Enhancement of field emission from multistage structure of carbon nanotube arrays

The field emission measurements for the multistage structured nanotubes (i.e., thin-multiwall and single wall carbon nanotubes grown on multiwall carbon nanotubes) were carried out and a low turn-on field of ~0.45 V/ μm, high emission current of 450 μA at a field of IV/μm and a large field enhancement factor of ~26200 were obtained. The thin multiwall carbon nanotubes (thin-MWNTs) and single wall carbon nanotubes (SWNTs) were grown on the regular arrays of vertically aligned multi wall carbon nanotubes (MWNTs) on porous silicon substrate by Chemical Vapor Deposition (CVD) method. The thin-MWNTs and SWNTs grown on MWNTs in this way have a multistage structure which gives higher enhancement of the electric field and hence the electron field emission.

Design, Fabrication, and Characterization of Carbon Nanotube Field Emission Devices for Advanced Applications

Carbon nanotubes (CNTs) have recently emerged as promising candidates for electron field emission (FE) cathodes in integrated FE devices. These nanostructured carbon materials possess exceptional properties and their synthesis can be thoroughly controlled. Their integration into advanced electronic devices, including not only FE cathodes, but sensors, energy storage devices, and circuit components, has seen rapid growth in recent years. The results of the studies presented here demonstrate that the CNT field emitter is an excellent candidate for next generation vacuum microelectronics and related electron emission devices in several advanced applications.

The work presented in this study addresses determining factors that currently confine the performance and application of CNT-FE devices. Characterization studies and improvements to the FE properties of CNTs, along with Micro-Electro-Mechanical Systems (MEMS) design and fabrication, were utilized in achieving these goals. Important performance limiting parameters, including emitter lifetime and failure from poor substrate adhesion, are examined. The compatibility and integration of CNT emitters with the governing MEMS substrate (i.e., polycrystalline silicon), and its impact on these performance limiting parameters, are reported. CNT growth mechanisms and kinetics were investigated and compared to silicon (100) to improve the design of CNT emitter integrated MEMS based electronic devices, specifically in vacuum microelectronic device (VMD) applications.

Improved growth allowed for design and development of novel cold-cathode FE devices utilizing CNT field emitters. A chemical ionization (CI) source based on a CNT-FE electron source was developed and evaluated in a commercial desktop mass spectrometer for explosives trace detection. This work demonstrated the first reported use of a CNT-based ion source capable of collecting CI mass spectra. The CNT-FE source demonstrated low power requirements, pulsing capabilities, and average lifetimes of over 320 hours when operated in constant emission mode under elevated pressures, without sacrificing performance. Additionally, a novel packaged ion source for miniature mass spectrometer applications using CNT emitters, a MEMS based Nier-type geometry, and a Low Temperature Cofired Ceramic (LTCC) 3D scaffold with integrated ion optics were developed and characterized. While previous research has shown other devices capable of collecting ion currents on chip, this LTCC packaged MEMS micro-ion source demonstrated improvements in energy and angular dispersion as well as the ability to direct the ions out of the packaged source and towards a mass analyzer. Simulations and experimental design, fabrication, and characterization were used to make these improvements.

Finally, novel CNT-FE devices were developed to investigate their potential to perform as active circuit elements in VMD circuits. Difficulty integrating devices at micron-scales has hindered the use of vacuum electronic devices in integrated circuits, despite the unique advantages they offer in select applications. Using a combination of particle trajectory simulation and experimental characterization, device performance in an integrated platform was investigated. Solutions to the difficulties in operating multiple devices in close proximity and enhancing electron transmission (i.e., reducing grid loss) are explored in detail. A systematic and iterative process was used to develop isolation structures that reduced crosstalk between neighboring devices from 15% on average, to nearly zero. Innovative geometries and a new operational mode reduced grid loss by nearly threefold, thereby improving transmission of the emitted cathode current to the anode from 25% in initial designs to 70% on average. These performance enhancements are important enablers for larger scale integration and for the realization of complex vacuum microelectronic circuits.

Al-based anodic oxide films structure observation using field emission gun scanning electron microscopy

In the present work, the anodic oxide films of Al, Al-Cu 4.5% and Al-Si 6.5% alloys are formed using direct and pulse current. In the case of Al-Cu and Al-Si alloys, the electrolyte used contains sulfuric acid and oxalic acid, meanwhile for Al the electrolyte contains sulfuric acid only. Al-Cu alloy was submitted to a heat treatment in order to decrease the effect of inter metallic phase theta upon the anodic film structure. Fractured samples were observed using a field emission gun scanning electron microscope JSM-6330F at (LME)/Brazilian Synchrotron Light Laboratory (LNLS), Campinas, SP, Brazil. The oxide film images enable evaluation of the pore size and form with a resolution similar to the transmission electron microscope (TEM) resolution. It is also observed that the anodizing process using pulse current produces an irregular structure of pore walls, and by direct cur-rent it is produced a rectilinear pore wall. (c) 2005 Elsevier B.V. All rights reserved.

Catalytic CO2 hydrogenation: study at the molecular scale using field emission techniques

An accurate characterization of the rhodium specimen was obtained via FIM experiments. Reaction behaviors between H2 and CO2 were observed in FEM mode at 700 K. At this temperature, CO desorption occurs, preventing CO+H2 reaction. Surface is mainly recovered by oxygen; reaction with hydrogen occurs. Finally, we can identify the reaction as the Reverse Water Gas Shift.

Spectroscopic studies of field-induced electron emission from isolated microstructures

A detailed investigation has been undertaken into the field induced electron emission (FIEE) mechanism that occurs at microscopically localised `sites' on uncoated and dielectric coated metallic electrodes. These processes have been investigated using two dedicated experimental systems that were developed for this study. The first is a novel combined photo/field emission microscope, which employs a UV source to stimulate photo-electrons from the sample surface in order to generate a topographical image. This system utilises an electrostatic lens column to provide identical optical properties under the different operating conditions required for purely topographical and combined photo/field imaging. The system has been demonstrated to have a resolution approaching 1m. Emission images have been obtained from carbon emission sites using this system to reveal that emission may occur from the edge triple junction or from the bulk of the carbon particle. An existing UHV electron spectrometer has been extensively rebuilt to incorporate a computer control and data acquisition system, improved sample handling and manipulation and a specimen heating stage. Details are given of a comprehensive study into the effects of sample heating on the emission process under conditions of both bulk and transient heating. Similar studies were also performed under conditions of both zero and high applied field. These show that the properties of emission sites are strongly temperature and field dependent thus indicating that the emission process is `non-metallic' in nature. The results have been shown to be consistent with an existing hot electron emission model.

Associating biosensing properties with the morphological structure of multilayers containing carbon nanotubes on field-effect devices

The control of molecular architecture provided by the layer-by-layer (LbL) technique has led to enhanced biosensors, in which advantageous features of distinct materials can be combined. Full optimization of biosensing performance, however, is only reached if the film morphology is suitable for the principle of detection of a specific biosensor. In this paper, we report a detailed morphology analysis of LbL films made with alternating layers of single-walled carbon nanotubes (SWNTs) and polyamidoamine (PAMAM) dendrimers, which were then covered with a layer of penicillinase (PEN). An optimized performance to detect penicillin G was obtained with 6-bilayer SWNT/PAMAM LbL films deposited on p-Si-SiO(2)-Ta(2)O(5) chips, used in biosensors based on a capacitive electrolyte-insulator-semiconductor (EIS) and a light-addressable potentiometric sensor (LAPS) structure, respectively. Field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) images indicated that the LbL films were porous, with a large surface area due to interconnection of SWNT into PAMAM layers. This morphology was instrumental for the adsorption of a larger quantity of PEN, with the resulting LbL film being highly stable. The experiments to detect penicillin were performed with constant-capacitance (Con Cap) and constant-current (CC) measurements for EIS and LAPS sensors, respectively, which revealed an enhanced detection signal and sensitivity of ca. 100 mV/decade for the field-effect sensors modified with the PAMAM/SWNT LbL film. It is concluded that controlling film morphology is essential for an enhanced performance of biosensors, not only in terms of sensitivity but also stability and response time. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Morphology and Blue Photoluminescence Emission of PbMoO(4) Processed in Conventional Hydrothermal

PbMoO(4) micro-octahedrons were prepared by the coprecipitation method at room temperature without the presence of surfactants and processed in a conventional hydrothermal at different temperatures (from 60 to 120 degrees C) for 10 min. These micro-octahedrons were structurally characterized by X-ray diffraction (XRD) and micro-Raman (MR) spectroscopy, and its morphology was investigated by field-emission gun scanning electron microscopy (FEG-SEM). The optical properties were analyzed by ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns and MR spectra confirmed that the PbMoO(4) micro-octahedrons are characterized by a scheelite-type tetragonal structure. FEG-SEM micrographs points, out that these structures present a polydisperse particle size distribution in consequence of a predominant growth mechanism via aggregation of particles. In addition, it was observed that the hydrothermal conditions favored a spontaneous formation of micro-octahedrons interconnected along a common crystallographic orientation (oriented-attachment), resulting in self-organized structures. An intense blue PL emission at room temperature was observed in these micro-octahedrons when they were excited with a 350 nm wavelength. The origin of the PL emissions as well as its intensity variations are explained by means of a model based on both distorted [MoO(4)] and [PbO(8)] clusters into the lattice.

Morphology and Blue Photoluminescence Emission of PbMoO4 Processed in Conventional Hydrothermal

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Red shift and higher photoluminescence emission of CCTO thin films undergoing pressure treatment

CCTO thin films were deposited on Pt(1 1 1)/Ti/SiO2/Si substrates using a chemical (polymeric precursor) and pressure method. Pressure effects on CCTO thin films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and optical properties which revealed that a pressure film (PF) is denser and more homogeneous than a chemical film (CF). Pressure also causes a decrease in the band gap and an increase in the photoluminescence (PL) emission of CCTO films which suggests that the pressure facilitates the displacement of Ti in the titanate clusters and the charge transference from TiO6 to [TiO5V0z], [TiO5V0z] to [CaO11V0z] and [TiO5V0z] to [CuO4]x. © 2013 Elsevier B.V. All rights reserved.

Photoluminescence emission at room temperature in zinc oxide nano-columns

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO 3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

MgTiO3 (MTO) thin films were prepared by the polymeric precursor method with posterior spin-coating deposition. The films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates and heat treated at 350 °C for 2 h and then heat treated at 400, 450, 500, 550, 600, 650 and 700 °C for 2 h. The degree of structural order−disorder, optical properties, and morphology of the MTO thin films were investigated by X-ray diffraction (XRD), micro-Raman spectroscopy (MR), ultraviolet− visible (UV−vis) absorption spectroscopy, photoluminescence (PL) measurements, and field-emission gun scanning electron microscopy (FEG-SEM) to investigate the morphology. XRD revealed that an increase in the annealing temperature resulted in a structural organization of MTO thin films. First-principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered asymmetric models. The electronic properties were analyzed, and the relevance of the present theoretical and experimental results was discussed in the light of PL behavior. The presence of localized electronic levels and a charge gradient in the band gap due to a break in the symmetry are responsible for the PL in disordered MTO lattice.

Very Intense Distinct Blue and Red Photoluminescence Emission in MgTiO3 Thin Films Prepared by the Polymeric Precursor Method: An Experimental and Theoretical Approach

MgTiO3 (MTO) thin films were prepared by the polymeric precursor method with posterior spin-coating deposition. The films were deposited on Pt(111)/Ti/SiO2/Si(100) substrates and heat treated at 350 degrees C for 2 h and then heat treated at 400, 450, 500, 550, 600, 650 and 700 C for 2 h. The degree of structural order disorder, optical properties, and morphology of the MTO thin films were investigated by X-ray diffraction (XRD), micro-Raman spectroscopy (MR), ultraviolet-visible (UV-vis) absorption spectroscopy, photoluminescence (PL) measurements, and field-emission gun scanning electron microscopy (FEG-SEM) to investigate the morphology. XRD revealed that an increase in the annealing temperature resulted in a structural organization of MTO thin films. First-principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered asymmetric models. The electronic properties were analyzed, and the relevance of the present theoretical and experimental results was discussed in the light of PL behavior. The presence of localized electronic levels and a charge gradient in the band gap due to a break in the symmetry are responsible for the PL in disordered MTO lattice.

Size-selective investigations of spectral and emission properties of small particles and nanotubes

In dieser Arbeit wurde die Elektronenemission von Nanopartikeln auf Oberflächen mittels spektroskopischen Photoelektronenmikroskopie untersucht. Speziell wurden metallische Nanocluster untersucht, als selbstorganisierte Ensembles auf Silizium oder Glassubstraten, sowie ferner ein Metall-Chalcogenid (MoS2) Nanoröhren-Prototyp auf Silizium. Der Hauptteil der Untersuchungen war auf die Wechselwirkung von fs-Laserstrahlung mit den Nanopartikeln konzentriert. Die Energie der Lichtquanten war kleiner als die Austrittsarbeit der untersuchten Proben, so dass Ein-Photonen-Photoemission ausgeschlossen werden konnte. Unsere Untersuchungen zeigten, dass ausgehend von einem kontinuierlichen Metallfilm bis hin zu Clusterfilmen ein anderer Emissionsmechanismus konkurrierend zur Multiphotonen-Photoemission auftritt und für kleine Cluster zu dominieren beginnt. Die Natur dieses neuen Mechanismus` wurde durch verschiedenartige Experimente untersucht. Der Übergang von einem kontinuierlichen zu einem Nanopartikelfilm ist begleitet von einer Zunahme des Emissionsstroms von mehr als eine Größenordnung. Die Photoemissions-Intensität wächst mit abnehmender zeitlicher Breite des Laserpulses, aber diese Abhängigkeit wird weniger steil mit sinkender Partikelgröße. Die experimentellen Resultate wurden durch verschiedene Elektronenemissions-Mechanismen erklärt, z.B. Multiphotonen-Photoemission (nPPE), thermionische Emission und thermisch unterstützte nPPE sowie optische Feldemission. Der erste Mechanismus überwiegt für kontinuierliche Filme und Partikel mit Größen oberhalb von mehreren zehn Nanometern, der zweite und dritte für Filme von Nanopartikeln von einer Größe von wenigen Nanometern. Die mikrospektroskopischen Messungen bestätigten den 2PPE-Emissionsmechanismus von dünnen Silberfilmen bei „blauer“ Laseranregung (hν=375-425nm). Das Einsetzen des Ferminiveaus ist relativ scharf und verschiebt sich um 2hν, wenn die Quantenenergie erhöht wird, wogegen es bei „roter“ Laseranregung (hν=750-850nm) deutlich verbreitert ist. Es zeigte sich, dass mit zunehmender Laserleistung die Ausbeute von niederenergetischen Elektronen schwächer zunimmt als die Ausbeute von höherenergetischen Elektronen nahe der Fermikante in einem Spektrum. Das ist ein klarer Hinweis auf eine Koexistenz verschiedener Emissionsmechanismen in einem Spektrum. Um die Größenabhängigkeit des Emissionsverhaltens theoretisch zu verstehen, wurde ein statistischer Zugang zur Lichtabsorption kleiner Metallpartikel abgeleitet und diskutiert. Die Elektronenemissionseigenschaften bei Laseranregung wurden in zusätzlichen Untersuchungen mit einer anderen Anregungsart verglichen, der Passage eines Tunnelstroms durch einen Metall-Clusterfilm nahe der Perkolationsschwelle. Die elektrischen und Emissionseigenschaften von stromtragenden Silberclusterfilmen, welche in einer schmalen Lücke (5-25 µm Breite) zwischen Silberkontakten auf einem Isolator hergestellt wurden, wurden zum ersten Mal mit einem Emissions-Elektronenmikroskop (EEM) untersucht. Die Elektronenemission beginnt im nicht-Ohmschen Bereich der Leitungsstrom-Spannungskurve des Clusterfilms. Wir untersuchten das Verhalten eines einzigen Emissionszentrums im EEM. Es zeigte sich, dass die Emissionszentren in einem stromleitenden Silberclusterfilm Punktquellen für Elektronen sind, welche hohe Emissions-Stromdichten (mehr als 100 A/cm2) tragen können. Die Breite der Energieverteilung der Elektronen von einem einzelnen Emissionszentrum wurde auf etwa 0.5-0.6 eV abgeschätzt. Als Emissionsmechanismus wird die thermionische Emission von dem „steady-state“ heißen Elektronengas in stromdurchflossenen metallischen Partikeln vorgeschlagen. Größenselektierte, einzelne auf Si-Substraten deponierte MoS2-Nanoröhren wurden mit einer Flugzeit-basierten Zweiphotonen-Photoemissions-Spektromikroskopie untersucht. Die Nanoröhren-Spektren wiesen bei fs-Laser Anregung eine erstaunlich hohe Emissionsintensität auf, deutlich höher als die SiOx Substratoberfläche. Dagegen waren die Röhren unsichtbar bei VUV-Anregung bei hν=21.2 eV. Eine ab-initio-Rechnung für einen MoS2-Slab erklärt die hohe Intensität durch eine hohe Dichte freier intermediärer Zustände beim Zweiphotonen-Übergang bei hν=3.1 eV.

High-density large-scale field emitter arrays for x-ray free electron laser cathodes

High brightness electron sources are of great importance for the operation of the hard X-ray free electron lasers. Field emission cathodes based on the double-gate metallic field emitter arrays (FEAs) can potentially offer higher brightness than the currently used ones. We report on the successful application of electron beam lithography for fabrication of the large-scale single-gate as well as double-gate FEAs. We demonstrate operational high-density single-gate FEAs with sub-micron pitch and total number of tips up to 106 as well as large-scale double-gate FEAs with large collimation gate apertures. The details of design, fabrication procedure and successful measurements of the emission current from the single- and double-gate cathodes are presented.