The origins in the transformation of ambipolar to n-type pentacene-based organic field-effect transistors

With aluminum (Al) source–drain electrodes, the transfer characteristics of pentacene-based organic field-effect transistors (OFETs) change from ambipolar to n-type after 24 h of storage in a nitrogen-filled glove box Chang et al. (2011) [16]. The time-dependent decrease of hole current is associated with the interfacial reaction at the Al source–drain electrodes and pentacene, which was studied by in-situ ultraviolet photoemission spectroscopy and X-ray photoelectron spectroscopy in this work. Experimental results indicate that the interface of the Al and pentacene is partially oxidized, but the similar oxidation was not observed at the interface of the pentacene and silver. The time-dependent oxidization of Al and pentacene creates an interfacial barrier to suppress the hole injection from Al electrodes (extraction of electrons from pentacene). However, it shows minor effect in the injection of electrons from Al electrode. Since the rate of oxidation is related to the contact area of the pentacene and Al, co-evaporating a thin Al:pentacene interlayer between the pentacene and Al electrodes expands the contact surface and accelerates the reaction, which is suitable for the fabrication of n-type only pentacene-based OFETs. This study highlights the impact of the interfacial reaction in Al/pentacene interface for the transformation of ambipolar to n-type OFETs.     

Insight into the charge transport and degradation mechanisms in organic transistors operating at elevated temperatures in air

Operational stability of organic devices at above-room-temperatures in ambient environment is of imminent practical importance. In this report, we have investigated the charge transport and degradation mechanisms in pentacene based organic field effect transistors (OFETs) operating in the temperatures ranging from 25 °C to 150 °C under ambient conditions. The thin film characterizations techniques (X-ray photoelectron spectroscopy, X-ray diffraction and atomic force microscopy) were used to establish the structural and chemical stability of pentacene thin films at temperatures up to 150 °C in ambient conditions. The electrical behavior of OFETs varies differently in different temperature bracket. Mobility, at temperatures below 110 °C, is found to be thermally activated in presence of traps and temperature independent in absence of traps. At temperatures above 110 °C mobility degrades due to polymorphism in pentacene or interfacial properties. The degradation of mobility is compensated with the decrease in threshold voltage at high temperatures and OFETs are operational at temperatures as high as 190 °C. 70 °C has been identified as the optimum temperature of operation for our OFETs where both device behavior and material properties are stable enough to ensure sustainable performance.     

Effects of thin film processing on pentacene/C60 bilayer solar cell performance

Solar cells based on pentacene/C₆₀ bilayer heterojunctions have been fabricated with a structure of ITO/poly(styrenesulfonate) (PEDOT:PSS)/pentacene (40 nm)/fullerene (C₆₀)(40 nm)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) (10 nm)/Al. The effect of pentacene crystalline domain size on performance was investigated by controlling the pentacene deposition rate. The devices show improved light-to-electricity conversion efficiencies from 0.49% to 1.12% under an AM 1.5 solar simulator (100 mW/cm²), when the pentacene evaporation rate is in a range of 5 Å/s–0.5 Å/s. Atomic force microscopy (AFM) measurements show that the pentacene films deposited by a slow evaporation rate have larger crystalline domains and a fewer amorphous domains, compared to films obtained by faster evaporation rates. Upon thermal annealing at 200 °C for 1 min, there is merging of pentacene crystalline domains. These changes in film morphology impact the charge separation at the donor/acceptor interface and the hole and electron mobilities, and hence, directly affect the device performance.     

Self-assembled monolayers mediated charge injection for high performance bottom-contact poly(3,3′′′-didodecylquaterthiophene) thin-film transistors

Device performance of bottom-contact poly(3,3′′′-didodecylquaterthiophene) (PQT-12) thin-film transistors (TFTs) was significantly improved via surface-modification of Au source–drain (S–D) electrodes with 1-decanethiol and 1H,1H,2H,2H-perfluorodecanethiol self-assembled monolayers (SAMs). By improving the PQT-12 morphology and modulating the Schottky barrier at electrode/PQT-12 contacts, the thiol SAMs chemisorbed onto Au surfaces can improve the charge carrier injection at electrode/PQT-12 contacts and result in dramatic enhancements in device mobilities. Device mobilities up to 0.09 and 0.19 cm² V⁻¹ s⁻¹ were obtained in high performance bottom-contact PQT-12 TFTs with 1-decanethiol and 1H,1H,2H,2H-perfluorodecanethiol SAMs surface-modified Au S–D electrodes, compared with 0.015 cm² V⁻¹ s⁻¹ in PQT-12 TFTs with bare Au electrodes. This work may provide a simple path to the fabrication of high performance, low-cost, and solution-processable bottom-contact OTFTs using fine lithography technology.     

Electronic structure of the pentacene–gold interface: A density-functional theory study

The structural and electronic properties of a pentacene monolayer adsorbed on the Au(1 1 1) surface have been studied with a density-functional theory (DFT) approach. A thermally stable adsorption geometry of the pentacene monolayer on the gold surface is found, from which the adsorption energy per pentacene molecule can be evaluated. Our results illustrate how the electron charge distribution initially present over the clean gold surface is pushed back upon adsorption of the pentacene monolayer; this push-back (pillow effect) leads to a significant work-function decrease for the modified gold surface. The electronic couplings between the highest occupied molecular orbital of pentacene and the Au(1 1 1) surface and between adjacent pentacene molecules within the monolayer, were extracted from the calculated band structures; the pentacene–gold surface electronic coupling is found to be about five times smaller than the electronic coupling between pentacene molecules.     

Organic field-effect transistors based on low-temperature processable transparent polymer dielectrics with low leakage current

A solution-based transparent polymer was investigated as the gate dielectric for organic field-effect transistors (OFETs). Organic thin films (400 nm) are readily fabricated by spin-coating a polyhydrazide solution under ambient conditions on the ITO substrates, followed by annealing at a low temperature (120 °C). The smooth transparent dielectrics exhibited excellent insulating properties with very low leakage current densities of ～10^?8 A/cm². High performance OFETs with evaporated pentacene as organic semiconductor function at a low operate voltage (?15 V). The mobility could reach as high as 0.7 cm²/Vs and on/off current ratio up to 10⁴. Solution-processed TIPS-pentacene OFETs also work well with this polymer dielectric.     

Bipolar charge transport in organic field-effect transistors: Enabling high mobilities and transport of photo-generated charge carriers by a molecular passivation layer

High mobility bipolar charge carrier transport in organic field-effect transistors (OFETs) can be enabled by a molecular passivation layer and selective electrode materials. Using tetratetracontane as passivation layer bipolar transport was realised in the organic semiconductors copper-phthalocyanine, diindenoperylene, pentacene, TIPS-pentacene and sexithiophene and mobilities of up to 0.1 cm²/V s were achieved for both electrons and holes. Furthermore, the trap and injection behaviour was analysed leading to a more general understanding of the transport levels of the used molecular semiconductors and their limitations for electron and hole transport in OFETs. With this knowledge the transistor operation can be further improved by applying two different electrode materials and a light-emitting transistor was demonstrated.Additionally, the effect of illumination on organic field-effect transistors was investigated for unipolar and bipolar devices. We find that the behaviour of photo-excited electrons and holes depends on the interface between the insulator and the semiconductor and the choice of contact materials. Whereas filling of electron traps by photo-generated charges and the related accumulation field are the reason for changes in charge carrier transport upon illumination without passivation layer, both types of charge carriers can be transported also in unipolar OFETs, if a passivation layer is present.     

Organic photovoltaic devices based on pentacene/N,N′-dioctyl-3,4,9,10-perylenedicarboximide heterojunctions

We have studied an organic photovoltaic cell based on an efficient donor/acceptor combination of pentacene/N,N′-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C₈) heterojunctions. Photocurrent spectra exhibited excellent light harvesting throughout the visible spectrum with maximum external quantum efficiency (EQE) of ～60%. PTCDI-C₈ layer provided significant contribution to the photocurrent due to its strong absorption properties and efficient exciton dissociation at pentacene/PTCDI-C₈ interface. Power conversion efficiency of about 1.2% has been achieved under AM 1.5 illumination. The device showed a low series resistance of 18 Ω cm² and a high shunt resistance of 2.5 kΩ cm², resulting in a high fill factor of 65%.     

Organic field-effect transistors based on single-crystalline active layer and top-gate insulator consistently fabricated by electrostatic spray deposition

An electrostatic spray deposition (ESD) method was applied to prepare both crystalline domains of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) and insulating films of poly(methyl methacrylate) (PMMA) for fabricating top-gate single-crystal organic field-effect transistors (OFETs). The electrical characteristics of the top-gate device were compared to those of the bottom-gate one (SiO₂ bottom-gate insulator) with the same active layer, and the lower charge-trap density at the interface between the top-gate insulator and single-crystalline active layer was demonstrated. The drain current compression in the output characteristics of the top-gate device, however, occurred due to the large parasitic resistance between the source/drain electrodes and accumulation channel. Reducing the thickness of the single-crystalline active layer resulted in a high charge-carrier mobility of 0.29 cm²/V s (channel length of 5 μm).     

Improving the performance of the organic thin-film transistors with thin insulating lithium fluoride buffer layer

The pentacene-based organic thin-film transistors (OTFTs) with a thin insulating lithium fluoride (LiF) buffer layer between the pentacene and source/drain electrodes were fabricated. Compared with conventional OTFTs, the introduction of the buffer layer (1 nm) leads to field-effect mobility increases from 0.16 to 0.5 cm²/Vs, and threshold voltage downshifts from −19 to −8 V for the linear region. The on/off current ratio is improved to a level of 10⁵ for the off-state current decreasing. These improvements are attributed to (i) tunneling injection through the LiF layer and (ii) interface dipole energy barrier decreasing and contact resistance reduction between pentacene and Au. The results demonstrate that it is an effective method to improve the device characteristics by using a buffer layer.     

Natural polyelectrolyte: Major ampullate spider silk for electrolyte organic field-effect transistors

The major ampullate (MA) silk collected from giant wood spiders Nephila pilipes consists of 12% glutamic acid (Glu) and 4% tyrosine (Tyr) acidic amino residues. The MA silk may act as a natural polyelectrolyte for organic field-effect transistors (OFETs). Pentacene and F₁₆CuPc OFETs were fabricated with the MA silk thin film as the gate dielectric. The MA silk thin film with surface roughness of 4 nm and surface energy of 36.1 mJ/m² was formed on glass using a hexafluoroisopropanol (HFIP) organic process. The MA silk gate dielectric in pentacene OFETs may improve the field-effect mobility (μ_FE,sat) value in the saturation regime from 0.11 in vacuum to 4.3 cm² V⁻¹ s⁻¹ in air ambient at ca. 70% RH. The corresponding threshold voltage (V_TH) value reduced from −6 V in vacuum to −0.5 V in air ambient. Similar to other polyelectrolytes, the changes of μ_FE,sat and V_TH may be explained by the generation of electric double layers (EDLs) in the MA silk thin film in air ambient due to water absorption.     

Effect of hydroxyl density on condensation behaviors of self-assembled monolayers and performance of pentacene-base organic thin-film transistors

A series of self-assembled monolayers (SAMs), comprising octadecyltrichlorosilane (ODTS), dodecyltrichlorosilane (DDTS), and hexamethyldisilazane (HMDS), were prepared to examine the effects of phase states and condensation behaviors of SAMs on the morphologies and performance of pentacene-based organic field-effect transistors (OFETs) by means of Fourier Transform Infrared (FT-IR) spectrometer, atomic force microscope (AFM), X-ray diffraction (XRD), and semiconductor parameter analyzer. Experimental results reveal that the treatment of SiO₂ substrates with O₂ plasma (denoted as O₂-SiO₂) and the preparation temperature of SAMs dramatically influence the morphologies of SAMs and the performance of corresponding pentacene-based (no purification) OFETs. When the SAMs were prepared at 30 °C, the OFET based on ODTS-treated O₂-SiO₂ substrate had the highest hole mobility, reaching as large as 1.15 cm² V^?1 s^?1, and an on/off current ratio in excess of 10⁵; these values are both much larger than those of a device based on ODTS-modified SiO₂ substrates without O₂ plasma treatment and O₂-SiO₂ substrates modified by ODTS SAMs prepared at other temperatures. OFETs based on O₂-SiO₂ substrates that were modified by DDTS and HMDS SAMs prepared at 4 °C performed best.     

Improving solution-processed n-type organic field-effect transistors by transfer-printed metal/semiconductor and semiconductor/semiconductor heterojunctions

Solution-processed n-type organic field effect transistors (OFETs) are in need of proper metal contact for improving injection and mobility, as well as balanced hole mobility for building logic circuit units. We address the two distinct problems by a simple technique of transfer-printing. Transfer-printed Au contacts on a terrylene-based semiconductor (TDI) significantly reduced the inverse subthreshold slope by 5.6 V/dec and enhanced the linear mobility by over 5 times compared to evaporated Au contacts. Hence, devices with a high-work-function metal (Au) are comparable with those with low-work-function metals (Al and Ca), indicating a fundamental advantage of transfer-printed electrodes in electron injection. We also transfer-printed a poly(3-hexylthiophene) (P3HT) layer onto TDI to construct a double-channel ambipolar transistor by a solution process for the first time. The transistor exhibits balanced hole and electron mobility (3.0 × 10⁻³ and 2.8 × 10⁻³ cm² V⁻¹ s⁻¹) even in a coplanar structure with symmetric Au electrodes. The technique is especially useful for reaching intrinsic mobility of new materials, and enables significant enlargement of the material tanks for solution-processed functional heterojunction OFETs.     

Ambipolar transport in transparent and flexible all-organic heterojunction field effect transistors at ambient conditions

We report on the realization of fully flexible and transparent n-type and ambipolar all-organic OFETs. A double layer, pentacene-C60 heterojunction, was used as the semiconductor layer. The contacts were made with poly(ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and patterned by means of Soft Lithography MicroContact Printing (μCP). Interestingly, as demonstrated by atomic force microscopy and X-ray diffraction investigations, growing C60 on a pre-deposited pentacene buffer layer leads to a clear improvement in the morphology and crystallinity of the deposited film allowing to obtain n-type conduction despite the very high electron injection barrier at the interface between PEDOT:PSS and C60. As a result, it was possible to realize n-type and ambipolar all-organic OFETs by optimizing the thicknesses of the pentacene buffer layer. All devices, measured in air, worked in accumulation mode with mobilities up to 1 × 10⁻² cm²/V s and 3.5 × 10⁻⁴ cm²/V s for p-type and n-type regimes, respectively. This is particularly interesting because it demonstrates, also for n-type and ambipolar transistors, the possibility of avoiding problems normally associated to metal contacts: the lack of mechanical robustness, flexibility, and the unfeasibility of realizing contacts with low cost techniques like printing or soft lithography. These results confirm the importance of the substrate properties for the ordered growth of organic semiconductors, which determines the transport properties of organic materials.     

In situ modification of low-cost Cu electrodes for high-performance low-voltage pentacene thin film transistors (TFTs)

We demonstrate low-voltage pentacene thin film transistors (TFTs) using in situ modified low-cost Cu (M-Cu) as source–drain (S/D) electrodes and solution-processed high capacitance (200 nF/cm²) gate dielectrics. Under a gate voltage of ?3 V, the device with M-Cu electrodes shows a much higher apparent mobility (1.0 cm²/V s), a positively shifted threshold voltage (?0.62 V), a lower contact resistance (0.11 MΩ) and a larger transconductance (12 μS) as compared to the device with conventional Au electrodes (corresponding parameters are 0.71 cm²/V s, ?1.44 V, 0.41 MΩ, and 5.7 μS, respectively). The enhancement in the device performance is attributed to the optimized interface properties between S/D electrodes and pentacene. Moreover, after encapsulation the M-Cu electrodes with a thin layer of Au in the aim of suppressing unfavorable surface oxidation, the electronic characteristics of the device are further improved, and highly enhanced apparent mobility (2.3 cm²/V s) and transconductance (19 μS) can be achieved arising from the increased conductivity of the electrode itself. Our study provides a simple and feasible approach to achieve high performance low-voltage OTFTs with low-cost S/D electrodes, which is desirable for large area applications.     

Ultra-thin and graded sliver electrodes for use in transparent pentacene field-effect transistors

The authors report the fabrication of efficient and transparent pentacene field-effect transistors (FETs) using a graded structure of ultra-thin silver (Ag) source and drain (S–D) electrodes. The S–D electrodes were prepared by thermal evaporation with a controlled deposition rate to form Ag layer with a graded structure, leading to a reduced injection barrier and smoothing the contact surface between the electrode and the pentacene channel. The sheet resistance of such Ag electrode was found to be as low as 9 Ω/sq. In addition, a hole-only behavior of device with Ag electrode characterized by current–voltage measurement and conductive atomic-force microscopy shows the injection property of high current flowing as compared with device using Au electrode, resulting in an efficient injection condition existing at the interface of the graded Ag/pentacene. Device characterization indicates the transparent pentacene FET with a graded ultra-thin Ag electrode and organic capping layer of N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine exhibits a high transmission rate of ∼75% in the range of visible light from 400 to 550 nm, a threshold voltage of −6.0 V, an on–off drain current ratio of 8.4 × 10⁵, and a field-effect mobility of 1.71 cm²/V s, thus significantly outperforming pentacene FETs with multilayer oxide electrodes or other transparent thin metal layers.     

Electron injection barrier and energy-level alignment at the Au/PDI8-CN2 interface via current–voltage measurements and ballistic emission microscopy

We probe electron transport across the Au/organic interface based on oriented thin films of the high-performance n-type perylene diimide semiconductor PDI8-CN₂. To this purpose, we prepared organic-on-inorganic Schottky diodes, with Au directly evaporated onto PDI8-CN₂ grown on n-Si. Temperature-dependent current–voltage characteristics and complementary ballistic electron emission microscopy studies reveal that rectification at the Au/PDI8-CN₂ interface is controlled by a spatially inhomogeneous injection barrier, that varies on a length scale of tens of nanometers according to a Gaussian distribution with mean value ∼0.94 eV and standard deviation ∼100 meV. The former gradually shifts to ∼1.04 eV on increasing PDI8-CN₂ thickness from 5 nm to 50 nm. Experimental evidences and general arguments further allow to establish the energetics at the Au/PDI8-CN₂ interface. Our work indicates injection-limited current flow in PDI8-CN₂-based devices with evaporated Au electrodes. Furthermore, it suggests chemical reactivity of PDI8-CN₂ with both Au and Si, driven by the lateral isocyano groups.     

Lower hole-injection barrier between pentacene and a 1-hexadecanethiol-modified gold substrate with a lowered work function

We used ultraviolet photoemission spectroscopy (UPS) to study the hole injection barrier at the interface between pentacene and a gold surface treated with 1-hexadecanethiol (HDT). Through these UPS in-situ experiments, we found that the energy barrier between HDT-modified gold and pentacene was 0.74 eV. This energy barrier was 0.11 eV smaller than that between bare gold and pentacene, despite the work function of HDT-modified gold being 1.08 eV lower than that of bare gold. This result does not follow the typical trend, whereby decreasing the work function of a metal increases the energy barrier. The observed behavior can be explained by two factors. First, the bare gold substrate exhibited a large interface dipole, whereas the HDT-modified gold did not. And second, pentacene on the HDT-modified gold substrate had a lower ionization energy than pentacene on bare gold. This finding can be explained in terms of the polarization energy related to the more crystalline structure of pentacene on the HDT-modified gold substrate, which was established by X-ray diffraction analysis. For comparison, we also measured the injection barrier between the amorphous organic semiconductor, N,N′-diphenyl-N,N′bis(1-naphthyl-1,1′-biphenyl-4,4′-diamine (α-NPD)), and HDT-modified gold.     

Alcohol-soluble polyfluorenes containing dibenzothiophene-S,S-dioxide segments for cathode interfacial layer in PLEDs and PSCs

A series of alcohol-soluble amino-functionalized polyfluorene derivatives (PF-N-S, PF-N-SC8 and PF-N-SOC8) comprising various ratios of dibenzothiophene-S,S-dioxide segments (S/SC8/SOC8) in the main chains, respectively, were synthesized and utilized as cathode interfacial layer (CIL) in polymer light-emitting diodes (PLEDs) and polymer solar cells (PSCs) with high-work-function Al (or Au) electrode. The polymers possess LUMO/HOMO levels at −2.78 to −3.53 eV/−5.69 to −6.32 eV. Multilayer PLEDs and PSCs with device configurations of ITO/PEDOT:PSS (40 nm)/P-PPV or PFO-DBT35:PCBM = 1:2 (80 nm)/CIL (3–15 nm)/Al (or Au) (100 nm) were fabricated. The PF-N-S-10/Al (or Au) cathode PLEDs displayed maximum luminous efficiency of 24.4 cd A⁻¹ (or 11.9 cd A⁻¹), significantly higher than bare Al (or Au) cathode device, exceeding well-known Ba/Al and poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN)/Al (or PFN/Au) cathode devices. The enhanced open-circuit voltages (V_ocs), electron reflux and reduced work functions clarify that the electron injection barrier from the Al (or Au) electrode can be lowered by inserting the polymers as CIL. The resulted PSCs also show device performances exceeding Al and PFN/Al cathode devices. The results indicate that PF-N-S, PF-N-SC8 and PF-N-SOC8 are excellent CIL materials for PLEDs and PSCs with high-work-function Al or Au electrode.     

High-performance diketopyrrolopyrrole-based organic field-effect transistors for flexible gas sensors

We demonstrate high-performance flexible polymer OFETs with P-29-DPP-SVS in various geometries. The mobilities of TG/BC OFETs are approximately 3.48 ± 0.93 cm²/V s on a glass substrate and 2.98 ± 0.19 cm²/V s on a PEN substrate. The flexible P-29-DPP-SVS OFETs exhibit excellent ambient and mechanical stabilities under a continuous bending stress of 1200 times at an R = 8.3 mm. In particular, the variation of μ_FET, V_Th and leakage current was very negligible (below 10%) after continuous bending stress. The BG/TC P-29-DPP-SVS OFETs on a PEN substrate applies to flexible NH₃ gas sensors. As the concentration of NH₃ increased, the channel resistance of P-29-DPP-SVS OFETs increased approximately 100 times from ∼10⁷ to ∼10⁹ Ω at V_SD = −5 V and V_GS = −5 V.