Introducing pinMOS Memory: A Novel, Nonvolatile Organic Memory Device

In recent decades, organic memory devices have been researched intensely and they can, among other application scenarios, play an important role in the vision of an internet of things. Most studies concentrate on storing charges in electronic traps or nanoparticles while memory types where the information is stored in the local charge up of an integrated capacitance and presented by capacitance received far less attention. Here, a new type of programmable organic capacitive memory called p-i-n-metal-oxide-semiconductor (pinMOS) memory is demonstrated with the possibility to store multiple states. Another attractive property is that this simple, diode-based pinMOS memory can be written as well as read electrically and optically. The pinMOS memory device shows excellent repeatability, an endurance of more than 104 write-read-erase-read cycles, and currently already over 24 h retention time. The working mechanism of the pinMOS memory under dynamic and steady-state operations is investigated to identify further optimization steps. The results reveal that the pinMOS memory principle is promising as a reliable capacitive memory device for future applications in electronic and photonic circuits like in neuromorphic computing or visual memory systems. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei

Charge Carrier Mobility Improvement in Diketopyrrolopyrrole Block-Copolymers by Shear Coating

Shear coating is a promising deposition method for upscaling device fabrication and enabling high throughput, and is furthermore suitable for translating to roll-to-roll processing. Although common polymer semiconductors (PSCs) are solution processible, they are still prone to mechanical failure upon stretching, limiting applications in e.g., electronic skin and health monitoring. Progress made towards mechanically compliant PSCs, e.g., the incorporation of soft segments into the polymer backbone, could not only allow such applications, but also benefit advanced fabrication methods, like roll-to-roll printing on flexible substrates, to produce the targeted devices. Tri-block copolymers (TBCs), consisting of an inner rigid semiconducting poly-diketo-pyrrolopyrrole-thienothiophene (PDPP-TT) block flanked by two soft elastomeric poly(dimethylsiloxane) (PDMS) chains, maintain good charge transport properties, while being mechanically soft and flexible. Potentially aiming at the fabrication of TBC-based wearable electronics by means of cost-efficient and scalable deposition methods (e.g., blade-coating), a tolerance of the electrical performance of the TBCs to the shear speed was investigated. Herein, we demonstrate that such TBCs can be deposited at high shear speeds (film formation up to a speed of 10 mm s−1). While such high speeds result in increased film thickness, no degradation of the electrical performance was observed, as was frequently reported for polymer−based OFETs. Instead, high shear speeds even led to a small improvement in the electrical performance: mobility increased from 0.06 cm2 V−1 s−1 at 0.5 mm s−1 to 0.16 cm2 V−1 s−1 at 7 mm s−1 for the TBC with 24 wt% PDMS, and for the TBC containing 37 wt% PDMS from 0.05 cm2 V−1 s−1 at 0.5 mm s−1 to 0.13 cm2 V−1 s−1 at 7 mm s−1. Interestingly, the improvement of mobility is not accompanied by any significant changes in morphology

Electronic Doping and Enhancement of n‐Channel Polycrystalline OFET Performance through Gate Oxide Modifications with Aminosilanes

Self-assembled monolayers (SAMs) are widely employed in organic field-effect transistors to modify the surface energy, surface roughness, film growth kinetics, and electrical surface potential of the gate oxide to control the device's operating voltage. In this study, amino-functionalized SAM molecules are compared to pure alkylsilane SAMS in terms of their impact on the electrical properties of organic field-effect transistors, using the n-type polycrystalline small molecule semiconductor material N,N′-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8). In order to understand the electronic impact of the amino groups, the effect of both the number of amino-containing functional groups and the SAM molecular length are systematically studied. Though amino-functionalized SAM materials have been studied previously, this study is, for the first time, able to shed light on the nature of the doping effect that occurs when the gate oxide is treated with polar aminosilane materials. By a comprehensive theoretical study of the interface on the molecular level, it is shown that the observed shift in the threshold voltage is caused by free charges, which are attracted to the PTCDI-C8 and are stabilized there by protonated aminosilanes. This attraction and the voltage shift can be systematically tuned by varying the length of the neutral terminal chain of the aminosilane. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH Gmb

Ultrasoft and High-Mobility Block Copolymers for Skin-Compatible Electronics

Polymer semiconductors (PSCs) are an essential component of organic field-effect transistors (OFETs), but their potential for stretchable electronics is limited by their brittleness and failure susceptibility upon strain. Herein, a covalent connection of two state-of-the-art polymers—semiconducting poly-diketo-pyrrolopyrrole-thienothiophene (PDPP-TT) and elastomeric poly(dimethylsiloxane) (PDMS)—in a single triblock copolymer (TBC) chain is reported, which enables high charge carrier mobility and low modulus in one system. Three TBCs containing up to 65 wt% PDMS were obtained, and the TBC with 65 wt% PDMS content exhibits mobilities up to 0.1 cm2 V−1 s−1, in the range of the fully conjugated reference polymer PDPP-TT (0.7 cm2 V−1 s−1). The TBC is ultrasoft with a low elastic modulus (5 MPa) in the range of mammalian tissue. The TBC exhibits an excellent stretchability and extraordinary durability, fully maintaining the initial electric conductivity in a doped state after 1500 cycles to 50% strain. © 2020 The Authors. Advanced Materials published by Wiley-VCH Gmb

Sequentially Processed P3HT/CN6-CP•−NBu4+ Films: Interfacial or Bulk Doping?

Derivatives of the hexacyano-[3]-radialene anion radical (CN6-CP•−) emerge as a promising new family of p-dopants having a doping strength comparable to that of archetypical dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ). Here, mixed solution (MxS) and sequential processing (SqP) doping methods are compared by using a model semiconductor poly(3-hexylthiophene) (P3HT) and the dopant CN6-CP•−NBu4 + (NBu4 + = tetrabutylammonium). MxS films show a moderate yet thickness-independent conductivity of ≈0.1 S cm−1. For the SqP case, the highest conductivity value of ≈6 S cm−1 is achieved for the thinnest (1.5–3 nm) films whereas conductivity drops two orders of magnitudes for 100 times thicker films. These results are explained in terms of an interfacial doping mechanism realized in the SqP films, where only layers close to the P3HT/dopant interface are doped efficiently, whereas internal P3HT layers remain essentially undoped. This structure is in agreement with transmission electron microscopy, atomic force microscopy, and Kelvin probe force microscopy results. The temperature-dependent conductivity measurements reveal a lower activation energy for charge carriers in SqP samples than in MxS films (79 meV vs 110 meV), which could be a reason for their superior conductivity. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinhei

Ultra-high mobility transparent organic thin film transistors grown by an off-centre spin-coating method

Organic semiconductors with higher carrier mobility and better transparency have been actively pursued for numerous applications, such as flat-panel display backplane and sensor arrays. The carrier mobility is an important figure of merit and is sensitively influenced by the crystallinity and the molecular arrangement in a crystal lattice. Here we describe the growth of a highly aligned meta-stable structure of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) from a blended solution of C8-BTBT and polystyrene by using a novel offcentre spin-coating method. Combined with a vertical phase separation of the blend, the highly aligned, meta-stable C8-BTBT films provide a significantly increased thin film transistor hole mobility up to 43 cm2 Vs�1 (25 cm2 Vs�1 on average), which is the highest value reported to date for all organic molecules. The resulting transistors show high transparency of 490% over the visible spectrum, indicating their potential for transparent, high-performance organic electronics

A Two-Dimensional Polyimide-Graphene Heterostructure with Ultra-fast Interlayer Charge Transfer

Two-dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic–inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on-water surface synthesis of large-area (cm2), monolayer 2D polyimide (2DPI) with 3.1-nm lattice. Such 2DPI comprises metal-free porphyrin and perylene units linked by imide bonds. We further achieve a scalable synthesis of 2DPI-graphene (2DPI-G) vdWHs via a face-to-face co-assembly of graphene and 2DPI on the water surface. Remarkably, femtosecond transient absorption spectroscopy reveals an ultra-fast interlayer charge transfer (ca. 60 fs) in the resultant 2DPI-G vdWH upon protonation by acid, which is equivalent to that of the fastest reports among inorganic 2D vdWHs. Such large interlayer electronic coupling is ascribed to the interlayer cation–π interaction between 2DP and graphene. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH Gmb

Investigating the morphology of bulk heterojunctions by laser photoemission electron microscopy

The nanoscale morphology of bulk heterojunctions is highly important for the charge dissociation and transport in organic solar cells and ultimately defines the performance of the cell. The visualization of this nano-morphology in terms of domain size and polymer orientation in a fast and straightforward way is therefore of great interest to evaluate the suitability of a film for efficient solar cells. Here, we demonstrate that the morphology of different blends of poly(3-hexylthiophene-2,5-diyl) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) can be imaged and analyzed by employing photoemission electron microscopy

A coronene-based semiconducting two-dimensional metal-organic framework with ferromagnetic behavior

Metal-organic frameworks (MOFs) have so far been highlighted for their potential roles in catalysis, gas storage and separation. However, the realization of high electrical conductivity (>10-3 S cm-1) and magnetic ordering in MOFs will afford them new functions for spintronics, which remains relatively unexplored. Here, we demonstrate the synthesis of a two-dimensional MOF by solvothermal methods using perthiolated coronene as a ligand and planar iron-bis(dithiolene) as linkages enabling a full π-d conjugation. This 2D MOF exhibits a high electrical conductivity of ~10 S cm-1 at 300 K, which decreases upon cooling, suggesting a typical semiconductor nature. Magnetization and 57Fe Mössbauer experiments reveal the evolution of ferromagnetism within nanoscale magnetic clusters below 20 K, thus evidencing exchange interactions between the intermediate spin S = 3/2 iron(III) centers via the delocalized π electrons. Our results illustrate that conjugated 2D MOFs have potential as ferromagnetic semiconductors for application in spintronics

Engineering crystalline quasi-two-dimensional polyaniline thin film with enhanced electrical and chemiresistive sensing performances

Engineering conducting polymer thin films with morphological homogeneity and long-range molecular ordering is intriguing to achieve high-performance organic electronics. Polyaniline (PANI) has attracted considerable interest due to its appealing electrical conductivity and diverse chemistry. However, the synthesis of large-area PANI thin film and the control of its crystallinity and thickness remain challenging because of the complex intermolecular interactions of aniline oligomers. Here we report a facile route combining air-water interface and surfactant monolayer as templates to synthesize crystalline quasi-two-dimensional (q2D) PANI with lateral size ~50 cm2 and tunable thickness (2.6-30 nm). The achieved q2D PANI exhibits anisotropic charge transport and a lateral conductivity up to 160 S cm-1 doped by hydrogen chloride (HCl). Moreover, the q2D PANI displays superior chemiresistive sensing toward ammonia (30 ppb), and volatile organic compounds (10 ppm). Our work highlights the q2D PANI as promising electroactive materials for thin-film organic electronics