Co-reporter:Peijian Wang and Michael D. Barnes
Nano Letters November 8, 2017 Volume 17(Issue 11) pp:6949-6949
Publication Date(Web):October 19, 2017
DOI:10.1021/acs.nanolett.7b03394
We report on spatially correlated wavelength-resolved photoluminescence and Kelvin probe force microscopy to probe ground state charge-transfer coupling and its correlation with pi-stacking order in nanoscale assemblies of a small molecule n-type organic semiconductor, tetraazaterrylene (TAT). We find a distinct upshift in surface potential contrast (SPC) corresponding to a decrease in work function in TAT in the transition from disordered spun-cast films to ordered crystalline nanowire assemblies, accompanied by a nanowire size dependence in the SPC shift suggesting that the shift depends on both ground state charge transfer interaction and a size (volume)-dependent intrinsic doping associated with the nitrogen substitutions. For the smallest nanowires studied (surface height ≈ 10–15 nm), the SPC shift with respect to disordered films is +110 meV, in close agreement with recent theoretical calculations. These results illustrate how “dark” (ground-state) interactions in organic semiconductors can be distinguished from “bright” (excited-state) exciton coupling typically assessed by spectral measurements alone.Keywords: charge transfer coupling; disorder; Kelvin probe force microscopy; molecular packing; photoluminescence spectra; Work function;
Co-reporter:Nicholas S. Colella, Joelle A. Labastide, Benjamin P. Cherniawski, Hilary B. Thompson, Sarah R. Marques, Lei Zhang, Özlem Usluer, James J. Watkins, Alejandro L. Briseno, and Michael D. Barnes
The Journal of Physical Chemistry Letters July 6, 2017 Volume 8(Issue 13) pp:2984-2984
Publication Date(Web):June 12, 2017
DOI:10.1021/acs.jpclett.7b01128
Supercritical fluids, exhibiting a combination of liquid-like solvation power and gas-like diffusivity, are a relatively unexplored medium for processing and crystallization of oligomer and polymeric semiconductors whose optoelectronic properties critically depend on the microstructure. Here we report oligomer crystallization from the polymer organic semiconductor, poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) in supercritical hexane, yielding needle-like single crystals up to several microns in length. We characterize the crystals’ photophysical properties by time- and polarization-resolved photoluminescence (TPRPL) spectroscopy. These techniques reveal two-dimensional interchromophore coupling facilitated by the high degree of π-stacking order within the crystal. Furthermore, the crystals obtained from supercritical fluid were found to be similar photophysically as the crystallites found in solution-cast thin films and distinct from solution-grown crystals that exhibited spectroscopic signatures indicative of different packing geometries.
Co-reporter:Mina Baghgar and Michael D. Barnes
ACS Nano 2015 Volume 9(Issue 7) pp:7105
Publication Date(Web):June 21, 2015
DOI:10.1021/acsnano.5b03422
We show that surface electronic properties of poly-3-hexylthiophene (P3HT) crystalline nanofibers as probed by Kelvin probe force microscopy (KPFM) depends sensitively on the degree of polymer packing order and dominant coupling type (e.g., H- or J-aggregate) as signaled by absorption or photoluminescence spectroscopy. Nominal HOMO energies between high molecular weight (J-aggregate) nanofibers and low-molecular weight (H-aggregate) nanofibers differ by ≈160 meV. This is consistent with shifts expected from H-type charge-transfer (CT) interactions that lower HOMO energies according to registration between thiophene moieties on adjacent polymer chains. These results show how KPFM combined with wavelength-resolved photoluminescence imaging can be used to extract information on “dark” (CT) interactions in polymer assemblies.Keywords: H/J aggregates; interchain coupling; Kelvin probe force microscopy; nanowires; P3HT; photoluminescence; poly-3-hexylthiophene;
Co-reporter:Jeffrey M. Lucas, Joelle A. Labastide, Lang Wei, Jonathan S. Tinkham, Michael D. Barnes, and Paul M. Lahti
The Journal of Physical Chemistry A 2015 Volume 119(Issue 29) pp:8010-8020
Publication Date(Web):June 30, 2015
DOI:10.1021/acs.jpca.5b02295
Rigid–flexible segmented block copolymers were synthesized and characterized as 4.5-oligophenylenevinylene chromophores tethered by flexible, conjugation-interrupting 1,2-ethanedioxy or 1,4-butanedioxy units. The flexible tethers allow the possibility of collapsed order chromophore assemblies within individual polymers by chain folding at specific sites much like an old fashioned, folding carpenter’s rule. Our results indicate that using a short, flexible tether in a rigid–flexible segmented copolymer can result in collapsed rodlike structures as signaled by strongly quenched photoluminescence, even after thermal annealing. Such ability to “program” folding and tertiary structure in conjugated copolymers is important for solid-state organic light emitting materials and understanding of organic chromophore self-assembly.
Co-reporter:A. J. Wise, Y. Zhang, J. Fan, F. Wudl, A. L. Briseno and M. D. Barnes
Physical Chemistry Chemical Physics 2014 vol. 16(Issue 30) pp:15825-15830
Publication Date(Web):24 Mar 2014
DOI:10.1039/C4CP00113C
Recent synthetic work has realized a novel (n-type) small-molecule acceptor, 7,8,15,16-tetra-aza-terrylene (TAT), single-crystals of which can be grown oriented along the c-axis crystallographic direction, and over-coated with pentacene to form a highly ordered donor/acceptor interface for use in organic photovoltaic devices. However, characterization of single TAT crystals reveals highly variable emission spectra and excited state dynamics – properties which strongly influence photovoltaic performance. Through the use of single-crystal widefield imaging, photoluminescence spectroscopy, time correlated single photon counting, and resonant Raman studies, we conclude that this variability is a result of long-lived low-energy trap-emission from packing defects. Interestingly, we also discovered that TAT crystals whose width exceeds ∼200 nm begin acting as waveguides and optical microcavity resonators for their own photoluminescence. Several strategies are proposed for leveraging the size-dependant optical properties of TAT pillars to further enhance device performance using this active layer design.
Co-reporter:Mina Baghgar, Austin M. Barnes, Emily Pentzer, Adam J. Wise, Brenton A. G. Hammer, Todd Emrick, Anthony D. Dinsmore, and Michael D. Barnes
ACS Nano 2014 Volume 8(Issue 8) pp:8344
Publication Date(Web):July 8, 2014
DOI:10.1021/nn502806d
Combined Kelvin probe force microscopy and wavelength-resolved photoluminescence measurements on individual pre- and post-cross-linked poly(3-hexylthiophene)-b-poly(3-methyl alcohol thiophene) (P3HT-b-P3MT) nanofibers have revealed striking differences in their optical and electronic properties driven by structural perturbation of the crystalline aggregate nanofiber structures after cross-linking. Chemical cross-linking from diblock copolymer P3HT-b-P3MT using a hexamethylene diisocyanate cross-linker produces a variety of morphologies including very small nanowires, nanofiber bundles, nanoribbons, and sheets, whose relative abundance can be controlled by reaction time and cross-linker concentration. While the different cross-linked morphologies have almost identical photophysical characteristics, KPFM measurements show that the surface potential contrast, related to the work function of the sample, depends sensitively on nanostructure morphology related to chain-packing disorder.Keywords: cross-linking; electronic and optical properties; Kelvin probe; morphology; P3HT; photoluminescence imaging and spectrum; polarization; work function
Co-reporter:Mina Baghgar, Emily Pentzer, Adam J. Wise, Joelle A. Labastide, Todd Emrick, and Michael D. Barnes
ACS Nano 2013 Volume 7(Issue 10) pp:8917
Publication Date(Web):September 4, 2013
DOI:10.1021/nn403392b
We show that mechanically and chemically robust functionalized poly(3-hexylthiophene) (P3HT) nanofibers can be made via chemical cross-linking. Dramatically different photophysical properties are observed depending on the choice of functionalizing moiety and cross-linking strategy. Starting with two different nanofiber families formed from (a) P3HT-b-P3MT or (b) P3HT-b-P3ST diblock copolymers, cross-linking to form robust nanowire structures was readily achieved by either a third-party cross-linking agent (hexamethylene diisocyanate, HDI) which links methoxy side chains on the P3MT system, or direct disulfide cross-link for the P3ST system. Although the nanofiber families have similar gross structure (and almost identical pre-cross-linked absorption spectra), they have completely different photophysics as signaled by ensemble and single nanofiber wavelength- and time-resolved photoluminescence as well as transient absorption (visible and near-IR) probes. For the P3ST diblock nanofibers, excitonic coupling appears to be essentially unchanged before and after cross-linking. In contrast, cross-linked P3MT nanofibers show photoluminescence similar in electronic origin, vibronic structure, and lifetime to unaggregated P3HT molecules, e.g., dissolved in an inert polymer matrix, suggesting almost complete extinction of excitonic coupling. We hypothesize that the different photophysical properties can be understood from structural perturbations resulting from the cross-linking: For the P3MT system, the DIC linker induces a high degree of strain on the P3HT aggregate block, thus disrupting both intra- and interchain coupling. For the P3ST system, the spatial extent of the cross-linking is approximately commensurate with the interlamellar spacing, resulting in a minimally perturbed aggregate structure.Keywords: copolymer; cross-link; exciton coupling; H/J aggregate; nanofiber; P3HT; photoluminescence
Co-reporter:Sibel Ebru Yalcin, Boqian Yang, Joelle A. Labastide, and Michael D. Barnes
The Journal of Physical Chemistry C 2012 Volume 116(Issue 29) pp:15847-15853
Publication Date(Web):June 26, 2012
DOI:10.1021/jp305857d
We report electrostatic force microscopy (EFM) studies combined with wavelength-resolved photoluminescence imaging of electron attachment to individual CdSe/ZnS quantum dots (QDs) coupled to semiconducting tin-doped indium oxide (ITO) substrates. Quantitative EFM measurements show unambiguous signatures of 2–3 excess electrons on individual QDs on ITO, while the distribution of measured recombination energies of QDs coupled to ITO shows ≈ −35 meV red shift (compared to QDs drop-cast on clean glass), the signature of a second-order quantum-confined Stark effect resulting from multiple-electron attachment to the QDs. We also show that the extent of QD charging can be tuned by modulating the ITO bias: EFM measurements show that ≈4 electrons are added to QDs under −2 V applied ITO bias, whereas only ≈2 electrons can be removed from the QDs for +2 V applied bias arising from Fermi level mismatch of ITO with respect to the QDs. Voltage-correlated spectral measurements on ITO coupled QDs showed a spectral modulation in their peak fluorescence energies, which can be attributed to addition or removal of electrons from the QDs.
Co-reporter:Joelle A. Labastide, Mina Baghgar, Aidan McKenna, and Michael D. Barnes
The Journal of Physical Chemistry C 2012 Volume 116(Issue 44) pp:23803-23811
Publication Date(Web):October 11, 2012
DOI:10.1021/jp308503u
Isolated nanofibers present unique opportunities to investigate excitonic processes and dynamics in a confined crystalline geometry, where structural order in the transverse (intrachain) and longitudinal (interchain) directions can be tuned by polymer molecular weight, regioregularity, and solvent processing conditions. We report on time- and polarization-resolved photoluminescence (TRPL) studies from isolated crystalline P3HT nanofibers (also known as nanowires), which reveal a highly reproducible short-time decay behavior, appearing as an amplified spontaneous emission process (biexciton annihilation) as signaled by a quadratic excitation power dependence in amplitude and decay rate. In the long-time (5–100 ns) regime, we observed a power-law decay in the photoluminescence similar to that seen in thin films and nanoparticles; however, for certain nanofiber families (prepared from p-xylene) we observe an extremely long-lived PL component which we postulate arises from deeply trapped carriers in chain packing faults within the NF. Finally, we probe depolarization dynamics in individual nanofibers using polarization-resolved TRPL measurements in which both arrival time and (parallel/perpendicular) polarization state relative to the nanofiber axis are resolved, delineating the different dynamics associated with intra- and interchain excitons.
Co-reporter:Michael D. Barnes;Mina Baghar
Journal of Polymer Science Part B: Polymer Physics 2012 Volume 50( Issue 15) pp:1121-1129
Publication Date(Web):
DOI:10.1002/polb.23105
Abstract
This mini-review on the photophysics of poly-alkyl thiophenes (e.g., P3HT) and its blends with electron-acceptor moeties such as fullerenes (e.g., PCBM) and carbon nanotubes focuses on highlights of recent literature on spectroscopic probes of exciton formation, diffusion, charge-separation, and transport in these materials. The literature in this area is vast: more than 3000 papers have been published in on P3HT (and related materials) and applications to organic solar energy harvesting devices over the last 20 years. Thus, no single review can capture the breadth and depth of this research. Here, we attempt to highlight some of the exciting new research efforts aimed at understanding photophysical processes in organic photovoltaic materials. This mini-review is organized as follows: First, a summary of the theoretical framework commonly used to describe fundamental physical processes of charge generation in organic (polymeric) semiconductor materials is presented. We then discuss recent exciting results on ultrafast spectroscopic probes of exciton dynamics in these materials. Finally, we present highlights of new research on polymer nanostructures (nanoparticles and nanofibers) and their exciting applications to organic photovoltaics. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012
Co-reporter:Sibel Ebru Yalcin, Joelle A. Labastide, Danielle L. Sowle, and Michael D. Barnes
Nano Letters 2011 Volume 11(Issue 10) pp:4425-4430
Publication Date(Web):September 9, 2011
DOI:10.1021/nl2026103
Spectrally resolved fluorescence imaging of single CdSe/ZnS quantum dots (QDs), charged by electrospray deposition under negative bias has revealed a surprising net blue shift (∼60 meV peak-to-peak) in the distribution of center frequencies in QD band-edge luminescence. Electrostatic force microscopy (EFM) on the electrospray QD samples showed a subpopulation of charged QDs with 4.7 ± 0.7 excess electrons, as well as a significant fraction of uncharged QDs as evidenced by the distinct cantilever response under bias. We show that the blue-shifted peak recombination energy can be understood as a first-order electronic perturbation that affects the band-edge electron- and hole-states differently. These studies provide new insight into the role of electronic perturbations of QD luminescence by excess charges.
Co-reporter:Joelle A. Labastide, Mina Baghgar, Irene Dujovne, Yipeng Yang, Anthony D. Dinsmore, Bobby G. Sumpter, Dhandapani Venkataraman, and Michael D. Barnes
The Journal of Physical Chemistry Letters 2011 Volume 2(Issue 24) pp:3085-3091
Publication Date(Web):November 16, 2011
DOI:10.1021/jz2012275
In this Perspective, we discuss the possibility of constructing binary nanoparticle superlattices for organic photovoltaic applications and some of the interesting new photophysics emerging from preliminary studies. We summarize recent advances in nanoparticle preparation and photophysical characterization and some of the very interesting observed departures from thin-film photoluminescence dynamics. We conclude by discussing some of the challenges ahead and the possibility of new emergent physics in the assembly of polymer nanoparticles into functional devices.
Co-reporter:Joelle A. Labastide, Mina Baghgar, Irene Dujovne, B. Harihara Venkatraman, David C. Ramsdell, Dhandapani Venkataraman, and Michael D. Barnes
The Journal of Physical Chemistry Letters 2011 Volume 2(Issue 17) pp:2089-2093
Publication Date(Web):August 1, 2011
DOI:10.1021/jz200958x
We report on a remarkable size and internal structure dependence on time- and polarization-resolved photoluminescence (PL) from individual regioregular rrP3HT (poly-3-(hexylthiophine)) nanoparticles. For the smallest particles (∼34 nm) with relatively low crystallinity (40%), the time evolution of polarization contrast is nearly stationary; for intermediate-sized particles (∼ 65 nm), depolarization occurs on a 1–2 ns time scale. The largest and most crystalline particles studied (118 nm, 70%) show a PL depolarization on a time scale of <50 ps. In every time regime, we observe P3HT nanoparticle PL dynamics that are qualitatively different from those of extended films and single-polymer chains, highlighted by intriguing differences in power law dynamics in the PL intensity at long times. This work may support the hypothesis that hierarchical assemblies of conducting polymer nanoparticles could offer a route to higher efficiency in organic photovoltaic systems.Keywords: luminescence; nanoparticles; P3HT; polarization;
Co-reporter:K. T. Early, K. D. McCarthy, M. Y. Odoi, P. K. Sudeep, T. Emrick and M. D. Barnes
ACS Nano 2009 Volume 3(Issue 2) pp:453
Publication Date(Web):February 3, 2009
DOI:10.1021/nn800785s
We report on linearly polarized absorption and emission from individual (4.3 nm) CdSe quantum dots whose surfaces are coordinated with monodisperse oligo-phenylene vinylene ligands. Shown previously to suppress quantum dot blinking, we demonstrate here that the electronic interaction of photoexcited ligands with the quantum dot core is manifested as a strong polarization anisotropy in absorption (M = 0.5), as well as distinct linear dipole emission patterns from the quantum dot core. Further, there is a correlation between the quantum dot emission moment and polarization orientation corresponding to the absorption maxima that is manifested as fluctuations in emission moment orientation in the X−Y plane. The observed polarization effects can be switched off by tuning the excitation away from the ligand absorption band. We propose a mechanism based on exciton dissociation from the photoexcited ligand, followed by the pinning of electrons at the quantum dot surface. The resulting Stark interaction is sufficiently strong to break the 2D degeneracy of the emission moment within the dot, and may therefore account for the linear dipole emission character.Keywords: CdSe quantum dots; defocused imaging; dipole transitions; ligand effects; polarization anisotropy; surface charges
Co-reporter:Ruthanne Hassey-Paradise;Austin Cyphersmith;Anna May Tilley;Tim Mortsolf;Dipankur Basak;Dhapani Venkataraman
Chirality 2009 Volume 21( Issue 1E) pp:E265-E276
Publication Date(Web):
DOI:10.1002/chir.20809
Abstract
Chirality in molecular systems plays profoundly important roles in chemistry and physics. Most chemistry students are introduced to the concept of chirality through demonstrations of the interaction of chiral molecules with polarized light manifested as an “optical rotation” leading to the “(+)” and “(−)” [or dextrorotatory (d-) and levorotatory (l-)] designations of chiral compounds, with the subsequent determination of absolute stereochemical configuration by chemical or physical means enabling application of the familiar “R” and “S” labels. Although the intrinsic molecular parameters that control the dissymmetric light-matter interaction in chiral systems are well understood, we have only recently begun to ask questions regarding the role of local molecular environment and hidden heterogeneities associated with the ensemble-averaged molecular chiroptical response. In this mini-review, we discuss some of our recent research on application of single-molecule spectroscopy as a tool for probing heterogeneities and fluctuations of chiroptical dissymmetries in condensed phase. Chirality 21:E265–E276, 2009. © 2009 Wiley-Liss, Inc.
Co-reporter:Michael Y. Odoi, Kevin T. Early, Ravisubhash Tangirala, Pallikkara K. Sudeep, Todd Emrick and Michael D. Barnes
The Journal of Physical Chemistry C 2009 Volume 113(Issue 31) pp:13462-13465
Publication Date(Web):July 9, 2009
DOI:10.1021/jp9051787
Fluorescence intensity fluctuations from individual CdSe quantum dots coordinated with oligo(phenylenevinylene) ligands (CdSe−OPV) have been previously observed to be qualitatively different from conventional capped CdSe quantum dots. In particular, the high degree of blinking suppression observed in these (inherently multichromophoric) systems was suggestive of multichromophoric emission. In this paper we describe results of second-order fluorescence intensity correlation function g(2)(τ) measurements from individual CdSe−OPV nanostructures to definitively assess the multiexcitonic character of the emission from these species. Our results point to a weak multiexcitonic character (g(2)(0) ≈ 0.2) under 405 nm excitation where both the organic ligand and quantum dot absorb. Using 514.5 nm excitation, where the ligand absorption is negligible, the quantum dot emission is completely antibunched (g(2)(0) ≈ 0.05), similar to that of ZnS-capped CdSe control samples. These results provide new insights into to the mechanism of intensity flickering and electronic interactions in composite quantum dot/conjugated organic composite systems.
Co-reporter:Ruthanne Hassey;Kevin D. McCarthy;Ellen Swain;Dipankar Basak;Dhapani Venkataraman
Chirality 2008 Volume 20( Issue 9) pp:1039-1046
Publication Date(Web):
DOI:10.1002/chir.20584
Abstract
We present results of fluorescence excitation circular dichroism studies of the chiroptical response of single (bridged triarylamine) helicene molecules immobilized at a polymer interface. We extract directly dissymmetry parameters, and corresponding probability distributions, associated with the single-molecule fluorescence excitation associated with modulation of a circular polarized excitation field for three different excitation wavelengths (405, 440, 457 nm) showing circular dichroism in bulk films. The observed single molecule chiroptical response is anomalously large in comparison with the results of time-dependent density functional calculations, and the observed defocused emission patterns seem to indicate a higher multipole nature to the transition probed. Our results provide new insights into chiroptical properties of chiral fluorophores that are hidden under the extensive averaging associated with conventional chiroptical probes. Chirality, 2008. © 2008 Wiley-Liss, Inc.
Co-reporter:Michael Y. Odoi;Hemali P. Rathnayake Dr.;Nathan I. Hammer Dr.;Paul M. Lahti
ChemPhysChem 2007 Volume 8(Issue 10) pp:1481-1486
Publication Date(Web):29 MAY 2007
DOI:10.1002/cphc.200700133
Single-molecule fluorescence measurements of 2,7-bis(3,4,5-trimethoxyphenylethenyl)fluorenone (OFOPV) reveal narrow emission spectra concentrated around 540 nm, with weak emission at longer wavelengths. The wide scattering of emission-maximum wavelengths is attributed to varying molecular environments, with dimers or higher-order aggregates contributing to the low-energy emission. This spectral distribution indicates that emission from monomers of this model fluorenone is mostly green, which is consistent with contaminant emission (g-bands) often observed in fluorene- and polyfluorene-based organic light emitting diode (OLED) devices. A histogram of center wavelengths from 118 single-molecule spectra shows good agreement with the green emission previously observed in thermally stressed 2,7-bis(3,4,5-trimethoxyphenylethenyl)-9,9-diethylfluorene (OFPV). Whereas bulk OFPV exhibits blue fluorescence at about 480 nm, OFOPV bulk thin film measurements reveal red luminescence shifted to 630 nm. This unexpected peak position for bulk OFOPV shifts to higher energies (ca. 540 nm) upon dilution in a solid-state matrix, suggesting that the bulk red emission finds its origins in interactions between fluorenone molecules. Explanations for this red emission include aggregate or excimer formation or intermolecular energy transfer between fluorenone molecules.
Co-reporter:Ruthanne Hassey;Ellen J. Swain;Nathan I. Hammer;Dhandapani Venkataraman
Science 2006 Vol 314(5804) pp:1437-1439
Publication Date(Web):01 Dec 2006
DOI:10.1126/science.1134231
Abstract
Chirally sensitive measurement techniques have generally been restricted to bulk samples. Here, we report the observation of fluorescence-detected circular dichroism (FDCD) from single (bridgedtriarylamine) helicene molecules by using an excitation wavelength (457 nanometers) in the vicinity of an electronic transition that shows circular dichroism in bulk samples. The distributions of dissymmetry (g) parameters by analysis of signals from pure M- and P-type diastereomers are almost perfect mirror images of one another, each spanning a range of both positive and negative values. In addition, we observe a well-defined structure in the histogram of dissymmetry parameters suggestive of specific molecular orientations at the polymer interface. These single-molecule results highlight strong intrinsic circular dichroism responses that can be obscured by cancellation effects in ensemble measurements of a randomly oriented bulk sample.
Co-reporter:A. J. Wise, Y. Zhang, J. Fan, F. Wudl, A. L. Briseno and M. D. Barnes
Physical Chemistry Chemical Physics 2014 - vol. 16(Issue 30) pp:NaN15830-15830
Publication Date(Web):2014/03/24
DOI:10.1039/C4CP00113C
Recent synthetic work has realized a novel (n-type) small-molecule acceptor, 7,8,15,16-tetra-aza-terrylene (TAT), single-crystals of which can be grown oriented along the c-axis crystallographic direction, and over-coated with pentacene to form a highly ordered donor/acceptor interface for use in organic photovoltaic devices. However, characterization of single TAT crystals reveals highly variable emission spectra and excited state dynamics – properties which strongly influence photovoltaic performance. Through the use of single-crystal widefield imaging, photoluminescence spectroscopy, time correlated single photon counting, and resonant Raman studies, we conclude that this variability is a result of long-lived low-energy trap-emission from packing defects. Interestingly, we also discovered that TAT crystals whose width exceeds ∼200 nm begin acting as waveguides and optical microcavity resonators for their own photoluminescence. Several strategies are proposed for leveraging the size-dependant optical properties of TAT pillars to further enhance device performance using this active layer design.