Preparation and characterization of Ag2ZnSn(S,Se)4 and its application in improvement of power conversion efficiency of Cu2ZnSn(S,Se)4-based solar cells

We fabricated high-quality n-type Ag₂ZnSnSe₄ (AZTSe) film with kesterite structure by using a simple solution method. A Cu₂ZnSnSe₄ (CZTSe)/AZTSe-based solar cell was designed and prepared by inserting AZTSe layer between CZTSe and CdS of the traditional CZTSe-based solar cell. Compared with the traditional device, an increase from 337 to 432 mV in open circuit voltage (V_oc) and an accompanying rise from 3.40% to 4.72% in power conversion efficiency (PCE) were observed. To well understand the PCE improvement of the CZTSe/AZTSe-based solar cells, we calculated the band alignments of CZTSe/AZTSe and CZTSe/CdS heterojunctions using first-principles calculations, demonstrating that the CZTSe/AZTSe and CZTSe/CdS interfaces have type-II and type-I band alignments, respectively. Moreover, the band offset of AZTSe/CdS is lager than the one of CZTSe/CdS. Combined with the calculation results, the mechanism of influence of the AZTSe on the PCE improvement is discussed in detail. Our conclusions show that the addition of the AZTSe layer is a potentially applicable method to obtain CZTSe-based solar cells with higher V_oc and PCE.     

CZTSe solar cells prepared by electrodeposition of Cu/Sn/Zn stack layer followed by selenization at low Se pressure

Cu₂ZnSnSe₄ (CZTSe) thin films are prepared by the electrodeposition of stack copper/tin/zinc (Cu/Sn/Zn) precursors, followed by selenization with a tin source at a substrate temperature of 530°C. Three selenization processes were performed herein to study the effects of the source of tin on the quality of CZTSe thin films that are formed at low Se pressure. Much elemental Sn is lost from CZTSe thin films during selenization without a source of tin. The loss of Sn from CZTSe thin films in selenization was suppressed herein using a tin source at 400°C (A2) or 530°C (A3). A copper-poor and zinc-rich CZTSe absorber layer with Cu/Sn, Zn/Sn, Cu/(Zn + Sn), and Zn/(Cu + Zn + Sn) with metallic element ratios of 1.86, 1.24, 0.83, and 0.3, respectively, was obtained in a selenization with a tin source at 530°C. The crystallized CZTSe thin film exhibited an increasingly (112)-preferred orientation at higher tin selenide (SnSe _x ) partial pressure. The lack of any obvious Mo-Se phase-related diffraction peaks in the X-ray diffraction (XRD) diffraction patterns may have arisen from the low Se pressure in the selenization processes. The scanning electron microscope (SEM) images reveal a compact surface morphology and a moderate grain size. CZTSe solar cells with an efficiency of 4.81% were produced by the low-cost fabrication process that is elucidated herein.     

Cu2ZnSnSe4 nanocrystals capped with S2? by ligand exchange: utilizing energy level alignment for efficiently reducing carrier rec ombination

In this work, we employed a convenient one-step synthesis method for synthesizing Cu₂ZnSnSe₄ (CZTSe) nanocrystals (NCs) in an excess selenium environment. This excess selenium situation enhanced the reaction of metal acetylacetonates with selenium, resulting in the burst nucleation of NCs at relatively low temperatures. The phase morphology and surface and optoelectronic properties of NCs before and after ligand exchange were discussed in depth. It was found that pure tetragonal-phase structure CZTSe NCs with approximately 1.7-eV bandgap could be synthesized. The removal of large organic molecules on CZTSe NCs after ligand exchange by S²⁻ decreased the resistivity. The bandgap of the films after ligand exchange by 550°C selenization was also decreased due to better crystallinity. For potential application in CZTSe solar cells, we constructed an energy level diagram to explain the mutual effect between the absorption layer and CdS layer. Using cyclic voltammetry (CV) measurement, we found that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of CZTSe films shifted down after ligand exchange. After energy level alignment at the CdS/CZTSe interface, a type I band alignment structure was more conveniently formed after ligand exchange. This structure acted as the barrier against injection electrons from ZnO to the CZTSe layer, and recombination would subsequently be depressed.     

太阳能薄膜铜锌锡硒纳米晶的制备与表征

以金属氯化物(氯化铜、氯化锌、氯化锡)为金属源,二氧化硒为前驱体,乙二醇为溶剂,在不同表面活性剂(PVP、聚氧乙烯月桂醚、聚乙二醇1 000、聚山梨酯80)和不同工艺(制备时间和制备温度)的条件下,采用溶剂热法一步合成六角片状的CZTSe纳米晶体颗粒,并采用X射线衍射仪、紫外可见分光光度计与SEM等手段对CZTSe纳米颗粒的物相、性能、形貌进行表征。实验结果表明,通过加入表面活性剂PVP并控制温度(200 ℃)和合成时间(30 h)可以取得禁带宽度约为1.5 eV、分布均匀、结构为六方片的晶粒,其与太阳能电池所需的最佳禁带宽度相近,有望在新一代太阳能电池中得到应用和推广。     

Studies in Lithium Oxide Systems: XI, Li2O–B2O3–P2O5

The glassforming region in the system was roughly outlined and liquidus data were obtained for the three joins LiPO₃-BPO₄, Li₄P₂O₇-BPO₄, and Li₃PO₄-Li₂B₄O₇. Compatibility relations for the ternary subsystems Li₄P₂O₇-BPO₄-P₂O₅ and Li₂O-Li₃PO₄-Li₂B₈O₁₃ were established. Two ternary compounds with the probable compositions 22Li₂O - 11B₂O₃ - 13P₂O₅ and 2Li₂O 3B₂O₃ P₂O₅ were detected.     

Pore Structure Evolution of Lanthana–Alumina Systems Prepared through Coprecipitation

Pure Al₂O₃ and different compositions of La₂O₃–Al₂O₃ samples have been prepared through coprecipitation. Even after heating at 1300°C, the compositions La₂O₃·11Al₂O₃ and La₂O₃·13Al₂O₃ had higher surface area compared to the pure Al₂O₃ and the La₂O₃·Al₂O₃ composition. Ethanol washing is an effective way for improving the textural stability of pure Al₂O₃ and La₂O₃–Al₂O₃ samples. The effect of steam on the thermal stability of La₂O₃·11Al₂O₃ has also been studied. La₂O₃·11Al₂O₃ sample is found to be stable in steam.     

Upconversion Luminescence in Er3+ Doped and Yb3+/Er3+ Codoped Yttria Nanocrystalline Powders

Y_1.9Er_0.1O₃ and Y_1.7Yb_0.2Er_0.1O₃ nanocrystalline powders were prepared via a reverse-strike coprecipitation method using nitrates and ammonia as raw materials. The obtained powders were of cubic-phase structure of Y₂O₃ and the particle size was in the range of ∼60–80 nm. Strong red (⁴F_9/2–⁴I_15/2) and green (²H_11/2/⁴S_3/2–⁴I_15/2) upconversion luminescence were observed in all the samples when excited with a 980-nm continuous wave diode laser. The possible upconversion mechanisms in Y_1.9Er_0.1O₃ and Y_1.7Yb_0.2Er_0.1O₃ were discussed. Power studies indicated that two-photon processes are responsible for the green and red upconversion luminescence in these systems. The codoping of Yb³⁺ greatly enhanced the red (⁴F_9/2–⁴I_15/2) upconversion emission.     

High-Temperature Active Oxidation of Chemically Vapor-Deposited Silicon Carbide in CO─CO2 Atmosphere

Active oxidation behavior of CVD-SiC in CO─CO₂ atmospheres was investigated using a thermogravimetric technique in the temperature range between 1823 and 1923 K. The gas pressure ratio, P _CO2/ P _CO, was controlled between 10⁻⁴ and 10⁻¹ at 0.1 MPa. Active oxidation rates (mass loss rates) showed maxima at a certain value of P _CO2/ P _CO, ( P _CO2/ P _CO )^*, In a P _CO2/ P _CO region lower than the ( P _CO2/ P _CO)^* a carbon layer was formed on the SiC surface. In a P _CO2/ P _CO region higher than the ( P _CO2/ P _CO)^*, silica particles or a porous silica layer was observed on the SiC surface.     

Effect of Additives on the Electromechanical Properties of Pb(Zr,Ti)O3–Pb(Y2/3W1/3)O3 Ceramics

Dielectric and piezoelectric properties of 0.02Pb(Y_2/3W_1/3)O₃ 0.98Pb(Zr0.52Ti0.48)O3 ceramics doped with additives (Nb₂O₅, La₂O₃, MnO₂, and Fe₂O₃) were investigated. The grain sizes of these ceramics decreased with increasing amounts of additives. For additions of MnO₂ and Fe₂O₃, dielectric losses decreased, while for Nb₂O₅ and La₂O₃, these values increased. The maximum values of the mechanical quality factor Q_m were found to be 956 and 975 for additions of 0.9 wt% Fe₂O₃ and 0.7 wt% MnO₂, respectively, but donor dopants (Nb₂O₅ and La₂O₃) did not change the values of Q_m . On the other hand, the piezoelectric constant d₃₃ and the electromechanical coupling factor k_p decreased with additions of MnO₂ and Fe₂O₃, but improved with additions of Nb₂O₅ and La₂O₃.     

Crystal Structure and Microwave dielectric Properties of Ba(Zn1/3Ta2/3)O3–(Sr,Ba)(Ga1/2Ta1/2)O3 Ceramics

The microwave dielectric properties and crystal structure of Ba(Zn_1/3Ta_2/3)O₃– (Sr,Ba)(Ga_1/2Ta_1/2)O₃ ceramics were investigated in the present study. The Q value of Ba(Zn_1/3Ta_2/3)O₃ was improved by adding 5 mol% Sr(Ga_1/2Ta_1/2)O₃. The maximum Q value of Q × f = 162000 GHz was obtained at 0.95Ba(Zn_1/3Ta_2/3)O₃. 0.05Sr(Ga_1/2Ta_1/2)O₃. For this composition, a lattice super structure caused by hexagonal ordering was observed. A further improvement in the Q value was attained when some Sr was replaced with Ba, and 0.95Ba(Zn_1/3Ta_2/3)O₃· 0.05(Sr_0.25Ba_0.75)(Ga_1/2Ta_1/2)O₃ exhibited a maximum Q value such that Q × f = 210000 GHz. Despite the increased Q value with the replacement of Sr by Ba, the c/a value, which indicates the degree of lattice distortion, remained constant near 3/2. The Q value thus improved without lattice distortion in the system Ba(Zn_1/3Ta_2/3)O₃-(Sr,Ba)(Ga_1/2Ta_1/2)O₃, whereas the improvement of Q value increased with lattice distortion in the solid solution system with Ba(Zn_1/3Ta_2/3)O₃ as an end member.     

Crystalline Phases and YAG Laser-Induced Crystallization in Sm2O3–Bi2O3–B2O3 Glasses

The glass formation region, crystalline phases, second harmonic (SH) generation, and Nd:yttrium aluminum garnet (YAG) laser-induced crystallization in the Sm₂O₃–Bi₂O₃–B₂O₃ system were clarified. The crystalline phases of Bi₄B₂O₉, Bi₃B₅O₁₂, BiBO₃, Sm _x Bi_{1− x} BO₃, and SmB₃O₆ were formed through the usual crystallization in an electric furnace. The crystallized glasses consisting of BiBO₃ and Sm _x Bi_{1− x} BO₃ showed SH generations. The formation of the nonlinear optical BiB₃O₆ phase was not confirmed. The formation (writing) region of crystal lines consisting of Sm _x Bi_{1− x} BO₃ by YAG laser irradiation was determined, in which Sm₂O₃ contents were∼10 mol%. The present study demonstrates that Sm₂O₃–Bi₂O₃–B₂O₃ glasses are promising materials for optical functional applications.     

Energy Transfer and Population Inversion in Heavy Metal Oxide Glasses Doped with Tm3+ and Tb3+

Emission properties and energy transfer of PbO–Bi₂O₃–Ga₂O₃–GeO₂ glasses codoped with Tm³⁺ and Tb³⁺ ions were investigated. The 1.48-μm emission due to the Tm³⁺:³H₄→³F₄ transition can be used to amplify the S-band (1460–1530-nm) signal light. With Tb³⁺ addition, the lifetime and emission intensity of the Tm³⁺:³F₄ level decreased sharply via the Tm³⁺:³F₄→Tb³⁺:⁷F_0,1,2 energy transfer. Population densities of the ³F₄ and ³H₄ levels in Tm³⁺ calculated from rate equations clearly verified that population inversion in Tm³⁺ ions became possible with as little as 0.1 mol% of Tb³⁺ addition.     

Phase Equilibria in the TiO2-Rich Region of the System BaO-TiO2

Phase relations in the system BaO-TiO₂ from 67 to 100 mol% TiO₂ were investigated at 1200° to 1450°C in O₂. Data were obtained by microstructural, X-ray, and thermal analyses. The existence of the stable compounds Ba₆Ti₁₇O₄₀, Ba₄Ti₁₃O₃₀, BaTi₄O₉, and Ba₂Ti₉O₂₀ was confirmed. The compound BaTi₂O₅ is unstable and either forms as a reaction intermediate below the solidus or crystallizes from the melt. The compounds Ba₆Ti₁₇O₄₀ and Ba₄Ti₁₃O₃₀ decompose in peritectic reactions, and BaTiO₃ and Ba₆Ti₁₇O₄₀ react to form a eutectic. Special conditions are required for the formation of Ba₂Ti₉O₂₀, which decomposes in a peritectoid reaction at 1420°C. The new phase diagram is presented.     

Effect of Praseodymium on Superconductivity and Magnetism in Y1–xPrxBa2Cu4O8 Prepared by Nitrite Pyrolysis Method

X-ray diffraction patterns show that most samples of Y_1-x Pr_xBa₂Cu₄O₈ examined in the present study contained a single YBa₂ Cu₄O₈ (1-2-4) superconductive phase for x<0.7.Lattice parameters a and b increased with Pr concentration, suggesting that most of the Pr is trivalent in Y_1-x Pr_x-Ba₂Cu₄O₈. The zero-resistance temperature, T _co, decreases monotonically from 80 K at x=0 to 12 K at x=0.65, and superconducting transition widths tend to broaden for x>0. The room-temperature resistivity changes linearly until x=0.7 and increases abruptly at x=-0.75. The critical concentration, x_cr, thus was estimated to be 0.7. The effective magnetic moments of Pr in Y _1-x Pr_xBa₂Cu₄O₈ were 3.63., 3.35, and 3.23, μ_B for x=0.2, 0.4 and 0.6, respectively. In the R_0.8 Pr_0.2Ba₂Cu₄O₈ system, the depression of T_c weakly depends on the ionic radius of rare-earth elements. Similarities and differences between Y _1-x Pr_xBa₂Cu₄O₈ and Y_1-xPr_x-Ba₂Cu₃O_7-y also were noted and are discussed in this paper.     

Energetics of Defect Fluorite and Pyrochlore Phases in Lanthanum and Gadolinium Hafnates

Aerodynamic levitation combined with laser heating was used to prepare melts in the HfO₂–La₂O₃ (–Gd₂O₃) systems. All melts crystallized upon quenching in oxygen. Hf₂La₂O₇ pyrochlore and Gd_0.5Hf_0.5O_1.75 fluorite phases were identified. Gd_0.5Hf_0.5O_1.75 fluorite was transformed into the pyrochlore structure by annealing at 1450°C. Pyrochlore that crystallized from HfO₂- La₂O₃ melts contained 31.6–34.2 mol% La₂O₃. The unit cell parameter increased linearly with La content from 10.736 to 10.789 Å. Drop solution calorimetric experiments were performed in 3Na₂O·4MoO₃ melt at 702°C. The enthalpies of formation from the oxides for pyrochlore phases are −107.0±5.0 kJ/mol for Hf₂La₂O₇ and −48.8±4.7 kJ/mol for Hf₂Gd₂O₇. The enthalpy of the pyrochlore–fluorite phase transition in Hf₂Gd₂O₇ is 23.6±3.1 kJ/mol.     

New MAX-Phase Compounds in the V–Cr–Al–C System

New layered compounds, (V_0.5Cr_0.5)₃AlC₂, (V_0.5Cr_0.5)₄AlC₃, and (V_0.5Cr_0.5)₅Al₂C₃ were synthesized by reactive hot pressing V, Cr, Al, and graphite powders. The crystal structures of these new phases were determined using a combination of X-ray diffraction and scanning transmission electron microscopy. (V_0.5Cr_0.5)₃AlC₂ is isotypical to Ti₃AlC₂; while (V_0.5Cr_0.5)₄AlC₃ has the Ti₄AlN₃ or α-Ta₄AlC₃-type crystal structure. (V_0.5Cr_0.5)₅Al₂C₃ is formed by periodically stacking of half-unit cells of (V_0.5Cr_0.5)₂AlC and (V_0.5Cr_0.5)₃AlC₂.     

Influence of SO3 on the Phase Relationship in the System CaO–SiO2–Al2O3–Fe2O3

The influence of the additive SO₃ on the phase relationships in the quaternary system CaO-SiO₂-Al₂O₃-Fe₂O₃ was investigated by observing the change of volume ratio of 3CaOSiO₂ (C₃S) to 2CaOSiO₂ (C₂S) + CaO (C) in the sintered material with the increase of SO₃ content. The primary phase volume of C₃S in the quaternary phase diagram shrank with the increase of SO₃ and disappeared when the SO₃ content exceeded 2.6 wt% in the sintered material. Changes in the peritectic reaction relationship between CaO (C), 2CaOSiO₂ (C₂S), 3CaOSiO₂ (C₃S), 3CaOAl₂O₃ (C₃A), 4CaOAl₂O₃Fe₂O₃ (C₄AF), and liquid were also observed and discussed.     

Diffuse Ferroelectric Phase Transition and Relaxor Behaviors in Ba-Based Bismuth Layer-Structured Compounds and La-Substituted SrBi4Ti4O15

The dielectric characteristics of BaBi₂Nb₂O₉, BaBi₄Ti₄O₁₅, BaBi₈Ti₇O₂₇, and La-substituted SrBi₄Ti₄O₄ were investigated to discuss their ferroelectric phase transition and relaxor behaviors. BaBi₂Nb₂O₉ showed typical relaxor behaviors, and a shift of T _m with increasing frequency was observed in BaBi₄Ti₄O₁₅ and SrBi_{4− x} La _x Ti₄O₁₅ ( x =0.8, 1.0) but they underwent a real paraelectric–ferroelectric phase transition on zero-field cooling, while BaBi₈Ti₇O₂₇ showed a normal ferroelectric nature. The reduced concentration and weakened coupling of the dipoles related to A-site bismuth are believed to be responsible for the appearance of short-range electric ordering and the relaxor behaviors in these bismuth layer-structured compounds.     

Glass-Ceramic Formation in the ZnO-P2O5 System and the Effect of Silica as a Nucleating Agent

Crystallization of a series of ZnO-P₂O₅ based glasses was investigated. ZnO-P₂O₅-CaO glasses could be converted most readily to glass-ceramics and crystallization of these led to formation of alpha-Zn₂P₂O₇, alpha-CaZn₂(PO₄)₂, and ß-CaZn₂(PO₄)₂ phases. A further phase has been tentatively identified as monoclinic (Zn,Ca)₂P₂O₇. The most promising glass-ceramic composition Z15 (59.4ZnO·33P₂O₅·6.6CaO·1SiO₂) crystallized to alpha-Zn₂P₂O₇ and ß-CaZn₂(PO₄)₂, the latter phase being stabilized by the presence of SiO₂ which also encouraged volume nucleation giving a fine-scale (submicrometer) microstructure.     

Phase Relations in the System Bi2O3-WO3

Phase relations in the system Bi₂O₃-WO₃ were studied from 500° to 1100°C. Four intermediate phases, 7Bi₂O₃· WO₃, 7Bi₂O₃· 2WO₃, Bi₂O₃· WO₃, and Bi₂O₃· 2WO₃, were found. The 7B₂O · WO₃ phase is tetragonal with a ₀= 5.52 Å and c ₀= 17.39 Å and transforms to the fcc structure at 784°C; 7Bi₂O₃· 2WO₃ has the fcc structure and forms an extensive range of solid solutions in the system. Both Bi₂O₃· WO₃ and Bi₂O₃· 2WO₃ are orthorhombic with (in Å) a ₀= 5.45, b ₀=5.46, c ₀= 16.42 and a ₀= 5.42, b ₀= 5.41, c ₀= 23.7, respectively. Two eutectic points and one peritectic exist in the system at, respectively, 905°± 3°C and 64 mol% WO₃, 907°± 3°C and 70 mol% WO₃, and 965°± 5°C and 10 mol% WO₃.