To form a union without having a child. The lengthening of the initial period of life in union before parenthood. A study based on European FFS data

Comunicació presentada a l'European Population Conference: "Migration and Migrants in Europe"(Sessió 53). Organitzat per l'European Association for Population Studies (EAPS); Centre d'Estudis Demogràfics. Barcelona, del 9 al 12 de juliol de 2008.The authors of the Second Demographic Transition scheme single out the postponement of the age at first childbearing as the main effect of the changes in habits of young adults associated with this transition. This postponement is accompanied by an increase in the length of the initial period of life in partnership when the couple has no plan yet to have children. This change is made possible by the use of contraceptive means by people living in partnerships in order to delay first childbearing. This is in sharp contrast with the First Demographic Transition, which was also characterized by the extension of the use of contraceptive means, but only after the birth of children. So contraception was used then to control fertility, when it is used nowadays to extend the period of life when no irreversible decisions, like having a child, have been made yet. In this work, we study various dimensions of this postponement of childbearing by couples. First, we try to quantify the magnitude of the increase in the duration of this initial period, when the couple delays parenthood. Second we have a look at the way this change in fertility behaviours in the first years of union change the duration model that was typical at the end of the First Demographic Transition. Finally, we investigate the possible determinants of the increase of this initial period using data on time spent by women studying and working, and of the transition from cohabitation to marriage. We use data from Fertility and Families Surveys for 17 countries and apply life table techniques and proportional hazard modelling.Un dels principals canvis associats a la Segona Transició Demogràfica és el retard en l'edat de tenir el primer fill, allargant-se el període d'unió sense plans de tenir-los. El retard és possible gràcies a la utilització dels mitjans anticonceptius, fet que contrasta amb la Primera Transició Demogràfica, a on els mitjans anticonceptius s'empraven després del naixement dels fills. En aquest estudi s'analitzen les diverses dimensions d'aquest ajornament. En primer lloc, es quantifica l'augment temporal d'aquest període inicial sense fills; en segon lloc s'analitza la forma en què aquest canvi modifica el model de la Primera Transició Demogràfica; finalment, s'apunten possibles determinants, emprant dades sobre el temps dedicat per les dones a estudiar i a treballar, i de la transició de la cohabitació al matrimoni. La font bàsica d'informació és la Fertility and Families Surveys , per a 17 països.Uno de los principales cambios asociados a la Segunda Transición Demográfica, es el aplazamiento en la edad de tener el primer hijo, ampliándose el período de unión sin planes de tenerlos. La demora es posible gracias a la utilización de los medios anticonceptivos, hecho que contrasta con la Primera Transición Demográfica, donde los medios anticonceptivos se utilizaban después del nacimiento de los hijos. En este estudio se analizan las dimensiones de este aplazamiento. En primer lugar, se cuantifica el aumento temporal de esta etapa inicial sin hijos; en segundo lugar, se analiza la forma en que este cambio modifica el modelo de la Primera Transición Demográfica; finalmente, se apuntan posibles determinantes utilizando datos sobre el tiempo dedicado por las mujeres a estudiar y a trabajar, y de la transición de la cohabitación al matrimonio. La fuente básica de información es la Fertility and Families Surveys, para 17 países

Charge Transport Limitations in Self-Assembled TiO₂ Photoanodes for Dye-Sensitized Solar Cells

Solid-state dye-sensitized solar cells offer the possibility of high-power conversion efficiencies due to theoretically lower fundamental losses in dye regeneration. Despite continuous progress, limitations in charge diffusion through the mesoporous photoanode still constrain the device thickness and hence result in reduced light absorption with the most common sensitizers. Here we examine block copolymer-assembled photoanodes with similar surface area and morphology but a large variation in crystal size. We observe that the crystal size has a profound effect on the electron transport, which is not explicable by considering solely the ratio between free and trapped electrons. Our results are consistent with the long-range mobility of conduction band electrons being strongly influenced by grain boundaries. Therefore, maximizing the crystal size while maintaining high enough surface area will be an important route forward

Oligothiophene Interlayer Effect on Photocurrent Generation for Hybrid TiO₂/P3HT Solar Cells

A series of conjugated 3-hexylthiophene derivatives with a cyanoacrylic acid group has been prepared with conjugation length from one up to five thiophene units (<b>1T</b>–<b>5T</b>). The UV–vis spectra, photoluminescence spectra, electrochemical data and DFT calculations show lowering of LUMO energies and red-shift of absorption into the visible as the thiophene chain length increases. TiO₂/P3HT solar cells were prepared with prior functionalization of the TiO₂ surface by <b>1T</b>–<b>5T</b> and studies include cells using undoped P3HT and using P3HT doped with H-TFSI. Without H-TFSI doping, photocurrent generation occurs from both the oligothiophene and P3HT. Doping the P3HT with H-TFSI quenches photocurrent generation from excitation of P3HT, but enables very effective charge extraction upon excitation of the oligothiophene. In this case, photocurrent generation increases with the light harvesting ability of <b>1T</b>–<b>5T</b> leading to a highest efficiency of 2.32% using <b>5T</b>. Overall, we have shown that P3HT can act in either charge generation or in charge collection, but does not effectively perform both functions simultaneously, and this illustrates a central challenge in the further development of TiO₂/P3HT solar cells

Well-Defined Nanostructured, Single-Crystalline TiO₂ Electron Transport Layer for Efficient Planar Perovskite Solar Cells

An electron transporting layer (ETL) plays an important role in extracting electrons from a perovskite layer and blocking recombination between electrons in the fluorine-doped tin oxide (FTO) and holes in the perovskite layers, especially in planar perovskite solar cells. Dense TiO₂ ETLs prepared by a solution-processed spin-coating method (S-TiO₂) are mainly used in devices due to their ease of fabrication. Herein, we found that fatal morphological defects at the S-TiO₂ interface due to a rough FTO surface, including an irregular film thickness, discontinuous areas, and poor physical contact between the S-TiO₂ and the FTO layers, were inevitable and lowered the charge transport properties through the planar perovskite solar cells. The effects of the morphological defects were mitigated in this work using a TiO₂ ETL produced from sputtering and anodization. This method produced a well-defined nanostructured TiO₂ ETL with an excellent transmittance, single-crystalline properties, a uniform film thickness, a large effective area, and defect-free physical contact with a rough substrate that provided outstanding electron extraction and hole blocking in a planar perovskite solar cell. In planar perovskite devices, anodized TiO₂ ETL (A-TiO₂) increased the power conversion efficiency by 22% (from 12.5 to 15.2%), and the stabilized maximum power output efficiency increased by 44% (from 8.9 to 12.8%) compared with S-TiO₂. This work highlights the importance of the ETL geometry for maximizing device performance and provides insights into achieving ideal ETL morphologies that remedy the drawbacks observed in conventional spin-coated ETLs

Homogeneous Emission Line Broadening in the Organo Lead Halide Perovskite CH₃NH₃PbI_3–<i>x</i>Cl_<i>x</i>

The organic–inorganic hybrid perovskites methylammonium lead iodide (CH₃NH₃PbI₃) and the partially chlorine-substituted mixed halide CH₃NH₃PbI_3–<i>x</i>Cl_<i>x</i> emit strong and broad photoluminescence (PL) around their band gap energy of ∼1.6 eV. However, the nature of the radiative decay channels behind the observed emission and, in particular, the spectral broadening mechanisms are still unclear. Here we investigate these processes for high-quality vapor-deposited films of CH₃NH₃PbI_3–<i>x</i>Cl_<i>x</i> using time- and excitation-energy dependent photoluminescence spectroscopy. We show that the PL spectrum is homogenously broadened with a line width of 103 meV most likely as a consequence of phonon coupling effects. Further analysis reveals that defects or trap states play a minor role in radiative decay channels. In terms of possible lasing applications, the emission spectrum of the perovskite is sufficiently broad to have potential for amplification of light pulses below 100 fs pulse duration

ZrO₂/TiO₂ Electron Collection Layer for Efficient Meso-Superstructured Hybrid Perovskite Solar Cells

Since the first reports of efficient organic–inorganic perovskite solar cells in 2012, an explosion of research activity has emerged around the world, which has led to a rise in the power conversion efficiencies (PCEs) to over 20%. Despite the impressive efficiency, a key area of the device which remains suboptimal is the electron extraction layer and its interface with the photoactive perovskite. Here, we implement an electron collection “bilayer” composed of a thin layer of zirconia coated with titania, sitting upon the transparent conductive oxide fluorine-doped tin oxide (FTO). With this double collection layer we have reached up to 17.9% power conversion efficiency, delivering a stabilized power output (SPO) of 17.0%, measured under simulated AM 1.5 sunlight of 100 mW cm^–2 irradiance. Finally, we propose a mechanism of the charge transfer processes within the fabricated architectures in order to explain the obtained performance of the devices

Band Gaps of the Lead-Free Halide Double Perovskites Cs₂BiAgCl₆ and Cs₂BiAgBr₆ from Theory and Experiment

The recent discovery of lead-free halide double perovskites with band gaps in the visible represents an important step forward in the design of environmentally friendly perovskite solar cells. Within this new family of semiconductors, Cs₂BiAgCl₆ and Cs₂BiAgBr₆ are stable compounds crystallizing in the elpasolite structure. Following the recent computational discovery and experimental synthesis of these compounds, a detailed investigation of their electronic properties is warranted in order to establish their potential as optoelectronic materials. In this work, we perform many-body perturbation theory calculations and obtain high accuracy band gaps for both compounds. In addition, we report on the synthesis of Cs₂BiAgBr₆ single crystals, which are stable in ambient conditions. From our complementary theoretical and experimental analysis, we are able to assign the indirect character of the band gaps and obtain both experimental and theoretical band gaps of these novel semiconductors that are in close agreement

The Importance of Perovskite Pore Filling in Organometal Mixed Halide Sensitized TiO₂‑Based Solar Cells

Emerging from the field of dye-sensitized solar cells, organometal halide perovskite-based solar cells have recently attracted considerable attention. In these devices, the perovskite light absorbers can also be used as charge transporting materials, changing the requirements for efficient device architectures. The perovskite deposition can vary from merely sensitizing the TiO₂ electron transporting scaffold as an endowment of small nanoparticles, to completely filling the pores where it acts as both light absorber and hole transporting material in one. By decreasing the TiO₂ scaffold layer thickness, we change the solar cell architecture from perovskite-sensitized to completely perovskite-filled. We find that the latter case leads to improvements in device performance because higher electron densities can be sustained in the TiO₂, improving electron transport rates and photovoltage. Importantly, the primary recombination pathway between the TiO₂ and the hole transporting material is blocked by the perovskite itself. This understanding helps to rationalize the high voltages attainable on mesoporous TiO₂-based perovskite solar cells

Enhanced Hole Extraction in Perovskite Solar Cells Through Carbon Nanotubes

Here, we report the use of polymer-wrapped carbon nanotubes as a means to enhance charge extraction through undoped spiro-OMeTAD. With this approach a good solar cell performance is achieved without the implementation of conventional doping methods. We demonstrate that a stratified two-layer architecture of sequentially deposited layers of carbon nanotubes and spiro-OMeTAD, outperforms a conventional blend of the hole-conductor and the carbon nanotubes. We also provide insights into the mechanism of the rapid hole extraction observed in the two-layer approach

Unraveling the Function of an MgO Interlayer in Both Electrolyte and Solid-State SnO₂ Based Dye-Sensitized Solar Cells

The coating of n-type mesoporous metal oxides with nanometer thick dielectric shells is a route that has proven to be successful at enhancing the efficiency of some families of dye-sensitized solar cells. The primary intention is to introduce a “surface passivation layer” to inhibit recombination between photoinduced electrons and holes across the dye-sensitized interface. However, the precise function of these dielectric interlayers is often ambiguous. Here, the role of a thin MgO interlayer conformally deposited over mesoporous SnO₂ in liquid electrolyte and solid-state dye-sensitized solar cells is investigated. For both families of devices the open-circuit voltage is increased by over 200 mV; however, the short-circuit photocurrent is increased for the solid-state cells, but reduced for the electrolyte based devices. Through electronic and spectroscopic characterization we deduce that there are four distinct influences of the MgO interlayer: It increases dye-loading, slows down recombination, slows down photoinduced electron transfer, and results in a greater than 200 mV shift in the conduction band edge, with respect to the electrolyte redox potential. The compilation of these four factors have differing effects and magnitudes in the solid-state and electrolyte DSCs but quantitatively account for the difference in device performances observed for both systems with and without the MgO shells. To the best of our knowledge, this is the most comprehensive account of the role of dielectric shells in dye-sensitized solar cells and will enable much better interfacial design of photoelectrodes for DSCs