Bandwidth and transient analysis of bilayer organic photodetectors

Utilization of organic photodetectors (OPDs) and their applications for assembling on flexible and curved substrates have increased in recent years. However, organic semiconductors suffer from low carrier mobility that demands an optimized design and precise modeling for their applications. The OPDs frequency bandwidth is one of the most important criteria that needs to be investigated carefully. In this paper a comprehensive physical time-domain framework is introduced for bandwidth calculations as well as other several evaluation criteria. This model is verified by experimental measurements. According to the results, increasing the reverse bias voltage boosts the bandwidth of OPD owing to the increase of the carrier mobility. Based on the introduced simulation approach, the trade-off between the bandwidth and the responsivity has been investigated and an efficient design method is also proposed which could effectively improve the OPD performance.     

X-ray Sensitive hybrid organic photodetectors with embedded CsPbBr3 perovskite quantum dots

X-ray detection is an important technology for medical diagnosis as well as industrial and security inspections. While today's commercial X-ray detectors are bulky, photodetectors based on organic semiconductors have attracted increasing attention owing to their low temperature processing capabilities, flexibility and low cost. Nonetheless, the low X-ray attenuation coefficient of organic semiconductors still hinders their practical application. Herein, a new organic-inorganic hybrid strategy is proposed to improve the X-ray sensitivity of organic photodetectors (OPDs). A solution-processed X-ray sensitive hybrid OPD is fabricated by embedding CsPbBr₃ quantum dots (QDs) into a P3HT:PC₆₁BM bulk heterojunction photodiode. The QDs, acting as embedded scintillators in the organic active layer, maintain a high radioluminescence. The proposed hybrid structure enables indirect X-ray detection in a comprehensive manner. These hybrid photodetectors exhibit suppressed dark current densities in the range of tens of picoamperes per square centimeters for different weight ratios of blended QDs. The best OPD achieves a sensitivity of 229.6 e nGy⁻¹ mm⁻² (3.67 μC Gy⁻¹ cm⁻²) and a dark current of 23.3 pA cm⁻² at a low operating voltage (−3 V) for 20–80 kV “soft” X-rays, thus representing great potential for the development of next generation low cost, portable, and highly sensitive X-ray detectors.     

Performance of ITO-free inverted organic bulk heterojunction photodetectors: Comparison with standard device architecture

We report on the fabrication of Indium Tin Oxide (ITO)-free inverted organic bulk heterojunction (BHJ) photodetectors of poly(3-hexylthiophene) (P3HT): 1-(3-methoxycarbonyl)-propyl-1-1-phenyl-(6,6) C61 (PCBM). The final inverted device structure is Cr/Al/Cr/P3HT:PCBM/poly-3,4-ethylenedioxythiophene:poly-styrenesulfonate (PEDOT:PSS)/Ag (Zimmermann et al., 2009) [1]. The device is top-absorbing with the light entering through the hole contact grid. We have fabricated standard devices with structure ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al in order to carry out a comparison study. Inverted photodetectors show slightly higher quantum efficiency and responsivity compared to standard devices. Frequency responses at different bias voltages were measured showing a maximum −3 dB cut-off frequency of 780 kHz and 700 kHz at −3 V for the standard and inverted structures respectively. Parameters extracted from the fit of a circuital model to the impedance spectroscopy measurements were used to estimate the photodiode cut-off frequency as function of bias.     

Low dark current inverted organic photodetectors employing MoOx:Al cathode interlayer

We report low dark current small molecule organic photodetectors (OPDs) with an inverted geometry for image sensor applications. Adopting a very thin MoO_x:Al cathode interlayer (CIL) in the inverted OPD with a reflective top electrode results in a remarkably low dark current density (J_d) of 5.6 nA/cm² at reverse bias of 3 V, while maintaining high external quantum efficiency (EQE) of 56.1% at visible wavelengths. The effectiveness of the CIL on the diode performance has been further identified by application to inverted OPDs with a semi-transparent top electrode, leading to a significantly low J_d of 0.25 nA/cm², moderately high EQE_{540 nm} of 25.8%, and subsequently high detectivity of 8.95 × 10¹² Jones at reverse bias of 3 V. Possible origins of reduced dark currents in the OPD by using the MoO_x:Al CIL are further described in terms of the change of interfacial energy barrier and surface morphology.     

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.     

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.     

Flexible organic light-emitting diodes with ZnS/Ag/ZnO/Ag/WO3 multilayer electrode as a transparent anode

We investigated the highly flexible, transparent and very low resistance ZnS/1st Ag/ZnO/2nd Ag/WO₃ (ZAZAW) multilayer electrodes on PET substrate as an anode in flexible organic light-emitting diodes (OLEDs). A theoretical calculation was first conducted to obtain the optimal thickness of the ZAZAW multilayer for high transparency. Its measured luminous transmittance was over 80% in the visible range with a very low sheet resistance of 2.17 Ω/sq., and it had good mechanical flexibility due to the ductility of Ag. Ag’s effect on optical and electrical properties was also studied. Flexible OLEDs devices that were fabricated on ZAZAW multilayer anode showed good hole injection properties comparable to those of ITO-based OLEDs due to the use of WO₃ as a hole injection layer. However, the electroluminescent properties of the ZAZAW-based OLEDs varied depending on WO₃ thickness. Although the transmittance of the ZAZAW electrode was reduced by tuning the WO₃ thickness to adjust the microcavity effect, the device efficiency could be enhanced above that of ITO-based OLEDs.     

High performance p-type organic thin film transistors with an intrinsically photopatternable,ultrathin polymer dielectric layer

A high-performing bottom-gate top-contact pentacene-based oTFT technology with an ultrathin (25–48 nm) and electrically dense photopatternable polymeric gate dielectric layer is reported. The photosensitive polymer poly((±)endo,exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE) is patterned directly by UV-exposure (λ = 254 nm) at a dose typical for conventionally used negative photoresists without the need for any additional photoinitiator. The polymer itself undergoes a photo-Fries rearrangement reaction under UV illumination, which is accompanied by a selective cross-linking of the macromolecules, leading to a change in solubility in organic solvents. This crosslinking reaction and the negative photoresist behavior are investigated by means of sol–gel analysis. The resulting transistors show a field-effect mobility up to 0.8 cm² V⁻¹ s⁻¹ at an operation voltage as low as −4.5 V. The ultra-low subthreshold swing in the order of 0.1 V dec⁻¹ as well as the completely hysteresis-free transistor characteristics are indicating a very low interface trap density. It can be shown that the device performance is completely stable upon UV-irradiation and development according to a very robust chemical rearrangement. The excellent interface properties, the high stability and the small thickness make the PNDPE gate dielectric a promising candidate for fast organic electronic circuits.     

Fully-printed,all-polymer,bendable and highly transparent complementary logic circuits

In this contribution we show a simple approach for the development of all-polymer based complementary logic circuits fabricated by printing on plastic, at low temperature and in ambient conditions. This is achieved by patterning, with a bottom-up approach, solely synthetic carbon-based materials, thus incorporating earth-abundant elements and enabling in perspective the recycling – a critical aspect for low-cost, disposable electronics. Though very simple, the approach leads to logic stages with a delay down to 30 μs, the shortest reported to date for all-polymer circuits, where each single component has been printed. Moreover, our circuits combine bendability and high transparency, favoring the adoption in several innovative applications for portable and wearable large-area electronics.     

Interfacial charging originated from the conductivity decrease of C60 layer in IZO/pentacene/C60/Al organic double-layer solar cells

The origin of interfacial charging process in double-layer organic solar cells (OSCs) was studied by using the normal structure of Indium–Zinc–Oxide/pentacene/C₆₀/Al and its inverted double-layer system. Optical electric-field-induced second-harmonic generation (EFISHG) measurement was employed and results suggested that interfacial charging in these two kinds of OSCs led to charge accumulation with opposite charge polarity, owing to the conductivity decrease of C₆₀ layer. Applying the EFISHG measurements to the inverted OSCs also showed that the significant charge accumulation on donor–acceptor interface is responsible for the low I–V performance of the inverted OSCs. Thus, Maxwell–Wagner type interfacial charging, which is governed by the conductivity of C₆₀, can cause the degradation of the I–V performance of OSCs. The protection of C₆₀ layer from the conductivity decrease is a way to improve OSCs performance.     

快响应光电探测器的瞬态特性测量

介绍了快响应光电探测器的发展动态，对其瞬态特性的测量原理和方法进行了综述，讨论此方面的发展趋势和限制因素。     

Flexible organic solar cells using an oxide/metal/oxide trilayer as transparent electrode

Organic solar cells (OSCs) have attracted much attention as a clean and renewable energy convention system, owning to the low-cost and easy-processing nature of organic semiconductors. While indium tin oxide (ITO) is commonly used in OSCs as the transparent conductive electrode, the rising cost of indium, the high temperature process and the poor flexibility of ITO, make it incompatible with large-scale roll-to-roll manufacture of OSCs. In this paper, the MoO₃/thin metal/MoO₃ trilayer structure was used to replace the ITO electrode in OSCs. The optical and electrical properties of the trilayer were shown to depend on the material and thickness of the intermediate metal layer. The maximum power conversion efficiency of up to 2.5% under simulated 1 sun AM 1.5 solar illumination was achieved for OSCs based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM), compared to a maximum efficiency of 3.1% for the ITO-based devices. Moreover, due to the flexible nature of the trilayer structure, the OSCs with the trilayer electrode exhibited good mechanical flexibility. The efficiency of the flexible device was only reduced by ∼6% from its original performance after 500 bending cycles with a bending radius of 1.3 cm. Therefore, the performance of the ITO-free devices on rigid/flexible substrates suggests that this oxide/metal/oxide trilayer electrode is a promising ITO replacement in OSCs.     

High-speed operation in printed organic inverter circuits with short channel length

We have demonstrated fast operation of printed organic inverter circuits. We employ a soluble organic semiconducting material which has high field-effect mobility and ink-jet printed source/drain electrodes with short channel length. Appropriate concentration of the semiconducting solution and modification layer of source/drain electrodes improve both mobility and on/off ratio. The fabricated transistors with a short channel length (4 μm) exhibit excellent mobility (1.2 cm²/V s), high on/off ratio (>10⁵) and operational stability. The diode-load inverter with a narrow channel and low parasitic capacitance operate at 8 kHz at 20 V. These results will lead to significant progress in applications of printed organic circuits.     

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.     

Reduced graphene oxide prepared at low temperature thermal treatment as transparent conductors for organic electronic applications

In this work, we obtain transparent conducting thin films of both chemically and thermally reduced graphene oxide. High-quality films are normally obtained with thermal treatments at temperatures about 1000 °C, while the highest temperatures employed during the thermal treatment in this work were as low as 400 °C, which is a mandatory condition when dealing with organic electronic devices on glass substrates. To reach such a low thermal treatment, a two-step oxidation process was employed in order to allow the formation of carbonyl chemical groups rather than epoxy functionalization. Each GO sample was structurally and chemically analysed by Infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), Ultraviolet–visible absorption spectroscopy (UV-VIS), Thermogravimetric analysis (TGA), Raman spectroscopy (RS), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The GO conducting thin films exhibited a sheet resistance of 3.2 × 10³ Ω/sq as well as a high transmittance: up to 80% at 550 nm. Furthermore, Raman spectroscopy, X-ray diffraction and AFM show that the thermally reduced thin films are mainly composed of single and bilayer GO sheets with a very low average roughness. Also, these GO thin films, with such surprising quality, have been employed as non-doped and metal free electrodes in organic light emitting diodes.     

Photolithographic patterning of organic photodetectors with a non-fluorinated photoresist system

We report on the fabrication of organic photodetectors (OPD) based on isolated islands of P3HT:PCBM. Pattern transfer to the active material was done with photolithography based on non-fluorinated solvents and the excessive organic semiconductor was removed with oxygen plasma reactive ion etching. The photoresist system used was found to be benign to the P3HT:PCBM layer as confirmed by absorption, thickness and roughness measurements. Current–voltage characteristics and external quantum efficiency (EQE) remained unchanged after the patterning process. It was demonstrated that it is possible to photolithographically pattern isolated islands with 200 μm edge length with the same dark current density (<10⁻⁵ A/cm² at −2 V bias voltage) and photocurrent density (>5 × 10⁻³ A/cm² at −2 V). Furthermore, concerning the solar cell performance, the patterned, small-area devices showed power conversion efficiency of 2.1% and fill-factor of 60%. Dark current was observed to depend on the size of the remaining semiconductor island, which was demonstrated on OPDs with diameter of 50 μm. The presented results show the feasibility of fabrication of isolated devices based on organic semiconductors patterned with non-fluorinated photolithography.     

Impact of organic inter-layer dielectric for improvement in mechanical flexibility of self-aligned coplanar in-Ga-Zn-O thin-film transistor

A novel device structure has been suggested to introduce organic inter-layer dielectric (ILD) for improving mechanical flexibility of self-aligned (SA) coplanar In-Ga-Zn-O (IGZO) thin-film transistor (TFT). The SA coplanar TFTs fabricated on poly(ethylene naphthalate) (PEN) substrate showed a high saturation mobility of 11.4 cm²/V∙s, low threshold voltage of 0.26 V, steep subthreshold swing of 115 mV/dec, and high on/off current ratio (~10⁹) at flat state. In the proposed structure, all-oxide gate stacks were defined into an island configuration embedded in the organic ILD, and hence, the mechanical stress applied to the active region could be effectively relieved. To investigate the feasibility of a new device concept, the mechanical properties of the fabricated TFTs were characterized. When the PEN thickness was varied 25 and 50 μm, the critical radius of curvature (R_C) values were estimated to be 1 and 3 mm, respectively, which were superior to those for conventional oxide devices. In addition, the mechanical durability during the cyclic bending test at R_C of 5 mm was significantly improved from 20,000 to 70,000 cycles when the PEN film thickness was reduced from 50 to 25 μm. The effects of PEN thickness on the mechanical stability of the SA coplanar TFTs were quantitatively discussed from a view point of surface strain. As a result, robust mechanical bendability of proposed device was confirmed even under harsh deformation conditions.     

Molybdenum oxide anode buffer layers for solution processed,blue phosphorescent small molecule organic light emitting diodes

In this work we present solution processed organic light emitting diodes (OLEDs) comprising small molecule, blue phosphorescent emitter layers from bis(4,6-difluorophenylpyridinato-N,C2)picolinatoiridium doped 4,4′,4″-tris(carbazol-9-yl)-triphenylamine and molybdenum trioxide (MoO₃) anode buffer layers. The latter were applied from a molybdenium(V)ethoxide precursor solution that was thermally converted to MoO₃ at moderate temperatures. The high work function MoO₃ facilitated hole injection into the emission layer. The MoO₃ layer properties were investigated by means of energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and Kelvin probe force microscopy. MoO₃ buffer layers performed superior to the commonly used poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and enabled an enhanced OLED device efficiency.