Poly‐3‐hexylthiophene doped with iron disulfide nanoparticles for hybrid solar cells

In this work, the pyrite crystalline phase of iron disulfide nanoparticles (FeS₂) about 20 to 30 nm was obtained by a two‐pot thermal method at 220°C. Subsequently, different concentrations of these nanoparticles were used as a doping agent for the conjugated poly‐3‐hexylthiophene (P3HT). The electrical resistivity of P3HT was decreased almost three orders of magnitude while adding FeS₂ nanoparticles as doping, and dichlorobenzene solvent was a determinant factor for the dispersion of polymer with nanoparticles. Doped‐P3HT dichlorobenzene solution was spin coated onto the FTO/TiO₂ substrate to fabricate the FTO/TiO₂/P3HT:FeS₂/C‐Au hybrid solar cells. Moreover, the power conversion efficiency (PCE) of hybrid devices was studied as a function of pyrite FeS₂ nanoparticle concentration. The highest efficiency of 0.83% was obtained at 1% concentration of FeS₂ nanoparticles. Hence, the results revealed that the FeS₂ nanoparticles could be considered as an alternative charge carrier to develop the bulk hybrid solar cells.     

Improved size distribution of AgBiS2 colloidal nanocrystals by optimized synthetic route enhances photovoltaic performance

Ternary silver bismuth sulfide (AgBiS₂) colloidal nanocrystals (NCs) have been recognized as a photovoltaic absorber for environmentally-friendly and low-temperature-processed thin film solar cells. However, previous synthetic methods involving hot injection of sulfur precursors into metal oleate precursor solutions do not provide a balance between nucleation and growth, leading to AgBiS₂ NCs with broad size distributions. Here, we demonstrate the modified synthetic route that size distribution of AgBiS₂ NCs can be improved by pre-adding the non-coordinating 1-octadecene (ODE) solvent into metal precursor solutions, leading to controlled concentration of coordinating oleic acid with improved hot-injection synthetic conditions. The addition of ODE as a non-coordinating solvent to metal precursor/oleic acid solution significantly suppresses variations in the concentration of coordinating oleic acid after injection of the sulfur precursor solution, leading to a homogenous reaction between the metal and sulfur precursors. For photovoltaic devices fabricated using the resultant AgBiS₂ NCs, the champion device shows power conversion efficiency (PCE) of 5.94% with an open-circuit voltage (V_OC) of 0.52 V. This performance is better than that a control device (PCE of 5.50% and V_OC of 0.49 V) because of the reduced energetic disorder and band tail broadening originating from the uniformly-sized AgBiS₂ NCs.     

Influence of oxygen and water related surface defects on the dye sensitized TiO2 solar cell

Oxygen- and water-related surface defects on porous TiO₂ (anatase) can be well controlled by the oxygen and water partial pressures and therefore such defects are of technological relevance for dye sensitized TiO₂ solar cells. We investigated the action of oxygen and water-related surface defects in situ by impedance spectroscopy, photoconductivity, photoluminescence, and optical transmission as well as by characterizing solar cells which were prepared under respective conditions. Oxygen loss from the TiO₂ surface leads to electrical doping by Ti³⁺/oxygen donor states. Such defects create recombination paths for injected electrons back into the electrolyte. Pre-treatment of porous TiO₂ by chemisorption of water increases the open circuit voltage of the solar cells without altering the short circuit current. Water-related surface defects decrease the saturation current of the diode, probably by raising the barrier height at the TiO₂/electrolyte interface.     

FeS2 thin films prepared by spray pyrolysis

In the present work FeS₂ films have been grown by spray pyrolysis followed by sulfidation. The structural, optical and electrical properties of these films have been investigated. The films were found to be n-type with an indirect band gap of 1.17 eV. These films have a high potential for use in thin film solar cells and photoelectrochemical cells.     

The influence of surface morphology of TiO2 coating on the performance of dye-sensitized solar cells

The optimization of solar energy conversion efficiency of dye-sensitized solar cells (DSSCs) was investigated by the tuning of TiO₂ photoelectrode's surface morphology. Double-layered TiO₂ photoelectrodes with four different structures were designed by the coating of TiO₂ suspension, incorporated with low and high molecular weight poly(ethylene glycol) as a binder. Among these four systems, P2P1, where P1 and P2 correspond to the molecular weight of 20,000 and 200,000, respectively, showed the highest efficiency under the conditions of identical film thickness and constant irradiation. This can be explained by the larger pore size and higher surface area of P2P1 TiO₂ electrode than the other materials as revealed by scanning electron microscopic (SEM) and Brunauer–Emmett–Teller (BET) analyses. Electrochemical Impedance Spectroscopy (EIS) analysis shows that P2P1 formulation displayed a smaller resistance than the others at the TiO₂/electrolyte interface. The best efficiency (η) of 9.04% with the short-circuit photocurrent density (J_sc) and open-circuit voltage (V_oc) of 18.9 mA/cm² and 0.74 V, respectively, was obtained for a solar cell by introducing the light-scattering particles to the TiO₂ nanoparticles matrix coated on FTO electrode having the sheet resistivity of 8 Ω/sq.     

UV light protection through TiO2 blocking layers for inverted organic solar cells

Fully organic solar cells (OSCs) based on polymers and fullerenes have attracted remarkable interest during the last decade and high power conversion efficiencies (PCEs) beyond 8% have been realized. However, air stability of these cells remains poor. The conventional geometry of OSCs utilizes strongly oxidizing metal top contacts like Al or Ca. These metals are easily oxidized in air resulting in rapid decrease of PCE if cells are not perfectly encapsulated. Using a thin electron-selective hole-blocking bottom layer like TiO₂ enables fabrication of solar cells in a so-called inverted geometry. In this geometry, noble metals like Ag or Au can be used as top contacts, which are less sensitive to ambient oxygen. Thus, air-stability of these inverted solar cells is significantly improved. In this study we investigate inverted polythiophene-methanofullerene solar cells. We find significant influence of the TiO₂ layer thickness on light absorption and illumination stability of the solar cells, as well as the trap filling by photoinduced carriers. Even though TiO₂ layers as thick as 500 nm seem not to be detrimental for charge transport, light intensity losses limit the device performance. In turn, illumination stability is better for thicker TiO₂ layers, which can serve as UV filters and protect the photoactive materials from degradation, when compared to thin TiO₂ layers. Considering these different effects we state that a thickness of 100 nm is the optimization of the TiO₂ layer.     

Contact angle measurements: an empirical diagnostic method for evaluation of thin film solar cell absorbers (CuInS2)

An empirical diagnostic method for the evaluation of solar cell grade CuInS₂ absorbers has been developed. The method involves the measurement of the contact angle between water and the CuInS₂ absorber before fabrication of a solar cell. The contact angle is expected to depend upon local inhomogeneity, chemical composition and surface morphology of the CuInS₂ absorber. The variation of these factors on the surface is supported with scanning electron micrographs, chemical analyses, laser scanning photocurrent mapping of various CuInS₂ absorbers and measurements of the solar cell performance. The contact angle has been found to be different at different places on the CuInS₂ surface. Empirically, it was found that for high conversion efficiency solar cells (>8–10.5%), the contact angle on CuInS₂ absorbers ranges between 53° and 63°. For low conversion efficiency solar cells (<6%), it is between 48° and 50°. Therefore, it is seen that contact angle measurements on CuInS₂ absorbers can be used to assess the quality of CuInS₂ absorbers prior to solar cell fabrication.     

Tri-layer antireflection coatings (SiO2/SiO2–TiO2/TiO2) for silicon solar cells using a sol–gel technique

Antireflection coatings (ARCs) have become one of the key issues for mass production of Si solar cells. They are generally performed by vacuum processes such as thermal evaporation, reactive sputtering, and plasma-enhanced chemical vapor deposition. In this work, a sol–gel method has been demonstrated to prepare the ARCs for the non-textured monocrystalline Si solar cells. The spin-coated TiO₂ single-layer, SiO₂/TiO₂ double-layer and SiO₂/SiO₂–TiO₂/TiO₂ triple-layer ARCs were deposited on the Si solar cells and they showed good uniformity in thickness. The measured average optical reflectance (400–1000 nm) was about 9.3, 6.2 and 3.2% for the single-layer, double-layer and triple-layer ARCs, respectively. Good correlation between theoretical and experimental data was obtained. Under a triple-layer ARC condition, a 39% improvement in the efficiency of the monocrystalline Si solar cell was achieved. These indicate that the sol–gel ARC process has high potential for low-cost solar cell fabrication.     

To make polymer: Quantum dot hybrid solar cells NIR-active by increasing diameter of PbSnanoparticles

We fabricate NIR-active solar cells based on PbS quantum dots and a conventional conjugated polymer. These devices act as solar cells under exclusively NIR wavelengths above 650 nm. Here PbS nanoparticles absorb photons in the NIR range that in turn generate excitons. We show that with an assistance from a strong electron-acceptor (TiO₂), these excitons can be dissociated to electrons and holes to yield a photocurrent in the external circuit. We then aim to extend the spectral window of the solar cells to higher wavelength region by increasing the diameter of PbS nanoparticles to make the cells further NIR-active. We observe that the short-circuit current (J_SC) shows a peak when the diameter of PbS nanoparticles increases. Here, the spectral window can be extended till conduction band-edge of PbS quantum dots falls below that of TiO₂ nanostructures cutting off the electron-transfer pathway. The NIR-active photovoltaic solar cells yield a short-circuit current (J_SC) of 1.0 mA/cm², open-circuit voltage (V_OC) of 0.42 V, and power conversion efficiency (η) of 0.16% and remain operative till 1200 nm.     

High-efficiency inverted polymer solar cells with solution-processed metal oxides

The selection of carrier transporting layer in polymer solar cells is an important issue because the nature and direction of carrier transport can be manipulated by inserting different functional layers in the device structure. In this work, we report a very efficient inverted polymer solar cell (PSC) system based on regioregular poly(3-hexylthiophene) and a n-type acceptor, bis-indene[C₆₀]. With a pair of metal oxides and the insertion of TiO₂ nanorods electron collecting layer between the ZnO thin film and the active layer, the device efficiency can be greatly improved. The contact area between the active layer and the electron collecting layer, as well as the thickness of active layer, can be increased with the incorporation of TiO₂ nanorods. As a result, photocurrent can be enhanced due to more absorption of light and more charge separation interface. In addition, the larger contact area and the crystalline TiO₂ nanorods provide a more efficient transporting route for the carriers to the cathode. The most efficient device demonstrated shows a high power conversion efficiency of 5.6% with the inverted structure.     

Influence of In2S3 film properties on the behavior of CuInS2/In2S3/ZnO type solar cells

Solar cells of CuInS₂/In₂S₃/ZnO type are studied as a function of the In₂S₃ buffer deposition conditions. In₂S₃ is deposited from an aqueous solution containing thioacetamide (TA), as sulfur precursor and In³⁺. In parallel, variable amounts of In₂O₃ are deposited that have an important influence on the buffer layer behavior. Starting from deposition conditions determined in a preliminary study, a set of parameters is chosen to be most determining for the buffer layer behavior, namely the solution temperature, the concentration of thioacetamide [TA], and the buffer thickness. The solar cell results are discussed in relation with these parameters. Higher efficiency is attained with buffer deposited at high temperature (70 °C) and [TA] (0.3 M). These conditions are characterized by short induction time, high deposition rate and low In₂O₃ content in the buffer. On the other hand, the film deposited at lower temperature has higher In₂O₃ content, and gives solar cell efficiency sharply decreasing with buffer thickness. This buffer type may attain higher conversion efficiencies if deposited on full covering very thin film.     

Thermal activated (“thermal”) battery technology: Part IIIa: FeS2 cathode material

This article presents an overview of the pyrite FeS₂ used as cathode material in thermally activated (“thermal”) batteries. A large emphasis was placed on the physicochemical properties and electrochemical performance of the pyrite FeS₂, including the discharge mechanisms, self-discharge phenomena, and recent developments.     

Doping CuSCN films for enhancement of conductivity: Application in dye-sensitized solid-state solar cells

Construction of dye-sensitized solid-state solar cells requires high band-gap (therefore, transparent) hole collectors which can be deposited on a dye-coated nanocrystalline semiconductor surface without denaturing the dye. Copper (I) thiocyanate (CuSCN) is an important p-type semiconductor satisfying the above requirements. However, the conductivity of this material, which depends on excess SCN, is not sufficiently high and polymerization of SCN prevents incorporation of sufficient amount of excess SCN during the process of synthesis of CuSCN. We have found that the conductivity of solid CuSCN can be increased by exposure to halogen gases which generate SCN or to a solution of (SCN)₂ in CCl₄. The latter method is suitable for doping of CuSCN films in dye-sensitized solid-state solar cells.     

Promising window layer of thin film Si solar cell with p–i–n structure prepared by using SiH2Cl2

The fabrication process for a-Si:H solar cells with p–i–n structure contains a problem of damage to the SnO₂ substrate particularly at higher process temperatures. We have reported that the suppression of darkening and wide optical gap (E_opt) are obtained by using SiH₂Cl₂ instead of SiH₄ as a source gas (Mater. Res. Soc. Symp. Proc. 609 (2000), in press). In this paper, p-type a-Si:H:(Cl) was investigated. Comparable E_opt and dark conductivity (σ_dark) to those of conventional a-SiC:H were obtained. Solar cells using this a-Si:H:(Cl) show higher current density (J_sc) and higher collection efficiency in all wavelength regions as compared to a p-layer not using chlorine processes. The newly developed p-layer has been applied to solar cells with p–i–n structure fabricated at higher substrate temperatures (T_s). Although the a-Si:H material deposited at higher substrate temperatures has been reported as being more stable against light soaking (21st IEEE PVSC Proceeding, Florida, USA, 1990, p. 1656), the high temperature processing is difficult to apply to the a-Si:H p–i–n structure because of the significant darkening of SnO₂ at higher T_s. With an a-Si:H:(Cl) buffer layer, a-Si:H solar cells can be fabricated at higher T_s (300°C) with reasonable cell performance. The best stabilized efficiency was 7.5% obtained at a T_s of 250°C.     

Analysis of heterointerface recombination by Zn1−xMgxO for window layer of Cu(In,Ga)Se2 solar cells

An adjustment of a conduction band offset (CBO) of a window/absorber heterointerface is important for high efficiency Cu(In,Ga)Se₂ (CIGS) solar cells. In this study, the heterointerface recombination was characterized by the reduction of the thickness of a CdS layer and the adjustment of a CBO value by a Zn_1−xMg_xO (ZMO) layer. In ZnO/CdS/CIGS solar cells, open-circuit voltage (V_oc) and shunt resistance (R_sh) decreased with reducing the CdS thickness. In constant, significant reductions of V_oc and R_sh were not observed in ZMO/CdS/CIGS solar cells. With decreasing the CdS thickness, the CBO of (ZnO or ZMO)/CIGS become dominant for recombination. Also, the dominant mechanisms of recombination of the CIGS solar cells are discussed by the estimation of an activation energy obtained from temperature-dependent current-voltage measurements.     

CuInS2/In2S3 thin film solar cell using spray pyrolysis technique having 9.5% efficiency

Copper indium sulfide (CuInS₂)/In₂S₃ solar cells were fabricated using spray pyrolysis method and high short circuit current density and moderate open circuit voltage were obtained by adjusting the condition of deposition and thickness of both the layers. Consequently, a relatively high efficiency of 9.5% (active area) was obtained without any anti-reflection coating. The cell structure was ITO/CuInS₂/In₂S₃/Ag. We avoided the usual cyanide etching and CdS buffer layer, both toxic, for the fabrication of the cell.     

CuInS2-Poly(3-(ethyl-4-butanoate)thiophene) nanocomposite solar cells: Preparation by an in situ formation route, performance and stability issues

In this contribution we present an in situ method for the preparation of CuInS₂-poly(3-(ethyl-4-butanoate)thiophene) (P3EBT) nanocomposite layers and their application in nanocomposite solar cells. A precursor solution containing copper and indium salts, thiourea and the conjugated polymer was prepared in pyridine, which was coated onto glass/ITO substrates followed by a heating step at 180 °C. The heating step induced the formation of the CuInS₂ nanoparticles homogeneously dispersed in the conjugated polymer matrix. The formation of the nanocomposite was investigated in situ by X-ray scattering techniques and TEM methods showing that nano-scaled CuInS₂ was formed. By addition of small amounts of zinc salt to the precursor solution, zinc containing CuInS₂ (ZCIS) was formed. ZCIS-P3EBT active layers exhibited higher V_OC than CuInS₂-P3EBT layers and showed efficiencies of about 0.4%. Additionally the stability of the solar cells was tested over a time scale of 172 h.     

Facile fabrication of mesoporous TiO2 electrodes for dye solar cells: chemical modification and repetitive coating

A chemical dispersing technique for preparing a coating paste of TiO₂ nanoparticles is disclosed to fabricate mesoporous electrodes for dye-sensitized TiO₂ solar cells. The suspension of TiO₂ (P-25) powder was stirred in aqueous nitric acid at 80°C, and then evaporated to dryness, giving the nitric acid-adsorbed P-25 powder. The coating paste was obtained by mixing the nitric acid-adsorbed P-25 with PEG (M_w 20,000) as a porosity-controlling agent and cellulosic polymer as a thickener. The mesoporous TiO₂ films were fabricated on conducting glasses by repetitive coating and calcined at 500°C (30 min). The TiO₂ film obtained by the five times repetitive coating (20 μm thickness) resulted in the 1.4 times higher energy conversion efficiency of the dye-sensitized solar cells than that of the one time coating TiO₂ film (V_oc=690 mV, J_sc=12.2 mA/cm², the fill FACTOR=0.71 and η=6.0%).     

A feasibility study of integrally colored Al–Si as a solar selective absorber

The solar selective properties of integrally colored Al–Si alloy (11.6 wt% Si) have been investigated. Optical measurements showed a continuous decrease of reflectance, i.e. an increase of absorptance, with increasing film thickness. A maximum solar absorption of 0.85 was achieved for Si–Al₂O₃ coatings thicker than 13 μm but such thick aluminum oxide coatings have very high thermal emittance.The reflectance of the Si–Al₂O₃ coated aluminum could be understood from a four flux radiative transfer theory. Using this theory the optical performance of the coating as a solar absorber was modeled for different size and volume fractions of silicon particles and coating thicknesses. A solar absorptance of just 0.90 can be achieved from a 10 μm thick coating of about 0.3 volume fraction of silicon. For thinner coatings (1 μm) the solar absorptance was only 0.70 for the same volume fraction.     

Characterization of N, N′-bis-2-(1-hydoxy-4-methylpentyl)-3, 4, 9, 10-perylene bis (dicarboximide) sensitized nanocrystalline TiO2 solar cells with polythiophene hole conductors

We have fabricated solid-state, dye-sensitized nanocrystalline TiO₂ solar cells (DSSC) based on perylene derivative dye, N,N′-bis-2-(1-hydoxy-4-methylpentyl)-3,4,9,10-perylene bis (dicarboximide) (HMPER) with two different polythiophenes as hole conductors; i.e. poly (3-octyl thiophene) (P3OT) and poly (3-hexyl thiophene) (P3HT), respectively. HMPER adsorbs strongly to the surface of nanocrystalline TiO₂ and inject electrons into TiO₂ conduction band upon absorption of light. Polythiophene derivatives are well-known materials as hole conductors in solid-state dye-sensitized solar cells. We obtained quite similar results with P3OT and P3HT yielding a short-circuit current density of around 80 μA/cm² and open-circuit voltage of around 0.7 V at 80 mW/cm² AM 1.5 light intensity. The results are compared with Ru-535 TBA-sensitized nc-TiO₂ cells prepared by using the same polythiophene derivatives.