1 Volt organic transistors with mixed self-assembled monolayer/Al2O3 gate dielectrics

Control of the threshold voltage and the subthreshold swing is critical for low voltage transistor operation. In this contribution, organic field-effect transistors (OFETs) operating at 1 V using ultra-thin (∼4 nm), self-assembled monolayer (SAM) modified aluminium oxide layers as the gate dielectric are demonstrated. A solution-processed donor–acceptor semiconducting polymer poly(3,6-di(2-thien-5-yl)-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione)thieno[3,2-b]thiophene) (PDPP2TTT) is used as the active layer. It is shown that the threshold voltage of the fabricated transistors can be simply tuned by carefully controlling the composition of the applied SAM. The optimised OFETs display threshold voltages around 0 V, low subthreshold slopes (150 ± 5 mV/dec), operate with negligible hysteresis and show average saturated field-effect mobilities in excess of 0.1 cm²/V s at 1 V.     

Pattern-deposition of light-emitting ZnO particulate film through biomimetic process using self-assembled monolayer template

We fabricated ZnO micropatterns by a novel process in an aqueous solution at low temperatures. Photo-patterned self-assembled monolayer with phenyl/OH-surface functional groups was used as a template. Site-selective electroless deposition of ZnO was realized on Pd catalyst adhered only to the phenyl-surfaces. The as-deposited ZnO shows 500-800 nm visible light photoluminescence, which would be related to OH ions introduced during deposition process. Patterned monochromatic cathodoluminescence image was successfully demonstrated for 1 μm-width lines.     

Effect of substrate temperature on vapor-phase self-assembly of n-octylphosphonic acid monolayer for low-voltage organic thin-film transistors

N-octylphosphonic acid (C₈PA) monolayer was self-assembled on aluminum oxide (AlO_x) from vapor in vacuum, while the substrate temperature was varied between 25 and 150 °C. The capacitance, water contact angle measurement, Fourier transform infrared (FTIR) spectroscopy, and atomic force microscopy (AFM) confirmed the presence of C₈PA on AlO_x for all growth temperatures. However, the structural and electrical properties of such monolayers depend on their growth temperature. The minimum surface roughness of 0.36 nm, the maximum water contact angle of 113.5° ± 1.4°, the lowest leakage current density of ∼10⁻⁷ A/cm² at 3 V, and the capacitance of 0.43 μF/cm² were obtained for AlO_x/C₈PA bi-layers with C₈PA deposited at 25 °C. The elevated temperature led to increased surface roughness, decreased water contact angle, increased leakage current, inferior molecular ordering, and lower molecular coverage; while the effect on the chemisorption of the phosphonate was minimal. Methyl and methylene FTIR vibrations associated with C₈PA aliphatic tails exhibited similar centre-peak wavenumbers to those observed for C₈PA monolayers assembled from solutions, presenting a viable ‘dry’ alternative to the existing solution process.     

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.     

Interface control of conventional n-type silicon/metal by n-channel organic semiconductor

The rectifying and interface state density properties of n-Si/violanthrone-79/Au metal-diode have been investigated by current-voltage and capacitance-conductance-frequency methods. The ideality factor, barrier height and average series resistance of the diode were found to be 2.07, 0.81 eV and 5.04 kΩ respectively. At higher voltages, the organic layer contributes to I-V characteristics of the diode due to space-charge injection into the organic semiconductor layer and the trapped-charge-limited current mechanism is dominant mechanism for the diode. The barrier height obtained from C-V measurement is lower than the barrier height obtained I-V measurement and the organic layer creates an excess physical barrier for the diode. The interface state density of the diode was found to be 1.70 × 10¹¹ eV⁻¹ cm⁻² at 0.2 V and 1.72 × 10¹¹ eV⁻¹ cm⁻² at 0.4 V.The obtained electronic parameters indicate that the organic layer provides the conventional n-type silicon/metal interface control option.     

金属保护层改善NiSi/Si肖特基势垒均匀性的研究

用溅射-退火反应的方法制作NiSi／Si肖特基二极管，采用Ti和Co两种金属保护层结构，以提高硅化物的形成质量。对肖特基二极管反向I-V特性的测量结果表明：相对于没有保护层的样品，有保护层样品的反向电流明显减小，而且Ti保护层结构比Co保护层结构的作用更明显；没有保护层的管子和有保护层的管子具有不同的边缘特性。实验数据能够很好地用非均匀肖特基势垒输运模型拟合。提取出的参数表明，保护层结构在不同程度上有效地提高了肖特基势全的均匀性，从而减小了肖特基二极管的反向电流；边缘特性的差异性也是由于肖特基势垒均匀性的改变而导致的。金属保护层能提高肖特基势全的均匀性是因为保护层抑制了工艺过程中的氧污染。     

The metal/organic monolayer interface in molecular electronic devices

The metal/molecules/metal is the basic device used to measure the electronic properties of organic molecules envisioned as the key components in molecular-scale devices (molecular diode, molecular wire, molecular memory, etc.). This review paper describes the main techniques used to fabricate a metal/molecules/metal device (or more generally electrode/molecules/electrode junctions, with electrodes made of metal or semiconductor). We discuss several problems encountered for the metallization of organic monolayers. The organic/electrode interface plays a strong role in the electronic properties of these molecular devices. We review some results on the relationships between the nature of the electrode/molecule interface (physisorbed or chemisorbed, evaporated metal electrode, mechanical contact, etc.) and the electronic transport properties of these molecular-scale devices. We also discuss the effects of symmetric versus asymmetric coupling of the two ends of the molecules with the electrodes.     

Structural ordering versus energy band alignment: Effects of self-assembled monolayers on the metal/semiconductor interfaces of small molecule organic thin-film transistors

A model describing the influence of self-assembled monolayers on the contact resistance of bottom-contact organic thin-film transistors is presented. The model takes the contact geometry, the energy level alignment and the structural order of the organic films into consideration when describing the contact effects of organic transistors. The treatment of the metal source/drain electrodes of the transistors by self-assembled monolayers allows for tuning the work function of the metal contact and an improved ordering of the organic molecules on top of the source/drain contacts. The results reveal that the contact resistance is mainly determined by the molecular ordering, rather than the tuning of the work function. The model is compared to experimentally measured contact resistances for different self-assembled monolayers.     

Interface control and photovoltaic properties of n-type silicon/metal junction by organic dye

The electronic parameters and photovoltaic properties of the Au/methylene blue/n-Si diodes were investigated by current-voltage and capacitance-conductance-frequency techniques. The diode exhibits a non-ideal behavior due the series resistance, organic layer and oxide layer. The barrier height (1.04 eV) of the Au/methylene blue/n-Si is higher than that of Au/n-Si Schottky diode (0.83 eV) due to an excess barrier formed by organic layer. The interface state density of the diode was determined using a conductance technique and was found to be 3.25 × 10¹² eV⁻¹ cm⁻². The diode shows a photovoltaic behavior with a maximum open circuit voltage V_oc of 0.23 V and short-circuit current I_sc of 20.8 μA under 100 mW/cm². It is evaluated that Au/methylene blue/n-Si is an organic-on-inorganic photodiode with the obtained electronic parameters and methylene blue organic dye controls the interface and electrical properties of conventional metal/n-type silicon junction.     

Conformal electroless deposition of Cu seed layer on a 60-nm trench pattern modified with a self-assembled monolayer

We have developed a novel activation technique for the conformal electroless deposition (ELD) of Cu on a SiO₂ substrate modified with an organic self-assembled monolayer. The SiO₂ substrate was modified with amine groups using 3-aminopropyltriethoxysilane and Au nanoparticles (AuNPs) to form a uniform, continuous catalyst for ELD. The Au catalytic layer formed on the amine-SiO₂ substrate was stabilized by electrostatic interactions between the positively charged protonated-amine self-assembled monolayer (SAM) and negatively charged AuNPs. Cu films were then electrolessly deposited on Au-catalyzed SiO₂ substrates. The Cu seed layer formed by this method showed a highly conformal and continuous structure. Cu electrodeposition on the 60-nm trench was demonstrated using an acid cupric sulfate electrolyte containing chloride, polyethylene glycol 4000 and bis(3-sulfopropyl)disulfide. The resulting electroplated Cu showed excellent filling capability and no voids or other defects were observed in a 60-nm trench pattern.     

Toward a better understanding of synthesis and processing of ceramic/self-assembled monolayer bilayer coatings

Ceramic/self-assembled monolayer (SAM) bilayer coatings can provide adequate protection for silicon devices, or act as a multipurpose coating for other electronic applications, due to synergistic effects by forming a hybrid coating structure. The organic SAM layer acts as a “template” for the growth of the ceramic layer, while the ceramic layer can provide protection from environmental and mechanical impact. Low-temperature solution-based deposition techniques, namely, an in-situ solution method (biomimetic) and a hydrothermal method, have been employed in this study. Specifically, phosphonate-based (diethyl phosphatoethyl triethoxy silane) SAMs were used as a template to generate a zirconia ceramic layer at low temperatures. Other organic templates such as -SiCl₃-, -OH-, -HSO₃-, or -CH₃-terminated SAMs were also examined. The reactions to grow the ceramic film were found to be pH sensitive. The ceramic and SAM coatings were characterized by a variety of analytical techniques. A pathway for the formation of the ceramic coating is also discussed.     

Bottom-contact small-molecule n-type organic field effect transistors achieved via simultaneous modification of electrode and dielectric surfaces

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.     

Overcoming the “retention vs. voltage” trade-off in nonvolatile organic memory: Ag nanoparticles covered with dipolar self-assembled monolayers as robust charge storage nodes

Organic non-volatile memory devices with significantly enhanced retention are explored with C₆₀ thin-film transistors containing silver nanoparticles (Ag-NPs) within gate dielectrics as charge storage nodes. Dipolar self-assembled monolayers covering Ag-NPs effectively prevent stored charges from being lost by providing an additional energy threshold for back-tunneling process. This enables long retention even with ultrathin tunneling dielectric layers, providing a simple means to realize long retention without causing an excessive increase in operation voltage.     

Large enhancement of hole injection in pentacene by modification of gold with conjugated self-assembled monolayers

Planar diodes with gold electrodes and a pentacene semiconductor layer were made and electrically characterized. The gold electrodes were modified with self-assembled monolayers of biphenylthiol and biphenylthiol substituted with a terminal fluorine atom (fluorobiphenylthiol). Atomic force microscopy of the pentacene layer reveals large morphological similarities when the film is grown on gold modified with either of the two kinds of self-assembled monolayer. This is at variance with the significant increase of the current observed when the gold electrodes are treated with fluorobiphelylthiol, with a bulk mobility rising up to 1 cm²/V s, while the treatment with biphelylthiol leads to a substantial decrease of the current. These results are interpreted in terms of adjustment of the injection barrier height as a result of the interface dipole induced by the self-assembled monolayer.     

Addressable growth of oriented organic semiconductor ultra-thin films on hydrophobic surface by direct dip-coating

Oriented organic field-effect transistor (OFET) stripe arrays on hydrophobic substrates were fabricated by fast dip-coating technique. The addressable growth was achieved by decreasing surface energy of the channel areas with respect to the electrodes via hydrophobic treatment. The higher surface energy of the electrodes allows solution to adhere and then organic semiconductors nucleate and bridge the channels after evaporation of the solvent. Area-selective behaviour can be controlled by adjusting surface property of transistor channel, geometry features of the gold electrodes, pulling speed and evaporation atmosphere. The mechanism behind is the competition between receding of the solution and evaporating of the solvent that generate the organic semiconductor films on the substrate. The patterned bottom-contact transistor arrays exhibit carrier mobility of 2.0 × 10⁻³ cm² V⁻¹ s⁻¹, while no field-effect characteristics can be detected for bottom-contact arrays without hydrophobic treatment. Such reliable, fast and solution-based patterned OFET arrays are highly desirable for large-scale and low-cost production.     

Probing carrier behavior in organic semiconductor device by electric field induced optical second harmonic generation measurement

Electric field induced optical second harmonic generation (EFISHG) measurement is capable of probing carrier motions in organic devices. By measuring nonlinear polarization induced in active layer of organic devices, the carrier motion is visualized. After summarizing the conventional SHG measurement as a tool for material characterization, we show that the EFISHG is a way for probing carrier motions, and thus extends the potentiality of the conventional SHG measurement. We employ the EFISHG measurement to probe carrier behaviors in double-layer metal-insulator–metal diodes, e.g., Au/TIPS-pentacene/PI/ITO diodes, and demonstrate how the time-resolved SHG measurement probes carrier motion in the diodes, in terms of the I–V and C–V characteristics. Results give an insightful picture on the carrier injection, and the succeeding carrier transport.     

Fabrication of organic semiconductor crystalline thin films and crystals from solution by confined crystallization

Highly crystalline thin films of organic semiconductors processed from solution for electronic devices are difficult to achieve due to a slow and preferential three-dimensional growth of the crystals. Here we describe the development of a processing technique to induce a preferential two-dimensional crystalline growth of organic semiconductors by means of minimizing one dimension and confining the solution in two dimensions into a thin layer. The versatility of the process is demonstrated by processing small molecules (TIPS-pentacene and C₆₀) and a polymer (P3HT), all from solvents with a relatively low boiling point, to obtain crystalline thin films. The thin films show an improved in-plane packing of the molecules compared to films processed under similar conditions by spin coating, which is beneficial for the use in organic field-effect transistors.     

Interface electronic structure between organic semiconductor film and electrode metal probed by photoelectron yield spectroscopy

We present an investigation of the interface between organic semiconductor films and metal substrates (organic/metal interface) using photoelectron yield spectroscopy (PYS) as the probing technique. PYS studies were conducted on the pentacene/Au, copper phthalocyanine (CuPc)/Au, and perfluorinated zinc phthalocyanine (F₁₆ZnPc)/Au, and the results were compared with literature results obtained using conventional ultraviolet photoemission spectroscopy (UPS). PYS is advantageous for probing the electronic structure of the organic/metal interface because of the relatively long mean free path of photoexcited electrons with very low kinetic energy in PYS, which enables the detection of the photoelectrons from the metal substrate buried deep in the organic film. We demonstrate herein that the use of PYS reduces the significance of the final state effect of the electronic density surrounding the photohole at the organic molecule generated after the photoemission; this effect is known as the electric polarization effect. Although this effect has a significant influence on the results obtained using conventional UPS, the reduced influence of the final state effect in PYS makes it possible to construct an energy level diagram at the organic/metal interface with greater accuracy than can be achieved with UPS. In addition, a novel mechanism of the photoelectron detection for PYS enables us to apply PYS to very thick organic films, and therefore, PYS provides a reliable value of ionization energy for organic films without the influence of the substrate.Because the interface electronic structure has a significant influence on the carrier injection properties of organic devices, the increased reliability of the information obtained by PYS will render it very useful for the improvement of device performance as well for understanding their operation principles.     

The mutual influence of surface energy and substrate temperature on the saturation mobility in organic semiconductors

We report on a mutual correlation between the substrate temperature during semiconductor deposition and the surface energy of the gate dielectric on the charge carrier mobility in bottom gate top contact organic field effect transistors (OFETs) with N,N′-diphenyl-3,4,9,10-perylene tetracarboxylic diimide (DP-PDI) as organic semiconductor.     

Electric potential mapping by thickness variation: A new method for model-free mobility determination in organic semiconductor thin films

Charge transport, with charge carrier mobility as main parameter, is one of the fundamental properties of semiconductors. In disordered systems like most organic semiconductors, the effective mobility is a function of the electric field, the charge carrier density, and temperature. Transport is often investigated in a space-charge limited current (SCLC) regime in thin film single carrier devices, where an electric current is driven in the direction perpendicular to the surface. Direct evaluation of the current–voltage characteristics, however, is problematic, because parasitic contributions from injection or extraction barriers can falsify results.