Combinatorial approach to new glasses

An 18-sample glass-melting furnace was newly developed and glass-forming compositional regions were found in lead-free B₂O₃-TeO₂-[xBaF₂/(100−x)BaO] ternary systems. The softening temperatures were measured in the systems to screen out low-melting compositions. The softening temperature ranges from 450 to 470 °C and the thermal expansion coefficient ranges (115-140)× 10⁻⁷ °C⁻¹. These values were comparable to those of typical lead-containing glasses. It was also found that substitution of BaF₂ for BaO effectively lowers the melting temperatures without changing the thermal expansion coefficient.     

Indium zinc oxide thin films deposited by sputtering at room temperature

The deposition of amorphous indium zinc oxide (IZO) thin films on glass substrates with n-type carrier concentrations between 10¹⁴ and 3 × 10²⁰ cm⁻³ by sputtering from single targets near room temperature was investigated as a function of power and process pressure. The resistivity of the films with In/Zn of ∼0.7 could be controlled between 5 × 10⁻³ and 10⁴ Ω cm by varying the power during deposition. The corresponding electron mobilities were 4-18 cm² V⁻¹ s⁻¹.The surface root-mean-square roughness was <1 nm under all conditions for film thicknesses of 200 nm. Thin film transistors with 1 μm gate length were fabricated on these IZO layers, showing enhancement mode operation with good pitch-off characteristics, threshold voltage 2.5 V and a maximum transconductance of 6 mS/mm. These films look promising for transparent thin film transistor applications.     

Metal-semiconductor transition in undoped ZnO films deposited by spray pyrolysis

ZnO films were deposited on glass substrate by using spray pyrolysis method. Films were deposited at different solution molarities 0.02 and 0.1 M. The films are highly transparent in the visible range of the electromagnetic spectrum with a transmission reaching up values to 90%. Band gaps were calculated as 3.24 and 3.28 eV with the help of transmission spectrums. When the solution molarity of the sprayed solution is increased from 0.02 to 0.1 M, carrier concentrations of the films increase from 1.6×10¹⁹ cm⁻³ to 5.1×10¹⁹ cm⁻³. Temperature-dependent conductivity measurements of these conducting and transparent films also showed, for the first time, a metal-semiconductor transition (MST). The deposited ZnO films show metallic conductivity above ∼420 K and semiconducting behavior at temperatures below it.     

Research on glass cells for He neutron spin filters

Glass cells play an important role in polarized ³He neutron spin filters. To evaluate the scattering and absorption contribution from glass cells during neutron scattering experiments, we measured small-angle scattering and neutron transmission in GE180 and other glasses. The small-angle neutron scattering measurements revealed that the glasses used for ³He spin filters have acceptably lower scattering: dΣ(Q)/dΩ=4-7×10⁻⁴ cm⁻¹ at Q=0.03-0.12 Å⁻¹. The transmission measurement was performed at J-PARC. Neutron transmission of about 92% through empty GE180 cells was observed over a wide wavelength range 0.014-7.0 Å. To pursue the possibility of being a structural influence on ³He spin relaxation in GE180 glass cells, we performed precise X-ray diffraction measurement using synchrotron radiation at SPring-8. From these measurements, a structural difference was observed among GE180 glasses with different thermal treatments.     

Effect of iron doping on the characterization and transport properties of calcium phosphate glassy semiconductors

X-ray diffraction (XRD), differential scanning calorimeter (DSC), density (d) and dc conductivity (σ) of the glasses in Fe₂O₃-CaO-P₂O₅ system were reported. The dc conductivity in the temperature range 303-453 K was measured. The overall features of these XRD curves confirm the amorphous nature of the present samples. The density of glasses increases from 2.750 to 2.892 g/cm³ with increasing Fe₂O₃ content as a result of a strengthening of cross-linking within glass network. The glass temperature values (T_g) of the present glasses were larger than those of tellurite glasses. This indicates a higher thermal stability of the glass in the present system. The glasses had conductivities ranging from 10⁻⁹ to 10⁻⁵ Sm⁻¹ at temperatures from 303 to 453 K. Electrical conduction of the glasses was confirmed to be due to non-adiabatic small polaron hopping and the conduction was primarily determined by hopping carrier mobility.     

Fluorophosphate glasses containing manganese

New fluorophosphate glasses based on MnF₂, NaPO₃ and MF_n (M=Zn²⁺, Sr²⁺, Mg²⁺, Ba²⁺, Li⁺, Na⁺ and K⁺) have been synthesised and characterized. Large vitreous areas were observed. Samples of 4 mm in thickness have been obtained. These glasses are easy to prepare and stable in ambient air. Depending on the composition and the nature of the M cation, glass transition temperature, T_g, lies between 230 and 314 °C, crystallisation temperature, T_x is between 320 and 475 °C. These glasses are pink coloured, and infrared transmission extends up to 4.5 μm with extrinsic OH⁻ absorption band at 3200 cm⁻¹ and other bands around 2200 and 1600 cm⁻¹ that relate to PO₄ tetrahedron vibration. Other physical properties including density, microhardness, Young modulus, thermal expansion and refractive index were investigated and correlated to composition.     

Thermoelectric properties of sol-gel derived cobaltite Bi2Ca2.4Co2Oy

Layered misfit cobaltite Bi₂Ca_2.4Co₂O_y has been synthesized by a sol-gel method. This compound exhibits large thermoelectric (TE) power (S_300 K∼170 μV K⁻¹), low resistivity (ρ_300 K∼42 mΩ cm) and relatively small thermal conductivity (κ_300 K∼2.8 W K⁻¹ m⁻¹) at room temperature. Furthermore, the resistivity of this compound displays a metallic behavior above T^?∼150 K with a semiconducting behavior below this temperature. This abnormal behavior in resistivity is analogous to those observed in Sr and Ba based misfit cobaltites. The observed features of the TE have been discussed based on the narrow band model.     

Transparent conductive ZnO:Al films grown by atomic layer deposition for Si-wire-based solar cells

Structural, electrical, and optical properties of atomic layer-controlled Al-doped ZnO (ZnO:Al) films grown by atomic layer deposition (ALD) on glass substrates were characterized at various growth temperatures for use as transparent electrodes. The Al atomic content in ZnO:Al films increased due to the reduced ZnO film growth rate with increasing temperature. The preferred orientation of ZnO:Al films was changed, and the optimum condition for best crystallinity was identified by varying the growth temperature. Furthermore, the carrier concentration of free electron was increased by substituting the Zn sites with Al atoms in the crystal, resulting from monolayer growth based on alternate self-limiting surface chemical reactions. The electrical resistivity of ZnO:Al film grown by ALD at 225 °C reached the lowest value of 8.45 × 10⁻⁴ Ω cm, with a carrier mobility of 9.00 cm² V⁻¹ s⁻¹ and optical transmittance of ∼93%. This result demonstrates that ZnO:Al films grown by ALD possess excellent potential for applications in electronic devices and displays as transparent electrodes and surface passivation layers.     

Near-infrared emissions and quantum efficiencies in Tm-doped heavy metal gallate glasses for S- and U-band amplifiers and 1.8 μm infrared laser

Intense 1.8 μm and efficient 1.48 μm infrared emissions have been recorded in Tm³⁺-doped alkali-barium-bismuth-gallate (LKBBG) glasses with low phonon energies under the excitation of 792 nm diode laser. The maximum emission cross-sections for 1.8 and 1.48 μm emission bands are derived to be 6.26×10⁻²¹ and 3.34×10⁻²¹ cm², respectively, and the peak values are much higher than those in Tm³⁺-doped ZBLAN glass. In low-concentration doping, the full-widths at half-maximum (FWHMs) of the two emission bands are 223 and 122 nm, and the quantum efficiencies of the ³F₄ and ³H₄ levels are proved to be ∼100% and 86%, respectively. When the doping concentration increases to 1 wt%, the quantum efficiency of the ³H₄ level is reduced to 60% due to the cross-relaxation processes in high-concentration doping. Efficient 1.8 μm infrared emission in Er³⁺/Tm³⁺-codoped LKBBG glass has also been achieved under the excitation of 970 nm diode laser, and the probability and the efficiency of non-radiative energy transfer from Er³⁺ to Tm³⁺ are as high as 354 s⁻¹ and 58.4%, respectively. Efficient and broad 1.8 and 1.48 μm infrared emission bands indicate that Tm³⁺-doped LKBBG glasses are suitable materials in developing S- and U-band amplifiers and 1.8 μm infrared laser.     

Electrical properties and redox stability of tantalum-doped strontium titanate for SOFC anodes

SrTa_xTi_1−xO₃ (STT) with x = 0.01, 0.05, and 0.10, has been investigated as a potential electron conductor for solid oxide fuel cell (SOFC) anodes. STT was found to be chemically stable under oxidizing and reducing conditions and chemically compatible with yttria-stabilized zirconia (YSZ). The coefficient of thermal expansion (CTE) was near that of YSZ, ranging from 11.3 to 11.8 × 10⁻⁶ K⁻¹. The conductive properties of bulk STT and porous STT-YSZ composites were studied under relevant SOFC operating temperatures and redox cycling conditions. In order to achieve reasonable conductivities, samples were initially reduced at 1673 K. Conductivity after redox cycling was higher for lower dopant concentrations. The redox stable conductivity of a porous composite with x = 0.01 was 1.1 S/cm at 1073 K in humidified H₂ (3% H₂O). Fuel cell tests indicated an anode impedance of 0.4 Ω cm² at 973 K in humidified H₂ for STT-YSZ anodes infiltrated with 3 wt.% CeO₂ and 1 wt.% Pd.     

Influence of ordering change on the optical and thermal properties of inflation polyethylene films

Changes of thermal diffusivity inside femtosecond laser-structured volumes as small as few percent were reliably determined (with standard deviation less than 1%) with miniaturized sensors. An increase of thermal diffusivity of a crystalline high-density polyethylene (HDPE) inflation films by 10-20% from the measured (1.16 ± 0.01) × 10⁻⁷ m² s⁻¹ value in regions not structured by femtosecond laser pulses is considerably larger than that of non-crystalline polymers, 0-3%. The origin of the change of thermal diffusivity are interplay between the laser induced disordering, voids’ formation, compaction, and changes in molecular orientation. It is shown that laser structuring can be used to modify thermal and optical properties. The birefringence and infrared spectroscopy with thermal imaging of CH₂ vibrations are confirming inter-relation between structural, optical, and thermal properties of the laser-structured crystalline HDPE inflation films. Birefringence modulation as high as Δn ∼ ± 1 × 10⁻³ is achieved with grating structures.     

High mobility W-doped In2O3 thin films: Effect of growth temperature and oxygen pressure on structural, electrical and optical properties

Highly conducting and transparent thin films of tungsten (W)-doped indium oxide were obtained using pulsed laser deposition to study the effect of growth temperature and oxygen pressure on structural, optical and electrical properties. The transparency of the films is seen to largely depend on the growth temperature. The electrical properties, however, are found to depend strongly on both the growth temperature and the oxygen pressure. High mobility (up to 358 cm² V⁻¹ s⁻¹), low resistivity (1.1 × 10⁻⁴ Ω cm), and relatively high transmittance (∼90%) tungsten-doped indium oxide films have been prepared at a growth temperature of 500 °C and an oxygen pressure of 1 × 10⁻⁶ bar.     

Pulsed Nd:YAG laser depositions of ITO and DLC films for OLED applications

Indium-tin oxide (ITO) films deposited on heated and non-heated glass substrates by a pulsed Nd:YAG laser at 355 nm and ∼2.5 J/cm² were used in the fabrication of simple organic light-emitting diodes (OLEDs), ITO/(PVK + Alq₃ + TPD)/Al. The ITO was deposited on heated glass substrates which possessed resistivity as low as ∼3 × 10⁻⁴ Ω cm, optical transmission as high as ∼92% and carrier concentration of about ∼5 × 10²⁰ cm⁻³, were comparable to the commercial ITO. Substrate heating transformed the ITO microstructure from amorphous to polycrystalline, as revealed by the XRD spectrum. While the polycrystalline ITO produced higher OLED brightness, it was still lower than that on the commercial ITO due to surface roughness. A DLC layer of ∼1.5 nm deposited on this ITO at laser fluence of >12.5 J/cm² improved its device brightness by suppressing the surface roughness effect.     

Structure and high pressure behaviour of organic crystals based on aromatically substituted 1,3,4-oxadiazoles

The crystalline structure of a new compound containing the 1,3,4-oxadiazole moiety, 4-(5-methyl-1,3,4-oxadiazole-2yl-)-N,N′-dimethyl-phenylamine (MODPA) was determined. It shows a monoclinic structure with space group P2₁/c and lattice parameters: a=1.02997(6), b=0.64840(4), c=1.58117(10) nm and β=99.4820(10)°. To study the intermolecular interactions in oxadiazole containing organic crystals, X-ray studies on MODPA and 2,5-diphenyl-1,3,4-oxadiazole (DPO) were performed up to 5 GPa at room temperature. The Murnaghan equation of state is used to describe the compression behaviour of both substances. From these results, the bulk modulus and its pressure derivative were determined. The values obtained are: K₀=6.3 GPa and K′₀=6.8 for MODPA and K₀=7.3 GPa and K′₀=6.7 for DPO. Additionally, measurements under increasing temperature at ambient pressure were carried out to evaluate the thermal expansion coefficient: α=1.8×10⁻⁴ K⁻¹ for MODPA and α=1.9×10⁻⁴ K⁻¹ for DPO.     

Optical properties of Er in MoO3-Bi2O3-TeO2 glasses

Erbium-doped MoO₃−Bi₂O₃−TeO₂ (MBT) glasses suitable for broadband optical amplifier applications have been fabricated and characterized optically. The maximum phonon band of undoped glasses is at 915 cm⁻¹, and the emission from the Er³⁺: ⁴I_13/2 → ⁴I_15/2 transition locates around 1.53 μm with a full width at half maximum (FWHM) of ∼80 nm. The lifetime and quantum efficiency of the ⁴I_13/2 level are 2.13 ms and ∼90%, respectively. Under the same measurement condition, the upconversion emission intensities at 550 nm in Er³⁺-doped MBT glasses is about 30 times weaker than that in Er³⁺-doped Na₂O−ZnO−TeO₂ (NZT) glasses.     

A study of thermal parameters of Ag50Pd50 alloy using X-ray diffraction

Thermal parameters of Ag₅₀Pd₅₀ alloy were studied using the in-situ X-ray diffraction (XRD) technique. Diffraction experiments in the temperature range 308-1178 K showed that the alloy forms a face centered cubic (fcc; A1-type) structure. Temperature dependence of the lattice parameter was investigated using the Bragg line displacement method. Results show that the lattice parameter for the alloy increases with increase in temperature. The temperature dependent XRD data was utilized to determine the mean linear thermal expansion (MLTE (%)) and coefficient of thermal expansion (CTE) ‘α’ in the mentioned temperature range. It was observed that the values of CTE vary between 9.3 and 14.6 [K⁻¹][10⁻⁶]. The same data was also utilized to determine the Debye temperatures Θ_D and mean square amplitude of vibration (MSAV) (u²(T)) for this alloy. Values of thermal parameters as determined in this investigation are in good agreement with the estimated values as well as with those for other alloys of noble metals.     

Study of molybdenum coordination state and crystallization behavior in MoO3-La2O3-B2O3 glasses by Raman spectroscopy

The ternary MoO₃-La₂O₃-B₂O₃ glasses containing a large amount of MoO₃ (10-50 mol%) are prepared, and their structure and crystallization behavior are examined from the Raman scattering spectrum measurements and X-ray diffraction analyses. It is found that the glass transition and crystallization temperatures and the thermal stability against crystallization decrease with increasing MoO₃ content. It is suggested that the main coordination state of Mo⁶⁺ ions in the glasses is isolated (MoO₄)²⁻ tetrahedral units giving strong Raman bands at 830-860 and 930 cm⁻¹. It is found that the crystalline phases in the crystallized glasses are mainly LaMoBO₆ and LaB₃O₆, and the main crystallization mechanism in MoO₃-La₂O₃-B₂O₃ glasses is surface crystallization. LaMoBO₆ crystals are found to give strong Raman bands at 810-830 and ∼910 cm⁻¹.     

Influence of B2O3 to the inhomogeneous broadening and spectroscopic properties of Er/Yb codoped fluorophosphate glasses

In a three-components fluorophosphate glass system, the introduction of H₃BO₃ brings some valuable influence to the spectroscopic and thermal properties of the glasses. With H₃BO₃ increases from 2 to 20 mol%, Ω₆, S_ed4I13/2, FWHM, T_g and fluorescence lifetime change from 3.21×10⁻²⁰ cm², 1.77×10⁻²⁰ cm², 45 nm, 480 °C and 8.8 ms to 4.66×10⁻²⁰ cm², 2.11×10⁻²⁰ cm², 50 nm, 541 °C and 7.4 ms, respectively. σ_abs, σ_emi, FWHM×τ_f×σ_emi has a maximum when H₃BO₃ is 11 mol%. T_g and T_x−T_g increases with H₃BO₃ introduction. Results showed that in fluorophosphate glasses, proper amount of B₂O₃ can be used as a modifier to suppress upconversion and improve spectroscopic properties, broadband property and crystallization stability of the glasses while keeps the fluorescence lifetime relatively high.     

Effects of SrO/ZnO on structure and properties of UV-transmitting borophosphosilicate glass

UV-transmitting borophosphosilicate glasses series, 2Al₂O₃−xSrO-(18−x)ZnO-33.3P₂O₅-16.7B₂O₃-30SiO₂ glasses with x=0-18 mol% were prepared and studied. The substitution of SrO for ZnO increases the density and the thermal expansion coefficient (α), but decreases the molar volume (V_m). The glass transition temperatures (T_g) and softening points (T_d) vary within a small range. The relative chemical durability was determined by measuring the weight loss of a polished glass sample after immersion in deionized water at 50 °C for 24 h, the chemical durability of the glasses increases when x≤9, and drops when x>9. With the increasing SrO content, the UV transmittance of the glasses decreases mildly. The compositional dependence of E_opt shows a decrease trend with increasing SrO content. The structural changes with the glass compositions were examined by FT-IR and Raman spectra.     

Opto-electrical properties of Ti-doped In2O3 thin films grown by pulsed laser deposition

By ablating titanium containing In₂O₃ target with a KrF excimer laser, highly conducting and transparent films on quartz were obtained to investigate the effects of growth temperature and oxygen pressure on the structural, optical and electrical properties of these films. We find that the transparency of the films depends more on the growth temperature and less on the oxygen pressure. Electrical properties, however, are found to be sensitive to both the growth temperature and oxygen pressure. We report in this paper that a growth temperature of 500 °C and an oxygen pressure of 7.5 × 10⁻⁷ bar lead to titanium-doped indium oxide films which have high mobility (up to 199 cm² V⁻¹ s⁻¹), low resistivity (9.8 × 10⁻⁵ Ω cm), and relatively high transmittance (∼88%).