shuhui

Publication date: 20 March 2019

Source: Joule, Volume 3, Issue 3

Author(s): Ik Jae Park, Jae Hyun Park, Su Geun Ji, Min-Ah Park, Ju Hee Jang, Jin Young Kim

Context & Scale

Summary

Graphical Abstract

Publication date: 20 March 2019

Source: Joule, Volume 3, Issue 3

Author(s): Wei Li, Mengxue Chen, Jinlong Cai, Emma L.K. Spooner, Huijun Zhang, Robert S. Gurney, Dan Liu, Zuo Xiao, David G. Lidzey, Liming Ding, Tao Wang

Context & Scale

Summary

Graphical Abstract

Small‐molecule‐based ternary BHJ solar cells with the SM donor DR3, the SM acceptor ICC6, and the fullerene PC₇₁BM yield high power conversion efficiencies nearing 11% for active layer thicknesses >200 nm. With low geminate and nongeminate recombination, long carrier lifetimes, and high/balanced carrier mobilities, the ternary system maintains PCEs >8% over a wide range of active layer thicknesses within 200–500 nm.

Abstract

Solution‐processed small molecule (SM) solar cells have the prospect to outperform their polymer‐fullerene counterparts. Considering that both SM donors/acceptors absorb in visible spectral range, higher expected photocurrents should in principle translate into higher power conversion efficiencies (PCEs). However, limited bulk‐heterojunction (BHJ) charge carrier mobility (<10^‐4 cm² V^‐1 s^‐1) and carrier lifetimes (<1 µs) often impose active layer thickness constraints on BHJ devices (≈100 nm), limiting external quantum efficiencies (EQEs) and photocurrent, and making large‐scale processing techniques particularly challenging. In this report, it is shown that ternary BHJs composed of the SM donor DR3TBDTT (DR3), the SM acceptor ICC6 and the fullerene acceptor PC₇₁BM can be used to achieve SM‐based ternary BHJ solar cells with active layer thicknesses >200 nm and PCEs nearing 11%. The examinations show that these remarkable figures are the result of i) significantly improved electron mobility (8.2 × 10^‐4 cm² V^‐1 s^‐1), ii) longer carrier lifetimes (2.4 µs), and iii) reduced geminate recombination within BHJ active layers to which PC₇₁BM has been added as ternary component. Optically thick (up to ≈500 nm) devices are shown to maintain PCEs >8%, and optimized DR3:ICC6:PC₇₁BM solar cells demonstrate long‐term shelf stability (dark) for >1000 h, in 55% humidity air environment.

Here, an AI treatment is developed that provides a general method for optimizing the interfacial properties of inorganic perovskite solar cells, which leads to proper band edge bending, decreased surface defects, and a high‐quality quantum dots–modified layer. These changes prove effective at decreasing recombination loss and improving hole extraction efficiency. As a result, the FAI‐treated champion device achieves long‐term stabilized power conversion efficiencies above 14%.

Abstract

Recently, inorganic CsPbI₂Br perovskite is attracting ever‐increasing attention for its outstanding optoelectronic properties and ambient phase stability. Here, an efficient CsPbI₂Br perovskite solar cell (PSC) is developed by: 1) using a dimension‐grading heterojunction based on a quantum dots (QDs)/bulk film structure, and 2) post‐treatment of the CsPbI₂Br QDs/film with organic iodine salt to form an ultrathin iodine‐ion–enriched perovskite layer on the top of the perovskite film. It is found that the above procedures generate proper band edge bending for improved carrier collection, resulting in effectively decreased recombination loss and improved hole extraction efficiency. Meanwhile, the organic capping layer from the iodine salt also surrounds the QDs and tunes the surface chemistry for further improved charge transport at the interface. As a result, the champion device achieves long‐term stabilized power conversion efficiency beyond 14%.

Scalable room‐temperature sputtering deposition of the SnO₂ electron transport layer (ETL) with reduced gap states has been demonstrated. Perovskite solar cells using a SnO₂ ETL show an efficiency up to 20.2% and a T₈₀ lifetime of 625 h. Mini‐modules with a 22.8 cm₂ aperture area show efficiencies over 12% and a T₈₀ lifetime of 515 h, which indicates the upscalability of our method.

Abstract

Stability and scalability have become the two main challenges for perovskite solar cells (PSCs) with the research focus in the field advancing toward commercialization. One of the prerequisites to solve these challenges is to develop a cost‐effective, uniform, and high quality electron transport layer that is compatible with stable PSCs. Sputtering deposition is widely employed for large area deposition of high quality thin films in the industry. Here the composition, structure, and electronic properties of room temperature sputtered SnO₂ are systematically studied. Ar and O₂ are used as the sputtering and reactive gas, respectively, and it is found that a highly oxidizing environment is essential for the formation of high quality SnO₂ films. With the optimized structure, SnO₂ films with high quality have been prepared. It is demonstrated that PSCs based on the sputtered SnO₂ electron transport layer show an efficiency up to 20.2% (stabilized power output of 19.8%) and a T₈₀ operational lifetime of 625 h. Furthermore, the uniform and thin sputtered SnO₂ film with high conductivity is promising for large area solar modules, which show efficiencies over 12% with an aperture area of 22.8 cm² fabricated on 5 × 5 cm² substrates (geometry fill factor = 91%), and a T₈₀ operational lifetime of 515 h.

The molecular order of nonfullerene electron acceptor INPIC‐4F is manipulated by varying the self‐organization time during solution casting. With the presence of solvent vapor, INPIC‐4F grows into spherulites with poor efficiency. On the contrary, casting on hot substrates promotes face‐on π−π stacking, which improves absorption as well as efficient exciton dissociation and balanced charge mobility for a maximum efficiency of 13.1%.

Abstract

Developing a fundamental understanding of the molecular order within the photoactive layer, and the influence therein of solution casting conditions, is a key factor in obtaining high power conversation efficiency (PCE) polymer solar cells. Herein, the molecular order in PBDB‐T:INPIC‐4F nonfullerene solar cells is tuned by control of the molecular organization time during film casting, and the crucial role of retarding the crystallization of INPIC‐4F in achieving high performance is demonstrated. When PBDB‐T:INPIC‐4F is cast with the presence of solvent vapor to prolong the organization time, INPIC‐4F molecules form spherulites with a polycrystalline structure, resulting in large phase separation and device efficiency below 10%. On the contrary, casting the film on a hot substrate is effective in suppressing the formation of the polycrystalline structure, and encourages face‐on π−π stacking of INPIC‐4F. This molecular transformation of INPIC‐4F significantly enhances the absorption ability of INPIC‐4F at long wavelengths and facilitates a fine phase separation to support efficient exciton dissociation and balanced charge transport, leading to the achievement of a maximum PCE of 13.1%. This work provides a rational guide for optimizing nonfullerene polymer solar cells consisting of highly crystallizable small molecular electron acceptors.

Large‐scaled sheet structured 2D multilayer SnS₂ triggers heterogeneous nucleation over the perovskite precursor film, bringing in balanced electron and hole transport at interfaces between electron transporting layers/perovskite and perovskite/hole transporting layer, and suppressing interfacial charge recombination, achieving the highest 20.12% power conversion efficiency that has so far been reported for perovskite solar cells using a 2D electron transporting layer.

Abstract

Herein, a 2D SnS₂ electron transporting layer is reported via self‐assembly stacking deposition for highly efficient planar perovskite solar cells, achieving over 20% power conversion efficiency under AM 1.5 G 100 mW cm⁻² light illumination. To the best of the authors' knowledge, this represents the highest efficiency that has so far been reported for perovskite solar cells using a 2D electron transporting layer. The large‐scaled 2D multilayer SnS₂ sheet structure triggers a heterogeneous nucleation over the perovskite precursor film. The intermolecular Pb⋅⋅⋅S interactions between perovskite and SnS₂ could passivate the interfacial trap states, which suppress charge recombination and thus facilitate electron extraction for balanced charge transport at interfaces between electron transporting layer/perovskite and hole transporting layer/perovskite. This work demonstrates that 2D materials have great potential for high‐performance perovskite solar cells.

Addressing the stability issue of perovskite solar cells for commercial applications

Addressing the stability issue of perovskite solar cells for commercial applications, Published online: 10 December 2018; doi:10.1038/s41467-018-07255-1

When translating photovoltaic technology from laboratory to commercial products, low cost, high power conversion efficiency, and high stability (long lifetime) are the three key metrics to consider in addition to other factors, such as low toxicity, low energy payback time, etc. As one of the most promising photovoltaic materials with high efficiency, today organic–inorganic metal halide perovskites draw tremendous attention from fundamental research, but their practical relevance still remains unclear owing to the notorious short device operation time. In this comment, we discuss the stability issue of perovskite photovoltaics and call for standardized protocols for device characterizations that could possibly match the silicon industrial standards.

Two phthalimide‐based high mobility polymers with a D‐A₁‐D‐A₂ backbone motif are synthesized. A remarkable power conversion efficiency of 12.74 and 13.31% is achieved from fluorinated phthalimide‐difluorobenzothiadiazole and phthalimide‐difluorobenzothiadiazole‐based nonfullerene polymer solar cells, respectively. The results demonstrate that phthalimides are excellent building blocks for enabling polymer semiconductors with outstanding solar cell performances.

Abstract

Highly efficient nonfullerene polymer solar cells (PSCs) are developed based on two new phthalimide‐based polymers phthalimide‐difluorobenzothiadiazole (PhI‐ffBT) and fluorinated phthalimide‐ffBT (ffPhI‐ffBT). Compared to all high‐performance polymers reported, which are exclusively based on benzo[1,2‐b:4,5‐b′]dithiophene (BDT), both PhI‐ffBT and ffPhI‐ffBT are BDT‐free and feature a D‐A₁‐D‐A₂ type backbone. Incorporating a second acceptor unit difluorobenzothiadiazole leads to polymers with low‐lying highest occupied molecular orbital levels (≈−5.6 eV) and a complementary absorption with the narrow bandgap nonfullerene acceptor IT‐4F. Moreover, these BDT‐free polymers show substantially higher hole mobilities than BDT‐based polymers, which are beneficial to charge transport and extraction in solar cells. The PSCs containing difluorinated phthalimide‐based polymer ffPhI‐ffBT achieve a substantial PCE of 12.74% and a large V _oc of 0.94 V, and the PSCs containing phthalimide‐based polymer PhI‐ffBT show a further increased PCE of 13.31% with a higher J _sc of 19.41 mA cm⁻² and a larger fill factor of 0.76. The 13.31% PCE is the highest value except the widely studied BDT‐based polymers and is also the highest among all benzothiadiazole‐based polymers. The results demonstrate that phthalimides are excellent building blocks for enabling donor polymers with the state‐of‐the‐art performance in nonfullerene PSCs and the BDT is not necessary for constructing such donor polymers.

Sn dopants trigger extrinsic self‐trapping of excitons in bulk 2D perovskite crystals, and afford broadband red‐to‐near‐infrared emission, with luminescence quantum yield increase from 0.7% to 6.0% (8.6‐fold). Random potential wells that the Sn dopants create preferentially localize excitons through the fast (sub‐picosecond) exciton diffusion, suppressing the original weak emissions from free and bound excitons.

Abstract

As emerging efficient emitters, metal‐halide perovskites offer the intriguing potential to the low‐cost light emitting devices. However, semiconductors generally suffer from severe luminescence quenching due to insufficient confinement of excitons (bound electron–hole pairs). Here, Sn‐triggered extrinsic self‐trapping of excitons in bulk 2D perovskite crystal, PEA₂PbI₄ (PEA = phenylethylammonium), is reported, where exciton self‐trapping never occurs in its pure state. By creating local potential wells, isoelectronic Sn dopants initiate the localization of excitons, which would further induce the large lattice deformation around the impurities to accommodate the self‐trapped excitons. With such self‐trapped states, the Sn‐doped perovskites generate broadband red‐to‐near‐infrared (NIR) emission at room temperature due to strong exciton–phonon coupling, with a remarkable quantum yield increase from 0.7% to 6.0% (8.6 folds), reaching 42.3% under a 100 mW cm⁻² excitation by extrapolation. The quantum yield enhancement stems from substantial higher thermal quench activation energy of self‐trapped excitons than that of free excitons (120 vs 35 meV). It is further revealed that the fast exciton diffusion involves in the initial energy transfer step by transient absorption spectroscopy. This dopant‐induced extrinsic exciton self‐trapping approach paves the way for extending the spectral range of perovskite emitters, and may find emerging application in efficient supercontinuum sources.

Perovskite solar cells have experienced a rapid development since the first report in 2012 with the power conversion efficiency approaching the theoretical limit. Device stability is still one of the remaining challenges for commercialisation. In this Review, the authors address the important role the charge selective contacts play in the long‐term stability of perovskite solar cells.

Abstract

Lead halide perovskite solar cells have rapidly achieved high efficiencies comparable to established commercial photovoltaic technologies. The main focus of the field is now shifting toward improving the device lifetime. Many efforts have been made to increase the stability of the perovskite compound and charge‐selective contacts. The electron and hole selective contacts are responsible for the transport of photogenerated charges out of the solar cell and are in intimate contact with the perovskite absorber. Besides the intrinsic stability of the selective contacts themselves, the interfaces at perovskite/selective contact and metal/selective contact play an important role in determining the overall operational lifetime of perovskite solar cells. This review discusses the impact of external factors, i.e., heat, UV‐light, oxygen, and moisture, and measured conditions, i.e., applied bias on the overall stability of perovskite solar cells (PSCs). The authors summarize and analyze the reported strategies, i.e., material engineering of selective contacts and interface engineering via the introduction of interlayers in the aim of enhancing the device stability of PSCs at elevated temperatures, high humidity, and UV irradiation. Finally, an outlook is provided with an emphasis on inorganic contacts that is believed to be the key to achieving highly stable PSCs.

A fast, nondestructive, camera‐based method to capture optical bandgap images of perovskite solar cells with micrometer‐scale spatial resolution is developed. This technique allows for the probing of relative variations in optical bandgaps across various solar cells, and for the resolution of bandgap inhomogeneity within the same device due to material degradation and impurities. The results are independently confirmed with other optical‐based techniques.

Abstract

A fast, nondestructive, camera‐based method to capture optical bandgap images of perovskite solar cells (PSCs) with micrometer‐scale spatial resolution is developed. This imaging technique utilizes well‐defined and relatively symmetrical band‐to‐band luminescence spectra emitted from perovskite materials, whose spectral peak locations coincide with absorption thresholds and thus represent their optical bandgaps. The technique is employed to capture relative variations in optical bandgaps across various PSCs, and to resolve optical bandgap inhomogeneity within the same device due to material degradation and impurities. Degradation and impurities are found to both cause optical bandgap shifts inside the materials. The results are confirmed with micro‐photoluminescence spectroscopy scans. The excellent agreement between the two techniques opens opportunities for this imaging concept to become a quantified, high spatial resolution, large‐area characterization tool of PSCs. This development continues to strengthen the high value of luminescence imaging for the research and development of this photovoltaic technology.

Light emitting diodes based on CsPbBr₃|Cs₄PbBr₆ composites are demonstrated with improved quantum efficiency, emission brightness, and device stability. The high brightness can be attributed to the enhanced radiative recombination from CsPbBr₃ crystallites confined in the Cs₄PbBr₆ host matrix. The unfavorable charge transport property of Cs₄PbBr₆ can be circumvented by optimizing the ratio and thickness of the CsPbBr₃|Cs₄PbBr₆ composite perovskite layer.

Abstract

CsPbBr₃ is a promising type of light‐emitting halide perovskite with inorganic composition and desirable thermal stability. The luminescence efficiency of pristine CsPbBr₃ thin films, however, appears to be limited. In this work, light emitting diodes based on CsPbBr₃|Cs₄PbBr₆ composites are demonstrated. Both quantum efficiency and emission brightness are improved significantly compared with similar devices constructed using pure CsPbBr₃. The high brightness can be attributed to the enhanced radiative recombination from CsPbBr₃ crystallites confined in the Cs₄PbBr₆ host matrix. The unfavorable charge transport property of Cs₄PbBr₆ can be circumvented by optimizing the ratio between the host and the guest components and the total thickness of the composite thin films. The inorganic composition of the emitting layer also leads to improved device stability under the condition of continuous operation.

Rapid crystallization is demonstrated to be necessary in achieving high‐quality 2DRP perovskite films by comparing dimethylacetamide (DMAC), N,N‐dimethylformamide, and dimethyl sulfoxide solvents. The improved stability and efficiency are observed using DMAC due to the accelerating crystallization rate of 2DRP perovskite crystals.

Abstract

Due to the additional introduction of bulky organic ammonium and the competition between bulky organic ammonium and methyl ammonium in 2D Ruddlesden‐Popper (2DRP) perovskite, the crystallization process becomes complicated. Here, it is demonstrated that the rapid crystallization controlled by processing solvents plays an important role in achieving high‐quality 2DRP perovskite films. It is found that the processing solvents, e.g., dimethylacetamide (DMAC), N,N‐dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), with a different polarity and boiling point, have almost no effect on crystal structure and phase distribution but have a remarkable effect on crystallization kinetics, crystal growth orientation, and crystallinity of 2DRP perovskite. Compared to polar aprotic solvent DMF and DMSO with a high boiling point, DMAC with low polarity and a suitable boiling point has a weak coordination to lead and ammonium salts and is easy to escape during solution processing, which is able to accelerate the crystallization rate of 2DRP perovskite. Benefitting from the rapid crystallization enabled high‐quality 2DRP perovskite films, the best‐performing device with improved stability and a power conversion efficiency of 12.15% is obtained using DMAC solvent. These findings may give guidance for solvent engineering for highly efficient 2DRP perovskite solar cells in the future.

Two novel spiro‐type hole‐transporting materials (HTMs) SCZF‐5 and SAF‐5 are designed based on different spiro‐cores, SZCF and SAF, respectively, and are applied in the perovskite solar cells. An impressive power conversion efficiency of 20.10% is achieved in the SCZF‐5‐based device, which is obviously higher than that of commercial HTM spiro‐OMeTAD (19.11%) and SAF‐5 (13.93%).

Abstract

Hole‐transporting materials (HTMs) play a significant role in hole transport and extraction for perovskite solar cells (PeSCs). As an important type of HTMs, the spiro‐architecture‐based material is widely used as small organic HTM in PeSCs with good photovoltaic performances. The skeletal modification of spiro‐based HTMs is a critical way of modifying energy level and hole mobility. Thus, many spiro alternatives are developed to optimize the spiro‐type HTMs. Herein, a novel carbazole‐based single‐spiro‐HTM named SCZF‐5 is designed and prepared for efficient PeSCs. In addition, another single‐spiro HTM SAF‐5 with reported 10‐phenyl‐10H‐spiro[acridine‐9,9′‐fluorene] (SAF) core is also synthesized for comparison. Through varying from SAF core to SCZF core as well as comparing with the classic 9,9′‐spiro‐bifluorene, it is found that the new HTM SCZF‐5 exhibits more impressive power conversion efficiency (PCE) of 20.10% than SAF‐5 (13.93%) and the commercial HTM spiro‐OMeTAD (19.11%). On the other hand, the SCZF‐5‐based device also has better durability in lifetime testing, indicating the newly designed SCZF by integrating carbazole into the spiro concept has good potential for developing effective HTMs.

A high dipole moment cation as a large organic spacer reduces the dielectric confinement effect and hence promotes separation of photogenerated electron–hole pairs in layered 2D perovskite materials, which leads to more efficient and stable perovskite solar cells.

Abstract

Layered 2D organic–inorganic hybrid perovskite is appearing as a rising star in the photovoltaic field, thanks to its superior moisture resistance by the organic spacer cations. Unfortunately, these cations lead to high exciton binding energy in the 2D perovskites, which suffers from lower efficiency in the devices. It thus requires a clear criterion to select/design appropriate organic spacer cations to improve the device efficiency based on this class of materials. Here, 2,2,2‐trifluoroethylamine (F₃EA⁺) is introduced to combine with butylammonium (BA⁺) cations as mixed spacers. While BA⁺ enables self‐assembly of 2D perovskite crystals by van der Waals interaction, the introduction of F₃EA⁺ spacers with a high dipole moment suppress nonradiative recombination and promote separation of photogenerated electron–hole pairs by taking the advantage of electronegativity of fluorine. The resultant solar cells based on [(BA)_{1– x} (F₃EA) _x ]₂(MA)₃Pb₄I₁₃ exhibit substantially increased open circuit voltage and fill factor compared with that of (BA)₂(MA)₃Pb₄I₁₃. The champion [(BA)_0.94(F₃EA)_0.06]₂(MA)₃Pb₄I₁₃ solar cell yields a power conversion efficiency of 12.51%, which is among the best performances so far. These findings suggest an effective strategy to design organic spacer cations in layered perovskite for solar cells and other optoelectronic applications.