Current Advancements in Material Research and Techniques Focusing on Lead-free Perovskite Solar Cells

Organic-inorganic lead halide perovskite solar cells (PSCs) recently achieved a photo-to-electricity conversion efficiency (PCE) of 22.1%. They drew much attention as promising photovoltaic devices. However, the Pb-based PSCs face great challenges for commercial and industrial applications due to the instability and the toxicity of perovskite materials. Herein, we summarize the current development of various types of Pb-free perovskites, such as the Sn-, Bi-, Ge-, Sr-, and Cu-based perovskites and their devices. In addition, we will address some remaining issues and prospects of the Pb-free PSCs

Photophysical Characterization and BSA Interaction of Direct Ring Carboxy Functionalized Symmetrical squaraine Dyes

A series of far-red sensitive symmetrical squaraine dyes bearing direct –COOH functionalized indole ring were synthesized, characterized and subjected to photophysical investigations. These symmetrical squaraine dyes were then subjected to investigate their interaction with bovine serum albumin (BSA) in Phosphate buffer solutions. All the squaraine dyes under investigation exhibit intense and sharp optical absorption mainly in the far-red wavelength region from 550 nm -700 nm having very high molar extinction coefficients from 1.3 × 105 dm3.mol−1.cm−1. A very small Stokes shift of 10-17 nm indicates the rigid conformational structure of squaraine chromophore. Interaction of these dyes with BSA leads to not only enhanced emission intensity but also bathochromically shifted absorption maximum due to formation of dye-BSA conjugate. These dyes bind strongly with BSA having about an order of magnitude higher binding constant as compared to the reported squaraine dyes. Amongst the symmetrical squaraine dyes investigated in this work one bearing substituents like trifluorobutyl as alkyl chain at N-position of indole ring and carboxylic acid on benzene ring at the terminal (SQ-26) exhibited highest association with the BSA having very high binding constant 8.01 × 106 M−1.12th International Conference on Nanomolecular Electronics (ICNME-2016), December 14-16, 2016, Kobe International Conference Center, Kobe, Japa

Combined theoretical and experimental approaches for development of squaraine dyes with small energy barrier for electron injection

A series of far-red sensitizing squaraine dyes has been systematically designed and synthesized in order to correlate the theoretically calculated values with their corresponding experimental parameters. Efforts have been directed towards determining the minimum thermodynamic energy barrier for the electron injection in the nanoporous TiO2 by logical molecular design. Theoretical calculations using Gaussian program package were performed for ground and excited states in both of the isolated gaseous state as well as in solution including the solvent effect using a self-consistent reaction field polarizable continuum model (PCM). Implementation of the PCM model or use of LSDA functional under TD-DFT calculations gives much better results for energetics as well as absorption maximum for all of the sensitizers used in this work. Newly designed symmetrical squaraine dye SQ-5 exhibits a minimum energy barrier of 0.16 eV for electron injection and shows photon harvesting behavior in far-red region with external photoconversion efficiency of 2.02% under simulated solar irradiation

Parametric Optimization of Experimental Conditions for Dye-Sensitized Solar Cells based on Far-red Sensitive Squaraine Dye

A far-red sensitive unsymmetrical squaraine dye SQ-41 has been synthesized and subjected to the fabrication of dye-sensitized solar cells by varying the various parameters in order attain optimum photoconversion efficiency (η). It has been demonstrated that an optimum ratio of dye to coadsorber, thickness of mesoporous TiO2 layer, redox electrolyte and surface treatment are necessary to enhance overall external η. In the case of surface treatment, it has been shown to exhibit pronounced device performance when both of the FTO as well mesoporous TiO2 surfaces were treated with aqueous TiCl4. In spite of very high molar extinction coefficient of dye SQ-41, 10-12 µm thickness of mesoporous TiO2 was found to be necessary to attain the maximum η.India-Japan Expert Group Meeting on Biomolecular Electronics & Organic Nanotechnology for Environment Preservation (IJEGMBE 2015), December 23-26, 2015, Fukuoka, Japa

First-principles study of electronic and optical properties of lead-free double perovskites Cs2NaBX6 (B = Sb, Bi; X = Cl, Br, I)

Organolead halide perovskite is regarded as the most promising light-harvesting material for next-generation solar cells; however, the intrinsic instability and toxicity of lead are still of great concern. Bismuth is ecofriendly and has electronic properties similar to those of lead, which has gradually attracted interest for optoelectronic applications. However, the valence state of bismuth is different from that of lead, eliminating the possibility of replacing lead by bismuth in organolead halide perovskites. To address this matter, one feasible strategy is to construct B-site double perovskites by the combination of Bi3+ and B+ in 1:1 ratio. In this work, lead-free halide double perovskites of the form Cs2NaBX6 (B = Sb, Bi; X = Cl, Br, I) were investigated by first-principles calculations. The electronic properties, optical absorption coefficients, and thermodynamic stability of these compounds were investigated to ascertain their potential application in solar energy conversion. The results provide theoretical support for the exploration of lead-free perovskite materials in potential optoelectronic applications

Optical Absorption, Charge Separation and Recombination Dynamics in Pb and Sn/Pb Cocktail Perovskite Solar Cells and Their Relationships to the Photovoltaic Properties

Due to the unique characteristics such as simple low-temperature preparation method and high efficiency with a record of over 20%, organometal trihalide perovskite (CH3NH3PbI3)-based solid-state hybrid solar cells have attracted an increasing interest since 2012 when it was reported. During the last several years, some of the fundamental photophysical properties of perovskite related to the high photovoltaic performance have been investigated. Optical absorption, charge separation and recombination are very important factors influencing the perovskite solar cell performance. In this chapter, our recent results of optical absorption, charge separation (electron and hole injection) and charge recombination dynamics at each interface in perovskite solar cells, and their relationships to photovoltaic properties will be introduced. Our results suggest that charge recombination is a key factor in improving the performance of the perovskite solar cells

Enhancement of carrier mobility along with anisotropic transport in non-regiocontrolled poly (3-hexylthiophene) films processed by floating film transfer method

A newly developed floating film transfer method (FTM) has been successfully utilized to fabricate oriented thin films of non-regiocontrolled poly (3-hexyl thiophene) (NR-P3HT) followed by the fabrication of organic field effect transistors (OFETs). AFM microstructural investigations demonstrate the facile molecular alignment of NR-P3HT by FTM leading to highly oriented macromolecular assemblies like fibrous domains with considerably enhanced π-conjugation length. FTM thin films of NR-P3HT not only show enhanced optical anisotropy (dichroic ratio >8) but also significantly improved FET characteristics. FTM films in its parallel orientation exhibited a significant improvement (>2 orders) in the FET mobility as compared to its spin-coated device counterparts

Solvent driven performance in thin floating-films of PBTTT for organic field effect transistor: Role of macroscopic orientation

Considering the advantages of floating film transfer method (FTM), we have investigated the optical and electronic characteristics of PBTTT-C14 thin-films prepared by the static and the dynamic casting on liquid substrate. It has been demonstrated that judicious selection of solvents during FTM switches the casting mode from the static casting (S-FTM) using high boiling point solvent to the dynamic casting (D-FTM) from low boiling point solvent. Although both of the methods provide the edge-on oriented structure of PBTTT-C14 by XRD, the structural and the optical analyses reveal relatively extended π-conjugation length in parallel D-FTM film as compared to that of S-FTM. A high field-effect mobility (μ) of 0.11 cm2/V.s was exhibited by OFETs fabricated by parallel D-FTM film even without any high temperature post-annealing up to the liquid crystalline phase transition. This observed value of μ for parallel D-FTM is 4.7 and 12.8 times higher than the isotropic S-FTM and the perpendicular D-FTM films, respectively

Influence of backbone structure on orientation of conjugated polymers in the dynamic casting of thin floating-films

Dynamic casting of conjugated polymer films on liquid-substrate is a unique method which provides thin floating-film and can be easily transferred on a desired substrate by stamping. The important feature in this procedure is associated with the formation of thin polymeric film during compression and solidification controlled by viscous drag of liquid substrate and solvent evaporation of the polymer, respectively. Lyotropic liquid-crystalline (LC) characteristics of conjugated polymer possibly assist to orient the polymer chain in one direction. It is found that this method produce highly oriented thin films (dichroic ratio > 5) of thiophene-based conjugated polymers such as PBTTT-C14, PQT-C12 and non-regiocontrolled poly(3-hexylthiophene) NR-P3HT. On the other hand, weak orientation intensity in regioregular poly(3-hexylthiophene) RR-P3HT was found. The mechanism for this diverse orientation in thiophene-based conjugated polymers is discussed in correlation with the backbone chemical structure and lyotropic LC phase transition during the floating-film formation

Photovoltaic Properties of CdSe Quantum Dot Sensitized Inverse Opal TiO2 Solar Cells: The Effect of TiCl4 Post Treatment

Recently, semiconductor quantum dot (QD) sensitized solar cells (QDSSCs) are expected to achieve higher conversion efficiency because of the large light absorption coefficient and multiple exciton generation in QDs. The morphology of TiO2 electrode is one of the most important factors in QDSSCs. Inverse opal (IO) TiO2 electrode, which has periodic mesoporous structure, is useful for QDSSCs because of better penetration of electrolyte than conventional nanoparticulate TiO2 electrode. In addition, the ordered three dimensional structure of IO-TiO2 would be better for electron transport. We have found that open circuit voltage Voc of QDSSCs with IO-TiO2 electrodes was much higher (0.2 V) than that with nanoparticulate TiO2 electrodes. But short circuit current density Jsc was lower in the case of IO-TiO2 electrodes because of the smaller surface area of IO-TiO2. In this study, for increasing surface area of IO-TiO2, we applied TiCl4 post treatment on IO-TiO2 and investigated the effect of the post treatment on photovoltaic properties of CdSe QD sensitized IO-TiO2 solar cells. It was found that Jsc could be enhanced due to TiCl4 post treatment, but decreased again for more than one cycle treatment, which indicates excess post treatment may lead to worse penetration of electrolyte. Our results indicate that the appropriate post treatment can improve the energy conversion efficiency of the QDSSCs