Bryce S. Richards

Photon Upconversion at Crystalline Organic-Organic Heterojunctions

Triplet transfer across a surface-anchored metal-organic-framework heterojunction is demonstrated by the observation of triplet-triplet annihilation photon -upconversion in a sensitizer-emitter heterostructure. Upconversion thresholds under 1 mW cm-2 are achieved. In the broader context, the double-electron-exchange mechanism of triplet transfer indicates that the heterojunction quality is sufficient for electrons to move between layers in this solution-processed crystalline heterostructure.

Bioinspired Superhydrophobic Highly Transmissive Films for Optical Applications

Inspired by the transparent hair layer on water plants Salvinia and Pistia, superhydrophobic flexible thin films, applicable as transparent coatings for optoelectronic devices, are introduced. Thin polymeric nanofur films are fabricated using a highly scalable hot pulling technique, in which heated sandblasted steel plates are used to create a dense layer of nano- and microhairs surrounding microcavities on a polymer surface. The superhydrophobic nanofur surface exhibits water contact angles of 166 ± 6°, sliding angles below 6°, and is self-cleaning against various contaminants. Additionally, subjecting thin nanofur to argon plasma reverses its surface wettability to hydrophilic and underwater superoleophobic. Thin nanofur films are transparent and demonstrate reflection values of less than 4% for wavelengths ranging from 300 to 800 nm when attached to a polymer substrate. Moreover, used as translucent self-standing film, the nanofur exhibits transmission values above 85% and high forward scattering. The potential of thin nanofur films for extracting substrate modes from organic light emitting diodes is tested and a relative increase of the luminous efficacy of above 10% is observed. Finally, thin nanofur is optically coupled to a multicrystalline silicon solar cell, resulting in a relative gain of 5.8% in photogenerated current compared to a bare photovoltaic device.

Self-absorption in upconverter luminescent layers: impact on quantum yield measurements and on designing optimized photovoltaic devices

This Letter details a theoretical investigation of self-absorption within an upconverter (UC) material, consisting of trivalent erbium (Er3+)-doped hexagonal sodium yttrium fluoride (β-NaYF4) and its implications on two experimental situations: the case of a quantum yield measurement, and on the effective performance in a UC-enhanced photovoltaic (PV) device. The study demonstrates that an optimization of the thickness is essential in order to reduce the effect of self-absorption and maximize the possible additional photocurrent that could be harvested. It also has been found that the external photoluminescence quantum yield (ePLQY) measured through an integrating sphere may result in an underestimation with respect to the performance that the UC material could achieve in a UC-PV device. Finally, it has been found the optimal thickness and the molar concentration of Er3+ ions are inversely proportional, suggesting that an optimal number (1.3-2.9·10(17)) of Er3+ ions should be contained within the UC layer.

Finely-tuned NIR-to-visible up-conversion in La2O3:Yb3+,Er3+ microcrystals with high quantum yield

Up-conversion (UC) materials whose emission color can be finely-tuned while a high UC quantum efficiency is maintained are desirable for many applications. Herein, we report near-infrared-to-visible La2O3:Yb3+,Er3+ (LYE) UC materials with a high internal quantum yield (UCQY) of 3.8%, external UCQY (brightness) of 1.6% and tunable emission color. UC emission colors from pure green to reddish-orange can be precisely tailored by simply controlling synthesis conditions, whilst maintaining the high UCQY. The internal UCQY and external UCQY of LYE yield better performance than both commercially available and other record UC phosphors reported in the literature under the same excitation conditions. The facile preparation combined with the color-tuning and high UCQYs make these materials attractive candidates for solar energy harvesting, sensors, 3D volumetric displays, solid state lasers and bio-imaging.

Monodisperse β-NaYF4:Yb3+,Tm3+ hexagonal microplates with efficient NIR-to-NIR up-conversion emission developed via ion exchange

Monodisperse β-NaYF4:Yb3+,Tm3+ (NYF) hexagonal microplates with efficient near-infrared (NIR)-to-NIR up-conversion (UC) developed via a new ion-exchange modified hydrothermal method are reported. Ion exchange modification (IEM) not only significantly increases the UC intensity by up to 1000 times and prolongs the emission lifetimes of Tm3+ and Yb3+, but also enables the monodisperse morphology and size of hexagonal microplates to be maintained. A high UC quantum efficiency (QE) of 3.1% is obtained for IEM β-NaYF4:20%Yb3+,1%Tm3+ when excited with 980 nm light at a power density of 10 W cm−2. The UC emission properties can be finely tailored by changing the NaF/NYF molar ratio (NYF represents lanthanide doped β-NaYF4) and the doping concentration of Tm3+. The two photon NIR UC emission centered at ∼803 nm (arising from Tm3+: 3H4 → 3H6) dominates the UC emission spectrum and high concentrations of Tm3+ favor NIR UC further. A proof-of-concept optical image of printed patterns is demonstrated to verify their applications in security. These results suggest the promising applications of the newly developed monodisperse β-NaYF4:Yb3+,Tm3+ hexagonal microplates in security, luminescent labels, solid-state lasers, amplifiers, and biomedicine.

Scalable perovskite/CIGS thin-film solar module with power conversion efficiency of 17.8%

All-thin film perovskite/CIGS multijunction solar modules, combining a semi-transparent perovskite top solar module stacked on a CIGS bottom solar module, are a promising route to surpass the efficiency limits of single-junction thin-film solar modules. In this work, we present a scalable thin-film perovskite/CIGS photovoltaic module with an area of 3.76 cm2 and a power conversion efficiency of 17.8%. Our prototype outperforms both the record single-junction perovskite solar module of the same area as well as the reference CIGS solar module. The presented perovskite/CIGS thin-film multijunction solar module makes use of the “4-terminal architecture”, which stacks the perovskite solar module in superstrate configuration on top of the CIGS solar module in substrate configuration. Both submodules apply a scalable interconnection scheme that can accommodate scale-up towards square meter scale thin-film multijunction solar modules. In order to identify the future potential of the presented stacked perovskite/CIGS thin-film solar module, we quantify the various losses in the presented prototype and identify the key challenges of this technology towards very high power conversion efficiencies.

Measurement procedure for absolute broadband infrared up-conversion photoluminescent quantum yields: Correcting for absorption/re-emission

The internal photoluminescent quantum yield (iPLQY)--defined as the ratio of emitted photons to those absorbed--is an important parameter in the evaluation and application of luminescent materials. The iPLQY is rarely reported due to the complexities in the calibration of such a measurement. Herein, an experimental method is proposed to correct for re-emission, which leads to an underestimation of the absorption under broadband excitation. Although traditionally the iPLQY is measured using monochromatic sources for linear materials, this advancement is necessary for nonlinear materials with wavelength dependent iPLQY, such as the application of up-conversion to solar energy harvesting. The method requires an additional measurement of the emission line shape that overlaps with the excitation and absorption spectra. Through scaling of the emission spectrum, at the long wavelength edge where an overlap of excitation does not occur, it is possible to better estimate the value of iPLQY. The method has been evaluated for a range of nonlinear material concentrations and under various irradiances to analyze the necessity and boundary conditions that favor the proposed method. Use of this refined method is important for a reliable measurement of iPLQY under a broad illumination source such as the Sun.

Co-precipitation synthesis and photoluminescence properties of BaTiF6:Mn4+:an efficient red phosphor for warm white LEDs

The investigation of efficient red phosphors is highly desired for the development of novel warm white light emitting diodes (WLEDs). In this paper, we report on an efficient red phosphor of Mn4+-activated BaTiF6 by a facile co-precipitation method as a promising candidate for warm white LEDs. BaTi1−xF6:xMn4+ phosphors show efficient pure red emission with a high quantum yield (QY) of 44.5% under 460 nm excitation. The BaTi1−xF6:xMn4+ phosphor exhibits a number of advantages. Firstly, the corresponding excitation/absorption profile matches the commercial blue LED chip well. Secondly, it also exhibits appropriate CIE coordinates (x = 0.694, y = 0.306) with an activation energy of 0.603 eV. The demonstration of a blue chip combined with a blend of yellow-emitting YAG:Ce3+ and newly developed BaTi0.97F6:0.03Mn4+ red phosphor greatly improved the colour rendering index (CRI) from 69.9 to 83.5, while significantly decreasing the correlated colour temperature (CCT) from 5088 to 4213 K, thus validating their application in warm white LEDs.

Room-Temperature High-Efficiency Solid-State Triplet–Triplet Annihilation Up-Conversion in Amorphous Poly(olefin sulfone)s

Triplet-triplet annihilation up-conversion (TTA-UC) is a developing technology that can enable spectral conversion under sunlight. Previously, it was found that efficient TTA-UC can be realized in polymer hosts for temperatures above the polymers glass transition (T > Tg). In contrast, TTA-UC with high quantum yield for temperatures below Tg is rarely reported. In this article, we report new polymer hosts in which efficient TTA-UC is observed well below Tg, when the polymer is in a fully solid state. The four poly(olefin sulfone) hosts were loaded with upconversion dyes, and absolute quantum yields of TTA-UC (ηTTA-UC) were measured. The highest value of ηTTA-UC = 2.1% was measured for poly(1-dodecene sulfone). Importantly, this value was the same in vacuum and at ambient conditions, indicating that the host material acts as a good oxygen barrier. We performed time-resolved luminescence experiments in order to elucidate the impact of elementary steps of TTA-UC. In addition to optical characterization, we used magic angle spinning solid-state NMR experiments to estimate the T2 transverse relaxation time. Relatively long T2 times measured for poly(olefin sulfone)s indicate an enhanced nanoscale fluidity in the studied (co)polymers, which unexpectedly coexists with a rigidity on the macroscale. This would explain the exceptional triplet energy transfer between the guest molecules, despite the macroscopic rigidity.

Excitonically coupled states in crystalline coordination networks

When chromophores are brought into close proximity, noncovalent interactions (π-π/CH-π) can lead to the formation of excitonically coupled states, which bestow new photophysical properties upon the aggregates. Because the properties of the new states not only depend on the strength of intermolecular interactions, but also on the relative orientation, supramolecular assemblies, where these parameters can be varied in a deliberate fashion, provide novel possibilities for the control of photophysical properties. This work reports that core-substituted naphthalene diimides (cNDIs) can be incorporated into surface-mounted metal- organic structures/frameworks (SURMOFs) to yield optical properties strikingly different from conventional aggregates of such molecules, for example, formed in solution or by crystallization. Organic linkers are used, based on cNDIs, well-known organic chromophores with numerous applications in different optoelectronic devices, to fabricate MOF thin films on transparent substrates. A thorough characterization of the properties of these highly ordered chromophoric assemblies reveals the presence of non-emissive excited states in the crystalline material. Structural modulations provide further insights into the nature of the coupling that gives rise to an excited-state energy level in the periodic structure.