Mesoporous Perovskite Solar Cells Research Articles

Design and upgrade of mesoporous perovskite solar cells

In recent years, there has been notable progress in the development of perovskite solar cells (PSCs), marked by significant advancements in efficiency, stability, and scalability. Among different device architectures and technical routes, mesoporous perovskite solar cells (MPSCs) based on TiO2/ZrO2/carbon scaffold and screen-printing fabrication process have shown unique advantages for mass production and commercialization due to the low material cost and scalable fabrication process. Through efforts on material optimization, interface engineering, and device design, the power conversion efficiency of MPSCs has steadily increased from the initial 6.64 ​% in 2013 to current 22.22 ​%. Attributing to the screen-printing-based fabrication process, printable mesoscopic PSCs have enabled large-area devices, from mini-modules to modules, and solar panels. In this review, we discuss the development and latest advances of MPSCs, and provide outlooks for further improving the performance of this promising photovoltaic technology.

The surface effect of chlorinated mesoscopic TiO2 in printable carbon-based perovskite solar cells

Printable HTM-free (HTM = hole-transporting material) mesoporous carbon-based perovskite solar cells (C-PSCs) are one of the most promising technologies. In this study, a high-quality chlorinated mesoscopic TiO2 (m-TiO2) film was obtained by hydrochloric acid (HCl) wet chemical process and applied in C-PSCs based on TiO2/ZrO2/(5-AVA)x(MA)1-xPbI3/C structures. Experimental results show that the PCE of chlorinated m-TiO2 C-PSCs greatly improved. Based on (5-AVA)x(MA)1-xPbI3, C-PSCs with TiO2 ETL treated with HCl aqueous solution achieved an average photovoltaic conversion efficiency of 9.36 %, which is an increase of 7.96 % in comparison with the efficiency of the device using unmodified TiO2 ETL, while the Voc and the Jsc were increased by 3.63 % and 2.63 %, respectively. In a 30-day aging test, C-PSCs based on (5-AVA)x(MA)1-xPbI3 and TiO2-HCl 1 exhibited excellent stability under ambient air conditions.

Electron injection and defect passivation for high-efficiency mesoporous perovskite solar cells.

Printable mesoscopic perovskite solar cells (p-MPSCs) do not require the added hole-transport layer needed in traditional p-n junctions but have also exhibited lower power conversion efficiencies of about 19%. We performed device simulation and carrier dynamics analysis to design a p-MPSC with mesoporous layers of semiconducting titanium dioxide, insulating zirconium dioxide, and conducting carbon infiltrated with perovskite that enabled three-dimensional injection of photoexcited electrons into titanium dioxide for collection at a transparent conductor layer. Holes underwent long-distance diffusion toward the carbon back electrode, and this carrier separation reduced recombination at the back contact. Nonradiative recombination at the bulk titanium dioxide/perovskite interface was reduced by ammonium phosphate modification. The resulting p-MPSCs achieved a power conversion efficiency of 22.2% and maintained 97% of their initial efficiency after 750 hours of maximum power point tracking at 55 ± 5°C.

Experimental and theoretical study of improved mesoporous titanium dioxide perovskite solar cell: The impact of modification with graphene oxide

The present study serves experimental and theoretical analyses in developing a hybrid advanced structure as a photolysis, which is based on electrospun Graphene Oxide-titanium dioxide (GO-TiO2) nanofibers as an electron transfer material (ETMs) functionalized for perovskite solar cell (PVSCs) with GO. The prepared ETMs were utilized for the synthesis of mixed-cation (FAPbI3)0.8(MAPbBr3)0.2. The effect of GO on TiO2 and their chemical structure, electronic and morphological characteristic were investigated and discussed. The elaborated device, namely ITO/Bl-TiO2/3 wt% GO-TiO2/(FAPbI3)0.8(MAPbBr3)0.2/spiro-MeTAD/Pt, displayed 20.14% disposition and conversion solar energy with fill factor (FF) of 1.176%, short circuit current density (Jsc) of 20.56 mA/cm2 and open circuit voltage (VOC) 0.912 V. The obtained efficiency is higher than titanium oxide (18.42%) and other prepared GO-TiO2 composite nanofibers based ETMs. The developed materials and device would facilitate elaboration of advanced functional materials and devices for energy storage applications.

Understanding the Anomalous J–V Curves in Carbon‐Based Perovskite Solar Cells as a Structural Transition Induced by Ion Diffusion

The investigation of hole transport layer‐free mesoporous carbon perovskite solar cells by analyzing current–voltage (J–V) curves under different scan rates, light intensities, and temperatures is presented. A distinctive bump in the curves is identified, previously reported in the literature. The voltage at the inflection point of this transition shows a linear correlation with the scan rate, directly yielding a characteristic relaxation time. Increasing temperature demonstrates a reduction in the magnitude and characteristic time of the bump. It also indicates an activation energy of 0.8 eV, suggesting a diffusion mechanism. Importantly, the intensity of the illumination has no influence on the overall behavior, indicating that the phenomenon is not a photovoltaic processes. It is proposed that the bump originates from transition between a metastable state at high scan rates and a stable one reached after relaxation. To accurately replicate the measured J–V curves, a novel lumped circuit model is introduced and validated. A schematic microstructural model depicts the reversible reduction in photocurrent as a decline in charge transfer capacity caused by the diffusion of large ions at the mesoporous titanuim dioxyde interface. Ultimately, this study also suggests a plausible reason for the well‐known hysteresis commonly observed with perovskite solar cells.

Well-organized SnO2 inverse opal monolayer as structured electron transport layer for high-efficiency perovskite solar cells

In mesoporous perovskite solar cells (mp-PSCs), an electron transport layer (ETL) plays an important role in charge extraction and transportation, and also its structure largely affects the crystallization and optical property of perovskite films. At present, the performance of PSCs based mesoporous SnO2 (mp-SnO2) still lags behind that based planar SnO2 due to problems in the fabrication process of mp-SnO2. Herein, a well-organized monolayer SnO2 inverse opal (SIO) is prepared as the structured ETL for perovskite solar cells. The unique periodic SIO structure exhibits an obvious optical coupling phenomenon, which enhances the light absorption of the perovskite layer. Furthermore, the well-organized SIO structure with appropriate pore size triggers the confined crystallization of perovskite films and optimizes the interface of SnO2/perovskites, suppressing the interfacial electron–hole recombination. As a result, the power conversion efficiency of mp-PSCs fabricated by the monolayer SIO is boosted from 19.63% to 22.01%. This work provides a creative strategy for construction of high-efficiency mp-PSCs based on SnO2.

Efficient and Stable Mesoporous CsSnI3 Perovskite Solar Cells via Imidazolium‐Based Ionic Liquid Additive

Inorganic tin halide perovskite compound with its eco‐friendly property has attracted tremendous attention of researchers in the field of lead‐free perovskite solar cells. However, the trap‐assisted nonradiative recombination caused by deep‐level defects originating from surface undercoordinated Sn2+ cations significantly deteriorates the CsSnI3 device's performance. Herein, adding low concentrations of an ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EMIMAc) shows promise in controlling deep‐level defects in CsSnI3 perovskites. Both experimental observation and theoretical simulation reveal that EMIMAc can have strong electrostatic attraction and coordination interaction with the surface undercoordinated Sn2+ through the lone electron pairs of carboxyl functional groups and the donated π electrons from electron‐rich imidazole moieties, leading to a reduced deep‐level defect density and a restrained nonradiative recombination. Consequently, the processed CsSnI3 perovskite solar cells based on a printable fluorine‐doped tin oxide/compact‐TiO2/mesoporous‐TiO2/Al2O3/NiO/carbon framework achieve a power conversion efficiency as high as 8.54%, which is the champion efficiency among all the reported CsSnI3 mesoporous perovskite solar cells up to now. In addition, the unencapsulated devices have shown an impressive long‐term stability with only ≈6% efficiency degradation after over 2000 h aging under nitrogen atmosphere.

Low-Temperature Processed Brookite Interfacial Modification for Perovskite Solar Cells with Improved Performance.

The scaffold layer plays an important role in transporting electrons and preventing carrier recombination in mesoporous perovskite solar cells (PSCs), so the engineering of the interface between the scaffold layer and the light absorption layer has attracted widespread concern. In this work, vertically grown TiO2 nanorods (NRs) as scaffold layers are fabricated and further treated with TiCl4 aqueous solution. It can be found that a thin brookite TiO2 nanoparticle (NP) layer is formed by the chemical bath deposition (CBD) method on the surface of every rutile NR with a low annealing temperature (150 °C), which is beneficial for the infiltration and growth of perovskite. The PSC based on the TiO2 NR/brookite NP structure shows the best power conversion of 15.2%, which is 56.37% higher than that of the PSC based on bare NRs (9.72%). This complex structure presents an improved pore filling fraction and better carrier transport capability with less trap-assisted carrier recombination. In addition, low-annealing-temperature-formed brookite NPs possess a more suitable edge potential for electrons to transport from the perovskite layer to the electron collection layer when compared with high-annealing-temperature-formed anatase NPs. The brookite phase TiO2 fabricated at a low temperature presents great potential for flexible PSCs.

A Geometrically Well-Defined and Systematically Tunable Experimental Model to Transition from Planar to Mesoporous Perovskite Solar Cells.

A series of perovskite solar cells with systematically varying surface area of the interface between n-type electron conducting layer (TiO2) and perovskite are prepared by using an ordered array of straight, cylindrical nanopores generated by anodizing an aluminum layer evaporated onto a transparent conducting electrode. A series of samples with pore length varied from 100 to 500 nm are compared to each other and complemented by a classical planar cell and a mesoporous counterpart. All samples are characterized in terms of morphology, chemistry, optical properties, and performance. All samples absorb light to the same degree, and the increased interface area does not generate enhanced recombination. However, the short circuit current density increases monotonically with the specific surface area, indicating improved charge extraction efficiency. The importance of the slow interfacial rearrangement of ions associated with planar perovskite cells is shown to decrease in a systematic manner as the interfacial surface area increases. The results demonstrate that planar and mesoporous cells obey to the same physical principles and differ from each other quantitatively, not qualitatively. Additionally, the study shows that a significantly lower TiO2 surface area compared to mesoporous TiO2 is needed for an equal charge extraction.

Effect of Ionic Liquid Methylammonium Acetate on the Performance of Hole-Transport Material-Free Mesoporous Perovskite Solar Cells with Carbon Electrode

Effect of Ionic Liquid Methylammonium Acetate on the Performance of Hole-Transport Material-Free Mesoporous Perovskite Solar Cells with Carbon Electrode

Optical Modelling of Planar and Fibre Perovskite Solar Cells

We present the optical modelling of a mesoporous fibre perovskite solar cell (PSC). It was conducted by means of the transmission line method (TLM), which was used to calculate the efficiency and short-circuit photo-current density of the cell. The TLM was first applied for a planar mesoporous PSC and verified with the experimental results from the literature. Numerical calculations for both planar and fibre PSC were conducted and analysed regarding their efficiency in terms of optical simulation. The importance of choosing the thin-film layers’ materials and thickness was demonstrated, and a potential improvement using anti-reflection coatings was also examined.

Photoelectric Properties of Planar and Mesoporous Structured Perovskite Solar Cells.

The high efficiency of perovskite solar cells strongly depends on the quality of perovskite films and carrier extraction layers. Here, we present the results of an investigation of the photoelectric properties of solar cells based on perovskite films grown on compact and mesoporous titanium dioxide layers. Kinetics of charge carrier transport and their extraction in triple-cation perovskite solar cells were studied by using transient photovoltage and time-resolved photoluminescence decay measurements. X-ray diffraction analysis revealed that the crystallinity of the perovskite films grown on mesoporous titanium dioxide is better compared to the films grown on compact TiO2. Mesoporous structured perovskite solar cells are found to have higher power conversion efficiency mainly due to enlarged perovskite/mesoporous -TiO2 interfacial area and better crystallinity of their perovskite films.

Highly Efficient Dopant-Free Cyano-Substituted Spiro-Type Hole-Transporting Materials for Perovskite Solar Cells

The hole-transporting material (HTM) is an important component of perovskite solar cells (PSCs) because it plays a crucial role in achieving high performance. The most frequently used HTM is 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamino)-9,9′-spirobifluorene (Spiro-OMeTAD). Spiro-OMeTAD requires dopants such as Li(TFSI) to realize high power conversion efficiencies (PCEs). However, these dopants cause severe instability issues in PSCs. The Spiro-OMeTAD layer also tends to undergo severe morphological deformation at high temperature, which produces large voids and further reduces the cell performance. These drawbacks must be overcome for the commercialization of PSCs. Therefore, it is strongly desirable to develop high-performance dopant-free HTMs to replace Spiro-OMeTAD. Here, we synthesize two cyano-substituted spirobifluorene-based HTMs, SF27 and SF48, for this purpose. These compounds are derived from Spiro-N, which is a Spiro-OMeTAD analogue obtained via the replacement of the p-methoxy substituents with strong electron-donating p-N,N-dimethylamino groups. The influence of cyano substituents on the optoelectronic properties, PCEs, and charge transport behavior in PSCs are investigated. These compounds have a highest occupied molecular orbital energy level that is well-matched to the valence band of perovskite layers. The hole mobility of SF48 (o-cyano-substituted) was determined to be higher than that of SF27 (m-cyano-substituted), although it is lower than those of Spiro-OMeTAD and the reference compound Spiro-N. Mesoporous PSCs were fabricated using these new HTMs without dopants under relatively low HTM concentration conditions, and the cell performance was compared to that of devices with Spiro-OMeTAD and Spiro-N. The PSC with non-doped SF48 exhibited a high PCE of 18.7%, which is comparable to that of the reference PSCs with doped Spiro-OMeTAD (18.6%). In addition, the thermal stability of SF48 at 85 °C in air was superior to that of Spiro-OMeTAD, both with and without dopants. Therefore, the SF48 spirobifluorene-based compound is determined to be quite effective as a high-performance dopant-free HTM for PSCs.

Beyond hydrophobicity: how F4-TCNQ doping of the hole transport material improves stability of mesoporous triple-cation perovskite solar cells

High uniformity of hydrophobic F4-TCNQ doping in the spiro-OMeTAD layer hinders the dopant migration towards the anode as well as the dopant aggregation, leading to a T80 shelf-lifetime of >1 year.

Cotton soot derived carbon nanoparticles for NiO supported processing temperature tuned ambient perovskite solar cells

The emergence of perovskite solar cells (PSCs) in a "catfish effect" of other conventional photovoltaic technologies with the massive growth of high-power conversion efficiency (PCE) has given a new direction to the entire solar energy field. Replacing traditional metal-based electrodes with carbon-based materials is one of the front-runners among many other investigations in this field due to its cost-effective processability and high stability. Carbon-based perovskite solar cells (c-PSCs) have shown great potential for the development of large scale photovoltaics. First of its kind, here we introduce a facile and cost-effective large scale carbon nanoparticles (CNPs) synthesis from mustard oil assisted cotton combustion for utilization in the mesoporous carbon-based perovskite solar cell (PSC). Also, we instigate two different directions of utilizing the carbon nanoparticles for a composite high temperature processed electrode (HTCN) and a low temperature processed electrode (LTCN) with detailed performance comparison. NiO/CNP composite thin film was used in high temperature processed electrodes, and for low temperature processed electrodes, separate NiO and CNP layers were deposited. The HTCN devices with the cell structure FTO/c-TiO2/m-TiO2/m-ZrO2/high-temperature NiO-CNP composite paste/infiltrated MAPI (CH3NH3PbI3) achieved a maximum PCE of 13.2%. In addition, high temperature based carbon devices had remarkable stability of ~ 1000 h (ambient condition), retaining almost 90% of their initial efficiency. In contrast, LTCN devices with configuration FTO/c-TiO2/m-TiO2/m-ZrO2/NiO/MAPI/low-temperature CNP had a PCE limit of 14.2%, maintaining ~ 72% of the initial PCE after 1000 h. Nevertheless, we believe this promising approach and the comparative study between the two different techniques would be highly suitable and adequate for the upcoming cutting-edge experimentations of PSC.

Improved morphology, structure and optical properties of CH3NH3PbI3 film via HQ additive in PbI2 precursor solution for efficient and stable mesoporous perovskite solar cells

The hybrid halide perovskite is a promising material among next-generation photovoltaic devices due to its high absorption coefficient, low-cost raw materials, and facile film and device fabrication. However, due to the nature of solution processing and lack of precise control over the crystallization of perovskite thin films, a variety of defects, for example, pinholes and grain boundaries can form as a result of the processing conditions that decrease their efficiency and stability. Further, controlling the surface morphology, grain size, charge recombination and optical properties in the perovskite layer is critical to enhancing the photovoltaic performance and stability of solar cells. Here, we mainly focus on a simple and effective method for crystal growth and defect passivation via additive engineering in CH3NH3PbI3 perovskite films were prepared by a two-step deposition process. For this purpose, we introduce the incorporation of hydroxyquinoline (HQ), as one of the Lewis bases with coordinating capability, into the perovskite precursor solution to control nucleation, crystal growth, and optical properties of prepared perovskite films. The results show that HQ additive has a good strategy to improve the perovskite film for perovskite solar cells (PSCs) applications. As a result, we realized stable and efficient mesoporous PSCs, prepared with 0.3 wt% HQ additive, with excellent reproducibility achieving a champion efficiency of 16.33%, higher than that of the pristine one (12.35%) and the ambient condition stability of devices retain 80% of the initial values after 30 days of storage, which is higher than that of pristine PSCs without HQ additive (25%).

Exploring the growth of MAPbI3 under different preparation methods for mesoporous perovskite solar cells

The control of the perovskite growth morphology plays an extremely critical role in mesoporous perovskite solar cells. In this paper, anatase TiO2 nanoparticles (NPs) with high crystallinity were synthesized by a hydrothermal method, and the thickness of the TiO2 mesoporous film (TiO2-MT) was adjusted with concentration of TiO2-NP slurry by controlling ethanol. The perovskite layers were prepared by the traditional two-step (TTS) method, and the improved two-step (ITS) method was used. It is proved that different preparation processes of the perovskite light-absorbing layers have a certain influence on the photoelectric performance of the cell device, but also, the thickness of the TiO2mesoporous film affects the electron transport efficiency at the TiO2/MAPbI3 interface and the suppression of electron–hole recombination through [Formula: see text]–[Formula: see text] positive and negative scanning, electrochemical impedance spectroscopy (EIS) and dark state [Formula: see text]–[Formula: see text] curve analysis of the device. By optimizing the thickness of the TiO2 mesoporous film, the short-circuit photocurrent density ([Formula: see text] of mesoporous perovskite solar cells (M-PSCs) based on the TiO2 mesoporous electron transporting layer of 400 nm thickness is 23.85 mA/cm2, and the optimal photoelectric conversion efficiency (PCE) is 15.38%.

Mesoporous perovskite solar cells with Al- and Zn-based metal-organic frameworks

The improvement of lead halide perovskites solar cells (PSC) by hydrophobic metal-organic frameworks (MOF) is one of the promising tools for modern photovoltaic technology to achieve stable and efficient thin-film devices. To show the MOF applicability for PSC, we incorporate two types of MOF: NH2-MIL-53(Al) and basolite Z1200 in n-i-p mesoporous MAPbI3 based solar cells that can add 2.2% efficiency by increasing main photovoltaic parameters. The simplicity of the proposed MOF’s integration allows to use and adopt this approach to incorporate other frameworks for thin-film perovskite devices.

Ethanol-incorporated lead iodide precursor solution for improving triple-cation perovskite performance

Herein, a solvent additive of ethanol is added into lead iodide precursor solution for mesoporous perovskite solar cells (PSCs). This solvent additive method achieving improved charge injection and hole blocking merits. Also, a power conversion efficiency (PCE) of 18.37% is obtained, a remarkable improvement in comparison that without ethanol additive. These enhancements are related to the better features of triple-cation perovskite as compared to untreated perovskite film, such as passivated grain boundaries, lower surface defects, higher crystallinity and mitigated electron–hole recombination processes.

Properties of the mesoporous perovskite solar cell by plasma surface activation with a titanium dioxide electrode

Perovskite solar cells (PSCs) have attracted considerable attention as accessible solar cells due to its ease of fabrication, high energy-conversion efficiency, and low manufacturing costs. This study explores the effect of plasma treatment over time (10, 20, 30 min) on the mesoporous titanium dioxide layer. The solar cell fabrication process was investigated to enhance the efficiency of the power conversion of the PSCs. After modifying the interface between the electron transporting layer and the perovskite layer by plasma surface activation, the plasma surface activation characteristics on the TiO2 electrode were studied. The performance of the PSCs was also studied.