products with very good biodegradation properties and can be used to obtain
acetic acid or LiClO4-based gel polymer electrolytes (GPEs) with high ionic conductivity and good stability. This article
presents the results of the ionic conductivity measurements of GPEs membranes based on crosslinked and plasticized
gelatin and on plasticized DNA as well as on inserted/extracted charge density of electrochemical devices (ECDs)
obtained with these samples. The membranes were analyzed by impedance spectroscopy, UV-Vis spectroscopy and the
ECDs by charge density measurements, respectively. At room temperature the measured ionic conductivity of the
membranes is in the range of 10-4-10-5 S/cm. It obeys predominantly an Arrhenius relationship in function of
temperature. The ECD with red gelatin changed the color from red to deep red and the ECD with DNA-based electrolyte
changes from transparent to blue. The inserted charge density values of these ECDs were of -3.0 mC/cm2 for the device
with red gelatin and -6.6 mC/cm2 for the ECD with DNA-based electrolyte. The reverse potential application promoted a
charge extraction and, as consequence, bleaching of the devices. Good ionic conductivity results combined with
transparency and good adhesion to the electrodes and promising preliminary results of small ECDs have shown that
gelatin and DNA-based GPEs are very promising materials to be used as gel polymer electrolytes in electrochromic
devices.
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We report the synthesis of five new hybrid polymeric structures obtained by free radical copolymerization of
some organic azo-based methacrylate monomers and 3-methacryloxypropyl trimethoxysilane (MEMO). The copolymers
are soluble in common solvents like methylene chloride, chloroform, dichlorbenzene, dimethylsulfoxide,
dimethylformamide. The copolymeric structures might be interesting from the point of view of nonlinear optical
response due to a rich content in chromophoric units determined by
H-NMR spectroscopy. The structures were also
characterized by FT-IR spectroscopy, TGA and SEC analysis.
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