skip to main content


This content will become publicly available on January 1, 2025

Title: Light-enhanced oxygen degradation of MAPbBr 3 single crystal

Organometal halide perovskites are promising materials for optoelectronic applications, whose commercial realization depends critically on their stability under multiple environmental factors.

 
more » « less
Award ID(s):
2050357
NSF-PAR ID:
10489282
Author(s) / Creator(s):
; ; ; ; ; ; ;
Publisher / Repository:
RSC
Date Published:
Journal Name:
Physical Chemistry Chemical Physics
ISSN:
1463-9076
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract One-dimensional c -axis-aligned BaZrO 3 (BZO) nanorods are regarded as strong one-dimensional artificial pinning centers (1D-APCs) in BZO-doped YaBa 2 Cu 3 O 7− x (BZO/YBCO) nanocomposite films. However, a microstructure analysis has revealed a defective, oxygen-deficient YBCO column around the BZO 1D-APCs due to the large lattice mismatch of ∼7.7% between the BZO (3a = 1.26 nm) and YBCO (c = 1.17 nm), which has been blamed for the reduced pinning efficiency of BZO 1D-APCs. Herein, we report a dynamic lattice enlargement approach on the tensile strained YBCO lattice during the BZO 1D-APCs growth to induce c -axis elongation of the YBCO lattice up to 1.26 nm near the BZO 1D-APC/YBCO interface via Ca/Cu substitution on single Cu-O planes of YBCO, which prevents the interfacial defect formation by reducing the BZO/YBCO lattice mismatch to ∼1.4%. Specifically, this is achieved by inserting thin Ca 0.3 Y 0.7 Ba 2 Cu 3 O 7− x (CaY-123) spacers as the Ca reservoir in 2–6 vol.% BZO/YBCO nanocomposite multilayer (ML) films. A defect-free, coherent BZO 1D-APC/YBCO interface is confirmed in transmission electron microscopy and elemental distribution analyses. Excitingly, up to five-fold enhancement of J c ( B ) at magnetic field B = 9.0 T// c -axis and 65 K–77 K was obtained in the ML samples as compared to their BZO/YBCO single-layer (SL) counterpart’s. This has led to a record high pinning force density F p together with significantly enhanced B max at which F p reaches its maximum value F p,max for BZO 1D-APCs at B // c -axis. At 65 K, the F p,max ∼158 GN m −3 and B max ∼ 8.0 T for the 6% BZO/YBCO ML samples represent a significant enhancement over F p,max ∼ 36.1 GN m −3 and B max ∼ 5.0 T for the 6% BZO/YBCO SL counterparts. This result not only illustrates the critical importance of a coherent BZO 1D-APC/YBCO interface in the pinning efficiency, but also provides a facile scheme to achieve such an interface to restore the pristine pinning efficiency of the BZO 1D-APCs. 
    more » « less
  2. Three new compounds in theAE‐Si‐P (AE= Sr, Eu, Ba) systems are reported. Sr2SiP4and Eu2SiP4, the first members of their respective ternary systems, are isostructural to previously reported Ba2SiP4and crystallize in the noncentrosymmetricI42d(no. 122) space group. Ba4Si3P8crystallizes in the new structure type, inP21/c(no. 14) space group,mP‐120 Pearson symbol, Wyckoff sequencee30. In the crystal structures of Sr2SiP4and Eu2SiP4all SiP4tetrahedral building blocks are connected via formation of P–P bonds forming a three‐dimensional framework. In the crystal structure of Ba4Si3P8, Si‐P tetrahedral chains formed by corner‐sharing, edge‐sharing, and P–P bonds are surrounded by Ba cations. This results in a quasi‐one‐dimensional structure. Electronic structure calculations and UV/Vis measurements suggest that theAE2SiP4(AE= Sr, Eu, Ba) are direct bandgap semiconductors with bandgaps of ca. 1.4 eV and have potential for thermoelectric applications.

     
    more » « less
  3. Abstract

    The new compounds Li2Mg2Si2S6and Li2Mg2Ge2S6have been prepared via traditional high‐temperature, solid‐state synthesis. The title compounds crystallize in the polar, noncentrosymmetric, trigonal space groupP31m(No. 157) and adopt a new structure type featuring staggered, ethane‐like (T2S6)6−units, where T=Si or Ge. These (T2S6)6−units are nestled within the holes of magnesium‐sulfide “layers” that are created through the edge‐sharing of MgS6octahedra. The holes found in the lithium‐sulfide “layers”, created by LiS6edge‐sharing octahedra, remain vacant, containing no (T2S6)6−anionic group. Through the face sharing of the respective MgS6and LiS6octahedra, the magnesium‐sulfide and lithium‐sulfide “layers” are stitched together resulting in an overall three‐dimensional structure. The optical bandgaps of Li2Mg2Si2S6and Li2Mg2Ge2S6are 3.24 and 3.18 eV, respectively, as estimated from optical diffuse reflectance UV‐Vis‐NIR spectroscopy. The compounds exhibit second harmonic generation responses of ∼0.24×KDP and ∼2.92×α‐quartz for Li2Mg2Si2S6and ∼0.17×KDP and ∼2.08×α‐quartz for Li2Mg2Ge2S6, using a Nd:YAG laser at 1.064 μm. Electronic structure calculations were performed using density functional theory and the linearized augmented plane‐wave approach within the WIEN2k software package. Examination of the electronic band structures shows that these compounds are indirect bandgap semiconductors.

     
    more » « less
  4. Abstract

    Raman scattering is a powerful probe oflocal structure (LS)of glasses. In Sodium Phosphate Glasses (SPGs), we show that bothLScomposed of Qnspecies andExtended Range Structures (ERS)composed of Long Chains (LCs), Large Rings (LRs), and Small Rings (SRs) can be decoded by Raman scattering. The trimodal distribution of P‐Oterminalstretch modes of Q2species and P‐Obridgingatx < 50% are manifestations of theseERS. These two pairs of triads of modes are uniquely identified with Q2units present in either LCs, or LRs, or SRs. The existence three phases of c‐NaPO3composed of 3‐membered rings, 6‐membered rings, and infinitely long chains has facilitated the identification. The Intermediate Phase (IP) in SPGs extends in the 37.5 < x < 46.0% range, the Stressed‐rigid Phase in the 46.0% < x < 50%, and the Flexible Phase in the 18% < x < 37.5% range of soda. We show the IP consists predominantly of LCs (82%), with a minority of LRs (15%) and SRs (3%). The LR‐ and SR‐fractions increase measurably in the non‐IP phases. The structural finding is in harmony with the high configurational entropy of the IP glasses that leads aging to be qualitatively suppressed.

     
    more » « less
  5. Abstract

    The Raman spectral behavior of N2, CO2, and CH4in ternary N2–CO2–CH4mixtures was studied from 22°C to 200°C and 10 to 500 bars. The peak position of N2in all mixtures is located at lower wavenumbers compared with pure N2at the same pressure (P)–temperature (T) (PT) conditions. The Fermi diad splitting in CO2is greater in the pure system than in the mixtures, and the Fermi diad splitting increases in the mixtures as CO2concentration increases at constantPandT. The peak position of CH4in the mixtures is shifted to higher wavenumbers compared with pure CH4at the samePTconditions. However, the relationship between peak position and CH4mole fraction is more complicated compared with the trends observed with N2and CO2. The relative order of the peak position isotherms of CH4and N2in the mixtures in pressure–peak position space mimics trends in the molar volume of the mixtures in pressure–molar volume space. Relationships between the direction of peak shift of individual components in the mixtures, the relative molar volumes of the mixtures, and the attraction and repulsion forces between molecules are developed. Additionally, the relationship between the peak position of N2in ternary N2–CO2–CH4mixtures with pressure is extended to other N2‐bearing systems to assess similarities in the Raman spectral behavior of N2in various systems.

     
    more » « less