Influence of radiofrequency power on compositional, structural and optical properties of amorphous silicon carbonitride films

The silicon carbonitride (SiCN) films were deposited on n-type Si (1 0 0) and glass substrates by the radiofrequency (RF) reactive magnetron sputtering of polycrystalline silicon target under mixed reactive gases of acetylene and nitrogen. The films have been characterized by energy dispersive spectrometer (EDS), atomic force microscope (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectrophotometer (UVS). The influence of RF power on the compositional, morphological, structural and optical properties of the SiCN films was investigated. The SiCN films deposited at room temperature are amorphous, and the C, Si and O compositions except N in the films are sensitive to the RF power. The surface roughness and optical band gap decrease as the RF power increases. The main bonds in the SiCN films are C-N, N-H_n, C-H_n, C-C, CN, Si-H and Si-C, and the intensities of the CN, Si-H and C-H_n bonds increase with increment of the RF power. The mechanisms of the influence of RF power on the characteristics of the films are discussed in detail.     

Electron affinity study of adamantane on Si(1 1 1)

Recently, tetramantane, a member of diamondoid series (C_4n+6H_4n+12), has shown to exhibit negative-electron-affinity effect which has a potential use for efficient electron emitting devices. Here, we explore the electronic property of adamantane (C₁₀H₁₆), the smallest member of the series. We prepare adamantane films on Si(1 1 1) substrates and then study their electronic structure with photoemission spectroscopy. Photoelectron spectra of adamantane on Si(1 1 1) have shown a peak at low-kinetic energy which could be a generic property of diamondoids. The possibility of the negative-electron-affinity effect in adamantane is further discussed.     

Influence of crystallization on the spectral features of nano-sized ferroelectric barium strontium titanate (Ba0.7Sr0.3Tio3) thin films

Ferroelectric barium strontium titanate (Ba_0.7Sr_0.3TiO₃)(BST) thin films have been prepared from barium 2-ethylhexanoate [Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂]_, strontium 2-ethylhexanoate [Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂] and titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄ precursors using a modified sol-gel technique. The precursor except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on pre-cleaned quartz substrates by spin coating. The structural and optical properties of films annealed at different temperatures have been investigated. The as-fired films were found to be amorphous that crystallized to the tetragonal phase after annealing at 550 °C for 1 h in air. The lattice constants “a” and “c” were found to be 3.974 A and 3.990 A, respectively. The grain sizes of the films annealed at 450, 500 and 550 °C were found to be 30.8, 36.0 and 39.8 nm respectively. The amorphous film showed very high transparency (∼95%), which decreases slightly after crystallization (∼90%). The band gap and refractive index of the amorphous and crystalline films were estimated. The optical dispersion data are also analyzed in the light of the single oscillator model and are discussed.     

Luminescent characteristics of CaTiO3:Pr thin films prepared by pulsed laser deposition method with various substrates

CaTiO₃:Pr³⁺ films were deposited on different substrates such as Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica using pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by XRD and SEM measurements. The films grown on the different substrates have different crystallinity and morphology. The FWHM of (2 0 0) peak are 0.18, 0.25, 0.28, and 0.30 for Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica, respectively. The grain sizes of phosphors grown on different substrates were estimated by using Scherrer's formula and the maximum crystallite size observed for the thin film grown on Al₂O₃ (0 0 0 1). The room temperature PL spectra exhibit only the red emission peak at 613 nm radiated from the transition of (¹D₂ → ³H₄) and the maximum PL intensity for the films grown on the Al₂O₃ (0 0 0 1) is 1.1, 1.4, and 3.7 times higher than that of the CaTiO₃:Pr³⁺ films grown on MgO (1 0 0), Si (1 0 0), and fused Sillica substrates, respectively. The crystallinity, surface morphology and luminescence spectra of thin-film phosphors were highly dependent on substrates.     

The influence of H2/(H2 + Ar) ratio on microstructure and optoelectronic properties of microcrystalline silicon films deposited by plasma-enhanced CVD

Hydrogenated microcrystalline silicon films were deposited by glow discharge decomposition of SiH₄ diluted in mixed gas of Ar and H₂. By investigating the dependence of the film crystallinity on the flow rates of Ar and H₂, we showed that the addition of Ar in diluted gas markedly improves the crystallinity due to an enhanced dissociation of SiH₄. The infrared-absorption spectrum reveals that the fraction of SiH bonding increases with increasing the rate ratio of H₂/(H₂ + Ar). The surface roughness of the films increases with increasing the flow rate ratio of H₂/(H₂ + Ar), which is attributed to the decrease of massive bombardment of Ar ions in the plasma. Refractive index and absorption coefficient of the films were obtained by simulating the optical transmission spectra using a modified envelope method. Electrical measurements of the films show that the dark conductivity increases and the activation energy decreases with the ratio of H₂/(H₂ + Ar). A reasonable explanation is presented for the dependence of the microstructure and optoelectronic properties on the flow rate ratio of H₂/(H₂ + Ar).     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Intrinsic coercivities of molecular beam epitaxy grown single-crystal Ni films on Ag buffer layer

Single-crystal Ni films were made by the molecular beam epitaxy (MBE) method on Si(1 0 0) and Si(1 1 0) substrates, respectively, with an 100 Å thick Ag buffer layer. The growth temperature T_S was 270 °C, and the film thickness t was 500 Å. From reflection high-energy electron diffraction (RHEED) patterns, the crystalline symmetries of the two films are clear and as expected. Intrinsic coercivities, H_C(1 0 0) and H_C(1 1 0), are plotted as a function of the angle of rotation ? around the crystal axes [1 0 0] and [1 1 0], respectively. The results show that both H_C(1 0 0) and H_C(1 1 0) exhibit mixed features of the crystalline (K_C) and the induced uniaxial magnetic (K_u) anisotropies. K_u is the magneto-elastic energy, due to lattice mismatch at the Ni/Ag interface. Moreover, the crystalline anisotropy fields, H_K(1 0 0) and H_K(1 1 0), and the induced anisotropy filed, H_u, can be calculated as a function of ?, respectively. Then, each H_C curve is fitted by the equation: H_C = H_o + H_K + H_u, where H_o is the isotropic pinning field. Meanwhile, domain structures were examined by the Bitter method, using Ferrofluid 707. On the Ni(1 0 0) film, we observed the charged cross-tie walls, and on the Ni(1 1 0) film, the un-charged Bloch walls.     

Effects of substrates on the structure and dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films

Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films were grown on Pt(1 1 1)/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel processing technique, respectively. The BTS thin films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si and annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates exhibited strong (1 1 1) and perfect (1 0 0) orientations, respectively. The BTS thin films grown on un-annealed Pt(1 1 1)/Ti/SiO₂/Si substrates showed random orientation with intense (1 1 0) peak, while the films deposited on un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate exhibited random orientation with intense (1 0 0) peak, respectively. The dielectric constant of the BTS films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si, annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si, un-annealed Pt(1 1 1)/Ti/SiO₂/Si and un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates was 512, 565, 386 and 437, respectively, measured at a frequency of 100 kHz. A high tunability of 49.7% was obtained for the films deposited on annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate, measured at the frequency of 100 kHz with an applied electric field of 200 kV/cm. The high tunability has been attributed to the (1 0 0) texture of the films and larger grain sizes.     

Write-once blue laser recording using silicon doped SbOx thin films prepared by reactive dc-magnetron sputtering

Si:SbO_x films have been deposited by reactive dc-magnetron sputtering from a Sb target with Si chips attached in Ar + O₂ with the relative O₂ content 7%. The as-deposited films contained Sb metal, Sb₂O₃, SiO, Si₂O₃ and SiO₂. The crystallization of Sb was responsible for the changes of optical properties of the films. The results of the blue laser recording test showed that the films had good writing sensitivity for blue laser beam (406.7 nm), and the recording marks were still clear even if the films were deposited in air 60 days, which demonstrated that doping silicon in SbO_x films can improve the stability of SbO_x films. High reflectivity contrast of about 36% was obtained at a writing power 6 mW and writing pulse width 300 ns.     

Investigation of thin TiO2 films cosputtered with Si species

Titanium dioxide (TiO₂) films were fabricated by cosputtering titanium (Ti) target and SiO₂ or Si slice with ion-beam-sputtering deposition (IBSD) technique and were postannealed at 450 °C for 6 h. The variations of oxygen bonding, which included high-binding-energy oxygen (HBO), bridging oxygen (BO), low-binding-energy oxygen (LBO), and three chemical states of titanium (Ti⁴⁺, Ti³⁺ and Ti²⁺) were analyzed by X-ray photoelectron spectroscopy (XPS). The enhancement of HBO and reduction of BO in O 1s spectra as functions of SiO₂ or Si amount in cosputtered film imply the formation of Si-O-Ti linkage. Corresponding increase of Ti³⁺ in Ti 2p spectra further confirmed the property modification of the cosputtered film resulting from the variation of the chemical bonding. An observed correlation between the chemical structure and optical properties, refractive index and extinction coefficient, of the SiO₂ or Si cosputtered films demonstrated that the change of chemical bonding in the film results in the modification of optical properties. Furthermore, it was found that the optical properties of the cosputtered films were strongly depended on the cosputtering targets. In case of the Si cosputtered films both the refractive indices and extinction coefficients were reduced after postannealing, however, the opposite trend was observed in SiO₂ cosputtered films.     

Structural and optical properties of a-Si1−xCx:H films synthesized by dc magnetron sputtering technique

Hydrogenated amorphous SiC films (a-Si_1−xC_x:H) were prepared by dc magnetron sputtering technique on p-type Si(1 0 0) and corning 9075 substrates at low temperature, by using 32 sprigs of silicon carbide (6H-SiC). The deposited a-Si_1−xC_x:H film was realized under a mixture of argon and hydrogen gases. The a-Si_1−xC_x:H films have been investigated by scanning electronic microscopy equipped with an EDS system (SEM-EDS), X-ray diffraction (XRD), secondary ions mass spectrometry (SIMS), Fourier transform infrared spectroscopy (FTIR), UV-vis-IR spectrophotometry, and photoluminescence (PL). XRD results showed that the deposited film was amorphous with a structure as a-Si_0.80C_0.20:H corresponding to 20 at.% carbon. The photoluminescence response of the samples was observed in the visible range at room temperature with two peaks centred at 463 nm (2.68 eV) and 542 nm (2.29 eV). In addition, the dependence of photoluminescence behaviour on film thickness for a certain carbon composition in hydrogenated amorphous SiC films (a-Si_1−xC_x:H) has been investigated.     

The surface modification of nanoporous SiOx thin films with a monofunctional organosilane

The surfaces of nanostructured, porous SiO_x/Si (air-oxidized Si) and SiO_x thin films, deposited by excimer laser ablation in He and He + O₂ gas ambients, respectively, have been modified by the deposition of a monofunctional organosilane. They were characterized using photoacoustic Fourier-transform infrared (FTIR) X-ray photoelectron (XPS) spectroscopies, and field-emission scanning electron microscopy (FESEM). Photoacoustic FTIR analysis indicates that the organosilane has hydrolyzed to form a silanol, which has chemically reacted with SiO_x through its surface silanol (SiOH) group, to form siloxane (SiOSi) structures. An enhanced IR spectral signal is found, due to the expansion and contraction of both the pores of the solid and the gas within them.     

Origin of photoluminescence in nanocrystalline Si:H films

We have studied the origin of photoluminescence (PL) from hydrogenated nanocrystalline silicon (nc-Si:H) films produced by a plasma-enhanced chemical vapor deposition technique using SiF₄/SiH₄/H₂ gas mixtures. The nc-Si:H films were characterized using X-ray diffraction, infrared, Raman spectroscopy, optical absorption and stress, and were examined for PL by varying the deposition temperature (T_d) under two different hydrogen flow rate ([H₂]) conditions. The PL exhibited two peaks at around 1.7-1.75 and 2.2-2.3 eV. The peak energy, E_PL, of the 1.7-1.75-eV PL band was found to shift as T_d or [H₂] changes. It was found that the decrease in T_d acts to decrease the average grain size, 〈δ〉, and to increase both the optical band gap, , and the E_PL values. By contrast, the increase in [H₂] decreased the 〈δ〉 value, while increased the values of and E_PL. Thus, as either T_d decreases or [H₂] increases, it is found that a decrease in 〈δ〉 corresponds well with increases in and E_PL. As a consequence, it was suggested that an increase in E_PL of the 1.7-1.75-eV PL band can be connected with an increase in , through a decrease in 〈δ〉. However, the PL process cannot be connected with the transition between both the bands, related to formation of nanocrystals. Based on these results, it was proposed that the use of both low T_d and high [H₂] conditions would allow to grow nc-Si:H films with small grains.     

Adsorption of organic molecules by photochemical reaction on Cl:Si(1 1 1) and H:Si(1 1 1) evaluated by HREELS

The covalent attachment of alkyl groups to silicon surfaces, via carbon-silicon bond formation, has been attempted using gas-surface reactions starting from Cl-terminated Si(1 1 1) or H:Si(1 1 1) under ultraviolet light irradiation. The formation of Cl-terminated Si(1 1 1) and its resulting stability were examined prior to deposition of organic molecules. High-resolution electron energy loss spectroscopy (HREELS) was utilized for detecting surface-bound adsorbates. The detection of photo-deposited organic species on Cl:Si(1 1 1) from gas-phase CH₄ or CH₂CH₂ was not significant. On H:Si(1 1 1), it was evident that after the photoreaction with gas-phase C₂H₅Cl, C₂H₅ groups were chemically bonded to the surface Si atoms through single covalent bonds. The C₂H₅ groups were thermally stable at temperatures below 600 K. Alkyl monolayers prepared on silicon surfaces by dry process will lead to a new prospective technology of nanoscale fabrication and biochemical applications.     

C-V studies on metal-ferroelectric bismuth vanadate (Bi2VO5.5)-semiconductor structure

Ferroelectric bismuth vanadate Bi₂VO_5.5 (BVO) thin films have been successfully grown on p-type Si(100) substrate by using chemical solution decomposition (CSD) technique followed by rapid thermal annealing (RTA). The crystalline nature of the films has been studied by X-ray diffraction (XRD). Atomic force microscopy (AFM) was used to study the microstructure of the films. The dielectric properties of the films were studied. The capacitance-voltage characteristics have been studied in metal-ferroelectric-insulator-semiconductor (MFIS) configuration. The dielectric constant of BVO thin films formed on Si(100) is about 146 measured at a frequency of 100 kHz at room temperature. The capacitance-voltage plot of a Bi₂VO_5.5 MFIS capacitor subjected to a dc polarizing voltages shows a memory window of 1.42 V during a sweep of ±5 V gate bias. The flatband voltage (V_f) shifts towards the positive direction rather than negative direction. This leads to the asymmetric behavior of the C-V curve and decrease in memory window. The oxide trap density at a ramp rate of 0.2 V/s was estimated to be as high as 1.45×10¹² cm⁻².     

Magnetic properties of core-shell catalyst nanoparticles for carbon nanotube growth

Two types of core-shell nanoparticles have been prepared by laser pyrolysis using Fe(CO)₅ and C₂H₂ or [(CH₃)₃Si]₂O as precursors and C₂H₄ as sensitizer. The first type (about 4 nm diameter) - produced by the decomposition of Fe(CO)₅ in the presence of C₂H₄ and C₂H₂ - consists of Fe cores protected by graphenic layers. The second type (mean particle size of about 14 nm) consists also of Fe cores, yet covered by few nm thick γ-Fe₂O₃/porous polycarbosiloxane shells resulted from the [(CH₃)₃Si]₂O decomposition and superficial oxidation after air exposure. The hysteresis loops suggest a room temperature superparamagnetic behavior of the Fe-C nanopowder and a weak ferromagnetic one for larger particles in the Fe-Fe₂O₃-polymer sample. Both types of nanoparticles were finally used as a catalyst for the carbon nanotube growth by seeding Si(100) substrates via drop-casting method. CNTs were grown by Hot-Filament Direct.Current PE CVD technique from C₂H₂ and H₂ at 980 K. It is suggested that the increased density and orientation degree observed for the multiwall nanotubes grown from Fe-Fe₂O₃-polymer nanoparticles could be due to their magnetic behavior and surface composition.     

Effect of Ni interlayer on stress level of CoSi2 films in Co/Ni/Si(1 0 0) bi-layered system

The effect of Ni interlayer on stress level of cobalt silicides was investigated. The X-ray diffraction patterns (XRD) show that low temperature formation of Co_1−xNi_xSi₂ solid solution was obtained while Ni interlayer was present in Co/Si system, which was confirmed by Auger electron spectrum (AES) and sheet resistance measurement. XRD was also used to measure the internal stress in CoSi₂ films by a 2θ_ψ − sin²ψ method. The result shows that the tensile stress in CoSi₂ films evidently decreased in Co/Ni/Si(1 0 0) system. The reduction of lattice mismatch, due to the presence of Ni in Co_xNi_1−xSi₂ solid solution, is proposed to explain this phenomenon.     

Pre-treatments applied to oxidized aluminum surfaces to modify the interfacial bonding with bis-1,2-(triethoxysilyl)ethane (BTSE): Part I. High-purity Al with native oxide

A remote microwave-generated H₂ plasma and heating to 250 °C were separately used to modify high-purity oxidized aluminum surfaces and to assess whether these treatments can help enhance adhesion with bis-1,2-(triethoxysilyl)ethane (BTSE) coatings. Different initial oxide surfaces were considered, corresponding to the native oxide and to surfaces formed by the Forest Products Laboratory (FPL) treatment applied for either 15 or 60 min. BTSE is applied from solution at pH 4, and competing processes of etching, protonation (to form OH groups) and coupling (to form AlOSi interfacial bonds) occur at the solid-liquid interface. Scanning electron microscopy (SEM) was used to determine how the topographies of the modified Al surfaces changed with the different pre-treatments and with exposure to a buffer solution of pH 4. Secondary-ion mass spectrometry (SIMS) was used to determine the direct amount of AlOSi interfacial bonds by measuring the ratio of peak intensities 71-70 amu, while X-ray photoelectron spectroscopy (XPS) was used to determine the overall strength of the silane coating adhesion by measuring the Si 2p signals before and after application of an ultrasonic rinse to the coated sample. Measured Al 2p and O 1s spectra helped assess how the different pre-treatments modified the various Al oxidized surfaces prior to BTSE coating. Pre-treated samples that showed increased AlOSi bonding after BTSE coating corresponded to surfaces, which did not show evidence of significant etching after exposure to a pH 4 environment. This suggests that such surfaces are more receptive to the coupling reaction during exposure to the BTSE coating solution. These surfaces include all H₂ plasma-treated samples, the heated native oxide and the sample that only received the 15 min FPL treatment. In contrast, other surfaces that show evidence of etching in pH 4 environments are samples that received lower amounts of AlOSi interfacial bonding. Overall, heating improved the BTSE adhesive bonding for the native Al oxide, while H₂ plasma treatment improved the BTSE bonding for surfaces that had initially been FPL-treated for 15 and 60 min.     

Epitaxial ZnO films grown on ZnO-buffered c-plane sapphire substrates by hydrothermal method

ZnO films are hydrothermally grown on ZnO-buffered c-plane sapphire substrates at a low temperature of 70 °C. A radio-frequency (RF) reactive magnetron sputtering has been used to grow the ZnO buffer layers. X-ray diffraction, scanning electron microscopy, and room temperature photoluminescence are carried out to characterize the structure, morphology and optical property of the films. It is found that the films are stress-free. The epitaxial relationship between the ZnO film and the c-plane sapphire substrate is found to be ZnO (0 0 0 1)||Al₂O₃ (0 0 0 1) in the surface normal and in plane. Sapphire treatment, as such acid etching, nitridation, and oxidation are found to influence the nucleation of the film growth, and the buffer layers determine the crystalline quality of the ZnO films. The maximum PL quantum efficiency of ZnO films grown with hydrothermal method is found to be about 80% of single-crystal ZnO.