The evolution of triphenylamine hole transport materials for efficient perovskite solar cells

In recent years, the dramatic increase in power conversion efficiency (PCE) coupled with a decrease in the total cost of third-generation solar cells has led to a significant increase in the collaborative research efforts of academic and industrial researchers. Such interdisciplinary studies have afforded novel materials, which in many cases are now ready to be brought to the marketplace. Within this framework, the field of perovskite solar cells (PSCs) is currently an important area of research due to their extraordinary light-harvesting properties. In particular, PSCs prepared via facile synthetic procedures, containing hole transport materials (HTMs) with versatile triphenylamine (TPA) structural cores, amenable to functionalization, have become a focus of intense global research activity. To optimize the efficiency of the solar cells to achieve efficiencies closer to rival silicon-based technology, TPA building blocks must exhibit favourable electrochemical, photophysical, and photochemical properties that can be chemically tuned in a rational manner. Although PSCs based on TPA building blocks exhibit attractive properties such as high-power efficiencies, a reduction in their synthetic costs coupled with higher stabilities and environmental considerations still need to be addressed. Considering the above, a detailed summary of the most promising compounds and current methodologies employed to overcome the remaining challenges in this field is provided. The objective of this review is to provide guidance to readers on exploring new avenues for the discovery of efficient TPA derivatives, to aid in the future development and advancement of TPA-based PSCs for commercial applications.

Charge collection and pore filling in solid-state dye-sensitized solar cells

Ilkay Cesar, Michael Graetzel, Robin Humphry-Baker, Henry Snaith, Shaik Mohammed Zakeeruddin

The solar to electrical power conversion efficiency for dye-sensitized solar cells (DSCs) incorporating a solid-state organic hole-transporter can be over 5%. However, this is for devices significantly thinner than the optical depth of the active composites and by comparison to the liquid electrolyte based DSCs, which exhibit efficiencies in excess of 10%, more than doubling of this efficiency is clearly attainable if all the steps in the photovoltaic process can be optimized. Two issues are currently being addressed by the field. The first aims at enhancing the electron diffusion length by either reducing the charge recombination or enhancing the charge transport rates. This should enable a larger fraction of photogenerated charges to be collected. The second, though less actively investigated, aims to improve the physical composite formation, which in this instance is the infiltration of mesoporous TiO2 with the organic hole-transporter 2,2',7,7'-tetrakis(N,N-di-p-methoxypheny-amine)-9,9'-spirobifluorene (spiro-MeOTAD). Here, we perform a broad experimental study to elucidate the limiting factors to the solar cell performance. We first investigate the charge transport and recombination in the solid-state dye-sensitized solar cell under realistic working conditions via small perturbation photovoltage and photocurrent decay measurements. From these measurements we deduce that the electron diffusion length near short-circuit is as long as 20 µm. However, at applied biases approaching open-circuit potential under realistic solar conditions, the diffusion length becomes comparable with the film thickness, ~2 µm, illustrating that real losses to open-circuit voltage, fill factor and hence efficiency are occurring due to ineffective charge collection. The long diffusion length near short-circuit, on the other hand, illustrates that another process, separate from ineffective charge collection, is rendering the solar cell less than ideal. We investigate the process of TiO2 mesopore infiltration with spiro-MeOTAD by examining the cross-sectional images of and performing photo-induced absorption spectroscopy on devices with a range of thickness, infiltrated with spiro-MeOTAD with a range of concentrations. We present our interpretation of the mechanism for material infiltration, and by improving the casting conditions demonstrate efficient charge collection through devices of over 7 µm in thickness. This investigation represents an improvement in our understanding of the limiting factors to the dye-sensitized solar cell. However, much work, focused on composite formation and improved kinetic competition, is required to realize the true potential of this concept.

2008

Strategies to Optimizing Dye-Sensitized Solar Cells

Sophie Wenger

Dye-sensitized solar cells (DSCs) constitute a novel class of hybrid organic-inorganic solar cells. At the heart of the device is a mesoporous film of titanium dioxide (TiO2) nanoparticles, which are coated with a monolayer of dye sensitive to the visible region of the solar spectrum. The role of the dye is similar to the role of chlorophyll in plants; it harvests solar light and transfers the energy via electron transfer to a suitable material (here TiO2) to produce electricity — as opposed to chemical energy in plants. DSCs are fabricated of abundant and cheap materials using inexpensive processes (e.g. screen-printing) and are likely to be a significant contributor to the future commercial photovoltaic technology portfolio. The work conducted during this thesis aimed at optimizing the DSC using three different strategies: The use of versatile organic sensitizers for stable and efficient DSCs, the study of tandem device architectures in combination with other solar cells to harvest a larger fraction of the solar spectrum, and the development of a validated optoelectric model of the DSC. Organic donor-π-acceptor dyes are an interesting alternative to the standard metal-organic complexes used in DSCs. Efficient photovoltaic conversion and stable performance could be demonstrated with three classes of donor systems, namely diphenylamine, difluorenylaminophenyl, and π-extended tetrathiafulvalene. The highest conversion efficiencies were obtained with a difluorenylaminophenyl donor system (η = 8.3 % with a volatile electrolyte and η = 7.6 % with a solvent-free ionic liquid, which was a new record for organic dyes at the time of publication). Surprisingly, efficient regeneration of the oxidized dye by the I-/I3- redox mediator was found with the π-extended tetrathiafulvalene system, even though the thermodynamic driving force was as low as 150 mV. So far driving forces of 300-500 mV had been regarded as necessary for efficient regeneration of the dye cation. Also, important structure-property relationships pertaining to the recombination of electrons with the electrolyte and to the stability of the device could be identified (i.e. effect of linear vs. branched structure, linker length, and moieties used). The power conversion efficiency of solar cells can be extended beyond the limit for a single cell (∼ 30 %) by using multiple cells with different optical gaps in a tandem device. DSCs and chalcopyrite Cu(In,Ga)Se2 (CIGS) solar cells have complementary optical gaps and are thus suitable systems for integration in a tandem device. It was shown that a monolithic DSC/CIGS tandem device has the potential for increased efficiency over a mechanically stacked device due to increased light transmission to the bottom cell, and a monolithic DSC/CIGS device with an initial efficiency of η = 12.2 % was demonstrated. The degradation of the devices — induced by the corrosion of the CIGS cell in contact with the I-/I3- redox mediator — could be retarded with a protective thin conformal ZnO/TiO2 oxide layer coated on the CIGS cell by atomic layer deposition. Finally, an experimentally validated optical and electrical model of the DSC has been developed to assist the optimization process, which is predominantly conducted by empirical means in the DSC research community. The optical model allows to accurately calculate the internal quantum efficiency of devices, i.e. the ratio of extracted electrons to absorbed photons by the dye, a crucial and so far difficult to determine characteristic. Intrinsic parameters — like injection efficiency, electron diffusion length, or distribution of trap states in the TiO2 — can be extracted from experimental steady-state and time-dependent data with the electric model. The model allows to make a comprehensive and quantitative loss analysis of the different optical and electric loss channels in the DSC. The model has been implemented with a graphical user interface for straightforward usage. All three optimization strategies — organic dyes, tandem architecture, and device modeling — developed during this thesis make a valuable contribution to the development and commercialization of inexpensive and high efficiency DSCs. They enable a comprehensive view of the system and pave the way for a systematic analysis and reduction of losses, which has been the ultimate route to success for several established photovoltaic technologies.

EPFL2010

Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells

Michael Graetzel, Jeong-Hyeok Im, Norman Pellet

Perovskite solar cells with submicrometre-thick CH3NH3PbI3 or CH3NH3PbI3-xClx active layers show a power conversion efficiency as high as 15%. However, compared to the best-performing device, the average efficiency was as low as 12%, with a large standard deviation (s.d.). Here, we report perovskite solar cells with an average efficiency exceeding 16% and best efficiency of 17%. This was enabled by the growth of CH3NH3PbI3 cuboids with a controlled size via a two-step spin-coating procedure. Spin-coating of a solution of CH3NH3I with different concentrations follows the spin-coating of PbI2, and the cuboid size of CH3NH3PbI3 is found to strongly depend on the concentration of CH3NH3I. Light-harvesting efficiency and charge-carrier extraction are significantly affected by the cuboid size. Under simulated one-sun illumination, average efficiencies of 16.4% (s.d. +/- 0.35), 16.3% (s.d. +/- 0.44) and 13.5% (s.d. +/- 0.34) are obtained from solutions of CH3NH3I with concentrations of 0.038 M, 0.050 M and 0.063 M, respectively. By controlling the size of the cuboids of CH3NH3PbI3 during their growth, we achieved the best efficiency of 17.01% with a photocurrent density of 21.64 mA cm(-2), open-circuit photovoltage of 1.056 V and fill factor of 0.741.