Minimizing geminate recombination losses in small-molecule-based organic solar cells

Small-molecule-based organic solar cells (OSCs) are a recurrent alternative to polymer-based OSCs. Due to the higher purity and definition of small molecules compared to polymers, the morphological requirements can be more relaxed. Here, we present a series of novel rhodanine-based small-molecule electron donors and blend them with the standard acceptor PC70BM. By performing a target analysis on femtosecond spectroscopy data, we quantify the rates of geminate charge recombination. We are able to reproduce these rates by applying the Marcus–Levich–Jortner equation, using results from quantum chemical calculations. This shows that in a series of differently substituted compounds, one can correctly predict trends in geminate recombination rates by relying only on quantities that are easy to measure (cyclic voltammetry, optical spectra) or that can be calculated by relatively inexpensive methods such as (TD)DFT. Our method should thus accelerate the search for high-performance small-molecule photovoltaic blends

Measuring the efficiency and charge carrier mobility of organic solar cells

P3HT single layer, P3HT/PCBM bilayer and P3HT/PCBM inverted bilayer devices were produced by spin coating organic layers onto ITO patterned glass in air, and clamping it with an Au coated silicon wafer, as top electrode, at the end (Figure13). Normal and inverted bilayer devices were also fabricated with and without PEDOT:PSS. All devices were divided into two groups by changing concentration of P3HT solution. The first group of devices contained 1.0 wt. % P3HT solution (P3HT in dichlorobenzene); the second group 0.56wt %. Power conversion efficiency, short circuit current, open circuit voltage, fill factor and maximum extracted power were measured on all produced devices. In contrast, all devices with 1.0wt % P3HT concentration showed better result than the devices with 0.56wt %. The highest result was obtained for P3HT single layer devices in both cases with short circuit current 56uA/cm2, open circuit voltage 0.94mV, maximum power 11.4uW/cm2 and power conversion efficiency of 0.11%. Inverted bilayer devices performed better than the non-inverted one. The devices with PEDOT:PSS got slightly better performance than the non-PEDOT:PSS used one. Charge carrier mobility measurement was done for all fabricated devices with charge extraction by linearly increasing voltage (CELIV) and dark injected space charge limited current (DI-SCLC) methods. All devices showed same magnitude of charge carrier mobility 10-5 cm2/V.s, the highest value still belongs to P3HT single layer device. The charge carrier mobility in all devices observed by DI-SCLC technique is one order of magnitude higher than by CELIV technique. This may be due to DI-SCLC method`s restriction on ohmic contacts between material and electrode.بۇ تەتقىقاتتا ئورگانىك ماتېرىيالدىن پايدىلنىپ ئۈچ خىل قۇياش ئىنىرگىيەلىك باتارىيە ئادەتتىكى ئۆي مۇھىتىدا ياساپ چىقىلدى. ئەڭ چوڭ توك كۈچى، ئەڭ                                                    يۇقىرى بېسىم، ئەڭ يۇقىرى قۇۋەت ۋە زەرەت يۆتكۈلۈش تېزلىكى ئۆلچەپ چىقىلدى ئۇيغۇر

Chirality sorted SWNTs and their effect on the performance of organic solar cells

Tesis Doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Física de la Materia Condensada. Fecha de lectura: 17-03-201

Effectof Growth Time, Growth Temperature and Light on Growth Mechanism of C60 nanorods

In this thesis work C60 nanorods were produced by Liquid-Liquid Interfacial Precipitation method (LLIP) assisted with 10 s of weak sonication. Ethanol and m-dichlorobenzene were used as poor and good solvents of C60, respectively. Five different temperatures, 4, 10, 20, 30, 40 and 50                         , were chosen as growth temperatures of different samples to investigate the effect of temperature on the grown structures. Different samples were prepared in the dark and under the light with various growth time to determine the effect of light and growth time on growth of C60 nanorods. The characterization of the grown C60 nanorods were conducted by transmission electron microscopy (TEM) and x-ray diffraction (XRD). The result of characterization indicated that the sonication introduced smaller C60 nanostructures; light irradiation and temperature increase (till 40 C0) during the growth time resulted in nanorods with smaller diameter, whereas the long growth time lead to the increase of the diameter of C60 nanorods. The as-grown C60 nanorods synthesized at different conditions possess an hcp crystal structure.   

Hole transporting materials for perovskite solar cells and a simple approach for determining the performance limiting factors

The synthesis and characterization of three novel HTMs with different highest occupied molecular orbital (HOMO) energy levels and their performances in MAPbI(3)-based devices in comparison with Spiro-OMeTAD is reported. Without systematic optimization, the HTMs performed well. The devices delivered fill factors comparable to the one with Spiro-OMeTAD but suffered from short-circuit current (J(SC)). Interestingly, despite the significant differences in HOMO energy levels, all three HTMs generated the same open-circuit voltage (V-OC). We explored the performance limiting factors of the HTMs by simple transient photovoltage/photocurrent (TPV/TPC) measurements along with drift-diffusion simulations. We found no correlation between HOMO energy levels of the HTMs and V-OC of the devices. Performances of the devices are limited by high trap density as well as low carrier mobility of the HTMs, and by the shunts present in the devices. Furthermore, the high trap density and low carrier mobility of the HTM are found to induce ion migration effect in the device causing slow decaying components in TPV/TPC. Nevertheless, it is confirmed that J(SC) and V-OC, measured at steady state, are not influenced by the ion migration effect. These HTMs can be improved further by optimizing their conductivity, trap density, morphology, and can be used as alternatives to Spiro-OMeTAD or other expensive, synthetically challenging HTMs. The simple and inexpensive approach presented in this work can also be applied for effectively evaluating charge transporting materials for perovskite solar cells.GM

Hole transporting materials for perovskite solar cells and a simple approach for determining the performance limiting factors

The synthesis and characterization of three novel HTMs with different highest occupied molecular orbital (HOMO) energy levels and their performances in MAPbI3-based devices in comparison with Spiro-OMeTAD is reported. Without systematic optimization, the HTMs performed well. The devices delivered fill factors comparable to the one with Spiro-OMeTAD but suffered from short-circuit current. Interestingly, despite the significant differences in HOMO energy levels, all three HTMs generated the same open-circuit voltage (VOC). We explored the performance limiting factors of the HTMs by simple transient photovoltage/photocurrent (TPV/TPC) measurements along with Drift-diffusion simulations. We found no correlation between HOMO energy levels of the HTMs and VOC of the devices. Performances of the devices are limited by high trap density as well as low carrier mobility of the HTMs, and by the shunts present in the devices. Furthermore, the high trap density and low carrier mobility of the HTM are found to induce ion migration effect in the device causing slow decaying components in TPV/TPC . Nevertheless, it is confirmed that JSC and VOC, measured at steady state, are not influenced by the ion migration effect. These HTMs can be improved further by optimizing their conductivity, trap density, morphology, and can be used as alternatives to Spiro-OMeTAD or other expensive, synthetically challenging HTMs. The simple and inexpensive approach presented in this work can also be applied for effectively evaluating charge transporting materials for perovskite solar cellsEuropean Research CouncilMINECOComunidad de MadridDepto. de Química OrgánicaFac. de Ciencias QuímicasTRUEpu

Chirality Specific Triplet Exciton Dynamics in Highly Enriched (6,5) and (7,5) Carbon Nanotube Networks

Single-walled carbon nanotubes (SWNTs) show high aspect ratio, thermal and chemical stability as well as charge mobility, and therefore appear ideally suited for improving charge extraction in organic photovoltaic (OPV) devices. Since typical charge extraction times in OPV devices are in the microsecond range, the interplay of the desired charged states with long-lived neutral states in SWNTs such as triplet excitons becomes important. Triplet excitons have recently been investigated in (6,5) SWNTs with an optical yield close to 32%. Here, we present transient absorption (TA) dynamics of (6,5)- and (7,5)-rich SWNT networks from the femtosecond to microsecond time scale. Comparing our TA spectra to results from a recent spectroelectrochemical study allows us to distinguish between contributions from charged and neutral photoexcitations. For long pump–probe delay times we identify an excess photobleach which we use as a chirality specific probe for the density of triplet excitons. We show that triplet energy transfer occurs between the (6,5) and the (7,5) chirality with a transfer time of about 70 ps. In contrast, no evidence of triplet exciton transfer is observed between (7,5) and (8,4) tubes. We find that the triplet yield is reduced at higher excitation densities, which points to singlet excitons as precursors for triplet states

Self-Assembled Amphiphilic Molecules for Highly Efficient Photocatalytic Hydrogen Evolution from Water

Self-assembled molecules for outstanding hydrogen evolution rate and durability should promise practical water splitting due to the versatile visible light absorption, low production cost, and ease of control. Here, we adapted an amphiphilic molecule as a building block for efficient small molecule based self-assembled photocatalyst for hydrogen evolution from water. The self-assembled molecules with platinum cocatalyst showed outstanding performance (turnover number similar to 27000) virtually comparable to the state-of-the-art metal oxide based photocatalysts with catalytic activity extending over days. Transient absorption studies in combination with quantum chemical calculations revealed that elaborate excited state engineering of the molecules resulted in such high performance of hydrogen evolution from water. This study shows that the self-assembled amphiphilic molecules could pave the way to more economical and reproducible production of hydrogen from water.N

Tracking the Light‐Induced Excited‐State Dynamics and Structural Configurations of an Extraordinarily Long‐Lived Metastable State at Room Temperature

Time‐resolved X‐ray (Tr‐XAS) and optical transient absorption (OTA) spectroscopy on the pico‐microsecond timescale coupled with density functional theory calculations are applied to study the light‐induced spin crossover processes of a Fe‐based macrocyclic complex in solution. Tr‐XAS analysis after light illumination shows the formation of a seven‐coordinated high‐spin quintet metastable state, which relaxes to a six‐coordinated high‐spin configuration before decaying to the ground state. Kinetic analysis of the macrocyclic complex reveals an unprecedented long‐lived decay lifetime of approximately 42.6 μs. Comparative studies with a non‐macrocyclic counterpart illustrate a significantly shortened approximately 568‐fold decay lifetime of about 75 ns, and highlight the importance of the ligand arrangement in stabilizing the reactivity of the excited state. Lastly, OTA analysis shows the seven‐coordinated high‐spin state to be formed within approximately 6.2 ps. These findings provide a complete understanding of the spin crossover reaction and relaxation pathways of the macrocyclic complex, and reveal the importance of a flexible coordination environment for their rational design

9-Aryl-phenalenones: Bioinspired thermally reversible photochromic compounds for photoswitching applications in the pico-to milliseconds range

Ultrafast photochromic molecules are being actively investigated to meet the demand for fast optical switching systems. Inspired on the irreversible cyclization of 9-phenylphenalenone plant metabolites to yield highly-coloured naphthoxanthenes for the purpose of defense against pathogens, aryl-substituted phenalenones have been developed that undergo a similar but reversible photochromic reaction. The lifetime of the naphthoxanthene photoisomer spans nine orders of magnitude, ranging from tens of picoseconds to tens of milliseconds depending on the electronic properties of the 9-aryl group