Formation of heterodimer nanocrystals: UO2/In2O3 and FePt/In2O3

This Article reports a mechanistic study on the formation of colloidal UO(2)/In(2)O(3) and FePt/In(2)O(3) heterodimer nanocrystals. These dimer nanocrystals were synthesized via the growth of In(2)O(3) as the epitaxial material onto the seed nanocrystals of UO(2) or FePt. The resulting dimer nanocrystals were characterized using X-ray powder diffraction (XRD), energy dispersion spectroscopy, transmission electron microscopy (TEM), scanning transmission electron microscopy, and high-resolution TEM (HRTEM). The results from XRD and HRTEM clearly show that lattice strains exist in both of these dimer nanocrystals. Interestingly, the lattice of In(2)O(3) expands in UO(2)/In(2)O(3) dimers, whereas FePt/In(2)O(3) dimers exhibit compressed In(2)O(3) lattices. Using HRTEM and nanocrystal structure simulations, we have identified the crystallographic orientation of the attachment of the two segments in these two types of dimers. An unconventional Miller index was introduced to describe the crystallographic orientation of these heterodimer nanocrystals. On the basis of the results herein as well as those from other researchers, we propose an empirical law for the determination of the crystallographic attachment orientation in heterodimers: instead of growth on the facet of the seed nanocrystals where lattice mismatch is minimized, the growth of an epitaxial material often chooses the crystal facets where the first atomic monolayer of this material has the strongest affinity for the seed nanocrystals.     

Size-controlled chalcopyrite CuInS2 nanocrystals: One-pot synthesis and optical characterization

Chalcopyrite ternary CuInS2 semiconductor nanocrystals have been synthesized via a facile one-pot chemical approach by using oleylamine and oleic acid as solvents.The as-prepared CuInS2 nanocrystals have been characterized by instrumental analyses such as X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM)/high-resolution TEM(HRTEM),energy-dispersive X-ray spectroscopy(EDS),UV-vis absorption spectroscopy(UV-vis) and photoluminescence(PL) spectroscopy.The particle sizes of the CuInS2 nanocrystals could be tuned from 2 to 10 nm by simply varying reaction conditions.Oleylamine,which acted as both a reductant and an effective capping agent,plays an important role in the size-controlled synthesis of CuInS2 nanocrystals.Based on a series of comparative experiments under different reaction conditions,the probable formation mechanism of CuInS2 nanocrystals has been proposed.Furthermore,the UV-vis absorption and PL emission spectra of the chalcopyrite CuInS2 nanocrystals have been found to be adjustable in the range of 527-815 nm and 625-800 nm,respectively,indicating their potential application in photovoltaic devices.     

Synthesis and characterization of single-crystalline In2O3 nanocrystals via solution dispersion

In this paper, In2O3 nanocrystals were prepared by solution dispersion from bulk indium. In2O3 nanocrystals with an average diameter of 30 nm have a single-crystalline phase and appear as a square or rhombohedral shape, and little spherical particles are also present. In addition, these nanocrystals show strong ultraviolet-blue emission.     

Amine-induced growth of an In2O3 shell on colloidal InP nanocrystals

A simple and rapid method for the growth of an In2O3 shell on colloidal InP nanocrystals is described, increasing their fluorescence efficiency by one order of magnitude.     

Solvothermal synthesis of well-dispersed NaMgF3 nanocrystals and their optical properties

Complex metal fluoride NaMgF(3) nanocrystals were successfully synthesized via a solvothermal method at a relatively low temperature with the presence of oleic acid, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, photoluminescence (PL) excitation and emission spectra, respectively. In the synthetic process, oleic acid as a surfactant played a crucial role in confining the growth and solubility of the NaMgF(3) nanocrystals. The as-prepared NaMgF(3) nanocrystals have quasi-spherical shape with a narrow distribution. A possible formation mechanism of the nanocrystals was proposed based on the effect of oleic acid. The as-prepared NaMgF(3) nanocrystals are highly crystalline and well-dispersed in cyclohexane to form stable and clear colloidal solutions, which demonstrate a strong emission band centered at 400 nm in photoluminescence (PL) spectra compared with the cyclohexane solvent. The PL properties of the colloidal solutions of the as-prepared nanocrystals can be ascribed to the trap states of surface defects.     

One-pot synthesis and third-order nonlinear optical properties of AgInS2 nanocrystals

Good quality colloidal nanocrystals of metastable orthorhombic phase of AgInS2 obtained by decomposing the single-precursor [(Ph3P)2AgIn(SCOPh)4] in a mixture of dodecanethiol and oleic acid at 125-200 degrees C, exhibit significant third order non-linear optical properties.     

Hierarchical CdSe-gold hybrid nanocrystals: synthesis and optical properties

The synthesis of hybrid nanostructures with controlled size, shape, composition and morphology has attracted increasing attention due to the fundamental and applicable interest. Here, we demonstrate the synthesis and optical properties of hierarchical CdSe-Au hybrid nanostructures with zinc blende (ZB) CdSe nanocrystals (NCs). For 3.5 nm ZB CdSe NCs, one Au cluster was deposited on each CdSe NC. Nevertheless, several Au clusters were selectively deposited on the apexes of 5 nm and 8 nm ZB CdSe NCs, resulting from the different reactivity of crystal facets. Furthermore, hierarchical CdSe-Au nanostructures with complex morphology were organized with the isolated CdSe-Au hybrid NCs by the coalescence of Au domains on the CdSe-Au hybrid NCs. UV-Vis spectra revealed a red tail upon the deposition of Au clusters. The chemical joint of Au on CdSe NCs was further confirmed by fluorescence quenching. The optical limiting performance of CdSe-Au hybrid NCs dispersed in toluene was investigated at 532 nm using a Nd:YAG laser with the pulse width of 8 ns.     

The thermostability and reactivity of GaP nanocrystals in oxygen: from GaP nanocrystals to Ga2O3 nanocrystals

The thermostability and reactivity of GaP nanocrystals in O(2) were investigated using the thermogravimetric analysis (TGA), differential thermal analysis (DTA), powder X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analysis techniques. alpha-Ga(2)O(3) nanoparticles, nano-hollow-particles, or nanorods and nanotubes can be separately obtained from the oxidation of nanocrystalline GaP at 400 degrees C for 30 min in dry O(2) atmosphere via manipulating different heating rates. Transmission electron microscopy (TEM) and energy-dispersive X-ray spectrometry (EDX) analysis showed that the products were all alpha-Ga(2)O(3) but with different morphologies when different heating rates were applied. The formation mechanisms of the different morphological alpha-Ga(2)O(3) nanocrystals were discussed.     

Low-temperature anomalies of two-photon absorption in In2O3 nanocrystals incorporated into PMMA matrixes

By using a method of two-photon absorption, it has been observed that monodisperse In2O3 nanocrystals (NCs) with sizes equal to approximately 14-24 nm show significant increase of two-photon absorption at low temperatures. When T = 40 K, the two-photon absorption coefficients for low-sized samples drastically increase, whereas such enhancement for the samples with averaged sizes above approximately 24 nm is not significant. The nondiagonal tensor components give one-order-less two-photon absorption values. A principal role in the observed dependences is played by interface nanolayers, demonstrating substantial contribution of nanoconfined effects. This phenomenon could only be observed in highly monodisperse NCs. Increase of the size distribution substantially suppresses the two-photon absorption observed. For the relatively large nanocrystals, the effects are comparable with those of the bulklike crystals. At the same time, the drastic increase at low temperatures may indicate a substantial role of the phonon subsystem.     

Time-resolved spectroscopic behavior of Fe2O3 and ZnFe2O4 nanocrystals

Using nanosecond (ns) and femtosecond (fs) time-resolved absorption spectroscopies (pump-probe technique), the carrier dynamics in transition metal oxide nanocrystals of alpha-Fe2O3 and ZnFe2O4 was studied during the photolysis process. For Fe2O3 and ZnFe2O4 nanocrystals, the fs measurements detect similar profiles of a positive nonlinear absorption in their capped nanocrystals, whereas much weak signals in the naked particles. In the nanosecond measurements Fe2O3 and ZnFe2O4 nanocrystals show obvious excitation-power dependent absorption properties and at the low pump power they show weak photobleaching, but at high pump power they produce positive nonlinear absorptions. For Fe2O3 nanocrystals, the threshold power of negative absorption (bleach) to positive absorption increases with reducing size, whereas for the ZnFe2O4 samples, the threshold powers reach minimum at a critical size of 11 nm, grow for both the bigger and the smaller nanocrystals. These results reflect the influences of their microscopic magnetic couplings and carrier correlation on biexciton absorption in Fe2O3 and ZnFe2O4 nanocrystals. All the results indicate that the time resolved photoabsorption techniques are useful to study the microscopic spin interactions and carrier correlations in transition metal oxide nanocrystals.     

Uniform In2S3 octahedron-built microspheres: Bioinspired synthesis and optical properties

Uniform In₂S₃ octahedron-built microspheres were synthesized by using a mild hydrothermal treatment in the presence of L-glutamic acid at 180 °C. The microsphere with an average size of 5 μm was composed of interconnected octahedrons with diameters in the range from 100 to 150 nm. The products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and X-ray photoelectron spectroscopy (XPS). The synthesis of various hollow and solid sphere structures and flower structures was achieved using different amino acids. This is the first report on synthesizing In₂S₃ nanostructures using different amino acids to modulate the morphology of the final products. Primary photoluminescence studies on the prepared In₂S₃ microspheres show promising results.     

In(OH)3 and In2O3 nanorod bundles and spheres: microemulsion-mediated hydrothermal synthesis and luminescence properties

Indium hydroxide, In(OH)3, nano-microstructures with two kinds of morphology, nanorod bundles (around 500 nm in length and 200 nm in diameter) and caddice spherelike agglomerates (around 750-1000 nm in diameter), were successfully prepared by the cetyltrimethylammonium bromide (CTAB)/water/cyclohexane/n-pentanol microemulsion-mediated hydrothermal process. Calcination of the In(OH)3 crystals with different morphologies (nanorod bundles and spheres) at 600 degrees C in air yielded In2O3 crystals with the same morphology. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. The pH values of microemulsion play an important role in the morphological control of the as-formed In(OH)3 nano-microstructures from the hydrothermal process. The formation mechanisms for the In(OH)3 nano-microstructures have been proposed on an aggregation mechanism. In2O3 nanorod bundles and spheres show a similar blue emission peaking around 416 and 439 nm under the 383-nm UV excitation, which is mainly attributed to the oxygen vacancies in the In2O3 nano-microstructures.     

One-pot synthesis of reverse type-I In2O3@In2S3 core-shell nanoparticles

A novel method to one-pot-synthesize high-quality In(2)O(3)@In(2)S(3) core-shell nanoparticles, consisting of a step of reducing In(2)O(3) core surface into a layer of active indium metal in high-temperature organic solution and a step of converting this layer to In(2)S(3) using CS(2), has been developed.     

High-quality sodium rare-earth fluoride nanocrystals: controlled synthesis and optical properties

We report a general synthesis of high-quality cubic (alpha-phase) and hexagonal (beta-phase) NaREF4 (RE: Pr to Lu, Y) nanocrystals (nanopolyhedra, nanorods, nanoplates, and nanospheres) and NaYF(4):Yb,Er/Tm nanocrystals (nanopolyhedra and nanoplates) via the co-thermolysis of Na(CF3COO) and RE(CF3COO)3 in oleic acid/oleylamine/1-octadecene. By tuning the ratio of Na/RE, solvent composition, reaction temperature and time, we can manipulate phase, shape, and size of the nanocrystals. On the basis of its alpha --> beta phase transition behavior, along the rare-earth series, NaREF4 can be divided into three groups (I: Pr and Nd; II: Sm to Tb; III: Dy to Lu, Y). The whole controlled-synthesis mechanism can be explained from the point of view of free energy. Photoluminescent measurements indicate that the value of I610/I590 and the overall emission intensity of the NaEuF4 nanocrystals are highly correlative with the symmetries of the Eu3+ ions in both the lattice and the surface.     

Synthesis of metastable hexagonal In2O3 nanocrystals by a precursor-dehydration route under ambient pressure

Single-crystalline metastable In₂O₃ nanocrystals with size in the range of 5–30 nm were, for the first time, synthesized by a precursor-dehydration route at 490°C under ambient pressure. The precursor was prepared by a hydrolysis solvothermal reaction using InCl₃·4H₂O as starting materials and ethylenediamine as solvent in the range of 180–230°C. It was found that the precursor had significant effect on the phase composition and phase structure of In₂O₃. Optical properties of the metastable In₂O₃ nanocrystals were investigated.     

Synthesis, characterization, and optical properties of In2O3 semiconductor nanowires

In2O3 semiconductor nanowires were synthesized by the chemical vapor deposition method through carbon thermal reduction at 900 degrees C with 95% Ar and 5% O2 gas flow. The In2O3 nanowires were characterized by field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence spectroscopy (PL). For the first time, we observed the formation of corundum-type h-In2O3 nanowires and branched In2O3 nanowires. The PL spectra of In2O3 nanowires show strong visible red emission at 1.85 eV (670 nm) at low temperature, possibly caused by a small amount of oxygen vacancies in the nanowire crystal structure.     

Synthesis,X-ray and optical characterizations of two new oxysulfides: LaInS2O and La5In3S9O3

Two new compounds, LaInS₂O and La₅In₃S₉O₃ were synthesized in the La–In–S–O quaternary system. Both compounds crystallize in the orthorhombic system with lattice constants a=20.5421(6) Å, b=14.8490(4) Å, c=3.9829(1) Å for LaInS₂O, and a=4.1018(1) Å, b=26.833(1) Å, c=16.023(1) Å for La₅In₃S₉O₃. The structure of La₅In₃S₉O₃ was solved from single-crystal X-ray data, in the space group Pbcm, with Z=4; it is built from three-atom-thick (100)_NaCl layers interleaved with fluorite-type ribbons, and is closely related to the structures of the known lanthanum and indium compounds La₁₀In₆S₁₇O₆ and La₄In₅S₁₃. Both compounds LaInS₂O and La₅In₃S₉O₃ exhibit a yellow color; measurement of their optical gaps gave 2.73 and 2.60 eV, respectively.     

Phase transformation of colloidal In2O3 nanocrystals driven by the interface nucleation mechanism: a kinetic study

The kinetics of phase transformation of colloidal In(2)O(3) nanocrystals (NCs) during their synthesis in solution was explored by a combination of structural and spectroscopic methods, including X-ray diffraction, transmission electron microscopy, and extended X-ray absorption fine structure spectroscopy. Johnson-Mehl-Avrami-Erofeyev-Kholmogorov (JMAEK) and the interface nucleation models were used to analyze the isothermal kinetic data for the phase transformation of NCs in the temperature range of 210-260 °C. The results show that NCs are initially stabilized in the metastable corundum (rh-In(2)O(3)) phase. The phase transformation occurs via nucleation of cubic bixbyite (bcc-In(2)O(3)) phase at the interface between contacting rh-In(2)O(3) NCs, and propagates rapidly throughout the NC volume. The activation energy of the phase transformation was determined from the Arrhenius expression to be 152 ± 60 kJ/mol. The interface nucleation rate is maximal at the beginning of the phase transformation process, and decreases over the course of the reaction due to a decrease in the concentration of rh-In(2)O(3) NCs in the reaction mixture. In situ high-temperature XRD patterns collected during nonisothermal treatment of In(2)O(3) NCs reveal that phase transformation of smaller NCs occurs at a faster rate and lower temperature, which is associated with their higher packing density and contact formation probability. Because NC surfaces and interfaces play a key role in phase transformation, their control through the synthesis conditions and reaction kinetics is an effective route to manipulate NC structure and properties.     

Size-controlled preparation of Cu2O octahedron nanocrystals and studies on their optical absorption

We report herein the size-controlled preparation of monodispersed cuprous oxide octahedron nanocrystals smaller than 100 nm. The method is based on the reduction of copper nitrate in Triton X-100 water-in-oil (w/o) microemulsions by gamma-irradiation. The average edge length of the octahedron-shaped nanocrystals varies from 45 to 95 nm as a function of the dose rate. The quantum confinement effect was illustrated by the blueshift in the optical absorption. In addition, the growth process was also traced by absorption spectra.     

Super crystal structures of octahedral c-In2O3 nanocrystals

The three-dimensional self-assembly of a nanocrystal superlattice, i.e., a super crystal, has attracted increasing attention. The small building blocks for assemblies are usually spherical nanocrystals. Recent progress indicates that it is possible to achieve a super crystal using cubic nanocrystals. We further analyze and describe two-dimensional and some three-dimensional assemblies of uniform cubic-phase In2O3 nanocrystals with an octahedral shape. In this article, we demonstrate our amazing observations on these kinds of super crystals (or superlattices) as a model system, report their scale in at least tens of microns, and show other interesting features such as steps, terraces, kinks, and vacancies which are similar to those from a single crystal. Based on electron microscopy observations, three types of well-defined octahedral nanocrystal packed structures in such super crystal systems are also identified. The investigation of octahedral super crystal systems provides an alternate direction in research that may extend the interest of superlattice study to a broad spectrum by enriching and varying the shape of elemental building blocks. This may potentially result in new concepts and more challenging applications such as soft X-ray photonics.