Polymer thin film properties as a function of temperature and pressure

We report on evanescent wave optical measurements of the glass transition temperature, T_g, of spin-cast PMMA films as a function of film thickness and molecular weight. It was found that for films of high molecular weight PMMA (M_n > 100,000 g mol⁻¹) a strong T_g depression occurs for films that are thinner than 100 nm in case they are deposited on hydrophobic substrates. This strong T_g depression of up to 25°C decreases if similarly thick films of PMMA of low molecular weights are investigated and vanishes completely for PMMA with M_n < 12,000 g mol⁻¹. For films made of these materials T_g is found to be identical to that of the bulk even for films as thin as 5 nm. The results might be interpreted in terms of free volume considerations. To check this assumption we also designed and built a pressure cell that can be used together with the evanscent wave optical techniques for similar measurement, but with the additional option to do the measurements at different pressures up to ca. 100 MPa to further vary the free volume of these polymer films in constrained geometry. Some first results obtained with this setup are also described.     

Thermal behaviors and characteristics of polylactide/poly(butylene succinate) blend films via reactive compatibilization and plasticization

Polylactide (PLA)/poly(butylene succinate) (PBS) blend films modified with a compatibilizer and a plasticizer were hot‐melted through a twin screw extruder and prepared by hydraulic press. Toluene diisocyanate (TDI) and polylactide‐grafted‐maleic anhydride (PLA‐g‐MA) were used as compatibilizers, while triethyl citrate and tricresyl phosphate acted as plasticizers. The effects of the type and content of compatibilizer and plasticizer on the mechanical characteristics, thermal properties, crystallization behavior, and phase morphology of the PLA/PBS blend films were investigated. Reactive compatibilization at increasing levels of TDI improved the compatibility of the PLA and PBS, affecting the toughness of the films. As evidenced by scanning electron microscope, the addition of TDI enhanced the interfacial adhesion of the blends, leading to the appearance of many elongated fibrils at the fracture surface. Furthermore, PLA/PBS blending with both TDI and PLA‐g‐MA led to an acceleration of the cold crystallization rate and an increment of the degree of crystallinity ( ). Toluene diisocyanate could be a more effective compatibilizer than PLA‐g‐MA for PLA/PBS blend films. The synergistic combination of compatibilizer and plasticizer brought a significant improvement in elongation at break and tensile‐impact toughness of the PLA/PBS blends, compared with neat PLA. Their failure mode changed from brittle to ductile due to the improved compatibility and molecular segment mobility of the PLA and PBS phases. Differential scanning calorimeter results revealed that the plasticizers triethyl citrate and tricresyl phosphate changed the thermal behavior of T_cc and T_m, affecting α′ and α crystal formations. However, these plasticizers only slightly improved the thermal stability of the films.     

Preparation of high molecular weight polybenzoxazine prepolymers containing siloxane unites and properties of their thermosets

High‐molecular‐weight polybenzoxazine prepolymers containing polydimethylsiloane unit in the main‐chain have been synthesized from α,ω‐bis(aminopropyl)polydimethylsiloxane (PDMS) (molecular weight = 248, 850, and 1622) and bisphenol‐A with formaldehyde. Moreover, another type of prepolymers was prepared using methylenedianiline (MDA) as codiamine with PDMS. The weight average molecular weight of the obtained prepolymers was estimated from size exclusion chromatography to be in the range of 8000–11,000. The chemical structures of the prepolymers were investigated by ¹H NMR and IR analyses. The prepolymers gave transparent free standing films by casting their dioxane solution. The prepolymer films after thermally cured up to 240 °C gave brown colored transparent and flexible polybenzoxazine films. Tensile test of the films revealed that the elongation at break increased with increasing the molecular weight of PDMS unit. Dynamic mechanical analysis of the thermosets showed that the T_gs were as high as 238–270 °C. The thermosets also revealed high thermal stability as evidenced by the 5% weight loss temperatures in the range of 324–384 °C from thermogravimetic analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Thiophosphate esters of cashew nutshell liquid derivatives as new antioxidants for poly(methyl methacrylate)

In this work, poly(methyl methacrylate) films 1% additivated with new thiophosphate esters antioxidants derived from technical Cashew Nutshell Liquid (CNSL), a byproduct of the cashew nut (Anacardium occidentale L.) industry, were investigated by thermogravimetry (TG/DTG) and differential scanning calorimetry (DSC) measurements under inert (N₂) and oxidative (synthetic air) atmospheres. Three new products were synthesized and characterized by GC/MS, ¹H and ³¹P NMR. The analyses were focused on the onset (T _e) and offset temperature (T _o) of degradation of the films, and on the maximum degradation temperature (T _MAX). It was observed that the thermal stability of the films increased with the addition of the thiophosphate ester antioxidants, which indicates that CNSL could be used as a natural source of phenolic material for the synthesis of antioxidants.     

Synthesis and Structural Characterization of β‐Ketoiminate‐Stabilized Gallium Hydrides for Chemical Vapor Deposition Applications

Bis‐β‐ketoimine ligands of the form [(CH₂)_n{N(H)C(Me)?CHC(Me)?O}₂] (LⁿH₂, n=2, 3 and 4) were employed in the formation of a range of gallium complexes [Ga(Lⁿ)X] (X=Cl, Me, H), which were characterised by NMR spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction analysis. The β‐ketoimine ligands have also been used for the stabilisation of rare gallium hydride species [Ga(Lⁿ)H] (n=2 ( 7 ); n=3 ( 8 )), which have been structurally characterised for the first time, confirming the formation of five‐coordinate, monomeric species. The stability of these hydrides has been probed through thermal analysis, revealing stability at temperatures in excess of 200 °C. The efficacy of all the gallium β‐ketoiminate complexes as molecular precursors for the deposition of gallium oxide thin films by chemical vapour deposition (CVD) has been investigated through thermogravimetric analysis and deposition studies, with the best results being found for a bimetallic gallium methyl complex [L³{GaMe₂}₂] ( 5 ) and the hydride [Ga(L³)H] ( 8 ). The resulting films ( F5 and F8 , respectively) were amorphous as‐deposited and thus were characterised primarily by XPS, EDXA and SEM techniques, which showed the formation of stoichiometric ( F5 ) and oxygen‐deficient ( F8 ) Ga₂O₃ thin films.     

Titanium Carbide Thin‐Film Electrodes: Characterization and Evaluation as Working Electrodes

Titanium carbide (TiC) polycrystalline thin films, obtained by a hybrid chemical vapor deposition/powder flowing technique, were characterized and used to assemble working electrodes. The potential window and the electrochemistry of standard redox couples ([Ru(NH₃)₆]³⁺, [Fe(CN)₆]^3?) have been investigated in cyclic voltammetry, demonstrating a behavior similar to glassy carbon electrodes. The quinone (Q)/hydroquinone(H₂Q) redox couple presented an interesting quasireversible behavior(E_p=0.07 mV) , confirmed also for other quinones.     

SURFACE RHEOLOGY OF POLYMERIC SOLIDS

Surface molecular motions of amorphous polymeric solids have been directly measured on the basis of scanningviscoelasticity microscopic (SVM) and lateral force microscopic (LFM) measurements. SVM and LFM measurements werecarried out for films of conventional monodisperse polystyrene (PS) with sec-butyl and proton-terminated end groups atroom temperature. In the case of the number-average molecular weight, M_n, less than ca. 4.0×10~4, the surface was in a glass-rubber transition state even though the bulk glass transition temperature, T_g was far above room temperature, meaning thatthe surface molecular motion was fairly active compared with that in the bulk. LFM measurements of the, monodisperse PSfilms at various scanning rates and temperatures revealed that the time-temperature superposition was applicable to thesurface mechanical relaxation behavior and also that the surface glass transition temperature, T_g~σ, was depressed incomparison with the bulk one even though the magnitude of M_n was fairly high at 1.40×10~5. The surface molecular motionof monodisperse PS with various chain end groups was investigated on the basis of temperature-dependent scanningviscoelasticity microscopy (TDSVM). The T_g~σs for the PS films with M_n of 4.9×10~6 to 1.45×10~6 measured by TDSVMwere smaller than those for the bulk one, with corresponding M_ns, and the T_g~σs for M_ns smaller than ca. 4.0×10~4 were lowerthan room temperature (293 K). The active thermal molecular motion at the polymeric solid surface can be interpreted interms of an excess free volume near the surface region induced by the surface localization of chain end groups. In the case ofM_n=ca. 5.0×10~4, the T_g~σs for the α, ω-diamino-terminated PS (α,ω-PS(NH_2)_2) and α, ω-dicarboxy-terminated PS (α, ω-PS(COOH)_2) films were higher than that of the PS film. The change of T_g~σ for the PS film with various chain end groups canbe explained in terms of the depth distribution of chain end groups at the surface region depending on the relativehydrophobicity.     

Influence of adsorbed oxygen on charge transport and chlorine gas-sensing characteristics of thin cobalt phthalocyanine films

We have investigated the morphology, charge transport, and gas-sensing characteristics of thin films of cobalt phthalocyanine (CoPc) deposited on glass and sapphire substrates, using molecular beam epitaxy (MBE). CoPc films deposited on glass were found to be highly disordered. The ambient oxygen was found to be chemisorbed and created deep trap states, which led not only to hysteretic current-voltage (J-V) characteristics but also reduce the charge mobility. These properties render them unsuitable for gas-sensing. On the other hand, films deposited on sapphire were polycrystalline, which was attributed to an improved molecule-substrate interaction. The physically sorbed oxygen only created shallow traps, and the J-V characteristics were non-hysteretic, rendering them suitable for gas-sensing applications. It was demonstrated that the ultrathin (20 nm) CoPc films deposited on sapphire acted as highly sensitive and selective sensors for chlorine present in the w _Cl concentration range of 5 × 10⁻⁹−2 × 10⁻⁶ (5–2000 ppb).     

Mechanically Stable Hydrophilic Films Based on Oxialkylated Macromers Polymerizable by UV Irradiation

The preparation and characterization of films based on ethoxylated and acrylated triethanolamine or ϵ-aminecaprolactam or acrylated block copolymer of ethylene oxide (EO) and propylene oxide (PO) are described. Chemical characterization of films and migration of the plasticizers through the films were monitored with electron spectroscopy for chemical analysis. The (EO)_x(PO)_y(EO)_x–3A film was shown to be unique in the sense that it efficiently prevents migration of hydrophobic species. © 1997 John Wiley & Sons, Ltd.     

Poly(?-caprolactone)-based ‘green’ plasticizers for poly(vinyl choride)

A series of proposed plasticizers for poly(vinyl chloride) (PVC), based on poly(?-caprolactone) (PCL) with octanoate and benzoate-terminal groups, were synthesized with various microstructures and molecular weights (MW) and tested for biodegradability as well as for mechanical performance, and leaching resistance in blends with PVC. The plasticization efficiency of each was characterized by measuring the glass transition temperature (T_g) and tensile properties of PCL/PVC blends. The PCL-octanoate plasticizers demonstrated plasticization efficiency similar to di(ethylhexyl) phthalate (DEHP) with the same plasticizer loading. PCL-benzoate/PVC blends had much higher T_gs (∼20 °C higher) compared to PCL-octanoate/PVC and DEHP/PVC blends. Yield stresses were about two times higher for PCL-benzoate/PVC blends compared to PCL-octanoate/PVC and DEHP/PVC blends, reflecting the stiffer nature of such blends. Biodegradation was rapid for all PCL-octanoates, with the exception of linear PCL-octanoates with arm molecular weights >10³ g mol⁻¹. Biodegradation rates of PCLs by Rhodococcus rhodocrous were not affected by microstructure for the range of PCL topologies studied (linear versus three or four arms) but were slower for PCLs made from commercial PCL-diols that had a central ether linkage due to the initiator used to make these compounds. Leaching resistance was higher as PCL molecular weight increased and, for pairs of comparable sized species, significantly less PCL-benzoate leached out compared to the PCL-octanoate. For the range of PCL topologies studied, the number of arms did not significantly affect leaching resistance. In summary, both the end group and the molecular weight influenced the leaching resistance of the PCL. PCL-octanoates were comparable plasticizers to DEHP in terms of the mechanical properties examined, and were rapidly degraded by a common soil microorganism.     

Polystyrene‐b‐poly(2,2,2‐trifluoroethyl acrylate)‐b‐polystyrene copolymers: Synthesis and fabrication of their hydrophobic porous films,spheres, and fibers

New block copolymers Polystyrene‐b‐poly (2,2,2‐trifluoroethyl acrylate)‐b‐Polystyrene (PS‐PTFEA‐PS) with controlled molecular weight (M_n=5000‐11000 g?mol^?1) and narrow molecular weight distribution (M_w/M_n=1.13‐1.17) were synthesized via RAFT polymerization. The molecular structure and component of PS‐PTFEA‐PS block copolymers were characterized through ¹H NMR, ¹⁹F NMR, GPC, FT‐IR and elemental analysis. The porous films of such copolymers with average pore size of 0.80‐1.34 μm and good regularity were fabricated via a static breath‐figure (BF) process. The effects of solvent, temperature, and polymer concentration on the surface morphology of such film were investigated. In addition, microstructured spheres and fibers of such block copolymers were fabricated by electrospinning process and observed by scanning electron microscopy (SEM). Furthermore, the hydrophobicity of porous films, spheres, and fibers was investigated. The porous film showed a good hydrophobicity with the water‐droplet contact angles of 129°, and the fibers showed higher hydrophobicity with the water‐droplet contact angles of 142°. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 678–685     

Controlled Release of Model Drug from Biodegradable Segmented Polyurethane Ureas: Morphological and Structural Features

Segmented polyurethane ureas (SPUUs), which are being used in implant devices, were evaluated as drug delivery matrices using theophylline as a model drug without much sacrificing the mechanical properties of films after drug doping. SPUUs were synthesized from aliphatic diisocyanate (lysine methyl ester diisocyante (LDI)), poly(caprolactone) diol with molecular weights 530, 1250 and 2000 and 1,4-butanediamine. Three series of segmented SPUUs were prepared with various soft segment lengths and were characterized by Fourier transform infrared spectroscopy, dynamic viscoelastic measurements and tensile testing. A single tanδ peak was observed in dynamic viscoelastic measurements, which revealed phase mixing of hard and soft segments. Low elongation at break was observed in case of PCL 2000 based SPUUs, may be due to partial cystallization of PCL segment. The degradation of SPUUs in alkaline solution and in vitro drug release of theophylline in pH 7.4 buffer were also investigated. The drug release behavior from these films were analyzed by the exponent relation M_t/M_∞ = ktⁿ, where k and n are constants and M_t/M_∞ is the fraction of drug released until time, t. The constant n was found to be close to 0.5 in all samples, which suggests the release of drug from these polymers can be explained by the Fickian diffusion model.     

Efficient Synthesis of Novel Plasticizers by Direct Palladium-Catalyzed Di- or Multi-carbonylations

Diesters are of fundamental importance in the chemical industry and are used for many applications, e.g. as plasticizers, surfactants, emulsifiers, and lubricants. Herein, we present a straightforward and efficient method for the selective synthesis of diesters via palladium-catalyzed direct carbonylation of di- or polyols with readily available alkenes. Key-to-success is the use of a specific palladium catalyst with the “built-in-base” ligand L16 providing esterification of all alcohols and a high n/iso ratio. The synthesized diesters were evaluated as potential plasticizers in PVC films by measuring the glass transition temperature (T_g) via differential scanning calorimetry (DSC).     

Amperometric Hydrogen Peroxide Biosensor Based on the Immobilization of Horseradish Peroxidase (HRP) on the Layer‐by‐Layer Assembly Films of Gold Colloidal Nanoparticles and Toluidine Blue

The precursor film was first formed on the Au electrode surface based on the self‐assembly of L ‐cysteine and the adsorption of gold colloidal nanoparticles (nano‐Au). Layer‐by‐layer (LBL) assembly films of toluidine blue (TB) and nano‐Au were fabricated by alternately immersing the electrode with precursor film into the solution of toluidine blue and gold colloid. Cyclic voltammetry (CV) and quartz crystal microbalance (QCM) were adopted to monitor the regular growth of {TB/Au} bilayer films. The successful assembly of {TB/Au}_n films brings a new strategy for electrochemical devices to construct layer‐by‐layer assembly films of nanomaterials and low molecular weight materials. In this article, {TB/Au}_n films were used as model films to fabricate a mediated H₂O₂ biosensor based on horseradish peroxidase, which responded rapidly to H₂O₂ in the linear range from 1.5×10^?7 mol/L to 8.6×10^?3 mol/L with a detection limit of 7.0×10^?8 mol/L. Morphologies of the final assembly films were characterized with scanning probe microscopy (SPM).     

Synthesis of poly(ethylene‐co‐vinyl alcohol)‐g‐polystyrene graft copolymer and their applications for ordered porous film and compatibilizer

A series of new functional poly(ethylene‐co‐vinyl alcohol)‐g‐polystyrene graft copolymers (EVAL‐g‐PS) with controlled molecular weight (M_n = 38,000–94,000 g mol^?1) and molecular weight distribution (M_w/M_n = 2.31–3.49) were synthesized via a grafting from methodology. The molecular structure and component of EVAL‐g‐PS graft copolymers were confirmed by the analysis of their ¹H NMR spectra and GPC curves. The porous films of such copolymers were fabricated via a static breath‐figure (BF) process. The influencing factors on the morphology of such porous films, such as solvent, temperature, polymer concentration, and molecular weight of polymer were investigated. Ordered porous film and better regularity was fabricated through a static BF process using EVAL‐g‐PS solution in CHCl₃. Scanning electron microscopy observation reveals that the EVAL‐g‐PS graft copolymer is an efficient compatibilizer for the blend system of low‐density polyethylene/polystyrene. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 516–524     

Recent advances in ferroelectric polymers

In the Polymer Electroprocessing Laboratory at Rutgers University, we have discovered that the odd-numbered nylons constitute the second known class of ferroelectric polymers^1–3, and that polarized films exhibit piezoelectric properties similar to poly(vinylidene fluoride) (PVF₂) and copolymers of PVF₂ and trifluoroethylene (PVF₂/PVF₃). A study of a series of these polymers including nylon 11, nylon 9, nylon 7 and nylon 5 showed that the remanent polarization produced in quenched, cold-drawn films was a linear function of polymer dipole density⁴. The highest remanent polarization produced was that of nylon 5, the value attained (P₁=125mC/m²) being approximately 2.5 times that of PVF₂. We also discovered that (unlike PVF₂ or PVF₂/PVF₃) the remanent polarization could be stabilized to elevated temperatures (close to the polymer melting point). For nylon 5, the remanent polarization and piezoelectric response was stable to over 250°C⁵. We showed that the hydrogen-bonded sheet structure in nylon 11 for quenched cold-drawn films was parallel to the plane of the film, and that after application of high electric fields the hydrogen-bonded sheet structure was rotated 90° to an orientation perpendicular to the plane of the film³. A detailed X-ray diffraction study of the effects of humidity and electroprocessing on the switching behavior of nylon 5, nylon 7 and nylon 11 films was carried out⁵. The piezoelectric and pyroelectric response⁶ of these films was also determined. The different switching mechanisms observed and the measured piezoelectric and pyroelectric properties will be presented and discussed.     

Vibrational energy-harvesting performance of bio-sourced flexible polyamide 11/layered silicate nanocomposite films

The energy-harvesting efficiency of melt processed polyamide 11 (PA11) films and its nanocomposites have been investigated as a function of filler type and content. In the present work, nanoclays have been used as structural modifiers in a PA11 matrix. The nanocomposites were prepared using layered clays, Cloisite 20A, 10A, and Na⁺, by extrusion process through varying the filler content, 1, 2, 4, and 5?wt.%. The crystalline structure of these nanocomposites has been studied by X-ray diffractometer. It has been demonstrated that layered silicates are not significant for the structural quality of the obtained nanocomposites. Regarding the interlayer peak of different clays, it has also been revealed that Cloisite 20A is partially exfoliated, whereas 10A and Na⁺ are totally exfoliated in the PA11 matrix. From mechanical and dynamic mechanical analyses, it was found that the addition of layered silicates results in an increase in mechanical properties. The piezoelectric strain coefficient d₃₃ and dielectric constant ε_R have been measured on polarized films at ambient temperature. Among all the prepared nanocomposites only Cloisite Na⁺-loaded PA11 nanocomposites showed the best piezoelectric constant. This observation showed that piezoelectric constant not only depends on the crystalline phases but also on the nature of the filler. Cloisite Na⁺ is more polar than other modified clays and high polarity leads to a better polarization response. A specific method for the quantification of energy vibration recovery has been developed for these nanocomposites. The capabilities of vibrational energy recovery were studied on PA11 loaded with Cloisite Na⁺.     

Internal plasticization of poly(vinyl) chloride using glutamic acid as a branched linker to incorporate four plasticizers per anchor point

Internal plasticization of polyvinyl chloride (PVC) using thermal azide‐alkyne Huisgen dipolar cycloaddition between azidized PVC and electron‐poor acetylenediamides incorporating a branched glutamic acid linker resulted in incorporation of four plasticizing moieties per attachment point on the polymer chain. A systematic study incorporating either alkyl or polyethylene glycol esters provided materials with varying degrees of plasticization, with depressed T_g values ranging from ?1 °C to 62 °C. Three interesting trends were observed. First, T_g values of PVC bearing various internal plasticizers were shown to decrease with increasing chain length of the plasticizing ester. Second, branched internal plasticizers bearing triethylene glycol chains had lower T_g values compared to those with similar length long‐chain alkyl groups. Finally, thermogravimetric analysis of these internally plasticized PVC samples revealed that these branched internal plasticizers bearing alkyl chains are more thermally stable than similarity branched plasticizers bearing triethylene glycol units. These internal tetra‐plasticizers were synthesized and attached to PVC‐azide in three simple synthetic steps. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1821–1835     

Effect of crystallographic structure on electrical and mechanical characteristics of Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>-Doped CeO<Subscript>2</Subscript> films

Electrical conductivity, dielectric permittivity and mechanical hardness of the polycrystalline CeO₂ + xSm₂O₃ (x = 0, 10.9–15.9 mol %) films prepared by Electron Beam Physical Vapour Deposition (EB-PVD) and Ionic Beam Assisted Deposition, (IBAD), techniques were investigated in dependence on their structure and microstructure influenced by the deposition conditions, namely composition, deposition temperature and Ar⁺ ion bombardment. The electrical conductivity of doped ceria prepared without Ar⁺ ion bombardment and investigated by the impedance spectroscopy, IS, was found to be predominantly ionic one under the oxidizing atmosphere/low-temperature conditions and the higher amounts of Sm₂O₃ (>10 mol %) used. The bulk conductivity as a part of total measured conductivity was a subject of interest because the grain boundary conductivity was found to be ∼3 orders of magnitude lower than the corresponding bulk conductivity. Ar⁺ ion bombardment acted as a reducer (Ce⁴⁺ → Ce³⁺) resulting in the development of electronic conductivity. Dielectric permittivity determined from the bulk parallel capacitance measured at room temperature and the frequency of 1 MHz, similarly as the mechanical hardness measured by indentation (classical Vickers and Depth Sensing Indentation-DSI) techniques were also found to be dependent on the deposition conditions. The approximative value of hardness for the investigated films deposited on the substrate was estimated using a simple phenomenological model described by the power function HV = HV ₀ + aP ^b and compared with the so-called apparent hardness (substrate + investigated film) determined by the classical Vickers formula. Results obtained are analyzed and discussed.     

Effect of pendant group on the second-order optical nonlinearity of sol–gel films

A series of organically modified sol–gel films with various acceptor groups were prepared and characterized. All the chromophores exhibit much larger microscopic optical nonlinearity compared with the classical chromophore DR1 in solvatochromic measurement. Using in situ second harmonic generation (SHG) technique, the optimal poling temperatures (T _opt) for sol–gel films were obtained. The second harmonic coefficients (d ₃₃) of hybrid films at the wavelength of 1,064 nm were in the range of 50.1–70.3 pm/V after corona poling under their T _opt. The NLO stabilities of these poled films were also investigated by tracing the d ₃₃ value as a function of temperature and time. One of the hybrid films, which was prepared from chromophore 2,4-dinitro-4′-(N,N-dihydroxyethyl) aminoazobenzene exhibited a combination of large optical nonlinearity and high NLO stability. Furthermore, the effects of molecular structure on the NLO property and thermal stability of the hybrid films were also discussed.