Surface Chemistry Controls Crystallinity of ZnS Nanoparticles

Gilbert, Benjamin; Huang, Feng; Lin, Zhang; Goodell, Carmen; Zhang, Hengzhong; Banfield, Jillian F.

doi:10.1021/nl052201c

Cited by 83 publications

(78 citation statements)

References 47 publications

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“…The transformation at 50 °C is faster than expected by Arrhenius analysis of the lower temperature data, suggesting an additional transformation mechanism operates higher temperature, most likely an aggregation effect. This magnitude of the activation energy indicates that the process does not involve water dissociation (19) or the breaking of ZnS bonds, but is associated with restructuring (bond bending) within the nanoparticles. If bonds were actually breaking and reforming, we would expect an activation energy on the order of hundreds of kilojoules per mole.…”

Section: ) Activation Energy Of the Transformationmentioning

confidence: 98%

Kinetics of Water Adsorption-Driven Structural Transformation of ZnS Nanoparticles

et al. 2008

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Nanoparticles of certain materials can respond structurally to changes in their surface environments. We have previously shown that methanol, water adsorption, and aggregation-disaggregation can change the structure of 3 nm diameter zinc sulfide (ZnS).However, in prior observations of water-driven structure change, aggregation may also have taken place. Therefore, we investigated the structural consequences of water adsorption alone on anhydrous nanoparticles that were dried to minimize changes in aggregation. Using simultaneously collected small-and wide-angle x-ray scattering (SAXS/WAXS) data, we show that water vapor adsorption alone drives a structural transformation in ZnS nanoparticles in the temperature range 22 -40 ˚C. The transition kinetics are strongly temperature dependent, with an activation energy of 58.1 ± 9.8 kJ/mol, consistent with atom displacement rather than bond breaking. At 50 ˚C, aggregate restructuring occurred, increasing the transition kinetics beyond the rate expected for water adsorption alone. The observation of isosbestic points in the WAXS data suggests that the particles do not transform continuously between the initial and final structural state but rather undergo an abrupt change from a less ordered to a more ordered state.

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Section: ) Activation Energy Of the Transformationmentioning

confidence: 98%

Kinetics of Water Adsorption-Driven Structural Transformation of ZnS Nanoparticles

et al. 2008

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“…[ 34 ] The negative charge at the NC surface introduces an electrostatic force, which leads to compressive strain in the NC core. [ 35 ] This compressive strain is serious for small Si NCs given their large surface-to-volume ratios. Therefore, it is observed that the lattice spacing of (111) decreases with the decrease of the NC size.…”

Section: Full Paper Full Paper Full Papermentioning

confidence: 99%

Size‐Dependent Structures and Optical Absorption of Boron‐Hyperdoped Silicon Nanocrystals

Zhou

et al. 2016

Advanced Optical Materials

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and intermediate-band transition for bulk Si. [ 19,20 ] For Si NCs, hyperdoping is also emerging as an effective means to obtain novel properties. [21][22][23][24][25][26] For instance, localized surface plasmon resonance (LSPR) may occur to hyperdoped Si NCs. [21][22][23] And the energy of the LSPR can be conveniently tuned by the doping level.It is well known that the properties of intrinsic Si NCs are critically dependent on the NC size. [ 27,28 ] However, the size effect for hyperdoped Si NCs has been hardly explored. Previous work simply focused on the effect of the doping level. It has been recently predicted that the LSPR of hyperdoped Si NCs can be controlled by not only the doping level but also the NC size. [ 29 ] This highlights that the critical role played by the size effect may remain for Si NCs after hyperdoping. Therefore, it is of great interest to also investigate the size effect for hyperdoped Si NCs. Knowledge concerning the effect of the NC size on the dependence of the properties of hyperdoped Si NCs on the doping level should be invaluable for the synthesis of hyperdoped Si NCs with desired functionality.In this work, Si NCs hyperdoped with different B-doping levels are considered. The dependence of the physical properties of hyperdoped Si NCs on the NC size is examined. It is shown that the largest Si NCs undergo a stronger reduction of the average lattice spacing upon doping with respect to the smallest ones. While Raman, subbandgap optical absorption and the LSPR spectra are all modifi ed with increasing B concentrations in Si NCs, they also indicate that the largest Si NCs are less affected by disorder and charge carrier surface scattering. As a result, there exists a range of doping concentrations where the LSPR energy can be blueshifted as the NC size decreases. Results and DiscussionBoth B-hyperdoped and undoped Si NCs with different sizes have been synthesized by using SiH 4 -based nonthermal plasma. [ 6,[30][31][32] The atomic concentrations of B in B-hyperdoped Si NCs are ≈17%, 36%, and 60%, which are measured with inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Transmission electron microscopy (TEM) and Raman

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“…The availability of particles with a variety of crystallinity provides a model system during which it's possible to see the interior disorder effects of nanoparticle, where properties like mechanical stiffness and fluorescent quantum yield are affected. PDF analysis showed that samples of ZnS nanoparticle with similar mean diameters (3.2-3.6 nm) however synthesized and treated differently possess a dramatic range of interior disorder [5].…”

Section: Synthesis Overviewmentioning

confidence: 99%

“…ZnS nanoparticles doped with transition metal ions are the most important material for research in semiconductor nanocrystals and suggest a new class of luminescent materials. The Mn +2 ion have the electronic configuration [Ar] 3d 5 , these d states of Mn +2 hybridize with the s-p states of ZnS lattice thus resulting in faster energy transition between the two,hence increasing the quantum efficiency. The Mn +2 ions have the broad emission peak that depends upon the host lattice [12][13][14][15].…”

Section: Doped Zinc Sulphidementioning

confidence: 99%

A Review on Zinc Sulphide Nanoparticles: From Synthesis, Properties to Applications

2016

J Bioelectron Nanotechnol

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In this paper the synthesis of zinc sulfide nanoparticles by different routes has been discussed. The emergence of nanotechnology and the synthesis of nanomaterials have revolutionized the field of science and technology. ZnS tends to show the most promising nanoscale morphologies among the inorganic semiconductors thus possessing versatile novel properties and applications. These applications include their use in Field Emitting Diodes (FET), electroluminescence, sensors (UV-light sensors, gas sensors, biosensors), flat panel displays. This article begins with the brief introduction to ZnS its structure, description of physical, chemical and electronic properties. Further followed by the recent experiments conducted in order to improve its nanoscale properties and thus idealizing its applications.

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Surface Chemistry Controls Crystallinity of ZnS Nanoparticles

Cited by 83 publications

References 47 publications

Kinetics of Water Adsorption-Driven Structural Transformation of ZnS Nanoparticles

Kinetics of Water Adsorption-Driven Structural Transformation of ZnS Nanoparticles

Size‐Dependent Structures and Optical Absorption of Boron‐Hyperdoped Silicon Nanocrystals

A Review on Zinc Sulphide Nanoparticles: From Synthesis, Properties to Applications

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