First demonstration of an all-solid-state optical cryocooler.

Solid-state optical refrigeration uses anti-Stokes fluorescence to cool macroscopic objects to cryogenic temperatures without vibrations. Crystals such as Yb3+-doped YLiF4 (YLF:Yb) have previously been laser-cooled to 91 K. In this study, we show for the first time laser cooling of a payload connected to a cooling crystal. A YLF:Yb crystal was placed inside a Herriott cell and pumped with a 1020-nm laser (47 W) to cool a HgCdTe sensor that is part of a working Fourier Transform Infrared (FTIR) spectrometer to 135 K. This first demonstration of an all-solid-state optical cryocooler was enabled by careful control of the various desired and undesired heat flows. Fluorescence heating of the payload was minimized by using a single-kink YLF thermal link between the YLF:Yb cooling crystal and the copper coldfinger that held the HgCdTe sensor. The adhesive-free bond between YLF and YLF:Yb showed excellent thermal reliability. This laser-cooled assembly was then supported by silica aerogel cylinders inside a vacuum clamshell to minimize undesired conductive and radiative heat loads from the warm surroundings. Our structure can serve as a baseline for future optical cryocooler devices.

Efficient quasi-monoenergetic ion beams from laser-driven relativistic plasmas.

Table-top laser-plasma ion accelerators have many exciting applications, many of which require ion beams with simultaneous narrow energy spread and high conversion efficiency. However, achieving these requirements has been elusive. Here we report the experimental demonstration of laser-driven ion beams with narrow energy spread and energies up to 18 MeV per nucleon and ∼5% conversion efficiency (that is 4 J out of 80-J laser). Using computer simulations we identify a self-organizing scheme that reduces the ion energy spread after the laser exits the plasma through persisting self-generated plasma electric (∼10(12) V m(-1)) and magnetic (∼10(4) T) fields. These results contribute to the development of next generation compact accelerators suitable for many applications such as isochoric heating for ion-fast ignition and producing warm dense matter for basic science.

Matching Solid-State to Solution-Phase Photoluminescence for Near-Unity Down-Conversion Efficiency Using Giant Quantum Dots.

Efficient, stable, and narrowband red-emitting fluorophores are needed as down-conversion materials for next-generation solid-state lighting that is both efficient and of high color quality. Semiconductor quantum dots (QDs) are nearly ideal color-shifting phosphors, but solution-phase efficiencies have not traditionally extended to the solid-state, with losses from both intrinsic and environmental effects. Here, we assess the impacts of temperature and flux on QD phosphor performance. By controlling QD core/shell structure, we realize near-unity down-conversion efficiency and enhanced operational stability. Furthermore, we show that a simple modification of the phosphor-coated light-emitting diode device-incorporation of a thin spacer layer-can afford reduced thermal or photon-flux quenching at high driving currents (>200 mA).

Developing Monolithic Nanoporous Gold with Hierarchical Bicontinuity Using Colloidal Bijels.

We report a universal platform for the synthesis of monolithic porous gold materials with hierarchical bicontinuous morphology and combined macro- and mesoporosity using a synergistic combination of nanocasting and chemical dealloying. This robust and accessible approach offers a new design paradigm for the parallel optimization of active surface area and mass transport in porous metal electrodes.

Thin film CdSe/CuSe photovoltaic on a flexible single walled carbon nanotube substrate.

Liquid phase deposition (LPD), using CdSO(4) and N,N-dimethyl selenourea, has been used to grow CdSe absorber layer onto single walled carbon nanotube (SWNT) derived back contact substrates. The nanotubes are imbedded in, and penetrate into, the CdSe absorber layer for the goal of enhancing excition dissociation and carrier transport. The Cd : Se film stoichiometry varied between 1 : 1.7 to 1 : 1.3 depending on the deposition conditions. The CdSe/SWNT layers show appropriate photoresponse. LPD was also used to grow a CuSe window layer onto which silver contacts were deposited. The resulting PV device shows a characteristic IV curve. Despite both the open circuit voltage (V(OC) = 1.28 mV) and short circuit current (I(SC) = 4.85 µA) being low, the resulting device is suggestive of the possibility of fabricating a flexible thin film (inorganic) solar cell by solution processes.

Fluorescent single-walled carbon nanotube aerogels in surfactant-free environments.

A general challenge in generating functional materials from nanoscale components is integrating them into useful composites that retain or enhance their properties of interest. Development of single walled carbon nanotube (SWNT) materials for optoelectronics and sensing has been especially challenging in that SWNT optical and electronic properties are highly sensitive to environmental interactions, which can be particularly severe in composite matrices. Percolation of SWNTs into aqueous silica gels shows promise as an important route for exploiting their properties, but retention of the aqueous and surfactant environment still impacts and limits optical response, while also limiting the range of conditions in which these materials may be applied. Here, we present for the first time an innovative approach to obtain highly fluorescent solution-free SWNT-silica aerogels, which provides access to novel photophysical properties. Strongly blue-shifted spectral features, revelation of new diameter-dependent gas-phase adsorption phenomena, and significant increase (approximately three times that at room temperature) in photoluminescence intensities at cryogenic temperatures all indicate greatly reduced SWNT-matrix interactions consistent with the SWNTs experiencing a surfactant-free environment. The results demonstrate that this solid-state nanomaterial will play an important role in further revealing the true intrinsic SWNT chemical and photophysical behaviors and represent for the first time a promising new solution- and surfactant-free material for advancing SWNT applications in sensing, photonics, and optoelectronics.

Synthesis and characterization of aryl substituted bis(2-pyridyl)amines and their copper olefin complexes: investigation of remote steric control over olefin binding.

The aryl-functionalized pyridylamine 2-(i)PrC(6)H(4)N(H)py (1) and bis(2-pyridyl)amines of the type ArN(py)(2) for Ar = Mes (2), 2,6-Et(2)C(6)H(3) (3), 2-(i)PrC(6)H(4) (4), 2,6-(i)Pr(2)C(6)H(3) (5), and 1-naph (6), have been prepared by the palladium-catalyzed cross-coupling of substituted anilines with 2-bromopyridine, and have been characterized by (1)H and (13)C NMR NMR, FTIR, MS, and TGA. Complexes of these new N-aryl bis(2-pyridyl)amines have been prepared for the acid salts [H{ArN(py)(2)}]BF(4) where Ar = Mes (7) and 2-(i)PrC(6)H(4) (8), and the dimeric bridged complexes [Cu{ArN(py)(2)}(µ-X)(Y)](2) where X/Y = Cl(-) and Ar = Ph (9), 2-(i)PrC(6)H(4) (10), and 1-naph (11), in addition to X = OH(-), Y = H(2)O and Ar = Mes (12). The olefin complexes [Cu(Ar-dpa)(styrene)]BF(4) for Ar = Ph (13), Mes (14), 2-(i)PrC(6)H(4) (15), and 1-naph (16), in addition to the norborylene complexes of Ar = Mes (17) and 2-(i)PrC(6)H(4) (18) have been prepared and characterized by (1)H and (13)C NMR, FTIR, and TGA. The crystal structures have been determined for compounds 1-17. Secondary amine 1 crystallizes in hydrogen-bonded head-to-tail dimers, while the N-aryl bis(2-pyridyl)amines 2-6 crystallize in a three-bladed propellar conformation, having nearly planar geometries about the amine nitrogen. The geometry about copper centers in the dimeric complexes 9-12 is distorted trigonal bypyramidal, with the axial positions occupied by one of the two pyridyl nitrogens and one of the bridging ligands (i.e., Cl or OH). The copper atoms in each of the olefin complexes 13-17 are coordinated to the two pyridine nitrogen atoms and the appropriate olefin; consistent with a pseudo three-coordinate Cu(I) cation. Distortion of pyridyl ring geometries about the copper centers, and concomitant bending of the aryl groups away from the CuN(amine) vectors were found to correlate with the steric bulk of the aryl group present in both dimeric and olefin complexes. Such distortion is also observed to a lesser extent in the acid salts as well. The (1)H and (13)C NMR spectra of [Cu(Ar-dpa)(olefin)]BF(4) exhibit an upfield shift in the olefin signal as compared to free olefin. A good correlation exists between the (1)H and (13)C NMR Δδ values and olefin dissociation temperatures, confirming that the shift of the olefin NMR resonances upon coordination is associated with the binding strength of the complex.

Dimensional standard for micro X-ray computed tomography.

The decrease in the cost of high end computing and the availability of high quality X-ray sources in the laboratory environment has led to an increased use of three-dimensional (3D) X-ray micro computed tomography (µCT). In the medical community, the primary concern for CT is calibrating for X-ray absorption and ascertaining the difference between healthy tissue and cancerous tissue or examining fractures. Absorption calibration is also important in the materials community, however confirming dimensional accuracy of voids, defects, machined parts, cracks, or the distribution of dispersed particles is typically more important. One key aspect of µCT that is often overlooked in the literature is the number of radiographs required for dimensional accuracy of the 3D reconstruction and minimization of image noise. In µCT, a number of radiographs are collected in theta increments as the sample is rotated at least 180°. They are typically collected in 1° increments (or 181 radiographs), 0.25° increments (721 radiographs), or some other multiple. The question that arises, especially in a laboratory based instrument, where the required exposure times are longer to get high-quality signal-to-noise compared to synchrotron sources, is what is the optimal number of images required to reach the volumetric statistics of the sample, and minimize the noise while not overly scanning the sample at a cost in time? A dimensional standard based upon NIST certified glass microspheres dispersed in a low density poly(styrene) matrix to answer this question is proposed. Experiments are shown that describe the microsphere size statistics as a function of number of radiographs calculated using a commercial software package, AvizoFire. These results are important in understanding the distribution of voids in a foam and confirming the accuracy of the 3D measurements obtained.

Wet catalyst-support films for production of vertically aligned carbon nanotubes.

A procedure for vertically aligned carbon nanotube (VA-CNT) production has been developed through liquid-phase deposition of alumoxanes (aluminum oxide hydroxides, boehmite) as a catalyst support. Through a simple spin-coating of alumoxane nanoparticles, uniform centimer-square thin film surfaces were coated and used as supports for subsequent deposition of metal catalyst. Uniform VA-CNTs are observed to grow from this film following deposition of both conventional evaporated Fe catalyst, as well as premade Fe nanoparticles drop-dried from the liquid phase. The quality and uniformity of the VA-CNTs are comparable to growth from conventional evaporated layers of Al(2)O(3). The combined use of alumoxane and Fe nanoparticles to coat surfaces represents an inexpensive and scalable approach to large-scale VA-CNT production that makes chemical vapor deposition significantly more competitive when compared to other CNT production techniques.

Nitrene addition to exfoliated graphene: a one-step route to highly functionalized graphene.

We demonstrate a high yield method of functionalizing graphene nanosheets through nitrene addition of azido-phenylalanine [Phe(N(3))] to exfoliated micro-crystalline graphite (microG). This method provides a direct route to highly functionalized graphene sheets. TEM analysis of the product shows few layer (n < 5) graphene sheets. The product was determined to have 1 phenylalanine substituent per 13 carbons.

High-yield organic dispersions of unfunctionalized graphene.

We report a simple, high-yield, method of producing homogeneous dispersions of unfunctionalized and nonoxidized graphene nanosheets in ortho-dichlorobenzene (ODCB). Sonication/centrifugation of various graphite materials results in stable homogeneous dispersions. ODCB dispersions of graphene avert the need for harsh oxidation chemistry and allow for chemical functionalization of graphene materials by a range of methods. Additionally, films produced from ODCB-graphene have high conductivity.

Ultrasmall copper nanoparticles from a hydrophobically immobilized surfactant template.

Ultrasmall copper nanoparticles are produced by N,N,N',N'-tetramethyl-p-phenylenediamine (TMPDA) reduction of aqueous Cu(2+) on a hydrophobically immobilized sodium dodecylbenzenesulfonate (SDBS) surfactant template in the presence of sodium citrate at room temperature. Single-walled carbon nanotubes (SWNTs) act as a scaffold controlling the size of the SDBS micelle, which in turn confines a limited number of copper ions near the nanotube surface. TMPDA reduction forms copper nanoparticles as confirmed by X-ray photoelectron spectroscopy and electron diffraction, whose size was determined by atomic force microscopy and transmission electron microscopy to be approximately 2 nm. Particles formed in the absence of the SWNT immobilizer range from 2 to 150 nm.

Functionalization of SWNTs to facilitate the coordination of metal ions, compounds and clusters.

The carboxylate residues of the open ends of aryl-tert-butyl and arylsulfonic acid side-walled functionalized single walled carbon nanotubes (SWNTs) have been investigated for the complexation conditions of the iron-molybdenum cluster [H(x)PMo(12)O(40)CH(4)Mo(72)Fe(30)(O(2)CMe)(15)O(254)(H(2)O)(98)] ("FeMoC"). A range of alternative donor groups for the attachment of FeMoC have been investigated for piranha etched SWNTs, dodecyl side-walled functionalized SWNTs (DD-SWNTs) and ultra-short SWNTs (US-SWNTs), including include pyridines, thiols and phosphines, using coupling reactions to either the carboxylate or hydroxide residues of the SWNTs' open ends. The functionalized SWNTs have been characterized by XPS, uptake of Fe(3+) and, where appropriate, MAS (31)P NMR. The efficacy of binding is dependent on the presence and identity of the ligand moiety. TEM and AFM of the SWNT-FeMoC conjugates show the presence of a 2-3 nm spherical feature on the tip of individual SWNTs.

Graphite epoxide.

Oxidation of graphite may be carried out by reaction with meta-chloroperoxybenzoic acid to yield graphite epoxide. Scanning tunneling microscopy (STM) showed that the functionalization occurs at the edges rather than on the basal plane of the graphite. Quantification of the epoxide content is possible through the deepoxidation reaction using MeReO3/PPh3.