Preparation and characterization of the ZnO:Al/Fe65Co35/ZnO:Al multifunctional films

The ferromagnetic transparent conducting film is a multifunctional film which has high visible transmittance, low resistivity and room-temperature ferromagnetism, simultaneously. In this article, ferromagnetic transparent conducting ZnO:Al/Fe₆₅Co₃₅/ZnO:Al multilayer films were fabricated by inserting a middle magnetic Fe₆₅Co₃₅ layer into aluminum-doped zinc oxide (ZnO:Al) matrix using a magnetron sputtering apparatus at substrate temperature ranging from room temperature (RT) to 400^∘C. The total film thickness was about 400 nm and the middle Fe₆₅Co₃₅ alloy layer was 4 nm. The influences of substrate temperature (T _s ) on the structural, electrical, optical and magnetic properties of the multilayer films were systemically investigated. The results showed that the microstructure and performance of the composite multilayer films strongly depended on the substrate temperature. The present results also showed that the inserted middle Fe₆₅Co₃₅ alloy thin layer played an important role in providing the RT ferromagnetism and decreasing the resistivity of the multilayer films. Therefore, it is possible to obtain a multifunctional film material with the combination of good optical transparency, high electrical conductivity and RT ferromagnetism.     

Variety of LaSrMnO structures induced by growth conditions and laser irradiation

Crystallographic phase transitions in perovskite-like LaSrMnO metallic oxides are studied. The transitions are induced when internal stresses generated during film synthesis (at temperatures between 450 and 730°C) vary (decrease or increase) upon subsequent irradiation by a KrF laser emitting in the UV range. As the synthesis temperature T _s grows, the rhombohedral-to-orthorhombic phase transition occurs at 650–670°C. The resistivity is shown to be either temperature-independent, ρ(T)=const, at T<T _crit, or varies and reaches a maximum, ρ(T)=ρ_max, at the Curie temperature T _c. Optical transmission spectra taken at photon energies ℏω=0.5–2.5 eV exhibit both a high (0.8–0.9) and low (0.1–0.3) transmission coefficient t, depending on the synthesis temperature. As follows from X-ray diffraction data, the laser irradiation causes a phase transition only in LaSrMnO films grown at T _s<650°C. Phases of different size scales appear: the long-range-order orthorhombic matrix and mesoscopic-range-order rhombohedral clusters are observed in the films grown at T _s=450–550°C and the rhombohedral matrix with orthorhombic clusters, in the films grown at T _s=550–650°C.     

CEMS study on diluted magneto titanium oxide films prepared by pulsed laser deposition

6% ⁵⁷Fe doped titanium oxide films, prepared by pulsed laser deposition (PLD) on sapphire substrate at 650°C under various vacuum conditions, were characterized mainly by conversion electron Mössbauer spectrometry (CEMS). Two magnetic sextets with hyperfine fields 33 and 29 T, and one doublet were observed in the CEMS spectra of TiO₂ films prepared under PO₂ = 10^?6 and 10^?8 torr, which showed ferromagnetism at room temperature, whereas only the doublet of paramagnetic Fe³⁺ species was observed for the film prepared under PO₂ = 10^?1 torr.     

Growth by laser ablation of Ti-based oxide films with different valency states

x La_2/3+yTiO_3-δ perovskite (with δ≤0.5) were deposited by the laser ablation technique from Li_0.33La_0.56TiO₃ targets. Their growth onto MgO substrateswas studied as a function of the oxygen pressure. For films grown in vacuum (10^-6 mbar), a La_0.63TiO_2.5 composition was obtained, meaning that Ti³⁺ alone is present in the films, while Li ions are not incorporated under these conditions. This material shows good electric conductivity (ρ=500 mΩ cm). By contrast, insulating films with a Li_0.1La_0.70TiO₃ composition corresponding to the Ti⁴⁺ species were obtained at high oxygen pressures (>0.05 mbar). For all conditions, textured films were grown with different orientations depending on the temperature and the oxygen pressure. Received: 10 September 1997/Accepted: 24 November 1997     

Structural and magnetic properties of thin epitaxial Fe films on (1 1 0) GaAs prepared by metalorganic chemical vapor deposition

Iron films have been grown on (1 1 0) GaAs substrates by atmospheric pressure metalorganic chemical vapor deposition at substrate temperatures (T_s) between 135°C and 400°C. X-ray diffraction (XRD) analysis showed that the Fe films grown at T_s between 200°C and 330°C were single crystals. Amorphous films were observed at T_s below 200°C and it was not possible to deposit films at T_s above 330°C. The full-width at half-maximum of the rocking curves showed that crystalline qualities were improved at T_s above 270°C. Single crystalline Fe films grown at different substrate temperature showed different structural behaviors in XRD measurements. Iron films grown at T_s between 200°C and 300°C showed bulk α-Fe like behavior regardless of film thickness (100–6400 Å). Meanwhile, Fe films grown at 330°C (144 and 300 Å) showed a biaxially compressed strain between substrate and epilayer, resulting in an expanded inter-planar spacing along the growth direction. Magnetization measurements showed that Fe films (>200 Å) grown at 280°C and 330°C were ferromagnetic with the in-plane easy axis along the [1 1 0] direction. For the thinner Fe films (⩽200 Å) regardless of growth temperature, square loops along the [1 0 0] easy axis were very weak and broad.     

Low temperature plasma production of hydrogenated nanocrystalline silicon thin films

The hydrogenated nanocrystalline silicon (nc-Si:H) thin films were produced by capacitively-coupled plasma enhanced chemical vapor deposition (PECVD) technique at low substrate temperatures (T_s ≈ 40–200 °C). Firstly, for particular growth parameters, the lowest stable T_s was determined to avoid temperature fluctuations during the film deposition. The influence of the T_s on the structural and optical properties of the films was investigated by the Fourier transform infrared (FTIR), UV–visible transmittance/reflectance and X-ray diffraction (XRD) spectroscopies. Also, the films deposited at the center of the PECVD electrode and those around the edge of the PECVD electrode were compared within each deposition cycle. The XRD and UV–visible reflectance analyses reveal the nanocrystalline phase for the films grown at the edge at all T_s and for the center films only at 200 °C. The crystallinity fraction and lateral dark conductivity decrease with lowered T_s. FTIR analyses were used to track the hydrogen content, void fraction and amorphous matrix volume fraction within the films. The optical constants obtained from the UV–visible transmittance spectroscopy were correlated well with the FTIR results. Finally, the optimal T_s was concluded for the application of the produced nc-Si:H in silicon-based thin film devices on plastic substrates.     

Development of sulphurized SnS thin film solar cells

Thin films of tin sulphide (SnS) have been grown by sulphurization of sputtered tin precursor layers in a closed chamber. The effect of sulphurization temperature (T_s) that varied in the range of 150–450 °C for a fixed sulphurization time of 120 min on SnS film was studied through various characterization techniques. X-ray photoelectron spectroscopy analysis demonstrated the transformation of metallic tin layers into SnS single phase for T_s between 300 °C and 350 °C. The X-ray diffraction measurements indicated that all the grown films had the (111) crystal plane as the preferred orientation and exhibited orthorhombic crystal structure. Raman analysis showed modes at 95 cm⁻¹, 189 cm⁻¹ and 218 cm⁻¹ are related to the A_g mode of SnS. AFM images revealed a granular change in the grain growth with the increase of T_s. The optical energy band gap values were estimated using the transmittance spectra and found to be varied from 1.2 eV to 1.6 eV with T_s. The Hall effect measurements showed that all the films were p-type conducting nature and the layers grown at 350 °C showed a low electrical resistivity of 64 Ω-cm, a net carrier concentration of 2 × 10¹⁶ cm⁻³ and mobility of 41 cm² V⁻¹ s⁻¹. With the use of sprayed Zn_0.76Mg_0.24O as a buffer layer and the sputtered ZnO:Al as window layer, the SnS based thin film solar cell was developed that showed a conversion efficiency of 2.02%.     

Structural, magnetic and electronic structure studies of Mn doped TiO2 thin films

We report structural, magnetic and electronic structure study of Mn doped TiO₂ thin films grown using pulsed laser deposition method. The films were characterized using X-ray diffraction (XRD), dc magnetization, X-ray magnetic circular dichroism (XMCD) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements. XRD results indicate that films exhibit single phase nature with rutile structure and exclude the secondary phase related to Mn metal cluster or any oxide phase of Mn. Magnetization studies reveal that both the films (3% and 5% Mn doped TiO₂) exhibit room temperature ferromagnetism and saturation magnetization increases with increase in concentration of Mn doping. The spectral features of XMCD at Mn L_3,2 edge show that Mn²⁺ ions contribute to the ferromagnetism. NEXAFS spectra measured at O K edge show a strong hybridization between Mn, Ti 3d and O 2p orbitals. NEXAFS spectra measured at Mn and Ti L_3,2 edge show that Mn exist in +2 valence state, whereas, Ti is in +4 state in Mn doped TiO₂ films.     

Temperature-dependent characteristics of pulse-laser-deposited (Pb,Sr)TiO<Subscript>3</Subscript> films at low temperatures

Pulsed laser deposition (PLD) of (Pb,Sr)TiO₃ (PSrT) film on Pt/SiO₂/Si at low substrate temperatures (T_s), ranging from 300–450 °C, has been investigated. As T_s increases, the films reveal coarsening clusters, improved crystallization of the perovskite phase, distinct capacitance–electric field (C–E) hysteretic loops and a larger dielectric constant. The 350 °C-deposited film shows strong (100) preferred orientation and optimum dielectric properties with the dielectric constant of ∼620. The current density increases as the measurement temperature and the electric field increase. Moreover, PSrT films exhibit a strong negative temperature coefficient of resistance (NTCR) behavior at temperatures ranging from 100 to 390 °C. PACS 81.15.Fg; 77.22.Ch; 68.60.Dv     

Effect of cobalt doping and annealing on properties of titania thin films prepared by sol-gel process

Undoped and cobalt doped titania (TiO₂) thin films have been prepared on Si(1 0 0) monocrystal and quartz substrate using the sol-gel deposition method and annealed in air at 450, 550, 650, 750, 850, 950 and 1050 °C. Several experimental techniques (AFM, XRD, Raman spectroscopy, XRR, EDX, XPS, XAS, UV-VIS spectroscopy) have been used to characterize these films. Further more the degree of light induced hydrophilicity was estimated by measuring the contact angle of a water droplet on the film. Increase of the annealing temperature and in smaller degree also cobalt doping predispose titania crystallite growth. The rutile phase was detected at lower temperatures in the cobalt doped films than in the undoped titania films. Cobalt in the cobalt doped TiO₂ was seen to be in Co²⁺ oxidation state, mainly in CoTiO₃ phase when films were annealed at temperatures higher than 650 °C. Cobalt compounds segregated into the sub-surface region and to the surface of the titania, where they formed islands. Cobalt doping red-shifted the fundamental absorption edge further into the visible range, however it did not enhance the light induced hydrophilicity of the thin film surface as compared to the undoped titania thin films.     

Influence of oxygen partial pressure on structural, transport and magnetic properties of Co doped films

Pulse laser deposited (PLD) thin films of Co doped TiO₂ on silicon and quartz substrates are investigated. A mixture (1:1) of argon and oxygen with various total pressures (6.6 mPa to 53 Pa) is used to vary the oxygen content in the samples. The crystal structure and transport/ magnetic properties of Co_xTi_1−xO_2−δ (x=0.01, 0.03, 0.06) thin films are found to have strong dependence on oxygen stoichiometry. X-ray diffraction (XRD) data reveal mixed phase material containing both anatase and rutile. However, the stability of each phase depends on the amount of oxygen present in the chamber during the growth of the films. X-ray Photoelectron Spectroscopy (XPS) shows the incorporation of Co in TiO₂ and is in the 2+ oxidation state. There occurs an enhancement in electrical conductivity and magnetization due to the off stoichiometric oxygen. The resistivity data follow a simple thermal activation model, giving carriers’ activation energies in the range of 20 to 140 meV. A bound magnetic polaron model is adopted to explain the observed magnetic behavior of the films.     

结构相变对Fe掺杂TiO2薄膜室温铁磁性的影响

采用直流磁控溅射方法在玻璃基底上制备了不同Fe掺杂浓度的TiO₂薄膜, 并对其晶体结构和磁特性进行了研究.在所有掺杂样品中,均观察到了室温铁磁性, 磁性源于Fe离子与其近邻空间分布的空穴相互作用. 在掺杂量为7%的锐钛矿相薄膜中观察到了最大的磁化强度. 随着Fe掺杂浓度的进一步增加, TiO₂的晶体结构逐渐由锐钛矿相向金红石相转变,并且磁性减弱. 不同结构的TiO₂中Ti–O键长不同,导致替代的磁性Fe离子与空穴的作用强度发生改变, 进而使其磁性发生变化. 关键词： 稀磁半导体 结构相变 铁磁性     

Ion implantation in amorphous germanium and silicon

The effects of Sb and Al implantation on the conductivity of amorphous Ge and Si film are reported. The room temperature conductivity of the vacuum deposited films is found to increase by a factor of 50 to 100 on implantation. The excess conductivity can be removed by annealing at 300°C for 6 hr. Results on a-Si films deposited in a partial pressure of H₂ also indicate that doping effect due to ion implantation is very small. The temperature dependence of conductivity of the films is found to obey a $\text{T}{}^{\mathrm{<mtext>?1</mtext><mtext>4</mtext>}}$ law before and after implantation. The value of T₀ is found to be rather insensitive to both hydrogenation and implantation.     

Conducting properties of In2O3:Sn thin films at low temperatures

Electrical conductivity, Hall effect and magnetoresistance of In₂O₃:Sn thin films deposited on a glass substrates at different temperatures and oxygen pressures, have been investigated in the temperature range 4.2–300 K. The observed temperature dependences of resistivity for films deposited at 230 °C as well as at nominally room temperatures were typical for metallic transport of electrons except temperature dependence of resistivity of the In₂O₃:Sn film deposited in the oxygen deficient atmosphere. The electrical measurements were accompanied by AFM and SEM studies of structural properties, as well as by XPS analysis. It is established that changes of morphology and crystallinity of ITO films modify the low-temperature behavior of resistivity, which still remains typical for metallic transport. This is not the case for the oxygen deficient ITO layer. XPS analysis shows that grown in situ oxygen deficient ITO films have enhanced DOS between the Fermi level and the valence band edge. The extra localized states behave as acceptors leading to a compensation of n-type ITO. That can explain lower n-type conductivity in this material crossing over to a Mott-type hopping at low temperatures. Results for the low temperature measurements of stoichiometric ITO layers indicate that they do not show any trace of metal-to-insulator transition even at 4.2 K. We conclude that, although ITO is considered as a highly doped wide-band gap semiconductor, its low-temperature properties are very different from those of conventional highly doped semiconductors.     

High-pressure phases in nanocrystalline Co(C) films obtained by pulsed plasma vaporization

The phase composition of nanocrystalline Co(C) films obtained by a new pulsed plasma vaporization technique was found by studying their atomic structure and magnetic properties. The films deposited at the substrate temperature T=50°C were of heterophase structure and consisted of a supersaturated solid Co(C) solution and the metastable Co₃C carbide. The films obtained at T=150°C represented a mechanical mixture of the metastable Co₃C and Co₂C carbides. The metastable Co₃C and Co₂C carbides obtained in a nanocrystalline state were high-pressure phases (～100 kbar). The thermal stability ranges of these metastable phases were determined.     

Phase transitions in the atomic, electronic, and magnetic subsystems of LaSrMnO films versus the synthesis temperature

The evolution of the cluster structure in amorphous LaSrMnO films as synthesis temperature T _s increases from 20 to 300°C is considered. Two order-disorder phase transitions with different scale parameters are observed. One of them, the aggregation of disordered atoms into small (～20 Å) amorphous clusters at T _s = 100°C, shows up as a sharp increase in the intensity of diffuse X-ray scattering (diffuse halo 1) with a simultaneous suppression of incoherent (background) scattering. At T _s > 150°C, disordering dominates (I _incoh = I _max) until the next stage of ordering sets in at T _s = 250?300°C. At this stage, the crystalline phase forms from large (>100 Å) crystalline clusters. This amorphous-crystalline phase transition is characterized by the appearance of Debye lines and a reduction of the halo intensity. The structural phase transition to long-range order is accompanied by a decrease in the LaSrMnO resistivity from 10¹⁰ to 10 Ω cm and a change from the tunneling mechanism of conductivity involving metallic clusters (which is typical of granulated systems) to the hopping mechanism with a hop variable length following the Mott law ρ ～ exp(T ^?1/4). In the magnetic subsystem, the paramagnetic-ferromagnetic phase transition occurs.     

Preparation of transparent conductive TiO2:Nb thin films by pulsed laser deposition

This study investigated the optical and electrical properties of Nb-doped TiO₂ thin films prepared by pulsed laser deposition (PLD). The PLD conditions were optimized to fabricate Nb-doped TiO₂ thin films with an improved electrical conductivity and crystalline structure. XRD analyses revealed that the deposition at room temperature in 0.92 Pa O₂ was suitable to produce anatase-type TiO₂. A Nb-doped TiO₂ thin film attained a resistivity as low as 6.7 × 10⁻⁴ Ω cm after annealing at 350 °C in vacuum (<10⁻⁵ Pa), thereby maintaining the transmittance as high as 60% in the UV-vis region.     

The role of the dopant in the magnetism of Fe-doped SnO2 films

Transparent pure and Fe-doped SnO₂ thin films were grown by pulsed laser deposition technique on LaAlO₃ substrates. X-ray diffraction shows that the films are polycrystalline and have the rutile structure. Surprisingly, the pure film presents magnetic-like behavior at room temperature with a saturated magnetization of almost one-third of the doped film (∼3.6 and 11.3 emu/g, respectively) and its magnetization could not be attributed to any impurity phase. Taking into account the magnetic moment measured in the pure film, the effective contribution of the impurity in the doped one can be inferred to be ∼2 μ_B per Fe atom. A large magnetic moment was also predicted by an ab initio calculation in the doped system, which increases if an oxygen vacancy is present near the Fe impurity.     

Nanostructured TiO x film on Si substrate: room temperature formation of TiSi x nanoclusters

We present a morphologic and spectroscopic study of cluster-assembled TiO _x films deposited by supersonic cluster beam source on clean silicon substrates. Data show the formation of nanometer—thick and uniform titanium silicides film at room temperature (RT). Formation of such thick TiSi _x film goes beyond the classical interfacial limit set by the Ti/Si diffusion barrier. The enhancement of Si diffusion through the TiO _x film is explained as a direct consequence of the porous film structure. Upon ultra high vacuum annealing beyond 600 °C, TiSi₂ is formed and the oxygen present in the film is completely desorbed. The morphology of the nanostructured silicides is very stable for thermal treatments in the RT—1000 °C range, with a slight cluster size increase, resulting in a film roughness an order of magnitude smaller than other TiO _x /Si and Ti/Si films in the same temperature range. The present results might have a broad impact in the development of new and simple TiSi synthesis methods that favour their integration into nanodevices.     

The Effect of Substrate Temperature on the Properties of Nanostructured Silicon Carbide Films Deposited by Hypersonic Plasma Particle Deposition

Nanostructured silicon carbide films have been deposited on molybdenum substrates by hypersonic plasma particle deposition. In this process a thermal plasma with injected reactants (SiCl₄ and CH₄) is expanded through a nozzle leading to the nucleation of ultrafine particles. Particles entrained in the supersonic flow are then inertially deposited in vacuum onto a temperature-controlled substrate, leading to the formation of a consolidated film. In the experiments reported, the deposition substrate temperature T_s has ranged from 250°C to 700°C, and the effect of T_s on film morphology, composition, and mechanical properties has been studied. Examination of the films by scanning electron microscopy has shown that the grain sizes in the films did not vary significantly with T_s. Micro-X-ray diffraction analysis of the deposits has shown that amorphous films are deposited at low T_s, while crystalline films are formed at high T_s. Rutherford backscattering spectrometry has indicated that the films are largely stoichiometric silicon carbide with small amounts of chlorine. The chlorine content decreases from 8% to 1.5% when the deposition temperature is raised from 450°C to 700°C. Nanoindentation and microindentation tests have been performed on as-deposited films to measure hardness, Young's modulus and to evaluate adhesion strength. The tests show that film adhesion, hardness and Young's modulus increase with increasing T_s. These results taken together demonstrate that in HPPD, as in vapor deposition processes, the substrate temperature may be used to control film properties, and that better quality films are obtained at higher substrate temperatures, i.e. T_s700°C.