Pristine and intercalated transition metal dichalcogenide superconductors
Richard A. Klemm
备注：
9 pages, 16 figures, invited review article published in a special edition on Superconducting Materials in honor of the 95th birthday year of Ted Geballe, edited by M. B. Maple, J. Hirsch, and F. Marsiglio
Transition metal dichalcogenides (TMDs) are quasi-two-dimensional layered compounds exhibiting strongly competing charge-density wave (CDW) and superconducting (SC) order parameters (OPs). The weak van der Waals interlayer bonding between hexagonal layers of octahedral or trigonal prismatic TMD building blocks allows for many polytypes. The non-superconducting $1T$ polytypes can have one or more CDWs. The $2H$ polytypes have two or more Fermi surfaces and saddle bands, allowing for dual orderings, which can be coexisting CDW and SC orderings, two SC gaps as in MgB$_2$, or two CDW gaps. The CDW transitions $T_{\rm CDW}$s usually greatly exceed the low superconducting $T_{\rm c}$s, their orbital OPs are generally highly anisotropic and can even contain nodes, are remarkably similar to the the high-$T_{\rm c}$ cuprate pseudogaps, and the SC OPs can be greatly affected by their presence. In 2$H$-NbSe$_2$, the CDW renders its general $s$-wave SC OP orbital symmetry to be highly anisotropic and strongly reduces its Josephson coupling strength ($I_{\rm c}R_{\rm n}$) with Pb. Pressure and intercalation generally suppress the CDWs, enhancing $T_{\rm c}$. The misfit intercalation compound (LaSe)$_{1.14}$(NbSe$_2$) and many intercalated $2H$-TMDs, such as TaS$_2$(pyridine)$_{1/2}$, have completely incoherent $c$-axis transport, dimensional-crossover effects, and behave as stacks of intrinsic Josephson junctions. Except for the anomalously large violation of the Pauli limit of the upper critical field of (LaSe)$_{1.14}$(NbSe$_2$), these properties are very similar to those of the cuprate Bi$_2$Sr$_2$CaCu$_2$O$_{8+δ}$ and of the organic layered superconductor, $κ$-(ET)$_2$Cu[N(CN)$_2$]Br. Intercalates of TMDs with water and metallic ions are very similar to Na$_x$CoO$_2\cdot y$H$_2$O.
We report first principles calculations, within density functional theory, of copper intercalated titanium diselenides, CuxTiSe2, for values of x ranging from 0 to 0.11. The effect of intercalation on the energy bands and densities of states of the host material is studied in order to better understand the cause of the superconductivity that was recently observed in these structures. We find that charge transfer from the copper atoms to the metal dichalcogenide host layers causes a gradual reduction in the number of holes in the otherwise semi-metallic pristine TiSe2, thus suppressing the char…
We report on a modified chemical vapor transport (CVT) methodology for the growth of pure and intercalated Zr, Ti, and Hf dichalcogenide single crystals, e.g. ZrTe2, Gd0.05ZrTe2, HfTe2, and Cu0.05TiTe2. While the most common method for CVT growth is carried out in quartz tubes subjected to a temperature gradient between the charge and the growth location, the growth using this isothermal-CVT (ICVT) method takes place isothermally in sealed quartz tubes placed horizontally in box furnaces, using iodine (I2) as the transport agent. The structure and composition of crystals were determined by mea…
Intercalation and stacking order modulation are two active ways in manipulating the interlayer interaction of transition metal dichalcogenides (TMDCs), which lead to a variety of emergent phases and allow for engineering material properties. Herein, the growth of Pb intercalated TMDCs--Pb(Ta$_{1+x}$Se$_2$)$_2$, the first 124-phase, is reported. Pb(Ta$_{1+x}$Se$_2$)$_2$ exhibits a unique two-step first-order structural phase transition at around 230 K. The transitions are solely associated with the stacking degree of freedom, evolving from a high temperature phase with ABC stacking and symmetry…
The weak van der Waals interlayer interactions in the transition metal dichalcogenide (TMD) materials have created a rich platform to study their exotic electronic properties through chemical doping or physical gating techniques. We reported bulk superconductivity up to 7.6 K through careful manipulation of the charge carrier density and interlayer spacing d in the chemically intercalated two dimensional 1T-SnSe2 phase. We found, for the first time in the two dimensional SnSe2, that polar organic molecules cointercalated with the alkali metal Li into the basal layers, thus significantly enhanc…
Angle-resolved photoemission spectroscopy is used to study the band-structure of superconducting electrochemically intercalated Cu$_x$Bi$_2$Se$_3$. We find that in these samples the band-gap at the $Γ$ point is much larger than in pristine Bi$_2$Se$_3$. Comparison to the results of band-structure calculations indicates that the origin of this large gap is internal stress caused by disorder created by the Cu intercalation. We suggest that the internal pressure may be necessary for superconductivity in Cu$_x$Bi$_2$Se$_3$.
We theoretically investigate the possibility of achieving a superconducting state in transition-metal dichalcogenide bilayers through intercalation, a process previously and widely used to achieve metallization and superconducting states in novel superconductors. For the Ca-intercalated bilayers MoS$_2$ and WS$_2$, we find that the superconducting state is characterized by an electron-phonon coupling constant larger than $1.0$ and a superconducting critical temperature of $13.3$ and $9.3$ K, respectively. These results are superior to other predicted or experimentally observed two-dimensional …
In this letter, we report the discovery of superconductivity in Li3Ca2C6. Several graphite intercalation compounds (GICs) with electron donors, are well known as superconductors. It is probably not astonishing, since it is generally admitted that low dimensionality promotes high superconducting transition temperatures. Superconductivity is lacking in pristine graphite, but after charging the graphene planes by intercalation, its electronic properties change considerably and superconducting behaviour can appear. Li3Ca2C6 is a ternary GIC, for which the intercalated sheets are very thick and pol…
Superconductivity and charge density wave (CDW) appear in the phase diagram of a variety of materials including the high - $T$$_c$ cuprate family and many transition metal dichalcogenides (TMDs). Their interplay may give rise to exotic quantum phenomena. Here, we show that superconducting arrays can spontaneously form in TiSe$_2$ - a TMD with coexisting superconductivity and CDW - after lithium ion intercalation. We induce a superconducting dome in the phase diagram of Li$_x$TiSe$_2$ by using the ionic solid-state gating technique. Around optimal doping, we observe magnetoresistance oscillatio…
2H-NbSe2 is the prototype and most frequently studied of the well-known transition metal dichalcogenide (TMDC) superconductors. Widely acknowledged to be a conventional superconductor, its transition temperature to the superconducting state (Tc) is 7.3 K - a Tc that is substantially higher than those seen for the majority of TMDCs, where Tcs between 2 and 4 K are the norm. Here we report the intercalation of Cu into 2H-NbSe2 to make CuxNbSe2. As is typically found when chemically altering an optimal superconductor, Tc decreases with increasing x, but the way that Tc is suppressed in this case …
The iron chalcogenides FeSe and FeS are superconductors composed of two-dimensional sheets held together by van der Waals interactions, which makes them prime candidates for the intercalation of various guest species. We review the intercalation chemistry of FeSe and FeS superconductors and discuss their synthesis, structure, and physical properties. Before we review the latest work in this area, we provide a brief background on the intercalation chemistry of other inorganic materials that exhibit enhanced superconducting properties upon intercalation, which include the transition metal dichal…
We report a low-temperature scanning tunneling microscopy study of the charge density wave (CDW) order in 1$T$-TiSe$_2$ and Cu$_{0.08}$TiSe$_2$. In pristine 1$T$-TiSe$_2$ we observe a long-range coherent commensurate CDW (C-CDW) order. In contrast, Cu$_{0.08}$TiSe$_{2}$ displays an incommensurate CDW (I-CDW) phase with localized C-CDW domains separated by domain walls. Density of states measurements indicate that the domain walls host an extra population of fermions near the Fermi level which may play a role in the emergence of superconductivity in this system. Fourier transform scanning tunne…
The layered transition metal chalcogenides have been a fertile land in solid state physics for many decades. Various MX2-type transition metal dichalcogenides, such as WTe2, IrTe2, and MoS2, have triggered great attention recently, either for the discovery of novel phenomena or some extreme or exotic physical properties, or for their potential applications. PdTe2 is a superconductor in the class of transition metal dichalcogenides, and superconductivity is enhanced in its Cu-intercalated form, Cu0.05PdTe2. It is important to study the electronic structures of PdTe2 and its intercalated form in…
Spin-orbit coupling in transition metal dichalcogenides (TMDCs) causes spin-valley locking giving rise to unconventional optical, transport, and superconducting properties. In this paper, we propose exotic superconductivity in bilayer group-IV TMDCs by symmetry control. The sublattice-dependent hidden spin-orbit coupling arising from local inversion symmetry breaking in the crystal structure may stabilize the odd-parity superconductivity by purely $s$-wave local pairing interaction. The stability of the odd-parity superconducting state depends on the bilayer stacking. The 2H$_b$ stacking in Mo…
Transition metal dichalcogenides (TMDCs) usually exhibit layered polytypic structures due to the weak interlayer coupling. 2H-NbSe2 is one of the most widely studied in the pristine TMDC family due to its high superconducting transition temperature (Tc = 7.3K) and the occurrence of a charge-density wave (CDW) order below 33 K. The coexistence of CDW with superconductivity poses an intriguing open question about the relationship between Fermi surface nesting and Cooper pairing. Past studies of this issue have mostly been focused on doping 2H-NbSe2 by 3d transition metals without significantly c…
The charge, spin, and composition degrees of freedom in high-entropy alloy endow it with tunable valence and spin states, infinite combinations and excellent mechanical performance. Meanwhile, the stacking, interlayer, and angle degrees of freedom in van der Waals material bring it with exceptional features and technological applications. Integration of these two distinct material categories while keeping their merits would be tempting. Based on this heuristic thinking, we design and explore a new range of materials (i.e., dichalcogenides, halides and phosphorus trisulfides) with multiple meta…
Chiral superconductors, a unique class of unconventional superconductors in which the complex superconducting order parameter winds clockwise or counter-clockwise in the momentum space, represent a topologically non-trivial system with direct implications for topological quantum computing. Intrinsic chiral superconductors are extremely rare, with only a few arguable examples including heavy fermion metals (UTe$_2$, UPt$_3$) and perovskite superconductor Sr$_2$RuO$_4$. Chiral molecules with neither mirror nor inversion symmetry have been widely investigated, in which the spin degeneracy may be …
It is well established that the occurrence of superconductivity in iron pnictides is closely related to the tetragonal to orthorhombic structural and antiferromagnetic (AFM) phase transitions. It, however, has not been clear whether the same scenario is appropriate for iron chalcogenide counterparts due to the absence of parent compounds for the latter family of superconductors. Here, we report the synthesis and structure determination of two novel phases in ethylenediamine intercalated FeSe, one is tetragonal and the other orthorhombic in room temperature, which can be stabilized with neutral…
We report an optical study of transition metal dichalcogenide 2$H$-TaS$_2$ and Na intercalated superconductor Na$_x$TaS$_2$ over a broad frequency range at various temperatures. A clear gap feature was observed for 2$H$-TaS$_2$ when it undergoes a CDW transition. The existence of a Drude component in $σ$$_1$($ω$) below T$_{CDW}$ indicates that the Fermi surface of 2$H$-TaS$_2$ is only partially gapped in CDW state. The spectral evolution of two different Na$_x$TaS$_2$ crystals further confirms that the partial gap structure observed in 2$H$-TaS$_2$ has a CDW origin. The CDW mechanism for 2$H$-…
Superconductivity commonly appears under pressure in charge density wave (CDW)-bearing transition metal dichalcogenides (TMDs), but has emerged so far only via either intercalation with electron donors or electrostatic doping in CDW-free TMDs. Theoretical calculations have predicted that the latter should be metallized through bandgap closure under pressure, but superconductivity remained elusive in pristine 2H-MoS2 upon substantial compression, where a pressure of up to 60 GPa only evidenced the metallic state. Here we report the emergence of superconductivity in pristine 2H-MoS2 at 90 GPa. T…
We study the effects of an external magnetic field on thensuperconducting phase diagram of a quasi-two-dimensional system of Dirac electrons at an arbitrary temperature. At zero temperature, there is a quantum phase transition connecting a normal and a superconducting phase, occurring at a critical line that corresponds to a magnetic field dependent critical coupling parameter, which should be observed in planar materials containing Dirac electrons, such as $Cu_xTiSe_2$. Moreover, the superconducting gap is obtained as a function of temperature, magnetic field and coupling parameter ($λ_{\rm R…
Single crystals of pristine and 6% Pd-intercalated 2H-TaSe$_2$ have been studied by means of $^{77}$Se nuclear magnetic resonance (NMR). The temperature dependence of the $^{77}$Se spectrum, with an unexpected line narrowing upon Pd intercalation, unravels the presence of correlated local lattice distortions far above the transition temperature of the charge density wave (CDW) order, thereby supporting a strong-coupling CDW mechanism in 2H-TaSe$_2$. While, the Knight shift data suggest that the incommensurate CDW transition involves a partial Fermi surface gap opening. As for spin dynamics, th…
2H-NbSe2 is known to be an archetype layered transitional metal dichalcogenide superconductor with a superconducting transition temperature of 7.3 K.In this article, we investigate the influence of Sn intercalation on superconducting properties of 2H-NbSe2. Sn being nonmagnetic and having no outer shell d-electrons unlike transition metals, one naively would presume that its effect on superconducting properties will be very marginal. However, our magnetic and transport studies reveal a significant reduction of both superconducting transition temperature and upper critical field [Tc and BC2 (0)…
