Single-layer FeSe Films Research Articles

Particle-hole mixed Bogoliubov quasiparticles and Cooper instability in single-unit-cell FeSe/SrTiO3 films

In conventional superconductors, Bogoliubov quasiparticles and Cooper instability provide a paradigm to describe the superconducting state and the superconducting transition, respectively. However, whether these concepts can be adapted to describe Fe-based superconductors requires rigorous examinations from experiments. Here, we report angle-resolved photoemission studies on single-layer FeSe films grown on SrTiO3 substrate. Due to the improved clarity, our results reveal both particle and hole branches of the energy band with clear quasiparticles. The dispersion and coherence factors are extracted, which unveil the particle-hole mixed Bogoliubov quasiparticles in the superconducting state of the FeSe/STO films. Effective pairing susceptibility is also deduced as a function of temperature, which indicates the persistence of Cooper instability in Fe-based superconductors.

Spectroscopic evidence of superconductivity pairing at 83\u2009K in single-layer FeSe/SrTiO3 films

Single-layer FeSe films grown on the SrTiO3 substrate (FeSe/STO) have attracted much attention because of their possible record-high superconducting critical temperature (Tc) and distinct electronic structures. However, it has been under debate on how high its Tc can really reach due to the inconsistency of the results from different measurements. Here we report spectroscopic evidence of superconductivity pairing at 83 K in single-layer FeSe/STO films. By preparing high-quality single-layer FeSe/STO films, we observe strong superconductivity-induced Bogoliubov back-bending bands that extend to rather high binding energy ~ 100 meV by high-resolution angle-resolved photoemission measurements. They provide a new definitive benchmark of superconductivity pairing that is directly observed up to 83 K. Moreover, we find that the pairing state can be further divided into two temperature regions. These results indicate that either Tc as high as 83 K is achievable, or there is a pseudogap formation from superconductivity fluctuation in single-layer FeSe/STO films.

Preformed Cooper Pairs in Layered FeSe-Based Superconductors.

Superconductivity arises from two distinct quantum phenomena: electron pairing and long-range phase coherence. In conventional superconductors, the two quantum phenomena generally take place simultaneously, while in the underdoped high- T_{c} cuprate superconductors, the electron pairing occurs at higher temperature than the long-range phase coherence. Recently, whether electron pairing is also prior to long-range phase coherence in single-layer FeSe film on SrTiO_{3} substrate is under debate. Here, by measuring Knight shift and nuclear spin-lattice relaxation rate, we unambiguously reveal a pseudogap behavior below T_{p}∼60 K in two kinds of layered FeSe-based superconductors with quasi2D nature. In the pseudogap regime, a weak diamagnetic signal and a remarkable Nernst effect are also observed, which indicates that the observed pseudogap behavior is related to superconducting fluctuations. These works confirm that strong phase fluctuation is an important character in the 2D iron-based superconductors as widely observed in high-T_{c} cuprate superconductors.

Atomically Thin Superconductors.

In recent years, atomically thin superconductors, including atomically thin elemental superconductors, single layer FeSe films, and few-layer cuprate superconductors, have been studied extensively. This hot research field is mainly driven by the discovery of significant superconductivity enhancement and high-temperature interface superconductivity in single-layer FeSe films epitaxially grown on SrTiO3 substrates in 2012. This study has attracted tremendous research interest and generated more studies focusing on further enhancing superconductivity and finding the origin of the superconductivity. A few years later, research on atomically thin superconductors has extended to cuprate superconductors, unveiling many intriguing properties that have neither been proposed or observed previously. These new discoveries challenge the current theory regarding the superconducting mechanism of unconventional superconductors and indicate new directions on how to achieve high-transition-temperature superconductors. Herein, this exciting recent progress is briefly discussed, with a focus on the recent progress in identifying new atomically thin superconductors.

Observation of Discrete Conventional Caroli-de Gennes-Matricon States in the Vortex Core of Single-Layer FeSe/SrTiO_{3}.

Using low-temperature scanning tunneling microscopy (STM), we studied the vortex states of single-layer FeSe film on a SrTiO_{3} (100) substrate, and the local behaviors of superconductivity at sample boundaries. We clearly observed multiple discrete Caroli-de Gennes-Matricon states in the vortex core, and quantitative analysis shows their energies well follow the formula: E=μΔ^{2}/E_{F}, where μ is a half integer (±1/2,±3/2,±5/2…) and Δ is the mean superconducting gap over the Fermi surface. Meanwhile, a fully gapped spectrum without states near zero bias is observed at the [110]_{Fe} oriented boundary of 1 and 2ML FeSe films, and atomic step edge of 1ML FeSe. Accompanied with theoretical calculations, our results indicate an s-wave pairing without sign change in the high-T_{C} FeSe/SrTiO_{3} superconductor.

Enhanced Superconducting State in FeSe/SrTiO_{3} by a Dynamic Interfacial Polaron Mechanism.

The observation of substantially enhanced superconductivity of single-layer FeSe films on SrTiO_{3} has stimulated intensive research interest. At present, conclusive experimental data on the corresponding electron-boson interaction is still missing. Here we use inelastic electron scattering spectroscopy and angle resolved photoemission spectroscopy to show that the electrons in these systems are dressed by the strongly polarized lattice distortions of the SrTiO_{3}, and the indispensable nonadiabatic nature of such a coupling leads to the formation of dynamic interfacial polarons. Furthermore, the collective motion of the polarons results in a polaronic plasmon mode, which is unambiguously correlated with the surface phonons of SrTiO_{3} in the presence of the FeSe films. A microscopic model is developed showing that the interfacial polaron-polaron interaction leads to the superconductivity enhancement.

Scanning tunneling microscopic observation of enhanced superconductivity in epitaxial Sn islands grown on SrTiO3 substrate

Recent experimental and theoretical studies of single-layer FeSe film grown on SrTiO3 have revealed interface enhanced superconductivity, which opens up a pathway to promote the superconducting transition temperature. Here, to investigate the role of SrTiO3 substrate in epitaxial superconducting film, we grew a conventional superconductor β-Sn (bulk Tc ∼ 3.72 K) onto SrTiO3 substrate by molecular beam epitaxy. By employing scanning tunneling microscope and spectroscopic measurements, an enhanced Tc of 8.2 K is found for epitaxial β-Sn islands, deduced by fitting the temperature dependence of the gap values using the BCS formula. The observed interfacial charge injection and enhanced electron–phonon coupling are responsible for this Tc enhancement. Moreover, the critical field of 8.3 T exhibits a tremendous increase due to the suppression of the vortex formation. Therefore, the coexistence of enhanced superconductivity and high critical field of Sn islands demonstrates a feasible and effective route to improve the superconductivity by growing the islands of conventional superconductors on perovskite-type titanium oxide substrates.

Identification of a large amount of excess Fe in superconducting single-layer FeSe/SrTiO3 films

The single-layer FeSe films grown on SrTiO3 (STO) substrates have attracted much attention because of its record high superconducting critical temperature (Tc). It is usually believed that the composition of the epitaxially grown single-layer FeSe/STO films is stoichiometric, i.e., the ratio of Fe and Se is 1:1. Here we report the identification of a large amount of excess Fe in the superconducting single-layer FeSe/STO films. By depositing Se onto the superconducting single-layer FeSe/STO films, we find by in situ scanning tunneling microscopy (STM) the formation of the second-layer FeSe islands on the top of the first layer during the annealing process at a surprisingly low temperature ($\sim$150{\deg}C) which is much lower than the usual growth temperature ($\sim$490{\deg}C). This observation is used to detect excess Fe and estimate its quantity in the single-layer FeSe/STO films. The amount of excess Fe detected is at least 20% that is surprisingly high for the superconducting single-layer FeSe/STO films. The discovery of such a large amount of excess Fe should be taken into account in understanding the high-Tc superconductivity and points to a likely route to further enhance Tc in the superconducting single-layer FeSe/STO films.

Magnetic fluctuations in single-layer FeSe

The electronic structure of single-layer FeSe films on SrTiO3 presents a quandary: experimentally there is no long-range magnetic order, but the observed bands are reasonably well described by density functional calculations assuming the checkerboard antiferromagnetic (CB-AFM) ordering despite this configuration not being the calculated ground state. Here we investigate the paramagnetic nature of this system via first-principles spin-spiral calculations. Fits of the spin-spiral dispersion to spin models place this S = 1 spin system in a region of parameter space where CB-AFM quantum fluctuations lead to a magnetically disordered paramagnetic state. Modeling the paramagnetic state as an incoherent superposition of spin-spiral states arising from thermal and/or quantum fluctuations, the resulting electronic bands around the Fermi level are found to closely resemble those of the ordered CB-AFM configuration, thus providing a consistent explanation of the angle-resolved photoemission observations. These results suggest that CB-AFM fluctuations play a more important role than previously thought.

Research progress on FeSe-based superconducting materials

FeSe-based superconductors, as an important part of the family of iron-based superconducting materials, have attracted intensive research interest in the field of condensed matter physics. The exploration and preparation of such superconducting materials is the basis for studying their physical properties. At present, the exploration of FeSe-based superconducting materials mainly focuses on intercalated materials and epitaxial single-layer FeSe films. Among them, the intercalated FeSe-based superconducting materials have unique properties and are numerous in variety. This paper introduces a series of FeSe-based high-temperature superconducting materials discovered in recent years, covering KxFe2Se2, AxNH3FeSe, LiOHFeSe and organic molecular intercalation FeSe, etc., their properties and impacts are also briefly described.

New Alkali-Metal- and 2-Phenethylamine-Intercalated Superconductors Ax(C8H11N)yFe1−zSe (A = Li, Na) with the Largest Interlayer Spacings and Tc ∼ 40 K

New FeSe-based intercalation superconductors, $A_x$(C$_8$H$_{11}$N)$_y$Fe$_{1-z}$Se ($A$ = Li, Na), with $T_\mathrm{c}$ = 39-44 K have been successfully synthesized via the intercalation of alkali metals and 2-phenethylamine into FeSe. The interlayer spacings, namely, the distances between neighboring Fe layers, $d$, of $A_x$(C$_8$H$_{11}$N)$_y$Fe$_{1-z}$Se ($A$ = Li, Na) are 19.04(6) and 18.0(1) {\AA}, respectively. These $d$ values are the largest among those of the FeSe-based intercalation compounds and are understood to be due to the intercalation of two molecules of 2-phenethylamine in series perpendicular to the FeSe layers. It appears that the relationship between $T_\mathrm{c}$ and $d$ in the FeSe-based intercalation superconductors is not domic but $T_\mathrm{c}$ is saturated at ~ 45 K, which is comparable to the $T_\mathrm{c}$ values of single-layer FeSe films, for $d$ $\geq$ 9 {\AA}.

Electronic structure and superconductivity of single-layer FeSe on Nb:SrTiO3/LaAlO3 with varied tensile strain

To understand the high temperature superconductivity at 65 K in single-layer FeSe films grown on Nb:SrTiO3 substrates, one crucial issue is to distinguish the effects of different interfacial interactions. In this paper, we decouple the effect of tensile strain with those of other interfacial interactions, and studying the corresponding electronic structure and superconducting gap behavior through in-situ angle resolved photoemission spectroscopy. By growing single-layer FeSe/Nb:SrTiO3/LaAlO3 heterostructures with varied thicknesses of Nb:SrTiO3 films, the tensile strain on FeSe is controlled from 0.6% to 3.7% while preserving other interfacial interactions as in single-layer FeSe grown on Nb:SrTiO3 substrate. The electronic correlation strength is weakened with reduced tensile strain. The superconducting transition temperature (Tc) is positively correlated with the tensile strain in single-layer FeSe/Nb:SrTiO3 when the film morphology is well ordered. Remarkably, the Tc remains 55 K in single-layer FeSe with negligible tensile strain. These results help to reveal the effect of tensile strain on the enhanced superconductivity in single-layer FeSe/Nb:SrTiO3.

Molecular beam epitaxy growth of multilayer FeSe thin film on SrTiO3 (001)

Single-layer FeSe film grown on SrTiO3(001) surface (STO surface) by molecular beam epitaxy has aroused a great research boom ever since the discovery of its huge superconductive energy gap which indicates a possible critical temperature (Tc) higher than the liquid nitrogen temperature. The interface enhanced superconductivity with a Tc above 100 K is revealed in an in situ electrical transport measurement by using a four-point probe installed in a scanning tunneling microscope (STM). Consequent research interest in multi-layer FeSe films grown on STO surface is also increasing. The quality of thick FeSe film, however, has not been well studied yet in previous studies, although it is related to the sample properties including superconductivity. Here, reflection high-energy electron diffraction (RHEED) is used to monitor the growths of multi-layer FeSe thin films on STO surface under different growth conditions. Combing the RHEED results with STM observations taken at various FeSe coverages, we find that the intensity evolution of the RHEED pattern in the early growth stage can be well explained by the step density model but not by the widely known facet model. The intensity evolution of the FeSe(02) diffraction streak exhibits a single-peak oscillation in the growing of the first layer of FeSe. As the oscillation does not depend on the grazing angle of the high-energy electron beam, the FeSe(02) diffraction streak is very suitable for calibrating the FeSe growth rate. In contrast, the intensity of the specular spot exhibits different evolution pattern when the grazing angle of electron beam is changed. It is found in STM observations that only at an appropriate substrate temperature and a growth rate can the high-quality multi-layer FeSe films be grown on STO substrates. If the growth temperature is too high, the FeSe molecules nucleate into islands so that FeSe films with various thickness values eventually come into being on the STO surface. If the growth temperature is too low, a different phase of FeSe film is formed. The optimal growth temperature is in a range from 400 ℃ to 430 ℃, within which a two-layer FeSe film grown at a low rate (0.15 layer/min) coveres the whole STO surface with a negligible number of small FeSe islands. In contrast, a larger growth rate is necessary for growing thicker FeSe film. This is because FeSe islands tend to come into form at steps when the growth rate is too low, which is more distinct in a thicker FeSe film. An STM image of 80-layer FeSe film grown under an optimal condition, i.e., the substrate temperature of 420 ℃ and the growth rate of 2.3 layer/min, shows that it is in a perfect layer-by-layer growth mode. These experimental results are useful for growing high-quality multi-layer FeSe films on STO substrates, which could be critical for studying their physical properties and relevant physical phenomena.

Plain s-wave superconductivity in single-layer FeSe on SrTiO3 probed by scanning tunnelling microscopy

Single-layer FeSe film on SrTiO3(001) was recently found to be the champion of interfacial superconducting systems, with a much enhanced superconductivity than the bulk iron-based superconductors. Its superconducting mechanism is of great interest. Although the film has a simple Fermi surface topology, its pairing symmetry is unsettled. Here by using low-temperature scanning tunneling microscopy (STM), we systematically investigated the superconductivity of single-layer FeSe/SrTiO3(001) films. We observed fully gapped tunneling spectrum and magnetic vortex lattice in the film. Quasi-particle interference (QPI) patterns reveal scatterings between and within the electron pockets, and put constraints on possible pairing symmetries. By introducing impurity atoms onto the sample, we show that the magnetic impurities (Cr, Mn) can locally suppress the superconductivity but the non-magnetic impurities (Zn, Ag and K) cannot. Our results indicate that single-layer FeSe/SrTiO3 has a plain s-wave paring symmetry whose order parameter has the same phase on all Fermi surface sections.

Development of micro-four-point probe in a scanning tunneling microscope for in situ electrical transport measurement.

Electrons at surface may behave differently from those in bulk of a material. Multi-functional tools are essential in comprehensive studies on a crystal surface. Here, we developed an in situ microscopic four-point probe (4PP) transport measurement system on the basis of a scanning tunneling microscope (STM). In particular, convenient replacement between STM tips and micro-4PPs enables systematic investigations of surface morphology, electronic structure, and electrical transport property of a same sample surface. Performances of the instrument are demonstrated with high-quality STM images, tunneling spectra, and low-noise electrical I-V characteristic curves of a single-layer FeSe film grown on a conductive SrTiO3 surface.

Electronic evidence of an insulator-superconductor crossover in single-layer FeSe/SrTiO3 films.

In high-temperature cuprate superconductors, it is now generally agreed that superconductivity is realized by doping an antiferromagnetic Mott (charge transfer) insulator. The doping-induced insulator-to-superconductor transition has been widely observed in cuprates, which provides important information for understanding the superconductivity mechanism. In the iron-based superconductors, however, the parent compound is mostly antiferromagnetic bad metal, raising a debate on whether an appropriate starting point should go with an itinerant picture or a localized picture. No evidence of doping-induced insulator-superconductor transition (or crossover) has been reported in the iron-based compounds so far. Here, we report an electronic evidence of an insulator-superconductor crossover observed in the single-layer FeSe film grown on a SrTiO3 substrate. By taking angle-resolved photoemission measurements on the electronic structure and energy gap, we have identified a clear evolution of an insulator to a superconductor with increasing carrier concentration. In particular, the insulator-superconductor crossover in FeSe/SrTiO3 film exhibits similar behaviors to that observed in the cuprate superconductors. Our results suggest that the observed insulator-superconductor crossover may be associated with the two-dimensionality that enhances electron localization or correlation. The reduced dimensionality and the interfacial effect provide a new pathway in searching for new phenomena and novel superconductors with a high transition temperature.

Superconductivity above 100 K in single-layer FeSe films on doped SrTiO3.

Recent experiments on FeSe films grown on SrTiO3 (STO) suggest that interface effects can be used as a means to reach superconducting critical temperatures (Tc) of up to 80 K (ref.). This is nearly ten times the Tc of bulk FeSe and higher than the record value of 56 K for known bulk Fe-based superconductors. Together with recent studies of superconductivity at oxide heterostructure interfaces, these results rekindle the long-standing idea that electron pairing at interfaces between two different materials can be tailored to achieve high-temperature superconductivity. Subsequent angle-resolved photoemission spectroscopy measurements of the FeSe/STO system revealed an electronic structure distinct from bulk FeSe (refs, ), with an energy gap vanishing at around 65 K. However, ex situ electrical transport measurements have so far detected zero resistance-the key experimental signature of superconductivity-only below 30 K. Here, we report the observation of superconductivity with Tc above 100 K in the FeSe/STO system by means of in situ four-point probe electrical transport measurements. This finding confirms FeSe/STO as an ideal material for studying high-Tc superconductivity.

Tuning the band structure and superconductivity in single-layer FeSe by interface engineering.

The interface between transition metal compounds provides a rich playground for emergent phenomena. Recently, significantly enhanced superconductivity has been reported for single-layer FeSe on Nb-doped SrTiO3 substrate. Yet it remains mysterious how the interface affects the superconductivity. Here we use in situ angle-resolved photoemission spectroscopy to investigate various FeSe-based heterostructures grown by molecular beam epitaxy, and uncover that electronic correlations and superconducting gap-closing temperature (Tg) are tuned by interfacial effects. Tg up to 75 K is observed in extremely tensile-strained single-layer FeSe on Nb-doped BaTiO3, which sets a record high pairing temperature for both Fe-based superconductor and monolayer-thick films, providing a promising prospect on realizing more cost-effective superconducting device. Moreover, our results exclude the direct correlation between superconductivity and tensile strain or the energy of an interfacial phonon mode, and highlight the critical and non-trivial role of FeSe/oxide interface on the high Tg, which provides new clues for understanding its origin.

Dichotomy of the electronic structure and superconductivity between single-layer and double-layer FeSe/SrTiO3 films.

The latest discovery of possible high-temperature superconductivity in the single-layer FeSe film grown on a SrTiO3 substrate has generated much attention. Initial work found that, while the single-layer FeSe/SrTiO3 film exhibits a clear signature of superconductivity, the double-layer film shows an insulating behaviour. Such a marked layer-dependent difference is surprising and the underlying origin remains unclear. Here we report a comparative angle-resolved photoemission study between the single-layer and double-layer FeSe/SrTiO3 films annealed in vacuum. We find that, different from the single-layer FeSe/SrTiO3 film, the double-layer FeSe/SrTiO3 film is hard to get doped and remains in the semiconducting/insulating state under an extensive annealing condition. Such a behaviour originates from the much reduced doping efficiency in the bottom FeSe layer of the double-layer FeSe/SrTiO3 film from the FeSe-SrTiO3 interface. These observations provide key insights in understanding the doping mechanism and the origin of superconductivity in the FeSe/SrTiO3 films.

Measurement of an Enhanced Superconducting Phase and a Pronounced Anisotropy of the Energy Gap of a Strained FeSe Single Layer inFeSe/Nb:SrTiO3/KTaO3Heterostructures Using Photoemission Spectroscopy

Single-layer FeSe films with an extremely expanded in-plane lattice constant of 3.99±0.02 Å are fabricated by epitaxially growing FeSe/Nb:SrTiO3/KTaO3 heterostructures and studied by insitu angle-resolved photoemission spectroscopy. Two elliptical electron pockets at the Brillouin zone corner are resolved with negligible hybridization between them, indicating that the symmetry of the low-energy electronic structure remains intact as a freestanding single-layer FeSe, although it is on a substrate. The superconducting gap closes at a record high temperature of 70K for the iron-based superconductors. Intriguingly, the superconducting gap distribution is anisotropic but nodeless around the electron pockets, with minima at the crossings of the two pockets. Our results place strong constraints on current theories.