Michelle D. Regulacio

Composition-Tunable Alloyed Semiconductor Nanocrystals

The ability to engineer the band gap energy of semiconductor nanocrystals has led to the development of nanomaterials with many new exciting properties and applications. Band gap engineering has thus proven to be an effective tool in the design of new nanocrystal-based semiconductor devices. As reported in numerous publications over the last three decades, tuning the size of nanocrystalline semiconductors is one way of adjusting the band gap energy. On the other hand, research on band gap engineering via control of nanocrystal composition, which is achieved by adjusting the constituent stoichiometries of alloyed semiconductors, is still in its infancy. In this Account, we summarize recent research on colloidal alloyed semiconductor nanocrystals that exhibit novel composition-tunable properties. Alloying of two semiconductors at the nanometer scale produces materials that display properties distinct not only from the properties of their bulk counterparts but also from those of their parent semiconductors. As a result, alloyed nanocrystals possess additional properties that are composition-dependent aside from the properties that emerge due to quantum confinement effects. For example, although the size-dependent emission wavelength of the widely studied CdSe nanocrystals can be continuously tuned to cover almost the entire visible spectrum, the near-infrared (NIR) region is far outside its spectral range. By contrast, certain alloy compositions of nanocrystalline CdSe(x)Te(1-x), an alloy of CdSe and CdTe, can efficiently emit light in the NIR spectral window. These NIR-emitting nanocrystals are potentially useful in several biomedical applications. In addition, highly stable nanocrystals formed by alloying CdSe with ZnSe (i.e., Zn(x)Cd(1-x)Se) emit blue light with excellent efficiency, a property seldom achieved by the parent binary systems. As a result, these materials can be used in short-wavelength optoelectronic devices. In the future, we foresee new discoveries related to these interesting nanoalloys. In particular, colloidal semiconductor nanoalloys that exhibit composition-dependent magnetic properties have yet to be reported. Further studies of the alloying mechanism are also needed to develop improved synthetic strategies for the preparation of these alloyed nanomaterials.

Multinary I-III-VI2 and I2-II-IV-VI4 Semiconductor Nanostructures for Photocatalytic Applications

Semiconductor nanostructures that can effectively serve as light-responsive photocatalysts have been of considerable interest over the past decade. This is because their use in light-induced photocatalysis can potentially address some of the most serious environmental and energy-related concerns facing the world today. One important application is photocatalytic hydrogen production from water under solar radiation. It is regarded as a clean and sustainable approach to hydrogen fuel generation because it makes use of renewable resources (i.e., sunlight and water), does not involve fossil fuel consumption, and does not result in environmental pollution or greenhouse gas emission. Another notable application is the photocatalytic degradation of nonbiodegradable dyes, which offers an effective way of ridding industrial wastewater of toxic organic pollutants prior to its release into the environment. Metal oxide semiconductors (e.g., TiO2) are the most widely studied class of semiconductor photocatalysts. Their nanostructured forms have been reported to efficiently generate hydrogen from water and effectively degrade organic dyes under ultraviolet-light irradiation. However, the wide band gap characteristic of most metal oxides precludes absorption of light in the visible region, which makes up a considerable portion of the solar radiation spectrum. Meanwhile, nanostructures of cadmium chalcogenide semiconductors (e.g., CdS), with their relatively narrow band gap that can be easily adjusted through size control and alloying, have displayed immense potential as visible-light-responsive photocatalysts, but the intrinsic toxicity of cadmium poses potential risks to human health and the environment. In developing new nanostructured semiconductors for light-driven photocatalysis, it is important to choose a semiconducting material that has a high absorption coefficient over a wide spectral range and is safe for use in real-world settings. Among the most promising candidates are the multinary chalcogenide semiconductors (MCSs), which include the ternary I-III-VI2 semiconductors (e.g., AgGaS2, CuInS2, and CuInSe2) and the quaternary I2-II-IV-VI4 semiconductors (e.g., Cu2ZnGeS4, Cu2ZnSnS4, and Ag2ZnSnS4). These inorganic compounds consist of environmentally benign elemental components, exhibit excellent light-harvesting properties, and possess band gap energies that are well-suited for solar photon absorption. Moreover, the band structures of these materials can be conveniently modified through alloying to boost their ability to harvest visible photons. In this Account, we provide a summary of recent research on the use of ternary I-III-VI2 and quaternary I2-II-IV-VI4 semiconductor nanostructures for light-induced photocatalytic applications, with focus on hydrogen production and organic dye degradation. We include a review of the solution-based methods that have been employed to prepare multinary chalcogenide semiconductor nanostructures of varying compositions, sizes, shapes, and crystal structures, which are factors that are known to have significant influence on the photocatalytic activity of semiconductor photocatalysts. The enhancement of photocatalytic performance through creation of hybrid nanoscale architectures is also presented. Lastly, views on the current challenges and future directions are discussed in the concluding section.

One-Pot Synthesis of Cu1.94S−CdS and Cu1.94S−ZnxCd1−xS Nanodisk Heterostructures

Nanodisk heterostructures consisting of monoclinic Cu(1.94)S and wurtzite CdS have been colloidally synthesized for the first time. Initially, hexagonal-shaped nanodisks of Cu(1.94)S were produced upon thermolysis of a copper complex in a solvent mixture of HDA and TOA at 250 °C. Rapid addition of Cd precursor to the reaction mixture resulted in the partial conversion of Cu(1.94)S into CdS, yielding Cu(1.94)S-CdS nanoheterostructures. The original morphology of the Cu(1.94)S nanodisks was conserved during the transformation. When Zn precursor was added together with the Cd precursor, Cu(1.94)S-Zn(x)Cd(1-x)S nanodisks were generated. These two-component nanostructures are potentially useful in the fabrication of heterojunction solar cells.

Alloyed (ZnS)x(CuInS2)(1-x) semiconductor nanorods: synthesis, bandgap tuning and photocatalytic properties.

Rod-like nanocrystals of the semiconductor alloy (ZnS)(x)(CuInS(2))(1-x) (ZCIS) have been colloidally prepared by using a one-pot non-injection-based synthetic strategy. The ZCIS nanorods crystallize in the hexagonal wurtzite structure and display preferential growth in the direction of the c axis. The bandgap of these quarternary alloyed nanorods can be conveniently tuned by varying the ratio of ZnS to CuInS(2). A non-linear relationship between the bandgap and the alloy composition is observed. The ZCIS nanorods are found to exhibit promising photocatalytic behaviour in visible-light-driven degradation of Rhodamine B.

Intrinsic Properties of Stoichiometric LaFePo

DC and ac magnetization, resistivity, specific-heat, and neutron-diffraction data reveal that stoichiometric LaFePO is metallic and non-superconducting above

Facile noninjection synthesis and photocatalytic properties of wurtzite-phase CuGaS2 nanocrystals with elongated morphologies

T=0.35\text{ }\text{K}

Alloyed ZnS-CuInS2 Semiconductor Nanorods and Their Nanoscale Heterostructures for Visible-Light-Driven Photocatalytic Hydrogen Generation.

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Rapid Copper Metallization of Textile Materials: a Controlled Two-Step Route to Achieve User-Defined Patterns under Ambient Conditions

\ensuremath{\gamma}=12.5\frac{\text{mJ}}{\text{mol}\text{ }{\text{K}}^{2}}

Preparation, Functionality, and Application of Metal Oxide-coated Noble Metal Nanoparticles.

. Neutron-diffraction data at room temperature and

COLLOIDAL PREPARATION OF MONODISPERSE NANOCRYSTALS

T=10\text{ }\text{K}