PVK Films Research Articles

Radial liquid crystal alignment based on circular rubbing of a substrate coated with poly(N-vinyl carbazole) film

This paper presents a simple method to produce radial liquid crystal (LC) alignment layers using circular rubbing of poly(N-vinyl carbazole) (PVK) films. The produced layer can be used for fabricating axially symmetric homogeneous–radial, homeotropic–radial and radial–radial LC alignment devices by combining a rubbed PVK-coated substrate with another one with a desired LC alignment layer. The transmittance–voltage curves of the fabricated LC devices at various positions are measured to examine the uniformity of the alignment effect. Additionally, the PVK film does not absorb visible light, and can be operated at high temperatures.

Synthesis and characterization of a solution processible deep blue light-emitting molecule composed of fluorene and pyrene units

A solution processible deep blue light-emitting molecule composed of pyrene and dialkylfluorene units, 1,6-bis(9,9′-dioctylfluorene-2-yl)pyrene (BDOFP) was synthesized and characterized. The synthesized compound was soluble in common organic solvents and the solution gave a smooth thin film after spin coating. The compound was characterized by using thermogravimetric analysis (TGA), differential calorimetry (DSC), UV–visible spectroscopy, fluorescence spectroscopy and cyclic voltammetry. The maximum UV–visible absorption and PL emission of BDOFP thin film were more red-shifted than those of BDOFP solution due to strong intermolecular interaction between flat segments. To improve color purity and film stability BDOFP was doped to a well-known charge-transporting polymer, poly(N-vinylcarbazole) (PVK). BDOFP thin film showed it maximum PL at 457 nm but the thin films of BDOFP doped PVK films showed it at 443 nm. Organic light-emitting diodes were fabricated with the simple structure of ITO/PEDOT:PSS/emitter/BmPyPB/LiF/Al configuration. BDOFP or three kinds of BDOFP:PVK blends with different ratios (10:90, 30:70, 50:50 by weight) were used as the emissive layers and [1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene] (BmPyPB) as the electron-transporting layer. All of light-emitting devices showed their electroluminescence in blue region of spectrum, especially EL using BDOFP: PVK (1:9) showed a deep-blue light emission with CIE coordinates of (0.14, 0.07). Maximum brightness, external quantum efficiency and current efficiency of the device were 500 cd/m2, 0.7% and 0.44 cd/A, respectively.

Polarization rotators fabricated by thermally-switched liquid crystal alignments based on rubbed poly(N-vinyl carbazole) films

This paper demonstrates the thermally-switched liquid crystal (LC) alignments based on a rubbed poly(N-vinyl carbazole) (PVK) film, and their application for polarization rotators. The mechanically rubbed PVK layer can induce a planar alignment of LCs with their director axis perpendicular to the direction of rubbing. This direction can be switched toward the rubbing direction by thermal treatment. Experimentally, the angle of re-orientation of the director axis increases with the temperature in a specific range of temperatures. In this study, the optical properties of linear and concentric polarization rotators, fabricated using a rubbed PVK film with thermal treatment, are examined.

The nature of trapping sites and recombination centres in PVK and PVK–PBD electroluminescent matrices seen by spectrally resolved thermoluminescence

Two electroluminescent polymer matrices poly(N-vinylcarbazole) (PVK) and PVK with 40 wt% of 2-tert-butylphenyl-5-biphenyl–1,3,4-oxadiazole (PBD) were studied using spectrally resolved thermoluminescence (SRTL) in the temperature range 15–325 K. The comparison of the SRTL results with the electroluminescence (EL) spectra has allowed identification of the localized (trapping) sites and the radiative recombination centres present in the investigated matrices. In the neat PVK films deep traps with a depth about 200 meV, related to triplet excimers dominate, while in the PVK–PBD (40 wt%) blend films the traps that are related to triplet exciplexes formed by the carbazole groups and the PBD molecules dominate. Depth of the traps in the PVK–PBD blend is somewhat lower than that in the neat PVK. An analysis of the EL spectra shows that in the PVK and in the PVK–PBD blend the dominant radiative centres are singlet excimers and singlet exciplexes, respectively. However, in the neat PVK some contributions of the triplet monomer and the triplet excimer states in the EL were also detected.

TOF‐GISANS investigation of polymer infiltration in mesoporous TiO2 films for photovoltaic applications

AbstractThe structure of porous TiO2 films and TiO2:poly(N‐vinylcarbazole) (PVK) composite films is investigated with time‐of‐flight grazing incidence small‐angle neutron scattering (TOF‐GISANS). The TiO2 films have been prepared by application of a sol–gel process with a diblock copolymer as structure directing agent, and the conductive polymer PVK is infiltrated in the porous network by spin coating and solution casting. The films show a hierarchical pore structure with mesopores 52 nm in size and additional large macropores with a diameter of about 180 nm. By matching the scattering contrast of the TiO2 with the polymer information about the penetration of the polymer in the pores is determined. Whereas in the PVK film prepared by solution casting the pores are filled to a high degree; in the spin coated film, PVK wets only the TiO2 pore walls and forms a solid overlying layer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1628–1635, 2010

Effects of solution processing on the photovoltaic response of poly(n‐vinyl carbazole) films

AbstractThe effects of solution processing on the photovoltaic response of poly(n‐vinyl carbazole) (PVK) films were investigated. PVK films were formed by spincasting onto glass coated with indium tin oxide (ITO) and poly(3,4‐ethylenedioxythiophene) (PEDOT)–polystyrenesulfonate (PSS). Some of the PVK films were redissolved in chlorobenzene and redried in the absence or presence of an electric field. Illuminated current–voltage characteristics were measured for an ITO/PEDOT:PSS/PVK/Ca:Al device. Films spincast from a 50 mg/mL solution, redissolved, and dried in the absence of the electric field exhibited a 26% higher charge collection efficiency than films dried in the presence of the electric field. The increased charge collection efficiency was attributed to changes in the molecular configuration of the PVK films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Electroplex emission of the blend film of PVK and DPVBi

Influences of electric fields on the emission from organic light-emitting diodes (OLEDs) based on poly(N-vinylcarbazole) (PVK) and 4′-bis(2-2diphenylvinyl)-1,1′-biphenyl (DPVBi) as the active emission layer are studied. Electroluminescence (EL) spectra of PVK:DPVBi (1:1 w/w) films show one new emission peak locating at 640nm compared with its photoluminescence (PL) spectra. There may be exists an electroplex emission between the PVK and DPVBi under high electric field strength. The emission intensity of peaking at 640nm strongly depends on the driving voltage, and the ratio of electroplex emission intensity to exciton emission intensity (Ielectroplex/Iexciton) increases with the increase of driving voltage.

Characterization and magnetic properties of conducting poly( N-vinylcarbazole)-capped magnetite nanocomposite Langmuir–Schaefer films

Functionalized poly( N-vinylcarbazole) (PVK) has been synthesized by an oxidative polymerization with capped magnetite nanoparticles (CMPs, 10, 20, and 30%) for the preparation of conducting polymer composites that possess both electrical and magnetic properties. Spectroscopic studies reveal the successful functionalization of the nanoparticles into the PVK matrix. I– V characteristics of the composite films show an increase in the conductivity of the PVK film due to the presence of CMPs. The magnetization data exhibit an appreciable hysteresis loop at room temperature. The composite samples reveal an ordered semi-conducting behavior.

Electroluminescence of poly(N-vinylcarbazole) films: fluorescence, phosphorescence and electromers

We have studied the electroluminescence (EL) properties of pure poly(N-vinylcarbazole) (PVK) films. Three types of light emission in the EL spectrum were observed, attributed to fluorescence, phosphorescence and electromers, respectively. The observation of electrophosphorescence from PVK films at room temperature is very meaningful, indicating that PVK can produce a large number of triplet excitons under an electric field at room temperature. Our results demonstrate clearly the reason why PVK is an excellent host material for phosphorescent polymer light-emitting diodes (PLEDs).

On the energy transfer from a polymer host to the rhenium(I) complex in OLEDs

Photoluminescence and electroluminescence of PVK films doped with fac-[ClRe(CO) 3(bpy)], bpy = 2,2′-bipyridine, are investigated. Photoluminescence spectra of spin-coated PVK films ( λ exc = 290 nm) exhibit a broad band centered at 405 nm. As the concentration of dopant increases, the polymer emission is quenched and a band at 555 nm appears (isosbestic point at 475 nm). In OLEDs with ITO/PEDOT:PSS/PVK/butylPBD/Al architecture doped with fac-[ClRe(CO) 3(bpy)], the polymer host emission is completely quenched even at the lowest concentration of dopant. The electroluminescence spectra of the devices show that there is an efficient energy transfer from the host to the dopant, which exhibits a very intense emission at 580 nm.

Enhanced emission from Alq3 in PVK/Alq3 blend films based on resonance energy transfer

AbstractIn this study, we present the optical properties of the poly(N‐vinylcarbazole) (PVK) films doped with tris(8‐hydroxyquinoline) aluminum (Alq3). It has been found that the photoluminescence (PL) spectrum of the PVK film overlaps well with the absorption band of Alq3. When excited at the absorption maximum of PVK, the doped PVK films show enhanced emissions from the Alq3 component. The PL enhancement is considered to be due to energy transfer from PVK to Alq3 in the doped PVK films by analyzing the PL, PL excitation, and time‐resolved fluorescence spectra. The energy transfer efficiency is increased with increasing the concentration of Alq3 in the doped PVK film according to time‐resolved fluorescence spectra. The energy transfer process has been discussed according to the Förster mechanism. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1772–1777, 2009

Photoluminescence of solution processed poly n‐vinyl carbazole films

AbstractThe photoluminescence (PL) of poly n‐vinyl carbazole (PVK) films formed by solution processing was investigated. PVK films were formed by spincasting onto bare glass or glass covered by films of indium tin oxide (ITO) and poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate)ethylene (PEDOT : PSS). Some of the spincast films were redissolved in chloroform solvent and redried both in the absence or presence of an electric field (6000 V/cm). The broad aggregate PL peak near 410 nm exhibited both blue and red shifts dependent upon the processing conditions. These shifts in PL were attributed to changes in the excimer populations associated with the molecular conformation of adjacent carbazole groups. The PL data were deconvoluted into two component peaks representing two excimers associated with overlap of only one (partial or P) or full overlap (F) of both aromatic rings on adjacent carbazole groups. It was concluded that the excimer population was dependent on the amount of residual solvent left in the film after processing and upon the type of substrate. The mechanism(s) controlling the molecular configurations was discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Silver nanoplates formed at the air/water and solid/water interfaces

Silver nanoparticles and nanoplates were prepared at the air/AgNO 3 aqueous solution interfaces under poly(9-vinylcarbazole) (PVK) monolayers when illuminated by UV-light at room temperature and elevated temperatures, respectively. When the illuminated films at the air/water interfaces were covered by carbon-coated copper grids, nanoplates were formed even at room temperature, and the size of the nanoplates was much larger than those formed at the air/water interface under the same experimental conditions, indicating that copper took part in the formation of Ag nanoplates through the galvanic displacement reaction between Cu and Ag + ions with the help of carbon layer to conduct electrons. It was found that the basal plane of these nanoplates is the (1 1 1) face of a face-centered cubic (fcc) Ag crystal. Although platelike structure can be formed at the carbon-coated copper grid/AgNO 3 aqueous solution interface without PVK film, it shows different features from those with PVK films, indicating that PVK film plays an important role in the formation of regular large nanoplates. Further observations indicate that special restrained microenvironment, adsorption of PVK molecules on a specific crystal face, anisotropic growth and attachment of the nanoparticles are responsible for the formation of the nanoplates.

In Situ GISAXS Study of Gold Film Growth on Conducting Polymer Films

The growth of a thin gold film on a conducting polymer surface from nucleation to formation of a continuous layer with a thickness of several nanometers is investigated in situ with grazing incidence small-angle X-ray scattering (GISAXS). Time resolution is achieved by performing the experiment in cycles of gold deposition on poly(N-vinylcarbazole) (PVK) and subsequently recording the GISAXS data. The 2D GISAXS patterns are simulated, and morphological parameters of the gold film on PVK such as the cluster size, shape, and correlation distance are extracted. For the quantitative description of the cluster size evolution, scaling laws are applied. The time evolution of the cluster morphology is explained with a growth model, suggesting a cluster growth proceeding in four steps, each dominated by a characteristic kinetic process: nucleation, lateral growth, coarsening, and vertical growth. A very limited amount of 6.5 wt % gold is observed to be incorporated inside a 1.2-nm-thick enrichment layer in the PVK film.

Dual functions of a new n-type conjugated dendrimer: light-emitting material and additive for polymer electroluminescent devices

We demonstrate a novel light-emitting diode (LED) of a graded bilayer structure that comprises poly(N-vinylcarbazole) (PVK) with good hole transport ability as the energy donor and a new distyrylanthracene-triazine-based dendrimer with enhanced electron transport ability as the light-emitting molecule. The device contains a graded bilayer structure of the PVK film covered with the dendrimer film prepared by sequential spin-casting of the dendrimer layer from a solvent that only swells the PVK layer. The bilayer device demonstrated a significantly enhanced electoluminescence quantum efficiency compared with the dendrimer single layer device or the PVK : dendrimer blend device with optimized composition. We also prepared composite LEDs with an MEH-PPV : emissive dendrimer blend. By doping the electron-deficient MEH-PPV layer with a small amount of the distyrylanthracene-triazine-based dendrimer, we could not only enhance the device performance but also depress the long-wavelength emission of MEH-PPV.

Hole mobility and trapping in PVK films doped with CdSe/CdS and CdSe quantum dots

Experimental study of the hole mobility in polyvinylcarbazole (PVK) films doped with two kinds of nanocrystals, on bare core CdSe and core-shell CdSe/CdS quantum dots, with concentrations ranging from 3 · 1010 to 3 · 1015 cm−3, is presented. The quantum dots investigated were made using colloidal chemistry. The hole mobility was measured using the time-of-flight technique as a function of the applied electrical field in the range 105–106 V/cm and for temperatures from 20°C to 50°C. The transient curves, being featureless on a linear plot, show on a double logarithmic scale a sharp inflection point indicating a dispersive carrier drift process. The recovered values of the mobility are in the range 3 · 10−8–10−6 cm2·V−1·s−1 and their field and temperature dependences can be analyzed formally within the framework of the Gaussian disorder model proposed by Bassler. The energetic disorder is, within the experimental accuracy, independent of the concentration and type of quantum dots for the CdSe quantum dots at all concentrations and for the CdS/CdSe quantum dots up to 1014 cm−3. The spatial disorder factors are very large (from 5.3 to 8.7) and do not depend in a systematic way upon the type and concentration of quantum dots (QDs). The experiments show that the apparent mobility does not change considerably with concentration, but it was found that the samples with CdSe/CdS quantum dots at concentrations from 1015 to 3 · 1015 cm−3 show a decreased photocurrent response. The dependence of the time-integrated transients (corresponding to the full charge value) upon the quantum-dot concentration has been determined. Differences in total photogenerated charge for pure and doped polymer films imply that the quantum dots of that type are the hole traps with capture times much more smaller than the transit time and with emission times a few orders longer than the transit time. CdSe quantum dots without a shell do not seem to exhibit the same properties as core shells and do not produce considerable changes in the charge transfer, even at a density of 1015 cm−3.

Properties of polymer light‐emitting diodes coated on surface‐treated ITO/glass substrates

AbstractWe fabricated blue polymer light‐emitting diodes (PLEDs) with indium tin oxide (ITO)/PEDOT : PSS/PVK/PFO‐poss/LiF/Al structures. All of the organic film layers were prepared by the spin‐coating method on plasma and heat‐treated ITO/glass substrates. The dependences of the optical and electrical properties of the PLEDs on the plasma and heat treatment of the ITO film and the introduction of poly(N‐vinylcarbazole) (PVK) layer were investigated. The AFM measurements indicated that the surface roughness of the ITO transparent film was improved by the plasma and heat treatment. In the emission spectra, the intensity of the excimer peaks of the PFO‐poss [polyhedral oligomeric silsesquioxane‐terminated poly(9,9‐dioctylfluorene)] emission layer were decreased for the PLED device with the PVK film layer compared with the one without the PVK layer. The maximum current density, luminance and current efficiency of the PLEDs were found to be about 470 mA/cm2, 486 cd/m2 at an input voltage of 12 V and 0.55 cd/A at 100 cd/m2 in luminance, respectively. The color coordinates (CIE chart) of the blue PLEDs were in the range of x = 0.17 ∼ 0.20, y = 0.13 ∼ 0.16, and the peak emission spectrum was about 430 nm, showing a good blue color. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Realization of write-once-read-many-times memory devices based on poly(N-vinylcarbazole) by thermally annealing

A nonvolatile write-once-read-many-time (WORM-time) memory device based on poly(N-vinylcarbazole) (PVK) films was realized by thermally annealing. The device can be fabricated using a simple spin coat method. It was found that the control of PVK film surface morphology by thermally annealing plays an important role in achieving the WORM memory properties. The memory device showed an ON/OFF current ratio as high as 104 and the retention time was over 2000 s without degradation. The formation and damage of the interface dipole at different electric fields have been attributed to the switching transition processes, leading to the transition from an Ohmic current of ON state to a tunneling injection limited current of OFF state. The achievement of easily fabricating WORM memory device based on soluble PVK film opens up an application field for polymer materials in organic electronics.

Layered TiO2 :PVK nano-composite thin films for photovoltaic applications

The influence of the solvent used for spin-coating on the homogeneity of poly(N-vinylcarbazole) (PVK) films is investigated. Homogenous films are obtained only by the use of toluene, solution in tetrahydrofuran (THF) and chloroform results in radially oriented inhomogeneities and films prepared by use of N-methylpyrrolidone and dimethylacetamide show particle formation during spin-coating. Layered nano-composite thin films are prepared by spin-coating a PVK film on top of a nano-structured titanium dioxide ( TiO2) layer. The TiO2 thin films are prepared by a sol-gel process using an amphiphilic copolymer as structure-directing agent. Structural characterisation of the TiO2 :PVK nano-composite films is done by field emission scanning electron microscopy (FESEM) and grazing-incidence small-angle scattering (GISAXS). Bare TiO2 films are probed for comparison. Light is basically only absorbed in the ultraviolet regime and absorption slightly increases upon addition of PVK, which makes the layered TiO2 :PVK nano-composite thin films good candidates for UV photovoltaic devices. Furthermore, absorption remains stable over a period of several days.

Effect of Physicochemical Properties of Solvents on Microstructure of Conducting Polymer Film for Non-Volatile Polymer Memory

The effect of physicochemical properties of solvents on the microstructure of polyvinyl carbazole (PVK) film for non-volatile polymer memory was investigated. For the solubilization of PVK molecules and the preparation of PVK films, four solvents with different physicochemical properties of the Hildebrand solubility parameter and vapor pressure were considered: chloroform, tetrahydrofuran (THF), 1,1,2,2-tetrachloroethane (TCE), and N,N-dimehtylformamide (DMF). The solubility of PVK molecules in the solvents was observed by ultraviolet-visible spectroscopy. PVK molecules were observed to be more soluble in chloroform, with a low Hildebrand solubility parameter, than solvents with higher values. The aggregated size and micro-/nano-topographical properties of PVK films were characterized using optical and atomic force microscopes. The PVK film cast from chloroform exhibited enhanced surface roughness compared to that from TCE and DMF. It was also confirmed that the microstructure of PVK film has an effect on the performance of non-volatile polymer memory.