Photoinduced Phase Research Articles

Suppressing the Phase Segregation with Potassium for Highly Efficient and Photostable Inverted Wide-Band Gap Halide Perovskite Solar Cells.

Wide-band gap (WBG) mixed-halide perovskites have drawn much attention because of their excellent optoelectronic properties and the potential to be deployed in tandem solar cells. Nevertheless, the bromine incorporation inevitably leads to photoinduced phase segregation in WBG mixed-halide perovskites. Herein, potassium is used to effectively suppress photoinduced phase segregation, which is visualized with confocal photoluminescence microscopy imaging. Strikingly, the potassium passivation not only inhibits the formation of the narrow-band gap subphase but also enhances the crystallinity of the WBG mixed-halide perovskite. In addition, the potassium-passivated WBG perovskite exhibits lower defect density, longer charge carrier lifetime, and better photostability. As a result, the optimized KI (2 mol %)-passivated WBG perovskite solar cells (PSCs) deliver a champion power conversion efficiency of 18.3% with negligible hysteresis. They maintain 98% of their initial efficiency after 400 h under 100 mW·cm-2 white light illumination in nitrogen.

Minimized surface deficiency on wide-bandgap perovskite for efficient indoor photovoltaics

Abstract Wide-bandgap perovskite solar cells (PVSCs) possess significant potential in providing reliable power sources for applications in the Internet of Things (IoT) ecosystem under indoor light illumination. However, the wide-bandgap PVSCs usually suffer from photo-induced phase segregation and non-radiative energy loss caused by the Shockley-Read-Hall (SRH) type trap-assisted recombination at the interfaces in the devices. To address these issues, a simple strategy by applying phenethylammonium halides to reduce the energy loss and suppress the phase segregation of wide-bandgap PVSCs is developed. The devices incorporated with phenethylammonium chloride (PEACl) is revealed to achieve a high open-circuit voltage (VOC) of 1.26 V, leading to a merit power conversion efficiency (PCE) of 18.3%, which is the best performance among the inverted wide-bandgap PVSCs (~1.75 eV) under one sun illumination. Meanwhile, the photovoltaic performance of the device is also significantly enhanced, especially under a white light-emitting diode (LED) with an illumination of 1000 lux, showing a PCE of 35.6% with a high VOC of 1.08 V. Impressively, the device delivers a minimum energy loss of 670 meV, which is among the smallest value reported for perovskite-based indoor photovoltaics.

Uncovering the Functional Role of Coherent Phonons during the Photoinduced Phase Transition in a Molecular Crystal

The atomic motions that make up phonons and molecular vibrations in molecular crystals influence their photophysical and electronic properties, including polaron formation, carrier mobility, and phase transitions. Discriminating between spectator and driving motions is a significant challenge hindering optimization. Unlocking this information and developing fine-tuned controls over actively participating phonon modes would not only lead to a stronger understanding of photochemistry but also provide a significant new tool in controlling solid state chemistry. We present a strategy using rationally designed double pulses to unveil the unique function of specific excited state phonon modes. Using ultrafast spectroscopy, we identified 50 and 90 cm-1 phonons involved in modulating the photoinduced spin-Peierls melting of potassium tetracyanoquinodimethane crystals. We show that the 50 cm-1 phonon specifically corresponds to the coherent nuclear wavepacket involved in the charge transfer component of the overall spin-Peierls phase melting process, while the 90 cm-1 phonon facilitates the phase transition component.

Photo-Induced Black Phase Stabilization of CsPbI3 QDs Films.

α-CsPbI3 quantum dots (QDs) show outstanding photoelectrical properties that had been harnessed in the fabrication of perovskite QDs solar cells. Nevertheless, the stabilization of the CsPbI3 perovskite cubic phase remains a challenge due to its own thermodynamic and the presence of surface defects. Herein, we report the optimization of the CsPbI3 QDs solar cells, by monitoring the structure, the morphology and the optoelectronic properties after a precise treatment, consisting of the conventional solvent washing with a time limited ultraviolet (UV) exposure combination, during the layer-by-layer deposition. The UV treatment compensates the defects coming from the essential but deleterious washing treatment. The material is stable for 200 h and the PCE improved by the 25% compared with that of the device without UV treatment. The photo-enhanced ion mobility mechanism is discussed as the main process for the CsPbI3 QDs and solar cell stability.

Photoinduced Phase Segregation Leading to Evident Open-Circuit Voltage Loss in Efficient Inorganic CsPbIBr2 Solar Cells.

The photoinduced phase segregation (PIPS) of mixed-halide perovskites (MHPs), due to halogen migration, has reaped considerable attention for its retroaction on film photostability and photovoltaic output. Nevertheless, the original mechanism is still unclear. Herein, taking the representative CsPbIBr2 material as an example, a confocal laser scanning microscope (CLSM) technique was adopted to track the PIPS and dark recovery procedures. Besides the aggregation of iodide-rich (I-rich) domains at grain boundaries (GBs), some sporadic iodide "islands" with a swifter light response also appear throughout the polycrystalline films. It illustrates again that GBs are not essential for iodide aggregation. Furthermore, the iodide "islands" have substantial influence on a device's open-circuit voltage (Voc), resulting in an obvious plunge in the first tens of seconds. Results reveal the internal reason for the failure to reach the larger Voc outputs expected from wide-bandgap perovskites. Importantly, this finding can help promote the exploration of an efficient means to stabilize MHPs.

Phase Transition Photodetection in Charge Density Wave Tantalum Disulfide.

The charge density wave (CDW) phase is a macroscopic quantum state with periodic charge density modulation accompanied by periodic lattice distortion in low-dimensional metals. External fields, such as an electric field and optical excitation, can trigger the transitions among different CDW states, leaving an under-explored mechanism and attracting great interest toward optoelectronic applications. Here, we explore a photoinduced phase transition in 1T-TaS2 under an electrical field. By analyzing the phase transition probability, we obtained a linear dependence of the phase transition barrier on the electric field and laser energy density. Additionally, the threshold laser energy for the phase transition decreases linearly with an increasing applied electrical field. Finally, picojoule photodetection was realized in the visible and near-infrared ranges near the CDW transition edge. Our work will promote the understanding of the CDW phase transition mechanism as well as open pathways for optoelectronic applications.

Universality and Breaking of Universality in Photo-induced Non-equilibrium Phase Transitions

Universality and Breaking of Universality in Photo-induced Non-equilibrium Phase Transitions

Photoinduced Metal-Like Phase of VO2 with Subns Recovery

Vanadium dioxide is a unique insulator–metal transition material with a near room temperature transition temperature that is a major focus of interest in burgeoning fields such as all-optical devices and neuromorphic computing. The photoinduced insulator–metal transition of VO2 is of particular interest for the development of ultrafast optical devices; however, the recovery dynamics of VO2 after a photoinduced insulator–metal transition must be better understood. Here, the time-resolved differential transmittance of VO2 after excitation by an ultrashort pump laser pulse and the recovery of VO2 back to its equilibrium state are studied. For pump laser fluences in a midfluence region, which is found to match the midfluence region for the recently discovered photoinduced monoclinic metal phase of VO2, a strong nonlinear change in the differential transmittance of VO2 with fast recovery is discovered. In the midfluence region, a 15 nm VO2 thin film is shown to have a differential transmittance at the saturation value of 14%, while exhibiting full recovery in less than 600 ps. These results demonstrate that the large changes in the optical properties of VO2 associated with its photoinduced insulator–metal transition can recover on subns time scales, allowing for efficient GHz speed all-optical and neuromorphic computing devices using VO2.

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.

How Chloride Suppresses Photoinduced Phase Segregation in Mixed Halide Perovskites

Halide ion mobility in metal halide perovskites plays an important role in dictating the overall device performance and long-term stability of perovskite solar cells. Alloying with chloride (Cl), w...

Photoinduced phase separation in the lead halides is a polaronic effect.

We present a perspective on recent observations of the photoinduced phase separation of halides in multi-component lead-halide perovskites. The spontaneous phase separation of an initial homogeneous solid solution under steady-state illumination conditions is found experimentally to be reversible, stochastic, weakly dependent on morphology, yet strongly dependent on composition and thermodynamic state. Regions enriched in a specific halide species that form upon phase separation are self-limiting in size, pinned to specific compositions, and grow in number in proportion to the steady-state carrier concentration until saturation. These empirical observations of robustness rule out explanations based on specific defect structures and point to the local modulation of an existing miscibility phase transition in the presence of excess charge carriers. A model for rationalizing existing observations based on the coupling between composition, strain, and charge density fluctuations through the formation of polarons is reviewed.

Sub-picosecond photo-induced displacive phase transition in two-dimensional MoTe2

Photo-induced phase transitions (PIPTs) provide an ultrafast, energy-efficient way for precisely manipulating the topological properties of transition-metal ditellurides and can be used to stabilize a topological phase in an otherwise semiconducting material. Using first-principles calculations, we demonstrate that the PIPT in monolayer MoTe2 from the semiconducting 2H phase to the topological 1T′ phase can be triggered purely by electronic excitations that soften multiple lattice vibrational modes. These softenings, driven by a Peierls-like mechanism within the conduction bands, lead to structural symmetry breaking within sub-picosecond timescales, which is shorter than the timescale of a thermally driven phase transition. The transition is predicted to be triggered by photons with energies over 1.96 eV, with an associated excited carrier density of 3.4 × 1014 cm−2, which enables a controllable phase transformation by varying the laser wavelength. Our results provide insight into the underlying physics of the phase transition in 2D transition-metal ditellurides and show an ultrafast phase-transition mechanism for manipulation of the topological properties of 2D systems.

Manipulation of crosslinking in photo-induced phase separated polymers to control morphology and thermo-mechanical properties

Photopolymerization-induced phase separation allows significant control over polymer morphology and properties for hybrid radical/cationic systems. Polymer nano/micro-structure and domain size/continuity of each incompatible phase can be manipulated by using different photopolymerization conditions and formulation chemistries. In this work we incorporate multifunctional monomers including hexanediol diacrylate (HDDA) and a hybrid acrylate-oxetane monomer (OXMA) to modify the domain size scale and phase-separated morphology of a butyl acrylate (BA) and difunctional oxetane (DOX) system. Photopolymerization of the DOX/BA system results in distinct and co-continuous soft acrylate and hard oxetane domains. Incorporating different amounts of HDDA or OXMA generates polymer morphologies with smaller size-scale continuous hard domains because of the reduction in time difference between phase separation onset and gel point. Additionally, thermomechanical analysis shows that two glass transition temperatures (Tg's) are created for the DOX/BA system as indicated by the tan(δ) profiles, confirming the formation of distinct phase-separated domains. The addition of a crosslinker significantly increases the Tg of acrylate-rich domain as much as 45 °C, forming less distinct and broad tan(δ) peaks. The formation of more integrated as well as small and continuous domains enhances the flexibility and strength of the phase-separated DOX/BA system. A 2-fold increase in both elongation at break and maximum stress is observed with the addition of small amounts of HDDA or OXMA, resulting in an almost 5-fold increase in toughness and 2-fold increase in impact strength compared to the DOX/BA system. These results demonstrate that phase separation and polymer morphology in radical/cationic systems can be directed using multi-functional monomers enabling enhancements in mechanical properties including tensile toughness and impact strength.

In Situ TEM Monitoring of Phase-Segregation in Inorganic Mixed Halide Perovskite.

Photoinduced phase separation, which limits the available band gap energies for photovoltaic applications, was reported for a range of mixed-halide perovskites. A microscopic understanding of the phase separation mechanism is still lacking but may be beneficial to rationalize limitations as well as enable the design of phase-stable perovskite semiconductors. In this letter, electron-beam-induced phase separations and transformations were investigated in a small crystallite of CsPb(Br0.8I0.2)3 by means of in situ high-resolution imaging in a transmission electron microscope. The acquired time series was evaluated using principal and independent component analysis to classify the structural change during the illumination by the electron beam. A more iodine-rich phase with the approximate composition of CsPb(Br0.6I0.4)3 was found to form at the edges of the particle, while a ternary pure bromide phase of CsPbBr3 remained at its center. These results provide an atomistic picture of in-grain phase segregation into iodide-rich phases at grain boundaries and bromide-rich phases in the interior of the grain.

Local Rearrangement of the Iodide Defect Structure Determines the Phase Segregation Effect in Mixed-Halide Perovskites.

Mixed-halide perovskites represent a particularly relevant case within the family of lead-halide perovskites. Beyond their technological relevance for a variety of optoelectronic devices, photoinduced structural changes characteristic of this type of material lead to extreme photophysical changes that are currently the subject of intense debate. Herein we show that the conspicuous photoinduced phase segregation characteristic of these materials is primarily the result of the local and metastable rearrangement of the iodide sublattice. A local photophysical study comprising spectrally resolved laser scanning confocal microscopy is employed to find a correlation between the defect density and the dynamics of photoinduced changes, which extend far from the illuminated region. We observe that iodide-rich regions evolve much faster from highly defective regions. Also, by altering the material composition, we find evidence for the interplay between the iodide-related defect distribution and the intra- and interdomain migration dynamics giving rise to the complexity of this process.

Predicted photoinduced topological phases in organic salt α−(BEDT-TTF)2I3

The emergence of photo-induced topological phases and their phase transitions are theoretically predicted in organic salt $\alpha$-(BEDT-TTF)$_2$I$_3$, which possesses inclined Dirac cones in its band structure. By analyzing a photo-driven tight-binding model describing conduction electrons in the BEDT-TTF layer using the Floquet theorem, we demonstrate that irradiation with circularly polarized light opens a gap at the Dirac points, and the system eventually becomes a Chern insulator characterized by a quantized topological invariant. A rich phase diagram is obtained in plane of amplitude and frequency of light, which contains Chern insulator, semimetal, and normal insulator phases. We find that the photo-induced Hall conductivity provides a sensitive means to detect the predicted phase evolutions experimentally. This work contributes towards developing the optical manipulation of electronic states in matter through broadening the range of target materials that manifest photo-induced topological phase transitions.

Potassium‐Induced Phase Stability Enables Stable and Efficient Wide‐Bandgap Perovskite Solar Cells

Wide‐bandgap perovskites have great potential to enable high‐efficiency tandem photovoltaics by combining with the well‐established low‐bandgap absorbers. However, such wide‐bandgap perovskites are often necessarily constructed with a high Br content, and thus faced with issues of phase segregation–induced photoinstability and high defect density, severely hindering their photovoltaic performance. Herein, a remarkable boost of the stability and efficiency of wide‐bandgap perovskite solar cells (PSCs) is demonstrated by simply incorporating potassium ions. Experiments have shown the interstitial occupancy of potassium ions in the perovskite lattice and the formation of 2D K2PbI4 at the grain boundaries, both can reduce the trap density and inhibit ion migration, and thus suppress nonradiative recombination and photoinduced phase segregation. The average power conversion efficiency (PCE) of photovoltaic devices based on the perovskite with 40% Br is improved from 15.28% to 17.94%, among which the champion efficiency is 18.38% with an optimal 15% KI incorporation. Importantly, the champion open‐circuit voltage (Voc) remains unchanged (≈1.25 V) even when the bandgap reduces from 1.80 to 1.75 eV due to KI doping, effectively reducing the Voc deficit. In addition, the unencapsulated cells can sustain 94% of the initial PCE after 2000 h of storage in ambient atmosphere, affirming their outstanding stability.

Reversible Photoinduced Phase Segregation and Origin of Long Carrier Lifetime in Mixed‐Halide Perovskite Films

AbstractMixed‐halide hybrid perovskite semiconductors have attracted tremendous attention as a promising candidate for efficient photovoltaic and light‐emitting devices. However, these perovskite materials may undergo phase segregation under light illumination, thus affecting their optoelectronic properties. Here, photoexcitation induced phase segregation in triple‐cation mixed‐halide perovskite films that yields to red‐shift in the photoluminescence response is reported. It is demonstrated that photoexcitation induced halide migration leads to the formation of smaller bandgap iodide‐rich and larger bandgap bromide‐rich domains in the perovskite film, where the phase segregation rate is found to follow the excitation power‐density as a power law. Results confirm that charge carrier lifetime increases due to the trapping of photoexcited carriers in the segregated smaller bandgap iodide‐rich domains. Interestingly, these photoinduced changes are fully reversible and thermally activated when the excitation power is turned off. A significant difference in activation energies for halide ion migration is observed during phase segregation and recovery process. Additionally, the emission linewidth broadening is investigated as a function of temperature which is governed by the exciton–optical phonon coupling. The mechanism of photoinduced phase segregation is interpreted based on exciton–phonon coupling strength in both mixed and demixed (segregated) states of perovskite films.

Improvement of crystallization in CVD diamond coating induced by femtosecond laser irradiation

Herein, structural modification of a chemical vapor deposit (CVD) diamond film by a low fluence femtosecond laser irradiation has been studied with Raman spectroscopy, X-ray adsorption fine structure (XAFS) spectroscopy, and X-ray diffraction (XRD). Polycrystalline CVD diamond films of approximately 20 μm thickness were irradiated with femtosecond laser of varied defocus distances corresponding to the laser fluence range of 0.1–127.3 J/cm2. At fluences below 1.27 J/cm2, although there was no observable change in the appearance of the film surface, however, the FWHM of the diamond peak in the Raman spectra was observed to reduce considerably from 17 to 7 cm−1. Furthermore, the higher fraction of diamond phase with the increase in laser fluence strongly suggests that the microstructure of the diamond film has been modified by the femtosecond laser. By employing XAFS measurement, it can be found that after irradiation, the weak π* fine structure in the pre-edge almost vanished in response to the significant increase in σ* adsorption; further, a distinct diamond crystal characteristic peak was observed, which further confirms the femtosecond laser-induced modification, and its occurrence inside the bulk film. XRD results also pointed out that the improved diamond crystallinity with the integral intensities increased by approximately 20% after the femtosecond irradiation. Based on the above-mentioned results, an improvement in the crystallinity of CVD diamond under the low-fluence femtosecond laser irradiation has been confirmed in this study; this is attributed to a photo-induced phase transition from amorphous carbon to diamond.

Large non-thermal contribution to picosecond strain pulse generation using the photo-induced phase transition in VO2

Picosecond strain pulses are a versatile tool for investigation of mechanical properties of meso- and nano-scale objects with high temporal and spatial resolutions. Generation of such pulses is traditionally realized via ultrafast laser excitation of a light-to-strain transducer involving thermoelastic, deformation potential, or inverse piezoelectric effects. These approaches unavoidably lead to heat dissipation and a temperature rise, which can modify delicate specimens, like biological tissues, and ultimately destroy the transducer itself limiting the amplitude of generated picosecond strain. Here we propose a non-thermal mechanism for generating picosecond strain pulses via ultrafast photo-induced first-order phase transitions (PIPTs). We perform experiments on vanadium dioxide VO2 films, which exhibit a first-order PIPT accompanied by a lattice change. We demonstrate that during femtosecond optical excitation of VO2 the PIPT alone contributes to ultrafast expansion of this material as large as 0.45%, which is not accompanied by heat dissipation, and, for excitation density of 8 mJ cm−2, exceeds the contribution from thermoelastic effect by a factor of five.