Elucidation of factors obstructing quality improvement of MOVPE-grown InN

A systematic study of the crystallographic and electrical/optical properties of MOVPE-grown InN was performed, and the factors that restrict the quality of MOVPE InN were elucidated. The quality of grown InN is highly dependant on the thermal decomposition of NH₃ as a nitrogen source. At a lower growth temperature (~550 °C) a shortage of active nitrogen, due to a lower decomposition rate of NH₃, causes the formation of N vacancies in the grown InN. With increasing growth temperature, a more stoichiometric crystal is grown and the electrical/optical properties improve. At temperatures above 600 °C, however, deterioration occurs at the N-face of In-polar InN near the substrate interface. This deterioration results in the formation of a porous layer during high temperature (~650 °C) growth. There are a few evidences that show that the hydrogen produced by NH₃ decomposition causes this degradation. Thus, improving the quality of MOVPE-grown InN by changing the growth temperature can be difficult. However, a short growth time at a high growth rate and a relatively high temperature is one effective way to solve this dilemma, and one can achieve carrier concentrations as low as 4×10¹⁸ cm⁻³ by growth at 650 °C for 30 min.     

Structural,electrical and optical properties of in-situ phosphorous-doped Ge layers

We have studied the impact of temperature and pressure on the structural and electronic properties of Ge:P layers grown with GeH₄+PH₃ on thick Ge buffers, themselves on Si(0 0 1). The maximum phosphorous atomic concentration [P] exponentially decreased as the growth temperature increased, irrespective of pressure (20 Torr, 100 Torr or 250 Torr). The highest values were however achieved at 100 Torr (3.6×10²⁰ cm^?3 at 400 °C, 2.5×10¹⁹ cm^?3 at 600 °C and 10¹⁹ cm^?3 at 750 °C). P atomic depth profiles, “box-like” at 400 °C, became trapezoidal at 600 °C and 750 °C, most likely because of surface segregation. The increase at 100 Torr of [P] with the PH₃ mass-flow, almost linear at 400 °C, saturated quite rapidly at much lower values at 600 °C and 750 °C. Adding PH₃ had however almost no impact on the Ge growth rate (be it at 400 °C or 750 °C). A growth temperature of 400 °C yielded Ge:P layers tensily-strained on the Ge buffers underneath, with a very high concentration of substitutional P atoms (5.4×10²⁰ cm^?3). Such layers were however rough and of rather low crystalline quality in X-ray Diffraction. Ge:P layers grown at 600 °C and 750 °C had the same lattice parameter and smooth surface morphology as the Ge:B buffers underneath, most likely because of lower P atomic concentrations (2.5×10¹⁹ cm^?3 and 10¹⁹ cm^?3, respectively). Four point probe measurements showed that almost all P atoms were electrically active at 600 °C and 750 °C (1/4th at 400 °C). Finally, room temperature photoluminescence measurements confirmed that high temperature Ge:P layers were of high optical quality, with a direct bandgap peak either slightly less intense (750 °C) or more intense (600 °C) than similar thickness intrinsic Ge layers. In contrast, highly phosphorous-doped Ge layers grown at 400 °C were of poor optical quality, in line with structural and electrical results.     

Intersubband transition at 1.55 μm in AlN/GaN multiple quantum wells by metal organic vapor phase epitaxy using the pulse injection method at 770 °C

Intersubband transition (ISBT) at 1.55 μm in AlN/GaN multi quantum wells (MQWs) was realized by metal organic vapor phase epitaxy (MOVPE) using the pulse injection (PI) method to grow GaN well layers at 770 °C. It was shown that a main factor for shifting ISBT wavelength to shorter region to cover 1.55 μm and improving ISBT properties of MQWs is the growth temperature of MQWs. Best structural and ISBT properties are observed at low growth temperature of 770 °C in this study. Carbon incorporation level in GaN layer grown by the PI method (PI-GaN) showed one order smaller value compared with that by the conventional continuous method. Moreover, further decrease in growth temperature to 770 °C did not show significant increase in carbon incorporation in PI-GaN layer. It clearly indicates that the PI method is very effective in reducing carbon concentration in GaN layer, especially at low temperature region. The low carbon concentration of 4×10¹⁸ cm^?3 released by the PI method was indispensable for realizing enough carrier concentration of 1.6×10¹⁹ cm^?3 to achieve strong ISBT at 1.55 μm.     

ZnO growth on Si with low-temperature ZnO buffer layers by ECR-assisted MBE

High-quality ZnO films were grown on Si(1 0 0) substrates with low-temperature (LT) ZnO buffer layers by an electron cyclotron resonance (ECR)-assisted molecular-beam epitaxy (MBE). In order to investigate the optimized buffer layer temperature, ZnO buffer layers of about 1.1 μm were grown at different growth temperatures of 350, 450 and 550 °C, followed by identical high-temperature (HT) ZnO films with the thickness of 0.7 μm at 550 °C. A ZnO buffer layer with a growth temperature of 450 °C (450 °C-buffer sample) was found to greatly enhance the crystalline quality of the top ZnO film compared to others. The root mean square (RMS) roughness (3.3 nm) of its surface is the smallest, compared to the 350 °C-buffer sample (6.7 nm), the 550 °C-buffer sample (7.4 nm), and the sample without a buffer layer (6.8 nm). X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurements were carried out on these samples at room temperature (RT) in order to characterize the crystalline quality of ZnO films. The preferential c-axis orientations of (0 0 2) ZnO were observed in the XRD spectra. The full-width at half-maximum (FWHM) value of the 450 °C-buffer sample was the narrowest as 0.209°, which indicated that the ZnO film with a buffer layer grown at this temperature was better for the subsequent ZnO growth at elevated temperature of 550 °C. Consistent with these results, the 450 °C-buffer sample exhibits the highest intensity and the smallest FWHM (130 meV) of the ultraviolet (UV) emission at 375 nm in the PL spectrum. The ZnO characteristic peak at 438.6 cm⁻¹ was found in Raman scattering spectra for all films with buffers, which is corresponding to the E₂ mode.     

Smooth titania nanotubes: Self-organization and stabilization of anatase phase

We present transmission electron microscopy and Raman scattering measurements showing that niobium inhibits the processes of nucleation and growth of anatase crystallites in the initial amorphous titania nanotubes and thus shifts the temperature of the complete amorphous-to-anatase phase transition to higher values up to 550 °C. Niobium dopants stabilize the anatase phase in titania nanotubes up to 650 °C. The size of anatase crystallites can reach 30–50 nm. Excess niobium atoms which are pulled off from the volume of anatase crystallite form polymeric or monomeric Ti–O–NbO groups at the interface area. Slight shift and broadening of E_g (144 cm^?1), A_1g (515 cm^?1) and E_g (630 cm^?1) modes in Raman spectra can be explained by niobium insertion into the anatase structure.     

Effect of OH-content on thermal and chemical properties of SnOP2O5 glasses

Glasses with 55–60 mol% SnO and 40–45 mol% P₂O₅ have shown extremely large differences in the chemical and thermal properties depending on the temperature at which they were melted. Glasses prepared at low melting temperature, 450–550 °C, had low T_g, 150–200 °C, and low chemical stability. Glasses prepared at high melting temperature, 800–1200 °C, had much higher T_g, 250–300 °C, and much higher chemical stability. No significant differences were found by ¹¹⁹Sn Mössbauer and ³¹P Nuclear Magnetic Resonance spectroscopy. Large differences in the OH-content could be detected as the reason by infrared absorption spectroscopy, thermal analyses, and ¹H Nuclear Magnetic Resonance spectroscopy. In samples with low T_g, a broad OH – vibration band around 3000 nm with an absorption intensity >20 cm^?1, bands at 2140 nm with intensity ～5 cm^?1, at 2038 nm with intensity ～2.7 cm^?1, and at 1564 nm with intensity ～0.4 cm^?1 were measured. These samples have shown a mass loss of 3–4 wt% by thermal gravimetric analyses under argon in the temperature range 400–1000 °C. No mass loss and only one broad OH-band with a maximum at 3150 nm and low absorption intensity <4 cm^?1 could be detected in samples melted at high temperature, 1000–1200 °C, which have much higher T_g, ～300 °C, and much higher chemical stability.     

Effect of tellurium deposition rate on the properties of Cu–In–Te based thin films and solar cells

To investigate the effects of tellurium (Te) deposition rate on the properties of Cu–In–Te based thin films (Cu/In=0.30–0.31), the films were grown on both bare and Mo-coated soda-lime glass substrates at 200 °C by co-evaporation using a molecular beam epitaxy system. The microstructural properties were examined by means of scanning electron microscopy and X-ray diffraction. The crystalline quality of the films was improved with increase in the deposition rate of Te, and exhibited a single CuIn₃Te₅ phase with a highly preferred (1 1 2) orientation. Te-deficient film (Te/(Cu+In)=1.07) grown with a low Te deposition rate showed a narrow bandgap of 0.99 eV at room temperature. The solar cell performance was affected by the deposition rate of Te. The best solar cell fabricated using CuIn₃Te₅ thin films grown with the highest deposition rate of Te (2.6 nm/s) yielded a total area (0.50 cm²) efficiency of 4.4% (V_oc=309 mV, J_sc=28.0 mA/cm², and FF=0.509) without light soaking.     

Processes of vapor phase growth of AIIBVI single crystals and structures based there upon

Results of investigations of semiconductor A^IIB^VI compounds (for example of CdTe and ZnTe) grown by the chemical vapor transport (CVT) method in a closed volume using three transfer agents containing a halogen, compound NH₄X (X = Cl, Br, I) are presented. The processes of vapor phase growth (composition of the vapor phase and mass transfer) in Me(Cd, Zn)Te–NH₄X (X = Cl, Br, I) systems have been calculated theoretically and the results are have been verified in growth experiments. Optoelectronic properties of the grown materials and barrier structures based there upon are discussed.     

Selection of post-growth treatment parameters for atomic layer deposition of structurally disordered TiO2 thin films

Routes to atomic layer-deposited TiO₂ films with decreased leakage have been studied by using electrical characterization techniques. The combination of post-deposition annealing parameters, time and temperature, which provides measurable aluminum–titanium oxide–silicon structures – i.e., having capacitance–voltage curves which show accumulation behavior – are 625 °C, 10 min for p-type substrates, and 550 °C, 10 min for n-type substrates. The best annealing conditions for p-type substrates are 625 °C with the length extended to 30 min, which produces an interfacial state density of about 5–6 × 10¹¹ cm^?2 eV^?1, and disordered-induced gap state density below our experimental limits. We have also proved that a post-deposition annealing must be applied to TiO₂/HfO₂ and HfO₂/TiO₂/HfO₂ stacked structures to obtain adequate measurability conditions.     

AlGaN/GaN HEMTs regrown by MBE on epi-ready semi-insulating GaN-on-sapphire with inhibited interface contamination

In this work, we show that, by carefully designing the subsurface Fe doping profile in SI-GaN templates grown by MOVPE and by optimizing the MBE regrowth conditions, a highly resistive GaN buffer can be achieved on these epi-ready GaN-on-sapphire templates without any addition of acceptors during the regrowth. As a result, high-quality high electron mobility transistors can be fabricated. Furthermore, we report on the excellent properties of two-dimensional electron gas and device performances with electron mobility greater than 2000 cm²/V s at room temperature and off-state buffer leakage currents as low as 5 μA/mm at 100 V.     

Annealing in water vapor as a new method for improvement of silicon thin film properties

Electronic properties of poly-Si thin films fabricated by atmospheric pressure chemical vapor deposition (APCVD) were improved by annealing in H₂O or D₂O vapors. Hall mobility was improved from 4.45 cm⁻²/V s to 25.1 cm⁻²/V s after 1 h D₂O vapor treatment at 300 °C, i.e., nearly the same value as after optimized plasma hydrogenation. Unlike the hydrogen plasma treatment, annealing did not introduce disorder into the material, judged by the width of Raman LO-TO band. Water vapor treatment is a novel approach to improvement of thin films properties, with potentially low cost suitable for mass production of solar cells, but its mechanism is not yet clear.     

Highly reflective AlGaAsSb/InP Bragg reflector at 1.55 μm grown by MOVPE

The metalorganic vapor-phase epitaxy growth of a highly reflective 24-pair AlGaAsSb/InP-distributed Bragg reflector (DBR) is reported for the first time. The influence of the growth parameters such as the V/III input ratio, the growth temperature and the pressure, the total H₂ flow, the gas velocity and the switching sequence of the source gases at the interfaces has been deeply investigated and optimized to achieve stable growth conditions. The DBR achieves a reflectivity as high as 99.5% around 1.55 μm, a uniform stable composition, and an excellent crystal quality over the 2 inch wafer, with a surface free of crosshatch and a defect density below 1/cm². For the optical characterizations, measurements of linear and nonlinear reflectivity, transmission, pump-probe and photoluminescence were done. The interfaces and bulk layers of InP/AlGaAsSb/InP heterostructures were analyzed by transmission electron microscopy. High resolution X-ray diffraction measurements were used to determine the composition shift in the growth plane of the DBR. The measurements show the high quality of the growth and demonstrate that thick AlGaAsSb/InP heterostructures can be grown by metalorganic vapor-phase epitaxy (MOVPE), and in particular DBRs above 1.31 μm.     

Growth improvement and characterization of AgGaxIn1−xSe2 chalcopyrite crystals using the horizontal Bridgman technique

AgGa_xIn_1?xSe₂ single crystals with x=0.4 have been grown by the horizontal Bridgman technique for nonlinear optical application requires phase matching. High purity polycrystalline synthesis of AgGa_xIn_1?xSe₂ was carried out at 850 °C, which is a relatively lower temperature compared to those in earlier reports, thus reducing secondary phase formation. An average Ga:In ratio of 62:38 (±3%) was measured using energy dispersive spectroscopy (EDS). As grown, a single crystal shows very high IR transmission of ～65% in the spectral range of 4000–600 cm^?1. There was no significant change in its IR transmission after annealing it at 500 °C for 20 days in vacuum in the presence of AgGa_xIn_1?xSe₂ powder. This indicates a low concentration of defects in the crystal. The results demonstrate that the improved new synthesis method for crystal growth was promising and that the quality of the crystal was good.     

Growth kinetics and boron doping of very high Ge content SiGe for source/drain engineering

We have studied the in-situ boron doping of high Ge content Si_1?xGe_x layers (x=0.3, 0.4 and 0.5). These layers have been grown at low pressure (20 Torr) and low temperature (600–650 °C) with a heavily chlorinated chemistry on blanket Si(0 0 1) substrates. Such a chemistry yields a full selectivity versus SiO₂ (isolation) and Si₃N₄ (sidewall spacers) on patterned wafers with gate stacks. We have quantified the impact of the diborane flow on the SiGe layer crystalline quality, its resistivity, the SiGe:B growth rate and the apparent Ge concentration. Resistivity values lower than 1 mΩ cm are easily achieved, all the more so for high Ge content layers. The SiGe growth rate increases and the apparent Ge concentration (from X-ray diffraction) decreases as the diborane flow increases. B atoms (much smaller than Si or Ge) indeed partially compensate the compressive strain in the SiGe:B layers. We have also probed the in-situ boron and phosphorus doping of Si at 750 °C, 20 Torr with a heavily chlorinated chemistry. The B ions concentration increases linearly with the diborane flow, then saturates at a value close to 4×10¹⁹ cm^?3. By contrast, the P ions concentration increases sub-linearly with the phosphine flow, with a maximum value close to 9×10¹⁸ cm^?3. Adding diborane (phosphine) to the gaseous mixture leads to a sharp increase (decrease) of the Si:B (the Si:P) growth rates, which has to be taken into account in device layers. All the know-how acquired will be most handy for the formation of in-situ doped recessed or raised sources and drains in metal-oxide semiconductor devices.     

Characterization of chitosan/PVA blended electrolyte doped with NH4I

The (chitosan–PVA)–NH₄I electrolytes have been prepared by the solution casting method. The prepared electrolytes are analyzed using Fourier transform infrared (FTIR) spectroscopy in order to determine the interaction between salt and the polymer blend hosts which can be deduced from the band shifting. From infrared spectra, shifts are observed at the amine, carboxamide, carbonyl and hydroxyl bands of chitosan and PVA. These shifts indicate that complexation has occurred. The crystallinity/amorphousness of the blended electrolytes has been examined by X-ray diffraction (XRD). XRD pattern shows that the crystallinity of chitosan–NH₄I electrolyte increases with PVA concentration. Impedance of the electrolytes has been measured using electrochemical impedance spectroscopy (EIS) over the frequency range from 50 Hz to 1 MHz. The highest conducting sample 55 wt.% (chitosan–PVA)–45 wt.% NH₄I has conductivity of 1.77 × 10^? 6 S cm^? 1. The chitosan:PVA ratio is 1:1. This is higher than the conductivity for the unblended electrolyte 55 wt.% chitosan–45 wt.% NH₄I which is 3.73 × 10^? 7 S cm^? 1. From ln τ versus 10³/T plot, the activation energy for relaxation process is 0.87 eV. This is different from activation energy for dc conductivity which is 0.38 eV. Ion conduction is by hopping.     

Synthesis and characterizations of phthaloyl chitosan-based polymer electrolytes

Phthaloyl chitosan (PhCh) has been synthesized by reacting excess phthalic anhydride with chitosan in the presence of nitrogen gas (N₂). Confirmation of phthaloyl chitosan structure by Fourier-transform infrared (FTIR) spectroscopy shows bands at 1773 and 1713 cm^? 1 attributable to the pthalimido group. From X-ray diffraction (XRD), the samples are largely amorphous. Thermal stability of chitosan is increased on phthaloylation. Ammonium thiocyanate (NH₄SCN) salt has been added to the solution of phthaloyl chitosan in N,N-dimethylformamide (DMF) before casting to form films. The amount of NH₄SCN salt added ranges from 5 to 50 wt. % concentration. The highest conductivity at 298 K is (2.42 ± 0.01) × 10^? 5 S cm^? 1 for the sample 70 wt. % PhCh-30 wt. % NH₄SCN. Impedance of the films has been measured at temperatures between 298 K and 373 K and in the frequency range from 0.1 Hz to 1 × 10⁷ Hz. Relaxation peaks are observed from dielectric loss and tangent delta variation with frequency at ambient and elevated temperatures in the frequency range investigated for the highest conducting sample. Decomposition voltage is ~ 2.07 V and transference number measurements show that charge conduction is mainly by ions.     

Properties of sodium-based ternary phosphate glasses produced from readily available phosphate salts

Three series of phosphate glasses were produced by melting together sodium phosphate salt (NaH₂PO₄) and the phosphate salts of either calcium (CaHPO₄), magnesium (MgHPO₄ · 3H₂O) or iron (FePO₄ · 2H₂O) in a 5% gold/95% platinum crucible at 1200 °C. The glass compositions were confirmed by EDX and XRD analysis. Glass transition temperature (T_g), density and durability in water were determined for all the compositions. Maximum metal oxide contents before devitrification were between 55% and 59% for CaO + Na₂O and 59% and 62% for MgO + Na₂O. The normalized equivalent for Fe₂O₃ + Na₂O was between 55% and 61%. Density values for the glasses lay between 2.49 and 2.75 g cm⁻³. T_gs lay between 295 °C and 470 °C. Degradation rates in deionized water at 37 °C lay between 0.03 g cm⁻² h⁻¹ for Na phosphate glasses and 9 × 10⁻⁶ g cm⁻² h⁻¹ for Ca phosphate glasses, 3 × 10⁻⁶ g cm⁻² h⁻¹ for Mg phosphate glasses and <3 × 10⁻⁶ g cm⁻² h⁻¹ for Fe phosphate glasses. The effect of metal addition on properties goes as Fe > Mg > Ca for degradation rates and T_g and Fe > Mg ≈ Ca for density. The change in properties with metal addition was seen to be linear for Fe and Ca additions but not with Mg addition. This is in agreement with the anomalous behavior of magnesium phosphate glasses.     

Properties and structure of (1 − x)Li2O–xNa2O–Al2O3–4SiO2 glass systems

(1 − x)Li₂O–xNa₂O–Al₂O₃–4SiO₂ glasses were studied for the progressive percentage substitution of Na₂O for Li₂O at the constant mole of Al₂O₃ and SiO₂. The crystallization temperature at the exothermic peak increased from 898 to 939 °C when the Na₂O content increases from 0 to 0.6 mol. The coefficient of thermal expansion and density of these as-quenched glasses increase from 6.54 × 10⁻⁶ °C⁻¹ to 10.1 × 10⁻⁶ °C⁻¹ and 2.378 g cm⁻³ to 2.533 g cm⁻³ when the Na₂O content increases from 0 to 0.4 mol, respectively. The electrical resistivity has a maximum value at Na₂O · (Li₂O + Na₂O)⁻¹ = 0.4. The activation energy of crystallization decreases from 444 to 284 kJ mol⁻¹ when the Na₂O content increased from 0 to 0.4 mol. Moreover, the activation energy increases from 284 kJ mol⁻¹ to 446 kJ mol⁻¹ when the Na₂O content increased from 0.4 to 0.6 mol. The FT-IR spectra show that the symmetric stretching mode of the SiO₄ tetrahedra (1035–1054 cm⁻¹) and AlO₄ octahedra (713–763 cm⁻¹) exhibiting that the network structure is built by SiO₄ tetrahedra and AlO₄.     

Solvothermal preparation of graphite-like C3N4 nanocrystals

Graphite-like C₃N₄ nanocrystals were synthesized by the reaction of CCl₄ and NH₄Cl at 400°C without any catalyst. XRD and TEM examinations indicate that the average size of the crystals is about 11 nm with a good crystallinity, and CN and C–N bonds can be observed at 1617.95 and 1271.09 cm⁻¹, respectively, in the IR spectrum.     

Redox reactions during temperature change in soda-lime–silicate melts doped with copper and iron or copper and manganese

Glasses with the base composition 16Na₂O · 10CaO · 74SiO₂ doped with copper and iron or copper and manganese were studied by high temperature UV–vis–NIR spectroscopy. The spectra exhibited distinct absorption bands attributed to the respective transition metal ions present (Cu²⁺, Fe²⁺, Fe³⁺, Mn³⁺). In glasses doped with only one polyvalent element, the absorption decreases linearly with increasing temperature, the absorption bands are shifted to smaller wave numbers and get broader. In glasses doped with two types of transition metals, the situation is the same up to a temperature of around 550 °C. At larger temperature, the Cu²⁺-absorption in glasses also co-doped with iron increases again, while in glasses doped with both copper and manganese the absorption is approximately the same as in glasses solely doped with copper. It is shown that this is due to redox reactions between polyvalent species. These reactions are frozen in at temperatures <550 °C.