Orientation of azobenzene molecules in polymer films induced by all-optical poling

A model of the alignment of azobenzene molecules in polymer film induced by all-optical poling is proposed and verified by experiment. We found that when the writing beams of frequencies ω and 2ω are both linearly polarized with their polarization directions parallel to each other, azobenzene molecules tend to reorient to the direction perpendicular to the writing beams polarization. At the end of the writing process, more molecules orient to the direction perpendicular to the writing beams polarization than those which orient to the parallel direction. The alignment of molecules parallel or perpendicular to the polarization of the writing beams is characteristic of polarity or no polarity, respectively. The alignment of molecules along the polarization of writing beams results in the second order nonlinearity in the polymer film. According to the model, a new method to improve the optical poling efficiency is put forward.     

偶氮聚合物薄膜的全光极化研究

报告了分散红共聚物膜HMMM-DR1,HMMM-DR19和偶氮侧链聚合物膜PCN6和PCN2的合成和制备, 并以HMMM-DR1和PCN6为代表比较研究了这两种具有不同吸收性质材料的全光极化特性,研究了他们的实时极化和弛豫过程,对他们的全光极化性质作了最基本的表征.研究了倍频光吸收对薄膜光极化效率的影响,讨论了偶氮聚合物材料光诱导二阶非线性极化率的效率和倍频光透射率之间的折衷关系,这对实用化的全光器件的研制是至关重要的.实验确证了在PCN6薄膜中实现了准相位匹配.对厚膜中光诱导二阶非线性极化率的弛豫抑制效应作出解释.     

Temperature dependence of the optical poling of azobenzene polyimide films

The temperature dependence of all-optical poling of azobenzene–polyimide films was experimentally investigated. The poling efficiency decreased with the increase of the sample temperature during the optical poling processes. The experimental result can be explained by considering the relation between the lifetime of the triplet-state of the azobenzene molecule and the repetition rate of the laser pulses used in the poling processes.     

Permanent light-induced polar orientation via all-optical poling and photothermal cross-linking in a polymer thin film

An epoxy-based crosslinkable polymer functionalized with nonlinear optical (NLO) photochromic dye known as Red Acid Magly was polarly oriented via thermally-assisted all-optical poling to enhance the photostability of the induced order. During the writing (seeding) process the film was cross-linked by heating with a hot-plate and irradiated simultaneously by the coherent superposition of the 1.06 μm fundamental and 0.532 μm second harmonic beams of a nanosecond pulsed Nd:YAG laser. We demonstrate that crosslinking between the polymer matrix and the pendant chromophore groups induced during the thermally-assisted all-optical poling procedure results in a stable light-induced second order susceptibility.     

Real-time monitoring of all-optical poling of azo-dye polymer thin film

Simultaneous writing and probing of photoinduced second-order susceptibility chi((2)) in an azo-dye polymer thin film is demonstrated. The method is based on the fact that tensor properties of chi((2)) provide different planes of polarization for seeding and signal second harmonics. Our technique allows the chi((2)) value to be monitored in real time, completely eliminating the distortion of optical poling that can occur in traditional probing configurations. The possibility of attaining high values of chi((2)) in a DR1-PMMA guest?host system under low seeding intensities is shown.     

Quasi-phase-matched gratings printed by all-optical poling in polymer films

The all-optical poling technique permits polar orientation of molecules. For efficient poling of thin films the relative phases, amplitudes, and polarizations of the two interfering beams must be controlled. We present an original stable one-arm interferometer that is specific to the recording of two-color interference. It relies on the index dispersion of optical glasses. This interference technique permits true real-time nonperturbative monitoring of the polar orientation process and easy all-optical poling of thin-film materials without the need for phase control. This new configuration opens the door to the realization of customized phase-matched wave-guided frequency-conversion devices for the near infrared.     

Stable frequency doubling by all-optical poling in dye-doped polymer optical fibers

We present experimental studies of all-optical poling (AOP) in large-core dye-doped poly(methyl methacrylate) plastic optical fibers. We show that the confinement of light within the fiber core permits us to reach the upper limit of second harmonic generation achievable by AOP using repeated trans-cis isomerization. Quantification of the output power indicates self-seeding that can counteract relaxation of the orientation during readout of the induced nonlinearity.     

Carrier-envelope phase measurement by all-optical poling with a polar side-chain polymer

Dependence of all-optical poling efficiency on carrier-envelope phase (CEP) could be measured using photoisomerization of dye molecules which are covalently bound to a polymer main chain and have large difference in static dipole moment between the ground state and excited state. Increased chromophore density leads to an order of magnitude reduction in signal-detection time from a dye doped polymer. Analysis of all-optical poling experiments with CEP changes clearly showed the presence of polarization restoring force to zero polarization. This enables resetting of SH activity in the all-optical poling process to be used for fast response loop of CEP stabilization. Phenomenological model could explain well the difference in the growth-and-decay dynamics of poling between sample of dye doped in polymer studied previously and that grafted to a polymer main chain used in the present paper.     

SiO2脊形条波导热极化引起的电光效应

通过理论模拟对具有上覆盖层的SiO₂脊形条波导结构进行了优化，在此基础上利用微电子工艺制作了SiO₂脊形波导Mach-Zehnder型电光调制器，并进行热极化引起的电光和非线性效应的研究.热极化过程大幅增强了样品的电光及非线性效应，二次电光系数由热极化前的1.56×10^-22(m/V)²提高到热极化后的8.50×10^-22(m/V)²，极化后得到了0.093pm/V的线性电光系数，对热极化的物理机理进行了理论分析. 关键词： 电光调制器 2光波导')" href="#">SiO₂光波导 电光效应 热极化     

χ polarization induced in molecular glass of conjugated compound by all-optical poling

The paper presents the first report on χ⁽²⁾ polarization induced in molecular glass of conjugated compound by all-optical poling. Transparent thin film of molecular glass of 1,4-bis[2-[4-[N,N-di(p-tolyl)amino]phenyl]vinyl]benzene (BTAPVB) was prepared using a spin-cast technique. Dipolar as well as octupolar components in BTAPVB contributed to the formation of photoinduced χ⁽²⁾ polarization. Growth rate of χ⁽²⁾ polarization has good linear relation with E_ω⁴E_2ω, which suggested that the simultaneous processes of two-photon (ω + 2ω) and three-photon (ω + ω + ω) excitation on the same electronic level contributed to the formation of photoinduced χ⁽²⁾ polarization.     

Dynamics of photoinduced second order nonlinearity in dimethylamino-nitrostilbene polymer thin films

All-optical encoding of macroscopic second order susceptibility in a dimethylamino-nitrostilbene (DANS) polymer thin film is demonstrated. We show that the main mechanism responsible for the induced nonlinearity in DANS polymer is the angular hole burning effect due to trans–cis isomerization as distinct from azo-polymers, in which considerable reorientation of trans-molecules occurs. The DANS sample exhibits better dark stability in comparison with azo-systems such as disperse red 1 polymethylmethacrylate (DR1–PMMA). The results are explained by the absence of thermal cis–trans relaxation in DANS–PMMA.     

Study on all-optical switching characteristics of ethyl orange-doped polymer film

The all-optical switching polymer thin films with azobenzene dye ethyl orange as the guest material and polyvinyl alcohol (PVA) as the host material were prepared by adulteration and spin-coating methods. The all-optical switching characteristics of the samples were measured at different intensities and modulation frequencies of the pump beam (532 nm, CW); the influence of doping concentration on the all-optical switching effect of the films was studied. It is shown that, under room temperature conditions and with a low pump power of 6 mW, the all-optical switch has a response time of about 2 ms and a modulation depth of 45%, and the maximal modulation depth reaches 90%. In addition, it is found that samples with higher doping concentration show a stronger all-optical switching effect but a larger background signal, and good switching performance is obtained by choosing the doping concentrations from 0.8% to 2% of the sample.     

Study on dipolar orientation and relaxation characteristics of guest-host polymers affected by corona poling parameters

The dipolar orientation and relaxation characteristics of guest-host polymers poled by corona poling have been studied in detail. The mechanisms of dipolar orientation affected by poling parameters (voltage, temperature, time and cooling velocity) in polymers have been analyzed by UV-Vis absorption spectra and microscope. The results show that with increasing poling voltage, the orientation order parameter increases to maximum and then drops. Also the same trend of orientation order parameter has been obtained with increasing poling temperature. While the orientation order parameter increases to saturation with increasing poling time. With the biexponential model analyzing, it is shown that the relaxation of dipolar orientation can be slowed by slowing the cooling velocity during the poling process.     

Optical limiting response by embedding copper phthalocyanine into polymer host

The multilayer film of PMMA containing mononuclear octakis(mercaptopropylisobutyl-POSS) substituted phthalocyaninato-copper (CuPc) was obtained by spin-coating on quartz substrate. The nonlinear absorption and optical limiting (OL) performance of CuPc have been described using the open-aperture Z-scan technique. The measurements were performed using collimated 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The results indicate that CuPc/PMMA composite exhibits a much larger nonlinear absorption coefficient, a lower saturable fluence and a lower absorption cross-section ratio for optical limiting when compared to the same CuPc molecules in solution. No evidence of film fatigue or degradation was observed in the CuPc/PMMA film after numerous scans at varying laser intensity. This material is a good candidate for optical limiting applications.     

Dynamic and geometric alignment of molecules induced by intense laser fields

We present a method to discuss simultaneously the relative importance of molecular dynamic and geometric alignment induced by intense laser fields in theoretical view. This method divides the process of molecular alignment into three steps, which are tightly correlated with that of molecular multielectron dissociative ionization and Coulomb explosion. A fourth-order Runge-Kutta algorithm and a developed counting approach are used to calculate the angular distribution of molecules in the first and second steps of molecular alignment. The last step is described by a field-ionization, Coulomb explosion model. The angular distribution of molecules at the critical distance originated from geometric alignment is obtained by calculating the volume of shells associated with a series of particular angle. The final angular distributions of molecules are obtained by properly weighting the results of three steps. The numerical results of distinguishing between dynamic and geometric alignment for certain conditions are presented and discussed. Our computational results show that the alignment mechanism, which dominates the observed anisotropy of angular distributions of ionic fragments for a given condition, is determined by the dependences of the extent of dynamic and geometric alignment on laser parameters and molecular parameters.     

摩擦导致的聚合物表层微观结构改变

应用大规模分子动力学方法, 模拟了锥形探头在非晶态聚合物薄膜表面的滑动摩擦过程, 研究了摩擦导致的聚合物薄膜表层微观结构改变, 以及探头与基体间黏着作用、滑动速度和分子链长度对基体表层微观结构改变的影响. 当探头与基体之间为黏着作用时, 摩擦导致基体表面滑痕区域的键取向沿滑动方向重新取向, 导致表层分子链回转半径沿滑动方向伸长, 并且这些表层微观结构的改变程度随滑动速度的减小而增大. 在摩擦导致结构改变的过程中, 链端单体和链中单体的贡献作用不同, 形成了不同的分子链拉伸变形机制. 当样本缠结度较大或探头滑动速度较小时, 相比于链中单体, 探头对链端单体的拖曳作用使更多分子链发生拉伸变形. 研究还发现, 在探头与聚合物薄膜系统中, 使薄膜表层微观结构发生改变是摩擦能量耗散的重要途径.     

Specific features of absorption and DSC for the DEA-CuCl4 nanoparticles incorporated into the PMMA polymer matrices

Diethylammonium tetrachlorcuprate NH₂(C₂H₅)₂CuCl₄ (DEA-CuCl₄) nanoparticles with sizes about 10 nm were synthesized and embedded into the PMMA polymer matrices. Using DSC temperature study a substantial influence of the polymer matrix on the phase transition temperatures was shown, reflecting a disturbing effect of principal 3d Cu-3p Cl metal-ligand charge transfer bands. Dependence of the absorption spectra on the nanocrystallites (NC) concentration was studied. It was established that an increase of the NC content results in spectral shift of CuCl₄ absorption bands. Explanation of this phenomenon has been suggested within a framework of first principle crystal field quantum chemical calculations.     

Determination of the macroscopic optical properties for the NAEC/PEK-c guest–host polymer films

The polyetherketone (PEK-c) guest–host polymer films doped with (4′-nitro)-3-azo-9-ethyl-carbazole (NAEC) were prepared. The films were poled by corona-onset poling at elevated temperature (COPET). The orientational order parameter of the chromophores NAEC in poled polymer film was determined by measuring the absorption spectra of the films before and after being poled. By using the two-level model, the measured dispersion of the refractive index of the polymer film, and the dispersion of the first hyperpolarizability of chromophore NAEC, the dispersion of the macroscopic second-order nonlinear optical (NLO) and linear electro-optic (EO) coefficients was evaluated for the NAEC/PEK-c guest–host polymer film.     

Spatial reorientation of azobenzene side groups of a liquid crystalline polymer induced by linearly polarized light

The photoinduced 3D orientational structures in films of a liquid crystalline polyester, containing azobenzene side groups, are studied both experimentally and theoretically. By using the null ellipsometry and the UV/Vis absorption spectroscopy, the preferential in-plane alignment of the azobenzene fragments and in-plane reorientation under irradiation with linearly polarized UV light are established. The uniaxial and biaxial orientational order of the azobenzene chromophores are detected. The biaxiality is observed in the intermediate stages of irradiation, whereas the uniaxial structure is maintained in the photosaturated state of the photo-orientation process. The components of the order parameter tensor of the azobenzene fragments are estimated for the initial state and after different doses of irradiation. The proposed theory takes into account biaxiality of the induced structures. Numerical analysis of the master equations for the order parameter tensor is found to yield the results that are in good agreement with the experimental dependencies of the order parameter components on the illumination time. Received 23 April 2001 and Received in final form 1 August 2001     

Measurement of the optical transmission modes and losses of the poled guest–host polymer NAEC/PEK-c planar waveguides

The polyetherketone (PEK-c) guest–host polymer planar waveguides doped with (4′-nitro)-3-azo-9-ethyl-carbazole (NAEC) were prepared. The waveguide films were poled by corona-onset poling at elevated temperature (COPET), and the corona poling setup includes a grid voltage making the surface-charge distribution uniform. By using the prism-in coupling method, the dark-line spectrum given by the reflected intensity versus the angle of incidence have been obtained, and the optical transmission losses of mth modes have been measured for the poled polymer waveguides at λ=632.8 nm. The measurement result showed that the optical loss of the fundamental mode is less than 0.7 dB cm⁻¹ for the TE polarization.