Far-infrared dielectric functions and phonon spectra of alloys determined by spectroscopic ellipsometry

We have used spectroscopic ellipsometry to determine the complex dielectric function of a series of ternary Be_xZn_1−xTe thin films grown by molecular beam epitaxy. The II–VI semiconductor alloys were grown on InP substrates that had an InGaAs buffer layer. After the growth, X-ray diffraction experiments were performed in order to determine the alloy concentration. A standard inversion technique was used to obtain the dielectric functions from the measured ellipsometric spectra, obtained between 2000 nm (5000 cm⁻¹) and 40,000 nm (250 cm⁻¹). By modelling the dielectric function as a collection of oscillators, representing longitudinal and transverse optical phonons of the Be_xZn_1−xTe lattice, we were able to recover the phonon spectra for this alloy system. It is argued that the additional phonon modes that are obtained from ellipsometry are best understood from the recently-proposed percolation model.     

Micro-Raman spectroscopy in polycrystalline CuInSe2 formation

The crystalline formation of CuInSe₂ thin films has been investigated using micro-Raman spectroscopy and AES composition analysis. It is confirmed that the Raman peaks are stongly dependent on the surface morphology and the Cu:In:Se ratio. In the films annealed at 315°C, crystalline grains larger than 2 m show Raman peaks at 174 cm^–1 and 258 cm^–1. The In content is very low and the Cu:Se ratio is about 1:1 in these grains. The low In concentration is thought to be due to the formation of In₂O₃ on the surface. On the other hand, random structures of 1–2 m grains found in films annealed at temperatures below 305°C show peaks at 174 cm^–1 and 186 cm^–1 instead of 258 cm^–1 and have a Cu:In:Se ratio of 1:1:3–4. Thus the 186 cm^–1 peak is thought to be related to a Cu, In-deficient phase when compared to stoichiometric CuInSe₂. The optimum annealing condition was found by analyzing the Raman spectra and composition of different crystalline CuInSe₂ grains. Films annealed under this condition exhibited a clear Raman peak at 174 cm^–1 and consisted of clusters of crystals less than 1 m in size.     

Development of a novel high speed (electron-mobility) epi-n-ZnO thin films by L-MBE for III–V opto-electronic devices

Intrinsic epitaxial zinc oxide (epi-ZnO) thin films were grown by laser-molecular beam epitaxy (L-MBE), i.e., pulsed laser deposition (PLD) technique using Johnson Matthey “specpure”-grade ZnO pellets. The effects of substrate temperatures on ZnO thin film growth, electrical conductivity (σ), mobility (μ) and carrier concentration (n) were studied. As well as the feasibility of developing high quality conducting oxide thin films was also studied simultaneously. The highest conductivity was found for optimized epi-ZnO thin films is σ=0.06×10³ ohm⁻¹ cm⁻¹ (n-type) (which is almost at the edge of semiconductivity range), carrier density n=0.316×10¹⁹ cm⁻³ and mobility μ=98 cm²/V s. The electrical studies further confirmed the semiconductor characteristics of epi-n-ZnO thin films. The relationship between the optical and electrical properties were also graphically enumerated. The electrical parameter values for the films were calculated, graphically enumerated and tabulated. As a novelty point of view, we have concluded that without doping and annealing, we have obtained optimum electrical conductivity with high optical transparency (95%) for as deposited ZnO thin films using PLD. Also, this is the first time that we have applied PLD made ZnO thin films to iso-, hetero-semiconductor–insulator–semiconductor (SIS) type solar cells as transparent conducting oxide (TCO) window layer. We hope that surely these data be helpful either as a scientific or technical basis in the semiconductor processing.     

Superconductivity induced phonon anomalies in the Raman spectra of Zn and Ni doped YBa2Cu3O7

Here we present Raman spectra of YBa₂(Cu_1–x Zn _x )₃O₇ and YBa₂(Cu_1–x Ni _x )₃O₇ as a function of temperature and Zn or Ni content. The temperature dependence of two modes at 340 and 440 cm^–1 is analyzed. Similarly to the infrared measurements it is found that Zn substantially suppresses the superconductivity induced phonon softening whereas, Ni does not affect much that effect. Moreover, the superconductivity induced phonon stiffening of the 440 cm^–1 mode completely disappeared with the Zn doping. We find this behaviour might support the model where Zn acts effectively as a magnetic pair breaker.     

Raman-spectroscopy study of PbTiO3 thin films grown on Si substrates by metalorganic chemical vapor deposition

Raman spectra have been investigated in PbTiO₃ thin films grown on Si by metalorganic chemical vapor deposition. A large grazing-angle scattering technique was taken to measure the temperature dependence of Raman spectra below room temperature. All Raman modes in the thin films are assigned and compared with those in the bulk single crystal, a newA ₁(TO) soft mode at 104 cm^–1 was recorded which satisfies the Curie-Weiss relation ² =A(T _c –T). Intensities of theA ₁(1TO) andE(1TO) modes were anomalously strengthened with increasing temperature. Raman modes for the thin films exhibit remarkable frequency downshift and upshift which is related to the effect of internal stress.     

IR Reflection of Thin Bi4Ge3O12 Films

The spectra of IR reflection of the systems thin Bi₄Ge₃O₁₂ film–substrate made of molten -SiO₂ quartz in the region 10–1600 cm^–1 at 295 K are investigatedterpretation of fundamental vibrations in the region 10–800 cm^–1 and two phonon processes in the region 800–1600 cm^–1 are considered.     

Far-infrared spectra of Pb1−xMnxTe alloys

Far-infrared reflectivity spectra of Pb_1−xMn_xTe (0.0001x0.1) single crystals were measured in the 10–250 cm⁻¹ range at room temperature. The analysis of the far-infrared spectra was made by a fitting procedure based on the model of coupled oscillators. In spite of the strong plasmon–LO phonon interaction, we found that the long wavelength optical phonon modes of these mixed crystals showed an intermediate one–two mode behavior.     

Quasiparticle recombination time in superconducting tin and normal electronic density of states at the fermi surface from tunnel junction experiments

We have measured the temperature dependence of the effective quasiparticle recombination time in superconducting tin tunnel junctions by current and laser pulse excitation. The experimental times show satisfactory agreement with calculations based on the ray acoustic lifetime model of Eisenmenger et al. taking into account the film thickness dependence of the phonon reabsorption, 2-phonon volume loss processes and phonon transmission from the junction into the substrate and liquid helium. On the basis of the BCS density of thermally excited quasiparticles and simplified rate equations for quasiparticle recombination, and from the analysis of measurements of decaying excess quasiparticle concentrations we obtain a mean valueN ₀=(2.73±0.03) 10²² eV^–1 cm^–3 for the electronic density of states at the Fermi Surface in thin, evaporated tin films. This value differs less than 5% from that obtained from the experimental electronic heat-capacity coefficient of the bulk material.IBM Zürich, Research Laboratory, CH-8803, Rüschlikon, Switzerland     

Electrical properties of doped 3-tetradecylpolypyrrole/metal devices

The electrical properties of devices made of doped 3-tetradecylpolypyrrole (PPy-C₁₄) thin films sandwiched between indium-tin-oxyde (ITO) and gold metal electrodes are reported. The current density–voltage (J–V) curves are asymmetric and nonlinear implying a non Ohmic rectifying contact. Using standard thermionic emission theory (Schottky) J–V characteristics were satisfactorily fitted with a saturation current of J₀=1.5×10^-5 A cm^-2, a barrier height of ϕ_b=0.7 eV, and an ideality factor of n=5.3. Characteristics from the plot of J–V versus 1/T show that the activation energy of the thermionic emission process is higher below the glass transition temperature of PPy-C₁₄ (T_g=45 °C) than above, which seems to indicate that the hopping conduction process is enhanced at T>T_g. The carrier concentration has been calculated from capacitance–voltage (C-V) measurements (N=1.9×10¹⁷ cm^-3) allowing estimation of the carrier mobility μ=2.6×10^-2 cm² V^-1 s^-1. PACS 73.61.Ph; 73.40.Sx; 73.30.+y     

R branch tuning characteristics of the13CH3F Raman FIR laser

Summary We described a¹³CH₃F Raman laser pumped by a grating tuned 20 atmospheres CO₂ laser. The emission characteristics of the¹³CH₃F laser extends from 14 cm^–1–35 cm^–1 and from 49 cm^–1–72 cm^–1; about 65% of these frequency ranges can be covered with tunable radiation. The characteristics shows a strong dependence on the rotaional quantum numbers of the states involved in the Raman laser transitions and, within each tuning interval, on the frequency offset with respect to the frequencies of resonant transitions. We obtained, at 51 cm^–1, a maximum FIR laser pulse energy of about 800 J (at a pump energy of 200 mJ), corresponding to a photon conversion of about 8%. In some cases we have observed simultaneous emission at a Raman and a cascade frequency. In addition, FIR emission power dependence on¹³CH₃F gas pressure and pump pulse power were investigated for different J quantum numbers.     

Thermal oxidation of n-type ZnN films made by -sputtering from a zinc nitride target, and their conversion into p-type films

Transparent p-type thin films, containing zinc oxide phases, have been fabricated from the oxidation of n-type zinc nitride films. The zinc nitride thin films were deposited by rf-magnetron sputtering from a zinc nitride target in pure N₂ and pure Ar plasma. Films deposited in Ar plasma were conductive (resistivity 4.7×10⁻² Ω cm and carrier concentrations around 10²⁰ cm⁻³) Zn-rich Zn_xN_y films of low transmittance, whereas Zn_xN_y films deposited in N₂ plasma showed high transmittance (>80%), but five orders of magnitude lower conductivity. Thermal oxidation up to 550 C converted all films into p-type materials, exhibiting high resistivity, 10²–10³ Ω cm, and carrier concentration around 10¹³ cm⁻³. However, upon oxidation, the Zn_xN_y films did not show the zinc oxide phase, whereas Zn-rich Zn_xN_y films were converted into films containing ZnO and ZnO₂ phases. All films exhibited transmittance >85% with a characteristic excitonic dip in the transmittance curve at 365 nm. Low temperature photoluminescence revealed the existence of exciton emissions at 3.36 and 3.305 eV for the p-type zinc oxide film.     

Bi-induced vibrational modes in GaAsBi

We have studied GaAs_1−xBi_x (up to x3%) using Raman scattering with two different polarization configurations. Two Bi-induced phonon modes are observed at 186 cm⁻¹ and 214 cm⁻¹ with increasing Raman intensity as the Bi concentration increases. By comparing Raman selection rules for the observed Bi-induced phonon modes with those for the substitutional N vibrational mode (GaN mode) in GaAsN, the phonon mode at 214 cm⁻¹ is identified as originating from substitutional Bi at the As site in GaAsBi.     

Far-infrared Fabry Perot filter of high transmission with high-Tc superconductor reflectors

We report on a far-infrared Fabry Perot filter with high-T _c superconductor reflectors that has a high peak-transmission. The filter consists of two plane parallel MgO plates, with the adjacent surfaces coated with YBa₂Cu₃O₇-gd thin films. The resonance frequencies are mainly determined by the distance between the films. We present data for a filter that has for the first order resonance at a frequency of 80 cm^–1a quality factor of 55 and a peak-transmissivity of 0.16. The shape of the transmission curve is determined by standing waves between the films and within the plates.     

Rapid growth of ultra thin SiO2 films by a large-area electron beam

Rapid growth of ultra thin oxide films (40–180Å) of silicon using a low-energy large-area electron beam has been performed with a pressure ratio of 31 (O₂/He) and a total pressure of 0.5–0.7 Torr. A higher oxidation rate of about 625Ų/s is found for shorter irradiation time of the e-beam in the e-beam dose range 0.75–3 Coulomb/cm² and at lower substrate temperature 540–740°C. AES and XPS demonstrated a rapid electron-stimulated oxidation process of the Si surface. For the grown ultra thin oxide films, C-V characteristics, dielectric strength, uniformity of the film over the entire Si wafer and its thickness as a function of the processing time of the e-beam are also presented.     

Ferroelectric properties of Nd-substituted bismuth titanate thin films processed at low temperature

Nd-substituted bismuth titanate Bi_3.54Nd_0.46Ti₃O₁₂ (BNT) thin films were prepared on (111)Pt/Ti/SiO₂/Si substrates by a sol–gel method. The BNT thin films processed at a low annealing temperature of ∼600 °C showed good ferroelectric properties. The randomly oriented BNT single phases and the improved ferroelectric properties were confirmed by X-ray diffraction and polarization–electric field hysteresis loops, respectively. The remanent polarization of the BNT thin films is 64 μC/cm², which is larger than that of Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films. After 10¹⁰ read/write switching cycles, the effective non-volatile charges showed no polarization fatigue. Regardless of the low annealing temperature of 600 °C, the BNT thin films had good ferroelectric properties with high remanent polarizations and strong fatigue resistances. PACS 77.84.Dy     

Study of the interface Si-nc/SiO2 by infrared spectroscopic ellipsometry and X-ray photoelectron spectroscopy

SiO_x films (1<x<2), 0.5 μm thick, have been elaborated by electron-gun evaporation. A thermal annealing of these films induced a phase separation leading to the formation of Si nanocrystals embedded in a SiO₂ matrix. These films have been studied by infrared spectroscopic ellipsometry and by X-ray photoelectron spectroscopy (XPS). The effective dielectric function of the thin films has been extracted in the 600–5000 cm⁻¹ range which allowed us to deduce the dielectric function of the matrix surrounding the Si-nc. A study of the Transverse Optical (TO) vibration mode has revealed the presence of SiO_x into the matrix. Before XPS measurements, the films have been etched in fluorhydric acid to remove the superficial SiO₂ layer formed during air exposure. The Si 2p core-level emission has been recorded. The decomposition of the Si 2p peak into contributions of the usual five tetrahedrons Si-(Si_4−nO_n) (n=0–4) has also revealed the presence of a SiO_x phase. Consistency between infra-red and XPS results is discussed.     

Resonant Raman scattering in Mn:ZnO dilute magnetic semiconductors

We report on micro-Raman measurements performed under various visible excitations on wurtzite Zn_1−xMn_xO thin films grown by MOCVD, for a wide range of Mn content (0<x<0.22). We observe a shift of the frequency of the E₂ phonon for increasing Mn content, indicating a substitution of the Mn atoms at the tetrahedral Zn sites of the host matrix. All spectra also reveal a dominant feature related to local vibrations of Mn atoms, as well as the A₁ (LO) phonon of the ZnMnO alloy. Both features are resonantly enhanced by the absorption of the incident laser light by internal transitions of the Mn²⁺ ions.     

Pulsed laser deposition of aluminate YAlO3 and LaAlO3 thin films for alternative gate dielectric applications

Amorphous aluminate YAlO₃ (YAO) thin films on n-type silicon wafers as gate dielectric layers of metal–oxide–semiconductor devices are prepared by pulsed laser deposition. As a comparison, amorphous aluminate LaAlO₃ (LAO) thin films are also prepared. The structural and electrical characterization shows that the as-prepared YAO films remain amorphous until 900 °C and the dielectric constant is ∼14. The measured leakage current of less than 10^-3 A/cm² at a bias of V_G=1.0 V for ∼40-nm-thick YAO and LAO films obeys the Fowler–Nordheim tunneling mechanism. It is revealed that the electrical property can be significantly affected by the oxygen pressure during deposition and post rapid thermal annealing, which may change the fixed negative charge density at the gate interface. PACS 77.55.+f; 81.15.Fg; 81.40.Ef     

Determination of the gap distribution in YBa2Cu3O7 using a far-infrared reflection-Fabry-Pérot device

This paper reports on far-infrared measurements of YBa₂Cu₃O₇ films oriented with the c-axis perpendicular to the surface, by using a silicon reflection Fabry-Pérot interferometer as a multireflection device. From these we could derive the dielectric function, the refractive index, the field penetration depth and the surface impedance of the material. The one order of magnitude higher sensitivity of the method compared to a direct reflectance measurement allowed to find an almost continuous gap distribution in the 70–215 cm^–1 region together with a separate gap at about 330 cm^–1. A quasizero gap absorption is found down to 20 cm^–1 even at low temperatures (10 K).     

Preparation of high J c YBa2Cu3O7−δ superconducting thin films by ion beam sputtering deposition

Preparation of high T _c and high J _c YBa₂Cu₃O_7– superconducting thin films by ion beam sputtering deposition is reported. The main factors affecting the composition of the films and the orientation of the crystal grains have been examined. Experimental results show that the Y, Ba and Cu composition of as-deposited films can be conveniently and accurately adjusted by a combined sputtering target which consists of a large sintered target of YBa₂Cu₃O_7– and a small one that is Ba and Cu rich (YBa_2.5Cu_3.3O_x). Fabrication conditions of highly oriented superconducting thin films are described. YBa₂Cu₃O_7– superconducting films with zero resistance at 88–90.5K and critical current density J _c (at 77K) of 1.5×10⁵ A/cm² are obtained.