14 research outputs found
{\AA}ngstr\"om-resolved Interfacial Structure in Organic-Inorganic Junctions
Charge transport processes at interfaces which are governed by complex
interfacial electronic structure play a crucial role in catalytic reactions,
energy storage, photovoltaics, and many biological processes. Here, the first
soft X-ray second harmonic generation (SXR-SHG) interfacial spectrum of a
buried interface (boron/Parylene-N) is reported. SXR-SHG shows distinct
spectral features that are not observed in X-ray absorption spectra,
demonstrating its extraordinary interfacial sensitivity. Comparison to
electronic structure calculations indicates a boron-organic separation distance
of 1.9 {\AA}, wherein changes as small as 0.1 {\AA} result in easily detectable
SXR-SHG spectral shifts (ca. 100s of meV). As SXR-SHG is inherently ultrafast
and sensitive to individual atomic layers, it creates the possibility to study
a variety of interfacial processes, e.g. catalysis, with ultrafast time
resolution and bond specificity.Comment: 19 page
Polarization-Resolved Extreme-Ultraviolet Second-Harmonic Generation From Linbo3
Second harmonic generation (SHG) spectroscopy ubiquitously enables the investigation of surface chemistry, interfacial chemistry, as well as symmetry properties in solids. Polarization-resolved SHG spectroscopy in the visible to infrared regime is regularly used to investigate electronic and magnetic order through their angular anisotropies within the crystal structure. However, the increasing complexity of novel materials and emerging phenomena hampers the interpretation of experiments solely based on the investigation of hybridized valence states. Here, polarization-resolved SHG in the extreme ultraviolet (XUV-SHG) is demonstrated for the first time, enabling element-resolved angular anisotropy investigations. In noncentrosymmetric LiNbO3, elemental contributions by lithium and niobium are clearly distinguished by energy dependent XUV-SHG measurements. This element-resolved and symmetry-sensitive experiment suggests that the displacement of Li ions in LiNbO3, which is known to lead to ferroelectricity, is accompanied by distortions to the Nb ion environment that breaks the inversion symmetry of the NbO6 octahedron as well. Our simulations show that the measured second harmonic spectrum is consistent with Li ion displacements from the centrosymmetric position while the Nb─O bonds are elongated and contracted by displacements of the O atoms. In addition, the polarization-resolved measurement of XUV-SHG shows excellent agreement with numerical predictions based on dipole-induced SHG commonly used in the optical wavelengths. Our result constitutes the first verification of the dipole-based SHG model in the XUV regime. The findings of this work pave the way for future angle and time-resolved XUV-SHG studies with elemental specificity in condensed matter systems
Polarization-Resolved Extreme Ultraviolet Second Harmonic Generation from LiNbO
Second harmonic generation (SHG) spectroscopy ubiquitously enables the
investigation of surface chemistry, interfacial chemistry as well as symmetry
properties in solids. Polarization-resolved SHG spectroscopy in the visible to
infrared regime is regularly used to investigate electronic and magnetic orders
through their angular anisotropies within the crystal structure. However, the
increasing complexity of novel materials and emerging phenomena hamper the
interpretation of experiments solely based on the investigation of hybridized
valence states. Here, polarization-resolved SHG in the extreme ultraviolet
(XUV-SHG) is demonstrated for the first time, enabling element-resolved angular
anisotropy investigations. In non-centrosymmetric LiNbO, elemental
contributions by lithium and niobium are clearly distinguished by energy
dependent XUV-SHG measurements. This element-resolved and symmetry-sensitive
experiment suggests that the displacement of Li ions in LiNbO, which is
known to lead to ferroelectricity, is accompanied by distortions to the Nb ion
environment that breaks the inversion symmetry of the NbO octahedron as
well. Our simulations show that the measured second harmonic spectrum is
consistent with Li ion displacements from the centrosymmetric position by
0.5 Angstrom while the Nb-O bonds are elongated/contracted by
displacements of the O atoms by 0.1 Angstrom. In addition, the
polarization-resolved measurement of XUV-SHG shows excellent agreement with
numerical predictions based on dipole-induced SHG commonly used in the optical
wavelengths. This constitutes the first verification of the dipole-based SHG
model in the XUV regime. The findings of this work pave the way for future
angle and time-resolved XUV-SHG studies with elemental specificity in condensed
matter systems
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Supramolecular assembly of blue and green halide perovskites with near-unity photoluminescence
The metal-halide ionic octahedron is the optoelectronic unit for halide perovskites, and a crown ether-assisted supramolecular assembly approach can pack various ionic octahedra into tunable symmetries. In this work, we demonstrate near-unity photoluminescence quantum yield (PLQY) blue and green emission with the supramolecular assembly of hafnium (Hf) and zirconium (Zr) halide octahedral clusters. (18C6@K)2HfBr6 powders showed blue emission with a near-unity PLQY (96.2%), and green emission was also achieved with (18C6@K)2ZrCl4Br2 powders at a PLQY of 82.7%. These highly emissive powders feature facile low-temperature solution-based synthesis conditions and maintain high PLQY in solution-processable semiconductor inks under ambient conditions, and they were used in thin-film displays and emissive three-dimensional-printed architectures that exhibited high spatial resolution
Signatures of Multiband Effects in High-Harmonic Generation in Monolayer
High-harmonic generation (HHG) in solids has been touted as a way to probe
ultrafast dynamics and crystal symmetries in condensed matter systems. Here, we
investigate the polarization properties of high-order harmonics generated in
monolayer MoS, as a function of crystal orientation relative to the
mid-infrared laser field polarization. At several different laser wavelengths
we experimentally observe a prominent angular shift of the parallel-polarized
odd harmonics for energies above approximately 3.5 eV, and our calculations
indicate that this shift originates in subtle differences in the recombination
dipole strengths involving multiple conduction bands. This observation is
material specific and is in addition to the angular dependence imposed by the
dynamical symmetry properties of the crystal interacting with the laser field,
and may pave the way for probing the vectorial character of multi-band
recombination dipoles
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Polarization-Resolved Extreme Ultraviolet Second Harmonic Generation from LiNbO
Second harmonic generation (SHG) spectroscopy ubiquitously enables the
investigation of surface chemistry, interfacial chemistry as well as symmetry
properties in solids. Polarization-resolved SHG spectroscopy in the visible to
infrared regime is regularly used to investigate electronic and magnetic orders
through their angular anisotropies within the crystal structure. However, the
increasing complexity of novel materials and emerging phenomena hamper the
interpretation of experiments solely based on the investigation of hybridized
valence states. Here, polarization-resolved SHG in the extreme ultraviolet
(XUV-SHG) is demonstrated for the first time, enabling element-resolved angular
anisotropy investigations. In non-centrosymmetric LiNbO, elemental
contributions by lithium and niobium are clearly distinguished by energy
dependent XUV-SHG measurements. This element-resolved and symmetry-sensitive
experiment suggests that the displacement of Li ions in LiNbO, which is
known to lead to ferroelectricity, is accompanied by distortions to the Nb ion
environment that breaks the inversion symmetry of the NbO octahedron as
well. Our simulations show that the measured second harmonic spectrum is
consistent with Li ion displacements from the centrosymmetric position by
0.5 Angstrom while the Nb-O bonds are elongated/contracted by
displacements of the O atoms by 0.1 Angstrom. In addition, the
polarization-resolved measurement of XUV-SHG shows excellent agreement with
numerical predictions based on dipole-induced SHG commonly used in the optical
wavelengths. This constitutes the first verification of the dipole-based SHG
model in the XUV regime. The findings of this work pave the way for future
angle and time-resolved XUV-SHG studies with elemental specificity in condensed
matter systems
Extreme Ultraviolet Second Harmonic Generation Spectroscopy in a Polar Metal.
The coexistence of ferroelectricity and metallicity seems paradoxical, since the itinerant electrons in metals should screen the long-range dipole interactions necessary for dipole ordering. The recent discovery of the polar metal LiOsO3 was therefore surprising [as discussed earlier in Y. Shi et al., Nat. Mater. 2013, 12, 1024]. It is thought that the coordination preferences of the Li play a key role in stabilizing the LiOsO3 polar metal phase, but an investigation from the combined viewpoints of core-state specificity and symmetry has yet to be done. Here, we apply the novel technique of extreme ultraviolet second harmonic generation (XUV-SHG) and find a sensitivity to the broken inversion symmetry in the polar metal phase of LiOsO3 with an enhanced feature above the Li K-edge that reflects the degree of Li atom displacement as corroborated by density functional theory calculations. These results pave the way for time-resolved probing of symmetry-breaking structural phase transitions on femtosecond time scales with element specificity
Recommended from our members
Extreme Ultraviolet Second Harmonic Generation Spectroscopy in a Polar Metal.
The coexistence of ferroelectricity and metallicity seems paradoxical, since the itinerant electrons in metals should screen the long-range dipole interactions necessary for dipole ordering. The recent discovery of the polar metal LiOsO3 was therefore surprising [as discussed earlier in Y. Shi et al., Nat. Mater. 2013, 12, 1024]. It is thought that the coordination preferences of the Li play a key role in stabilizing the LiOsO3 polar metal phase, but an investigation from the combined viewpoints of core-state specificity and symmetry has yet to be done. Here, we apply the novel technique of extreme ultraviolet second harmonic generation (XUV-SHG) and find a sensitivity to the broken inversion symmetry in the polar metal phase of LiOsO3 with an enhanced feature above the Li K-edge that reflects the degree of Li atom displacement as corroborated by density functional theory calculations. These results pave the way for time-resolved probing of symmetry-breaking structural phase transitions on femtosecond time scales with element specificity
Recommended from our members
Ångström-resolved Interfacial Structure in Organic-Inorganic Junctions
Charge transport processes at interfaces which are governed by complex
interfacial electronic structure play a crucial role in catalytic reactions,
energy storage, photovoltaics, and many biological processes. Here, the first
soft X-ray second harmonic generation (SXR-SHG) interfacial spectrum of a
buried interface (boron/Parylene-N) is reported. SXR-SHG shows distinct
spectral features that are not observed in X-ray absorption spectra,
demonstrating its extraordinary interfacial sensitivity. Comparison to
electronic structure calculations indicates a boron-organic separation distance
of 1.9 {\AA}, wherein changes as small as 0.1 {\AA} result in easily detectable
SXR-SHG spectral shifts (ca. 100s of meV). As SXR-SHG is inherently ultrafast
and sensitive to individual atomic layers, it creates the possibility to study
a variety of interfacial processes, e.g. catalysis, with ultrafast time
resolution and bond specificity