Ultraviolet-visible and surface-enhanced Raman scattering spectroscopy studies on self-assembled films of ruthenium phthalocyanine on organic monolayer-modified silver substrates

A self-assembled film of ruthenium phthalocyanine (RuPc) fabricated on a silver substrate pre-modified with a monolayer of 4-mercaptopyridine (PySH) or 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was studied by ultraviolet-visible (UV-Vis) and surface enhanced Raman scattering (SERS) spectroscopy. PySH or BPENB was used as a ligand to link RuPc since they not only modify the silver substrate, but also deliver a pyridyl group pointing out from the silver surface. Therefore, we can explore the relationship between the structure and orientation of metallophthalocyanine and the substrate modified by the two kinds of organic-monolayers with the different conjugates and molecular lengths. UV-Vis bands due to the organic-monolayer (PySH or BPENB) modified silver films shift to longer wavelengths and a new band arising from the metallophthlocyanine appears, suggesting the binding of RuPc to PySH/BPENB, as well as the interaction between the marcocycle of RuPc and the ring of PySH/BPENB. Vibrational bands arising from both the RuPc and PySH/BPENB moieties appear clearly in the SERS spectra of the RuPc-PySH/BPENB composite films, indicating that RuPc is successfully assembled on the top of PySH/BPENB film. The shifts and relative intensity changes of bands due to PySH or BPENB in the SERS spectra imply the binding of the metallophthalocyanine to the pyridyl group in the composite films. Furthermore, the comparison of the SERS spectra revealed that the orientations of PySH and BPENB in the two kinds of composite films are different; the BPENB moiety in the RuPc-BPENB composite film is more perpendicular to the silver surface compared with the PySH moiety in the RuPc-PySH composite film.     

The effect of NO2 doping on the gas sensing properties of copper phthalocyanine thin film devices

In this work we report the effect on the NO₂ gas sensing properties of initially doping CuPc thin films with oxygen (in air) and NO₂ for room temperature operation. The pre-treatment with NO₂ is shown to improve the gas sensing properties by providing both an increase in the magnitude of the conductivity change for a given NO₂ concentration and a significant improvement in the recovery time. Data presented suggest that a simple time derivative of the change in current may provide a measure of concentration for real time gas sensing applications.     

Sol-gel reaction stability studied: Influence in the formation temperature and properties of ferroelectric thin films

Lead zirconium titanate (PZT) sol-gel solutions were prepared based on distilled lead acetate precursor solutions. A detailed analysis of the distillation effect on the lead precursor and the final PZT solution were carried out by Infrared and Raman techniques. It was found that the increase in the number of distillation steps experienced by the lead precursor solutions removes the constitutional water and increases the lead acetate-2-methoxyethanol interconnectivity; thus improving stability and avoiding the aging effect of the resulting PZT solutions. The thermal decomposition process of the PZT solutions was analyzed based on the thermogravimetric (TG) and differential thermogravimetric analysis (DTA) measurements. It was found that as the number of distillation steps in the lead precursor solutions increases, the decomposition rate increases and the formation temperature of pure perovskite PZT films decreases. X-ray diffraction (XRD) technique was used to study the film phase formation. A pure perovskite phase at 500 °C was found by the XRD analysis after the second distillation step. Scanning electron microscope technique was used to carry out the microstructural analysis. Dense microstructure was found in all analyzed films and an incipient columnar grain growth was revealed in PZT films prepared based on lead precursor solution with more than three distillation steps. The dependence of the dielectric, ferroelectric and piezoelectric properties on the number of distillation steps was revealed and a correlation between the distillation process, film microstructure properties and electrical performance was established.     

Photoinduced charge transfer through films containing poly(hexylthiophene), phthalocyanine, and porphyrin-fullerene layers

Efficient photoinduced interlayer electron transfer from a phthalocyanine derivative, ZnPH4, to porphyrin cation of a porphyrin-fullerene donor-acceptor dyad was demonstrated by using time-resolved photovoltage technique. Multicomponent thin films with desired layer arrangements were constructed by the Langmuir-Blodgett and spin-coating methods in order to study charge transfer in solid state. As a contradiction to the photovoltage experiments, the dyad monolayer in the film structure did not enhance the current amplitude in electrochemical photocurrent measurements. This is associated with a weak electronic interaction between fullerene and aqueous electrolyte, reducing the photocurrent generation. The use of poly(3-hexylthiophene) as a hole conducting layer was shown to improve photocurrent yield of the device by forming efficient heterojunction together with the ZnPH4 layer.     

Studies on phase transformation and molecular orientation in nanostructured zinc phthalocyanine thin films annealed at different temperatures

Studies on the electronic and optical properties of thin films of organometallic compounds such as phthalocyanine are very important for the development of devices based on these compounds. The nucleation and grain growth mechanism play an important role for the final electronic as well as optoelectronic properties of the organic and organometallic thin films. The present article deals with the change in the film morphology, grain orientation of nanocrystallites and optical properties of zinc phthalocyanines (ZnPc) thin films as a function of the post deposition annealing temperature. The effect of annealing temperature on the optical and structural property of vacuum evaporated ZnPc thin films deposited at room temperature (30 °C) on quartz glass and Si(100) substrates has been investigated. The thin films have been characterized by the UV-vis optical absorption spectra, X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy. From the studies of UV-vis absorption spectra and XRD data, a metastable α to β-phase transformation has been observed when the thin films were annealed at a temperature greater than about 250 °C. The FESEM images have shown the particlelike structure at room temperature and the structure became rodlike when the films were annealed at high temperatures. TEM image of ZnPc film dissolved in ethanol has shown spectacular rod-shaped crystallites. High resolution transmission electron microscopy image of a single nanorod has shown beautiful “honey-comb” like structure. Particle size and root mean square roughness were calculated from AFM images. The changes in band gap energy with increase in annealing temperature have been evaluated.     

Effect of temperature on thermal expansion and anharmonicity in Cu2ZnSnS4 thin films grown by co-sputtering and sulfurization

Copper zinc tin sulfide (CZTS, made from the earth abundant and non-toxic materials) is a quaternary semiconducting compound which has received increasing interest for solar cells applications. In this study, CZTS thin film has been grown by co-sputtering Cu, Zn and Sn metal targets and sulfurizing it in H₂S. XRD, SEM, EDS, XRF and optical studies show that these films are suitable for solar cell applications. The temperature-dependent Raman spectroscopic study on CZTS thin ?lm was carried out in the temperature range of 80–450 K. A decrease in the intensity of “A” mode Raman peaks, shift of Raman peaks towards lower frequency and increase in the line width have been observed with increase in temperature. Raman “A” mode shifts from 337 cm⁻¹ at 80 K to 329 cm⁻¹ at 450 K. The peak at 288 cm⁻¹ disappears when the measurement was taken at 450 K. Based on experimental results and fittings of anharmonic equation; it has been shown that these effects are due to thermal expansion and interaction of the phonon with other phonons which arise at higher temperature. These phonons interact resulting in damping of the “A” mode phonon intensity. It was concluded that in order to truly analyze multicomponent compounds, Raman studies should be carried out at low temperature.     

Effects of oxygen flow ratios and annealing temperatures on Raman and photoluminescence of titanium oxide thin films deposited by reactive magnetron sputtering

Titanium oxide (TiO_x) thin films were deposited on the Si(100) substrates by direct-current reactive magnetron sputtering at 3-15 % oxygen flow ratios (FO₂% = FO₂/(FO₂ + FAr) × 100%), and then annealed by rapid thermal annealing (RTA) at 350-750 °C for 2 min in air. The phase, bonding and luminescence behaviors of the as-deposited and annealed TiO_x thin films were analyzed by X-ray diffraction (XRD), Raman spectroscopy and photoluminescence (PL) spectroscopy, respectively. The as-deposited TiO_x films were amorphous from XRD and showed weak Raman intensity. In contrast, the distinct crystalline peaks of anatase and rutile phases were detected after RTA at 550-750 °C from both XRD and Raman spectra. A mixture of anatase and rutile phases was obtained by RTA at 3 FO₂% and its amount increased with annealing temperature. Only the anatase phase was detected in the 6-15 FO₂% specimens after RTA. The PL spectra of all post-annealed TiO_x films showed a broad peak in visible light region. The PL peak of TiO_x film at 3 FO₂% at 750 °C annealing can be fitted into two Gaussian peaks at ~ 486 nm (2.55 eV) and ~ 588 nm (2.11 eV) which were attributed to deep-level emissions of oxygen vacancies in the rutile and anatase phases, respectively. The peak around 550 nm was observed at 6-15 FO₂% which is attributed to electron-hole pair recombination from oxygen vacancy state in anatase phase to valence band. The variation of intensity of PL peaks is concerned with the formation of the rutile and anatase phases at different FO₂% and annealing temperatures.     

The carbonization of thin polyaniline films

Polyaniline films on silicon and ceramic supports were prepared in situ during the oxidative polymerization of aniline. The films were heated up to 500 °C in an inert nitrogen atmosphere. The changes in molecular structure during the carbonization have been studied by infrared spectroscopy and Raman scattering using 514, 633 and 785 nm laser excitation lines. The transformation from polyaniline salt to the base form has been detected above 100 °C. The conversion to nitrogen-containing carbon-like material followed above 200 °C. The molecular structure of the films produced during heating to 500 °C contains crosslinked phenazine-like and oxidized quinonoid units. The aniline oligomers deposited on the support in the early stages of aniline oxidation are stable during heating as it has been observed by resonance Raman scattering using 785 nm laser excitation line. The water contact angles changed after carbonization, and the films became more hydrophilic as carbonization progressed.     

氧化锌薄膜的拉曼光谱研究

利用拉曼光谱结合X射线衍射分析对未掺杂和掺杂的ZnO薄膜，陶瓷薄膜进行了研究，ZnO薄膜及ZnO陶瓷薄膜均由sol-gel法制备，掺杂组份有Bi2O3,Sb2O3,MnO和Cr2O3等。结果表明，未掺杂的薄膜的ZnO主晶相均表现出显著的定向生长特征，其拉曼光谱特征谱峰为437cm^-1，谱峰强度随薄膜退火温度的提高略有增强，掺杂后ZnO的拉曼谱峰发生了红移，掺Bi2O3后ZnO的拉曼谱峰由347cm^-1移质移至434cm^-1，掺Sb2O3后ZnO的拉曼谱峰移至435cm^-1，而掺杂Bi2O3,Sb2O3,MnO和Cr2O3等组份的ZnO陶瓷薄膜的ZnO拉曼谱峰则移至434cm^-1，说明掺杂元素进入了ZnO晶格，引起了晶格的变化，ZnO薄膜性能不仅受次晶相组成的影响，而且受因掺杂元素进入而引起的ZnO晶格畸变的影响。     

Effects of temperature on structural and morphological features of CoPc and CoPcF16 thin films

Herein investigation of the effects of substrate temperature on the structural and morphological features of both cobalt(II) phthalocyanine (CoPc) and cobalt(II) hexadecafluorophthalocyanine (CoPcF₁₆) thin films is presented. For these purposes thin films of CoPc and CoPcF₁₆ prepared by organic molecular beam deposition were investigated by means of optical absorption spectroscopy, X-ray diffraction, Raman spectroscopy, and atomic force microscopy. Concerning the degree of crystallinity, the morphology, the phase composition and the preferential molecular orientation of both CoPc and CoPcF₁₆ thin films, we found out that the increase of substrate temperature during growth influences these properties of the above-mentioned thin film systems (CoPc vs. CoPcF₁₆) in a different way.     

Comparative study of surface morphology of copper phthalocyanine ultra thin films deposited on Si (111) native and RCA-cleaned substrates

Comparative study of substrate doping influence on surface morphology of 16-nm CuPc ultra-thin layers deposited on RCA-cleaned Si (111)/SiO₂ substrates was carried out. The structure and the morphology of thin films were investigated by X-ray photoelectron spectroscopy and atomic force microscopy. The investigations were aimed to provide information whether substrate doping type can be used as one of the parameters for engineering of the sensing layers structure. Atomic force microscopy images and results of photoemission experiments did not reveal any significant differences in morphology and surface chemistry between used substrates. Observed differences in surface morphology of organic overlayer could be caused by different substrate doping. The CuPc film grown on p-type RCA-Si (111) shows a compact network of densely packed crystallites, while the CuPc film deposited on n-type RCA-Si (111) reveals a slightly more open network of larger crystallites. These observations are confirmed by values of roughness, which is 0.97 nm and 1.47 nm for CuPc film on RCA-cleaned p- and n-type substrates, respectively. Results were compared with data obtained for similar 16-nm-thick CuPc layers deposited on n- and p-type Si (111) covered with native oxide. Good agreement between results of both studies was found out.     

Effects of annealing temperature on microstructure and electrical properties of Mn-Co-Ni-O thin films

Mn_1.85Co_0.3Ni_0.85O₄ (MCN) thin films were prepared on Al₂O₃ substrates by chemical solution deposition method at different annealing temperature (650, 700, 750 and 800 °C). Effects of annealing temperature on microstructure and electrical properties of MCN thin films were investigated. The MCN thin film annealed at 750 °C is of good crystallization and compact surface. It shows lower resistance (4.8 MΩ) and higher sensitivity (3720.6 K) than those of other prepared films. It also has small aging coefficient (3.7%) after aging at 150 °C for 360 h. The advantages of good properties make MCN thin film very promising for integrated devices.     

Structural and surface property study of sputter deposited transparent conductive Nb-doped titanium oxide films

We have investigated structural and surface property of transparent conductive Nb-doped titanium oxides (TNO) thin film with high conductivity of 10⁻⁴ Ω cm order which were made by RF-magnetron sputtering at high deposition rates followed by an annealing in vacuum. The grain sizes of TNO evaluated by atomic force microscope were found to become larger by annealing at temperature higher than 500 °C. The measured work functions of the TNO films using ultra-violet light photoelectron spectroscopy were 5.02-5.47 eV, and depended on TNO grain size and on the amount of surface weakly bound oxygen that was estimated from peak area intensities of O(1 s) X-ray photoelectron spectra.     

Effects of substrate temperature on the surface of polymer thin films prepared by R.F. sputtering with a polyimide target

In this study, we characterized polymer thin films deposited by a conventional radio frequency sputtering apparatus introduced into argon and nitrogen gases with a polyimide target onto copper substrates.Heating effects due to heating the copper substrate at 250 °C in the sputtering on tribological and adhesion properties of thin films were investigated with measuring friction coefficient, wear durability and pull strength. Surface roughness of the nitrogen sputtered thin film decreased by the heating. Friction coefficient of argon and nitrogen sputtered thin films prepared at 250 °C was almost the same level as that prepared at room temperature, respectively. Wear durability of these thin films and adhesion strength between these thin films and copper substrate decreased by the heating.     

Morphology, surface topography and optical studies on electron beam evaporated MgO thin films

Electron beam evaporated thin films of MgO powder synthesized by burning of magnesium ribbon in air and sol-gel technique are studied for their microstructure (SEM), surface topography (AFM), and optical transmission behaviour (UV-visible spectroscopy). MgO thin films are shown to be either continuous or have mesh like morphology. The bar regions are believed to be of magnesium hydroxide formed due to absorption of moisture. Their AFM images exhibit columnar/pyramidal/truncated cone structure, providing support to the 3D Stranski-Krastanov model for film growth. Further, they are shown to have high transmittance (∼90%) in the wavelength range 400–600 nm, but absorb radiation below 350 nm substantially giving signature of a band transition.     

Self-doped polyaniline films prepared by electropolymerization in the presence of sulfonated nickel phthalocyanine

It is shown that the addition of tetrasulfonated nickel phthalocyanine (NiTSPc) to an acidic solution of aniline results in an accelerated deposition of polyaniline (PANI) from such a solution using the electrochemical potential cycling method. The electrodeposited polyaniline includes NiTSPc to form a composite film that retains its electroactivity in a wide pH range due to the self-doping effect. The thus formed composite PANI-NiTSPc film exhibits catalytic activity toward the electrooxidation of ascorbic acid in a nearly neutral buffer (pH 7.4).     

Influence of ambient air exposure on surface chemistry and electronic properties of thin copper phthalocyanine sensing layers

In this paper we present photoemission studies of the influence of 12-hour exposure to the ambient air on the chemical and electronic properties of thin 16-nm copper phthalocyanine (CuPc) sensing layers deposited on n- and p-type silicon Si(111) substrates covered with the native oxide. The surface chemistry and electronic parameters of organic thin film including surface band bending, work function, electron affinity and their variations upon the exposure have been monitored with X-ray photoemission spectroscopy and ultraviolet photoemission spectroscopy techniques. We found that after the exposure, the surface chemistry of CuPc remained unaffected, however the work function and surface band bending increased by 0.55 eV and 0.45 eV for the layers on n-Si and by 0.25 eV and 0.30 eV for those on p-Si. Additionally, we detected a slight surface dipole at CuPc on n-Si manifested by a small shift in electron affinity of 0.10 eV. In order to explain these changes we developed a model basing on the interaction of ionic species with the phthalocyanine surface.     

Effects of low temperature on the characteristics of tantalum thin films

In this paper the effects of substrate temperature (room temperature - 350 °C) on the phase composition and crystallization orientation of the tantalum thin film deposited by direct current magnetron sputtering in an extremely low power deposition regime are presented. In this experiment, heating the substrates to 350 °C resulted in the growth of the hard and brittle tetragonal crystalline structure (β-Ta). Deposited tantalum has a conical structure with large voided boundaries. Sheet resistance of samples is much larger than for the convenient conductors which decreased with increasing the substrate temperature.     

Effect of samarium addition and annealing on the properties of electrodeposited ceria thin films

Samarium (Sm)-doped ceria (CeO₂) (SDC) is a promising material for high temperature electrochemical devices. Our work demonstrates that thin SDC films can be prepared by a cost-effective electrodeposition method at a low-temperature (30 °C) and − 0.8 V/SCE (saturated calomel electrode) potential. Analysis of the structural properties of the obtained SDC films, as-grown and annealed at 600 °C, has been carried out by X-ray diffraction (XRD). Morphology and film composition were studied using scanning electronic microscopy and energy dispersive X-ray analysis. Vibrational properties were determined by Raman spectroscopy. The effects of samarium addition into the deposition bath on the final film composition have been studied. According to XRD results, film crystallographic properties are directly linked to the percentage of Sm incorporated in the CeO₂ lattice. We report on the electrochemical deposition of the SDC films performed over a large range of Sm additions (0-30%). The effect of temperature annealing has been studied as well.