No Arabic abstract
Artificial lighting is a widespread technology which consumes large amounts of energy. Triplet-triplet annihilation photochemical upconversion is a method of converting light to a higher frequency. Here, we show theoretically that photochemical upconversion can be applied to Watt-scale lighting, with performance closely approaching the 50% quantum yield upper limit. We describe the dynamic equilibrium of an efficient device consisting of an LED, an upconverting material, and an optical cavity from optical and thermal perspectives.
Photochemical upconversion is a promising way to boost the efficiency of solar cells using triplet exciton annihilation. Currently, predicting the performance of photochemical upconversion devices is challenging. We present an open source software package which takes experimental parameters as inputs and gives the figure of merit of an upconversion system, enabling theory-driven design of better solar energy devices. We incorporate the statistical distribution of triplet excitons between the sensitizer and the emitter. Using the dynamic quenching effect of the sensitizer on emitter triplet excitons, we show that the optimal sensitizer concentration can be below the sensitizer solubility limit in liquid devices. These theoretical contributions can explain, without use of heavy atom-induced triplet exciton formation or phenyl group rotation, the experimental failure of zinc octaethylporphyrin to effectively sensitize diphenylanthracene, where platinum octaethylporphyrin succeeds. Our predictions indicate a change in direction for device design that will reduce triplet exciton losses.
A two-dimensional (2D) ZnS photonic crystal was deposited on the surface of a one-dimensional (1D) III-nitride micro cavity light-emitting diode (LED), to intermix the light extraction features of both structures (1D+2D). The deposition of an ideal micro-cavity optical thickness of lambda/2 is impractical for III-nitride LEDs, and in realistic multi-mode devices a large fraction of the light is lost to internal refraction as guided light. Therefore, a 2D photonic crystal on the surface of the LED was used to diffract and thus redirect this guided light out of the semiconductor over several hundred microns. Additionally, the employment of a post-epitaxy ZnS 2D photonic crystal avoided the typical etching into the GaN:Mg contact layer, a procedure which can cause damage to the near surface.
Silver nanoparticles dispersed on the surface of an inverted GaN LED were found to plasmonically enhance the near-bandedge emission. The resonant surface plasmon coupling led to a significant enhancement in the exciton decay rate and the ensemble of nanoparticles provided a mechanism to scatter the coupled energy as free space radiation. The inverted LED structure employed a tunnel junction to avoid the standard thick p+ GaN current spreading contact layer. In contrast to a standard design, the top contact was a thin n++ AlGaN layer, which brought the quantum well into the fringing field of the silver nanoparticles. This proximity allowed the excitons induced within the quantum well to couple to the surface plasmons, which in turn led to the enhanced band edge emission from the LED.
Two-photon photopolymerization delivers prints without support structures and minimizes layering artifacts in a broad range of materials. This volumetric printing approach scans a focused light source throughout the entire volume of a resin vat and takes advantage of the quadratic power dependence of two photon absorption to produce photopolymerization exclusively at the focal point. While this approach has advantages, the widespread adoption of two photon photopolymerization is hindered by the need for expensive ultrafast lasers and extremely slow print speeds. Here we present an analogous quadratic process, triplet-triplet-annihilation-driven 3D printing, that enables volumetric printing at a focal point driven by <4 milliwatt-power continuous wave excitation. To induce photopolymerization deep within a vat, the key advance is the nanoencapsulation of photon upconversion solution within a silica shell decorated with solubilizing polymer ligands. This scalable self-assembly approach allows for scatter-free nanocapsule dispersal in a variety of organic media without leaking the capsule contents. We further introduce an excitonic strategy to systematically control the upconversion threshold to support either monovoxel or parallelized printing schemes, printing at power densities multiple orders of magnitude lower than power densities required for two-photon-based 3D printing. The application of upconversion nanocapsules to volumetric 3D printing provides access to the benefits of volumetric printing without the current cost, power, and speed drawbacks. The materials demonstrated here open opportunities for other triplet fusion upconversion-controlled applications.
We investigate a semiconductor $p$-$n$ junction in contact with superconducting leads that is operated under forward bias as a light-emitting diode. The presence of superconductivity results in a significant increase of the electroluminescence in a certain frequency window. We demonstrate that the tunneling of Cooper pairs induces an additional luminescence peak on resonance. There is a transfer of superconducting to photonic coherence which results in the emission of entangled photon pairs and squeezing of the fluctuations in the quadrature amplitudes of the emitted light. The squeezing angle can be electrically manipulated by changing the relative phase of the order parameters in the superconductors. We finally derive the conditions for lasing in the system and show that the laser threshold is reduced due to superconductivity. This shows how macroscopic coherence of a superconductor can be used to control the properties of light.