Mahui

Fullerene‐free ternary polymer solar cells with high photovoltaic performance and stability are reported by employing a blend of two similar structure fullerene‐free small molecule as electron acceptors. A power conversion efficiency of 12.57% is achieved with an open‐circuit voltage of 0.91 V, a short‐circuit current density of 19.94 mA cm⁻², and a fill factor of 0.696.

Abstract

Fullerene‐free organic solar cells (OSCs) are fabricated using a blend of J61 polymer as donor and the blend of m‐3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(4‐hexyl phenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′] dithiophene (ITIC) and ITIC‐Th as electron acceptor. The blend of m‐ITIC and ITIC‐Th as electron acceptor due to the similar lowest unoccupied molecular orbital energy levels and good compatibility among J61, m‐ITIC, and ITIC‐Th, are beneficial for the small energy barrier at the m‐ITIC:ITIC‐Th interface. Simultaneously, the ternary photoactive layer can maintain the optimize film morphology and beneficial to ensure effective suppression of charge recombination at the three kind materials interface. The power conversion efficiency of ternary OSCs achieves to 12.57% when the blend of m‐ITIC:ITIC‐Th (the ratio of m‐ITIC:ITIC‐Th is 40:60) as electron acceptor, with enhanced open‐circuit voltage (V _OC) of 0.91 V, short‐circuit current densities (J _SC) of 19.94 mA cm⁻², and fill factor of 69.6%. Moreover, the optimal ternary OSCs show enhanced thermal stability and photostability than the binary OSCs. This study indicates that the blend of m‐ITIC and ITIC‐Th as electron acceptor and J61 as donor is a promising strategy to fabricate high performance and stable OSCs.

Nature Materials, Published online: 09 September 2019; doi:10.1038/s41563-019-0478-1

The changes in photophysical properties of mixed‐halide perovskite films under solar‐equivalent illumination are studied. The illumination generates localized low‐bandgap surface domains, onto which photoexcited charge carriers transfer and recombine with high radiative efficiency. The fraction of radiative and nonradiative (Auger) recombination bandgap can be balanced to achieve extremely high photoluminescence quantum yields at low excitation densities.

Abstract

Mixed‐halide lead perovskites have attracted significant attention in the field of photovoltaics and other optoelectronic applications due to their promising bandgap tunability and device performance. Here, the changes in photoluminescence and photoconductance of solution‐processed triple‐cation mixed‐halide (Cs_0.06MA_0.15FA_0.79)Pb(Br_0.4I_0.6)₃ perovskite films (MA: methylammonium, FA: formamidinium) are studied under solar‐equivalent illumination. It is found that the illumination leads to localized surface sites of iodide‐rich perovskite intermixed with passivating PbI₂ material. Time‐ and spectrally resolved photoluminescence measurements reveal that photoexcited charges efficiently transfer to the passivated iodide‐rich perovskite surface layer, leading to high local carrier densities on these sites. The carriers on this surface layer therefore recombine with a high radiative efficiency, with the photoluminescence quantum efficiency of the film under solar excitation densities increasing from 3% to over 45%. At higher excitation densities, nonradiative Auger recombination starts to dominate due to the extremely high concentration of charges on the surface layer. This work reveals new insight into phase segregation of mixed‐halide mixed‐cation perovskites, as well as routes to highly luminescent films by controlling charge density and transfer in novel device structures.

The variation of A‐site cations is promising to achieve enhanced properties; however, it is limited to a few available choices of methylamine, formamidine, and cesium. Halogenated methylammoniums are reported as novel A cations to broaden the family of hybrid perovskites, which breaks through the limitation of A cations.

Abstract

3D perovskites with typical structure of ABX₃ are emerging as key materials to achieve high‐performance optoelectronic devices. The variation of A‐site cation is promising to achieve enhanced properties; however, is limited to a few available choices of methylamine, formamidine, and cesium. In this work, halogenated‐methylammoniums are developed as A cation to broaden the family of hybrid perovskites. Single crystals and colloidal nanocrystals of halogenated‐methylammoniums based perovskites are successfully synthesized, showing bright future as alternatives for device exploration. In particular, the improved thermal stability and low exciton binding energy from single crystals measurements are demonstrated and bright tunable emission from blue to green for colloidal nanocrystals is achieved.

Application of the proposed slow post‐annealing for layered 2D perovskite solar cells based on BA₂MA₃Pb₄I₁₃ photo‐absorber leads to a favorable alignment on the multi‐perovskite phases and resultant champion power conversion efficiency to 17.26%, showing simultaneously enhanced open‐circuit voltage and short‐circuit current.

Abstract

Layered Ruddlesden–Popper (RP) phase (2D) halide perovskites have attracted tremendous attention due to the wide tunability on their optoelectronic properties and excellent robustness in photovoltaic devices. However, charge extraction/transport and ultimate power conversion efficiency (PCE) in 2D perovskite solar cells (PSCs) are still limited by the non‐eliminable quantum well effect. Here, a slow post‐annealing (SPA) process is proposed for BA₂MA₃Pb₄I₁₃ (n = 4) 2D PSCs by which a champion PCE of 17.26% is achieved with simultaneously enhanced open‐circuit voltage, short‐circuit current, and fill factor. Investigation with optical spectroscopy coupled with structural analyses indicates that enhanced crystal orientation and favorable alignment on the multiple perovskite phases (from the 2D phase near bottom to quasi‐3D phase near top regions) is obtained with SPA treatment, which promotes carrier transport/extraction and suppresses Shockley–Read–Hall charge recombination in the solar cell. As far as it is known, the reported PCE is so far the highest efficiency in RP phase 2D PSCs based on butylamine (BA) spacers (n = 4). The SPA‐processed devices exhibit a satisfactory stability with <4.5% degradation after 2000 h under N₂ environment without encapsulation. The demonstrated process strategy offers a promising route to push forward the performance in 2D PSCs toward realistic photovoltaic applications.

Recent progress of inorganic perovskite materials and photovoltaic solar cells is summarized, including materials design, methods for preparing high‐quality perovskite films, phase instabilities, nanocrystals, quantum dots, lead‐free perovskites, device process, and upscaling. In addition, the energy loss mechanisms within the device are discussed and relevant methods are proposed accordingly.

Abstract

All‐inorganic perovskites are considered to be one of the most appealing research hotspots in the field of perovskite photovoltaics in the past 3 years due to their superior thermal stability compared to their organic–inorganic hybrid counterparts. The power‐conversion efficiency has reached 17.06% and the number of important publications is ever increasing. Here, the progress of inorganic perovskites is systematically highlighted, covering materials design, preparation of high‐quality perovskite films, and avoidance of phase instabilities. Inorganic perovskites, nanocrystals, quantum dots, and lead‐free compounds are discussed and the corresponding device performances are reviewed, which have been realized on both rigid and flexible substrates. Methods for stabilization of the cubic phase of low‐bandgap inorganic perovskites are emphasized, which is a prerequisite for highly efficient and stable solar cells. In addition, energy loss mechanisms both in the bulk of the perovskite and at the interfaces of perovskite and charge selective layers are unraveled. Reported approaches to reduce these charge‐carrier recombination losses are summarized and complemented by methods proposed from our side. Finally, the potential of inorganic perovskites as stable absorbers is assessed, which opens up new perspectives toward the commercialization of inorganic perovskite solar cells.

The changes in photophysical properties of mixed‐halide perovskite films under solar‐equivalent illumination are studied. The illumination generates localized low‐bandgap surface domains, onto which photoexcited charge carriers transfer and recombine with high radiative efficiency. The fraction of radiative and nonradiative (Auger) recombination bandgap can be balanced to achieve extremely high photoluminescence quantum yields at low excitation densities.

Abstract

Mixed‐halide lead perovskites have attracted significant attention in the field of photovoltaics and other optoelectronic applications due to their promising bandgap tunability and device performance. Here, the changes in photoluminescence and photoconductance of solution‐processed triple‐cation mixed‐halide (Cs_0.06MA_0.15FA_0.79)Pb(Br_0.4I_0.6)₃ perovskite films (MA: methylammonium, FA: formamidinium) are studied under solar‐equivalent illumination. It is found that the illumination leads to localized surface sites of iodide‐rich perovskite intermixed with passivating PbI₂ material. Time‐ and spectrally resolved photoluminescence measurements reveal that photoexcited charges efficiently transfer to the passivated iodide‐rich perovskite surface layer, leading to high local carrier densities on these sites. The carriers on this surface layer therefore recombine with a high radiative efficiency, with the photoluminescence quantum efficiency of the film under solar excitation densities increasing from 3% to over 45%. At higher excitation densities, nonradiative Auger recombination starts to dominate due to the extremely high concentration of charges on the surface layer. This work reveals new insight into phase segregation of mixed‐halide mixed‐cation perovskites, as well as routes to highly luminescent films by controlling charge density and transfer in novel device structures.

The variation of A‐site cations is promising to achieve enhanced properties; however, it is limited to a few available choices of methylamine, formamidine, and cesium. Halogenated methylammoniums are reported as novel A cations to broaden the family of hybrid perovskites, which breaks through the limitation of A cations.

Abstract

3D perovskites with typical structure of ABX₃ are emerging as key materials to achieve high‐performance optoelectronic devices. The variation of A‐site cation is promising to achieve enhanced properties; however, is limited to a few available choices of methylamine, formamidine, and cesium. In this work, halogenated‐methylammoniums are developed as A cation to broaden the family of hybrid perovskites. Single crystals and colloidal nanocrystals of halogenated‐methylammoniums based perovskites are successfully synthesized, showing bright future as alternatives for device exploration. In particular, the improved thermal stability and low exciton binding energy from single crystals measurements are demonstrated and bright tunable emission from blue to green for colloidal nanocrystals is achieved.

The OH…I⁻ hydrogen bonding interactions between poly(vinyl alcohol) (PVA) and FASnI₃ have the effects of introducing nucleation sites, slowing down crystal growth, directing the crystal orientation, reducing the trap states, and suppressing the migration of the ions. By adding PVA, the FASnI₃–PVA perovskite solar cells attain improved power conversion efficiency and stability.

Abstract

Tin‐based perovskites with narrow bandgaps and high charge‐carrier mobilities are promising candidates for the preparation of efficient lead‐free perovskite solar cells (PSCs). However, the crystalline rate of tin‐based perovskites is much faster, leading to abundant trap states and much lower open‐circuit voltage (V _oc). Here, hydrogen bonding is introduced to retard the crystalline rate of the FASnI₃ perovskite. By adding poly(vinyl alcohol) (PVA), the OH…I⁻ hydrogen bonding interactions between PVA and FASnI₃ have the effects of introducing nucleation sites, slowing down the crystal growth, directing the crystal orientation, reducing the trap states, and suppressing the migration of the iodide ions. In the presence of the PVA additive, the FASnI₃–PVA PSCs attain higher power conversion efficiency of 8.9% under a reverse scan with significantly improved V _oc from 0.55 to 0.63 V, which is one of the highest V _oc values for FASnI₃‐based PSCs. More importantly, the FASnI₃–PVA PSCs exhibit striking long‐term stability, with no decay in efficiency after 400 h of operation at the maximum power point. This approach, which makes use of the OH…I⁻ hydrogen bonding interactions between PVA and FASnI₃, is generally applicable for improving the efficiency and stability of the FASnI₃‐based PSCs.

By rationally tuning the molecular interaction and energy level alignments of the donors and acceptors, when both donor and acceptor are fluorinated or both are not fluorinated, high‐performance organic photovoltaics can be realized. With the enlarged absorption, ideal morphology, and efficient charge transfer, devices based on the PBDB‐T‐F/Y1‐4F blend and PBDB‐T‐F/Y6 exhibit power conversion efficiencies as high as 14.8% and 15.9%, respectively.

Abstract

The performance of organic photovoltaics (OPVs) has rapidly improved over the past years. Recent work in material design has primarily focused on developing near‐infrared nonfullerene acceptors with broadening absorption that pair with commercialized donor polymers; in the meanwhile, the influence of the morphology of the blend film and the energy level alignment on the efficiency of charge separation needs to be synthetically considered. Herein, the selection rule of the donor/acceptor blend is demonstrated by rationally considering the molecular interaction and energy level alignment, and highly efficient OPV devices using both‐fluorinated or both‐nonfluorinated donor/acceptor blends are realized. With the enlarged absorption, ideal morphology, and efficient charge transfer, the devices based on the PBDB‐T‐F/Y1‐4F blend and PBDB‐T‐F/Y6 exhibit champion power conversion efficiencies as high as 14.8% and 15.9%, respectively.

In article no. 1900224, Mohammad Khaja Nazeeruddin, Paul J. Dyson, Vytautas Getautis, and co‐workers present a novel hole transporting material, termed V1160, based on four N,N′‐bis(3‐methylphenyl)‐N,N′‐diphenylbenzidine‐type fragments, fused by a Tröger's base core. The material is synthetically robust and demonstrates a promising power conversion efficiency of over 18%. Moreover, V1160‐based devices exhibit improved performances in dopant‐free configurations and superior stability.

In article no. 1900119, Zong‐Xiang Xu and co‐workers synthesize isomer‐pure 2,9,16,24‐tetra‐n‐butyl‐Zn (II) phthalocyanine (RE‐ZnBu₄Pc) through ring expanding of symmetric tri‐n‐butyl‐substituted boron subphthalocyanine as a dopant‐free hole transporting material (HTM) in planar conventional perovskite solar cells, which offers higher efficiency, long‐term stability, and reproducibility than HTMs based on ZnBu₄Pc with an isomer mixture.

In article no. 1900078, Changlei Wang, Xiaofeng Li, Yanfa Yan, and co‐workers report that the introduction of block copolymer F127 could passivate grain boundaries and enhance the hydrophobicity of perovskite films simultaneously, resulting in highly efficient planar and flexible perovskite solar cells with good stability.

In article no. 1900199, Ana F. Nogueira and co‐workers modify perovskite surfaces with alkylammonium chloride, which increases the stability of the solar cells, making it last longer when exposed to environmental conditions. After the modification, 2D/3D structures are formed and their chemical structures are identified. This mixture makes the films more humidity tolerant.

This review provides a systematic overview of self‐powered integrated systems based on perovskite solar cells, including integrated energy storage devices, integrated artificial photosynthesis devices, and other self‐powered integrated devices. The key strategies for fabricating these devices are discussed to further the understanding of fundamental device physics. The current challenges and future perspective are provided.

Integrated smart portable devices (e.g., self‐powered devices) that utilize the environment‐friendly energy (e.g., solar energy) by means of photovoltaic technology (e.g., solar cell) are a popular concept in the current technological development trend. As a key component of integrated devices, photovoltaic devices acting as a bridge between solar energy and working devices play an important role in the whole system performance. The emergence of perovskite solar cells (PSCs) with high power conversion efficiencies (over 25%) allows for the possibility and appearance of many multifunctional self‐powered integrated devices. In this review, a systematic overview of self‐powered integrated devices based on PSCs that are reported so far is provided, including integrated energy storage devices, integrated artificial photosynthesis devices, and other self‐powered integrated devices. The key strategies for fabricating these devices and performance are also discussed to further the understanding of fundamental device physics. Finally, the current challenging issues and future perspective are provided to promote the development of self‐powered integrated devices based on PSCs in the near future.

Perovskite solar cells fabricated on aluminum‐doped zinc oxide (AZO)/quartz substrates are shown with a record efficiency of 15%, and their radiation hardness to 150 keV protons is presented. The cells show robust stability up to 10¹³ protons cm⁻², with degradation at 10¹⁴ and 10¹⁵ protons ccm⁻². Transient photovoltage measurements show an increase in minority carrier density and lifetime from 10¹² protons cm⁻².

Perovskite solar cells (PSCs) have gained increasing interest for space applications. However, before they can be deployed into space, their resistance to ionizing radiations, such as high‐energy protons, must be demonstrated. Herein, the effect of 150 keV protons on the performance of PSCs based on aluminum‐doped zinc oxide (AZO) transparent conducting oxide (TCO) is investigated. A record power conversion efficiency of 15% and 13.6% is obtained for cells based on AZO under AM1.5G and AM0 illumination, respectively. It is demonstrated that PSCs can withstand proton irradiation up to 10¹³ protons cm⁻² without significant loss in efficiency. From 10¹⁴ protons cm⁻², a decrease in short‐circuit current of PSCs is observed, which is consistent with interfacial degradation due to deterioration of the Spiro‐OMeTAD holes transport layer during proton irradiation. The structural and optical properties of perovskite remain intact up to high fluence levels. Although shallow trap states are induced by proton irradiation in perovskite bulk at low fluence levels, charges are released efficiently and are not detrimental to the cell's performance. This work highlights the potential of PSCs based on AZO TCO to be used for space applications and gives a deeper understanding of interfacial degradation due to proton irradiation.

Recent progress of inorganic perovskite materials and photovoltaic solar cells is summarized, including materials design, methods for preparing high‐quality perovskite films, phase instabilities, nanocrystals, quantum dots, lead‐free perovskites, device process, and upscaling. In addition, the energy loss mechanisms within the device are discussed and relevant methods are proposed accordingly.

Abstract

All‐inorganic perovskites are considered to be one of the most appealing research hotspots in the field of perovskite photovoltaics in the past 3 years due to their superior thermal stability compared to their organic–inorganic hybrid counterparts. The power‐conversion efficiency has reached 17.06% and the number of important publications is ever increasing. Here, the progress of inorganic perovskites is systematically highlighted, covering materials design, preparation of high‐quality perovskite films, and avoidance of phase instabilities. Inorganic perovskites, nanocrystals, quantum dots, and lead‐free compounds are discussed and the corresponding device performances are reviewed, which have been realized on both rigid and flexible substrates. Methods for stabilization of the cubic phase of low‐bandgap inorganic perovskites are emphasized, which is a prerequisite for highly efficient and stable solar cells. In addition, energy loss mechanisms both in the bulk of the perovskite and at the interfaces of perovskite and charge selective layers are unraveled. Reported approaches to reduce these charge‐carrier recombination losses are summarized and complemented by methods proposed from our side. Finally, the potential of inorganic perovskites as stable absorbers is assessed, which opens up new perspectives toward the commercialization of inorganic perovskite solar cells.

Publication date: November 2019

Source: Nano Energy, Volume 65

Author(s): Hao Gu, Chao Liang, Yingdong Xia, Qi Wei, Tanghao Liu, Yingguo Yang, Wei Hui, Haoran Chen, Tingting Niu, Lingfeng Chao, Zhiheng Wu, Xiaoji Xie, Jian Qiu, Guosheng Shao, Xingyu Gao, Guichuan Xing, Yonghua Chen, Wei Huang

Graphical abstract

The ACI perovskite with micro-meter crystals are vertically stacked with preferential crystal orientation. In each microcrystal, the low-dimensional ACI perovskites are crystalized in the 3D perovskite nanoscale networks. Such nanoscale hybridization prompts ultrafast (0.3 ps) and efficient charge carrier localization from low-dimensional ACI perovskites to 3D perovskite and the subsequent fast and efficient charge carrier extraction from the 3D networks to the extraction layers. Based on the optimized ACI perovskite film, planar heterojunction PSC achieved a high PCE exceeding 16% and kept 80% of the initial value for over 2400 h.

Application of the proposed slow post‐annealing for layered 2D perovskite solar cells based on BA₂MA₃Pb₄I₁₃ photo‐absorber leads to a favorable alignment on the multi‐perovskite phases and resultant champion power conversion efficiency to 17.26%, showing simultaneously enhanced open‐circuit voltage and short‐circuit current.

Abstract

Layered Ruddlesden–Popper (RP) phase (2D) halide perovskites have attracted tremendous attention due to the wide tunability on their optoelectronic properties and excellent robustness in photovoltaic devices. However, charge extraction/transport and ultimate power conversion efficiency (PCE) in 2D perovskite solar cells (PSCs) are still limited by the non‐eliminable quantum well effect. Here, a slow post‐annealing (SPA) process is proposed for BA₂MA₃Pb₄I₁₃ (n = 4) 2D PSCs by which a champion PCE of 17.26% is achieved with simultaneously enhanced open‐circuit voltage, short‐circuit current, and fill factor. Investigation with optical spectroscopy coupled with structural analyses indicates that enhanced crystal orientation and favorable alignment on the multiple perovskite phases (from the 2D phase near bottom to quasi‐3D phase near top regions) is obtained with SPA treatment, which promotes carrier transport/extraction and suppresses Shockley–Read–Hall charge recombination in the solar cell. As far as it is known, the reported PCE is so far the highest efficiency in RP phase 2D PSCs based on butylamine (BA) spacers (n = 4). The SPA‐processed devices exhibit a satisfactory stability with <4.5% degradation after 2000 h under N₂ environment without encapsulation. The demonstrated process strategy offers a promising route to push forward the performance in 2D PSCs toward realistic photovoltaic applications.