Organic-inorganic hybrid perovskites have attracted attention as successful light harvesting materials for mesoscopic solid-state solar cells and led to record breaking effi ciencies. The photovoltaic performance of these devices is greatly dependent on the fi lm morphology, which in turn is dependent on the deposition techniques and subsequent treatments employed. In this work the perovskite fi lm is deposited by spin-coating a precursor solution of PbCl 2 and CH 3 NH 3 I (1 to 3 molar ratio) in dimethylformamide. Here, the role of the temperature used in the annealing process required to convert the as deposited solution into the perovskite material is investigated. It is found that the conversion requires suffi ciently high temperatures to ensure the vaporization of solvent and the crystallization of the perovskite material. However, increasing the annealing temperature too high leads to the additional formation of PbI 2 , which is detrimental to the photovoltaic performance. Furthermore, the effect of the annealing temperature on the fi lm formation, morphology, and composition is examined and correlated with the photovoltaic performance and device working mechanisms.
Chemical doping is an important strategy to alter the charge-transport properties of both molecular and polymeric organic semiconductors that find widespread application in organic electronic devices. We report on the use of a new class of Co(III) complexes as p-type dopants for triarylamine-based hole conductors such as spiro-MeOTAD and their application in solid-state dye-sensitized solar cells (ssDSCs). We show that the proposed compounds fulfill the requirements for this application and that the discussed strategy is promising for tuning the conductivity of spiro-MeOTAD in ssDSCs, without having to rely on the commonly employed photo-doping. By using a recently developed high molar extinction coefficient organic D-π-A sensitizer and p-doped spiro-MeOTAD as hole conductor, we achieved a record power conversion efficiency of 7.2%, measured under standard solar conditions (AM1.5G, 100 mW cm(-2)). We expect these promising new dopants to find widespread applications in organic electronics in general and photovoltaics in particular.
Mesoscopic solid-state solar cells based on the inorganic-organic hybrid perovskite CH3NH3PbI3 in conjunction with the amorphous organic semiconductor spiro-MeOTAD as a hole transport material (HTM) are investigated using impedance spectroscopy (IS). A model to interpret the frequency response of these devices is established by expanding and elaborating on the existing models used for the liquid and solid-state dye-sensitized solar cells. Furthermore, the influence of changing the additive concentrations of tert-butylpyridine and LiTFSI in the HTM and varying the HTM overlayer thickness on top of the sub-micrometer thick TiO2 on the extracted IS parameters is investigated. The internal electrical processes of such devices are studied and correlated with the overall device performance. In particular, the features in the IS responses that are attributed to the ionic and electronic transport properties of the perovskite material and manifest as a slow response at low frequency and an additional RC element at intermediate frequency, respectively, are explored.
Recently organic–inorganic
hybrid perovskites have attracted
attention as light harvesting materials in mesoscopic cells. While
a considerable number of deposition and formation methods have been
reported for the perovskite crystalline material, most involve an
annealing step. As such, the thermal behavior of this material and
its individual components is of crucial interest. Here, we examine
the thermal properties of the CH3NH3PbX3 (X = I or Cl) perovskite using thermogravimetric analysis.
The role of the precursors is exposed, and the effect of the formation
of excess organic species is investigated. The sublimation behavior
of the organic component is intensively scrutinized. Furthermore,
differential scanning calorimetry is employed to probe the crystal
phase structure, revealing subtle differences depending on the deposition
method.
The internal transport and recombination parameters of solid-state dye-sensitized solar cells (ssDSCs) using the amorphous organic semiconductor 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-MeOTAD) as a hole transport material (HTM) are investigated using electrical impedance spectroscopy. Devices were fabricated using flat and nanostructured TiO2 and compared to systems using nanostructured ZrO2 to differentiate between the transport processes within the different components of the ssDSC. The effect of chemically p-doping the HTM on its transport was investigated, and its temperature dependence was examined and analyzed using the Arrhenius equation. Using this approach the activation energy of the hole hopping transport within the undoped spiro-MeOTAD film was determined to be 0.34 ± 0.02 and 0.40 ± 0.02 eV for the mesoporous TiO2 and ZrO2 systems, respectively.
In solid-state dye-sensitized solar cells (ssDSCs), the poor pore filling of the mesoporous semiconductor and the short diffusion length of charge carriers in the hole-transport material (HTM) have limited the mesoscopic titania layer to a thickness of 2–3 μm. To increase the amount of light harvested by ssDSCs, organic dyes with high molar extinction coefficients are of great importance and have been the focus of intensive research. Here we investigate ssDSCs using an organic D−π–A dye, coded Y123, and 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene as a hole-transport material, exhibiting 934 mV open-circuit potential and 6.9% efficiency at standard solar conditions (AM1.5G, 100 mW cm–2), which is a significant improvement compared to the analogue dyes C218, C220, and JK2 (V
oc values of 795, 781, and 914 mV, respectively). An upward shift in the conduction band edge was observed from photovoltage transient decay and impedance spectroscopy measurements for devices sensitized with Y123 and JK2 dyes compared to the device using C220 as sensitizer, in agreement with the high photovoltage response of the corresponding ssDSCs. This work highlights the importance of the interaction between the HTM and the dye-sensitized TiO2 surface for the design of ssDSCs.
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