-
[show abstract]
[hide abstract]
ABSTRACT: Hybrid nanoparticle (NP) arrays based on particles of different sizes and chemistries are highly desirable to obtain tunable properties for nanodevices. A simple approach is demonstrated that precisely controls the spatial organization of NPs within block copolymer supramolecular frameworks based on the ratio of the NP size to the block copolymer periodicity. A range of hybrid NP assemblies in thin films, ranging from 1D chains, 2D lattices, and 3D arrays and networks of NPs, are demonstrated.
Journal of the American Chemical Society 01/2013; · 9.91 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Nanocrystals of cadmium selenide exhibit a form of polytypism, with stable forms in both the wurtzite and zinc blende crystal structures. As a result, wurtzite nanorods of cadmium selenide tend to form stacking faults of zinc blende along the c-axis. These faults were found to preferentially form during the growth of the (001) face, which accounts for 40% of the rod's total length. Since II-VI semiconductor nanorods lack inversion symmetry along the c-axis of the particle, the two ends of the nanorod may be identified by this anisotropic distribution of faults.
Nano Letters 12/2012; · 13.20 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Squaring the circle: Carbon monoxide was used to grow faceted cube-like platinum tips on semiconductor nanorods. These novel hybrid structures reveal a new degree of synthetic control and might allow control over the catalytic activity of nanoscale photocatalysts by adding defined faceting.
Angewandte Chemie International Edition 11/2012; · 13.45 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: III-V nanocrystals displaying high crystallinity and low size dispersity are difficult to access by direct synthesis from molecular precursors. Here, we demonstrate that cation exchange of cadmium pnictide nanocrystals with group 13 ions yields monodisperse, crystalline III-V nanocrystals, including GaAs, InAs, GaP, and InP. This report highlights the versatility of cation exchange for accessing nanocrystals with covalent lattices.
Journal of the American Chemical Society 11/2012; · 9.91 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: The kinetics and thermodynamics of structural transformations under pressure depend strongly on particle size due to the influence of surface free energy. By suitable design of surface structure, composition, and passivation it is possible, in principle, to prepare nanocrystals in structures inaccessible to bulk materials. However, few realizations of such extreme size-dependent behavior exist. Here, we show with molecular dynamics computer simulation that in a model of CdSe/ZnS core/shell nanocrystals the core high-pressure structure can be made metastable under ambient conditions by tuning the thickness of the shell. In nanocrystals with thick shells, we furthermore observe a wurtzite to NiAs transformation, which does not occur in the pure bulk materials. These phenomena are linked to a fundamental change in the atomistic transformation mechanism from heterogeneous nucleation at the surface to homogeneous nucleation in the crystal core.
Nano Letters 07/2012; · 13.20 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Ferroelectricity in finite-dimensional systems continues to arouse interest, motivated by predictions of vortex polarization states and the utility of ferroelectric nanomaterials in memory devices, actuators and other applications. Critical to these areas of research are the nanoscale polarization structure and scaling limit of ferroelectric order, which are determined here in individual nanocrystals comprising a single ferroelectric domain. Maps of ferroelectric structural distortions obtained from aberration-corrected transmission electron microscopy, combined with holographic polarization imaging, indicate the persistence of a linearly ordered and monodomain polarization state at nanometre dimensions. Room-temperature polarization switching is demonstrated down to ~5 nm dimensions. Ferroelectric coherence is facilitated in part by control of particle morphology, which along with electrostatic boundary conditions is found to determine the spatial extent of cooperative ferroelectric distortions. This work points the way to multi-Tbit/in(2) memories and provides a glimpse of the structural and electrical manifestations of ferroelectricity down to its ultimate limits.
Nature Material 07/2012; 11(8):700-9. · 32.84 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We demonstrate a new light trapping technique that exploits dielectric core-shell optical antennas to strongly enhance solar absorption. This approach can allow the thickness of active materials in solar cells lowered by almost 1 order of magnitude without scarifying solar absorption capability. For example, it can enable a 70 nm thick hydrogenated amorphous silicon (a-Si:H) thin film to absorb 90% of incident solar radiation above the bandgap, which would otherwise require a thickness of 400 nm in typical antireflective coated thin films. This strong enhancement arises from a controlled optical antenna effect in patterned core-shell nanostructures that consist of absorbing semiconductors and nonabsorbing dielectric materials. This core-shell optical antenna benefits from a multiplication of enhancements contributed by leaky mode resonances (LMRs) in the semiconductor part and antireflection effects in the dielectric part. We investigate the fundamental mechanism for this enhancement multiplication and demonstrate that the size ratio of the semiconductor and the dielectric parts in the core-shell structure is key for optimizing the enhancement. By enabling strong solar absorption enhancement, this approach holds promise for cost reduction and efficiency improvement of solar conversion devices, including solar cells and solar-to-fuel systems. It can generally apply to a wide range of inorganic and organic active materials. This dielectric core-shell antenna can also find applications in other photonic devices such as photodetectors, sensors, and solid-state lighting diodes.
Nano Letters 06/2012; 12(7):3674-81. · 13.20 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Nanostructured light trapping has emerged as a promising route toward improved efficiency in solar cells. We use coupled optical and electrical modeling to guide optimization of such nanostructures. We study thin-film n-i-p a-Si:H devices and demonstrate that nanostructures can be tailored to minimize absorption in the doped a-Si:H, improving carrier collection efficiency. This suggests a method for device optimization in which optical design not only maximizes absorption, but also ensures resulting carriers are efficiently collected.
Nano Letters 05/2012; 12(6):2894-900. · 13.20 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: In conventional spectroscopy, transitions between electronic levels are governed by the electric dipole selection rule because electric quadrupole, magnetic dipole, and coupled electric dipole-magnetic dipole transitions are forbidden in a far field. We demonstrated that by using nanostructured electromagnetic fields, the selection rules of absorption spectroscopy could be fundamentally manipulated. We also show that forbidden transitions between discrete quantum levels in a semiconductor nanorod structure are allowed within the near-field of a noble metal nanoparticle. Atomistic simulations analyzed by an effective mass model reveal the breakdown of the dipolar selection rules where quadrupole and octupole transitions are allowed. Our demonstration could be generalized to the use of nanostructured near-fields for enhancing light-matter interactions that are typically weak or forbidden.
Proceedings of the National Academy of Sciences 05/2012; 109(21):8016-9. · 9.68 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We introduce a new type of liquid cell for in situ transmission electron microscopy (TEM) based on entrapment of a liquid film between layers of graphene. The graphene liquid cell facilitates atomic-level resolution imaging while sustaining the most realistic liquid conditions achievable under electron-beam radiation. We employ this cell to explore the mechanism of colloidal platinum nanocrystal growth. Direct atomic-resolution imaging allows us to visualize critical steps in the process, including site-selective coalescence, structural reshaping after coalescence, and surface faceting.
Science 04/2012; 336(6077):61-4. · 31.20 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We used a fluorogenic reaction to study in conjunction the photocatalytic properties for both active sites (trapped photogenerated electrons and holes) on individual Sb-doped TiO(2) nanorods with single-molecule fluorescence microscopy. It was found that active sites around trapped holes show higher activity, stronger binding ability, and a different dissociation mechanism for the same substrate and product molecules in comparison with the active sites around trapped electrons. These differences could be elucidated by a model involving the charged microenvironments around the active sites.
Journal of the American Chemical Society 03/2012; 134(9):3946-9. · 9.91 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Pure crystals: Ion exchange of semiconductor nanocrystals yielded materials with poor optoelectronic properties such as low photoluminescence quantum yields. The reason for the low quantum yields of these nanocrystals are impurities at the level of a few atoms per nanocrystal. Cation-exchanged nanostructures, however, could be purified post exchange from such impurities resulting in high-quality nanocrystals.
Angewandte Chemie International Edition 03/2012; 51(10):2387-90. · 13.45 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Direct imaging of nanoparticle solutions by liquid phase transmission electron microscopy has enabled unique in situ studies of nanoparticle motion and growth. In the present work, we report on real-time formation of two-dimensional nanoparticle arrays in the very low diffusive limit, where nanoparticles are mainly driven by capillary forces and solvent fluctuations. We find that superlattice formation appears to be segregated into multiple regimes. Initially, the solvent front drags the nanoparticles, condensing them into an amorphous agglomerate. Subsequently, the nanoparticle crystallization into an array is driven by local fluctuations. Following the crystallization event, superlattice growth can also occur via the addition of individual nanoparticles drawn from outlying regions by different solvent fronts. The dragging mechanism is consistent with simulations based on a coarse-grained lattice gas model at the same limit.
ACS Nano 03/2012; 6(3):2078-85. · 10.77 Impact Factor
-
Angewandte Chemie International Edition 09/2011; 50(43):10203-7. · 13.45 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: We investigated the effect of PbSe quantum dot size on the performance of Schottky solar cells made in an ITO/PEDOT/PbSe/aluminum structure, varying the PbSe nanoparticle diameter from 1 to 3 nm. In this highly confined regime, we find that the larger particle bandgap can lead to higher open-circuit voltages (∼0.6 V), and thus an increase in overall efficiency compared to previously reported devices of this structure. To carry out this study, we modified existing synthesis methods to obtain ultrasmall PbSe nanocrystals with diameters as small as 1 nm, where the nanocrystal size is controlled by adjusting the growth temperature. As expected, we find that photocurrent decreases with size due to reduced absorption and increased recombination, but we also find that the open-circuit voltage begins to decrease for particles with diameters smaller than 2 nm, most likely due to reduced collection efficiency. Owing to this effect, we find peak performance for devices made with PbSe dots with a first exciton energy of ∼1.6 eV (2.3 nm diameter), with a typical efficiency of 3.5%, and a champion device efficiency of 4.57%. Comparing the external quantum efficiency of our devices to an optical model reveals that the photocurrent is also strongly affected by the coherent interference in the thin film due to Fabry-Pérot cavity modes within the PbSe layer. Our results demonstrate that even in this simple device architecture, fine-tuning of the nanoparticle size can lead to substantial improvements in efficiency.
ACS Nano 09/2011; 5(10):8140-7. · 10.77 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: In this work, H(2) absorption and desorption in faceted, crystalline Au/Pd core/shell nanocrystals and their interaction with a SiO(x)/Si support were studied at the single-particle level. Dark-field microscopy was used to monitor the changing optical properties of these Au/Pd nanoparticles (NPs) upon exposure to H(2) as reversible H(2) uptake from the Pd shell proceeded. Analysis of the heterogeneous ensemble of NPs revealed the H(2) uptake trajectory of each nanocrystal to be shape-dependent. Differences in particle uptake trajectories were observed for individual particles with different shapes, faceting, and Pd shell thickness. In addition to palladium hydride formation, the single-particle trajectories were able to decipher specific instances where palladium silicide formation and Au/Pd interdiffusion occurred and helped us determine that this was more frequently seen in those particles within an ensemble having thicker Pd shells. This noninvasive, plasmonic-based direct sensing technique shows the importance of single-particle experiments in catalytically active systems and provides a foundation for studying more complex catalytic processes in inhomogeneous NP systems.
Journal of the American Chemical Society 08/2011; 133(34):13220-3. · 9.91 Impact Factor
-
Jong Min Yuk,
Kwanpyo Kim,
Benjamín Alemán,
William Regan,
Ji Hoon Ryu,
Jungwon Park,
Peter Ercius,
Hyuck Mo Lee, A Paul Alivisatos,
Michael F Crommie,
Jeong Yong Lee,
Alex Zettl
[show abstract]
[hide abstract]
ABSTRACT: We report a new and highly versatile approach to artificial layered materials synthesis which borrows concepts of molecular beam epitaxy, self-assembly, and graphite intercalation compounds. It readily yields stacks of graphene (or other two-dimensional sheets) separated by virtually any kind of "guest" species. The new material can be "sandwich like", for which the guest species are relatively closely spaced and form a near-continuous inner layer of the sandwich, or "veil like", where the guest species are widely separated, with each guest individually draped within a close-fitting, protective yet atomically thin graphene net or veil. The veils and sandwiches can be intermixed and used as a two-dimensional platform to control the movements and chemical interactions of guest species.
Nano Letters 08/2011; 11(8):3290-4. · 13.20 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: The study of first-order structural transformations has been of great interest to scientists in many disciplines. Expectations from phase-transition theory are that the system fluctuates between two equilibrium structures near the transition point and that the region of transition broadens in small crystals. We report the direct observation of structural fluctuations within a single nanocrystal using transmission electron microscopy. We observed trajectories of structural transformations in individual nanocrystals with atomic resolution, which reveal details of the fluctuation dynamics, including nucleation, phase propagation, and pinning of structural domains by defects. Such observations provide crucial insight for the understanding of microscopic pathways of phase transitions.
Science 07/2011; 333(6039):206-9. · 31.20 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Plasmon rulers can be used to determine nanoscale distances within chemical or biological species. They are based on the spectral shift of the scattering spectrum when two plasmonic nanoparticles approach one another. However, the one-dimensionality of current plasmon rulers hampers the comprehensive understanding of many intriguing processes in soft matter, which take place in three dimensions. We demonstrated a three-dimensional plasmon ruler that is based on coupled plasmonic oligomers in combination with high-resolution plasmon spectroscopy. This enables retrieval of the complete spatial configuration of complex macromolecular and biological processes as well as their dynamic evolution.
Science 06/2011; 332(6036):1407-10. · 31.20 Impact Factor
-
[show abstract]
[hide abstract]
ABSTRACT: Recent advances in the synthesis of multicomponent nanocrystals have enabled the design of nanocrystal molecules with unique photophysical behavior and functionality. Here we demonstrate a highly luminescent nanocrystal molecule, the CdSe/CdS core/shell tetrapod, which is designed to have weak vibronic coupling between excited states and thereby violates Kasha's rule via emission from multiple excited levels. Using single particle photoluminescence spectroscopy, we show that in addition to the expected LUMO to HOMO radiative transition, a higher energy transition is allowed via spatially indirect recombination. The oscillator strength of this transition can be experimentally controlled, enabling control over carrier behavior and localization at the nanoscale.
Nano Letters 06/2011; 11(6):2358-62. · 13.20 Impact Factor
