Characterization of indium zinc oxide thin films prepared by pulsed laser deposition using a Zn3In2O6 target

Using a Zn₃In₂O₆ target, indium-zinc oxide films were prepared by pulsed laser deposition. The influence of the substrate deposition temperature and the oxygen pressure on the structure, optical and electrical properties were studied. Crystalline films are obtained for substrate temperatures above 200°C. At the optimum substrate deposition temperature of 500°C and the optimum oxygen pressure of 10⁻³ mbar, both conditions that indeed lead to the highest conductivity, Zn₃In₂O₆ films exhibit a transparency of 85% in the visible region and a conductivity of 1000 S/cm. Depositions carried out in oxygen and reducing gas, 93% Ar/7% H₂, result in large discrepancies between the target stoichiometry and the film composition. The Zn/In (at.%) ratio of 1.5 is only preserved for oxygen pressures of 10⁻²–10⁻³ mbar and a 93% Ar/7% H₂ pressure of 10⁻² mbar. The optical properties are basically not affected by the type of atmosphere used during the film deposition, unlike the conductivity which significantly increases from 80 to 1400 S/cm for a film deposited in 10⁻² mbar of O₂ and in 93% Ar/7% H₂, respectively.     

R.f. plasma deposition from hexamethyldisiloxane-oxygen mixtures

Hexamethyldisiloxane (HMDSO) has been used as a precursor for the deposition of silicon dioxide films at low substrate temperature (25–400°C) by plasma enhanced chemical vapour deposition processing. Effects of the partial pressure of oxygen in the discharge on the deposition rate and the composition of the films are investigated. The deposition rate is found to decrease with increasing oxygen concentration in the HMDSO/O₂ mixture. The chemical composition of the formed films was characterized by X-ray photoelectron spectroscopy and infrared spectroscopy. Over 40% of the oxygen in the gas phase the carbon content of films deposited from HMDSO/O₂ mixtures is less than 5%.     

Effect of negatively charged species on the growth behavior of silicon films in hot wire chemical vapor deposition

The deposition behavior of silicon in hot wire chemical vapor deposition was investigated, focusing on the generation of negatively charged species in the gas phase using a gas mixture of 20% SiH₄ and 80% H₂ at a 450 °C substrate temperature under a working pressure of 66.7 Pa. A negative current of 6–21 µA/cm² was measured on the substrate at all processing conditions, and its absolute value increased with increasing wire temperature in the range of 1400 °C–1900 °C. The surface roughness of the films deposited on the silicon wafers increased with increasing wire temperature in the range of 1510 °C–1800 °C. The film growth rate on the positively biased substrates (+ 100 V, + 200 V) was higher than that on the neutral (0 V) and negatively biased substrates (− 100 V, − 200 V, − 300 V). These results indicate that the negatively charged species are generated in the gas phase and contribute to deposition. The surface roughness evolved during deposition was attributed to the electrostatic interaction between these negatively charged species and the negatively charged growing surface.     

Structure and conducting properties of La0.5Sr0.5CoO3−δ films on YSZ

La_0.5Sr_0.5CoO_3−δ (LSCO) thin films were deposited on yttria stabilized zirconia (YSZ) substrates by pulsed laser deposition (PLD) for application to thin film solid oxide fuel cell electrodes. During the deposition, the substrate temperature was varied from 450 to 750°C, and the oxygen pressure in the chamber was varied from 80 to 310 mTorr. Films deposited at 650°C and an oxygen background pressure of 150 mTorr were mostly (100) oriented. Deposition at higher temperatures or under lower oxygen pressures lead to mostly (110) oriented films. Films with low electrical resistivity of 10⁻³ Ω·cm were obtained.     

Pulsed laser deposition of NiTi shape memory alloy thin films with optimum parameters

A series of experiments was carried out to optimize the pulsed laser deposition parameters for the fabrication of high quality NiTi shape memory alloy thin films. Smooth NiTi shape memory alloy thin films were deposited at high growth rate with optimum deposition parameters based on the analysis of the relationships among the morphology of the target surface and the deposited thin film, the laser energy, the target–substrate distance, the thin film composition and its growth rate. Crystal structures and phase transformation temperatures of the annealed Ni_49.7Ti_50.3 thin film were characterized by using X-ray diffraction and differential scanning calorimetry, respectively. The martensitic transformation temperature of the crystallized Ni_49.7Ti_50.3 thin film is found to be lower than room temperature and 27°C lower than that of the NiTi target material. These results are attributed to the refined grain size of the thin film and its composition, which deviates slightly from Ni₅₀Ti₅₀.     

In Situ Thermocouples in Macro-Components Fabricated Using SALD and SALDVI Techniques. III. Fabrication and Properties of the SiC/C Thermocouple Device

Fabrication of a SiC/C thermocouple embedded in an arbitrarily-shaped SiC macro-component has been demonstrated using an integrated Selective Area Laser Deposition (SALD) with the closely related Selective Area Laser Deposition Vapor Infiltration (SALDVI) process. SALD is used to make the embedded thermocouple devices in situ and SALDVI to fabricate the macro-components. The thermocouple elements, silicon carbide and carbon lines, and the electrical insulation layer, Si₃N₄, have been deposited from tetramethylsilane (TMS), acetylene, and a gas mixture of TMS and ammonia, respectively. It is found that the fabricated in situ thermocouples respond sensitively to temperature variation. Furthermore, the electric signal of the embedded thermocouple is very stable and reproducible in response to thermal cycling. This is not the case when the thermocouple is not embedded in the SiC matrix because of the oxidation of the thermocouple elements.     

Fabrication of robust Bi3.25La0.75Ti3O12 thin film resistant to hydrogen damage

Ferroelectric bismuth lanthanum titanate (Bi_3.25La_0.75Ti₃O₁₂; BLT) thin films were deposited on Pt/TiO₂/SiO₂/Si substrate by chemical solution deposition method. The films were crystallized in the temperature range of 600–700 °C. The spontaneous polarization (P_s) and the switching polarization (2P_r) of BLT film annealed at 700 °C for 30 min were 22.6 μC/cm² and 29.1 μC/cm², respectively. Moreover, the BLT capacitor did not show any significant reduction of hysteresis for 90 min at 300 °C in the forming gas atmosphere.     

Epitaxial aluminum nitride films on sapphire formed by pulsed laser deposition

Highly oriented aluminum nitride thin films were grown on sapphire (0001)-substrate by pulsed laser deposition technique. Characterization was done by X-ray-diffraction, elastic recoil detection analysis and Rutherford backscattering/channeling measurements. The epitaxial properties were studied as function of the substrate temperature and the deposition rate. An epitaxial relation to the sapphire substrate is found to be AlN [0001] || Al₂O₃ [0001] and AlN [11 0] || Al₂O₃ [10 0]. XRD-texture-analysis on films deposited at 850°C shows a full width half maximum Δω of 0.13° (rocking curve) and Δ of 1.1° (in-plane).     

Residual stress in silicon films deposited by LPCVD from disilane

Measurements of the thermomechanical stress in amorphous silicon films deposited by low pressure chemical vapour deposition (LPCVD) from disilane Si₂H₆ are reported as a function of the deposition parameters (temperature, gas pressure and wafer spacing). Major influences of the deposition temperature and the deposition rate are put into evidence and related to the films ordering and hydrogenation. The effects of a 600°C anneal are also investigated and a transition from highly compressive to highly tensile stress is characterised whatever the deposition. Such behaviour has been explained thanks to hydrogen atoms out-diffusion and crystallisation effects.     

Reduction of carbon impurities in silicon oxide films prepared by rf plasma-enhanced CVD

Silicon oxide films were deposited at near room temperature by a remote-type radio frequency plasma-enhanced chemical vapor deposition using a mixture of tetramethoxysilane and oxygen as source gas. The temperature of the reactor wall was controlled from 25 to 150°C. Carbon impurities which existed as Si–CH₃ in the deposited films were reduced markedly when the substrate temperature was kept higher than the wall temperature during deposition. The optimum substrate temperature was 50°C to obtain carbon-free silicon oxide films at a wall temperature of 30°C. X-Ray photoelectron spectroscopic analyses of the films proved that carbon impurities existed only on the film surfaces.     

Deposition of Sm2O3 doped CeO2 thin films from Ce(DPM)4 and Sm(DPM)3 (DPM=2,2,6,6-tetramethyl-3,5-heptanedionato) by aerosol-assisted metal–organic chemical vapor deposition

Samarium-doped ceria (SDC) thin films were prepared from Sm(DPM)₃ (DPM = 2,2,6,6-tetramethyl-3,5-heptanedionato) and Ce(DPM)₄ using the aerosol-assisted metal–organic chemical vapor deposition method. -Al₂O₃ and NiO-YSZ (YSZ = Y₂O₃-stabilized ZrO₂) disks were chosen as substrates in order to investigate the difference in the growth process on the two substrates. Single cubic structure could be obtained on either -Al₂O₃ or NiO-YSZ substrates at deposition temperatures above 450 °C; the similar structure between YSZ and SDC results in matching growth compared with the deposition on -Al₂O₃ substrate. A typical columnar structure could be obtained at 650 °C on -Al₂O₃ substrate and a more uniform surface was produced on NiO-YSZ substrate at 500 °C. The composition of SDC film deposited at 450 °C is close to that of precursor solution (Sm : Ce = 1 : 4), higher or lower deposition temperature will both lead to sharp deviation from this elemental ratio. The different thermal properties of Sm(DPM)₃ and Ce(DPM)₄ may be the key reason for the variation in composition with the increase of deposition temperature.     

Deposition and dielectric properties of CaCu3Ti4O12 thin films on Pt/Ti/SiO2/Si substrates using pulsed-laser deposition

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates using pulsed-laser deposition technique. The crystalline structure and the surface morphology of the CCTO thin films were greatly affected by the substrate temperature and oxygen pressure. Thin films with a (2 2 0) preferential orientation were obtained at the substrate temperature above 700 °C and oxygen pressure above 13.3 Pa. The 480-nm thin films deposited under 720 °C and 26.6 Pa have a fairly high dielectric constant of near 2000 at 10 kHz and room temperature. The values of the dielectric constant and loss and their temperature-dependence under different frequency are comparable with those obtained in the epitaxial CCTO films grown on oxide substrates.     

Ozone-enhanced molecular beam deposition of nickel oxide (NiO) for sensor applications

For the deposition of nickel oxide (NiO) a molecular beam deposition process in an ozone atmosphere was developed. Pure gaseous ozone is received from a cooling system, which stores only O₃ at −78°C from a O₂/O₃ gas mixture stream, created with an ozone generator. The ozone is released by heating up the system to room temperature. For the deposition process nickel is evaporated while a constant ozone partial pressure is adjusted in the growth chamber. The reactive species of ozone reacts on the substrate surface with the impinging metal atoms to form the compound. This process was carried out in an ultra high vacuum (UHV) chamber to create pure nickel oxide films at room temperature and to study the fundamental layer properties for sensor applications. These films were characterized with respect to their stoichiometric and optical properties by Auger Electron spectroscopy and ellipsometry. The gas sensitivity of the films (as deposited and annealed) on various gases (H₂, NH₃, NO₂, SO₂, CO) was investigated by work function measurements.     

Effects of deposition parameters on the crystallinity of CeO2 thin films deposited on Si(100) substrates by r.f.-magnetron sputtering

Deposition temperature, r.f.-power and seed layer deposition time were important parameters effecting the crystallinity of CeO₂ thin films deposited by r.f.-magnetron sputtering on Si(100) substrates. The CeO₂ (200) peak was notable for a deposition temperature above 600°C. With decreased r.f.-power and thus lower deposition rate, the intensity of the CeO₂(200) peak increased. When the seed layer deposition time was less than 20 s, the CeO₂(200) peak dominated. Transmission electron microscopy (TEM) diffraction revealed that the deposited CeO₂ thin film had a polycrystalline structure. Annealing at 950°C in O₂ atmosphere for 30 min increased and sharpened the CeO₂(200) peak.     

Electrical properties of evaporated polycrystalline Ge thin-films

Electrical properties of Ge thin films evaporated on Si₃N₄ CVD-coated Si substrate were improved by introducing a heat treatment after the deposition of Ge films. Evaporation conditions were optimized by changing the substrate temperature and deposition rate, and then, heat treatment was performed. At substrate temperatures during the evaporation lower than 300 °C and higher than 400 °C, deposited films were amorphous and polycrystalline, respectively. At substrate temperatures lower than 400 °C, Ge films were evaporated without degrading the surface roughness. The Hall mobility of films evaporated at room temperature increased with increasing the substrate and heating temperature and showed about 400 cm² V⁻¹ s⁻¹ for the hole concentration of 4 × 10¹⁷ cm⁻³ at the heating temperature of 900 °C. This value was almost comparable to that of p-type Ge single crystal.     

Al2O3 formation on Si by catalytic chemical vapor deposition

Catalytic chemical vapor deposition (Cat-CVD) has been developed to deposit alumina (Al₂O₃) thin films on silicon (Si) crystals using N₂ bubbled tri-methyl aluminum [Al(CH₃)₃, TMA] and molecular oxygen (O₂) as source species and tungsten wires as a catalyzer. The catalyzer dissociated TMA at approximately 600 °C. The maximum deposition rate was 18 nm min⁻¹ at a catalyzer temperature of 1000 °C and substrate temperature of 800 °C. Metal oxide semiconductor (MOS) diodes were fabricated using gates composed of 32.5-nm-thick alumina film deposited at a substrate temperature of 400 °C. The capacitance measurements resulted in a relative dielectric constant of 7.4, fixed charge density of 1.74×10¹² cm⁻², small hysteresis voltage of 0.12 V, and very few interface trapping charges. The leakage current was 5.01×10⁻⁷ A cm⁻² at a gate bias of 1 V.     

Atmospheric pressure chemical vapour deposition of SnSe and SnSe2 thin films on glass

Atmospheric pressure chemical vapour deposition of tin monoselenide and tin diselenide films on glass substrate was achieved by reaction of diethyl selenide with tin tetrachloride at 350–650 °C. X-ray diffraction showed that all the films were crystalline and matched the reported pattern for SnSe and/or SnSe₂. Wavelength dispersive analysis by X-rays show a variable Sn:Se ratio from 1:1 to 1:2 depending on conditions. The deposition temperature, flow rates and position on the substrate determined whether mixed SnSe–SnSe₂, pure SnSe or pure SnSe₂ thin films could be obtained. SnSe films were obtained at 650 °C with a SnCl₄ to Et₂Se ratio greater than 10. The SnSe films were silver–black in appearance and adhesive. SnSe₂ films were obtained at 600–650 °C they had a black appearance and were composed of 10 to 80 μm sized adherent crystals. Films of SnSe only 100 nm thick showed complete absorbtion at 300–1100 nm.     

Improving narrow bandgap a-SiGe:H alloys grown by hot-wire chemical vapor deposition

We have improved the electronic properties of narrow-bandgap (Tauc gap below 1.5 eV) amorphous-silicon germanium alloys (a-SiGe:H) grown by hot-wire chemical vapor deposition (HWCVD) by lowering the substrate temperature and deposition rate. Prior to this work, we were unable to grow a-SiGe:H alloys with bandgaps below 1.5 eV that had photo-to-dark conductivity ratios comparable with our plasma-enhanced CVD (PECVD) grown materials [B.P. Nelson et al., Mater. Res. Soc. Symp. 507 (1998) 447]. Decreasing the filament diameter from our standard configuration of 0.5 mm to 0.38 or 0.25 mm provides first big improvements in the photoresponse of these alloys. Lowering the substrate temperature from our previous optimal temperatures (T_sub starting at 435 °C) to at 250 °C provides additional photo-to-dark conductivity ratio increasing by two orders of magnitude for growth conditions containing 20–30% GeH₄ in the gas phase (relative to the total GeH₄+SiH₄ flow).     

Growth of c-GaN films on GaAs(100) using hot-wire CVD

Cubic gallium nitride (GaN) films were grown on nitrided layers of GaAs(100) by hot-wire chemical vapor deposition. The nitrided layer was also formed by NH_x radicals generated on a tungsten hot-wire surface. Nitridation conditions for the growth of GaN with a cubic-type structure were investigated. As a result, GaN film with a preponderant cubic phase was grown on the GaAs surface layer nitrided at a substrate temperature of 550 °C, a filament temperature of 1200 °C and an ammonia (NH₃) pressure of 1 Torr.