Study of CuI thin films properties for application as anode buffer layer in organic solar cells

After chemico-physical characterization of CuI thin films, the structures indium tin oxide (ITO) /CuI are systematically studied. We show that the morphology of the 3 nm thick CuI film depends on its deposition rate. To obtain smooth homogeneous CuI film, it is necessary to depose it at 0.005 nm/s. After optimization of the deposition conditions of CuI, it is shown that it behaves like a template for the organic layer. For instance, when the organic film is copper-phthalocyanine, the molecules which are usually perpendicular to the plane of the substrate lie parallel to it when deposited onto CuI. In a same way, when the electron donor is a prophyrin derivative, CuI allows to double the power conversion efficiency of the cells based on the heterojunction porphyrin/C-60. When CuI is used as anode buffer layer, it increases systematically the short circuit current, the open circuit voltage, thus the efficiency of the organic solar cell. These effects are related, not only to the improvement of the band matching between the ITO and the electron donor, but also to the templating effect of the CuI. Moreover, we show that the beneficial effect of CuI. is effective, not only with ITO, but also with fluorine doped tin oxide

Efficient hole-transporting layer MoO3:CuI deposited by co-evaporation in organic photovoltaic cells

In order to improve hole collection at the interface anode/electron donor in organic photovoltaic cells, it is necessary to insert a hole transporting layer. CuI was shown to be a very efficient hole transporting layer. However, its tendency to be quite rough tends to induce leakage currents and it is necessary to use a very slow deposition rate for CuI to avoid such negative effect. Herein, we show that the co-deposition of MoO3 and CuI avoids this difficulty and allows deposition of a homogeneous efficient hole-collecting layer at an acceptable deposition rate. Via an XPS study, we show that blending MoO3:CuI improves the hole collection efficiency through an increase of the gap state density. This increase is due to the formation of Mo5þ following interaction between MoO3 and CuI. Not only does the co-evaporation process allow for decreasing significantly the deposition time of the hole transporting layer, but also it increases the efficiency of the device based on the planar heterojunction, CuPc/C60

Dielectric/metal/dielectric alternative transparent electrode: observations on stability/degradation

The use of indium-free transparent conductive electrodes is of great interest for organic optoelectronic devices. Among the possible replacements for ITO, dielectric/metal/dielectric (D/M/D) multilayer structures have already proven to be quite efficient. One issue with organic devices is their lifetime, which depends not only on the organic molecules used but also on the electrodes. Therefore we study the variation, with elapsed time, of the electrical and optical properties of different D/M/D structures, with M  =  Ag or Cu/Ag. Six years after realization, it has been shown that if some structures retained an acceptable conductivity, some others became non-conductive. For a sample which remains conductive, in the case of a PET/MoO3/Ag/MoO3 multilayer structure, the sheet resistance changes from 5 Ω/sq–17 Ω/sq after six years. This evolution can be compared to that of a PET/ITO electrode that varies from 25 Ω/sq–900 Ω/sq after six years. It means that not only are the PET/MoO3/Ag/MoO3 multilayer structures more flexible than PET/ITO, but they can also be more stable. Nevertheless, if some PET/MoO3/Ag/MoO3 multilayer structures are quite stable, some others are not. This possible degradation appears to be caused primarily by the physical agglomeration of Ag, which can result in Ag film disruption. This Ag diffusion seems to be caused by humidity-induced degradation in these Ag-based D/M/D structures. Initially, defects begin to grow at a \u27nucleus\u27, usually a microscopic particle (or pinhole, etc), and then they spread radially outward to form a nearly circular pattern. For a critical density of such defects, the structure becomes non-conductive. Moreover the effect of humidity promotes Ag electrochemical reactions that produce Ag+ ions and enhances surface diffusivity with AgCl formation

Improved performance of organic solar cells by growth optimization of MoO3/CuI double-anode buffer

We investigated the effect of a CuI anode buffer layer (ABL) on the molecular orientation of the copper phthalocyanine (CuPc) in organic photovoltaic cells (OPV cells), and we compare it to the effect of MoO3 buffer layer. While, in the presence of CuI, the CuPc molecules lie down parallel to the substrate, they stand up perpendicular in the case of MoO3. We show that the optical absorption, the morphology, and the JV characteristics of the OPV cells depends strongly on the orientation of the CuPc molecules. The improvement of the OPV cells performance is related to the property modifications induced by the change in molecule orientation. We show that the improvement of the OPV cell performance through the templating effect of CuI depends strongly on the deposition rate of the CuI, because the CuI thin-film morphology depends on this deposition rate. In this context, we show that the use of a double-ABL MoO3/CuI leads to a significant improvement of the cell performance. These results are discussed on the basis of the dual function of MoO3 and CuI. While both of them reduce the hole-injection barrier, CuI improves the CuPc film absorbance through specific molecular order and MoO3 prevents the OPV cells from leakage-path formation

Mo(SxOy) thin films deposited by electrochemistry for application in organic photovoltaic cells

In this study, Mo(SxOy) thin films were deposited onto fluorine doped tin oxide (FTO) using pulsed electrochemical deposition method. It is shown by scanning electron microscopy, energy-dispersive spectroscopy and X-ray photoelectron spectroscopy that after water cleaning the deposited Mo(SxOy) film corresponds to a hybrid layer MoSx:MoO3. This hybrid is used as anode buffer layer (ABL) in planar organic photovoltaic cells (OPVCs) based on the couple copper-phthalocyanine/fullerene. It is shown that it is necessary to proceed to a soft annealing-5 min at 150 °C- of the anode FTO/Mo(SxOy) to clean the ABL surface in order to obtain efficient contact with the organic material. The OPVC with the optimum Mo(SxOy) thickness, 12 nm, showed a power conversion efficiency, PCE = 1.41% under an illumination of AM1.5, which is 12% higher than that achieved with a simple MoO3 ABL. This improvement is attributed to the fact that using a hybrid MoS2:MoO3 ABL allows to combine the advantages of its both constituents. The MoSx blocks the electrons, while the high work function of MoO3 induces a high hole extraction efficiency at the interface electron donor/anode

Hydrogen in acapulcoites and lodranites: A unique source of water for planetesimals in the inner Solar System

Acapulcoites and lodranites are primitive achondrites, sampling a common planetesimal formed a few million years after calcium-aluminium rich inclusions in the inner Solar System, that provides information into melting and differentiation processes in the early inner Solar System. The chemistry and mineralogy of their chondritic parent body lies in between enstatite and ordinary chondrites. As they record a range in planetary differentiation degree, from 1% up to 20% partial melting, with lodranites experiencing the most melt extraction, we investigate (i) the behaviour of hydrogen in terms of abundance and isotopic composition during the early stages of planetary differentiation and (ii) the source(s) of hydrogen for the acapulcoite-lodranite parent body in order to place it in our current understanding of the source(s) of water in the inner Solar System. In this study, we analysed water content and hydrogen isotopic composition of phosphates and nominally anhydrous minerals in a range of acapulcoite and lodranite meteorite samples. While apatites seemed to have recorded a degassing signature, no such variations were observed in the H2O–δD systematics of the nominally anhydrous minerals suggesting that subsequent to their crystallisation, acapulcoites and lodranites experienced minimal modifications to their volatile composition during thermal metamorphism and partial melting. The low abundance of water in acapulcoite and lodranite nominally anhydrous minerals (i.e., average 5.2±1.6 μg/g H2O) suggests that their parent body was much drier than what has been estimated for enstatite and ordinary chondrite parent bodies. We estimated a bulk water content for the acapulcoite-lodranite parent body of 3 to 19 μg/g H2O, similar to the ureilite parent body. The hydrogen isotopic composition of nominally anhydrous minerals in acapulcoites and lodranites (–211±145‰), and in particular for the two falls Acapulco and Lodran (–239±149‰), matches with the hydrogen isotopic composition recorded by nominally anhydrous minerals in ordinary chondrite falls, eucrites, S–type asteroid Itokawa, consistent with a common source of water for the inner Solar System planetesimals, isotopically distinctive to bulk carbonaceous chondrites

Chondritic chlorine isotope composition of acapulcoites and lodranites

Bulk rock chondrites and Earth’s reservoirs share a common chlorine isotopic value, while more differentiated bodies such as the Moon or Vesta record significant chlorine isotopic fractionation in their Ca phosphates. As such, an important but scarcely studied parameter is the effect of melting and differentiation processes on chlorine concentration and isotopic composition of a planetesimal. Here we report chlorine abundances and isotopic compositions for apatite in a range of primitive achondrites, acapulcoites and lodranites. These meteorites originated from a parent body that experienced some partial melting, allowing an assessment of chlorine behaviour during the early stages of planetary evolution in the inner Solar System. Overall, while bulk rock estimates of F and Cl abundances are indicative of degassing during the early stages of partial melting, no chlorine isotopic fractionation is recorded in apatite. Consequently, acapulcoites and lodranites retain their chondritic precursor isotopic signature for chlorine

Broadening of the transmission range of dielectric/metal multilayer structures by using different metals

ZnS/M12/ZnS structures, with M12 ¼ Ag, Cu or Cu/Ag, were deposited under vacuum by simple joule heating effect (sublimation or evaporation). The optimum thicknesses of the different layers were experimentally determined: 50/45 nm for ZnS, 11 nm for Ag, 16 nm for Cu and 3 nm/9 nm for Cu/Ag. The presence of the double metal Cu/Ag interlayer induces a significant broadening of the optical transmittance spectrum of these structures. The properties of the structures depend strongly on deposition rate of the different films. When the deposition rates of ZnS, Cu are 0.15 nm/s and 0.30 nm/s for Ag, the averaged transmission, between 400 nm and 1000 nm is 85% while the sheet resistance is 5.0 ± 0.2 Ω/sq. These performances allow achieving an averaged factor of merit ΦM, between 400 nm and 700 nm, of 70 x 10-3 Ω-1. This averaged value tends toward those usually achieved by transparent conductive oxides

Tissemouminites: A new group of primitive achondrites spanning the transition between acapulcoites and winonaites

The Northwest Africa (NWA) 090 meteorite, initially classified as an acapulcoite, presents petrological, chemical, and isotopic characteristics comparable to a group of seven primitive winonaites: Dhofar 1222, NWA 725, NWA 1052, NWA 1054, NWA 1058, NWA 1463, and NWA 8614. Five of these samples were previously classified as acapulcoites or ungrouped achondrites before being reclassified as winonaites based on their oxygen isotopic compositions. These misclassifications are indicative of the particular compositional nature of these primitive achondrites. All contain relict chondrules and a lower closure temperature of metamorphism of 820 ± 20 °C compared to other typical winonaites, as well as mineral elemental compositions similar to those of acapulcoites. The oxygen isotopic signature of these samples, δ17O of 1.18 ± 0.17‰, δ18O of 3.18 ± 0.30‰, and Δ17O of −0.47 ± 0.02, is in fact resolvable from both acapulcoites and winonaites. We investigate the relationship between these eight primitive achondrites, typical winonaites, and acapulcoites, to redefine petrological, mineralogical, and geochemical criteria of primitive achondrite classification. Distinguishing between winonaites, acapulcoites, and this group of eight primitive achondrites can be unambiguously done using a combination of several mineralogical and chemical criteria. A combination of olivine fayalite content and FeO/MnO ratio, as well as plagioclase potassium content allow us to separate these three groups without the absolute necessity of oxygen isotope analyses. NWA 090 as well as the other seven primitive achondrites, although related to winonaites, are most likely derived from a parent body distinct from winonaites and acapulcoites–lodranites, and define a new group of primitive achondrites that can be referred to as tissemouminites

Evidence against water delivery by impacts within 10 million years of planetesimal formation

The quenched (rapidly-cooled) angrite meteorites, which formed in the inner Solar System, record large-scale planetary mixing in the first few Ma of Solar System history, and therefore, provide a unique opportunity to investigate the role of impacts in terms of water addition to the growing planetesimals. Here we investigate the H isotopic composition and H2O abundance of relict olivine grains that survived impact melting within Asuka (A) 12,209 and compare them with impact melt-produced groundmass fractions using in-situ nanoscale secondary ion mass spectrometry (NanoSIMS). These analyses test if the angrite parent body (APB) acquired a CC-like H isotopic composition before early large-scale impact mixing and/or acquired volatiles by subsequent impact(s). Furthermore, we analyse the H isotopic composition and H2O abundance of later-forming plutonic (NWA 4801), intermediate (NWA 10,463) and dunitic (NWA 8535) angrite meteorites to assess the role of impacts, in terms of volatile delivery, during the first 50 Ma of the inner Solar System history. The H isotopic composition of most quenched angrites appears to be affected by degassing. Consequently, we opt to use the weighted average δD of pyroxenes and olivines in the plutonic angrite, NWA 4801, to estimate the original composition of the APB (-235 ± 113 ‰ 1σ, n = 18), in agreement with recent studies on the hydrogen isotopic signatures of mineral-hosted melt inclusions in D'Orbigny and Sahara 99,555. Additionally, we use the H2O abundances of NWA 4801 pyroxene (7.9 ± 1 µg/g 2σ) and olivine (6.1 ± 0.6 µg/g 2σ) to estimate the lower (85 to 110 µg/g) and upper (519 to 1089 µg/g) limits of the primitive APB mantle H2O content, implying that the APB was one of the most hydrated bodies in the early inner Solar System. The similarity of δD/H2O systematics in the relict olivine grains and groundmass olivine within A 12,209 argues against water delivery through impacts in the early inner Solar System. Overall, the non-carbonaceous reservoir in the inner Solar System appears to retain a single source of water, which isotopically resembles either water ice in carbonaceous chondrite parent bodies or fractionated nebula water