Pulsed laser deposition of single-crystalline Cu7In3/CuIn0.8Ga0.2Se2 core/shell nanowires

Single-crystalline Cu₇In₃/CuIn_0.8Ga_0.2Se₂ (CI/CIGS) core/shell nanowires are fabricated by pulsed laser deposition with Ni nanoparticles as catalyst. The CI/CIGS core/shell nanowires are made up of single-crystalline CI cores surrounded by single-crystalline CIGS shells. The CI/CIGS nanowires are grown at a considerably low temperature (350°C ~ 450°C) by vapor-liquid-solid mode combined with vapor-solid mode. The distribution density of the nanowires increases with the increasing of the deposition duration, and the substrate temperature determines the lengths of the nanowires. The U-V absorption spectra of the CIGS thin films with and without the CI/CIGS core/shell nanowires demonstrate that the CI/CIGS nanowires can remarkably enhance the absorption of CIGS thin films in the spectrum range of 300 to 900 nm.

PACS

61.46. + w; 61.41.e; 81.15.Fg; 81.07.b     

Investigation of bulk hybrid heterojunction solar cells based on Cu(In,Ga)Se2 nanocrystals

This work presents the systematic studies of bulk hybrid heterojunction solar cells based on Cu(In, Ga)Se₂ (CIGS) nanocrystals (NCs) embedded in poly(3-hexylthiophene) matrix. The CIGS NCs of approximately 17 nm in diameter were homogeneously blended with P3HT layer to form an active layer of a photovoltaic device. The blend ratios of CIGS NCs to P3HT, solvent effects on thin film morphologies, interface between P3HT/CIGS NCs and post-production annealing of devices were investigated, and the best performance of photovoltaic devices was measured under AM 1.5 simulated solar illumination (100 mW/cm²).     

3-D solar cells by electrochemical-deposited Se layer as extremely-thin absorber and hole conducting layer on nanocrystalline TiO2 electrode

Ag₂S quantum dots were deposited on the surface of TiO₂ nanorod arrays by a two-step photodeposition. The prepared TiO₂ nanorod arrays as well as the Ag₂S deposited electrodes were characterized by X-ray diffraction, scanning electron microscope, and transmission electron microscope, suggesting a large coverage of Ag₂S quantum dots on the ordered TiO₂ nanorod arrays. UV–vis absorption spectra of Ag₂S deposited electrodes show a broad absorption range of the visible light. The quantum dot-sensitized solar cells (QDSSCs) based on these electrodes were fabricated, and the photoelectrochemical properties were examined. A high photocurrent density of 10.25 mA/cm² with a conversion efficiency of 0.98% at AM 1.5 solar light of 100 mW/cm² was obtained with an optimal photodeposition time. The performance of the QDSSC at different incident light intensities was also investigated. The results display a better performance at a lower incident light level with a conversion efficiency of 1.25% at 47 mW/cm².     

In situ growth of CuInS2 nanocrystals on nanoporous TiO2 film for constructing inorganic/organic heterojunction solar cells

Inorganic/organic heterojunction solar cells (HSCs) have attracted increasing attention as a cost-effective alternative to conventional solar cells. This work presents an HSC by in situ growth of CuInS₂(CIS) layer as the photoabsorption material on nanoporous TiO₂ film with the use of poly(3-hexylthiophene) (P3HT) as hole-transport material. The in situ growth of CIS nanocrystals has been realized by solvothermally treating nanoporous TiO₂ film in ethanol solution containing InCl₃ · 4H₂O, CuSO₄ · 5H₂O, and thioacetamide with a constant concentration ratio of 1:1:2. InCl₃ concentration plays a significant role in controlling the surface morphology of CIS layer. When InCl₃ concentration is 0.1 M, there is a layer of CIS flower-shaped superstructures on TiO₂ film, and CIS superstructures are in fact composed of ultrathin nanoplates as ‘petals’ with plenty of nanopores. In addition, the nanopores of TiO₂ film are filled by CIS nanocrystals, as confirmed using scanning electron microscopy image and by energy dispersive spectroscopy line scan analysis. Subsequently, HSC with a structure of FTO/TiO₂/CIS/P3HT/PEDOT:PSS/Au has been fabricated, and it yields a power conversion efficiency of 1.4%. Further improvement of the efficiency can be expected by the optimization of the morphology and thickness of CIS layer and the device structure.     

Field modulation in Na-incorporated Cu(In,Ga)Se2 (CIGS) polycrystalline films influenced by alloy-hardening and pair-annihilation probabilities

The influence of Na on Cu(In,Ga)Se2 (CIGS) solar cells was investigated. A gradient profile of the Na in the CIGS absorber layer can induce an electric field modulation and significantly strengthen the back surface field effect. This field modulation originates from a grain growth model introduced by a combination of alloy-hardening and pair-annihilation probabilities, wherein the Cu supply and Na diffusion together screen the driving force of the grain boundary motion (GBM) by alloy hardening, which indicates a specific GBM pinning by Cu and Na. The pair annihilation between the ubiquitously evolving GBMs has a coincident probability with the alloy-hardening event.PACS: 88. 40. H-, 81. 10. Aj, 81. 40. Cd.     

Improving the efficiency of ITO/nc-TiO2/CdS/P3HT:PCBM/PEDOT:PSS/Ag inverted solar cells by sensitizing TiO2 nanocrystalline film with chemical bath-deposited CdS quantum dots

An improvement in the power conversion efficiency (PCE) of the inverted organic solar cell (ITO/nc-TiO₂/P3HT:PCBM/PEDOT:PSS/Ag) is realized by depositing CdS quantum dots (QDs) on a nanocrystalline TiO₂ (nc-TiO₂) film as a light absorption material and an electron-selective material. The CdS QDs were deposited via a chemical bath deposition (CBD) method. Our results show that the best PCE of 3.37% for the ITO/nc-TiO₂/CdS/P3HT:PCBM/PEDOT:PSS/Ag cell is about 1.13 times that (2.98%) of the cell without CdS QDs (i.e., ITO/nc-TiO₂/P3HT:PCBM/PEDOT:PSS/Ag). The improved PCE can be mainly attributed to the increased light absorption and the reduced recombination of charge carriers from the TiO₂ to the P3HT:PCBM film due to the introduced CdS QDs.     

Effects of surface modification on the cycling stability of LiNi0.8Co0.2O2 electrodes by CeO2 coating

A high-performance LiNi_0.8Co_0.2O₂ cathode was successfully fabricated by a sol-gel coating of CeO₂ to the surface of the LiNi_0.8Co_0.2O₂ powder and subsequent heat treatment at 700 °C for 5 h. The surface-modified and pristine LiNi_0.8Co_0.2O₂ powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), slow rate cyclic voltammogram (CV), and differential scanning calorimetry (DSC). Unlike pristine LiNi_0.8Co_0.2O₂, the CeO₂-coated LiNi_0.8Co_0.2O₂ cathode exhibits no decrease in its original specific capacity of 182 mAh/g (versus lithium metal) and excellent capacity retention (95% of its initial capacity) between 4.5 and 2.8 V after 55 cycles. The results indicate that the surface treatment should be an effective way to improve the comprehensive properties of the cathode materials for lithium ion batteries.     

Effect of TiO2 rutile nanorods on the photoelectrodes of dye-sensitized solar cells

In order to enhance the electron transport on the photoelectrodes of dye-sensitized solar cells, one-dimensional rutile nanorods were prepared using electrospun TiO₂ nanofibers. The grain size of the nanorods increased with increasing temperature. Electrochemical impedance spectroscopy measurements revealed reduced interface resistance of the cells with the one-dimensional rutile nanorods due to the improved electron transport and the enhanced electrolyte penetration. Intensity-modulated photocurrent/photovoltage spectroscopy showed that the one-dimensional rutile nanorods provided the electrons with a moving pathway and suppressed the recombination of photogenerated electrons. However, an excessive quantity of rutile nanorods created an obstacle to the electrons moving in the TiO₂ thin film. The photoelectrode with 7 wt.% rutile nanorods optimized the performance of the dye-sensitized solar cells.     

Effect of TiO2 nanotubes with TiCl4 treatment on the photoelectrode of dye-sensitized solar cells

In this study, we used the electrochemical anodization to prepare TiO₂ nanotube arrays and applied them on the photoelectrode of dye-sensitized solar cells. In the field emission scanning electron microscopy analysis, the lengths of TiO₂ nanotube arrays prepared by electrochemical anodization can be obtained with approximately 10 to 30 μm. After titanium tetrachloride (TiCl₄) treatment, the walls of TiO₂ nanotubes were coated with TiO₂ nanoparticles. XRD patterns showed that the oxygen-annealed TiO₂ nanotubes have a better anatase phase. The conversion efficiency with different lengths of TiO₂ nanotube photoelectrodes is 3.21%, 4.35%, and 4.34% with 10, 20, and 30 μm, respectively. After TiCl₄ treatment, the efficiency of TiO₂ nanotube photoelectrode for dye-sensitized solar cell can be improved up to 6.58%. In the analysis of electrochemical impedance spectroscopy, the value of R_k (charge transfer resistance related to recombination of electrons) decreases from 26.1 to 17.4 Ω when TiO₂ nanotubes were treated with TiCl₄. These results indicate that TiO₂ nanotubes treated with TiCl₄ can increase the surface area of TiO₂ nanotubes, resulting in the increase of dye adsorption and have great help for the increase of the conversion efficiency of DSSCs.     

Enhancing the performance of dye-sensitized solar cells based on an organic dye by incorporating TiO2 nanotube in a TiO2 nanoparticle film

The photoelectrochemical properties of a high molar extinction coefficient charge transfer organic dye containing thienylfluorene segment called FL, and the effect of incorporating TiO₂ nanotube (TiNT) in TiO₂ nanoparticle film along with the above dye on the photovoltaic performance of dye-sensitized solar cells (DSSCs) were investigated. The influence of soaking time of the TiO₂ electrode in dye solution and the effect of varying its concentration, on the solar cell efficiency was also studied. Cyclic voltammetric (CV) analysis revealed the linear relationship between the anodic peak current and the scan rate, indicating a surface-confined diffusion process.The surface morphology of TiNT was characterized using SEM, TEM and XRD. The open-circuit voltage (V_OC) of the DSSC increased with the increase in the wt% of TiNT and shows optimal value at about 5 wt%, which is correlated with the suppression of the electron recombination as found out from the electron lifetime studies.The electrochemical impedance spectroscopy (EIS) technique was employed to quantify the charge transport resistance (R_ct) and electron lifetime under different ratios of the TiNT/nanoparticle. The electron lifetimes of the DSSCs based on FL and N3 dye were very close to one another and the DSSC based on the FL showed respectable photovoltaic performance of ca. 7.8% under the light intensity of 100 mW cm⁻² (AM 1.5G).     

Effect of Al2O3 nanoparticles on the electrochemical characteristics of P(VDF-HFP)-based polymer electrolyte

Alumina (Al₂O₃) nanoparticles have been used as fillers in the preparation of poly(vinylidenefluoride-co-hexafluorpropylene) (P(VDF-HFP))-based porous polymer electrolyte. The degree of crystallization of polymer film filled with Al₂O₃ nanoparticles decreases with increase of the mass fraction of Al₂O₃ nanoparticles and the amorphous phases of polymer film expand accordingly. The Al₂O₃ nanoparticles play the role of solid plasticizer for polymer matrix. Nevertheless that excessive Al₂O₃ nanoparticles existing in polymer matrix leads to micro-phase separation between polymer matrix and fillers. As a result, both ionic conductivity and lithium ions transference number reduces whereas the activation energy for ions transport increases. When the polymer film is filled with 10% of the mass fraction of Al₂O₃ nanoparticles, polymer electrolyte possesses the ionic conductivity up to 1.95 × 10⁻³ S cm⁻¹ and the lithium ions transference number to 0.73 while the activation energy for ions transport of them falls to 5.6 kJ mol⁻¹. Effect of Al₂O₃ on the electrochemical properties of polymer electrolyte has been investigated in this paper. Analysis of FTIR spectra shows that there is the interaction between Al₂O₃ nanoparticles and polymer chains.     

Effect of ZnO:Cs2CO3 on the performance of organic photovoltaics

We demonstrate a new solution-processed electron transport layer (ETL), zinc oxide doped with cesium carbonate (ZnO:Cs₂CO₃), for achieving organic photovoltaics (OPVs) with good operational stability at ambient air. An OPV employing the ZnO:Cs₂CO₃ ETL exhibits a fill factor of 62%, an open circuit voltage of 0.90 V, and a short circuit current density of −6.14 mA/cm² along with 3.43% power conversion efficiency. The device demonstrated air stability for a period over 4 weeks. In addition, we also studied the device structure dependence on the performance of organic photovoltaics. Thus, we conclude that ZnO:Cs₂CO₃ ETL could be employed in a suitable architecture to achieve high-performance OPV.     

Effect of compressed TiO2 nanoparticle thin film thickness on the performance of dye-sensitized solar cells

In this study, dye-sensitized solar cells (DSSCs) were fabricated using nanocrystalline titanium dioxide (TiO₂) nanoparticles as photoanode. Photoanode thin films were prepared by doctor blading method with 420 kg/cm² of mechanical compression process and heat treatment in the air at 500°C for 30 min. The optimal thickness of the TiO₂ NP photoanode is 26.6 μm with an efficiency of 9.01% under AM 1.5G illumination at 100 mW/cm². The efficiency is around two times higher than that of conventional DSSCs with an uncompressed photoanode. The open-circuit voltage of DSSCs decreases as the thickness increases. One DSSC (sample D) has the highest conversion efficiency while it has the maximum short-circuit current density. The results indicate that the short-circuit current density is a compromise between two conflict factors: enlargement of the surface area by increasing photoanode thickness and extension of the electron diffusion length to the electrode as the thickness increases.     

Conversion enhancement of flexible dye-sensitized solar cells based on TiO2 nanotube arrays with TiO2 nanoparticles by electrophoretic deposition

We prepared highly ordered titanium dioxide nanotube arrays (TNAs) by anodizing Ti foils in F⁻ containing electrolyte. The thickness and dye loading amount of TNAs were 26 μm and 1.06 × 10⁻⁷ mol cm⁻², respectively. TiO₂ nanoparticles (TNPs) were electrophoretically deposited on the inner wall of nanotube to produce coated nanotube arrays (TNAP). The dye loading was increased to 1.56 × 10⁻⁷ mol cm⁻², and the electron transport rate improved. TNAs and TNAP were sensitized with ruthenium dye N3 to yield dye-sensitized TiO₂ nanotube solar cells. The power conversion efficiency of TNA-based dye-sensitized solar cells (DSSCs) was 4.28%, whereas the efficiency of TNAP-based DSSCs increased to 6.28% when illuminated from the counter electrode. The increase of power conversion efficiency of TNAP-based DSSCs is ascribed to the increased surface area of TNAs and the faster electron transport rate.     

Electrochemical study of one-step electrodeposition of copper–indium–gallium alloys in acidic conditions as precursor layers for Cu(In,Ga)Se2 thin film solar cells

This paper investigates one step electrodeposition of copper indium gallium metallic precursor layers for preparing CuIn_1−xGa_xSe₂ (CIGS) absorber layers in thin film solar cells (0 ≤ x ≤ 1). Electrodeposition was carried out in acidic aqueous solutions at about pH 2. At first partial single or binary electrodeposition systems Cu, In, Ga, Cu–Ga, Cu–In were investigated by cyclic voltammetry. Then ternary Cu–In–Ga electrodeposition system was studied. The nature of the supporting electrolyte (sodium sulfate vs. sodium chloride) and the influence of sodium citrate were more specifically investigated. The applied potential, the pH and the nature of the electrolyte were optimized to obtain x values around 0.3 needed for high efficiency devices. Depositions were carried out under potentiostatic conditions in a paddle cell configuration. The electrodeposited Cu–In–Ga alloys were annealed under Se atmosphere at temperatures between 400 and 600 °C to produce CIGS absorbers. Films were characterized by XRF, SEM and XRD analysis. Device efficiencies up to 9.3% are achieved for optimal gallium content.     

Improving the efficiency of dye-sensitized Zn2SnO4 solar cells: The role of Al ions

The dye-sensitized Zn₂SnO₄ solar cells were treated with Al³⁺ ions to enhance the power conversion efficiency for the first time. Usually, the surface treatment on photoanodes with Al³⁺ ions generated an overlayer of Al₂O₃. For Zn₂SnO₄ photoanode, another reaction pathway was found. The treatment with Al³⁺ ions led to decreasing open circuit voltage, and a 22.6% enhancement of efficiency. Mott–Schottky measurements revealed that the flat band of Zn₂SnO₄ had a positive shift owing to the introduction of Al³⁺ ions. XPS confirmed that Al³⁺ ions were introduced into the lattice of Zn₂SnO₄ and occupied the position of Sn⁴⁺, resulting in decreased conduction band edge. TEM demonstrated the size of Zn₂SnO₄ nanoparticles became larger due to the reaction of Al³⁺ with Zn₂SnO₄. Although the adsorption amounts of dyes lowered by 21%, the driving force for electron injection was greatly enhanced as a result of decreased conduction band edge, resulting in significantly enhanced cell efficiency.     

Improvement of the physical properties of ZnO/CdTe core-shell nanowire arrays by CdCl2 heat treatment for solar cells

CdTe is an important compound semiconductor for solar cells, and its use in nanowire-based heterostructures may become a critical requirement, owing to the potential scarcity of tellurium. The effects of the CdCl₂ heat treatment are investigated on the physical properties of vertically aligned ZnO/CdTe core-shell nanowire arrays grown by combining chemical bath deposition with close space sublimation. It is found that recrystallization phenomena are induced by the CdCl₂ heat treatment in the CdTe shell composed of nanograins: its crystallinity is improved while grain growth and texture randomization occur. The presence of a tellurium crystalline phase that may decorate grain boundaries is also revealed. The CdCl₂ heat treatment further favors the chlorine doping of the CdTe shell with the formation of chlorine A-centers and can result in the passivation of grain boundaries. The absorption properties of ZnO/CdTe core-shell nanowire arrays are highly efficient, and more than 80% of the incident light can be absorbed in the spectral range of the solar irradiance. The resulting photovoltaic properties of solar cells made from ZnO/CdTe core-shell nanowire arrays covered with CuSCN/Au back-side contact are also improved after the CdCl₂ heat treatment. However, recombination and trap phenomena are expected to operate, and the collection of the holes that are mainly photo-generated in the CdTe shell from the CuSCN/Au back-side contact is presumably identified as the main critical point in these solar cells.     

Realizing the enhancement of interfacial interaction in semicrystalline polymer/filler composites via interfacial crystallization

Polymer/filler composites have been widely used in various areas. One of the keys to achieve the high performance of these composites is good interfacial interaction between polymer matrix and filler. As a relatively new approach, the possibility to enhance polymer/filler interfacial interaction via crystallization of polymer on the surface of fillers, i.e., interfacial crystallization, is summarized and discussed in this paper. Interfacial crystallization has attracted tremendous interest in the past several decades, and some unique hybrid crystalline structures have been observed, including hybrid shish-kebab and hybrid shish-calabash structures in which the filler served as the shish and crystalline polymer as the kebab/calabash. Thus, the manipulation of the interfacial crystallization architecture offers a potential highly effective route to achieve strong polymer/filler interaction. This review is based on the latest development of interfacial crystallization in polymer/filler composites and will be organized as follows. The structural/morphological features of various interfacial crystallization fashions are described first. Subsequently, various influences on the final structure/morphology of hybrid crystallization and the nucleation and/or growth mechanisms of crystallization behaviors at polymer/filler interface are reviewed. Then recent studies on interfacial crystallization induced interfacial enhancement ascertained by different research methodologies are addressed, including a comparative analysis to highlight the positive role of interfacial crystallization on the resultant mechanical reinforcement. Finally, a conclusion, including future perspectives, is presented.