X-ray Photoemission Spectroscopy Measurements Research Articles

Epitaxial growth and band offsets of β -(ScxGa1− x)2O3 thin films grown on (100) β -Ga2O3 substrate

β-(ScxGa1−x)2O3 (x = 0–0.36) thin films were epitaxially grown on (100) β-Ga2O3 substrates by oxygen-radical-assisted pulsed-laser deposition. β-(ScxGa1−x)2O3 epilayers were coherently strained up to x = 0.30, although the presence of a structural disorder was implied when x > 0.2. The bandgap energies measured by reflection electron energy loss spectroscopy increased from 4.56 to 5.25 eV with increasing Sc content. In β-(ScxGa1−x)2O3 epilayers, a slightly negative bandgap bowing behavior with a bowing parameter of −0.4 eV was observed, resulting in a larger bandgap increase than in β-(AlxGa1−x)2O3 epilayers with identical x. X-ray photoemission spectroscopy measurement revealed that the valence-band and conduction-band offsets of β-(Sc0.17Ga0.83)2O3 epilayer with respect to β-Ga2O3 were 0.0 and 0.3 eV, respectively.

Peeling-induced interfacial roughness and charging for enhanced triboelectric power generation

To date, there have been a lot of efforts to enhance the conversion efficiency of triboelectric nanogenerators (TENGs) via physical and chemical modifications of the polymer surface. Herein, we report that a facile peeling of polymer from a substrate can enhance the triboelectric power output. The peeling of spin-coated polydimethylsiloxane (PDMS) from glass and polytetrafluoroethylene (PTFE) substrates has revealed a considerable increase in interfacial roughness and lateral friction. Surface-sensitive X-ray photoemission spectroscopy and non-contact current measurements have also revealed the transfer of counter-material and interfacial charging. The surface roughness of peeled PDMS is significant for the PTFE substrate, while the surface charge is significant for the glass substrate. The triboelectric output power density for peeled PDMS from the substrate is similar, 10.3 µW/cm2, but significantly larger than that for as-grown PDMS (2.2 µW/cm2). The peeling strength of PDMS significantly increases for glass compared to PTFE after the oxygen plasma treatment of substrates. The triboelectric charge of peeled PDMS from a plasma-treated glass substrate is almost 1.3 times larger than that from a PTFE substrate. This work implies that peeling polymer from a rough substrate with a large adhesion force would be a facile and effective way to increase the triboelectric power output, without any delicate surface treatments.

In situ photoemission spectroscopies to reveal surface transfer doping on hydrogenated milled nanodiamonds

Nanodiamonds (ND) exhibit exceptional chemical, electronic, thermal, and optical properties, making them valuable for applications in nanomedicine, energy, quantum technologies, advanced lubricants, and polymer composites. Surface analysis techniques such as X-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS) and reflection electron energy loss spectroscopy (REELS) are critical for understanding the surface properties of nanomaterials, including nanodiamonds. This study investigates hydrogenated milled nanodiamonds (H-MND) by integrating UPS and XPS measurements with REELS. Through in situ annealing within an ultra-high vacuum (UHV) chamber, we examine the impact of surface termination on surface conductivity, focusing on the role of adsorbates. Our findings reveal that a surface transfer doping mechanism, akin to that observed in bulk diamond, governs a pseudo p-type conductivity in H-MND. The conductivity dependence on ambient exposure, water, and subsequent annealing demonstrates its reversibility. The study also discusses the nature of electron acceptors and the influence of ND facets on conductivity.

Observation of the multiple magnetic phases in double perovskite Pr1.8La0.2CoFeO6

The structural and magnetic properties of the double perovskite Pr1.8La0.2CoFeO6 have been investigated. The X-ray diffraction study shows that the system acquires room-temperature orthorhombic phase with the Pnma space group. The X-ray photoemission spectroscopy (XPS) measurement confirmed that the B-site ions are present in mixed valence states i.e. Co has been found in Co2+ and Co3+ valance states whereas Fe has been found in Fe3+/Fe4+. Magnetic measurements of the system confirm the existence of several fascinating magnetic behaviors, such as long-range canted antiferromagnetism withTN ∼ 271 K, giant exchange bias, and re-entrant cluster glass phase (TG ∼ 33 K). Field-dependent magnetization shows a large spontaneous exchange bias; HSEB∼ 1.8 kOe and giant conventional exchange bias, HCEB∼ 2.4 kOe at 5 K. Antiferromagnetic materials with large exchange bias can be utilized in high-density spintronic devices. Temperature-dependent Raman study demonstrates that the observed phonon mode exhibits anomalous behavior close to the magnetic transition temperature. Analysis of anomalous softening of phonon mode below TN, clarifies the presence of significant spin-phonon coupling while the magnetostriction effect does not play any significant role in the observed phonon anomaly.

Accelerating X-ray photoemission spectroscopy measurements using Bayesian super-resolution

This study applies Bayesian super-resolution to X-ray photoelectron spectroscopy (XPS), achieving up to a 20-fold reduction in measurement time while preserving data quality. Traditional XPS, crucial for surface analysis, typically requires extensive measurement durations. Our methodology significantly accelerates the process, as demonstrated with glass and Polytetrafluoroethylene samples, where we reduced measurement times by up to 1/20th without compromising spectral accuracy. This approach decreases noise levels and retains spectral integrity, offering a highly efficient solution for XPS. This innovation is particularly valuable in material science, enabling rapid, reliable surface analysis.

Allotropic transition of Dirac semimetal α-Sn to superconductor β-Sn induced by focused-ion-beam irradiation

Diamond-type structure allotrope α-Sn is attracting much attention as a topological Dirac semimetal (TDS). In this study, we demonstrate that α-Sn undergoes a phase transition to another allotrope β-Sn with superconductivity at low temperature by irradiating with a focused Ga ion beam (FIB). To clarify the transition mechanism, we performed x-ray photoemission spectroscopy (XPS) measurements on an α-Sn thin film irradiated with FIB and an as-grown α-Sn thin film. The XPS results suggest that the local annealing, which is one of the side effects of FIB, causes the transformation from α-Sn into β-Sn. Furthermore, the difference in the chemical states between α-Sn and β-Sn can be quantitatively explained by the crystal structures rather than the degree of metallicity reflecting the conductivity. These results propose a way of fabricating TDS/superconductor in-plane heterostructures based on α-Sn and β-Sn.

The dehydration mechanism of Na and K birnessites: a comprehensive multitechnique study.

The structural, spectroscopic and electronic properties of Na and K birnessites were investigated from ambient conditions (birA) to complete dehydration, and the involved mechanisms were scrutinized. Density Functional Theory (DFT) simulations were employed to derive structural models for lamellar A0.33MnO2·xH2O (A = Na+ or K+, x = 0 or 0.66), subsequently compared with the experimental results obtained for Na0.30MnO2·0.75H2O and K0.22MnO2·0.77H2O materials. Thermal analysis (TGA-DSC), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, and Near Ambient Pressure X-ray Photoemission Spectroscopy (NAP-XPS) measurements were conducted for both birnessites. Dehydration under vacuum, annealing, or controlled relative humidity were considered. Results indicated that complete birnessite dehydration was a two-stage process. In the first stage, water removal from the interlayer of fully hydrated birnessite (birA) down to a molar H2O/A ratio of ∼2 (birB) led to the progressive shrinkage of the interlayer distance (3% for Na birnessite, 1% for K birnessite). In the second stage, water-free (birC) domains with a shorter interlayer distance (20% for Na birnessite, 10% for K birnessite) appeared and coexisted with birB domains. Then, birB was essentially transformed into birC when complete dehydration was achieved. The vibrational properties of birA were consistent with strong intermolecular interactions among water molecules, whereas partially dehydrated birnessite (birB) showed a distinct feature, with 3 (for Na-bir) and 2 (for K-bir) vibrations that were reproduced by DFT calculations for organized water into the interlayer (x = 0.66). The study also demonstrated that the electronic structure of Na birnessite depends on the interlayer water content. The external Na+ electronic level (Na 2p) was slightly destabilized (+0.3 eV binding energy) under near ambient conditions (birA) compared to drier conditions (birB and birC).

Crystal structural, magnetic, and dielectric properties of Cobalt−doped breathing pyrochlore LiInCr4−xCoxO8

Here, the structural, magnetic, and dielectric features of breathing pyrochlore LiInCr4−xCoxO8 were investigated. The XRD analysis showed changes in Cr–Cr length and distorted CrO6 octahedral as Co ion doping level rises. The x-ray photoemission spectroscopy measurements showed that there are both Co2+ and Co3+ ions in the LiInCr4−xCoxO8 compounds. The difference between temperature-dependent magnetization curves during field cooling and zero-field cooling suggested that there is a spin-glass state, which was verified by the heat capacity measurement. Doping affects the bond length, which affects the magnetic properties and electronic properties. The dielectric characteristics were systematically studied, and the temperature dependence of the dielectric loss and dielectric constant was examined in the temperature range of 323−573 K at various frequencies. The dielectric behavior strongly changes with the change in temperature and/or frequency. The activation energies of grain boundary resistance of doped samples show a decreasing trend with increasing doping.

Bright photoluminescence from CdSe quantum dots conjugated with metal phthalocyanines

Engineering organic/inorganic nanohybrids is one of the emerging tracks in material science to search for new nanomaterials with tailored and/or enhanced properties. In this work, we report the synthesis of CdSe quantum dots (QDs) conjugated with selected metal phthalocyanine (MPc), e.g., ZnPc and CuPc, utilizing the hot-injection organometallic method. The prepared pristine and conjugated QD systems exhibit practically identical particle size and spherical morphology and feature the characteristic CdSe excitonic peaks in their optical absorption spectra. The successful incorporation of ZnPc or CuPc molecules is ensured by the appearance of their sharp Q-band peaks in the optical absorption and the Zn2p or Cu2p core levels in the X-ray photoemission spectroscopy (XPS) measurements. The pure CdSe QDs sample of selected size (∼4.0 nm) exhibits well-defined photoluminescence (PL) peak at the limit of the green range, which is remarkably enhanced for the conjugated QD systems, reaching ∼250 % for the CuPc/CdSe QDs. Such prominent PL enhancement is attributed to Förster resonance energy transfer stimulated by deep B-band emissions from CuPc molecules combined with charge transfer from MPc molecules to CdSe QDs. Furthermore, the emission is greatly amplified upon prolonged exposure to laser beam, exceeding 400 % of the initial CuPc/CdSe emission after only 40 min of exposure time, yet without significant changes in their emission color. Thus, these MPc/CdSe conjugated QD systems are promising nanomaterials for intense white light sources.

Redox Behavior of Arsenic (III) and Copper (II) Mixtures on Ultraflat Au (111) Thin Film Electrodes

The electrochemical behavior of arsenic on gold (Au) electrodes surfaces is of great interest as As is well-recognized as a highly toxic and relatively ubiquitous ground water species. The United States Environmental Protection Agency (USEPA) and World Health Organization (WHO) drinking water standards for arsenic are 10 PPB, or 𝜇g L-1 [1]. These minute ion concentrations necessitate the use of analytical methods with high sensitivity and a low susceptibility to cross interferences. Electrochemical stripping voltammetry is a well-established electroanalytical method for arsenic ions [2]. Polycrystalline gold electrodes are often used due to their high redox stability and relatively low overpotential for hydrogen evolution. We recently explored the use of ultra-flat, thin film, Au(111) electrodes to replace polycrystalline Au for As stripping voltammetry. Previous studies on oriented single crystals showed relatively narrow stripping peaks with greatly improved peak to background ratios on the (111) surfaces [3]. We observed comparatively similar or better stripping behavior on the Au(111) thin film electrodes with correspondingly far less gold usage per electrode. Unfortunately, copper is a known interference for arsenic stripping electroanalysis, with a strong affinity for UPD deposition on gold. We therefore studied the deposition behavior of Cu on Au(111) thin film electrodes and the co- deposition of Cu and As on the Au(111) thin film electrodes to evaluate cross interference effects. Copper redox behavior in 0.5M H2SO4 was characterized by cyclic voltammetry, electro- deposition and linear stripping voltammetry (LSV) measurements. Strong Cu UPD behavior was observed on Au(111) thin films with sharper, better defined redox peaks than polycrystalline electrodes. Arsenic and Cu ions were also co-deposited over a wide range of Cu (II) and As (III) concentrations. Complex redox behavior was observed with strong indications of Cu-As alloy formation. This was confirmed via angle resolved, X-ray Photoemission Spectroscopy (XPS) measurements. Our results also indicate that the electrodeposition efficiency during LSV of As is increased by the co-deposition of Cu. The results of this study have important implications for understanding the nature of Cu (II) interference with electrochemical detection of trace As (III) in water.[1] USEPA. National Secondary Drinking Water Regulations. 2009. https://www.epa.gov/sdwa/drinking-water- regulations-and-contaminants (accessed.[2] USEPA. METHOD 7063: ARSENIC IN AQUEOUS SAMPLES AND EXTRACTSBY ANODIC STRIPPING VOLTAMMETRY (ASV). 1996.[3] Casuse-Driovínto, T. Q.; Rizo, R.; Benavidez, A.; Brearley, A. J.; Cerrato, J. M.; Garzon, F. H.; Herrero, E.; Feliu, J. M. Increased Sensitivity and Selectivity for As(III) Detection at the Au(111) Surface: Single Crystals and Ultraflat Thin Films Comparison. The Journal of Physical Chemistry C 2022, 126 (48), 20343-20353. DOI: 10.1021/acs.jpcc.2c05541.

Differences in the Ti4+/Ti3+ Redox Reactions between Li4Ti5O12 and LiTi2(PO4)3 Observed By Soft X-Ray Spectroscopy

Clarification of the redox reaction in electrode materials for Li-ion batteries is essential to obtain strategies to improve the performances such as charge-discharge capacity, voltage and cyclability. We focus on the difference in voltage, i.e., redox potential between Li4Ti5O12 (LTO) and LiTi2(PO4)3 (LTP). Spinel-type LTO with a redox potential around 1.5 V vs Li/Li+ is one of the anode materials [1], while the main redox potential of LTP (NASICON-type structure) is around 2.4 V vs Li/Li+ [2]. Although the difference in redox potential is as large as ~0.9 V, it has been thought to be that Ti4+/Ti3+ redox couple is identical for both LTO and LTP. Here, we demonstrate the electronic-structure analysis of LTO and LTP by using soft X-ray absorption spectroscopy (XAS) and soft X-ray photoemission spectroscopy (XPS). Operando Ti L 2,3-edge XAS by use of an all-solid-state cell [3,4] successfully revealed reversible Ti4+/Ti3+ redox reactions by discharge/charge for both materials, but the XAS line shapes were different. By analyzing the spectra using multiplet calculation [5], differences in the crystal-field splitting for the TiO6 octahedron and O 2p -> Ti 3d charge-transfer (CT) effect were found. The different CT effect was also confirmed by Ti 2p-3d resonant XPS measurements for the initial-state LTO and LTP samples. Moreover, the difference in redox potential is mostly explained by the energy levels of the pre-edge structures in the O K-edge XAS calibrated with the O 1s XPS spectra. In the presentation, the understandings of the spectroscopic results will be discussed in detail.

Study of magnetic induction heating of Li0.25Zn0.3Co0.15Fe2.3O nanoparticles

Five different batches of Li0.25Zn0.3Co0.15Fe2.3O4 (LZC) nanoparticles were prepared by sol-gel method. Of these five batches, one has a very small mean size of ∼6.0 nm and the others have mean sizes of ∼11.9, 47.3, 114 and 139 nm. The phase formation of the nanoparticles is confirmed by analysing the X-ray diffraction (XRD) patterns using the Rietveld method. To ensure phase formation, further structural analyses, namely transmission electron microscopy, Raman spectroscopy and x-ray photoemission spectroscopy measurements are performed. Before analysing the magnetic properties of the prepared nanoparticles, Mössbauer spectra are recorded both at room temperature and at 77 K to determine the magnetic nature and hyperfine behaviour of the nanoparticles. The resence of magnetically blocked states is estimated by recording the dynamic hysteresis loops and then to gain insight into the magnetic properties of this particular Li-Zn-Co-ferrite stoichiometry, static M − H loops and field cooled and zero field cooled M-T curves are extracted using a vibrating sample magnetometer. Finally, the applicability of prepared nanoparticles as a heat mediator in magnetic induction heating is studied in an external field of 335 Oe intensity and 290 kHz frequency. The highest specific absorption rate (SAR) is found to be ∼212 W/gFerrite for 47.3 nm nanoparticles at a concentration of only 1 mg/mL.

Granular metals with SiN x dielectrics

Understanding and controlling nanoscale interface phenomena, such as band bending and secondary phase formation, is crucial for electronic device optimization. In granular metal (GM) studies, where metal nanoparticles are embedded in an insulating matrix, the importance of interface phenomena is frequently neglected. We demonstrate that GMs can serve as an exemplar system for evaluating the role of secondary phases at interfaces through a combination of x-ray photoemission spectroscopy (XPS) and electrical transport studies. We investigated SiN x as an alternative to more commonly used oxide-insulators, as SiN x -based GMs may enable high temperature applications when paired with refractory metals. Comparing Co-SiN x and Mo-SiN x GMs, we found that, in the tunneling-dominated insulating regime, Mo-SiN x had reduced metal-silicide formation and orders-of-magnitude lower conductivity. XPS measurements indicate that metal-silicide and metal-nitride formation are mitigatable concerns in Mo-SiN x . Given the metal-oxide formation seen in other GMs, SiN x is an appealing alternative for metals that readily oxidize. Furthermore, SiN x provides a path to metal-nitride nanostructures, potentially useful for various applications in plasmonics, optics, and sensing.

Effect of the growth orientation on the physical properties of Sr2CoNbO6 thin films

We study the effect of the growth orientation on the structural, electronic, and hence transport properties of Sr2CoNbO6 thin films grown on the orthorhombic NGO(100) and cubic MgO(100) substrates. The x-ray diffraction patterns show the growth of the thin film along the a axis resulting in the asymmetric (b≠c) in-plane compressive strain in the case of NGO(100), whereas along the c axis with tensile strain in the case of MgO(100) substrate. The temperature dependent resistivity measurements indicate the lower electronic conductivity for the film grown on the NGO(100) substrate, which is found to be correlated with the higher degree of the oxygen deficiencies and, hence, a larger concentration of the insulating Co2+ in this sample. Further, the x-ray photoemission spectroscopy measurements show that Sr and Nb are present in the 2+ and 4+ valence state, whereas Co exists in the 2+, 3+, and 4+ states, a fraction of which was found to vary with the growth orientation. Moreover, the analysis of leakage current using the sum exponent model indicates the presence of two different relaxation mechanisms in these samples.

La4Ga2S8O3: A Rare-Earth Gallium Oxysulfide with Disulfide Ions.

Band gap engineering using multiple anions is an established approach to novel photocatalysts that exhibit suitable band gap energies for water splitting and high photocorrosion resistance. However, few studies have been conducted on photocatalysts with polyanions, including polychalcogenide ions. Here, we present a new quaternary gallium oxysulfide with disulfide pairs (S2)2-, La4Ga2S8O3, grown out of a KI molten salt. Single-crystal X-ray diffraction analysis revealed that the oxysulfide crystallizes in the orthorhombic space group Pbcn with lattice constants of a = 18.3330(6) Å, b = 13.0590(5) Å, and c = 5.9022(3) Å. In the crystal structure, the GaS4-based zigzag chains and OLa4-based fluorite-like strips are independently arranged in two dimensions, which alternately stack via the disulfide pairs along the third direction. The oxysulfide is a direct-type semiconductor with a band gap of 2.45 eV. First-principles calculations combined with X-ray photoemission spectroscopy measurements show that S 3p states derived from the disulfide pairs dominate the valence band maximum and conduction band minimum, and these band-edge positions are suitable for the oxidation and reduction of water. Our comprehensive study based on the electronic structure suggests that the disulfide pairs make La4Ga2S8O3 a potential photocatalyst for water splitting under visible-light irradiation.

Effect of current density on the solid electrolyte interphase formation at the lithium∣Li6PS5Cl interface

Understanding the chemical composition and morphological evolution of the solid electrolyte interphase (SEI) formed at the interface between the lithium metal electrode and an inorganic solid-state electrolyte is crucial for developing reliable all-solid-state lithium batteries. To better understand the interaction between these cell components, we carry out X-ray photoemission spectroscopy (XPS) measurements during lithium plating on the surface of a Li6PS5Cl solid-state electrolyte pellet using an electron beam. The analyses of the XPS data highlight the role of Li plating current density on the evolution of a uniform and ionically conductive (i.e., Li3P-rich) SEI capable of decreasing the electrode∣solid electrolyte interfacial resistance. The XPS findings are validated via electrochemical impedance spectrsocopy measurements of all-solid-state lithium-based cells.

Interaction of Hydrogen with Cu-Modified Cerium Oxide Surfaces

We investigate the interaction between molecular hydrogen and ultrathin epitaxial CeO2 films modified with a 2% concentration of Cu atoms using X-ray photoemission spectroscopy (XPS) during thermal reduction cycles in H2. The XPS measurements are combined with density functional theory calculations to obtain further insight into the observed modifications of the film surface. Our results show that the presence of Cu atoms decreases the barrier for H2 dissociation in comparison to that on pure ceria surfaces, leading to the formation of surface OH groups after exposure to H2. Moreover, surface oxygen vacancies are generated already at mild temperatures (470 K), most likely via water formation and desorption. The presence of surface oxygen vacancies and hydroxyls contributes to the observed large increase in surface Ce3+ concentration with increasing reduction temperature. In spite of these atomic scale modifications, the surface morphology observed by scanning tunneling microscopy remains substantially unchanged on the length scale of tens of nm.

Bi0.5Pb0.5FeO3 with Unusual Pb Charge Disproportionation: Indication of a Systematic Charge Distribution Change in Bi0.5Pb0.5MO3 (M: 3d Transition Metal).

Bi0.5Pb0.5FeO3 with 1:1 mixture of Bi and Pb having charge degrees of freedom at the A-site of perovskite oxide ABO3 is obtained for the first time by high-pressure synthesis. Comprehensive synchrotron X-ray powder diffraction, optical second harmonic generation, Mössbauer spectroscopy, and hard X-ray photoemission spectroscopy measurements revealed that Bi0.5Pb0.5FeO3 is a canted antiferromagnetic insulator crystalizing in a nonpolar tetragonal I4/mcm structure with √2a × √2a × 2a unit cell and has unusually Pb charge disproportionated Bi3+0.5Pb2+0.25Pb4+0.25Fe3+O3 charge distribution. The valence of transition metal M in Bi0.5Pb0.5MO3 changes from 3.5+ to 3+ and finally to 2+ from Mn to Fe and to Ni, from left to right in the periodic table as the 3d-level becomes deeper. The valences of Bi and Pb increase to compensate for the decrease in the M's valence, and Pb changes from 6s2 (2+) to 6s0 (4+) before Bi changes.

The Damage Analysis for Irradiation Tolerant Spin-Driven Thermoelectric Device Based on Single-Crystalline Y₃Fe₅O₁₂/Pt Heterostructures

Spin-driven thermoelectric (STE) generation based on the combination of the spin Seebeck effect (SSE) and inverse spin Hall effect is an alternative to conventional semiconductor-based thermocouples as it is large scale, low cost, and environment-friendly. The STE device is thought to be radiation hard, making it attractive for space and nuclear technology applications. By using magnetometry, transmission electron microscopy, and the hard X-ray photoemission spectroscopy (HAXPES) measurements, we show that an STE device made of single-crystalline Y <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> Fe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">12</sub> (YIG)/Pt heterostructures has tolerance to irradiation of high-energy heavy ion beams. We used 200 MeV gold ion beams modeling cumulative damages due to fission products emitted from the surface of spent nuclear fuels. By varying the dose level, we confirmed that the thermoelectric and magnetic properties of the single-crystalline YIG/Pt STE device are finite at the ion-irradiation dose up to 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">12</sup> ions/cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> fluence. In addition, the HAXPES measurements were performed to understand the effects at the interface of YIG/Pt. The HAXPES data suggest that the chemical reaction regarding Fe and O that diminishes the SSE signals is promoted with the increase of the irradiation dose. The understandings of the damage analysis in YIG/Pt are beneficial for developing better STE devices applicable to harsh environmental usages.

Elucidating the Role of Antisolvents on the Surface Chemistry and Optoelectronic Properties of CsPbBrxI3-x Perovskite Nanocrystals.

Colloidal lead-halide perovskite nanocrystals (LHP NCs) have emerged over the past decade as leading candidates for efficient next-generation optoelectronic devices, but their properties and performance critically depend on how they are purified. While antisolvents are widely used for purification, a detailed understanding of how the polarity of the antisolvent influences the surface chemistry and composition of the NCs is missing in the field. Here, we fill this knowledge gap by studying the surface chemistry of purified CsPbBrxI3-x NCs as the model system, which in itself is considered a promising candidate for pure-red light-emitting diodes and top-cells for tandem photovoltaics. Interestingly, we find that as the polarity of the antisolvent increases (from methyl acetate to acetone to butanol), there is a blueshift in the photoluminescence (PL) peak of the NCs along with a decrease in PL quantum yield (PLQY). Through transmission electron microscopy and X-ray photoemission spectroscopy measurements, we find that these changes in PL properties arise from antisolvent-induced iodide removal, which leads to a change in halide composition and, thus, the bandgap. Using detailed nuclear magnetic resonance (NMR) and Fourier-transform infrared spectroscopy (FTIR) measurements along with density functional theory calculations, we propose that more polar antisolvents favor the detachment of the oleic acid and oleylamine ligands, which undergo amide condensation reactions, leading to the removal of iodide anions from the NC surface bound to these ligands. This work shows that careful selection of low-polarity antisolvents is a critical part of designing the synthesis of NCs to achieve high PLQYs with minimal defect-mediated phase segregation.