The Role of Grain Boundaries in Organic-Inorganic Hybrid Perovskite Solar Cells and its Current Enhancement Strategies:A Review

Grain boundaries(GBs)in perovskite polycrystalline films are the most sensitive place for the formation of the defect states and the accumulation of impurities.Thus,abundant works have been carried out to explore their properties and then try to solve the induced problems.Currently,two important issues remain.First,the role of GBs in charge carrier dynamics is unclear due to their component complexity/defect tolerance nature and the insufficiency in testing accuracy.Some works conclude that GBs are benign,while others consider GBs as carrier recombination centers.Things for sure are the deterioration in ion transport and perovskite decomposition.Second,to solve the known hazards of GBs,a lot of additives have been added to anchoring ions and passivate defects.But in most of those works,GBs and perovskite surfaces are treated in the same manner ignoring the fact that GB is essentially a homogeneous junction in a narrow and slender space,while surface is a heterogeneous junction with a stratified structure.In this review,we focus on works insight into GBs and additives for them.Additionally,we also discuss the prospects of the maturity of GB exploration toward upscaling the manufacture of perovskite photovoltaic and related optoelectronic devices.

Plasma induced grain boundaries to boost electrochemical reduction of CO_(2)to formate

Bismuth-based catalysts are highly promising for the electrochemical carbon dioxide reduction reaction(eCO_(2)RR)to formate product.However,achieving high activity and selectivity towards formate and ensuring long-term stability remains challenging.This work reports the oxygen plasma inducing strategy to construct the abundant grain boundaries of Bi/BiO_x on ultrathin two-dimensional Bi nanosheets.The oxygen plasma-treated Bi nanosheet(OP-Bi)exhibits over 90%Faradaic efficiency(FE)for formate at a wide potential range from-0.5 to-1.1 V,and maintains a great stability catalytic performance without significant decay over 30 h in flow cell.Moreover,membrane electrode assembly(MEA)device with OPBi as catalyst sustains the robust current density of 100 mA cm^(-2)over 50 h,maintaining a formate FE above 90%.In addition,rechargeable Zn-CO_(2)battery presents the peak power density of1.22 mW cm^(-2)with OP-Bi as bifunctional catalyst.The mechanism experiments demonstrate that the high-density grain boundaries of OP-Bi provide more exposed active sites,faster electron transfer capacity,and the stronger intrinsic activity of Bi atoms.In situ spectroscopy and theo retical calculations further elucidate that the unsaturated Bi coordination atoms between the grain boundaries can effectively activate CO_(2)molecules through elongating the C-O bond,and reducing the formation energy barrier of the key intermediate(^(*)OCOH),thereby enhancing the catalytic performance of eCO_(2)RR to formate product.

Modeling the Interaction between Vacancies and Grain Boundaries during Ductile Fracture

The experimental results in previous studies have indicated that during the ductile fracture of pure metals,vacancies aggregate and form voids at grain boundaries.However,the physical mechanism underlying this phenomenon remains not fully understood.This study derives the equilibrium distribution of vacancies analytically by following thermodynamics and the micromechanics of crystal defects.This derivation suggests that vacancies cluster in regions under hydrostatic compression to minimize the elastic strain energy.Subsequently,a finite element model is developed for examining more general scenarios of interaction between vacancies and grain boundaries.This model is first verified and validated through comparison with some available analytical solutions,demonstrating consistency between finite element simulation results and analytical solutions within a specified numerical accuracy.A systematic numerical study is then conducted to investigate the mechanism that might govern the micromechanical interaction between grain boundaries and the profuse vacancies typically generated during plastic deformation.The simulation results indicate that the reduction in total elastic strain energy can indeed drive vacancies toward grain boundaries,potentially facilitating void nucleation in ductile fracture.

Effects of Fe solid solute on grain boundaries of bi-crystal Cu: A molecular dynamics simulation

Grain boundaries(GBs)play a crucial role on the structural stability and mechanical properties of Cu and its alloys.In this work,molecular dynamics(MD)simulations are employed to study the effects of Fe solutes on the formation energy,excess volume,dislocations and melting behaviors of GBs in CuFe alloys.It is illustrated that Fe solute affects the structural stability of Cu GBs substantially,the formation energy of GBs is reduced,but the thickness and melting point of GBs are increased,that is,the structural stability of Cu GBs is significantly improved owing to the Fe solutes.A strong scaling law exists between the formation energy,excess volume,thickness and melting point of GBs.Therefore,Fe solid solute plays an important role in the characteristics of GBs in bi-crystal Cu.

Precipitation sequence of η phase along low-angle grain boundaries in Al-Zn-Mg-Cu alloy during artificial aging

The precipitation sequence of η（MgZn2） phase along low-angle grain boundaries in Al-Zn-Mg-Cu alloy was investigated by examining samples aged at 135 ℃ for various times from 5 min to 6 h. High resolution transmission electron microscopy （HRTEM） observations and energy dispersive X-ray spectroscopy （EDX） analysis indicate that the precipitation sequence of η phase along low-angle grain boundaries should be supersaturated solid solution （SSS）→vacancy-rich clusters （VRC）→GP Ⅱ zones→η＇→η. Based on the theory of non-equilibrium grain boundary segregation （NGS） and non-equilibrium grain boundary co-segregation （NGCS）, the excessive solute elements gradually segregate to the grain boundaries by the diffusion of the solute-vacancy complex during aging treatment. The grain boundary segregation plays an important role in the nucleation and growth of VRC, GP Ⅱ zones, η＇ phase as well as η phase.

Behaviors of Lanthanum and Cerium on Grain Boundaries in Carbon Manganese Clean Steel

The behaviors of La and Ce on gram boundaries in carbon manganese clean steel were investigated by high-reso- lution transmission elecetron microscope （HRTEM）, scanning elecetron microscopy（SEM ）, energy dispersive spectrometer （EDS） and X-ray diffraction（XRD） analysis. The existing forms of rare earths （RE） in clean steel were as follows： dissolved in sohd solution, forming inclusion or second phase containing RE （RE-Fe-P, La-P, Fe-La eutectic and Fe-Ce phase）. The dissolved La or Ce segregated at grain boundaries. The segregation of both S and P at gram boundaries was reduced with suitable RE content. The impact toughness of the steel was improved obviously. La and Ce had effecets on purifying molten steel and modifying inclusions in clean steel, whereas with excessive La or Ce, La-Fe-P, La-P and Fe-La eutecetic phase or Ce-Fe-P and Fe-Ce intermetallic compound would form along grain boundaries, causing the impact energy to decrease significantly.

Stress Field of Non-equilibrium Grain Boundaries in Nano-crystalline Metals

Introducing the stress distribution near grain boundaries to improve the dislocation pileup model for the Halt-Petch (H-P) relation, the continuous distribution of dislocations in the pileup could be solved by means of Tschebysheff polynomials for the Hilbert transformation. An analytical formula of the stress intensity factor for the dislocation pileup is obtained. The reverse H-P relation may be explained by the modified dislocation-pileup-model.

Carrier Transport Across Grain Boundaries in Polycrystalline Silicon Thin Film Transistors

We established a model for investigating polycrystalline silicon（poly-Si） thin film transistors（TFTs）.The effect of grain boundaries（GBs） on the transfer characteristics of TFT was analyzed by considering the number and the width of grain boundaries in the channel region,and the dominant transport mechanism of carrier across grain boundaries was subsequently determined.It is shown that the thermionic emission（TE） is dominant in the subthreshold operating region of TFT regardless of the number and the width of grain boundary.To a poly-Si TFT model with a 1 nm-width grain boundary,in the linear region,thermionic emission is similar to that of tunneling（TU）,however,with increasing grain boundary width and number,tunneling becomes dominant.

Formation of I1 stacking fault by deformation defect evolution from grain boundaries in Mg

I_(1)stacking faults(SFs)in Mg alloys are regarded as the nucleation sites of<c+a>dislocations that are critical for these alloys to achieve high ductility.Previously it was proposed that the formation of I_(1)SFs requires the accumulations of a large number of vacancies,which are difficult to achieve at low temperatures.In this study,molecular dynamics(MD)and molecular statics(MS)simulations based on empirical interatomic potentials were applied to investigate the deformation defect evolutions from the symmetric tilt grain boundaries(GBs)in Mg and Mg-Y alloys under external loading along<c>-axis.The results show the planar faults(PFs)on Pyramidal I planes first appear due to the nucleation and glide of(1/2 c+p)partial dislocations from GBs,where p=1/3(1010).These partial dislocations with pyramidal PFs interact with other defects,including pyramidal PFs themselves,GBs,and ppartial dislocations,generating a large amount of I_(1)SFs.Detailed analyses show the nucleation and growth of I_(1)SFs are achieved by atomic shuffle events and deformation defect reactions without the requirements of vacancy diffusion.Our simulations also suggest the Y clusters at GBs can reduce the critical stress for the formation of pyramidal PFs and I_(1)SFs,which provide a possible reason for the experimental observations that Y promotes the<c+a>dislocation activities.

An Elasticity Model Considering Grain Boundaries and Tensile Orientations for Directionally Solidified Superalloys

In order to investigate the elastic properties of directionally solidified(DS)superalloys,an elasticity model called boundaries elastic model(GBE model),considering grain boundaries and tensile orientations,is proposed in this paper.Two assumptions are adopted in the GBE model:(1)The displacement of grains,which moves along the perpendicular direction,is restricted by the grain boundaries;(2)Grain boundaries influence region(GBIR)is formed around the grain boundaries.Based on the single crystal(SC)calculation method of elastic properties,the GBE model can well predict macroscopic equivalent elastic modulus(Young’s modulus)of DS superalloys under different tensile orientations effectively.To demonstrate the correctness of the GBE model,3D finite element simulation is adopted and tensile experiments on a Ni3Al?base DS superalloy(IC10)along five tensile orientations are carried out.Meanwhile,the grain boundaries are observed by light microscopy and transmission electron microscope(TEM).Therefore,the GBE model is proved to be feasible by comparing the simulated results with the experiments.

Spatially Resolved Analytical Electron Microscopy at Grain Boundaries of α-Al_2O_3

In this work the electronic structure and the impurity excess of the basal and rhombohedral twin grain boundaries are investigated, using electron energy loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDXS). The measurability of electronic structures of the twin grain boundaries are discussed by comparing theoretical density of states (DOS) from bulk material with interfacial DOS, obtained from local density functional theory (LDFT) calculations.

Inhomogeneity of Grain Boundaries of ZnO Varistor

The zinc oxide varistor with a low threshold voltage and large grain size was derived with ZnO crystalline seeds from a molten salt process The chemical composition and I-V characteristics of single grains and single grain boundaries were determined by means of energy dispersive spectrum (EDS) and microcontact measurement respectively. Temperatu re dependence of dielectric loss at various frequencies and voltage dependence of capacitance were carefully measured. Based on these experimental data. the barrier heights of giain boundaries are estimated to be 0.2. 0.5 and 0.6 eV respectively corresponding to thick, th in and direct contact grain boundaries. In addition. a computerized electrical circuit simufation is employed in simulating I-V characteristics of single grain boundary within ZnO varistor. By adjustjng parameters of resistor and diode, a general agreement between the measured data and simulated curves is achieved

Diffusion of Hydrogen along the Grain Boundaries in Ni_3Al Alloys

The diffusivity of hydrogen in two Ni3Al alloys (No.1 and No.2) has been measured in the temperature range of 100 degreesC to 420 degreesC using an ultrahigh vacuum gaseous permeation technique. The diffusivity data fall into two segments, in which the hydrogen diffusivity adheres to the Arrhenius form, respectively. From the hydrogen diffusivity, it is conjectured that the hydrogen diffusivity reflects the hydrogen transportation along the grain boundaries at lower temperature and the hydrogen transportation in the lattice at higher temperature. The intergranular fracture of Lit-type intermetallics induced by hydrogen at relative low temperature results from hydrogen transportation along the grain boundaries and not in the lattice.

Molecular dynamics simulation of fracture behaviors of <110> tilt grain boundaries in γ-TiAl

Molecular dynamics(MD) simulations were carried out to study the fracture behaviors of several symmetric tilt grain boundaries in γ-Ti Al bicrystals with <110> misorientation axes. Tensile deformation along direction perpendicular to grain boundary was simulated under various strain rates and temperatures. The results indicate that the relative orientation of the grains and the presence of certain atom units are two critical factors of the interface structure affecting the stress required for dislocation nucleation. Dislocations nucleate and extend at or near the symmetric tilt grain boundaries during the tensile deformation of Σ3(111) 109.5°, Σ9(221) 141.1° and Σ27(552) 148.4° interfaces. For Σ27(115) 31.6° and Σ11(113) 50.5° interfaces, the interfaces fractured directly in a cleavage manner due to no dislocation emitted from the boundary. The tensile fracture mechanisms of the bicrystals are that micro-cracks nucleate at the grain boundary and propagate along the interface. The variance of crack propagation is whether there is accommodation of plastic region at the crack tips.

Influence of sub-grain boundaries on quenching process of an Al-Zn-Mg-Cu alloy

The effects of sub-grain boundaries on the quenching sensitivity and the precipitation behavior in Al-7.01Zn-1.26Mg- 1.43Cu alloy were investigated by an end-quenching test. Specimens were solution treated at 440 ℃ and 480 ℃ to get different recrystallization fractions, respectively. The results show that the maximum hardness value of the Al-Zn-Mg-Cu alloy can be improved by the sub-grain boundaries, but the depth of age-hardening layer decreases significantly. The precipitation temperature and the activation energy are reduced by the changes of surface energy, which is induced by sub-grain boundaries. So, the precipitation process from η phase to η phase becomes much easier. In this way, an increase in the number of sub-grain boundaries promotes the precipitation of MgZn2 particles, especially η＇-MgZn2.

Electronic Theoretical Study of the Interaction between Rare Earth Elements and Impurities at Grain Boundaries in Steel

The model of dislocations was used to construct the model of grain boundary (GB) with pure rare earths, and rare earth elements and impurities. The influence of the interaction between rare earth elements and impurities on the cohesive properties of 5.3° low angle GB of Fe was investigated by the recursion method. The calculated results of environment sensitive embeding energy( E ESE ) show that the preferential segregation of rare earth elements towards GBs exists. Calculations of bond order integrals (BOI) show that rare earth elements increase the cohesive strength of low angle GB, and impurities such as S, P weaken the intergranular cohesion of the GB. So rare earth element of proper quantity added in steel not only cleanses other harmful impurities off the GBs, but also enhances the intergranular cohesion. This elucidates the action mechanism of rare earth elements in steel from electronic level and offers theoretical evidence for applications of rare earth elements in steels.

CYCLIC HARDENING BEHAVIOR OF POLYCRYSTALS WITH PENETRABLE GRAIN BOUNDARIES:TWO-DIMENSIONAL DISCRETE DISLOCATION DYNAMICS SIMULATION

A two-dimensional discrete dislocation dynamics （DDD） technology by Giessen and Needleman （1995）, which has been extended by integrating a dislocation-grain boundary interaction model, is used to computationally analyze the micro-cyclic plastic response of polycrystals containing micron-sized grains, with special attentions to significant influence of dislocationpenetrable grain boundaries （GBs） on the micro-plastic cyclic responses of polycrystals and underlying dislocation mechanism. Toward this end, a typical polycrystalline rectangular specimen under simple tension-compression loading is considered. Results show that, with the increase of cycle accumulative strain, continual dislocation accumulation and enhanced dislocation-dislocation interactions induce the cyclic hardening behavior; however, when a dynamic balance among dislocation nucleation, penetration through GB and dislocation annihilation is approximately established, cyclic stress gradually tends to saturate. In addition, other factors, including the grain size, cyclic strain amplitude and its history, also have considerable influences on the cyclic hardening and saturation.

ANELASTIC RELAXATIONS ASSOCIATED WITH LOCAL DISORDERING AT GRAIN BOUNDARIES

Internal friction and micro-creep measurements were performed with high-purity aluminium bamboo-crystal specimens.The relaxation strength was found to decrease with the decrease of temperature and became zero at about 0.4 T_m(T_m is the melting temperature).This re- flects the occurrence of local disordering in the bamboo boundary region at this temperature. This result conforms to the picture of grain-boundary disordering constructed by atomic simulation studies.

Nano-capillary induced assemble of quantum dots on perovskite grain boundaries for efficient and stable perovskite solar cells

In recent years, perovskite solar cells(PSCs) have propelled into the limelight owing to rapid development of efficiency;however, the abundant defects at the perovskite grain boundaries result in unwanted energy loss and structural degradation. Here, the grain boundaries of perovskite polycrystalline films have been found to act as nanocapillaries for capturing perovskite quantum dots(PQDs), which enable the conformal assemble of PQDs at the top interspace between perovskite grains. The existence of PQDs passivated the surface defects, optimized the interfacial band alignments, and ultimately improved the power conversion efficiency from 19.27% to 22.47% in inverted PSCs. Our findings open up the possibility of selective assembly and structural modulation of the perovskite nanostructures towards efficient and stable PSCs.

Determination of Neutron Irradiation-Induced Phosphorus Segregation on Grain Boundaries in a P-doped 2.25Cr1Mo Steel

Irradiation-induced impurity segregation to grain boundaries is one of the important radiation effects on materials. For this reason, phosphorus segregation to prior austenite grain boundaries in a P-doped 2.25Cr1Mo steel subjected to neutron irradiation is examined using field emission gun scanning transmission electron microscopy (FEGSTEM) with energy dispersive X-ray microanalysis (EDX). The steel samples are irradiated around 270 and 400℃, respectively. The irradiation dose rate and dose are -1.05×10-8 dpa/s and -0.042 dpa respectively for 270℃ irradiation, and 1.7×10-8 dpa/s and 0.13 dpa respectively for 400℃ irradiation. The FEGSTEM results indicate that there is no apparent phosphorus segregation during 270℃ irradiation but there is some during 400℃ irradiation.