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.     

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.     

Electrical and interface state density properties of the 4H-nSiC/[6,6]-phenyl C61-butyric acid methyl ester/Au diode

The electrical and interface state density properties of the Ni/4H-nSiC/PCBM/Au diode have been investigated by current-voltage, capacitance-voltage and conductance-frequency methods. The ideality factor, barrier height and series resistance values of the diode were found to be 2.28, 1.10 eV and 3.76 × 10⁴ Ω, respectively. The diode shows a non-ideal I-V behaviour with an ideality factor greater than unity that could be ascribed to the interfacial layer, interface states and series resistance. The obtained barrier height (1.10 eV) of the Ni/4H-nSiC/PCBM/Au diode is lower than that of Ni/4H-nSiC diode (1.32 eV). This indicates that the PCBM organic layer induces a change of 160 meV in the barrier height of the Ni/4H-nSiC diode. The interface state density of the diode was determined from G_p/ω-f plots and was of order of 5.61 × 10¹² eV⁻¹ cm⁻².     

Modification of metal/semiconductor junctions by self-assembled monolayer organic films

Two new metal/molecule/semiconductor contacts, Au/n-Si/TDA/Au and Au/p-Si/ODM/Au, were fabricated to understand effect of organic compounds, tridecylamine and octadecylmercaptan self-assembled monolayer (SAM) films, on electrical charge transport properties of the metal/semiconductor junctions. The morphology of the organic monolayers deposited on Si substrates was investigated by atomic force microscopy. The molecular coverage of ODM deposited on p-Si is poorer than that of TDA on n-Si substrate. The ideality factors of the p-Si/ODM and n-Si/TDA diodes were found to be 1.66 and 1.48, respectively. The electrical results show that the tridecylamine monolayer passivated junction has a lower ideality factor. The ideality factor indicates clear dependence on two different type functional groups R-SH (Thiol) and R-NH₂ (Amin) groups and it increases with different functional groups of organic molecule. The barrier height φ_b value of the n-Si/TDA diode is smaller than that of p-Si/ODM diode, as a result of chain length of the SAM organic molecules. The interface state density D_it values of the diodes were determined using conductance technique. The n-Si/TDA diode has the smaller interface state density according to p-Si/ODM diode.We have evaluated that the organic molecules control the electronic parameters of metal/semiconductor diodes and thus, organic modification helps to get one step closer towards to new organic assisted silicon based microelectronic devices.     

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.     

Solution processed small molecule organic interfacial layers for low dark current polymer photodiodes

We demonstrate a small molecule solution processed hole interfacial layer approach to improve the dark current characteristics of polymer photodiodes. The two hole blocking materials under investigation 3-phenyl-4(1′-naphthyl)-5-phenyl-1,2,4-triazole (TAZ) and 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole (TPBi) are spincoated from ethanol as an orthogonal solvent on top of a P3HT:PCBM active layer. We reduce the dark current at a bias voltage of −1 V by a factor of 17.2 by introducing a TAZ interfacial layer while keeping the responsivity unchanged.     

The effect of charge extraction layers on the photo-stability of vacuum-deposited versus solution-coated organic solar cells

Organic solar cells (OSCs) are studied for their photo-stability in inert atmosphere. Polymer solar cells with a bulk heterojunction (BHJ) of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) are contrasted with small molecule solar cells with a BHJ of chloroindium phthalocyanine (ClInPc) and C₆₀-fullerene. A series of charge extraction layers at the hole and electron collecting contacts are examined for their role in OSC performance and stability. The inter-compatibilities of these extraction layers in vacuum-deposited small molecule OSCs (SM-OSCs) versus solution-coated polymer OSCs (P-OSCs) are explored. Through photo-stability studies, we show that interfacial extraction layers are necessary to avoid contact photo-degradation, which otherwise leads to strong reductions in OSC efficiencies. We also highlight certain extraction layer combinations that result in strong inter-electrode degradation, and we discuss incompatibilities in extraction layers among SM-OSCs versus P-OSCs. Our results suggest that the presence of excitons at the organic-electrode interface likely plays a critical role in contact photo-degradation. By minimizing contact photo-degradation, which dominates the majority of short-term OSC degradation, a new avenue for studying OSC stability behavior and opportunities to focus on other losses in OSCs become possible.     

Modeling of spiking analog neural circuits using organic semiconductor thin film transistors with silicon oxide nitride semiconductor gates

This paper uses the results of the characterization of amorphous semiconductor thin film transistors (TFTs) with the quasi-permanent memory structure referred to as silicon oxide nitride semiconductor (SONOS) gates, to model spiking neural circuits. SONOS gates were fabricated and characterized. In addition, MOSFETs using organic copper phthalocyanine (CuPc) were fabricated with these SONOS gates to demonstrate proof of concept performance. Analog spiking circuits were then modeled using these low performance TFTs to demonstrate the general suitability of organic TFTs in neural circuits. The basic circuit utilizes a standard comparator with charge and discharge circuits. A simple Hebbian learning circuit was added to charge and discharge the SONOS device. The use of these elements allows for the design and fabrication of high-density 3-dimensional circuits that can achieve the interconnect density of biological neural systems.     

Control of interfacial charges of organic semiconductor by a surface polarized layer for high noise-margin inverters with full-swing capability

We present the control mechanism for interfacial charges in an organic field-effect transistor (OFET) by the introduction of a surface polarized layer (SPL), interfaced with a p-type organic semiconductor (p-OS), which generates a transverse dipolar field. The concept of such SPL enables to develop a high noise-margin full-swing inverter of the p-OS, pentacene, on a single substrate. The transverse dipolar field of the SPL of a fluorinated polymer, placed between the p-OS and a gate insulator, plays an essential role in the accumulation of holes at the interface due to the surface dipoles of the fluorinated polymer. Owing to the interfacial holes, the drain current of the p-type OFET becomes to saturate at zero gate voltage and its magnitude lies between the on-current and off-current of a conventional OFET with no SPL. This allows directly the high noise-margin and the full-swing capability of an organic inverter based on the p-OS material.     

Interfacial modifying layer-driven high-performance organic thin-film transistors and their nitrogen dioxide gas sensors

Organic thin-film transistors (OTFTs) based on bottom-gate bottom-contact configuration were fabricated by inserting two kinds of modifying layers at the interface of source/drain electrode and organic semiconductor, while nitrogen dioxide (NO₂) sensing capability was also evaluated based on the obtained OTFTs. Compared to OTFT without interfacial layer, the field-effect mobility (μ) was enhanced from 0.018 cm²/Vs to 0.15 cm²/Vs by incorporating with MoO_x interfacial layer. Moreover, when exposed to 30 ppm NO₂, the saturation current and μ of OTFT with MoO_x interfacial layer increase 22.7% and 26.7%, respectively, while in original OTFT, the values are only 3.0% and 3.7%, respectively. The mechanism of performance improvement of OTFT sensor was systematically studied by focusing on the interface of source/drain electrode and organic semiconductor. The reduced contact resistance leads to higher μ, meanwhile, pentacene morphology modulation on MoO_x contributes to better diffusion of NO₂ molecules. As a result, higher μ and more diffused gas molecules enhance the gas sensing property of the transistor.     

Organic/metal hybrid cathode for transparent organic light-emitting diodes

We report a highly transparent organic/metal hybrid cathode of a Cs-doped electron transport layer (Cs-ETL)/Ag for transparent organic light-emitting diode (TOLED) applications. Particular attention is paid to the surface morphology on the Ag film and its influence on the optical transparency and electrical conductivity. With the use of Cs-ETL, a smooth and continuous surface morphology of Ag film was achieved, leading to a high transmittance of ～75% in TOLED with a low sheet resistance of 4.5 Ω/Sq in cathode film. We successfully applied our Cs-ETL/Ag transparent cathode to fabricate highly transparent OLEDs. Our approach suggests a new electrode structure for transparent OLED applications.     

Analysis of interface states and series resistance of Ag/SiO2/n-Si MIS Schottky diode using current-voltage and impedance spectroscopy methods

The electrical characteristics and interface state density properties of Ag/SiO₂/n-Si metal-insulator-semiconductor diode have been analyzed by current-voltage and impedance spectroscopy techniques. The electronic parameters such as barrier height, ideality factor and average series resistance were determined and were found to be 0.62 eV, 1.91 and 975.8 Ω, respectively. The calculated ideality factor shows that Ag/SiO₂/n-Si structure obeys a metal-interfacial layer-semiconductor configuration rather than ideal Schottky barrier diode. The interface state density of the diode is of order of ∼10¹¹ eV⁻¹ cm⁻². The dielectrical relaxation mechanism of the diode is analyzed by Cole-Cole plots, indicating the presence of single relaxation mechanism. It is evaluated that the interfacial oxide layer modifies electrical parameters such as interface state density, series resistance and barrier height of Ag/SiO₂/n-Si diode.     

A surface modification layer capable of tolerating substrate contamination on transparent electrodes of organic electronic devices

An organic molecule, hexaazatriphenylene hexacarbonitrile (HAT-CN), is found that it can be used not only as a hole-injecting material but also a surface modification material to clean contaminated substrate electrodes for the fabrication of organic electronic devices. As an example, HAT-CN can modify or “clean” indium-tin-oxide (ITO) anode surface in organic light-emitting diodes (OLEDs). Negative effect from ITO surface contamination on the electroluminescence performance of OLEDs can be dramatically reduced with this modification layer. As a result, the OLEDs with the same device architecture but with different ITO surface conditions, even with intentional contamination, can all exhibit substantially identical and superior electroluminescence performance. The surface modification function of this material is feasibly useful for the real fabrications of OLEDs as well as for advanced research on other organic electronic devices.     

Stress-induced degradation of p- and n-type organic thin-film-transistors in the ON and OFF states

In this work we analyzed the effect of different stress configurations on p- and n-type organic thin-film-transistors, to emulate the various operating conditions in a real application. Devices showed the largest degradation when they are stressed in the ON condition, because of the uniform charge injection and defect generation in the whole channel area. Charge trapping kinetics and mobility degradation was also strongly dependent on the semiconductor type, suggesting a key-role of the semiconductor on the device reliability.     

Generation-recombination in disordered organic semiconductor: Application to the characterization of traps

The presence of traps in organic semiconductor based electronic devices affects considerably their performances and their stability. The Shockley-Read-Hall (SRH) model is generally used to extract the trap parameters from the experimental results. In this paper, we propose to adapt the SRH formalism to disordered organic semiconductors by considering a hopping transport process and Gaussian distributions for both mobile and trapped carriers. The model is used to extract multiple trap parameters from charge based Deep Level Transient Spectroscopy (Q-DLTS) spectrum. Calculation of the charge transients are given in detail. The model predicts that the activation energy of the trap should not follow an Arrhenius plot on large temperature ranges. Also, the charge transients are no longer exponential when considering Gaussian trap distributions, enlarging the Q-DLTS peaks. The model fits the Q-DLTS spectra measured on organic diodes with a limited number of trap contributions with a good agreement. It is found that an increase of the material rate of disorder reduces the extracted trap energy distances to the LUMO but has no influence on the extracted trap distribution widths. This work shows the importance of considering the specific properties of organic materials to study their properties and their trap distributions.     

Dark current and photovoltage models on the formation of depletion region in C60/NPB organic heterojunctions

We establish quantitative models on the formation of depletion regions in organic photodiodes (OPD) based on fullerene/N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (C₆₀/NPB) heterojunctions. The models describe the relation of dark current and open-circuit voltage to the deposited thickness of C₆₀ or NPB. Interfacial electronic structures, such as built-in potential, the charge density, the minimized thicknesses of completely developed depletion regions and the energy level bending on each side of the heterojunction were derived from the fitting model. Also, we observed a shift of depletion region from NPB to C₆₀ due to the relative change of charge density under illumination. The device performance proved the reasonability of the models. This paper provides a universally applicable method to probe the interfacial information of organic semiconductors.     

Exciton-induced degradation of organic/electrode interfaces in ultraviolet organic photodetectors

We study the degradation mechanisms of ultraviolet (UV) organic photodetectors (OPDs). Contrary to expectations, we determine that the bulk of the organic layers in UV OPDs is stable under prolonged UV irradiation, showing no detectable changes in photophysical characteristics such as photoluminescence yield and exciton lifetime and thus not contributing to the observed degradation behavior of UV OPDs. However, the results show that the organic/electrode interfaces in UV OPDs, including indium tin oxide (ITO)/organic and organic/metal ones, are susceptible to UV irradiation, leading to a deterioration in both charge injection and extraction across the interfaces. The degradation of the organic/electrode interfaces in UV OPDs is essentially induced by UV-generated excitons in their vicinity and may be responsible for nearly 100% of the photo-current loss of UV OPDs. Approaches for improving the photo-stability of organic/electrode interfaces, and thus the lifetime of UV OPDs, are also investigated. We demonstrate that the use of thin (∼0.5 nm) interfacial layers such as lithium acetylacetonate at organic/metal interfaces can significantly reduce the interfacial degradation, and the use of appropriate hole transport materials such as N,N′-bis (naphthalen-1-yl)-N,N′-bis(phenyl) benzidine at ITO/organic interfaces can greatly improve the interfacial photo-stability.     

Improving performance of TIPS pentacene-based organic thin film transistors with small-molecule additives

This work demonstrates an effective approach to improve both charge transport and performance consistency in solution-processed organic thin-film transistors (OTFTs) by blending 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene, or TP) with a series of small-molecule additives: 4-butylbenzoic acid (BBA), 4-hexylbenzoic acid (HBA), and 4-octylbenzoic acid (OBA). These three small molecules share a benzoic acid moiety, but have different length of hydrophobic tails. The self-assembled interfacial layer of small molecules on the gate oxide surface leads to uniform deposition of TP crystal seeds and facilitates TP to grow along the tilted orientation of substrate, which results in a film of enhanced crystal orientation and areal coverage. OTFTs based on TP/small molecule blends demonstrate greatly improved average hole mobility and performance consistency, which correlates with the length of hydrophobic tail of the small-molecule additives.     

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.     

Stable growth of large-area single crystalline thin films from an organic semiconductor/polymer blend solution for high-mobility organic field-effect transistors

We developed an effective and steady solution-processing technique for a small molecule–type semiconductor, C₁₀–DNBDT–NW, by adding an amorphous PMMA polymer to produce stable growth of a two-dimensional large-area single-crystalline thin film by effective phase separation at a crucially faster processing speed compared to the case without the addition of a polymer. By using this solution-processing technique, it is noteworthy that the single-crystalline films of C₁₀–DNBDT–NW/PMMA exhibit the highest and average mobilities of 17 and 10.6 cm²/Vs, respectively. Furthermore, we also show the limitations of two-dimensional continuous growth of a single-crystalline film in terms of the solution technique.