Layered Germanium Hybrid Perovskite Bromides: Insights from Experiments and First‐Principles Calculations

Metal halide perovskites are maturing as materials for efficient, yet low cost solar cells and light‐emitting diodes, with improving operational stability and reliability. To date however, most perovskite‐based devices contain Pb, which poses environmental concerns due to its toxicity; lead‐free alternatives are of importance to facilitate the development of perovskite‐based devices. Here, the germanium‐based Ruddledsen–Popper series (CH₃(CH₂)₃NH₃)₂(CH₃NH₃)_n?1Ge_nBr_3n+1 is investigated, derived from the parent 3D (n = ∞) CH₃NH₃GeBr₃ perovskite. Divalent germanium is a promising, nontoxic alternative to Pb²⁺ and the layered, 2D structure appears promising to bolster light emission, long‐term durability, and moisture tolerance. The work, which combines experiments and first principle calculations, highlights that in germanium bromide perovskites the optical bandgap is weakly affected by 2D confinement and the highly stereochemically active 4s² lone pair preludes to possible ferroelectricity, a topic still debated in Pb‐containing compounds.     

A comprehensive theoretical study of halide perovskites ABX3

Solar cells based on halide perovskites have recently been attractive due to their excellent power conversion efficiency (PCE), lower cost and simple manufacture. Here, a series of halide perovskites (ABX₃: A = CH₃NH₃, CH(NH₂)₂, Cs, Rb; B = Pb, Sn, Ge; X = I, Br, Cl, F) were investigated by Density Functional Theory (DFT) calculations, together with Shockley-Queisser Maximum Solar Cell Efficiency (S-Q) and Spectroscopic Limited Maximum Efficiency (SLME) mathematical models. The results indicate that: the electronic structure of germanium perovskites bears a close similarity to that of lead perovskites with a small energy difference between the nonbonding orbital and antibonding orbitals, but with a large energy difference comparing with that of tin perovskites (0.6–1.7 eV for CsGeI₃ at Z point of the Brillouin zone, 0.7–1.4 eV for CH₃NH₃PbI₃ and 1.4–2.2 eV for CH₃NH₃SnI₃ at R point of the Brillouin zone), which is attributable to the atomic level, where the 4s orbital energy of Ge (−11.5 eV) is close to the 6s orbital energy of Pb (−11.6 eV), but the 5s orbital energy of Sn (−10.1 eV) is significantly high. Therefore, germanium perovskites possess as high absorption coefficient around solar spectrum as lead perovskites, while tin perovskites only have low absorption coefficient, which makes the short-circuit current of CsGeI₃ and CH₃NH₃PbI₃ (0.017 Acm⁻² and 0.016 Acm⁻², simulated by SLME with a 200 nm absorber under AM1.5G) are higher than that of CH₃NH₃SnI₃ (0.015 Acm⁻²) even if the bandgap of CsGeI₃ and CH₃NH₃PbI₃ (1.51 eV and 1.55 eV) are larger than that of CH₃NH₃SnI₃ (1.21 eV). Meanwhile, the effective mass of electrons and holes are approximate for germanium perovskites and lead perovskites (0.14:0.19 for CsGeI₃ and 0.12:0.12 for CH₃NH₃PbI₃), indicating a balanced electrons and holes transport, whereas the electrons transport is much slower than the holes transport for tin perovskites due to the effective mass of electron is much larger than that of hole (0.17:0.04 for CH₃NH₃SnI₃). As a result, the PCE of CsGeI₃ (27.9%) and CH₃NH₃PbI₃ (26.7%) is higher than that of CH₃NH₃SnI₃ (19.9%).     

Calculation studies on point defects in perovskite solar cells

The close-to-optimal band gap, large absorption coefficient, low manufacturing cost and rapid increase in power conversion efficiency make the organic-inorganic hybrid halide (CH₃NH₃PbI₃) and related perovskite solar cells very promising for commercialization. The properties of point defects in the absorber layer semiconductors have important influence on the photovoltaic performance of solar cells, so the investigation on the defect properties in the perovskite semiconductors is necessary for the optimization of their photovoltaic performance. In this work, we give a brief review to the first-principles calculation studies on the defect properties in a series of perovskite semiconductors, including the organic-inorganic hybrid perovskites and inorganic halide perovskites. Experimental identification of these point defects and characterization of their properties are called for.     

High‐Performance Flexible Broadband Photodetector Based on Organolead Halide Perovskite

Organolead halide perovskites have attracted extensive attentions as light harvesting materials for solar cells recently, because of its high charge‐carrier mobilities, high photoconversion efficiencies, low energy cost, ease of deposition, and so on. Herein, with CH₃NH₃PbI₃ film deposited on flexible ITO coated substrate, the first organolead halide perovskite based broadband photodetector is demonstrated. The organolead halide perovskite photodetector is sensitive to a broadband wavelength from the ultraviolet light to entire visible light, showing a photo‐responsivity of 3.49 A W^?1, 0.0367 A W^?1, an external quantum efficiency of 1.19×10³%, 5.84% at 365 nm and 780 nm with a voltage bias of 3 V, respectively. Additionally, the as‐fabricated photodetector exhibit excellent flexibility and robustness with no obvious variation of photocurrent after bending for several times. The organolead halide perovskite photodetector with high sensitivity, high speed and broad spectrum photoresponse is promising for further practical applications. And this platform creates new opportunities for the development of low‐cost, solution‐processed and high‐efficiency photodetectors.     

Controllable Perovskite Crystallization by Water Additive for High‐Performance Solar Cells

A key issue for perovskite solar cells is the stability of perovskite materials due to moisture effects under ambient conditions, although their efficiency is improved constantly. Herein, an improved CH₃NH₃PbI_3?xCl_x perovskite quality is demonstrated with good crystallization and stability by using water as an additive during crystal perovskite growth. Incorporating suitable water additives in N,N‐dimethylformamide (DMF) leads to controllable growth of perovskites due to the lower boiling point and the higher vapor pressure of water compared with DMF. In addition, CH₃NH₃PbI_3?xCl_x · nH₂O hydrated perovskites, which can be resistant to the corrosion by water molecules to some extent, are assumed to be generated during the annealing process. Accordingly, water additive based perovskite solar cells present a high power conversion efficiency of 16.06% and improved cell stability under ambient conditions compared with the references. The findings in this work provide a route to control the growth of crystal perovskites and a clue to improve the stability of organic–inorganic halide perovskites.     

Oriented Crystallization of Mixed‐Cation Tin Halides for Highly Efficient and Stable Lead‐Free Perovskite Solar Cells

As the most promising lead‐free branch, tin halide perovskites suffer from the severe oxidation from Sn²⁺ to Sn⁴⁺, which results in the unsatisfactory conversion efficiency far from what they deserve. In this work, by facile incorporation of methylammonium bromide in composition engineering, formamidinium and methylammonium mixed cations tin halide perovskite films with ultrahighly oriented crystallization are synthesized with the preferential facet of (001), and that oxidation is suppressed with obviously declined trap density. MA⁺ ions are responsible for that impressive orientation while Br^‐ ions account for their bandgap modulation. Depending on high quality of the optimal MA_0.25FA_0.75SnI_2.75Br_0.25 perovskite films, their device conversion efficiency surges to 9.31% in contrast to 5.02% of the control formamidinium tin triiodide perovskite (FASnI₃) device, along with almost eliminated hysteresis. That also results in the outstanding device stability, maintaining above 80% of the initial efficiency after 300 h of light soaking while the control FASnI₃ device fails within 120 h. This paper definitely paves a facile and effective way to develop high‐efficiency tin halide perovskites solar cells, optoelectronic devices, and beyond.     

Fluorinated Organic A-Cation Enabling High-Performance Hysteresis-Free 2D/3D Hybrid Tin Perovskite Transistors

2D tin-based perovskites have gained considerable attention for use in diverse optoelectronic applications, such as solar cells, lasers, and thin-film transistors (TFTs), owing to their good stability and optoelectronic properties. However, their intrinsic charge-transport properties are limited, and the insulating bulky organic ligands hinder the achievement of high-mobility electronics. Blending 3D counterparts into 2D perovskites to form 2D/3D hybrid structures is a synergistic approach that combine the high mobility and stability of 3D and 2D perovskites, respectively. In this study, reliable p-channel 2D/3D tin-based hybrid perovskite TFTs comprising 3D formamidinium tin iodide (FASnI₃) and 2D fluorinated 4-fluoro-phenethylammonium tin iodide ((4-FPEA)₂SnI₄) are reported. The optimized FPEA-incorporated TFTs show a high hole mobility of 12 cm² V⁻¹ s⁻¹, an on/off current ratio of over 10⁸, and a subthreshold swing of 0.09 V dec⁻¹ with negligible hysteresis. This excellent p-type characteristic is compatible with n-type metal-oxide TFT for constructing complementary electronics. Two procedures of antisolvent engineering and device patterning are further proposed to address the key concern of low-performance reproducibility of perovskite TFTs. This study provides an alternative A-cation engineering method for achieving high-performance and reliable tin-halide perovskite electronics.     

High‐Performance Near‐IR Photodetector Using Low‐Bandgap MA0.5FA0.5Pb0.5Sn0.5I3 Perovskite

Photodetectors with ultrafast response are explored using inorganic/organic hybrid perovskites. High responsivity and fast optoelectronic response are achieved due to the exceptional semiconducting properties of perovskite materials. However, most of the perovskite‐based photodetectors exploited to date are centered on Pb‐based perovskites, which only afford spectral response across the visible spectrum. This study demonstrates a high‐performance near‐IR (NIR) photodetector using a stable low‐bandgap Sn‐containing perovskite, (CH₃NH₃)_0.5(NH₂CHNH₂)_0.5Pb_0.5Sn_0.5I₃ (MA_0.5FA_0.5Pb_0.5Sn_0.5I₃), which is processed with an antioxidant additive, ascorbic acid (AA). The addition of AA effectively strengthens the stability of Sn‐containing perovskite against oxygen, thereby significantly inhibiting the leakage current. Consequently, the derived photodetector shows high responsivity with a detectivity of over 10¹² Jones ranging from 800 to 970 nm. Such low‐cost, solution processable NIR photodetectors with high performance show promising potential for future optoelectronic applications.     

Controlled Growth and Reliable Thickness‐Dependent Properties of Organic–Inorganic Perovskite Platelet Crystal

Organolead halide perovskites (e.g., CH₃NH₃PbI₃) have caught tremendous attention for their excellent optoelectronic properties and applications, especially as the active material for solar cells. Perovskite crystal quality and dimension is crucial for the fabrication of high‐performance optoelectronic and photovoltaic devices. Herein the controlled synthesis of organolead halide perovskite CH₃NH₃PbI₃ nanoplatelets on SiO₂/Si substrates is investigated via a convenient two‐step vapor transport deposition technique. The thickness and size of the perovskite can be well‐controlled from few‐layers to hundred nanometers by altering the synthesis time and temperature. Raman characterizations reveal that the evolutions of Raman peaks are sensitive to the thickness. Furthermore, from the time‐resolved photoluminescence measurements, the best optoelectronic performance of the perovskite platelet is attributed with thickness of ≈30 nm to its dominant longest lifetime (≈4.5 ns) of perovskite excitons, which means lower surface traps or defects. This work supplies an alternative to the synthesis of high‐quality organic perovskite and their possible optoelectronic applications with the most suitable materials.     

Organic–Inorganic Perovskite Light‐Emitting Electrochemical Cells with a Large Capacitance

While perovskite light‐emitting diodes typically made with high work function anodes and low work function cathodes have recently gained intense interests. Perovskite light‐emitting devices with two high work function electrodes with interesting features are demonstrated here. Firstly, electroluminescence can be easily obtained from both forward and reverse biases. Secondly, the results of impedance spectroscopy indicate that the ionic conductivity in the iodide perovskite (CH₃NH₃PbI₃) is large with a value of ≈10^?8 S cm^?1. Thirdly, the shift of the emission spectrum in the mixed halide perovskite (CH₃NH₃PbI_3?xBr_x) light‐emitting devices indicates that I^? ions are mobile in the perovskites. Fourthly, this work shows that the accumulated ions at the interfaces result in a large capacitance (≈100 μF cm^?2). The above results conclusively prove that the organic–inorganic halide perovskites are solid electrolytes with mixed ionic and electronic conductivity and the light‐emitting device is a light‐emitting electrochemical cell. The work also suggests that the organic–inorganic halide perovskites are potential energy‐storage materials, which may be applicable in the field of solid‐state supercapacitors and batteries.     

Nitrogen‐Dopant‐Induced Organic–Inorganic Hybrid Perovskite Crystal Growth on Carbon Nanotubes

Interfacial engineering of organic–inorganic halide perovskites in conjunction with different functional materials is anticipated to offer novel heterojunction structures with unique functionalities. Unfortunately, complex material compositions and structures of the organic–inorganic hybrid materials make it difficult to tailor a desirable intermolecular interaction at the interface. Spontaneous and highly specific nucleation of perovskite crystals, that is, methylammonium lead iodide perovskite (CH₃NH₃PbI₃, MAPbI₃) at nitrogen‐doped carbon nanotube (NCNT) surfaces for the self‐assembly of MAPbI₃/NCNT hybrids is reported. It is demonstrated that the lone‐pair electrons of pyridinic nitrogen‐dopant sites at NCNTs mediate specific interactions with the cationic component in the perovskite structure and serve as the nucleation sites via coordinate bonding formation, as supported by X‐ray photoelectron spectroscopy and density functional theory calculation. The potential suitability of MAPbI₃/NCNT hybrids is presented for highly sensitive and selective NO₂ sensing layer. This work suggests a reliable self‐assembly route to the molecular level hybridization of organic–inorganic halide perovskites by employing the substitutional dopant sites at graphene‐based nanomaterials.     

Stability Improvement of Tin-Based Halide Perovskite by Precursor-Solution Regulation with Dual-Functional Reagents

Tin-based halide perovskites have attracted great attention in the perovskite solar cells (PSCs) community with their suitable band gaps, excellent optoelectronic properties, and non-toxicity. However, because of their poor chemical stability, it is challenging to fabricate highly stable and efficient tin PSCs (TPSCs). In this study, the origin of the Sn²⁺ oxidation ahead of film formation is concentrated on, and it is found that the ionization of SnI₂ in precursor plays a decisive role. Accordingly, SnI₂ dissociation and the subsequent Sn²⁺ oxidation can be restricted in precursor by employing reductive complexes as additives. This dual-functional source-regulating strategy effectively helps prepare high-quality perovskite films with low Sn⁴⁺ defect densities. As a result, the unencapsulated TPSCs show a considerable power-conversion efficiency of 10.03% (certified 9.38%) and maintain 90% of its initial efficiency after 1000 h of light aging testing.     

Halide Perovskite Materials for Energy Storage Applications

Halide perovskites, traditionally a solar‐cell material that exhibits superior energy conversion properties, have recently been deployed in energy storage systems such as lithium‐ion batteries and photorechargeable batteries. Here, recent progress in halide perovskite‐based energy storage systems is presented, focusing on halide perovskite lithium‐ion batteries and halide perovskite photorechargeable batteries. Halide‐perovskite‐based supercapacitors and photosupercapacitors are also discussed. The photorechargeable batteries and photorechargeable supercapacitors employ solar energy to photocharge the battery; this saves energy and improves device portability. These lightweight, integrated halide perovskite‐based systems, which are pertinent to electric vehicles and portable electronic devices, are reviewed in detail. Suggestions on future research into the design of halide‐perovskite‐based energy storage materials are also given. This review provides a foundation for the development of integrated lightweight energy conversion and storage materials.     

A Self‐Powered and Stable All‐Perovskite Photodetector–Solar Cell Nanosystem

Hybrid organic–inorganic perovskites have attracted intensive interest as light absorbing materials in solid‐state solar cells. Herein, we demonstrate a high‐performance CH₃NH₃PbI₃‐based perovskite photodetector constructed on the flexible indium tin oxide (ITO) coated substrate even after 200 bending cycles. The as‐fabricated devices show high responsivity, broad spectrum response from ultraviolet to whole visible light, long‐term stability, and high on‐off ratio. Particularly, atomic layer deposition technique was used to deposit the ultrathin Al₂O₃ film on devices, functioning as a protection layer to effectively enhance the stability and durability of perovskite photodetectors. The first all‐perovskite self‐powered nanosystem was successfully assembled by integrating a perovskite solar cell with a perovskite photodetector. Driven by the perovskite solar cell, the photodetector exhibits fast and stable response to illuminated light at a low working voltage less than 1.0 V. This stable integrated nanosystem has promising applications in which photodetectors can work in harsh environments without external power sources.     

Room‐Temperature Partial Conversion of α‐FAPbI3 Perovskite Phase via PbI2 Solvation Enables High‐Performance Solar Cells

The two‐step conversion process consisting of metal halide deposition followed by conversion to hybrid perovskite has been successfully applied toward producing high‐quality solar cells of the archetypal MAPbI₃ hybrid perovskite, but the conversion of other halide perovskites, such as the lower bandgap FAPbI₃, is more challenging and tends to be hampered by the formation of hexagonal nonperovskite polymorph of FAPbI₃, requiring Cs addition and/or extensive thermal annealing. Here, an efficient room‐temperature conversion route of PbI₂ into the α‐FAPbI₃ perovskite phase without the use of cesium is demonstrated. Using in situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) and quartz crystal microbalance with dissipation (QCM‐D), the conversion behaviors of the PbI₂ precursor from its different states are compared. α‐FAPbI₃ forms spontaneously and efficiently at room temperature from P₂ (ordered solvated polymorphs with DMF) without hexagonal phase formation and leads to complete conversion after thermal annealing. The average power conversion efficiency (PCE) of the fabricated solar cells is greatly improved from 16.0(±0.32)% (conversion from annealed PbI₂) to 17.23(±0.28)% (from solvated PbI₂) with a champion device PCE > 18% due to reduction of carrier recombination rate. This work provides new design rules toward the room‐temperature phase transformation and processing of hybrid perovskite films based on FA⁺ cation without the need for Cs⁺ or mixed halide formulation.     

Electronic Structures and Photoconversion Mechanism in Perovskite/Fullerene Heterojunctions

It has been generally believed and assumed that organometal halide perovskites would form type II P–N junctions with fullerene derivatives (C₆₀ or PCBM), and the P–N junctions would provide driving force for exciton dissociation in perovskite‐based solar cell. To the best of our knowledge, there is so far no experiment proof on this assumption. On the other hand, whether photogenerated excitons can intrinsically dissociate into free carrier in the perovskite without any assistance from a P–N junction is still controversial. To address these, the interfacial electronic structures of a vacuum‐deposited perovskite/C₆₀ and a solution‐processed perovskite/PCBM junctions is directly measured by ultraviolet photoelectron spectroscopy. Contrary to the common believes, both junctions are found to be type I N–N junctions with band gap of the perovskites embedded by that of the fullerenes. Meanwhile, device with such a charge inert junction can still effectively functions as a solar cell. These results give direct experimental evidence that excitons are dissociated to free carriers in the perovskite film even without any assistance from a P–N junction.     

Sn-Based Self-Powered Ultrafast Perovskite Photodetectors with Highly Crystalline Order for Flexible Imaging Applications

Sn-based perovskite materials are promising lead-free alternatives in thin film photodetectors (PDs) for applications such as optical communications, night visions and biomedical near-infrared imaging systems. However, constructing Sn-based photodetectors with high sensitivity, ultrafast response, and good operation stability has been a challenge. Herein, the phenyl-ethyl ammonium (PEA⁺) additive is introduced in pristine FASnI₃, which regulates the thin film growth, passivates the trap/defect states, prevents Sn²⁺/Sn⁴⁺oxidation, and releases the crystal strain. The Resulting FA_0.8PEA_0.2SnI₃ thin films exhibit highly crystalline order and flexibility. A self-powered PD using FA_0.8PEA_0.2SnI₃ as the active layer demonstrates excellent responsivity of 0.262 W⁻¹, detectivity of 2.3 × 10¹¹ Jones. And it possesses the fastest rise and decay time of 25 µs and 42 µs as compared with the state-of-art Sn-based perovskite PDs. The transient absorption spectroscopy analysis validates greatly reduced trapping states and defects of FASnI₃ with the PEA⁺ film for ultrafast response. A flexible Sn-based perovskite PD without any encapsulation in air continuously shows ultrafast responses after 10,000 bending cycles. Meanwhile, a flexible imaging system can be realized by a 5 × 5 PD array with good sensing results. This study shows great potential in nontoxic and ultrafast Sn-based perovskite PDs for flexible imaging applications.     

Scalable,Template Driven Formation of Highly Crystalline Lead-Tin Halide Perovskite Films

Low bandgap lead-tin halide perovskites are predicted to be candidates to maximize the performance of single junction and tandem solar cells based on metal halide perovskites. In spite of the tremendous progress in lab-scale device efficiency, devices fabricated with scalable techniques fail to reach the same efficiencies, which hinder their potential industrialization. Herein, a method is proposed that involves a template of a 2D perovskite deposited with a scalable technique (blade coating), which is then converted in situ to form a highly crystalline 3D lead-tin perovskite. These templated grown films are alloyed with stoichiometric ratio and are highly oriented with the (l00) planes aligning parallel to the substrate. The low surface/volume ratio of the obtained single-crystal-like films contributes to their enhanced stability in different environments. Finally, the converted films are demonstrated as active layer for solar cells, opening up the opportunity to develop this scalable technique for the growth of highly crystalline hybrid halide perovskites for photovoltaic devices.     

Solvent Recrystallization-Enabled Green Amplified Spontaneous Emissions with an Ultra-Low Threshold from Pinhole-Free Perovskite Films

Green and amplified spontaneous emissions with low thresholds are crucial for the development of solution-processable perovskite light sources. Although mixed-cation CsPbBr₃ perovskites are highly promising, pinholes are inevitably formed during the spin-coating process, which results in considerable optical losses. This study proposes a solvent recrystallization strategy to reduce the number of pinholes and enhance the crystallinity of (Cs, FA, MA)PbBr₃/NMA (FA = CH(NH₂)₂, MA = CH₃NH₃, and NMA = C₁₁H₉NH₃) films in a dimethyl sulfoxide gas environment. Amplified spontaneous green emissions are produced with a low threshold of 1.44 μJ cm⁻² and a high net modal gain of 1176 cm⁻¹. The reduced threshold is attributed to the relatively low propagation loss and suppressed Auger recombination, which results from the formation of a pinhole-free surface and enlarged grain size. These results can be utilized in the development of high-performance perovskite laser devices.     

Efficient and Ambient‐Air‐Stable Solar Cell with Highly Oriented 2D@3D Perovskites

3D organic–inorganic lead halide perovskites have shown great potential in efficient photovoltaic devices. However, the low stability of the 3D perovskite layer and random arrangement of the perovskite crystals hinder its commercialization road. Herein, a highly oriented 2D@3D ((AVA)₂PbI₄@MAPbI₃) perovskite structure combining the advantages of both 2D and 3D perovskite is fabricated through an in situ route. The highest power conversion efficiency (PCE) of 18.0% is observed from a 2D@3D perovskite solar cell (PSC), and it also shows significantly enhanced device stability under both inert (90% of initial PCE for 32 d) and ambient conditions (72% of initial PCE for 20 d) without encapsulation. The high efficiency of 18.0% and nearly twofold improvement of device stability in ambient compared with pure 3D PSCs confirm that such 2D@3D perovskite structure is an effective strategy for high performance and increasing stability and thus will enable the timely commercialization of PSCs.