Influence of Alkoxy Chain Length on the Properties of Two‐Dimensionally Expanded Azulene‐Core‐Based Hole‐Transporting Materials for Efficient Perovskite Solar Cells

Truong, Minh Anh; Lee, Jae-Hyun; Nakamura, Tomoya; Seo, Ji‐Youn; Jung, Mina; Ozaki, Masaharu; Shimazaki, Ai; Shioya, Nobutaka; Hasegawa, Takeshi; Murata, Yasujiro; Zakeeruddin, Shaik M.; Grätzel, Michaël; Murdey, Richard; Wakamiya, Atsushi

doi:10.1002/chem.201806317

Cited by 24 publications

(23 citation statements)

References 50 publications

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“… 30 , 31 However, the peripheral part is equally or of even more importance in fine tuning the properties of the HTM. 32 , 33 Generally, such spiro-centered HTMs are designed by linking prebrominated spiro core species with diphenylamine or borylated triphenylamine, both having electron-rich methoxy groups using C–N or C–C cross-coupling reactions, respectively. These reactions demand severe procedures that result in several disadvantages including inert reaction conditions, costly transition-metal catalysts, and time-consuming purification procedures due to the inherent formation of side products.…”

Section: Introductionmentioning

confidence: 99%

Cut from the Same Cloth: Enamine-Derived Spirobifluorenes as Hole Transporters for Perovskite Solar Cells

et al. 2021

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To attain commercial viability, perovskite solar cells (PSCs) have to be reasonably priced, highly efficient, and stable for a long period of time. Although a new record of a certified power conversion efficiency (PCE) value over 25% was achieved, PSC performance is limited by the lack of hole-transporting materials (HTMs), which extract positive charges from the light-absorbing perovskite layer and carry them to the electrode. Here, we report spirobifluorene-based HTMs with finely tuned energy levels, high glass-transition temperature, and excellent charge mobility and conductivity enabled by molecularly engineered enamine arms. HTMs are synthesized using simple condensation chemistry, which does not require costly catalysts, inert reaction conditions, and time-consuming product purification procedures. Enamine-derived HTMs allow the fabrication of PSCs reaching a maximum PCE of 19.2% and stability comparable to spiro-OMeTAD. This work demonstrates that simple enamine condensation reactions could be used as a universal path to obtain HTMs for highly efficient and stable PSCs.

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Section: Introductionmentioning

confidence: 99%

Cut from the Same Cloth: Enamine-Derived Spirobifluorenes as Hole Transporters for Perovskite Solar Cells

et al. 2021

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“…Our group reported the highly oriented structure of Nafion thin films on SiO x [34], MgO [35,36], sputtered Pt [37], and sputtered Au [36] surfaces by infrared p-polarized multiple-angle incidence resolution spectrometry (pMAIRS), which was developed by Hasegawa and co-workers [38][39][40], as presented in Figure 2(a-d). IR pMAIRS offers the molecular orientation for each functional group to various functional materials such as derivatives of polythiophene [41,42], porphyrin [43], pentacene [44], fullerene [45], naphthalene diimide [46], phthalimide [47], azulene [48], metal-oxide nanowire [49], polymer brushes [50], and polyimide [51]. Because this spectroscopic method is an infrared spectroscopic method, it is useful because it is applicable to non-crystalline materials.…”

Section: Introductionmentioning

confidence: 99%

Progress on highly proton-conductive polymer thin films with organized structure and molecularly oriented structure

Nagao

2020

Science and Technology of Advanced Materials

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Several current topics are introduced in this review, with particular attention to highly protonconductive polymer thin films with organized structure and molecularly oriented structure. Organized structure and molecularly oriented structure are anticipated as more promising approaches than conventional less-molecular-ordered structure to elucidate mechanisms of high proton conduction and control proton conduction. This review introduces related polymer materials and molecular design using lyotropic liquid crystals and hydrogen bond networks for high proton conduction. It also outlines the use of substrate surfaces and external fields, such as pressure and centrifugal force, for organizing structures and molecularly oriented structures.

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“…Truong et al. [ 36 ] also synthesized a series of 2D expanded azulene‐core‐based π‐systems ( 17 – 20 ) with different alkyl chain lengths in the alkoxy moieties connected to the partially oxygen‐bridged triarylamine skeletons. Among them, the PSCs with HTM containing n ‐butyl side chains showed the best performance, with a power conversion efficiency of 18.9%.…”

Section: Azulene‐based Moleculesmentioning

confidence: 99%

Azulene‐Based Molecules, Polymers, and Frameworks for Optoelectronic and Energy Applications

Huang

Zhao

et al. 2020

Small Methods

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has a large dipole moment of 1.08 D. [2] By contrast, naphthalene, which only contains two fused six-membered rings, has a dipole moment of 0 D. Azulene, which was discovered and named by Piesse in 1863, has attracted considerable interest since its discovery in petroleum exploitation. [3] In 1937, Plattner and Pfau published their pioneering report on the synthesis of azulene. [4] However, their method was not practical due to its low azulene yield. In the 1950s, Ziegler and Hafner formulated a highly efficient and practical method for synthesizing azulene and its derivatives. [5] Because azulene is difficult to synthesize and has a low natural abundance, research on azulene-based molecules and materials is less advanced relative to research on its isomer. Direct functionalization of 1-and/ or 3-positions is a common and effective method of producing azulene derivatives. However, direct functionalization of other positions is much harder, e.g., bromination of 6-and 1,3-positions, [6] nucleophilic addition to obtain 6-subsituted azulene, [7] borylation at 2-position, [8] arylation at the 2-position, [9] and so on. The electron distribution in the front-line molecular orbitals (MOs) must usually be considered when functionalizing azulene. Because of resonance delocalization, the oddnumbered position of azulene, which is electron-rich, easily reacts with electrophilic compounds. Among the odd-numbered azulene varieties, 1-and 3-azulene have the highest activity. [10] By Azulene has a considerably larger dipole moment than its isomer naphthalene; it also has unique physicochemical properties, including different reactivities on five-and seven-membered rings, a dark color, a narrow gap between the highest occupied molecular orbital and lowest unoccupied molecular orbital, and stimulus response. Although azulene was discovered more than 100 years ago, the use of azulene-based derivatives can be traced back to five centuries ago. Due to its unusual structure, azulene-based molecules and materials are widely used in various fields. However, studies on azulene-based materials have long been hindered by difficulties in the synthesis. Considerably fewer studies have been conducted on azulene-based derivatives than on naphthalene-based derivatives. This perspective paper mainly introduces recent reports on the synthesis of azulene-based aromatic molecules, conjugated polymers, and coordination polymers, in addition to azulene-based frameworks. The structure-property relationship, optoelectronic applications, and energy-related applications of azulene-based derivatives are reviewed, including their use in near-infrared absorption, organic field-effect transistors, organic solar cells, and microsupercapacitors.

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Influence of Alkoxy Chain Length on the Properties of Two‐Dimensionally Expanded Azulene‐Core‐Based Hole‐Transporting Materials for Efficient Perovskite Solar Cells

Cited by 24 publications

References 50 publications

Cut from the Same Cloth: Enamine-Derived Spirobifluorenes as Hole Transporters for Perovskite Solar Cells

Cut from the Same Cloth: Enamine-Derived Spirobifluorenes as Hole Transporters for Perovskite Solar Cells

Progress on highly proton-conductive polymer thin films with organized structure and molecularly oriented structure

Azulene‐Based Molecules, Polymers, and Frameworks for Optoelectronic and Energy Applications

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