Measurement of Electrophysiological Signals In Vitro Using High-Performance Organic Electrochemical Transistors

Biological environments use ions in charge transport for information transmission. The properties of mixed electronic and ionic conductivity in organic materials make them ideal candidates to transduce physiological information into electronically processable signals. A device proven to be highly successful in measuring such information is the organic electrochemical transistor (OECT). Previous electrophysiological measurements performed using OECTs show superior signal-to-noise ratios than electrodes at low frequencies. Subsequent development has significantly improved critical performance parameters such as transconductance and response time. Here, interdigitated-electrode OECTs are fabricated on flexible substrates, with one such state-of-the-art device achieving a peak transconductance of 139 mS with a 138 µs response time. The devices are implemented into an array with interconnects suitable for micro-electrocorticographic application and eight architecture variations are compared. The two best-performing arrays are subject to the full electrophysiological spectrum using prerecorded signals. With frequency filtering, kHz-scale frequencies with 10 µV-scale voltages are resolved. This is supported by a novel quantification of the noise, which compares the gate voltage input and drain current output. These results demonstrate that high-performance OECTs can resolve the full electrophysiological spectrum and suggest that superior signal-to-noise ratios could be achieved in high frequency measurements of multiunit activity.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Directing-Group-Free C7-Alkylations of N-Alkylindoles Mediated by Cationic Zirconium Complexes: Role of Brønsted Acid for Catalytic Manifold

Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold.     

Organic–Inorganic Hybrid Gold Halide Perovskites: Structural Diversity through Cation Size

Crystal structures of a series of organic–inorganic hybrid gold iodide perovskites, formulated as A₂[Au^II₂][Au^IIII₄] [A=methylammonium (MA) ( 1 ) and formamidinium (FA) ( 2 )], A′₂[I₃]_1−x[Au^II₂]_x[Au^IIII₄] [A′=imidazolium (IMD) ( 3 ), guanidinium (GUA) ( 4 ), dimethylammonium (DMA) ( 5 ), pyridinium (PY) ( 6 ), and piperizinium (PIP) ( 7 )], systematically changed depending on the cation size. In addition, triiodide (I₃⁻) ions were partly incorporated into the AuI₂⁻ sites of 3 – 7 , whereas they were not incorporated into those of 1 and 2 . Such a difference comes from the size of the organic cation. Optical absorption spectra showed characteristic intervalence charge-transfer bands from Au^I to Au^III species, and the optical band gap increased as the size of the cation became larger.     

Organic Nanoparticles: Preparation,Self‐Assembly,and Properties

The strong tendency of organic nanoparticles to rapidly self‐assemble into highly aligned superlattices at room temperature when solution‐cast from dispersions or spray‐coated directly onto various substrates is described. The nanoparticle dispersions are stable for years. The novel precipitation process used is believed to result in molecular distances and alignments in the nanoparticles that are not normally possible. Functional organic light‐emitting diodes (OLEDs)—which have the same host–dopant emissive‐material composition—with process‐tunable electroluminescence have been built with these nanoparticles, indicating the presence of novel nanostructures. For example, only changing the conditions of the precipitation process changes the OLED emission from green light to yellow.     

双层有机电致发光器件有机层厚度优化的数值研究

在陷阱电荷限制电流传导理论的基础上,提出了双层有机电致发光器件的数值模型,研究了结构为"阳极/空穴输运层(HTL)/发光层(EML)/阴极"的器件中电流密度和量子效率随有机层的特征陷阱能量、陷阱密度和载流子迁移率的依赖关系. 研究发现,对于给定的HTL和EML的特征陷阱能量、陷阱密度和载流子迁移率,存在一个最优的HTL和EML之间的厚度比率,在此最优厚度比下,器件的电流密度和量子效率达到最大.通过有机层厚度的优化,器件的电流密度和量子效率可提高多达两个数量级.另外,还研究了最优厚度比随有机层特征陷阱能量、总陷阱密度和载流子迁移率之间的定量关系.     

Extracting Light from Polymer Light‐Emitting Diodes Using Stamped Bragg Gratings

In this paper, we describe a method for increasing the external efficiency of polymer light‐emitting diodes (LEDs) by coupling out waveguided light with Bragg gratings. We numerically model the waveguide modes in a typical LED structure and demonstrate how optimizing layer thicknesses and reducing waveguide absorption can enhance the grating outcoupling. The gratings were created by a soft‐lithography technique that minimizes changes to the conventional LED structure. Using one‐dimensional and two‐dimensional gratings, we were able to increase the forward‐directed emission by 47 % and 70 %, respectively, and the external quantum efficiency by 15 % and 25 %.     

Platinum Binuclear Complexes as Phosphorescent Dopants for Monochromatic and White Organic Light‐Emitting Diodes

Efficient blue‐, green‐, and red‐light‐emitting organic diodes are fabricated using binuclear platinum complexes as phosphorescent dopants. The series of complexes used here have pyrazolate bridging ligands and the general formula C^∧NPt(μ‐pz)₂PtC^∧N (where C^∧N = 2‐(4′,6′‐difluorophenyl)pyridinato‐N,C^2′, pz = pyrazole ( 1 ), 3‐methyl‐5‐tert‐butylpyrazole ( 2 ), and 3,5‐bis(tert‐butyl)pyrazole ( 3 )). The Pt–Pt distance in the complexes, which decreases in the order 1 > 2 > 3 , solely determines the electroluminescence color of the organic light‐emitting diodes (OLEDs). Blue OLEDs fabricated using 8 % 1 doped into a 3,5‐bis(N‐carbazolyl)benzene (mCP) host have a quantum efficiency of 4.3 % at 120 Cd m^–2, a brightness of 3900 Cd m^–2 at 12 V, and Commission Internationale de L'Eclairage (CIE) coordinates of (0.11, 0.24). Green and red OLEDs fabricated with 2 and 3 , respectively, also give high quantum efficiencies (～ 6.7 %), with CIE coordinates of (0.31, 0.63) and (0.59, 0.46), respectively. The current‐density–voltage characteristics of devices made using dopants 2 and 3 indicate that hole trapping is enhanced by short Pt–Pt distances (< 3.1 Å). Blue electrophosphorescence is achieved by taking advantage of the binuclear molecular geometry in order to suppress dopant intermolecular interactions. No evidence of low‐energy emission from aggregate states is observed in OLEDs made with 50 % 1 doped into mCP. OLEDs made using 100 % 1 as an emissive layer display red luminescence, which is believed to originate from distorted complexes with compressed Pt–Pt separations located in defect sites within the neat film. White OLEDs are fabricated using 1 and 3 in three different device architectures, either with one or two dopants in dual emissive layers or both dopants in a single emissive layer. All the white OLEDs have high quantum efficiency (～ 5 %) and brightness (～ 600 Cd m^–2 at 10 V).     

不同表面预处理对有机电致发光显示器性能的影响

从生产角度研究了基板表面的预处理工艺对OLED性能的影响,分别用UVOzone、氧Plasma以及两者相结合的方式对基板进行表面处理,并按照生产工艺制作器件,从接触角、方阻以及光电特性等测试结果对各种表面处理的样品进行比较。结果表明以上处理都改善了器件性能,不同程度提高了器件的清洁度、亮度和发光效率,其中UVOzone和氧Plasma结合的方式处理效果最为显著,器件在10V时亮度达到79920cd/m2,比其他两种处理方式亮度提高约25%。     

Conventional Electron Microscopy and Electron Holography of Organic Solar Cells

Organic solar cells are a promising route towards large‐area and low‐price photovoltaic systems. The devices are composed of at least two layers: the hole‐transport layer and the electron‐transport layer. The light absorption can occur in one or both layers. At the interface of the layers the excitons are separated into charge carriers, and every layer deals with one type of carrier. Higher efficiencies of the separation process can be obtained by using a mixed layer containing both materials to obtain a very high interface area. Although the structure of the mixed layers used plays a crucial role for the device performance, until now the morphologies have not been elucidated. In order to correlate physical and optical findings with structure and morphology for the materials in question, electron microscopy experiments were performed on the single components as well as on the layer systems. The conventional electron microscope is a poor phase microscope. As consequence, weak‐phase objects like organic molecules have to be stained or imaged under strong defocus to produce an observable contrast. Artifacts caused by chemical staining and the appearance of Fresnel diffraction using the defocus technique represent the main problems of conventional microscopy. These artifacts can be avoided using electron holography. Holograms of ultrathin sections of thin layers composed of organic dye molecules were recorded. Subsequently, the phase images were reconstructed. In this manner, we succeeded in obtaining high‐contrast electron micrographs without applying staining or defocus. In addition, holograms of crystalline C₆₀ and zinc phthalocyanine were successfully recorded. Holography has been shown to be a useful tool to image beam‐sensitive and weak‐phase objects without artifacts.