Photochromic Dithienylethene Monolayer-Modified Gold Nanoparticles as a Tunable Floating Gate in the Fabrication of Nonvolatile Organic Memory.

Nonvolatile memory (NVM) devices were fabricated by implanting a self-assembled monolayer (SAM) of functional dithienylethene (DTE) derivative on the gold nanoparticle (Au-NP) surface in a pentacene-based organic transistor. The Au-NPs and DTE served as a charge-trapping medium and tunneling barrier layer, respectively. The transfer characteristic of the NVM device showed a narrow hysteresis window and wide memory window, indicating that the DTE-SAM served as a variable barrier layer to regulate the trapping and detrapping of external free charges at the Au-NPs. The energy gap introduced by the DTE-SAM is modulated through photoisomerization between a ring-open form and a ring-closed form by absorbing UV or visible light. For a memory device, the ring-closed DTE allows more free charge injection into the trapping sites, and the ring-open one better retains the trapped charges. A longer anchoring alkanethiol chain at the DTE moiety can further extend the device's retention time. For the NVM operation, programming with the ring-closed DTE and then switching the DTE structure to the ring-open form for erasing can facilitate the charge trapping and charge retention with the same molecule compared to operating all in the ring-open form or all in the ring-closed form of DTE. The structural characterization and electronic characteristics of these devices are discussed in detail.

Self-Assembly Behavior of Diacetylenic Acid Molecules upon Vapor Deposition: Odd-Even Effect on the Film Morphology.

A series of linear carboxylic acids containing diacetylenic units at different positions along the chain (C12 H25 (C≡C)2 (CH2 )n COOH, n=7-11) were vacuum-deposited on clean silica substrates. The morphologies of the initial films after UV irradiation were studied. A clear odd-even effect on the morphology of the initial film was observed in that, depending on the spacer length between the diacetylenic unit and carboxyl head group, rings or dendrites of acid dimer layers were obtained. A molecular dynamic simulation of the aggregation process suggests that two competing intermolecular interactions and thus aggregation directions are involved and modulated by the odd or even carbon chain length. Further modulation of the interaction by substitution of a phenyl group at the terminus of the chain or by changing the carboxyl head group to an amidobenzoic acid head group led to a similar odd-even effect but with different dimensions or trends, which can be rationalized similarly. These results give the opportunity to create aligned conjugated polymer chains of different dimensions through self-assembly for applications in molecular/organic electronics.

Synergy of Ionic and Dipolar Effects by Molecular Design for pH Sensing beyond the Nernstian Limit.

Knowledge of interfacial interactions between analytes and functionalized sensor surfaces, from where the signal originates, is key to the development and application of electronic sensors. The present work explores the tunability of pH sensitivity by the synergy of surface charge and molecular dipole moment induced by interfacial proton interactions. This synergy is demonstrated on a silicon-nanoribbon field-effect transistor (SiNR-FET) by functionalizing the sensor surface with properly designed chromophore molecules. The chromophore molecules can interact with protons and lead to appreciable changes in interface dipole moment as well as in surface charge state. In addition, the dipole moment can be tuned not only by the substituent on the chromophore but also by the anion in the electrolyte interacting with the protonated chromophore. By designing surface molecules to enhance the surface dipole moment upon protonation, an above-Nernstian pH sensitivity is achieved on the SiNR-FET sensor. This finding may bring an innovative strategy for tailoring the sensitivity of the SiNR-FET-based pH sensor toward a wide range of applications.

Nonlinear Polyfused Aromatics with Extended π-Conjugation from Phenanthrotriphenylene, Tetracene, and Pentacene: Syntheses, Crystal Packings, and Properties.

New classes of nonlinear polyaromatics with extended conjugation at lateral and longitudinal directions from triphenylene, tetracene, and pentacene backbones are reported. These planar and twisted polyfused aromatics are obtained through specific and selective multifold Scholl reactions from predesigned polyaryls. These derivatives displayed shifted or perfect cofacial packing motifs. Single crystals of one derivative, phenanthro[9,10: b]triphenylene, were used as p-channel materials in fabricating transistor devices, which exhibited an average mobility of 0.38 cm2 V-1 s-1 and a maximum mobility reaching 1.15 cm2 V-1 s-1.

Organic transistor memory with a charge storage molecular double-floating-gate monolayer.

A flexible, low-voltage, and nonvolatile memory device was fabricated by implanting a functional monolayer on an aluminum oxide dielectric surface in a pentacene-based organic transistor. The monolayer-forming molecule contains a phosphonic acid group as the anchoring moiety and a charge-trapping core group flanked between two alkyl chain spacers as the charge trapping site. The memory characteristics strongly depend on the monolayer used due to the localized charge-trapping capability for different core groups, including the diacetylenic (DA) unit as the hole carrier trap, the naphthalenetetracarboxyldiimide (ND) unit as the electron carrier trap, and the one with both DA and ND units present, respectively. The device with the monolayer carrying both DA and ND groups has a larger memory window than that for the one containing DA only and a longer retention time than that for the one containing DA or ND only, giving a memory window of 1.4 V and a retention time around 10(9) s. This device with hybrid organic monolayer/inorganic dielectrics also exhibited rather stable device characteristics upon bending of the polymeric substrate.

Azobenzene-functionalized gold nanoparticles as hybrid double-floating-gate in pentacene thin-film transistors/memories with enhanced response, retention, and memory windows.

Gold nanoparticles (Au-NPs) with surfaces covered with a self-assembled monolayer of azobenzene derivatives were prepared at the interface of dielectric insulator SiO2 and pentacene thin film. Transistors constructed with these composite channel materials exhibited electric bistability upon different gate biases, with the monolayer serving as a barrier layer, a work function modulator, as well as additional charge trapping sites at the Au-NPs/semiconductor interface at the same time. In comparison with simple alkanethiol monolayer-covered Au-NPs, the CH3-substituted azobenzene-functionalized Au-NPs result in a transistor memory device with about 70% more charges trapped, much faster response time as well as higher retention time. Besides, depending on the substituent on the azobenzene moieties (CH3, H, or CF3) and the tethering alkyl chain length, the speed at which the carriers are trapped (affecting switching response) and the stability of the carriers that are trapped (affecting memory retention) can be modulated to improve the device performance. The structural characterization and electronic characteristics of these devices will be detailed.

Electric bistability induced by incorporating self-assembled monolayers/aggregated clusters of azobenzene derivatives in pentacene-based thin-film transistors.

Composite films of pentacene and a series of azobenzene derivatives are prepared and used as the active channel material in top-contact, bottom-gate field-effect transistors. The transistors exhibit high field-effect mobility as well as large I-V hysteresis as a function of the gate bias history. The azobenzene moieties, incorporated either in the form of self-assembled monolayer or discrete multilayer clusters at the dielectric surface, result in electric bistability of the pentacene-based transistor either by photoexcitation or gate biasing. The direction of threshold voltage shifts, size of hysteresis, response time, and retention characteristics all strongly depend on the substituent on the benzene ring. The results show that introducing a monolayer of azobenzene moieties results in formation of charge carrier traps responsible for slower switching between the bistable states and longer retention time. With clusters of azobenzene moieties as the trap sites, the switching is faster but the retention is shorter. Detailed film structure analyses and correlation with the transistor/memory properties of these devices are provided.

Approaching charge balance in organic light-emitting diodes by tuning charge injection barriers with mixed monolayers.

Self-assembled monolayers (SAMs) of binary mixtures of 1-butylphosphonic acid and the trifluoromethyl-terminated analogue (4,4,4-trifluoro-1-butylphosphonic acid) were formed on ITO surfaces to tune the work function of ITO over a range of 5.0 to 5.75 eV by varying the mixing ratio of the two adsorbents. The mixed SAM-modified ITO surfaces were used as the anode in the fabrication of OLED devices with a configuration of ITO/SAM/HTL/Alq3/MX/Al, where HTL was the NPB or BPAPF hole-transporting layer and MX was the LiF or Cs(2)CO(3) injection layer. It was shown that, depending on the HTL or MX used, the maximum device current and the maximum luminance efficiency occurred with anodes of different modifications because of a shift in the point of hole/electron carrier balance. This provides information on the charge balance in the device and points to the direction to improve the performance.