Spectral Characteristics of C60-Conducting Polymer Junctions: Various Molecular D-A Type Photocells

Abstract

We have found recently that thin film layered heterojunction between C₆₀ and conducting polymer, like poly(3-alkylthiophene) (PAT) shows a photovoltaic effect due to photoinduced charge transfer at the interface. Here we describe two other examples of such photocells in RO-PPV/C₆₀ and PPP/C₆₀ heterojunctions and study their spectral characteristics. Contrary to conventional inorganic semiconductor p-n junction photocells, the C₆₀-PAT junction can be rather viewed as molecular donor-acceptor (D-A) type photocell in which the processes of photogeneration and separation of charge carriers are quite distinct. In a p-n junction free electron-hole pairs are known to be primarily photogenerated at interband transition and then separated in the internal electric field of the barrier, while in D-A molecular photocell mainly neutral excitons are first created by light, with charges being primarily separated at the narrow interface region due to D-A type intermolecular charge transfer interactions. We analyze how this processes depend on the wavelength of the pumping light and on the polarity and magnitude of the applied voltage.     

Ferroelectric PbTiO3 Powders and Thin Films Derived from Sol-Gel Processing

Lead titanate powders and thin films were prepared by the sol-gel process of metal alkoxide solutions and solvents. From DSC measurements, phase transition temperature of crystallized PbTiO₃ powders was obtained at about 484 °C. From XRD investigation, it was confirmed that the tetragonal phase of polycrystalline PbTiO₃ thin films is formed by coating of concentrated solution on all of the substrates we used after heat treatment above 500 °C. It was found by SEM and ellipsometric analysis that the thin film coated with 0.25 M concentrated solutions once had an average thickness of about 720 Å. Surfaces of thin films were crack-free, uniform, and its average grain size investigated by SEM was 0.6–0.8 μm. Band gap energy of PbTiO₃ thin film coated on the Al₂O₃ (2243) substrate was 3.45 eV, which is assumed to be due to the direct band to band transition. Dielectric constant (ϵ) and dielectric loss (tan δ) of PbTiO₃ thin film amounted to 60–70 and 0.01–0.02 in the region of 10 kHz ∼ 1 MHz at room temperature, respectively, and transition temperature was 486 °C at 1 MHz. From the hysteresis loop of PbTiO₃ thin film, spontaneous polarization of 12 μC/cm² and coercive filed of 45 kV/cm were obtained.     

Edge misfit dislocations in the GeSi/Si(001) pair: Conditions and specific features of high-quantity generation

Dislocation structure of Ge_xSi_1?x films (x=0.4?0.8) grown by molecular-beam epitaxy on Si(001) substrates was studied by means of transmission electron microscopy. It was found that the density of edge MDs formed at the early stage of plastic strain relaxation in the films could exceed the density of 60° MDs. In our previous publications, a predominant mechanism underlying the early formation of edge misfit dislocations (MD) in Ge_xSi_1?x/Si films with x>0.4 was identified; this mechanism involves the following processes. A 60° glissile MD provokes nucleation of a complementary 60° MD gliding on a mirror-like tilted plane (111). A new edge MD forms as a result of interaction of the two complementary 60° MDs, and the length of the newly formed edge MD can then be increased following the motion of the “arms” of the complementary 60° MDs. Based on this scenario of the edge MD generation process, we have calculated the critical thickness of insertion of an edge MD into GeSi layers of different compositions using the force balance model. The obtained values were found to be more than twice lower than the similar values for 60° MDs. This result suggests that a promising strategy towards obtaining dislocation arrays dominated by 90° dislocations in MBE-grown Ge_xSi_1?x/Si films can be implemented through preliminary growth on the substrate of a thin, slightly relaxed buffer layer with 60° MDs present in this layer. The dislocated buffer layer, acting as a source of threading dislocations, promotes the strain relaxation in the main growing film through nucleation of edge MDs in the film/buffer interface. It was shown that in the presence of threading dislocations penetrating from the relaxed buffer into the film nucleation of edge MDs in the stressed film can be initiated even if the film thickness remains small in comparison with the critical thickness for insertion of 60° MDs. Examples of such unusual MD generation processes are found in the literature.     

Accurate measurement of deposition rates for growth of Bi‐based oxide thin films

Bi‐based oxide thin films are important superconducting materials because of its wide applicability, high transition temperatures, and low toxicity. To achieve high quality Bi‐based oxide thin films by molecular beam epitaxy (MBE), the composition is a key parameter. Here, Bi, Cu, Cu/Sr and Cu/Ca thin films on glass substrates prepared by MBE have been examined by using both X‐ray reflectivity and surface profiler. The thickness and surface roughness were obtained through calculation and simulation. In comparison with the film thicknesses measured by these two methods, they are in good agreement. The lines of thickness deposition rate (R) versus source temperature (T) are according with LogR=a+b/T based on Clausius‐Clapeyron equation. Moreover, the Bi_2.1Ca_ySr_1.9‐yCuO_6+δ thin films with different composition and thickness were successfully prepared by MBE by applying the thickness deposition rate lines. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of Cu2ZnSnSe4 nanocrystals prepared by one pot route

Quaternary compound Cu₂ZnSnSe₄ (CZTSe) is one of the most promising absorber layer materials for thin film solar cells. In present work, the CZTSe nanocrystals were successfully synthesized via one pot route, and the influences of reaction temperature on the structural, compositional, morphological and optical properties of as‐synthesized CZTSe nanocrystals were investigated in detail via X‐ray powder diffraction (XRD), energy dispersive X‐ray spectrometry (EDS), transmission electron microscopy (TEM) and UV‐Vis spectrophotometry, respectively. The characterization results of as‐synthesized nanocrystals, under optimal synthesis condition (250 °C, 1 h), indicated that the nanocrystals was monodispersed with polycrystalline, the size was in the range of 10–15 nm, and the band gap energy was around 1.44 eV which is very closed to the best band gap energy for the solar cell. All results suggested that the as‐synthesized CZTSe nanocrystals were good light absorber layer material for thin film solar cell.     

Investigation of the Interaction between C60 and Si Atoms

Abstract

The interaction between C₆₀ and Si atoms was investigated using X-ray photoelectron spec-troscopy (XPS) for the photo-irradiated Si-deposited C₆₀ film in order to establish a method of a synthesis for the Si-coated C₆₀. It was found that the Cls spectrum of the photo-irradiated film contains a peak due to C-Si bonding, while no peak due to C-Si bonding was observed for the film before photo-irradiation. This indicates that Si atoms stick to C₆₀ when using the present method.     

Optical and structural properties of lead iodide thin films prepared by vacuum evaporation method

Thermally processed lead iodide (PbI₂) thin films were prepared by the vacuum evaporation method in a constant ambient. Measured thickness of the film was verified analytically from the optical transmittance data in a wavelength range between 300 and 1600 nm. From the Tauc relation for the non‐direct inter band transition, the optical band gap of the film was found to be 2.58 eV for film thickness 300 nm. X‐ray diffraction analysis confirmed that PbI₂ films are polycrystalline, having hexagonal structure. The low fluctuation in Urbach energy indicates that the grain size is quite small. The present findings are in agreement with the other results. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of Polycrystalline Cu Films as Solar Selective Coatings

Copper thin films (5–150 nm) were prepared by vacuum deposition with different rates (0.7, 1.5 and 3 nm/s). The position, intensity and profile of X-ray diffraction lines were analysed to study the phases, the crystallographic preferred orientation as well as the residual strain and crystallite size. The fcc polycrystalline Cu phase was revealed and no oxide phases were identified. The films were highly oriented with 〈111〉 fiber texture. The ratio of P₁₁₁/P₂₀₀ increased with the film thickness. Thus, in case of amorphous substrate, the type of the crystallographic texture of a film depends mainly on the structure of the deposited material. The crystallite size increases while the residual strain decreases, as the film thickness or the deposition rate is increased. The crystallite size was very small compared with the film thickness. The effect of deposition rate was pronounced specially from 0.7 to 1.5 nm/s.     

Nanocomposite SiO2(Si) films as a medium for non-volatile memory

Nanocomposite SiO₂(Si) films containing Si nanocrystals (NCs) in a SiO₂ dielectric matrix obtained through (i) plasma enhanced chemical vapor deposition (PE CVD) or (ii) pulse laser deposition (PLD) have been investigated as a medium for charge storage. The C–V method was used to characterize charging effects in the MIS structure (capacitor) with a nanocomposite SiO₂(Si) film as an insulator. The obtained results indicate (i) the capture of small negative charge at the positive gate voltage in the nanocomposite SiO₂(Si) film, (ii) significant capture of positive charge at the negative gate voltage, and that (iii) the difference between the positive and negative charge captured in both cases cannot be explained by dropping a part of the positive gate voltage in the semiconductor’s depletion region. A model of charge transport and capture in nanocrystals of nanocomposite SiO₂(Si) film is proposed to explain the experimental results.     

Effect of oxygen content on barrier properties of silicon oxide thin film deposited by dual ion-beam sputtering

A silicon oxide thin film barrier was prepared with various oxygen contents and its chemical composition, surface morphology and optical and barrier properties were related to the deposition conditions used. Our study showed that under Ar and O₂ assisted process conditions, a stoichiometric silicon oxide thin film formed at a critical oxygen content during deposition of 40-50%. The thin films deposited at the critical condition showed the lowest surface roughness giving similar or higher optical transmittance than that of the bare polycarbonate (PC) substrate. The boiling and tensile strength test performed on the thin film deposited with assisted ions before the deposition process showed improvement in the adhesion between the oxide layer and the polymer substrate. In addition, interface modification to improve for improving the barrier layer properties of the silicon oxide thin film was achieved through the introduction of dual ion beam sputtering without pre-treatment.     

Structure and properties of hydrogenated amorphous silicon carbide thin films deposited by PECVD

a-Si_1?xC_x:H films are deposited by RF plasma enhanced chemical vapor deposition (PECVD) at different RF powers with hydrogen-diluted silane and methane mixture as reactive gases. The structure and properties of the thin films are measured by infrared spectroscope (IR), Raman scattering spectroscope and ultra violet–visible transmission spectroscope (UV–vis), respectively. Results show that the optical band gap of the a-Si_1?xC_x:H thin films increases with increasing Si–C bond fraction. It can be easily controlled through controlling Si–C bond formed by modulating deposition power. At low deposition power, the bond configuration of the a-Si_1?xC_x:H thin film is more disordered owing to the distinct different bond lengths and bond strengths between Si and C atoms. At a too high deposition power, it becomes still high disordered due to dangling bonds appearing in the a-Si_1?xC_x:H thin film. The low disordered bond configuration appears in the thin film deposited with moderate deposition power density of about 2.5 W/cm².     

Synthesis of spindle‐shaped α‐FeOOH and α‐Fe2O3 nanocrystals

Spindle‐shaped α‐FeOOH nanocrystals were facilely synthesized using a poly (vinyl pyrrolidone) (PVP)‐assisted route under hydrothermal conditions. The chemical compositions and morphol‐ogies of the as‐prepared samples were characterized in detail by X‐ray power diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM). The experimental results reveal that these spindle‐shaped α‐FeOOH nanocrystals have self‐organized into assemblies with hierarchical nanostructures. The crucial roles of PVP in the hydrothermal synthesis of hierarchical α‐FeOOH nanostructures were discussed. The possible formation mechanism was also suggested. Moreover, the spindle‐shaped α‐Fe₂O₃ nanocrystals could be easily obtained after calcining the α‐FeOOH prepared by the PVP‐assisted hydrothermal process. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation and characterization of ZrO2-SiO2 binary films for planar optical waveguides

ZrO₂-SiO₂ binary films for active optical waveguides were prepared by the sol-gel method with zirconium oxychloride and tetraethoxysilane as precursors. The main factors that influence the film thickness and refractive index have been found. The relationship between the film refractive index composition and heat treatment temperature has been determined. The continuous tuning of the thickness and refractive index of the thin films has also been achieved, which will open up new possibilities in the development of active optical waveguides.     

The effect of solvent ratio and water on the growth of C60 nanowhiskers

The growth of C₆₀ nanowhiskers (C₆₀NWs) prepared by a modified liquid–liquid interfacial precipitation method is investigated, focusing on the effect of solvent ratio and water content in the C₆₀–toluene–isopropyl alcohol (IPA) solution system. The precipitation of C₆₀NWs was markedly influenced by the solvent ratio of toluene to IPA, and the C₆₀NWs were found to grow longer above a critical diameter (D_c), which depends on the solvent ratio. The addition of a small amount of H₂O to the C₆₀–toluene–IPA solution promoted the growth of C₆₀NWs. This catalytic effect of water on the growth of C₆₀NWs was confirmed also by the experiment using heavy water (D₂O) and by the decrease of growth activation energy of C₆₀NWs with increase of H₂O content in the C₆₀–toluene–IPA solution.     

Synthesis of epitaxial Y-type magnetoplumbite thin films by quick optimization with combinatorial pulsed laser deposition

Y-type magnetoplumbite (Ba₂Co₂Fe₁₂O₂₂:Co₂Y) epitaxial thin films with such a huge lattice parameter as 43.5 Å have been synthesized for the first time. Combinatorial thin film technology was successfully employed to eliminate an impurity phase in the film by quickly optimizing such reaction parameters as the deposition temperature and the thickness of pre-deposition of CoO layer. The coupling of combinatorial pulsed laser deposition and subsequent concurrent X-ray diffraction, both of which we have developed, is a promising way to high throughput optimization of thin film growth and properties.     

Preparation and properties of titanium silicide coating glass by CVD

Titanium silicide thin films were prepared on glass substrates by chemical vapor deposition using SiH₄ and TiCl₄ as the precursors. The phase structure of the thin films was identified by XRD. The surface morphology of the thin films was observed by FESEM. The sheet resistance and optical behaviors of the thin films were measured by the four point resistivity test system and FTIR spectrometer, respectively. Titanium disilicide (TiSi₂) thin films with the face-centered orthorhombic structure are formed. The suitable formation temperature of the TiSi₂ crystalline phase is about 710 °C. The formation of TiSi₂ crystalline phase is dependent on the thickness of thin films and a quantity of the crystalline phase of TiSi₂ in the thin film is directly related to mole ratio of SiH₄/TiCl₄. The sheet resistance of the TiSi₂ thin films is dependent on the formation of the TiSi₂ crystalline phase. With the mole ratio of SiH₄/TiCl₄ of 3, the lowest sheet resistance (0.7 Ω/□) of titanium silicide thin film is formed at 710 °C. The maximum reflectance of the TiSi₂ thin films is about 0.95 on the broad IR heat radiation. A related reaction mechanism was proposed.     

Synthesis of type-I textured tungsten disulfide thin films on quartz substrate

Tungsten disulfide (WS₂) films were obtained by solid state reaction of spray deposited WO₃ with gaseous sulfur i.e. solid gas phase reaction (SGP). The XRD and SEM studies revealed the formation of WS₂ thin films on quartz substrate with a mixed type-I and type-II texture. The WS₂ thin films prepared with a controlled heating/cooling rate of 323 K/h. during the sulfurization were free from cracks while those prepared with higher heating/cooling rate during the sulfurization suffer from cracks. The former WS₂ thin film comprises well defined hexagonal crystallites with larger size (2 μm) and thickness. The complete conversion of WO₃ into WS₂ was observed when sulfurization carried out in evacuated quartz ampoule containing sulfur. A low oxygen and carbon content was observed in XPS spectrum due to air exposure of the sample which is removed by in-situ Ar cleaning. XPS and EDS studies showed that the films are stoichiometric.     

Influence of amorphous buffer layers on the crystallinity of sputter-deposited undoped ZnO films

Undoped ZnO films were deposited by radio frequency (RF) magnetron sputtering on amorphous buffer layers such as SiO_x, SiO_xN_y, and SiN_x prepared by plasma enhanced chemical vapor deposition (PECVD) for dielectric layer in thin film transistor (TFT) application. ZnO was also deposited directly on glass and quartz substrate for comparison. It was found that continuous films were formed in the thickness up to 10 nm on all buffer layers. The crystallinity of ZnO films was improved in the order on quartz>SiO_x >SiO_xN_y>glass>SiN_x according to the investigated intensities of (0 0 2) XRD peaks. The crystallite sizes of ZnO were in the order of SiO_x～glass >SiN_x. Stable XRD parameters of ZnO thin films were obtained to the thickness from 40 to 100 nm grown on SiO_x insulator for TFT application. Investigation of the ZnO thin films by atomic force microscope (AFM) revealed that grain size and roughness obtained on SiN_x were larger than those on SiO_x and glass. Hence, both nucleation and crystallinity of sputtered ZnO thin films remarkably depended on amorphous buffer layers.     

In Situ FT-IR Study of an Electron-Beam Induced Reaction of C60 Film

Abstract

The structural modification induced by electron-beam (EB) in a C₆₀ film and its kinetics have been studied using in situ high-resolution FT-IR spectroscopy. Similar to studies on photoirradiated K_xC₆₀ fim, was found that a coalescence reaction between adjacent C₆₀ molecules takes place. In order to investigate the interaction between an incident electron and Cgg molecules, the time-dependence of the amounts of C₆₀ on the EB irradiation was examined. It was found that the reaction rate exhibits a linear dependence on the reactant concentration and nonlinear dependence on the incident current.