Ligang Yuan

The latest breakthroughs in interface and defect engineering as applied to metal halide perovskite solar cells and light‐emitting diodes (LEDs) are reviewed in order to shed light on their necessity and importance in tuning the optoelectronic properties of devices in an attempt to realize the best‐performing solar cells and LEDs.

Abstract

Metal halide perovskites have been in the limelight in recent years due to their enormous potential for use in optoelectronic devices, owing to their unique combination of properties, such as high absorption coefficient, long charge‐carrier diffusion lengths, and high defect tolerance. Perovskite‐based solar cells and light‐emitting diodes (LEDs) have achieved remarkable breakthroughs in a comparatively short amount of time. As of writing, a certified power conversion efficiency of 22.7% and an external quantum efficiency of over 10% have been achieved for perovskite solar cells and LEDs, respectively. Interfaces and defects have a critical influence on the properties and operational stability of metal halide perovskite optoelectronic devices. Therefore, interface and defect engineering are crucial to control the behavior of the charge carriers and to grow high quality, defect‐free perovskite crystals. Herein, a comprehensive review of various strategies that attempt to modify the interfacial characteristics, control the crystal growth, and understand the defect physics in metal halide perovskites, for both solar cell and LED applications, is presented. Lastly, based on the latest advances and breakthroughs, perspectives and possible directions forward in a bid to transcend what has already been achieved in this vast field of metal halide perovskite optoelectronic devices are discussed.

The factors that limit the luminescence efficiency (LE) of metal halide perovskite (MHP) light‐emitting diodes (PeLEDs) are reviewed by categorizing them into i) photophysical properties of MHPs, ii) morphological factors, and iii) problems caused by device architectures. Various strategies to overcome those LE‐limiting factors in MHPs and PeLEDs, and research directions to further increase the LE of MHPs are discussed.

Abstract

Metal‐halide perovskites (MHPs) are well suited to be vivid natural color emitters due to their superior optical and electrical properties, such as narrow emission linewidths, easily and widely tunable emission wavelengths, low material cost, and high charge carrier mobility. Since the first development of MHP light‐emitting diodes (PeLEDs) in 2014, many researchers have tried to understand the properties of MHP emitters and the limitations to luminescence efficiency (LE) of PeLEDs, and have devoted efforts to increase the LE of MHP emitters and PeLEDs. Within three and half years, PeLEDs have shown rapidly increased LE from external quantum efficiency ≈0.1% to ≈14.36%. Herein, the factors that limit the LE of PeLEDs are reviewed; the factors are characterized into the following groups: i) photophysical properties of MHP crystals, ii) morphological factors of MHP layers, and iii) problems caused by device architectures. Then, the strategies to overcome those luminescence‐limiting factors in MHP emitters and PeLEDs are critically evaluated. Finally, research directions to further increase the LE of MHP emitters and the potential of MHPs as a core component in next‐generation displays and solid‐state lightings are suggested.

The approaches and the consequences of lead replacement in lead halide perovskite solar cells are summarized. The theoretical understanding of the electronic, optical, and defect properties of lead and lead‐free halide perovskites and perovskite derivatives is reviewed, explaining why all reported lead‐free perovskite solar cells underperform compared to lead halide perovskite solar cells.

Abstract

Despite the exciting progress on power conversion efficiencies, the commercialization of the emerging lead (Pb) halide perovskite solar cell technology still faces significant challenges, one of which is the inclusion of toxic Pb. Searching for Pb‐free perovskite solar cell absorbers is currently an attractive research direction. The approaches used for and the consequences of Pb replacement are reviewed herein. Reviews on the theoretical understanding of the electronic, optical, and defect properties of Pb and Pb‐free halide perovskites and perovskite derivatives are provided, as well as the experimental results available in the literature. The theoretical understanding explains well why Pb halide perovskites exhibit superior photovoltaic properties, but Pb‐free perovskites and perovskite derivatives do not.

In parallel with the tremendous progress in the efficiency of perovskite solar cells, research on the issue of instability has attracted enormous attention. In this review, the strategies to enhance the stability from the perspectives of the device structure, the photoactive layer, hole‐ and electron‐transporting layers, electrode materials, and device encapsulation are portrayed.

Abstract

In this review, the factors influencing the power conversion efficiency (PCE) of perovskite solar cells (PSCs) is emphasized. The PCE of PSCs has remarkably increased from 3.8% to 23.7%, but on the other hand, poor stability is one of the main facets that creates a huge barrier in the commercialization of PSCs. Herein, a concise overview of the current efforts to enhance the stability of PSCs is provided; moreover, the degradation causes and mechanisms are summarized. The strategies to improve device stability are portrayed in terms of structural effects, a photoactive layer, hole‐ and electron‐transporting layers, electrode materials, and device encapsulation. Last but not least, the economic feasibility of PSCs is also vividly discussed.

The use of hydrogels enables transfer‐printing of poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate thin films from glass substrates onto various soft substrates. Taking advantage of this technique, skin‐attachable organic electrochemical transistors (OECTs) are fabricated on commercially available tattoo paper. Wearable tattoo‐OECTs are further demonstrated with the integration of a wireless readout system.

Abstract

The use of conducting polymers such as poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) for the development of soft organic bioelectronic devices, such as organic electrochemical transistors (OECTs), is rapidly increasing. However, directly manipulating conducting polymer thin films on soft substrates remains challenging, which hinders the development of conformable organic bioelectronic devices. A facile transfer‐printing of conducting polymer thin films from conventional rigid substrates to flexible substrates offers an alternative solution. In this work, it is reported that PEDOT:PSS thin films on glass substrates, once mixed with surfactants, can be delaminated with hydrogels and thereafter be transferred to soft substrates without any further treatments. The proposed method allows easy, fast, and reliable transferring of patterned PEDOT:PSS thin films from glass substrates onto various soft substrates, facilitating their application in soft organic bioelectronics. By taking advantage of this method, skin‐attachable tattoo‐OECTs are demonstrated, relevant for conformable, imperceptible, and wearable organic biosensing.

Organic photovoltaic (OPV) cells promise to have a good photovoltaic performance under the indoor light environment. Via optimizing the active layers, 1 cm² OPV cells are fabricated and a top power conversion efficiency of 22% under 1000 lux illumination is demonstrated.

Abstract

Organic photovoltaic (OPV) technologies have the advantages of fabricating larger‐area and light‐weight solar panels on flexible substrates by low‐cost roll‐to‐toll production. Recently, OPV cells have achieved many significant advances with power conversion efficiency (PCE) increasing rapidly. However, large‐scale solar farms using OPV modules still face great challenges, such as device stability. Herein, the applications of OPV cells in indoor light environments are studied. Via optimizing the active layers to have a good match with the indoor light source, 1 cm² OPV cells are fabricated and a top PCE of 22% under 1000 lux light‐emitting diode (2700 K) illumination is demonstrated. In this work, the light intensities are measured carefully. Incorporated with the external quantum efficiency and photon flux spectrum, the integral current densities of the cells are calculated to confirm the reliability of the photovoltaic measurement. In addition, the devices show much better stability under continuous indoor light illumination. The results suggest that designing wide‐bandgap active materials to meet the requirements for the indoor OPV cells has a great potential in achieving higher photovoltaic performance.

Causes of intrinsic and extrinsic instability of perovskite materials and related mechanisms are discussed in terms of their chemical‐bonding nature. Understanding the critical mechanisms rationalizes the chemical approaches to mitigate the degradation in perovskite solar cells.

Abstract

Chemical bonding dictates not only the optoelectronic properties of materials, but also the intrinsic and extrinsic stability of materials. Here, the causes of intrinsic and extrinsic instability of perovskite materials are reviewed considering their correlation with the unique chemical‐bonding nature of perovskite materials. There are a number of key standardized stability tests established by the International Electrotechnical Commission for commercialized photovoltaic modules. Based on these procedures, the possible causes and related mechanisms of the material degradation that can arise during the test procedures are identified, which are discussed in terms of their chemical bonds. Based on the understanding of the critical causes, promising strategies for mitigating the causes to enhance the stability of perovskite solar cells are summarized. The stability of the state‐of‐the‐art perovskite solar cells implies a need for the development of improved stability‐testing protocols to move onto the next stage toward commercialization.

Structure steering of MS _x /TiO₂ heterojunctions in photodegradation, water splitting, and CO₂ conversion are reviewed herein, mainly focusing on improved light harvesting, effective interfacial charge transfer, and affordable active sites for surface chemical reactions. Special focus is given to the quantum dot sensitized solar cells.

Abstract

Developing efficient and affordable catalysts is of great significance for energy and environmental sustainability. Heterostructure photocatalysts exhibit a better performance than either of the parent phases as it changes the band bending at the interfaces and provides a driving force for carrier separation, thus mitigating the effects of carrier recombination and back‐reaction. Herein, the photo/electrochemical applications of a variety of metal sulfides (MS _x ) (MoS₂, CdS, CuS, PbS, SnS₂, ZnS, Ag₂S, Bi₂S₃, and In₂S₃)/TiO₂ heterojunctions are summarized, including organic degradation, water splitting, and CO₂ reduction conversion. First, a general introduction on each MS _x material (especially bandgap structures) will be given. Then the photo/electrochemical applications based on MS _x /TiO₂ heterostructures are reviewed from the perspective of light harvesting ability, charge carrier separation and transportation, and surface chemical reactions. Special focus is given to CdS/TiO₂ and PbS/TiO₂‐based quantum dot sensitized solar cells. Ternary composites by taking advantages of positive synergetic effects are also well summarized. Finally, conclusions are made regarding approaches for structure design, and the authors' perspective on future architectural design and electrode construction is given. This work will make up the gap for TiO₂ nanocomposites and shed light on the fabrication of more efficient MS _x ‐metal oxide junctions in photo/electrochemical applications.

Large‐area perovskite films are deposited by a scalable blade coating method on flexible glass substrates at room temperature and in an ambient environment. Additive engineering by ammonium chloride effectively controls the perovskite crystallization and improves film quality. The flexible perovskite module achieves a record efficiency of 15.86% on a large aperture area of 42.9 cm².

Abstract

Perovskite materials are good candidates for flexible photovoltaic applications due to their strong absorption and low‐temperature processing, but efficient flexible perovskite modules have not yet been realized. Here, a record efficiency flexible perovskite solar module is demonstrated by blade coating high‐quality perovskite films on flexible Corning Willow Glass using additive engineering. Ammonium chloride (NH₄Cl) is added into the perovskite precursor solution to retard the nucleation which prevents voids formation at the interface of perovskite and glass. The addition of NH₄Cl also suppresses the formation of PbI₂ and reduces the trap density in the perovskite films. The implementation of NH₄Cl enables the fabrication of single junction flexible perovskite solar devices with an efficiency of 19.72% on small‐area cells and a record aperture efficiency of 15.86% on modules with an area of 42.9 cm². This work provides a simple way to scale up high‐efficiency flexible perovskite modules for various applications.

Publication date: February 2020

Source: Solar Energy Materials and Solar Cells, Volume 205

Author(s): Çağla Odabaşı, Ramazan Yıldırım

A postdeposition treatment is designed to modify the photoactive layer of perovskite solar cell (PSC) by spin‐coating p‐aminobenzoic acid (PABA). The PABA treatment can enhance V _OC, fill factor, and power conversion efficiency. The performance improvement is attributed to the suppression of carrier trap states. PABA post‐treatment provides a promising strategy and potential option for high performance solar cells.

Abstract

Various approaches of interface engineering are shown to be effective in improving the device performance of organic–inorganic hybrid perovskite solar cells (PSCs). The modification of the photoactive layer of PSC, CH₃NH₃PbI₃ (MAPbI₃), by spin‐coating a layer of p‐aminobenzoic acid (PABA), which can significantly enhance the open‐circuit voltage (V _OC), the fill factor (FF), and the power conversion efficiency (PCE) of PSCs, is herein reported. The champion device shows a short‐circuit current (J _SC) of 22.83 mA cm⁻², V _OC of 1.167 V, FF of 0.768, and PCE of 20.47%. The improvement in photovoltaic performance is attributed to the suppression of carrier trap states and the improvement in the morphologies of perovskite films. This work demonstrates a simple and effective protocol to enhance the device performance, and provides an insight into the influence of PABA post‐treatment on the charge carrier dynamics.

Photoluminescence heterogeneities in films of the Ruddlesden–Popper perovskite phenylethylammonium lead iodide are systematically investigated. The stoichiometry of the precursor solution has a strong impact on the optical quality of the resulting film. Even in films cast from stoichiometric solutions, large spatial variations in trap state density exist and are correlated to a thermally‐activated nonradiative recombination channel.

Abstract

2D Ruddlesden–Popper perovskites are interesting for a variety of applications owing to their tunable optical properties and their excellent ambient stability. As these materials are processable from solution, they hold the promise of procuring flexible and cost‐effective films through large‐scale fabrication techniques. However, such solution‐based deposition techniques often induce large degrees of heterogeneity due to poorly controlled crystallization. The microscopic properties of films of (PEA)₂PbI₄ cast from precursor solutions of different stoichiometry are therefore investigated. The stoichiometry of the precursor solution is found to have a large impact on the crystallinity, morphology, and optical properties of the resulting thin films. Even for films cast from stoichiometric precursors, differences in photoluminescence intensities occur on a subgranular level. The heterogeneity in these films is found to be thermally activated with an activation energy of 0.4 eV for the emergence of local variations in nonradiative recombination rates. The spatial variation in the distribution of trap states is attributed to local fluctuations in the stoichiometry. In line with this, the surface can successfully be passivated by providing an excess of phenylethylammonium iodide (PEAI) to an as‐cast film, enhancing the photoluminescence by as much as 85% without significantly altering the film's morphology.

Here a method to grow wafer‐size thin halide perovskite multiple crystals on aqueous solution surface is reported. The efficiency of lateral‐structure solar cells based on the single‐crystalline perovskite wafer reaches 5.9%.

Abstract

Solar‐grade single or multiple crystalline wafers are needed in large quantities in the solar cell industry, and are generally formed by a top‐down process from crystal ingots, which causes a significant waste of materials and energy during slicing, polishing, and other processing. Here, a bottom‐up technique that allows the growth of wafer‐size hybrid perovskite multiple crystals directly from aqueous solution is reported. Single‐crystalline hybrid perovskite wafers with centimeter size are grown at the top surface of a perovskite precursor solution. As well as saving raw materials, this method provides unprecedented advantages such as easily tunable thickness and rapid growth of the crystals. These crystalline wafers show high crystallinity, broader light absorption, and a long carrier recombination lifetime, comparable with those of bulk single crystals. Lateral‐structure perovskite solar cells made of these crystals demonstrate a record power conversion efficiency of 5.9%.

Tetrafluoroborate (BF₄ ⁻) anion can be successfully incorporated into a mixed‐ion perovskite crystal frame, leading to lattice relaxation and a longer photoluminescence lifetime, higher recombination resistance, and 1–2 orders magnitude lower trap density in prepared perovskite solar cells. These advantages result in an improved power conversion efficiency of 20.16% from 17.55% due to enhanced open‐circuit voltage and fill factor.

Abstract

Composition engineering is a particularly simple and effective approach especially using mixed cations and halide anions to optimize the morphology, crystallinity, and light absorption of perovskite films. However, there are very few reports on the use of anion substitutions to develop uniform and highly crystalline perovskite films with large grain size and reduced defects. Here, the first report of employing tetrafluoroborate (BF₄ ⁻) anion substitutions to improve the properties of (FA = formamidinium, MA = methylammonium (FAPbI₃)_0.83(MAPbBr₃)_0.17) perovskite films is demonstrated. The BF₄ ⁻ can be successfully incorporated into a mixed‐ion perovskite crystal frame, leading to lattice relaxation and a longer photoluminescence lifetime, higher recombination resistance, and 1–2 orders magnitude lower trap density in prepared perovskite films and derived solar cells. These advantages benefit the performance of perovskite solar cells (PVSCs), resulting in an improved power conversion efficiency (PCE) of 20.16% from 17.55% due to enhanced open‐circuit voltage (V _OC) and fill factor. This is the highest PCE for BF₄ ⁻ anion substituted lead halide PVSCs reported to date. This work provides insight for further exploration of anion substitutions in perovskites to enhance the performance of PVSCs and other optoelectronic devices.

Scalable room‐temperature sputtering deposition of the SnO₂ electron transport layer (ETL) with reduced gap states is 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.

New‐type 2D/3D perovskites are designed by first introducing two hydrophobic ammonium salt cations with halogen functional groups into 3D perovskite. The 2D/3D perovskite devices exhibit an optimal power conversion efficiency as high as 20.08% under 1 sun irradiation and superior stability when exposed to humidity, temperature, and continuous UV irradiation.

Abstract

2D perovskites have attracted extensive attention due to their excellent stability compared with 3D perovskites. However, the intrinsic hydrophilicity of introduced alkylammonium salts effects the humidity stability of 2D/3D perovskites. Devices based on longer chain alkylammonium salts show improvement in hydrophobicity but lower efficiency due to the poorer charge transport among various layers. To solve this issue, two hydrophobic short‐chain alkylammonium salts with halogen functional groups (2‐chloroethylamine, CEA⁺ and 2‐bromoethylamine, BEA⁺) are introduced into (Cs_0.1FA_0.9)Pb(I_0.9Br_0.1)₃ 3D perovskites to form 2D/3D perovskite structure, which achieve high‐quality perovskite films with better crystallization and morphology. The optimal 2D/3D perovskite solar cells (PSCs) with 5% CEA⁺ display a power conversion efficiency (PCE) as high as 20.08% under 1 sun irradiation. Because of the notable hydrophobicity of alkylammonium cations with halogen functional groups and the formed 2D/3D perovskite structure, the optimal PSCs exhibit superior moisture resistance and retain 92% initial PCE after aging at 50 ± 5% relative humidity for 2400 h. This work opens up a new direction for the design of new‐type 2D/3D PSCs with improved performance by employing proper alkylammonium salts with different functional groups.

Here, urea treatment of hole transport layer (e.g., poly(3,4‐ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS)) is reported to effectively tune its morphology, conductivity, and work function for improving the efficiency and stability of inverted CH₃NH₃PbI₃ perovskite solar cells.

Abstract

Interface engineering is critical to the development of highly efficient perovskite solar cells. Here, urea treatment of hole transport layer (e.g., poly(3,4‐ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS)) is reported to effectively tune its morphology, conductivity, and work function for improving the efficiency and stability of inverted MAPbI₃ perovskite solar cells (PSCs). This treatment has significantly increased MAPbI₃ photovoltaic performance to 18.8% for the urea treated PEDOT:PSS PSCs from 14.4% for pristine PEDOT:PSS devices. The use of urea controls phase separation between PEDOT and PSS segments, leading to the formation of a unique fiber‐shaped PEDOT:PSS film morphology with well‐organized charge transport pathways for improved conductivity from 0.2 S cm⁻¹ for pristine PEDOT:PSS to 12.75 S cm⁻¹ for 5 wt% urea treated PEDOT:PSS. The urea‐treatment also addresses a general challenge associated with the acidic nature of PEDOT:PSS, leading to a much improved ambient stability of PSCs. In addition, the device hysteresis is significantly minimized by optimizing the urea content in the treatment.

The application of formamidinium (FA)‐based perovskite solar cells has largely been hindered by phase transition from the dark cubic phase to yellow orthorhombic phase. Here, a highly efficient and phase stable FA‐based perovskite solar cell is fabricated by using NbF₅ as a novel additive. NbF₅ can improve the quality of perovskite films and effectively suppress the formation of the yellow δ‐phase.

Abstract

The HC(NH₂)₂ ⁺(FA⁺) is a well‐known substitute to CH₃NH₃ ⁺(MA⁺) for its capability to extend light utilization for improved power conversion efficiency for perovskite solar cells; unfortunately, the dark cubic phase (α‐phase) can easily transition to the yellow orthorhombic phase (δ‐phase) at room temperature, an issue that prevents its commercial application. In this report, an inorganic material (NbF₅) is developed to stabilize the desired α‐phase perovskite material by incorporating NbF₅ additive into the perovskite films. It is found that the NbF₅ additive effectively suppresses the formation of the yellow δ‐phase in the perovskite synthesis and aging process, thus enhancing the humidity and light‐soaking stability of the perovskite film. As a result, the perovskite solar cells with the NbF₅ additive exhibit improved air stability by tenfold, retaining nearly 80% of their initial efficiency after aging in air for 50 d. In addition, under full‐sun AM 1.5 G illumination of a xenon lamp without any UV‐reduction, the perovskite solar cells with the NbF₅ additive also show fivefold improved illumination stability than the control devices without NbF₅.

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.

The current status of both low‐bandgap mixed Sn‐Pb perovskite solar cells and all‐perovskite tandem solar cells are summarized in this review. Possible strategies for further improving the performance and stability of the devices based on mixed Sn‐Pb perovskites are also discussed.

Abstract

Efficient organic–inorganic metal halide perovskite absorbers have gained tremendous research interest in the past decade due to their super optoelectronic properties and defect tolerance. Lead (Pb) halide perovskites enable highly efficient perovskite solar cells (PSCs) with a record power conversion efficiency (PCE) of over 23%. However, the energy bandgaps of Pb halide perovskites are larger than the optimal bandgap for single junction solar cells, governed by the Shockley–Queisser (SQ) radiative limit. Mixed tin (Sn)‐Pb halide perovskites have drawn significant attention, since their bandgap can be tuned to below 1.2 eV, which opens a door for fabricating all‐perovskite tandem solar cells that can break the SQ radiative limit. This review summarizes the development of low‐bandgap mixed Sn‐Pb PSCs and their applications in all‐perovskite tandem solar cells. Its aim is to facilitate the development of new approaches to achieve high efficiency low‐bandgap single‐junction mixed Sn‐Pb PSCs and all‐perovskite tandem solar cells.

Their superior optoelectronic properties and stability endow organic–inorganic halide perovskite single crystals great potential for high‐efficiency and stable photovoltaics. This progress report summarizes recent exciting developments and future perspectives for perovskite single crystal solar cells, which may attract more attention and provide guidelines for further development in this emerging field.

Abstract

The efficiency of perovskite solar cells has increased to a certified value of 25.2% in the past 10 years, benefiting from the superior properties of metal halide perovskite materials. Compared with the widely investigated polycrystalline thin films, single crystal perovskites without grain boundaries have better optoelectronic properties, showing great potential for photovoltaics with higher efficiency and stability. Additionally, single crystal perovskite solar cells are a fantastic model system for further investigating the working principles related to the surface and grain boundaries of perovskite materials. Unfortunately, only a handful of groups have participated in the development of single crystal perovskite solar cells; thus, the development of this area lags far behind that of its polycrystalline counterpart. Therefore, a review paper that discusses the recent developments and challenges of single crystal perovskite solar cells is urgently required to provide guidelines for this emerging field. In this progress report, the optical and electrical properties of single crystal and polycrystalline perovskite thin films are compared, followed by the recent developments in the growth of single crystal perovskite thin films and the photovoltaic applications of this material. Finally, the challenges and perspectives of single crystal perovskite solar cells are discussed in detail.

Ternary organic solar cells based on nonfullerene 3TP3T‐4F and 3TP3T‐IC guest acceptors and PM:Y6 binary host are investigated. The incorporation of 15% 3TP3T‐4F leads to an impressive efficiency of 16.7% (certified as 16.2%) for PM6:Y6:3TP3T‐4F ternary organic solar cells, higher than that (15.6%) of PM6:Y6:3TP3T‐4F devices, which is mainly ascribed to the compatibility between the third component and the host materials.

Abstract

A ternary structure has been demonstrated as being an effective strategy to realize high power conversion efficiency (PCE) in organic solar cells (OSCs); however, general materials selection rules still remain incompletely understood. In this work, two nonfullerene small‐molecule acceptors 3TP3T‐4F and 3TP3T‐IC are synthesized and incorporated as a third component in PM6:Y6 binary blends. The photovoltaic behaviors in the resultant ternary OSCs differ significantly, despite the comparable energy levels. It is found that incorporation of 15% 3TP3T‐4F into the PM6:Y6 blend results in facilitating exciton dissociation, increasing charge transport, and reducing trap‐assisted recombination. All these features are responsible for the enlarged PCE of 16.7% (certified as 16.2%) in the PM6:Y6:3TP3T‐4F ternary OSCs, higher than that (15.6%) in the 3TP3T‐IC containing ternary devices. The performance differences are mainly ascribed to the compatibility between the third component and the host materials. The 3TP3T‐4F guest acceptor exhibits an excellent compatibility with Y6, tending to form well‐mixed phases in the ternary blend without disrupting the favored bicontinuous transport networks, whereas 3TP3T‐IC displays a morphological incompatibility with Y6. This work highlights the importance of considering the compatibility for materials selection toward high‐efficiency ternary organic OSCs.

Herein, it is demonstrated that solution‐processed dopant‐free spiro molecules can serve as superior hole‐transport materials (HTMs) to fabricate efficient inverted (p‐i‐n) perovskite solar cells. An entirely solution process is achieved by rational choice of orthogonal solvent, which allows to deposit uniform and pinhole‐free perovskite films without compromising the hole‐extraction capability of the spiro interlayers.

Spiro‐linked compounds have been used as benchmark hole‐transport materials (HTMs) for the construction of efficient normal architecture (n‐i‐p) perovskite solar cells (PSCs). However, the heavy reliance on the use of dopants not only complicates the device fabrication but imposes long‐term stability concern of the devices. Herein, it is reported that solution‐processed dopant‐free spiro molecules can serve as superior HTMs to fabricate efficient inverted (p‐i‐n) PSCs. Rational choice of orthogonal solvent allows us to solution deposit uniform and pinhole‐free perovskite films without compromising the hole‐extraction capability of the spiro‐based interface layers. To illustrate the generality of the strategy, three spiro‐linked molecules are investigated side by side as HTMs in one‐step solution‐processed CH₃NH₃PbI₃ PSCs. Due to the favored energy‐level alignment and high hole mobility, solar cells based on the HTM of spiro‐TTB yield a high efficiency of 18.38% with open‐circuit voltages (V _OC) up to 1.09 V. These results suggest that small molecular HTMs commonly developed for normal structure devices can be of great potential to fabricate cost‐effective and highly efficient inverted PSCs.

Quantum dots are regarded as neutralized charged intermedia to transfer ligands for interfacial modification, which can significantly adjust surface electric properties to reduce V _OC loss and improve device performance. A stable V _OC enhancement with excellent reproducibility is fulfilled by simple solution‐processed QDs modification, achieving 20.6% power conversion efficiency (PCE) and enhanced stability.

The tremendous passion for inverted planar heterojunction perovskite solar cells (PSCs) is originated from their great tendency in the roll‐to‐roll process‐compatible fabrication and huge potential for integration into tandem solar cells. But the device efficiency is still lower than regular structured PSCs. Engineering of the cathode interface to efficiently control and reduce V _OC loss lights a lamp for increasing electrochemical properties and boosting overall performance. Herein, a simple interfacial modification strategy is developed by introducing a hybrid ligand interfacial layer to reduce V _OC loss in PSCs with inverted planar structure. Heavily washed QDs are used as neutral charged intermedia to enable alloying reaction to transfer ligands without damage to perovskite (PVK). A band bending is immediately generated on the top surface of PVK film after QDs modification, which is directly confirmed by ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe force microscopy (KPFM). This contributes to ≈50 mV reduced V _OC loss, leading to a V _OC of 1.15 V and a power conversion efficiency (PCE) of 20.6% in inverted PSCs. Meanwhile, enhanced stability is achieved for these devices after QDs modification, in which PCE is maintained at >90% of initial value after 1000 h storage.

Herein, the dipolar polarization in a quasi‐2D organic–inorganic hybrid‐perovskite nanorod network–based solar cell using impedance spectroscopy is studied. Electric field and photoinduced dipole–dipole interaction plays an important role for the solar cell working at steady states.

Layered quasi‐2D organic–inorganic hybrid perovskites (OIHPs) prevent oxygen and moisture permeation, for long‐lifetime photovoltaic performance. Unfortunately, the electrical and photoinduced surface and dipolar polarizations caused due to the presence of the organic cation spacer in the structure remain unclear. Herein, a high‐performance planar quasi‐2D OIHP solar cell comprising (PEA)₂(MA)₃Pb₄I₁₃ (n = 4) is designed. It displays a large area coverage and an interconnected nanorod network, which contributes to efficient light absorption and charge carrier transport. The surface and dipolar polarizations exhibit remarkable light intensity and electric field–dependent characteristics at short‐circuit‐current (J _sc) and steady‐state (i.e., V _oc) conditions. More importantly, Voc exhibits a nonlinear behavior at steady states. Such a unique feature is in accordance with the dipolar polarization measured at the same condition. The phenomenon can be explained by the significant dipole–dipole interaction at lower electric field strengths. At higher field strengths, the screen of the dipoles due to charge accumulation at the surface of the organic cation spacer leads to slower increment of Voc. Thus, carefully designing the quasi‐2D perovskite nanostructure, together with the dielectric property of the organic cation spacer, may play an exceptionally important role for future high‐performance quasi‐2D perovskite solar cells.

Publication date: Available online 12 November 2019

Source: Nano Energy

Author(s): Yuanyuan Zhao, Jialong Duan, Yudi Wang, Xiya Yang, Qunwei Tang

Graphical abstract

Precise stress control of CsPbBr₃ perovskite film maximizes grain size and minimizes grain boundary defects. The all-inorganic CsPbBr₃ solar cell achieves a champion PCE of 10.71% with an ultrahigh V_oc of 1.622 V.

A carrier‐resolved photo‐Hall characterization technique is employed to simultaneously access majority/minority carrier properties as a function of light intensity for CH₃NH₃PbI₃ perovskite films processed without and with photovoltaic performance‐enhancing additives. Measurements on films with variable grain size reveal the passivation of bulk defects and n‐doping effect with PbI₂ excess and relative insensitivity to grain boundary density and thiocyanate additive concentration.

Abstract

With power conversion efficiencies now exceeding 25%, hybrid perovskite solar cells require deeper understanding of defects and processing to further approach the Shockley‐Queisser limit. One approach for processing enhancement and defect reduction involves additive engineering—, e.g., addition of MASCN (MA = methylammonium) and excess PbI₂ have been shown to modify film grain structure and improve performance. However, the underlying impact of these additives on transport and recombination properties remains to be fully elucidated. In this study, a newly developed carrier‐resolved photo‐Hall (CRPH) characterization technique is used that gives access to both majority and minority carrier properties within the same sample and over a wide range of illumination conditions. CRPH measurements on n‐type MAPbI₃ films reveal an order of magnitude increase in carrier recombination lifetime and electron density for 5% excess PbI₂ added to the precursor solution, with little change noted in electron and hole mobility values. Grain size variation (120–2100 nm) and MASCN addition induce no significant change in carrier‐related parameters considered, highlighting the benign nature of the grain boundaries and that excess PbI₂ must predominantly passivate bulk defects rather than defects situated at grain boundaries. This study offers a unique picture of additive impact on MAPbI₃ optoelectronic properties as elucidated by the new CRPH approach.