Narrow gap a-SiGe:H grown by hot-wire chemical vapor deposition

We have improved the quality of our narrow bandgap a-SiGe:H grown by hot-wire chemical vapor deposition (HWCVD) by decreasing our W filament diameter and our substrate temperature. We now grow a-SiGe:H with Tauc bandgaps below 1.5 eV having a photoresponse equal to or better than our plasma enhanced CVD grown alloys. We enhanced the transport properties—as measured by the photoconductivity frequency mixing technique—relative to previous HWCVD results. These improved alloys do not necessarily show an improvement in the degree of structural heterogeneity on the nanometer scale as measured by small-angle X-ray scattering. Decreasing both the filament temperature and substrate temperature produced a film with relatively low structural heterogeneity while photoluminescence showed an order of magnitude increase in defect density for a similar change in the process.     

First principles total energy studies of the adsorption of germane on Ge(001)-c(2 × 4)

We perform first principles total energy calculations to study the energetics, and the atomic structure of the adsorption of germane (GeH₄) molecules on the Ge(001)-c(2 × 4) surface. The adsorption of a GeH₄ unit occurs after its dissociation into a germanium trihydride (GeH₃) and a hydrogen atom and a subsequent decomposition into a germanium dihydride (GeH₂) subunit and H atoms. Consequently, we first consider the adsorption of GeH₂ in two different configurations; the on-dimer and the intra-row geometries. Similar to the adsorption of SiH₂ and GeH₂ on Si(001), it is found that the on-dimer site is more stable than the intra-row geometry by 0.13 eV. However, in the adsorption of a GeH₂ fragment together with two H atoms we find that the intra-row geometry is energetically more favorable, again, similar to the adsorption of SiH₂ and GeH₂ (plus two H atoms) on the Si(001) surface.     

Effects of Annealing on the Conductivity of C60 Thin Films

Films of C₆₀, at different stages of annealing of T_t=200°and 300°C have been electrically characterized over the temperature domain from -130°C to T_t. X-ray diffraction revealed a random polycrystalline fee structure with stacking defects of an intrinsic nature, due to deposition conditions. The value of room-temperature conductivity was found to be in the range (6.3-1.0) *10^-10 (0cm)^-1. In the stable annealed state the conductivity showed an activated temperature dependence above 423 K and a non-activated dependence below 330-280 K. The activation energies E_a = 0.8 eV (film thickness 0.70 μm) and E_a = 1.0 eV (film thickness 2.40 μm) were in good agreement with the energy gap values (1.63 eV and 2.08 eV) which were deduced from the absorption spectral dependence. Annealing decreased the non-activated contribution to conduction, extending the intrinsic conduction temperature range.     

Doping and electrical characteristics of in-situ heavily B-doped Si1−x−yGexCy films epitaxially grown using ultraclean LPCVD

Doping and electrical characteristics of in-situ heavily B-doped Si_1−x−yGe_xC_y (0.22<x<0.6, 0<y<0.02) films epitaxially grown on Si(100) were investigated. The epitaxial growth was carried out at 550°C in a SiH₄–GeH₄–CH₃SiH₃–B₂H₆–H₂ gas mixture using an ultraclean hot-wall low-pressure chemical vapor deposition (LPCVD) system. It was found that the deposition rate increased with increasing GeH₄ partial pressure, and only at high GeH₄ partial pressure did it decrease with increasing B₂H₆ as well as CH₃SiH₃ partial pressures. With the B₂H₆ addition, the Ge and C fractions scarcely changed and the B concentration (C_B) increased proportionally. The C fraction increased proportionally with increasing CH₃SiH₃ partial pressures. These results can be explained by the modified Langmuir-type adsorption and reaction scheme. In B-doped Si_1−x−yGe_xC_y with y=0.0054 or below, the carrier concentration was nearly equal to C_B up to approximately 2×10²⁰ cm⁻³ and was saturated at approximately 5×10²⁰ cm⁻³, regardless of the Ge fraction. The B-doped Si_1−x−yGe_xC_y with high Ge and C fractions contained some electrically inactive B even at the lower C_B region. Resistivity measurements show that the existence of C in the film enhances alloy scattering. The discrepancy between the observed lattice constant and the calculated value at the higher Ge and C fraction suggests that the B and C atoms exist at the interstitial site more preferentially.     

Dielectric properties of AlN films prepared by laser-induced chemical vapour deposition

The dielectric properties and electrical conductivity of AlN films deposited by laser-induced chemical vapour deposition (LCVD) are studied for a range of growth conditions. The static dielectric constant is 8.0 ± 0.2 over the frequency range 10²−10⁷ Hz and breakdown electric fields better than 10⁶ V cm⁻¹ are found for all films grown at temperatures above 130°C. The resistivity of the films grown under optimum conditions (substrate temperature above 170°C, NH₃/TMA flow rate ratio greater than 300 and a deposition pressure of 1–2 Torr) is about 10¹⁴ Ω cm and two conduction mechanisms can be identified. At low fields, F < 5 × 10⁵ V cm⁻¹ and conductivity is ohmic with a temperature dependence showing a thermal activation energy of 50–100 meV, compatible with the presumed shallow donor-like states. At high fields, F > 1 × 10⁶ V cm⁻¹, a Poole-Frenkel (field-induced emission) process dominates, with electrons activated from traps at about 0.7–1.2 eV below the conduction band edge. A trap in this depth region is well-known in AlN. At fields between 4 and 7 × 10⁵ V cm⁻¹ both conduction paths contribute significantly. The degradation of properties under non-ideal growth conditions of low temperature or low precursor V/III ratio is described.     

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.     

Properties of tantalum oxide thin films grown by atomic layer deposition

Thin tantalum oxide films were deposited using atomic layer deposition from TaCl₅ and H₂O at temperatures in the range 80–500 °C. The films deposited at temperatures below 300 °C were predominantly amorphous, whereas those grown at higher temperatures were polycrystalline containing the phases TaO₂ and Ta₂O₅. The oxygen to tantalum mass concentration ratio corresponded to that of TaO₂ at all growth temperatures. The optical band gap was close to 4.2 eV for amorphous films and ranged from 3.9 to 4.5 eV for polycrystalline films. The refractive index measured at λ = 550 nm increased from 1.97 to 2.20 with an increase in growth temperature from 80 to 300 °C. The films deposited at 80 °C showed low absorption with absorption coefficients of less than 100 cm⁻¹ in the visible region.     

Formation of a highly oriented FeO thin film by phase transition of Fe3O4 and Fe nanocrystallines

A highly oriented FeO thin film was formed from a Fe₃O₄ thin film containing Fe nanocrystallines by post-annealing at 600°C. Fe₃O₄ thin films were grown on Si(100) substrates by ion beam sputter deposition under oxygen ambient. The stoichiometry of the iron oxide thin film could be precisely controlled by in situ X-ray photoelectron spectroscopy (XPS). X-ray diffraction (XRD) pattern of the Fe₃O₄ thin film grown at substrate temperature of 300°C showed a mixed phase of Fe₃O₄ and Fe nanocrystallines with a preferred orientation (110). However, the mixed phase was converted to a highly oriented FeO(200) phase by post-annealing at 600°C. This could be inverted as a result of Ostwald ripening of the Fe₃O₄ and Fe nanocrystallines.     

Atomic layer deposition of calcium oxide and calcium hafnium oxide films using calcium cyclopentadienyl precursor

Calcium oxide and calcium hafnium oxide thin films were grown by atomic layer deposition on borosilicate glass and silicon substrates in the temperature range of 205–300 °C. The calcium oxide films were grown from novel calcium cyclopentadienyl precursor and water. Calcium oxide films possessed refractive index 1.75–1.80. Calcium oxide films grown without Al₂O₃ capping layer occurred hygroscopic and converted to Ca(OH)₂ after exposure to air. As-deposited CaO films were (200)-oriented. CaO covered with Al₂O₃ capping layers contained relatively low amounts of hydrogen and re-oriented into (111) direction upon annealing at 900 °C. In order to examine the application of CaO in high-permittivity dielectric layers, mixtures of Ca and Hf oxides were grown by alternate CaO and HfO₂ growth cycles at 230 and 300 °C. HfCl₄ was used as a hafnium precursor. When grown at 230 °C, the films were amorphous with equal amounts of Ca and Hf constituents (15 at.%). These films crystallized upon annealing at 750 °C, showing X-ray diffraction peaks characteristic of hafnium-rich phases such as Ca₂Hf₇O₁₆ or Ca₆Hf₁₉O₄₄. At 300 °C, the relative Ca content remained below 8 at.%. The crystallized phase well matched with rhombohedral Ca₂Hf₇O₁₆. The dielectric films grown on Si(100) substrates possessed effective permittivity values in the range of 12.8–14.2.     

Composition and electronic properties of a-SiGe:H alloys produced from ultrathin layers of a-Si:H/a-Ge:H

Hydrogenated amorphous silicon-germanium (a-SiGe:H) alloys were prepared from a-Si:H (0.5 nm)/a-Ge:H(0.4–1.26 nm) multilayers at 200 °C by the r.f. glow discharge technique. The optical bandgap was controlled by changing the thickness of the a-Ge:H layers as well as the hydrogen dilution during its deposition. The configuration of bonded hydrogen was investigated by infrared absorption measurements of Si–H and Ge–H vibrational modes. The structure and photoconductivity of the prepared films were systematically investigated as functions of their optical gap. It is found that the optical and electrical properties of multilayer alloys are improved compared to a-SiGe:H films produced from a mixture of hydrides SiH₄+GeH₄, even when diluted with hydrogen. Films of optical gap 1.3E_3.51.5eV show high photosensitivity and low void fraction.     

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.     

Field-lowering carrier excitation in cadmium arsenide thin films

Cadmium arsenide is a II–V semiconductor which exhibits n-type intrinsic conductivity with high mobility up to μ_n=1.0–1.5 m²/V s. Potential applications include magnetoresistors and both thermal and photodetectors, which require electrical characterization over a wide range of deposition and measurement conditions. The films were prepared by vacuum evaporation with deposition rates in the range 0.5–6.0 nm/s and substrate temperatures maintained at constant values of 20–120°C. Sandwich-type samples were deposited with film thicknesses of 0.1–1.1 μm using evaporated electrodes of Ag and occasionally Au or Al. Above a typical electric field F_b of up to 5×10⁷ V/m all samples showed instabilities characteristic of dielectric breakdown or electroforming. Below this field they showed a high-field conduction process with logJ∝V^1/2, where J is the current density and V the applied voltage. This type of dependence is indicative of carrier excitation over a potential barrier whose effective barrier height has been lowered by the high electric field. The field-lowering coefficient β had a value of (1.2–5.3)×10⁻⁵ eV m^1/2/V^1/2 which is reasonably consistent with the theoretical value of β_PF=2.19×10⁻⁵ eV m^1/2/V^1/2 expected when the field-lowering occurs at donor-like centres in the semiconductor (Poole–Frenkel effect). For thinner films Schottky emission was more probable. The effects of the film thickness, electrode materials, deposition rate, and substrate temperature on the conductivity behaviour are discussed.     

Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH₄ (silane), H₂ (hydrogen), and O₂ (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 °C for film deposition on glass and crystalline silicon substrates at 200 °C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 °C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing SiOSi bonds and typical SiH bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations.     

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).     

Transparent conducting F-doped SnO2 thin films grown by pulsed laser deposition

Transparent conducting fluorine-doped tin oxide (SnO₂:F) films have been deposited on glass substrates by pulsed laser deposition. The structural, electrical and optical properties of the SnO₂:F films have been investigated as a function of F-doping level and substrate deposition temperature. The optimum target composition for high conductivity was found to be 10 wt.% SnF₂ + 90 wt.% SnO₂. Under optimized deposition conditions (T_s = 300 °C, and 7.33 Pa of O₂), electrical resistivity of 5 × 10^− 4 Ω-cm, sheet resistance of 12.5 Ω/□, average optical transmittance of 87% in the visible range, and optical band-gap of 4.25 eV were obtained for 400 nm thick SnO₂:F films. Atomic force microscopy measurements for these SnO₂:F films indicated that their root-mean-square surface roughness ( 6 Å) was superior to that of commercially available chemical vapor deposited SnO₂:F films ( 85 Å).     

Carburization performance of Incoloy 800HT in CH4/H2 gas mixtures

Carburization performance of Incoloy 800HT has been studied after cyclic and isothermal exposures to CH₄/H₂ carburizing gas mixtures at high temperatures for 500 h. At 800 °C in 2% CH₄/H₂, Incoloy 800HT suffered external oxidation and carburization, the external continuous layer of reaction products consists primarily of Cr₇C₃, Mn_1.5Cr_1.5O₄, and FeCr₂O₄ with Fe(Cr, Al)₂O₄ as a minor phase. At 1100 °C in 10% CH₄/H₂, external carburization did not occur likely due to high carbon dissolution in the alloy substrate at this temperature. A thermodynamic analysis indicated that 1000 °C was an approximate critical temperature, below which the environment should result in mixed oxidizing/carburizing behavior, while above this temperature reducing carburizing behavior should occur. The experimental results approximately agree with the thermodynamic analysis. Metal dusting was not observed under highly carburizing conditions (a_C>1). The size and morphology of Cr-rich phases (or Cr-carbides) are both temperature- and time-dependent, while the external continuity is more temperature-dependent rather than time-dependent.     

Dielectric and ionic conduction properties in LiYF4 single crystals

A LiYF₄ single crystal was grown by the Czochralski technique in an Ar-gas atmosphere. The complex dielectric constants and complex impedances are measured in the range of 100 Hz–10 MHz and up to 200°C for a c-plate of a LiYF₄ single crystal. The LiYF₄ reveals a strong low frequency dielectric dispersion below 300 kHz, from room temperature to 200°C. It is believed that the strong dielectric dispersion is related to the ionic hopping conduction, which arises mainly from the jumping of Li⁺-ions between neighboring sites, with an activation energy of Δ=0.49 eV. The conduction mechanism seems to be the non-interacting Debye type and the relaxation times satisfy the Arrhenius relation.     

Influence of substrate temperature on atomic layer growth and properties of HfO2 thin films

Atomic layer growth of hafnium dioxide from HfCl₄ and H₂O has been studied at substrate temperatures ranging from 180–600°C. A quartz crystal microbalance was used for the real-time investigation of deposition kinetics and processes affecting the growth rate. It was shown that the layer-by-layer growth was self-limited at temperatures above 180°C. The data of ex situ measurements revealed that the structure, density and optical properties of the films depended on the growth temperature. The absorption coefficient of amorphous films grown at 225°C was below 40 mm⁻¹ in the spectral range of 260–850 nm. The refractive index of the films grown at 225°C was 2.2 and 2.0 at 260 and 580 nm, respectively. The polycrystalline films with monoclinic structure grown at 500°C had about 5% higher refractive index but more than an order of magnitude higher optical losses caused by light absorption and/or scattering.     

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.     

Preparation of Pt-PtOx thin films as electrode for memory capacitors

Pt-PtO_x thin films were prepared on Si(100) substrates at temperatures from 30 to 700°C by reactive r.f. magnetron sputtering with platinum target. Deposition atmosphere was varied with O₂/Ar flow ratio. The deposited films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Resistively of the deposited films was measured by d.c. four probe method. The films mainly consisted of amorphous PtO and Pt₃O₄ (or Pt₂O₃) below 400°C, and amorphous Pt was increased in the film as a deposition temperature increased to 600°C. When deposition temperature was thoroughly increased, (111) oriented pure Pt films were formed at 700°C. Compounds included in the films strongly depended on substrate temperature rather than O₂/Ar flow ratio. Electrical resistivity of Pt-PtO_x films was measured to be from the order of 10⁻¹ Ω cm to 10⁻⁵ Ω cm, which was related to the amount of Pt phase included in the deposited films.