Pressure Induced Enlargement and Ionic Current Rectification In

Pressure Induced Enlargement and Ionic Current Rectiﬁcation in Symmetric Nanopores

Sebastian J. Davis,1 Michal Macha,1 Andrey Chernev,1 David M. Huang,2 Aleksandra Radenovic,1, ∗ and Sanjin Marion1, ∗ 1Laboratory of Nanoscale Biology, Institute of Bioengineering, School of Engineering, EPFL, 1015 Lausanne, Switzerland 2Department of Chemistry, School of Physical Sciences, The University of Adelaide, Adelaide, Australia Nanopores in solid state membranes are a tool able to probe nanofluidic phenomena, or can act as a single molecular sensor. They also have diverse applications in filtration, desalination, or osmotic power generation. Many of these applications involve chemical, or hydrostatic pressure differences which act on both the supporting membrane, and the ion transport through the pore. By using pressure differences between the sides of the membrane, and an alternating current approach to probe ion transport, we investigate two distinct physical phenomena: the elastic deformation of the membrane through the measurement of strain at the nanopore, and the growth of ionic current rectification with pressure due to pore entrance effects.

I. INTRODUCTION translocations.24,25 No experiments have been performed so far with nanopores in elastic solid-state membranes, Nanopores are a single molecule tool with diverse ap- although such membranes are usually used in condi- plications in bio-sensing,1,2 osmotic power generation3 tions of osmotic or hydraulic pressure gradients which and water desalination.4 A nanoscale pore separates two could influence pore properties like ion selectivity and 3,4,26 reservoirs filled with electrolyte. Monitoring ion trans- water permeability. Theoretical work on sub-nm port through the pore yields information about a passing pores in 2D materials indicates the presence of strong 27–31 analyte such as DNA, or on non-linear phenomena such mechanosensitivity to lateral stresses. To realize as ionic current rectification (ICR)5 and other nanoflu- a truly mechanosensitive solid-state sensor, one which 32 idic effects.6–8 Solid state nanopores are readily made would mimic mechanosensitive biological channels, in silicon nitride suspended membranes since they are one needs to first understand the elastic behaviour of compatible with standard lithography techniques. Pores nanopores in solid state membranes. in these suspended membranes can be used as such, as This study aims to quantify the role of hydraulic pres- in this study, or can further support a membrane made sure in modulating ion transport in thin symmetrical of quasi-2D materials such as molybdenum disulphide, nanopores using a phase sensitive amplifier enhancing hexagonal boron nitride, or graphene in which a small the sensitivity. We decouple two independent physical pore can be further drilled.9 phenomena. First, that the pressure induced deforma- The combination of hydrostatic pressure gradients tion of the supporting membrane causes an enlargement with nanopores has so far been mostly used to study ana- in the nanopore size. This allows direct measurement of lyte translocations,10–13 the surface charge of the pore,14 the local membrane stress in a liquid environment as a or as a tool to control wetting.15. It has been shown that precursor for stressing 2D material nanopores and prob- 28 pressure can strongly influence the ion transport prop- ing mechanosensitivity. Secondly, we demonstrate that erties of a nanopore or nanochannel depending on the pressure induced-fluid flow produces ionic current rectifi- system’s resistance to hydraulic fluid flow, and modu- cation despite the lack of the usually required geometrical 5,7 late ion transport.16,17 On the other hand, ionic current asymmetry in the pore. This is opposite to the so far rectification,7 which is linked to ion selectivity, has been reported role of pressure in reducing ICR in asymmetrical 18,19 found to be reduced in conical pores under the influence nanopores . of pressure induced fluid flow.18,19 The application of pressure on thin supported mem- arXiv:2007.12083v1 [cond-mat.soft] 23 Jul 2020 branes is a well established technique for studying the II. PRESSURE APPLICATION elastic properties of thin films. Blistering of thin mem- EXPERIMENTAL SETUP branes such as silicon nitride,20 or blistering and de- 21–23 lamination of 2D materials has been extensively To study how hydrostatic pressure and potential dif- studied in dry conditions. Studies in liquid and with ferences influence the ion transport through a solid nanopores have so far been restricted to nanopores state nanopore we use a sealed, pressure-tight chamber drilled in elastomeric membranes for studying analyte (See Materials and Methods and figure 1a) as described previously.15 After a sample consisting of a membrane with an 80 nm diameter nanopore is mounted into the chamber, the system is wetted with a degassed 1 M KCL ∗ sanjin.marion@epfl.ch, aleksandra.radenovic@epfl.ch buffered solution under 7 bar compression pressure. Pres- 2 a) AgCl electrode b) 600 R = 1.5 MΩ R = 1.7 MΩ 400

200 0 -200 ~ Current [nA] -400

Lock-In A -600

-1 -0.5 0 0.5 1 Voltage [V] -P +P c) Degassed solution 1.000

0.998

(P=0) 0.996 AC

Si SiN 0.994 (P)/R

-P +P AC 0.992 R a = 12 µm a = 30 µm 0.990 -1 0 1 Pressure [bar]

FIG. 1: Application of pressure to solid state nanopores. a) Schematic in side view of the sealed pressure chamber channels and electrical measurement. Zoom below shows the chip area and the convention of pressure sign chosen for this study. b) DC IV curves for two representative samples having two different membrane sizes but similar pore sizes of d0 ≈ 80 nm. Lines are linear fits giving resistance values of 1.5 MΩ and 1.7 MΩ. c) Mean values of resistance RAC as a function of pressure normalized by the value of the resistance under no pressure RAC (P = 0). The curves represent the same samples as in panel (b) with two distinct square membrane sizes of side lengths a = 12 µm and 30 µm. Lines on the positive pressure side correspond to a fit to eq. 2 without residual stress giving a = 12.8 ± 1.0 µm, and a = 30.6 ± 6.2 µm respectively. The corresponding total deflection of the membrane at P = 1500 mbar is w0 = 3.2 ± 0.8 µm, and 2.7 ± 0.6 µm respectively. sure P is applied on the sample membrane using a mi- potential difference V , and a pressure difference P be- crofluidics pressure controller. We define positive pres- tween the two sides of the membrane is of the form sure as being applied from the front-side of the membrane I = G(V,P )V + HsP , where Hs is the streaming con- (flat side), and negative pressure is defined as being ap- ductance, and G(V,P ) the electrical conductance. Tak- plied from the back-side (etch-side) (as seen on figure ing into account that the non-linearity in conductance 1a). A potential difference V between the two sides of is almost negligible (figure 1b), we perform a Taylor ex- the membrane is applied and read with Ag/AgCl elec- pansion of the conductance G(V,P ) ≈ G1(P ) + G2(P )V , trodes. Measurements of current I versus applied po- with G1 and G2 corresponding to the linear and first 15 tential V are shown on figure 1b. Only samples showing nonlinear contribution. The conductance term G1 has stable conductance and current noise levels over the span contributions from the pore interior, and the access re- 2 −1 of the measurement were considered for further analysis gion resistance and obeys G1 = σ 4L/πd + 1/d , (See Supporting information Sec. S2). where d is the diameter of the nanopore, L the thick- The current response of the nanopore to an external ness of the membrane, and σ the bulk conductance of 3

33,34 2 the solution. One measure of the nonlinearity in ion d(P ) = d0 (1 + (P )) where (P ) = (1 − ν )σr(P )/E is 5,7 transport is the ionic current rectification (ICR) ratio the pressure dependent strain, σr is the radial stress in which we define as: the membrane, and d0 is the pore diameter under no applied stress. Thus by precisely measuring the change in |I(+V,P ) − I(V = 0,P )| r(V,P ) = the nanopore resistance, we obtain the value of the local |I(−V,P ) − I(V = 0,P )| strain/stress at the membrane. (1) G1(P ) + G2(P )|V | The elastic response of silicon nitride membranes is ≈ well studied20,23 which allows us to validate our model G1(P ) − G2(P )|V | of pore enlargement. The elastic response will depend to exclude any streaming contribution. on the applied pressure P as well as the geometric and In order to deconvolute the linear and nonlinear ion elastic parameters of the membrane: a the size of the transport contributions of the nanopore, and eliminate square membrane, L the thickness of the membrane, E any streaming current contribution, we perform all mea- the Young’s modulus, and ν the Poisson ratio. In ad- surements using a quasi-static AC measurement. All AC dition, even under no external pressure load, the mem- measurements are performed using a sinusoidal voltage at brane will have some degree of residual stress σ0 acting a frequency of f = 1 Hz, where the resistance matches the to either stretch or compress the membrane in the lat- DC measured value and no signal leakage through para- eral direction. In this regime, neglecting bending of the sitic chip capacitance is present.15 We use a phase sen- membrane, and assuming that the stress is constant all sitive amplifier, which can independently measure both over the membrane, the stress can be described by:20 G and G by averaging out any components of the mea- 1 2 EP 2a2 sured current which are not at the base measurement 3 2 σr − σ0σr − 2 2 = 0. (2) frequency f or one of its multiples. Thus the current 6L (1 − ν) measured with the AC voltage does not have the stream- By inserting the pressure dependent diameter d(P ) into ing contribution included, and we obtain the total cur- the conductivity of the nanopore G we are able to re- rent which has two independently measured components 1 2 produce the dependence of the strain at the pore at I1 = G1(P )VAC and I2 = G2(P )VAC, which are used to different pressures. Figure 2a shows a fit of the strain calculate the ICR ratio r defined in equation 1. We there- measured due to nanopore enlargement at different val- fore perform AC measurements, with high precision, to −1 ues of the pressure difference P and applied sinusoidal extract the linear pore resistance RAC = G1 , and the voltage amplitude. The elastic parameters are taken to ionic current rectification r at different pressures P (See be ν = 0.23, L = 20 nm, and E = 200 GPa, which is the Supporting information S2 for details). average Young modulus dependent on the specifics of the fabrication procedure.37 The positive pressure behaviour is fitted at a driving potential of 25 mV to a simplified III. STRAIN INDUCED PORE ENLARGEMENT σ0 = 0 case, while the negative pressure is fitted with the residual strain included in the fit. We find excel- When pressure is applied to one side of the suspended lent agreement with the model for low electrical driving silicon nitride membrane it blisters due to the result- potentials, and can also correctly obtain the membrane ing strain. Its deformation can be modelled as a thin sizes for different samples (figure 1c). sheet under large elastic deformations due to a uniform While the prediction of the membrane size shows that load in the direction perpendicular to the plane of the the simplified σ0 = 0 case is in good agreement with the 35 membrane. The system under study has a d0 = 80 nm behaviour it is not sufficient to completely explain the diameter pore in the center of the square membrane of asymmetry at low voltage in the negative pressure (as side length a = 10 − 30 µm. This hole can be treated seen in figure 2b). A fit assuming a constant σ0 in the as a small perturbation which will not significantly in- negative pressure direction gives values of up to 1 GPa, fluence the stress distribution in the membrane. As we much higher than usually reported values of below 500 38,39 measure the resistance of the pore RAC, and this resis- MPa for different growth conditions, and not sup- tance is related to its diameter d, any change of resistance ported by the low level of deformation of the membranes with pressure can be related with a modification of the we measured by atomic force microscopy (Supporting fig- pore diameter. The resistance decreases independently ure S4). In addition, residual stress of the membrane of the direction of applied pressure (figure 1c), and does would affect both the positive and negative pressure be- not depend on the nanopore surface charge (Support- haviour and as such does not explain the observed asym- ing figure S6). The measured change of pore resistance metry with pressure. We propose that the cause of this RAC with pressure is attributed to the local strain at the effect is due to the back side etched cavity present on the nanopore due to stress in the membrane. As the stress is chips (figure 2a). Application of pressure to the back- radially symmetric at the center of the membrane, and side of the chip induces forces on the etched silicon walls the elastic model for the membrane involves only linear inside the cavity which tends to stretch the suspended elastic deformations in the plane of the membrane, the membrane and modify the residual strain. Assuming a change in size of the nanopore is trivially shown36 to be pressure dependent residual stress for the negative side 4 a) b) 25 mV 1.025 400 mV 800 mV 1.020

1.015 1 + ε 1.010

1.000 -1.5 -1.0 -0.5 0 0.5 1.0 1.5 Pressure [bar] c) x103

-2

α -4 -6 0 0.1 0.2 0.3 2 2 (VAC) [V ] FIG. 2: Elastic response of membranes under pressure: strain induced enlargement. a) Schematic of the chip and membrane with nanopore. The initial configuration under zero applied pressure is shown as well as two schematics showing the deformation of the membrane under both positive, and negative pressure. This deformation due to strain enlarges the pore, d(−P ) and d(+P ). The negative pressure is also shown to act on the etched walls of the back-side of the chip which is responsible for the asymmetry in pressure response. b) Normalised strain value as a function of pressure for the same membrane at a low bias voltage of VAC = 25 mV (blue squares), and two larger bias voltages of VAC = 400 mV (green triangles), and V0 = 800 mV (red circles). All AC voltages are given in root mean square values of the amplitude. Dashed black lines correspond to the fit of the stress to Eq. (2). For positive pressures the fit is done with σ0 = 0 fixed, and for the negative side with the full stress eq. (2). c) Voltage dependence of the residual stress factor α with the dashed line corresponding to a quadratic fit to applied voltage VAC. Error bars represent the standard deviation as obtained from the fit.

of the form σ0 = αP we find a value of α ≈ −6000 at eral percent of strain due to electrostriction. This stress the lowest applied sinusoidal potential for negative pres- counterbalances the pressure induced residual stress dis- sures (figure 2c). This value can be rationalised from cussed above returning a symmetric pressure profile at geometrical considerations. The applied pressure will in- high voltage. At large voltages the measured data devi- ◦ duce a force Fin ∝ LSiP sin(54, 74 ), where LSi = 380 ates from the model and we assume that the stresses in µm is the thickness of the silicon substrate, with the an- these cases are no longer within the range of validity of gle 54, 74◦ defined by crystallographic planes. This esti- eq. 2. mate gives a comparable induced residual stress factor of ◦ α ≈ LSi sin(54 )/L ≈ −10000 while neglecting any fine effects dependent on the manufacturing process. IV. PRESSURE INDUCED IONIC CURRENT Although including a pressure dependent residual RECTIFICATION stress on the negative pressure side explains most of the measured behaviour, figure 2c shows that the induced After studying pore enlargement under pressure, we residual stress factor α depends quadratically on the investigate how pressure modifies the nonlinear conduc- applied voltage. We propose that this effect is due to tivity of the nanopore quantified by ICR. Figure 3 shows electrostriction of the underlying chip material which is how the ICR ratio increases with applied pressure up to known to occur for all dielectrics at high electric field re- a maximum value at P ≈ 500 mbar, and then starts to gardless of crystal symmetry.40,41 Considering the thick- reduce with a higher pressure magnitude. The decrease ness of the materials in question, the electric field at 800 in ICR with an increase in pressure is well known,18,19,42 mV RMS is on the order of 2 kV/m over the silicon sub- but to our knowledge an increase in ICR with pressure strate and on the order of 40 MV/m over the 20 nm has not yet been reported. The magnitude of ICR is thick silicon nitride membrane, sufficient to produce sev- known to be strongly dependent on the surface charge,5,7 5 a) b)

1.004 1.008

pH = 8 V = 0.1 V pH = 3 V = 0.2 V pH = 12

V = 0.4 V r(P)

r(P) 1.002 1.004

1.000 1.000 -1 0 1 -1 0 1 c) Pressure [bar] d) Pressure [bar] 1.020 ∑ = -5 mC/m2 0.00 ∑ = -50 mC/m2 P = 0.5 bar ∑ = -100 mC/m2 P = 2 bar P = 0 bar 1.015 -0.01 1.010 P r(P) z = 0 1.005 -0.02

1.000 - Du(-z;P,-V) Du(z;P,V) 0 0.5 1 1.5 2 5 10 Pressure [bar] z [nm]

FIG. 3: Pressure-induced rectification in symmetric solid state nanopores. a) Rectification r as a function of pressure P for different driving voltages VAC. The magnitude of the pressure dependent effect is seen to be approximately linear in voltage. Rectification values are corrected by pressure sweeping for baseline drift and offsets as described in the Materials and Methods. b) Measured rectification for three different pH values, corresponding to different surface charge densities. Corresponding streaming current measurements are provided on Supporting figure S5. c) Rectification extracted from a COMSOL model of a solid state nanopore under pressure. The model shows only positive pressure as it is symmetric by design. Surface charges of −5 mC/m2, −50 mC/m2, and −100 mC/m2 are chosen to simulate the pH 3, 8, and 12 case respectively. d) Spatial asymmetry in the Dukhin number for positive and negative bias Du(z; P,V )−Du(−z; P, −V ) along the pore axis. Three representative pressures are shown, corresponding to P = 0, approximate maximum in ICR at P = 0.5 bar, and in the region of ICR reduction with pressure at P = 2 bar. Inset shows the radially symmetric FEM simulation geometry, pressure direction, and z axis. so we change its value by varying the pH of the solu- (FEM) modelling in COMSOL multiphysics. Coupled tion. The point of zero charge for silicon nitride mem- Poisson-Nernst-Planck-Stokes equations are solved with branes is known to be ≈ pH 4.14 Figure 3b shows how a different static pressures between the two electrolyte pH larger than 8 increases the ICR magnitude due to a reservoirs while varying the surface charge Σ, DC voltage slight increase in surface charge while not changing the bias, and pressure (See Supporting information Sec. S5). pressure dependence. Conversely going near the point Considering the complete decoupling of the strain effect of zero charge at pH 3 completely removes any pressure no change in shape of the pore due to the elastic defor- dependence of ICR. Here the magnitude of ICR is small mations is considered. Figure 3c shows the FEM values as we use a high salt concentration (1 M KCl), but is of rectification computed based on eq. 1 as a function of expected to grow at lower concentrations due to a larger pressure for three surface charge values chosen to simu- contribution from the surface double layer.43 late the effect of experimental pH changes. Only positive pressure gradients are shown since the measurement is by To explain the origin of the pressure induced ionic definition symmetric in pressure. The FEM model com- current rectification, we perform finite element method 6 pletely captures the behaviour seen in the experimental V. CONCLUSIONS data on figure 3b, with an increase in r at low pressures before a turnover and decrease at higher pressures. The By coupling a nanopore inside a thin elastic supported measured decrease in magnitude of the effect as the sur- silicon nitride membrane immersed in liquid, we demon- face charge is reduced is also captured. strated how one can use AC measurements of ion transport coupled with hydrostatic pressure to precisely measure two separate physical phenomena. By monitoring the size of a nanopore while the membrane is undergoing The rectification behaviour can be rationalised in pressure induced blistering, we demonstrate that one can terms of perturbations to the ion distributions in and precisely measure local strain in the membrane. As these around the nanopore caused by pressure-induced advec- membranes are typically used as a support for 2D mate- tion. ICR in a nanapore has been shown previously to be rial nanopore measurements, this can be the first step in controlled by the spatial variation in the axial direction z measuring mechanosensitivity in 2D materials27–31 as it of the local Dukhin number Du(z), with stronger asym- allows calibration and control of applied stresses. Stress metry of Du(z) between the pore ends yielding stronger in the 2D membrane under deformation is expected to 7 rectification. The Dukhin number measures the relative cause restructuring of the bonds in the nanopore edges, magnitude of surface to bulk ionic conduction. For a opening up a pathway for ion transport, in direct anal- 1:1 electrolyte, and in the absence of Debye layer overlap ogy to biological ion channels.32 This could provide a hc+(z)−c−(z)i in the pore, Du(z) = − , where c± 2(c+(z,r=0)+c−(z,r=0)) stress-sensitive alternative to the newly reported pres- are the positive and negative ion concentrations, h· · · i sure sensitive ion transpor behaviour in single digit car- denotes an average over the pore cross-section, and r is bon nanotubes.17 In addition to strain induced enlarge- the radial coordinate.7 Pressure-driven flow induces spa- ment of nanopores, we have shown how thin nanopores tial asymmetry in Du(z) since conservation of ion cur- can induce nonlinear transport phenomena such as ionic rent as the bulk solution is transported into the charged current rectification. This is in contrast to the so far re- nanopore perturbs both the local ionic charge density ported effect of the reduction of ICR with pressure.18,19 nc = e(c+ − c−), and local total ion concentration Similar to systems which have liquid flow slippage, like 17 16 ctot = c+ + c− (Supplemental figures S8 and S9 respec- long carbon nanotubes , or angstrom slits , membranes tively), particularly when coupled with the applied elec- in almost-2D membranes have low hydraulic resistance tric field. At sufficiently high pressures, however, con- which, along with access effects, produces novel nonlin- vection completely replaces the fluid inside the nanopore ear nanofluidic phenomena. by the bulk solution, reducing the spatial variation of Du(z) and diminishing ICR, as observed in both experiments and FEM simulations. The spatial asymmetry of SUPPORTING INFORMATION Du(z) at positive versus negative bias ±V for different pressures P from the FEM simulations is quantified by The supporting information contains the Materials and Du(z; P,V )−Du(−z; P, −V ) in figure 3d, which confirms methods section, details about the strain and ionic cur- that the asymmetry is greatest at an intermediate pres- rent rectification measurements and FEM model details sure corresponding to the strongest rectification. with additional plots.

AUTHOR CONTRIBUTIONS The pressure-induced asymmetry in Du(z) is localized to the pore ends in the FEM simulations (figure 3d). S.J.D. performed the experiments, analysed the data Thus, rectification is expected to be controlled by a di- and performed FEM simulations. S.M. designed and ud mensionless Pécletnumber Pe = D quantifying the rel- built the experimental set-up and built the FEM model. ative importance of ion advection compared with diffu- M.M. designed the microfluidic chamber and performed sion in which the characteristic length scale is the pore AFM imaging. A.C. fabricated devices. A.R. and S.M. diameter d. Here u is the average pressure-driven fluid supervised the research. D.M.H. provided an explanation velocity and D the diffusivity of the ions (which is ap- for the ionic current rectification. S.J.D. and S.M. wrote + − proximately the same for K and Cl ). Rectification is the manuscript with all authors providing important sug- expected to be pronounced for Pe > 1 and to diminish gestions for the experiments, discussing the results, and as Pe → ∞. Consistent with this picture, the maximum contributing to the manuscript. rectification factor in the experiments and FEM simulations (at P ≈ 500 mbar) occurs at Pe ≈ 7, if we take 2 d P 44 ACKNOWLEDGEMENT u ≈ 2η(16L+3πd) , the average fluid velocity magnitude across a nanopore of length L and diameter d for fluid viscosity η due to an applied pressure P and use the ex- The authors thank Marko Popovic and Alex Smolyan- perimental/simulation parameter values. itsky for useful discussions on the membrane elas- 7 ticity. This work was financially supported by the pean Union’s Horizon 2020 research and innovation pro- Swiss National Science Foundation (SNSF) Consolida- gramme under the Marie Skodowska-Curie grant agree- tor grant (BIONIC BSCGI0 157802) and from the Euro- ment No 754462.

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