Min Jae Ko

Highly Efficient Copper–Indium–Selenide Quantum Dot Solar Cells: Suppression of Carrier Recombination by Controlled ZnS Overlayers

Copper-indium-selenide (CISe) quantum dots (QDs) are a promising alternative to the toxic cadmium- and lead-chalcogenide QDs generally used in photovoltaics due to their low toxicity, narrow band gap, and high absorption coefficient. Here, we demonstrate that the photovoltaic performance of CISe QD-sensitized solar cells (QDSCs) can be greatly enhanced simply by optimizing the thickness of ZnS overlayers on the QD-sensitized TiO2 electrodes. By roughly doubling the thickness of the overlayers compared to the conventional one, conversion efficiency is enhanced by about 40%. Impedance studies reveal that the thick ZnS overlayers do not affect the energetic characteristics of the photoanode, yet enhance the kinetic characteristics, leading to more efficient photovoltaic performance. In particular, both interfacial electron recombination with the electrolyte and nonradiative recombination associated with QDs are significantly reduced. As a result, our best cell yields a conversion efficiency of 8.10% under standard solar illumination, a record high for heavy metal-free QD solar cells to date.

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.

Synergistic enhancement and mechanism study of mechanical and moisture stability of perovskite solar cells introducing polyethylene-imine into the CH3NH3PbI3/HTM interface

High performance perovskite solar cells with high stability in moist air are required for their practical applications. We have developed a simple approach to enhance device stability via the introduction of a polyethyleneimine (PEI) compatibilizer between the perovskite (CH3NH3PbI3) and upper hole transporting material layers (HTMs). The PEI effectively reduces moisture intrusion into the CH3NH3PbI3 layer under a high humidity condition. Moreover, the incorporation of PEI increases the adhesion at the CH3NH3PbI3/HTM interface, which allows the protective HTMs to strongly adhere onto the CH3NH3PbI3 layer during degradation and significantly decreases the direct exposure of CH3NH3PbI3 to moist air. As a result, the solar cell device was found to exhibit remarkably improved moisture stability, maintaining a performance of 85% for 14 days of exposure to 85% relative humidity without any encapsulation. We investigated the effects of the PEI introduction on the perovskite solar cell properties and demonstrated for the first time that the strong adhesion of the CH3NH3PbI3/HTM layer results in a perovskite solar cell device that is not only mechanically stable but also exhibits high long-term stability.

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.

Rapid sintering of TiO2 photoelectrodes using intense pulsed white light for flexible dye-sensitized solar cells

Intense pulsed white light (IPWL) sintering was carried out at room temperature, which is suitable dye-sensitized solar cells (DSSCs) fabrication process on plastic substrates for the mass production. Five seconds irradiation of IPWL on TiO2 electrode significantly improves the photocurrent density and power conversion efficiency of DSSCs by more than 110% and 115%, respectively, compared to the DSSCs without IPWL treatment. These improvements were mainly attributed to the enhanced interconnection between the TiO2 nanoparticles induced by IPWL illumination, which is confirmed by the impedance spectra analysis.

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.

Controlled synthesis of multi-armed P3HT star polymers with gold nanoparticle core

Well-defined multi-armed P3HT star polymers with a gold nanoparticle (NP) core were synthesized by an arm-first method based on a ligand exchange reaction between linear end-functionalized P3HT (P3HT-SH) and gold NPs. A high loading amount of gold NPs to P3HT-SH with a relatively lower molecular weight gave a higher yield of star polymers (∼70%) with a high molecular weight (Mw = 2867k, PDI = 2.1), and the number of P3HT arm chains on one gold NP was 119. The P3HT star polymer with a gold NP core was well-dispersed both in solution and in solid, which was interestingly not crystalline because of the unique 3-dimenstional structure. In addition, surface plasmon resonance (SPR) absorption from the gold NP, as the core of the star polymer, was more enhanced both in solution and in solid, in comparison to those with non end-functionalized P3HT arm chains (P3HT-allyl); however, PL emission was more diminished because of the molecularly contacted P3HT arm chain and gold NP core. This was then introduced in an active layer consisting of P3HT:PCBM in an organic solar cell to increase optical absorption by the SPR effect from the gold NP, however, the device efficiency was rather decreased compared to that of the reference device without gold NPs, which was probably due to direct electron transfer between the gold NP and P3HT.

Novel π-extended porphyrin derivatives for use in dye-sensitized solar cells

Two novel donor-π-acceptor (D-π-A type) porphyrin dyes were successfully synthesized and use in a dye-sensitized solar cell (DSSC). The molecular structures of both porphyrins are composed of the same dialkyl-substituted diphenylamino unit acting as the donor part, and two bisalkoxyphenyl substituents at the 5,15-meso positions. The acceptor part is composed of different ethyne-linked π-extended bridges, and a cyanoacrylic acid (Dye I) or carboxyphenyl (Dye II) moiety acting as anchoring groups. In order to investigate the effects of including the π-extended bridge between the porphyrin and acceptor unit, two different π-extended bridges such as 2,2′-bithiophene and 2-(phenylethynyl)-thiophene, were employed. In particular, Dye II contains two triple bonds between donor substituted porphyrin and carboxylic acid group. These modifications could potentially reduce dye aggregation on the TiO2 surface. The charge recombination resistance and diffusion length for the cells with Dye II were relatively higher for all the measured ranges of bias potentials, implying that electron recombination loss from injected electrons was highly suppressed when Dye II molecules were adsorbed on the TiO2 surface. Eventually, Dye II containing a 2,2′-bithiophene π-spacer and anchored trough a carboxyphenyl group exhibited a superior power conversion efficiency of 6.7% under AM 1.5 illumination (100 mW.cm-2) in a photoactive area of 0.46 cm2 than Dye I with a 2-(phenylethynyl)thiophene (PCE = 3.5%) anchored through a cyanoacrylic group.

Synthesis of porphyrin sensitizers with a thiazole group as an efficient π-spacer: potential application in dye-sensitized solar cells

Herein, we report porphyrin sensitizers for DSSCs, coded CNU-OC8 and CNU-TBU, which were synthesized using a donor–π-bridge–acceptor approach. The porphyrin sensitizers were subjected to electrochemical experiments to study their electron distribution, intramolecular charge transfer and HOMO–LUMO levels. The optical and photovoltaic properties of these synthesized porphyrins were measured and compared with those of the YD2-OC8 benchmark dye. To further characterize, we simulated the electrochemical and optical properties of the dyes, which are perfectly in agreement with the experimental data. The new CNU-OC8 and CNU-TBU porphyrin sensitizers provided power conversion efficiencies of 6.49% and 3.19%, respectively, compared to a conversion efficiency of 6.10% for YD2-OC8 under similar conditions. These results indicate that CNU-OC8 exhibits better photovoltaic performance than the benchmark YD2-OC8 sensitizer in a liquid I−/I3− redox electrolyte.

Synergistic strategies for the preparation of highly efficient dye-sensitized solar cells on plastic substrates: combination of chemical and physical sintering

Preparation of well-interconnected TiO2 electrodes at low temperature is critical for the fabrication of highly efficient dye-sensitized solar cells (DSCs) on plastic substrates. Herein we explore a synergistic approach using a combination of chemical and physical sintering. We formulate a binder-free TiO2 paste based on “nanoglue” as the chemical sintering agent, and use it to construct a photoelectrode on plastic by low-temperature physical compression to further improve the connectivity of TiO2 films. We systematically investigated the factors affecting the photovoltaic performance and found the conditions to achieve electron diffusion lengths as long as 25 μm and charge collection efficiencies as high as 95%, as electrochemical impedance spectroscopy measurements indicate. We apply this approach to obtain a DSC deposited on plastic displaying 6.4% power conversion efficiency based on commercial P25 titania particles.