Low-voltage organic field-effect transistors and inverters enabled by ultrathin cross-linked polymers as gate dielectrics

The quest for high-performance organic thin-film transistor (OTFT) gate dielectrics is of intense current interest. Beyond having excellent insulating properties, such materials must meet other stringent requirements for optimum OTFT function: efficient low-temperature solution fabrication, mechanical flexibility, and compatibility with diverse gate materials and organic semiconductors. The OTFTs should function at low biases to minimize power consumption, hence the dielectric must exhibit large gate capacitance. We report the realization of new spin-coatable, ultrathin (<20 nm) cross-linked polymer blends exhibiting excellent insulating properties (leakage current densities approximately 10(-)(8) Acm(-)(2)), large capacitances (up to approximately 300 nF cm(-)(2)), and enabling low-voltage OTFT functions. These dielectrics exhibit good uniformity over areas approximately 150 cm(2), are insoluble in common solvents, can be patterned using standard microelectronic etching methodologies, and adhere to/are compatible with n(+)-Si, ITO, and Al gates, and with a wide range of p- and n-type semiconductors. Using these dielectrics, complementary invertors have been fabricated which function at 2 V.     

B(C6F5)3- vs Al(C6F5)3-derived metallocenium ion pairs. Structural, thermochemical, and structural dynamic divergences

The thermodynamic and structural characteristics of Al(C6F(5)3-derived vs B(C6F5)3-derived group 4 metallocenium ion pairs are quantified. Reaction of 1.0 equiv of B(C6F5)3 or 1.0 or 2.0 equiv of Al(C6F5)3 with rac-C2H4(eta5-Ind)2Zr(CH3)2 (rac-(EBI)Zr(CH3)2) yields rac-(EBI)Zr(CH3)(+)H3CB(C6)F5)(3)(-) (1a), rac-(EBI)Zr(CH3)+H3CAl(C6F5)(3)(-) (1b), and rac-(EBI)Zr2+[H3CAl(C6F5)3](-)(2) (1c), respectively. X-ray crystallographic analysis of 1b indicates the H3CAl(C6F5)(3)(-) anion coordinates to the metal center via a bridging methyl in a manner similar to B(C6F5)3-derived metallocenium ion pairs. However, the Zr-(CH3)(bridging) and Al-(CH3)(bridging) bond lengths of 1b (2.505(4) A and 2.026(4) A, respectively) indicate the methyl group is less completely abstracted in 1b than in typical B(C6F5)3-derived ion pairs. Ion pair formation enthalpies (DeltaH(ipf)) determined by isoperibol solution calorimetry in toluene from the neutral precursors are -21.9(6) kcal mol(-1) (1a), -14.0(15) kcal mol(-1) (1b), and -2.1(1) kcal mol(-1) (1b-->1c), indicating Al(C6F5)3 to have significantly less methide affinity than B(C6F5)3. Analogous experiments with Me2Si(eta5-Me4C5)(t-BuN)Ti(CH3)2 indicate a similar trend. Furthermore, kinetic parameters for ion pair epimerization by cocatalyst exchange (ce) and anion exchange (ae), determined by line-broadening in VT NMR spectra over the range 25-75 degrees C, are DeltaH++(ce) = 22(1) kcal mol(-1), DeltaS++(ce) = 8.2(4) eu, DeltaH++(ae) = 14(2) kcal mol(-1), and DeltaS++(ae) = -15(2) eu for 1a. Line broadening for 1b is not detectable until just below the temperature where decomposition becomes significant ( approximately 75-80 degrees C), but estimation of the activation parameters at 72 degrees C gives DeltaH++(ce) approximately 22 kcal mol(-1)and DeltaH++(ae) approximately 16 kcal mol(-1), consistent with the bridging methide being more strongly bound to the zirconocenium center than in 1a.     

Solution-deposited organic-inorganic hybrid multilayer gate dielectrics. Design, synthesis, microstructures, and electrical properties with thin-film transistors

We report here on the rational synthesis, processing, and dielectric properties of novel layer-by-layer organic/inorganic hybrid multilayer dielectric films enabled by polarizable π-electron phosphonic acid building blocks and ultrathin ZrO(2) layers. These new zirconia-based self-assembled nanodielectric (Zr-SAND) films (5-12 nm thick) are readily fabricated via solution processes under ambient atmosphere. Attractive Zr-SAND properties include amenability to accurate control of film thickness, large-area uniformity, well-defined nanostructure, exceptionally large electrical capacitance (up to 750 nF/cm(2)), excellent insulating properties (leakage current densities as low as 10(-7) A/cm(2)), and excellent thermal stability. Thin-film transistors (TFTs) fabricated with pentacene and PDIF-CN(2) as representative organic semiconductors and zinc-tin-oxide (Zn-Sn-O) as a representative inorganic semiconductor function well at low voltages (<±4.0 V). Furthermore, the TFT performance parameters of representative organic semiconductors deposited on Zr-SAND films, functionalized on the surface with various alkylphosphonic acid self-assembled monolayers, are investigated and shown to correlate closely with the alkylphosphonic acid chain dimensions.     

Molecular and Electronic‐Structure Basis of the Ambipolar Behavior of Naphthalimide–Terthiophene Derivatives: Implementation in Organic Field‐Effect Transistors

A new family of naphthalimide‐fused thienopyrazine derivatives for ambipolar charge transport in organic field‐effect transistors is presented. Their electronic and molecular structures were elucidated through optical and vibrational spectroscopy aided by DFT calculations. The results indicate that these compounds have completely planar molecular skeletons which promote good film crystallinity and low reorganization energies for both electron and hole transport. Their performance in organic field‐effect transistors is compared with twisted and planar naphthaleneamidine monoimide‐fused terthiophenes in order to understand the origin of ambipolarity in this new series of molecular semiconductors.     

In-situ probe of gate dielectric-semiconductor interfacial order in organic transistors: origin and control of large performance sensitivities

Organic thin film transistor (OTFT) performance is highly materials interface-dependent, and dramatic performance enhancements can be achieved by properly modifying the semiconductor/gate dielectric interface. However, the origin of these effects is not well understood, as this is a classic "buried interface" problem that has traditionally been difficult to address. Here we address the question of how n-octadecylsilane (OTS)-derived self-assembled monolayers (SAMs) on Si/SiO(2) gate dielectrics affect the OTFT performance of the archetypical small-molecule p-type semiconductors P-BTDT (phenylbenzo[d,d]thieno[3,2-b;4,5-b]dithiophene) and pentacene using combined in situ sum frequency generation spectroscopy, atomic force microscopy, and grazing incidence and reflectance X-ray scattering. The molecular order and orientation of the OTFT components at the dielectric/semiconductor interface is probed as a function of SAM growth mode in order to understand how this impacts the overlying semiconductor growth mode, packing, crystallinity, and carrier mobility, and hence, transistor performance. This understanding, using a new, humidity-specific growth procedure, leads to a reproducible, scalable process for highly ordered OTS SAMs, which in turn nucleates highly ordered p-type semiconductor film growth, and optimizes OTFT performance. Surprisingly, the combined data reveal that while SAM molecular order dramatically impacts semiconductor crystalline domain size and carrier mobility, it does not significantly influence the local orientation of the overlying organic semiconductor molecules.     

The small unit cell reconstructions of SrTiO3(1 1 1)

We analyze the basic structural units of simple reconstructions of the (1 1 1) surface of SrTiO₃ using density functional calculations. The prime focus is to answer three questions: what is the most appropriate functional to use; how accurate are the energies; what are the dominant low-energy structures and where do they lie on the surface phase diagram. Using test calculations of representative small molecules we compare conventional PBE-GGA with higher-order methods such as the TPSS meta-GGA and on-site hybrid methods PBE0 and TPSSh, the later being the most accurate. There are large effects due to reduction of the metal d oxygen sp hybridization when using the hybrid methods which are equivalent to a dynamical GGA + U, which leads to rather substantial improvements in the atomization energies of simple calibration molecules, even though the d-electron density for titanium compounds is rather small. By comparing the errors of the different methods we are able to generate an estimate of the theoretical error, which is about 0.25 eV per 1 × 1 unit cell, with changes of 0.5-1.0 eV per 1 × 1 cell with the more accurate method relative to conventional GGA. An analysis of the plausible structures reveals a new low-energy TiO₂-rich configuration with octahedral co-ordination. This structure can act as a template for layers of either TiO or Ti₂O₃, consistent with experimental results. The results also suggest that both the fracture surface and the stoichiometric SrTiO₃(1 1 1) surface should spontaneously disproportionate into SrO and TiO₂ rich domains.     

Isolation of light filth from ground oregano and ground marjoram: a modification using isopropanol as a defatting agent: in-house study

A procedural modification of the AOAC Official Method for extracting light filth from ground oregano and ground marjoram was tested in an intralaboratory study. The modified method specifies isopropanol defatting, 975.49A(a), rather than chloroform-isopropanol defatting, 975.49A(b), followed by direct flotation as directed in AOAC Official Method, 975.49B(b). The modified method provided comparable results in less time while also providing safety, health, and financial benefits.     

Characterization of transparent conducting oxide surfaces using self-assembled electroactive monolayers

The electronic properties of various transparent conducting oxide (TCO) surfaces are probed electrochemically via self-assembled monolayers (SAMs). A novel graftable probe molecule having a tethered trichlorosilyl group and a redox-active ferrocenyl functionality (Fc(CH2) 4SiCl3) is synthesized for this purpose. This molecule can be self-assembled via covalent bonds to form monolayers on various TCO surfaces. On as-received ITO, saturation coverage of 6.6 x 10(-10) mol/cm2 by a close-packed monolayer and an electron-transfer rate of 6.65 s(-1) is achieved after 9 h of chemisorption, as determined by cyclic voltammetry (CV) and synchrotron X-ray reflectivity. With this molecular probe, it is found that O2 plasma-treated ITO has a significantly greater electroactive coverage of 7.9 x 10 (-10) mol/cm2 than as-received ITO. CV studies of this redox SAM on five different TCO surfaces reveal that MOCVD-derived CdO exhibits the greatest electroactive coverage (8.1 x 10(-10) mol/cm2) and MOCVD-derived ZITO (ZnIn2.0Sn1.5O) exhibits the highest electron transfer rate (7.12 s(-1)).     

Polarity identification of GaN bulk single crystals (0001) surface by Auger electron spectroscopy

An attempt to identify the polarity of (0001) polar surface of GaN bulk single crystals grown by high nitrogen pressure solution method has been made using Auger electron spectroscopy (AES). AES concentration depth profiles of the top layer in (0001) direction starting from both (0001) faces of the sample have been measured. Distinct difference in the Ga concentration at the sample surface of both faces has been observed. The dependence of Ga eoncentration on depth is also different for both faces of the sample.