Fabrication of excitonic luminescent inorganic-organic hybrid nano- and microcrystals

Inorganic-organic (IO) hybrid nano- and microcrystals are fabricated by a low-cost, environmentally friendly and easily scaled-up route. Lead(II) iodide (PbI 2) nano/microcrystals are obtained by solvothermal techniques and subsequent IO hybrid (C 12H 25NH 3) 2PbI 4 crystals are produced by intercalation of the organic moiety. The hexagonally shaped crystals obtained range in size from 20 nm to ∼7 μm. Sequential stacking of inorganic/organic layers in these IO hybrid crystals results in strong room-temperature exciton photoluminescence, wherein the excitons are confined within the inorganic sheets. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Structural tunability and switchable exciton emission in inorganic-organic hybrids with mixed halides

Room-temperature tunable excitonic photoluminescence is demonstrated in alloy-tuned layered Inorganic-Organic (IO) hybrids, (C12H 25NH3)2PbI4(1-y)Br4y (y = 0 to 1). These perovskite IO hybrids adopt structures with alternating stacks of low-dimensional inorganic and organic layers, considered to be naturally self-assembled multiple quantum wells. These systems resemble stacked monolayer 2D semiconductors since no interlayer coupling exists. Thin films of IO hybrids exhibit sharp and strong photoluminescence (PL) at room-temperature due to stable excitons formed within the low-dimensional inorganic layers. Systematic variation in the observed exciton PL from 510 nm to 350 nm as the alloy composition is changed, is attributed to the structural readjustment of crystal packing upon increase of the Br content in the Pb-I inorganic network. The energy separation between exciton absorption and PL is attributed to the modified exciton density of states and diffusion of excitons from relatively higher energy states corresponding to bromine rich sites towards the lower energy iodine sites. Apart from compositional fluctuations, these excitons show remarkable reversible flips at temperature-induced phase transitions. All the results are successfully correlated with thermal and structural studies. Such structural engineering flexibility in these hybrids allows selective tuning of desirable exciton properties within suitable operating temperature ranges. Such wide-range PL tunability and reversible exciton switching in these novel IO hybrids paves the way to potential applications in new generation of optoelectronic devices. © 2013 AIP Publishing LLC.

Photosynthetic inorganic carbon utilization of gametophytes and sporophytes of Undaria pinnatifida (Phaeophyceae)

The characteristics of inorganic carbon assimilation by photosynthesis were investigated in male and female gametophytes and juvenile sporophytes of Undaria pinnatifida. Gametophytes and sporophytes have detectable extracellular and intracellular carbonic anhydrase (CA) activity, and the CA inhibitor, acetazolamide (AZ), significantly inhibited their photosynthesis O-2 evolution. In pH-drift experiments, it was found that gametophytes did not raise the final pH of seawater above 9.00 (CO2 concentrations of about 2.2 mu M), indicating a low ability to utilize inorganic carbon. In contrast, sporophytes rapidly raised pH to over 9.53 and depleted the free CO2 Concentration to less than 0.16 mu M. The apparent photosynthetic affinity for CO2 was almost the same for gametophytes and sporophytes, whereas gametophytes had a much lower affinity for HCO3- than sporophytes. Two inhibitors of band 3 anion exchange protein (DIDS and SITS) inhibited the photosynthesis of gametophytes but not that of sporophytes. It was indicated that both gametophytes and sporophytes were capable of using HCO3-, which involved the external CA activity, and a direct HCO3- use also occurred in the former, but the latter showed a greater capacity of HCO3- use than the former. In addition, male and female gametophytes did not show great differences in the inorganic carbon uptake mechanism underlying photosynthesis.

Changes in the patterns of inorganic nitrogen and TN/TP ratio and the associated mechanism of biological regulation in the shallow lakes of the middle and lower reaches of the Yangtze River

The changes of NH3-N, NO3-N, NO2-N and TN/TP were studied during growth and non-growth season in 33 subtropical shallow lakes in the middle and lower reaches of the Yangtze River. There were significant positive correlations among all nutrient concentrations, and the correlations were better in growth season than in non-growth season. When TP > 0.1 mgL(-1), NH3-N increased sharply in non-growth season with increasing TP, and NO3-N increased in growth season but decreased in non-growth season with TP. These might be attributed to lower dissolved oxygen and low temperature in non-growth season of the hypereutrophic lakes, since nitrification is more sensitive to dissolved oxygen and temperature than anti nitrification. When 0.1 mgL(-1)> TP > 0.035 mgL(-1), TN and all kinds of inorganic nitrogen were lower in growth season than in non-growth season, and phytoplankton might be the vital regulating factor. When TP < 0.035 mgL(-1), inorganic nitrogen concentrations were relatively low and NH3-N, NO2-N had significant correlations with phytoplankton, indicating that NH3-N and NO2-N might be limiting factors to phytoplankton. In addition, TN/TP went down with decline in TIP concentration, and TN and inorganic nitrogen concentrations were obviously lower in growth season than in non-growth season, suggesting that decreasing nitrogen (especially NH3-N and NO3-N) was an important reason for the decreasing TN/TP in growth season. The ranges of TN/TP were closely related to trophic level in both growth and non-growth seasons, and it is apparent that in the eutrophic and hypertrophic state the TN/TP ratio was obviously lower in growth season than in non-growth season. The changes of the TN/TP ratio were closely correlated with trophic levels, and both declines of TN in the water column and TP release from the sediment were important factors for the decline of the TN/TP ratio in growth season.

In situ intercalation dynamics in inorganic-organic layered perovskite thin films.

The properties of layered inorganic semiconductors can be manipulated by the insertion of foreign molecular species via a process known as intercalation. In the present study, we investigate the phenomenon of organic moiety (R-NH3I) intercalation in layered metal-halide (PbI2)-based inorganic semiconductors, leading to the formation of inorganic-organic (IO) perovskites [(R-NH3)2PbI4]. During this intercalation strong resonant exciton optical transitions are created, enabling study of the dynamics of this process. Simultaneous in situ photoluminescence (PL) and transmission measurements are used to track the structural and exciton evolution. On the basis of the experimental observations, a model is proposed which explains the process of IO perovskite formation during intercalation of the organic moiety through the inorganic semiconductor layers. The interplay between precursor film thickness and organic solution concentration/solvent highlights the role of van der Waals interactions between the layers, as well as the need for maintaining stoichiometry during intercalation. Nucleation and growth occurring during intercalation matches a Johnson-Mehl-Avrami-Kolmogorov model, with results fitting both ideal and nonideal cases.

Photosynthetic utilization of inorganic carbon in the economic brown alga, Hizikia Fusiforme (Sargassaceae) from the South China Sea

The mechanism of inorganic carbon (C-i) acquisition by the economic brown macroalga, Hizikia fusiforme (Harv.) Okamura (Sargassaceae), was investigated to characterize its photosynthetic physiology. Both intracellular and extracellular carbonic anhydrase (CA) were detected, with the external CA activity accounting for about 5% of the total. Hizikia fusiforme showed higher rates of photosynthetic oxygen evolution at alkaline pH than those theoretically derived from the rates of uncatalyzed CO2 production from bicarbonate and exhibited a high pH compensation point (pH 9.66). The external CA inhibitor, acetazolamide, significantly depressed the photosynthetic oxygen evolution, whereas the anion-exchanger inhibitor 4,4'-diisothiocyano-stilbene-2,2'-disulfonate had no inhibitory effect on it, implying the alga was capable of using HCO3- as a source of C-i for its photosynthesis via the mediation of the external CA. CO2 concentrations in the culture media affected its photosynthetic properties. A high level of CO2 (10,000 ppmv) resulted in a decrease in the external CA activity; however, a low CO2 level (20 ppmv) led to no changes in the external CA activity but raised the intracellular CA activity. Parallel to the reduction in the external CA activity at the high CO2 was a reduction in the photosynthetic CO2 affinity. Decreased activity of the external CA in the high CO2 grown samples led to reduced sensitiveness of photosynthesis to the addition of acetazolamide at alkaline pH. It was clearly indicated that H. fusiforme, which showed CO2-limited photosynthesis with the half-saturating concentration of C-i exceeding that of seawater, did not operate active HCO3- uptake but used it via the extracellular CA for its photosynthetic carbon fixation.

Photosynthetic responses to inorganic carbon in Ulva lactuca under aquatic and aerial states

Intertidal macroalgae experience continual alternation of photosynthesis between aquatic state at high tide and aerial state at low tide. The comparative photosynthetic responses to inorganic carbon were investigated in the common intertidal macroalga Ulva lactuca L. along the coast of Shantou between aquatic and aerial state. The inorganic carbon dissolved in seawater at present could fully (at 10 degreesC or 20 degreesC) or nearly (at 30 degreesC) saturate the aquatic photosynthesis of U. lactuca. However, the aerial photosynthesis was limited by current ambient atmospheric CO2 level, and such a limitation was more severe at higher temperature (20degrees - 30degrees T) than at lower temperature (10 T). The carbon-saturated maximal photosynthesis of U. lactuca under aerial state was much greater than that under aquatic state at 10 degreesC and 20 degreesC, while the maximal photosynthesis under both states was similar at 30 degreesC. The aerial values of K-m (CO2) for photosynthesis were higher than the aquatic values. On the contrary, the values of apparent photosynthetic CO2 conductance under aerial state were considerably lower than that under aquatic state. It was concluded that the increase of atmospheric CO2 would enhance the primary productivity of U. lactuca through stimulating the photosynthesis under aerial state during low tide.

Effects of CO2 enrichment on the bloom-forming cyanobacterium Microcystis aeruginosa (Cyanophyceae): Physiological responses and relationships with the availability of dissolved inorganic carbon

Microcystis aeruginosa Kutz. 7820 was cultured at 350 and 700 muL.L-1 CO2 to assess the impacts of doubled atmospheric CO2 concentration on this bloom-forming cyanobacterium. Doubling Of CO2 concentration in the airflow enhanced its growth by 52%-77%, with pH values decreased and dissolved inorganic carbon (DIC) increased in the medium. Photosynthetic efficiencies and dark respiratory rates expressed per unit chl a tended to increase with the doubling of CO2. However, saturating irradiances for photosynthesis and light-saturated photosynthetic rates normalized to cell number tended to decrease with the increase of DIC in the medium. Doubling of CO2 concentration in the airflow had less effect on DIC-saturated photosynthetic rates and apparent photosynthetic affinities for DIC. In the exponential phase, CO2 and HCO3- levels in the medium were higher than those required to saturate photosynthesis. Cultures with surface aeration were DIC limited in the stationary phase. The rate of CO2 dissolution into the liquid increased proportionally when CO2 in air was raised from 350 to 700 muL.L-1, thus increasing the availability of DIC in the medium and enhancing the rate of photosynthesis. Doubled CO2 could enhance CO2 dissolution, lower pH values, and influence the ionization fractions of various DIC species even when the photosynthesis was not DIC limited. Consequently, HCO3- concentrations in cultures were significantly higher than in controls, and the photosynthetic energy cost for the operation of CO2 concentrating mechanism might decrease.

Fabrication of ZnO and its enhancement of charge injection and transport in hybrid organic/inorganic light emitting devices

ZnO nanocrystals were synthesized by hydrolysis in methanol. X-ray diffraction and photoluminescence spectra confirm that good crystallized ZnO nanoparticles were formed. Utilizing those ZnO nanoparticles and poly [2- methoxy-5 - (3',7'-dimethyloctyloxy)- 1,4-phenylenevinylene] (MDMO-PPV), light emitting devices with indium tin oxide (ITO)/poly(3,4-oxyethyleneoxy-thiophene):poly(styrene sulfonate) (PEDOT:PSS)/ ZnO:MDMO-PPV/Al and ITO/PEDOT:PSS/MDMO-PPV/Al structures were fabricated. Electrolummescence (EL) spectra reveal that EL yield of hybrid MDMO-PPV and ZnO nanocrystals devices increased greatly as compared with pristine MDMO-PPV devices. The current-voltage characteristics indicate that addition of ZnO nanocrystals can facilitate electrical injection and charge transport. The decreased energy barrier to electron injection is responsible for the increased efficiency of electron injection. (c) 2007 Elsevier B.V. All rights reserved.

Assembly of side-functional monomers with inorganic nanometer particles

Monomers of methacrylate with various pi -conjugated pendants were designed and prepared in our laboratory, The monomer with suitable end-group was successfully assembled with nano-scale inorganic particles to form an orderly-aligned structure that showed special optical properties, both absorption and emission band were much red-shifted compared with the monomer, A new type of organic/inorganic hybrid materials was obtained by in situ polymerization of the assembly, The hybrid materials could also show special optical properties as the assembly, This might open a new route to tune the emission color.

Organic/inorganic hybrid solar cells based on SnS/SnO nanocrystals and MDMO-PPV

SnS/SnO heterojunction structured nanocrystals with zigzag rod-like connected morphology were prepared by using a simple two-step method. Bulk heterojunction solar cells were fabricated using the SnS/SnO nanocrystals blended with poly(2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene) (MDMO-PPV) as the active layer. Compared with solar cells using SnS nanoparticles hybridized with MDMO-PPV as the active layer, the SnS/SnO devices showed better performance, with a power conversion efficiency higher by about one order in magnitude.