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.     

Mechanism of Crystal Formation in Ruddlesden–Popper Sn‐Based Perovskites

Knowledge of the mechanism of formation, orientation, and location of phases inside thin perovskite films is essential to optimize their optoelectronic properties. Among the most promising, low toxicity, lead‐free perovskites, the tin‐based ones are receiving much attention. Here, an extensive in situ and ex situ structural study is performed on the mechanism of crystallization from solution of 3D formamidinium tin iodide (FASnI₃), 2D phenylethylammonium tin iodide (PEA₂SnI₄), and hybrid PEA₂FA_n?1Sn_nI_3n+1 Ruddlesden–Popper perovskites. Addition of small amounts of low‐dimensional component promotes oriented 3D‐like crystallite growth in the top part of the film, together with an aligned quasi‐2D bottom‐rich phase. The sporadic bulk nucleation occurring in the pure 3D system is negligible in the pure 2D and in the hybrid systems with sufficiently high PEA content, where only surface crystallization occurs. Moreover, tin‐based perovskites form through a direct conversion of a disordered precursor phase without forming ordered solvated intermediates and thus without the need of thermal annealing steps. The findings are used to explain the device performances over a wide range of composition and shed light onto the mechanism of the formation of one of the most promising Sn‐based perovskites, providing opportunities to further improve the performances of these interesting Pb‐free materials.     

Compositional and Dimensional Control of 2D and Quasi‐2D Lead Halide Perovskites in Water

Blue light emitting two dimensional (2D) and quasi‐2D layered halide perovskites (LHPs) are gaining attention in solid‐state lighting applications but their fragile stability in humid condition is one of the most pressing issues for their practical applications. Though water is much greener and cost effective, organic solvents must be used during synthesis as well as the device fabrication process for these LHPs due to their water‐sensitivity/instability and consequently, water‐stable blue‐light emitting 2D and quasi‐2D LHPs have not been documented yet. Here, water‐mediated facile and cost‐effective syntheses, characterizations, and optical properties of 16 organic–inorganic hybrid compounds are reported including 2D (A′)₂PbX₄ (A′ = butylammonium, X = Cl/Br/I) (8 compounds), 3D perovskites (4), and quasi‐2D (A′)_pA_x?1B_xX_3x+1 LHPs (A = methylammonium) (4) in water. Here, both composition and dimension of LHPs are tuned in water, which has never been explored yet. Furthermore, the dual emissive nature is observed in quasi‐2D perovskites, where the intensity of two photoluminescence (PL) peaks are governed by 2D and 3D inorganic layers. The Pb(OH)₂‐coated 2D and quasi‐2D perovskites are highly stable in water even after several months. In addition, single particle imaging is performed to correlate structural–optical property of these LHPs.     

Low‐Dimensional Lead‐Free Inorganic Perovskites for Resistive Switching with Ultralow Bias

3D organic–inorganic and all‐inorganic lead halide perovskites have been intensively pursued for resistive switching memories in recent years. Unfortunately, instability and lead toxicity are two foremost challenges for their large‐scale commercial applications. Dimensional reduction and composition engineering are effective means to overcome these challenges. Herein, low‐dimensional inorganic lead‐free Cs₃Bi₂I₉ and CsBi₃I₁₀ perovskite‐like films are exploited for resistive switching memory applications. Both devices demonstrate stable switching with ultrahigh on/off ratios (≈10⁶), ultralow operation voltages (as low as 0.12 V), and self‐compliance characteristics. 0D Cs₃Bi₂I₉‐based device shows better retention time and larger reset voltage than the 2D CsBi₃I₁₀‐based device. Multilevel resistive switching behavior is also observed by modulating the current compliance, contributing to the device tunability. The resistive switching mechanism is hinged on the formation and rupture of conductive filaments of halide vacancies in the perovskite films, which is correlated with the formation of AgI_x layers at the electrode/perovskite interface. This study enriches the library of switching materials with all‐inorganic lead‐free halide perovskites and offers new insights on tuning the operation of solution‐processed memory devices.     

High‐Performance Planar Solar Cells Based On CH3NH3PbI3‐xClx Perovskites with Determined Chlorine Mole Fraction

Solution‐processable hybrid perovskite solar cells are a new member of next generation photovoltaics. In the present work, a low‐temperature two‐step dipping method is proposed for the fabrication of CH₃NH₃PbI_3‐xCl_x perovskite films on the indium tin oxide glass/poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) substrate. The bandgaps of the CH₃NH₃PbI_3‐xCl_x perovskite films are tuned in the range between 1.54 and 1.59 eV by adjusting the PbCl₂ mole fraction (n_Cl/(n_Cl + n_I)) in the initial mixed precursor solution from 0.10 to 0.40. The maximum chlorine mole fraction measured by a unique potentiometric titration method in the produced CH₃NH₃PbI_3‐xCl_x films can be up to 0.220 ± 0.020 (x = 0.660 ± 0.060), which is much higher than that produced by a one‐step spin‐coating method (0.056 ± 0.015, x = 0.17 ± 0.04). The corresponding solar cell with the CH₃NH₃PbI_2.34±0.06Cl_0.66±0.06 perovskite film sandwiched between PEDOT:PSS and C₆₀ layers exhibits a power conversion efficiency as high as 14.5%. Meanwhile, the open‐circuit potential (V_oc) of the device reaches 1.11 V, which is the highest V_oc reported in the perovskite solar cells fabricated on PEDOT:PSS so far.     

Highly Luminescent and Stable Green Quasi‐2D Perovskite‐Embedded Polymer Sheets by Inkjet Printing

Perovskite materials serve as promising candidates for display and lighting due to their excellent optical properties, including tunable bandgaps and efficient luminescence. However, their efficiency and stability must be improved for further application. In this work, quasi‐two‐dimensional (quasi‐2D) perovskites embedded in different polymers are prepared by inkjet printing to construct any luminescent patterns/pictures on the polymer substrates. The optimized quantum yield reaches over 65% by polyvinyl‐chloride‐based quasi‐2D perovskite composites. In addition, as‐fabricated perovskite?polymer composites with patterns show excellent resistance to abrasion, moisture, light irradiation, and chemical erosion by various solvents. Both quantum yield and lifetime are superior to those reported to date. These achievements are attributed to the introduction of the PEA⁺ cations to improve the luminance and stability of perovskite. This patterned composite can be useful for color‐conversion films with low cost and large‐scale fabrication.     

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.     

Stoichiometry Control for the Tuning of Grain Passivation and Domain Distribution in Green Quasi‐2D Metal Halide Perovskite Films and Light‐Emitting Diodes

Quasi‐2D metal halide perovskite films are promising for efficient light‐emitting diodes (LEDs), because of their efficient radiative recombination and suppressed trap‐assisted quenching compared with pure 3D perovskites. However, because of the multidomain polycrystalline nature of solution‐processed quasi‐2D perovskite films, the composition engineering always impacts the emitting properties with complicated mechanisms. Here, defect passivation and domain distribution of quasi‐2D perovskite films prepared with various precursor compositions are systematically studied. As a result, in perovskite films prepared from stoichiometric quasi‐2D precursor compositions, large organic ammonium cations function well as passivators. In comparison, precursor compositions of simply adding large organic halide salt into a 3D perovskite precursor ensure not only the defect passivation but also the effective formation of quasi‐2D perovskite domains, avoiding unfavorable appearance of low‐order domains. Quasi‐2D perovskite films fabricated with a well‐designed precursor composition achieve a high photoluminescence quantum yield of 95.3% and an external quantum efficiency of 14.7% in LEDs.     

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.     

Formamidinium‐Based Dion‐Jacobson Layered Hybrid Perovskites: Structural Complexity and Optoelectronic Properties

Layered hybrid perovskites have emerged as a promising alternative to stabilizing hybrid organic–inorganic perovskite materials, which are predominantly based on Ruddlesden‐Popper structures. Formamidinium (FA)‐based Dion‐Jacobson perovskite analogs are developed that feature bifunctional organic spacers separating the hybrid perovskite slabs by introducing 1,4‐phenylenedimethanammonium (PDMA) organic moieties. While these materials demonstrate competitive performances as compared to other FA‐based low‐dimensional perovskite solar cells, the underlying mechanisms for this behavior remain elusive. Here, the structural complexity and optoelectronic properties of materials featuring (PDMA)FA_n–1Pb_nI_3n+1 (n = 1–3) formulations are unraveled using a combination of techniques, including X‐ray scattering measurements in conjunction with molecular dynamics simulations and density functional theory calculations. While theoretical calculations suggest that layered Dion‐Jacobson perovskite structures are more prominent with the increasing number of inorganic layers (n), this is accompanied with an increase in formation energies that render n > 2 compositions difficult to obtain, in accordance with the experimental evidence. Moreover, the underlying intermolecular interactions and their templating effects on the Dion‐Jacobson structure are elucidated, defining the optoelectronic properties. Consequently, despite the challenge to obtain phase‐pure n > 1 compositions, time‐resolved microwave conductivity measurements reveal high photoconductivities and long charge carrier lifetimes. This comprehensive analysis thereby reveals critical features for advancing layered hybrid perovskite optoelectronics.     

Self‐Additive Low‐Dimensional Ruddlesden–Popper Perovskite by the Incorporation of Glycine Hydrochloride for High‐Performance and Stable Solar Cells

The recent rise of low‐dimensional Ruddlesden–Popper (RP) perovskites is notable for superior humidity stability, however they suffer from low power conversion efficiency (PCE). Suitable organic spacer cations with special properties display a critical effect on the performance and stability of perovskite solar cells (PSCs). Herein, a new strategy of designing self‐additive low‐dimensional RP perovskites is first proposed by employing a glycine salt (Gly⁺) with outstanding additive effect to improve the photovoltaic performance. Due to the strong interaction between C?O and Pb²⁺, the Gly⁺ can become a nucleation center and be beneficial to uniform and fast growth of the Gly‐based RP perovskites with larger grain sizes, leading to reduced grain boundary and increased carrier transport. As a result, the Gly‐based self‐additive low‐dimensional RP perovskites exhibit remarkable photoelectric properties, yielding the highest PCE of 18.06% for Gly (n = 8) devices and 15.61% for Gly (n = 4) devices with negligible hysteresis. Furthermore, the Gly‐based devices without encapsulation show excellent long‐term stability against humidity, heat, and UV light in comparison to BA‐based low‐dimensional PSCs. This approach provides a feasible design strategy of new‐type low‐dimensional RP perovskites to obtain highly efficient and stable devices for next‐generation photovoltaic applications.     

Co‐Interlayer Engineering toward Efficient Green Quasi‐Two‐Dimensional Perovskite Light‐Emitting Diodes

With respect to three‐dimensional (3D) perovskites, quasi‐two‐dimensional (quasi‐2D) perovskites have unique advantages in light‐emitting devices (LEDs), such as strong exciton binding energy and good phase stability. Interlayer ligand engineering is a key issue to endow them with these properties. Rational design principles for interlayer materials and their processing techniques remain open to investigation. A co‐interlayer engineering strategy is developed to give efficient quasi‐2D perovskites by employing phenylbutylammonium bromide (PBABr) and propylammonium bromide (PABr) as the ligand materials. Preparation of these co‐interlayer quasi‐2D perovskite films is simple and highly controllable without using antisolvent treatment. Crystallization and morphology are readily manipulated by tuning the ratio of co‐interlayer components. Various optical techniques, including steady and ultrafast transient absorption and photoluminescence spectroscopies, are used to investigate their excitonic properties. Photoluminescence quantum yield (PLQY) of the perovskite film is dramatically improved to 89% due to the combined optimization of exciton binding energy and suppression of trap state formation. Accordingly, a high current efficiency of 66.1 cd A^?1 and an external quantum efficiency of 15.1% are achieved for green co‐interlayer quasi‐2D perovskite LEDs without using any light out‐coupling techniques, indicating that co‐interlayer engineering is a simple and effective approach to develop high‐performance perovskite electroluminescence devices.     

Light‐Responsive Ion‐Redistribution‐Induced Resistive Switching in Hybrid Perovskite Schottky Junctions

Hybrid Perovskites have emerged as a class of highly versatile functional materials with applications in solar cells, photodetectors, transistors, and lasers. Recently, there have also been reports on perovskite‐based resistive switching (RS) memories, but there remain open questions regarding device stability and switching mechanism. Here, an RS memory based on a high‐quality capacitor structure made of an MAPbBr₃ (CH₃NH₃PbBr₃) perovskite layer sandwiched between Au and indium tin oxide (ITO) electrodes is reported. Such perovskite devices exhibit reliable RS with an ON/OFF ratio greater than 10³, endurance over 10³ cycles, and a retention time of 10⁴ s. The analysis suggests that the RS operation hinges on the migration of charged ions, most likely MA vacancies, which reversibly modifies the perovskite bulk transport and the Schottky barrier at the MAPbBr₃/ITO interface. Such perovskite memory devices can also be fabricated on flexible polyethylene terephthalate substrates with high bendability and reliability. Furthermore, it is found that reference devices made of another hybrid perovskite MAPbI₃ consistently exhibit filament‐type switching behavior. This work elucidates the important role of processing‐dependent defects in the charge transport of hybrid perovskites and provides insights on the ion‐redistribution‐based RS in perovskite memory devices.     

Expanded Phase Distribution in Low Average Layer-Number 2D Perovskite Films: Toward Efficient Semitransparent Solar Cells

The application of low average layer-number (〈n〉 ≤ 2) 2D perovskites in semitransparent photovoltaics (ST-PVs) has been hindered by their strong exciton binding energy and high electrical anisotropy. Here, the phase distribution is expanded fully and orderly to enable efficient charge transport in 2D (NMA)₂(MA)Pb₂I₇ (NMA: 1-naphthylmethylammonium, MA: CH₃NH₃⁺) perovskite films by regulating the sedimentation dynamics of organic cation-based colloids. Ammonium chloride is synergistically introduced to enhance the phase separation further and construct a favorable out-of-plane orientation. The wide and graded phase distribution well aligns the energy level to facilitate charge transfer. As a result, the first application of an average 〈n〉 = 2 2D perovskite is implemented in ST-PVs with visible power conversion efficiency (PCE) of 7.52% and high average visible transmittance (AVT) of 40.5%. This study offers a new candidate and an effective strategy for efficient and stable ST-PVs and is relevant to other perovskite optoelectronic devices.     

Record‐Low‐Threshold Lasers Based on Atomically Smooth Triangular Nanoplatelet Perovskite

Single‐crystalline perovskites are ideal candidates for lasing and other optoelectronic applications. Although significant efforts have been made to grow both bulk single‐crystalline perovskites in liquid solution, their dimensions are still too large to make nanoscale whispering‐gallery‐mode (WGM) resonator based lasers that possess high quality (Q) factor and small volume. Besides, most reported perovskite resonators do not possess atomically smooth surfaces and facets, which limits the Q and thereby increases the lasing threshold. Here, atomically smooth triangular PbI₂ templates are fabricated on a mica substrate by the vapor phase deposition method and are converted to atomically smooth perovskites which have regular and unwrinkled facets with average surface roughness less than 2 nm. By using a CH₃NH₃PbI₃ nanoplatelet with a side length of 27 µm and thickness of 80 nm, room temperature WGM lasing with a Q up to 2600 is demonstrated, the highest reported for hybrid organic–inorganic perovskite nanoplatelets. In addition, the volume of the WGM mode is reduced significantly in comparison with the prior reports. The realized high‐quality triangular CH₃NH₃PbI₃ perovskite nanoplatelets with high Q factor and small volume are expected to perform as ideal cavities for long pulse durations lasers and would find potential applications in integrated optoelectronic devices.     

Near‐Infrared Photoresponse of One‐Sided Abrupt MAPbI3/TiO2 Heterojunction through a Tunneling Process

Trap states in semiconductors usually degrade charge separation and collection in photovoltaics due to trap‐mediated nonradiative recombination. Here, it is found that perovskite can be heavily doped in low concentration with non‐ignorable broadband infrared absorption in thick films and their trap states accumulate electrons through infrared excitation and hot carrier cooling. A hybrid one‐sided abrupt perovskite/TiO₂ p‐N heterojunction is demonstrated that enables partial collection of these trap‐filled charges through a tunneling process instead of detrimental recombination. The tunneling is from broadband trap states in the wide depleted p‐type perovskite, across the barrier of the narrow depleted TiO₂ region (<5 nm), to the N‐type TiO₂ electrode. The trap states inject carriers into TiO₂ through tunneling and produce around‐unity peak external quantum efficiency, giving rise to near‐infrared photovoltaics. The near‐infrared response allows photodetecting devices to work in both diode and conductor modes. This work opens a new avenue to explore the near‐infrared application of hybrid perovskites.     

Efficient Perovskite Hybrid Photovoltaics via Alcohol‐Vapor Annealing Treatment

In this work, alcohol‐vapor solvent annealing treatment on CH₃NH₃PbI₃ thin films is reported, aiming to improve the crystal growth and increase the grain size of the CH₃NH₃PbI₃ crystal, thus boosting the performance of perovskite photovoltaics. By selectively controlling the CH₃NH₃I precursor, larger‐grain size, higher crystallinity, and pinhole‐free CH₃NH₃PbI₃ thin films are realized, which result in enhanced charge carrier diffusion length, decreased charge carrier recombination, and suppressed dark currents. As a result, over 43% enhanced efficiency along with high reproducibility and eliminated photocurrent hysteresis behavior are observed from perovskite hybrid solar cells (pero‐HSCs) where the CH₃NH₃PbI₃ thin films are treated by methanol vapor as compared with that of pristine pero‐HSCs where the CH₃NH₃PbI₃ thin films are without any alcohol vapor treatment. In addition, the dramatically restrained dark currents and raised photocurrents give rise to over ten times enhanced detectivities for perovskite hybrid photodetectors, reaching over 10¹³ cm Hz^1/2 W^?1 (Jones) from 375 to 800 nm. These results demonstrate that the method provides a simple and facile way to boost the device performance of perovskite photovoltaics.     

Scalable All‐Evaporation Fabrication of Efficient Light‐Emitting Diodes with Hybrid 2D–3D Perovskite Nanostructures

Quasi‐2D (Q2D) lead halide perovskites have emerged as promising materials for light‐emitting diodes (LEDs) due to their tunable emission, slowed‐down carrier diffusion, and improved stability. However, they are primarily fabricated through solution methods, which hinders its large‐scale manufacture and practical applications. Physical‐vapor‐deposition (PVD) methods have well demonstrated the capability for reproducible, scalable, and layer‐by‐layer fabrication of high quality organic/inorganic thin films. Herein, for the first time, the full‐evaporation fabrication of organic–inorganic hybrid ((BA)₂Cs_n?1Pb_nBr_3n+1) Q2D–3D PeLEDs is demonstrated. The morphology and crystal phase of the perovskite are controlled from 3D to 2D by modulating material composition, annealing temperature, and film thicknesses. The confinement of carriers in 3D layers and the energy funnel effect are discovered and discussed. Importantly, a record high external quantum efficiency (EQE) of 5.3% based on evaporation method is achieved. Moreover, a centimeter‐scale PeLED (1.5 cm × 2 cm) is obtained. Furthermore, the T₅₀ lifetime of the device with an initial brightness of 100 cd m^?2 is found to be 90 min with a thin layer PMMA passivation, which is among the longest for all PVD processed PeLEDs. Overall, this work casts a solid stepping stone towards the fabrication of high‐performance PeLEDs on a large‐scale.     

Tailoring the Functionality of Organic Spacer Cations for Efficient and Stable Quasi‐2D Perovskite Solar Cells

The recent development of quasi‐2D perovskite solar cells have drawn significant attention due to the improved stability of these materials and devices against moisture compared to their 3D counterparts. However, the optoelectronic properties of 2D perovskites need to be optimized in order to achieve high efficiency. In this work, the effect of spacer cations, i.e., phenethylammonium (PEA), 4‐fluorophenethylammonium (F‐PEA), and 4‐methoxyphenethylammonium (MeO‐PEA) on the optoelectronic properties and device performance of quasi‐2D perovskites is systematically studied. It is observed that both larger and more hydrophobic cations can improve perovskite stability against moisture, while larger size can adversely influence the device performance. Interestingly, with F‐PEA or MeO‐PEA, distribution of n value can be shifted toward high 3D content in quasi‐2D perovskite layers, which enables lower bandgaps and possibly lower exciton binding energy. Due to the best charge transport and lowest bandgap, the F‐PEAI‐based quasi‐2D perovskite (n = 5) solar cell shows a highest power conversion efficiency (PCE) of 14.5% with excellent stability in air with a humidity of 40–50%, keeping 90% of the original PCE after 40 d. It is believed that the approach may open a way for the design of new organic spacer cations for stable low‐dimensional hybrid perovskites with high performance.     

Synthesis of Two‐Dimensional Perovskite by Inverse Temperature Crystallization and Studies of Exciton States by Two‐Photon Excitation Spectroscopy

Two‐dimensional (2D) organic–inorganic hybrid perovskites (OIHPs), a natural multiple‐quantum‐well structure with quasi‐2D electronic properties, have recently emerged as a promising class of semiconducting materials for photovoltaic and optoelectronic applications. However, facile synthesis of high‐quality 2D OIHPs single crystals is still lacking. The layer dependence of the exciton binding energy of (C₄H₉NH₃)₂PbI₄ (C4PI), a widely studied 2D OIHP, is still debated. Herein, a novel synthesis technique based on inverse temperature crystallization in a binary‐solvent system is used to prepare 2D OIHPs and a systematic study of excitonic states of the synthesized 2D OIHPs by two‐photon excitation (TPE) spectroscopy is conducted. The obtained TPE spectra indicate that the exciton binding energies are similar for C4PI nanosheets and bulk crystals with different number of layers, most likely due to the intrinsically weak interlayer coupling. Further, the dark excitonic 2p states of (C₆H₅(CH₂)₂NH₃)₂PbI₄ (PEPI) and C4PI are also observed by TPE spectroscopy. The results provide a novel synthesis protocol and insight into exciton properties of 2D OIHPs.