3D printing of hollow geometries using blocking liquid substitution stereolithography.

Micrometer scale arbitrary hollow geometries within a solid are needed for a variety of applications including microfluidics, thermal management and metamaterials. A major challenge to 3D printing hollow geometries using stereolithography is the ability to retain empty spaces in between the solidified regions. In order to prevent unwanted polymerization of the trapped resin in the hollow spaces-known as print-through-significant constraints are generally imposed on the primary process parameters such as resin formulation, exposure conditions and layer thickness. Here, we report on a stereolithography process which substitutes the trapped resin with a UV blocking liquid to mitigate print-through. We investigate the mechanism of the developed process and determine guidelines for the formulation of the blocking liquid. The reported method decouples the relationship between the primary process parameters and their effect on print-through. Without having to optimize the primary process parameters to reduce print-through, hollow heights that exceed the limits of conventional stereolithography can be realized. We demonstrate fabrication of a variety of complex hollow geometries with cross-sectional features ranging from tens of micrometer to hundreds of micrometers in size. With the framework presented, this method may be employed for 3D printing functional hollow geometries for a variety of applications, and with improved freedom over the printing process (e.g. material choices, speed and resulting properties of the printed parts).

Efficient near-infrared polymer and organic light-emitting diodes based on electrophosphorescence from (tetraphenyltetranaphtho[2,3]porphyrin)platinum(II).

The new metalloporphyrin Pt(tptnp), where tptnp = tetraphenyltetranaphtho[2,3]porphyrin, has been prepared and subjected to photophysical and electrooptical device studies. In degassed toluene solution at room temperature Pt(tptnp) features efficient phosphorescence emission with lambda(max) 883 nm with a quantum efficiency of 0.22. The complex has been used as the active phosphor in polymer and organic light-emitting diodes. Polymer light-emitting diodes based on a spin-coated emissive layer consisting of a blend of Pt(tptnp) doped in poly(9-vinylcarbazole) and 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole exhibit near-IR emission with lambda(max) 896 nm, with a maximum external quantum efficiency (EQE) of 0.4% and a maximum radiant emittance of 100 muW/cm(2). Organic light-emitting diodes prepared via vapor deposition of all layers and that feature an optimized multilayer hole injection and electron blocking layer heterostructure with an emissive layer consisting of 4,4'-bis(carbazol-9-yl)biphenyl (CBP) doped with Pt(tptnp) exhibit a maximum EQE of 3.8% and a maximum radiant emittance of 1.8 mW/cm(2). The polymer and organic light-emitting diodes characterized in this study exhibit record high efficiency for devices that emit in the near-IR at lambda >800 nm.

Photophysics of diplatinum polyynediyl oligomers: chain length dependence of the triplet state in sp carbon chains.

The series of polyynes with the structure trans, trans-[Ar-Pt(P 2)-(C[triple bond]C) n -Pt(P 2)-Ar], where P = tri( p-tolyl)phosphine, Ar = p-tolyl, and n = 3, 4, 5, 6 (6, 8, 10, 12 sp carbon atoms), has been subjected to a comprehensive photophysical investigation. At low temperature ( T < 140 K) in a 2-methyltetrahydrofuran (MTHF) glass, the complexes exhibit moderately efficient phosphorescence appearing as a series of narrow (fwhm < 200 cm (-1)) vibronic bands separated by ca. 2100 cm (-1). The emission is assigned to a (3)pi,pi* triplet state that is concentrated on the sp carbon chain, and the vibronic progression arises from coupling of the excitation to the -C[triple bond]C- stretch. The 0-0 energy of the phosphorescence decreases with increasing sp carbon chain length, spanning a range of over 6000 cm (-1) across the series. Transient absorption spectroscopy carried out at ambient temperature confirms that the (3)pi,pi* triplet is produced efficiently, and it displays a strongly allowed triplet-triplet absorption. In the MTHF solvent glass ( T < 140 K), the emission lifetimes increase with emission energy. Analysis of the triplet nonradiative decay rates reveals a quantitative energy gap law correlation. The nonradiative decay rates can be calculated by using parameters recovered from a single-mode Franck-Condon fit of the emission spectra.

An iridium(III) complex that exhibits dual mechanism nonlinear absorption.

The photophysical properties of the complex (L)Ir(ppy)(2)(+), where ppy = 2-phenylpyridine and L = 4,4'-(2,2'-bipyridine-5,5'-diylbis(ethyne-2,1-diyl))bis(N,N-dihexylaniline), have been investigated under one- and two-photon excitation conditions. In THF solution, the complex exhibits broad ground-state absorption with lambda(max) approximately 500 nm and weak photoluminescence with lambda(max) approximately 730 nm. Excitation of (L)Ir(ppy)(2)(+) at 355 nm produces a long-lived excited state (tau approximately 1 mus) that features a strong excited-state absorption in the near-infrared (lambda(max) approximately 875 nm, Deltaepsilon approximately 6.1 x 10(4) M(-1) cm(-1)). Photoluminescence and transient absorption studies of (L)Ir(ppy)(2)(+) carried out using 5 ns, 1064 nm pulsed excitation demonstrate that the same long-lived and strongly absorbing excited state can be efficiently produced by two-photon absorption. Solutions of the complex in THF display nonlinear absorption of 5 ns, 1064 nm pulses in a process that is believed to involve a combination of two-photon absorption and reverse saturable absorption.

A platinum acetylide polymer with sterically demanding substituents: effect of aggregation on the triplet excited state.

The effect of interchain interaction on the triplet excited state is explored in two Pt-acetylide polymers of the type [-trans-Pt(PBu(3))(2)-C triple bond C-Ar-C triple bond C-](n), where Ar is either 1,4-phenylene or is based on the pentiptycene unit (polymers 2 and 3, respectively). To explore the effect of interchain interaction in Pt-acetylide materials, the optical properties of parent polymer 2 are compared with those of polymer 3 in which interchain interaction is precluded by the sterically bulky pentiptycene moiety. Insight into the effect of the pentiptycene unit on packing in the solid state comes from the X-ray structure of monomer 1b, Ph-C triple bond C-[trans-Pt(PBu(3))(2)]-C triple bond C-Ar-C triple bond C-[trans-Pt(PBu(3))(2)]-C triple bond C-Ph. Spectroscopic studies indicate that weak phosphorescence emission from an interchain aggregate is observed from parent polymer 2, both in solution and in the solid state. By contrast, the photophysics of 3 is dominated by the intrachain triplet exciton. Interestingly, the phosphorescence emission of polymer 3 in the solid state is nearly superimposable with that of a single crystal of monomer 1b, suggesting that the solid polymer experiences an environment that is similar to that of the monomer in the crystal.