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

Minimal Effect of the Hole-Transport Material Ionization Potential on the Open-Circuit Voltage of Perovskite Solar Cells

Hole-transport material optimization is an important step toward maximizing the efficiency of perovskite solar cells. Here, we investigate the role of one hole-transport material property, the ionization potential, on the performance of perovskite solar cells. We employ a device architecture that allows us to systematically tune the ionization potential while avoiding any impact to other device parameters, and we find that for a wide range of ionization potentials the photovoltaic performance is minimally affected. This finding relaxes the requirement for the development of hole-transport materials with particular ionization potentials, allowing for the optimization of hole-transport materials that can improve performance in differing ways such as through increased stability or decreased parasitic absorption

Mechanism of Tin Oxidation and Stabilization by Lead Substitution in Tin Halide Perovskites

The recent development of efficient binary tin- and lead-based metal halide perovskite solar cells has enabled the development of all-perovskite tandem solar cells, which offer a unique opportunity to deliver high performance at low cost. Tin halide perovskites, however, are prone to oxidation, where the Sn²⁺ cations oxidize to Sn⁴⁺ upon air exposure. Here, we identify reaction products and elucidate the oxidation mechanism of both ASnI₃ and ASn_0.5Pb_0.5I₃ (where A can be made of methylammonium, formamidinium, cesium, or a combination of these) perovskites and find that substituting lead onto the B site fundamentally changes the oxidation mechanism of tin-based metal halide perovskites to make them more stable than would be expected by simply considering the decrease in tin content. This work provides guidelines for developing stable small band gap materials that could be used in all-perovskite tandems

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

Hole Transport Materials with Low Glass Transition Temperatures and High Solubility for Application in Solid-State Dye-Sensitized Solar Cells

We present the synthesis and device characterization of new hole transport materials (HTMs) for application in solid-state dye-sensitized solar cells (ssDSSCs). In addition to possessing electrical properties well suited for ssDSSCs, these new HTMs have low glass transition temperatures, low melting points, and high solubility, which make them promising candidates for increased pore filling into mesoporous titania films. Using standard device fabrication methods and Z907 as the sensitizing dye, power conversion efficiencies (PCE) of 2.94% in 2-μm-thick cells were achieved, rivaling the PCE obtained by control devices using the state-of-the-art HTM spiro-OMeTAD. In 6-μm-thick cells, the device performance is shown to be higher than that obtained using spiro-OMeTAD, making these new HTMs promising for preparing high-efficiency ssDSSCs

Barrier Design to Prevent Metal-Induced Degradation and Improve Thermal Stability in Perovskite Solar Cells

Metal-contact-induced degradation and escape of volatile species from perovskite solar cells necessitate excellent diffusion barrier layers. We show that metal-induced degradation limits thermal stability in several perovskite chemistries with Au, Cu, and Ag gridlines even when the metal is separated from the perovskite by a layer of indium tin oxide (ITO). Channels in a sputtered ITO layer that align with perovskite grain boundaries are pathways for metal and halide diffusion into or out of the perovskite. Planarizing the perovskite morphology with a spin-cast organic charge-transport layer results in a subsequently deposited ITO layer that is uniform and impermeable. We show that it is critical to seal the edges of the active layers to prevent escape of volatile species. We demonstrate 1000 h thermal stability at 85 °C in CH₃NH₃PbI₃ solar cells with complete-coverage silver contacts. Our barrier layer design enables long-term thermal stability of perovskite solar cells, a critical step to commercialization

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

Cross-Linkable, Solvent-Resistant Fullerene Contacts for Robust and Efficient Perovskite Solar Cells with Increased <i>J</i>_SC and <i>V</i>_OC

The active layers of perovskite solar cells are also structural layers and are central to ensuring that the structural integrity of the device is maintained over its operational lifetime. Our work evaluating the fracture energies of conventional and inverted solution-processed MAPbI₃ perovskite solar cells has revealed that the MAPbI₃ perovskite exhibits a fracture resistance of only ∼0.5 J/m², while solar cells containing fullerene electron transport layers fracture at even lower values, below ∼0.25 J/m². To address this weakness, a novel styrene-functionalized fullerene derivative, <b>MPMIC</b>_<b>60</b>, has been developed as a replacement for the fragile PC₆₁BM and C₆₀ transport layers. <b>MPMIC</b>_<b>60</b> can be transformed into a solvent-resistant material through curing at 250 °C. As-deposited films of <b>MPMIC</b>_<b>60</b> exhibit a marked 10-fold enhancement in fracture resistance over PC₆₁BM and a 14-fold enhancement over C₆₀. Conventional-geometry perovskite solar cells utilizing cured films of <b>MPMIC</b>_<b>60</b> showed a significant, 205% improvement in fracture resistance while exhibiting only a 7% drop in PCE (13.8% vs 14.8% PCE) in comparison to the C₆₀ control, enabling larger <i>V</i>_OC and <i>J</i>_SC values. Inverted cells fabricated with <b>MPMIC</b>_<b>60</b> exhibited a 438% improvement in fracture resistance with only a 6% reduction in PCE (12.3% vs 13.1%) in comparison to those utilizing PC₆₁BM, again producing a higher <i>J</i>_SC

Compositional Engineering for Efficient Wide Band Gap Perovskites with Improved Stability to Photoinduced Phase Segregation

Metal halide perovskites are attractive candidates for the wide band gap absorber in tandem solar cells. While their band gap can be tuned by partial halide substitution, mixed halide perovskites often have lower open-circuit voltage than would be expected and experience photoinduced trap formation caused by halide segregation. We investigate solar cell performance and photostability across a compositional space of formamidinium (FA) and cesium (Cs) at the A-site at various halide compositions and show that using more Cs at the A-site rather than more Br at the X-site to raise band gap is more ideal as it improves both <i>V</i>_OC and photostability. We develop band gap maps and design criteria for the selection of perovskite compositions within the Cs_<i>x</i>FA_1–<i>x</i>Pb­(Br_<i>y</i>I_1–<i>y</i>)₃, space. With this, we identify perovskites with tandem-relevant band gaps of 1.68 and 1.75 eV that demonstrate high device efficiencies of 17.4 and 16.3%, respectively, and significantly improved photostability compared to that of the higher Br-containing compositions

Employing PEDOT as the p‑Type Charge Collection Layer in Regular Organic–Inorganic Perovskite Solar Cells

Organic–inorganic halide perovskite solar cells have recently emerged as high-performance photovoltaic devices with low cost, promising for affordable large-scale energy production, with laboratory cells already exceeding 20% power conversion efficiency (PCE). To date, a relatively expensive organic hole-conducting molecule with low conductivity, namely spiro-OMeTAD (2,2′,7,7′-tetrakis­(<i>N</i>,<i>N</i>-di-<i>p</i>-methoxyphenyl-amine) 9,9′- spirobifluorene), is employed widely to achieve highly efficient perovskite solar cells. Here, we report that by replacing spiro-OMeTAD with much cheaper and highly conductive poly­(3,4-ethylenedioxythiophene) (PEDOT) we can achieve PCE of up to 14.5%, with PEDOT cast from a toluene based ink. However, the stabilized power output of the PEDOT-based devices is only 6.6%, in comparison to 9.4% for the spiro-OMeTAD-based cells. We deduce that accelerated recombination is the cause for this lower stabilized power output and postulate that reduced levels of p-doping are required to match the stabilized performance of Spiro-OMeTAD. The entirely of the materials employed in the perovskite solar cell are now available at commodity scale and extremely inexpensive