Identifying the Molecular Origins of High-Performance in Organic Photodetectors Based on Highly Intermixed Bulk Heterojunction Blends.

A bulk-heterojunction (BHJ) structure of organic semiconductor blend is widely used in photon-to-electron converting devices such as organic photodetectors (OPD) and photovoltaics (OPV). However, the impact of the molecular structure on the interfacial electronic states and optoelectronic properties of the constituent organic semiconductors is still unclear, limiting further development of these devices for commercialization. Herein, the critical role of donor molecular structure on OPD performance is identified in highly intermixed BHJ blends containing a small-molecule donor and C60 acceptor. Blending introduces a twisted structure in the donor molecule and a strong coupling between donor and acceptor molecules. This results in ultrafast exciton separation (<1 ps), producing bound (binding energy ∼135 meV), localized (∼0.9 nm), and highly emissive interfacial charge transfer (CT) states. These interfacial CT states undergo efficient dissociation under an applied electric field, leading to highly efficient OPDs in reverse bias but poor OPVs. Further structural twisting and molecular-scale aggregation of the donor molecules occur in blends upon thermal annealing just above the transition temperature of 150 °C at which donor molecules start to reorganize themselves without any apparent macroscopic phase-segregation. These subtle structural changes lead to significant improvements in charge transport and OPD performance, yielding ultralow dark currents (∼10-10 A cm-2), 2-fold faster charge extraction (in µs), and nearly an order of magnitude increase in effective carrier mobility. Our results provide molecular insights into high-performance OPDs by identifying the role of subtle molecular structural changes on device performance and highlight key differences in the design of BHJ blends for OPD and OPV devices.

Author Correction: Surface plasmon enhanced Organic color image sensor with Ag nanoparticles coated with silicon oxynitride.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Surface plasmon enhanced Organic color image sensor with Ag nanoparticles coated with silicon oxynitride.

As organic photodetectors with less than 1 µm pixel size are in demand, a new way of enhancing the sensitivity of the photodetectors is required to compensate for its degradation due to the reduction in pixel size. Here, we used Ag nanoparticles coated with SiOxNy as a light-absorbing layer to realize the scale-down of the pixel size without the loss of sensitivity. The surface plasmon resonance appeared at the interface between Ag nanoparticles and SiOxNy. The plasmon resonance endowed the organic photodetector with boosted photon absorption and external quantum efficiency. As the Ag nanoparticles with SiOxNy are easily deposited on ITO/SiO2, it can be adapted into various organic color image sensors. The plasmon-supported organic photodetector is a promising solution for realizing color image sensors with high resolution below 1 µm.

Green-light-selective organic photodiodes for full-color imaging.

In this work, organic photodiodes (OPDs) based on two newly synthesized p-type dipolar small molecules are reported for application to green-light-selective OPDs. In order to reduce the blue-color absorption induced by the use of C60 as the n-type material in a bulk heterojunction (BHJ), the electron donor:electron acceptor composition ratio is tuned in the BHJ. With this light manipulation approach, the blue-wavelength external quantum efficiency (EQE) is minimized to 18% after reducing the C60 concentration in the center part of the BHJ. The two p-type molecules get a cyanine-like character with intense and sharp absorption in the green color by adjusting the strength of their donating and accepting parts and by choosing a selenophene unit as a π-linker. When combined to C60, the green-wavelength EQE reaches 70% in a complete device composed of two transparent electrodes. Finally, the optical simulation shows the good color-balance performance of hybrid full-color image sensor without an additional filter by using the developed green OPD as the top-layer in stacked device architecture.

Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates.

Benzothieno[60]fullerenes were synthesized using fullerenyl cations as key intermediates. The reaction proceeded through a nucleophilic attack of the sulfur atom as a weak nucleophile to the fullerenyl cation electrophile. A monoarylated fullerene, (2-methylthiophenyl)hydro[60]fullerene, C60ArH (Ar = C6H4-SMe-2 and so on; four derivatives) was subjected to deprotonation with KO tBu to form a fullerenyl anion ArC60-, followed by oxidation using I2 to generate a fullerenyl cation ArC60+, leading to intramolecular demethylative cyclization via fullerene cation-S interaction to the product. Electrochemical and computational studies revealed slightly narrower band gap of this compound than usual fullerene derivatives because of the relatively high-lying HOMO of the fused thieno moiety.

The role of defects in organic image sensors for green photodiode.

Controlling defect states in a buffer layer for organic photo devices is one of the vital factors which have great influence on the device performance. Defect states in silicon oxynitride (SiOxNy) buffer layer for organic photo devices can be controlled by introducing appropriate dopant materials. We performed ab initio simulations to identify the effect on doping SiOxNy with carbon (C), boron (B), and phosphorous (P) atoms. The results unveil that hole defects in the SiOxNy layer diminish with the phosphorous doping. Based on the simulation results, we fabricate the small molecule organic photodetector (OPD) including the phosphorous-doped SiOxNy buffer layer and the active film of blended naphthalene-based donor and C60 acceptor molecules, which shows excellent enhancement in the external quantum efficiency (EQE). The results of our charge-based deep level transient spectroscopy (Q-DLTS) measurements confirmed that the EQE enhancement originates from the decrease of the hole traps induced by the reduced hole defects. The method of controlling the defect states in SiOxNy buffer layers by the doping can be used to improve the performance in various organic photo devices.

Narrow-Band Organic Photodiodes for High-Resolution Imaging.

There are growing opportunities and demands for image sensors that produce higher-resolution images, even in low-light conditions. Increasing the light input areas through 3D architecture within the same pixel size can be an effective solution to address this issue. Organic photodiodes (OPDs) that possess wavelength selectivity can allow for advancements in this regard. Here, we report on novel push-pull D-π-A dyes specially designed for Gaussian-shaped, narrow-band absorption and the high photoelectric conversion. These p-type organic dyes work both as a color filter and as a source of photocurrents with linear and fast light responses, high sensitivity, and excellent stability, when combined with C60 to form bulk heterojunctions (BHJs). The effectiveness of the OPD composed of the active color filter was demonstrated by obtaining a full-color image using a camera that contained an organic/Si hybrid complementary metal-oxide-semiconductor (CMOS) color image sensor.

Dibenzothiopheno[6,5-b:6',5'-f]thieno[3,2-b]thiophene (DBTTT): high-performance small-molecule organic semiconductor for field-effect transistors.

We present the synthesis, characterization, and structural analysis of a thiophene-rich heteroacene, dibenzothiopheno[6,5-b:6',5'-f]thieno[3,2-b]thiophene (DBTTT) as well as its application in field-effect transistors. The design of DBTTT is based on the enhancement of intermolecular charge transfer through strong S-S interactions. Crystal structure analysis showed that the intermolecular π-π distance is shortened and that the packing density is higher than those of the electronically equivalent benzene analogue, dinaphtho-[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT). The highest hole mobility we obtained in polycrystalline DBTTT thin-film transistors was 19.3 cm(2)·V(-1)·s(-1), six times higher than that of DNTT-based transistors. The observed isotropic angular mobilities and thermal stabilities at temperatures up to 140 °C indicate the great potential of DBTTT for attaining device uniformity and processability.

Organic-on-silicon complementary metal-oxide-semiconductor colour image sensors.

Complementary metal-oxide-semiconductor (CMOS) colour image sensors are representative examples of light-detection devices. To achieve extremely high resolutions, the pixel sizes of the CMOS image sensors must be reduced to less than a micron, which in turn significantly limits the number of photons that can be captured by each pixel using silicon (Si)-based technology (i.e., this reduction in pixel size results in a loss of sensitivity). Here, we demonstrate a novel and efficient method of increasing the sensitivity and resolution of the CMOS image sensors by superposing an organic photodiode (OPD) onto a CMOS circuit with Si photodiodes, which consequently doubles the light-input surface area of each pixel. To realise this concept, we developed organic semiconductor materials with absorption properties selective to green light and successfully fabricated highly efficient green-light-sensitive OPDs without colour filters. We found that such a top light-receiving OPD, which is selective to specific green wavelengths, demonstrates great potential when combined with a newly designed Si-based CMOS circuit containing only blue and red colour filters. To demonstrate the effectiveness of this state-of-the-art hybrid colour image sensor, we acquired a real full-colour image using a camera that contained the organic-on-Si hybrid CMOS colour image sensor.

Plasmonic optical interference.

Understanding optical interference is of great importance in fundamental and analytical optical design for next-generation personal, industrial, and military applications. So far, various researches have been performed for optical interference phenomena, but there have been no reports on plasmonic optical interference. Here, we report that optical interference could be effectively coupled with surface plasmons, resulting in enhanced optical absorption. We prepared a three-dimensional (3D) plasmonic nanostructure that consists of a plasmonic layer at the top, a nanoporous dielectric layer at the center, and a mirror layer at the bottom. The plasmonic layer mediates strong plasmonic absorption when the constructive interference pattern is matched with the plasmonic component. By tailoring the thickness of the dielectric layer, the strong plasmonic absorption can facilely be controlled and covers the full visible range. The plasmonic interference in the 3D nanostructure thus creates brilliant structural colors. We develop a design equation to determine the thickness of the dielectric layer in a 3D plasmonic nanostructure that could create the maximum absorption at a given wavelength. It is further demonstrated that the 3D plasmonic nanostructure can be realized on a flexible substrate. Our 3D plasmonic nanostructures will have a huge impact on the fields of optoelectronic systems, biochemical optical sensors, and spectral imaging.

Green-sensitive organic photodetectors with high sensitivity and spectral selectivity using subphthalocyanine derivatives.

Green-sensitive organic photodetectors (OPDs) with high sensitivity and spectral selectivity using boron subphthalocyanine chloride (SubPc) derivatives are reported. The OPDs composed of SubPc and dicyanovinyl terthiophene derivative (DCV3T) demonstrated the highest green-sensitivity with maximum external quantum efficiency (EQE) of 62.6 % at an applied voltage of -5 V, but wide full-width-at-half-maximum (FWHM) of 211 nm. The optimized performance considering spectral selectivity was achieved from the composition of N,N-dimethyl quinacridone (DMQA) and SubPc showing the high specific detectivity (D*) of 2.34 × 10(12) cm Hz(1/2)/W, the EQE value of 60.1% at -5 V, and narrow FWHM of 131 nm. In spite of the sharp absorption property of SubPc with the maximum wavelength (λmax) at 586 nm, the EQE spectrum showed favorable green-sensitivity characterized by smooth waveform with λmax at 560 nm, which is induced from the high reflectance of SubPc centered at 605 nm. The photoresponsivity of the OPD devices was found to be consistent with their absorptance. Optimized DMQA/SubPc device showed the lowest value of blue crosstalk (0.42) and moderate red crosstalk (0.37), suggesting its promising application as a green-sensitive OPD.

Reliable and uniform thin-film transistor arrays based on inkjet-printed polymer semiconductors for full color reflective displays.

Stable uniform performance inkjet-printed polymer transistor arrays, which allow demonstration of flexible full-color displays, were achieved by new ambient processable conjugated copolymer semiconductor, and OTFT devices incorporating this material showed high mobility values>1.0 cm2 V(-1) s(-1). Bias-stress stability of the devices was improved with a channel-passivation layer, which suppresses the density of trap states at the channel interface.

High-mobility and low-power thin-film transistors based on multilayer MoS2 crystals.

Unlike graphene, the existence of bandgaps (1-2 eV) in the layered semiconductor molybdenum disulphide, combined with mobility enhancement by dielectric engineering, offers an attractive possibility of using single-layer molybdenum disulphide field-effect transistors in low-power switching devices. However, the complicated process of fabricating single-layer molybdenum disulphide with an additional high-k dielectric layer may significantly limit its compatibility with commercial fabrication. Here we show the first comprehensive investigation of process-friendly multilayer molybdenum disulphide field-effect transistors to demonstrate a compelling case for their applications in thin-film transistors. Our multilayer molybdenum disulphide field-effect transistors exhibited high mobilities (>100 cm(2) V(-1) s(-1)), near-ideal subthreshold swings (~70 mV per decade) and robust current saturation over a large voltage window. With simulations based on Shockley's long-channel transistor model and calculations of scattering mechanisms, these results provide potentially important implications in the fabrication of high-resolution large-area displays and further scientific investigation of various physical properties expected in other layered semiconductors.

Bright color optical switching device by polymer network liquid crystal with a specular reflector.

The color optical switching device by polymer network liquid crystal (PNLC) with color filter on a specular reflector shows excellent performance; white reflectance of 22%, color gamut of 32%, and contrast ratio up to 50:1 in reflective mode measurement. The view-angle dependence of the reflectance can be adjusted by changing the PNLC thickness. The color chromaticity shown by the device is close to the limit value of color filters, and its value nearly remains with respect to the operating voltage. These optical properties of the device can be explained from the prediction based on multiple interactions between the light and the droplets of liquid crystal. The high reflectance, vivid color image, and moderate responds time allow the PNLC device to drive good color moving image. It can widely extend the applications of the reflective device.

Thermal conversion of electronic and electrical properties of AuCl3-doped single-walled carbon nanotubes.

By using carbon-free inorganic atomic layer involving heat treatment from 150 to 300 °C, environmentally stable and permanent modulation of the electronic and electrical properties of single-walled carbon nanotubes (SWCNTs) from p-type to ambi-polar and possibly to n-type has been demonstrated. At low heat treatment temperature, a strong p-doping effect from Au(3+) ions to CNTs due to a large difference in reduction potential between them is dominant. However at higher temperature, the gold species are thermally reduced, and thermally induced CNT-Cl finally occurs by the decomposition reaction of AuCl(3). Thus, in the AuCl(3)-doped SWCNTs treated at higher temperature, the p-type doping effect is suppressed and an n-type property from CNT-Cl is thermally induced. Thermal conversion of the majority carrier type of AuCl(3)-doped SWNTs is systematically investigated by combining various optical and electrical tools.

Control of electronic structure of graphene by various dopants and their effects on a nanogenerator.

It is essential to control the electronic structure of graphene in order to apply graphene films for use in electrodes. We have introduced chemical dopants that modulate the electronic properties of few-layer graphene films synthesized by chemical vapor deposition. The work function, sheet carrier density, mobility, and sheet resistance of these films were systematically modulated by the reduction potential values of dopants. We further demonstrated that the power generation of a nanogenerator was strongly influenced by the choice of a graphene electrode with a modified work function. The off-current was well quenched in graphene films with high work functions (Au-doped) due to the formation of high Schottky barrier heights, whereas leakage current was observed in graphene films with low work functions (viologen-doped), due to nearly ohmic contact.

Solution-processed, high-performance n-channel organic microwire transistors.

The development of solution-processable, high-performance n-channel organic semiconductors is crucial to realizing low-cost, all-organic complementary circuits. Single-crystalline organic semiconductor nano/microwires (NWs/MWs) have great potential as active materials in solution-formed high-performance transistors. However, the technology to integrate these elements into functional networks with controlled alignment and density lags far behind their inorganic counterparts. Here, we report a solution-processing approach to achieve high-performance air-stable n-channel organic transistors (the field-effect mobility (mu) up to 0.24 cm(2)/Vs for MW networks) comprising high mobility, solution-synthesized single-crystalline organic semiconducting MWs (mu as high as 1.4 cm(2)/Vs for individual MWs) and a filtration-and-transfer (FAT) alignment method. The FAT method enables facile control over both alignment and density of MWs. Our approach presents a route toward solution-processed, high-performance organic transistors and could be used for directed assembly of various functional organic and inorganic NWs/MWs.

Vertical alignment of carbon nanotubes using the magneto-evaporation method.

We developed a novel method of vertical alignment of SWNTs using a single-step process for the simultaneous vertical alignment of the SWNTs by a magnetic field and the fixation of their alignment by means of the direct evaporation of the films. We fabricated Fe-oxide/SWNT samples that are reacted by iron-oleate complex, oleic acid and cut SWNTs in 1-octadecene. The Fe-oxide/SWNT samples are dispersed in N,N-dimethylformamide and the resulting solution was deposited on an ITO glass substrate using the spraying method with magnetic field. After evaporation of the SWNT solution in the presence of a magnetic field, we transferred the nanotubes to the vacuum-evaporator chamber, and titanium is evaporated by e-beam evaporation to hold the vertical alignment of the SWNTs. The resulting SWNTs exhibit the formation of a high degree of vertically aligned SNWTs over a large area. We showed that the degree of orientation of the SWNTs is strongly influenced by the field strength, film thickness of the evaporating molecules and evaporating rates. This technique takes significant advantages of the alignment of SWNTs with high aspect ratio at room temperature, without any organic binders and without the need for further alignment procedures. Moreover, this method might be applicable to other anisotropic materials with high aspect ratio.

Self-sorted, aligned nanotube networks for thin-film transistors.

To find use in electronics, single-walled carbon nanotubes need to be efficiently separated by electronic type and aligned to ensure optimal and reproducible electronic properties. We report the fabrication of single-walled carbon nanotube (SWNT) network field-effect transistors, deposited from solution, possessing controllable topology and an on/off ratio as high as 900,000. The spin-assisted alignment and density of the SWNTs are tuned by different surfaces that effectively vary the degree of interaction with surface functionalities in the device channel. This leads to a self-sorted SWNT network in which nanotube chirality separation and simultaneous control of density and alignment occur in one step during device fabrication. Micro-Raman experiments corroborate device results as a function of surface chemistry, indicating enrichment of the specific SWNT electronic type absorbed onto the modified dielectric.