Chemical modification of the electronic conducting states in polymer nanodevices

Organic materials offer new electronic functionality not available in inorganic devices. However, the integration of organic compounds within nanoscale electronic circuitry poses new challenges for materials physics and chemistry. Typically, the electronic states in organic materials are energetically misaligned with the Fermi level of metal contacts. Here, we study the voltage-induced change in conductivity in nanoscale devices comprising a monolayer of polyelectrolyte macromolecules. The devices are fabricated using integrated shadow masks. Reversible switching is observed between conducting (ON) and non-conducting (OFF) states in the devices. The open design of our devices easily permits chemical modification of the polyelectrolyte, which we show has a pronounced effect on the ON-OFF switching. We suggest that the switching voltage ionizes the polymers, creating a conducting channel of electronic levels aligned with the contact Fermi level.     

Transparent electronics: Schottky barrier and heterojunction considerations

Transparent electronics employs wide band gap semi-conductors which are transparent in the visible portion of the electromagnetic spectrum for the fabrication of electronic devices and circuits. Current and future transparent electronics applications require the use of wide band gap oxide semi-conductor interfaces as contacts and rectifiers, as well as for passivation and barrier-shaping layers. Modern Schottky barrier and heterojunction theory can be applied to the assessment of such interfaces, and is reviewed for this purpose from a charge transfer, energy band diagram perspective. Ideal interface formation theory is envisaged as originating from Fermi level mediated charge transfer giving rise to a macroscopic interfacial dipole, while non-ideal theory involves charge neutrality level mediated charge transfer giving rise to a microscopic interfacial dipole. This interface formation theory is applied to the problem of indium tin oxide (ITO) - zinc oxide and ITO - tin oxide interfaces, confirming their utility as injecting source-drain contacts in transparent thin-film transistors.     

Pressure-induced transition-temperature reduction in ZnS nanoparticles

The study of the structural transition in nanoscale materials is of particular interest for their potential applications. In the present study, we have observed a lower temperature T = 250?°C for the phase transition from the sphalerite structure to the wurtzite structure in ZnS nanoparticles under a pressure of 1?GPa, as compared to those, T = 400 and 1020?°C, for ZnS nanoparticles and bulk ZnS under normal pressure, respectively. The reduced transition temperature is attributed to the applied pressure leading to tight particle-particle contacts, which change the surface (or interfacial) environment of the nanoparticles and thus their surface (or interfacial) energy.     

Solution-processed ultraviolet photodetectors based on colloidal ZnO nanoparticles

A "visible-blind" solution-processed UV photodetector is realized on the basis of colloidal ZnO nanoparticles. The devices exhibit low dark currents with a resistance >1 TOmega and high UV photocurrent efficiencies with a responsivity of 61 A/W at an average intensity of 1.06 mW/cm(2) illumination at 370 nm. The characteristic times for the rise and fall of the photocurrent are <0.1 s and about 1 s, respectively. The photocurrent of the device is associated with a light-induced desorption of oxygen from the nanoparticle surfaces, thus removing electron traps and increasing the free carrier density which in turn reduces the Schottky barrier between contacts and ZnO nanoparticles for electron injection. The devices are promising for use in large-area UV photodetector applications.     

Core-shell nanostructured nanoparticle films as chemically sensitive interfaces

This paper reports the results of an investigation of vapor molecule sorption at different types of nanostructured nanoparticle films. Core-shell nanoparticles of two different core sizes, AU2-nm and Au5-nm, and molecular linkers of two different binding properties, 1,9-nonanedithiol and 11-mercaptoundecanoic acid, are utilized as building blocks for constructing chemically sensitive interfaces. The work couples measurements of two different transducers, interdigitated microelectrodes and quartz crystal microbalance, to determine the correlation of the electronic resistance change and the mass loading with vapor sorption. The responses to vapor sorption at these nanostructured interfaces are demonstrated to be dependent on the core size of nanoparticles and the chemical nature of linking molecules. The difference of molecular interactions of vapor molecules at the nanostructured interface is shown to have a significant impact on the response profile and sensitivity. For the tested vapor molecules, while there are small differences for the sorption of nonpolar and hydrophobic vapor molecules, there are striking differences for the sorption of polar and hydrophilic vapor molecules at these nanostructured interfacial materials. The implication of the findings to the delineation of design parameters for constructing core-shell nanoparticle assemblies as chemically sensitive interfacial materials is also discussed.     

Magnetic colloidosomes derived from nanoparticle interfacial self-assembly

Based on the interfacial self-assembly of magnetite nanoparticles, we demonstrate the formation of colloidosomes with shells predominantly composed of monolayers of liquid-like, close-packed nanoparticles. The gelation of aqueous phase with agarose leads to robust and water-dispersible nanoparticle colloidosomes, allowing encapsulation of various water soluble materials. The cutoff of the nanoparticle colloidosomes obtained is primarily defined by the nanoparticle size. This controllable permeability should be of great importance for the encapsulation application.     

A Scalable Nickel–Cellulose Hybrid Metamaterial with Broadband Light Absorption for Efficient Solar Distillation

Sophisticated metastructures are usually required to broaden the inherently narrowband plasmonic absorption of light for applications such as solar desalination, photodetection, and thermoelectrics. Here, nonresonant nickel nanoparticles (diameters < 20 nm) are embedded into cellulose microfibers via a nanoconfinement effect, producing an intrinsically broadband metamaterial with 97.1% solar-weighted absorption. Interband transitions rather than plasmonic resonance dominate the optical absorption throughout the solar spectrum due to a high density of electronic states near the Fermi level of nickel. Field solar purification of sewage and seawater based on the metamaterial demonstrates high solar-to-water efficiencies of 47.9–65.8%. More importantly, the solution-processed metamaterial is mass-producible (1.8 × 0.3 m²), low-cost, flexible, and durable (even effective after 7 h boiling in water), which are critical to the commercialization of portable solar-desalination and domestic-water-purification devices. This work also broadens material choices beyond plasmonic metals for the light absorption in photothermal and photocatalytic applications.     

Alkyl-functionalized oxide-free silicon nanoparticles: synthesis and optical properties

Highly monodisperse silicon nanoparticles (1.57 +/- 0.21 nm) are synthesized with a covalently attached alkyl monolayer on a gram scale. Infrared spectroscopy shows that these silicon nanoparticles contain only a few oxygen atoms per nanoparticle. XPS spectra clearly show the presence of unoxidized Si and attached alkyl chains. Owing to the relatively efficient synthesis (yields approximately 100-fold higher than of those previously reported) the molar extinction coefficient epsilon can be measured: epsilon(max) = 1.7 x 10(-4) M(-1)cm(-1), only a factor of 4 lower than that of CdS and CdSe nanoparticles of that size. The quantum yield of emission ranges from 0.12 (C(10)H(21)-capping) to 0.23 (C(16)H(33)-capping). UV/Vis absorption and emission spectroscopy show clear vibrational progressions (974 +/- 14 cm(-1); up to five vibrational bands visible at room temperature), resembling bulk SiC phonons, which support the monodispersity observed by TEM. This was also confirmed by time-resolved fluorescence anisotropy measurements, which display a strictly monoexponential decay that can only be indicative of monodisperse, ball-shaped nanoparticles.     

Photovoltaic heterojunctions of inorganic semiconductors in the defective limit

A large amount of current research in thin film photovoltaics based on inorganic semiconductors aims to deposit and process these active layers using inexpensive and low temperature processing methods resulting in high densities of electronic states in the bandgap associated with structural and point defects. We define semiconductors in which the Fermi level is pinned throughout the bulk as being at the defective limit and explore the consequences for heterojunctions designed to separate photocarriers. Using this novel concept of the defective limit, heterojunction band offsets can be predicted for less-common materials such as the earth-abundant materials also under intense investigation. Because of the Fermi level pinning in the bulk, only Type II heterojunctions will separate charges but the high defect concentrations will also result in small minority carrier diffusion lengths. These limitations require the use of nanostructured device architectures for cells of such materials with appreciable power conversion efficiency.     

Nanoparticle-wetted surfaces for relays and energy transmission contacts

Submonolayer coatings of noble-metal nanoparticle liquids (NPLs) are shown to provide replenishable surfaces with robust asperities and metallic conductivity that extends the durability of electrical relays by 10 to 100 times (depending on the current driven through the contact) as compared to alternative approaches. NPLs are single-component materials consisting of a metal nanoparticle core (5-20 nm Au or Pt nanoparticles) surrounded by a covalently tethered ionic-liquid corona of 1.5 to 2 nm. Common relay failure modes, such as stiction, surface distortion, and contact shorting, are suppressed with the addition of a submonolayer of NPLs to the contact surfaces. This distribution of NPLs results in a force profile for a contact-retraction cycle that is distinct from bare Au contacts and thicker, multilayer coatings of NPLs. Postmortem examination reveals a substantial decrease in topological change of the electrode surface relative to bare contacts, as well as an indication of lateral migration of the nanoparticles from the periphery towards the contact. A general extension of this concept to dynamic physical interfaces experiencing impact, sliding, or rolling affords alternatives to increase reliability and reduced losses for transmittance of electrical and mechanical energy.     

Synergistic Effect of Hydroxyl and Carboxyl Groups on Promoting Nanoparticle Occlusion within Calcite

Direct occlusion of guest nanoparticles into host crystals enables the straightforward preparation for various of nanocomposite materials with emerging properties. Therefore, it is highly desirable to elucidate the ‘design rules’ that govern efficient nanoparticle occlusion. Herein, a series of sterically-stabilized nanoparticles are rationally prepared, where the surface stabilizer chains of such nanoparticles are composed of either poly(methacrylic acid), or poly(glycerol monomethacrylate), or poly((2-hydroxy-3-(methacryloyloxy)propyl)serine). Systematic investigation reveals that hydroxyl groups and carboxyl groups play a synergistic role in driving nanoparticle incorporation into calcite crystals, where the hydroxyl groups enhance colloidal stability of the nanoparticles and the carboxyl groups provide binding sites for efficient occlusion. The generality of these findings is further validated by extending it to polymer-stabilized gold nanoparticles. This study demonstrates that precision synthesis of polymer stabilizers comprising of synergistic functional groups can significantly promote nanoparticle occlusion, thus enabling the efficient construction of organic-inorganic hybrid materials via nanoparticle occlusion strategy.     

Ion-induced elongation of gold nanoparticles in silica by irradiation with Ag and Cu swift heavy ions: track radius and energy loss threshold

Systematic investigations of the energy loss threshold above which the irradiation-induced elongation of spherical Au nanoparticles occurs are reported. Silica films containing Au nanoparticles with average diameters of 15-80 nm embedded within a single plane were irradiated with 12-54 MeV Ag and 10-45 MeV Cu ions at 300 K and at normal incidence. We demonstrate that the efficiency of the ion-induced nanoparticle elongation increases linearly with the electronic energy transferred per ion track length unit from the energetic ions to the silica film. Ion beam shaping occurs above a threshold value of the specific electronic energy transfer. Three relevant regions are identified with respect to the original size of the Au nanoparticles. For 15 and 30 nm diameter particles, elongation occurs for electronic stopping power larger than 3.5 keV nm(-1). For Au nanoparticles with 40-50 nm diameter an electronic stopping power above 5.5 keV nm(-1) is required for elongation to be observed. Elongation of Au nanoparticles with 80 nm diameter is observed for electronic stopping between ～ 7-8 keV nm(-1). For all combinations of ions and energies, the ion track temperature profiles are calculated within the framework of the thermal spike model. The correlation between experimental results and simulated data indicates a thermal origin of the increase in the elongation rate with increasing the track diameter.     

Revealing structure and electronic properties at organic interfaces using TEM

Molecules and atoms at material interfaces have properties that are distinct from those found in the bulk. Distinguishing the interfacial species from the bulk species is the inherent difficulty of interfacial analysis. For organic photovoltaic devices, the interface between the donor and acceptor materials is the location for exciton dissociation. Dissociation is thought to occur via a complex route effected by microstructure and the electronic energy levels. The scale of these devices and the soft nature of these materials create an additional level of difficulty for identification and analysis at these interfaces. The transmission electron microscope (TEM) and the spectroscopic techniques it incorporates can allow the properties of the donor-acceptor interfaces to be revealed. Cross-sectional sample preparation, using modern focused ion beam instruments, enables these buried interfaces to be uncovered with minimal damage for high resolution analysis. This powerful instrument combination has the ability to draw conclusions about interface morphology, structure and electronic properties of organic donor-acceptor interfaces at the molecular scale. Recent publications have demonstrated these abilities, and this article aims to summarise some of that work and provide scope for the future.     

Thermoelectricity in fullerene-metal heterojunctions

Thermoelectricty in heterojunctions, where a single-molecule is trapped between metal electrodes, has been used to understand transport properties at organic-inorganic interfaces. (1) The transport in these systems is highly dependent on the energy level alignment between the molecular orbitals and the Fermi level (or work function) of the metal contacts. To date, the majority of single-molecule measurements have focused on simple small molecules where transport is dominated through the highest occupied molecular orbital. (2, 3) In these systems, energy level alignment is limited by the absence of electrode materials with low Fermi levels (i.e., large work functions). Alternatively, more controllable alignment between molecular orbitals and the Fermi level can be achieved with molecules whose transport is dominated by the lowest unoccupied molecular orbital (LUMO) because of readily available metals with lower work functions. Herein, we report molecular junction thermoelectric measurements of fullerene molecules (i.e., C(60), PCBM, and C(70)) trapped between metallic electrodes (i.e., Pt, Au, Ag). Fullerene junctions demonstrate the first strongly n-type molecular thermopower corresponding to transport through the LUMO, and the highest measured magnitude of molecular thermopower to date. While the electronic conductance of fullerenes is highly variable, due to fullerene's variable bonding geometries with the electrodes, the thermopower shows predictable trends based on the alignment of the LUMO with the work function of the electrodes. Both the magnitude and trend of the thermopower suggest that heterostructuring organic and inorganic materials at the nanoscale can further enhance thermoelectric performance, therein providing a new pathway for designing thermoelectric materials.     

NiFe Nanoparticles: A Soft Magnetic Material?

Polytetrahedral NiFe nanoparticles with diameters of (2.8+/-0.3) nm have been obtained by hydrogenation of Ni[(COD)(2)] (COD=1,5-cyclooctadiene) and Fe[{N(SiMe(3))(2)}(2)] at 150 degrees C using stearic acid and hexadecylamine as stabilizing ligands. The nanoparticles are superparamagnetic at room temperature and display a blocking temperature of 17.6 K. Their anisotropy (2.7x10(5)J m(-3)) is determined to be more than two orders of magnitude higher than that of the bulk NiFe alloy (10(3)J m(-3)) and is close to that determined for Fe nanoparticles of the same size. Still, they display a magnetization of (1.69+/-0.05) mu(B) per metallic atom, identical to that of the bulk NiFe alloy. Combining the results from X-ray absorption and M?ssbauer studies, we evidence a progressive enrichment in iron atoms from the core to the surface of the nanoparticles. These results are discussed in relation to both size and chemical effects. They show the main role played by the enriched Fe surface on the magnetic properties and address the feasibility of soft magnetic materials at the nanoscale.     

Surface studies of crystalline and amorphous Zn-In-Sn-O transparent conducting oxides

X-ray and ultraviolet photoelectron spectroscopy (UPS) studies were made of in situ RF magnetron-sputtered crystalline (c) and amorphous (a) Zn-In-Sn-O (ZITO) thin films, ex situ pulsed laser deposited c- and a-ZITO thin films, and bulk ZITO ceramics. Cosubstitution of Zn and Sn for In results in an increase of the In core level binding energy at a given Fermi level compared to that measured in undoped and Sn-doped In₂O₃ (ITO). In plots of work function vs. Fermi level, in situ c-ZITO and a-ZITO films have low ionization potentials (7.0-7.7 eV) that are similar to undoped In₂O₃. In contrast, dry-air-annealed in situ films, ex situ films, and bulk ceramics have higher ionization potentials (7.7-8.1 eV) that are more similar to ITO and match well with previous work on air-exposed surfaces. Kelvin Probe measurements were made of select a-ZITO films exposed to air and ultraviolet/ozone-treated so as to measure work functions under conditions commonly employed for device fabrication. Results (4.8-5.3 eV) were in good agreement with the UPS work functions of oxygen-exposed materials and with literature values. Lastly, a parallelogram plot of work function vs. Fermi level shows that a wider range of work functions is achievable in ZITO materials as compared to other transparent conducting oxides (Sb-doped SnO₂, Al-doped ZnO, Sn-doped In₂O₃), making ZITO more versatile for applications.     

Lowering the Schottky Barrier Height by Graphene/Ag Electrodes for High‐Mobility MoS2 Field‐Effect Transistors

2D transition metal dichalcogenides (TMDCs) have emerged as promising candidates for post‐silicon nanoelectronics owing to their unique and outstanding semiconducting properties. However, contact engineering for these materials to create high‐performance devices while adapting for large‐area fabrication is still in its nascent stages. In this study, graphene/Ag contacts are introduced into MoS₂ devices, for which a graphene film synthesized by chemical vapor deposition (CVD) is inserted between a CVD‐grown MoS₂ film and a Ag electrode as an interfacial layer. The MoS₂ field‐effect transistors with graphene/Ag contacts show improved electrical and photoelectrical properties, achieving a field‐effect mobility of 35 cm² V^?1 s^?1, an on/off current ratio of 4 × 10⁸, and a photoresponsivity of 2160 A W^?1, compared to those of devices with conventional Ti/Au contacts. These improvements are attributed to the low work function of Ag and the tunability of graphene Fermi level; the n‐doping of Ag in graphene decreases its Fermi level, thereby reducing the Schottky barrier height and contact resistance between the MoS₂ and electrodes. This demonstration of contact interface engineering with CVD‐grown MoS₂ and graphene is a key step toward the practical application of atomically thin TMDC‐based devices with low‐resistance contacts for high‐performance large‐area electronics and optoelectronics.     

Effects of metallic nanoparticle doped flux on the interfacial intermetallic compounds between lead-free solder ball and copper substrate

Lead free solders currently in use are prone to develop thick interfacial intermetallic compound layers with rough morphology which are detrimental to the long term solder joint reliability. A novel method has been developed to control the morphology and growth of intermetallic compound layers between lead-free Sn–3.0Ag–0.5Cu solder ball and copper substrate by doping a water soluble flux with metallic nanoparticles. Four types of metallic nanoparticles (nickel, cobalt, molybdenum and titanium) were used to investigate their effects on the wetting behavior and interfacial microstructural evaluations after reflow. Nanoparticles were dispersed manually with a water soluble flux and the resulting nanoparticle doped flux was placed on copper substrate. Lead-free Sn–3.0Ag–0.5Cu solder balls of diameter 0.45 mm were placed on top of the flux and were reflowed at a peak temperature of 240 °C for 45 s. Angle of contact, wetting area and interfacial microstructure were studied by optical microscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. It was observed that the angle of contact increased and wetting area decreased with the addition of cobalt, molybdenum and titanium nanoparticles to flux. On the other hand, wettability improved with the addition of nickel nanoparticles. Cross-sectional micrographs revealed that both nickel and cobalt nanoparticle doping transformed the morphology of Cu₆Sn₅ from a typical scallop type to a planer one and reduced the intermetallic compound thickness under optimum condition. These effects were suggested to be related to in-situ interfacial alloying at the interface during reflow. The minimum amount of nanoparticles required to produce the planer morphology was found to be 0.1 wt.% for both nickel and cobalt. Molybdenum and titanium nanoparticles neither appear to undergo alloying during reflow nor have any influence at the solder/substrate interfacial reaction. Thus, doping of flux with appropriate metallic nanoparticles can be successfully used to control the morphology and growth of intermetallic compound layers at the solder/substrate interface which is expected to lead to better reliability of electronic devices.     

Core/Shell ZnO/ZnS Nanoparticle Electron Transport Layers Enable Efficient All-Solution-Processed Perovskite Light-Emitting Diodes

Solution-processed perovskite-based light-emitting diodes (PeLEDs) are promising candidates for low-cost, large-area displays, while severe deterioration of the perovskite light-emitting layer occurs during deposition of electron transport layers from solution in an issue. Herein, core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer in PeLED based on quasi-2D PEA₂Cs_n−1Pb_nBr_3n+1 (PEA = phenylethylammonium) perovskite are employed. The deposition of ZnS shell mitigates trap states on ZnO core by anchoring sulfur to oxygen vacancies, and at the same time removes residual hydroxyl groups, which helps to suppress the interfacial trap-assisted non-radiative recombination and the deprotonation reaction between the perovskite layer and ZnO. The core/shell ZnO/ZnS nanoparticles show comparably high electron mobility to pristine ZnO nanoparticles, combined with the reduced energy barrier between the electron transport layer and the perovskite layer, improving the charge injection balance in PeLEDs. As a result, the optimized PeLEDs employing core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer exhibit high peak luminance reaching 32 400 cd m⁻², external quantum efficiency of 10.3%, and 20-fold extended longevity as compared to the devices utilizing ZnO nanoparticles, which represents one of the highest overall performances for solution-processed PeLEDs.     

纳米颗粒胶体动压空化射流抛光技术初探(英文)

为了高效加工优质的超光滑表面,提出了一种超光滑表面加工的新方法:纳米颗粒胶体动压空化射流抛光(HCJP).此法利用纳米颗粒与工件表面之间的界面化学反应实现工件表面的原子级去除,并且利用空化射流中的水力空化现象强化加工过程中的机械与化学作用以提高加工效率.设计了HCJP原型装置,并在此基础上对HCJP技术进行了初步实验.结果表明,较低的系统压力有利于得到优质的表面,使用该方法能在K9玻璃上得到粗糙度值在1 nm左右的超光滑表面,证明此技术可以广泛应用于超光滑表面的加工.