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Accurate measurements of semiconductor nanocrystal (NC) emission quantum yields (QYs) are critical to condensed phase optical refrigeration. Of particular relevance to measuring NC QYs is a longstanding debate as to whether an excitation energy-dependent (EED) QY exists. Various reports indicate existence of NC EED QYs, suggesting that the phenomenon is linked to specific ensemble properties. We therefore investigate here the existence of EED QYs in two NC systems (CsPbBr3 and CdSe) that are possible candidates for use in optical refrigeration. The influence of NC size, size-distribution, surface ligand, and as-made emission QYs are investigated. Existence of EED QYs is assessed using two approaches (an absolute approach using an integrating sphere and a relative approach involving excitation spectroscopy). Altogether, our results show no evidence of EED QYs across samples. This suggests that parameters beyond those mentioned above are responsible for observations of NC EED QYs.

Hole trapping at iodine (I) sites in MAPbBr1.5I1.5 mixed halide perovskites (MHP) is responsible for iodine migration and its eventual expulsion into solution. We have now modulated the photoinduce...

Size-dependent photoluminescence Stokes shifts (ΔEs) universally exist in CsPbX3 (X = Cl-, Br-, or I-) perovskite nanocrystals (NCs). ΔEs values, which range from ∼15 to 100 meV for NCs with average edge lengths (l) from approximately 13 to 3 nm, are halide-dependent such that ΔEs(CsPbI3) > ΔEs(CsPbBr3) ≳ ΔEs(CsPbCl3). Observed size-dependent Stokes shifts are not artifacts of ensemble size distributions as demonstrated through measurements of single CsPbBr3 NC Stokes shifts (⟨ΔEs⟩ = 42 ± 5 meV), which are in near quantitative agreement with associated ensemble (l = 6.8 ± 0.8 nm) ΔEs values (ΔEs ≈ 50 meV). Transient differential absorption measurements additionally illustrate no significant spectral dynamics on the picosecond time scale that would contribute to ΔEs. This excludes polaron formation as being responsible for ΔEs. Altogether, the results point to an origin for ΔEs, intrinsic to the size-dependent electronic properties of individual perovskite NCs.

Light-induced halide segregation is an intrinsic instability of mixed-halide perovskites, which complicates their successful use in tandem solar cells. Methods to suppress this phenomenon remain elusive because of its ambiguous origin. Beal et al. demonstrate that photostability is not an exclusive property of perovskite crystal structure and instead highlight the need for a microscopic understanding of the phenomenon.

Light is known to induce segregation of iodine and bromine in mixed-halide perovskites. Counterintuitively, it is now shown that irradiation at higher intensity reverses this process, leading to halide remixing.

Recent experiments by Raino et al. ( Nature 2018, 563, 671−675) have documented cooperative emission from CsPbBr3 nanocrystal superlattices, exhibiting the hallmarks of low-temperature superradianc...

Over the past two decades, there have been sizable efforts to realize condensed phase optical cooling. To date, however, there have been no verifiable demonstrations of semiconductor-based laser cooling. Recently, advances in the synthesis of semiconductor nanostructures have led to the availability of high-quality semiconductor nanocrystals, which possess superior optical properties relative to their bulk counterparts. In this review, we describe how these nanostructures can be used to demonstrate condensed phase laser cooling. We begin with a description of charge carrier dynamics in semiconductor nanocrystals and nanostructures under both above gap and below-gap excitation. Two critical parameters for realizing laser cooling are identified: emission quantum yield and upconversion efficiency. We report the literature values of these two parameters for different nanocrystal/nanostructure systems as well as the measurement approaches used to estimate them. We identify CsPbBr3 nanocrystals as a potential system by which to demonstrate verifiable laser cooling given their ease of synthesis, near-unity emission quantum yields and sizable upconversion efficiencies. Feasibility is further demonstrated through numerical simulations of CsPbBr3 nanocrystals embedded in an aerogel matrix. Our survey generally reveals that optimized semiconductor nanocrystals and nanostructures are poised to demonstrate condensed phase laser cooling in the near future. Advances toward cooling semiconductor nanostructures using light have been reviewed by researchers in the US. Laser light can cool clouds of atoms to ultralow temperatures. Cooling of solids works because when light absorbed by matter is re-emitted, it can carry some of the matter’s thermal energy with it. To date only gases have been successfully cooled to very low temperatures. Masaru Kuno and colleagues from the University of Notre Dame summarize why achieving the optical cooling of solids is so difficult and how the properties of semiconductor nanocrystals might make laser cooling possible. The authors believe that laser cooling in semiconductors could be demonstrated in the near future, offering the potential for integrating this effect into optoelectronic devices. Overview of up-conversion based condensed phase laser cooling of semiconductor nanostructures. Two critical parameters dictate the likelihood of realizing solid state optical refrigeration: nanostructure emission quantum yield and up-conversion efficiency. This review summarizes both parameters for existing high emission quantum yield semiconductor nanostructures such as CdSe and CsPbBr3. CsPbBr3 nanocrystals, in particular, possess optimal parameters for cooling, namely near unity emission quantum yields and up-conversion efficiencies up to 75%. This makes them promising materials for verifiable demonstrations of condensed phase laser cooling.

The facile solution-processability of methylammonium lead halide (CH3NH3PbI3) perovskites has catalyzed the development of inexpensive, hybrid perovskite-based optoelectronics. It is apparent, though, that solution-processed CH3NH3PbI3 films possess local emission heterogeneities, stemming from electronic disorder in the material. Herein we investigate the spatially resolved emission properties of CH3NH3PbI3 thin films through detailed emission intensity versus excitation intensity measurements. These studies enable us to establish the existence of nonuniform trap density variations wherein regions of CH3NH3PbI3 films exhibit effective free carrier recombination while others exhibit emission dynamics strongly influenced by the presence of trap states. Such trap density variations lead to spatially varying emission quantum yields and correspondingly impact the performance of both methylammonium lead halide perovskite solar cells and other hybrid perovskite-based devices. Of additional note is that the observed spatial extent of the optical disorder extends over length scales greater than that of underlying crystalline domains, suggesting the existence of other factors, beyond grain boundary-related nonradiative recombination channels, which lead to significant intrafilm optical heterogeneities.

We provide, for the first time, direct experimental evidence for heterogeneous blinking in reduced graphene oxide (rGO) during photolysis. The spatially resolved intermittency originates from regions within individual rGO sheets and shows 1/f-like power spectral density. We describe the evolution of rGO blinking using the multiple recombination center (MRC) model that captures common features of nanoscale blinking. Our results illustrate the universal nature of blinking and suggest a common microscopic origin for the effect.

We report for the first time the synthesis of large, free-standing, Mo2O2(μ-S)2(Et2dtc)2 (MoDTC) nanosheets (NSs), which exhibit an electron-beam induced crystalline-to-amorphous phase transition. Both electron beam ionization and femtosecond (fs) optical excitation induce the phase transition, which is size-, morphology-, and composition-preserving. Resulting NSs are the largest, free-standing regularly shaped two-dimensional amorphous nanostructures made to date. More importantly, amorphization is accompanied by dramatic changes to the NS electrical and optical response wherein resulting amorphous species exhibit room-temperature conductivities 5 orders of magnitude larger than those of their crystalline counterparts. This enhancement likely stems from the amorphization-induced formation of sulfur vacancy-related defects and is supported by temperature-dependent transport measurements, which reveal efficient variable range hopping. MoDTC NSs represent one instance of a broader class of transition metal ...

We demonstrate the use of cation exchange to synthesize ultrathin and thickness-controlled Cu2-xSe nanosheets (NSs) beginning with CdSe NSs. In this manner, extremely thin (i.e., 1.6 nm thickness) Cu2-xSe NSs, beyond which can be made directly, have been obtained. Furthermore, they represent the thinnest NSs produced via cation exchange. Notably, the exchange reaction preserves the starting morphology of the CdSe sheets and also retains their cubic crystal structure. The resulting nonstoichiometric and cubic Cu2-xSe NSs are stable and do not exhibit any signs of Cu or Se oxidation after exposure to air for 2 weeks. Resulting NSs also show the existence of a localized surface plasmon resonance in the infrared due to the presence of copper vacancies. Efforts to isolate intermediates during the cation exchange reaction show that it occurs via a mechanism where entire sheets are rapidly converted into the final product once the exchange reaction commences, precluding the isolation of alloyed species.

Laser reduction of graphene oxide (GO) offers unique opportunities for the rapid, nonchemical production of graphene. By tuning relevant reduction parameters, the band gap and conductivity of reduced GO can be precisely controlled. In situ monitoring of single layer GO reduction is therefore essential. In this report, we show the direct observation of laser-induced, single layer GO reduction through correlated changes to its absorption and emission. Absorption/emission movies illustrate the initial stages of single layer GO reduction, its transition to reduced-GO (rGO) as well as its subsequent decomposition upon prolonged laser illumination. These studies reveal GO’s photoreduction life cycle and through it native GO/rGO absorption coefficients, their intrasheet distributions as well as their spatial heterogeneities. Extracted absorption coefficients for unreduced GO are α405 nm ≈ 6.5 ± 1.1 × 104 cm–1, α520 nm ≈ 2.1 ± 0.4 × 104 cm–1, and α640 nm ≈ 1.1 ± 0.3 × 104 cm–1 while corresponding rGO α-values are α405 nm ≈ 21.6 ± 0.6 × 104 cm–1, α520 nm ≈ 16.9 ± 0.4 × 104 cm–1, and α640 nm ≈ 14.5 ± 0.4 × 104 cm–1. More importantly, the correlated absorption/emission imaging provides us with unprecedented insight into GO’s underlying photoreduction mechanism, given our ability to spatially resolve its kinetics and to connect local rate constants to activation energies. On a broader level, the developed absorption imaging is general and can be applied toward investigating the optical properties of other two-dimensional materials, especially those that are nonemissive and are invisible to current single molecule optical techniques. Fil: Sokolov, Denis A.. University Of Notre Dame-Indiana; Estados Unidos Fil: Morozov, Yurii V.. University Of Notre Dame-Indiana; Estados Unidos. Taras Shevchenko National University of Kiev; Rusia Fil: McDonald, Matthew P.. University Of Notre Dame-Indiana; Estados Unidos Fil: Vietmeyer, Felix. University Of Notre Dame-Indiana; Estados Unidos Fil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Kuno, Masaru. University Of Notre Dame-Indiana; Estados Unidos

We show the general functionalization of cotton fabrics using solution-synthesized CdSe and CdTe nanowires (NWs). Conformal coatings onto individual cotton fibers have been achieved through various physical and chemical approaches. Some involve the electrostatic attraction of NWs to cotton charged positively with a Van de Graaff generator or via 2,3-epoxypropyltrimethylammonium chloride treatments. Resulting NW-functionalized textiles consist of dense, conformal coatings and have been characterized for their UV-visible absorption as well as Raman activity. We demonstrate potential uses of these functionalized textiles through two proof-of-concept applications. The first entails barcoding cotton using the unique Raman signature of the NWs. We also demonstrate the surface-enhancement of their Raman signatures using codeposited Au. A second demonstration takes advantage of the photoconductive nature of semiconductor NWs to create cotton-based photodetectors. Apart from these illustrations, NW-functionalized cotton textiles may possess other uses in the realm of medical, anticounterfeiting, and photocatalytic applications.

Graphene's success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in field-effect transistors, spin- and valley-tronics, thermoelectrics, and topological insulators, among many other applications.

To better understand the role nanoscale heterojunctions play in the photocatalytic generation of hydrogen, we have designed several model one-dimensional (1D) heterostructures based on CdSe nanowires (NWs). Specifically, CdSe/CdS core/shell NWs and Au nanoparticle (NP)-decorated core and core/shell NWs have been produced using facile solution chemistries. These systems enable us to explore sources for efficient charge separation and enhanced carrier lifetimes important to photocatalytic processes. We find that visible light H2 generation efficiencies in the produced hybrid 1D structures increase in the order CdSeCdSe/Au NPCdSe/CdS/Au NPCdSe/CdS with a maximum H2 generation rate of 58.06 ± 3.59 μmol h(-1) g(-1) for CdSe/CdS core/shell NWs. This is 30 times larger than the activity of bare CdSe NWs. Using femtosecond transient differential absorption spectroscopy, we subsequently provide mechanistic insight into the role nanoscale heterojunctions play by directly monitoring charge flow and accumulation in these hybrid systems. In turn, we explain the observed trend in H2 generation rates with an important outcome being direct evidence for heterojunction-influenced charge transfer enhancements of relevant chemical reduction processes.

Two-dimensional (2D) nanomaterials have recently received significant attention because of their attractiveness for use in many nanostructured devices. Layered transition-metal dichalcogenides are of particular interest because reducing their dimensionality causes changes in their already anisotropic physical and chemical properties. The present study describes the first bottom-up solution-phase synthesis of thin highly crystalline titanium disulfide (TiS2) nanosheets (NSs) using abundant low-cost molecular precursors. The obtained TiS2 NSs have average dimensions of ∼500 nm × 500 nm in the basal plane and have thicknesses of ∼5 nm. They exhibit broad absorption in the visible that tails out into the near-infrared. The obtained results demonstrate new opportunities in synthesizing low-dimensional 2D nanomaterials with potential use in various photochemical energy applications.

Semiconductor nanostructures produced by wet chemical synthesis are extremely heterogeneous, which makes single particle techniques a useful way to interrogate their properties. In this paper the ultrafast dynamics of single CdTe nanowires are studied by transient absorption microscopy. The wires have lengths of several micrometers and lateral dimensions on the order of 30 nm. The transient absorption traces show very fast decays, which are assigned to charge carrier trapping into surface defects. The time constants vary for different wires due to differences in the energetics and/or density of surface trap sites. Measurements performed at the band edge compared to the near-IR give slightly different time constants, implying that the dynamics for electron and hole trapping are different. The rate of charge carrier trapping was observed to slow down at high carrier densities, which was attributed to trap-state filling. Modulations due to the fundamental and first overtone of the acoustic breathing mode were also observed in the transient absorption traces. The quality factors for these modes were similar to those measured for metal nanostructures, and indicate a complex interaction with the environment.

There has recently been much work on using nanowires for various applications. Examples include photodetectors and photovoltaics. One of the main reasons for this stems from the nanowire’s asymmetr...

We investigate the excitation polarization anisotropy of individual semiconductor nanowires (NWs) by monitoring their band edge emission above 680 nm in order to clarify the origin of their strong polarization response. Samples studied include both CdSe and CdSe/CdS core/shell nanowires grown using solution chemistry as well as analogous wires made via chemical-vapor-deposition (CVD). In the limit of optically thick wires, with radii above ∼25 nm, we find NW optical responses consistent with the interaction between strong dielectric contrast influences and the onset of bulk-like behavior. Namely, a sizable wavelength dependence of the excitation polarization anisotropy (ρ(exc)) exists when NW diameters become comparable to the wavelength of light inside the wire. As a consequence, pronounced ρ(exc) rolloffs occur at short wavelengths. By contrast, thinner wires do not exhibit such wavelength dependencies, in agreement with earlier studies. We quantitatively explain observed wavelength sensitivities by modeling the NW as an absorbing dielectric cylinder under plane wave excitation. A comparison of predicted ρ(exc)-values to experimental numbers shows good agreement and confirms the existence of wavelength-dependent ρ(exc)-values in optically thick wires. Additional results of the model include generalized expressions for NW linear absorption cross-sections under parallel, perpendicular, and circularly polarized excitation. This study therefore adds to a growing body of knowledge about NW polarization anisotropies, specifically, their response in a size regime where dielectric contrast effects compete with the onset of bulk-like behavior.

Polarization-sensitive photodetectors are demonstrated using solution-synthesized CdSe nanowire (NW) solids. Photocurrent action spectra taken with a tunable white light source match the solution linear absorption spectra of the NWs, showing that the NW network is responsible for the device photoconductivity. Temperature-dependent transport measurements reveal that carriers responsible for the dark current through the nanowire solids are thermally excited across CdSe band gap. The NWs are aligned using dielectrophoresis between prepatterned electrodes using conventional optical photolithography. The photocurrent through the NW solid is found to be polarization-sensitive, consistent with complementary absorption (emission) measurements of both single wires and their ensembles. The range of solution-processed semiconducting NW materials, their facile synthesis, ease of device fabrication, and compatibility with a variety of substrates make them attractive for potential nanoscale polarization-sensitive photodetectors.

The origin of sizable absorption polarization anisotropies (ρabs) in one-dimensional (1D) semiconductor nanowires (NWs) has been debated. Invoked explanations employ either classical or quantum mechanical origins, where the classical approach suggests dielectric constant mismatches between the NW and its surrounding environment as the predominant source of observed polarization sensitivities. At the same time, the confinement-influenced mixing of states suggests a sizable contribution from polarization-sensitive transition selection rules. Sufficient evidence exists in the literature to support either claim. However, in all cases, these observations stem from excitation polarization anisotropy (ρexc) studies, which only indirectly measure ρabs. In this manuscript, we directly measure the band edge extinction polarization anisotropies (ρext) of individual CdSe NWs using single NW extinction spectroscopy. Observed polarization anisotropies possess distinct spectral features and wavelength dependencies that correlate well with theoretical transition selection rules derived from a six-band k·p theory used to model the electronic structure of CdSe NWs.

Ultrafast relaxation dynamics of charge carriers in CdSe quantum wires with diameters between 6 and 8 nm are studied as a function of carrier density. At high electron-hole pair densities above 10(19) cm(-3) the dominant process for carrier cooling is the "bimolecular" Auger recombination of one-dimensional (1D) excitons. However, below this excitation level an unexpected transition from a bimolecular (exciton-exciton) to a three-carrier Auger relaxation mechanism occurs. Thus, depending on excitation intensity, electron-hole pair relaxation dynamics in the nanowires exhibit either 1D or 0D (quantum dot) character. This dual nature of the recovery kinetics defines an optimal intensity for achieving optical gain in solution-grown nanowires given the different carrier-density-dependent scaling of relaxation rates in either regime.

Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ∼434.29 ± 27.40 μmol h(-1) g(-1) under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities.

Fluorescence “blinking” kinetics of isolated colloidal InP quantum dots (QDs) are investigated via confocal single molecule microscopy. Analysis of fluorescence trajectories reveals inverse power law behavior (∝ 1/τm) in on/off time probability densities with mon ≈ 2.0(2) and moff ≈ 1.5(1). Such an inverse power law in both on/off times is inconsistent with a static distribution of electron/hole trapping sites and highlights the role of fluctuations in the QD nanoenvironment.

Graphene oxide (GO) is an important precursor in the production of chemically derived graphene. During reduction, GO’s electrical conductivity and band gap change gradually. Doping and chemical functionalization are also possible, illustrating GO’s immense potential in creating functional devices through control of its local hybridization. Here we show that laser-induced photolysis controllably reduces individual single-layer GO sheets. The reaction can be followed in real time through sizable decreases in GO’s photoluminescence efficiency along with spectral blueshifts. As-produced reduced graphene oxide (rGO) sheets undergo additional photolysis, characterized by dramatic emission enhancements and spectral redshifts. Both GO’s reduction and subsequent conversion to photobrightened rGO are captured through movies of their photoluminescence kinetics. Rate maps illustrate sizable spatial and temporal heterogeneities in sp2 domain growth and reveal how reduction “flows” across GO and rGO sheets. The observed heterogeneous reduction kinetics provides mechanistic insight into GO’s conversion to chemically derived graphene and highlights opportunities for overcoming its dynamic, chemical disorder. Fil: McDonald, Matthew P. . University Of Notre Dame-indiana; Estados Unidos Fil: Eltom, Ahmed . University Of Waterloo; Canadá Fil: Vietmeyer, Felix . University Of Notre Dame-indiana; Estados Unidos Fil: Thapa, Janak . Illinois Wesleyan University; Estados Unidos Fil: Morozov, Yurii V. . Taras Shevchenko National University of Kiev; Ucrania Fil: Sokolov, Denis A. . University Of Notre Dame-indiana; Estados Unidos Fil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires; Argentina Fil: Vinodgopal, Kizhanipuram . North Carolina Central University; Estados Unidos Fil: Kamat, Prashant V. . University Of Notre Dame-indiana; Estados Unidos Fil: Kuno, Masaru . University Of Notre Dame-indiana; Estados Unidos

CdSe nanowires show reversible emission intensity enhancements when subjected to electric field strengths ranging from 5 to 22 MV/m. Under alternating positive and negative biases, emission intensity modulation depths of 14 ± 7% are observed. Individual wires are studied by placing them in parallel plate capacitor-like structures and monitoring their emission intensities via single nanostructure microscopy. Observed emission sensitivities are rationalized by the field-induced modulation of carrier detrapping rates from NW defect sites responsible for nonradiative relaxation processes. The exclusion of these states from subsequent photophysics leads to observed photoluminescence quantum yield enhancements. We quantitatively explain the phenomenon by developing a kinetic model to account for field-induced variations of carrier detrapping rates. The observed phenomenon allows direct visualization of trap state behavior in individual CdSe nanowires and represents a first step toward developing new optical techniques that can probe defects in low-dimensional materials.

The electrostatic alignment and directed assembly of semiconductor nanowires into macroscopic, centimeter-long yarns is demonstrated. Different morphologies can be produced, including longitudinally segmented/graded yarns or mixed composition fibers. Nanowire yarns display long range photoconductivities and open up exciting opportunities for potential use in future nanowire-based textiles or in solar photovoltaics.

High-quality compositionally tunable ternary PbSe(x)S(1-x) (x = 0.23, 0.39, 0.49, 0.68, and 0.90) nanowires (NWs) and their binary analogues have been grown using solution-liquid-solid growth with lead(II) diethyldithiocarbamate, Pb(S(2)CNEt(2))(2), and lead(II) imido(bis(selenodiisopropylphosphinate)), Pb((SeP(i)Pr(2))(2)N)(2), as single-source precursors. The alloyed nature of PbSe(x)S(1-x) wires was confirmed using ensemble X-ray diffraction and energy dispersive X-ray spectroscopy (EDXS). Single NW EDXS line scans taken along the length of individual wires show no compositional gradients. NW compositions were independently confirmed using inductively coupled plasma atomic emission spectroscopy. Slight stoichiometric deviations occur but never exceed 13.3% of the expected composition, based on the amount of introduced precursor. In all cases, resulting nanowires have been characterized using transmission electron microscopy. Mean diameters are between 9 and 15 nm with accompanying lengths that range from 4 to 10 μm. Associated selected area electron diffraction patterns indicate that the PbSe(x)S(1-x), PbSe, and PbS NWs all possess the same002growth direction, with diffraction patterns consistent with an underlying rock salt crystal structure.

Here we show the first direct extinction spectra of single one-dimensional (1D) semiconductor nanostructures obtained at room temperature utilizing a spatial modulation approach. (1) For these materials, ensemble averaging in conventional extinction spectroscopy has limited our understanding of the interplay between carrier confinement and their electrostatic interactions. (2-4) By probing individual CdSe nanowires (NWs), we have identified and assigned size-dependent exciton transitions occurring across the visible. In turn, we have revealed the existence of room temperature 1D excitons in the narrowest NWs.

High quality ZnSe nanowires (NWs) and complementary ZnSe/CdSe core/shell species have been synthesized using a recently developed solution-liquid-solid (SLS) growth technique. In particular, bismuth salts as opposed to pre-synthesized Bi or Au/Bi nanoparticles have been used to grow NWs at low temperatures in solution. Resulting wires are characterized using transmission electron microscopy and possess mean ensemble diameters between 15 and 28 nm with accompanying lengths ranging from 4-10 μm. Subsequent solution-based overcoating chemistry results in ZnSe wires covered with CdSe nanocrystals. By varying the shell's growth time, different thicknesses can be obtained and range from 8 to 21 nm. More interestingly, the mean constituent CdSe nanocrystal diameter can be varied and results in size-dependent shell emission spectra. Fil: Petchsang, Nattasamon. University of Notre Dame; Estados Unidos. Thailand Ministry of Education; Tailandia. Mahidol University; Tailandia Fil: Shapoval, Liubov. Herzen State Pedagogical University Of Russia; Rusia Fil: Vietmeyer, Felix. University of Notre Dame; Estados Unidos Fil: Yu, Yanghai. University Of Wisconsin Madison; Fil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Tang, I-Ming. Mahidol University; Tailandia. Thailand Ministry Of Education; Tailandia Fil: Kosel, Thomas H.. University of Notre Dame; Estados Unidos Fil: Kuno, Masaru. University of Notre Dame; Estados Unidos

Absorption cross sections ((sigma)abs) of single branched CdSe nanowires (NWs) have been measured by photothermal heterodyne imaging (PHI). Specifically, PHI signals from isolated gold nanoparticles (NPs) with known cross sections were compared to those of individual CdSe NWs excited at 532 nm. This allowed us to determine average NW absorption cross sections at 532 nm of (sigma)abs = (3.17 +/- 0.44) x 10(-11) cm2/microm (standard error reported). This agrees well with a theoretical value obtained using a classical electromagnetic analysis ((sigma)abs = 5.00 x 10(-11) cm2/microm) and also with prior ensemble estimates. Furthermore, NWs exhibit significant absorption polarization sensitivities consistent with prior NW excitation polarization anisotropy measurements. This has enabled additional estimates of the absorption cross section parallel ((sigma)abs) and perpendicular ((sigma)abs(perpendicular) to the NW growth axis, as well as the corresponding NW absorption anisotropy ((rho)abs). Resulting values of (sigma)abs = (5.6 +/- 1.1) x 10(-11) cm2/microm, (sigma)abs(perpendicular) = (1.26 +/- 0.21) x 10(-11) cm2/microm, and (rho)abs = 0.63+/- 0.04 (standard errors reported) are again in good agreement with theoretical predictions. These measurements all indicate sizable NW absorption cross sections and ultimately suggest the possibility of future direct single NW absorption studies.

The band edge optical characterization of solution-synthesized CdS nanowires (NWs) is described. Investigated wires are made through a solution-liquid-solid approach that entails the use of low-melting bimetallic catalyst particles to seed NW growth. Resulting diameters are approximately 14 nm, and lengths exceed 1 microm. Ensemble diameter distributions are approximately 13%, with corresponding intrawire diameter variations of approximately 5%. High-resolution transmission electron micrographs show that the wires are highly crystalline and have the wurtzite structure with growth along at least two directions: [0001] and [1010]. Band edge emission is observed with estimated quantum yields between approximately 0.05% and 1%. Complementary photoluminescence excitation spectra show structure consistent with the linear absorption. Carrier cooling dynamics are subsequently examined through ensemble lifetime and transient differential absorption measurements. The former reveals unexpectedly long band edge decays that extend beyond tens of nanoseconds. The latter indicates rapid intraband carrier cooling on time scales of 300-400 fs. Subsequent recovery at the band edge contains significant Auger contributions at high intensities which are usurped by other, possibly surface-related, carrier relaxation pathways at lower intensities. Furthermore, an unusual intensity-dependent transient broadening is seen, connected with these long decays. The effect likely stems from band-filling on the basis of an analysis of observed spectral shifts and line widths.

While the polarization sensitivity of single or aligned NW ensembles is well-known, this article reports on the existence of residual photocurrent polarization sensitivities in random NW networks. In these studies, CdSe and CdTe NWs were deposited onto glass substrates and contacted with Au electrodes separated by 30-110 microm gaps. SEM and AFM images of resulting devices show isotropically distributed NWs between the electrodes. Complementary high resolution TEM micrographs reveal component NWs to be highly crystalline with diameters between 10 and 20 nm and with lengths ranging from 1 to 10 microm. When illuminated with visible (linearly polarized) light, such random NW networks exhibit significant photocurrent anisotropies rho = 0.25 (sigma = 0.04) [rho = 0.22 (sigma = 0.04)] for CdSe (CdTe) NWs. Corresponding bandwidth measurements yield device polarization sensitivities up to 100 Hz. Additional studies have investigated the effects of varying the electrode potential, gap width, and spatial excitation profile. These experiments suggest electrode orientation as the determining factor behind the polarization sensitivity of NW devices. A simple geometric model has been developed to qualitatively explain the phenomenon. The main conclusion from these studies, however, is that polarization sensitive devices can be made from random NW networks without the need to align component wires.

Carbazole molecules containing thiol functional groups, when attached to CdSe nanowires (NWs), facilitate hole transport across semiconductor interfaces. The improved hole transfer rate is evidenced by increased electron lifetimes and better photovoltaic performance. Nanowire solar cells (NWSCs) with carbazole treatment delivered a power conversion efficiency of 0.46%, which is an order of magnitude improvement over untreated films. The illumination of the sample during the electrophoretic deposition of nanowires also had a profound effect in obtaining stable and higher photocurrents.