Nanoscale doping of polymeric semiconductors with confined electrochemical ion implantation.

Nanoresolved doping of polymeric semiconductors can overcome scaling limitations to create highly integrated flexible electronics, but remains a fundamental challenge due to isotropic diffusion of the dopants. Here we report a general methodology for achieving nanoscale ion-implantation-like electrochemical doping of polymeric semiconductors. This approach involves confining counterion electromigration within a glassy electrolyte composed of room-temperature ionic liquids and high-glass-transition-temperature insulating polymers. By precisely adjusting the electrolyte glass transition temperature (Tg) and the operating temperature (T), we create a highly localized electric field distribution and achieve anisotropic ion migration that is nearly vertical to the nanotip electrodes. The confined doping produces an excellent resolution of 56 nm with a lateral-extended doping length down to as little as 9.3 nm. We reveal a universal exponential dependence of the doping resolution on the temperature difference (Tg - T) that can be used to depict the doping resolution for almost infinite polymeric semiconductors. Moreover, we demonstrate its implications in a range of polymer electronic devices, including a 200% performance-enhanced organic transistor and a lateral p-n diode with seamless junction widths of <100 nm. Combined with a further demonstration in the scalability of the nanoscale doping, this concept may open up new opportunities for polymer-based nanoelectronics.

Formation of covalent metal-carbon contacts assisted by Ag+ for single molecule junctions.

Covalent metal-carbon (M-C) contacts have long been pursued for constructing robust and high-performance molecular devices. Existing methods for creating such contacts usually rely on direct chemical reactions between metal electrodes and designed molecular ligands. An inherent limitation of this approach is that the commonly used metal electrodes (e.g., Au) are chemically inert, making it generally difficult to form covalent M-C bonds with molecules. Intriguingly, employing the scanning tunneling microscope-break junction technique, we find that simply adding Ag+ ions to molecular solution enables direct covalent bonding of terminal alkynes to Au electrodes. The bonding process is driven by Ag+ ion coupled in situ reactions and efficiently creates covalent Au/Ag-C interfaces in single molecule junctions. This metal ion assisted method avoids the need for complex synthesis of molecular ligands and works robustly for a wide range of alkyne-terminated molecules, offering a facile and versatile approach for precisely tuning the metal-molecule interface.

Boosting the Thermoelectric Performance of the Doped DPP-EDOT Conjugated Polymer by Incorporating an Ionic Additive.

The thermoelectric (TE) performance of organic materials is limited by the coupling of Seebeck coefficient and electrical conductivity. Herein a new strategy is reported to boost the Seebeck coefficient of conjugated polymer without significantly reducing the electrical conductivity by incorporation of an ionic additive DPPNMe3 Br. The doped polymer PDPP-EDOT thin film exhibits high electrical conductivity up to 1377 ± 109 S cm-1 but low Seebeck coefficient below 30 µV K-1 and a maximum power factor of 59 ± 10 µW m-1 K-2 . Interestingly, incorporation of small amount (at a molar ratio of 1:30) of DPPNMe3 Br into PDPP-EDOT results in the significant enhancement of Seebeck coefficient along with the slight decrease of electrical conductivity after doping. Consequently, the power factor (PF) is boosted to 571 ± 38 µW m-1 K-2 and ZT reaches 0.28 ± 0.02 at 130 °C, which is among the highest for the reported organic TE materials. Based on the theoretical calculation, it is assumed that the enhancement of TE performance for the doped PDPP-EDOT by DPPNMe3 Br is mainly attributed to the increase of energetic disorder for PDPP-EDOT.

Iminyl-Radical-Mediated Formation of Covalent Au-N Bonds for Molecular Junctions.

The interaction between organic radicals and transition metals plays a crucial role in radical-mediated chemical reactions, functional devices, and biocatalysis. Characterizing such interactions, however, remains a long-standing challenge due to the inherently high reactivity of radical species. Here, using a scanning tunneling microscope breaking junction (STM-BJ) technique, we are able to detect the interaction mode between iminyl radicals and the gold surface at a single molecule level. We show that the free iminyl radicals generated through photochemical N-O bond homolysis of oxime esters react toward the gold electrode surface and produce covalent Au-N bonds. Intriguingly, we find that the Au-N bonding reactions lead to the formation of robust and highly conductive single-molecule junctions. These findings provide not only insights into the mechanism of iminyl-radical-involved reactions but also a facile photolysis method to create a new type of covalent electrode-molecule bonding contact for molecular devices.

Cleavage of non-polar C(sp2)‒C(sp2) bonds in cycloparaphenylenes via electric field-catalyzed electrophilic aromatic substitution.

Electrophilic aromatic substitution (EAS) is one of the most fundamental reactions in organic chemistry. Using an oriented external electric field (OEEF) instead of traditional reagents to tune the EAS reactivity can offer an environmentally friendly method to synthesize aromatic compounds and hold the promise of broadening its scope. Despite these advantages, OEEF catalysis of EAS is difficult to realize, due to the challenge of microscopically orienting OEEF along the direction of electron reorganizations. In this work, we demonstrate OEEF-catalyzed EAS reactions in a series of cycloparaphenylenes (CPPs) using the scanning tunneling microscope break junction (STM-BJ) technique. Crucially, the unique radial π-conjugation of CPPs enables a desired alignment for the OEEF to catalyze the EAS with Au STM tip (or substrate) acting as an electrophile. Under mild conditions, the OEEF-catalyzed EAS reactions can cleave the inherently inert C(sp2)-C(sp2) bond, leading to high-yield (~97%) formation of linear oligophenylenes terminated with covalent Au-C bonds. These results not only demonstrate the feasibility of OEEF catalysis of EAS, but also offer a way of exploring new mechanistic principles of classic organic reactions aided by OEEF.

Triggering ZT to 0.40 by Engineering Orientation in One Polymeric Semiconductor.

Breaking the thermoelectric (TE) trade-off relationship is an important task for maximizing the TE performance of polymeric semiconductors. Existing efforts have focused on designing high-mobility semiconductors and achieving ordered molecular doping, ignoring the critical role of the molecular orientation during TE conversion. Herein, the achievement of ZT to 0.40 is reported by fine-tuning the molecular orientation of one diketopyrrolopyrrole (DPP)-based polymer (DPP-BTz). Films with bimodal molecular orientation yield superior doping efficiency by increasing the lamellar spacing and achieve increased splitting between the Fermi energy and the transport energy to enhance the thermopower. These factors contribute to the simultaneous improvement in the Seebeck coefficient and electrical conductivity in an unexpected manner. Importantly, the bimodal film exhibits a maximum power factor of up to 346 µW m-1 K-2 , >400% higher than that of unimodal films. These results demonstrate the great potential of molecular orientation engineering in polymeric semiconductors for developing state-of-the-art organic TE (OTE) materials.

Highly efficient charge transport across carbon nanobelts.

Carbon nanobelts (CNBs) are a new form of nanocarbon that has promising applications in optoelectronics due to their unique belt-shaped π-conjugated systems. Recent synthetic breakthrough has led to the access to various CNBs, but their optoelectronic properties have not been explored yet. In this work, we study the electronic transport performance of a series of CNBs by incorporating them into molecular devices using the scanning tunneling microscope break junction technique. We show that, by tuning the bridging groups between the adjacent benzenes in the CNBs, we can achieve remarkably high conductance close to 0.1 G0, nearly one order of magnitude higher than their nanoring counterpart cycloparaphenylene. Density functional theory-based calculations further elucidate the crucial role of the structural distortion played in facilitating the unique radial π-electron delocalization and charge transport across the belt-shaped carbon skeletons. These results develop a basic understanding of electronic transport properties of CNBs and lay the foundation for further exploration of CNB-based optoelectronic applications.

A high mobility air-stable n-type organic small molecule semiconductor with high UV-visible-to-NIR photoresponse.

An organic semiconductor with high carrier mobility and efficient light absorption over a wide spectral range is of the most important yet challenging material for constructing a broadband responsive organic photodetector. However, the development of such organic semiconductors, especially for air-stable n-type organic small molecule semiconductors, is still at an early stage. Here we report the fabrication of high-performance n-type semiconducting crystalline nanosheets and the development of air-stable field-effect transistors, phototransistors, with high response over a broad spectrum. The n-type small molecule semiconductor is assembled into a crystalline nanosheet based on the solvent-phase interfacial self-assembly method. N-type field-effect transistors with high electron mobility are fabricated and their electrical performances exhibit excellent air stability. Impressively, the demonstrated phototransistors exhibit an ultrahigh responsivity over a wide spectral range from 365 to 940 nm, with a maximum photoresponsivity of 9.2 × 105 A W-1 and specific detectivity of 5.26 × 1013 Jones, which is the best performance among the reported n-type organic small molecule-based phototransistors.

The Increasing Number of Electron Reservoirs in Nonporous, High-Conducting Coordination Polymers Cux BHT (x = 3, 4, and 5, BHT = Benzenehexathiol) for Improved Faradaic Capacitance.

Although asymmetric supercapacitors (ASCs) can achieve high energy density, the lifespan and power density are severely suppressed due to the low conductivity of using pseudocapacitive or battery-type electrode materials. Recently, nonporous conductive coordination polymers (c-CPs) have sparked interests in supercapacitors. However, their performance is expected to be limited by the nonporous features, low specific surface area and absence of ion-diffusion channels. Here, it is demonstrated that the capacity of nonporous CPs will be significantly enhanced by maximizing the number of faradaic redox sites in their structures through a comparative investigation on three highly conductive nonporous c-CPs, Cux BHT(x = 3, 4, 5.5). They show excellent capacitance of 312.1 F g-1 (374.5 C g-1 ) (Cu3 BHT), 186.7 F g-1 (224.0 C g-1 ) (Cu4 BHT) and 89.2 F g-1 (107.0 C g-1 ) (Cu5.5 BHT) at 0.5 A g-1 in a sequence related to the number of electron storage units in structures and outstanding rate performance and cycle stability. Furthermore, the constructed Cu3 BHT//MnO2 ASC device exhibits capacity retention of 92% (after 1500 cycles at 3 A g-1 ) and delivers a high energy density of 39.1 Wh kg-1 at power density of 549.6 W kg-1 within a large working potential window of 0-2.2 V.

Synthesis of a monolayer fullerene network.

Two-dimensional (2D) carbon materials, such as graphene, have attracted particular attention owing to the exceptional carrier transport characteristics that arise from the unique π-electron system in their conjugated carbon network structure1-4. To complement zero-bandgap graphene, material scientists have devoted considerable effort to identifying 2D carbon materials5-8. However, it is a challenge to prepare large-sized single-crystal 2D carbon materials with moderate bandgaps5,9. Here we prepare a single-crystal 2D carbon material, namely monolayer quasi-hexagonal-phase fullerene (C60), with a large size via an interlayer bonding cleavage strategy. In this monolayer polymeric C60, cluster cages of C60 are covalently bonded with each other in a plane, forming a regular topology that is distinct from that in conventional 2D materials. Monolayer polymeric C60 exhibits high crystallinity and good thermodynamic stability, and the electronic band structure measurement reveals a transport bandgap of about 1.6 electronvolts. Furthermore, an asymmetric lattice structure endows monolayer polymeric C60 with notable in-plane anisotropic properties, including anisotropic phonon modes and conductivity. This 2D carbon material with a moderate bandgap and unique topological structure offers an interesting platform for potential application in 2D electronic devices.

Correction: Chemical structure modulation in conductive MOFs by adjusting the oxidation state of the ligand and introducing alkali metal ions.

Correction for 'Chemical structure modulation in conductive MOFs by adjusting the oxidation state of the ligand and introducing alkali metal ions' by Xiaoyu Wu et al., Chem. Commun., 2022, 58, 2702-2705, DOI: 10.1039/D1CC06407J.

Tetrathiafulvalenes as anchors for building highly conductive and mechanically tunable molecular junctions.

The interface between molecules and electrodes has great impact on charge transport of molecular devices. Precisely manipulating the structure and electronic coupling of electrode-molecule interface at a molecular level is very challenging. Here, we develop new molecular junctions based on tetrathiafulvalene (TTF)-fused naphthalene diimide (NDI) molecules which are anchored to gold electrodes through direct TTF-Au contacts formed via Au-S bonding. These contacts enable highly efficient orbital hybridization of gold electrodes and the conducting π-channels, yielding strong electrode-molecule coupling and remarkably high conductivity in the junctions. By further introducing additional thiohexyl (SHe) anchors to the TTF units, we develop molecular wires with multiple binding sites and demonstrate reversibly switchable electrode-molecule contacts and junction conductance through mechanical control. These findings show a superb electrode-molecule interface and provide a new strategy for precisely tunning the conductance of molecular devices towards new functions.

Chemical structure modulation in conductive MOFs by adjusting the oxidation state of the ligand and introducing alkali metal ions.

The metal-organic frameworks (MOFs) have attracted more and more attention and some MOFs have shown advanced electrical conductivity. Based on previous work about MnTHBQ (THBQ = tetrahydroxy-1,4-benzoquinone), we present two strategies, variation of the ligands' oxidation states and introducing alkali ions (Rb+ or Cs+), to modulate the structures of MOFs and obtained three new MOFs: MnHHB (HHB = hexahydroxybenzene), MnRbTHBQ and MnCsTHBQ. Different from the cubic lattices in the group of Pm3̄ of MnTHBQ, they exhibit hexagonal unit cells in the group of P6/mmm. This work highlights the importance of the oxidation state of the ligand in constructing the out-of-plane charge transport pathway and indicates that employing a redox-active ligand or adding alkali metal ions could be an optional strategy for manipulating the characteristics of MOFs.

Advances in materials and devices for mimicking sensory adaptation.

Adaptive devices, which aim to adjust electrical behaviors autonomically to external stimuli, are considered to be attractive candidates for next-generation artificial perception systems. Compared with typical electronic devices with stable signal output, adaptive devices possess unique features in exhibiting dynamic fitness to varying environments. To meet this requirement, increasing efforts have been made focusing on developing new materials, functional interfaces and novel device geometry for sensory perception applications. In this review, we summarize the recent advances in materials and devices for mimicking sensory adaptation. Keeping this in mind, we first introduce the fundamentals of biological sensory adaptation. Thereafter, the recent progress in mimicking sensory adaptation, such as tactile and visual adaptive systems, is overviewed. Moreover, we suggest five strategies to construct adaptive devices. Finally, challenges and perspectives are proposed to highlight the directions that deserve focused attention in this flourishing field.

Single cycloparaphenylene molecule devices: Achieving large conductance modulation via tuning radial π-conjugation.

Conjugated macrocycles cycloparaphenylenes (CPPs) have unusual size-dependent electronic properties because of their unique radially π-conjugated structures. Contrary to linearly π-conjugated molecules, their highest occupied molecular orbital (HOMO)­lowest unoccupied molecular orbital (LUMO) gap shrinks as the molecular size reduces, and this feature can, in principle, be leveraged to achieve unexpected size-dependent transport properties. Here, we examine charge transport characteristics of [n]CPPs (n = 5 to 12) at the single molecule level using the scanning tunneling microscope­break junction technique. We find that the [n]CPPs have a much higher conductance than their linear oligoparaphenylene counterparts at small ring size and at the same time show a large tunneling attenuation coefficient comparable to saturated alkane series. These results show that the radially π-conjugated molecular systems can offer much larger conductance modulation range than standard linear molecules and can be a new platform for building molecular devices with highly tunable transport behaviors.

An Oligonucleotide-Distortion-Responsive Organic Transistor for Platinum-Drug-Induced DNA-Damage Detection.

Organic transistor with DNA-damage evaluation ability can open up novel opportunities for bioelectronic devices. Even though trace amounts of drugs can cause cumulative gene damage in vivo, the extremely low occurrence proportion makes them hardly transduced into detectable electric signals. Here, an ultrasensitive DNA-damage sensor based on an oligonucleotide-distortion-responsive organic transistor (DROT) is reported by creating controllable conformation change of double-stranded DNA on the surface of organic semiconductors. In combination with interfacial charge redistribution and efficient signal amplification, the DROT provides an ultrasensitive single-site DNA-damage response with 20.5 s even upon 1 × 10-12 m cisplatin. The high generalizability of this DROT to three generations of classical platinum drugs and gene-relevant DNA damage is demonstrated. A biochip is further designed for intelligent damage analysis in complex environments, which holds the potential for high-throughput biotoxicity evaluation and drug screening in the future.

1D Mixed-Stack Cocrystals Based on Perylene Diimide toward Ambipolar Charge Transport.

There is very limited repertoire of organic ambipolar semiconductors to date. Electron donor-acceptor alternative stacking is a unique and important binary motif for 1D mixed-stack cocrystals, opening up possibilities for the development of organic ambipolar semiconductors. Herein, four 1D mixed-stack cocrystals using N,N'-bis(perfluorobutyl)-1,7-dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDICNF) as the acceptor and anthracene, pyrene, perylene, and meso-diphenyl tetrathia[22]annulene[2,1,2,1] (DPTTA) as the donors are achieved in a stoichiometric ratio (D:A = 1:1) through solution or vapor processed methods. Their packing structures, energy levels, charge transfer interactions, coassembling behaviors, and molecular orientations are systematically investigated by single-crystal X-ray analysis, absorption spectra, fluorescence quenching, Job's curve plot, and polarized photoluminescence measurements with the help of theoretical calculations. The donor-acceptor alternative stacking direction coincides with the long axis for all the four cocrystals. The field-effect transistors based on Pyrene-PDICNF show the electron mobility up to 0.19 cm2 V-1 s-1 , which is the highest value among perylene diimide-based cocrystals. Moreover, DPTTA-PDICNF cocrystals possess well-balanced electron and hole mobility with 1.7 × 10-2 and 2.0 × 10-2  cm2 V-1 s-1 respectively due to both hole and electron strong superexchange interactions, shedding light on the design of 1D mixed-stack cocrystals with excellent ambipolar transport behaviors.

Persistent Conjugated Backbone and Disordered Lamellar Packing Impart Polymers with Efficient n-Doping and High Conductivities.

Solution-processable highly conductive polymers are of great interest in emerging electronic applications. For p-doped polymers, conductivities as high a nearly 105 S cm-1 have been reported. In the case of n-doped polymers, they often fall well short of the high values noted above, which might be achievable, if much higher charge-carrier mobilities determined could be realized in combination with high charge-carrier densities. This is in part due to inefficient doping and dopant ions disturbing the ordering of polymers, limiting efficient charge transport and ultimately the achievable conductivities. Here, n-doped polymers that achieve a high conductivity of more than 90 S cm-1 by a simple solution-based co-deposition method are reported. Two conjugated polymers with rigid planar backbones, but with disordered crystalline structures, exhibit surprising structural tolerance to, and excellent miscibility with, commonly used n-dopants. These properties allow both high concentrations and high mobility of the charge carriers to be realized simultaneously in n-doped polymers, resulting in excellent electrical conductivity and thermoelectric performance.

Chemical doping of organic semiconductors for thermoelectric applications.

Doping is essential to manipulate the electrical performance of both thermoelectric (TE) materials and organic semiconductors (OSCs). Although organic thermoelectric (OTE) materials have experienced a rapid development over the past decade, the chemical doping of OSCs for TE applications lags behind, which has limited further breakthroughs in this cutting-edge field. Recently, increasing efforts have been devoted to the development of energetically matched host and dopant molecules, exploring novel doping methods and revealing the doping mechanisms. This tutorial review covers the basic mechanisms, fundamental requirements, recent advances and remaining challenges of chemical doping in OSCs for TE applications. We first present the basic knowledge of the trade-off relationship in TE materials and its critical requirements for doped OSCs, followed by a brief introduction of recent advances in the molecular design of OSCs and dopants. Moreover, we provide an overview of the existing categories of doping mechanisms and methods, and more importantly, emphasize the summarized doping strategies for the state-of-the-art OTE materials. Finally, challenges and perspectives on the chemical doping of OSCs are proposed to highlight the research directions that deserve attention towards a bright future of OTE materials.

Highly Conducting Organic-Inorganic Hybrid Copper Sulfides Cux C6 S6 (x=4 or 5.5): Ligand-Based Oxidation-Induced Chemical and Electronic Structure Modulation.

Conductive coordination polymers (CPs) have potential in a wide range of applications because of their inherent structural and functional diversity. Three electrically conductive CPs (Cux C6 S6 , x=3, 4 or 5.5) derived from the same organic linker (benzenehexathiol) and metal node (copper(I)) were synthesized and studied. Cux C6 S6 materials are organic-inorganic hybrid copper sulfides comprising a π-π stacking structure and cooper sulfur networks. Charge-transport pathways within the network facilitate conductivity and offer control of the Fermi level through modulation of the oxidation level of the non-innocent redox-active ligand. Two Cux C6 S6 (x=4 or 5.5) CPs display high electrical conductivity and they feature a tunable structural topology and electronic structure. Cu4 C6 S6 and Cu5.5 C6 S6 act as degenerate semiconductors. Moreover, Cu5.5 C6 S6 is a p-type thermoelectric material with a ZT value of 0.12 at 390 K, which is a record-breaking performance for p-type CPs.