The photovoltaics of organic–inorganic lead halide perovskite materials have shown rapid improvements in solar cell performance, surpassing the top efficiency of semiconductor compounds such as CdTe and CIGS (copper indium gallium selenide) used in solar cells in just about a decade. Perovskite preparation via simple and inexpensive solution processes demonstrates the immense potential of this thin-film solar cell technology to become a low-cost alternative to the presently commercially available photovoltaic technologies. Significant developments in almost all aspects of perovskite solar cells and discoveries of some fascinating properties of such hybrid perovskites have been made recently. This Review describes the fundamentals, recent research progress, present status, and our views on future prospects of perovskite-based photovoltaics, with discussions focused on strategies to improve both intrinsic and extrinsic (environmental) stabilities of high-efficiency devices. Strategies and challenges regardi...

Halide Perovskite Photovoltaics: Background, Status, and Future Prospects

The bulk-heterojunction blend of an electron donor and an electron acceptor material is the key component in a solution-processed organic photovoltaic device. In the past decades, a p-type conjugated polymer and an n-type fullerene derivative have been the most commonly used electron donor and electron acceptor, respectively. While most advances of the device performance come from the design of new polymer donors, fullerene derivatives have almost been exclusively used as electron acceptors in organic photovoltaics. Recently, nonfullerene acceptor materials, particularly small molecules and oligomers, have emerged as a promising alternative to replace fullerene derivatives. Compared to fullerenes, these new acceptors are generally synthesized from diversified, low-cost routes based on building block materials with extraordinary chemical, thermal, and photostability. The facile functionalization of these molecules affords excellent tunability to their optoelectronic and electrochemical properties. Within t...

Nonfullerene Acceptor Molecules for Bulk Heterojunction Organic Solar Cells

Perovskite solar cells (PSCs) with efficiencies greater than 20% have been realized only with expensive organic hole-transporting materials. We demonstrate PSCs that achieve stabilized efficiencies exceeding 20% with copper(I) thiocyanate (CuSCN) as the hole extraction layer. A fast solvent removal method enabled the creation of compact, highly conformal CuSCN layers that facilitate rapid carrier extraction and collection. The PSCs showed high thermal stability under long-term heating, although their operational stability was poor. This instability originated from potential-induced degradation of the CuSCN/Au contact. The addition of a conductive reduced graphene oxide spacer layer between CuSCN and gold allowed PSCs to retain >95% of their initial efficiency after aging at a maximum power point for 1000 hours under full solar intensity at 60°C. Under both continuous full-sun illumination and thermal stress, CuSCN-based devices surpassed the stability of spiro-OMeTAD–based PSCs.

https://science.sciencemag.org/content/sci/early/2017/09/27/science.aam5655.full.pdf

Perovskite solar cells with CuSCN hole extraction layers yield stabilized efficiencies greater than 20

Organic and inorganic hybrid perovskites (e.g., CH(3)NH(3)PbI(3)), with advantages of facile processing, tunable bandgaps, and superior charge-transfer properties, have emerged as a new class of revolutionary optoelectronic semiconductors promising for various applications. Perovskite solar cells constructed with a variety of configurations have demonstrated unprecedented progress in efficiency, reaching about 20% from multiple groups after only several years of active research. A key to this success is the development of various solution-synthesis and film-deposition techniques for controlling the morphology and composition of hybrid perovskites. The rapid progress in material synthesis and device fabrication has also promoted the development of other optoelectronic applications including light-emitting diodes, photodetectors, and transistors. Both experimental and theoretical investigations on organic-inorganic hybrid perovskites have enabled some critical fundamental understandings of this material system. Recent studies have also demonstrated progress in addressing the potential stability issue, which has been identified as a main challenge for future research on halide perovskites. Here, we review recent progress on hybrid perovskites including basic chemical and crystal structures, chemical synthesis of bulk/nanocrystals and thin films with their chemical and physical properties, device configurations, operation principles for various optoelectronic applications (with a focus on solar cells), and photophysics of charge-carrier dynamics. We also discuss the importance of further understanding of the fundamental properties of hybrid perovskites, especially those related to chemical and structural stabilities.

Organic–inorganic hybrid lead halide perovskites for optoelectronic and electronic applications

With rapid progress in a power conversion efficiency (PCE) to reach 25%, metal halide perovskite-based solar cells became a game-changer in a photovoltaic performance race. Triggered by the development of the solid-state perovskite solar cell in 2012, intense follow-up research works on structure design, materials chemistry, process engineering, and device physics have contributed to the revolutionary evolution of the solid-state perovskite solar cell to be a strong candidate for a next-generation solar energy harvester. The high efficiency in combination with the low cost of materials and processes are the selling points of this cell over commercial silicon or other organic and inorganic solar cells. The characteristic features of perovskite materials may enable further advancement of the PCE beyond those afforded by the silicon solar cells, toward the Shockley-Queisser limit. This review summarizes the fundamentals behind the optoelectronic properties of perovskite materials, as well as the important approaches to fabricating high-efficiency perovskite solar cells. Furthermore, possible next-generation strategies for enhancing the PCE over the Shockley-Queisser limit are discussed.

High-Efficiency Perovskite Solar Cells.

Although inorganic hole-transport materials usually possess high chemical stability, hole mobility, and low cost, the efficiency of most of inorganic hole conductor-based perovskite solar cells is still much lower than that of the traditional organic hole conductor-based cells. Here, we have successfully fabricated high quality CH3NH3PbI3 films on top of a CuSCN layer by utilizing a one-step fast deposition-crystallization method, which have lower surface roughness and smaller interface contact resistance between the perovskite layer and the selective contacts in comparison with the films prepared by a conventional two-step sequential deposition process. The average efficiency of the CuSCN-based inverted planar CH3NH3PbI3 solar cells has been improved to 15.6% with a highest PCE of 16.6%, which is comparable to that of the traditional organic hole conductor-based cells, and may promote wider application of the inexpensive inorganic materials in perovskite solar cells.

CuSCN-Based Inverted Planar Perovskite Solar Cell with an Average PCE of 15.6%.

In this work, a fully tin-based, mixed-organic-cation perovskite absorber (FA) x (MA)1-x SnI3 (FA = NH2CH = NH2+, MA = CH3NH3+) for lead-free perovskite solar cells (PSCs) with inverted structure is presented. By optimizing the ratio of FA and MA cations, a maximum power conversion efficiency of 8.12% is achieved for the (FA)0.75(MA)0.25SnI3-based device along with a high open-circuit voltage of 0.61 V, which originates from improved perovskite film morphology and inhibits recombination process in the device. The cation-mixing approach proves to be a facile method for the efficiency enhancement of tin-based PSCs.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201700204

Mixed-Organic-Cation Tin Iodide for Lead-Free Perovskite Solar Cells with an Efficiency of 8.12.

It is extremely significant to study the trap state passivation and minimize the trap states of perovskite to achieve high-performance perovskite solar cells (PSCs). Here, we have first revealed and demonstrated that a novel p-type conductor Cu(thiourea)I [Cu(Tu)I] incorporated in perovskite layer can effectively passivate the trap states of perovskite via interacting with the under-coordinated metal cations and halide anions at the perovskite crystal surface. The trap state energy level of perovskite can be shallowed from 0.35–0.45 eV to 0.25–0.35 eV. In addition, the incorporated Cu(Tu)I can participate in constructing the p–i bulk heterojunctions with perovskite, leading to an increase of the depletion width from 126 to 265 nm, which is advantageous for accelerating hole transport and reducing charge carrier recombination. For these two synergistic effects, Cu(Tu)I can play a much better role than that of the traditional p-type conductor CuI, probably due to its identical valence band maximum with that...

A Breakthrough Efficiency of 19.9% Obtained in Inverted Perovskite Solar Cells by Using an Efficient Trap State Passivator Cu(thiourea)I

Hybrid organic–inorganic halide-perovskite-based solar cells have achieved notable progress. A hot topic in this field is exploring inexpensive, stable and effective hole-transporting materials (HTMs) in order to improve the device performance and be favorable for large-scale production in the future. The HTMs have been proven to be an important component of perovskite solar cells, which can form selective contact being favorable for reducing charge recombination and effective hole collection, thus resulting in the enhancement of the open-circuit voltage and the fill factor. Here, an overview of the design and development of HTMs is given, mainly divided into conductive polymers, inorganic p-type semiconductors in inverted-structure-based planar perovskite solar cells. The influences of their mobility, work function and film property on device performance are discussed.

Senyun Ye

Papers

CuSCN-Based Inverted Planar Perovskite Solar Cell with an Average PCE of 15.6%.

Mixed-Organic-Cation Tin Iodide for Lead-Free Perovskite Solar Cells with an Efficiency of 8.12.

A Breakthrough Efficiency of 19.9% Obtained in Inverted Perovskite Solar Cells by Using an Efficient Trap State Passivator Cu(thiourea)I

Hole‐Transporting Materials in Inverted Planar Perovskite Solar Cells

A 19.0% efficiency achieved in CuOx-based inverted CH3NH3PbI3−xClx solar cells by an effective Cl doping method