Anisotropic carrier transport properties of highly aligned oligophenylenevinylenes in organic field-effect transistors

We have studied the electronic excitations of fluorinated copper phthalocyanine, CuPcF₁₆, thin films using electron energy-loss spectroscopy in transmission. This allowed for the derivation of the dielectric function in a wide energy range. Furthermore, we have analyzed the lowest excitation feature using a Lorentz model, which enabled the determination of the dielectric background in the energy range of the gap excitation, and an analysis of the momentum dependence of the spectral intensities at low energies.     

The dielectric function of potassium-doped zinc-phthalocyanine

We have studied the electronic excitations of potassium-doped zinc-phthalocyanine using electron energy-loss spectroscopy. This allowed the determination of the complex dielectric function ε(ω) in an energy range between 0 and 70 eV. Our results reveal distinct changes of the electronic excitation spectra going from ZnPc to K₄ZnPc. They can be used as data basis for future optical characterization of potassium-doped ZnPc films. PACS 71.20.Rv; 78.20.-e     

The effect of crystalline structure on zero-phonon and phonon-assisted emission in ZnS:Mn

The zero-phonon line (ZPL) emission spectra of cubic, faulted and hexagonal ZnS/Mn, have been obtained using laser excitation and enable us to determine specific electronic transitions associated with each crystalline structure. It is shown that the phonon-assisted emission does not depend on the structure and that the vibrational localized mode with an A₁ representation, which is preponderant with respect to the other impurity induced modes, is the only recurring phonon.     

Resonance and composition effects on the Raman scattering from silver-gold alloy clusters

Low-frequency Raman scattering experiments have been performed on thin films consisting of pure gold or gold-silver alloy clusters embedded in alumina matrix. It is clearly shown that the quadrupolar vibrational modes are observed by Raman scattering because of the effect of resonance with the excitation of the electronic surface dipolar plasmon. This is due to the strong coupling between the collective electronic dipolar excitation and the quadrupolar vibrational modes. This effect of resonance does not exist with the core electron excitations. The mixing of the conduction electron dipolar excitation (surface plasmon) with the core electrons leads to the quenching of the resonant Raman scattering. Received 16 November 2000     

Preparation and electronic structure of phase pure K3C60

Phase pure K₃C₆₀ films have been grown using vacuum distillation. The structure of such films could be shown to be face centered cubic consistent with X-ray diffraction studies. The electronic structure of the films has been studied using electron energy-loss spectroscopy in transmission. From C1s core excitation measurements the unoccupied density of states has been determined. Performing the dielectric function has been derived in a wide energy range (0–45 eV). It is shown that the low energy part of the optical conductivity cannot be understood within a simple free electron model but that interband transitions between the three conduction bands have to be taken into account. The spectral weight of interband transitions between valence and conduction bands shows strong momentum dependence due to optical selection rules demonstrating the molecular-like nature of the electronic states.     

Metallization of the Ge(111) surface at high-temperature probed by energy-loss and Auger spectroscopies

We present new electron energy-loss spectroscopy (EELS) and Auger (AES) experiments aimed to study the structural transition of the Ge(111) surface taking place at high temperatures. Our advanced high-temperature set-up allowed us to collect accurate EELS spectra near the M_2,3 excitation edges and AES MMV and MVV spectra, corresponding to different probing depths ranging from 4 to 10 Å. The metallization of the surface has been clearly detected by the shift of the M_2,3 edge and of the MMV, MVV Auger energies. A detailed study of the transition has been performed using a fine temperature step under thermal equilibrium conditions. The AES and EELS experiments show that a sudden semiconductor-metal transition takes place at about 1000 K involving mainly the topmost layers. Deeper layers within 10 Å are also involved in the metallization process (in a range of 10 above 1010 K) and a smooth change in the topmost layers is also observed at higher temperatures up to 1070 K. These transitions are not fully reversible upon cooling (down to 870 K). Structural and electronic characteristics of the surface transition are discussed in light of available models.     

Broad excitation of Er luminescence in Er-doped HfO2 films

We investigated the broad and sensitized luminescence properties of Er-doped HfO₂ films synthesized by pulsed laser deposition (PLD) and ion implantation techniques. In the investigation we focused on the mechanism of energy transfer in the host matrix. Based on the comparison of photoluminescence (PL), photoluminescence excitation (PLE), and cathode-luminescence (CL), as well as on microstructure measurements, an excitation transfer process resulting in the broad excitation for Er, luminescence at 1540 nm, is identified. In this process, the oxygen vacancies and Hf in the host HfO₂ serve mainly as effective sensitizers for neighboring Er ions in the nonresonant excitation process. Furthermore, the direct Er³⁺ intra-4f transitions and full spectral emission of Er ions in the HfO₂ matrix are clearly observed under the wide-spectrum excitation in the CL measurement. This reveals more detailed features for the energy transfer and transition processes.     

High-throughput characterization of local conductivity of Nd0.9Ca0.1Ba2Cu3O7−δ thin film by the low-temperature scanning microwave microscope

We developed a scanning microwave microscope (SμM) designed for high-throughput electric-property screening as well as for rapid construction of electronic phase diagrams at low temperatures. As a sensor probe, we used a high-Qλ/4 coaxial cavity resonator to which a thin needle with ball-tip end was attached. The sensor module was mounted on the low-temperature XYZ stage, which allowed us to map out the change of resonance frequency and quality factor due to the local tip-sample interaction at low temperatures. From the measurements of combinatorial thin films, such as Ti_1−xCo_xO_2−δ and Nd_0.9Ca_0.1Ba₂Cu₃O_7−δ (NCBCO), it was demonstrated that this SμM system has enough performance for the high-throughput characterization of sample conductance under variable temperature conditions.     

Mechanism of fluorescence energy transfer in aqueous solution cadmium sulfide quantum dots

Cadmium sulfide (CdS) quantum dots (QDs) prepared by a convenient chemical method have been characterized using absorption, fluorescence, and photoluminescence excitation techniques. The photoluminescence excitation studies show that there is an electron transfer from the surface adsorbate (thiourea) to CdS QDs in aqueous solution. The excitation band with peak maximum at 5.8 eV is assigned to the electronic transitions in the chemisorbed thiourea, whereas the excitation band between 3.45 and 3.7 eV corresponds to the band-to-band transition within the nanocrystalline CdS host. The absorption spectroscopy of the CdS QD solutions shows a strong absorption peak which is generated from thiourea. The band-edge fluorescence of the CdS QDs has also been investigated. It is shown that the fluorescence property of the CdS QDs can be enhanced by adding cadmium chloride (CdCl₂) solution.     

Ultrafast dynamics in the excited hydrogen atom transfer states of ammonia clusters

Neutral ammonia clusters (NH₃)_m are photo-excited to the electronic state by a deep UV femtosecond laser pump pulse. Within a few hundred femtoseconds a significant fraction of the clusters rearrange to form an H-transfer state (NH₃)_m-2NH₄(3s)NH₂ with the subunit NH₄ in its 3s electronic ground state. This state is then electronically excited by a time-delayed infrared control pulse of variable wavelength. Finally, a third (probe) pulse in the UV ionizes the clusters for detection. The lifetime of the excited (NH₃)_m-2NH₄(3p)NH₂ states is found to vary between 2.7 and 0.13 ps depending on cluster size and excitation energy. It increases drastically upon deuteration. The corresponding cluster size-dependent photoelectron spectra allow us to disentangle the underlying energetics of the excitation and ionization process and reveal additional processes, such as nonresonant ionization or dissociative ionization. The experimental findings suggest that the excited H-transfer ammonia complexes with m > 2 are deactivated by an internal conversion process back to the electronically lowest H-transfer state followed by fast dissociation. Received 22 September 2001 and Received in final form 31 January 2002     

Effect of the growth conditions on the structural properties of CuInSe2 thin films obtained by the technique of close spaced vapor transport

Thin films of polycrystalline CuInSe₂ were deposited on Pyrex substrates using a simple system of close spaced vapor transport (CSVT). The used CSVT system is an open horizontal reactor, this does not require vacuum, a gas flow is enough. During the growth phase, the CSVT system is continuously crossed by argon gas. A study on the influence of the source temperature and the deposition duration on the structural properties of the deposited films is reported. Analyses by X-ray diffraction have shown that these films are polycrystalline and have a chalcopyrite structure. The preferential orientation of the (112) plane was obtained for the films deposited at 550 ^°C. From the X-ray spectra we calculated the lattice parameters a and c, the ratio c/a was found to be close to 2. The characterization of the deposited films by an energy dispersion spectrometer (EDS) has shown that their chemical composition is quasistoichiometric with a ratio Cu/In varying from 0.96 to 1.10. Analysis with a scanning electron microscope (SEM) of the deposited films surface has shown that those slightly rich in indium present a more homogeneous morphology and smaller crystallites sizes than the films slightly rich in copper. The measurement of the photoconductivity of the prepared compound has allowed us to determine the value of its gap at room temperature. It was found to be close to 0.99 eV.     

Substrate effect on electronic sputtering yield in polycrystalline fluoride (LiF, CaF2 and BaF2) thin films

Influence of substrate on electronic sputtering of fluoride (LiF, CaF₂ and BaF₂) thin films, 10 and 100 nm thin, under dense electronic excitation of 120 MeV Ag²⁵⁺ ions irradiation is investigated. The sputtering yield of the films deposited on insulating (glass) and semiconducting (Si) substrates are determined by elastic recoil detection analysis technique. Results revealed that sputtering yield is higher, up to 7.4 × 10⁶ atoms/ion for LiF film on glass substrate, than that is reported for bulk materials/crystals (∼10⁴ atoms/ion), while a lower value of the yield (2.3 × 10⁶ atoms/ion) is observed for film deposited on Si substrate. The increase in the yield for thin films as compared to bulk material is a combined effect of the insulator substrate used for deposition and reduced film dimension. The results are explained in the framework of thermal spike model along with substrate and size effects in thin films. It is also observed that the material with higher band gap showed higher sputtering yield.     

Photoreflectance characterization of CdTe thin films grown by Molecular Beam Epitaxy on GaAs(100)

CdTe films have been grown on top of GaAs(100) by means of Molecular Beam Epitaxy (MBE) at 300 °C substrate temperature. Different procedures for the CdTe growth and for the preparation of the GaAs substrates resulted in diverse crystalline qualities of the CdTe films. We present the results obtained from PhotoReflectance (PR) measurements of these films employing HeNe and Ar-ion lasers as modulating excitation. For Ar excitation, the ratio of CdTe to GaAs signal strength for the E ₀ transition is enhanced, allowing a differentiation of the contributions from film and substrate. Both the PR line shape and intensity are correlated to the structural quality of the CdTe films. One of the samples presented a below-band-gap transition of the GaAs substrate around 30±5 meV from E ₀ which is attributed to donor states produced by Te atoms diffused in the interface; this result demonstrates the high sensitivity of the photoreflectance technique to the structural properties of interfaces.     

Electronic structure and self-assembling processes in platinum metalloporphyrins: photoemission and AFM studies

The main goal of this paper is to investigate the electronic structure of valence band and core levels as well as surface topography of pristine tetraphenylporphyrin and Pt-based compounds Pt-TPP(p-COOH₃)₄, Pt-TPP(m-OCH₃)₄, PtCl₂-TPP(m-OCH₃)₄ thin films. The electronic structure of various Pt-based metalloporphyrins which were investigated in dependence on their chemical structure and spectra were measured by high-resolution X-ray photoelectron spectroscopy (XPS) of valence band and Pt4f, Pt4d, C1s, O1s, N1s core levels. Results of atomic force microscopy (AFM) studies of topography and self-assembling processes in thin films of porphyrines are presented and discussed.     

RF-plasma assisted pulsed laser deposition of nitrogen-doped SrTiO3 thin films

Perovskite-type nitrogen substituted SrTiO₃ thin films were deposited with a one-step process by RF-plasma assisted pulsed laser deposition from a SrTiO₃ target using a N₂ plasma, while deposition with a NH₃ plasma yields films with almost no incorporated nitrogen. The deposited films exhibit a cubic perovskite-type crystal structure and reveal oriented growth on MgO(100) substrates. The unit cell parameters of the studied N-doped SrTiO₃ films range within 3.905<a<3.918 Å, which is slightly larger than for SrTiO₃ (a=3.905 Å). The nitrogen content in the deposited films varies from 0.2 to 0.7 atom%. The amount of incorporated nitrogen in the films decreases with increasing RF-power, while the N₂ flow rate does not have any pronounced influence on the N content. Nitrogen incorporation results in an increased optical absorption at 400–600 nm, which is associated with N(2p) energy states that have a higher energy level than the valence band in strontium titanate. The optical band gap energies in the studied N-doped SrTiO₃ films are at 3.2–3.3 eV, which is very similar to that of pure strontium titanate (～3.2 eV). Films deposited with NH₃ for the RF-plasma exhibit a lower degree of crystallinity and reveal almost no nitrogen incorporation into the crystal lattice.     

Nonlinear optical absorption in Bi3TiNbO9 thin films using Z-scan?technique

Bi₃TiNbO₉ (BTN) thin films with layered perovskite structure were fabricated on fused silica by pulsed laser deposition. The XRD pattern revealed that the films are single-phase perovskite and highly (00l) textured. Their fundamental optical constants, such as band gap, linear refractive index, and linear absorption coefficient, were obtained by optical transmittance measurements. The dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The nonlinear optical absorption of the films was investigated by single beam Z-scan method at a wavelength of 800 nm with laser duration of 80 fs. We obtained the nonlinear absorption coefficient β=1.44×10⁻⁷ m/W. The results show that the BTN thin films are promising for applications in absorbing-type optical devices.     

Lifetime of optical phonons in fs-laser excited bismuth

This paper presents experimental and theoretical results on the temperature-dependent optical response of a single crystal of bismuth to excitation by femtosecond laser pulses. We demonstrate that the measured damping rate of the transient reflectivity oscillations relates to the lifetime of optical phonons. The lifetime is the inverse rate of the decay of optical phonons into two acoustic phonons. This lifetime also indicates the approach to the vibration instability (catastrophe) threshold that manifests the beginning of the disordering of a solid crystal and transition to a liquid state. We observe the red shift of phonon frequency, which increases with the rise of the initial lattice temperature. The red shift is different from the previously observed red shift proportional to the electron temperature, and thus to the excitation laser fluence. The coherent phonon excitation process imprinted into the initial change in the reflectivity and the following reflectivity oscillations allowed us to uncover the temporal phonon history preceding the structural transformation of solid Bi.     

Electronic properties of thin films of laser-ablated Al2O3

Laser ablation coupled to mass quadrupole spectrometry (LAMQS) has been used to prepare thin films of aluminum oxide deposited on Si substrates starting from commercial Al₂O₃ polycrystalline targets. X-ray photoemission (XPS) and reflection electron energy loss spectroscopy (REELS) have allowed the investigation of the electronic properties of the produced films. In particular, it was found that the Al/O atomic ratio assumes a value very near to 0.7 (stoichiometric ratio) only for films deposited normally with respect to the target surface, while films grown at larger deposition angles are more rich in oxygen content.The composition, the mass density, the optical energy gap, the complex dielectric function and refraction index of the films have been calculated and compared with the results obtained from our starting target material and with the literature. The morphology of the deposited samples has been analyzed by the AFM technique.     

Optical properties of in situ doped and undoped titania nanocatalysts and doped titania sol-gel nanofilms

In this paper we present spectroscopic properties of doped and undoped titanium dioxide (TiO₂) as nanofilms prepared by the sol-gel process with rhodamine 6G doping and studied by photoacoustic absorption, excitation and emission spectroscopy. The absorption spectra of TiO₂ thin films doped with rhodamine 6G at very low concentration during their preparation show two absorption bands, one at 2.3 eV attributed to molecular dimmer formation, which is responsible for the fluorescence quenching of the sample and the other at 3.0 eV attributed to TiO₂ absorption, which subsequently yields a strong emission band at 600 nm. The electronic band structure and optical properties of the rutile phase of TiO₂ are calculated employing a fully relativistic, full-potential, linearized, augmented plane-wave (FPLAPW) method within the local density approximation (LDA). Comparison of this calculation with experimental data for TiO₂ films prepared for undoped sol-gels and by sputtering is performed.     

Synthesis of DLC films by PLD from liquid target and dependence of film properties on the synthesis conditions

DLC (Diamond-like carbon films) were prepared by pulsed laser ablation of a liquid target at substrate temperatures from 18 to 600°C using 248 nm KrF excimer laser. The sp³ hybridization state carbon formation was additionally promoted by gaseous H₂O₂ flow through the reaction chamber and substrate excitation by the same laser beam. Deposited DLC films were characterised by Raman scattering spectroscopy and atomic force microscopy (AFM). Comparative AFM and Raman study shows that the increase in the content of sp³ type bonding in DLC is in correlation with the increase of the surface roughness of the samples prepared.