Self-assembled Monolayer Field-effect Transistors Research Articles

Oligothiophene Phosphonic Acids for Self-Assembled Monolayer Field-Effect Transistors.

Semiconducting self-assembled monolayers (SAMs) represent highly relevant components for the fabrication of organic thin-film electronics because they enable the precise formation of active π-conjugates in terms of orientation and layer thickness. In this work, we demonstrate self-assembled monolayer field-effect transistors (SAMFETs) composed of phosphonic acid oligomers of 3-hexylthiophene (oligothiophenes-OT) with systematic variations of thiophene repeating units (5, 10, and 20). The devices exhibit stable lateral charge transport with increased mobility as a function of thiophene unit counts. Importantly, our work reveals the packing and intermolecular order of varied-chain-length SAMs at the molecular scale via X-ray reflectivity (XRR) and quantitative X-ray photoelectron spectroscopy (XPS). Short oligomers (OT5-PA and OT10-PA) arrange almost perpendicular to the substrate, forming highly ordered SAMs, whereas the long-chain OT20-PA exhibits a folded structure. By tuning the molecular order in the monolayers via the SAM substitution reaction, the OT20-PA devices show a tripling in mobility.

Effect of Structure and Disorder on the Charge Transport in Defined Self-Assembled Monolayers of Organic Semiconductors.

Self-assembled monolayer field-effect transistors (SAMFETs) are not only a promising type of organic electronic device but also allow detailed analyses of structure-property correlations. The influence of the morphology on the charge transport is particularly pronounced, due to the confined monolayer of 2D-π-stacked organic semiconductor molecules. The morphology, in turn, is governed by relatively weak van-der-Waals interactions and is thus prone to dynamic structural fluctuations. Accordingly, combining electronic and physical characterization and time-averaged X-ray analyses with the dynamic information available at atomic resolution from simulations allows us to characterize self-assembled monolayer (SAM) based devices in great detail. For this purpose, we have constructed transistors based on SAMs of two molecules that consist of the organic p-type semiconductor benzothieno[3,2-b][1]benzothiophene (BTBT), linked to a C11 or C12 alkylphosphonic acid. Both molecules form ordered SAMs; however, our experiments show that the size of the crystalline domains and the charge-transport properties vary considerably in the two systems. These findings were confirmed by molecular dynamics (MD) simulations and semiempirical molecular-orbital electronic-structure calculations, performed on snapshots from the MD simulations at different times, revealing, in atomistic detail, how the charge transport in organic semiconductors is influenced and limited by dynamic disorder.

Self-assembled monolayer field-effect transistors based on oligo-9,9'-dioctylfluorene phosphonic acids.

The use of functional oligomers of π-conjugated oligofluorenes led to a region-selective assembly of amorphous monolayers which exhibit robust lateral charge transport pathways in self-assembled monolayer field-effect transistors over long distances and even in mixed monolayers of semiconducting and insulating molecules. This oligomer concept might stimulate a new molecular design of self-assembling semiconducting materials.

Enhanced Performance of Self‐Assembled Monolayer Field‐Effect Transistors with Top‐Contact Geometry through Molecular Tailoring, Heated Assembly, and Thermal Annealing

Low‐voltage self‐assembled monolayer field‐effect transistors (SAMFETs) that operate under an applied bias of less than −3 V and a high hole mobility of 10−2 cm2 V−1 s−1 are reported. A self‐assembled monolayer (SAM) with a quaterthiophene semiconducting core and a phosphonic acid binding group is used to fabricate SAMFETs on both high‐voltage (AlOx/300 nm SiO2) and low‐voltage (HfO2) dielectric platforms. High performance is achieved through enhanced SAM packing density via a heated assembly process and through improved electrical contact between SAM semiconductor and metal electrodes. Enhanced electrical contact is obtained by utilizing a functional methylthio head group combined with thermal annealing post gold source/drain electrode deposition to facilitate the interaction between SAM and electrode.

Tuning the molecular order of C60-based self-assembled monolayers in field-effect transistors.

The control of order in organic semiconductor systems is crucial to achieve desired properties in electronic devices. We have studied the order in fullerene functionalized self-assembled monolayers by mixing the active molecules with supporting alkyl phosphonic acids of different chain length. By adjusting the length of the molecules, structural modifications of the alignment of the C60 head groups within the SAM can be tuned in a controlled way. These changes on the sub-nanometre scale were analysed by grazing incidence X-ray diffraction and X-ray reflectivity. To study the electron transport properties across these layers, self-assembled monolayer field-effect transistors (SAMFETs) were fabricated containing only the single fullerene monolayer as semiconductor. Electrical measurements revealed that a high 2D crystalline order is not the only important aspect. If the fullerene head groups are too confined by the supporting alkyl phosphonic acid molecules, defects in the crystalline C60 film, such as grain boundaries, start to strongly limit the charge transport properties. By close interpretation of the results of structural investigations and correlating them to the results of electrical characterization, an optimum chain length of the supporting alkyl phosphonic acids in the range of C10 was determined. With this study we show that minor changes in the order on the sub-nanometre scale, can strongly influence electronic properties of functional self-assembled monolayers.

Trichlorosilanes as Anchoring Groups for Phenylene‐Thiophene Molecular Monolayer Field Effect Transistors

Self assembled monolayer field effect transistors (SAMFETs) are reported using a phenylene‐thiophene containing semiconducting mesogen attached through a trichlorosilane anchoring group. Monolayer films, covalently attached to silicon dioxide substrates, form in less than 10 h from solution, thanks to the accelerated reaction of the trichlorosilane anchor. Devices exhibit mobilities as high as 1.7 × 10−2 cm2 V−1 s−1, currents of up to 15 μA (on/off current ratio of 106) with device yields close to unity over large areas for channel lengths up to 100 μm.

Self-assembled organic semiconductors for monolayer field-effect transistors

Recent data on the structures and properties of self-organized molecules used for the production of the semiconducting layer in self-assembled organic monolayer field-effect transistors are reviewed. Methods for fabrication of these transistors are presented together with their advantages and shortcomings. Electric characteristics of the produced devices are compared. Major structural regularities for selection of the reactive group in self-organized semiconductor oligomer molecules are elucidated with respect to the type of substrate.

Simulating "soft" electronics.

Simulating electronic devices built from flexible organic molecules requires both adequate conformational sampling and a reliable quantum mechanical description of the electronics of the system. The former is best achieved using classical (force field) molecular-dynamics simulations, from which individual geometries (“snapshots”) can be used for subsequent quantum mechanical calculations. As the repeating unit in the classical simulations typically involves thousands of atoms, the quantum mechanical techniques must also be able to handle many thousands of atoms quickly and effectively on modern parallel hardware. The newly developed EMPIRE program has been used in such a scheme to perform simulations on self-assembled-monolayer field-effect transistors (SAMFETs). Calculations of the size needed require novel interpretation and post-processing techniques based on local properties calculated on grids, rather than the more traditional population analyses. The results of simulations using the techniques described above will be presented and the algorithms and parallelization strategies implemented to be able to calculate as many as 100,000 atoms on 1,024 cores.

Region-Selective Self-Assembly of Functionalized Carbon Allotropes from Solution

Approaches for the selective self-assembly of functionalized carbon allotropes from solution are developed and validated for 0D-fullerenes, 1D-carbon nanotubes and 2D-graphene. By choosing the right molecular interaction of self-assembled monolayers (serving the surface) with the functionalization features of carbon materials, which provide the solubility but also serve the driving force for assembly, we demonstrate a region-selective and self-terminating assembly of the materials. Active layers of the carbon allotropes can be selectively deposited in the channel region of thin-film transistor (TFT) devices by this approach. As an example for a 0D system, molecules of C60 functionalized octadecylphosphonic acids are used to realize self-assembled monolayer field-effect transistors (SAMFETs) based on a selective molecular exchange reaction of stearic acid in the channel region. For noncovalently functionalized single-walled carbon nanotubes (SWCNTs) and graphene oxide (GO) flakes, the electrostatic Coulomb interactions between the functional groups of the carbon allotropes and the charged head groups of a SAM dielectric layer are utilized to implement the selective deposition.

Oligothiophene-based monolayer field-effect transistors prepared by Langmuir-Blodgett technique

Quinquethiophene-based monolayer organic field-effect transistors (OFETs) prepared by Langmuir-Blodgett (LB) technique show hole mobilities up to 10−2 cm2/Vs and On/Off ratios up to 106. Functional logic LB monolayer devices operating in air have been demonstrated. The performance of LB OFETs is comparable to self-assembled monolayer field-effect transistors (SAMFETs) devices prepared by self-assembly from solution using the same organosilicon oligothiophene despite the LB OFET monolayer is weakly bounded to the dielectric surface. Taking into account that the LB technique is a fast and rather easy process, these findings highlight a high potential of LB technique for ultrathin organic electronics.

Low‐Voltage Self‐Assembled Monolayer Field‐Effect Transistors on Flexible Substrates

Self-assembled monolayer field-effect transistors (SAMFETs) of BTBT functionalized phosphonic acids are fabricated. The molecular design enables device operation with charge carrier mobilities up to 10(-2) cm(2) V(-1) s(-1) and for the first time SAMFETs which operate on rough, flexible PEN substrates even under mechanical substrate bending.

Improving the Charge Transport in Self-Assembled Monolayer Field-Effect Transistors: From Theory to Devices

A three-pronged approach has been used to design rational improvements in self-assembled monolayer field-effect transistors: classical molecular dynamics (MD) simulations to investigate atomistic structure, large-scale quantum mechanical (QM) calculations for electronic properties, and device fabrication and characterization as the ultimate goal. The MD simulations reveal the effect of using two-component monolayers to achieve intact dielectric insulating layers and a well-defined semiconductor channel. The QM calculations identify improved conduction paths in the monolayers that consist of an optimum mixing ratio of the components. These results have been used both to confirm the predictions of the calculations and to optimize real devices. Monolayers were characterized with X-ray reflectivity measurements and by electronic characterization of complete devices.

N-Type self-assembled monolayer field-effect transistors for flexible organic electronics

Within this work we present n-type self-assembled monolayer field-effect transistors (SAMFETs) based on a novel perylene bisimide. The molecule spontaneously forms a covalently fixed monolayer on top of an aluminium oxide dielectric via a phosphonic acid anchor group. Detailed studies revealed an amorphous, two-dimensional semiconducting sheet on top of the dielectric. Reliable transistors with electron mobilities on the order of 10−3cm2/Vs with limited hysteresis were achieved on rigid as well on flexible substrates. Furthermore, a flexible NMOS-bias inverter based on SAMFETs is demonstrated for the first time.

N‐Type Self‐Assembled Monolayer Field‐Effect Transistors and Complementary Inverters

AbstractThis work describes n‐type self‐assembled monolayer field‐effect transistors (SAMFETs) based on a perylene derivative which is covalently fixed to an aluminum oxide dielectric via a phosphonic acid linker. N‐type SAMFETs spontaneously formed by a single layer of active molecules are demonstrated for transistor channel length up to 100 μm. Highly reproducible transistors with electron mobilities of 1.5 × 10−3 cm2 V−1 s−1 and on/off current ratios up to 105 are obtained. By implementing n‐type and p‐type transistors in one device, a complimentary inverter based solely on SAMFETs is demonstrated for the first time.

Spin cast self-assembled monolayer field effect transistors

Top-contact self-assembled monolayer field-effect transistors (SAMFETs) were fabricated through both spin-coating and solution assembly of a semiconducting phosphonic acid-based molecule (11-(5⁗-butyl-[2,2′;5′,2″;5″,2‴;5‴,2⁗]quinquethiophen-5-yl)undecylphosphonic acid) (BQT-PA). The field-effect mobilities of both spin-cast and solution assembled SAMFETs were 1.1–8.0×10−6cm2V−1s−1 for a wide range of channel lengths (between 12 and 80μm). The molecular monolayers were characterized by atomic force microscopy (AFM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was found that the BQT-PA monolayer films exhibit dense surface coverage, bidentate binding, and tilt angles of ∼32° and ∼44° for the thiophene rings and alkyl chain, respectively. These results indicate that rapid throughput of fabricating SAMFETs is possible even by spin-coating.

Low-Voltage p- and n-Type Organic Self-Assembled Monolayer Field Effect Transistors

We report on p- and n-type organic self-assembled monolayer field effect transistors. On the base of quaterthiophene and fullerene units, multifunctional molecules were synthesized, which have the ability to self-assemble and provide multifunctional monolayers. The self-assembly approach, based on phosphonic acids, is very robust and allows the fabrication of functional devices even on larger areas. The p- and n-type transistor devices with only one molecular active layer were demonstrated for transistor channel lengths up to 10 μm. The monolayer composition is proven by electrical experiments and by high-resolution transmission electron microscopy, electron energy loss spectroscopy, XPS, and AFM experiments. Because of the molecular design and the contribution of isolating alkyl chains to the hybrid dielectric, our devices operate at low supply voltages (-4 V to +4 V), which is a key requirement for practical use and simplifies the integration in standard applications. The monolayer devices operate in ambient air and show hole and electron mobilities of 10(-5) cm(2)/(V s) and 10(-4) cm(2)/(V s) respectively. In particular the n-type operation of self-assembled monolayer transistors has not been reported before. Hereby, structure-property relations of the SAMs have been studied. Furthermore an approach to protect the sensitive C(60) from immediate degradation within the molecular design is provided.

Gas sensing with self-assembled monolayer field-effect transistors

A new sensitive gas sensor based on a self-assembled monolayer field-effect transistor (SAMFET) was used to detect the biomarker nitric oxide. A SAMFET based sensor is highly sensitive because the analyte and the active channel are separated by only one monolayer. SAMFETs were functionalised for direct NO detection using iron porphyrin as a specific receptor. Upon exposure to NO a threshold voltage shift towards positive gate biases was observed. The sensor response was examined as a function of NO concentration. High sensitivity has been demonstrated by detection of ppb concentrations of NO. Preliminary measurements have been performed to determine the selectivity.

Monolayer coverage and channel length set the mobility in self-assembled monolayer field-effect transistors

The mobility of self-assembled monolayer field-effect transistors (SAMFETs) traditionally decreases dramatically with increasing channel length. Recently, however, SAMFETs using liquid-crystalline molecules have been shown to have bulk-like mobilities that are virtually independent of channel length. Here, we reconcile these scaling relations by showing that the mobility in liquid crystalline SAMFETs depends exponentially on the channel length only when the monolayer is incomplete. We explain this dependence both numerically and analytically, and show that charge transport is not affected by carrier injection, grain boundaries or conducting island size. At partial coverage, that is when the monolayer is incomplete, liquid-crystalline SAMFETs thus form a unique model system to study size-dependent conductance originating from charge percolation in two dimensions.

Evaluations and Considerations for Self-Assembled Monolayer Field-Effect Transistors

We elucidate the key chemical and physical requirements necessary for the future successful design and fabrication of molecular field-effect devices. We show that the molecular assembly, device fabrication, and electrical measurements of reported self-assembled monolayer field-effect transistors (SAMFETs) cannot be reproduced. Carrier tunneling and device electrostatics place minimum molecular lengths of L > 2.5−3 nm and minimum gate dielectric thickness tdielectric ≲ L/1.5 for such devices. In conflict with reported SAMFET device characteristics, for the values of L and tdielectric in these structures, it is fundamentally impossible to either turn the devices off or to obtain a significant field-effect. Synthesis, assembly, and characterization of functionalized molecular systems and fabrication and characterization of appropriately scaled device structures may enable the successful preparation of a molecular field-effect transistor.