Understanding electron transport, dissipation, and fluctuations at sub-micron length scales is critical for the continued miniaturization of electronic and optical devices, as well as atom and ion traps, and for the electrical control of solid-state quantum circuits. While it is well-known that electronic transport in small samples defies the conventional wisdom associated with macroscopic devices, resistance-free transport is difficult to observe directly. Most of the measurements demonstrating these effects make use of Ohmic contacts attached to sub-micron scale samples and observe quantized but finite resistance corresponding to the voltage drop at the contact of such a system with a macroscopic conductor. Techniques for non-invasive probing of electron transport are required because they can provide insights into electronic dynamics at small length scales.
In an aspect, a method of making measurements, including, providing a sensor with at least one solid state electronic spin; irradiating the sensor with radiation from an electromagnetic radiation source that manipulates the solid state electronic spins to produce spin-dependent fluorescence, wherein the spin-dependent fluorescence decays as a function of relaxation time; providing a target material in the proximity of the sensor, wherein, thermally induced currents (Johnson noise) present in the target material alters the fluorescence decay of the solid state electronic spins as a function of relaxation time; and determining a difference in the solid state spins spin-dependent fluorescence decay in the presence and absence of the target material and correlating the difference with a property of the sensor and/or target material.
In some embodiments, the property of the target material measured is localized at a length scale of 10-100 nm. In some other embodiments, the property measured is the resistance values within the target material. In some other embodiments, the property measured is the temperature of the of the target material.
In some embodiments, the property measured is the distance of the target material from the surface of the sensor.
In some embodiments, the property measured is the distance of the solid state electronic spins from the surface of the sensor.
In some embodiments, the sensor comprises a diamond crystal lattice. In some other embodiments, the solid state electronic spins comprises a defect in the diamond crystal lattice. In some other embodiment, the defect comprises a nitrogen vacancy center in a diamond crystal lattice.
In some embodiments, the electromagnetic radiation source is a laser. In some embodiments, the laser source emits light having wavelength of about 532 nanometers.
In some embodiments the target material is in contact with the sensor. In some other embodiments, the target material is not in contact with the sensor.
In some embodiments, the target material is a conductive material. In some embodiments, the target material is a metal. In some embodiments, the target material is silver. In some embodiments, the target material is copper.
In some embodiments, the target material is a single crystal. In some embodiments, the target material is polycrystalline.
In some embodiments, the target material is a conductive polymer.
The following figures are provided for the purpose of illustration only and are not intended to be limiting.
A method of making measurements using thermally induced currents, known as Johnson noise, is described. Johnson noise is the electronic and magnetic noise generated by the thermal agitation of the charge carriers, such as electrons, inside a material at equilibrium. The interaction of the magnetic Johnson noise with a sensor having solid state spins with spin-dependent fluorescence is used for measurement of properties of a sensor and/or target material.
When the sensor is irradiated with an electromagnetic radiation, the solid state spins absorb energy and emit fluorescence with a characteristic relaxation time that can be measured. However, the relaxation time of the solid state spin is altered when a target material with magnetic Johnson noise is brought in the proximity of the solid state spin. Among other parameters, the difference in the relaxation time of the solid state spin's spin-dependent fluorescence is correlated with the distance between the target material and the surface of the sensor, the temperature of the target material, and the resistance of the target material.
In an aspect, a method of making measurements, including providing a sensor with at least one solid state electronic spin; irradiating the sensor with radiation from the electromagnetic radiation source manipulates the solid state electronic spins to produce spin-dependent fluorescence, wherein the spin-dependent fluorescence decays as a function of relaxation time; providing a target material in the proximity of the sensor, wherein, thermally induced currents (Johnson noise) present in the target material alter the fluorescence decay of the solid state electronic spins as a function of relaxation time; and determining a difference in the solid state spins spin-dependent fluorescence decay in the presence and absence of the target material and correlating the difference with a property of the sensor and/or target material.
Currently, techniques do not exist to measure properties such as temperature and resistance of materials at resolutions in the length scale of 10-100 nm. Advantageously, using the method disclosed here enables the measurement of properties of the target material at a localized length scales of 10-100 nm. In some embodiments, the method is used for measuring the resistance values within the target material. In some other embodiments, the method is used for measuring the temperature of the target material.
In some embodiments, the method is used for measuring the distance of the target material from the surface of the sensor. In some embodiments, the method is used for measuring the distance of the solid state electronic spins from the surface of the sensor.
In some embodiments, the target material is a conductive material. Conductive materials such as metals can be used as target materials as the magnetic Johnson noise associated with these is large and can interact effectively with the solid state spins as described above. In some embodiments, the target material is silver. In another embodiment, the target material is copper. In yet another embodiment, the target material is a conductive polymer. In some other embodiments, the target material is a single crystal. In some other embodiments, the target material is polycrystalline.
In some embodiments, the sensor is a high purity diamond. In some other embodiments, the solid state electronic spin system is a NV spin. A NV spin in diamond is a crystallographic defect in the structure of a diamond, e.g., an empty position in a diamond's lattice. The NV spin is found as a defect in the lattice structure of a single crystal diamond. The NV impurity is based in the lattice of carbon atoms, where two adjacent sites are altered such that one carbon atom is replaced with a nitrogen atom and the other space is left vacant. The vacancies may interact with interstitial atoms, such as nitrogen, and may act as color centers by absorbing visible light. NV defects are visible as red spots when illuminated by a laser of the appropriate color. In some embodiments, the proximal NV spin is located about 5 nm to 50 nm below the diamond surface. In some other embodiments, the NV spin is located at about 2 to 50 nm, or 2 to 100 nm, or 1 to 100 nm or 1 to 200 nm, or 1 to 500 nm below the diamond surface.
In an aspect, the method includes use of the electromagnetic fluctuations associated with Johnson noise close to a conducting surface, which can be directly linked to the dielectric function at similar length scales, providing a non-invasive probe of electronic transport inside the metal. Advantageously, in some embodiments, measurements over a range of distances, such as 20-200 nm and temperatures, such as 10-300 K are possible.
In some embodiments, the target material is in contact with the sensor. In some other embodiments, the target material is not in contact with the sensor. Advantageously, when the target material is not in contact with the sensor, measurements in cryogenic conditions are more reliable and accurate since the sensor does not act as a heat sink causing errors in measurement.
In an aspect, the method makes use of the electronic spin associated with NV defect centers defect centers in diamond to study the spectral, spatial, and temperature dependence of Johnson noise emanating from conductors. The magnetic Johnson noise results in a reduction of the spin lifetime of individual NV electronic spins, thereby allowing a probe of the intrinsic properties of the conductor non-invasively over a wide range of parameters. In some embodiments, individual, optically resolvable, NV centers are implanted ˜15 nm below the surface of a ˜30-μm thick diamond sample. A silver film is then deposited on or positioned on the diamond surface.
To test the scaling of Johnson noise with distance (d) to the metal, a layer of SiO2 is deposited on the diamond surface with a gradually increasing thickness.
To investigate the dependence of the noise on temperature and conductivity, a 100-nm polycrystalline silver film on a diamond sample was deposited and the T1 of a single NV beneath the silver over a range of temperatures (˜10-295 K) was measured. The measured relaxation rate for a single NV near the silver increased with temperature for thermal noise, as shown by the red circles in
To analyze the dependence of the NV spin relaxation rate on distance, temperature, and conductivity, a model in which an electronic spin-½ qubit with Larmor frequency ωL is positioned at a distance d from the surface of a metal was used. For silver at room temperature the skin depth at ωL is δ≠1 μm; consequently when d<100 nm, the “quasi-static” limit d<<δ applies. The thermal limit kBT>>ℏωL is valid for all temperatures in this disclosure. In this regime the magnetic noise spectral density perpendicular to the silver surface is given by
where σ is the temperature-dependent conductivity of the metal as defined by the Drude model. This scaling can be intuitively understood by considering the magnetic field generated by a single thermal electron in the metal at the NV position, Bo=(μoevth)/(4πd2), where the thermal velocity vth∝sqrt(kB T/me), me is the effective mass of electrons in silver and e is the electron charge. In the limit d<<δ screening can be safely ignored, and the NV experiences the magnetic field spectrum arising from N independent electrons in a volume V, SB ∝Vn B02τc, where n is the electron density and τc is the correlation time of the noise, given by the average time between electron scattering events, τc=l/vF, where l is the electron mean free path and vF is the Fermi velocity. Recognizing that the NV is sensitive to the motion of electrons within a sensing volume V∝d3, we arrive at the scaling given by Eq. 1, with σ=(ne2τc)/(me). Applying Fermi's golden rule and accounting for the orientation and spin-1 of the NV yields the relaxation rate for the |ms=0 state
where g≈2 is the electron g-factor, μB is the Bohr magneton, and θ≠54.7″ is the angle of the NV dipole relative to the surface normal vector. In
Remarkably, very different results were obtained when the polycrystalline film was replaced with single-crystal silver. A 1.5-μm thick single-crystal silver film grown by sputtering onto silicon was placed in contact with the diamond surface.
To analyze these observations, it is noted that the conventional theoretical approach resulting in Equation 2 treats the motion of the electrons in the metal as entirely diffusive, using Ohm's law, J(r, t)=σE(r, t), to associate the bulk conductivity of the metal with the magnitude of the thermal currents. While accurately describing the observed relaxation rates next to the polycrystalline material, where the resistivity of the film is dominated by electron scattering off of grain boundaries (Inset,
This regime of magnetic Johnson noise was analyzed theoretically using the Lindhard form non-local dielectric function for the metal modified for finite electron scattering times. Comparison of this model (solid line in
While ballistic electron motion in nanoscale structures has previously been studied and utilized, our approach allows for non-invasive probing of this and related phenomena, and provides the possibility for studying mesoscopic physics in macroscopic samples. The combination of sensitivity and spatial resolution demonstrated here enables direct probing of current fluctuations in the proximity of individual impurities, with potential applications such as imaging of Kondo states and probing of novel two-dimensional materials, where our technique may allow for the spatially resolved probing of edge states. Likewise, it could enable investigation of the origin of 1/f flux noise by probing magnetic fluctuations near superconducting Josephson circuits. Finally, as Johnson noise presents an important limitation to the control of classical and quantum mechanical devices at small length scales, the present results demonstrate that this limitation can be circumvented by operating below the length scale determined by the electron mean free path.
The invention is illustrated in the following examples, which are for purposes of illustration only and not intended to be limiting of the invention.
The experiments were performed using 30 micron thick electronic grade diamonds grown, thinned, and polished by Element Six with a natural isotopic abundance of carbon. Shallow NV centers were generated through Nitrogen-14 implantation at 6 keV energy at a density of 2×109/cm 2, followed by annealing at 800° C. The single-crystal silver films were grown by sputtering at 300° C. onto a (111) oriented single-crystal silicon substrate, with a deposition rate of ˜1.5 nm/s. The polycrystalline silver films were evaporated directly onto the diamond. A 5-nm layer of silica (SiO2) was grown on the diamond surface prior to the metal deposition to preserve NV properties. Temperature dependence measurements were performed in a Montana Instruments closed cycle cryostat.
The single-crystalline silver films were grown using direct current plasma sputtering (AJA International Orion 3). The sputtering targets used were 99.99% pure silver (Kurt Lesker, Inc). Films were deposited onto prime-grade, degenerately doped (111)-Si wafers (0.0015-0.005 Ω-cm). The substrates were ultrasonically cleaned in acetone, followed by a 2:1 sulfuric acid:hydrogen peroxide solution to eliminate organics. The substrates were then immersed in 49% hydrofluoric acid for 10-15 seconds to remove any native oxide. Next, the substrates were rapidly transferred into the sputtering chamber and the chamber was pumped down to minimize re-oxidation of the surface. Upon reaching a base pressure of about 5×10-7 Torr, the substrate was heated to 300° C. and silver was deposited at a rate of 1.5-1.7 nm/s.
Following the growth, multiple characterization techniques were used to test the quality of the deposited films. The crystallinity and surface quality of the films were probed via transmission electron microscopy (TEM) and atomic force microscopy (see
Crystal orientation and average grain size of the silver samples were measured with electron backscatter diffraction (EBSD). For the polycrystalline films a 100 nm film deposited on 5 nm of SiO2 on (100) silicon is used as a reference. In the insets of
AFM and profilometer scans were performed on the implantation-side surface of the diamond used for the single-crystal silver measurements, as shown in
Distance-dependence studies of the noise were carried out by growing a spacer layer of SiO2 between the evaporated silver metal and diamond. A 5-nm thick film of SiO2 was first deposited via CVD on the diamond. A 100 μm thick sapphire slide was then placed ˜300 μm above the surface of a diamond crystal-bonded to a silicon carrier wafer (see illustration in
For the temperature dependence measurements under evaporated polycrystalline silver (
The device used in this experiment was fabricated using optical contact bonding between the diamond and the single-crystal silver surfaces. The diamond sample was prepared for bonding by cleaning in a boiling 1:1:1 solution of nitric, sulfuric, and perchloric acids for at least one hour, directly prior to bonding. After growth, the single-crystal silver films were stored with a 50 nm capping layer of alumina to prevent surface oxidation. Directly prior to the bonding process, the alumina capping layer was stripped away in hydrofluoric acid. The diamond was then placed NV side down in contact with the freshly exposed silver surface. A drop of de-ionized water was placed on top of the diamond and allowed to wick in-between the diamond and the silver, and the diamond was lightly pressed against the silver from above, while the two samples were blow-dried with a nitrogen spray gun, leaving the diamond bonded directly to the silver surface. This procedure was performed in a cleanroom, with careful attention to the cleanliness of the tweezers and sample holders. The final device used in this experiment demonstrated very robust bonding between the diamond and the silver, and survived multiple thermal cycles from 300-10 K.
From Fermi's golden rule and the fluctuation-dissipation theorem, the decay rate from |ms=0> to |ms=1> for a spin-1 system at a distance z above the surface of a metal at temperature T, with level separation co and magnetic dipole moment in the ith direction is then given by
and rp and rs denote the Fresnel Coefficients for plane waves incident on the material interface for p and s polarized light, respectively. We choose a coordinate system in which the z axis is perpendicular to the material interface; as SBαβ is a diagonal tensor in this coordinate system, we drop one index and denote the diagonal elements by identifying SBii=SBi. We have also assumed off-diagonal density matrix elements to be 0, ρij=<i|ρ|j>=Σδij, consistent with T*2 of the NVs in our experiment being much faster than the population dynamics of system.
Explicitly, the reflection coefficients for a single material boundary are given by
where we have assumed μi≈1 in all space, consistent with the materials used in this study. In the case of a spin above a metal, the above coefficients are valid when the thickness of the metal greatly exceeds the skin depth or when the spin-metal distance is much less than the thickness. To take into account the finite thickness of the film, the reflection coefficients take the form
where a is the thickness of the film.
Finite thickness effects have a significant impact on the noise power spectrum outside of the film. The distance and temperature dependence experiments, depicted in
Furthermore, in the experiments involving polycrystalline silver, an extra 5 nm layer of SiO2 lies between the diamond and the metal. Such a geometry can also be accounted for with the appropriate reflection coefficients. However, because μ≈1 in diamond and SiO2, the length scales z and electromagnetic field wave vectors |k|=ϵω/c such that |k|z >>l, and the electromagnetic response is dominated by |ϵ2|=ϵAg>>{|ϵDiamond|, |ϵSiO2|}, the effects of the diamond medium and the silica layer are both negligible.
It is convenient to perform approximations to the integrals in equations (S2) and (S3) to gain insight into the decay rate behavior in different regimes. In particular, in the case of a full metallic half space, and in the regime where the electromagnetic wavelength is much larger than the skin depth of the metal, λ>>δ, and the skin depth is much larger than the spin's distance to the metal, δ>>z,
In this regime, known as the quasi-static regime, the decay rate, as described in equation (S1), is proportional to 1/z, and thus T1=1/Γ∝z.
We also must account for the orientation of the magnetic dipole of our NV centers when calculating the expected decay rate. The decay rate from |ms=0> to |ms=1> for a spin-1 system with a quantization axis making an angle θ with {circumflex over (z)}, the vector normal to the metal surface, in the quasi-static limit is given by
where in our temperature and frequency range of interest (T >4 K and ω<20 GHz), coth(hω/2kBT)≈2kBT/hω, and we choose our coordinate system such that the spin is always in the x −z plane. All diamond samples used in the experiment are cut such that all four possible NV dipole orientations make the same angle θ=½ (180°−cos−1(⅓))≈54.7° with {circumflex over (z)}.
We also must account for the population dynamics of our three level spin-1 coupled to a magnetic noise bath. The rate equations for this system are given by
which, for boundary conditions ρ00(t=0)=1, give the solution
ρ00(t)=⅔exp(−3γt)+⅓. (S16)
Thus, the population decay from the ms=0 state is a factor 3 larger than the rate given by equation (S14), and we arrive at
which is equivalent to equation (2) given in the main text.
To take into account the ballistic nature of the electron motion in the silver, we introduce a non-local permittivity. In this regime we find SBz≈2SBx still holds, so for simplicity in the discussion that follows we consider only SBz. With the Lindhard form modified for finite electron lifetime, the s polarized reflection coefficient becomes
with k2=p2+κ2 and the transverse permittivity defined as
and the function ƒt defined as
and ωp is the electron plasma frequency, v is the electron scattering rate, ω is the frequency of radiation, and vƒ is the Fermi velocity. In the above expressions, the non-locality manifests itself through the k dependence of the permittivity. In order to derive an analytical expression for SBz in the limit z→0, we first rewrite the SBz in terms of the rescaled, dimensionless momentum p˜=(υƒ/v)p and introduce
In the regime of our interest α˜106, we can replace √{square root over (1α2+ρ2)} with ip˜ to good approximation. Also, by separating the real and imaginary parts of the numerator and the denominator of equation (S22), it can be shown that when v/ω˜103>>1, the imaginary part of rs is well-approximated by
Finally, the substitution of equation (S23) into equation (S21) and the change of variables p˜=r cos (θ), and κ˜=r sin (θ), and tan (φ)=1/r give us
where the dimensionless function C(a) is given by
The function C(a) has a logarithmic divergence
ln (a) in the limit a→0. This originates from integration over infinitely large momentum p in the integral in equation (S3). Therefore, we introduce a physical cut-off, which modifies the range of integration for φ from [0, π/2] to [φ, π/2] with tan
Using kcut=2π/aAg with aAg=0.4 nm, the lattice spacing of silver, we obtain well-defined behavior in the limit z→0, Ccut(2vz/vƒ)≈4.6π, which leads to Eq. 3.
From equation (S17), it is clear that the noise spectrum of magnetic Johnson noise is white for frequencies over which coth (hω/2kBT)≈2kBT/hω. We verify this by applying an external magnetic field, B∥, along the NV axis to tune the NV spin transition frequencies
ω±=Δ+2gμB B∥/h (S26)
where ω± denotes the transition frequency from the |ms=0> to the |ms=±1> states, Δ denotes the NV spin ground state zero-field splitting (2π×2.88 GHz), and gμB is the NV electronic spin magnetic moment. We measure the relaxation rate when the NV is initially polarized in the |0> state, and when it is initially polarized in the |±1> states. Based on the rate equations given in section 1.2 (equation (S15)), the population relaxation from the |0> state is given by equation S16, while the population relaxation from the |±1> state takes the following form:
We observe excellent agreement with these predictions, and simultaneously fit to the relaxation from the |0> and |±1> states with only a single decay rate γ. A representative data set and fit are shown in
For NVs implanted at shallow depth such as the ones used in this work, we occasionally observe short NV T1 times for NVs under bare diamond (see Table 1). The origin of the fast decay is unclear. No spatial correlations in T1 are observed for the NVs with reduced T1 times.
Due to the variability in NV T1 times under bare diamond, when measuring under silver a spread in the T1 times of the NVs is observed, as shown in
In the theoretical prediction for the distance-dependent relaxation rate shown in
When estimating the distance to the film for the NVs plotted in
This new distribution is used to determine the expected value and standard deviation of the depth of the NV selected at each point along the ramp. For example, if n=5 NVs are measured at one point along the ramp, from the above probability distribution function Pmax, the expected value for the depth of the deepest NV measured is 27 nm with a standard deviation of 7 nm, while at a point where n=10 NVs are measured the likely distribution of depths is 30±6 nm. These depths are then added to thickness of the ramp at that point to give the total distance to the silver surface plotted in
In the temperature-dependence measurements shown in
In total, the T1 of 25 NVs close to the single-crystal silver sample were measured at 12 temperatures, in three different spatial regions on the sample. Each region was 40 μm×40 μm in size, and the regions were each spatially separated from each other by more than 100 μm. Of the 25 measured NVs, 16 were in region A (blue triangles in
The gap between the diamond and silver was qualitatively apparent based on a number of separate observations. A variation in the brightness of the NVs is observed in the different regions when exposed to the same laser power at the objective, which we attribute primarily to optical interference coming from the reflections off the silver and diamond surfaces. In addition, we measured reduced NV optical excited state lifetimes in region A (the region in contact with silver) which is attributed to quenching from the silver (see Table 2). An accumulation of a small amount of fluorescent background on the diamond surface is also observed over time in regions B and C, which was absent from region A, as would be expected if the diamond and silver were in direct contact there.
The T1 time at room temperature of all 25 NVs was also subsequently measured after the silver sample was removed. Of these NVs, one NV in region A was rejected because the measured T1 times under silver were not repeatable, and one NV in region B was rejected because it had very short T1 times even at low temperatures (<300 μs at 8 K) leaving 23 NVs that compose the dataset shown in
Those skilled in the art would readily appreciate that all parameters and configurations described herein are meant to be exemplary and that actual parameters and configurations will depend upon the specific application for which the systems and methods of the present invention are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that the invention may be practiced otherwise than as specifically described. The present invention is directed to each individual feature, system, or method described herein. In addition, any combination of two or more such features, systems or methods, if such features, systems or methods are not mutually inconsistent, is included within the scope of the present invention.
This application claims the benefit of priority under 35 U.S.C § 119(e) to co-pending U.S. application Ser. No. 62/109,271, filed Jan. 29, 2015, the content of which are incorporated by reference in its entirety.
This invention was made with government support under Grant No. HR0011-111-C-0073 awarded by the Defense Advanced Research Projects Agency (DARPA), Grant No. PHY-1125846 awarded by National Science Foundation (NSF), Grant No. 5710003324 awarded by Army Research Office (ARO), and Grant No. 5710003095 awarded by NSF. The government has certain rights in this invention.
Filing Document | Filing Date | Country | Kind |
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PCT/US16/15710 | 1/29/2016 | WO | 00 |
Number | Date | Country | |
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62109271 | Jan 2015 | US |