Role of Exciton Lifetime, Energetic Offsets, and Disorder in Voltage Loss of Bulk Heterojunction Organic Solar Cells.

Recently, the power conversion efficiency (PCE) of organic solar cells (OSCs) has significantly progressed with a rapid increase from 10 to 19% due to state-of-the-art research on nonfullerene acceptor molecules and various device processing strategies. However, OSCs still exhibit significant open circuit voltage loss (ΔVOC ∼ 0.6 V) due to high energetic offsets and molecular disorder. In this work, we present a systematic investigation to determine the effects of energetic offset and disorder on different recombination losses in open circuit voltage (VOC) using 13 different photoactive layers, wherein the PCE and ΔVOC vary in the ranges of 2.21-14.74% and 0.561-1.443 V, respectively. The detailed voltage loss analysis of all these devices was carried out, and voltage losses were correlated with energetic offset and disorder. This has enabled us to identify the key features for minimizing the voltage loss like: (1) a low energy offset between the donor and acceptor molecular states is essential to attain a nonradiative voltage loss (ΔVOC, nrad) as low as ∼200 meV and (2) Urbach energy, which is a measure of the materials' disorder and packing, should be low for the minimization of the radiative voltage loss (ΔVOC, rad). In addition, time-resolved photoluminescence spectroscopy was employed to further understand the exciton dynamics of pristine materials and donor-acceptor blends. It was observed that the absorbers with ultralong exciton lifetime (∼1000 ps) produce higher efficiencies. The current study emphasizes the importance of simultaneously testing photovoltaic performance and active layer exciton dynamics for rational device optimization and opens new prospects for designing novel molecules with fine-tuning of energetic offset and disorder with longer exciton lifetime which is the effective strategy to boost the efficiency of OSCs to their modified Shockley-Queisser (SQ) limit by minimizing radiative and nonradiative voltage losses.

Understanding the linear and nonlinear optical responses of few-layer exfoliated MoS2and WS2nanoflakes: experimental and simulation studies.

Understanding the linear and nonlinear optical (NLO) responses of two-dimensional nanomaterials is essential to effectively utilize them in various optoelectronic applications. Here, few-layer MoS2and WS2nanoflakes with lateral size less than 200 nm were prepared by liquid-phase exfoliation, and their linear and NLO responses were studied simultaneously using experimental measurements and theoretical simulations. Finite-difference time-domain (FDTD) simulations confirmed the redshift in the excitonic transitions when the thickness was increased above 10 nm indicating the layer-number dependent bandgap of nanoflakes. WS2nanoflakes exhibited around 5 times higher absorption to scattering cross-section ratio than MoS2nanoflakes at various wavelengths. Open aperture Z scan analysis of both the MoS2and WS2nanoflakes using 532 nm nanosecond laser pulses reveals strong nonlinear absorption activity with effective nonlinear absorption coefficient (ßeff) of 120 cm GW-1and 180 cm GW-1, respectively, which was attributed to the combined contributions of ground, singlet excited and triplet excited state absorption. FDTD simulation results also showed the signature of strong absorption density of few layer nanoflakes which may be account for their excellent NLO characteristics. Optical limiting threshold values of MoS2and WS2nanoflakes were obtained as ∼1.96 J cm-2and 0.88 J cm-2, respectively, which are better than many of the reported values. Intensity dependent switching from saturable absorption (SA) to reverse SA was also observed for MoS2nanoflakes when the laser intensity increased from 0.14 to 0.27 GW cm-2. The present study provides valuable information to improve the selection of two-dimensional nanomaterials for the design of highly efficient linear and nonlinear optoelectronic devices.

Defect mediated improved charge carrier dynamics in hybrid bulk-heterojunction solar cell induced by phase pure iron pyrite nanocubes.

In this article, the synthesis of phase pure iron pyrite nanocubes (FeS2NCs) and their various effects on the charge carrier dynamics and photovoltaic performances of P3HT:PC71BM based hybrid bulk-heterojunction solar cells have been studied. The optimum doping concentration of FeS2NCs was found to be 0.3 wt%. For the optimally doped devices, the short-circuit current density was found to have improved from 5.47 to 7.99 mA cm-2leading to an overall cell efficiency improvement from 2.10% to 3.22% as compared to the undoped reference devices. The enhancement in photovoltaic performance is mainly attributed to the formation of localized energy states near the band edges leading to higher carrier generation rate by 72% whereas carrier dissociation probability is also increased by 13%. Urbach energy estimation reveals that the optimally doped devices have achieved a relatively balanced amount of localized states resulting in reduced non-radiative recombination. Such localized defect states formation with FeS2NCs doping was also found to have significant influence over the charge carrier dynamics of the active layer. Transient photocurrent and photovoltage studies revealed that FeS2NCs assist in faster carrier extraction by reducing the transport time from 1.4 to 0.6µs and by enhancing carrier recombination time from 51.7 to 78.9µs for the reference and optimum devices respectively. Such an unorthodox approach of defect state assisted efficiency improvement demonstrates the importance of simultaneously understanding the charge carrier dynamics and photovoltaic performance for rational device optimization, and opens new prospects for developing high-efficiency solution processable hybrid devices.

Kinetics of Ion Transport in Perovskite Active Layers and Its Implications for Active Layer Stability.

Solar cells fabricated using alkyl ammonium metal halides as light absorbers have the right combination of high power conversion efficiency and ease of fabrication to realize inexpensive but efficient thin film solar cells. However, they degrade under prolonged exposure to sunlight. Herein, we show that this degradation is quasi-reversible, and that it can be greatly lessened by simple modifications of the solar cell operating conditions. We studied perovskite devices using electrochemical impedance spectroscopy (EIS) with methylammonium (MA)-, formamidinium (FA)-, and MA(x)FA(1-x) lead triiodide as active layers. From variable temperature EIS studies, we found that the diffusion coefficient using MA ions was greater than when using FA ions. Structural studies using powder X-ray diffraction (PXRD) show that for MAPbI3 a structural change and lattice expansion occurs at device operating temperatures. On the basis of EIS and PXRD studies, we postulate that in MAPbI3 the predominant mechanism of accelerated device degradation under sunlight involves thermally activated fast ion transport coupled with a lattice-expanding phase transition, both of which are facilitated by absorption of the infrared component of the solar spectrum. Using these findings, we show that the devices show greatly improved operation lifetimes and stability under white-light emitting diodes, or under a solar simulator with an infrared cutoff filter or with cooling.

Bulk charge carrier transport in push-pull type organic semiconductor.

Operation of organic electronic and optoelectronic devices relies on charge transport properties of active layer materials. The magnitude of charge carrier mobility, a key efficiency metrics of charge transport properties, is determined by the chemical structure of molecular units and their crystallographic packing motifs, as well as strongly depends on the film fabrication approaches that produce films with different degrees of anisotropy and structural order. Probed by the time-of-flight and grazing incidence X-ray diffraction techniques, bulk charge carrier transport, molecular packing, and film morphology in different structural phases of push-pull type organic semiconductor, 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophen]-5yl)benzo[c][1,2,5] thiadiazole), one of the most efficient small-molecule photovoltaic materials to-date, are described herein. In the isotropic phase, the material is ambipolar with high mobilities for a fluid state. The electron and hole mobilities at the phase onset at 210.78 °C are 1.0 × 10(-3) cm(2)/(V s) and 6.5 × 10(-4) cm(2)/(V s), respectively. Analysis of the temperature and electric field dependences of the mobilities in the framework of Gaussian disorder formalism suggests larger energetic and positional disorder for electron transport sites. Below 210 °C, crystallization into a polycrystalline film with a triclinic unit cell symmetry and high degree of anisotropy leads to a 10-fold increase of hole mobility. The mobility is limited by the charge transfer along the direction of branched alkyl side chains. Below 90 °C, faster cooling rates produce even higher hole mobilities up to 2 × 10(-2) cm(2)/(V s) at 25 °C because of the more isotropic orientations of crystalline domains. These properties facilitate in understanding efficient material performance in photovoltaic devices and will guide further development of materials and devices.

Solution-processed photovoltaics with a 3,6-bis(diarylamino)fluoren-9-ylidene malononitrile.

3,6-Bis(N,N-dianisylamino)-fluoren-9-ylidene malononitrile (FMBDAA36) was used as an electron donor material in solution-processed organic photovoltaic devices with configuration ITO/PEDOT:PSS/(1:3[w/w] FMBDAA36:PC71BM)/LiF/Al to give power conversion efficiencies up to 4.1% with open circuit voltage VOC = 0.89 V, short circuit current JSC = 10.35 mA cm(-2), and fill factor FF = 44.8%. Conductive atomic force microscopy of the active layer showed granular separation of regions exhibiting easy versus difficult hole transport, consistent with bulk heterojunction type phase separation of FMBDAA36 and PC71BM, respectively. Single-crystal X-ray diffraction analysis showed pure FMBDAA36 to form columnar π-stacks with a 3.3 Å intermolecular spacing.

Crystallinity and morphology effects on a solvent-processed solar cell using a triarylamine-substituted squaraine.

2,4-Bis[4'-(N,N-di(4″-hydroxyphenyl)amino)-2',6'-dihydroxyphenyl]squaraine (Sq-TAA-OH, optical bandgap 1.4 eV, HOMO level -5.3 eV by ultraviolet photoelectron spectroscopy) is used as an active layer material in solution processed, bulk-heterojunction organic photovoltaic cells with configuration ITO/PEDOT:PSS/Sq-TAA-OH:PC71BM/LiF/Al. Power conversion efficiencies (PCEs) up to 4.8% are obtained by a well-reproducible procedure using a mixture of good and poor Sq-TAA-OH solubilizing organic solvents, with diiodooctane (DIO) additive to make a bulk heterojunction layer, followed by thermal annealing, to give optimized V(OC) = 0.84-0.86 V, J(SC) = 10 mA cm(-2), and FF = 0.53. X-ray diffraction and scattering studies of pristine, pure Sq-TAA-OH solution-cast films show d-spacing features similar to single-crystal packing and spacing. The DIO additive in a good solvent/poor solvent mixture apparently broadens the size distribution of Sq-TAA-OH crystallites in pristine films, but thermal annealing provides a narrower size distribution. Direct X-ray diffraction and scattering morphological studies of "as-fabricated" active layers show improved Sq-TAA-OH/PC71BM phase separation and formation of crystallites, ∼48 nm in size, under conditions that give the best PCE.