Breaking the bottleneck of lead-free perovskite solar cells through dimensionality modulation.

The emerging perovskite solar cell (PSC) technology has attracted significant attention due to its superior power conversion efficiency (PCE) among the thin-film photovoltaic technologies. However, the toxicity of lead and poor stability of lead halide materials hinder their commercialization. In this case, after a decade of effort, various categories of lead-free perovskites and perovskite-like materials have been developed, including tin halide perovskites, double perovskites, defect-structured perovskites, and rudorffites. However, the performance of the corresponding devices still falls short of expectations, especially their PCE. The limitations mainly originate from either the unstable lattice structure of these materials, which causes the distortion of their octahedra, or their low dimensionality (e.g., structural and electronic dimensionality)-correlated poor carrier transport and self-trapping effect, accelerating nonradiative recombination. Therefore, understanding the relationship between the structures and performance in these emerging candidates and leveraging these insights to design or modify new lead-free perovskites is of great significance. Herein, we review the variety of dimensionalities in different categories of lead-free perovskites and perovskite-like materials and conclude that dimensionality is an important aspect among the crucial indexes that determine the performance of lead-free PSCs. In addition, we summarize the modulation of both structural and electronic dimensionality, and the corresponding enhanced optoelectronic properties in different categories. Finally, perspectives on the future development of lead-free perovskites and perovskite-like materials for photovoltaic applications are provided. We hope that this review will provide researchers with a concise overview of these emerging materials and help them leverage dimensionality to break the bottleneck in photovoltaic applications.

Ruddlesden-Popper Perovskite Nanocrystals as Interface Modification Layer for Efficient Perovskite Solar Cells.

Perovskite nanocrystals are advantageous for interfacial passivation of perovskite solar cells (PSCs), but the insulating long alkyl chain surface ligands impede the charge transfer, while the conventional ligand exchange would possibly introduce surface defects to the nanocrystals. In this work, we reported novel in situ modification of CsPbBr3 nanocrystals using a short chain conjugated molecule 2-methoxyphenylethylammonium iodide (2-MeO-PEAI) for interfacial passivation of PSCs. Transmission electron microscopy studies with atomic resolution unveil the transformation from cubic CsPbBr3 to Ruddlesden-Popper phase (RPP) nanocrystals due to halogen exchange. Synergic passivation by the RPP nanocrystals and 2-MeO-PEA+ has led to suppressed interface defects and enhanced charge carrier transport. Consequently, PSCs with in situ modified RPP nanocrystals achieved a champion power conversion efficiency of 24.39%, along with an improvement in stability. This work brings insights into the microstructural evolution of perovskite nanocrystals, providing a novel and feasible approach for interfacial passivation of PSCs.

Exciton and bi-exciton mechanisms in amplified spontaneous emission from CsPbBr3 perovskite thin films.

We studied temperature-dependent amplified spontaneous emission (ASE) in CsPbBr3 perovskite thin films. For temperatures 180-360 K, a narrow-band lasing is observed. However, a new accompanying ASE band appears below 180 K, indicating a more complicated behavior. The two ASE bands are strongly correlated and in competition; they are assigned as exciton and bi-exciton recombination. We estimated the exciton binding energy (EB = 27.3 meV) and that of the bi-exciton, which is lower than the EB. The reduced effective mass of the exciton is estimated as µ = 0.11 me. This discovery identifies more details of the ASE phenomenon.

Investigation on binding energy and reduced effective mass of exciton in organic-inorganic hybrid lead perovskite films by a pure optical method.

The exciton binding energy and its reduced effective mass in hybrid lead perovskite, which play a key role in the process of excitons forming, largely determine the excellent optical properties of the perovskite materials and hence, the device performance. We introduce the systematic measurements on these two parameters of the organic-inorganic hybrid perovskite films of (MA/FA)Pb(Br/I)3 by a unique temperature and density-resolved optical spectroscopic method. The method is simple and straightforward, since it directly observes the exciton ionization and recombination. Our results describe the fundamental photoelectric properties for understanding the excellent performance of the perovskite materials.

Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes.

Colloidal perovskite nanocrystals (PNCs) display bright luminescence for light-emitting diode (LED) applications; however, they require post-synthesis ligand exchange that may cause surface degradation and defect formation. In situ-formed PNCs achieve improved surface passivation using a straightforward synthetic approach, but their LED performance at the green wavelength is not yet comparable with that of colloidal PNC devices. Here, it is found that the limitations of in situ-formed PNCs stem from uncontrolled formation kinetics: conventional surface ligands confine perovskite nuclei but fail to delay crystal growth. A bifunctional carboxylic-acid-containing ammonium hydrobromide ligand that separates crystal growth from nucleation is introduced, leading to the formation of quantum-confined PNC solids exhibiting a narrow size distribution. Controlled crystallization is further coupled with defect passivation using deprotonated phosphinates, enabling improvements in photoluminescence quantum yield to near unity. Green LEDs are fabricated with a maximum current efficiency of 109 cd A-1 and an average external quantum efficiency of 22.5% across 25 devices, exceeding the performance of their colloidal PNC-based counterparts. A 45.6 h operating half-time is further documented for an unencapsulated device in N2 with an initial brightness of 100 cd m-2 .

In-plane stimulated emission of polycrystalline CH3NH3PbBr3 perovskite thin films.

Hybrid organic-inorganic lead halide perovskites have been investigated extensively within the last decades, for its great potential in efficient solar cells and as an ideal light source. Among the studies on stimulated emission (SE), the emission is either out-of-plane for polycrystalline films or in-plane with randomly aligned single microcrystals and nanowires. In this work, we revealed in-plane propagation of SE from bromine-based perovskite polycrystalline thin films (CH3NH3PbBr3, or MAPbBr3). The output from in-plane SE is an order higher than the out-of-plane emission. It is proposed that large crystalline flakes in the films lead to the in-plane lasing phenomena. The output coupling can be found at grain boundaries, intergrain gaps, and artificial structures. Simulative results support the experimental phenomenon that large crystalline grains are profitable for in-plane propagation and over 90% photons can be sufficiently outcoupled when the gap is larger than a micron. Considering the fabrication and handling convenience, we propose that the MAPbBr3 thin films can be easily integrated for in-plane applications as the light source for photonic chips etc.

Efficient and Stable Perovskite Solar Cell with High Open-Circuit Voltage by Dimensional Interface Modification.

High-efficiency organic-inorganic hybrid perovskite solar cells have experienced rapid development and attracted significant attention in recent years. However, instability to an ambient environment such as moisture is a facile challenge for the application of perovskite solar cells. Herein, 1,8-octanediammonium iodide (ODAI) is employed to construct a two-dimensional modified interface by in situ combined with residual PbI2 on the formamidinium lead iodide (FAPbI3) perovskite surface. The ODA2+ ion seems to lie horizontally on the surface of a three-dimensional perovskite due to its substitution for two FA+ ions, which could protect the bulk perovskite more effectively. The unencapsulated perovskite solar cells showed notably improved stability, which remained 92% of its initial efficiency after storing in an ambient environment for 120 days. In addition, a higher open-circuit voltage of 1.13 V compared to that of the control device (1.04 V) was obtained due to the interface energy level modification and defect passivation. A champion power conversion efficiency of 21.18% was therefore obtained with a stabilized power output of 20.64% at the maximum power point for planar perovskite solar cells.

To Greatly Reduce Defects via Photoannealing for High-Quality Perovskite Films.

The performance of perovskite solar cells (PSCs) depends on the crystallization of the perovskite layer. Herein, we demonstrate an effective photoannealing (PA) process by a halogen lamp. During the PA process, on the one hand, the lower energy photon, that is, near IR up to ∼1015 nm photon, drives the crystallization of the perovskite film, similar to the conventional thermal annealing (TA). On the other hand, the higher energy photon of PA can excite the trapped carriers and release the space charges, thus leading to an ideal perovskite layer with better crystallinity and lower density of defect when compared to that of TA. A maximum power conversion efficiency (PCE) has been obtained to be 20.41% in the CH3NH3PbI3-based planar PSCs based on PA because of the increase of Jsc and Voc, much higher than the control device based on the conventional TA with a maximum PCE of 18.08%. Therefore, this result demonstrates that PA is an effective method to promote the device performances and reduce the fabrication cost, which provides a potential approach for the commercial application of perovskite devices.

Solution-Processed Cu9S5 as a Hole Transport Layer for Efficient and Stable Perovskite Solar Cells.

Organic-inorganic perovskite solar cells have seen tremendous developments in recent years. As a hole transport material, 2,2',7,7'-tetrakis( N, N-di- p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) is widely used in n-i-p perovskite solar cells. However, it may lead to the perovskite film degradation due to the dopant lithium bis((trifluoromethyl)sulfonyl)amide (Li-TFSI), which has strong hydrophilicity. Cu9S5 is considered as a superior p-type transport material, which also has a favorable energy level matching with the highest occupied molecular orbital of Spiro-OMeTAD. Herein, a solution-processed organic-inorganic-integrated hole transport layer was reported, which is composed of the undoped Spiro-OMeTAD and Cu9S5 layer. Since there is no Li-TFSI doping, it is extremely conductive to the long-term stability of the solar cells. In the meantime, we proposed a method to adjust the lowest unoccupied molecular orbital (LUMO) of SnO2 via nitrogen implantation (N:SnO2). The LUMO of SnO2 can be tuned from -4.33 to -3.91 eV, which matches well with the LUMO of CH3NH3PbI3 (-3.90 eV), and thus helps to reduce hysteresis. The modified hole and electron transport layers were applied in n-i-p perovskite solar cells, which achieve a maximum power conversion efficiency (PCE) of 17.10 and 96% retention of PCE after 1200 h in air atmosphere without any encapsulation.

The Dawn of Lead-Free Perovskite Solar Cell: Highly Stable Double Perovskite Cs2AgBiBr6 Film.

Recently, lead-free double perovskites have emerged as a promising environmentally friendly photovoltaic material for their intrinsic thermodynamic stability, appropriate bandgaps, small carrier effective masses, and low exciton binding energies. However, currently no solar cell based on these double perovskites has been reported, due to the challenge in film processing. Herein, a first lead-free double perovskite planar heterojunction solar cell with a high quality Cs2AgBiBr6 film, fabricated by low-pressure assisted solution processing under ambient conditions, is reported. The device presents a best power conversion efficiency of 1.44%. The preliminary efficiency and the high stability under ambient condition without encapsulation, together with the high film quality with simple processing, demonstrate promise for lead-free perovskite solar cells.

High Crystallization of Perovskite Film by a Fast Electric Current Annealing Process.

High-efficiency organic-inorganic hybrid perovskite solar cells have experienced rapid development and attracted significant attention in recent years. Crystal growth as an important factor would significantly influence the quality of perovskite films and ultimately the device performance, which usually requires thermal annealing for 10 min or more. Herein, we demonstrate a new method to get high crystallization of perovskite film by electric current annealing for just 5 s. In contrast to conventional thermal annealing, a homogeneous perovskite film was formed with larger grains and fewer pinholes, leading to a better performance of the device with higher open-circuit voltage and fill factor. An average power conversion efficiency of 17.02% with electric current annealing was obtained, which is higher than that of devices with a conventional thermal annealing process (16.05%). This facile electric current annealing process with less energy loss and time consumption shows great potential in the industrial mass production of photovoltaic devices.

Ion Implantation-Modified Fluorine-Doped Tin Oxide by Zirconium with Continuously Tunable Work Function and Its Application in Perovskite Solar Cells.

In recent years, perovskite solar cells have drawn a widespread attention. As an electrode material, fluorine-doped tin oxide (FTO) is widely used in various kinds of solar cells. However, the relatively low work function (WF) (∼4.6 eV) limits its application. The potential barrier between the transparent conductive oxide electrode and the hole transport layer (HTL) in inverted perovskite solar cells results in a decrease in device performance. In this paper, we propose a method to adjust WF of FTO by implanting zirconium ions into the FTO surface. The WF of FTO can be precisely and continuously tuned between 4.59 and 5.55 eV through different dopant concentration of zirconium. In the meantime, the modified FTO, which had a WF of 5.1 eV to match well the highest occupied molecular orbital energy level of poly(3,4-ethylenedioxylenethiophene):polystyrene sulfonate, was used as the HTL in inverted planar perovskite solar cells. Compared with the pristine FTO electrode-based device, the open circuit voltage increased from 0.82 to 0.91 V, and the power conversion efficiency increased from 11.6 to 14.0%.

High-Performance Self-powered Photodetectors Based on ZnO/ZnS Core-Shell Nanorod Arrays.

In recent years, there is an urgent demand for high-performance ultraviolet photodetectors with high photosensitivity, fast responsivity, and excellent spectral selectivity. In this letter, we report a self-powered photoelectrochemical cell-type UV detector using the ZnO/ZnS core-shell nanorod array as the active photoanode and deionized water as the electrolyte. This photodetector demonstrates an excellent spectral selectivity and a rapid photoresponse time of about 0.04 s. And the maximum responsivity is more than 0.056 (A/W) at 340 nm, which shows an improvement of 180 % compared to detectors based on the bare ZnO nanorods. This improved photoresponsivity can be understood from the step-like band energy alignment of the ZnO/ZnS interface, which will accelerate the separation of photoexcited electron-hole pairs and improve the efficiency of the photodetector. Considering its uncomplicated low-cost fabrication process, and environment-friendly feature, this self-powered device is a promising candidate for UV detector application.

ZnO nanosheet arrays constructed on weaved titanium wire for CdS-sensitized solar cells.

Ordered ZnO nanosheet arrays were grown on weaved titanium wires by a low-temperature hydrothermal method. CdS nanoparticles were deposited onto the ZnO nanosheet arrays using the successive ionic layer adsorption and reaction method to make a photoanode. Nanoparticle-sensitized solar cells were assembled using these CdS/ZnO nanostructured photoanodes, and their photovoltaic performance was studied systematically. The best light-to-electricity conversion efficiency was obtained to be 2.17% under 100 mW/cm2 illumination, and a remarkable short-circuit photocurrent density of approximately 20.1 mA/cm2 was recorded, which could attribute to the relatively direct pathways for transportation of electrons provided by ZnO nanosheet arrays as well as the direct contact between ZnO and weaved titanium wires. These results indicate that CdS/ZnO nanostructures on weaved titanium wires would open a novel possibility for applications of low-cost solar cells.

CdS quantum dot-sensitized solar cells based on nano-branched TiO2 arrays.

Nano-branched rutile TiO2 nanorod arrays were grown on F:SnO2 conductive glass (FTO) by a facile, two-step wet chemical synthesis process at low temperature. The length of the nanobranches was tailored by controlling the growth time, after which CdS quantum dots were deposited on the nano-branched TiO2 arrays using the successive ionic layer adsorption and reaction method to make a photoanode for quantum dot-sensitized solar cells (QDSCs). The photovoltaic properties of the CdS-sensitized nano-branched TiO2 solar cells were studied systematically. A short-circuit current intensity of approximately 7 mA/cm2 and a light-to-electricity conversion efficiency of 0.95% were recorded for cells based on optimized nano-branched TiO2 arrays, indicating an increase of 138% compared to those based on unbranched TiO2 nanorod arrays. The improved performance is attributed to a markedly enlarged surface area provided by the nanobranches and better electron conductivity in the one-dimensional, well-aligned TiO2 nanorod trunks.