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In this paper, we report on n-alkyl phosphonic acid (PA) self-assembled monolayer (SAM)/hafnium oxide (HfO(2)) hybrid dielectrics utilizing the advantages of SAMs for control over the dielectric/semiconductor interface with those of high-k metal oxides for low-voltage organic thin film transistors (OTFTs). By systematically varying the number of carbon atoms of the n-alkyl PA SAM from six to eighteen on HfO(2) with stable and low leakage current density, we observe how the structural nature of the SAM affects the thin-film crystal structure and morphology, and subsequent device performance of low-voltage pentacene based OTFTs. We find that two primary structural factors of the SAM play a critical role in optimizing the device electrical characteristics, namely, the order/disorder of the SAM and its physical thickness. High saturation-field-effect mobilities result at a balance between disordered SAMs to promote large pentacene grains and thick SAMs to aid in physically buffering the charge carriers in pentacene from the adverse effects of the underlying high-k oxide. Employing the appropriate n-alkyl PA SAM/HfO(2) hybrid dielectrics, pentacene-based OTFTs operate under -2.0 V with low hysteresis, on-off current ratios above 1 x 10(6), threshold voltages below -0.6 V, subthreshold slopes as low as 100 mV dec(-1), and field-effect mobilities as high as 1.8 cm(2) V(-1) s(-1).

A systematic study of six phosphonic acid (PA) self-assembled monolayers (SAMs) with tailored molecular structures is performed to evaluate their effectiveness as dielectric modifying layers in organic field-effect transistors (OFETs) and determine the relationship between SAM structural order, surface homogeneity, and surface energy in dictating device performance. SAM structures and surface properties are examined by near edge X-ray absorption fine structure (NEXAFS) spectroscopy, contact angle goniometry, and atomic force microscopy (AFM). Top-contact pentacene OFET devices are fabricated on SAM modified Si with a thermally grown oxide layer as a dielectric. For less ordered methyl- and phenyl-terminated alkyl ~(CH2)12 PA SAMs of varying surface energies, pentacene OFETs show high charge carrier mobilities up to 4.1 cm2 V−1 s−1. It is hypothesized that for these SAMs, mitigation of molecular scale roughness and subsequent control of surface homogeneity allow for large pentacene grain growth leading to high performance pentacene OFET devices. PA SAMs that contain bulky terminal groups or are highly crystalline in nature do not allow for a homogenous surface at a molecular level and result in charge carrier mobilities of 1.3 cm2 V−1 s−1 or less. For all molecules used in this study, no causal relationship between SAM surface energy and charge carrier mobility in pentacene FET devices is observed.

Low-voltage, n-type organic field effect transistors (OFETs) with simultaneously modified bottom-contact (BC) electrodes and dielectric were compared to their top-contact (TC) counterparts. The devices modified with 6-phenoxyhexylphosphonic acid (Ph6PA) self-assembled monolayer (SAM) showed similar performance, morphology, and contact resistance. Electron mobility of C60 devices were 0.212 and 0.320 cm2 V−1 s−1 and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) devices were 0.04 and 0.06 cm2 V−1 s−1 for TC and BC devices, respectively. Low contact resistance between 11 and 45 kΩ cm was found regardless of device architecture or n-type semiconductor used. This work shows it is possible to fabricate solution processable low-voltage bottom-contact devices with performance that is similar or better than their top-contact counterparts without the addition of complex and time-consuming processing steps.

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 −6 cm 2 V −1 s −1 for a wide range of channel lengths (between 12 and 80 μm). 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.

Conjugated polymers are a novel class of solution-processable semiconducting materials with intriguing optoelectronic properties. [ 1 ] They have received great attention as active components in organic electronic devices such as organic photovoltaic cells (OPVs), organic light-emitting diodes (OLEDs), and organic fi eld-effect transistors (OFETs) due to their light weight, facile tuning of electronic properties through molecular engineering, and ease of processing. The performance and lifetime of conjugated polymer-based electronic devices are critically dependent on the bulk properties of the active materials and the interfacial properties of electrode/polymer contacts. [ 2–4 ] In these devices, the electrode(s) either inject charge into or extract charges from the organic semiconductor layer(s). Mismatch of the work functions between metal or metal oxide electrodes and molecular orbital energy levels of organic semiconductors can lead to high contact resistance, which decreases the charge injection and extraction effi ciency. Therefore, it is essential to minimize contact resistance at the electrode/organic semiconductor interface. To improve charge injection/extraction across the electrode/ organic semiconductor interface, several strategies have been developed. One is to tune the interfacial dipole across the electrode/semiconductor interface to reduce the injection/collection energy barrier. This can be achieved by modifying the electrode surface with self-assembled dipolar molecules to tune the energy level alignment at the semiconductor/electrode interface. [ 5–7 ] Alternatively, the introduction of a thin layer of polymer surfactant that contains polar side chains between the conjugate polymer/electrode interface can also be used to improve the interfacial properties. The polar side chains can provide not

An efficient process is developed by spin-coating a single-component, self-assembled monolayer (SAM) to simultaneously modify the bottom-contact electrode and dielectric surfaces of organic thin-film transistors (OTFTs). This efficient interface modification is achieved using n-alkyl phosphonic acid based SAMs to prime silver bottom-contacts and hafnium oxide (HfO{sub 2}) dielectrics in low-voltage OTFTs. Surface characterization using near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), and spectroscopic ellipsometry suggest this process yields structurally well-defined phosphonate SAMs on both metal and oxide surfaces. Rational selection of the alkyl length of the SAM leads to greatly enhanced performance for both n-channel (C60) and p-channel (pentacene) based OTFTs. Specifically, SAMs of n-octylphos-phonic acid (OPA) provide both low-contact resistance at the bottom-contact electrodes and excellent interfacial properties for compact semiconductor grain growth with high carrier mobilities. OTFTs based on OPA modifi ed silver electrode/HfO{sub 2} dielectric bottom-contact structures can be operated using < 3V with low contact resistance (down to 700 Ohm-cm), low subthreshold swing (as low as 75 mV dec{sup -1}), high on/off current ratios of 107, and charge carrier mobilities as high as 4.6 and 0.8 cm{sup 2} V{supmore » -1} s{sup -1}, for C60 and pentacene, respectively. These results demonstrate that this is a simple and efficient process for improving the performance of bottom-contact OTFTs.« less

The self-assembling properties of two rationally designed discotic π-conjugated hexaazatrinaphthylene (HATNA) molecules have been studied. In appropriate solvent systems, both ester-dodecyl-substituted and amide-dodecyl-substituted HATNAs self-assembled into nanowires and formed organogels. These nanowires could be easily transferred onto solid supports through spin casting for morphological study. In addition to the solution-based self-assembly method, solvent-vapor annealing (SVA) was explored as an alternative way to control the organization of supramolecular nanowires on surfaces. It was found that amorphous thin film of HATNA molecules transformed gradually into nanowire structures through a nucleation and growth mechanism during the SVA process. Several parameters including the preordering of molecules in the original thin film, choice of solvent vapors, annealing times, and surface properties were tuned to create different supramolecular organizations. Under particular conditions, aligned nanowires with preferential direction can be achieved.

The phenyl groups of polystyrene (PS) thin films untreated and thermally treated at 80 and 120 °C assume tilt angles of 27°, 39° and 62°, respectively. The PS films were inserted between SiO 2 and organic semiconductors as buffer layers for organic thin-film transistors (OTFTs). The results showed that a flat orientation of phenyl ring at the surface of the PS films optimized the surface energy of PS film, resulting in higher crystallinity of pentacene films deposited onto it and an improved interconnection between the pentacene crystalline domains. The device with the PS film thermally treated at 120 °C showed superior performance, affording a mobility as high as 4 cm 2 /V s, an on/off ratio of about 10 7 –10 8 and a threshold voltage of about 6.5 V in the saturation region.

High dielectric constant (k) metal oxides such as hafnium oxide (HfO2) have gained significant interest due to their applications in microelectronics. In order to study and control the surface properties of hafnium oxide, self-assembled monolayers (SAMs) of four different long aliphatic molecules with binding groups of phosphonic acid, carboxylic acid, and catechol were formed and characterized. Surface modification was performed to improve the interface between metal oxide and top deposited materials as well as to create suitable dielectric properties, that is, leakage current and capacitance densities, which are important in organic thin film transistors. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, contact angle goniometry, atomic force microscopy (AFM), and simple metal-HfO2-SAM-metal devices were used to characterize the surfaces before and after SAM modification on sol-gel processed hafnium oxide. The alkylphosphonic acid provided the best monolayer formation on sol-gel processed hafnium oxide to generate a well-packed, ultrathin dielectric exhibiting a low leakage current density of 2x10(-8) A/cm2 at an applied voltage of -2.0 V and high capacitance density of 0.55 microF/cm2 at 10 kHz. Dialkylcatechol showed similar characteristics and the potential for using the catechol SAMs to modify HfO2 surfaces. In addition, the integration of this alkylphosphonic acid SAM/hafnium oxide hybrid dielectric into pentacene-based thin film transistors yields low-voltage operation within 1.5 V and improved performance over bare hafnium oxide.

A low band gap polymer based on the copolymerization between benzodithiophene and thieno-pyrroledione units has been investigated in both conventional and inverted polymer bulk-heterojunction photovoltaic cells. High power conversion efficiencies of more than 4% in both device structures were demonstrated.

Two amorphous fullerenes, TPA-PCBM and MF-PCBM, have been developed as efficient electron acceptors to induce a highly stable morphology of active layer in polymer photovoltaic devices. The power conversion efficiency (PCE) of devices using both materials show no degradation, even after 10 h annealing at 150 °C.

Both high charge carrier mobility in OFETs and high power conversion efficiency in solar cells were demonstrated in a series of amorphous metallated π-conjugated polymers. The best solar cell performance is based on a high field-effect mobility (μh = 1.0 × 10−2 cm2 V−1 s−1) polymer blended with PC71BM leading to a power conversion efficiency of PCE = 4.13%.

A new organic semiconductor (BT-TTF) based on molecular moieties of benzothiadiazole and tetrathiafulvalene was designed and synthesized, and its structure, molecular packing and charge-transporting properties were determined. Thermal properties, electrochemical behaviors, and optical absorption of this molecule were studied by using differential scanning calorimetry/thermal gravimetric analysis, cyclic voltammetry, and ultraviolet-visible spectroscopy, respectively. Its bulk and nanowire single crystals were prepared and characterized by X-ray crystallography, scanning electron microscopy, transmission electron microscopy, and field-effect transistors. It is found that short intermolecular S···S (3.41 Å), S···C (3.49 Å), and S···N (3.05 Å) contacts define the solid-state structure of BT-TTF single crystals which π-stack along the [100] with interplanar distances of 3.49 Å. Solvent-cast single-crystal nanowire transistors showed mobilities as large as 0.36 cm2/(V s) with current on/off ratios of 1×10(6). This study further illustrates the impact of molecular design and a demonstration of high-performance single-crystal nanowire transistors from the resulting semiconductor.

Ultra-thin self-assembled monolayer (SAM)-oxide hybrid dielectrics have gained significant interest for their application in low-voltage organic thin film transistors (OTFTs). A [8-(11-phenoxy-undecyloxy)-octyl]phosphonic acid (PhO-19-PA) SAM on ultrathin AlO x (2.5 nm) has been developed to significantly enhance the dielectric performance of inorganic oxides through reduction of leakage current while maintaining similar capacitance to the underlying oxide structure. Rapid processing of this SAM in ambient conditions is achieved by spin coating, however, as-cast monolayer density is not sufficient for dielectric applications. Thermal annealing of a bulk spun-cast PhO-19-PA molecular film is explored as a mechanism for SAM densification. SAM density, or surface coverage, and order are examined as a function of annealing temperature. These SAM characteristics are probed through atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure spectroscopy (NEXAFS). It is found that at temperatures sufficient to melt the as-cast bulk molecular film, SAM densification is achieved; leading to a rapid processing technique for high performance SAM-oxide hybrid dielectric systems utilizing a single wet processing step. To demonstrate low-voltage devices based on this hybrid dielectric (with leakage current density of 7.7 × 10 −8 A cm −2 and capacitance density of 0.62 μF cm −2 at 3 V), pentacene thin-film transistors (OTFTs) are fabricated and yield sub 2 V operation and charge carrier mobilites of up to 1.1 cm 2 V −1 s −1 .

Insulating and semiconducting molecular phosphonic acid (PA) self-assembled monolayers (SAMs) have been developed for applications in organic field-effect transistors (OFETs) for low-power, low-cost flexible electronics. Multifunctional SAMs on ultrathin metal oxides, such as hafnium oxide and aluminum oxide, are shown to enable (1) low-voltage (sub 2 V) OFETs through dielectric and interface engineering on rigid and plastic substrates, (2) simultaneous one-component modification of source-drain and dielectric surfaces in bottom-contact OFETs, and (3) SAM-FETs based on molecular monolayer semiconductors. The combination of excellent dielectric and interfacial properties results in high-performance OFETs with low-subthreshold slopes down to 75 mV dec(-1), high I(on)/I(off) ratios of 10(5)-10(7), contact resistance down to 700 Ω cm, charge carrier mobilities of 0.1-4.6 cm(2) V(-1) s(-1), and general applicability to solution-processed and vacuum-deposited n-type and p-type organic and polymer semiconductors.

The impact of thermally active molecular rotational and translational relaxation modes on the friction dissipation process involving smooth nano-asperity contacts has been studied by atomic force microscopy, using the widely known Eyring analysis and a recently introduced method, dubbed intrinsic friction analysis. Two distinctly different model systems, i.e., monolayers of octadecyl-phosphonic acid (ODPA) and thin films of poly(tert-butyl acrylate) (PtBA) were investigated regarding shear-rate critical dissipation phenomena originating from diverging mode coupling behaviors between the external shear perturbation and the internal molecular modes of relaxation. Rapidly (ODPA) versus slowly (PtBA) relaxing systems, in comparison to the sliding rate, revealed monotonous logarithmic and nonmonotonous spectral shear rate dependences, respectively. Shear coupled, enthalpic activation energies of 46 kJ/mol for ODPA and of 35 and ∼65 kJ/mol for PtBA (below and above the glass transition) were found that could be attributed to intrinsic modes of relaxations. Also, entropic energies involved in the cooperative backbone mobility of PtBA could be quantified, dwarfing the activation energy by more than a factor of five. This study provides (i) a material specific understanding of the molecular scale dissipation process in shear compliant substances, (ii) analyses of material intrinsic shear-rate mode coupling, shear coordination and energetics, (iii) a verification of Eyring's model applied to tribological systems toward material intrinsic specificity, and (iv) a valuable extension of the Eyring analysis for complex macromolecular systems that are slowly relaxing, and thus, exhibit shear-rate mode coupling.

An efficient process is developed for modifying Si with self-assembled monolayers (SAMs) through in situ metal oxide surface activation and microcontact printing or spin-coating of phosphonic-acid-based molecules. The utility of this process is demonstrated by fabricating self-organized and solution-processed low-voltage organic thin-film transistors enabled by patterned and spin-cast phosphonate SAM/metal oxide hybrid dielectrics.

An efficient process is developed by spin-coating a single-component, self-assembled monolayer (SAM) to simultaneously modify the bottom-contact electrode and dielectric surfaces of organic thin-film transistors (OTFTs). This effi cient interface modifi cation is achieved using n-alkyl phosphonic acid based SAMs to prime silver bottom-contacts and hafnium oxide (HfO2) dielectrics in low-voltage OTFTs. Surface characterization using near edge X-ray absorption fi ne structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), and spectroscopic ellipsometry suggest this process yields structurally well-defi ned phosphonate SAMs on both metal and oxide surfaces. Rational selection of the alkyl length of the SAM leads to greatly enhanced performance for both n-channel (C60) and p-channel (pentacene) based OTFTs. Specifi cally, SAMs of n-octylphos-phonic acid (OPA) provide both low-contact resistance at the bottom-contact electrodes and excellent interfacial properties for compact semiconductor grain growth with high carrier mobilities. OTFTs based on OPA modifi ed silver electrode/HfO2 dielectric bottom-contact structures can be operated using < 3V with low contact resistance (down to 700 Ohm-cm), low subthreshold swing (as low as 75 mV dec−1), high on/off current ratios of 107, and charge carrier mobilities as high as 4.6 and 0.8 cm2 V−1 s−1, for C60 and pentacene, respectively. These results demonstrate that this is a simple and efficient process for improving the performance of bottom-contact OTFTs.

A series of low band-gap conjugated polymers (PDTC, PDTSi and PDTP) containing electron-rich C-, Si-, and N-bridged bithiophene and electron-deficient thienopyrroledione units were synthesized viaStille coupling polymerization. All these polymers possess a low-lying energy level for the highest occupied molecular orbital (HOMO) (as low as −5.44 eV). As a result, photovoltaic devices derived from these polymers show high open circuit voltage (Voc as high as 0.91 V). These rigid polymers also possess respectable hole mobilities of 1.50 × 10−3, 6.0 × 10−4, and 3.9 × 10−4 cm2 V−1s−1 for PDTC, PDTSi, and PDTP, respectively. The combined high Voc and good hole mobility enable bulk hetero-junction photovoltaic cells to be fabricated with relatively high power conversion efficiency (PCE as high as 3.74% for the PDTC-based device).

Reversible switching characteristics of organic nonvolatile memory transistors (ONVMTs) using chemically synthesized graphene oxide (GO) nanosheets as a charge-trapping layer are reported. The transfer curves of GO based ONVMTs showed large gate bias dependent hysteresis with threshold voltage shifts over 20 V. After writing and erasing, stored data were well maintained showing more than two orders of ON/OFF ratio (ION/IOFF=∼102) for 104 s. These results suggest that GO nanosheets are one potential candidate as the charge-trapping layer in ONVMTs.

Precise control over the threshold voltage of pentacene-based organic thin film transistors was achieved by inserting a genetically engineered quartz-binding polypeptide at the semiconductor-dielectric interface. A 30 V range was accessed with the same peptide by adjusting the pH of the solution for peptide assembly while leaving other device properties unaffected. Mobility of 0.1–0.2 cm2 V−1 s−1 and on/off current ratio of >106 could be achieved for all devices regardless of the presence of the neutral peptide or the peptide assembled in acidic or basic conditions. This shift in threshold voltages is explained by the generation of charged species and dipoles due to variation in assembling conditions. Controlling device characteristics such as threshold voltage is essential for integration of transistors into electronic circuits.

Low-voltage pentacene-based organic thin film transistors (OTFTs) are demonstrated with polystyrene (PS)/hafnium oxide (HfOx) hybrid dielectrics. Thermal annealing of PS films on HfOx at 120 °C (PS-120) induces a flatter orientation of the phenyl groups (tilt angle 65°) at the surface compared to PS films without annealing (PS-RT) (tilt angle 31°). The flatter phenyl group orientation leads to better matching of surface energy between pentacene and PS. Pentacene deposited on PS-120 display higher quality thin films with larger grain sizes and higher crystallinity. Pentacene OTFTs with PS-120/HfOx hybrid dielectrics can operate at low-voltage (

A vacuum-free solution processed hybrid dielectric composed of an n-octadecyl-phosphonic acid self-assembled monolayer on amorphous sol-gel processed hafnium oxide (HfOx) is demonstrated for low-voltage polymer semiconductor-based thin film transistors (TFTs). The phosphonic acid/HfOx hybrid dielectric provides high capacitance (0.41 μF/cm2), low leakage current (5×10−8 A/cm2), and is compatible with plastic substrates. The utility of this dielectric is demonstrated by fabricating high performance polymer TFTs based on a spin coated thiophene-thiazolothiazole copolymer with operating voltages under −2 V, negligible hysteresis, subthreshold slopes as low as 100 mV/dec, and hole mobilities up to 0.11 cm2 V s.

A vacuum-free solution processed hybrid dielectric composed of an anthryl-alkyl-phosphonic acid (π-σ-PA) self-assembled monolayer on an amorphous sol–gel processed hafnium oxide (HfOx) is demonstrated for low-voltage organic thin film transistors (OTFTs) on plastic substrates. The π-σ-PA/HfOx hybrid dielectric provides high capacitance (0.54 µF cm−2) and low leakage current (2 × 10−8 A cm−2), and has a chemically and electrically compatible dielectric interface for evaporated and solution processed acene semiconductors. The utility of this dielectric is demonstrated by fabricating pentacene and 6,13-bis(triisopropyl-silylethynyl) pentacene (TIPS-PEN) based OTFTs with operating voltages under 2 V, subthreshold slopes as low as 100 mV dec−1, and average mobilities of 0.32 cm2 V−1 s−1 and 0.38 cm2 V−1 s−1, for pentacene and TIPS-PEN, respectively.

C60-based organic thin film transistors (OTFTs) have been fabricated using a n-octadecylphosphonic acid self-assembled monolayer/sol-gel processed hafnium oxide hybrid dielectric. With the combination of high capacitance (580 nF/cm2) and low leakage current density (8×10−9 A/cm2), this hybrid dielectric yields C60 OTFTs operating under 1.5 V with an average n-channel saturation field-effect mobility of 0.28 cm2/V s, high on-off current ratio of 105, and low subthreshold slope of 100 mV/decade. The low surface energy of the n-octadecylphosphonic acid allows C60 to form a thin film with large grains that provide an efficient charge carrier pathway for the low-voltage OTFTs.

Pentacene-based organic thin-film transistors (OTFTs) have been fabricated using π-σ-phosphonic acid self-assembled monolayers (SAMs) on top of aluminum oxide as the gate dielectrics. With ultrathin dielectrics, high capacitances up to 760nF∕cm2 and low leakage current densities of 10−8A∕cm2 at 2V could be obtained, allowing operation of OTFTs within −3V. Vast improvements in the gate leakage current (∼2 orders), on/off current ratio (1 order), and subthreshold slope down to 85mV∕decade are achieved compared to control devices without SAMs. The OTFTs with pentacene vapor deposited at room temperature on SAM dielectrics-modified substrates exhibit mobilities of 0.14–0.30cm2∕Vs, on/off current ratios of 105, and threshold voltages of −(1.3–1.5)V.

We report improved device performance of poly(3-hexylthiophene) (P3HT) and [6,6]phenyl C61butyric acid methyl ester (PCBM)-based inverted bulk-heterojunction (BHJ) solar cells through the modified interface of the TiO2/BHJ with a series of carboxylic acid functionalized self-assembled monolayers (SAMs). The SAMs reduce the series resistance and improve the shunt resistance of the cell leading to increased fill factor and photocurrent density. Different aspects of device improvement can be affected depending on the nature of the SAMs. Modification with a C60-SAM shows the largest enhancement leading to a 35% improvement (η = 3.78%) over unmodified inverted devices (η = 2.80%). This SAM serves multiple functions to affect the photoinduced charge transfer at the interface to reduce the recombination of charges, passivation of inorganic surface trap states, improve the exciton dissociation efficiency at the polymer/TiO2 interface as well as a template to influence the overlayer BHJ distribution of phases, morphology and crystallinity leading to better charge selectivity and improved solar cell performance.