Precise Control Of Composition Research Articles

First-principles approach to the first step of metal–phosphine bond formation to synthesize alloyed quantum dots using dissimilar metal precursors

InP-based quantum dots are promising candidates as Cd-free quantum dots; however, they require sharper fluorescence to satisfy the next-generation display standard. For this purpose, a deeper understanding of the crystal growth scheme and well-designed organometallic precursors are needed. Density functional theory calculations were used to find the activation barriers for the initial reaction of Zn, Ga, and In precursors with tris(trimethylsilyl)phosphine, and differences in reactivity between dissimilar metal precursors were revealed. The coordinations of the P precursor to Zn, In, and Ga precursors were found to differ significantly, depending on the coordination number and the ionic radius, and these results were consistent with reports that found that InZnP can be alloyed, but InGaP is not easily alloyed. The activation energies become close to each other when using thiol ligands with less steric hindrance in monodentate ligands. These results will lead to achieving precise composition control and great luminescence properties.

Electrical polarization induced by atomically engineered compositional gradient in complex oxide solid solution

Control of inhomogeneity in materials in order to avoid unexpected effects to the system remains a challenge. In this study, we seek to engineer inhomogeneity in materials and anticipate new properties. Through precise control of composition at the atomic scale, an electrical polarization is induced in the composition-graded LaAlO3–SrTiO3 solid solution epitaxially deposited on NdGaO3 substrates. By tailoring the direction of compositional gradient, the relationship between structure and electrical polarization is simulated via phase-field modeling and revealed by a combination of scanning transmission electron microscopy and scanning probe microscopy. The analysis of the results indicates that the induced polarization is due to the flexoelectric effect in the compositional gradient system. The results of this study provide a new pathway for obtaining a new material genome. Moreover, by a suitable design of the new genome, that is, by using different combinations of compositional gradient geometries, local conduction can be obtained and manipulated, providing a new approach to obtain the desired properties.

High-Performance Thin-Film Transistors of Quaternary Indium-Zinc-Tin Oxide Films Grown by Atomic Layer Deposition.

A new deposition technique is required to grow the active oxide semiconductor layer for emerging oxide electronics beyond the conventional sputtering technique. Atomic layer deposition (ALD) has the benefits of versatile composition control, low defect density in films, and conformal growth over a complex structure, which can hardly be obtained with sputtering. This study demonstrates the feasibility of growing amorphous In-Zn-Sn-O (a-IZTO) through ALD for oxide thin-film transistor (TFT) applications. In the ALD of the a-IZTO film, the growth behavior indicates that there exists a growth correlation between the precursor molecules and the film surface where the ALD reaction occurs. This provides a detailed understanding of the ALD process that is required for precise composition control. The a-IZTO film with In/Zn/Sn = 10:70:20 was chosen for high-performance TFTs, among other compositions, regarding the field-effect mobility (μFE), turn-on voltage ( Von), and subthreshold swing (SS) voltage. The optimized TFT device with the a-IZTO film thickness of 8 nm revealed a high performance with a μFE of 22 cm2 V-1 s-1, Von of 0.8 V, and SS of 0.15 V dec-1 after annealing at 400 °C for 30 min. Furthermore, an emerging device such as a vertical channel TFT was demonstrated. Thus, the a-IZTO ALD process could offer promising opportunities for a variety of emerging oxide electronics beyond planar TFTs.

Facile solid-state synthesis for producing molybdenum and tungsten co-doped monoclinic BiVO4 as the photocatalyst for photoelectrochemical water oxidation

BiVO4 has been widely applied as photocatalysts for water oxidation, owing to preferable band configuration and small band gap for absorbing wide range of light. Synthesizing BiVO4 is usually based on wet routes, which are more complex and require extra steps for separating photocatalysts from solutions. A novel solid-state synthesis is firstly proposed in this study to efficiently synthesize BiVO4 by simply mixing bismuth and vanadium salts without other mediums and directly annealing the mixture at 450°C. Heteroatom-doping of BiVO4 is also achieved by annealing the mixture of W and Mo salts along with bismuth and vanadium precursors to increase the carrier concentration and accelerating the charge transfer. The W and Mo co-doped BiVO4 electrode with the W:Mo ratio of 1:1 shows the highest photocurrent density of 0.21 mA/cm2 at 1.23 V versus reversible hydrogen electrode and the smallest onset potential of 0.686 V versus reversible hydrogen electrode under air mass 1.5 solar illumination. This study successfully realizes the efficient fabrication of BiVO4 and the incorporation of W and Mo dopants using the solid-state synthesis. Applying this manner cannot only reduce the synthesis time but also provide more precise control of the element composition. Further developments of the co-catalyst/photocatalyst system are expected to be realized by applying this novel solid-state synthesis.

Highly active oxygen evolution reaction model electrode based on supported gas-phase NiFe clusters

Under alkaline conditions mixed NiFe oxides/oxyhydroxides are among the most active catalysts for the oxygen evolution reaction (OER). Here we investigate Ni0.5Fe0.5 clusters as a well-defined model highly active electrocatalyst system for the OER. The electrodes were prepared using gas-phase deposition of mixed Ni0.5Fe0.5 metallic clusters produced by cluster beam deposition (CBD), a technique offering precise control of composition and loading. Highly dispersed Ni0.5Fe0.5 clusters were deposited at 1 equivalent monolayer and used as OER catalyst in 1 M KOH. The low loading allows assessment of the intrinsic catalytic activity and their extensive structural characterization by XAFS and XPS spectroscopies. Ni0.5Fe0.5 clusters demonstrate high stability as there is no apparent potential increase after a 12 h constant current density anodization test. After electrochemical aging, the lowest overpotential was achieved and amounts to 372 mV at 10 mA cm−2. The Tafel slope reaches 37 mV dec−1. The measured electrochemical activity is also compared with other systems. After OER reaction in KOH the cluster surface is enriched in NiOOH, while concomitant Fe depletion from the catalyst surface is observed. These findings help to shed light on the formed active phase at the nanoscale.

Thermal activation of charge carriers in ionic and electronic semiconductor β-AgIVVO3 and β-AgIVVO3@VV 1.6VIV 0.4O4.8 composite xerogels.

Silver vanadium oxide (SVO) and Silver Vanadium Oxide/Vanadium Oxide (SVO@VO) composite hydrogels are formed from the self-entanglement of β-AgVO3 nanoribbons and slightly reduced vanadium oxide (VO) (VV1.6VIV0.4O4.8) nanoribbons; respectively. Starting from randomly distributed nanoribbons within hydrogels, and after a controlled drying process, a homogeneous xerogel system containing tuneable SVO : VO ratios from 1 : 0 to 1 : 1 can be obtained. The precise nanoribbons compositional control of these composite system can serve as a tool to tune the electrical properties of the xerogels, as it has been demonstrated in this work by impedance spectroscopy (IS) experiments. Indeed, depending on the composition and temperature conditions, composite xerogels can behave as electronic, protonic or high temperature ionic conductors. In addition, the electric and protonic conductivity of the composite xerogels can be enhanced (until a critical irreversible point), through the temperature triggered charge carrier creation. As concluded from thermogravimetry, IR, UV-Vis and EPR spectroscopy studies, besides the SVO : VO ratio, the thermal induced oxidation/reduction of V5+ to V4+, and thermally triggered release of strongly bonded water molecules at the nanoribbon surface are the two key variables that control the electric and ionic conduction processes within the SVO and composite SVO/VO xerogels.

Chimney effect of the interface in metal oxide/metal composite catalysts on the hydrogen evolution reaction

Precise atomic-level control of composition and geometric structure at the interface between two catalyst components can effectively tune the catalytic properties. Herein, we found a “chimney effect” formed on the interface between the metal oxide and Nickel metal for the hydrogen evolution reaction, using density functional theory calculations and experimental methods. This special chemical environment around the interface leads the neighboring sites to be immune to the H2O* and OH* adsorption and to only selectively adsorb H* properly. Meanwhile, it is also beneficial for the smooth adsorption of the reactant (H*) on the interface and the easy desorption of the product (H2) from the catalyst surface (ΔGH* close to zero). This phenomenon appears similar to a chimney of hydrogen evolution around the metal oxide/metal interface. Such “chimney effect” is a result of the interfacial charge transfer between the metal and metal oxide, and should be the nature of the interface-induced synergistic effect in metal oxide/metal composite catalysts for HER. Experiments further confirm that the catalytic activity of metal oxide/metal composites for HER can be enhanced by increasing the amount of the chimney - the interfacial metal atoms.

Facile synthesis and size dependent visible light photo catalytic properties of bio-compatible silver nanoclusters

Recently tremendous research efforts have been carried out to synthesize metal nanocluster owing to their wide applications in bio-imaging, nonlinear optical materials and catalysis. To explore such applications a precise control of size and composition of the metal nanoclusters are highly desirable. Here we report controlled synthesis and characterization of water soluble silver nanocluster ligated with glutathione. We have developed facile methodologies to prepare nanoclusters with distinct optical and catalytic properties. To achieve tunable size, optical property and chemical composition, here we mainly modulate the nature of metallic salt precursor, reducing agent and reaction conditions. Catalytic properties of as synthesized nanoclusters are explored in visible light induced photo-Fenton like processes for the degradation of model water pollutants such as methyl orange (MO) and Rhodamine B (RhB). The present research work investigates the influence of size of silver nanoclusters (Ag NCs) on photo Fenton like processes under visible light.

Comparing strategies for improving efficiencies in vacuum processed Cu2ZnSnSe4 solar cells

In this study, we detail a Cu2ZnSnSe4 based solar cell fabrication process based on the selenization of metallic precursor stacks with elemental Se. 9.4% efficient devices without antireflection coating have been obtained. First, reproducibility issues of the process are carefully shown and discussed. It is demonstrated that device performances are strongly impacted by the precise control of the precursor composition. Then, starting from this robust process, a review of existing strategies to improve kesterite efficiencies is conducted. A significant increase in efficiency (+1.4% absolute efficiency and +50 mV VOC) is obtained with absorber surface treatment and post-annealing, while no effect of Ge incorporation in the precursor stack is observed. This contradictory result to most of the recent publications raises the question of the universality of this strategy to improve kesterite solar cell performance. Finding a universal activation step to boost kesterite efficiencies and bring it to the market remains a crucial need for the community.

Direct Visualization of the Structural Transformation between the Lyotropic Liquid Crystalline Lamellar and Bicontinuous Cubic Mesophase.

The transition between the lyotropic liquid crystalline lamellar and the bicontinuous cubic mesophase drives multiple fundamental cellular processes involving changes in cell membrane topology, including endocytosis and membrane budding. While several theoretical models have been proposed to explain this dynamic transformation, experimental validation of these models has been challenging because of the short-lived nature of the intermediates present during the phase transition. Herein, we report the direct observation of a lamellar-to-bicontinuous cubic phase transition in nanoscale dispersions using a combination of cryogenic transmission electron microscopy and static small-angle X-ray scattering. The results represent the first experimental confirmation of a theoretical model which proposed that the bicontinuous cubic phase originates from the center of a lamellar vesicle then propagates outward via the formation of interlamellar attachments and stalks. The observation was possible because of the precise control of the lipid composition to place the dispersion systems at the phase boundary of a lamellar and a cubic phase, allowing for the creation of long-lived structural intermediates. By the surveying of the nanoparticles using cryogenic transmission electron microscopy, a complete phase transition sequence was established.

Temperature controlled properties of sub-micron thin SnS films

Tin sulphide (SnS) thin films deposited by thermal evaporation on glass substrates are studied for different substrate temperatures. The increase in substrate temperature results in the increase of the crystallite size and change in orientation of the films. The crystal structure of the films is that of SnS only and for temperatures ≤300 °C the films are of random orientation, whereas for higher temperatures the films become (040) oriented. The variation of Sn/S composition was accompanied by a reduction in optical energy bandgap from 1.47 to 1.31 eV as the substrate temperature increases. The Urbach energy was found stable at 0.169 ± 0.002 eV for temperature up to 350 °C. Photoluminescence emission was observed only for films exhibiting stoichiometric properties and shows that a precise control of the film composition is critical to fabricate devices while an increase in grain size will be essential to achieve high efficiency.

Sp-d Exchange Interactions in Wave Function Engineered Colloidal CdSe/Mn:CdS Hetero-Nanoplatelets.

In two-dimensional (2D) colloidal semiconductor nanoplatelets, which are atomically flat nanocrystals, the precise control of thickness and composition on the atomic scale allows for the synthesis of heterostructures with well-defined electron and hole wave function distributions. Introducing transition metal dopants with a monolayer precision enables tailored magnetic exchange interactions between dopants and band states. Here, we use the absorption based technique of magnetic circular dichroism (MCD) to directly prove the exchange coupling of magnetic dopants with the band charge carriers in hetero-nanoplatelets with CdSe core and manganese-doped CdS shell (CdSe/Mn:CdS). We show that the strength of both the electron as well as the hole exchange interactions with the dopants can be tuned by varying the nanoplatelets architecture with monolayer accuracy. As MCD is highly sensitive for excitonic resonances, excited level spectroscopy allows us to resolve and identify, in combination with wave function calculations, several excited state transitions including spin-orbit split-off excitonic contributions. Thus, our study not only demonstrates the possibility to expand the extraordinary physical properties of colloidal nanoplatelets toward magneto-optical functionality by transition metal doping but also provides an insight into the excited state electronic structure in this novel two-dimensional material.

Preparation of Sn loss-free Cu2SnS3 thin films by an oxide route for solar cell

Ternary Cu2SnS3 (CTS) thin films have attracted lots of attention due to its low cost, nontoxic element for solar cell. However, Tin losses always happen during sulfurization, which will affect the phase purity and morphology of CTS thin films and relevant solar cell. In this work, a low cost oxides route was used to prepare CTS thin films. The influences of sulfurizaton temperature on the crystal structure, morphology and composition were studied carefully. From the XRD, SEM and EDX results, it was found that the stable oxides were conducive to alleviate the Sn loss even at the higher sulfurization temperature (580 °C). Meanwhile, the crystal structure evolution along annealing temperature was also observed from mixed phase (Monoclinic and Tetragonal) to single phase Monoclinic. The Monoclinic CTS thin films sulfurized at 580 °C were used to fabricate CTS solar cell with Mo/CTS/CdS/ZnO/AZO/Ag structure, exhibiting efficiency of 0.16%. The comparable Voc of 300 mV was achieved by benefiting from the precise composition control. Besides, the photoelectric properties of the device were carefully studied as well. This study provides a low-cost and facile strategy for the fabrication of Sn-loss free CTS solar cells.

Real Time Spectroscopic Ellipsometry Analysis of First Stage CuIn1-xGaxSe₂ Growth: Indium-Gallium Selenide Co-Evaporation.

Real time spectroscopic ellipsometry (RTSE) has been applied for in-situ monitoring of the first stage of copper indium-gallium diselenide (CIGS) thin film deposition by the three-stage co-evaporation process used for fabrication of high efficiency thin film photovoltaic (PV) devices. The first stage entails the growth of indium-gallium selenide (In1−xGax)2Se3 (IGS) on a substrate of Mo-coated soda lime glass maintained at a temperature of 400 °C. This is a critical stage of CIGS deposition because a large fraction of the final film thickness is deposited, and as a result precise compositional control is desired in order to achieve the optimum performance of the resulting CIGS solar cell. RTSE is sensitive to monolayer level film growth processes and can provide accurate measurements of bulk and surface roughness layer thicknesses. These in turn enable accurate measurements of the bulk layer optical response in the form of the complex dielectric function ε = ε1 − iε2, spectra. Here, RTSE has been used to obtain the (ε1, ε2) spectra at the measurement temperature of 400 °C for IGS thin films of different Ga contents (x) deduced from different ranges of accumulated bulk layer thickness during the deposition process. Applying an analytical expression in common for each of the (ε1, ε2) spectra of these IGS films, oscillator parameters have been obtained in the best fits and these parameters in turn have been fitted with polynomials in x. From the resulting database of polynomial coefficients, the (ε1, ε2) spectra can be generated for any composition of IGS from the single parameter, x. The results have served as an RTSE fingerprint for IGS composition and have provided further structural information beyond simply thicknesses, for example information related to film density and grain size. The deduced IGS structural evolution and the (ε1, ε2) spectra have been interpreted as well in relation to observations from scanning electron microscopy, X-ray diffractometry and energy-dispersive X-ray spectroscopy profiling analyses. Overall the structural, optical and compositional analysis possible by RTSE has assisted in understanding the growth and properties of three stage CIGS absorbers for solar cells and shows future promise for enhancing cell performance through monitoring and control.

A molecular approach to magnetic metallic nanostructures from metallopolymer precursors

In recent years, metallopolymers have attracted much attention as precursors to generate magnetic metal/metal alloy nanoparticles (NPs) through pyrolysis or photolysis because they offer the advantages of ease of solution processability, atomic level mixing and stoichiometric control over composition. The as-generated NPs usually possess narrow size distributions with precise control of composition and density per unit area. Moreover, patterned NPs can be achieved on various substrates in this way owing to the good film-forming property of metallopolymers and such work is important for many applications based on metal nanostructures. By combining the merits of both the solution processability of metallopolymers and nanoimprint lithography (NIL), a new platform can be created for fabricating bit-patterned media (BPM) and the next-generation of nanoscale ultra-high-density magnetic data storage devices. Furthermore, most of these metallopolymers can be used directly as a negative-tone resist to generate magnetic metallic nanostructures by electron-beam lithography and UV photolithography. Self-assembly and subsequent pyrolysis of metalloblock copolymers can also afford well-patterned magnetic metal or metal alloy NPs in situ with periodicity down to dozens of nanometers. In this review, we highlight the use of metallopolymer precursors for the synthesis of magnetic metal/metal alloy NPs and their nanostructures and the related applications.

Controlled formation of chitosan particles by a clock reaction.

Clock reactions allow precise control of chemical composition in the time domain. Such nonlinear chemical systems have recently been introduced to mimic the self-assembly pathways common in living organisms. Here, we demonstrate the use of a clock reaction to trigger the formation of polymeric nanoparticles. By adjusting the delay of a formaldehyde clock reaction, we controlled the precipitation of chitosan to form particles with sizes tunable in a wide range (from about 200 to 600 nm diameter). The chemical structure of chitosan was not significantly perturbed by the clock reagents.

Live event reconstruction in an optically read out GEM-based TPC

Combining strong signal amplification made possible by Gaseous Electron Multipliers (GEMs) with the high spatial resolution provided by optical readout, highly performing radiation detectors can be realized. An optically read out GEM-based Time Projection Chamber (TPC) is presented. The device permits 3D track reconstruction by combining the 2D projections obtained with a CCD camera with timing information from a photomultiplier tube. Owing to the intuitive 2D representation of the tracks in the images and to automated control, data acquisition and event reconstruction algorithms, the optically read out TPC permits live display of reconstructed tracks in three dimensions. An Ar/CF4 (80/20%) gas mixture was used to maximize scintillation yield in the visible wavelength region matching the quantum efficiency of the camera. The device is integrated in a UHV-grade vessel allowing for precise control of the gas composition and purity. Long term studies in sealed mode operation revealed a minor decrease in the scintillation light intensity.

Encoding Highly Nonequilibrium Boron Concentrations and Abrupt Morphology in p-Type/n-Type Silicon Nanowire Superlattices.

Although silicon (Si) nanowires (NWs) grown by a vapor-liquid-solid (VLS) mechanism have been demonstrated for a range of photonic, electronic, and solar-energy applications, continued progress with these NW-based technologies requires increasingly precise compositional and morphological control of the growth process. However, VLS growth typically encounters problems such as nonselective deposition on sidewalls, inadvertent kinking, unintentional or inhomogeneous doping, and catalyst-induced compositional gradients. Here, we overcome several of these difficulties and report the synthesis of uniform, linear, and degenerately doped Si NW superlattices with abrupt transitions between p-type, intrinsic, and n-type segments. The synthesis of these structures is enabled by in situ chlorination of the NW surface with hydrochloric acid (HCl) at temperatures ranging from 500 to 700 °C, yielding uniform NWs with minimal nonselective growth. Surprisingly, we find the boron (B) doping level in p-type segments to be at least 1 order of magnitude above the solid solubility limit, an effect that we attribute to a high incorporation of B in the liquid catalyst and kinetic trapping of B during crystallization at the liquid-solid interface to yield a highly nonequilibrium concentration. For growth at 510 °C, four-point-probe measurements yield active doping levels of at least 4.5 × 1019 cm-3, which is comparable to the phosphorus (P) doping level of n-type segments. Because the B and P dopants are in sufficiently high concentrations for the Si to be degenerately doped, both segments inhibit the etching of Si in aqueous potassium hydroxide (KOH) solution. Moreover, we find that the dopant transitions are abrupt, facilitating nanoscale morphological control in both B- and P-doped segments through selective KOH etching of the NW with a spatial resolution of ∼10 nm. The results presented herein enable the growth of complex, degenerately doped p-n junction nanostructures that can be explored for a variety of advanced applications, such as Esaki diodes, multijunction solar cells, and tunneling field-effect transistors.

Self-regulation of Bi/(Bi+Fe) ratio in metalorganic chemical vapor deposition of BiFeO3 thin films

Metalorganic chemical vapor deposition (MOCVD) is one of the suitable techniques for practical applications of BiFeO3 films. To develop the potential of MOCVD as a device fabrication process, we investigated the relationship between the film and gas compositions, and the growth under highly oxidizing conditions using O2 and O3 gases. In the growth of epitaxial BiFeO3 thin films on SrRuO3-covered 4° vicinal SrTiO3(001) at 620 °C, the self-regulation of the film composition was achieved for Bi and Fe precursor supply ratios between 62.1 to 78.5% under O2 and 56.1 to 73.2% under 5 wt % O3-mixed O2 atmospheres. The leakage was very sensitive to the precursor supply ratio and oxidizing gas. 150-nm-thick MOCVD-BiFeO3 films grown using O2+O3 gas showed the minimum leakage current density of 2.3 × 10−7 A/cm2 at +1 V. The highly oxidizing growth conditions using O3 can suppress the leakage while precise composition control is required.

Controlled Isotropic and Anisotropic Shell Growth in β-NaLnF4 Nanocrystals Induced by Precursor Injection Rate

Precise morphology and composition control is vital for designing multifunctional lanthanide-doped core/shell nanocrystals. Herein, we report controlled isotropic and anisotropic shell growth techniques in hexagonal sodium rare-earth tetrafluoride (β-NaLnF4) nanocrystals by exploiting the kinetics of the shell growth. A drastic change of the shell morphology was observed by changing the injection rate of the shell precursors while keeping all other reaction conditions constant. We obtained isotropic shell growth for fast sequential injection and a preferred growth of the shell layers along the crystal's c-axis [001] for slow dropwise injection. Using this slow shell growth technique, we have grown rod-like shells around different almost spherical core nanocrystals. Bright and efficient upconversion was measured for both isotropic and rod-like shells around β-NaYF4 nanocrystals doped with Yb3+/Er3+ and Yb3+/Tm3+. Photoluminescence upconversion quantum yield and lifetime measurements reveal the high quality of the core/shell nanocrystal. Furthermore, multishell rod-like nanostructures have been prepared with optically active cores and tips separated by an inert intermediate shell layer. The controlled anisotropic shell growth allows the design of new core/multishell nanostructures and enables independent investigations of the chemistry and physics of different nanocrystal facets.