José Darío Perea

Abnormal strong burn-in degradation of highly efficient polymer solar cells caused by spinodal donor-acceptor demixing

The performance of organic solar cells is determined by the delicate, meticulously optimized bulk-heterojunction microstructure, which consists of finely mixed and relatively separated donor/acceptor regions. Here we demonstrate an abnormal strong burn-in degradation in highly efficient polymer solar cells caused by spinodal demixing of the donor and acceptor phases, which dramatically reduces charge generation and can be attributed to the inherently low miscibility of both materials. Even though the microstructure can be kinetically tuned for achieving high-performance, the inherently low miscibility of donor and acceptor leads to spontaneous phase separation in the solid state, even at room temperature and in the dark. A theoretical calculation of the molecular parameters and construction of the spinodal phase diagrams highlight molecular incompatibilities between the donor and acceptor as a dominant mechanism for burn-in degradation, which is to date the major short-time loss reducing the performance and stability of organic solar cells.

Brightly Luminescent and Color-Tunable Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals

In the past few years, hybrid organic-inorganic and all-inorganic metal halide perovskite nanocrystals have become one of the most interesting materials for optoelectronic applications. Here, we report a facile and rapid room temperature synthesis of 15-25 nm formamidinium CH(NH2)2PbX3 (X = Cl, Br, I, or mixed Cl/Br and Br/I) colloidal nanocrystals by ligand-assisted reprecipitation (LARP). The cubic and platelet-like nanocrystals with their emission in the range of 415-740 nm, full width at half-maximum (fwhm) of 20-44 nm, and radiative lifetimes of 5-166 ns enable band gap tuning by halide composition as well as by their thickness tailoring; they have a high photoluminescence quantum yield (up to 85%), colloidal and thermodynamic stability. Combined with surface modification that prevents degradation by water, this nanocrystalline material is an ideal candidate for optoelectronic devices and applications. In addition, optoelectronic measurements verify that the photodetector based on FAPbI3 nanocrystals paves the way for perovskite quantum dot photovoltaics.

Understanding the correlation and balance between the miscibility and optoelectronic properties of polymer–fullerene solar cells

Organic photovoltaics is one of the most promising technologies for sustainable green energy supply. Because of their high electron affinity and superior electron-transporting ability, fullerene-based materials are deemed as very strong electron-accepting components in organic solar cells. However, the most widely used fullerene-based acceptors, such as phenyl-C61-butyric acid methyl ester, exhibit limited microstructural stability and unsatisfactory thermal stability owing to their insufficient compatibility with organic donors. Here, we in-depth investigate the carrier dynamics along with structural evolution and analyze the acceptor loadings in optimized bulk-heterojunction (BHJ) solar cells as a function of the polymer–fullerene miscibility. The polymer–fullerene miscibility has more influential effects than the crystallinity of single components on the optimized acceptor : donor ratio in polymer–fullerene solar cells. The findings demonstrated in this work suggest that the balance between the miscibility of BHJ composites and their optoelectronic properties has to be carefully considered for future development and optimization of OPV solar cells based on BHJ composites. Miscibility is proposed in addition to crystallinity as a further design criterion for long lived and efficient solar cells.

Suppressing photooxidation of conjugated polymers and their blends with fullerenes through nickel chelates

Conjugated polymer semiconductors offer unique advantages over conventional semiconductors but tend to suffer from electro-optic performance roll-off, mainly due to reduced photofastness. Here, we demonstrate that the commodity nickel chelate nickel(II) dibutyldithiocarbamate, Ni(dtc)2, effectively inhibits photooxidation across a wide range of prototypical π-conjugated polymer semiconductors and blends. The addition of 2–10 wt% of Ni(dtc)2 increases the resilience of otherwise quickly photobleaching semiconducting thin films, even in the presence of detrimental, radical forming processing additives. Using electron spin resonance spectroscopy and sensitive oxygen probes, we found that Ni(dtc)2 acts as a broadband stabilizer that inhibits both the formation of reactive radicals and singlet oxygen. The mechanism of stabilization is of sacrificial nature, but contains non-sacrificial contributions in polymers where singlet oxygen is a key driver of photooxidation. Ultrafast pump–probe spectroscopy reveals quenching of triplet excited states as the central mechanism of non-sacrificial stabilization. When introduced into the active layer of organic photovoltaic devices, Ni(dtc)2 retards the short circuit current loss in air without affecting the sensitive morphology of bulk heterojunctions and without major sacrifices in semiconductor properties. Antioxidants based on nickel complexes thus constitute functional stabilizers for elucidating degradation mechanisms in organic semiconductors and represent a cost-effective route toward organic electronic appliances with extended longevity.

Towards a full understanding of regioisomer effects of indene-C60 bisadduct acceptors in bulk heterojunction polymer solar cells

Indene-C60 bisadduct (IC60BA), which can offer a significantly higher open-circuit voltage (Voc) than monoadducts, has become the research focus as electron acceptor materials in polymer solar cells (PSCs) in recent years. However, despite its popularity, IC60BA have always been applied in PSCs as mixture of several regioisomers and the nature of this mixture has never been fully investigated and understood. Herein, for the first time, 12 major regioisomers of IC60BA were isolated and a full investigation was carried out with respect to their structure, abundance, solubility and their corresponding photovoltaic performance. The results show that the PSCs based on these regioisomeric structures present very diverse PCE and their photovoltaic performance was dramatically affected not only by the relative indene positions but also by the steric orientation of the two indene groups. Electrochemical studies further revealed that the effect of energetic disorder inside the IC60BA regioisomers on their photovoltaic performance is insignificant when applied in PSCs. However, the steric structures and solubility of the regioisomers were found to have significant impact on the morphology and bulk properties of the active layer of PSCs, which give rise to very different PCE of devices based on IC60BA regioisomers with different structures.

Suppression of Thermally Induced Fullerene Aggregation in Polyfullerene-Based Multiacceptor Organic Solar Cells

A novel main-chain polyfullerene, poly[fullerene-alt-2,5-bis(octyloxy)terephthalaldehyde] (PPC4), is investigated for its hypothesized superior morphological stability as an electron-accepting material in organic photovoltaics relative to the widely used fullerene phenyl-C61-butyric acid methyl ester (PCBM). When mixed with poly(3-hexylthiophene-2,5-diyl) (P3HT), PPC4 affords low-charge-generation yields because of poor intermixing within the blend. The adoption of a multiacceptor system, by introducing PCBM into the P3HT:polyfullerene blend, was found to lead to a 3-fold enhancement in charge generation, affording power conversion efficiencies very close to that of the prototypical P3HT:PCBM binary control. Upon thermal stressing and in contrast to the P3HT:PCBM binary, photovoltaic devices based on the multiacceptor system demonstrated significantly improved stability, outperforming the control because of suppression of the PCBM migration and aggregation processes responsible for rapid device failure. We rationalize the influence of the fullerene miscibility and its implications on the device performance in terms of a thermodynamic model based on Flory-Huggins solution theory. Finally, the potential universal applicability of this approach for thermal stabilization of organic solar cells is demonstrated, utilizing an alternative low-band-gap polymer-donor system.

Correction to Brightly Luminescent and Color-Tunable Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals

Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals Ievgen Levchuk,* Andres Osvet, Xiaofeng Tang, Marco Brandl, Jose ́ Darío Perea, Florian Hoegl, Gebhard J. Matt, Rainer Hock, Miroslaw Batentschuk, and Christoph J. Brabec Nano Lett. 2017, 17 (5), pp 2765−2770. DOI:10.1021/acs.nanolett.6b04781 O page 2766, line 25 (left side) of the main text, “rapidly injected a DMF solution of PbX2 and MAX” should be “rapidly injected a DMF solution of PbX2 and FAX”. Addition/Correction