A review of finite size effects in quasi-zero dimensional superconductors.

Quantum confinement and surface effects (SEs) dramatically modify most solid state phenomena as one approaches the nanometer scale, and superconductivity is no exception. Though we may expect significant modifications from bulk superconducting properties when the system dimensions become smaller than the characteristic length scales for bulk superconductors-such as the coherence length or the penetration depth-it is now established that there is a third length scale which ultimately determines the critical size at which Cooper pairing is destroyed. In quasi-zero-dimensional (0D) superconductors (e.g. nanocrystalline materials, isolated or embedded nanoparticles), one may define a critical particle diameter below which the mean energy level spacing arising from quantum confinement becomes equal to the bulk superconducting energy gap. The so-called Anderson criterion provides a remarkably accurate estimate of the limiting size for the destabilization of superconductivity in nanosystems. This review of size effects in quasi-0D superconductors is organized as follows. A general summary of size effects in nanostructured superconductors (section 1) is followed by a brief overview of their synthesis (section 2) and characterization using a variety of techniques (section 3). Section 4 reviews the size-evolution of important superconducting parameters-the transition temperature, critical fields and critical current-as the Anderson limit is approached from above. We then discuss the effect of thermodynamic fluctuations (section 5), which become significant in confined systems. Improvements in fabrication methods and the increasing feasibility of addressing individual nanoparticles using scanning probe techniques have lately opened up new directions in the study of nanoscale superconductivity. Section 6 reviews both experimental and theoretical aspects of the recently discovered phenomena of 'parity effect' and 'shell effect' that lead to a strong, non-monotonic size dependence of the superconducting energy gap and associated properties. Finally, we discuss in section 7 the properties of ordered heterostructures (bilayers and multilayers of alternating superconducting and normal phases) and disordered heterostructures (nanocomposites consisting of superconducting and normal phases), which are primarily controlled by the proximity effect.

Observation of shell effects in superconducting nanoparticles of Sn.

In a zero-dimensional superconductor, quantum size effects (QSE) not only set the limit to superconductivity, but are also at the heart of new phenomena such as shell effects, which have been predicted to result in large enhancements of the superconducting energy gap. Here, we experimentally demonstrate these QSE through measurements on single, isolated Pb and Sn nanoparticles. In both systems superconductivity is ultimately quenched at sizes governed by the dominance of the quantum fluctuations of the order parameter. However, before the destruction of superconductivity, in Sn nanoparticles we observe giant oscillations in the superconducting energy gap with particle size leading to enhancements as large as 60%. These oscillations are the first experimental proof of coherent shell effects in nanoscale superconductors. Contrarily, we observe no such oscillations in the gap for Pb nanoparticles, which is ascribed to the suppression of shell effects for shorter coherence lengths. Our study paves the way to exploit QSE in boosting superconductivity in low-dimensional systems.

Superfluid density from magnetic penetration depth measurements in Nb-Cu 3D nano-composite films.

Superconductivity in 3D Nb-Cu nanocomposite granular films have been studied with varying thickness for two different compositions, Nb rich with 88 at% of Nb and Cu rich with 46 at% of Nb. For both compositions, the superconducting transition temperature (Tc) decreases with decreasing film thickness. For any thickness, doubling the Cu content in the films decreases the Tc by about 2 K. To explore if phase fluctuations play any role in superconductivity in these 3D films, the superfluid stiffness (JS) of the films was measured using low frequency two-coil mutual inductance (M) technique. Interestingly, the measurement of M in magnetic fields showed two peaks in the imaginary component of M for both Nb rich and Cu rich films. The two peaks were associated with the pair-breaking effect of the magnetic field on the intra and inter-granular coupling in these films consisting of random network of superconductor (S) and normal metal (N) nano-particles. Furthermore, JS was seen to decrease with decreasing film thickness and increasing Cu content. However, for all films studied JS remained higher than the superconducting energy gap (∆) indicating that phase fluctuations do not play any role in superconductivity in the film thickness and composition range investigated. Our results indicate that an interplay of quantum size effects (QSE) and superconducting proximity effect (SPE) controls the Tc with composition in these 3D nano-composite films.

The influence of nanoscale phase separation and devitrification on the electrical transport properties of amorphous Cu-Nb alloy thin films.

The formation of amorphous phases in immiscible alloys with a large positive enthalpy of mixing is thermodynamically unfavorable. Co-sputter deposited Cu-Nb films exhibit a nanoscale phase separation into Cu-rich and Nb-rich amorphous regions. They show relatively high room temperature resistivity, a negative temperature coefficient of resistance (TCR), and an incomplete superconducting transition with onset at 3.7 K. Annealing the nanophase-separated amorphous films at 200 °C results in the nucleation of fcc Cu-rich nanocrystals within an Nb-rich amorphous matrix. This film exhibits multiple resistance steps, eventually showing a sharp drop with (T(C))(onset) = 3.7 K. Annealing at 350 °C leads to complete devitrification via the formation of large bcc Nb-rich grains encapsulating the existing fcc Cu nanocrystals. These films show low room temperature resistivity, positive TCR, and a sharp superconducting transition with onset at 5.2 K. The electrical transport and superconducting behavior appear to be consistent with a two-stage crystallization process.

Competing effects of surface phonon softening and quantum size effects on the superconducting properties of nanostructured Pb.

The superconducting transition temperature (T(C)) in nanostructured Pb decreases from 7.24 to 6.4 K as the particle size is reduced from 65 to 7 nm, below which superconductivity is lost rather abruptly. In contrast, there is a large enhancement in the upper critical field (H(C2)) in the same size regime. We explore the origin of the unusual robustness of T(C) over such a large particle size range in nanostructured Pb by measuring the temperature dependence of the superconducting energy gap in planar tunnel junctions of Al/Al(2)O(3)/nano-Pb. We show that below 22 nm, the electron-phonon coupling strength increases monotonically with decreasing particle size, and almost exactly compensates for the quantum size effect, which is expected to suppress T(C).

Point contact Andreev reflection studies of a non-centro symmetric superconductor Re6Zr.

Re6Zr, a non-centrosymmetric superconductor is an interesting system as recent experimental evidence suggests that the superconducting state breaks time reversal symmetry. This implies a mixing of spin singlet-triplet states leading to a complex order parameter in this system. Here, we report point contact Andreev Reflection (PCAR) measurements on a single crystal of Re6Zr (superconducting transition temperature (Tc) = 6.78 K). We observe multiple gap features in the PCAR spectra which depends on the type of tip and contact. Spectral features appear at voltages 1.0 ± 0.1 mV, 0.75 ± 0.05 mV and 0.45 ± 0.1 mV suggesting that there are at least more than one band contributing to superconductivity. However, strong surface inter-band scattering is possibly responsible for the uncertainty in observing them together distinctly in a single contact in the PCAR measurements. Interestingly, the bulk gap (Δ = 1.95kBTc = 1.1 meV) is occasionally observed in PCAR spectra, mostly with ferromagnetic tips. The gap features associated with the other two smaller gaps disappear at the bulk Tc. In addition, no anisotropy in the upper critical field was observed. Our results suggest an unconventional superconducting order in this compound: Multiband singlet states dominated by inter-band pairing which break the time reversal symmetry or singlet mixed with triplet states.

TADF and exciplex emission in a xanthone-carbazole derivative and tuning of its electroluminescence with applied voltage.

Materials showing white light emission have found applications in a variety of solid state devices especially in display technology. For white light emission, doping of red (R), green (G) and blue (B) emitters in a host matrix is commonly practised. However, finding RGB emitters of similar stability with homogenous doping is challenging. Furthermore, such devices suffer from color purity in the long run. Small organic light emitters, capable of colour tuning and having a broad emission spectrum are in high demand as they provide colour stability, reproducibility, a simple device geometry and high efficiency. Recently, it has been shown that the efficiency of OLEDs can be enhanced by employing thermally activated delayed fluorescence (TADF) materials. Here, we designed and synthesised a xanthone-carbazole based D-A-D material (Xan-Cbz) for TADF properties. Blue TADF emission, in neat thin films, at 470 nm was observed and further investigated by studying delayed fluorescence and lifetime measurements. In addition, a blend of Xan-Cbz with NPD shows exciplex emission at 525 nm in thin film. OLEDs based on Xan-Cbz were fabricated using several device configurations. OLEDs having the device configuration ITO/PEDOT:PSS/NPD/Xan-Cbz/Bphen/LiF-Al showed a luminance of 1.96 × 104 Cd m-2 (at a current density of 50 mA cm-2) and V ON at ∼6 V. Electroluminescence showed the features of both neat emission (470 nm) of Xan-Cbz and its exciplex (525 nm) with NPD. Further, colour tuning was observed as a function of applied voltage and the ratio of light intensity (I 525/I 470) of neat and exciplex emission was found to decrease with increasing voltage. Greenish-blue emission (CIE coordinates: 0.202, 0.382) from Xan-Cbz OLEDs was obtained. Xan-Cbz showed its neat emission (at 470 nm) in ITO/PEDOT:PSS/CBP/Xan-Cbz/Bphen/LiF-Al and pure exciplex emission (at 525 nm) in ITO/PEDOT:PSS/NPD:Xan-Cbz/Bphen/LiF-Al device configurations. Thus in this article we showed blue TADF emission, exciplex emission and voltage dependent color tuning in OLEDs based on a small organic emitter.

Sputter deposition of self-organized nanoclusters through porous anodic alumina templates.

Silver nanoparticles were sputter deposited through self organized hexagonally ordered porous anodic alumina templates that were fabricated using a two-step anodization process. The average pore diameter of the template was 90 nm and the interpore spacing was 120 nm. Atomic force microscope studies of the sputter-deposited silver nanoparticle array on a Si substrate indicate an approximate replication of the porous anodic alumina mask. The nature of the deposition depends strongly on the process parameters such as sputtering voltage, ambient pressure and substrate temperature. We report a detailed study of the sputtering conditions that lead to an optimal deposition through the template.

Critical analysis of soft point contact Andreev reflection spectra between superconducting films and pressed In.

We present a critical analysis of an alternative technique of point contact Andreev reflection (PCAR) spectroscopy used to extract energy resolved information of superconductors which is based on making 'soft-contacts' between superconductors and indium. This technique is not sensitive to mechanical vibrations and hence can be used in a cryogen free platform increasing its accessibility to users having no access to cryogenic liquids. Through our experiments on large number of superconducting films we show that the PCAR spectra below the T c of In show sub-harmonic gap structures consistent with the theory of multiple Andreev reflection (MAR) and a zero bias conductance (ZBC) anomaly associated with the Josephson supercurrent. Furthermore, we demonstrate that large contact resistance with low transparency ballistic contacts in the PCAR regime are required to obtain reliable spectroscopic data. One limitation of the technique arises for low contact resistance junctions where the superconducting proximity effect (SPE) reduces the value of the superconducting energy gap.

Mechanism of the size dependence of the superconducting transition of nanostructured Nb.

A direct measurement of the superconducting energy gap by point contact spectroscopy in nanostructured Nb films shows that the gap decreases with a reduction in the average particle size. The superconducting T(c), obtained from transport and magnetic measurements, also decreases with size and scales with the energy gap. The size dependence of the superconducting properties in this intermediate coupling type II superconductor is therefore governed by changes in the electronic density of states rather than by phonon softening. Consistent with the Anderson criterion, no T(c) was observed for sizes below 8 nm.