Two-photon Photoemission Spectroscopy Research Articles

Endothermic Charge Separation Occurs Spontaneously in Non-Fullerene Acceptor/Polymer Bulk Heterojunction.

Organic photovoltaics (OPVs) based on non-fullerene acceptors (NFAs) have achieved a power conversion efficiency close to 20%. These NFA OPVs can generate free carriers efficiently despite a very small energy level offset at the donor/acceptor interface. Why these NFAs can enable efficient charge separation (CS) with low energy losses remains an open question. Here, the CS process in the PM6:Y6 bulk heterojunction is probed by time-resolved two-photon photoemission spectroscopy. It is found that the CS, the conversion from bound charge transfer (CT) excitons to free carriers, is an endothermic process with an enthalpy barrier of 0.15eV. The CS can occur spontaneously despite being an endothermic process, which implies that it is driven by entropy. It is further argued that the morphology of the PM6:Y6 film and the anisotropic electron delocalization restrict the electron and hole wavefunctions within the CT exciton such that they can primarily contact each other through point-like junctions. This configuration can maximize the entropic driving force.

Unraveling Electron Dynamics in p-type Indium Phosphide (100): A Time-Resolved Two-Photon Photoemission Study.

Renewable ("green") hydrogen production through direct photoelectrochemical (PEC) water splitting is a potential key contributor to the sustainable energy mix of the future. We investigate the potential of indium phosphide (InP) as a reference material among III-V semiconductors for PEC and photovoltaic (PV) applications. The p(2 × 2)/c(4 × 2)-reconstructed phosphorus-terminated p-doped InP(100) (P-rich p-InP) surface is the focus of our investigation. We employ time-resolved two-photon photoemission (tr-2PPE) spectroscopy to study electronic states near the band gap with an emphasis on normally unoccupied conduction band states that are inaccessible through conventional single-photon emission methods. The study shows the complexity of the p-InP electronic band structure and reveals the presence of at least nine distinct states between the valence band edge and vacuum energy, including a valence band state, a surface defect state pinning the Fermi level, six unoccupied surface resonances within the conduction band, as well as a cluster of states about 1.6 eV above the CBM, identified as a bulk-to-surface transition. Furthermore, we determined the decay constants of five of the conduction band states, enabling us to track electron relaxation through the bulk and surface conduction bands. This comprehensive understanding of the electron dynamics in p-InP(100) lays the foundation for further exploration and surface engineering to enhance the properties and applications of p-InP-based III-V-compounds for, e.g., efficient and cost-effective PEC hydrogen production and highly efficient PV cells.

Probing of Photocarrier Electrons and Excitons at an Organic Monolayer Film Studied by Two-Photon Photoemission Spectroscopy

Probing of Photocarrier Electrons and Excitons at an Organic Monolayer Film Studied by Two-Photon Photoemission Spectroscopy

Site-Selective Excitation of Ti3+ Ions in Rutile TiO2 via Anisotropic Intra-Atomic 3d → 3d Transition.

Site-selective excitation (SSE), which is usually realized by tuning the wavelength of absorbed light, is an ideal way to study bond-selective chemistry, analyze the crystal structure, investigate protein conformation, etc., eventually leading to active manipulation of desired processes. Herein, SSE has been explored in (110)-, (100)-, and (011)-faced rutile TiO2, a prototypical material in both surface science and photocatalysis fields. Using ultraviolet photoelectron spectroscopy and photon energy-, substrate orientation-, and laser polarization-dependent two-photon photoemission spectroscopy (2PPE), intra-atomic 3d → 3d transition from the split Ti3+ 3d orbitals, i.e., band gap states and excited states at ∼1.00 eV below and ∼2.40 eV above the Fermi level, respectively, has been proven for all of the samples, suggesting that it is a common property of this material. The distinct structure of rutile TiO2 results in the anisotropic 3d → 3d transitions with the transition dipole moment along the long axes ([110] and [11̅0]) of TiO6 blocking units. This anisotropy facilitates the selective excitation of Ti3+ ions in the two types of TiO6, which cannot be realized by conventional wavelength tuning, via polarization alignment of the excitation source. Discovery in this work builds the foundation for future investigation of site-selective photophysical and photochemical processes and eventually possible active manipulation in this material at the atomic level.

Localized surface plasmon resonances of size-selected large silver nanoclusters (n = 70-100) soft-landed on a C60 organic substrate.

Silver nanoclusters (Agn NCs) exhibit a remarkable optical property known as localized surface plasmon resonance (LSPR) in the visible to ultraviolet wavelengths. In this study, we address the size gap in LSPR responses between small NCs and nano-islands by synthesizing large Agn NCs with a countable number of atoms (n = 70-100) using a magnetron sputtering method, which were precisely size-selected and soft-landed onto substrates. The monodispersed Agn NCs were immobilized on a pre-decorated substrate with fullerene (C60) molecules, and their LSPR behaviors were characterized using two-photon photoemission (2PPE) spectroscopy. Due to the distinct polarization selectivity of incident light associated with LSPR, the intensity ratio between p- and s-polarized lights (Ip/Is) in 2PPE spectroscopy serves as a reliable indicator of LSPR and its structural correlations. From n = 70 to 100, the Ip/Is value gradually decreases as the cluster size increases. This decrease is attributed to the enhancement of s-polarized light (Is), indicating that large Agn NCs on a C60 substrate undergo a deformation from spherical to flattened geometries, particularly above approximately n = 55.

Determination of energetic positions of electronic states and the exciton dynamics in a π-expanded N-heterotriangulene derivative adsorbed on Au(111).

Bridged triarylamines, so-called N-heterotriangulenes (N-HTAs) are promising organic semiconductors for applications in optoelectronic devices. Thereby the electronic structure at organic/metal interfaces and within thin films as well as the electronically excited states dynamics after optical excitation is essential for the performance of organic-molecule-based devices. Here, we investigated the energy level alignment and the excited state dynamics of a N-HTA derivative adsorbed on Au(111) by means of energy- and time-resolved two-photon photoemission spectroscopy. We quantitatively determined the energetic positions of several occupied and unoccupied molecular (transport levels) and excitonic states (optical gap) in detail. A transport gap of 3.20 eV and an optical gap of 2.58 eV is determined, resulting in an exciton binding energy of 0.62 eV. With the first time-resolved investigation on a N-HTA compound we gained insights into the exciton dynamics and resolved processes on the femtosecond to picosecond timescale.

Ultrafast electron dynamics in a topological surface state observed in two-dimensional momentum space

We study ultrafast population dynamics in the topological surface state of Sb_2Te_3 in two-dimensional momentum space with time- and angle-resolved two-photon photoemission spectroscopy. Linearly polarized mid-infrared pump pulses are used to permit a direct optical excitation across the Dirac point. We show that this resonant excitation is strongly enhanced within the Dirac cone along three of the six {bar{Gamma }}–{bar{M}} directions and results in a macroscopic photocurrent when the plane of incidence is aligned along a {bar{Gamma }}–{bar{K}} direction. Our experimental approach makes it possible to disentangle the decay of transiently excited population and photocurent by elastic and inelastic electron scattering within the full Dirac cone in unprecedented detail. This is utilized to show that doping of Sb_2Te_3 by vanadium atoms strongly enhances inelastic electron scattering to lower energies, but only scarcely affects elastic scattering around the Dirac cone.

Two-Photon Photoemission Spectroscopy and Microscopy for Electronic and Plasmonic Characterizations of Molecularly Designed Organic Surfaces.

Functional surfaces decorated with organic molecules and/or nanoclusters (NCs) composed of several tens of atoms are promising for use in future photoelectronic substrates, whose functionalities are governed by molecular local electronic/plasmonic excitations at the interfaces. Here, we combine two-photon photoemission spectroscopy (2P-PES) and microscopy (2P-PEEM) to investigate the local excited-state dynamics at organic surfaces functionalized with NCs. The 2P-PES and 2P-PEEM for organic fullerene (C60) layers on graphite and Au substrates demonstrated photophysical characterization of electronic and plasmonic properties, including propagating surface plasmon polaritons (SPPs). The SPP propagation at the Au interface buried by overlayered C60 can be visualized by Agn NC deposition, which enhances plasmon-induced hot electrons, where the threshold number of Ag atoms (n ≥ 9) for the plasmonic response is revealed by the size dependence of 2P-PES for Agn NCs on C60 layers.

Ultrafast electron dynamics in Au/Fe/MgO(001) analyzed by Au- and Fe-selective pumping in time-resolved two-photon photoemission spectroscopy: Separation of excitations in adjacent metallic layers

The transport of optically excited, hot electrons in heterostructures is analyzed by femtosecond, time-resolved two-photon photoelectron emission spectroscopy (2PPE) for epitaxial Au/Fe/MgO(001). We compare the temporal evolution of the 2PPE intensity upon optically pumping Fe or Au, while the probing occurs on the Au surface. In the case of Fe-side pumping, assuming independent relaxation in the Fe and Au layers, we determine the hot electron relaxation times in these individual layers by an analysis of the Au layer thickness dependence of the observed, effective electron lifetimes in the heterostructure. We show in addition that such a systematic analysis fails for the case of Au-side pumping due to the spatially distributed optical excitation density, which varies with the Au layer thickness. This work extends a previous study [Beyazit et al., Phys. Rev. Lett. 125, 076803 (2020)] by new data leading to reduced error bars in the determined lifetimes and by a non-linear term in the Au-thickness dependent data analysis which contributes for similar Fe and Au film thicknesses.

Effect of PbPc on electron structure and carrier dynamics of black phosphorus

Using lead phthalocyanine (PbPc) as surface doping material on black phosphorous (BP) we observe enhanced photo-excited carriers in the PbPc/BP heterostructure. The interfacial energy level alignment is investigated with ultra violet photoemission spectroscopy (UPS) and x-ray photoemission spectroscopy (XPS). The heterojunction is type I with gap of BP nested in that of PbPc, facilitating confinement of electrons and holes in BP. Ultrafast time-resolved two-photon photoemission (TR-2PPE) spectroscopy is used to study the influence of PbPc on the photo excited unoccupied electronic states and the dynamics of the relaxation processes. Monolayer PbPc can greatly increase the pump excited hot electrons and the 2 photon emission of BP. The enhanced population in the intermediate states is attributed to the straddling of the band alignment which benefits the photo excited electrons in PbPc transferring to BP. Density functional theory calculations supported the interface dipole and charge redistribution. Our results provide a fundamental understanding of the excellent opto-electrical response of PbPc/BP interface of promising application in the high efficient photo detectors.

Unoccupied topological surface state in MnBi2Te4

The unoccupied part of the band structure in the magnetic topological insulator MnBi$_2$Te$_4$ is studied by first-principles calculations. We find a second, unoccupied topological surface state with similar electronic structure to the celebrated occupied topological surface state. This state is energetically located approximate $1.6$ eV above the occupied Dirac surface state around $\Gamma$ point, which permit it to be directly observed by the two-photon angle-resolved photoemission spectroscopy. We propose a unified effective model for the occupied and unoccupied surface states. Due to the direct optical coupling between these two surface states, we further propose two optical effects to detect the unoccupied surface state. One is the polar Kerr effect in odd layer from nonvanishing ac Hall conductance $\sigma_{xy}(\omega)$, and the other is higher-order terahertz-sideband generation in even layer, where the non-vanishining Berry curvature of the unoccupied surface state is directly observed from the giant Faraday rotation of optical emission.

Hybridization-Induced Image Potential States with Large Effective Mass in Lead Phthalocyanine Overlayers on Graphene

The structural and electronic properties of lead phthalocyanine (PbPc) adsorbed on graphene are studied theoretically using the van der Waals density functional method. It is revealed that an extended state analogous to an image potential state (IPS) emerges in a close-packed PbPc monolayer, hybridizing with the lowest IPS of graphene to form bonding and antibonding states at the PbPc–graphene interface. The impact of the PbPc adsorption manifests itself as increased effective masses of the hybrid IPSs as compared with those on pristine graphene. In particular, the bonding IPS exhibits a marked anisotropy in the effective mass, reflecting the uniaxially elongated unit cell adopted in the present calculations, whereas the antibonding one has an almost isotropic effective mass, which is comparable to experimental results obtained with two-photon photoemission spectroscopy of PbPc on highly oriented pyrolytic graphite and on single crystalline graphite. It is also shown that the increase in the effective masses is triggered by the hybridization with unoccupied molecular orbitals of PbPc that is localized at the Pb atom.

Impact of molecular distribution on unoccupied image potential states of PbPc/HOPG surfaces

Two-photon photoemission (2PPE) spectroscopy revealed modified image potential states (IPSs) of sub-monolayer lead phthalocyanine (PbPc) films on graphite (HOPG). Angle-resolved (AR) 2PPE for room temperature films showed unique energy/momentum maps in which the inside of the parabolic dispersion curve of IPS on HOPG area is filled up to a specific energy. For cooled films, AR maps showed two parabolic curves originating from IPSs on HOPG areas and PbPc islands. The changes are explained with simple models of electron scattering by molecular islands. IPS feature is an indicator of nano-scale superstructures, which are not easily assessed by other experiments.

TiO2 Polarons in the Time Domain: Implications for Photocatalysis.

Exploiting the availability of solar energy to produce valuable chemicals is imperative in our quest for a sustainable energy cycle. TiO2 has emerged as an efficient photocatalyst, and as such its photochemistry has been studied extensively. It is well-known that polaronic defect states impact the activity of this chemistry. As such, understanding the fundamental excitation mechanisms deserves the attention of the scientific community. However, isolating the contribution of polarons to these processes has required increasingly creative experimental techniques and expensive theory. In this Perspective, we discuss recent advances in this field, with a particular focus on two-photon photoemission spectroscopy (2PPE) and density functional theory (DFT), and discuss the implications for photocatalysis.

Combining two-photon photoemission and transient absorption spectroscopy to resolve hot carrier cooling in 2D perovskite single crystals: the effect of surface layer

We investigate HC cooling in two-dimensional perovskite single-crystals by applying two complementary ultrafast techniques and observe spatial sensitivity of cooling.

Competition between Coulomb and van der Waals Interactions in Xe-Cs^{+} Aggregates on Cu(111) Surfaces.

Microscopic insight into interactions is a key for understanding the properties of heterogenous interfaces. We analyze local attraction in noncovalently bonded Xe-Cs^{+} aggregates and monolayers on Cu(111) as well as repulsion upon electron transfer. Using two-photon photoemission spectroscopy, scanning tunneling microscopy, and coupled cluster calculations combined with an image-charge model, we explain the intricate impact Xe has on Cs^{+}/Cu(111). We find that attraction between Cs^{+} and Xe counterbalances the screened Coulomb repulsion between Cs^{+} ions on Cu(111). Furthermore, we observe that the Cs 6s electron is repelled from Cu(111) due to xenon's electron density. Together, this yields a dual, i.e., attractive or repulsive, response of Xe depending on the positive or negative charge of the respective counterparticle, which emphasizes the importance of the Coulomb interaction in these systems.

Ultrafast Ferroelectric Ordering on the Surface of a Topological Semimetal MoTe2.

Transient tuning of material properties by light usually requires intense laser fields in the nonlinear excitation regime. Here, we report ultrafast ferroelectric ordering on the surface of a paraelectric topological semimetal 1T'-MoTe2 in the linear excitation regime, with the order parameter directly proportional to the excitation intensity. The ferroelectric ordering, driven by a transient electric field created by electrons trapped ångstroms away from the surface in the image potential state (IPS), is evidenced in two-photon photoemission spectroscopy showing the energy relaxation rate proportional to IPS electron density, but with negligible change in the free-electron-like parallel dispersion. First-principles calculations reveal an improper ferroelectric ordering associated with an anharmonic interlayer shearing mode. Our findings demonstrate an ultrafast charge-based pathway for creating transient polarization orders.

Anisotropic d-d Transition in Rutile TiO2.

The band gap state of TiO2, which is dominated by Ti3+ 3d character, is of great relevance to light absorption, electron trapping, charge recombination, and conduction band structure. Despite the importance, the explanation of the excitation from this state is controversial. To this end, the electronic structures of TiO2(110) and TiO2(011)-(2 × 1) have been systematically measured with two-photon photoemission spectroscopy. The results reveal the anisotropic nature of the electronic structure in rutile TiO2 at seemingly equivalent directions of [110] and [11̅0], the long axes of the TiO6 blocking unit. Although the resonant energy of these two d-d transitions is identical, the energy levels are systematically shifted by 0.1 eV. We propose this anisotropy originates from the broken symmetry of the rutile TiO2 crystals caused by the surface. The proposed asymmetry-caused electronic structure anisotropy could be generalized to other similar materials and may affect associated catalytic properties. This work provides an important benchmark for related calculations.

Timescales of excited state relaxation in α−RuCl3 observed by time-resolved two-photon photoemission spectroscopy

The nonequilibrium properties of strongly correlated materials present a target in the search for new phases of matter. It is important to observe the types of excitations that exist in these materials and their associated relaxation dynamics. We have studied the photoexcitations in a spin-orbit assisted Mott insulator $\ensuremath{\alpha}\text{\ensuremath{-}}\mathrm{Ru}{\mathrm{Cl}}_{3}$ using time-resolved two-photon photoemission spectroscopy and transient reflection spectroscopy. We find that photoexcited carriers (doublons) in the upper Hubbard band rapidly relax to Mott-Hubbard excitons on a timescale of less than 200 fs. Subsequently, further relaxation of these lower-energy quasiparticles occurs with an energy-dependent time constant of that ranges from 370 to 600 fs due to exciton cooling. The population of Mott-Hubbard excitons persists for timescales up to several microseconds.

Polaron-Adsorbate Coupling at the TiO2(110)-Carboxylate Interface.

Understanding how adsorbates influence polaron behavior is of fundamental importance in describing the catalytic properties of TiO2. Carboxylic acids adsorb readily at TiO2 surfaces, yet their influence on polaronic states is unknown. Using UV photoemission spectroscopy (UPS), two-photon photoemission spectroscopy (2PPE), and density functional theory (DFT) we show that dissociative adsorption of formic and acetic acids has profound, yet different, effects on the surface density, crystal field, and photoexcitation of polarons in rutile TiO2(110). We also show that these variations are governed by the contrasting electrostatic properties of the acids, which impacts the extent of polaron–adsorbate coupling. The density of polarons in the surface region increases more in formate-terminated TiO2(110) relative to acetate. Consequently, increased coupling gives rise to new photoexcitation channels via states 3.83 eV above the Fermi level. The onset of this process is 3.45 eV, likely adding to the catalytic photoyield.