Two/Quasi-two-dimensional perovskite-based heterostructures:construction,properties and applications

Two-dimensional(2D)/quasi-2D organic-inorganic halide perovskites are regarded as naturally formed multiple quantum wells with inorganic layers isolated by long organic chains,which exhibit layered structure,large exciton binding energy,strong nonlinear optical effect,tunable bandgap via changing the layer number or chemical composition,improved environmental stability,and excellent optoelectronic properties.The extensive choice of long organic chains endows 2D/quasi-2D perovskites with tunable electron-phonon coupling strength,chirality,or ferroelectricity properties.In particular,the layered nature of 2D/quasi-2D perovskites allows us to exfoliate them to thin plates to integrate with other materials to form heterostructures,the fundamental structural units for optoelectronic devices,which would greatly extend the functionalities in view of the diversity of 2D/quasi-2D perovskites.In this paper,the recent achievements of 2D/quasi-2D perovskite-based heterostructures are reviewed.First,the structure and physical properties of 2D/quasi-2D perovskites are introduced.We then discuss the construction and characterizations of 2D/quasi-2D perovskite-based heterostructures and highlight the prominent optical properties of the constructed heterostructures.Further,the potential applications of 2D/quasi-2D perovskite-based heterostructures in photovoltaic devices,light emitting devices,photodetectors/phototransistors,and valleytronic devices are demonstrated.Finally,we summarize the current challenges and propose further research directions in the field of 2D/quasi-2D perovskite-based heterostructures.

Could two-dimensional perovskites fundamentally solve the instability of perovskite photovoltaics

The high efficiency and low production cost enable the halide perovskite solar cells as a promising technology for the next generation photovoltaics.Nevertheless,the relatively poor stability of the organic–inorganic halide perovskites hinders their commercial applications.In the past few years,two-dimensional(2D)perovskite has emerged as a more stable alternative to the three-dimensional(3D)counterparts and attracted intense research interests.Although many attempts and advances have been made,it is still ambiguous that whether the 2D perovskites could bring closure to the stability issue.To answer this essential question,a systematic study of the nature of 2D halide perovskites is necessary.Here,we focus on the stability investigations of 2D perovskites from different perspectives,especially light,heat,ion migration and strain.Several remaining challenges and opening problems are also discussed.With further material and device engineering,we believe that the 2D perovskites would promote perovskite solar cells to a promising future.

Small molecule interfacial cross-linker for highly efficient two-dimensional perovskite solar cells

The nonradiative recombination of charge carriers at the hole transport layer(HTL)/perovskite interface generally induces remarkable performance loss of the inverted two-dimensional perovskite solar cells(2D PSCs). Herein, a cross-linkable small molecule of 2-mercaptoimidazole(2-MI) was introduced into the nickel oxide(NiO_(x))/2D perovskite interface. Experiments have confirmed the formation of Ni-N covalent bond by N atom in the 2-MI and Ni in the NiO_(x) and the coordinating between S atom of 2-MI and under-coordinated Pb^(2+) near to the NiO_(x)/perovskite interface, which contributes to creating a crosslinking between NiO_(x)/perovskite interface to restrain charge carrier recombination and enhance the extraction of hole carriers at the interface. Besides, the 2-MI modification layer is also beneficial for promoting the crystallinity of 2D perovskite. Consequently, the inverted 2D PSCs with 2-MI modification achieved the best power conversion efficiency of 15%. This paves a route to acquire highly efficient 2D PSCs by constructing a cross-linking at the NiO_(x)HTL/2D perovskite interface.

Device simulation of quasi-two-dimensional perovskite/silicon tandem solar cells towards 30%-efficiency

Perovskite/silicon(Si) tandem solar cells have been recognized as the next-generation photovoltaic technology with efficiency over 30% and low cost. However, the intrinsic instability of traditional three-dimensional(3D) hybrid perovskite seriously hinders the lifetimes of tandem devices. In this work, the quasi-two-dimensional(2D)(BA)_(2)(MA)_(n-1)Pbn I_(3n+1)(n = 1, 2, 3, 4, 5)(where MA denotes methylammonium and BA represents butylammonium), with senior stability and wider bandgap, are first used as an absorber of semitransparent top perovskite solar cells(PSCs) to construct a fourterminal(4T) tandem devices with a bottom Si-heterojunction cell. The device model is established by Silvaco Atlas based on experimental parameters. Simulation results show that in the optimized tandem device, the top cell(n = 4) obtains a power conversion efficiency(PCE) of 17.39% and the Si bottom cell shows a PCE of 11.44%, thus an overall PCE of 28.83%. Furthermore, by introducing a 90-nm lithium fluoride(LiF) anti-reflection layer to reduce the surface reflection loss, the current density(J_(sc)) of the top cell is enhanced from 15.56 m A/cm^(2) to 17.09 m A/cm^(2), the corresponding PCE reaches 19.05%, and the tandem PCE increases to 30.58%. Simultaneously, in the cases of n = 3, 4, and 5, all the tandem PCEs exceed the limiting theoretical efficiency of Si cells. Therefore, the 4T quasi-2D perovskite/Si devices provide a more cost-effective tandem strategy and long-term stability solutions.

Hydrophobic long-chain two-dimensional perovskite scintillators for underwater X-ray imaging

The underwater X-ray imaging technology development is significant to subaqueous target reconnaissance/detection/identification, subfluvial archaeology,submerged resource exploration, etc. As the core of X-ray imaging detection, the scintillator has been plagued by inherent moisture absorption and decomposition, and strict requirements for seamless packaging and waterproofing.Here, we designed a manganese-doped two-dimensional(2D) perovskite scintillator modified by hydrophobic longchain organic amine through the combination of component and doping engineering. The modified perovskites show high water repellency that can be used as an underwater X-ray scintillator. X-ray images of aquatic organisms or other objects with a high spatial resolution of10 lp·mm^(-1) at a big view field(32 mm × 32 mm) were obtained by scintillation screen. This hydrophobic perovskite scintillator based on molecular design is of great promise in underwater X-ray nondestructive testing technology development.

Tuning exciton dynamics by the dielectric confinement effect in quasi-two-dimensional perovskites

The dielectric confinement effect plays an essential role in optoelectronic devices.Existing studies on the relationship between the dielectric confinement and the photoelectric properties are inadequate.Herein,three organic spacers with different dielectric constants are employed to tune the exciton dynamics of quasi-two-dimensional(quasi-2D)Ruddlesden–Popper perovskite films.Femtosecond transient absorption spectroscopy reveals that the small dielectric constant ligand enables a weak dynamic disorder and a large modulation depth of the coherent phonons,resulting in a more complete energy transfer and the inhibition of a trap-mediated nonradiative recombination.Additionally,the increase in the bulk-ligand dielectric constant reduces the corresponding exciton binding energy and then suppresses the Auger recombination,which is beneficial for high-luminance lightemitting diodes.This work emphasizes the importance of dielectric confinement for regulating the exciton dynamics of layered perovskites.

High-performance flexible perovskite photodetectors based on single-crystal-like two-dimensional Ruddlesden-Popper thin films

Two-dimensional Ruddlesden-Popper(2DRP)perovskites have attracted intense research interest for optoelectronic applications,due to their tunable optoelectronic properties and better environmental stability than their threedimensional counterparts.Furthermore,high-performance photodetectors based on single-crystal and polycrystalline thin-films 2DRP perovskites have shown great potential for practical application.However,the complex growth process of single-crystal membranes and uncontrollable phase distribution of polycrystalline films hinder the further development of 2DRP perovskites photodetectors.Herein,we report a series of high-performance photodetectors based on single-crystal-like phase-pure 2DRP perovskite films by designing a novel spacer source.Experimental and theoretical evidence demonstrates that phase-pure films substantially suppress defect states and ion migration.These highly sensitive photodetectors show I_(light)/I_(dark) ratio exceeding 3×10^(4),responsivities exceeding 16 A/W,and detectivities exceeding 3×10^(13) Jones,which are higher at least by 1 order than those of traditional mixed-phase thinfilms 2DRP devices(close to the reported single-crystal devices).More importantly,this strategy can significantly enhance the operational stability of optoelectronic devices and pave the way to large-area flexible productions.

Optical properties of two-dimensional perovskites

The optical properties of two-dimensional(2D)perovskites recently receive numerous research focus thanks to the strong quantum and dielectric confinement effects.In addition to the strong excitonic effect at room temperature,2D perovskites also have appealing features that their optical properties can be flexibly tuned by alternating organic or inorganic layers.Particularly,2D chiral perovskites and 2D perovskites based heterostructures are emerging as new platforms to extend their functionalities.To optimize performance of 2D perovskites-based optoelectronic devices,it is critical to understand the fundamentals and explore the strategies to engineer their optical properties.This review begins with an introduction to the excitons and self-trapped excitons of 2D perovskites.Subsequently,inorganic/organic layer effects on optical properties and 2D perovskites based heterostructures are discussed.We also discussed the nonlinear optical properties of 2D perovskite.We are looking forward to that this review can stimulate more efforts to understand and optimize the optical properties of 2D perovskites.

Brightness and Lifetime Improved Light-Emitting Diodes from Sr-Doped Quasi-Two-Dimensional Perovskite Layers

Green Perovskite Light-Emitting Diodes(PeLEDs)have attracted wide attention for full spectrum displays.However,the inferior film morphology and luminescence property of quasi-two-dimensional(quasi-2D)perovskite layers limit the photoelectric property of the PeLEDs.In this paper,the effect of strontium(Sr)doped in quasi-2D perovskite layers is investigated to obtain a high-quality active layer.The morphologies and optical properties of Sr-doped quasi-2D perovskite films with different concentrations are studied.With the addition of strontium,more low-dimensional-layer perovskite phases(n D 2 and n D 3)appear in quasi-2D perovskite films,providing efficient intraband carrier funneling pathway and facilitating radiative recombination.The photoluminescence(PL)peak intensity of optimized Sr-doped quasi-2D perovskite layers increases 50%compared with the non-strontium counterpart.Moreover,green PeLEDs based on a Sr-doped quasi-2D perovskite layer reach a maximum luminance(Lmax)of 2943.77 cd/m^(2),which is three times of the control device.The electroluminescence(EL)peaks of Maximum External Quantum Efficiency(MEQE)and Lmax of Sr-doped PeLEDs exhibite a slight shift,indicating the excellent stability and performance of Sr-doped devices.The optimized device can continuously operate for 360 s at MEQE driving voltage,resulting in a half-lifetime of60 s,which is 3-fold greater than that of the control PeLEDs.

High-performance photodetectors based on two-dimensional perovskite crystals with alternating interlayer cations

Organic-inorganic halide perovskite,as a low-cost,solution-processable material with remarkable optoelectronic properties,is ideal candidate to fabricate high-performance photodetectors and is expected to significantly reduce device costs.Compared to the common Dion-Jacobson and Ruddlesden-Popper two-dimensional(2D)layered hybrid perovskite compounds,the perovskites with alternating cations in the interlayer(ACI)phase show higher crystal symmetry and narrower optical bandgaps,which exhibit great potential for excellent photodetection performance.Herein,we report a high-performance photodetector based on the 2D bilayered hybrid lead halide perovskite single crystal with the ACI phase(GAMA_(2)Pb_(2)I_(7);GA=C(NH_(2))_(3)and MA=CH_(3)NH_(3)).The single-crystal photodetector exhibits high photoresponsivity of 1.56,2.54,and 2.60 A/W for incident light wavelengths of 405,532,and 635 nm under 9.82 nW,respectively,together with the correspondingly high detectivity values of 1.86×10^(12),3.04×10^(12),and 3.11×10^(12)Jones under the same operating conditions.Meanwhile,a high-resolution imaging sensor is built based on the GAMA_(2)Pb_(2)I_(7)single-crystal photodetector,confirming the high stability and photosensitivity of the imaging system.These results show that the 2D hybrid lead halide perovskites with alternating interlayer cations are promising for high-performance visible light photodetectors and imaging systems.

Two-dimensional perovskite Pb_(2)Nb_(3)O_(10) photodetectors

For the first time,we report high-performance two-dimensional(2D)perovskite Pb_(2)Nb_(3)O_(10) photodetectors(PNO PDs).The few-layer PNO nanosheets are obtained successfully through a simple calcination and liquid exfoliation method.The individual PNO nanosheet devices with various structures(Au-PNO-Au,Au-PNO-Ti,Ti-PNO-Ti)are fabricated and investigated.The Au-PNO-Ti device exhibits a high rectification factor(∼102)owing to a large Schottky barrier difference between the PNO nanosheet and two asymmetric electrodes.Notably,the Au-PNO-Ti device shows excellent self-powered performance,including high responsivity(2.8 A/W),high detectivity(1.1×10^(12) Jones),and fast speed(0.2/1.2 ms)at 350 nm light illumination.This work not only suggests the performance of the PNO nanosheet PDs but also sheds light on the development of high-stability and high-performance devices based on 2D perovskite niobate in the future.

Influence of Organic Cations on the Crystal and Electronic Structures of Two-dimensional Lead Iodide Perovskites

The crystal structures and electronic structures(including band gap,project density of states,partial charge density,effective mass and electron localization function)of the 2D lead iodide perovskites hybrids with different organic spacer cations of 4-fluorophenylethanaminium(4F-PEA^(+)),ethanolamine(EA^(+)),thienylethylamine(TEA^(+))were investigated using first-principles calculations.It was found the higher dipole moment,the stronger the hydrogen bonding between the organic amino and iodide in the inorganic layer,and the larger the[PbI_(6)]^(4-)octahedral distortions in these crystal structure.Further quantifying the degree of the distortions using OctaDist software showed that the distortion of adjacent[PbI_(6)]^(4-)octahedra had a decisive effect on the band gap.Specifically,the greater deviation of Pb-I-Pb bond angles from 180°,together with the larger distortion of multiple[PbI_(6)]^(4-)octahedron resulted in a wider band gap,which was verified by calculated band gap using different DFT methods.The results outlined the relationships of hydrogen bonding,ocathedra distortion and band structure in 2D perovskites,highlighting the importance of the cations on the structural tuning and optoelectronic properties.

Ternary solvent boosts two-dimensional perovskites

In the past few years,organic–inorganic/inorganic lead halide perovskites,most notably CH3NH3Pb I3and its mixed cation/anion compounds,have attracted tremendous research interests in a wide range of different disciplines,which is largely initialized by their unprecedented success in low-cost and highly efficient solar cells.With certified efficiencies of over 22%in the lab-scale devices,

Superior photovoltaics/optoelectronics of two-dimensional halide perovskites

Taking advantage of the excellent stability and photoelectric properties,two-dimensional(2D)organicinorganic halide perovskites have been widely researched and applied in optoelectronic and photovoltaic devices.The remarkable properties are attributed to the unique quantum well structures by intercalating large organic ammonium space layers.In this review,we first summarize the crystal structures and growth methods of 2D halide perovskite crystals.Then,the distinctive optical characteristics and enhanced stability under high humidity,phase stability,suppressed ion migration,and high formation energy,are discussed in detail.Furthermore,we discuss orientation control in 2D perovskite films.The applications of 2D perovskites in solar cells,photo detectors and X-ray detectors are discussed in detail.Finally,we propose an outlook and perspectives to overcome the present challenges and broaden this new class of perovskite materials with other 2D nanomaterials.

Stabilizing perovskite precursors with the reductive natural amino acid for printable mesoscopic perovskite solar cells

Solution processability significantly advances the development of highly-efficient perovskite solar cells.However,the precursor solution tends to undergo irreversible degradation reactions,impairing the device performance and reproducibility.Here,we utilize a reductive natural amino acid,Nacetylcysteine(NALC),to stabilize the precursor solution for printable carbon-based hole-conductorfree mesoscopic perovskite solar cells.We find that I_(2) can be generated in the aged solution containing methylammonium iodide(MI) in an inert atmosphere and speed up the MA-FA^(+)(formamidinium) reaction which produces large-size cations and hinders the formation of perovskite phase.NALC effectively stabilizes the precursor via its sulfhydryl group which reduces I_(2) back to I^(-)and provides H^(+).The NALC-stabilized precursor which is aged for 1440 h leads to devices with a power conversion efficiency equivalent to 98% of that for devices prepared with the fresh precursor.Furthermore,NALC improves the device power conversion efficiency from 16.16% to 18.41% along with enhanced stability under atmospheric conditions by modifying grain boundaries in perovskite films and reducing associated defects.

Pressure-Induced Distinct Self-Trapped Exciton Emission in Sb^(3+)-Doped Cs_(2)NaInCl_(6)Double Perovskite

The Cs_(2)NaInCl_(6)double perovskite is one of the most promising lead-free perovskites due to its exceptional stability and straightforward synthesis.However,it faces challenges related to inefficient photoluminescence.Doping and high pressure are employed to tailor the optical properties of Cs_(2)NaInCl_(6).Herein,Sb^(3+)doped Cs_(2)NaInCl_(6)(Sb^(3+):Cs_(2)NaInCl_(6))was synthesized and it exhibits blue emission with a photoluminescence quantum yield of up to 37.3%.Further,by employing pressure tuning,a blue stable emission under a very wide range from 2.7 GPa to 9.8 GPa is realized in Sb^(3+):Cs_(2)NaInCl_(6).Subsequently,the emission intensity of Sb^(3+):Cs_(2)NaInCl_(6)experiences a significant increase(3.3 times)at 19.0 GPa.It is revealed that the pressure-induced distinct emissions can be attributed to the carrier self-trapping and detrapping between Cs_(2)NaInCl_(6)and Sb^(3+).Notably,the lattice compression in the cubic phase inevitably modifies the band gap of Sb^(3+):Cs_(2)NaInCl_(6).Our findings provide valuable insights into effects of the high pressure in further boosting unique emission characteristics but also offer promising opportunities for development of doped double perovskites with enhanced optical functionalities.

Effect of drying methods on perovskite films and solar cells

The high efficiency,solution processibility,and flexibility of perovskite solar cells make them promising candidates for the photovoltaic industry[1−8].The deposition method is one of the most critical factors that affect the performance of perovskite films.Various deposition methods have been developed to make perovskite films,including spin-coating,slotdie coating.

Chemical vapor deposition for perovskite solar cells and modules

Metal halide perovskites are promising materials for solar cells because of high power conversion efficiency(PCE),tun-able bandgap,high defect tolerance,long carrier diffusion length,and low-cost fabrication[1-7].The PCE for perovskite solar cells(PSCs)reaches 26.14%for single-junction cells,29.1%for perovskite/perovskite tandem cells and 33.9%for perovskite/silicon tandem cells,being comparable to that for silicon and other thin-film solar cells[8-10].Perovskite solar cells have been made by solution methods including spin-coat-ing,blade coating and printing[11,12].

Author Correction: ITO-free silicon-integrated perovskite electrochemical cell for light-emission and light-detection

Correction to:Opto-Electronic Advances https://doi.org/10.29026/oea.2023.220154 published online 26 April 2023 After the publication of this article1,it was brought to our attention that calculations of the PeLEC device elec-troluminescent(EL)efficiency contained a mistake,leading to an inaccurate quantity value.The device’s maxim-um EL efficiency constitutes not‘~120 klm/W’but‘4.3 lm/W’instead.Correction details are listed below.

Room-temperature synthesis of full-component APbX_(3)perovskite nanocrystal inks for optoelectronic applications

Lead halide perovskite nanocrystals(PNCs)have received great research interests due to their excellent optoelectronic properties.However,high temperature,inert gas protection and insulating long-chain ligands are used during the conventional hot-injection synthesis of PNCs,which limits their practical applications.In this work,we first develop a simple and scalable polar-solvent-free method for the preparation of full-component APbX_(3)(A=Cs,methylammonium(MA),formamidinium(FA),X=Cl,Br,I)PNCs under ambient condition.Through an exothermic reaction between butylamine(BA)and propionic acid(PA)short ligands,the PbX_(2) precursors could be well dissolved without use of any polar solvent.Meanwhile,the relatively lower growth rate of PNCs in our room-temperature reaction enables us to modulate the synthetic procedure to enhance the scalability(40-fold)and achieve large-scale synthesis.The resultant short ligands passivated PNC inks are compatible with varying solution depositing technique like spray coating for large-area film.Finally,we showcase that adopting the as-prepared MAPbI_(3) PNC inks,a self-powered photodetector is fabricated and shows a high photoresponsivity.These results demonstrate that our ambient-condition synthetic approach can accelerate the preparation of tunable and ready-to-use PNCs towards commercial optoelectronic applications.