Electronic conduction in vitreous semiconductors in the pseudo-binary system (As2S3)1-x(PbS)x

AC conductivity and dielectric relaxation measurements of the bulk amorphous compositions in the pseudo-binary system (As₂S₃)_1-x(PbS)_x (x = 0, 0.1, 0.4 and 0.5) in the frequency range 500 Hz-10 kHz and in the temperature span 180–450 K are reported. The temperature dependence of the ac conductivity, σ_ac(ω), has a broad structure at all frequencies in compositions with x = 0.1, 0.4 and 0.5 whose peak position is not thermally activated. A similar structure was also observed in the data on the dielectric constant, ε₁, which peaked at a frequency of 1 kHz in the composition with x = 0.5. Analysis of the results using the correlated barrier hopping model revealed that the electronic conduction takes place by single polaron and bipolaron hopping processes at high and low temperatures, respectively, in compositions containing Pb. The microstructure and phase-separation in the glasses containing Pb influence the electrical transport and dielectric dispersion. This study has revealed the possible presence of a phase transformation at around 300 K at a frequency of 1 kHz in the dielectric dispersion behaviour of composition with x = 0.5.     

Electronic traps in mixed Si1−xGexO2 films

Thermally stimulated luminescence (TSL) and infrared (IR) spectroscopy were measured in plasma grown Si_1−xGe_xO₂ (x=0, 0.08, 0.15, 0.25, 0.5) with different thicknesses (12–40 nm). A comparison with the TSL properties of thermally grown SiO₂ and GeO₂ was also performed. A main IR absorption structure was detected, due to the superposition of the peaks related to the asymmetric O stretching modes of (i) Si–O–Si (at ≈1060 cm⁻¹) and (ii) Si–O–Ge (at 1001 cm⁻¹). Another peak at ≈860 cm⁻¹ was observed only for Ge concentrations, x>0.15, corresponding to the asymmetric O stretching mode in Ge–O–Ge bonds. A TSL peak was observed at 70°C, and a smaller structure at around 200°C. The 70°C peak was more intense in all Ge rich layers than in plasma grown SiO₂. Based on the thickness dependence of the signal intensity we propose that at Ge concentrations 0.25x0.5 TSL active defects are localised at interfacial regions (oxide/semiconductor, Ge poor/Ge rich internal interface, oxide external surface/atmosphere). Based on similarities between TSL glow curves in plasma grown Si_1−xGe_xO₂, thermally grown GeO₂ and SiO₂ we propose that oxygen vacancy related defects are trapping states in Si_1−xGe_xO₂ and GeO₂.     

Compositional dependence of the optical gap in Ge1−xSx, Ge40−xSbxS60 and (As2S3)x(Sb2S3)1−x non-crystalline systems

An attempt is made to calculate the compositional dependence of the optical gap (E_g) in Ge_1−xS_x, Ge_40−xSb_xS₆₀ and (As₂S₃)_x(Sb₂S₃)_1−x non-crystalline systems in an alloy-like approach. From the comparison of both the experimental dependence of E_g and the calculated ones using the Shimakawa relation [E_{g AB} = YE_{g A} + (1−Y)E_{g B}] it is assumed that this equation is useful for such systems or parts of the systems which behave like almost ideal solutions.     

Elastic properties of GexAsySe100−x−y glasses

The elastic properties of Ge_xAs_ySe_100−x−y (0x30; 10y40) glasses have been studied. The results were analyzed in terms of the dependence on the theoretical mean coordination number (mean number of covalent bonds per atom) m (m=2+(2x+y)×0.01). Three ranges of m (2.1m2.51, 2.51<m2.78, 2.78<m3) were revealed, where different dependencies of elastic moduli (Young’s modulus, shear modulus) and Poisson’s ratio of glasses on m were observed.     

X-ray scattering studies of the short and medium range ordering in AsxTe1−x glasses

The structures of As_xTe_1−x(x = 0.2, 0.4, and 0.5) glasses are studied using the differential X-ray anomalous scattering technique. The partial distribution functions have also been obtained for the stoichiometric As₂Te₃ glass, giving information on the medium range ordering. All the glasses show chemical disorder to differing extents, the As₂Te₃ glass being the most disordered. The Te coordination number undergoes a change at x=0.4 where it is 2.5 compared with 2 for AsTe. This change indicates the existence of about 50% of threefold Te sites in the stoichiometric glass, as well as in the Te-rich glasses. Some of the physical properties of the glasses may be explained based on these results.     

Atomic structure of Al55(Cr1−xMnx)15Si30 metallic glasses observed by neutron diffraction

An atomic structure of Al₅₅(Cr_1−xMn_x)₁₅Si₃₀ (x = 0, 0.49,1) metallic glasses was studied by neutron diffraction. An advantage of the neutron diffraction technique was fully exploited by utilizing the negative scattering length of Mn to form a neutron zero scattering ‘alloy’ for the component Cr_0.51Mn_0.49 in this quaternary Al---(Cr, Mn)---Si alloy. This allows the atomic distribution of the resulting quasibinary Al---Si metallic glass to be derived directly. Moreover, the (Al, Si)---TM (TM = Mn, Cr) and TM---TM pair correlations were also extracted by taking appropriate linear combinations of the atomic structures for the Al₅₅(Cr_1−xMn_x)₁₅Si₃₀ (x = 0, 0.49, 1) metallic glasses. A sharp first peak in the (Al,Si) ---TM pair correlations thus obtained led to the conclusion that a strong attractive interaction exists between (Al, Si) and TM atoms and, hence, that the presence of the TM atoms is responsible for the formation of an amorphous phase.     

Effect of Yb content on purity and crystal growth of Ba2NaNb5O15

Growth by the micro-pulling-down technique (μ-PD) of homogeneous and crack-free fiber single crystals with composition Ba₂Na_1−xYb_xNb₅O₁₅ (0<x<0.08) is reported. The effect of Yb³⁺ addition to barium sodium niobate (BNN, x=0), having the tungsten bronze-type structure, was examined by room temperature X-ray powder diffraction and differential thermal analysis coupled to thermogravimetry. In the region of the monophased field the structure is tetragonal from x=0.02 to 0.16. Volume change is mainly by variation of the a-axis length. Addition of Yb³⁺ to BNN could be effective for the production of high optical quality, crack-free, bulk crystals by the Czochralski technique.     

Physical properties of amorphous Ge20Sb25−xBixSe55 thin films

The influence of substitution of Sb atoms by Bi atoms on the electrical and optical properties of thin films of the Ge₂₀Sb_25−xBi_xSe₅₅ [0x15] system are reported. Results of dc conductivity and thermoelectric power measurements between 150 and 450 K show that the Ge---Sb---Se system is chemically modified by addition of large concentrations of Bi atoms between X=5 and X=10 at.%). A transition from p-type for Sb-doped to n-type for Bi-doped films and a decrease of resistivity is observed. The absorption edge shifts to shorter wavelength, thereby decreasing the optical band gap of the system. Compositional dependences of electrical conductivity, thermoelectric power, and the appearance of n-type conduction are discussed from the stand point of chemical bonds formed in the films and related to the defect states produced due to incorporation of Bi atoms in high concentrations. The coexistence of band and hopping conduction is proposed. The ac conductivity in 0.1–10.0 kHz frequency and 150–450 K temperature range was found to obey a power law σ(ω, T) = Aω^s. The results were interpreted in terms of Elliott's theory, which assumes correlated barrier hopping (CBH) between the charged defect centres. It was found that computed results from the CBH model and experimental one are qualitative agreement for the present materials.     

XPS and electroluminescence studies on SrS1−xSex and ZnS1−xSex thin films deposited by atomic layer deposition technique

SrS_1−xSe_x and ZnS_1−xSe_x thin films were deposited by the atomic layer deposition (ALD) technique using elemental selenium as the Se source, thus avoiding use of H₂Se or organometallic selenium compounds. X-ray diffraction (XRD) analysis showed that the films were solid solutions and X-ray photoelectron spectroscopy (XPS) data showed that the surface of both ZnS_1−xSe_x and SrS_1−xSe_x were covered with an oxide and carbon-containing contaminants from exposure to air. The oxidation of SrS_1−xSe_x extended into the film and peak shifts from sulfate were found on the surface. Luminance measurements showed that emission intensity of the ZnS_1−xSe_x:Mn alternating current thin film electroluminescent (ACTFEL) devices at fixed voltage was almost the same as that of the ZnS:Mn device, while emission intensity of the SrS_1−xSe_x:Ce devices decreased markedly as compared to the SrS:Ce device. Emission colors of the devices were altered only slightly due to selenium addition.     

Compositional control of CdxZn1−xSe grown by photoassisted organometallic vapor phase epitaxy

The photoassisted OMVPE growth technique is important for the fabrication of blue/green laser diodes based on Cd_xZn_1−xSe quantum wells. Low temperature growth with photoassistance is key to the fabrication of these devices, however, the compositional control of Cd_xZn_1−xSe becomes increasingly difficult as the growth temperature is reduced. We have studied the compositional control of Cd_xZn_1−xSe using the sources DMCd, DMZn, and DMSe, with irradiation from a Hg arc lamp. We studied the dependence of the composition on the growth temperature, irradiation intensity, and source mass flows. The composition x increases with increasing temperature and decreases with increasing irradiation intensity. The solid-phase composition is a non-linear function of the gas-phase composition X. The slope of this characteristic, dx/dX, should be minimized for good compositional control. At 475°C without photoassistance, dx/dX is 1.75 near a composition of 20%, as determined from the data of Parbrook et al. Decreasing the temperature increases dx/dX. At 370°C with 12 mW/cm², dx/dX ≈ 13 and at 350°C with 58 mW/cm² dx/dX ≈ 60. We have investigated this behavior at 370°C with 12 mW/cm² irradiation by studying both the composition and the growth rate as a function of the gas-phase composition. The growth rate is non-monotonic, and is minimum for a gas-phase composition of 0.20. The behavior is quite complex, and is not fully understood at the present time. Nonetheless, our results indicate that the Cd-bearing precursor is adsorbed much more strongly than the Zn-bearing precursor. In addition to this, the introduction of the DMCd strongly inhibits the growth of ZnSe. We have achieved sufficiently good compositional control at 370°C and 12 mW/cm² to grow ZnSe/Cd_xZn_1−xSe/ZnSe multiple quantum well structures. More work is necessary in order to clarify the roles of irradiation intensity and VI/II ratio so that good compositional control can be achieved at lower growth temperatures.     

A glass-forming system with compound-forming tendency: As4S6---P4S10

Glasses in the quasi-binary system (As₄S₆)_x(P₄S₁₀)_1−x x = 0.1, …, 1.0, are produced and studied by thermal analysis, X-ray, and Raman spectroscopy. The phase diagram of the system and the critical cooling rate for glass formation both have their maximum at x = 0.5, corresponding to the compound As₂P₂S₈; the X-ray structure of recrystallized samples can be described as a sum of the As₂P₂S₈ (x = 0.5)- and the P₄S₁₀-structure (As₄S₆ not visible); Raman spectra of the glasses are again sums of As₂P₂S₈- and As₄S₆/P₄S₁₀-spectra. All these observations support the assumption that a stable building block corresponding to the 1:1 compound As₂P₂S₈ and surplus As₄S₆ (or P₄₁₀) are the essential elements of the structure in the glasses.     

Cd1−xZnxTe: Growth and characterization of crystals for X-ray and gamma-ray detectors

The choice a suitable crystal growth method and a reasonable x value is of profound importance in the preparation of high quality Cd_1−xZn_xTe crystals for x-ray and gamma-ray detectors. The present paper reviews the evolution and development of Cd_1−xZn_xTe crystal growth for x-ray and gamma-ray detectors. At the same time, emphasis is put upon finding the relationship between the x value and the quality of the Cd_1−xZn_xTe. Three sets of Cd_1−xZn_xTe ingots with different x values, specifically 0.10, 0.15, and 0.20 were grown by the vertical Bridgman method (VBM) and characterized. Their x specification was then correlated with their dislocation densities, Te precipitates, inclusions, IR transmission, resistivities, and impurity concentrations, respectively. It was found that VBM Cd_0.85Zn_0.15Te as grown in this paper possessed the best choice of qualities with respect to defects and impurities.     

Effect of Asi on the optical properties of Ga1−xInxAs/InP grown by molecular beam epitaxy

This report focuses on the effect of the As species and the V/III ratio on the optical properties of Ga_1−xIn_xAs/InP grown by molecular beam epitaxy (MBE). The band gap energies of the layers were measured by low temperature photoluminescence (PL) while the indium contents x were determined by X-ray for samples in the investigated range of 0.50<x<0.56. For the analysis of these data we considered the model of Kuo et al. which we confined with a correction for the different measurement temperatures in PL (4.2 K) and X-ray (300 K). Using As₄ with an effective V/III ratio higher than 1.3, we find the best agreement of the band gap energies and predictions of the theory. A lower V/III ratio always implies a reduction of the band gap energy to values 5-15 meV lower than expected. In contrast, using As₂ the PL data fit quite well independent of the effective V/III ratio above unity.     

XAS study of lanthanum coordination environments in glasses of the system K2O---SiO2---La2O3

The La L₁ and L₃ XANES and L₃ EXAFS have been investigated for the series of glasses 10K₂O---50SiO₂---x La₂O₃ (x = 1, 5, 10) and (10 − x)K₂O---40SiO₂−(x/3)La₂O₃ (x = 7.5, 5, 2.5) and model compounds La₂O₃, LaAlO₃, LaPO₄, La₂NiO₄, La₂CuO₄ and La(OH)₃. An edge resonance at 25 eV above the L₁ edge in the glass spectra is concentration-dependent, decreasing in intensity with increasing lanthanum concentration. The 2s → nd forbidden transition increases with La₂O₃ concentration, indicating a reduction in the ‘average’ site symmetry of the first coordination shell of La. Mapping _X(k) space, which is a new and promising technique, was employed to extract bond distance, coordination number and thermal parameters from the EXAFS. By this method, one calculates the complete _X(k) space a function of all physically reasonable values of the adjusted parameters in all possible combinations. The advantage in this method is the assurance of a global minimum. Bond lengths were comparable to those obtained by Fourier transforming the phase corrected EXAFS. The values are 2.42 Å (± 0.03 Å) for La---O. The coordination numbers (N ≤ 7 ± 1.5) were derived by mapping and comparison to the published structures for other La compounds. _X(k) mapping is compared with least-squares fitting the data, and the correlation between the Debye-Waller factor and coordination number is also discussed.     

Photocurrent measurements on GaAs1−xNx epilayers grown by metalorganic chemical vapor deposition

GaAs_1−xN_x epilayers were grown on a GaAs(0 0 1) substrate by metalorganic chemical vapor deposition. Composition was determined by high resolution X-ray diffraction. Band gap was measured from 77 to 400 K by using photocurrent measurements. The photocurrent spectra show clear near-band-edge peak and their peak energies drastically decrease with increasing nitrogen composition due to band gap bowing in the GaAs_1−xN_x epilayers. Those red shifts were particularly notable for low nitrogen compositions. However, the shifts tended to saturate when the nitrogen composition become higher than 0.98%. When the nitrogen composition is in the range 1.68–3.11%, the measured temperature dependence of the energy band gap was nicely fitted. However, the properties for the nitrogen composition range 0.31–0.98% could not be fitted with a single fitting model. This result indicates that the bowing parameter reaches 25.39 eV for low nitrogen incorporation (x=0.31%), and decreases with increasing nitrogen composition.     

Growth of Cu(AlxGa1−x)SSe pentenary alloy crystals by iodine chemical vapor transport method

Single crystals of Cu(Al_xGa_1−x)SSe pentenary alloys were successfully grown by the vapor transport technique using iodine as a transport agent. Systematic measurements of the basic crystal properties were carried out using powder X-ray, photoluminescence (PL), photoreflectance (PR), and Van der Pauw methods. Dependence of the lattice constants, exciton transition energies, and PL peak energies on Al composition, x, were examined in detail. The lattice constants obeyed Vegard's law. A quadratic dependence of exciton transition energies on x was found. The broadening parameters in the PR spectrum increase monotonically with increasing x, the results showing that the crystal quality degrades with increasing x. Exciton-related PL peaks were found for 0 ≤ x ≤ 0.77 at 77 K.     

Heavily carbon-doped p-type (In)GaAs grown by gas-source molecular beam epitaxy using diiodomethane

Heavily carbon-doped p-type In_xGa_1−xAs (0≤x<0.49) was successfully grown by gas-source molecular beam epitaxy using diiodomethane (CH₂I₂), triethylindium (TEIn), triethylgallium (TEGa) and AsH₃. Hole concentrations as high as 2.1×10²⁰ cm⁻³ were achieved in GaAs at an electrical activation efficiency of 100%. For In_xGa_1−xAs, both the hole and the atomic carbon concentrations gradually decreased as the InAs mole fraction, x, increased from 0.41 to 0.49. Hole concentrations of 5.1×10¹⁸ and 1.5×10¹⁹ cm⁻³ for x = 0.49 and x = 0.41, respectively, were obtained by a preliminary experiment. After post-growth annealing (500°C, 5 min under As₄ pressure), the hole concentration increased to 6.2×10¹⁸ cm⁻³ for x = 0.49, probably due to the activation of hydrogen-passivated carbon accepters.     

Heavily carbon-doped p-type InGaAs by MOMBE

Carbon-doped In_xGa_1−xAs layers (x=0−0.96) were grown by metalorganic molecular beam epitaxy (MOMBE) using trimethylgallium (TMG), solid arsenic (As₄) and solid indium (In) as sources of Ga, As and In, respectively. The carrier concentration is strongly affected by growth temperature and indium beam flux. Heavy p-type doping is obtained for smaller In compositions. The hole concentration decreases with the indium composition from 0 to 0.8, and then the conductivity type changes from p to n at x=0.8. Hole concentrations of 1.0×10¹⁹ and 1.2×10¹⁸ cm^-3 are obtained for x=0.3 and 0.54, respectively. These values are significantly higher than those reported on carbon-doped In_xGa_1−xAs by MBE. Preliminary results on carbon-doped GaAs/In_xGa_1−xAs strained layer superlattices are also discussed.     

Influence of chlorine-fluorine substitution on the electrical properties of some fluoride glasses

Study of electrical properties of two series of glasses (ZrF₄)₅₄(BaF₂)₃₀(ThF₄)₅(LaF₃)₃(RbF)_8(1−x)(RbCl)_8x (0 x 1) and (ZrF₄)₅₀(BaF₂)₃₀(ThF₄)₅(LaF₃)₃(RbF)_12(1−x)(RbCl)_12x (0 x 1) demonstrates the existence of a mixed mobile anion effect in these anion-conducting glasses. The effective medium approach has been applied to these materials: a satisfactory fitting is obtained as a function of the Cl/(Cl + F) ratio and temperature; the ionic transport in these glasses takes place along preferential pathways.     

Small-angle X-ray scattering studies of a-Si1−xGex: H alloys

Small-angle X-ray scattering (SAXS) is used to study a-Si:H, a-Ge:H, and a-Si_1−xGe_x: H alloys prepared by plasma-enhanced CVD methods. These amorphous semiconductors show various types of scattering characteristics related to their composition, deposition method, and deposition conditions. For poor quality alloys at low scattering vectors, h, the scattering curve shows an I(h)h⁻² dependence, because of the fractal nature of the inhomogeneities present. Also, a-Ge:H shows these features. Therefore, it is concluded that the inhomogeneities arise principally from clustering of Ge atoms.