Investigations on thiourea content in ternary Sn–Ag–Cu bath using electrochemical studies

We have developed a methane sulfonic acid (MSA) based ternary electrolytic bath for co-deposition of the eutectic Sn–Ag–Cu films. The bath contains thiourea (TU), which functioned as an effective chelating agent in controlling the bath stability as well as the elemental and microstructural properties of the deposited film. A study of the bath behaviour at TU concentrations in the range 0.06–0.2 M is undertaken with the help of elemental and microstructure analysis, cyclic voltammetry (CV) and impedance analysis. The deposited films have close to eutectic composition with slightly higher Cu content for all the TU concentrations. On the other hand, the microstructure is found to be increasingly refined with increasing TU content. The CV and impedance analysis confirm chelation of Ag and Cu with TU and absence of such chelation with Sn ions. It also indicates close deposition potentials for each metal ion. Impedance analysis specifically reveals presence of an adsorbed insulating film on cathode surface, contributed by MSA or water. It also reveals competitive deposition between the insulating film and metal ions.     

Effect of surfactant on the bath stability and electrodeposition of Sn-Ag-Cu films

A methanesulphonic acid based bath for the co-deposition of Sn-Ag-Cu films is developed. The bath contains thiourea as chelating agent, while iso-octyl phenoxy polyethoxy ethanol (OPPE) is added as a non-ionic surfactant. Studies show that OPPE plays a major role in improving the bath stability from few hours up to 1 week. However, there is no evidence of any strong chelation between any metal ion and OPPE. There is a slight modification in the reduction potentials of individual ions after addition of OPPE, which is attributed to some weak bonding through the lone-pair electrons of this molecule. Bath investigations confirm that thiourea forms chelates with electropositive Ag⁺ and Cu²⁺ ions and alters their deposition potentials. Consequently, the deposition of three elements takes place at a single potential of − 0.541 V. The proposed bath is capable of depositing Sn-Ag-Cu films having near eutectic composition that remains consistent even with increase in current density beyond 5 mA cm^− 2. This is attributed to the three metals reaching their limiting current density. The deposited films have compact microstructure with grain size in the range 6-8 μm and thickness in the range 20-100 μm. The studies show that OPPE brings about refinement in film microstructure.     

A preliminary study of coping styles of applicants for counselor education and their relations to admission criteria

Responses of 100 applicants to a counselor education program were analyzed for their coping styles and the relations of these coping styles to a set of sociodemographic, academic, and experiential variables obtained during the application process. Seven factor-analytically derived coping styles are described. No significant relationships were found between these coping styles and the remaining variables.     

Lower bounds on the state complexity of linear tail-biting trellises

Lower bounds on the state complexity of linear tail-biting trellises are presented. One bound generalizes the total-span bound, while another bound can be regarded as a generalization of the cut-set bound. It is shown by examples that the new bounds may be tighter than any of the existing lower bounds.     

Electronic Structure and Optoelectronic Properties of Bismuth Oxyiodide Robust against Percent‐Level Iodine‐, Oxygen‐, and Bismuth‐Related Surface Defects

In the search for nontoxic alternatives to lead‐halide perovskites, bismuth oxyiodide (BiOI) has emerged as a promising contender. BiOI is air‐stable for over three months, demonstrates promising early‐stage photovoltaic performance and, importantly, is predicted from calculations to tolerate vacancy and antisite defects. Here, whether BiOI tolerates point defects is experimentally investigated. BiOI thin films are annealed at a low temperature of 100 °C under vacuum (25 Pa absolute pressure). There is a relative reduction in the surface atomic fraction of iodine by over 40%, reduction in the surface bismuth fraction by over 5%, and an increase in the surface oxygen fraction by over 45%. Unexpectedly, the Bi 4f_7/2 core level position, Fermi level position, and valence band density of states of BiOI are not significantly changed. Further, the charge‐carrier lifetime, photoluminescence intensity, and the performance of the vacuum‐annealed BiOI films in solar cells remain unchanged. The results show BiOI to be electronically and optoelectronically robust to percent‐level changes in surface composition. However, from photoinduced current transient spectroscopy measurements, it is found that the as‐grown BiOI films have deep traps located ≈0.3 and 0.6 eV from the band edge. These traps limit the charge‐carrier lifetimes of BiOI, and future improvements in the performance of BiOI photovoltaics will need to focus on identifying their origin. Nevertheless, these deep traps are three to four orders of magnitude less concentrated than the surface point defects induced through vacuum annealing. The charge‐carrier lifetimes of the BiOI films are also orders of magnitude longer than if these surface defects were recombination active. This work therefore shows BiOI to be robust against processing conditions that lead to percent‐level iodine‐, bismuth‐, and oxygen‐related surface defects. This will simplify and reduce the cost of fabricating BiOI‐based electronic devices, and stands in contrast to the defect‐sensitivity of traditional covalent semiconductors.     

Solvent additives for tuning the photovoltaic properties of polymer-fullerene solar cells

We use solvent additives as a simple method to tune the photovoltaic performance of poly-3-hexylthiophene (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojuncton solar cells. 1,2-dichlorobenzene (oDCB) was used as the reference solvent; chlorobenzene (CB) and 1,2,3,4-tetrahydronaphthalene (THN) were used as additives to influence film formation. An increase in the short circuit current and the power conversion efficiency of solar cells with blends cast from mixed solvents was observed. Blends prepared with THN, the highest boiling point solvent, resulted in the best device performance, while blends prepared with the pure reference solvent resulted in the lowest photocurrent. In-plane investigations of the morphology using transmission electron microscopy (TEM) revealed improved phase segregation for blends prepared with mixed solvents, and increased crystallinity in the P3HT phase is demonstrated using atomic force microscopy (AFM) coupled with Kelvin probe force microscopy (KPFM). Optical modeling reveals that the increase in the photocurrent is not due to changes in the optical properties of the blends. Electrical characterization reveals that the electron mobilities decrease slightly in blends cast from mixed solvents, corresponding to a decrease in the fill factor and an increase in P3HT crystallinity observed at the surface of the blend. The increase in the photovoltaic performance is discussed in terms of increased charge separation at the donor-acceptor interface due to increased ordering in the P3HT phase induced by the solvent additives.     

The Effect of Ageing on Exciton Dynamics,Charge Separation,and Recombination in P3HT/PCBM Photovoltaic Blends

A study of how light‐induced degradation influences the fundamental photophysical processes in the active layer of poly(3‐hexylthiophene)/[6,6]‐phenyl C₆₁‐butyric acid methyl ester (P3HT/PCBM) solar cells is presented. Non‐encapsulated samples are systematically aged by exposure to AM 1.5 illumination in the presence of dry air for different periods of time. The extent of degradation is quantified by the relative loss in the absorption maximum of the P3HT, which is varied in the range 0% to 20%. For degraded samples an increasing loss in the number of excitons within the P3HT domains is observed with longer ageing periods. This loss occurs rapidly, within the first 15 ps after photoexcitation. A more pronounced decrease in the population of polarons than excitons is observed, which also occurs on a timescale of a few picoseconds. These observations, complemented by a quantitative analysis of the polaron and exciton population dynamics, unravel two primary loss mechanisms for the performances of aged P3HT/PCBM solar cells. One is an initial ultrafast decrease in the polaron generation, apparently not related to the exciton diffusion to the polymer/fullerene interface; the second, less significant, is a loss in the exciton population within the photoexcited P3HT domains. The steady‐state photoinduced absorption spectra of degraded samples exhibits the appearance of a signal ascribed to triplet excitons, which is absent for non‐degraded samples. This latter observation is interpreted considering the formation of degraded sites where intersystem crossing and triplet exciton formation is more effective. The photovoltaic characteristics of same blends are also studied and discussed by comparing the decrease in the overall power conversion efficiency of solar cells.     

Linear tail-biting trellises, the square-root bound, andapplications for Reed-Muller codes

Linear tail-biting trellises for block codes are considered. By introducing the notions of subtrellis, merging interval, and sub-tail-biting trellis, some structural properties of linear tail-biting trellises are proved. It is shown that a linear tail-biting trellis always has a certain simple structure, the parallel-merged-cosets structure. A necessary condition required from a linear code in order to have a linear tail-biting trellis representation that achieves the square root bound is presented. Finally, the above condition is used to show that for r⩾2 and m⩾4r-1 or r⩾4 and r+3⩽m⩽[(4r+5)/3] the Reed-Muller code RM(r, m) under any bit order cannot be represented by a linear tail-biting trellis whose state complexity is half of that of the minimal (conventional) trellis for the code under the standard bit order     

The Physics of Light Emission in Halide Perovskite Devices

Light emission is a critical property that must be maximized and controlled to reach the performance limits in optoelectronic devices such as photovoltaic solar cells and light‐emitting diodes. Halide perovskites are an exciting family of materials for these applications owing to uniquely promising attributes that favor strong luminescence in device structures. Herein, the current understanding of the physics of light emission in state‐of‐the‐art metal‐halide perovskite devices is presented. Photon generation and management, and how these can be further exploited in device structures, are discussed. Key processes involved in photoluminescence and electroluminescence in devices as well as recent efforts to reduce nonradiative losses in neat films and interfaces are discussed. Finally, pathways toward reaching device efficiency limits and how the unique properties of perovskites provide a tremendous opportunity to significantly disrupt both the power generation and lighting industries are outlined.