Publications


Quantification of Photophysical Processes in All-Polymer Bulk Heterojunction Solar Cells

SOLAR RRL 4 (2020) ARTN 2000181

AH Balawi, Z Kan, J Gorenflot, P Guarracino, N Chaturvedi, A Privitera, S Liu, Y Gao, L Franco, P Beaujuge, F Laquai


On the absence of triplet exciton loss pathways in non-fullerene acceptor based organic solar cells

MATERIALS HORIZONS 7 (2020) 1641-1649

MS Kotova, G Londi, J Junker, S Dietz, A Privitera, K Tvingstedt, D Beljonne, A Sperlich, V Dyakonov


Exciton efficiency beyond the spin statistical limit in organic light emitting diodes based on anthracene derivatives

Journal of Materials Chemistry C Royal Society of Chemistry (RSC) (2020)

N Sharma, MY Wong, D Hall, E Spuling, F Tenopala-Carmona, A Privitera, G Copley, DB Cordes, A Slawin, C Murawski, MC Gather, D Beljonne, Y Olivier, IDW Samuel, E Zysman-Colman

<p>We report two donor&ndash;acceptor (D&ndash;A) materials based on a cyanoanthracene acceptor paired with diphenylamine (<strong>DPAAnCN</strong>) and carbazole (<strong>CzAnCN</strong>) donor moieties. These compounds show hybrid locally excited (LE) charge-transfer (CT) excited states (HLCT), which we demonstrated through a combined photophysical and computational study. Vacuum-deposited organic light emitting diodes (OLEDs) using these HLCT emitters exhibit maximum external quantum efficiencies (EQE<sub>max</sub>) close to 6%, with impressive exciton utilization efficiency (<em>&Phi;</em><sub>s</sub>) of &gt;50%, far exceeding the spin statistic limit of 25%. We rule out triplet&ndash;triplet annihilation and thermally activated delayed fluorescence as triplet harvesting mechanisms along with horizontal orientation of emitters to enhance light outcoupling and, instead, propose a &ldquo;hot exciton&rdquo; channel involving the nearly isoenergetic T<sub>2</sub>&nbsp;and S<sub>1</sub>&nbsp;states.</p>


Ultrafast Charge Dynamics in Dilute-Donor versus Highly Intermixed TAPC:C60 Organic Solar Cell Blends.

The journal of physical chemistry letters (2020)

GJ Moore, M Causa', JF Martinez Hardigree, S Karuthedath, IR Ramirez, A Jungbluth, F Laquai, MK Riede, N Banerji

Elucidating the interplay between film morphology, photophysics, and device performance of bulk heterojunction (BHJ) organic photovoltaics remains challenging. Here, we use the well-defined morphology of vapor-deposited di-[4-(N,N-di-p-tolyl-amino)-phenyl]cyclohexane (TAPC):C60 blends to address charge generation and recombination by transient ultrafast spectroscopy. We gain relevant new insights to the functioning of dilute-donor (5% TAPC) fullerene-based BHJs compared to molecularly intermixed systems (50% TAPC). First, we show that intermolecular charge transfer (CT) excitons in the C60 clusters of dilute BHJs rapidly localize to Frenkel excitons prior to dissociating at the donor:acceptor interface. Thus, both Frenkel and CT excitons generate photocurrent over the entire fullerene absorption range. Second, we selectively monitor interfacial and bulk C60 clusters via their electro-absorption, demonstrating an energetic gradient that assists free charge generation. Third, we identify a fast (< 1 ns) recombination channel, whereby free electrons recombine with trapped holes on isolated TAPC molecules. This can harm the performance of dilute solar cells, unless the electrons are rapidly extracted in efficient devices.


Simple technique for determining the refractive index of phase-change materials using near-infrared reflectometry

Optical Materials Express The Optical Society 10 (2020) 1675-1675

E Gemo, S Kesava, C Ruiz De Galarreta, L Trimby, S García-Cuevas Carrillo, M Riede, A Baldycheva, A Alexeev, C Wright


Efficiency enhancement of small molecule organic solar cells using hexapropyltruxene as an interface layer

JOURNAL OF MATERIALS CHEMISTRY C 8 (2020) 4909-4918

H Ye, SV Kesava, JFM Hardigree, RE Brown, G Mazzotta, R Warren, PJ Skabara, M Riede

This journal is © The Royal Society of Chemistry. The quenching of excitons in organic solar cells can play a significant role in limiting their power conversion efficiency (PCE). In this article, we investigate the effect of a thin layer of hexapropyltruxene inserted at the interface between the electron donor boron subphthalocyanine chloride (SubPc) and its underlying hole contact in planar heterojunction solar cells. We find that a 3.8 nm hexapropyltruxene interlayer between the molybdenum oxide (MoOx) hole contact and SubPc is sufficient to improve PCE in SubPc/C60 fullerene solar cells from 2.6% to 3.0%, a ∼20% performance improvement. While the absorption stays roughly the same, the comparison of external and internal quantum efficiencies reveals a significant increase in SubPc's contribution to the current for light with wavelengths between 520 and 600 nm. Microstructure and surface morphology assessed with in situ Grazing-Incidence Wide-Angle X-Ray Scattering (GIWAXS) and Atomic Force Microscopy (AFM), are evaluated alongside in situ spectroscopic ellipsometry, and photoluminescence measurements. The microstructural investigations demonstrate changes to the surface and bulk of SubPc grown atop a hexapropyltruxene interlayer indicating that the latter acts as a template layer in a similar way as MoOx. However, the improvement in PCE is found to be mainly via reduced exciton quenching at the MoOx contact with the insertion of the hexapropyltruxene layer.


Filamentary high-resolution electrical probes for nanoengineering

Nano Letters American Chemical Society 20 (2020) 1067–1073-

JHE Soh, GS Sarwat, G Mazzotta, BF Porter, MK Riede, R Nicholas, JS Kim, H Bhaskaran

Confining electric fields to a nanoscale region is challenging yet crucial for applications such as high resolution probing of electrical properties of materials and electric-field manipulation of nanoparticles. State-of-the-art techniques involving atomic force microscopy typically have a lateral resolution limit of tens of nanometers due to limitations in the probe geometry and stray electric fields that extend over space. Engineering the probes is the most direct approach to improving this resolution limit. However, current methods to fabricate high-resolution probes, which can effectively confine the electric fields laterally involve expensive and sophisticated probe manipulation, which has limited the use of this approach. Here, we demonstrate that nanoscale phase switching of configurable thin films on probes can result in high-resolution electrical probes. These configurable coatings can be both germanium-antimony-tellurium (GST) as well as amorphous-carbon, materials known to undergo electric field-induced non-volatile, yet reversible switching. By forming a localized conductive filament through phase transition, we demonstrate a spatial resolution of electrical field beyond the geometrical limitations of commercial platinum probes (i.e. an improvement of ~48%). We then utilize these confined electric fields to manipulate nanoparticles with single nanoparticle precision via dielectrophoresis. Our results advance the field of nanomanufacturing and metrology with direct applications for pick and place assembly at the nanoscale.


Controlling energy levels and Fermi level en route to fully tailored energetics in organic semiconductors

Nature Communications Nature Research 10 (2019) 5538

R Warren, A Privitera, P Kaienburg, AE Lauritzen, O Thimm, J Nelson, M Riede

Simultaneous control over both the energy levels and Fermi level, a key breakthrough for inorganic electronics, has yet to be shown for organic semiconductors. Here, energy level tuning and molecular doping are combined to demonstrate controlled shifts in ionisation potential and Fermi level of an organic thin film. This is achieved by p-doping a blend of two host molecules, zinc phthalocyanine and its eight-times fluorinated derivative, with tunable energy levels based on mixing ratio. The doping efficiency is found to depend on host mixing ratio, which is explained using a statistical model that includes both shifts of the host's ionisation potentials and, importantly, the electron affinity of the dopant. Therefore, the energy level tuning effect has a crucial impact on the molecular doping process. The practice of comparing host and dopant energy levels must consider the long-range electrostatic shifts to consistently explain the doping mechanism in organic semiconductors.


Solubilization of Carbon Nanotubes with Ethylene-Vinyl Acetate for Solution-Processed Conductive Films and Charge Extraction Layers in Perovskite Solar Cells.

ACS Appl Mater Interfaces (2018)

G Mazzotta, M Dollmann, SN Habisreutinger, MG Christoforo, Z Wang, HJ Snaith, MK Riede, RJ Nicholas

Carbon nanotube (CNT) solubilization via non-covalent wrapping of conjugated semiconducting polymers is a common technique used to produce stable dispersions for depositing CNTs from solution. Here, we report the use of a non-conjugated insulating polymer, ethylene vinyl acetate (EVA), to disperse multi- and single-walled CNTs (MWCNT and SWCNT) in organic solvents. We demonstrate that despite the insulating nature of the EVA, we can produce semitransparent films with conductivities of up to 34 S/cm. We show, using photoluminescence spectroscopy, that the EVA strongly binds to individual CNTs, thus making them soluble, preventing aggregation, and facilitating the deposition of high-quality films. To prove the good electronic properties of this composite, we have fabricated perovskite solar cells using EVA/SWCNTs and EVA/MWCNTs as selective hole contact, obtaining power conversion efficiencies of up to 17.1%, demonstrating that the insulating polymer does not prevent the charge transfer from the active material to the CNTs.


Tuning the ambipolar behaviour of organic field effect transistors via band engineering

AIP ADVANCES 9 (2019) ARTN 035202

PR Warren, JFM Hardigree, AE Lauritzen, J Nelson, M Riede


Hole Transport in Low-Donor-Content Organic Solar Cells.

The journal of physical chemistry letters (2018) 5496-5501

D Spoltore, A Hofacker, J Benduhn, S Ullbrich, M Nyman, O Zeika, S Schellhammer, Y Fan, I Ramirez, S Barlow, M Riede, SR Marder, F Ortmann, K Vandewal

Organic solar cells with an electron donor diluted in a fullerene matrix have a reduced density of donor-fullerene contacts, resulting in decreased free-carrier recombination and increased open-circuit voltages. However, the low donor concentration prevents the formation of percolation pathways for holes. Notwithstanding, high (>75%) external quantum efficiencies can be reached, suggesting an effective hole-transport mechanism. Here, we perform a systematic study of the hole mobilities of 18 donors, diluted at ∼6 mol % in C60, with varying frontier energy level offsets and relaxation energies. We find that hole transport between isolated donor molecules occurs by long-range tunneling through several fullerene molecules, with the hole mobilities being correlated to the relaxation energy of the donor. The transport mechanism presented in this study is of general relevance to bulk heterojunction organic solar cells where mixed phases of fullerene containing a small fraction of a donor material or vice versa are present as well.


Modification of the fluorinated tin oxide/electron-transporting material interface by a strong reductant and its effect on perovskite solar cell efficiency

Molecular Systems Design and Engineering Royal Society of Chemistry 3 (2018) 741-747

F Pulvirenti, B Wegner, NK Noel, G Mazzotta, R Hill, JB Patel, LM Herz, MB Johnston, MK Riede, HJ Snaith, N Koch, S Barlow

To date, the most efficient hybrid metal halide peroskite solar cells employ TiO2 as electron-transporting material (ETM), making these devices unstable under UV light exposure. Replacing TiO2 with fullerene derivatives has been shown to result in improved electronic contact and increased device lifetime, making it of interest to assess whether similar improvements can be achieved by using other organic semiconductors as ETMs. In this work, we investigate perylene-3,4:9,10-tetracarboxylic bis(benzimidazole) as a vacuum-processable ETM, and we minimize electron-collection losses at the electron-selective contact by depositing pentamethylcyclopentadienyl cyclopentadienyl rhodium dimer, (RhCp*Cp)2, on fluorinated tin oxide. With (RhCp*Cp)2 as an interlayer, ohmic contacts can be formed, there is interfacial doping of the ETM, and stabilized power conversion efficiencies of up to 14.2% are obtained.


How Contact Layers Control Shunting Losses from Pinholes in Thin-Film Solar Cells

JOURNAL OF PHYSICAL CHEMISTRY C 122 (2018) 27263-27272

P Kaienburg, P Hartnage, BE Pieters, J Yu, D Grabowski, Z Liu, J Haddad, U Rau, T Kircharte


Engineering interactions in QDs–PCBM blends: a surface chemistry approach

Nanoscale Royal Society of Chemistry 10 (2018) 11913-11922

A Privitera, M Righetto, F Carraro, L Bolzonello, C Ferrante, L Franco, R Bozio

Here we present a comprehensive study on the photophysics of QDs–fullerene blends, aiming to elucidate the impact of ligands on the extraction of carriers from QDs. We investigated how three different ligands (oleylamine, octadecanethiol and propanethiol) influence the dynamics of charge generation, separation, and recombination in blends of CdSe/CdS core/shell QDs and PCBM. We accessed each relevant process directly by combining the results from both optical and magnetic spectroscopies. Transient absorption measurements revealed a faster interaction dynamics in thiol-capped ligands. Through phenomenological modeling of the interaction processes, i.e., energy transfer and electron transfer, we estimated the suppression of exciton migration and the enhancement of electron transfer processes when alkyl–thiols are employed as ligands. Contextually, we report the profound impact of the ligands’ alkyl chain length, leading to strengthened interactions with PCBM acceptors. Quantitatively, we measured a 10-fold increase in the electron transfer rate when oleylamine ligands were exchanged with propanethiol ligands. EPR spectroscopy gave access to subtle details regarding both the enhanced charge generation and lower binding energy of charge-transfer states in blends compared to PCBM alone. Moreover, through pulsed EPR techniques, we inferred the localization of deep electron traps in localized sites close to QDs in the blends. Therefore, our thorough characterization evidenced the essential role of ligands in determining QD interactions. We believe that these discoveries will contribute to the efficient incorporation of QDs in existing organic PV technologies.


Publisher Correction: High irradiance performance of metal halide perovskites for concentrator photovoltaics

Nature Energy Springer Nature America, Inc (2018)

Z Wang, Q Lin, B Wenger, M Christoforo, Y-H Lin, MT Klug, MICHAEL Johnston, LAURA Herz, HJ Snaith

© 2018, Springer Nature Limited. When this Article was originally published, an old version of the associated Supplementary Information file was uploaded. This has now been replaced.


Femtosecond dynamics of photoexcited C60 films

Journal of Physical Chemistry Letters American Chemical Society (2018)

M Causa', IR Ramirez, JMF Hardigree, MK Riede, N Banerjii

The well-known organic semiconductor C60 is attracting renewed attention due to its centimetre-long electron diffusion length and high performance of solar cells containing 95% fullerene. Yet, its photophysical properties remain poorly understood. Here, we elucidate the dynamics of Frenkel and intermolecular (inter- C60) charge transfer (CT) excitons in neat and diluted C60 films from high quality femtosecond transient absorption (TA) measurements, performed at low fluences and free from oxygen or pump-induced photo-dimerization. We find from preferential excitation of either species that the CT excitons give rise to a strong electro-absorption signal but are extremely short-lived. The Frenkel exciton relaxation and triplet yield depend strongly on the C60 aggregation. Finally, TA measurements on full devices with applied electric field allow us to optically monitor the dissociation of CT excitons into free charges for the first time and to demonstrate the influence of cluster size on the spectral signature of the C60 anion.


Understanding Thermal Admittance Spectroscopy in Low-Mobility Semiconductors

JOURNAL OF PHYSICAL CHEMISTRY C 122 (2018) 9795-9803

S Wang, P Kaienburg, B Klingebiel, D Schillings, T Kirchartz


Key Tradeoffs Limiting the Performance of Organic Photovoltaics

Advanced Energy Materials (2018)

I Ramirez, M Causa', Y Zhong, N Banerji, M Riede

© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. 2017 saw the publication of several new material systems that challenge the long-held notion that a driving force is necessary for efficient exciton dissociation in organic photovoltaics (OPVs) and that a loss of ≈0.6 eV between the energy of the charge transfer state E ct and the energy corresponding to open circuit is general. In light of these developments, the authors combine insights from device physics and spectroscopy to review the two key tradeoffs limiting OPV performances. These are the tradeoff between the charge carrier generation efficiency and the achievable open circuit voltage (V oc ) and the tradeoff between device thickness (light absorption) and fill factor. The emergence of several competitive nonfullerene acceptors (NFAs) is exciting for both of these. The authors analyze what makes these materials compare favorably to fullerenes, including the potential role of molecular vibrations, and discuss both design criteria for new molecules and the achievable power conversion efficiencies.


Carbon nanotubes for quantum dot photovoltaics with enhanced light management and charge transport

ACS Photonics American Chemical Society 5 (2018) 4854-4863

Y Tazawa, S Habisreutinger, N Zhang, DAF Gregory, G Nagamine, S Kesava, G Mazzotta, H Assender, MK Riede, L Padilha, RJ Nicholas, AAR Watt

Colloidal quantum dot (CQD)-based photovoltaics are an emerging low-cost solar cell technology with power conversion efficiencies exceeding 10%, i.e., high enough to be interesting for commercialization. Well-controlled and understood charge carrier transport through the device stack is required to make the next step in efficiency improvements. In this paper, polymer-wrapped single-walled carbon nanotube (SWNT) films embedded in an insulating poly(methyl methacrylate) (PMMA) matrix and capped by a thermally evaporated Au electrode are investigated as a composite hole transport layer and optical spacer. Employing transient absorption spectroscopy we show that the SWNTs enhance the charge transfer rate from CQD to CQD, ZnO, or SWNT. In order to pinpoint the underlying mechanism for the improvement, we investigate the energetics of the junction by measuring the relative alignment of the band edges, using Kelvin probe and cyclic voltammetry. Measuring the external quantum efficiency and absorption we find that the improvement is not mainly from electronic improvements but from enhanced absorption of the CQD absorber. We demonstrate experimentally and theoretically, by employing a transfer-matrix model, that the transparent PMMA matrix acts as an optical spacer, which leads to an enhanced absorption in the absorber layer. With these electronic and optical enhancements, the efficiency of the PbS CQD solar cells improved from 4.0% to 6.0%.


High irradiance performance of metal halide perovskites for concentrator photovoltaics

Nature Energy Nature Publishing Group 3 (2018) 855-861

Z Wang, Q Lin, B Wenger, MG Christoforo, Y-H Lin, MT Klug, MB Johnston, LM Herz, HJ Snaith

Traditionally, III–V multi-junction cells have been used in concentrator photovoltaic (CPV) applications, which deliver extremely high efficiencies but have failed to compete with ‘flat-plate’ silicon technologies owing to cost. Here, we assess the feasibility of using metal halide perovskites for CPVs, and we evaluate their device performance and stability under concentrated light. Under simulated sunlight, we achieve a peak efficiency of 23.6% under 14 Suns (that is, 14 times the standard solar irradiance), as compared to 21.1% under 1 Sun, and measure 1.26 V open-circuit voltage under 53 Suns, for a material with a bandgap of 1.63 eV. Importantly, our encapsulated devices maintain over 90% of their original efficiency after 150 h aging under 10 Suns at maximum power point. Our work reveals the potential of perovskite CPVs, and may lead to new PV deployment strategies combining perovskites with low-concentration factor and lower-accuracy solar tracking systems.

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