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1.
Electron‐injecting interlayers (ILs) which are stable in air, inject electrons efficiently, block holes, and block quenching of excitons, are very important to realize efficient inverted polymer light‐emitting diodes (IPLEDs). Two air‐stable polymer electron‐injecting interlayers (ILs), branched polyethyleneimine (PEI) and polyethyleneimine ethoxylated (PEIE) for use in IPLEDs are introduced, and the roles of the ILs in IPLEDs comparing these with a conventional Cs2CO3 IL are elucidated. These polymer ILs can reduce the electron injection barrier between ZnO and emitting layer by decreasing the work function (WF) of underlying ZnO, thereby effectively facilitating electron injection into the emitting layer. WF of ZnO covered by PEI is found to be lower than that covered by PEIE due to higher [N+]/[C] ratio of PEI. Furthermore, they can block the quenching of excitons and increase the luminous efficiency of devices. Thus, IPLEDs with PEI IL of optimum thickness (8 nm) show current efficiency (13.5 cd A–1), which is dramatically higher than that of IPLEDs with a Cs2CO3 IL (8 cd A‐1).  相似文献   

2.
Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.  相似文献   

3.
Electron field emission, electrons emitted from solid surfaces under high electric field, offers significant scientific interests in materials sciences and potential optoelectronics applications. 2D atomic layers, such as MoS2, exhibit fascinating properties for diverse applications in next‐generation nanodevices and rich physical phenomena for fundamental research. However, the study on field emission of semiconducting monolayers is lacking owing to its low efficiency and stability of electron emission. Here, electron field emission of the geometrically modulated monolayer semiconductors suspended with 1D nanoarrays is demonstrated. Chemical vapor deposition synthesis of two prototype monolayers of transition metal dichalcogenides (TMD), MoS2 and MoSe2, is presented and their diverse band structures offer an ideal platform to explore the fundamental process of the electron emission in the TMD. Geometrical modulation and charge transfer of the semiconducting monolayers can be significantly tuned with the structural suspension with the 1D ZnO nanoarrays. Possible mechanisms on the enhanced electron emission of the 2D monolayers are discussed. With geometrical control of the monolayers, a highly efficient and stable electron emission of TMD monolayers is achieved in low turn‐on electric fields, enabling applications on electrons sources and opening a new avenue toward geometrically tuned atomic layers.  相似文献   

4.
High performance indium tin oxide (ITO)‐free small molecule organic solar cells and organic light‐emitting diodes (OLEDs) are demonstrated using optimized ZnO electrodes with alternative non‐metallic co‐dopants. The co‐doping of hydrogen and fluorine reduces the metal content of ZnO thin films, resulting in a low absorption coefficient, a high transmittance, and a low refractive index as well as the high conductivity, which are needed for the application in organic solar cells and OLEDs. While the established metal‐doped ZnO films have good electrical and optical properties, their application in organic devices is not as efficient as other alternative electrode approaches. The optimized ZnO electrodes presented here are employed in organic solar cells as well as OLEDs and allow not only the replacement of ITO, but also significantly improve the efficiency compared to lab‐standard ITO. The enhanced performance is attributed to outstanding optical properties and spontaneously nanostructured surfaces of the ZnO films with non‐metallic co‐dopants and their straightforward integration with molecular doping technology, which avoids several common drawbacks of ZnO electrodes. The observations show that optimized ZnO films with non‐metallic co‐dopants are a promising and competitive electrode for low‐cost and high performance organic solar cells and OLEDs.  相似文献   

5.
The functionality of interfaces in hybrid inorganic/organic (opto)electronic devices is determined by the alignment of the respective frontier energy levels at both sides of the heterojunctions. Controlling the interface electronic landscape is a key element for achieving favourable level alignment for energy and charge transfer processes. Here, it is shown that the electronic properties of polar ZnO surfaces can be reversibly modified using organic photochromic switches. By employing a range of surface characterization techniques combined with density functional theory calculations, it is demonstrated that self‐assembled monolayers (SAMs) of photochromic phosphonic acid diarylethenes (PA‐DAEs) can be employed to reversibly change the electronic properties of polar ZnO/SAM structures by light stimuli. The highest occupied molecular orbital level of PA‐DAE is raised by 0.7 eV and the lowest unoccupied one lowered by 0.9 eV, respectively, upon illumination by ultraviolet light and the levels shift back to their original position upon illumination by green light. The results thus provide a pathway to tailor hybrid interface electronic properties in a dynamic manner upon simple light illumination, which can be exploited to reversibly tune the electrical properties of photoswitchable (opto)electronic devices.  相似文献   

6.
Using a representative model system, here electronic and structural properties of aromatic self‐assembled monolayers (SAMs) are described that contain an embedded, dipolar group. As polar unit, pyrimidine is used, with its orientation in the molecular backbone and, consequently, the direction of the embedded dipole moment being varied. The electronic and structural properties of these embedded‐dipole SAMs are thoroughly analyzed using a number of complementary characterization techniques combined with quantum‐mechanical modeling. It is shown that such mid‐chain‐substituted monolayers are highly interesting from both fundamental and application viewpoints, as the dipolar groups are found to induce a potential discontinuity inside the monolayer, electrostatically shifting the core‐level energies in the regions above and below the dipoles relative to one another. These SAMs also allow for tuning the substrate work function in a controlled manner independent of the docking chemistry and, most importantly, without modifying the SAM‐ambient interface.  相似文献   

7.
The shape of crystalline particles is recognized as one important parameter for the adjustment of functional properties of inorganic materials. The surfaces of a thermodynamically stable crystal correspond to a set of lattice planes determined by the minimum interface energy. Thus, a morphology deviating from the most stable state correlates to either a change of the proportion of those surfaces to each other or ultimately a new set of surfaces emerges. At the nanoscale, when the surface‐to‐volume ratio is large, it is expected that a change in morphology implies a measurable alteration of properties. Here, the synthesis of nanocrystalline ZnO nano­particles possessing a new non‐equilibrium shape is presented. The reaction of special organometallic precursors at the interface of a water‐in‐oil emulsion facilitates the synthesis of fairly monodisperse prismatic ZnO nanocrystallites with an adjustable aspect ratio in gram amounts. It is found that the special morphology influences the bulk properties of the ZnO materials. Contrary to the well‐known quantum size effect (smaller particles produce a blue‐shift), a shortening of the ZnO nanoprisms induces a decrease in the bandgap (red‐shift). This effect is due to the influence of an electric field inside the particles caused by the polarity of the surfaces terminating the nanoprisms (the quantum‐confined Stark effect).  相似文献   

8.
《Microelectronic Engineering》2007,84(9-10):1857-1860
A systematic analysis of the different methods of work function (WF) tuning for gate stacks using fully silicided (FUSI) gate electrodes is presented. We show that FUSI gates have the potential to meet the WF requirements for future nodes, including high performance applications, achieving band edge WF, with total WF range of up to ∼900 meV. The introduction of dopants (such as Sb, As, P, B) by ion implantation is shown to be effective to tune the WF of NiSi or Ni3Si2 on SiO2 or SiON by ∼550 meV, but is ineffective on HfSiON or for Ni-richer silicides. Different silicide phases can be used for Ni FUSI gates on HfSiON dielectrics, taking advantage of the higher WF of metal-rich silicides, achieving a WF range of ∼400 meV. This method is not effective, however, on SiON dielectrics. The introduction of Lanthanides by several techniques (such as dielectric cap deposition, ion implantation into poly-Si, or at metal deposition) that result in the modification of the dielectric, is found, for Ni FUSI gates, to achieve low WF (∼4.0 eV) suitable for NMOS. Similarly, incorporation of Al can be used to achieve PMOS type WF, as well as the use of metal-rich Ni and/or Pt based FUSI gates (with WF as high as 5.0 eV).  相似文献   

9.
The size‐ and morphology‐controlled growth of ZnO nanowire (NW) arrays is potentially of interest for the design of advanced catalysts and nanodevices. By adjusting the reaction temperature, shelled structures of ZnO made of bunched ZnO NW arrays are prepared, grown out of metallic Zn microspheres through a wet‐chemical route in a closed Teflon reactor. In this process, ZnO NWs are nucleated and subsequently grown into NWs on the surfaces of the microspheres as well as in strong alkali solution under the condition of the pre‐existence of zincate (ZnO22–) ions. At a higher temperature (200 °C), three different types of bunched ZnO NW or sub‐micrometer rodlike (SMR) aggregates are observed. At room temperature, however, the bunched ZnO NW arrays are found only to occur on the Zn microsphere surface, while double‐pyramid‐shaped or rhombus‐shaped ZnO particles are formed in solution. The ZnO NWs exhibit an ultrathin structure with a length of ca. 500 nm and a diameter of ca. 10 nm. The phenomenon may be well understood by the temperature‐dependent growth process involved in different nucleation sources. A growth mechanism has been proposed in which the degree of ZnO22–saturation in the reaction solution plays a key role in controlling the nucleation and growth of the ZnO NWs or SMRs as well as in oxidizing the metallic Zn microspheres. Based on this consideration, ultrathin ZnO NW cluster arrays on the Zn microspheres are successfully obtained. Raman spectroscopy and photoluminescence measurements of the ultrathin ZnO NW cluster arrays have also been performed.  相似文献   

10.
Silicon heterojunction (SHJ) solar cells are highly interesting, because of their high efficiency and low cost fabrication. So far, the most applied transparent conductive oxide (TCO) is indium tin oxide (ITO). The replacement of ITO with cheaper, more abundant and environmental friendly material with texturing capability is a promising way to reduce the production cost of the future SHJ solar cells. Here, we report on the fabrication of the SHJ solar cells with direct current‐sputtered aluminum‐doped zinc oxide (ZnO:Al) as an alternative TCO. Furthermore, we address several important differences between ITO and the ZnO:Al layers including a high Schottky barrier at the emitter/ZnO:Al interface and a high intrinsic resistivity of the ZnO:Al layers. To overcome the high Schottky barrier, we suggest employing micro‐crystalline silicon (µc‐Si:H) emitter, which also improves temperature threshold and passivation of the solar cell precursor. In addition, we report on the extensive studies of the effect of the ZnO:Al deposition parameters including layer thickness, oxygen flow, power density and temperature on the electrical properties of the fabricated SHJ solar cells. Finally, the results of our study indicate that the ZnO:Al deposition parameters significantly affect the electrical properties of the obtained solar cell. By understanding and fine‐tuning all these parameters, a high conversion efficiency of 19.2% on flat wafer (small area (5 × 5 mm2) and without any front metal grid) is achieved. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

11.
The energy level alignment between organic semiconductors (OSCs) and the respective (metal) electrodes in organic electronic devices is of key importance for efficient charge carrier injection. For many years, researchers have attempted to control this energy level alignment by means of functional self‐assembled monolayers or the insertion of thin injection layers (made, e.g., of doped OCSs or pure dopants). The present work demonstrates an alternative to these approaches, namely the use of phthalocyanine monolayers as contact primers, which are deposited onto noble metal electrodes by means of vacuum deposition. It is shown that polar as well as non‐polar phthalocyanines modify the work functions of clean Au(111) and Ag(111) surfaces as a function of their coverage and thus enable quantitative control of the metal work functions. This behavior is successfully replicated for the respective polycrystalline metal surfaces and it is found that full monolayers can even withstand air exposure when protected by sacrificial multilayers, which are afterward removed by thermal desorption.  相似文献   

12.
3D continuous ZnO morphologies with characteristic feature sizes on the 10 nm length scale are attractive for electronic device manufacture. However, their synthesis remains a challenge because of the low crystallization temperature of ZnO. Here, we report a method for the robust and reliable synthesis of fully crystalline 3D mesoporous ZnO networks by means of atomic layer deposition (ALD) of ZnO into a self‐assembled block copolymer template. By carefully optimizing the processing conditions we are able to synthesize several‐micrometer‐thick layers of mesoporous ZnO networks with a strut width of 30 nm. Two 3D mesoporous morphologies are manufactured: a periodic gyroid structure and a random worm‐like morphology. Exploiting the ALD property to conformally coat complex surfaces of high aspect ratio, the channel network of a 3D continuous channel network of a self‐assembled block copolymer is replicated into ZnO. X‐ray photoemission spectroscopy and x‐ray diffraction measurements reveal that the chemical composition of the mesoporous structures is uniform and consists of wurtzite‐ZnO throughout the film. Scanning electron microscopy reveals an average pore dimension of 30 nm. The potential of this material for a hybrid photovoltaic application is demonstrated by the manufacture of a poly(3‐hexylthiophene)/ZnO solar cell.  相似文献   

13.
Homogenous crystallization in solution, in the absence of external influences, is expected to lead to growth that is symmetric at least in two opposite facets. Such was not the case when we attempted to synthesize ZnO nanostructures by employing a solvothermal technique. The reaction product, instead, consisted of bullet‐shaped tiny single crystals with an abrupt hexagonal base and a sharp tip. A careful analysis of the product and the intermediate states of the synthesis reveals that one of the reaction intermediates with sheet‐like morphology acts as a self‐sacrificing template and induces such unexpected and novel growth. The synthesis was further extended to dope the nanobullets with nitrogen as previous studies showed this can induce p‐type behavior in ZnO, which is technologically complementary to the naturally occurring n‐type ZnO. Herein, a soft‐chemical approach is used for the first time for this purpose, which is otherwise accomplished with high‐temperature techniques. Cathodoluminesce (CL) investigations reveal stable optical behavior within a pure nanobullet. On the other hand, the CL spectra derived from the surfaces and the cores of the doped samples are different, pointing at a N‐rich core. Finally, even though N‐doped ZnO is known to have high electrical conductivity, the study now demonstrates that the field‐emission properties of ZnO can also be greatly enhanced by means of N doping.  相似文献   

14.
Physical phenomena such as energy quantization have to‐date been overlooked in solution‐processed inorganic semiconducting layers, owing to heterogeneity in layer thickness uniformity unlike some of their vacuum‐deposited counterparts. Recent reports of the growth of uniform, ultrathin (<5 nm) metal‐oxide semiconductors from solution, however, have potentially opened the door to such phenomena manifesting themselves. Here, a theoretical framework is developed for energy quantization in inorganic semiconductor layers with appreciable surface roughness, as compared to the mean layer thickness, and present experimental evidence of the existence of quantized energy states in spin‐cast layers of zinc oxide (ZnO). As‐grown ZnO layers are found to be remarkably continuous and uniform with controllable thicknesses in the range 2–24 nm and exhibit a characteristic widening of the energy bandgap with reducing thickness in agreement with theoretical predictions. Using sequentially spin‐cast layers of ZnO as the bulk semiconductor and quantum well materials, and gallium oxide or organic self‐assembled monolayers as the barrier materials, two terminal electronic devices are demonstrated, the current–voltage characteristics of which resemble closely those of double‐barrier resonant‐tunneling diodes. As‐fabricated all‐oxide/hybrid devices exhibit a characteristic negative‐differential conductance region with peak‐to‐valley ratios in the range 2–7.  相似文献   

15.
Smart pH‐responsive surfaces that could autonomously induce unidirectional wetting of acid and base with reversed directions are fabricated. The smart surfaces, consisting of chemistry‐asymmetric “Janus” silicon cylinder arrays (Si‐CAs), are prepared by precise modification of functional groups on each cylinder unit. Herein, amino and carboxyl groups are chosen as typical pH‐responsive groups, owing to their protonation/deprotonation effect in response to pH of the contacted aqueous solution. One side of the Si‐CAs is modified by poly(2‐(dimethylamino)ethyl methacrylate), while the other side is modified by mixed self‐assembled monolayers of 1‐dodecanethiol and 11‐mercaptoundecanoic acid. On such surfaces, it is observed that acid and base wet in a unidirectional manner toward corresponding directions that are modified by amino or carboxyl groups, which is caused by asynchronous change of wetting property on two sides of the asymmetric structures. The as‐prepared Janus surfaces could regulate the wetting behavior of acid and base and could direct unidirectional wetting of water with reversed directions when the surfaces are treated by strong acid or base. Due to the excellent response capability, the smart surfaces are potential candidates to be applied in sensors, microfluidics, oil/water separation, and smart interfacial design.  相似文献   

16.
Despite multiple research approaches to prevent bacterial colonization on surfaces, device‐associated infections are currently responsible for about 50% of nosocomial infections in Europe and significantly increase health care costs, which demands development of advanced antibacterial surface coatings. Here, novel antimicrobial composite materials incorporating zinc oxide nanoparticles (ZnO NP) into biocompatible poly(N‐isopropylacrylamide) (PNIPAAm) hydrogel layers are prepared by mixing the PNIPAAm prepolymer with ZnO NP, followed by spin‐coating and photocrosslinking. Scanning electron microscopy (SEM) characterization of the composite film morphology reveals a homogeneous distribution of the ZnO NP throughout the film for every applied NP/polymer ratio. The optical properties of the embedded NP are not affected by the matrix as confirmed by UV‐vis spectroscopy. The nanocomposite films exhibit bactericidal behavior towards Escherichia coli (E. coli) for a ZnO concentration as low as ≈0.74 μg cm?2 (1.33 mmol cm?3), which is determined by inductively coupled plasma optical emission spectrometry. In contrast, the coatings are found to be non‐cytotoxic towards a mammalian cell line (NIH/3T3) at bactericidal loadings of ZnO over an extended period of seven days. The differential toxicity of the ZnO/hydrogel nanocomposite thin films between bacterial and cellular species qualifies them as promising candidates for novel biomedical device coatings.  相似文献   

17.
A novel ZnO hierarchical micro/nanoarchitecture is fabricated by a facile solvothermal approach in an aqueous solution of ethylenediamine (EDA). This complex architecture is of a core/shell structure, composed of dense nanosheet‐built networks that stand on a hexagonal‐pyramid‐like microcrystal (core part). The ZnO hexagonal micropyramid has external surfaces that consist of a basal plane (000 ) and lateral planes {0 11}. The nanosheets are a uniform thickness of about 10 nm and have a single‐crystal structure with sheet‐planar surfaces as {2 0} planes. These nanosheets interlace and overlap each other with an angle of 60° or 120°, and assemble into a discernible net‐ or grid‐like morphology (about 100 nm in grid‐size) on the micropyramid, which shows a high specific surface area (185.6 m2 g?1). Such a ZnO micro/nanoarchitecture is new in the family of ZnO nanostructures. Its formation depends on the concentration of the EDA solution as well as on the type of zinc source. A two‐step sequential growth model is proposed based on observations from a time‐dependent morphology evolution process. Importantly, such structured ZnO has shown a strong structure‐induced enhancement of photocatalytic performance and has exhibited a much better photocatalytic property and durability for the photodegradation of methyl orange than that of other nanostructured ZnO, such as the powders of nanoparticles, nanosheets, and nanoneedles. This is mainly attributed to its higher surface‐to‐volume ratio and stability against aggregation. This work not only gives insight into understanding the hierarchical growth behaviour of complex ZnO micro/nanoarchitectures in a solution‐phase synthetic system, but also provides an efficient route to enhance the photocatalytic performance of ZnO, which could also be extended to other catalysts, such as the inherently excellent TiO2, if they are of the same hierarchical micro/nanoarchitecture with an open and porous nanostructured surface layer.  相似文献   

18.
The first models of mesoporous ZnO/Pt Janus micromotors that show fuel‐free and light‐powered propulsion depending on the interface roughness are shown. Two models of ZnO semiconducting particles with distinct surface morphologies and pore structures are synthesized by self‐aggregation of primary nanoparticles and nanosheets into nanoscale rough and smooth microparticles, respectively. The self‐assembled nanosheet model (smooth) provides a large surface for the formation of a continuous Pt layer with strong adherence, whereas the discontinuous Pt species take place inside the inter‐nanoparticles pores in the self‐assembled nanoparticle model (rough). The effects of the interface, surface porosity, defect, and charge transfer on the light‐powered motion for both well‐designed mesoporous ZnO/Pt Janus micromotors are investigated and compared to find the underlying propulsion mechanisms. The degradation of two model pollutants is demonstrated as a proof‐of‐concept application of these carefully engineered Janus micromotors. In this work, it is shown that by discreet material fabrication together with semiconductor/metal interface charge transport interpretation, it would be possible to develop new light‐driven Janus micromotors based on other photocatalysts containing active surfaces such as TiO2.  相似文献   

19.
A systematic study on controlled synthesis of ZnO nanotetrapods by combining metal‐vapor transport, oxidative nucleation/growth, fast‐flow quenching, and water‐assisted cleaning is reported. The technique developed in this work makes possible the fabrication of ZnO nanotetrapods with different morphologies, with arm diameters down to 17 nm, and with arm lengths ranging from 50 nm up to a few micrometers. The octa‐twin model is verified for the growth of the ZnO nanotetrapods. Photoluminescence (PL) studies indicate a higher level of surface and subsurface oxygen vacancies for smaller ZnO nanotetrapods. The ZnO nanotetrapods are first used for the fabrication of resistor‐type humidity sensors, which show high sensitivity, quick response/recovery, long lifetime, and a wide range of humidity response. These favorite characteristics of the humidity sensors are ascribed to the unique morphology of the nanotetrapods, which can create a film with faceted pores and large internal surfaces.  相似文献   

20.
As an alternative to expensive extracellular matrix (ECM) proteins generally applied as coatings in Petri dishes used for cell binding, an innovative system based on epoxide‐functionalized monolayers capable of protein binding is proposed. Since cells bind to material surfaces through proteins, protein‐binding surfaces should also promote cell binding. Here we investigate how the cell‐binding properties of an epoxide‐functionalized surface compares with ECM protein gel coated surfaces and tissue culture polystyrene control surfaces. Glass surfaces are functionalized with glycidoxypropyltriethoxysilane (GOPS), which results in an epoxide‐functionalized surface capable of binding proteins through an epoxide–amine reaction. Advancing contact angle measurements and atomic force microscopy measurements confirm the formation of a homogeneous GOPS monolayer. This monolayer is micropatterned with fluorescein‐labeled ECM protein gel by microcontact printing (µCP). Confocal laser scanning microscopy (CLSM) shows accurately transferred ECM protein gel micropatterns. Osteoblasts that are seeded on these micropatterned substrates show a clear preference for adhering to the epoxide‐functionalized areas. The morphology of these cultured osteoblasts is needle‐like with high aspect ratios. As controls, osteoblasts are cultured on GOPS‐functionalized surfaces, unstructured ECM protein gel surfaces, and tissue culture polystyrene (TCPS). The GOPS surfaces demonstrate a drastic increase in cell adhesion after 2 h, whilst the other tests show no adverse effects of this surface on the osteoblasts as compared to ECM and TCPS. CLSM shows healthy cell morphologies on each surface. It is demonstrated for the first time that epoxide groups outperform ECM protein gel in cell adhesion, thereby providing new routes for cost‐effective coatings that improve biocompatibility as well as exciting, new methodologies to control and direct cell adhesion.  相似文献   

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