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.

Characterization of defect removal in hydrogenated and deuterated amorphous silicon thin film transistors

Thin film transistors (TFTs) utilizing an hydrogenated amorphous silicon (a-Si:H) channel layer exhibit a shift in the threshold voltage with time under the application of a gate bias voltage due to the creation of metastable defects. These defects are removed by annealing the device with zero gate bias applied. The defect removal process can be characterized by a thermalization energy which is, in turn, dependent upon an attempt-to-escape frequency for defect removal. The threshold voltage of both hydrogenated and deuterated amorphous silicon (a-Si:D) TFTs has been measured as a function of annealing time and temperature. Using a molecular dynamics simulation of hydrogen and deuterium in a silicon network in the H2 * configuration, it is shown that the experimental results are consistent with an attempt-to-escape frequency of (4.4 ± 0.3) × 1013 Hz and (5.7 ± 0.3) × 1013 Hz for a-Si:H and a-Si:D respectively which is attributed to the oscillation of the Si-H and Si-D bonds. Using this approach, it becomes possible to describe defect removal in hydrogenated and deuterated material by the thermalization energies of (1.552 ± 0.003) eV and (1.559 ± 0.003) eV respectively. This correlates with the energy per atom of the Si-H and Si-D bonds. © 2006 Elsevier B.V. All rights reserved.

Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams.

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Rigorous finite-time guarantees for optimization on continuous domains by simulated annealing

Simulated annealing is a popular method for approaching the solution of a global optimization problem. Existing results on its performance apply to discrete combinatorial optimization where the optimization variables can assume only a finite set of possible values. We introduce a new general formulation of simulated annealing which allows one to guarantee finite-time performance in the optimization of functions of continuous variables. The results hold universally for any optimization problem on a bounded domain and establish a connection between simulated annealing and up-to-date theory of convergence of Markov chain Monte Carlo methods on continuous domains. This work is inspired by the concept of finite-time learning with known accuracy and confidence developed in statistical learning theory.

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.

Simulated Annealing: Rigorous finite-time guarantees for optimization on continuous domains

Simulated annealing is a popular method for approaching the solution of a global optimization problem. Existing results on its performance apply to discrete combinatorial optimization where the optimization variables can assume only a finite set of possible values. We introduce a new general formulation of simulated annealing which allows one to guarantee finite-time performance in the optimization of functions of continuous variables. The results hold universally for any optimization problem on a bounded domain and establish a connection between simulated annealing and up-to-date theory of convergence of Markov chain Monte Carlo methods on continuous domains. This work is inspired by the concept of finite-time learning with known accuracy and confidence developed in statistical learning theory.

COMPARISON OF MILLISECOND ANNEALING OF B IMPLANTS AND ISOTHERMAL ANNEALING FOR TIMES OF A FEW SECONDS.

The annealing behaviour of B implants in the millisecond time regime using a combination of swept line beam and background heating is compared with isothermal annealing with heating cycles of a few seconds. Carrier concentration profiles show that under annealing conditions which restrict diffusion, millisecond processing gives higher activation of B implants than isothermal heating. Transmission electron microscopy shows that millisecond annealing also results in a lower defect density.

RESIDUAL DEFECTS FOLLOWING RAPID ANNEALING OF BORON IMPLANTED SILICON WITH AND WITHOUT PREAMORPHISATION BY SILICON IMPLANTATION.

Implants of boron into silicon which has been made amorphous by silicon implantation have a shallower depth profile than the same implants into silicon. This results in higher activation and restricted diffusion of the B implants after annealing, and there are also significant differences in the microstructure after annealing compared with B implants into silicon. Rapid isothermal heating with an electron beam and furnace treatments are used to characterize the defect structure as a function of time and temperature. Defects are seen to influence the diffusion of non-substitutional boron.

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.

Changes in the Mg profile and in dislocations induced by high temperature annealing of blue LEDs

The efficiency of the injection and recombination processes in InGaN/GaN LEDs is governed by the properties of the active region of the devices, which strongly depend on the conditions used for the growth of the epitaxial material. To improve device quality, it is very important to understand how the high temperatures used during the growth process can modify the quality of the epitaxial material. With this paper we present a study of the modifications in the properties of InGaN/GaN LED structures induced by high temperature annealing: thermal stress tests were carried out at 900 °C, in nitrogen atmosphere, on selected samples. The efficiency and the recombination dynamics were evaluated by photoluminescence measurements (both integrated and time-resolved), while the properties of the epitaxial material were studied by Secondary Ion Mass Spectroscopy (SIMS) and Rutherford Backscattering (RBS) channeling measurements. Results indicate that exposure to high temperatures may lead to: (i) a significant increase in the photoluminescence efficiency of the devices; (ii) a decrease in the parasitic emission bands located between 380 nm and 400 nm; (iii) an increase in carrier lifetime, as detected by time-resolved photoluminescence measurements. The increase in device efficiency is tentatively ascribed to an improvement in the crystallographic quality of the samples. © 2013 SPIE.

Effects of buffer layer properties and annealing process on bulk heterojunction morphology and organic solar cell performance

The performance of polymer-fullerene bulk heterojunction (BHJ) solar cells is strongly dependent on the vertical distribution of the donor and acceptor regions within the BHJ layer. In this work, we investigate in detail the effect of the hole transport layer (HTL) physical properties and the thermal annealing on the BHJ morphology and the solar cell performance. For this purpose, we have prepared solar cells with four distinct formulations of poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) buffer layers. The samples were subjected to thermal annealing, applied either before (pre-annealing) or after (post-annealing) the cathode metal deposition. The effect of the HTL and the annealing process on the BHJ ingredient distribution - namely, poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) - has been studied by spectroscopic ellipsometry and atomic force microscopy. The results revealed P3HT segregation at the top region of the films, which had a detrimental effect on all pre-annealed devices, whereas PCBM was found to accumulate at the bottom interface. This demixing process depends on the PEDOT:PSS surface energy; the more hydrophilic the surface the more profound is the vertical phase separation within the BHJ. At the same time those samples suffer from high recombination losses as evident from the analysis of the J-V measurements obtained in the dark. Our results underline the significant effect of the HTL-active and active-ETL (electron transport layer) interfacial composition that should be taken into account during the optimization of all polymer-fullerene solar cells. © 2012 The Royal Society of Chemistry.