Light-induced Phase Segregation Research Articles

Influence of Hole Transport Layers on Buried Interface in Wide-Bandgap Perovskite Phase Segregation.

Light-induced phase segregation, particularly when incorporating bromine to widen the bandgap, presents significant challenges to the stability and commercialization of perovskite solar cells. This study explores the influence of hole transport layers, specifically poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA) and [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACz), on the dynamics of phase segregation. Through detailed characterization of the buried interface, we demonstrate that Me-4PACz enhances perovskite photostability, surpassing the performance of PTAA. Nanoscale analyses using in situ Kelvin probe force microscopy and quantitative nanomechanical mapping techniques elucidate defect distribution at the buried interface during phase segregation, highlighting the critical role of substrate wettability in perovskite growth and interface integrity. The integration of these characterization techniques provides a thorough understanding of the impact of the buried bottom interface on perovskite growth and phase segregation.

Phase-stable wide-bandgap perovskites enabled by suppressed ion migration

Wide-bandgap (>1.7 eV) perovskites suffer from severe light-induced phase segregation due to high bromine content, causing irreversible damage to devices stability. However, the strategies of suppressing photoinduced phase segregation and related mechanisms have not been fully disclosed. Here, we report a new passivation agent 4-aminotetrahydrothiopyran hydrochloride (4-ATpHCl) with multifunctional groups for the interface treatment of a 1.77-eV wide-bandgap perovskite film. 4-ATpH+ impeded halogen ion migration by anchoring on the perovskite surface, leading to the inhibition of phase segregation and thus the passivation of defects, which is ascribed to the interaction of 4-ATpH+ with perovskite and the formation of low-dimensional perovskites. Finally, the champion device achieved an efficiency of 19.32% with an open-circuit voltage (VOC) of 1.314 V and a fill factor of 83.32%. Moreover, 4-ATpHCl modified device exhibited significant improved stability as compared with control one. The target device maintained 80% of its initial efficiency after 519 h of maximum power output (MPP) tracking under 1 sun illumination, however, the control device showed a rapid decrease in efficiency after 267 h. Finally, an efficiency of 27.38% of the champion 4-terminal all-perovskite tandem solar cell was achieved by mechanically stacking this wide-bandgap top subcell with a 1.25-eV low-bandgap perovskite bottom subcell.

Suppressing Halide Segregation via Pyridine-Derivative Isomers Enables Efficient 1.68 eV Bandgap Perovskite Solar Cells.

Light-induced phase segregation is one of the main issues restricting the efficiency and stability of wide-bandgap perovskite solar cells (WBG PSCs). Small organic molecules with abundant functional groups can passivate various defects, and therefore suppress the ionic migration channels for phase segregation. Herein, a series of pyridine-derivative isomers containing amino and carboxyl are applied to modify the perovskite surface. The amino, carboxyl, and N-terminal of pyridine in all of these molecules can interact with undercoordinated Pb2+ through coordination bonds and suppress halide ions migration via hydrogen bonding. Among them, the 5-amino-3-pyridine carboxyl acid (APA-3) treated devices win the champion performance, enabling an efficiency of 22.35% (certified 22.17%) using the 1.68 eV perovskite, which represents one of the highest values for WBG-PSCs. This is believed to be due to the more symmetric spatial distribution of the three functional groups of APA-3, which provides a better passivation effect independent of the molecular arrangement orientation. Therefore, the APA-3 passivated perovskite shows the slightest halide segregation, the lowest defect density, and the least nonradiative recombination. Moreover, the APA-3 passivated device retains 90% of the initial efficiency after 985 h of operation at the maximum power point, representing the robust durability of WBG-PSCs under working conditions.

"Whole-Body" Fluorination for Highly Efficient and Ultra-Stable All-Inorganic Halide Perovskite Quantum Dots.

Inherent "soft" ionic lattice nature of halide perovskite quantum dots (QDs), triggered by the weak Pb-X (X=Cl, Br, I) bond, is recognized as the primary culprit for their serious instability. A promising way is to construct exceedingly strong ionic interaction inside the QDs and increase their crystal cohesive energy by substituting the interior X- with highly electronegative F- , however, which is challenging and hitherto remains unreported. Here, a "whole-body" fluorination strategy is proposed for strengthening the interior bonding architecture of QDs, wherein the F- are uniformly distributed throughout the whole nanocrystal encompassing both the interior lattice and surface, successfully stabilizing their "soft" crystal lattice and passivating surface defects. This approach effectively mitigates their intrinsic instability issues including light-induced phase segregation. As a result, light-emitting devices based on these QDs exhibit exceptional efficiency and remarkable stability.

Suppressed phase segregation for triple-junction perovskite solar cells

The tunable bandgaps and facile fabrication of perovskites make them attractive for multi-junction photovoltaics1,2. However, light-induced phase segregation limits their efficiency and stability3-5: this occurs in wide-bandgap (>1.65 electronvolts) iodide/bromide mixed perovskite absorbers, and becomes even more acute in the top cells of triple-junction solar photovoltaics that require a fully 2.0-electron-volt bandgap absorber2,6. Here we report that lattice distortion in iodide/bromide mixed perovskites is correlated with the suppression of phase segregation, generating an increased ion-migration energy barrier arising from the decreased average interatomic distance between the A-site cation and iodide. Using an approximately 2.0-electron-volt rubidium/caesium mixed-cation inorganic perovskite with large lattice distortion in the top subcell, we fabricated all-perovskite triple-junction solar cells and achieved an efficiency of 24.3 per cent (23.3 per cent certified quasi-steady-state efficiency) with an open-circuit voltage of 3.21 volts. This is, to our knowledge, the first reported certified efficiency for perovskite-based triple-junction solar cells. The triple-junction devices retain 80 per cent of their initial efficiency following 420 hours of operation at the maximum power point.

Light-Induced Phase Segregation Evolution of All-Inorganic Mixed Halide Perovskites

Light-induced phase segregation in mixed halide perovskites is a major roadblock for commercialization of optoelectronics utilizing these materials. We investigate the phenomenon in a model material system consisting of only surfaces and the bulk of a single-crystalline-like microplate. We utilize environmental in-situ time-dependent photoluminescence spectroscopy to observe the bandgap evolution of phase segregation under illumination. This enables analysis of the evolution of the iodide-rich phase composition as a function of the environment (i.e., surface defects) and carrier concentration. Our study provides microscopic insights into the relationship among photocarrier generations, surface structural defects, and subsequently iodide ion migrations that result in the complex evolution of phase segregation. We elucidate the significance of surface defects with respect to the evolution of phase segregation, which may provide new perspectives for modulating ion migration by engineering of defects and carrier concentrations.

Suppressing Phase Segregation in Wide Bandgap Perovskites for Monolithic Perovskite/Organic Tandem Solar Cells with Reduced Voltage Loss.

Wide bandgap (WBG) perovskites through tuning iodine/bromine ratios are capable of merging with narrow bandgap organic bulk heterojunctions to construct tandem solar cells to overcome the Shockley-Queisser limitation. However, WBG perovskites readily suffer from light-induced halide ion migration, leading to detrimental phase segregation and hence severe open-circuit voltage (VOC ) loss. Here, to solve this issue, lead thiocyanate (Pb(SCN)2 ) and 2-thiopheneethylammonium chloride (TEACl) are synergistically employed to passivate and stabilize WBG perovskites with 1.79eV bandgap. It is demonstrated that the synergetic employment of Pb(SCN)2 and TEACl suppresses light-induced phase segregation, passivates WBG perovskite defects, and reduces non-radiative recombination, hence alleviating VOC loss. As a result, optimized WBG perovskite solar cells (PSCs) are obtained with an impressive VOC of 1.26V and power conversion efficiency (PCE) over 17.0%. Furthermore, the interconnection layer is optimized to minimize the VOC loss and construct two-terminal perovskite/organic tandem solar cells with a narrow bandgap organic blend bulk heterojunction of PM6:Y6 and achieve a champion PCE of 22.29% with a high VOC of 2.072V. In addition, these tandem solar cells maintain 81% of their initial efficiency after 1000h continuous tracking at the maximum power point (MPP) under 100 mW cm-2 white light illumination.

Hole Trapping in Halide Perovskites Induces Phase Segregation

ConspectusMetal halide perovskites have garnered a great deal of attention for their applications in photovoltaics, LEDs, and radiation detection. The ease of solution processing high-quality perovskite semiconductors with large absorption coefficients and tolerance to native defects is decidedly attractive. Additionally, the ability to precisely tune the band gap of halide perovskites through compositional alloying of the halide ion is of particular interest for a range of applications, especially for tandem solar cells. However, under steady state light irradiation, an initially homogeneous mixed halide perovskite (MHP) will form local domains that are rich in one halide ion (e.g., Br or I). This light-induced phase segregation in MHPs forms iodide-rich domains that act as charge carrier traps and lowers the efficiency of perovskite-based devices. Thus, phase segregation poses a serious challenge to the implementation of MHPs in real-world device settings. Interestingly, when a phase segregated MHP film is placed in the dark, entropic driving forces become dominant and the segregated perovskite remixes and returns to its initially homogeneous state. Several key mechanistic details of phase segregation have been elucidated over the years. However, there are still aspects of halide segregation that are not clear, and there is ongoing debate in the literature as to what are the key factors that contribute to the mechanism.This Account discusses recent results that point to the specific role of hole trapping in phase segregation. Interestingly, generation of holes through above-band-gap excitation or through electrochemical injection increases ion migration and leads to phase segregation. The thermodynamic and redox properties of halide perovskites provide a strong driving force for hole trapping and oxidation of iodide species in MHPs. However, mobile halide species within the perovskite lattice take time to migrate and generate halide-rich domains. When in contact with a nonpolar solvent, the migration of iodine species is further extended to expulsion of iodine from the perovskite film. Thus, the mobility of halides and their susceptibility to hole-induced oxidation play a crucial role in determining the long-term stability of metal halide perovskites. Strategies to gain kinetic control over ion migration to slow phase segregation are needed to overcome these hurdles and achieve stable mixed halide perovskites. Modification of the perovskite composition through introduction of different cations or halide ions, or introduction of low-dimensional perovskite phases may suppress phase segregation. Thus, in achieving stability and improving the efficiency of perovskite solar cells and light emitting devices with minimal impacts, suppression of segregation remains the key factor.

Photoinduced iodide repulsion and halides-demixing in layered perovskites

Mixing halides in metal halide perovskites (MHPs) is an effective approach for adjusting the MHPs bandgap for applications in tandem solar cells. However, mixed-halide (MH-) MHPs undergo light-induced phase segregation (LIPS) under continuous illumination. Therefore, understanding the mechanism of LIPS is necessary for developing stable MH-MHPs. In this work, we investigated LIPS in layered (L) MHPs and discovered a critical role of spacer cations in LIPS. Through probing chemical changes of LIPS, we unveil light-induced iodide repulsion and the formation of Br-rich-phase in illuminated regions during LIPS. This discovery also gives insight into the LIPS process in three-dimensional (3D) MHPs. By further investigating LIPS in 3D MHPs, we reveal that LIPS induces not only the formation of Br-rich and I-rich domains but also an overall change of halide distribution along the film thickness direction. Moreover, LIPS is more significant in bulk due to a larger population of photogenerated charge carriers. Overall, this study reveals the chemical mechanism of LIPS in MHPs and its potential effect on device performance, offering insight into understanding the LIPS mechanism and improving the stability of MHPs.

Correlating light-induced deep defects and phase segregation in mixed-halide perovskites

The correlation between rate of light-induced phase segregation and deep defect formation observed in mixed-halide perovskites. The importance of grain size in determining the rate and terminal phase of segregation was highlighted.

Concurrent cationic and anionic perovskite defect passivation enables 27.4% perovskite/silicon tandems with suppression of halide segregation

<h2>Summary</h2> Stable and efficient perovskite/silicon tandem solar cells require defect passivation and suppression of light-induced phase segregation of the wide-band-gap perovskite. Here, we report how molecules containing both electron-rich and electron-poor moieties, such as phenformin hydrochloride (PhenHCl), can satisfy both requirements, independent of the perovskite's surface chemical composition and its grain boundaries and interfaces. PhenHCl-passivated wide-band-gap (∼1.68 eV) perovskite <i>p-i-n</i> single-junction solar cells deliver an open-circuit voltage (<i>V</i>_OC) ∼100 mV higher than control devices, resulting in power conversion efficiencies (PCEs) up to 20.5%. These devices do not show any <i>V</i>_OC losses after more than 3,000 h of thermal stress at 85°C in a nitrogen ambient. Moreover, PhenHCl passivation improves the PCE of textured perovskite/silicon tandem solar cells from 25.4% to 27.4%. Our findings provide critical insights for improved passivation of metal halide perovskite surfaces and the fabrication of highly efficient and stable perovskite-based single-junction and tandem solar cells.

Stabilizing Mixed Halide Lead Perovskites against Photoinduced Phase Segregation by A-Site Cation Alloying

Mixed halide perovskites as top absorbers with relatively high bandgaps (Eg > 1.70 eV) are essential for tandem and multijunction solar cells. Light-induced phase segregation of mixed halide perovs...

Light-induced reversal of ion segregation in mixed-halide perovskites.

Bandgap instability due to light-induced phase segregation in mixed-halide perovskites presents a major challenge for their future commercial use. Here we demonstrate that photoinduced halide-ion segregation can be completely reversed at sufficiently high illumination intensities, enabling control of the optical bandgap of a mixed-halide perovskite single crystal by optimizing the input photogenerated carrier density. We develop a polaron-based two-dimensional lattice model that rationalizes the experimentally observed phenomena by assuming that the driving force for photoinduced halide segregation is dependent on carrier-induced strain gradients that vanish at high carrier densities. Using illumination sources with different excitation intensities, we demonstrate write-read-erase experiments showing that it is possible to store information in the form of latent images over several minutes. The ability to control the local halide-ion composition with light intensity opens opportunities for the use of mixed-halide perovskites in concentrator and tandem solar cells, as well as in high-power light-emissive devices and optical memory applications.

Inhibition of Phase Segregation in Cesium Lead Mixed-Halide Perovskites by B-Site Doping.

SummaryThe emergence of all-inorganic halide perovskites has shown great potential in photovoltaic and optoelectronic devices. However, the photo-induced phase segregation in lead mixed-halide perovskites has severely limited their application. Herein, by real-time monitoring the photoluminescence (PL) spectra of metal mixed-halide perovskites under light irradiation, we found that the photo-induced phase transition can be significantly inhibited by B-site doping. For pristine mixed-halide perovskites, an intermediate phase of CsPbBrxI3-x can only be stabilized under low excitation power. After introducing Sn2+ ions, such intermediate phase can be stabilized in nitrogen atmosphere under high excitation power and phase segregation can be started after the exposure in oxygen due to oxidization of Sn2+. Replacing Sn2+ by Mn2+ can further improve the intermediate phase's tolerance to oxygen proving that B-site doping in perovskites structure by Sn2+ or Mn2+ could effectively minimize the light-induced phase segregation and promote them to serve as promising candidates in photovoltaic and light-emitting devices.

Illumination-Induced Phase Segregation and Suppressed Solubility Limit in Br-Rich Mixed-Halide Inorganic Perovskites.

Mixing halides in perovskites has emerged as an effective strategy for tuning the band gap for optoelectronic applications and tackling the stability bottleneck. However, notable photoluminescence evolution has been observed in mixed-halide perovskites under external stimuli such as light illumination, which is attributed to phase segregation with halide inhomogeneity. In this work, we investigate the light illumination effect on the optical properties of all-inorganic mixed-halide perovskite CsPb(Br1-xIx)3 in the Br-rich regime. It is found that the critical iodine concentration, defined as the solubility limit against phase segregation, is significantly suppressed by light illumination to an extremely low level (x < 0.025), although the formation energy calculation suggests a wide range of halide mixing. Furthermore, at high I concentrations (x ≥ 0.2), the phase segregation can be rectified via dark storage within 1 h, but much slower and incomplete reversibility is observed at lower I concentrations. In the all-inorganic mixed-halide perovskite films, the light-induced phase segregation above the solubility limit is also accompanied by a monotonous increase in fluorescence lifetime. Last, we propose that light-induced phase segregation enables the potential application of encrypting erasable information in perovskite films with the aid of tailored light exposure and photoluminescence mapping.

Complex evolution of photoluminescence during phase segregation of MAPb(I1-xBrx)3 mixed halide perovskite

Under illumination, the photoluminescence of a mixed-halide perovskite such as MAPb(I1-xBrx)3 is known to undergo a significant intensity enhancement while spectrally shifting to lower energies. The evolution of low energy photoluminescence is attributed to the formation of iodide rich domains due to phase segregation. This process is detrimental for optoelectronic devices however the mechanism is not well-understood. Here we present a real-time study of the photoluminescence evolution in MAPb(I1-xBrx)3 samples during light-induced phase segregation. We show that the evolution of photoluminescence proceeds via several intermediate stages making it more complex than previously suggested. Within the first few seconds of photo-excitation, we found a very rapid formation of a short-lived intense photoluminescence band with a peak energy even lower than the final emission of the fully segregated sample. We propose that this emission comes from small pure iodide nano-domains formed during the initial stage of photo-induced phase-segregation.

Structural Origins of Light-Induced Phase Segregation in Organic-Inorganic Halide Perovskite Photovoltaic Materials

<h2>Summary</h2> Organic-inorganic metal-halide perovskite materials offer a promising route to reducing the dollars-per-watt cost of solar energy due to their good optoelectronic properties and facile, scalable processing. Compositional tuning allows for the preparation of absorbers with band gaps tailor-made for specific tandem and single-junction applications, but photoinduced phase segregation in mixed-halide materials leads to the formation of low-band-gap regions that reduce the voltage of devices. This work explores the structural origins of photoinduced phase segregation in FA_yCs_1−yPb(Br_xI_1−x)₃ perovskite alloys. We use synchrotron X-ray diffraction to map the solvus between the cubic and cubic-tetragonal mixed-phase region and time-dependent photoluminescence to assess stability under illumination. We show that the correlation between crystallographic phase and phase-segregation behavior is imperfect, so phase is not the sole determinant of optical stability. Instead, we consider several possible mechanisms that could underlie the dependence of optical stability on perovskite composition.

Phase segregation due to ion migration in all-inorganic mixed-halide perovskite nanocrystals

Semiconductor mixed-halide perovskites featured with a tunable energy bandgap are ideal candidates for light absorbers in tandem solar cells as well as fluorescent materials in light-emitting diodes and nanoscale lasers. These device advancements are currently hindered by the light-induced phase segregation effect, whereby ion migration would yield smaller-bandgap domains with red-shifted photoluminescence. Here we show that upon laser excitation all-inorganic mixed-halide nanocrystals unexpectedly exhibit a blue shift in the photoluminescence peak that can revert back in the dark, thus depicting the processes of ion migration out of and back to the originally excited nanocrystals. Interestingly, this reversible photoluminescence shift can also be induced by electrical biasing of mixed-halide nanocrystals without the injection of charge carriers. The above findings suggest that it is the local electric field that breaks the ionic bonds in mixed-halide nanocrystals, which could be a universal origin for light-induced phase segregation observed in other mixed-halide perovskite materials.

Amide-Catalyzed Phase-Selective Crystallization Reduces Defect Density in Wide-Bandgap Perovskites.

Wide-bandgap (WBG) formamidinium-cesium (FA-Cs) lead iodide-bromide mixed perovskites are promising materials for front cells well-matched with crystalline silicon to form tandem solar cells. They offer avenues to augment the performance of widely deployed commercial solar cells. However, phase instability, high open-circuit voltage (Voc ) deficit, and large hysteresis limit this otherwise promising technology. Here, by controlling the crystallization of FA-Cs WBG perovskite with the aid of a formamide cosolvent, light-induced phase segregation and hysteresis in perovskite solar cells are suppressed. The highly polar solvent additive formamide induces direct formation of the black perovskite phase, bypassing the yellow phases, thereby reducing the density of defects in films. As a result, the optimized WBG perovskite solar cells (PSCs) (Eg ≈ 1.75 eV) exhibit a high Voc of 1.23 V, reduced hysteresis, and a power conversion efficiency (PCE) of 17.8%. A PCE of 15.2% on 1.1 cm2 solar cells, the highest among the reported efficiencies for large-area PSCs having this bandgap is also demonstrated. These perovskites show excellent phase stability and thermal stability, as well as long-term air stability. They maintain ≈95% of their initial PCE after 1300 h of storage in dry air without encapsulation.

Light and Electrically Induced Phase Segregation and Its Impact on the Stability of Quadruple Cation High Bandgap Perovskite Solar Cells

Perovskite material with a bandgap of 1.7-1.8 eV is highly desirable for the top cell in a tandem configuration with a lower bandgap bottom cell, such as a silicon cell. This can be achieved by alloying iodide and bromide anions, but light-induced phase-segregation phenomena are often observed in perovskite films of this kind, with implications for solar cell efficiency. Here, we investigate light-induced phase segregation inside quadruple-cation perovskite material in a complete cell structure and find that the magnitude of this phenomenon is dependent on the operating condition of the solar cell. Under short-circuit and even maximum power point conditions, phase segregation is found to be negligible compared to the magnitude of segregation under open-circuit conditions. In accordance with the finding, perovskite cells based on quadruple-cation perovskite with 1.73 eV bandgap retain 94% of the original efficiency after 12 h operation at the maximum power point, while the cell only retains 82% of the original efficiency after 12 h operation at the open-circuit condition. This result highlights the need to have standard methods including light/dark and bias condition for testing the stability of perovskite solar cells. Additionally, phase segregation is observed when the cell was forward biased at 1.2 V in the dark, which indicates that photoexcitation is not required to induce phase segregation.