Lead(II) 2-Ethylhexanoate for Simultaneous Modulated Crystallization and Surface Shielding to Boost Perovskite Solar Cell Efficiency and Stability.

The bulk and surface of a perovskite light-harvesting layer are two pivotal aspects affecting its carrier transport and long-term stability. In this work, lead(II) 2-ethylhexanoate (LDE) is introduced via an antisolvent process into perovskite films to change the reaction kinetics of the crystallization process, resulting in a high-quality perovskite film. Meanwhile, a carboxyl functional group with a long alkyl chain coordinates with the Pb cation, reducing the defect density related to unsaturated Pb atoms. Moreover, the long alkyl chains form a protecting layer at the surface of the perovskite film to prevent chemical attack by water and air, prolonging the lifetime of perovskite devices. Consequently, the assembled device demonstrates a power conversion efficiency (PCE) of 24.84%. Both of the thermal and operational stability are significantly improved due to reduced ion-migration channels.

Chelate Coordination Strengthens Surface Termination to Attain High-Efficiency Perovskite Solar Cells.

Solar cell efficiency and stability are two key metrics to determine whether a photovoltaic device is viable for commercial applications. The surface termination of the perovskite layer plays a pivotal role in not only the photoelectric conversion efficiency (PCE) but also the stability of assembled perovskite solar cells (PSCs). Herein, a strong chelate coordination bond is designed to terminate the surface of the perovskite absorber layer. On the one hand, the ligand anions bind with Pb cations via a bidentate chelating bond to restrict the ion migration, and the chelate surface termination changes the surface from hydrophilic to hydrophobic. Both are beneficial to improving the long-term stability. On the other hand, the formation of the chelating bonding effectively eliminates the deep-level defects including PbI and Pb clusters on the Pb-I and FA-I terminations, respectively, as confirmed by theoretical simulation and experimental results. Consequently, the PCE is increased to 24.52%, open circuit voltage to 1.19 V, and fill factor to 81.53%; all three are among the highest for hybrid perovskite cells. The present strategy provides a straightforward means to enhance both the PCE and long-term stability of PSCs.

Polar Species for Effective Dielectric Regulation to Achieve High-Performance CsPbI3 Solar Cells.

Nonradiative losses caused by defects are the main obstacles to further advancing the efficiency and stability of perovskite solar cells (PSCs). There is focused research to boost the device performance by reducing the number of defects and deactivating defects; however, little attention is paid to the defect-capture capacity. Here, upon systematically examining the defect-capture capacity, highly polarized fluorinated species are designed to modulate the dielectric properties of the perovskite material to minimize its defect-capture radius. On the one hand, fluorinated polar species strengthen the defect dielectric-screening effect via enhancing the dielectric constant of the perovskite film, thus reducing the defect-capture radius. On the other, the fluorinated iodized salt replenishes the I-vacancy defects at the surface, hence lowering the defect density. Consequently, the power-conversion efficiency of an all-inorganic CsPbI3 PSC is increased to as high as 20.5% with an open-circuit voltage of 1.2 V and a fill factor of 82.87%, all of which are among the highest in their respective categories. Furthermore, the fluorinated species modification also produces a hydrophobic umbrella yielding significantly improved humidity tolerance, and hence long-term stability. The present strategy provides a general approach to effectually regulate the defect-capture radius, thus enhancing the optoelectronic performance.

Defects in CsPbX3 Perovskite: From Understanding to Effective Manipulation for High-Performance Solar Cells.

The rapid development of all inorganic metal perovskite (CsPbX3 , X represents halogen) materials holds great promise for top-cells in tandem junctions due to their glorious thermal stability and continuous adjustable band gap in a wide range. Due to the presence of defects, the power conversion efficiency (PCE) of CsPbX3 perovskite solar cells (PSCs) is still substantially below the Shockley-Queisser (SQ) limit. Therefore, it is imperative to have an in-depth understanding of the defects in PSCs, thus to evaluate their impact on device performances and to develop corresponding strategies to manipulate defects in PSCs for further promoting their photoelectric properties. In this review, the latest progress in defect passivation in the CsPbX3 PSCs field is summarized. Starting from the effect of non-radiative recombination on open circuit voltage (Voc ) losses, the defect physics, tolerance, self-healing, and the effect of defects on the photovoltaic properties are discussed. Some techniques to identify defects are compared based on quantitative and qualitative analysis. Then, passivation manipulation is discussed in detail, the defect passivation mechanisms are proposed, and the passivation agents in CsPbX3 thin films are classified. Finally, directions for future research about defect manipulation that will push the field to progress forward are outlined.

Molten-Salt-Assisted CsPbI3 Perovskite Crystallization for Nearly 20%-Efficiency Solar Cells.

Dynamic manipulation of crystallization is pivotal to the quality of polycrystalline films. A molten-salt-assisted crystallization (MSAC) strategy is presented to improve grain growth of the all-inorganic perovskite films. Compared with the traditional solvent annealing, MSAC enables more intensive mass transfer by means of convection and diffusion, which is beneficial to the interaction among the precursor colloids and to inducing in-plane growth of perovskite grains, resulting in the formation of high-quality perovskite films with suppressed pinhole and crack formation. Additionally, the introduction of molten salt alters the intermediate phases, and thus changes the crystallization pathways by reducing the energy barrier to produce films with desired optical and electrical properties. As a result, the MSAC strategy endows the devices with champion steady-state output efficiency of 19.83% and open-circuit voltage (Voc ) as high as 1.2 V, among the highest for this type of solar cell, thanks to its effectively reduced Voc deficit.

Morphology Evolution of a High-Efficiency PSC by Modulating the Vapor Process.

The morphological quality of the photoactive layer is the key component affecting the performance metrics of a photovoltaic device. Therefore, fine adjustment of the crystallization dynamics is urgently required. By manipulating the amount of dimethyl sulfoxide (DMSO) remaining in the spin-coated perovskite films during the annealing treatment, an obvious morphological evolution arises. The crystallization kinetics is significantly altered due to the formation of intermediate phases and the variation of DMSO vapor pressure via producing the semienclosed space with a covering. On the one hand, the obviously formed intermediate phase MA2 Pb3 I8 (DMSO)2 retards the crystallization process. On the other hand, the DMSO vapor in the semienclosed space intrigues the recrystallization process and results in Ostwald ripening to produce large-aspect-ratio grains with fewer defect states, decreased carrier doping, and longer carrier lifetimes. Thus, nonradiative processes are greatly suppressed. Besides, combined with X-ray photoelectron spectroscopy measurement and the surface energy of MAI- and PbI-terminated surface model calculated by density functional theory, the defect states are identified and the causes of Pb0 defect states are explained. Using this strategy, a high power conversion efficiency of 20.09% is achieved based on MAPbI3 photovoltaic solar cell, and the long-term ambient shelf and thermal stability are obviously improved.

Fabrication of a High-Quality Cu2ZnSn(S,Se)4 Absorber Layer via an Aqueous Solution Process and Application in Solar Cells.

The development of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells determines the prospect of thin-film photovoltaic devices because of some of their strengths. However, the usual solution fabrication processes of CZTSSe absorbing layers are either too tedious or highly toxic. Here, we have developed an alternative strategy to prepare kesterite CZTSSe absorber films with a simple and low-toxicity solution process by replacing the commonly employed thiol-based compounds using the glycolic acid aqueous solution, which significantly reduces the environment pollution and toxicity, providing a possibility toward the green solvent process. The power conversion efficiency of 6.81% has been acquired based the aqueous solution-processed CZTSSe thin film via optimizing the fabrication technology.

A straightforward chemical approach for excellent In2S3 electron transport layer for high-efficiency perovskite solar cells.

Perovskite solar cells (PSCs) have attracted significant attention in recent years owing to some of their advantages: high-efficiency, low cost and ease of fabrication. In perovskite photovoltaic devices, charge transport layers play a vital role for selectively extracting and transporting photo-generated electrons and holes to opposite electrodes. Therefore, it is very important to prepare high-quality charge transport layers using simple processes at low cost. As reported, In2S-based electron selective layers display excellent performance including high solar-cell efficiency and negligible hysteresis. In this study, a simple chemical method was developed to prepare In2S3 thin films as the electron selective layers in organic-inorganic hybrid perovskite photovoltaic devices to shorten the fabrication time and simplify the technology, which can provide a new avenue for a low-cost and solution-processed method. By optimizing the preparation conditions, it was demonstrated that In2S3 thin film prepared using our straightforward chemical approach have higher electron extraction efficiency and comparable efficiency compared with archetypical TiO2 as the electron transport layer (ETL) in perovskite photovoltaic device.

Alkali Metal Doping for Improved CH3NH3PbI3 Perovskite Solar Cells.

Organic-inorganic hybrid halide perovskites are proven to be a promising semiconductor material as the absorber layer of solar cells. However, the perovskite films always suffer from nonuniform coverage or high trap state density due to the polycrystalline characteristics, which degrade the photoelectric properties of thin films. Herein, the alkali metal ions which are stable against oxidation and reduction are used in the perovskite precursor solution to induce the process of crystallization and nucleation, then affect the properties of the perovskite film. It is found that the addition of the alkali metal ions clearly improves the quality of perovskite film: enlarges the grain sizes, reduces the defect state density, passivates the grain boundaries, increases the built-in potential (Vbi), resulting to the enhancement in the power conversion efficiency of perovskite thin film solar cell.

Organic-Inorganic Hybrid Perovskite with Controlled Dopant Modification and Application in Photovoltaic Device.

Organic-inorganic hybrid perovskite as a kind of promising photovoltaic material is booming due to its low-cost, high defect tolerance, and easy fabrication, which result in the huge potential in industrial production. In the pursuit of high efficiency photovoltaic devices, high-quality absorbing layer is essential. Therefore, developing organic-inorganic hybrid perovskite thin films with good coverage, improved uniformity, and crystalline in a single pass deposition is of great concern in realizing good performance of perovskite thin-film solar cell. Here, it is found that the introduction of suitable amounts of LiI plays a dramatically positive role in enlarging the grain size and reducing the grain boundaries of absorbing layer. In addition, the carrier lifetime and built-in potential of the LiI doped perovskite device are observed to increase. Thus, it leads to about 15% gain in solar cell efficiency comparing to that without the LiI doping. Meanwhile, a hysteresis reduction is observed and 18.16% power conversion efficiency is achieved in LiI doped perovskite device, as well.

Solution-Processed Nb:SnO2 Electron Transport Layer for Efficient Planar Perovskite Solar Cells.

Electron transport layer (ETL), facilitating charge carrier separation and electron extraction, is a key component in planar perovskite solar cells (PSCs). We developed an effective ETL using low-temperature solution-processed Nb-doped SnO2 (Nb:SnO2). Compared to the pristine SnO2, the power conversion efficiency of PSCs based on Nb:SnO2 ETL is raised to 17.57% from 15.13%. The splendid performance is attributed to the excellent optical and electronic properties of the Nb:SnO2 material, such as smooth surface, high electron mobility, appropriate electrical conductivity, therefore making a better growth platform for a high quality perovskite absorber layer. Experimental analyses reveal that the Nb:SnO2 ETL significantly enhances the electron extraction and effectively suppresses charge recombination, leading to improved solar cell performance.

Kesterite Cu2Zn(Sn,Ge)(S,Se)4 thin film with controlled Ge-doping for photovoltaic application.

Cu2ZnSn(S,Se)4 (CZTSSe) semiconductors have been a focus of extensive research effort owing to low-toxicity, high abundance and low material cost. Yet, the CZTSSe thin film solar cell has a low open-circuit voltage value that presents challenges. Herein, using GeSe2 as a new Ge source material, we have achieved a wider band gap CZTSSe-based semiconductor absorber layer with its band-gap controlled by adjusting the ratio of SnS2 : GeSe2 used. In addition, the Cu2Zn(Sn,Ge)(S,Se)4 thin films were prepared with optimal Ge doping (30%) and solar cells were fabricated to attain a respectable power conversion efficiency of 4.8% under 1.5 AM with an active area of 0.19 cm(2) without an anti-reflection layer.

Solution-processed highly efficient Cu2ZnSnSe4 thin film solar cells by dissolution of elemental Cu, Zn, Sn, and Se powders.

Solution deposition approaches play an important role in reducing the manufacturing cost of Cu2ZnSnSe4 (CZTSe) thin film solar cells. Here, we present a novel precursor-based solution approach to fabricate highly efficient CZTSe solar cells. In this approach, low-cost elemental Cu, Zn, Sn, and Se powders were simultaneously dissolved in the solution of thioglycolic acid and ethanolamine, forming a homogeneous CZTSe precursor solution to deposit CZTSe nanocrystal thin films. Based on high-quality CZTSe absorber layer, pure selenide CZTSe solar cell with a photoelectric conversion efficiency of 8.02% has been achieved without antireflection coating.

Fabrication of Cu2ZnSn(S,Se)4 solar cells via an ethanol-based sol-gel route using SnS2 as Sn source.

Cu2ZnSn(S,Se)4 semiconductor is a promising absorber layer material in thin film solar cells due to its own virtues. In this work, high quality Cu2ZnSn(S,Se)4 thin films have been successfully fabricated by an ethanol-based sol-gel approach. Different from those conventional sol-gel approaches, SnS2 was used as the tin source to replace the most commonly used SnCl2 in order to avoid the possible chlorine contamination. In addition, sodium was found to improve the short-circuit current and fill factor rather than the open-circuit voltage due to the decrease of the thickness of small-grained layer. The selenized Cu2ZnSn(S,Se)4 thin films showed large densely packed grains and smooth surface morphology, and a power conversion efficiency of 6.52% has been realized for Cu2ZnSn(S,Se)4 thin film solar cell without antireflective coating.

Fabrication of a Cu2ZnSn(S,Se)4 photovoltaic device by a low-toxicity ethanol solution process.

Homogeneous molecular precursor solutions are excellent choices for obtaining smooth absorber layers, and they offer the potential to significantly lower the manufacturing cost of solar cells. Here, we present a thermally degradable metal butyldithiocarbamate-based solution approach to fabricate Cu2ZnSn(S,Se)4 solar cells. Low-cost Cu2O, ZnO, and SnO were used as the starting materials and were dissolved in the ethanol solution of butyldithiocarbamic acid. By tuning the composition of the Cu2ZnSn(S,Se)4 thin film, a power conversion efficiency of 6.03% on the basis of the active area has been achieved.