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Bismuth- and antimony-based materials, such as A3M2X9 and AMSX2 (A = cation, M = Bi, Sb, S = sulfur, X = halogen), are promising candidates as the counterpart to lead halide perovskite. However, th...

Two novel homo and hetero three-dimensional nanographenes, NG1 and NG2, featuring a cyclooctatetraene core are designed, synthesized, and characterized. A concise and efficient bottom-up methodolog...

A new compound (1) formed by two antiparallelly disposed tetracyano thienoquinoidal units has been synthesized and studied by electrochemistry, UV/Vis-NIR, IR, EPR, and transient spectroscopy. Self-assembly of 1 on a Au(111) surface has been investigated by scanning tunneling microscopy. Experiments have been rationalized by quantum chemical calculations. 1 exhibits a unique charge distribution in its anionic form, with a gradient of charge yielding a neat molecular in-plane electric dipole momentum, which transforms out-of-plane after surface deposition due to twisted→folded conformational change and to partial charge transfer from Au(111). Intermolecular van der Waals interactions and antiparallel trapezoidal shape fitting lead to the formation of an optimal dense on Au(111) two-dimensional assembly of 1., The authors thank the Spanish Ministry of Science, Innovation and Universities MCIU (projects CTQ2017-83531-R, RED2018-102815-T, MAT2017-85089-C2-1-R), Centro de Excelencia Severo Ochoa grants (SEV-2016-0686, SEV-2015-0496 and FUNFUTURE CEX2019-000917-S) and the CAM (QUIMTRONIC-CM project Y2018/NMT-4783). We thank MINECO/FEDER of the Spanish Government (projects PGC2018-098533-B-100 and PID2019-109555GB-I00), the Eusko Jaurlaritza (Basque Government, project PIBA19-0004) and the Junta de Andalucía, Spain (UMA18FEDERJA057). We also thank the Research Central Services (SCAI) of the University of Málaga and the Donostia International Physics Center (DIPC) Computer Center. We thank Dr. Juwon Oh and Prof. Donhgo Kim from the Spectroscopy Laboratory for Functional π-electronic Systems and Department of Chemistry, Yonsei University in Korea for the generous gift of the TRIR and UV/Vis transient absorption spectroscopy data.

In this work, we assess the possible reasons for the differences observed in open circuit voltage (VOC) in mixed cation perovskite solar cells when comparing four different hole transport materials (HTMs), namely TAE‐1, TAE‐3, TAE‐4 and spiro‐OMeTAD. All these HTMs present close chemical and physical properties. Additionally to the evaluation of the HTM influence on recombination, we find that, upon deposition of the organic HTM on top of the perovskite, there is an important change in the energy levels position, and the impact on the device VOC is discussed. We consider that this experimental observation could be general for other organic HTMs and would justify the difficulties for finding molecules and materials that could improve the efficiency of perovskite solar cells overcoming the solar‐to‐energy conversion efficiency of solar cells made using spiro‐OMeTAD as holes selective contact., EP and AVF thank MINECO (projects CTQ2013-47183 and CTQ2017- 89814-P). NM thanks the European Research Council (ERC-320441- Chirallcarbon), the CAM (Y2018/NMT-4783QUIMTRONIC-CM) and the Spanish Ministry of Economy and Competitiveness MINECO (projects CTQ2014-52045-R, CTQ2015-71154-P, CTQ2016-80042-R, CTQ2017-83531-R and CTQ2016-81911-REDT). NM also thanks the Alexander von Humboldt Foundation and the Unidad de Excelencia Severo Ochoa SEV-2016-0686 is acknowledged. EP and AV are also grateful to ICIQ and ICREA for economical support. EB and CO thank the Generalitat de Catalunya 2017 SGR668 and 2017 SGR669, the MINEICO projects MAT2016-77852-C2-1-R (AEI/FEDER, UE), MAT2015-68994-REDC and the ‘‘Severo Ochoa’’ Program for Centers of Excellence in R&D (SEV-2015-0496). IG thanks Jesús Jiménez López for the fruitful discussions.

Fused oligothiophene-based π-conjugated organic derivatives have been widely used in electronic devices. In particular, two-dimensional (2D) heteroarenes offer the possibility of broadening the scope by extending the π-conjugated framework, which endows enhanced charge transport properties due to the potential intermolecular π–π stacking. Here, the synthesis and characterization of two new small-molecule hole-transporting materials (HTMs) for perovskite solar cells (PSCs) are reported. The newly custom-made compounds are based on dibenzoquinquethiophene (DBQT) and dibenzosexithiophene (DBST) cores, which are covalently linked to triphenylamine moieties to successfully afford the four-armed tetrakistriphenylamine (TTPA) derivatives TTPA–DBQT and TTPA–DBST. The combination of these novel central scaffolds with the electron-donor TTPA units bestow the resulting HTMs with the appropriate energy levels and, therefore, good electronic contact with the perovskite for extracting the hole efficiently. TTPA–DBQT su...

Two novel and simple donor-π-bridge-donor (D-π-D) hole-transporting materials (HTMs) containing two units of the p-methoxytriphenylamine (TPA) electron donor group covalently bridged by means of the 3,4-dimethoxyselenophene spacer through single and triple bonds are reported. The optoelectronic and thermal properties of the new selenium-containing HTMs have been determined using standard experimental techniques and theoretical density functional theory (DFT) calculations. The selenium-based HTMs have been incorporated in mesoporous perovskite solar cells (PSCs) in combination with the triple-cation perovskite [(FAPbI3 )0.87 (MAPbBr3 )0.13 ]0.92 [CsPbI3 ]0.08 . Limited values of power conversion efficiencies, up to 13.4 %, in comparison with the archetype spiro-OMeTAD (17.8 %), were obtained. The reduced efficiencies showed by the new HTMs are attributed to their poor film-forming ability, which constrains their photovoltaic performance due to the appearance of structural defects (pinholes).

Onion-like carbon nanoparticles were synthesized from diamond nanoparticles to be used as the precursor for graphene oxide quantum dots. Onion-like carbon nanoparticles were exfoliated to produce two types of nanoparticles, graphene oxide quantum dots that showed size-dependent fluorescence and highly stable inner cores. Multicolor fluorescent quantum dots were obtained and characterized using different techniques. Polyacrylamide gel electrophoresis showed a range of emission wavelengths spanning from red to blue with the highest intensity shown by green fluorescence. Using high-resolution transmission electron microscopy, we calculated a unit cell size of 2.47 A in a highly oxidized and defected structure of graphene oxide. A diameter of ca. 4 nm and radius of gyration of ca. 11 A were calculated using small-angle X-ray scattering. Finally, the change in fluorescence of the quantum dots was studied when single-stranded DNA that is recognized by telomerase was attached to the quantum dots. Their interaction with the telomerase present in cancer cells was observed and a change was seen after six days, providing an important application of these modified graphene oxide quantum dots for cancer sensing.

Three hole-transporting materials (HTMs) were prepared following a straightforward synthetic route by cross-linking arylamine-based ligands with a simple thieno[3,2-b]thiophene (TbT) core. The novel HTMs were fully characterized with standard techniques to gain insight into their optical and electrochemical properties and were incorporated in solution-processed mesoporous (FAPbI3)0.85(MAPbBr3)0.15 perovskite-based solar cells. The similar molecular structure of the synthesized HTMs was leveraged to investigate the role that the bridging units between the conjugated TbT core and the peripheral arylamine units plays on their properties and thereby on the photovoltaic response. A remarkable power conversion efficiency exceeding 18% was achieved for one of the TbT derivatives, which was slightly higher than the value measured for the benchmark spiro-OMeTAD.

The improvement of the long-term stability of perovskite-based solar cells (PSCs) toward commercialization is closely linked to the development of cutting-edge charge-transporting materials. The progress on the design and the synthesis of new hole-transporting materials (HTMs) is synergistically attaining both top efficiencies and promising stability. Herein, the synthesis and characterization of two doped-HTMs based on electron-rich spiranic cores, namely, 9H-quinolinophenoxazine (spiro-POZ) and 9H-quinolinophenothiazine (spiro-PTZ), are presented. The novel HTMs exhibit excellent solubility, optimal highest occupied molecular orbital energy, and excellent thermal stability with glass transition temperatures higher than those for spiro-OMeTAD. [(FAPbI3)0.87(MAPbBr3)0.13]0.92[CsPbI3]0.08-based solar cells using the new spiro-type HTMs deliver power conversion efficiencies (PCEs) around 17% for mesoporous cells, and higher than 18% in planar configurations, matching the PCE of spiro-OMeTAD. Remarkably, doped spiro-POZ and spiro-PTZ exhibit excellent long-term stability in planar devices, retaining over 84% of their initial efficiency after more than 300 days of exposure to ambient conditions. Furthermore, after 1200 h under continuous 1 sun illumination, the PCE of the PSCs based on spiro-POZ and spiro-PTZ decreases by only 6%.

Three hole-transporting materials (HTMs) were prepared following a straightforward synthetic route by cross-linking arylamine-based ligands with a simple thieno[3,2

A flexible, saddle-like, π-conjugated skeleton composed of four fused thiophene rings forming a cyclooctatetrathiophene (CoTh) with four triphenylamines (CoTh-TTPA) is presented as a hole-transporting material (HTM) for perovskite solar cells. The new HTM shows a bright red color stemming from a direct conjugation between the TPA groups and the central CoTh scaffold. This results in a charge transfer band due to the combination of the weak acceptor moiety, the CoTh unit, and the electron-donating p-methoxytriphenylamine groups. CoTh-TTPA exhibits a suitable highest-occupied molecular orbital (HOMO) level in relation to the valence band edge of the perovskite, which ensures efficient hole extraction at the perovskite/HTM interface. It has been applied as the HTM in combination with a mixed perovskite ([FAPbI3]0.85[MAPbBr3]0.15) and a state-of-the-art triple cation perovskite ([(FAPbI3)0.87(MAPbBr3)0.13]0.92[CsPbI3]0.08) reaching noticeable light-to-energy conversion efficiencies of 16.3 and 15.9%, respectively. These values are slightly lower than those measured for the benchmark spiro-OMeTAD HTM. The HTM properties have been analyzed by means of photoluminescence and conductivity experiments, which demonstrated a better hole extraction and conductivity for spiro-OMeTAD.

Hybrid covalent/supramolecular porphyrin–fullerene structures were synthesized as highly efficient molecular wires with a remarkably low attenuation factor (β=0.07±0.01 A−1). Hydrogen-bonding interactions and p-phenylene oligomers of different lengths are responsible for efficient electron transfer in the molecular wires.

Photovoltaic solar cells based on perovskites have come to the forefront in science by achieving exceptional power conversion efficiencies (PCEs) in less than a decade of research. This “still young” generation of solar cells is currently rivalling, in PCEs, well-established technologies, such as cadmium telluride (CdTe) and silicon. Further improvements in device stability by means of innovative materials are yet to come, with technology becoming closer to meeting the market requirements. Emerging from this groundbreaking discovery, a great number of charge transporting materials have flourished, which is particularly true for hole transporting materials (HTMs). The huge number of molecules prepared stem from design and engineering of a wide variety of new and also chemically modified old molecules where organic synthesis has played a fundamental role. In this review, the contribution of chemistry through those synthetic protocols used for producing new and innovative HTMs from relatively simple organic molecules is presented in a rational and systematic manner. The variety and impact of synthetic strategies followed, the structure–property relationship and stability, conductivity and device performance are highlighted from a chemical viewpoint.