Multi-walled carbon nanotube conductivity enhancement and band gap widening via rapid pulsed thermal annealing

Herein we report on the transport characteristics of rapid pulsed vacuum-arc thermally annealed, individual and network multi-walled carbon nanotubes. Substantially reduced defect densities (by at least an order of magnitude), measured by micro-Raman spectroscopy, and were achieved by partial reconstruction of the bamboo-type defects during thermal pulsing compared with more traditional single-pulse thermal annealing. Rapid pulsed annealed processed networks and individual multi-walled nanotubes showed a consistent increase in conductivity (of over a factor of five at room temperature), attributed to the reduced number density of resistive axial interfaces and, in the case of network samples, the possible formation of structural bonds between crossed nanotubes. Compared to the highly defective as-grown nanotubes, the pulsed annealed samples exhibited reduced temperature sensitivity in their transport characteristics signifying the dominance of scattering events from structural defects. Transport measurements in the annealed multi-walled nanotubes deviated from linear Ohmic, typically metallic, behavior to an increasingly semiconducting-like behavior attributed to thermally induced axial strains. Rapid pulsed annealed networks had an estimated band gap of 11.26 meV (as-grown; 6.17 meV), and this observed band gap enhancement was inherently more pronounced for individual nanotubes compared with the networks most likely attributed to mechanical pinning effect of the probing electrodes which possibly amplifies the strain induced band gap. In all instances the estimated room temperature band gaps increased by a factor of two. The gating performance of back-gated thin-film transistor structures verified that the observed weak semiconductivity (p-type) inferred from the transport characteristic at room temperature. © 2014 Copyright Taylor & Francis Group, LLC.

TIME RESOLVED REFLECTIVITY MEASUREMENTS APPLIED TO RAPID ISOTHERMAL ANNEALING OF ION IMPLANTED SILICON.

The annealing of ion implantation damage in silicon by rapid isothermal heating has been monitored by the time resolved reflectivity (TRR) method. This technique was applied simultaneously at a wavelength of 632. 8nm and also at 1152nm, where the optical absorption coefficient of silicon is less. The two wavelength method simplifies the interpretation of TRR results, extends the measurement depth and allows good resolution of the position of the interface between amorphous and crystalline silicon. The regrowth of amorphous layers in silicon, created by self implantation and implanted with electrically active impurities, was observed. Regrowth in rapid isothermal annealing occurs during the heating up stage of typical thermal cycles. Impurities such as B, P, and As increase the regrowth rate in a manner consistent with a vacancy model for regrowth. The maximum regrowth rate in boron implanted silicon is limited by the solid solubility.

Stress reduction and bond stability during thermal annealing of tetrahedral amorphous carbon

A comprehensive study of the stress release and structural changes caused by postdeposition thermal annealing of tetrahedral amorphous carbon (ta-C) on Si has been carried out. Complete stress relief occurs at 600-700°C and is accompanied by minimal structural modifications, as indicated by electron energy loss spectroscopy, Raman spectroscopy, and optical gap measurements. Further annealing in vacuum converts sp3 sites to sp2 with a drastic change occurring after 1100°C. The field emitting behavior is substantially retained up to the complete stress relief, confirming that ta-C is a robust emitting material. © 1999 American Institute of Physics.

TRANSIENT SCANNING ELECTRON BEAM ANNEALING METHODS USED TO STUDY DIFFUSION AND DEFECTS IN IMPLANTED SILICON.

Rapid thermal annealing of arsenic and boron difluoride implants, such as those used for source/drain regions in CMOS, has been carried out using a scanning electron beam annealer, as part of a study of transient diffusion effects. Three types of e-beam anneal have been performed, with peak temperatures in the range 900 -1200 degree C; the normal isothermal e-beam anneals, together with sub-second fast anneals and 'dual-pulse' anneals, in which the sample undergoes an isothermal pre-anneal followed by rapid heating to the required anneal temperature is less than 0. 5s. The diffusion occuring during these anneal cycles has been modelled using SPS-1D, an implant and diffusion modelling program developed by one of the authors. This has been modified to incorporate simulated temperature vs. time cycles for the anneals. Results are presented applying the usual equilibrium clustering model, a transient point-defect enhancement to the diffusivity proposed recently by Fair and a new dynamic clustering model for arsenic. Good agreement with SIMS measurements is obtained using the dynamic clustering model, without recourse to a transient defect model.

Optical investigations of the effect of solvent and thermal annealing on the optoelectronic properties of Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) films

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most promising conducting polymers that can be used as transparent electrode or as buffer layer for organic electronic devices. However, when used as an electrode, its conductivity has to be optimized either by the addition of solvents or by post-deposition processing. In this work, we investigate the effect of the addition of the polar solvent dimethylsulfoxide (DMSO) to an aqueous PEDOT:PSS solution on its optical and electrical properties by the implementation of the Drude model for the analysis of the measured pseudo-dielectric function by Spectroscopic Ellipsometry from the near infrared to the visible-far ultraviolet spectral range. The results show that the addition of DMSO increases significantly the film conductivity, which reaches a maximum value at an optimum DMSO concentration as it has confirmed by experimentally measured conductivity values. The post-deposition thermal annealing has been found to have a smaller effect on the film conductivity. © 2013 Elsevier B.V.

Evolution of vertical phase separation in P3HT:PCBM thin films induced by thermal annealing

The achievement of the desirable morphology at the nanometer scale of bulk heterojunctions consisting of a conjugated polymer with fullerene derivatives is a prerequisite in order to optimize the power conversion efficiency of organic solar cells. The various experimental conditions such as the choice of solvent, drying rates and annealing have been found to significantly affect the blend morphology and the final performance of the photovoltaic device. In this work, we focus on the effects of post deposition thermal annealing at 140 °C on the blend morphology, the optical and structural properties of bulk heterojunctions that consist of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM). The post thermal annealing modifies the distribution of the P3HT and the PCBM inside the blend films, as it has been found by Spectroscopic Ellipsometry studies in the visible to far-ultraviolet spectral range. Phase separation was identified by AFM and GIXRD as a result of a slow drying process which took place after the spin coating process. The increase of the annealing time resulted to a significant increase of the P3HT crystallinity at the top regions of the blend films. © 2011 Elsevier B.V. All rights reserved.

Thermal annealing effect on the nanomechanical properties and structure of P3HT:PCBM thin films

Nanostructured polymer-fullerene thin films are among the most prominent materials for application in high efficient polymer solar cells. Specifically, poly(3-hexylthiophene) (P3HT) and fullerene derivatives (PCBM) blends are used as the donor/acceptor materials forming a bulk heterojunction. Although P3HT:PCBM properties have been extensively studied, less light has been set on its nanomechanical properties, which affect the device service life. In this work Atomic Force Acoustic Microscopy (AFAM), Atomic Force Spectroscopy and Nanoindentation were used to study the effect of the fullerene presence and the annealing on the P3HT:PCBM nanomechanical behavior. The P3HT:PCBM thin films were prepared by spin coating on glass substrates and then annealed at 100 °C and 145 °C for 30 min. Large phase separation was identified by optical and Atomic Force Microscopy (AFM) for the annealed samples. Needle-like PCBM crystals were formed and an increase of the polymer crystallinity degree with the increase of the annealing temperature was confirmed by X-ray diffraction. AFAM characterization revealed the presence of aggregates close to stiff PCBM crystals, possibly consisting of amorphous P3HT material. AFM force-distance curves showed a continuous change in stiffness in the vicinity of the PCBM crystals, due to the PCBM depletion near its crystals, and the AFM indentation provided qualitative results about the changes in P3HT nanomechanical response after annealing. © 2011 Elsevier B.V. All rights reserved.

Synthesis and luminescence properties of erbium silicate thin films

We have studied the structure and the room temperature luminescence of erbium silicate thin films deposited by rf magnetron sputtering. Films deposited on silicon oxide layers are characterized by good structural properties and excellent stability. The optical properties of these films are strongly improved by rapid thermal annealing processes performed in the range of temperature 800-1250 °C. In fact through the reduction of the defect density of the material, a very efficient room temperature photoluminescence at 1535 nm is obtained. We have also investigated the influence of the annealing ambient, by finding that treatments in O2 atmosphere are significantly more efficient in improving the optical properties of the material with respect to processes in N2. Upconversion effects become effective only when erbium silicate is excited with high pump powers. The evidence that all Er atoms (about 1022 cm-3) in erbium silicate films are optically active suggests interesting perspectives for optoelectronic applications of this material. © 2007 Elsevier B.V. All rights reserved.

The influence of substrate on the properties of Er2O3 films grown by magnetron sputtering

The structural properties and the room temperature luminescence of Er2O3 thin films deposited by RF magnetron sputtering have been studied. Films characterized by good morphological properties have been obtained by using a SiO2 interlayer between the film and the Si substrate. The evolution of the properties of the Er2O3 films due to rapid thermal annealing processes in O2 ambient performed at temperatures in the range 800-1200 °C has been investigated in details. The existence of well-defined annealing conditions (temperature of 1100 °C or higher) allowing to avoid the occurrence of extensive chemical reactions with the oxidized substrate has been demonstrated and an increase of the photoluminescence (PL) intensity by about a factor of 40 with respect to the as deposited material has been observed. The enhanced efficiency of the photon emission process has been correlated with the longer lifetime of the PL signal. The same annealing processes are less effective when Er2O3 is deposited on Si. In this latter case interfacial reactions and pit formation occur, leading to a material characterized by stronger non-radiative phenomena that limit the PL efficiency. © 2006 Elsevier B.V. All rights reserved.

Thermal evolution of Er silicate thin films grown by rf magnetron sputtering

Stoichiometric Er silicate thin films, monosilicate (Er2SiO 5) and disilicate (Er2Si2O7), have been grown on c-Si substrates by rf magnetron sputtering. The influence of annealing temperature in the range 1000-1200 °C in oxidizing ambient (O 2) on the structural and optical properties has been studied. In spite of the known reactivity of rare earth silicates towards silicon, Rutherford backscattering spectrometry shows that undesired chemical reactions between the film and the substrate can be strongly limited by using rapid thermal treatments. Monosilicate and disilicate films crystallize at 1100 and 1200 °C, respectively, as shown by x-ray diffraction analysis; the crystalline structures have been identified in both cases. Moreover, photoluminescence (PL) measurements have demonstrated that the highest PL intensity is obtained for Er2Si2O7 film annealed at 1200 °C. In fact, this treatment allows us to reduce the defect density in the film, in particular by saturating oxygen vacancies, as also confirmed by the increase of the lifetime of the PL signal. © 2008 IOP Publishing Ltd.

Some observations describing the electrochemical surface annealing of austenitic stainless steel

Cold-worked austenitic stainless steels have been subject to a pulsed electrochemical treatment in fairly concentrated aqueous solutions of sodium nitrite. The electrochemical reactions that occur transform the strain-induced martensite phase, originally formed by the cold work, back to the austenite phase. However, unlike the conventional thermal annealing process, electrochemically induced surface annealing also hardens the surface of the alloy. Because the process causes transformation of the surface martensite, we term it "electrochemical surface annealing", despite the fact that it results in an increase in surface hardness.

Millisecond processing beyond chip technology: From electronics to photonics

There is a clear and increasing interest in short time annealing processing far below one second, i.e. the lower limit of Rapid Thermal Processing (RTP) called spike annealing. This was driven by the need of suppressing the so-called Transient Enhanced Diffusion in advanced boronimplanted shallow pn-junctions in silicon technology. Meanwhile the interest in flash lamp annealing (FLA) in the millisecond range spread out into other fields related to silicon technology and beyond. This paper reports on recent experiments regarding shallow junction engineering in germanium, annealing of ITO layers on glass and plastic foil to form an conductive layer as well as investigations which we did during the last years in the field of wide band gap semiconductor materials (SiC, ZnO). A more common feature evolving from our work was related to the modeling of wafer stress during millisecond thermal processing with flash lamps. Finally recent achievements in the field of silicon-based light emission basing on Metal-Oxide-Semiconductor Light Emitting Devices will be reported. © 2007 IEEE.

Electric conduction improvement of well-structured multi-walled carbon nanotubes

We characterized the electrical conductance of well-structured multi-walled carbon nanotubes (MWCNTs) which had post-treated by a rapid vacuum arc thermal annealing process and structure defects in these nanotubes are removed. We found that the after rapid vacuum arc annealing, the conductivity of well-structured MWCNTs can be improved by an order of magnitude. We also investigated the conductivity of MWCNTs bundle by the variation of temperatures. These results show that the conductance of annealed defect-free MWCNTs is sensitive to temperature imply the phonon scatting dominated the electron conductions. Compare to the well-structured MWCNTs, the defect scattering dominated the electron conduction in the as-grown control sample which has large amount of structure defects. A detail measurement of electron conduction from an individual well-structured MWCNT shows that the conductivity increases with temperatures which imply such MWCNTs exhibited semiconductor properties. We also produced back-gated field-effect transistors using these MWCNTs. It shows that the well-structured MWCNT can act as p-type semiconductor. © 2010 IEEE.