Integration of an M-phthalocyanine layer into solution-processed organic photovoltaic cells for improved spectral coverage

Photovoltaic devices made from blended poly(3,3?-didodecylquaterthiophene) (PQT-12) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) incorporating an additional interlayer of M-phthalocyanine (M-Pc) have been characterized using current-voltage response, UV-visible absorption and external quantum efficiency. The introduction of H₂Pc, CuPc, ClInPc or TiOPc layers improves device performance compared to conventional bulk-heterojunction PQT-12:PCBM cells without M-Pc. Devices with M-Pc show increased absorption and free charge generation at longer wavelengths and have higher open circuit voltage. Polymorphic changes from solvent interaction are observed in TiOPc films during fabrication. Power conversion efficiencies of 0.79% are achieved for this modified bulk-heterojunction solar cell.     

Synthesis and characterization of a novel fullerene derivative for use in organic solar cells

A novel fullerene derivative with an N-hexylphenothiazine moiety, PTZ-C_60, was synthesized and characterized. The new synthesized fullerene showed good solubility in common organic solvents such as toluene, chlorobenzene and 1, 2 dichlorobenzene. The synthetic product PTZ-C₆₀ was characterized by ¹H and ¹³C NMR, FT-IR and UV-vis spectroscopy. Photovoltaic devices were fabricated using the new fullerene derivative as the electron acceptor and P3HT as the electron donor. The configuration of the device was as follows: ITO/PEDOT:PSS/active layer/LiF/Al. The weight ratios of the electron donor to the acceptor in the active layer were 1:0.5, 1:0.7, and 1:1. The open-circuit voltage (V_oc) of the fabricated devices was found to be higher than that of devices based on C₆₀ because the LUMO energy level of the new fullerene derivative was higher than that of C₆₀. Further, the power conversion efficiency (PCE) of these devices was observed to be high when annealing was carried out at 150 °C for 5 min and the thickness of the active layer was 80 nm. The maximum V_oc, short-circuit current density, and PCE of the best device were 0.608 V, 4.393 mA/cm², and 1.29%, respectively.     

Exergy evaluation of biomass steam gasification via interconnected fluidized beds

This paper presents the thermodynamic assessment of biomass steam gasification via interconnected fluidized beds (IFB) system. The performance examined included the composition, yield and higher heating value (HHV) of dry syngas, and exergy efficiencies of the process. Two exergy efficiencies were calculated for the cases with and without heat recovery, respectively. The effects of steam‐to‐biomass ratio (S/B), gasification temperature, and pressure on the thermodynamic performances were investigated based on a modified modeling of the IFB system. The results showed that at given gasification temperature and pressure, the exergy efficiencies and dry syngas yield reached the maximums when S/B was at the corresponding carbon boundary point (S/B_CBP). The HHV of the dry syngas continuously decreased with the increase of S/B. Moreover, the exergy efficiency with heat recovery was averagely a dozen percentage points higher than that without heat recovery. Under atmospheric conditions, lower gasification temperature favored the yield and HHV of dry syngas at various S/B. In addition, it also favored the exergy efficiencies of the process when S/B is approximately larger than 0.75. Under pressurized conditions, higher gasification pressure favored both the yield and HHV of dry syngas, as well as the exergy efficiencies at different S/B. Copyright © 2013 John Wiley & Sons, Ltd.     

Rubrene as an additive in M-phthalocyanine/fullerene organic solar cells

Photovoltaic devices made from metallo-phthalocyanine/fullerene (M-Pc/C₆₀) with 5,6,11,12-tetraphenylnaphthacene (rubrene) as an additive are fabricated and characterized. The effect of rubrene is examined for 4 different M-phthalocyanines – H₂Pc, ZnPc, ClInPc, and VOPc – to represent 4 different valencies of the central moiety of M-Pc. In each case, rubrene has shown a notable increase in the open circuit voltage and in the case of the ClInPc and VOPc results in an increase in the overall power conversion efficiency. Through measurement of external quantum efficiency, it is shown that the increased efficiency is due to increased V_oc and not due to the photocurrent contribution from the complementary absorption profile of rubrene. Finally, the photostability of rubrene-based cells is studied, showing that unencapsulated devices decay rapidly in air as a result of the formation of rubrene peroxide, as evidenced by significant decay of the UV–vis absorption and direct measurement of the cell performance over a time period as short as several minutes.     

Development of highly efficient thin film silicon solar cells on texture-etched zinc oxide-coated glass substrates

ZnO films prepared by magnetron sputtering on glass substrates and textured by post-deposition chemical etching are applied as substrates for p–i–n solar cells. Using both rf and dc sputtering, similar surface textures can be achieved upon etching. Excellent light trapping is demonstrated by high quantum efficiencies at long wavelengths for microcrystalline silicon solar cells. Applying an optimized microcrystalline/amorphous p-layer design, stacked solar cells with amorphous silicon top cells yield similarly high stabilized efficiencies on ZnO as on state-of-the-art SnO₂ (9.2% for a-Si/a-Si). The efficiencies are significantly higher than on SnO₂-coated float glass as used for module production.     

Higher fullerenes as electron acceptors for polymer solar cells: A quantum chemical study

In the present study, we have used quantum chemical methods to study the energy levels of the frontier orbitals of higher fullerene derivatives (from C₇₀ to C₈₄ and having the same addend as in [6,6]-phenyl C₆₁-butyric acid methyl ester) with the aim to understand if they can be used as electron acceptors in bulk heterojunction polymer–fullerene solar cells. Higher fullerenes have a stronger and broader absorption compared to C₆₀ and they can improve the current output of the corresponding devices. The geometries of all the compounds were optimized with the density functional theory at the B3LYP/3-21G* level of calculation. The lowest unoccupied molecular orbital (LUMO) levels of the investigated compounds correlate well with the reduction potentials (obtained by cyclic voltammetry) of the already prepared species. We found that the LUMO level depends not only on the fullerene size (number of carbons of the cage) and constitutional isomer, but also on the position and, in some cases, the addend orientation. This issue should be considered because for a proper device operation, a well-defined LUMO is required. The position of the LUMO level of some higher fullerene derivatives can be suitable for low-bandgap polymers.     

Structure–function relationships of fullerene esters in polymer solar cells: unexpected structural effects on lifetime and efficiency

We report both transport measurements and spectroscopic data of polymer/fullerene blend photovoltaics using a small library of fullerene esters to correlate device properties with a range of functionality and structural diversity of the ester substituent. We observe that minor structural changes can lead to significant and surprising differences in device efficiency and lifetime. For example we have found that isomeric R‐groups in the fullerene ester‐based devices we have studied have dramatically different efficiencies. The characteristic lifetimes derived from both transport and spectroscopic measurements are generally comparable; however, some more rapid effects in specific fullerene esters are not observed spectroscopically. It is apparent from our results that each fullerene derivative requires re‐optimization to reveal the best device performance. Furthermore we conclude that a library approach is essential for evaluating the effects of structural differences in the constituent molecules and serves as important device optimization method that is not being currently employed in photovoltaic investigations. Copyright © 2015 John Wiley & Sons, Ltd.     

Photovoltaic effects of a:C/C60/Si (p–i–n) solar cell structures

An attempt to improve the efficiency of the heterojunction p-a:C/n-Si has been made by introducing the highly insulating C₆₀ layer between the semiconductor layers of the cell structure. The conductivity of the implanted films is found to increase during the implantation process and it is attributed to the complete disintegration of the fullerene molecules. The efficiency of this structure is found to be 0.1% under AM 1.5 conditions which is ten times higher than the cell fabricated using the boron ion implanted fullerene without the insulating layer.     

Technical assessment of synthetic natural gas （SNG） production from agricul- ture residuals

This paper presents thermodynamic evaluations of the agriculture residual-to-SNG process by thermochemical conversion, which mainly consists of the interconnected fluidized beds, hot gas cleaning, fluidized bed methanation reactor and Selexol absorption unit. The process was modeled using Aspen Plus software. The process performances, i.e., CH 4 content in SNG, higher heating value and yield of SNG, exergy efficiencies with and without heat recovery, unit power consumption, were evaluated firstly. The results indicate that when the other parameters remain unchanged, the steam-to-biomass ratio at carbon boundary point is the optimal value for the process. Improving the preheating temperatures of air and gasifying agent is beneficial for the SNG yield and exergy efficiencies. Due to the effects of CO 2 removal efficiency, there are two optimization objectives for the SNG production process: (I) to maximize CH 4 content in SNG, or (II) to maximize SNG yield. Further, the comparison among different feedstocks indicates that the decreasing order of SNG yield is: corn stalk > wheat straw > rice straw. The evaluation on the potential of agriculture-based SNG shows that the potential annual production of agriculture residual-based SNG could be between 555×10 8～611×10 8 m 3 with utilization of 100% of the available unexplored resources. The agriculture residual-based SNG could play a significant role on solving the big shortfall of China’s natural gas supply in future.     

Photoinduced FT-IR spectroscopy and CW-photocurrent measurements of conjugated polymers and fullerenes blended into a conventional polymer matrix

In this work we present an investigation of the photoexcited states in conjugated polymer (donor) – fullerene (acceptor) interpenetrating networks embedded into conventional polymer hosts like polystyrene (PS), polyvinylcarbazole (PVK) or polyvinylbenzylchloride (PVBC) (guest – host approach), using photoinduced FT-IR spectroscopy. We discuss the influence of the specific host polymer matrices on the photoexcited states of the photoactive guests and investigate the photoinduced electron transfer by analysis of the infrared activated vibrational (IRAV) bands of poly-3-octylthiophene (P3OT) in comparative studies. Solar cells based on mixtures of poly [2-methoxy, 5-(3′,7′-dimethyl-octyloxy)]-p-phenylene vinylene (MDMO-PPV), a highly soluble fullerene derivative [6 and 6]-phenyl C₆₁-butyric acid methyl ester (PCBM) and a conventional polymer (PS, PVK or PVBC) are characterized. We studied the current–voltage characteristics of devices and determined the energy conversion and electron/photon conversion efficiencies.     

Network structure organic photovoltaic devices prepared by electrochemical copolymerization

Characteristics of the organic photovoltaic devices prepared by in-situ electrochemical copolymerization of substituted fullerene with alkylthiophene were studied. The active layer was formed by direct electrochemical copolymerization between thiophene moiety substituted fullerene and 3-octylthiophene on PEDOT-coated indium tin oxide (ITO) glass, where fullerene is anchored within conducting polymer chain through covalent bonding. Since two monomers utilized in this study had an opposite oxidation potential, the step potential bias method was used to copolymerize these two monomers. Bias potential and concentration of monomers were carefully controlled so that blend ratio of composite film was exactly same as monomer feed. Power conversion efficiency of electrochemically copolymerized photovoltaic device changed within experimental error ranges for before and after heat treatment. Meanwhile, composite films prepared by spin coating of blend of poly(3-octylthiophene) and PCBM showed morphological changes after heat treatment at 8 °C for 1 h according to field emission scanning electron microscopy (FE-SEM) study. This study suggests a new approach for preventing migration of fullerene from its optimized morphology.     

Fullerene-(π-conjugated oligomer) dyads as active photovoltaic materials

The recent developments on organic photovoltaic cells using covalently linked fullerene-(π-conjugated oligomer) ensembles as the active layer are reviewed. This molecular approach appears to be particularly interesting since the bicontinuous donor–acceptor network obtained by chemically linking the hole-conducting moiety to the electron-conducting fullerene subunit prevents any problem arising from bad contacts at the junction, as observed for polymer/C₆₀ blends. Furthermore, the behavior of a unique molecule in a photovoltaic cell and the study of its electronic properties means one can easily obtain the structure/activity relationships leading to a better understanding of the photovoltaic conversion. Finally, this new synthetic approach offers great versatility for design tuning of the photovoltaic system.     

The effect of fullerene doping on photoelectric conversion using titanyl phthalocyanine and a perylene pigment

The effect of fullerene (C₆₀) doping on photoelectric conversion using titanyl phthalocyanine (TiOPc) and a perylene pigment, N, N′-dimethyl-3,4 : 9,10-perylenebis(dicarboximide) (MPCI), was investigated. A new three-layer cell, ITO/MPCI/C₆₀-doped TiOPc/TiOPc/Au, exhibited a higher quantum yield for charge-carrier photogeneration than a two-layer cell without the C₆₀-doped TiOPc layer, ITO/MPCI/TiOPc/Au, upon irradiation with monochromatic light which TiOPc mainly absorbs. The three-layer cell showed a high conversion efficiency of 0.63% for incident white light at an intensity of ca. 100 mW cm⁻².     

Microstructures and photovoltaic properties of C60 based solar cells with copper oxides,CuInS2, phthalocyanines,porphyrin, PVK,nanodiamond, germanium and exciton diffusion blocking layers

Abstract

Organic solar cells have a potential for use in lightweight, flexible, inexpensive and large scale solar cells. However, significant improvements of photovoltaic efficiencies are mandatory for use in future solar power plants. One of the improvements is donor–acceptor proximity in the devices, which are called bulk heterojunction solar cells. Bulk heterojunction is an efficient method to generate free charge carriers, and the charge transfer is possible at the semiconductor interface. The purpose of the present work is to fabricate and characterise C₆₀ based solar cells with copper oxides, CuInS₂, phthalocyanines, porphyrin, poly-vinylcarbazole, nanodiamond, germanium and exciton diffusion blocking layers. In the present work, C₆₀ and fullerenol [C₆₀(OH)_10–12] were used for n-type semiconductors, and metal copper oxides, metal phthalocyanine derivative, porphyrin and poly-vinylcarbazole were used for p-type semiconductors. In addition, nanodiamond and germanium based molecules were added into the active layers of the solar cells. The novel aspect of the research is to investigate the relation between properties and microstructures of the solar cells using transmission electron microscopy, X-ray diffraction and electronic structure calculation. The impact of the research concerns the study of organic solar cells by means of microstructural analysis, property measurements and theoretical calculations.     

Hydrogen production through biomass gasification in supercritical water: A review from exergy aspect

Hydrogen production through supercritical water gasification (SWG) of biomass has been widely studied. This study reviews the main factors from exergy aspect, and these include feedstock characteristics, biomass concentration, gasification temperature, residence time, reaction catalyst, and reactor pressure. The results show that the exergy efficiencies of hydrogen production are mainly in the range of 0.04–42.05%. Biomass feedstock may affect hydrogen production by changing the H₂ yield and the heating value of biomass. Increases in biomass concentrations decrease the exergy efficiencies, increases in gasification temperatures generally increase the exergy efficiencies, and increases in residence times may initially increase and finally decrease the exergy efficiencies. Reaction catalysts also have positive effects on the exergy efficiencies, and the reviewed results show that the effects are followed KOH > K₂CO₃ > NaOH > Na₂CO₃. Reactor pressure may have positive, negative or negligible effects on the exergy efficiencies.     

Modeling the optical absorption within conjugated polymer/fullerene-based bulk-heterojunction organic solar cells

In this paper, we report our results on the modeling of the optical properties of the bulk-heterojunction “plastic solar cells”, consisting of a solid-state blend of the conjugated polymer poly-[2-(3,7-dimethyloctyloxy)-5-methyloxy]-para-phenylene-vinylene and the fullerene C₆₀ derivative 1-(3-methoxycarbonyl) propyl-1-phenyl [6,6]C₆₁. Upon illuminating these cells with the standard AM 1.5 solar spectrum, the short circuit current can be determined for any given internal quantum efficiency as a function of the active layer thickness. In addition, the depth profiles of photoinduced charge generation rates are calculated. Based on the agreement of this modeling with experimentally determined efficiencies of these solar cells, an internal quantum efficiency of about 80% has been estimated.     

Stability and photodegradation of phthalocyanines and hematoporphyrin doped PMMA as solar concentrators

Luminescent solar concentrator samples using polymethylmethacrylate (PMMA) as the matrix with phthalocyanine, nickel-phthalocyanine and hematoporphyrin IX dichloride laser dyes were prepared by a casting method. Optical absorption measurements were carried out at room temperature across the 200–900 nm wavelength region both before and after the samples were exposed to sunlight for two weeks. The degradation of PMMA–dye samples, measured by absorption, was found to obey a first-order kinetic equation. Values of the optical band gaps (E_g) have been obtained for the direct allowed transitions before and after the samples were exposed to sunlight. The tail width of localized states in the band gap (E_u) was calculated from Urbach’s formula. Photodegradation studies revealed that the phthalocyanine dye systems are the most stable. Emission spectra and quantum efficiency were also investigated, and phthalocyanine dyes were shown to have a lower Stokes shift and a higher fluorescence quantum yield (Q_f) than the hematoporphyrin IX dichloride. Collectively, these results suggest that PMMA doped with phthalocyanines provide the better system for use in fluorescent solar collector systems.     

Co-gasification of catechol and starch in supercritical water for hydrogen production

Hydrogen production from waste feedstocks using supercritical water gasification (SCWG) is a promising approach towards cleaner fuel production and a solution for hard to treat wastes. In this study, the catalytic co-gasification of starch and catechol as models of carbohydrates and phenol compounds was investigated in a batch reactor at 28 MPa, 400–500 °C, from 10 to 30 min. The effects of reaction conditions, and the addition of calcium oxide (CaO) as a carbon dioxide (CO₂) sorbent and TiO₂ as catalyst on the gas yields and product distribution were investigated. Employing TiO₂ as a catalyst alone had no significant effect on the H₂ yield but when combined with CaO increased the hydrogen yield by 35% and promoted higher total organic carbon (TOC) reduction efficiencies. The process liquid effluent was characterized using GC–MS, with the results showing that the major non-polar components were phenol, substituted phenols, and cresols. An overall reaction scheme is provided.     

H,OH and COOH functionalized magnesium phthalocyanine as a catalyst for oxygen reduction reaction (ORR) – A DFT study

Platinum is an efficient catalyst for a fuel cell, however of its high cost and rarity on Earth, it becomes necessary to predict an effective, low cost, and abundantly available catalyst. Here, hydrogen (H), hydroxyl (OH) and carboxyl (COOH) group functionalized magnesium phthalocyanine (MgPc) are considered as catalysts to enhance oxygen reduction reaction (ORR) mechanism via direct four-electron reduction reaction. The density functional theory (DFT) based results show that the reactions occur on the top site of the magnesium (Mg) metal center than the edge site of the phthalocyanines (Pcs). From thermochemical parameters, the reactions are highly exothermic, hence feasible. The atoms in molecules (AIM) analysis reveals that the adsorbates stabilize over catalysts through ionic, covalent, hydrogen and weak interactions. The adsorption energy and reversible potential of the intermediates and product on phthalocyanines shows that MgPc(OH)₁₆ is a better catalyst for the ORR process. Conclusively, this study establishes that phthalocyanines are promising materials as a catalyst for ORR which is vital for fuel cell applications.     

A review on biomass‐based hydrogen production and potential applications

In this paper, a detailed review is presented to discuss biomass‐based hydrogen production systems and their applications. Some optimum hydrogen production and operating conditions are studied through a comprehensive sensitivity analysis on the hydrogen yield from steam biomass gasification. In addition, a hybrid system, which combines a biomass‐based hydrogen production system and a solid oxide fuel cell unit is considered for performance assessment. A comparative thermodynamic study also is undertaken to investigate various operational aspects through energy and exergy efficiencies. The results of this study show that there are various key parameters affecting the hydrogen production process and system performance. They also indicate that it is possible to increase the hydrogen yield from 70 to 107 g H₂ per kg of sawdust wood. By studying the energy and exergy efficiencies, the performance assessment shows the potential to produce hydrogen from steam biomass gasification. The study further reveals a strong potential of this system as it utilizes steam biomass gasification for hydrogen production. To evaluate the system performance, the efficiencies are calculated at particular pressures, temperatures, current densities, and fuel utilization factors. It is found that there is a strong potential in the gasification temperature range 1023–1423 K to increase energy efficiency with a hydrogen yield from 45 to 55% and the exergy efficiency with hydrogen yield from 22 to 32%, respectively, whereas the exergy efficiency of electricity production decreases from 56 to 49.4%. Hydrogen production by steam sawdust gasification appears to be an ultimate option for hydrogen production based on the parametric studies and performance assessments that were carried out through energy and exergy efficiencies. Finally, the system integration is an attractive option for better performance. Copyright © 2012 John Wiley & Sons, Ltd.