Performance Of Optoelectronic Devices Research Articles

Machine learning for accelerated bandgap prediction in strain-engineered quaternary III-V semiconductors.

Quaternary III-V semiconductors are one of the most promising material classes in optoelectronics. The bandgap and its character, direct or indirect, are the most important fundamental properties determining the performance and characteristics of optoelectronic devices. Experimental approaches screening a large range of possible combinations of III- and V-elements with variations in composition and strain are impractical for every target application. We present a combination of accurate first-principles calculations and machine learning based approaches to predict the properties of the bandgap for quaternary III-V semiconductors. By learning bandgap magnitudes and their nature at density functional theory accuracy based solely on the composition and strain features of the materials as an input, we develop a computationally efficient yet highly accurate machine learning approach that can be applied to a large number of compositions and strain values. This allows for a computationally efficient prediction of a vast range of materials under different strains, offering the possibility of virtual screening of multinary III-V materials for optoelectronic applications.

Optimized Substrate Orientations for Highly Uniform Metal Halide Perovskite Film Deposition.

Uniform optoelectronic quality of metal halide perovskite (MHP) films is critical for scalable production in large-area applications, such as photovoltaics and displays. While vapor-based MHP film deposition is advantageous for this purpose, achieving film uniformity can be challenging due to uneven temperature distribution and precursor concentration over the substrate. Here, we propose optimized substrate orientations for the vapor-based fabrication of homogeneous MAPbI3 thin films, involving a PbI2 primary layer deposition and subsequent conversion using vaporized methylammonium iodide (MAI). Leveraging computational fluid dynamics (CFD) simulations, we confirm that vertical positioning during the PbI2 layer growth yields a uniform film with a narrow temperature distribution and minimal boundary layer thickness. However, during the subsequent conversion step, horizontal substrate positioning results in spatially more uniform MAPbI3 thickness and grain size compared to the vertical placement due to enhanced MAI intercalation. From this optimized substrate positioning, we observe substantial optical homogeneity across the substrate on a centimeter scale, along with uniform and enhanced optoelectronic device performance within photodetector arrays. Our results offer a potential path toward the scalable production of highly uniform perovskite films.

Theoretical and Experimental Study of Optical Losses in a Periodic/Quasiperiodic Structure Based on Porous Si-SiO2

This study investigates the reduction of optical losses in periodic/quasiperiodic structures made of porous Si-SiO2 through a dry oxidation process. Due to their unique optical properties, these structures hold great promise for various optoelectronic applications. By carefully engineering the composition and geometry of the structures, we fabricate periodic/quasiperiodic structures on a quartz substrate using an electrochemical anodization technique and subsequently subject them to dry oxidation at two different temperatures. The structure exhibits two localized modes in the transmission and reflection spectra. Unoxidized and oxidized structures’ complex refractive index and filling factors are determined theoretically and experimentally. Optical characterization reveals that the porous Si-SiO2 structures exhibit lower absorption losses and improved transmission than the pure porous silicon structures. Additionally, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) confirm the presence of porous Si-SiO2 and reduced silicon content. Our study demonstrates that dry oxidation effectively decreases Rayleigh scattering losses, leading to enhanced optical performance and potential applications in efficient optoelectronic devices and systems based on silicon. For instance, periodic/quasiperiodic structures could soon be used as light-emitting devices inside the field of optoelectronics, adding photoluminescent nanoparticles to activate the localized modes.

Interfacial photoconductivity effect of type-I and type-II Sb2Se3/Si heterojunctions for THz wave modulation

An in-depth understanding of the photoconductivity and photocarrier density at the interface is of great significance for improving the performance of optoelectronic devices. However, extraction of the photoconductivity and photocarrier density at the heterojunction interface remains elusive. Herein, we have obtained the photoconductivity and photocarrier density of 173 nm Sb2Se3/Si (type-I heterojunction) and 90 nm Sb2Se3/Si (type-II heterojunction) utilizing terahertz (THz) time-domain spectroscopy (THz-TDS) and a theoretical Drude model. Since type-I heterojunctions accelerate carrier recombination and type-II heterojunctions accelerate carrier separation, the photoconductivity and photocarrier density of the type-II heterojunction (21.8 × 104 S⋅m−1, 1.5 × 1015 cm−3) are higher than those of the type-I heterojunction (11.8 × 104 S⋅m−1, 0.8 × 1015 cm−3). These results demonstrate that a type-II heterojunction is superior to a type-I heterojunction for THz wave modulation. This work highlights THz-TDS as an effective tool for studying photoconductivity and photocarrier density at the heterojunction interface. In turn, the intriguing interfacial photoconductivity effect provides a way to improve the THz wave modulation performance.

Multifunctional Short-Chain 2-Thiophenealkylammonium Bromide Ligand-Assisted Perovskite Quantum Dots for Efficient Light-Emitting Diodes.

Lead halide perovskite quantum dots (QDs) have attracted great interest for application in light-emitting diodes (LEDs) due to their high photoluminescence quantum yield (PLQY), solution processability, and high color purity, showing great potential for next-generation full-color display and lighting technologies. Conventional long-chain insulating oleic acid (OA)/oleamine (OAm) ligands exhibit dynamic binding to the surface of QDs, resulting in a plethora of extra surface defects and inferior optoelectronic properties. Herein, a sole multifunctional ligand with optimized carbon chain length, that is, 2-thiophenepropylamine bromide (ThPABr), was creatively designed and introduced into CsPbBr3 QDs, which not only replaces OAm and provides a bromine source but also coordinates with the uncoordinated surface Pb2+ of QDs through the thiophene, passivating surface defects and increasing the PLQY of the film to 83%. More importantly, the interaction between the electron donor-thiophene ring and QDs can enhance electron injection and improve carrier balance. The resulting green LED exhibited significant performance improvement, showing ultrahigh spectral stability under high operating voltage, achieving a maximum external quantum efficiency of 10.5%, and extending the operating lifetime to 5-fold that of the reference. Designing a single multifunctional ligand presents a promising and convenient strategy for selecting surface ligands that can enhance the performance of LEDs or other optoelectronic devices.

Unfolding the Correlation between Solution Aggregation and Solid-State Crystal Orientation in Donor-Acceptor Copolymers via Solvent Additive Processing.

Tailoring the crystal orientation of donor-acceptor (D-A) copolymers is vital for boosting the performance of optoelectronic devices. Despite recent advances in controlling the crystal orientation of D-A copolymers in films, the investigation into their aggregates in solution and the correlation between the solution aggregates and solid-state crystal orientation has been limited. Herein, an effective solvent additive strategy is reported for tuning solution aggregates and the consequent solid-state structures of poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2)). Specifically, the addition of 1-decanethiol (10-thiol) to the P(NDI2OD-T2) chloroform solution promoted the aggregation of P(NDI2OD-T2) chains because of the improved planarization of the backbones, which changed their crystal orientation in the film from coexisting edge-on and face-on to dominant edge-on when produced by drop-casting. The mechanism of this crystal orientation transformation is elucidated based on the interaction between 10-thiol and the side chains of P(NDI2OD-T2). The optical properties of P(NDI2OD-T2) films with different crystalline structures are closely correlated. Notably, the 10-thiol-enabled facile tailoring of the crystal orientation in P(NDI2OD-T2) can be readily applied to other D-A copolymers of interest. The findings of this study highlight a robust solvent additive strategy for regulating solution aggregates and crystal orientation in D-A copolymer films, which have applications in many optoelectronic devices.

Computational study of inorganic halide cubic perovskite KMnX3 (X = Cl, Br) for energy harvesting applications

Nowadays, halide perovskites being an exciting class of materials with bountiful features have gained enormous research focus (theoretical and experimental) by the scientists/academicians for designing novel and inexpensive materials with improved performance for next-generation photovoltaics and optoelectronic devices. Here, inorganic halide perovskites, i.e., KMnX3 (X = Cl, Br) are explored by density functional theory (DFT) while utilizing through WIEN2K simulator. The structural, optoelectronic, and elastic properties were investigated by using PBE-GGA + mBJ exchange potential, which confirmed the metallic behavior for both compounds. Optical analysis has unveiled the high absorption, high conductivity, and low reflectivity of these materials. The mechanical parameters and the elastic constants (Cij) obeyed Born stability criteria and confirmed the mechanical stability of both compounds. The calculated values of Poisson’s ratio and Pugh’s criteria have endorsed the ductile character of KMnBr3, whereas KMnCl3 has shown near ductile character as well as anisotropic nature. After rigorous analysis of the structural, optoelectronic, and elastic properties in the cubic phase, it can be claimed that these halide perovskites are potential materials that provide a foundation to further insight and exploration for energy harvesting and energy storage applications.

Optimizing broadband metamaterial absorber using deep reinforcement learning

Optimization of the geometry of broadband metamaterial absorbers is crucial for improving the performance of optoelectronic devices. However, a large number of geometric parameters should be considered to achieve broad absorption, which is time-consuming. Herein, we propose a rapid and simple method for optimizing metamaterial absorbers dedicated to thermal radiation absorption using deep reinforcement learning. Deep reinforcement learning generated an ideal geometry for a broadband metamaterial absorber after 4 h, demonstrating the effectiveness of this technique for the rapid and effective optimization of metamaterial absorbers.

Reversible and Irreversible Layer Edge Relaxation in Laser‐Radiation‐Hardened 2D Organic–Inorganic Perovskite Crystals

The layer edge states or low energy state (LES) in 2D hybrid organic–inorganic perovskites demonstrate a prolonged carrier lifetime for better performance of optoelectronic devices. However, the fundamental understanding of LES in 2D perovskites is still inconclusive. Herein, a photoluminescence (PL) study of LES in 2D Ruddlesden–Popper perovskites is presented with n = 2 and n = 3 from their cleaved cross sections that are more stable than the natural edge. The PL measurements clearly observe reversible, and irreversible surface relaxations (case I and case II) in three laser intensity ranges, further supported by a PL excitation cycle from low to high laser intensity, and vice versa. The PL wavelength of LES is tunable with laser intensity and blueshifts with increasing laser intensity during irreversible surface relaxation process (case I). Fluorescence lifetime imaging (FLIM) shows that the LES has a longer lifetime than the band‐edge emission in the sample without a photodegradation, while the BE lifetime becomes relatively longer in the area with a photodegradation. The presented laser tunable LES and the related irreversible relaxation process provide a new insight that can help improve the photostability in 2D perovskites and understand roles of LESs in optoelectronic device performance.

Bandgap Engineering of BiIns Nanowire for Wide‐Spectrum, High‐Responsivity, and Polarimetric‐Sensitive Detection

AbstractOptical devices based on alloying semiconductors offer a plethora of new possibilities for detection across a broad spectrum. Among these devices, nanowire‐based devices have gained much attention due to their remarkable specific surface area properties in terms of material synthesis, device structure, and performance. In this work, (BixIn1−x)2S3 nanowires are designed by controlling the ratio of Bi and In atoms. The atomic ratio directly affects the electronic band structure of the crystal, thereby further optimizing the performance of optoelectronic devices. According to the experimental results, Bi1.28In0.72S3 nanowire‐based photodetectors obtain the most excellent photoresponse performance. The typical device demonstrates a spectral response from deep ultraviolet (DUV 254 nm) to near‐infrared (NIR 1064 nm) and achieves a maximum dichroic ratio of photoresponse of 1.5 under polarization‐angle‐sensitive detection in the 266–808 nm range. It also exhibits a photoresponse of 10.1 A W−1 and a photodetectivity of 5.7 × 1010 Jones under 532 nm light irradiation. Additionally, the photodetector displays a fast response speed with a rise/fall time of 5/4.7 ms. Finally, “CSU” and puppy images produced by this device further demonstrate the effectiveness of alloying semiconductors in creating wide‐spectrum, high‐responsivity, fast‐response, and polarimetric‐sensitive photodetectors.

Chemical Doping of Organic and Coordination Polymers for Thermoelectric and Spintronic Applications: A Theoretical Understanding.

ConspectusThe controlled doping of organic semiconductors (OSCs) is crucial not only for improving the performance of electronic and optoelectronic devices but also for enabling efficient thermoelectric conversion and spintronic applications. The mechanism of doping for OSCs is fundamentally different from that of their inorganic counterparts. In particular, the interplay between dopants and host materials is complicated considering the low dielectric constant, strong lattice-charge interaction, and flexible nature of materials. Recent experimental breakthroughs in the molecular design of dopants and the precise doping with high spatial resolution call for more profound understandings as to how the dopant interacts with the charge introduced to OSCs and how the admixture of dopants alters the electronic properties of host materials before one can exploit controllable doping to realize desired functionalities.By employing state-of-the-art computational tools, we revealed the effects of doping in representative and emerging organic and coordination polymers aiming toward thermoelectric and spintronic applications. We showed that dopants and hosts should be taken as an integrated system, and the type of charge-transfer interaction between them is the key for spin polarization. First, we found doping-induced modifications to the electronic band in a potassium-doped coordination polymer, an n-type thermoelectric material. The charge localization due to the Coulomb interaction between the completely ionized dopant and the injected charge on the polymer backbone and also the polaron band formation at low doping levels are responsible for the nonmonotonic temperature dependence of the conductivity and Seebeck coefficient observed in recent experiments. The mechanistic insights gained from these results have provided important guidelines on how to control the doping level and working temperature to achieve a high thermoelectric conversion efficiency. Next, we demonstrated that the ionized dopants scatter charge carriers via screened Coulomb interactions, and it may become a dominant scattering mechanism in doped polymers. After incorporating the ionized dopant scattering mechanism in PEDOT:Tos, a p-type thermoelectric polymer, we were able to reproduce the measured Seebeck coefficient-electrical conductivity relationship spanning a wide range of doping levels, highlighting the importance of ionized dopant scattering in charge transport.In the two cases described above, charge injection is enabled by integral charge transfer between the dopant and host polymers. In a third example, we showed that a novel type of stacked two-dimensional polymer, conjugated covalent organic frameworks (COFs) with closed-shell electronic structures, can be spin polarized by iodine doping via fractional charge transfer even at high doping levels. We then manifested that magnetization can be attained in nonmagnetic materials lacking metal d electrons and further designed two new COFs with tunable spintronic structure and magnetic interactions after the iodine doping. These findings have suggested a practical route to enable spin polarization in nonradical materials by chemical doping via orbital hybridization, which holds great promise for flexible spintronic applications.

Narrow‐Bandgap Mixed 0D/1D Bismuth Bromide Perovskite Hydrate Enabled by Aromatic Ditertiary Ammonium Spacer

AbstractPerovskite hydrates have attracted extensive attention in diverse fields with intriguing optoelectronic properties, while their structural distortions usually cause large band gaps, which yield inferior light absorption and diminished optoelectronic device performance. Herein, modulating the structural distortion by steric hindrance effects is reported. Specifically, an N,N,N′,N′‐tetramethyl‐1,4‐phenylenediammonium (TMPD)2+ is adopted to template regular BiBr5 chains by interacting with bismuth bromide via weakening and reorienting H‐bonds, yielding a mixed 0D/1D (TMPD)2Bi2Br10.H2O with a narrow bandgap of 1.89 eV. The 0D/1D (TMPD)2Bi2Br10.H2O can be reversibly transformed into 0D (TMPD)2Bi2Br10 (Eg = 2.55 eV) with good cycling behavior. The (TMPD)2Bi2Br10.H2O turns out to be more stable than (TMPD)2Bi2Br10, and a mechanism involving vacancy‐assisted bromide ion migration is proposed for understanding the formation of BiBr5 chains. Density functional theory (DFT) calculations indicate that the (TMPD)2+ triggered hydration has a crucial impact on the downshift of the conduction band edge, thus decreasing the band gap. Moreover, the (TMPD)2Bi2Br10.H2O single crystal exhibits promising photoconductive behavior under a high moisture atmosphere, showing superiority over the conventional CH3NH3PbI3 perovskites that cannot survive moisture. This finding offers new insights into developing narrow band gap perovskite hydrates toward practical optoelectronic applications.

Formation of Single‐Chain Anionic Bolaamphiphiles on Indium Tin Oxide Surfaces through Self‐Assembly To Improve Optoelectronic Device Performance

AbstractThe surface of indium tin oxide (ITO) was modified with bolaamphiphilic (BA) materials to tune the energy‐level alignment of electrodes in optoelectronic devices (OEDs). Tuning the energy‐level alignment of the electrode is crucial for enhancing OED efficiency by improving carrier injection. Although the dielectric properties of organic solvents influence the formation of BA self‐assembled monolayers (SAMs), our study found that the intermolecular forces of the dissolved BA materials and the solution medium are more important for the formation of a well‐ordered film on the electrode. Our results also showed efficient tunneling phenomenon between the electrode and the hole transport layer (HTL) using BA material. The holes were transported to the tunnel junctions where the Fermi energy was sufficiently close to the HOMO band of the BA. Therefore, the tunnel barrier height of the ITO/HTL of the OED was reduced, and favorable conditions for hole injection was created, resulting in a 2–3 times increase in luminance and current density. It is believed that the larger area of interface contact between electrode/BA/HTL and the formation of well‐ordered BA layers are responsible for the improved performance of the BA‐modified electrode surface and OED.

Evolution of surface recombination property of silicon wafers during laser irradiation by differential photocarrier radiometry

Understanding the surface recombination property of semiconductor materials is beneficial for improving the performance of optoelectronic devices. In this paper, differential photocarrier radiometry (PCR) is carried out to investigate the evolution of the surface recombination velocities of silicon wafers induced by laser irradiation. The PCR signal and the surface recombination velocities were found to be strongly dependent on the quality of the wafer surface and the duration of laser irradiation. The native oxide surface was more susceptible to laser irradiation than the Al2O3 passivated surface due to more surface defects being annealed. A surface-defect annealing model was used to explain the transient behavior of the PCR signal and the surface recombination velocity.

Deciphering the role of (Er3+/Nd3+) co-doping effect on TiO2 as an improved electron transport layer in perovskite solar cells

Charge injection and transport at the interface of the electron transport layer (ETL) and perovskite interface are crucial for the perovskite solar cell (PSC) device performance. Titanium dioxide (TiO2) is well established as a photoanode in numerous solar energy conversion and storage. The bandgap engineering of TiO2 by Rare-Earth (RE)-doping has become a significant way to improve the optoelectronic device performance. This study demonstrates the improved performance of Rare-Earth doped TiO2 (RETO) photoanode based solar cells under the doping of Er3+, Nd3+ and following codoping of the (Er3+/Nd3+) effect. It is note that the Er, and Nd dopants are responsible for producing Ti3+ states and the oxygen vacancies near the surface, which drives the charge transportation much more effectively. With the (Er/Nd) codoping into TiO2, the band structure of TiO2 is modified better to make a quasi-Ohmic contact with the perovskites, by fermi level shifting as well changes in the conduction band minima (ECBM) energy states. This results evidence the preliminary conformation for the improvement of Jsc and Voc. Furthermore, the photoluminescence (PL) emission quenching effects of perovskite-deposited RETO attributes the suppression in the charge recombination. By insight into all these favourable results in the(Er3+/Nd3+) codoped TiO2, the RETO photoanode-based perovskite solar cell (PSC) devices were constructed and exhibited improved photovoltaic properties. The composition of (Er0.002Nd0.002Ti0.996O2) ETL employed PSC reported with a better photoconversion efficiency (PCE %) among all the compositions.

Self-Powered Sb2Te3/MoS2 Heterojunction Broadband Photodetector on Flexible Substrate from Visible to Near Infrared

Van der Waals (vdWs) heterostructures, assembled by stacking of two-dimensional (2D) crystal layers, have emerged as a promising new material system for high-performance optoelectronic applications, such as thin film transistors, photodetectors, and light-emitters. In this study, we showcase an innovative device that leverages strain-tuning capabilities, utilizing a MoS2/Sb2Te3 vdWs p-n heterojunction architecture designed explicitly for photodetection across the visible to near-infrared spectrum. These heterojunction devices provide ultra-low dark currents as small as 4.3 pA, a robust photoresponsivity of 0.12 A W−1, and reasonable response times characterized by rising and falling durations of 0.197 s and 0.138 s, respectively. These novel devices exhibit remarkable tunability under the application of compressive strain up to 0.3%. The introduction of strain at the heterojunction interface influences the bandgap of the materials, resulting in a significant alteration of the heterojunction’s band structure. This subsequently shifts the detector’s optical absorption properties. The proposed strategy of strain-induced engineering of the stacked 2D crystal materials allows the tuning of the electronic and optical properties of the device. Such a technique enables fine-tuning of the optoelectronic performance of vdWs devices, paving the way for tunable high-performance, low-power consumption applications. This development also holds significant potential for applications in wearable sensor technology and flexible electro-optic circuits.

Ultrafast energy transfer from perovskite quantum dots to chromophore

Energy transfer plays an essential role in inorganic semiconductor nanocrystal-chromophore hybrids which show potential applications in light collection and emitting. The understanding of the fundamental mechanics of energy transfer processes is vital to enhance the performance of light-harvesting optoelectronic devices. Here we report the effect of varying donor sizes on energy transfer from perovskite nanocrystals to chromophore molecules. Both single energy transfer and triplet transfer mechanisms have been identified to occur between CsPbBr3 quantum dots linked to a Rhodamine B dye. The ease of adjusting optical properties via particle-size controlling provides a particular platform to accommodate excited-state couplings in perovskite-chromophore hybrids.

A perspective on piezotronics and piezo-phototronics based on the third and fourth generation semiconductors

The rapid development of semiconductor materials and devices has brought tremendous development opportunities to optoelectronics, intelligent manufacturing, Internet of Things, power electronics, and even innovative energy technologies. Among them, the third and fourth generation semiconductors represented by ZnO, GaN, SiC, and Ga2O3 are two kinds of emerging strategic material systems. Due to their large energy bandgaps, they exhibit excellent performance in application scenarios of high voltage, high frequency, and high temperature resistance, making them great candidates in high-power, radio frequency, and optoelectronic devices. The third and fourth generation semiconductors usually possess non-centrosymmetric crystal structures, which makes the piezoelectric polarization effect a fundamental characteristic for the third and fourth generation semiconductors in contrast to the first and second generation semiconductors as represented by Si, Ge, and GaAs. Research studies on the coupling of piezoelectricity, semiconductor, and light excitation properties were coined as piezotronics and piezo-phototronics in 2007 and 2010, respectively, by Zhong Lin Wang. The piezotronic and piezo-phototronic effects open another avenue for further improvement of the performance of electronic and optoelectronic devices. This Perspective will first introduce the basic concepts and principles of piezotronics and piezo-phototronics and the basic characteristics of the third and fourth generation semiconductors. Then, progress, challenges, and opportunities of ideal materials, comprehensive physical models, and outstanding applications based on piezotronics and piezo-phototronics are presented with emphasis. Finally, conclusions and outlooks are drawn for the piezotronics and piezo-phototronics based on the third and fourth generation semiconductors.

Van der Waals integrated plasmonic Au array for self-powered MoS2 photodetector

2D transition metal dichalcogenides such as MoS2 are promising candidates for optoelectronics because of atomically thin nature and strong light–matter interaction. However, the poor light absorption limited their photodetection performance. Surface plasma resonance (SPR) can improve light absorption, but the defects introduced during the metal deposition process limit their responsivity and response time. In this work, we transfer a plasmonic Au array onto MoS2 surface, in which van der Waals (vdWs) contact forms between defect-free Au array–MoS2 interface. The Au/MoS2 heterostructure photodetector performs 1.8 ms rising time, 186.6 A/W responsivity, and 1.41 × 1012 Jones detectivity. The damage free vdWs fabrication method also makes it possible to integrate the engineered SPR Au array with functional polymer for flexible electronics. Thus, a vdWs plasmonic Au array/MoS2/P(VDF-TrFE) photodetector with a 1.28 × 103 rectification ratio has been obtained. This approach not only optimizes the performance of the 2D optoelectronic devices but also expands the scope of its potential applications.

Quantum Confinement Breaking: Orbital Coupling in 2D Ruddlesden–Popper Perovskites Enables Efficient Solar Cells

Abstract2D Ruddlesden–Popper perovskites have become emerging photovoltaic materials due to their intrinsic structure stability. Here, a concept of “quantum confinement breaking” in 2D perovskites is proposed using organic semiconductor spacers with suitable energy levels based on theoretical calculation and experimental results. An interesting finding is that there is intensive orbital coupling between the bithiophenemethylammonium (BThMA) spacer and adjacent inorganic layers in (BThMA)2PbI4, resulting in the breaking of the multiple quantum well structure. In comparison, no orbital interactions exist in (BPhMA)2PbI4 due to the wide bandgap of the biphenemethylammonium (BPhMA) spacer. Benefitting from the improved film quality, increased dielectric constant, and reduced binding energy, the (BThMA)2MAn−1PbnI3n+1 (n = 5) perovskite‐based device displays an outstanding power conversion efficiency (PCE) of 18.05%, which is much higher than that of the BPhMA‐based device (PCE = 12.69%) and among the best efficiency in 2D PSCs based on long conjugated spacers. The results provide an important implication for the effects of orbital interactions between organic semiconductor spacers and the adjacent [PbI6]4− octahedron layer on the performance of 2D perovskite solar cells and other optoelectronic devices.