shuhui

The rapid development of n‐type polymers has boosted the efficiency of all‐polymer solar cells, which has improved from 2% to 10 % in only seven years. There is a strong need to summarize the design criteria, synthesis, structure–property relationships and recent advances of n‐type polymers, which is addressed in this review. Moreover, the challenges and prospects for further development of all‐PSCs are briefly discussed.

Abstract

All‐polymer solar cells (all‐PSCs) based on n‐ and p‐type polymers have emerged as promising alternatives to fullerene‐based solar cells due to their unique advantages such as good chemical and electronic adjustability, and better thermal and photochemical stabilities. Rapid advances have been made in the development of n‐type polymers consisting of various electron acceptor units for all‐PSCs. So far, more than 200 n‐type polymer acceptors have been reported. In the last seven years, the power conversion efficiency (PCE) of all‐PSCs rapidly increased and has now surpassed 10%, meaning they are approaching the performance of state‐of‐the‐art solar cells using fullerene derivatives as acceptors. This review discusses the design criteria, synthesis, and structure–property relationships of n‐type polymers that have been used in all‐PSCs. Additionally, it highlights the recent progress toward photovoltaic performance enhancement of binary, ternary, and tandem all‐PSCs. Finally, the challenges and prospects for further development of all‐PSCs are briefly considered.

An effective approach to low temperature, solution‐processed ZnO electron‐transport layers (ETLs) for perovskite solar cells by combustion synthesis is developed. Due to the intrinsic passivation effects, high crystallinity, matched energy levels, ideal surface topography, and good chemical compatibility with the perovskite layer, combustion‐processed ZnO electron transport layers enable power conversion efficiencies approaching 17–20% for three representative perovskite systems without ETL doping or surface functionalization.

Abstract

Perovskite solar cells (PSCs) have advanced rapidly with power conversion efficiencies (PCEs) now exceeding 22%. Due to the long diffusion lengths of charge carriers in the photoactive layer, a PSC device architecture comprising an electron‐ transporting layer (ETL) is essential to optimize charge flow and collection for maximum performance. Here, a novel approach is reported to low temperature, solution‐processed ZnO ETLs for PSCs using combustion synthesis. Due to the intrinsic passivation effects, high crystallinity, matched energy levels, ideal surface topography, and good chemical compatibility with the perovskite layer, this combustion‐derived ZnO enables PCEs approaching 17–20% for three types of perovskite materials systems with no need for ETL doping or surface functionalization.

Through the rational molecular design of fluorination, the work function of the conjugated polymer (CP) is enhanced from 4.83 to 5.00 eV. Consequently, the CP can be used to modify efficient active layers consisting of polymer donors with a deep HOMO level, such as PBDB‐T‐2F:IT‐4F, and an outstanding power conversion efficiency of 12.7% is achieved in the corresponding device without V _oc loss.

Abstract

Since the highest occupied molecular orbital (HOMO) level of donors in organic solar cells (OSCs) is being constantly downshifted for achieving high open‐circuit voltage (V _oc), a further enhancement of the anode work function (WF) is required. Herein, an effective approach of fluorination is demonstrated to simultaneously improve the WF and transparency for anode interlayer (AIL) material. By fluorination, in combination with the dialysis treatment in LiCl solution, the WF of PCP‐2F‐Li could be significantly enhanced from 4.86 to 5.0 eV, as compared to PCP‐Na. Meanwhile, the transparency of the polymer is also improved. As a result, PCP‐2F‐Li can be used to modify efficient active layers consisting of polymer donors with deep HOMO levels, such as PBDB‐T‐2F:IT‐4F, and an outstanding power conversion efficiency (PCE) of 12.7% is achieved in the corresponding device with a high V _oc of 0.84 V. This result represents the highest efficiency for the OSCs using a solution‐processed pH‐neutral AIL, which is beneficial to the low‐cost fabrication of high‐performance OSCs with improved stability. More importantly, PCP‐2F‐Li could be processed by blade coating for making large‐area device of 1 cm², and a PCE of 10.6% is achieved, bringing a promising prospect for the large‐area device fabrication.

Processing of selenium solar cells: Selenium was used for the fabrication of the first solar cells in 1876. The current study presents the processing of selenium thin film solar cells with modern approaches and characterization. Controlling the film morphology by tuning the fabrication conditions allows optimizing the device efficiency and suggesting paths for future improvements.

Abstract

The first solid‐state solar cells, fabricated ≈140 years ago, were based on selenium; these early studies initiated the modern research on photovoltaic materials. Selenium shows high absorption coefficient and mobility, making it an attractive absorber for high bandgap thin film solar cells. Moreover, the simplicity of a single element absorber, its low‐temperature processing, and intrinsic environmental stability enable the utilization of selenium in extremely cheap and scalable solar cells. In this paper, a detailed study of selenium solar cell fabrication is presented, and the key factors that affect the selenium film morphology and the resulting device efficiency are presented. Specifically, the crystallization process from amorphous film into functional crystalline device is studied. The importance of controlling the process is shown, and methods to align the growth orientation are suggested. Finally, the crystallization process under illumination, which has general importance for the fabrication of thin film photovoltaics, is investigated. Specifically for selenium, the illumination significantly improves the film morphology and leads to device efficiency of 5.2%, with open‐circuit voltage of 0.911 V, short‐circuit current density of 10.2 mA cm⁻², and fill factor of 55.0%. These findings form a solid foundation for future improvements of the photovoltaic material and device architecture.

Publication date: 20 March 2019

Source: Joule, Volume 3, Issue 3

Author(s): Xin Song, Nicola Gasparini, Masrur Morshed Nahid, Sri Harish Kumar Paleti, Jin-Liang Wang, Harald Ade, Derya Baran

Context & Scale

Summary

Graphical Abstract

Unveiling the operation mechanism of layered perovskite solar cells

Unveiling the operation mechanism of layered perovskite solar cells, Published online: 01 March 2019; doi:10.1038/s41467-019-08958-9

Optical anisotropy in hybrid metal halide perovskites is demonstrated and the first account of the linear electro‐optic effect in these materials reported. These findings, along with the flexibility and solution‐processability of these materials, may suggest new applications for hybrid metal halide perovskites in polarizing optics and electro‐optic modulators.

Abstract

Rapid and efficient conversion of electrical signals to optical signals is needed in telecommunications and data network interconnection. The linear electro‐optic (EO) effect in noncentrosymmetric materials offers a pathway to such conversion. Conventional inorganic EO materials make on‐chip integration challenging, while organic nonlinear molecules suffer from thermodynamic molecular disordering that decreases the EO coefficient of the material. It has been posited that hybrid metal halide perovskites could potentially combine the advantages of inorganic materials (stable crystal orientation) with those of organic materials (solution processing). Here, layered metal halide perovskites are reported and investigated for in‐plane birefringence and linear electro‐optic response. Phenylmethylammonium lead chloride (PMA₂PbCl₄) crystals are grown that exhibit a noncentrosymmetric space group. Birefringence measurements and Raman spectroscopy confirm optical and structural anisotropy in the material. By applying an electric field on the crystal surface, the linear EO effect in PMA₂PbCl₄ is reported and its EO coefficient is determined to be 1.40 pm V⁻¹. This is the first demonstration of this effect in hybrid metal halide perovskites, materials that feature both highly ordered crystalline structures and solution processability. The in‐plane birefringence and electro‐optic response reveal that layered perovskite crystals could be further explored for potential applications in polarizing optics and EO modulation.

Recent advances in probing polar domains in methylammonium lead iodide thin films and their implications for perovskite solar cells are reviewed. The fundamental crystal properties and the formation of domains with predominant in‐plane polarization, as monitored with piezoresponse force microscopy, provide evidence of the semiconducting ferroelectric nature of methylammonium lead iodide thin films.

Abstract

Whether or not methylammonium lead iodide (MAPbI₃) is a ferroelectric semiconductor has caused controversy in the literature, fueled by many misunderstandings and imprecise definitions. Correlating recent literature reports and generic crystal properties with the authors' experimental evidence, the authors show that MAPbI₃ thin‐films are indeed semiconducting ferroelectrics and exhibit spontaneous polarization upon transition from the cubic high‐temperature phase to the tetragonal phase at room temperature. The polarization is predominantly oriented in‐plane and is organized in characteristic domains as probed with piezoresponse force microscopy. Drift‐diffusion simulations based on experimental patterns of polarized domains indicate a reduction of the Shockley–Read–Hall recombination of charge carriers within the perovskite grains due to the ferroelectric built‐in field and allow reproduction of the electrical solar cell properties.

Publication date: May 2019

Source: Nano Energy, Volume 59

Author(s): Miao Zhang, Ruijie Ming, Wei Gao, Qiaoshi An, Xiaoling Ma, Zhenghao Hu, Chuluo Yang, Fujun Zhang

Abstract

Graphical abstract

Organic solar cells achieve over 15% efficiency through the use of a copolymer donor, and simultaneously enhanced open‐circuit voltage and short‐circuit current density are obtained. High‐performance solar cells are adaptable for environment‐friendly solvents using a blade‐coating method, while showing better photostability than the corresponding ternary solar cells.

Abstract

Ternary blending and copolymerization strategies have proven advantageous in boosting the photovoltaic performance of organic solar cells. Here, 15% efficiency solar cells using copolymerization donors are demonstrated, where the electron‐withdrawing unit, ester‐substituted thiophene, is incorporated into a PBDB‐TF polymer to downshift the molecular energy and broaden the absorption. Copolymer‐based solar cells suitable for large‐area devices can be fabricated by a blade‐coating method from a nonhalogen and nonaromatic solvent mixture. Although ternary solar cells can achieve comparable efficiencies, they are not suitable for environment‐friendly processing conditions and show relatively low photostability compared to copolymer‐based devices. These results not only demonstrate high‐efficiency organic photovoltaic cells via copolymerization strategies but also provide important insights into their applications in practical production.

An easy and scalable methylamine (MA) gas healing method was realized for inorganic cesium based perovskite (CsPbX₃) layer by incorporating a certain amount of MAX (X=I or Br) initiator into the raw film. It was found that the excess MAX could accelerate the absorption rate of the MA gas into the CsPbX₃ film and quickly turn it into a liquid intermediate phase. Through the healing process, a high uniform and high crystallinity CsPbX₃ film with enhanced device performance was achieved. Moreover, the chemical interaction between a series of halides and MA gas molecules were studied and the results could offer guidance in further optimization of the healing strategy.

Humidity‐stable perovskite films are prepared by exploiting the self‐assembled monolayer formation of water‐soluble triazolium ionic liquids (ILs) on a hydrophilic perovksite surface. This strategy means that the devices exhibit good humidity stability, maintaining around 80% initial efficiency for 3500 h under 40 ± 5% humidity. Tuning the molecule structure of the ILs achieves a maximum power conversion efficiency (PCE) of 20.03%.

Abstract

Despite being a promising candidate for next‐generation photovoltaics, perovskite solar cells (PSCs) exhibit limited stability that hinders their practical application. In order to improve the humidity stability of PSCs, herein, a series of ionic liquids (ILs) “1‐alkyl‐4‐amino‐1,2,4‐triazolium” (termed as RATZ; R represents alkyl chain, and ATZ represents 4‐amino‐1,2,4‐triazolium) as cations are designed and used as additives in methylammonium lead iodide (MAPbI₃) perovskite precursor solution, obtaining triazolium ILs‐modified PSCs for the first time (termed as MA/RATZ PSCs). As opposed to from traditional methods that seek to improve the stability of PSCs by functionalizing perovskite film with hydrophobic molecules, humidity‐stable perovskite films are prepared by exploiting the self‐assembled monolayer (SAM) formation of water‐soluble triazolium ILs on a hydrophilic perovskite surface. The mechanism is validated by experimental and theoretical calculation. This strategy means that the MA/RATZ devices exhibit good humidity stability, maintaining around 80% initial efficiency for 3500 h under 40 ± 5% relative humidity. Meanwhile, the MA/RATZ PSCs exhibit enhanced thermal stability and photostability. Tuning the molecule structure of the ILs additives achieves a maximum power conversion efficiency (PCE) of 20.03%. This work demonstrates the potential of using triazolium ILs as additives and SAM and molecular design to achieve high performance PSCs.

The unstable properties of hybrid perovskites, such as crystal phase transition, fragmentation of organic molecules, and hydrogen bond dissociation, are reviewed, and the importance of additives in structurally stabilizing formamidinium lead trihalide in place of methylammonium is emphasized.

Abstract

Hybrid lead halide perovskite materials are used in solar cells and show efficiencies greater than 23%. Furthermore, they are applied in light‐emitting diodes, X‐ray detectors, thin‐film transistors, thermoelectrics, and memory devices. Lead trihalide hybrid materials contain methylammonium (MA) or formamidinium (FA) (or a mixture), or long alkylammonium halides, as alternative organic cations. However, the intrinsic stability of hybrid lead halide perovskites is not very high, and they are chemically unstable when exposed to moisture, light, or heat because of their organic contents and low formation energies. Therefore, although improvements in the chemical stability are crucial, changing the material composition is challenging because it is directly related to the desired application requirements. Fortunately, hybrid lead halide perovskites have a very high tolerance toward changes in physical properties arising from doping or addition of different cations and anions, in many cases showing improved properties. Here, the intrinsic instability of hybrid lead halide perovskites is reviewed in relation to the crystal phase and chemical stability. It is suggested that FA should be used for lead halide perovskites for chemical stability instead of MA. Furthermore, additives that stabilize the crystal phase with α‐FAPbI₃ should eschew MA.

Integrated perovskite/bulk‐heterojunction (BHJ) organic solar cells have shown great potential to further improve their performance by combining the advantages of perovskite solar cells and NIR BHJ organic solar cells. Combining with the maintained high V _OC, higher efficiencies are expected by fully optimizing the perovskite layers and NIR BHJ layers through device engineering and materials innovations.

Abstract

The recently emerged integrated perovskite/bulk‐heterojunction (BHJ) organic solar cells (IPOSCs) without any recombination layers have generated wide attention. This type of device structure can take the advantages of tandem cells using both perovskite solar and near‐infrared (NIR) BHJ organic solar materials for wide‐range sunlight absorption and the simple fabrication of single junction cells, as the low bandgap BHJ layer can provide additional light harvesting in the NIR region and the high open‐circuit voltage can be maintained at the same time. This progress report highlights the recent developments in such IPOSCs and the possible challenges ahead. In addition, the recent development of perovskite solar cells and NIR organic solar cells is also covered to fully underline the importance and potential of IPOSCs.

Photocurrent–voltage hysteresis in perovskite solar cells (PSCs) induced by ion migration combined with nonradiative recombination near the interface depends on perovskite composition and device structure. Among the methods attempted to reduce the hysteresis, potassium ion doping is found to be a universal approach toward hysteresis‐free PSCs regardless of perovskite composition.

Abstract

Current‐density–voltage (J–V) hysteresis in perovskite solar cells (PSCs) is a critical issue because it is related to power conversion efficiency and stability. Although parameters affecting the hysteresis have been already reported and reviewed, little investigation is reported on scan‐direction‐dependent J–V curves depending on perovskite composition. This review investigates J–V hysteric behaviors depending on perovskite composition in normal mesoscopic and planar structure. In addition, methodologies toward hysteresis‐free PSCs are proposed. There is a specific trend in hysteresis in terms of J–V curve shape depending on composition. Ion migration combined with nonradiative recombination near interfaces plays a critical role in generating hysteresis. Interfacial engineering is found to be an effective method to reduce the hysteresis; however, bulk defect engineering is the most promising method to remove the hysteresis. Among the studied methods, KI doping is proved to be a universal approach toward hysteresis‐free PSCs regardless of perovskite composition. It is proposed from the current studies that engineering of perovskite film near the electron transporting layer (ETL) and the hole transporting layer (HTL) is of vital importance for achieving hysteresis‐free PSCs and extremely high efficiency.