Bandgap engineering of monodispersed Cu(2-x)S(y)Se(1-y) nanocrystals through chalcogen ratio and crystal structure

Bandgap engineering is important in light-absorption optimization of nanocrystals (NCs) for applications such as highly efficient solar cells. Herein, a facile one-pot method is developed to synthesize monodispersed ternary alloyed copper sulfide selenide (Cu(2-x)S(y)Se(1-y)) NCs with tunable composition, structure, and morphology. The energy bandgaps can be tuned with the chalcogen ratio, and the crystal structure of the NCs is found to produce an effect on their bandgap and light absorption. The results are significant in bandgap engineering of semiconductor NCs.     

Electron Paramagnetic Resonance Study of PbSe,PbTe, and PbTe:In Semiconductors Obtained by the Pulsed Laser Deposition Method

The magnetic properties of lead selenide (PbSe) and indium-doped lead telluride (PbTe:In) composites have been studied by using the electron paramagnetic resonance (EPR) technique. The samples were obtained by using the pulsed laser deposition method (PLD). Temperature dependences of the EPR spectra were obtained. The analysis of the temperature dependencies of the integral intensity of the EPR spectra was performed using the Curie–Weiss law. In these materials, the paramagnetic centers of Pb¹⁺ and Pb³⁺ ions were identified. The results are discussed.     

Synchrotron X-ray studies of Al(1-y)Ti(y) formation and re-hydriding inhibition in Ti-enhanced NaAlH4

NaAlH4 samples with Ti additives (TiCl3, TiF3, and Ti(OBu)4) have been investigated by synchrotron X-ray diffraction in order to unveil the nature of Ti. No crystalline Ti-containing phases were observed after ball milling of NaAlH4 with the additives, neither as a solid solution in NaAlH4 nor as secondary phases. However, after cycling, a high-angle shoulder of Al is observed in the same position with 10% TiCl3 as that with 2% Ti(OBu)4, but with considerably higher intensity, indicating that the shoulder is caused by Ti. After prolonged reabsorption, there is only a small fraction of free Al phase left to react with Na3AlH6, whereas the shoulder caused by Al(1-y)Ti(y) is dominating. The Ti-containing phase causing the shoulder therefore contains less Ti than Al3Ti, and the aluminum in this phase is too strongly bound to react with Na3AlH6 to form NaAlH4. The composition of the Al(1-y)Ti(y) phase is estimated from quantitative phase analysis of powder X-ray diffraction data to be Al(0.85)Ti(0.15). Formation of this phase may explain the reduction of capacity beyond the theoretical reduction from the dead weight of the additive and the reaction between the additive and NaAlH4.     

Temperature and pressure evolution of the crystal structure of A(x)(Fe(1-y)Se)2 (A = Cs, Rb, K) studied by synchrotron powder diffraction

Temperature-dependent synchrotron powder diffraction on Cs(0.83)(Fe(0.86)Se)(2) revealed first-order I4/m to I4/mmm structural transformation around 216 °C associated with a disorder of the Fe vacancies. Irreversibility observed during the transition is likely associated with a mobility of the intercalated alkali atoms. Pressure-dependent synchrotron powder diffraction on Cs(0.83)(Fe(1-y)Se)(2), Rb(0.85)(Fe(1-y)Se)(2), and K(0.8)(Fe(1-y)Se)(2) (y ~ 0.14) indicated that the I4/m superstructure reflections are present up to pressures of 120 kbar. This may indicate that the ordering of the Fe vacancies is present in both superconducting and nonsuperconductive states.     

Torsional angular dependence of 1J(Se,Se) and Fermi contact control of 4J(Se,Se): analysis of nJ(Se,Se) (n=1-4) based on molecular orbital theory

(n)J(Se,Se) (n=1-4) nuclear couplings between Se atoms were analyzed by using molecular orbital (MO) theory as the first step to investigating the nature of bonded and nonbonded (n)J(Se,Se) interactions between Se atoms. The values were calculated by employing Slater-type triple xi basis sets at the DFT level, which were applied to structures optimized with the Gaussian 03 program. The contribution from each occupied MO (psi(i)) and psi(i)-->psi(a) (psi(a)=unoccupied MO) transition was evaluated separately. 1J(Se,Se) was calculated for the MeSeSeMe model compound, which showed a typical dependence on the torsion angle (phi(C(Me)SeSeC(Me))). This dependence explains the small values (< or =64 Hz) of 1Jobsd(Se,Se) observed for RSeSeR' and large values (330-380 Hz) of 1Jobsd(Se,Se) observed for 4-substituted naphtho[1,8-c,d]-1,2-diselenoles, which correspond to synperiplanar diselenides. The HOMO-->LUMO and HOMO-1-->LUMO transitions contribute the most to 1J(Se,Se) at phi=0 and 180 degrees to give large values of 1J(Se,Se), whereas various transitions contribute and cancel each other out at phi=90 degrees to give small values of 1J(Se,Se). Large 4Jobsd(Se,Se) values were also observed in the nonbonded Se...Se, Se...Se=O, and O=Se...Se=O interactions at naphthalene 1,8-positions. The Fermi contact (FC) term contributes significantly to 4J(Se,Se), whereas the paramagnetic spin-orbit (PSO) term contributes significantly to 1J(Se,Se). 2J(Se,Se) and 3J(Se,Se) were analyzed in a similar manner and a torsional angular dependence was confirmed for 3J(Se,Se). Depending on the structure, the main contribution to (n)J(Se,Se) (n=2, 3) is from the FC term, with a lesser contribution from the PSO term. Analysis of each transition enabled us to identify and clearly visualize the origin and mechanism of the couplings.     

Low frequency Raman spectra of barium borate glasses in the system (BaCl2)y[(BaO)x(B2O3)1-y-x]1-y for various x and y

Low frequency Raman spectra of glasses of the types (BaO)_x·(B₂O₃)_1−x and (BaCl₂)_y·[(BaO)_x·(B₂O₃)₁-_y-_x]₁-_y have been reported. The temperature reduced Raman spectra show peaks at 67, 116 and 140 cm⁻¹ for the binary glass. The bands at 116 and 140 cm⁻¹ are ascribed to the librational motions of the borate groups and the 67 cm⁻¹ band arises because of the limited structural correlation range (SCR) of the glass network, causing a maximum of the frequency dependent Raman coupling coefficient. Due to addition of BaO in v-B₂O₃, the oxygen are mostly incorporated in the formation of BO₄ units; however large Ba²⁺ ions also enhance the number of non-bridging oxygen at higher concentrations of dopant. These barium ions as well as chlorine ions are accomodated in the interstitial vacancies of the glass network which leads to an expansion of the network structure.     

M/(MgO)y(CeO2)1－y(M=Ni、Co、Cu)催化剂的催化甲烷燃烧性能

采用溶胶凝胶法制备了M/(MgO)_y(CeO2)_1－y(M=Ni、Co、Cu)催化剂. 研究了催化剂Ni/(MgO)y(CeO₂)_1－y催化活性与Ce含量的关系, 当y＝0.9时, 催化剂的活性和稳定性最好. 对比研究了(MgO)_0.9(CeO2)_0.1为载体, 负载Ni、Co、Cu活性组分的催化剂催化甲烷燃烧性能. 结果表明, 负载Cu的催化剂活性最好, 但二次评价后催化剂已烧结；负载Ni的催化剂活性与负载Cu的催化剂相差不大, 且稳定性最好, 经1000 ℃焙烧的Ni/(MgO)_0.9(CeO2)_0.1催化剂比表面仍有14.32 m₂•g^－1, 具有较高的催化活性和很好的热稳定性；负载Co的催化剂活性不如前两者, 稳定性居中, 但比表面降低得最少, 抗烧结能力强.     

Preliminary studies in the electrodeposition of PbSe/PbTe superlattice thin films via electrochemical atomic layer deposition (ALD)

This paper concerns the electrochemical growth of compound semiconductor thin film superlattice structures using electrochemical atomic layer deposition (ALD). Electrochemical ALD is the electrochemical analogue of atomic layer epitaxy (ALE) and ALD, methods based on nanofilm formation an atomic layer at a time, using surface-limited reactions. Underpotential deposition (UPD) is a type of electrochemical surfaced-limited reaction used in the present studies for the formation of PbSe/PbTe superlattices via electrochemical ALD. PbSe/PbTe thin-film superlattices with modulation wavelengths (periods) of 4.2 and 7.0 nm are reported here. These films were characterized using electron probe microanalysis, X- ray diffraction, atomic force microscopy (AFM), and infrared reflection absorption measurements. The 4.2 nm period superlattice was grown after deposition of 10 PbSe cycles, as a prelayer, resulting in an overall composition of PbSe0.52Te0.48. The 7.0 nm period superlattice was grown after deposition of 100 PbTe cycle prelayer, resulting for an overall composition of PbSe0.44Te0.56. The primary Bragg diffraction peak position, 2theta, for the 4.2 superlattice was consistent with the average (111) angles for PbSe and PbTe. First-order satellite peaks, as well as a second, were observed, indicating a high-quality superlattice film. For the 7.0 nm superlattice, Bragg peaks for both the (200) and (111) planes of the PbSe/PbTe superlattice were observed, with satellite peaks shifted 1 degrees closer to the (111), consistent with the larger period of the superlattice. AFM suggested conformal superlattice growth on the Au on glass substrate. Band gaps for the 4.2 and 7.0 nm period superlattices were measured as 0.48 and 0.38 eV, respectively.     

Design of energy band alignment at the Zn(1-x)Mg(x)O/Cu(In,Ga)Se2 interface for Cd-free Cu(In,Ga)Se2 solar cells

The electronic band structure at the Zn(1-x)Mg(x)O/Cu(In(0.7)Ga(0.3))Se(2) interface was investigated for its potential application in Cd-free Cu(In,Ga)Se(2) thin film solar cells. Zn(1-x)Mg(x)O thin films with various Mg contents were grown by atomic layer deposition on Cu(In(0.7)Ga(0.3))Se(2) absorbers, which were deposited by the co-evaporation of Cu, In, Ga, and Se elemental sources. The electron emissions from the valence band and core levels were measured by a depth profile technique using X-ray and ultraviolet photoelectron spectroscopy. The valence band maximum positions are around 3.17 eV for both Zn(0.9)Mg(0.1)O and Zn(0.8)Mg(0.2)O films, while the valence band maximum value for CIGS is 0.48 eV. As a result, the valence band offset value between the bulk Zn(1-x)Mg(x)O (x = 0.1 and x = 0.2) region and the bulk CIGS region was 2.69 eV. The valence band offset value at the Zn(1-x)Mg(x)O/CIGS interface was found to be 2.55 eV after considering a small band bending in the interface region. The bandgap energy of Zn(1-x)Mg(x)O films increased from 3.25 to 3.76 eV as the Mg content increased from 0% to 25%. The combination of the valence band offset values and the bandgap energy of Zn(1-x)Mg(x)O films results in the flat (0 eV) and cliff (-0.23 eV) conduction band alignments at the Zn(0.8)Mg(0.2)O/Cu(In(0.7)Ga(0.3))Se(2) and Zn(0.9)Mg(0.1)O/Cu(In(0.7)Ga(0.3))Se(2) interfaces, respectively. The experimental results suggest that the bandgap energy of Zn(1-x)Mg(x)O films is the main factor that determines the conduction band offset at the Zn(1-x)Mg(x)O/Cu(In(0.7)Ga(0.3))Se(2) interface. Based on these results, we conclude that a Zn(1-x)Mg(x)O film with a relatively high bandgap energy is necessary to create a suitable conduction band offset at the Zn(1-x)Mg(x)O/CIGS interface to obtain a robust heterojunction. Also, ALD Zn(1-x)Mg(x)O films can be considered as a promising alternative buffer material to replace the toxic CdS for environmental safety.     

Flow injection for the determination of Se(IV) and Se(VI) by hydride generation atomic absorption spectrometry with microwave oven on-line prereduction of Se(VI) to Se(IV)

An on-line flow injection system has been developed for the selective determination of Se(IV) and Se(VI) in citric fruit juices and geothermal waters by hydride generation atomic absorption spectrometry with microwave-aided heating prereduction of Se(VI) to Se(IV). The samples and the prereductant solutions (4 mol l⁻¹ HCl for Se(IV) and 12 mol l⁻¹ HCl for Se(VI)) which circulated in a closed-flow circuit were injected by means of a time-based injector. This mixture was displaced by a carrier solution of 1% v/v of hydrochloric acid through a PTFE coil located inside the focused microwave oven and mixed downstream with a borohydride solution to generate the hydride. The linear ranges were 0–120 and 0–100 μg l⁻¹ of Se(IV) and Se(VI), respectively. The detection limits were 1.0 μg l⁻¹ for Se(IV) and 1.5 μg l⁻¹ for Se(VI). The precision (about 2.0–2.5% RSD) and recoveries (96–98% for Se(IV) and 94–98% for Se(VI)) were good. Total selenium values were also obtained by electrothermal atomic absorption spectrometry which agreed with the content of both selenium species. The sample throughput was about 50 measurements per hour. The main advantage of the method is that the selective determination of Se(IV) and Se(VI) in citric fruit juices and geothermal waters is performed in a closed system with a minimum sample manipulation, exposure to the environment, minimum sample waste and operator attention.     

Preparation and Characterization of High Purity Al（2-x）Mg（x＋y）Ti（1-y）O（5-0.5x-y） Solid Solution

A small amount of mineralizer MgO was added into Al2TiO5 synthesized from the sludge of aluminum factory to form Al（2-x）Mg（x＋y）Ti（1-y）O（5-0.5x-y） solid solution and inhibit the decomposition of Al2TiO5 solid solution. It increased the content of Al2TiO5 solid solution and improved the thermal stability of materials. In this work,XRD and SEM methods were adopted to characterize the crystalline structure and microstructure of each kind of sample. Rietveld Quantification method was used to determine the content of crystalline phases in each sample. Results show as follows： the optimal addition concentration of MgO was 2.0%,and the corresponding content of Al2TiO5 solid solution which displayed irregular bulk shape was 100%; the addition of mineralizer MgO could enhance the flexural strength and thermal stability of Al2TiO5 solid solution materials. The optimal addition concentration of MgO determined by performance analysis was 2.0%,and its corresponding retention rate of thermal-shock flexural strength was 86.4%. Structure analysis and performance analysis resulted in good accordance.     

微波反应合成纳米Ba1-xZnxTi1-ySnyO3介电材料及其结构、性能研究

采用微波反应技术,合成了一系列Ba1-xZnxTi1-ySnyO3固溶体纳米粉末（0≤ x≤0.3,0≤y≤0.5),XRD物相分析和d间距一组成图证明,产品为立方晶系的完全 互溶取代固溶体,结果符合Vegard定律。TEM形貌观察,粒子为均匀球形,平均粒 径40nm。通过制陶实验,分别测定了该系列固溶体的室温介电常数、介电损失以及 介电常数随温度的变化,结果发现,采用化学方法在BaTiO3中掺入适量锌和锡,由 于掺杂离子均匀进入母体晶格,引起tc降低,室温介电常数达12000以上,介电损 耗仅为0.007。纳米粉体的烧结温度为1150℃,比传统微米级粉体的烧结温度降低 200－250℃。     

Sequential determination of Se(IV) and Se(VI) by flow injection-hydride generation-atomic absorption spectrometry with HCl/HBr microwave aided pre-reduction of Se(VI) to Se(IV)

In this study a flow injection (FI) system used in conjunction with hydride generation (HG), atomic absorption spectrometry (AAS) and microwave (MW) aided pre-reduction of selenite (Se(IV)) to selenate (Se(IV)) with HCl:HBr has been developed in order to differentiate both inorganic selenium species. As full control of the MW reduction step is possible, the experimental approach allows the use of milder acidic conditions (10% v/v of HCl and HBr) than those conventionally accomplished with hydrochloric acid alone (≥50% v/v). Experimental parameters were optimized by the univariate optimization method. In either case, the linear range was from 1.0 to 30 μg l⁻¹. The detection limits based on 3σ of the blank signal were 0.25 μg l⁻¹ for Se(IV) and 0.30 μg l⁻¹ for Se(VI). The reproducibility, about 3% RSD and recoveries of different amounts of Se(VI) and Se(IV) added to water and orange juice samples (97–103%) were good. The main advantage of the proposed method is that the sequential determination of Se(IV) and Se(VI) is performed at a high sampling frequency (ca. 50 samples per h) in a closed system without Se losses, and with a minimum sample waste, operator attention, and sample manipulation.     

J(77Se,1H) and J(77Se,13C) couplings of seleno‐carbohydrates obtained by 77Se satellite 1D 13C spectroscopy and 77Se selective HR‐HMBC spectroscopy

Seleno‐carbohydrates are those in which the oxygen of the glycosidic bond or the hydroxyl group is artificially replaced with selenium. This substitution changes ¹H and ¹³C chemical shifts and produces spin coupling constants involving ⁷⁷Se. Coupling constants, such as ^2‐3J(⁷⁷Se, ¹H), are likely to be useful for conformational analyses of glycans because such couplings are never observed in natural glycans. Several papers have discussed the relationship between ^2‐3J(⁷⁷Se, ¹H) and conformation; however, only few reports describe ^1‐3J(⁷⁷Se, ¹³C), which could also be useful. Here, we obtain ⁷⁷Se coupling constants of seleno‐carbohydrates from ⁷⁷Se‐selective HR‐HMBC and ⁷⁷Se satellites in 1D ¹³C spectra and examine their conformations using the Newman projection scheme.     

Influence of a nano phase segregation on the thermoelectric properties of the p-type doped stannite compound Cu(2+x)Zn(1-x)GeSe4

Engineering nanostructure in bulk thermoelectric materials has recently been established as an effective approach to scatter phonons, reducing the phonon mean free path, without simultaneously decreasing the electron mean free path for an improvement of the performance of thermoelectric materials. Herein the synthesis, phase stability, and thermoelectric properties of the solid solutions Cu(2+x)Zn(1-x)GeSe(4) (x = 0-0.1) are reported. The substitution of Zn(2+) with Cu(+) introduces holes as charge carriers in the system and results in an enhancement of the thermoelectric efficiency. Nano-sized impurities formed via phase segregation at higher dopant contents have been identified and are located at the grain boundaries of the material. The impurities lead to enhanced phonon scattering, a significant reduction in lattice thermal conductivity, and therefore an increase in the thermoelectric figure of merit in these materials. This study also reveals the existence of an insulator-to-metal transition at 450 K.     

Optimization of the reduction of Se(VI) to Se(IV) in a microwave oven

 Parameters for the reduction of Se(VI) to Se(IV) in HCl medium by heating in a microwave oven have been optimized. The reduction resulted to be quantitative applying 100% power, corresponding to 600 W heating for 2 min in 6 mol/L or for 3 min in 4 mol/L HCl. The behavior of selenomethionine and selenocystine under the optimized reduction conditions was studied in order to evaluate a possible interference of these selenium species in the determination of Se(VI). The final determination of Se(IV), and Se(VI) were done by hydride generation-atomic absorption spectrometry. The analytical merits of the method are reported. The method was applied to the selective determination of Se(IV), and Se(VI) in spiked river and lake water. Received: 6 December 1996/Revised: 1 April 1997/Accepted: 3 April 1997     

Relationship between the electrochemical behavior and Li arrangement in Li(x)M(y)Mn(2-y)O4 (M = Co, Cr) with spinel structure

The relationship between the electrochemical behavior and the arrangement of lithium/vacancies has been investigated with electrochemical Li removal in Li(x)M(y)Mn(2-y)O4 (x < or = 1.0, 0.0 < or = y < or = 0.3, M = Co, Cr). It was shown that the electrochemical removal proceeds via two voltage regions: (1) approximately 3.9 V at x > or = approximately 0.5 and (2) approximately 4.2 V at x < or = approximately 0.5. To understand the stepwise behavior, entropy measurement of reaction, DeltaS(obs), was performed by using the electrochemical methods. The changes of the sign in deltaS(obs) from negative to positive at the composition x approximately 0.50 in Li(x)M(y)Mn(2-y)O4 indicated that the ordered arrangement of Li/vacancies was formed with electrochemical Li removal. Moreover, such an ordering was suppressed by the substitution of Co3+ and Cr3+ for Mn3+. To clarify the nature and origin of Li/vacancy ordering, the Monte Carlo simulation was performed in view of Coulombic interaction. The simulation reproduced the formation of a new phase arising from Li/vacancy ordering at x = 0.50 in Li(x)Mn2O4. In addition, the ordered arrangement of Li/vacancy at x = 0.5 was perturbed by the trivalent M3+ replacement in spinel structure due to the local clustering of Li+ around M3+. Consequently, the electrochemical behavior in spinel LiMn2O4 was deeply related to the Coulombic interactions, proved by the fact that experimentally observed changes in entropy agreed well with Monte Carlo simulation based on the Coulombic interaction.     

1H, 13C and 77Se NMR study of tetraselenafulvalene derivatives supported by novel H(Se)C and H(C)Se triple-resonance experiments at natural abundance

A series of substituted tetraselenafulvalenes (TSeFs) was studied in solution using 1H, 13C and 77Se NMR spectroscopy. Chemical shifts and heteronuclear coupling constant values were determined and assigned. Novel two-dimensional H(Se)C and H(C)Se triple-resonance correlation experiments were applied at natural abundance in order to accomplish 13C and 77Se signal assignments. Using this approach, all the signals were unambiguously assigned and atom connectivity was established in the studied TSeF derivatives. These experiments, allowing signal assignments of quaternary carbons, may find wide application in the study of substituted TSeF and other organoselenium compounds. To the best of our knowledge, triple-resonance experiments with proton detection have been applied to organoselenium compounds for the first time.     

Influence of vacancy ordering on the percolative behavior of (Li(1)(-x)Na(x))(3y)La(2/3-y)TiO(3) perovskites

Influence of the vacancy concentration on the Li conductivity of the (Li(1-x)Na(x))(0.2)La(0.6)TiO(3) and (Li(1-x)Na(x)(0.5)La(0.5)TiO(3) perovskite series, with 0 < or = x < 1, has been investigated by neutron diffraction (ND), impedance spectroscopy (IS), nuclear magnetic resonance (NMR), and Monte Carlo simulations. In both series, Li(+) ions occupy unit cell faces, but Na(+) ions are located at A sites of the perovskite. From this fact, the amount of vacant A sites that participate in Li conductivity is given by the expression n(v) = [Li] + square, where square is the nominal vacancy concentration. Substitution of Li by Na decreases the amount of vacancies, reducing drastically the Li conductivity when n(v) approaches the percolation threshold of the perovskite conduction network. In disordered (Li(1-x)Na(x))(0.5)La(0.5)TiO(3) perovskites, the percolation threshold is 0.31; however, in ordered (Li(1-x)Na(x))(0.2)La(0.6)TiO(3) perovskites, this parameter changes to 0.26. Near the percolation threshold, the amount of mobile Li species deduced by (7)Li NMR spectroscopy is lower than that derived from structural formulas but higher than deduced from dc conductivity measurements. Conductivity values have been explained by Monte Carlo simulations, which assume a random walk for Li ions in the conduction network of the perovskite. In these simulations, distribution of vacancies conforms to structural models deduced from ND experiments.