掲載種別：研究論文（学術雑誌）   出版者・発行元：Proceedings of the National Academy of Sciences  

Thin-film devices that transduce the chemical activity of ions into electronic signals are essential components in various applications, including healthcare diagnostics and environmental monitoring. Combinations of organic semiconductors (OSCs) and ion-selective materials have been explored for developing solution-processable ion sensors. However, the necessity of reference electrodes (REs) and operational stability in ion-permeable OSCs have posed questions regarding whether reliable measurements with thin-film components are attainable with OSCs. Herein, we report electric double-layer transistors (EDLTs) with OSCs in single-crystal forms for ion sensing. Our EDLTs demonstrated high operational stability, with a one-to-one relationship between the source electrode potential and device resistance, and served as quasi-REs (qRE). When our EDLT is served as qRE, its drift was as small as 0.5 mV/h and comparable to that of commonly employed REs. In our system, the semiconductor–electrolyte interface is self-passivated by the alkyl chains of OSCs in single-crystal structures, with the two-dimensional transport layer appearing unaltered upon gating. EDLT arrays with ion-selective and nonselective liquid junctions enable ion concentration sensing without a conventional RE. These findings provide opportunities to develop thin-film devices based on OSCs for easy integration and reliable measurements.

DOI： 10.1073/pnas.2405933121

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Springer Science and Business Media LLC  

Abstract

Control of electrical doping is indispensable in any semiconductor device, and both efficient hole and electron doping are required for many devices. In organic semiconductors, however, electron doping has been essentially more problematic compared to hole doping because in general organic semiconductors have low electron affinities and require dopants with low ionization potentials that are often air-sensitive. Here, we adapt an efficient molecular doping method, so-called ion-exchange doping, to dope electrons in a polymeric semiconductor. We initially reduce the polymeric semiconductor using one electron transfer from molecular dopants, and then the ionized dopants in the resulting air-unstable films are replaced with secondary ions via cation exchange. Improved ambient stability and crystallinity of the doped polymeric semiconductors are achieved when a specific bulky molecular cation was chosen as the secondary ion, compared to conventional methods. The presented strategy can overcome the trade-off relationship between reducing capability and ambient stability in molecular dopants, and a wider selection of dopant ions will help to realize ambient-stable electron conductors.

DOI： 10.1038/s43246-024-00507-2

researchmap

その他リンク： https://www.nature.com/articles/s43246-024-00507-2

掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/admt.202301673

Scopus

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry (RSC)  

[8]Thienophenacene analogues offer excellent single-crystal platforms for hole transport owing to their characteristic molecular orbitals and sufficiently small effective masses.

DOI： 10.1039/d4cc02767a

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/acs.macromol.3c00211

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

Abstract

Large‐area single‐crystalline thin films of n‐type organic semiconductors (OSCs) fabricated via solution‐processed techniques are urgently demanded for high‐end electronics. However, the lack of molecular designs that concomitantly offer excellent charge‐carrier transport, solution‐processability, and chemical/thermal robustness for n‐type OSCs limits the understanding of fundamental charge‐transport properties and impedes the realization of large‐area electronics. The benzo[de]isoquinolino[1,8‐gh]quinolinetetracarboxylic diimide (BQQDI) π‐electron system with phenethyl substituents (PhC₂–BQQDI) demonstrates high electron mobility and robustness but its strong aggregation results in unsatisfactory solubility and solution‐processability. In this work, an asymmetric molecular design approach is reported that harnesses the favorable charge transport of PhC₂–BQQDI, while introducing alkyl chains to improve the solubility and solution‐processability. An effective synthetic strategy is developed to obtain the target asymmetric BQQDI (PhC₂–BQQDI–C_n). Interestingly, linear alkyl chains of PhC₂–BQQDI–C_n (n = 5–7) exhibit an unusual molecular mimicry geometry with a gauche conformation and resilience to dynamic disorders. Asymmetric PhC₂–BQQDI–C₅ demonstrates excellent electron mobility and centimeter‐scale continuous single‐crystalline thin films, which are two orders of magnitude larger than that of PhC₂–BQQDI, allowing for the investigation of electron transport anisotropy and applicable electronics.

DOI： 10.1002/advs.202207440

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Thermoelectric energy harvesters based on p- and n-type organic semiconductors are in high demand, while the air stability of n-type devices has long been a challenge. Here, we demonstrate that supramolecular salt-functionalized n-doped ladder-type conducting polymers exhibit excellent stability in the presence of dry air.

DOI： 10.1039/d3cc00840a

PubMed

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Oxford University Press ({OUP})  

<jats:title>Abstract</jats:title>
<jats:p>Organic radicals are widely used as linkers or ligands to synthesize molecular magnetic materials. However, studies regarding the molecular anisotropies of radical-based magnetic materials and their multifunctionalities are rare. Herein, a photoisomerizable diarylethene ligand was used to form {[CoIII(3,5-DTSQ·–)(3,5-DTCat2–)]2(6F-DAE-py2)}·3CH3CN·H2O (o-1·3CH3CN·H2O, 6F-DAE-py2 = 1,2-bis(2-methyl-5-(4-pyridyl)-3-thienyl)perfluorocyclopentene), a valence tautomeric (VT) coordination polymer. We directly observed dual radicals for a single crystal using high-field/-frequency (∼13.3 T and ∼360 GHz) electron paramagnetic resonance (EPR) spectroscopy along the c axis, which was further confirmed by angle-dependent Q-band EPR spectroscopy. Moreover, a conductive anomaly close to the VT transition temperature was observed only when probes were attached at the ab plane of the single crystal, indicative of synergy between valence tautomerism and conductivity. Structural anisotropy studies and density functional theory (DFT) calculations revealed that this synergy is due to electron transfer associated with valence tautomerism. This study presents the first example of dual-radical-based molecular anisotropy and charge-transfer-induced conductive anisotropy in a photoswitchable coordination polymer.</jats:p>

DOI： 10.1093/nsr/nwad047

researchmap

その他リンク： https://academic.oup.com/nsr/article-pdf/10/6/nwad047/50910384/nwad047.pdf

掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s43246-023-00331-0

researchmap

掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.202206417

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry (RSC)  

A solid/ionic gel dual-gate transistor is demonstrated using a bilayer single-crystal organic semiconductor. Hole mobilities in the bottom layer are accelerated by simultaneous charge-carrier modulation by electrolyte-gating to the top layer.

DOI： 10.1039/d3cp00782k

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry (RSC)  

Polarized FT-IR spectra of the Pt–I semiconductive nanowire, [Pt(en)2I](Asp-C_n)₂·H₂O, revealed that the first Pt^III–Pt^III AV state for n ≥ 13.

DOI： 10.1039/d3cc04285e

researchmap

掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/aelm.202200452

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/jacs.2c01357

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

DOI： 10.1246/bcsj.20220051

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

DOI： 10.1246/cl.210804

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41467-022-28875-8

Web of Science

researchmap

掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.accounts.1c00548

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

<jats:p>Thermally induced electron–hole dissociation was suggested by current–voltage characteristics and dielectric properties in bromo-bridged one-dimensional Mott-insulators, [Pd(en)<jats:sub>2</jats:sub>Br](Suc-C<jats:sub><jats:italic>n</jats:italic></jats:sub>)<jats:sub>2</jats:sub>·H<jats:sub>2</jats:sub>O (<jats:italic>n</jats:italic> = 5 and 6).</jats:p>

DOI： 10.1039/d2cp00051b

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Springer Science and Business Media {LLC}  

<jats:title>Abstract</jats:title><jats:p>The interface of organic semiconductor films is of particular importance with respect to various electrochemical devices such as transistors and solar cells. In this study, we developed a new spectroscopic system, namely electrochemical attenuated total reflectance ultraviolet (EC-ATR-UV) spectroscopy, which can access the interfacial area. Ionic liquid-gated organic field-effect transistors (IL-gated OFETs) were successfully fabricated on the ATR prism. Spectral changes of the organic semiconductor were then investigated in relation to the gate voltage application and IL species, and the magnitude of spectral changes was found to correlate positively with the drain current. Additionally, the Stark shifts of not only the organic semiconductor, but also of the IL on the organic semiconductor films were detected. This new method can be applied to other electrochemical devices such as organic thin film solar cells, in which the interfacial region is crucial to their functioning.</jats:p>

DOI： 10.1038/s42004-021-00525-y

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Springer Science and Business Media {LLC}  

<jats:title>Abstract</jats:title><jats:p>Self-organization in <jats:italic>π</jats:italic>-conjugated polymers gives rise to a highly ordered lamellar structure, in which inter-chain stacking spontaneously forms two-dimensional conjugated sheets. This multi-layer stacked nature of semicrystalline polymers allows the inclusion of various functional molecules. In particular, redox-triggered ion-intercalation is an ideal system for molecular doping, for which extremely high charge carrier density has been achieved. Here, we conducted a detailed structural analysis and electron density simulation to pinpoint exactly where the guest dopants are located periodically in the void space in a polymer’s lamellae. Our findings are indicative of an intercalation compound of layered polymers and a guest intercalant. We show that a homogeneous cocrystal structure can be realized throughout the host polymer medium, which is proved by the observation of coherent carrier transport. The intercalation cocrystal nature gives the best achievable doping level in semicrystalline polymers and excellent environmental stability. These findings should open up possibilities for tuning the collective dynamics of functional molecules through intercalation phenomena.</jats:p>

DOI： 10.1038/s43246-021-00148-9

researchmap

掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/advs.202101998

researchmap

掲載種別：研究論文（学術雑誌）  

DOI： 10.1063/5.0058666

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Springer Science and Business Media {LLC}  

<jats:title>Abstract</jats:title><jats:p>Benzo[<jats:italic>de</jats:italic>]isoquinolino[1,8-<jats:italic>gh</jats:italic>]quinolinetetracarboxylic diimide (BQQDI) is an n-type organic semiconductor that has shown unique multi-fold intermolecular hydrogen-bonding interactions, leading to aggregated structures with excellent charge transports and electron mobility properties. However, the strong intermolecular anchoring of BQQDI presents challenges for fine-tuning the molecular assembly and improving the semiconducting properties. Herein, we report the design and synthesis of two BQQDI derivatives with phenyl- and cyclohexyl substituents (Ph–BQQDI and Cy<jats:sub>6</jats:sub>–BQQDI), where the two organic semiconductors show distinct molecular assemblies and degrees of intermolecular orbital overlaps. In addition, the difference in their packing motifs leads to strikingly different band structures that give rise to contrasting charge-transport capabilities. More specifically, Cy<jats:sub>6</jats:sub>–BQQDI bearing bulky substituents exhibits isotropic intermolecular orbital overlaps resulting in equal averaged transfer integrals in both π-π stacking directions, even when dynamic disorders are taken into account; whereas Ph–BQQDI exhibits anisotropic averaged transfer integrals in these directions. As a result, Cy<jats:sub>6</jats:sub>–BQQDI shows excellent device performances in both single-crystalline and polycrystalline thin-film organic field-effect transistors up to 2.3 and 1.0 cm<jats:sup>2</jats:sup> V<jats:sup>−1</jats:sup> s<jats:sup>−1</jats:sup>, respectively.</jats:p>

DOI： 10.1038/s42004-021-00583-2

PubMed

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/admi.202100033

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.jpclett.0c03012

researchmap

掲載種別：研究論文（学術雑誌）  

DOI： 10.1063/5.0038128

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/advs.202002065

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

<p>Air stability of n-doped polymers is improved by using a strongly reducing, dimeric dopant instead of cobaltocene.</p>

DOI： 10.1039/d0tc05931e

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/adma.202003245

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Springer Science and Business Media {LLC}  

<jats:title>Abstract</jats:title><jats:p>Solution-processed organic thin film transistors (OTFTs) are an essential building block for next-generation printed electronic devices. Organic semiconductors (OSCs) that can spontaneously form a molecular assembly play a vital role in the fabrication of OTFTs. OTFT fabrication processes consist of sequential deposition of functional layers, which inherently brings significant difficulties in realizing ideal properties because underlayers are likely to be damaged by application of subsequent layers. These difficulties are particularly prominent when forming metal contact electrodes directly on an OSC surface, due to thermal damage during vacuum evaporation and the effect of solvents during subsequent photolithography. In this work, we demonstrate a simple and facile technique to transfer contact electrodes to ultrathin OSC films and form an ideal metal/OSC interface. Photolithographically defined metal electrodes are transferred and laminated using a polymeric bilayer thin film. One layer is a thick sacrificial polymer film that makes the overall film easier to handle and is water-soluble for dissolution later. The other is a thin buffer film that helps the template adhere to a substrate electrostatically. The present technique does not induce any fatal damage in the substrate OSC layers, which leads to successful fabrication of OTFTs composed of monolayer OSC films with a mobility of higher than 10 cm<jats:sup>2</jats:sup> V<jats:sup>−1</jats:sup> s<jats:sup>−1</jats:sup>, a subthreshold swing of less than 100 mV decade<jats:sup>−1</jats:sup>, and a low contact resistance of 175 Ω⋅cm. The reproducibility of efficient contact fabrication was confirmed by the operation of a 10 × 10 array of monolayer OTFTs. The technique developed here constitutes a key step forward not only for practical OTFT fabrication but also potentially for all existing vertically stacked organic devices, such as light-emitting diodes and solar cells.</jats:p>

DOI： 10.1038/s41598-020-61536-8

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.chemmater.0c01888

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/jacs.0c05522

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/adfm.202003977

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/adfm.202000489

researchmap

掲載種別：研究論文（学術雑誌）  

DOI： 10.1063/5.0006651

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Association for the Advancement of Science ({AAAS})  

DOI： 10.1126/sciadv.aaz0632

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.201905439

researchmap

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.201905439

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.201903934

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Proceedings of the National Academy of Sciences  

<jats:p>Thin film transistors (TFTs) are indispensable building blocks in any electronic device and play vital roles in switching, processing, and transmitting electronic information. TFT fabrication processes inherently require the sequential deposition of metal, semiconductor, and dielectric layers and so on, which makes it difficult to achieve reliable production of highly integrated devices. The integration issues are more apparent in organic TFTs (OTFTs), particularly for solution-processed organic semiconductors due to limits on which underlayers are compatible with the printing technologies. We demonstrate a ground-breaking methodology to integrate an active, semiconducting layer of OTFTs. In this method, a solution-processed, semiconducting membrane composed of few-molecular-layer–thick single-crystal organic semiconductors is exfoliated by water as a self-standing ultrathin membrane on the water surface and then transferred directly to any given underlayer. The ultrathin, semiconducting membrane preserves its original single crystallinity, resulting in excellent electronic properties with a high mobility up to 12<jats:inline-formula><m:math xmlns:m="http://www.w3.org/1998/Math/MathML" overflow="scroll"><m:msup><m:mrow><m:mi mathvariant="normal">c</m:mi><m:mi mathvariant="normal">m</m:mi></m:mrow><m:mrow><m:mn>2</m:mn></m:mrow></m:msup><m:mo>⋅</m:mo><m:msup><m:mrow><m:mi mathvariant="normal">V</m:mi></m:mrow><m:mrow><m:mo>−</m:mo><m:mn>1</m:mn></m:mrow></m:msup><m:mo>⋅</m:mo><m:msup><m:mrow><m:mi mathvariant="normal">s</m:mi></m:mrow><m:mrow><m:mo>−</m:mo><m:mn>1</m:mn></m:mrow></m:msup></m:math></jats:inline-formula>. The ability to achieve transfer of wafer-scale single crystals with almost no deterioration of electrical properties means the present method is scalable. The demonstrations in this study show that the present transfer method can revolutionize printed electronics and constitute a key step forward in TFT fabrication processes.</jats:p>

DOI： 10.1073/pnas.1909932116

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：{IOP} Publishing  

DOI： 10.1088/2058-8585/ab603b

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

<p>Sulphur-containing V-shaped π-electron systems with substituents based on a phenyl key block exhibit band-like hole transport and high thermal durability.</p>

DOI： 10.1039/d0tc03318a

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41598-019-50294-x

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.190276

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41586-019-1504-9

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201901288

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.orglett.9b01239

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

<p>XAFS measurements were performed on three representative bromo-bridged palladium chain compounds to detect their oxidation states.</p>

DOI： 10.1039/c9dt01684h

researchmap

掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.orgel.2018.06.029

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.inorgchem.7b03051

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/acs.inorgchem.7b02566

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.orgel.2017.05.050

researchmap

記述言語：日本語   出版者・発行元：公益社団法人 応用物理学会  

DOI： 10.11470/jsapmeeting.2017.2.0_2527

CiNii Research

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsami.7b02867

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1063/1.4981774

researchmap

掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

DOI： 10.1039/C7TC03905K

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.chemmater.5b04143

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

<p>We report how mechanical and dynamical properties in formate-based perovskites can be manipulated by the preparation of an A-site solid-solution.</p>

DOI： 10.1039/c6sc01247g

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

<p>This paper reviews the recent progress in charge-bistable Pd(<sc>iii</sc>)/Pd(<sc>ii</sc>,<sc>iv</sc>) coordination polymers (MX chains). The temperature-, pressure- and photo-induced phase transitions have been demonstrated, proposing MX chains as a material for optical switching devices.</p>

DOI： 10.1039/c5dt00439j

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

<p>Polymorphism in formate-based dense metal–organic frameworks with the general formula ABX₃ is predicted by quantum chemical calculations and confirmed experimentally.</p>

DOI： 10.1039/c5cc06190c

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ic502071u

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1103/physrevlett.113.096403

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

<p>We synthesized and characterized bromide-bridged Pd(<sc>iii</sc>) chain complexes, [Pd(en)₂Br](MalC_n–Y)₂·H₂O (en = ethylenediamine; MalC_n–Y = dialkyl sulfomalonate; <italic>n</italic>: the number of carbon atoms) (<italic>n</italic> = 7 and 12), which were in averaged valence states at room temperature.</p>

DOI： 10.1039/c4cc02547d

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c3dt32890b

researchmap

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1143/jpsj.81.074705

researchmap