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La3-xTe4 is a very promising high-temperature candidate applied in next-generation Radioisotope Thermoelectric Generators (RTGs). Conventional synthesis of such materials is based on the mechanochemical method, which makes the sample difficult to purify due to the high-energy ball milling. In this report, a novel synthetic method is developed, which utilizes Te-vapor transport and solid-phase diffusion to efficiently produce the RE3-xTe4 phases (RE = La, Ce, Pr, Nd). Notably, this method obviates the requirement for high-energy ball-milling instruments, conventionally indispensable in the mechanochemical syntheses. For as-synthesized La2.74Te4 material, a high figure of merit of 1.5 is achieved at 1073 K, owning to the reduced electronic thermal conductivity with metal impurities well eliminated.
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Flip chip bonding technology on gold-tin (Au-Sn) microbumps for MEMS (Micro Electro Mechanical Systems) and 3D packaging is becoming increasingly important in the electronics industry. The main advantages of Au-Sn microbumps are a low electrical resistance, high electrical reliability, and fine pitch. However, the bonding temperature is relatively high, and the forming mechanism of an intermetallic compound (IMC) is complicated. In this study, Au-Sn solid-state diffusion (SSD) bonding is performed using the thermal gradient bonding (TGB) method, which lowers bonding temperature and gains high bonding strength in a short time. Firstly, Au-Sn microbumps with a low roughness are prepared by using an optimized process. Then, Au-Sn bonding parameters including bonding temperature, bonding time, and bonding pressure are optimized to obtain a higher bonding quality. The shear strength of 23.898 MPa is obtained when bonding in the HCOOH environment for 10 min at the gradient temperature of 150 °C/250 °C with a bonding pressure of more than 10 MPa. The IMC of Au-Sn is found to be Au-Sn and Au5Sn. The effect of annealing time on the IMC is also investigated. More and more Au5Sn is generated with an increase in annealing time, and Au5Sn is formed after Sn is depleted. Finally, the effect of annealing time on the IMC is verified by using finite element simulation, and the bonding strength of IMC was found to be higher when the bonding temperature is 150 °C at the cold side and 250 °C at the hot side. The temperature in the bonding area can reach 200 °C, which proves that the Au-Sn bonding process is solid-state diffusion because the temperature gradient reaches 2500 °C/cm.
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Due to the excellent photonic and electrical properties of metal halide perovskite materials, perovskite light-emitting devices have the potential to replace OLED devices as the next-generation of commercial light-emitting devices. In this article, we controlled the surface morphology of PbBr2 using an in situ dynamic thermal crystallization process, which increased the specific surface area of the films and promoted the solid-state diffusion rate. The CsPbBr3 PeLEDs prepared using this method achieved a maximum current efficiency of 7.1 cd/A at the voltage of 5 V, which was 200% higher than devices prepared using traditional spin-coating processes. These results proved that the in situ thermal dynamic crystallization process effectively improved the film quality of perovskite materials.
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Many minerals and compounds show thermoluminescence (TL) properties but only a few of them can meet the requirements of an ideal dosimeter. Several phosphate materials have been studied for low-dose dosimetryin recent times. Among the various phosphates, ABPO4-type material shows interesting TL properties. In this study, an ABPO4-type (A = Lithium, B=Calcium) phosphor is synthesized using a modified solid-state diffusion method. Temperature is maintained below 800 °C in every step of phosphor preparation to obtain the pure phase of Lithium calcium phosphate (LiCaPO4). The purpose of this work is to synthesize LiCaPO4 using a simple method, examine its structural and luminescence properties in order to gain a deeper understanding of its TL characteristics. The general TL properties, such as TL glow curve, dose linearity, sensitivity, and fading, are investigated. Additionally, this study aims to determine various kinetic parameters through Glow Curve Deconvolution (GCD) method using the Origin Lab software together with the Chen model. XRD analysis confirmed the phase purity of the phosphor with a rhombohedral structure. Lattice parameters, unit cell volume, grain size, dislocated density, and microstrain were also calculated from XRD data. Raman analysis and Fourier Transform Infrared analysis were used to collect information about molecular bonds, vibrations, identity, and structure of the phosphor. To investigate TL properties and associated kinetic parameters, the phosphor was irradiated with 6.0 MV (photon energy) and 6.0 MeV (electron energy) from a linear accelerator for doses ranging from 0.5 Gy to 6.0 Gy. For both photon and electron energy, TL glow curves have two identical peaks near 200 °C and 240 °C.The TL glow curves for 0.5 Gy-6 Gy are deconvoluted, then fitted with the appropriate model and then calculated the kinetic parameters. Kinetic parameters such as geometric factor (µg), order of kinetics, activation energy (E), and frequency factor (s) are obtained from Chen's peak shape method. The dose against the TL intensity curve shows that the response is almost linear in the investigated dose range. For photon and electron energy, the phosphor is found to be the most sensitive at 2.0 Gy and 4.0 Gy, respectively. The phosphor shows a low fading and after 28 days of exposure, it shows a signal loss of better than 3%. The studied TL properties suggest the suitability of LiCaPO4 in radiation dosimetry and associated fields.
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In the present study, a powder of Ti-18Zr-15Nb biomedical alloy with spongy morphology and with more than 95% vol. of ß-Ti was obtained by reducing the constituent oxides with calcium hydride. The influence of the synthesis temperature, the exposure time, and the density of the charge (TiO2 + ZrO2 + Nb2O5 + CaH2) on the mechanism and kinetics of the calcium hydride synthesis of the Ti-18Zr-15Nb ß-alloy was studied. Temperature and exposure time were established as crucial parameters with the help of regression analysis. Moreover, the correlation between the homogeneity of the powder obtained and the lattice microstrain of ß-Ti is shown. As a result, temperatures above 1200 °C and an exposure time longer than 12 h are required to obtain a Ti-18Zr-15Nb powder with a single ß-phase structure and uniformly distributed elements. The analysis of ß-phase growth kinetics revealed that the formation of ß-Ti occurs due to the solid-state diffusion interaction between Ti, Nb, and Zr under the calcium hydride reduction of TiO2 + ZrO2 + Nb2O5, and the spongy morphology of reduced α-Ti is inherited by the ß-phase. Thus, the results obtained provide a promising approach for manufacturing biocompatible porous implants from ß-Ti alloys that are believed to be attractive candidates for biomedical applications. Moreover, the current study develops and deepens the theory and practical aspects of the metallothermic synthesis of metallic materials and can be compelling to specialists in powder metallurgy.
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Diffusion bonding experiments followed by tensile testing were conducted on cylindrical pairs of AA6061-AA1050 aluminum alloys. The influence of bonding time, atmosphere and surface roughness on the resulting interface strength was studied. Metallurgical characterization was performed to study the quality of the bonded interface for different process conditions, and also to investigate the process of oxide formation on the specimen surface. Finite element analysis of the bonding experiments was used to study the thermo-mechanical fields during the bonding process. Using a cohesive zone approach for modelling the bonded interface, the bond strength for the different process parameters was quantified. The results demonstrate that high bond strength can be obtained even for specimens bonded in an air furnace, provided the surface roughness is low. When the surface roughness increases, specimens bonded in air show a reduction in interface strength, which is not observed for specimens bonded in vacuum. Inspection of the bonded interface suggests that this reduction in interface strength can be attributed to oxidation and pockets of air trapped between the asperities of the contact surface, which hinder diffusion and plastic flow.
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Prussian blue analogs (PBAs) featuring large interstitial voids and rigid structures are broadly recognized as promising cathode materials for sodium-ion batteries. Nevertheless, the conventionally prepared PBAs inevitably suffer from inferior crystallinity and lattice defects, leading to low specific capacity, poor rate capability, and unsatisfied long-term stability. As the Na+ migration within PBAs is directly dependent on the periodic lattice arrangement, it is of essential significance to improve the crystallinity of PBAs and hence ensure long-range lattice periodicity. Herein, a chemical inhibition strategy is developed to prepare a highly crystallized Prussian blue (Na2Fe4[Fe(CN)6]3), which displays an outstanding rate performance (78 mAh g-1 at 100 C) and long life-span properties (62% capacity retention after 2000 cycles) in sodium storage. Experimental results and kinetic analyses demonstrate the efficient electron transfer and smooth ion diffusion within the bulk phase of highly crystallized Prussian blue. Moreover, in situ X-ray diffraction and in situ Raman spectroscopy results demonstrate the robust crystalline framework and reversible phase transformation between cubic and rhombohedral within the charge-discharge process. This research provides an innovative way to optimize PBAs for advanced rechargeable batteries from the perspective of crystallinity.
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In organic device applications, a high contact resistance between metal electrodes and organic semiconductors prevents an efficient charge injection and extraction, which fundamentally limits the device performance. Recently, various contact doping methods have been reported as an effective way to resolve the contact resistance problem. However, the contact doping has not been explored extensively in organic field effect transistors (OFETs) due to dopant diffusion problem, which significantly degrades the device stability by damaging the ON/OFF switching performance. Here, the stability of a contact doping method is improved by incorporating "dopant-blockade molecules" in the poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) film in order to suppress the diffusion of the dopant molecules. By carefully selecting the dopant-blockade molecules for effectively blocking the dopant diffusion paths, the ON/OFF ratio of PBTTT OFETs can be maintained over 2 months. This work will maximize the potential of OFETs by employing the contact doping method as a promising route toward resolving the contact resistance problem.
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Detailed understanding of charge diffusion processes in a lithium-ion battery is crucial to enable its systematic improvement. Experimental investigation of diffusion at the interface between active particles and the electrolyte is challenging but warrants investigation as it can introduce resistances that, for example, limit the charge and discharge rates. Here, we show an approach to study diffusion at interfaces using muon spin spectroscopy. By performing measurements on LiFePO4 platelets with different sizes, we determine how diffusion through the LiFePO4 (010) interface differs from that in the center of the particle (i.e., bulk diffusion). We perform ab initio calculations to aid the understanding of the results and show the relevance of our interfacial diffusion measurement to electrochemical performance through cyclic voltammetry measurements. These results indicate that surface engineering can be used to improve the performance of lithium-ion batteries.
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Organic semiconductors (OSCs) have been widely studied due to their merits such as mechanical flexibility, solution processability, and large-area fabrication. However, OSC devices still have to overcome contact resistance issues for better performances. Because of the Schottky contact at the metal-OSC interfaces, a non-ideal transfer curve feature often appears in the low-drain voltage region. To improve the contact properties of OSCs, there have been several methods reported, including interface treatment by self-assembled monolayers and introducing charge injection layers. Here, a selective contact doping of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4 -TCNQ) by solid-state diffusion in poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) to enhance carrier injection in bottom-gate PBTTT organic field-effect transistors (OFETs) is demonstrated. Furthermore, the effect of post-doping treatment on diffusion of F4 -TCNQ molecules in order to improve the device stability is investigated. In addition, the application of the doping technique to the low-voltage operation of PBTTT OFETs with high-k gate dielectrics demonstrated a potential for designing scalable and low-power organic devices by utilizing doping of conjugated polymers.
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Quaternary high-entropy ceramic (HEC) composite was synthesized from HfC, Mo2C, TaC, and TiC in pulsed current processing. A high-entropy solid solution that contained all principal elements along with a minor amount of a Ta-rich phase was observed in the microstructure. The high entropy phase and Ta-rich phase displayed a face-centered cubic (FCC) crystal structure with similar lattice parameters, suggesting that TaC acted as a solvent carbide during phase evolution. The addition of B4C to the quaternary carbide system induced the formation of two high-entropy solid solutions with different elemental compositions. With the increase in the number of principal elements, on the addition of B4C, the crystal structure of the HEC phase transformed from FCC to a hexagonal structure. The study on the effect of starting particle sizes on the phase composition and properties of the HEC composites showed that reducing the size of solute carbide components HfC, Mo2C, and TiC could effectively promote the interdiffusion process, resulting in a higher fraction of a hexagonal structured HEC phase in the material. On the other hand, tuning the particle size of solvent carbide, TaC, showed a negligible effect on the composition of the final product. However, reducing the TaC size from -325 mesh down to <1 µm resulted in an improvement of the nanohardness of the HEC composite from 21 GPa to 23 GPa. These findings suggested the possibility of forming a high-entropy ceramic phase despite the vast difference in the precursor crystal structures, provided a clearer understanding of the phase transformation process which could be applied for the designing of HEC materials.
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Undoped and cerium doped Calcium sulfide (CaS) phosphors were synthesized using solid state diffusion method. The X-ray diffraction pattern revealed that both undoped and doped CaS crystallites have cubic structure with average crystallite size varying from 20 to 30 nm. Scanning electron micrographs indicated that Ce doped CaS phosphors were composed of whiskers with different dimensions and orientations. The optical properties of undoped and Ce doped particles were characterized using Photoluminescence (PL) and UV-Vis absorption spectroscopy. The PL emission spectrum of cerium doped CaS phosphors for an excitation wavelength 465 nm showed a main peak at 500 nm and a shoulder peak at 556 nm due to 5d â 4f transition in Ce3+ ions. The variation of PL intensity with cerium concentration was investigated and the maximum PL intensity was obtained for a doping concentration of 3 wt.%. The optical band gap of the samples was estimated from the diffuse reflectance spectrum and was found to increase with increase in cerium concentration. The enhanced optical properties of these phosphors can be exploited in various optoelectronic devices including displays and bioimaging techniques.
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Metal structures on insulators are essential components in advanced electronic and nanooptical systems. Their electronic and optical properties are closely tied to their crystal quality, due to the strong dependence of carrier transport and band structure on defects and grain boundaries. Here we report a method for creating patterned single-crystal metal microstructures on amorphous insulating substrates, using liquid phase epitaxy. In this process, the patterned metal microstructures are encapsulated in an insulating crucible, together with a small seed of a differing material. The system is heated to temperatures above the metal melting point, followed by cooling and metal crystallization. During the heating process, the metal and seed form a high-melting-point solid solution, which directs liquid epitaxial metal growth. High yield of single-crystal metal with different sizes is confirmed with electron backscatter diffraction images, after removing the insulating crucible. Unexpectedly, the metal microstructures crystallize with the [Formula: see text] direction normal to the plane of the film. This platform technology will enable the large-scale integration of high-performance plasmonic and electronic nanosystems.
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Metal/metal oxides have attracted extensive research interest because of their combination of functional properties and compatibility with industry. Diffusion and thermal reliability have become essential issues that require detailed study to develop atomic-scaled functional devices. In this work, the diffusional reaction behavior that transforms piezoelectric ZnO into magnetic Fe3 O4 is investigated at the atomic scale. The growth kinetics of metal oxides are systematically studied through macro- and microanalyses. The growth rates are evaluated by morphology changes, which determine whether the growth behavior was a diffusion- or reaction-controlled process. Furthermore, atom attachment on the kink step is observed at the atomic scale, which has important implications for the thermodynamics of functional metal oxides. Faster growth planes simultaneously decrease, which result in the predominance of low surface energy planes. These results directly reveal the atomic formation process of metal oxide via solid-state diffusion. In addition, the nanofabricated method provides a novel approach to investigate metal oxide evolution and sheds light on diffusional reaction behavior. More importantly, the results and phenomena of this study provide considerable inspiration to enhance the material stability and reliability of metal/oxide-based devices.
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Sodium-ion battery technologies are known to suffer from kinetic problems associated with the solid-state diffusion of Na+ in intercalation electrodes, which results in suppressed specific capacity and degraded rate performance. Here, a controllable selective etching approach is developed for the synthesis of Prussian blue analogue (PBA) with enhanced sodium storage activity. On the basis of time-dependent experiments, a defect-induced morphological evolution mechanism from nanocube to nanoflower structure is proposed. Through in situ X-ray diffraction measurement and computational analysis, this unique structure is revealed to provide higher Na+ diffusion dynamics and negligible volume change during the sodiation/desodiation processes. As a sodium ion battery cathode, the PBA exhibits a discharge capacity of 90 mA h g-1, which is in good agreement with the complete low spin FeLS(C) redox reaction. It also demonstrates an outstanding rate capability of 71.0 mA h g-1 at 44.4 C, as well as an unprecedented cycling reversibility over 5000 times.
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Eu(2+)-doped Ba3Si6O12N2 phosphors were prepared successfully via a modified solid-state diffusion method. The phosphors were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence measurements. These phosphors were effectively excited at 355 nm and an intense emission peaking in the range 480 nm to 525 nm in the blue region was observed. The optimized dopant concentration was determined to be 1 mol% of Eu(2+) ion. The colour coordinates for phosphor were found to be (0.196, 0.326) in the blue region. This phosphor may find application for near-ultraviolet (NUV) excited lamp phosphors. The thermoluminescence study shows the complex glow curve. Trapping parameters (activation energy and frequency factor) were calculated for individual deconvoluted peaks by Chen's peak shape method, the initial rise method and the whole glow peak method.
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Bário/química , Európio/química , Luminescência , Medições Luminescentes , Nitrogênio/química , Oxigênio/química , Silício/química , Modelos MolecularesRESUMO
A series of Eu(3+)-, Ce(3+)-, Dy(3+)- and Tb(3+)-doped (Y,Gd)BO3 phosphors was synthesized by a solid-state diffusion method. X-Ray diffraction confirmed their hexagonal structure and the scanning electron microscopy results showed crystalline particles. The excitation spectra revealed that (Y,Gd)BO3 phosphors doped with Eu(3+), Ce(3+), Dy(3+) and Tb(3+) are effectively excited with near UV-light of 395 nm/blue light, 364, 351 and 314 nm, respectively. Photoluminescence spectra of Eu(3+)-, Ce(3+)- and Tb(3+)/Dy(3+)-doped phosphor showed intense emission of reddish orange, blue and white light, respectively. The phosphor Y0.60Gd0.38BO3:Ce0.02 showed CIE 1931 color coordinates of (0.158, 0.031) and better color purity compared with commercially available blue BAM:Eu(2+) phosphor. The phosphor (Y,Gd)BO3 doped with Eu(3+), Dy(3+) and Tb(3+) showed CIE 1931 color coordinates of (0.667, 0.332), (0.251, 0.299) and (0.333, 0.391) respectively. Significant photoluminescence characteristics of the prepared phosphors indicate that they might serve as potential candidates for blue chip and near-UV white light-emitting diode applications.
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Boro/química , Elementos da Série dos Lantanídeos/química , Luminescência , Oxigênio/química , Raios Ultravioleta , Ítrio/química , Processos FotoquímicosRESUMO
In this study, Li6 Y1-x Eux (BO3 )3 phosphor was successfully synthesized using a modified solid-state diffusion method. The Eu(3+) ion concentration was varied at 0.05, 0.1, 0.2, 0.5 and 1 mol%. The phosphor was characterized for phase purity, morphology, luminescent properties and molecular transmission at room temperature. The XRD pattern suggests a result closely matching the standard JCPDS file (#80-0843). The emission and excitation spectra were followed to discover the luminescence traits. The excitation spectra indicate that the current phosphor can be efficiently excited at 395 nm and at 466 nm (blue light) to give emission at 595 and 614 nm due to the (5) D0 â (7) Fj transition of Eu(3+) ions. Concentration quenching was observed at 0.5 mol% Eu(3+) in the Li6 Y1-x Eux (BO3 )3 host lattice. Strong red emission with CIE chromaticity coordinates of phosphor is x = 0.63 and y = 0.36 achieved with dominant red emission at 614 nm the (5) D0 â (7) F2 electric dipole transition of Eu(3+) ions. The novel Li6 Y1-x Eux (BO3 )3 phosphor may be a suitable red-emitting component for solid-state lighting using double-excited wavelengths, i.e. near-UV at 395 nm and blue light at 466 nm. Copyright © 2015 John Wiley & Sons, Ltd.
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Boratos/química , Európio/química , Iluminação , Lítio/química , Luminescência , Substâncias Luminescentes/química , Ítrio/química , Medições LuminescentesRESUMO
HYPOTHESIS: The purpose of the present work is the development of a kinetic model for the adsorption of As(III) and As(V) onto tetravalent manganese feroxyhyte (δ-Fe0.75Mn0.25OOH), which have been recently proved to be very efficient adsorbent for the particular species. EXPERIMENTS: In this respect equilibrium and adsorption kinetic experiments onto this type of adsorbent for As(III) and As(V) were performed. Two sizes of adsorbate particles are tested in order to acquire better insight to the adsorption process. RESULTS: The adsorption kinetic curves cannot be described by the well-known adsorption kinetic models so a detailed model that takes into account the structure of the adsorbent particle is developed. The model parameters were extracted by the requirement of agreement between model and experimental results. The batch model developed here is necessary for the development of models for fixed bed adsorption devices in order to exploit the commercial prospects of the particular adsorbent. This work constitutes the first attempt of kinetic study and adsorption model development for the specific very promising adsorbent.
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Doping elements in hematite nanostructures is a promising approach to improve the photoelectrochemical (PEC) water-splitting performance of hematite photoanodes. However, uniform doping with precise control on doping amount and morphology is the major challenge for quantitatively investigating the PEC water-splitting enhancement. Here, we report on the design and synthesis of uniform titanium (Ti)-doped hematite nanorods with precise control of the Ti amount and morphology for highly effective PEC water splitting using an atomic layer deposition assisted solid-state diffusion method. We found that Ti doping promoted band bending and increased the carrier density as well as the surface state. Remarkably, these uniformly doped hematite nanorods exhibited high PEC performance with a pronounced photocurrent density of 2.28 mA/cm(2) at 1.23 V vs reversible hydrogen electrode (RHE) and 4.18 mA/cm(2) at 1.70 V vs RHE, respectively. Furthermore, as-prepared Ti-doping hematite nanorods performed excellent repeatability and durability; over 80% of the as-fabricated photoanodes reproduced the steady photocurrent density of 1.9-2.2 mA/cm(2) at 1.23 V vs RHE at least 3 h in a strong alkaline electrolyte solution.