1. Introduction
Superconducting nanowires have attracted interest for several decades, both fundamental interest in superconductivity in reduced dimensions and for the development of applications. Applications in technological devices have grown out of these studies, with photon detectors, relevant to application in both astronomy [
1] and quantum technologies [
2], being probably the most significant application to date. Interest in a new range of devices in superconducting nanowires was sparked by the publication in 2006 of a proposal [
3] that superconducting nanowire devices could form a new class of component elements, based on a phenomenon termed coherent quantum phase-slip (CQPS). In such devices [
4], the superconducting nanowire operates as the charge–flux dual device to the Josephson junction, a device that itself led to the development of many technologically useful devices following its discovery in the 1960s. The charge–flux duality means that the roles of quantum conjugate variables charge (or charge number) and magnetic flux (or superconducting phase) are exchanged. (This also implies the exchange of other related quantities including current-voltage and inductance-capacitance.) Particular interest has been attracted by the prospect that the superconducting nanowires could form the basis of a quantum current standard, the charge–flux dual to the Josephson voltage standard. In such a device, the time-averaged transport current passing along a voltage-biased nanowire as it is irradiated with microwaves exhibits step-like structures as the voltage bias is varied, and these could be used to calibrate the current, potentially very precisely.
Quantum phase-slips may occur in superconducting nanowires with cross-sectional dimensions
, where
is the superconducting coherence length, the shortest characteristic length on which the properties of a superconductor can vary. A quantum phase-slip (QPS) process may actually be coherent or incoherent. Coherent quantum phase-slips involve coherent quantum tunnelling between states corresponding to different numbers of flux quanta on the two sides of the nanowire, such that the system may end up in superpositions of these states. This is the charge–flux dual of the Josephson junction, in which the behaviour results from coherent quantum tunnelling between states corresponding to different numbers of Cooper pairs on the two sides of a weak link. If, on the other hand, a QPS process is not sufficiently strong to lead to a final state that is a superposition of states corresponding to different numbers of flux quanta on the two sides of the nanowire, incoherent quantum phase-slips may still occur. These comprise individual 2
phase-slips occurring within the nanowire, with associated dissipation, which shows up as a measurable resistance for the nanowire. Each phase-slip event corresponds to the transfer of one quantum of magnetic flux from one side of the nanowire to the other. Incoherent QPS are conceptually related to (also incoherent) thermally activated phase-slips (TAPS) [
5], where incoherent QPS involves tunnelling through the energy barrier between the states and TAPS involves thermal activation over the energy barrier. However, it is coherent quantum phase-slips that are of use for charge–flux-dual applications.
The characteristic macroscopic manifestation of coherent QPS in the DC geometry is zero conductance below a critical voltage
. Although this has similarities to Coulomb blockade features in Josephson junctions and tunnel junctions [
6,
7], strong evidence that coherent quantum phase-slip effects are indeed to be found in suitably fabricated superconducting nanowires has been provided through several careful experiments [
8,
9,
10,
11,
12], including a recent report [
12] in which a gate tuned the interference between two CQPS elements in the expected way. A number of these convincing experiments were RF spectroscopy experiments [
8,
11,
12] and were carried out in a geometry that does not allow characterisation of the QPS nanowire by DC transport, the geometry relevant for the proposed quantum current standard. To date, there have been very few reports in DC transport of coherent QPS effects. The basic signature of CQPS in DC transport, a current blockade below a critical voltage, has been reported in a NbSi nanowire by Webster et al. [
9] with
μV. Hongisto et al. [
10] also reported
features in two NbSi nanowires, up to 480 μV, and furthermore showed evidence for quantum interference between two CQPS elements. Critical voltage features were also observed in [
13,
14].
In DC transport measurements on devices with related physics, measurements of the temperature dependence of resistance,
, have historically been very useful for their characterisation. Measurements of a residual resistance remaining in superconducting nanowires just below the superconducting transition temperature
in the 1970s revealed the presence of TAPS. In later studies of the superconductor–insulator transition in both thin films [
15,
16] and nanowires [
17,
18], measurements of samples’
enabled characterisation of the samples’ properties, showing a dependence of
on the disorder level, with
for
giving an indication of the proximity to the superconductor–insulator transition. Both early measurements on superconducting nanowires in a DC-transport configuration relating to observation of QPS, and many reports since, have likewise focussed on the
behaviour. Non-zero resistance persisting below
at temperatures lower than expected for TAPS has been observed by multiple groups, and this has frequently been interpreted as evidence for incoherent QPS. Although the underlying effect in incoherent QPS is quantum tunnelling, a temperature dependence nonetheless arises as a result of the temperature dependence of other physical properties of the system, particularly the superconducting coherence length
. Physical models of QPS, which have adjustable parameters, have been successfully fitted to such
data [
19]. Since there are other possible explanations of a persisting residual resistance below
, further tests, such as fitting to the current-voltage dependence
below
, are valuable. While in fact very few of the past reports have included such information on the
dependence, Altomare et al. [
20] and Makise et al. [
21] reported low-temperature
matching expectations for QPS behaviour, strengthening, for these measurements, if not more widely, the interpretation that the tail in the
arises from incoherent QPS.
The absence of further reports of the
feature that is characteristic of CQPS in DC
measurements, despite, anecdotally, experimental efforts by several research groups, hints at experimental challenges in realising all the requirements for CQPS in the technologically useful DC-transport geometry [
22]. QPS are expected in nanowires with cross-sectional dimensions
, and another key requirement is maximising the characteristic energy scale for quantum phase-slips,
. In a nanowire with cross-sectional dimensions
,
may be expressed [
23] as:
where
l is the length of the nanowire,
is the normal-state resistance of a coherence length of nanowire,
its sheet resistance,
the low-temperature normal-state resistance,
w the nanowire width,
kΩ the resistance quantum for Cooper pairs and
a and
b numerical constants of order unity.
should therefore be maximised in order to maximise
. Coherent QPS should only be expected in the limit
. The characteristic voltage scale for the critical voltage in a simple CQPS nanowire is
, and
is also the characteristic scale for the width of voltage steps at constant current in the proposed dual-Shapiro effect, which provides another motivation for maximising
.
Mooij et al. [
23] also showed that the environment a nanowire is embedded in affects whether or not quantum fluctuations in a CQPS nanowire lead to a blockade of current. Specifically, they argued that a current blockade occurs (i.e., CQPS drive the nanowire into an insulating state) for values of the ratio
greater than a critical value
, where
is the inductive energy associated with the series inductance
L in the circuit and
is the quantum of magnetic flux. A larger series inductance in the circuit therefore promotes the formation of a current blockade. Additionally, as for the Josephson voltage standard [
24], in order to obtain stable step features, for the charge–flux dual current standard, there are requirements on the parameters of the embedding circuit. This means that a series resistance of an appropriate value should be included in a CQPS-nanowire current-standard circuit [
22].
As shown by the form of Equation (
1), for
to be non-negligible, the superconducting material must have a large value of
. This requires a high low-temperature sheet-resistance
, implying a high kinetic inductance. Obtaining homogeneous materials satisfying this requirement is arguably more demanding than satisfying the requirement that the cross-sectional dimensions of the nanowire be of the order of
. To satisfy the requirement of large
, convenient materials systems to work with for CQPS applications are two-component superconductors, which exhibit a superconductor–insulator transition as the composition varies. Close to the superconductor–insulator transition, on the superconducting side of it, the material exhibits a high normal-state resistivity, as required for CQPS devices. The
of the nanowires must also be high enough that the device can be operated far below it, so as to minimise the existence of thermally excited quasiparticles, although in practice, to date, this condition has been less stringent than the requirement for coherent quantum phase-slips that
. In the Bardeen–Cooper–Schrieffer (BCS) theory of superconductivity, the coherence length scales inversely with
, so there is a trade-off between
and
; a system with workable values for both parameters must be chosen. Several candidate material systems have been used for superconducting nanowires, including InO
x, NbN, NbSi, MoGe and Ti [
8,
9,
10,
11,
12,
13,
14,
18,
21,
22,
25,
26,
27].
The detailed properties of materials at the nanoscale are often dependent on the means of fabrication, and so it is important that several means of generating nanowires are assessed. Experimental realisations of these superconducting nanowires have focussed either on the use of molecular templating techniques [
17,
18] or on the use of subtractive fabrication techniques [
19,
25]. In the latter, a thin film of the superconducting material is first deposited onto a substrate and then processed to remove material and leave a narrow nanowire. For fabricating nanowires with widths below 50 nm, lithography using an electron beam or a focussed ion beam is a natural choice for defining the nanowires. Deposition onto clean substrates followed by removal of unwanted superconducting-film material by etching is preferred to lift-off-based fabrication as it avoids both issues of film contamination by the resist during film deposition and the need to use a double-layer resist to avoid so-called ‘lily padding’ of the deposited film where metal deposited on sidewalls remains attached to the sides of the nanowire following lift-off.
As already indicated, the nanowires should be embedded in a high-impedance environment. This also isolates the nanowire from environmental influence. Thin-film inductors may be formed by wider lengths of the same superconducting material, which have substantial kinetic inductance in the superconducting state, but which are wide enough that their quantum phase-slip rate is negligible. If thin-film resistors are required, these may be formed by depositing an additional material to form part of the circuit [
28].
In practice, controlling the properties of the superconducting material close to the superconductor–insulator transition is far from trivial. The superconducting properties of a material are modified in very thin films and also in very narrow nanowires within such films. Inhomogeneities are present as a result of randomness in the film deposition process. Such inhomogeneities both may become accentuated during the etching process and also become more relevant to the electrical properties in a narrow nanowire as the width decreases towards the length scale of inhomogeneities in the film. Furthermore, close enough to the superconductor–insulator transition, an inhomogeneous electronic state of the film is expected on theoretical grounds [
29] to be induced even in a perfect material by very small variations due to offset charges in the substrate.
In this article, we report investigations carried out in niobium nitride. We have investigated the variation in the properties of the material as its dimensions are reduced down to nanowires. We assess three different fabrication technologies for creating narrow nanowires and demonstrate their use for generating nanowires with width dimensions below 20 nm. We report a range of superconducting and CQPS properties that we have observed in such nanowires, interpret the results, discuss their implications and outline challenges that will be relevant to others seeking to carry out similar studies.
3. Discussion
Table 1 collects relevant parameters for several nanowires we have fabricated. It may be observed that the different types of behaviour do not show a simple correlation with variations in any of the nominal physical dimensions of the material, and we have also found that this is a typical feature of the behaviour in other nanowires we have measured (data not shown here). Such differences are usually posited to be due to variations in the cross-section of the nanowire along its length, with the CQPS properties arising from just the smallest cross-section point of the nanowire, although this is difficult to be definitive about in the absence of control and/or characterisation at the atomic scale.
The observation of nanowire-to-nanowire variability of properties has apparent implications for technological applications. Sample-to-sample variability in properties has previously been observed in nanowire samples [
23,
32], and variations in properties have been explained systematically according to a relationship that is not trivially determined by a single variable such as
or
, but that depends on several variables. Within the analysis of Mooij et al. [
23], whether a nanowire displays superconducting or insulating behaviour is expected to depend on both
and the nanowire length
l, with a critical resistance in the case of no additional series inductance,
, where
and
a and
b are the numerical constants appearing in Equation (
1). In [
23], they take
to be 0.3. Taking the values used in [
23] for
b and
c along with
= 5 nm, for
l = 1 μm the relation gives
, with smaller
for longer nanowires. All our nanowires therefore should lie on the insulating side of this boundary, yet our nanowires do not show behaviour as insulating (i.e., as large
) as expected for their length on the basis of this calculation. Possible explanations for this include that the values used for
b and
c should be modified for our material system or that the length within our nanowires in which CQPS is occurring is much smaller than their physical length.
It is also possible that the relevant active cross-sectional dimensions of the nanowires are smaller than the measured physical dimensions. An interesting comparison for these samples is of the sample dimensions to the superconducting coherence length in NbN in the dirty limit, expected to be a few nanometres [
35]. We have observed behaviour characteristic of CQPS in samples that ostensibly have a width and a thickness of a factor up to ∼10-times greater than
. At first sight, this is rather surprising. It is not in fact a strict requirement that a nanowire have
in order for QPS to be observed. Rather, since the smallest volume in which superconductivity is required to fluctuate to enable a
slip in the phase difference between the two sides is
, the energy barrier for such a fluctuation, the superconducting condensation energy of this volume, is proportional to the volume fluctuating. Where either or both of the cross-sectional dimensions exceed
, this therefore leads to an additional factor
and/or
multiplying the numerical factor
b in Equation (
1), leading to an expected exponential suppression of
by factors
and
whenever either of these is greater than 1. Our nanowires are significantly wider and thicker than the coherence length, and yet we observe behaviour characteristic of CQPS. There are a number of possible explanations for this. It is conceivable, though seems unlikely, that the QPS energy scale for the material is extremely large, meaning that even when exponentially suppressed, it is still significant, and that nanowires with dimensions
would have such a large
that measurements would show zero conductance for any practical value of voltage bias. Another, perhaps more likely, possibility is that the relevant volume fluctuating is smaller than the value
determined from the measured physical dimensions
w and
d. The cross-sectional area of the nanowire carrying the supercurrent could be smaller than the physical dimensions as a result of a dead layer at the interface with the substrate and the external surfaces as a result of oxidation after deposition. It is also possible that inhomogeneities in the material could give a distribution of cross-sectional areas along the length of the nanowire. In that case, in view of the exponential dependence of the QPS energy on the cross-sectional area, the properties would be dominated by the region or regions of the nanowire with the smallest cross-sectional area [
36]. A distribution in cross-sectional areas could arise either as a result of variation in the physical dimensions along the length of the nanowire (see
Section 3.1) or as a result of more microscopic inhomogeneity such as is expected to be induced close to the superconductor–insulator transition [
29] and that might lead to a percolating pathway through the nanowire.
While the nanowire length has not been a major focus of this study, we are nonetheless able to make some inferences in relation to nanowire length. The nanowires investigated in this study were ∼1–10 μm long, similar to the lengths employed in [
9,
10], but longer than the nanowires employed in [
8,
11,
12], which were in the range of 30–750 nm. Two previous works have argued that collective excitations in longer nanowires might suppress CQPS effects [
37,
38]. The present observations of critical voltage features in long nanowires, along with the already-reported observations [
9,
10], provide basic empirical experimental evidence that CQPS effects are still relevant in long nanowires, although it remains an open question whether these long nanowires should actually rather be viewed as a series of shorter nanowires because of inhomogeneity, as discussed above.
Nanowire NbN80/1, in which the substantial critical voltage ≈5 mV has been observed, was one of only two nanowires reported here in which series inductance and resistance were included. Nanowire NbN81/2, deposited in the same experimental run and nominally having a very similar width, as well as also similarly incorporating series inductance and resistance, shows no feature at all. It appears likely that a composition closer to the superconductor–insulator transition, as indicated by the dependence, is a critical factor in determining the substantial for nanowire NbN80/1; the series inductance and resistance elements may also be important, but are clearly not sufficient. The different compositions in the two co-deposited samples may indicate that the thickness of nanowire NbN80/1 is smaller, as a result of thickness variations during deposition or more likely due to over-etching. It is clear that the observations of these two nanowires indicate variability in nanowire properties and highlight an outstanding challenge in reproducibly obtaining nanowires exhibiting strong QPS.
3.1. Fabrication Challenges
The different fabrication methods we have utilised have different characteristic features and different advantages and disadvantages. Using both EBL and Ne-FIB, we have obtained nanowires with widths nm. Nanowire widths of 15–20 nm are routine to generate using the EBL negative-resist process using hydrogen silsesquioxane (HSQ) as the resist. We have obtained nanowire widths of ≈20 nm via the cut-out technique, using polymethyl methacrylate (PMMA) as the resist. Ne-FIB is able to generate nanowires with widths below 25 nm, although fabrication becomes more challenging for the narrowest nanowires. Although the results we report showing a critical voltage feature have been measured in samples fabricated using the negative resist technique with HSQ, we believe that the ultimate widths obtainable by the other two techniques are small enough that they are also suitable for use for fabrication of nanowires for use as CQPS elements.
The processes determining the morphology and roughness of the nanowires are different for nanowires fabricated via EBL and via Ne-FIB. For EBL-fabricated (negative resist or positive-resist cut-out) nanowires, the sidewall morphology is affected by the sidewall of the resist mask. The edges of a resist mask with non-vertical sidewalls will be etched through prior to completion of etching, leading to transfer of the resist mask profile into the NbN nanowire. Where nonuniformities in thickness of the resist are present, these might also be transferred into the nanowire profile—an issue that is more relevant for PMMA resist as the polymer molecule sizes are ≈20 nm, with inhomogeneities in the resist at shorter length scales limiting the uniformity of the feature definition at those scales. The chemistry of the reactive ion etch process and the isotropic element of its chemical action also affect the morphology and roughness of the NbN material remaining after RIE. In particular, since different components of the nanowire, such as oxides, etch at different rates, the RIE processing will tend to accentuate inhomogeneities present in the deposited film as the nanowire is defined.
Etching by Ne-FIB, on the other hand, is directionally highly anisotropic, a feature that is beneficial for well-defined vertical sidewalls. Of course, this process is not, in practice, perfect. The ion beam has a Gaussian beam profile rather than being perfectly confined; however, the limiting factor for sidewall definition is actually scattering once the beam enters the material [
39], and this leads to damage to and/or milling of regions beyond the diameter of the incident beam. We take care during Ne-FIB processing to minimise the ion dose supplied to parts of the sample other than those we are milling, in order to minimise damage to other regions of the sample. Some initial imaging is required in order to locate the region to be milled. Our FIB instrument also has the ability to make use of helium ions, which, being lighter atoms, cause even less damage. We typically initially locate the region to be milled while imaging with helium, before switching to neon for the milling. In practice, obtaining very fine features relies on the drift due to charging and mechanical effects during the time required for milling being small compared to the resolution required. Sample drift due to charging may be minimised by prior wire-bonding of the sample bond pads to ground, and charging during imaging may be further reduced by the use of an electron flood gun, which allows neutralisation of charging of the substrate as a result of the ion-beam bombardment.
For samples fabricated using a negative-resist mask, with HSQ, several experimental challenges have informed the parameters we use. Firstly, the thickness of the HSQ layer should be chosen to satisfy two competing requirements. The HSQ layer is etched along with the NbN during the RIE stage, albeit at a slower rate, and therefore must be sufficiently thick to protect the NbN nanowire underneath it while the unwanted areas of NbN are removed. The maximum resist thickness is set by aspect-ratio considerations: an HSQ feature that, after EBL patterning, has a high aspect ratio, i.e., its thickness is much greater than its width, is mechanically unstable and may fall over during development or drying. The ideal thickness for the HSQ layer would be such that it is just removed at the end of the RIE stage.
Adhesion during patterning is an issue that we have tackled. While good adhesion of HSQ to the underlying NbN film for features with both in-plane dimensions
μm is found, in some samples the narrow nanowire sections of the HSQ resist-mask apparently can float off the NbN film during development. While even long nanowire sections of the resist-mask may sometimes land intact on the substrate following development [
34], this is an undesirable feature for a fabrication process, and we have addressed the problem by introducing “anchoring” when using long sections of NbN, whether nanowire or inductive line, that is, introducing periodic anchors into the inductive line which have both in-plane dimensions
μm. We have observed an issue of kinks developing in long nanowires (as seen to a small extent in
Figure 3a), a factor that favours the fabrication of sections of nanowire shorter than several μm in length. We expect that both the aspect-ratio and adhesion issues would also not be an issue in short-enough nanowires, since such structures are more mechanically stable against lateral forces applied to the top of the nanowire furthest from its ends.
3.2. IV Measurement Considerations
measurements should be made using careful filtering [
19]. In the comparisons we have made of the temperature variation of the resistance with and without the use of filters (not shown here), we have observed, when measuring without filtering, a resistive tail below
that resembles the resistive tails frequently observed in nanowires and successfully fitted to models of thermally activated or quantum phase-slips. However, when the measurement is repeated with proper filtering, no tail is observed. This implies that the observed resistive tail was an experimental artefact induced by noise being conducted down the measurement lines and shows the importance of careful filtering of experimental lines.
Another highly relevant issue in measurements of nanowires undergoing coherent quantum phase-slips is the presence of long time-constants before the steady state response is reached following a change in bias [
13]. As mentioned above, it is important to embed the nanowire in a high-impedance environment with
, and an effect associated with this is that the combination of this high impedance with the cable, filter and parasitic capacitances acts as a low-pass filter removing high-frequency noise from the measurement lines. However, a superconducting nanowire undergoing CQPS can behave as an impedance
, and the combination of this impedance and the resistance of series thin-film resistance with cable, filter and/or parasitic capacitances leads to
time constants for the capacitances to charge up to an equilibrium state, during which time a fraction of the current registered in the experimental current measurement is actually flowing into these capacitances rather than through the sample. The time constants can typically be 1–10 s, and in extreme cases above 100 s, in which case measurements become impractical. This should be a consideration in the design of filters and cabling for measurements on these nanowire systems; in particular, capacitances included in filters should not be made too high-value.
A further consideration in circuit design relates to mitigating self-heating in the devices. Since coupling between electron and phonon systems is weak at mK temperatures, such devices are prone to overheating when dissipation is present. In order to minimise such heating, thin-film resistors should be designed to have as large a volume as possible to achieve the required resistance value [
9], since maximising the volume maximises the interaction between the electron and phonon systems.