The Influence of Substituent Orientation on the Photovoltaic Performance of Phthalocyanine-Sensitized Solar Cells

This is the peer reviewed version of the following article:Chemistry - A European Journal 22.13 (2016): 4369-4373, which has been published in final form at http://dx.doi.org/10.1002/chem.201600166. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-ArchivingPhthalocyanines (Pcs) are used as sensitizers in dye-sensitized solar cells (DSSCs) because of their stability and intense absorption in the red and near-IR regions. Impressive progress has been made in photovoltaic efficiencies by introduction of bulky peripheral substituents to help suppress macrocycle aggregation. To reach benchmark efficiencies reported for other related dyes, new designs need to be explored. Single carboxy-ZnPc regioisomers substituted at the non-peripheral positions by rigid aryl groups have now been studied, which has shed light on the influence of steric hindrance and/or orientation of the substituent around the anchoring group on the photovoltaic response. The regioisomer bearing the aryl group far away from the anchoring group produces a more effective sensitization of the TiO2 films and higher short-circuit photocurrent density (Jsc). Taking advantage of the good photovoltaic performance in the near-IR region of this ZnPc, it was combined with another appropriate dye for panchromatic sensitization of the mesoporous photoelectrode and an increase of the overall device efficiencyFinancial support from the European Union (FP7-ENERGY-2012- 1 framework, GLOBASOL project, Proposal No 309194-2), from the Spanish MINECO (CTQ2014-52869-P), Comunidad de Madrid (FOTOCARBON S2013/MIT-2841), and MECD (F.P.U. fellowship to L.T.) is gratefully acknowledge

Efficient and Stable Perovskite Solar Cells by Tailoring of Interfaces

The interface tailoring is crucial for the efficiency and stability of Perovskite Solar Cells (PSCs). The reported interface engineering primarily focuses on the energy level turning and trap state passivation to improve the photovoltaic performance of PSCs. In this review, molecule modifications are classified according to the basics of electron transfer mechanisms for the interface tailoring of materials. An in‐depth analysis of energy level modification and trap passivation, as well as the universal Density Functional Theory (DFT) method employed in interface tailoring. In addition, strategies to address environmental protection and large‐scale mini‐modules fabrication by interface engineering are also discussed. This review can guide the researchers in understanding interface engineering to design interface materials for efficient, stable, and eco‐friendly PSCs

Phthalocyanines and Porphyrinoid Analogues as Hole-and Electron-Transporting Materials for Perovskite Solar Cells

Organic–inorganic lead halide perovskite absorbers in combination with electron and hole transporting selective contacts result in power conversion efficiencies of over 23% under AM 1.5 sun conditions. The advantage of perovskite solar cells is their simple fabrication through solution-processing methods either in n-i-p or p-i-n configurations. Using TiO2 or SnO2 as an electron transporting layer, a compositionally engineered perovskite as an absorber layer, and Spiro-OMeTAD as a HTM, several groups have reported over 20% efficiency. Though perovskite solar cells reached comparable efficiency to that of crystalline silicon ones, their stability remains a bottleneck for commercialization partly due to the use of doped Spiro-OMeTAD. Several organic and inorganic hole transporting materials have been explored to increase the stability and power conversion efficiency of perovskite solar cells. IIn this review, we analyse the stability and efficiency of perovskite solar cells incorporating phthalocyanine and porphyrin macrocycles as hole- and electron transporting materials. The π–π stacking orientation of these macrocycles on the perovskite surface is important in facilitating a vertical charge transport, resulting in high power conversion efficiencyWe are grateful for the financial support of the MINECO, Spain (CTQ2017-85393-P) and the Comunidad de Madrid (FOTOCARBON, S2013/MIT-2841). IMDEA Nanociencia acknowledges support from the ‘Severo Ochoa’ Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686). MKN thanks the EPFL and the Swiss National Science Foundatio

Dispositivos optoelectrónicos basados en perovskitas orgánico-inorgánico conteniendo el catión guanidinio

La presente investigación se enfoca en el campo de dispositivos optoelectrónicos, concretamente en células solares basadas en perovskitas hibrídas orgánicas-inorgánicas, las cuales han emergido recientemente como un material prometedor para complementar o reemplazar a las actuales células solares basadas en silicio (Si). Los investigadores del Departamento de Química Física y Termodinámica Aplicada/ Instituto de Química Fina y Nanoquímica (UCO) en colaboración con el Group of Molecular Engineering of Functional Materials (EPFL) han logrado introducir el catión Guanidinio (Gua) en la red cristalina de la perovskita MAPbI3, basada en metilamonio (MA) y yoduro de plomo (PbI2), sustituyendo hasta un 25% de MA por Gua. Estos resultados son sorprendentes debido a que el radio catiónico del Guanidinio está por encima del límite de tolerancia de Goldsmith (0.8-1), el cual predice la formación de una estructura cristalina cubica. Este nuevo material GuaxMA(1-x)PbI3 (0 ≤ x ≤ 0.25) presenta una mayor estabilidad a la humedad y al oxígeno que su antecesor el MAPbI3. Además, conserva sus propiedades ópticas, las cuales fueron verificadas al fabricar células solares de alta eficiencia (hasta un 20%) y sometiéndolas a un test de estrés de mil horas bajo iluminación constante y a una temperatura de 65ºC (equivalente a 1333 días bajo condiciones normales). Este hallazgo abre la puerta a la incorporación de nuevas especies con radios catiónicos que excedan el límite teórico de Goldsmith

Creative Spaces in Suburban Places: Creative Place Making within the Suburban Context

In the 1970s, urban regeneration processes that took place in many industrialised inner-city cores initiated a new economic and cultural vitality that made a departure from an industrial past, on towards a post-industrial future. Today, these postindus- trial cities are home to the 'creative industries', in which through their development, economic and social benefits have become increasingly visible. Hence, urban planners and policy makers worldwide are working to create strategies to ensure certain places become or remain 'creative places.' Richard Florida’s work has become particularly influential within the creative development discourse, as has Charles Landry’s. But as the first wave of creative development planning and policy implementation wanes, important questions are emerging. It is by now clear that most creative development approaches in the attempt to create an 'ideal creative place', have only yet focused on the inner-city core. In this research, the focus is shifted away from the inner-city to where most people of the developed world live: the suburbs. The thesis therefore, asks how a suburb can better provide for its suburban creative class, support creative processes and regenerate into a creative place. This is explored by the formulation of a creative development strategy for Johnsonville; a suburb within Wellington City of New Zealand. The research’s findings suggest that within any suburban creative development agenda, there should be: - An underlying urban development plan that sets out measures in strengthening the suburb’s Diversity, Connectivity and Authenticity; - An explicit attempt in supporting creative enterprises and their functioning, such as proposing ‘Creative Cluster’ formations and associated ‘Incubation’ facilities; - An overall consciousness for the suburban community’s social cohesion and wellbeing. The usefulness of this research and its findings lies within the practise of urban planning, design, and policy implementation, offering a theoretical basis and template for the evaluation and development of suburb’s urban creativity

Ionic polarization-induced current-voltage hysteresis in ch3nh3pbx3 perovskite solar cells

CH3NH3PbX3 (MAPbX3) perovskites have attracted considerable attention as absorber materials for solar light harvesting, reaching solar to power conversion efficiencies above 20%. In spite of the rapid evolution of the efficiencies, the understanding of basic properties of these semiconductors is still ongoing. One phenomenon with so far unclear origin is the so-called hysteresis in the current–voltage characteristics of these solar cells. Here we investigate the origin of this phenomenon with a combined experimental and computational approach. Experimentally the activation energy for the hysteretic process is determined and compared with the computational results. First-principles simulations show that the timescale for MAþ rotation excludes a MA-related ferroelectric effect as possible origin for the observed hysteresis. On the other hand, the computationally determined activation energies for halide ion (vacancy) migration are in excellent agreement with the experimentally determined values, suggesting that the migration of this species causes the observed hysteretic behaviour of these solar cells

Modulating the electron transporting properties of Subphthalocyanines for inverted perovskite solar cells

The lack of organic non-fullerene ETMs with good electron transport and device stability is an important problem for the further development and commercialization of perovskite solar cells. Herein, the use of SubPcs as ETMs in PSCs is explored. To this end, we analyze the influence of SubPc peripheral functionalization on the efficiency and stability of p-i-n PSCs. Specifically, ETMs based on three SubPcs (with either six or twelve peripheral fluorine and chlorine atoms) have been incorporated into PSCs with the perovskite layer deposited by solution processing (CsFAMAPbIBr). The device performance and morphology of these devices are deeply analyzed using several techniques, and the interfacial effects induced by the SubPcs are studied using photoluminescence and TR-PL. It is observed that the device stability is significantly improved upon insertion the SubPc layer. Moreover, the impact of the SubPc layer-thickness is assessed. Thus, a maximum power conversion efficiency of 13.6% was achieved with the champion devic

Non-aggregated Zn(ii)octa(2,6-diphenylphenoxy) phthalocyanine as a hole transporting material for efficient perovskite solar cells

A non-aggregated Zn(ii)octa(2,6-diphenylphenoxy) phthalocyanine (coded as TT80) has been used as a hole-transporting material for perovskite solar cells. The cells were fabricated under three different configurations by changing the uptake solvent (chlorobenzene or toluene) and incorporating additives (bis(trifluoromethane) sulfonimide lithium salt (LiTFSI) and 4-tert-butylpyridine (TBP). A power conversion efficiency of 6.7% (AM1.5G standard conditions) was achieved for the best cell under optimized configurationWe are grateful for the financial support of the MEC, Spain (CTQ2014-52869/BQU), Comunidad de Madrid, Spain (FOTOCARBON, S2013/MIT-2841), and the European Union within the FP7-ENERGY-2012-1, nr. 309194-2, GLOBALSOL project. M. K. N. thanks the European Union for funding within the Seventh Framework Program [FP7/2007–2013] under the grant agreement no. 604032 of the MESO projec