We report two types of the tin-based solar cells, namely, lead-free tin perovskite solar cells (Sn-PVK-PV), tin lead alloyed perovskite solar cells (SnPb-PVK-PV). Tin oxide is well-known as the electron transport layer of solar cells such as Pb-PVK PV, dye-sensitized solar cells and organic solar cells. We found that SnOx works as the HTL of the Sn-PVK PV. The basic structure is as follows: FTO glass/SnOx/Sn-PVK/C60/BCP/Ag. Efficiency over 14% and the carrier dynamics are reported. All-perovskite tandem solar cells consisting of Pb-PVK-PV (top cell) and PbSn-PVK-PV (bottom cells) are reported. PbSn-PVK PV efficiency was improved by using hybrid SAM layers working as the HTL. The efficiency over 26% is reported.
Conventional dye-sensitized solar cells (DSSCs) require two transparent conductive oxide (TCO) glasses as working and counter electrodes and are one of the most costly components posing an appreciable cost burden for production and commercialization. To circumvent this issue, we propose a TCO-free device structure utilizing titanium (Ti) sheets as a substitute for TCO. This back contact device structure not only allows the removal of the costly TCO component from the working electrode but also enhances the extent of photons absorbed by the photoanode. A flat titanium sheet with microholes (FTS-MH) was successfully applied to fabricate cylindrical TCO-free-DSSCs) with a titanium sheet as a back contact electrode. When the H2O2 surface-treated FTS-MH substrate generating dense anatase TiO2 nanosheets was used as a photoanode, there was a pronounced improvement in efficiency from 5.76% to 8.59%. This was mainly attributed to the lower interfacial resistance facilitated by improved electrical contact between the conducting FTS-MH substrate and mesoporous TiO2 layer since enhancement in the dye loading was only 8.6%.
Recently, Sn perovskite solar cell (Sn PVK PV) are attracting attention. However, the efficiency was still lower than that of Pb perovskite solar cells. Recently, the Sn PVK PVs with efficiency higher than 10% have been reported from several research groups. The crystal defects include the presence of Sn4+, Sn2+ defect, I- defect, the presence of Sn0, the interstitial I- and so on. In order to decrease these defect densities, we have proposed some processes such as addition of Ge2+ ion, introduction of ethylammonium cation into A site, and surface passivation of perovskite grain boundary with diaminoethane dilute solution. Our results on efficiency enhancement (13%) is explained by the conduction and valence band energy level against carrier trap depth. In addition, an inverted SnPb perovskite solar cells with 23.3% efficiency is discussed from the view point of optimization of energy alignment.
Grätzel solar cells are reported in a transparent conducting oxide-less (TCO-less) back-contact dye-sensitized solar cell (BC-DSC) architecture using a stainless steel mesh-protected working electrode along with nanoporous TiO2 semiconductor and metal-free D205 dye. Liquid electrolytes play a significant role for the dye regeneration in the working operation of TCO-less BC-DSCs; therefore, we report the effectiveness of two different commonly utilized electrolytes (iodine- and cobalt-based redox shuttles) for the construction and performance of TCO-less dye-sensitized solar cells (DSCs). Differential performance of DSCs thus fabricated was interpreted utilizing impedance spectral and lifetime analysis. It was found that although utilization of cobalt bipyridyl complex-based electrolyte was able to harvest higher photons in the lower wavelength region (330 to 430 nm) as compared to its iodine electrolyte counterparts, hampered dye regeneration due to reduced driving force and slower ion diffusion in combination with higher charge transport resistance at TiO2 / dye / electrolyte was responsible for relatively hampered photovoltaic performance at peak absorption.
Certified efficiency of halogenated Pb-perovskite solar cells has reached 25.2 %. Because of the Pb usage restriction, researches on Pb free perovskite solar cells have been focused on. Halogenated Sn-perovskite is one of candidates for the Pb-free perovskite solar cells. In spite of the similarities of the electronic properties between Pb-perovskite and Sn-perovskite, the efficiency of the Sn-perovskite solar cell was still about 10%, which is far below that of Pb-perovskite solar cells. We report Ge ion doped Sn-perovskite solar cells (Pb free) with 13% efficiency by optimizing A site cations in ASnI3 composition and surface passivation.
Despite the high-efficiency of these lead-based perovskite solar cells, the problem associated from the toxic nature of lead has open a new research direction which focuses on lead-free perovskite materials. As an alternative, tin has been proposed to replace lead. The highest efficiency obtained with Sn only perovskite was 9 % which was based on 2D and 3D mixture of FASnI3. However, Sn-based perovskites are known to have low stability in air. The use of germanium-based perovskite in solar cell was first realized by Krishnamoorthy et. al. The measured solar cell performance was notably low, 0.11 % for CsGeI3 and 0.20 % for MAGeI3. A theoretical study exploring hybrid tin and germanium perovskite showed that it is possible to prepare a stable Sn-Ge perovskite material that absorbs the sunlight spectrum. In this study, a new type of SnGe mixed metal perovskite solar cells are reported with enhanced efficiency and stability. In this report, FA0.75MA0.25Sn1-xGexI3 (abbreviated as SnGe(x)-PVK) were used for the mixed metal SnGe perovskite. XRD spectra showed that the structure is perovskite.
The structure of Ge-doped Sn perovskite was also discussed from the view point of band gap, conduction and valence band level, XPS analysis, and the urbach energy. It can be concluded that most of the Ge atoms passivate the surface of the Sn perovskite (graded structure).For SnGe(0)-PVK device, the averageJsc was 17.61 mA/cm2, VOC was 0.46 V, FF was 0.41 and PCE of 3.31 %. Upon doping with 5 wt% of Ge, the JSC increased up to 19.80 mA/cm2, FF improved up to 0.55 with an overall efficiency of 4.48 %. Upon increasing the Ge content more than 10wt%, all the photovoltaic parameters decreased significantly which resulted in an efficiency as low as 0.80 % for SnGe(0.2)-PVK device. After optimization, 7.75% of SnGe(5)-PVK device is reported. Significant effect on Ge doping was seen in the enhancement of the stability. The stability in air has been improved significantly with the Ge doping, retaining 80 % of its original performance, remarkable stability enhancement, compared with 10 % retention for non-doped sample. This work provides a platform for further research on lead-free Sn-Ge based perovskite solar cells.
Thin perovskite solar cells are under intensive interest since they reduce the amount of absorber layer, especially toxic lead in methylammonium lead iodide (MAPbI3) devices and have wide application in semitransparent and tandem solar cells. However, due to the decrease of the layer thickness, thin perovskite devices with weak light-harvesting have poor performance. Moreover, the performance of plasmonic thin perovskite devices by incorporating noncoupling metal NPs cannot give comparable performance with normal devices. In this perspective, we discuss the implication of employing random silver-gold heterodimers in MAPbI3 solar cells with the aim of establishing some guidelines for the efficient ultrathin perovskite solar cells. This method induces an extraordinarily high light-harvesting for ultrathin perovskite film. And the underlying physical mechanism behind the enhanced absorption is deeply investigated by plasmon hybridization, dipolar–dipolar coupling method and FDTD simulation. We notice that perovskite embedded silver-gold heterodimer overcomes the vanished antibonding plasmon resononse (σ * ) in nonjunction area of gold/silver homodimer. A 150-nm perovskite film with embedded random silver-gold heterodimers with 80 nm size and 25 nm gap distance processes 28.15% absorption enhancement compared to the reference film, which is higher than the reported 10% for gold homodimers. And we also predict a realistic solution-processed, easy, and low-cost fabrication method, which provide a means to realize highly efficient ultrathin perovskite solar cell including other absorber-based photovoltaics.
Absorption edge of perovskite (PVK) solar cells consisting of MAPbI3 is 800nm. According to our simulation, light harvesting in the area of near IR is also necessary for enhancing the efficiency more. We have already reported that mixed metal perovskite (MAPbSnI3) shows photo-conversion in IR region (1-6). The short circuit current (Jsc) was high, reaching to 30 mA/cm2 because of the wide range of light harvesting. However, the open-circuit voltage (Voc) was lower than 0.3 V and the estimated voltage loss was 0.6-0.7 V, which was much larger than that of MAPbI3 (0.4 V), suggesting the presence of high density charge recombination center. We found that Ti-O-Sn bonds formed at the interface between Tiania and MAPbSnI3 layer, create trap states, resulting in increasing charge recombination at the interfaces. The surface trap density and the trap depth was quantitatively monitored by thermally stimulated current methods. When the Ti-O-Sn linkage was formed at the interface between TiO2 and PVK, the trap density increased by one order of magnitude. The interface was analyzed by XPS and confirmed that Ti-O-Sn linkage was formed. After removing the Ti-O-Sn bond at the interface between TiO2 and MAPbSnI3, the efficiency drastically increased from 4.0 % to 13.8 % and the stability was improved. It was proved that interface architecture is quite important for enhancing the MAPbSnI3 solar cells.
References
1. S. Nakabayashi, et al., J. Photonics for Energy; 2015, 5, 057410. 2. Y. Ogomi, et al., J. Phys. Chem. Lett. 2014, 5, 1004-1011.
A flat titanium sheet with microholes (FTS-MH) has been utilized to fabricate transparent conductive oxide-less dye-sensitized solar cells (TCO-less DSSCs) in back contact device architecture. Utilization of FTS-MH to fabricate a TCO-less photoanode offers several advantages in terms of simplicity and ease of fabrication as compared with the TCO-less DSSCs structure reported previously. Hydrogen peroxide (H2O2) surface treatments on FTS-MH have shown important factors to enhance the photoanode properties. H2O2 surface treatment is able to change the surface morphology of FTS-MH, and the created anatase titanium dioxide (TiO2) nanostructures increase the surface contact between the FTS-MH and the coated mesoporous TiO2. Electrochemical impedance investigations reveled that improvements of the FTS-MH/TiO2 and TiO2/dye/electrolyte interface led to hampered charge recombination resulting in enhancement of both short-circuit current density and open-circuit voltage, respectively. Even after removal of both TCO layers, our complete TCO-less DSSCs exhibited a power conversion efficiency of 7.25% under simulated solar irradiation.
In order to examine the interface structure of TiO2/perovskite layer, quartz crystal microbalance sensor (QCM) was used. On the QCM sensor, TiO2 layer was fabricated and the PbI2 solution in Dimethylformamide (DMF) was passed on the QCM sensor to estimate the adsorption density of the PbI2 on the titania2. The amount of PbI2 adsorption on TiO2 surface increased as the adsorption time and leveled off at a certain time. PbI2 still remained even after the solvent only (DMF) was passed on the TiO2 layer on QCM (namely rinsing with DMF), suggesting that the PbI2 was tightly bonded on the TiO2 surface. The bonding structure was found to be Ti-O-Pb linkage by XPS analysis. We concluded that the Ti-OH on the surface of TiO2 reacts with I-Pb-I to form Ti-O-Pb-I and HI (Fig.1 B). The surface trap density was measured by thermally stimulated current (TSC) method. Before the PbI2 passivation, the trap density of TiO2 was 1019 cm3. The trap density decreased to 1016/cm3 after the PbI2 passivation, suggesting that the TiO2 surface trap was passivated with I-Pb-I. The passivation density was tuned by the concentration of PbI2 in DMF, by which TiO2 layer was passivated. Perovskite solar cells were fabricated on the passivated TiO2 layer with various PbI2 passivation densities by one step process (mixture of PbI2 + MAI in DMF). It was found that Jsc increased with an increase in the Ti-O-Pb density. We concluded that the interface between TiO2 and perovskite layer has passivation structure consisting of Ti-O-Pb-I which decreases the trap density of the interfaces and supresses charge recombination.
The effect of Cl anion on high efficiency is still controversial when perovskite layer is prepared by one step method from the mixture of MAI and PbCl2. It was found that adsorption density of PbCl2 on TiO2 surface was much higher than that of PbI2 from the experiment using QCM sensor. After the surface was washed with DMF, Cl and Pb were detected. These results suggest that the TiO2 surface was much more passivated by PbCl2 than by PbI2. This may explain partially the high efficiency when the perovskite layer was fabricated by one step process consisting of MAI and PbCl2 solution. We also observed that the crystal size increased with an increase in the amount of Cl anion which of course one of the explanation of the high efficiency.
The interface of hole transport layer/perovskite layer, and between perovskite layer /perovskite layer (grain boundary) was passivated with organic amines. The passivation was also effective for increasing Voc and Jsc. This was explained by the results of transient absorption spectroscopy that the charge recombination time between hole transport payer/perovskite layer increased from 0.3 μsec to 60 μsec.
Adsorption of PbI2 onto a titania layer was monitored by a quartz crystal microbalance system in solution. The amount of PbI2 adsorbed on the titania layer increased with an increase in the PbI2 concentration in dimethylformamide (DMF). However, PbI2 remained after being rinsed with DMF, suggesting that PbI2 is rigidly bonded to the surface of the titania. The x-ray photoelectron spectroscopy measurement of PbI2 adsorbed on the titania substrate showed that the Pb compound has a composition of PbI0.33, not PbI2, suggesting that part of the Pb-I reacts with the HO-Ti moieties of titania to form Pb-O-Ti linkages. Trap density as measured by the thermally stimulated current method decreased after PbI2 passivation. Perovskite solar cells consisting of porous titania passivated with PbI2 had a higher efficiency than those without the passivation. It was concluded that PbI2 passivation of porous titania surfaces is one of the crucial approaches for enhancing the efficiency of perovskite solar cells with a scaffold layer of porous titania.
We have succeeded in harvesting energy in the NIR region by using Sn halide based perovskite materials. The cell has the following composition: F-doped SnO2 layered glass/compact titania layer/porous titania layer/Sn based perovskite material/ p-type polymer semiconductor. The edge of the incident photon to current efficiency (IPCE) edge reached 1040 nm. 4.18 % efficiency with open circuit efficiency (Voc):0.42 V, fill factor (FF): 0.5, short circuit current (Jsc): 20.04 mA/cm2 is reported.
Certified efficiency of dye-sensitized solar cells (DSC) with a cell area larger than 1 cm2 reached
11.0%, which is almost same as that of amorphous silicon type solar cells. However, the efficiency is
not as high as 20-25 % of crystal silicon type solar cells. Therefore, researches to find
photo-conversion systems in the area of near infrared and infrared regions are being done to
increase the efficiency. It has been reported that the efficiency of DSCs is affected by
dye-adsorption behaviors on titania surfaces. However, there was no report on how dyes are
adsorbed on titania and the relationship between dye adsorption and solar cell efficiency. We now
report the adsorption behavior of dye molecules, which are monitored by Quartz Crystal
Microbalance (QCM), and discuss the role of dye aggregation inhibitors which affect seriously the
solar cell efficiency.
Fabrication and photovoltaic performances for flexible transparent conductive oxide-less (TCO-less) flat and cylinder dye-sensitized solar cells (DSCs) are reported. The cylinder solar cell consists of a porous silicone tube, a protected stainless steel metal mesh (protected SUS mesh) working as a counter electrode, a gel electrolyte sheet, a dye/porous titania layer fabricated on a protected SUS mesh working as a anode, and a thermally shrinkable plastic tube, from the inside to the outside. The thermally shrinkable tube was used to reduce the gap between a cathode and an anode. In addition, a porous silicone tube was used for injecting electrolytes smoothly into the gel electrolyte layer. 5.08% efficiency (FF: 0.68; Voc: 0.68 V; Jsc: 11.07 mA/cm2) was observed. A flexible TCO-less flat DSCs with 6.1% efficiency which was improved by narrowing a gap between two electrodes is also reported.
KEYWORDS: Dye sensitized solar cells, Absorption, Adsorption, Solar energy, Solar cells, Molecular aggregates, Dysprosium, Mass attenuation coefficient, Photovoltaics, Titanium dioxide
Creation of molecular asymmetry in the organic sensitizing dyes has been demonstrated for enhancing the
photoconversion efficiency due to unidirectional flow of electron after the photoexcitation. Molecular structures for
direct indole ring carboxy-functionalized unsymmetrical squaraine dyes have been optimized by fine tuning the
molecular structures and judicious selection of the substituents to prevent the dye aggregation and electron
recombination. Best efficiency of 4.42 % was achieved for unsymmetrical squaraine dye SQ-64 with a short circuit
current density of 11.22 mA/cm2, a fill factor of 0.61 and an open circuit voltage of 0.64 V under standard AM 1.5
simulated solar irradiation.
Fiber and pillar tandem dye-sensitized solar cells (DSCs), which do not need transparent conductive oxideless layer tandem cells (TCO-less TAN), are fabricated and their fundamental tandem properties are evaluated. TCO-less TAN cells consist of a light-splitting waveguide and TCO-less DSCs. The TCO-less DSC is composed of a nanoporous titania back-contacted with a porous Ti electrode or a nanoporous titania sheet supported by a stainless steel mesh whose surface was protected with TiOx thin layers. Two kinds of light-splitting structures are introduced. One is a light-splitting structure in which polystyrene particles with different diameters are dispersed in water. The other consists of dichroic mirrors. These light-splitting structures are coupled with TCO-less DSCs stained with dyes absorbing light corresponding to these split lights. Open circuit voltages (Voc) of these TCO-less tandem DSCs are two times (two tandem structure) or three times (three tandem structure) higher than those of the corresponding single cells, demonstrating that these structures work as tandem cells.
Some items to increase photovoltaic performances of dye sensitized solar cells (DSC) are reported.
Focus is put on the fabrication of the electron collection path and ionic path. In order to increase the
surface coverage of TiO2 nano-particles with dye molecules, the dye adsorption on TiO2 layers was
carried out under a pressurized CO2 atmosphere (CO2 process). The CO2 process promoted the dye
adsorption and shortened the dye adsorption time to 1/10 - 1/100. In addition, solar cells prepared by the
CO2 process had higher Voc and Jsc than those prepared by the conventional dipping process. The
increase in the photovoltaic performance was explained by the large electron diffusion coefficient in TiO2
layers and by longer electron life time in TiO2 layers. Thermally stimulated current measurement (TSC)
implied that the surface electron trap on the TiO2 nano-particle was passivated by the sufficient dye
adsorptions on the TiO2 surfaces. In addition, it was found that the dye aggregation was prevented by
the CO2 process, which increased the photovoltaic performances. Hybrid dye sensitized solar cells
having two-dye-layer-structures were fabricated by the CO2 process for the first time in order to absorb
the light having wide range of wavelength. In addition, three-dimensional W electrodes were fabricated
on the thick TiO2 layer in order to collect electrons in the TiO2 layer effectively. Solid type DSCs are
reported. High performance quasi-solid DSCs were fabricated by preparing ionic paths in the
quasi-solid electrolyte layers. The ionic path was fabricated by the surface modification of the straight
nano-pore walls in a porous Al2O3 membrane, where, I-/I3- ion species were concentrated and were
expected to diffuse by Grötthuss mechanism.
Quasi-solid dye sensitized solar cells (Q-DSSC) were fabricated by employing gel electrolytes containing ionic liquids and gelators. Sufficient physical contacts between nano-crystalline TiO2 particles and gel electrolytes in nano-porous TiO2 layers were achieved by solidifying gel electrolyte precursors after the cells are filled with the electrolytes. Photo-currents increased largely by embedding carboxylic acids among dye molecules on TiO2 crystals. The nano-porous TiO2 electrolytes were fabricated by dipping the dye anchored TiO2 substrates in dilute solutions of carboxylic acids. It was found that resistances in the TiO2 layers decreased by these treatments.
Application of polysilanes for a deep UV (DUV) bottom anti- reflective coating (BARC), in order to resolve the problem posed by the insufficient anti-reflection with thin conventional organic BARC applied on transparent dielectric film, is described. The newly developed polysilane anti- reflective coating has the real part of refractive index, n equals 2.00, and the imaginary part, k equals 0.23 at 248 nm. The polysilane coating is immiscible with a chemically amplified photoresist, and is not removable during normal wet development of photoresist. Etching rate of the polysilane is 2 times faster than that of DUV resist during BARC etching, and lower than that of DUV resist during dielectric film etching. The polysilane layer is easily removed by ashing using O2 gas process. Using thick polysilane coating, it can realize both the suppression of the interface reflection between the resist and BARC and good critical dimension control on dielectric film.
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