Hybrid pn-junction solar cells based on layers of inorganic nanocrystals and organic semiconductors: optimization of layer thickness by considering the width of the depletion region.

We report the formation and characterization of hybrid pn-junction solar cells based on a layer of copper diffused silver indium disulfide (AgInS2@Cu) nanoparticles and another layer of copper phthalocyanine (CuPc) molecules. With copper diffusion in the nanocrystals, their optical absorption and hence the activity of the hybrid pn-junction solar cells was extended towards the near-IR region. To decrease the particle-to-particle separation for improved carrier transport through the inorganic layer, we replaced the long-chain ligands of copper-diffused nanocrystals in each monolayer with short-ones. Under illumination, the hybrid pn-junctions yielded a higher short-circuit current as compared to the combined contribution of the Schottky junctions based on the components. A wider depletion region at the interface between the two active layers in the pn-junction device as compared to that of the Schottky junctions has been considered to analyze the results. Capacitance-voltage characteristics under a dark condition supported such a hypothesis. We also determined the width of the depletion region in the two layers separately so that a pn-junction could be formed with a tailored thickness of the two materials. Such a "fully-depleted" device resulted in an improved photovoltaic performance, primarily due to lessening of the internal resistance of the hybrid pn-junction solar cells.

Substrate-controlled band positions in CH3NH3PbI3 perovskite films.

Using X-ray and ultraviolet photoelectron spectroscopy, the surface band positions of solution-processed CH3NH3PbI3 perovskite thin films deposited on an insulating substrate (Al2O3), various n-type (TiO2, ZrO2, ZnO, and F:SnO2 (FTO)) substrates, and various p-type (PEDOT:PSS, NiO, and Cu2O) substrates are studied. Many-body GW calculations of the valence band density of states, with spin-orbit interactions included, show a clear correspondence with our experimental spectra and are used to confirm our assignment of the valence band maximum. These surface-sensitive photoelectron spectroscopy measurements result in shifting of the CH3NH3PbI3 valence band position relative to the Fermi energy as a function of substrate type, where the valence band to Fermi energy difference reflects the substrate type (insulating-, n-, or p-type). Specifically, the insulating- and n-type substrates increase the CH3NH3PbI3 valence band to Fermi energy difference to the extent of pinning the conduction band to the Fermi level; whereas, the p-type substrates decrease the valence band to Fermi energy difference. This observation implies that the substrate's properties enable control over the band alignment of CH3NH3PbI3 perovskite thin-film devices, potentially allowing for new device architectures as well as more efficient devices.

Factors that predict compliance in a virtual cardiac rehabilitation program.

BACKGROUND: Despite the well-established benefits of cardiac rehabilitation (CR) for patients with cardiovascular disease (CVD), participation in CR remain low. Virtual CR programs present a unique opportunity to promote utilization. To date, few virtual CR cohorts have been analyzed for compliance. This study aims to determine factors that predict compliance within a large virtual CR program in the United States. METHODS: We analyzed 1409 patients enrolled in the Kaiser Permanente Mid-Atlantic States Virtual CR program that consists of 12 CR sessions via telephone. Demographic characteristics, as well as body weight, blood pressure, HbA1c level, and smoking status were collected at admission. Patients were further classified by CVD diagnosis codes. Compliance was defined as at least 75% (9/12 sessions) attendance. Data was analyzed using simple and multiple regression models with significance defined as P < 0.05. RESULTS: Age was the single strongest predictor for virtual CR compliance (adjusted R2 = 0.58; P < 0.001), and non-compliant patients were younger. HbA1C level, CVD diagnosis codes, and smoking status each moderately predicted compliance (adjusted R2 = 0.48, 0.42, and 0.31, respectively; P < 0.001). Smoking and HbA1C level combined in a multiple regression model significantly improved prediction of compliance (adjusted R2 = 0.79, P < 0.01). Sex, baseline weight or hypertension were not significant predictors of CR compliance. CONCLUSIONS: Age, diabetes, CVD diagnoses, smoking status at admission are independent predictors of compliance in a large virtual CR program. Targeted intervention could be designed accordingly to improve CR compliance.

Cu2ZnSnS4 (CZTS) nanoparticle based nontoxic and earth-abundant hybrid pn-junction solar cells.

A heterojunction between a layer of CZTS nanoparticles and a layer of fullerene derivatives forms a pn-junction. We have used such an inorganic-organic hybrid pn-junction device for solar cell applications. As routes to optimize device performance, interdot separation has been reduced by replacing long-chain ligands of the quantum dots with short-chain ligands and thickness of the CZTS layer has been varied. We have shown that the CZTS-fullerene interface could dissociate photogenerated excitons due to the depletion region formed at the pn-junction. From capacitance-voltage characteristics, we have determined the width of the depletion region, and compared it with the parameters of devices based on the components of the heterojunction. The results demonstrate solar cell applications based on nontoxic and earth-abundant materials.

Differential regional gene expression from cardiac dyssynchrony induced by chronic right ventricular free wall pacing in the mouse.

Routine clinical right ventricular pacing generates left ventricular dyssynchrony manifested by early septal shortening followed by late lateral contraction, which, in turn, reciprocally stretches the septum. Dyssynchrony is disadvantageous to cardiac mechanoenergetics and worsens clinical prognosis, yet little is known about its molecular consequences. Here, we report the influence of cardiac dyssynchrony on regional cardiac gene expression in mice. Mice were implanted with a custom-designed miniature cardiac pacemaker and subjected to 1-wk overdrive right ventricular free wall pacing (720 beats/min, baseline heart rate 520-620 beats/min) to generate dyssynchrony (pacemaker: 3-V lithium battery, rate programmable, 1.5 g, bipolar lead). Electrical capture was confirmed by pulsed-wave Doppler and dyssynchrony by echocardiography. Gene expression from the left ventricular septal and lateral wall myocardium was assessed by microarray (dual-dye method, Agilent) using oligonucleotide probes and dye swap. Identical analysis was applied to four synchronously contracting controls. Of the 22,000 genes surveyed, only 18 genes displayed significant (P < 0.01) differential expression between septal/lateral walls >1.5 times that in synchronous controls. Gene changes were confirmed by quantitative PCR with excellent correlations. Most of the genes (n = 16) showed greater septal expression. Of particular interest were seven genes coding proteins involved with stretch responses, matrix remodeling, stem cell differentiation to myocyte lineage, and Purkinje fiber differentiation. One week of iatrogenic cardiac dyssynchrony triggered regional differential expression in relatively few select genes. Such analysis using a murine implantable pacemaker should facilitate molecular studies of cardiac dyssynchrony and help elucidate novel mechanisms by which stress/stretch stimuli due to dyssynchrony impact the normal and failing heart.

Heterodimers formed through a partial anionic exchange process: scanning tunneling spectroscopy to monitor bands across the junction vis-à-vis photoinduced charge separation.

We report controlled formation of heterodimers and their charge separation properties. CdS|CdTe heterodimers were formed through an anionic exchange process of CdS nanostructures. With control over the duration of the anionic exchange process, bulk|dot, bulk|bulk, and then dot|bulk phases of the semiconductors could be observed to have formed. A mapping of density of states as derived from scanning tunneling spectroscopy (STS) brought out conduction and valence band-edges along the nanostructures and heterodimers. The CdS|CdTe heterodimers evidenced a type-II band-alignment between the semiconductors along with the formation of a depletion region at the interface. The width (of the depletion region) and the energy-offset at the interface depended on the size of the semiconductors. We report that the width that is instrumental for photoinduced charge separation in the heterodimers has a direct correlation with the performance of hybrid bulk-heterojunction solar cells based on the nanostructures in a polymer matrix.

Improvement in PbS-based Hybrid Bulk-Heterojunction Solar Cells through Band Alignment via Bismuth Doping in the Nanocrystals.

We introduce dopants in lead sulfide (PbS) quantum dots (QDs) in forming hybrid bulk-heterojunction (BHJ) solar cells. Because an increase in the content of bismuth as dopants in PbS QDs transforms the intrinsic p-type semiconductor into an n-type one, the band alignment between a conjugated polymer and the doped QDs changes upon doping affecting performance of BHJ solar cells. From scanning tunneling spectroscopy (STS) of the doped QDs, we observe a shift in their Fermi energy leading to formation of a type II band alignment in the polymer:doped-QD interface. We also show that the dopants improve electron-conduction process through the QDs. With the dopants controlling both band alignments at the interface and the conduction process, we show that the dopant concentration in QDs influences open-circuit voltage unfavorably and short-circuit current in a beneficial manner. The device performance of hybrid BHJ solar cells is hence maximized at an optimum concentration of bismuth in PbS QDs.