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Antonio Facchetti

Publications and source records attributed to Antonio Facchetti.

At least 19 recordsLinked to original sources
PubMed2006

Quantum chemical analysis of electronic structure and n- and p-type charge transport in perfluoroarene-modified oligothiophene semiconductors.

Density-functional theory (DFT) is employed to investigate the structural, electronic, and transport properties of several isomeric fluoroarene-oligothiophene-based semiconductors. Three oligothiophene systems varying in the perfluoroarene group positions within the molecule are studied to understand the electronic structure leading to the observed mobility values and to the n- or p-type behavior in these structures. Analyses of both intermolecular interactions in dimers and extended interactions in crystalline structures afford considerable insight into the electronic properties and carrier mobilities of these materials, as well as the polarity of the charge carriers. From the calculated carrier effective masses, we find that sterically governed molecular planarity plays a crucial role in the transport properties of these semiconductors. Our calculations correlate well with experimentally obtained geometries, highest-occupied molecular orbital (HOMO)/lowest-unoccupied molecular orbital (LUMO) energies, and the experimental carrier mobility trends among the systems investigated.

Journal Article↗
PubMed2006

High-capacitance organic nanodielectrics: effective medium models of their response.

Molecular and macromolecular high-permittivity organic gate dielectric materials have been the focus of recent experimental research as a consequence of their promising properties for organic and inorganic field effect transistor (FET) applications. Two types of molecular thin films, self-assembled nanodielectrics (SANDs) and cross-linked polymer blends (CPBs), have been shown experimentally to afford high capacitances and low FET operating voltages. In an effort to design optimized nanostructures having even larger capacitances, lower leakage current densities, and further reduced FET operating voltages, we discuss approaches for computing the effective permittivities of each nanodielectric motif and investigate how molecular arrangements impact overall device capacitance. The calculated frequency-dependent capacitances, derived from Maxwell-Wagner theory applied to the Maxwell-Garnett effective medium approximation, agree fairly well with the experimental values for the two types of nanodielectrics. Predictions of larger capacitance SANDs are made with the two-capacitors-in-series equivalent circuit, where the layered, self-assembled structure is viewed as two different capacitors. The Maxwell-Garnett and Polder-Van Santen effective medium approximations are used to predict the dielectric response of higher permittivity polymer cross-linked blends. In calculations showing good agreement between theory and experiment, and with all parameters being equal, it is found that greater capacitances should be achievable with cross-linked composites than with layered composites.

Journal Article↗
PubMed2006

High-performance transparent inorganic-organic hybrid thin-film n-type transistors.

High-performance thin-film transistors (TFTs) that can be fabricated at low temperature and are mechanically flexible, optically transparent and compatible with diverse substrate materials are of great current interest. To function at low biases to minimize power consumption, such devices must also contain a high-mobility semiconductor and/or a high-capacitance gate dielectric. Here we report transparent inorganic-organic hybrid n-type TFTs fabricated at room temperature by combining In2O3 thin films grown by ion-assisted deposition, with nanoscale organic dielectrics self-assembled in a solution-phase process. Such TFTs combine the advantages of a high-mobility transparent inorganic semiconductor with an ultrathin high-capacitance/low-leakage organic gate dielectric. The resulting, completely transparent TFTs exhibit excellent operating characteristics near 1.0 V with large field-effect mobilities of >120 cm2 V(-1) s(-1), drain-source current on/off modulation ratio (I(on)/I(off)) approximately 10(5), near-zero threshold voltages and sub-threshold gate voltage swings of 90 mV per decade. The results suggest new strategies for achieving 'invisible' optoelectronics.

Journal Article↗
PubMed2006

Gate dielectric chemical structure-organic field-effect transistor performance correlations for electron, hole, and ambipolar organic semiconductors.

This study describes a general approach for probing semiconductor-dielectric interfacial chemistry effects on organic field-effect transistor performance parameters using bilayer gate dielectrics. Organic semiconductors exhibiting p-/n-type or ambipolar majority charge transport are grown on six different bilayer dielectric structures consisting of various spin-coated polymers/HMDS on 300 nm SiO(2)/p(+)-Si, and are characterized by AFM, SEM, and WAXRD, followed by transistor electrical characterization. In the case of air-sensitive (generally high LUMO energy) n-type semiconductors, dielectric surface modifications induce large variations in the corresponding OTFT performance parameters although the film morphologies and microstructures remain similar. In marked contrast, the device performance of air-stable n-type and p-type semiconductors is not significantly affected by the same dielectric surface modifications. Among the bilayer dielectric structures examined, nonpolar polystyrene coatings on SiO(2) having minimal gate leakage and surface roughness significantly enhance the mobilities of overlying air-sensitive n-type semiconductors to as high as approximately 2 cm(2)/(V s) for alpha,omega-diperfluorohexylcarbonylquaterthiophene polystyrene/SiO(2). Electron trapping due to silanol and carbonyl functionalities at the semiconductor-dielectric interface is identified as the principal origin of the mobility sensitivity to the various surface chemistries in the case of n-type semiconductors having high LUMO energies. Thiophene-based n-type semiconductors exhibiting similar film morphologies and microstructures on various bilayer gate dielectrics therefore provide an incisive means to probe TFT performance parameters versus semiconductor-dielectric interface relationships.

Journal Article↗
PubMed2006

Dithienosilole- and dibenzosilole-thiophene copolymers as semiconductors for organic thin-film transistors.

The synthesis and physicochemical properties of a new class of thiophene/arenesilole-containing pi-conjugated polymers are reported. Examples of this new polymer class include the following: poly(2,5-bis(3',3' '-dihexylsilylene-2',2' '-bithieno)thiophene) (TS6T1), poly(2,5'-bis(3' ',3' ''-dihexylsilylene-2' ',2' ''-bithieno)bithiophene) (TS6T2), poly(2,5'-bis(2' ',2' ''-dioctylsilylene-1' ',1' ''-biphenyl)thiophene) (BS8T1), and poly(2,5'-bis(2' ',2' ''-dioctylsilylene-1' ',1' ''-biphenyl)bithiophene) (BS8T2). Organic field-effect transistors (OFETs) with hole carrier mobilities as high as 0.02-0.06 cm2/V s in air, low turn-on voltages, and current on/off ratios >105-106 are fabricated using solution processing techniques with the above polymers as the active channel layer. OFETs based on this polymer class exhibit excellent ambient operational stability.

Journal Article↗
PubMed2006

Fluorocarbon-modified organic semiconductors: molecular architecture, electronic, and crystal structure tuning of arene- versus fluoroarene-thiophene oligomer thin-film properties.

We present here the systematic synthesis and comparative physicochemical characterization of a series of regiochemically varied and core size extension-modulated arene(perfluoroarene)-thiophene oligomers. The molecules investigated are: 5,5''-diphenyl-2,2':5',2'':5'',2'''-quaterthiophene (1), 5,5'-bis[1-[4-(thien-2-yl)phenyl]]-2,2'-dithiophene (2), 4,4'-bis[5-(2,2'-dithiophenyl)]-biphenyl (3), 5,5''-diperfluorophenyl-2,2':5',2'':5'',2'''-quaterthiophene (4), 5,5'-bis[1-[4-(thien-2-yl)perfluorophenyl]]-2,2'-dithiophene (5), 4,4'-bis[5-(2,2'-dithiophenyl)]-perfluorobiphenyl (6), 5,5''-diperfluorophenyl-2,2':5',2''-tertthiophene (7), 5,5'-diperfluorophenyl-2,2'-dihiophene (8), and 5,5-diperfluorophenylthiophene (9). Trends in optical absorption and emission parameters, molecular structures as defined by single-crystal X-ray diffraction, as well as electrochemical redox processes are described. The morphologies and microstructures of the vapor-deposited films grown over a range of growth temperatures have also been characterized. Field-effect transistor (FET) measurements demonstrate that all of these materials are FET-active and, depending on the molecular architecture, exhibit comparably good p- or n-type mobility when optimum film microstructural order is achieved. A very large n-channel mobility of approximately 0.5 cm2/Vs with I(on)/I(off) ratios > 10(8) is achieved for films of 4.

Crystallography, X-Ray↗
PubMed2006

Gate-planarized low-operating voltage organic field-effect transistors enabled by hot polymer pressing/embedding of conducting metal lines.

A new process for fabricating patterned, gate-planarized organic field-effect transistors (OFETs) based on hot polymer pressing/embedding of conducting metal features is demonstrated. This methodology is applicable to a variety of gate conductors and polymer matrices. Vapor-deposited Al and Au and printed Ag lines as narrow as 15 mum are transferred from a substrate donor to the hot-pressed polymer, resulting in a new smooth, flat, self-planarized gate-plastic substrate composite on which thin polymer insulators can be spin-coated with great uniformity. OFETs fabricated on these structures with both p- and n-type semiconductors function at low voltages, opening new routes to printed electronic circuits and products.

Journal Article↗
PubMed2006

Strategies for electrooptic film fabrication. Influence of pyrrole-pyridine-based dibranched chromophore architecture on covalent self-assembly, thin-film microstructure, and nonlinear optical response.

The new dibranched, heterocyclic "push-pull" chromophores bis{1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane (1), 1-(pyrid-4-yl)-2-(N-methyl-5-formylpyrrol-2-yl)ethylene (2), {1-(N-methylpyridinium-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}{(1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane (3), N-methyl-2-[1-(N-methylpyrid-4-yl)ethen-2-yl]-5-[pyrid-4-yl]ethen-2-yl]pyrrole iodide (4), bis{1-(N-methyl-4-pyridinio)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane iodide (5), and N-methyl-2,5-[1-(N-methylpyrid-4-yl)ethen-2-yl]pyrrole iodide (6) have been synthesized and characterized. The neutral (1 and 2) and monomethyl salts (3 and 4) undergo chemisorptive reaction with iodobenzyl-functionalized surfaces to afford chromophore monolayers SA-1/SA-2 and SA-3/SA-4, respectively. Molecular structures and other physicochemical properties have been defined by (1)H NMR, optical spectroscopy, and XRD. Thin-film characterization by a variety of techniques (optical spectroscopy, specular X-ray reflectivity, atomic force microscopy, X-ray photoelectron spectroscopy, and angle-dependent polarized second harmonic generation) underscore the importance of the chromophore molecular architecture as well as film growth method on film microstructure and optical/electrooptic response.

Journal Article↗
PubMed2006

Monolayer to multilayer nanostructural growth transition in N-type oligothiophenes on Au(111) and implications for organic field-effect transistor performance.

The evolution in growth morphology and molecular orientation of n-type semiconducting alpha,omega-diperfluorohexyl-quaterthiophene (DFH-4T) on Au(111) is investigated by scanning tunneling microscopy and scanning tunneling spectroscopy as the film thickness is increased from one monolayer to multilayers. Monolayer-thick DFH-4T films are amorphous and morphologically featureless with a large pit density, whereas multilayer films exhibit drastically different terraced structures consisting of overlapping platelets. Large changes in DFH-4T molecular orientation are observed on transitioning from two to four monolayers. Parallel electrical characterization of top-versus-bottom contact configuration DFH-4T FETs with Au source/drain electrodes reveals greatly different mobilities (mu(TOP) = 1.1 +/- 0.2 10(-2) cm(2)V(-1)s(-1) versus mu(BOTTOM) = 2.3 +/- 0.5 10(-5) cm(2)V(-1)s(-1)) and contact resistances (R(C-TOP) = 4-12 MOmegacm vs R(C-BOTTOM) > 1 GOmegacm). This study provides important information on the organic semiconductor-source\drain electrode interfaces and explains why top-contact OFET devices typically have superior performance. By direct visualization, it demonstrates that the DFH-4T film growth transition from monolayer to multilayer on Au is accompanied by dramatic morphology and molecular orientation changes, starting from an amorphous, pitted, and disordered monolayer, to crystalline and smooth bi/tetralayers but with the molecules reoriented by 90 degrees . These chemisorption-derived inhomogenities at the contact-molecule interface and the large monolayer --> multilayer --> bulk microstructural changes are in accord with the large bottom-contact device resistance and poor OFET performance.

Electric Conductivity↗
PubMed2005

Organic nanodielectrics for low voltage carbon nanotube thin film transistors and complementary logic gates.

We report the implementation of three dimensionally cross-linked, organic nanodielectric multilayers as ultrathin gate dielectrics for a type of thin film transistor device that uses networks of single-walled carbon nanotubes as effective semiconductor thin films. Unipolar n- and p-channel devices are demonstrated by use of polymer coatings to control the behavior of the networks. Monolithically integrating these devices yields complementary logic gates. The organic multilayers provide exceptionally good gate dielectrics for these systems and allow for low voltage, low hysteresis operation. The excellent performance characteristics suggest that organic dielectrics of this general type could provide a promising path to SWNT-based thin film electronics.

Crystallography, X-Ray↗
PubMed2005

High electron mobility in solution-cast and vapor-deposited phenacyl-quaterthiophene-based field-effect transistors: toward N-type polythiophenes.

New carbonyl-functionalized quaterthiophenes, 5,5' ''-diperfluorophenylcarbonyl-2,2':5',2' ':5' ',2' ''-quaterthiophene [DFCO-4T], 5,5' ''-diphenyl-2,2':5',2' ':5' ',2' ''-quaterthiophene [DPCO-4T], and a polymer having the same basic motif as DFCO-4T, poly{1,4-bis[(3'-n-octyl-2,2'-dithiophene)carbonyl]-2,3,5,6-tetrafluorobenzene} [P(COFCO-4T)], have been synthesized, characterized, and the crystal structures of the molecules determined. Field-effect transistors fabricated with vapor-deposited and solution-cast films of DFCO-4T exhibit very high Ion:Ioff current ratios (up to 108) and electron mobilities up to approximately 0.51 and approximately 0.25 cm2.V-1.s-1, respectively. Solution-cast blends of P(COFCO-4T) and DFCO-4T (1:1 weight ratio) exhibit an electron mobility of approximately 0.01 cm2.V-1.s-1 (Ion:Ioff = 104).

Journal Article↗
PubMed2005

Incisive structure-spectroscopic correlation in oligothiophenes functionalized with (+/-) inductive/mesomeric fluorine groups: joint Raman and DFT study.

This paper presents a combined experimental Raman and density functional theory (DFT) study of a series of oligothiophenes with variable pi-core lengths and substituted at the alpha,omega- and beta,beta'-terminal positions with perfluorohexyl, perfluorohexylcarbonyl, perfluoroarene, and cyano groups. The study covers the neutral and the electrochemically oxidized samples. The spectra have been assigned with the help of B3LYP/6-31G** calculations and interpreted by the predictions of effective conjugation coordinate (ECC) theory. Direct relationships between the bond length alternation (BLA) parameters and the Raman wavenumbers of the two most important bands of the spectra have been outlined showing the collective character of their electronic and vibrational properties. It is found that the topology of the thienyl electronic structure is not uniform along the conjugated core with the external rings more aromatic, whereas for the innermost part the pi-electron delocalization is greater and extends with the increment of chain length. Perfluorohexyl substitution finely tunes the electronic properties via negative inductive effects. The beta,beta' isomers exhibit larger conformational distortion, which strongly modifies the mean conjugation length. Oxidation provokes electronic structure quinoidization spreading over the whole system but more marked in the central part of the pi-core. The Raman features associated to quinoidization in the oxidized species have been interpreted in relation to the oligomer core length and the substitution regiochemistry.

Crystallography, X-Ray↗
PubMed2005

Efficient synthesis and structural characteristics of zwitterionic twisted pi-electron system biaryls.

A series of unconventional twisted pi-electron system molecules has been synthesized via Suzuki cross-coupling of two sterically hindered arenes. Crystallographic analysis of these molecules reveals a large ring-ring dihedral twist angle (87 degrees ) and a highly charge-separated zwitterionic ground state. An efficient conversion of phenols into aryl halides is also reported. [reaction: see text]

Journal Article↗
PubMed2005

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.

Journal Article↗
PubMed2005

Sigma-pi molecular dielectric multilayers for low-voltage organic thin-film transistors.

Very thin (2.3-5.5 nm) self-assembled organic dielectric multilayers have been integrated into organic thin-film transistor structures to achieve sub-1-V operating characteristics. These new dielectrics are fabricated by means of layer-by-layer solution phase deposition of molecular silicon precursors, resulting in smooth, nanostructurally well defined, strongly adherent, thermally stable, virtually pinhole-free, organosiloxane thin films having exceptionally large electrical capacitances (up to approximately 2,500 nF.cm(-2)), excellent insulating properties (leakage current densities as low as 10(-9) A.cm(-2)), and single-layer dielectric constant (k)of approximately 16. These 3D self-assembled multilayers enable organic thin-film transistor function at very low source-drain, gate, and threshold voltages (<1 V) and are compatible with a broad variety of vapor- or solution-deposited p- and n-channel organic semiconductors.

Chemical Engineering↗
PubMed2005

Organic thin-film transistors based on carbonyl-functionalized quaterthiophenes: high mobility N-channel semiconductors and ambipolar transport.

New carbonyl-functionalized quaterthiophenes, 5, 5' ''-diheptanoyl-2,2':5',2' ':5' ',2' ''-quaterthiophene (DHCO-4T), 5, 5' ''-diperfluorohexylcarbonyl-2,2':5',2' ':5' ',2' ''-quaterthiophene (DFHCO-4T), and 2,7-[bis-(5-perfluorohexylcarbonylthien-2-yl)]-4H-cyclopenta[2,1-b:3,4-b']-dithiophen-4-one (DFHCO-4TCO) have been synthesized and characterized. Field-effect transistors fabricated with these materials exhibit high electron mobilities both in a vacuum (up to 0.6 cm2 V-1 s-1) and in air (up to 0.02 cm2 V-1 s-1) and very high Ion:Ioff currents ratios (>107). DHCO-4T is the first organic material exhibiting excellent ambipolar transport (mue/muh up to 0.1/0.01 cm2 V-1 s-1, (Ion:Ioff)e/(Ion:Ioff)h up to 107/108 for the same device) over a broad range of deposition temperatures. These materials are therefore promising for organic complementary circuits.

Journal Article↗
PubMed2005

Low operating voltage single ZnO nanowire field-effect transistors enabled by self-assembled organic gate nanodielectrics.

The development of nanowire transistors enabled by appropriate dielectrics is of great interest for flexible electronic and display applications. In this study, nanowire field-effect transistors (NW-FETs) composed of individual ZnO nanowires are fabricated using a self-assembled superlattice (SAS) as the gate insulator. The 15-nm SAS film used in this study consists of four interlinked layer-by-layer self-assembled organic monolayers and exhibits excellent insulating properties with a large specific capacitance, 180 nF/cm2, and a low leakage current density, 1 x 10(-8) A/cm2. SAS-based ZnO NW-FETs display excellent drain current saturation at Vds = 0.5 V, a threshold voltage (Vth) of -0.4 V, a channel mobility of approximately 196 cm2/V s, an on-off current ratio of approximately 10(4), and a subthreshold slope of 400 mV/dec. For comparison, ZnO NW-FETs are also fabricated using 70-nm SiO2 as the gate insulator. Implementation of the SAS gate dielectric reduces the NW-FET operating voltage dramatically with more than 1 order of magnitude enhancement of the on-current. These results strongly indicate that SAS-based ZnO NW-FETs are promising candidates for future flexible display and logic technologies.

Journal Article↗