Compositional and Interfacial Modification of Cu2 ZnSn(S,Se)4 Thin-Film Solar Cells Prepared by Electrochemical Deposition.

A highly efficient Cu2 ZnSn(S,Se)4 (CZTSSe)-based thin-film solar cell (9.9%) was prepared using an electrochemical deposition method followed by thermal annealing. The Cu-Zn-Sn alloy films was grown on a Mo-coated glass substrate using a one-pot electrochemical deposition process, and the metallic precursor films was annealed under a mixed atmosphere of S and Se to form CZTSSe thin films with bandgap energies ranging from 1.0 to 1.2 eV. The compositional modification of the S/(S+Se) ratio shows a trade-off effect between the photocurrent and photovoltage, resulting in an optimum bandgap of roughly 1.14 eV. In addition, the increased S content near the p-n junction reduces the dark current and interface recombination, resulting in a further enhancement of the open-circuit voltage. As a result of the compositional and interfacial modification, the best CZTSSe-based thin-film solar cell exhibits a conversion efficiency of 9.9%, which is among the highest efficiencies reported so far for electrochemically deposited CZTSSe-based thin-film solar cells.

Completely transparent conducting oxide-free and flexible dye-sensitized solar cells fabricated on plastic substrates.

To achieve commercialization and widespread application of next-generation photovoltaics, it is important to develop flexible and cost-effective devices. Given this, the elimination of expensive transparent conducting oxides (TCO) and replacement of conventional glass substrates with flexible plastic substrates presents a viable strategy to realize extremely low-cost photovoltaics with a potentially wide applicability. To this end, we report a completely TCO-free and flexible dye-sensitized solar cell (DSSC) fabricated on a plastic substrate using a unique transfer method and back-contact architecture. By adopting unique transfer techniques, the working and counter electrodes were fabricated by transferring high-temperature-annealed TiO2 and Pt/carbon films, respectively, onto flexible plastic substrates without any exfoliation. The fabricated working electrode with the conventional counter electrode exhibited a record efficiency for flexible DSSCs of 8.10%, despite its TCO-free structure. In addition, the completely TCO-free and flexible DSSC exhibited a remarkable efficiency of 7.27%. Furthermore, by using an organic hole-transporting material (spiro-MeOTAD) with the same transfer method, solid-state flexible TCO-free DSSCs were also successfully fabricated, yielding a promising efficiency of 3.36%.

Monolithic DSSC/CIGS tandem solar cell fabricated by a solution process.

Tandem architecture between organic (dye-sensitized solar cell, DSSC) and inorganic (CuInGaSe2 thin film solar cell, CIGS) single-junction solar cells was constructed particularly based on a solution process. Arc-plasma deposition was employed for the Pt interfacial layer to minimize the damage to the layers of the CIGS bottom cell. Solar cell efficiency of 13% was achieved, which is significant progress from individual single-junction solar cells (e.g., 7.25 and 6.2% for DSSC and CIGS, respectively).

Tailoring of energy levels in D-π-A organic dyes via fluorination of acceptor units for efficient dye-sensitized solar cells.

A molecular design is presented for tailoring the energy levels in D-π-A organic dyes through fluorination of their acceptor units, which is aimed at achieving efficient dye-sensitized solar cells (DSSCs). This is achieved by exploiting the chemical structure of common D-π-A organic dyes and incorporating one or two fluorine atoms at the ortho-positions of the cyanoacetic acid as additional acceptor units. As the number of incorporated fluorine atoms increases, the LUMO energy level of the organic dye is gradually lowered due to the electron-withdrawing effect of fluorine, which ultimately results in a gradual reduction of the HOMO-LUMO energy gap and an improvement in the spectral response. Systematic investigation of the effects of incorporating fluorine on the photovoltaic properties of DSSCs reveals an upshift in the conduction-band potential of the TiO2 electrode during impedance analysis; however, the incorporation of fluorine also results in an increased electron recombination rate, leading to a decrease in the open-circuit voltage (Voc). Despite this limitation, the conversion efficiency is gradually enhanced as the number of incorporated fluorine atoms is increased, which is attributed to the highly improved spectral response and photocurrent.

Triple-junction hybrid tandem solar cells with amorphous silicon and polymer-fullerene blends.

Organic-inorganic hybrid tandem solar cells attract a considerable amount of attention due to their potential for realizing high efficiency photovoltaic devices at a low cost. Here, highly efficient triple-junction (TJ) hybrid tandem solar cells consisting of a double-junction (DJ) amorphous silicon (a-Si) cell and an organic photovoltaic (OPV) rear cell were developed. In order to design the TJ device in a logical manner, a simulation was carried out based on optical absorption and internal quantum efficiency. In the TJ architecture, the high-energy photons were utilized in a more efficient way than in the previously reported a-Si/OPV DJ devices, leading to a significant improvement in the overall efficiency by means of a voltage gain. The interface engineering such as tin-doped In2O3 deposition as an interlayer and its UV-ozone treatment resulted in the further improvement in the performance of the TJ solar cells. As a result, a power conversion efficiency of 7.81% was achieved with an open-circuit voltage of 2.35 V. The wavelength-resolved absorption profile provides deeper insight into the detailed optical response of the TJ hybrid solar cells.

Enhanced photovoltaic properties and long-term stability in plasmonic dye-sensitized solar cells via noncorrosive redox mediator.

We demonstrate the localized surface plasmon resonance (LSPR) effect, which can enhance the photovoltaic properties of dye-sensitized solar cells (DSSCs), and the long-term stability of size-controlled plasmonic structures using a noncorrosive redox mediator. Gold nanoparticles (Au NPs) were synthesized with a phase transfer method based on ligand exchange. This synthetic method is advantageous because the uniformly sized Au NPs, can be mass produced and easily applied to DSSC photoanodes. The plasmonic DSSCs showed an 11% improvement of power conversion efficiency due to the incorporation of 0.07 wt % Au NPs, compared to the reference DSSCs without Au NPs. The improved efficiency was primarily due to the enhanced photocurrent generation by LSPR effect. With the cobalt redox mediator, the long-term stability of the plasmonic structures also significantly increased. The plasmonic DSSCs with cobalt(II/III) tris(2,2'-bipyridine) ([Co(bpy)3](2+/3+)) redox mediator maintained the LSPR effect with stable photovoltaic performance for 1000 h. This is, to our knowledge, the first demonstration of the long-term stability of plasmonic nanostructures in plasmonic DSSCs based on liquid electrolytes. As a result, the enhanced long-term stability of plasmonic NPs via a noncorrosive redox mediator will increase the feasibility of plasmonic DSSCs.

Nanoscopic management of molecular packing and orientation of small molecules by a combination of linear and branched alkyl side chains.

We synthesized a series of acceptor-donor-acceptor-type small molecules (SIDPP-EE, SIDPP-EO, SIDPP-OE, and SIDPP-OO) consisting of a dithienosilole (SI) electron-donating moiety and two diketopyrrolopyrrole (DPP) electron-withdrawing moieties each bearing linear n-octyl (O) and/or branched 2-ethylhexyl (E) alkyl side chains. X-ray diffraction patterns revealed that SIDPP-EE and SIDPP-EO films were highly crystalline with pronounced edge-on orientation, whereas SIDPP-OE and SIDPP-OO films were less crystalline with a radial distribution of molecular orientations. Near-edge X-ray absorption fine structure spectroscopy disclosed an edge-on orientation with a molecular backbone tilt angle of ∼22° for both SIDPP-EE and SIDPP-EO. Our analysis of the molecular packing and orientation indicated that the shorter 2-ethylhexyl groups on the SI core promote tight π-π stacking of the molecular backbone, whereas n-octyl groups on the SI core hinder close π-π stacking to some degree. Conversely, the longer linear n-octyl groups on the DPP arms facilitate close intermolecular packing via octyl-octyl interdigitation. Quantum mechanics/molecular mechanics molecular dynamics simulations determined the optimal three-dimensional positions of the flexible alkyl side chains of the SI and DPP units, which elucidates the structural cause of the molecular packing and orientation explicitly. The alkyl-chain-dependent molecular stacking significantly affected the electrical properties of the molecular films. The edge-on oriented molecules showed high hole mobilities in organic field-effect transistors, while the radially oriented molecules exhibited high photovoltaic properties in organic photovoltaic cells. These results demonstrate that appropriate positioning of alkyl side chains can modulate crystallinity and molecular orientation in SIDPP films, which ultimately have a profound impact on carrier transport and photovoltaic performance.

A facile and rapid process to fabricate platinum counter electrode in dye-sensitized solar cell using nanosecond pulsed laser sintering at room temperature.

To fabricate the platinum (Pt) counter electrode in dye-sensitized solar cells (DSSCs), rapid and low sintering process was carried out using nanosecond pulsed laser sintering (LS) method based on third harmonic (355 nm) of an Nd:YAG laser at room temperature. The surface morphology of LS-Pt on fluorine-doped tin oxide (FTO) electrode showed thin and compact structure, consisting of particles size of - 10-30 nm and thickness of below 30 nm. The DSSCs with the LS-Pt/FTO counter electrodes displayed the power conversion efficiency of 4.4% with short-circuit current = 9.07 mA/cm2, open-circuit voltage = 0.79 V and fill factor = 61.3.

Highly efficient copper-zinc-tin-selenide (CZTSe) solar cells by electrodeposition.

Highly efficient copper-zinc-tin-selenide (Cu2ZnSnSe4 ; CZTSe) thin-film solar cells are prepared via the electrodepostion technique. A metallic alloy precursor (CZT) film with a Cu-poor, Zn-rich composition is directly deposited from a single aqueous bath under a constant current, and the precursor film is converted to CZTSe by annealing under a Se atmosphere at temperatures ranging from 400 °C to 600 °C. The crystallization of CZTSe starts at 400 °C and is completed at 500 °C, while crystal growth continues at higher temperatures. Owing to compromises between enhanced crystallinity and poor physical properties, CZTSe thin films annealed at 550 °C exhibit the best and most-stable device performances, reaching up to 8.0 % active efficiency; among the highest efficiencies for CZTSe thin-film solar cells prepared by electrodeposition. Further analysis of the electronic properties and a comparison with another state-of-the-art device prepared from a hydrazine-based solution, suggests that the conversion efficiency can be further improved by optimizing parameters such as film thickness, antireflection coating, MoSe2 formation, and p-n junction properties.

Carrier lifetime extension via the incorporation of robust hole/electron blocking layers in bulk heterojunction polymer solar cells.

We report the achievement of a power conversion efficiency (PCE) improvement in P3HT:PCBM-based bulk-heterojunction type polymer solar cells using photocrosslinked P3HT (c-P3HT) as the electron blocking/hole extraction layer and titanium oxide nanoparticles (TiO2) as the hole blocking/electron extraction layer. Devices prepared with a 20 nm thick c-P3HT layer showed an improved PCE of 3.4% compared to devices prepared without the c-P3HT layer (PCE = 3.0%). This improvement was attributed to an extension in the carrier lifetime and an enhancement in the carrier mobility. The incorporation of the c-P3HT layer lengthened (by more than a factor of 2) the carrier lifetime and increased (by a factor of 5) the hole mobility. These results suggest that the c-P3HT layer not only prevented non-geminate recombination but it also improved carrier transport. The PCE was further improved to 4.0% through the insertion of a TiO2 layer that acted as an effective hole-blocking layer at the interface between the photoactive layer and the cathode. This work demonstrates that the incorporation of solution-processable hole and electron blocking/extraction layers offers an effective means for preventing nongeminate recombination at the interfaces between a photoactive layer and an electrode in bulk-heterojunction-type polymer solar cells.

Colloidal solution-processed CuInSe2 solar cells with significantly improved efficiency up to 9% by morphological improvement.

We demonstrate here that an improvement in the green density leads to a great enhancement in the photovoltaic performance of CuInSe2 (CISe) solar cells fabricated with Cu-In nanoparticle precursor films via colloidal solution deposition. Cold-isostatic pressing (CIP) increases the precursor film density by ca. 20%, which results in an appreciable improvement in the microstructural features of the sintered CISe film in terms of a lower porosity, a more uniform surface morphology, and a thinner MoSe2 layer. The low-band-gap (1.0 eV) CISe solar cells with the CIP-treated films exhibit greatly enhanced open-circuit voltage (V(OC), typically from 0.265 to 0.413 V) and fill factor (FF, typically from 0.34 to 0.55), compared to the control devices. As a consequence, an almost 3-fold increase in the average efficiency, from 3.0 to 8.2% (with the highest value of 9.02%), is realized. Diode analysis reveals that the enhanced V(OC) and FF are essentially attributed to the reduced reverse saturation current density and diode ideality factor. This is associated with suppressed recombination, likely due to the reduction in recombination sites at grain/air surfaces, intergranular interfaces, and defective CISe/CdS junctions. From the temperature dependences of V(OC), it is revealed that CIP-treated devices suffer less from interface recombination.

Rapid dye adsorption via surface modification of TiO2 photoanodes for dye-sensitized solar cells.

A facile method for increasing the reaction rate of dye adsorption, which is the most time-consuming step in the production of dye-sensitized solar cells (DSSCs), was developed. Treatment of a TiO2 photoanode with aqueous nitric acid solution (pH 1) remarkably reduced the reaction time required to anchor a carboxylate anion of the dye onto the TiO2 nanoparticle surface. After optimization of the reaction conditions, the dye adsorption process became 18 times faster than that of the conventional adsorption method. We studied the influence of the nitric acid treatment on the properties of TiO2 nanostructures, binding modes of the dye, and adsorption kinetics, and found that the reaction rate improved via the synergistic effects of the following: (1) electrostatic attraction between the positively charged TiO2 surface and ruthenium anion increases the collision frequency between the adsorbent and the anchoring group of the dye; (2) the weak anchoring affinity of NO3(-) in nitric acid with metal oxides enables the rapid coordination of an anionic dye with the metal oxide; and (3) sufficient acidity of the nitric acid solution effectively increases the positive charge density on the TiO2 surface without degrading or transforming the TiO2 nanostructure. These results demonstrate the developed method is effective for reducing the overall fabrication time without sacrificing the performance and long-term stability of DSSCs.

Water-based thixotropic polymer gel electrolyte for dye-sensitized solar cells.

For the practical application of dye-sensitized solar cells (DSSCs), it is important to replace the conventional organic solvents based electrolyte with environmentally friendly and stable ones, due to the toxicity and leakage problems. Here we report a noble water-based thixotropic polymer gel electrolyte containing xanthan gum, which satisfies both the environmentally friendliness and stability against leakage and water intrusion. For application in DSSCs, it was possible to infiltrate the prepared electrolyte into the mesoporous TiO2 electrode at the fluidic state, resulting in sufficient penetration. As a result, this electrolyte exhibited similar conversion efficiency (4.78% at 100 mW cm(-2)) and an enhanced long-term stability compared to a water-based liquid electrolyte. The effects of water on the photovoltaic properties were examined elaborately from the cyclic voltammetry curves and impedance spectra. Despite the positive shift in the conduction band potential of the TiO2 electrode, the open-circuit voltage was enhanced by addition of water in the electrolyte due to the greater positive shift in the I(-)/I3(-) redox potential. However, due to the dye desorption and decreased diffusion coefficient caused by the water content, the short-circuit photocurrent density was reduced. These results will provide great insight into the development of efficient and stable water-based electrolytes.

Photovoltaic properties of high efficiency plastic dye-sensitized solar cells employing interparticle binding agent "nanoglue".

An interparticle binding agent, or nanoglue, was synthesized by a sol-gel process, which facilitated the preparation of well-interconnected TiO2 electrodes at low-temperatures for plastic dye-sensitized solar cells. The viscosity of the nanoglue-based pastes was seven times higher than that obtained in pastes without any nanoglue. The increased viscosity was sufficiently high enough for coating thick films to fabricate TiO2 electrodes. The structural and photovoltaic properties of the films were extensively investigated by varying the amounts of nanoglue. A reduced pore size and greatly enhanced surface area were observed in the nanoglue-based films. Improved interparticle connectivity, resulting in faster electron transport, was confirmed by photocurrent transient spectroscopy and electrochemical impedance measurements of the nanoglue-based films. The electron diffusion length and charge collection efficiency were also enhanced in these nanoglue-based films. A maximum conversion efficiency of 5.43% was achieved in films containing 20 wt% nanoglue fabricated on a plastic substrate under one-sun illumination, even without any additional treatment.

Electrodynamically sprayed thin films of aqueous dispersible graphene nanosheets: highly efficient cathodes for dye-sensitized solar cells.

Highly efficient cathodes for dye-sensitized solar cells (DSSCs) were developed using thin films of graphene nanosheets (GNS), which were fabricated by the electrospray method (e-spray) using aqueous dispersions of chemically driven GNS. The e-sprayed GNS films had the appropriate properties to be an efficient counter electrode (CE) for DSSCs; sufficient electrocatalytic activity for I(-)/I3(-) redox couples and low charge transfer resistance (RCT) at the CE/electrolyte interface as characterized by cyclic voltammetry and electrochemical impedance analysis. The performance of the GNS film based CEs was optimized by manipulating the density of surface chemical functional groups and plane conjugation of GNS via post thermal annealing (TA). Upon TA, the oxygen-containing surface functional groups, which have been shown to improve electrocatalytic activity of carbon based materials, were significantly reduced, while the electrical conductivity was enhanced by ∼40 times. The improvement of electrocatalytic activity and fill factor (FF) with reduced RCT of DSSCs after TA was primarily attributed to the increased charge transport within the GNS films, while the chemically prepared GNS typically contained sufficient defects, edges and surface functional groups for electrocatalysis. The performance of the DSSCs using our GNS-CEs was nearly identical (>95%) to the DSSCs using the state-of-the-art CE, thermolytically prepared Pt crystals. Our e-sprayed GNS-CE based DSSCs had a higher FF (69.7%) and cell efficiency (6.93%) when compared previously reported graphene based CEs for DSSCs, demonstrating the outstanding properties of graphene as the electrodes in electrochemical devices.

Suppressed recombination in quantum dot-sensitized solar cells with blocking layers on FTO substrates.

The compact and thin TiO2 blocking layers (c-TiO2) were formed on F-doped SnO2 (FTO) substrate in quantum dots-sensitized solar cells (QSSCs) by chemical deposition. The c-TiO2 layers induced indirect contact between electrolyte and FTO electrode, which reduced leakage in QSSCs. The QSSCs showed power conversion efficiency (Eff) of 3.85% in the presence of c-TiO2 layers which leads to 21% improved compared to that without c-TiO2 layers (Eff = 3.18%). The presence of the c-TiO2 layers in QSSCs also improved the stability under illumination.

Cu(I)-containing room temperature ionic liquids as selective and reversible absorbents for propyne.

A Cu(i)-containing room temperature ionic liquid (Cu-RTIL), prepared from CuCl and 1,3-dimethylimidazolium methylphosphite ([DMIM][MeHPO(3)]), was found to reversibly and selectively interact with propyne over propylene. Cu-RTIL exhibited 12 times higher propyne absorption capacity and 14 times higher ideal propyne/propylene selectivity than [DMIM][MeHPO(3)]. Fast atom bombardment (FAB)-mass spectral and computational results with Cu-RTIL (CuCl/[DMIM][MeHPO(3)] = 1/2) strongly imply that the Cu-RTIL contains stable methylphosphite-coordinated anionic Cu(i) species such as CuCl(MeHPO(3))(-) and Cu(MeHPO(3))(2)(-). Computational studies on the optimized structures demonstrate that the preferential absorption of propyne over propylene in a Cu-RTIL originates from the difference in the interaction mode between the coordinated phosphite ligand and propyne or propylene. Strong π-complexation of propylene and propyne with Cu in Cu-RTIL is not observed.

Facile synthesis of mesoporous silica sublayer with hierarchical pore structure on ceramic membrane using anionic polyelectrolyte.

A facile method for introducing mesoporous silica sublayer onto the surface of a ceramic membrane for use in liquid-phase separation is described. To reduce the electrostatic repulsion between the mesoporous silica sol and the ceramic membrane in highly acidic conditions (pH < 2), thus facilitating the approach of hydrolyzed silica sol to the surface of the membrane, poly(sodium 4-styrenesulfonate) (Na+PSS-, denoted as PSS-) was used as an ionic linker. The use of PSS- led to a significant reduction in positive charge on the ceramic membrane, as confirmed by experimental titration data. Consistent with the titration results, the amount of mesoporous silica particles on the surface of the ceramic membrane was low, in the absence of PSS- treatment, whereas mesoporous silica sublayer with hierarchical pore structure was produced, when 1 wt % PSS- was used. The results show that mesoporous silica grows in the confined surface, eventually forming a multistacked surface architecture. The mesoporous silica sublayer contained uniform, ordered (P6 mm) mesopores of ca. 7.5 nm from mesoporous silica as well as macropores ( approximately mum) from interparticle voids, as evidenced by transmission electron microscopy and scanning electron microscopy analyses. The morphologies of the supported mesoporous silica could be manipulated, thus permitting the generation of uniform needlelike forms or uniform spheroid particles by varying the concentration of PSS-.