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SCO 090-602 : SCO OpenServer Release 6 Master Advanced Certified Engineer Exam

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SCO Study Guide

exceptional switching endurance affords for high-decision surface temperature mapping the usage of a spin-crossover movie | 090-602 Cheatsheet and Free test PDF

Spin-transition homes and switching endurance of 1

Compound 1 is a molecular SCO complex35 (Fig. 1a) which can be deposited within the kind of extremely good, huge-area, nanometer-thick films with the aid of vacuum thermal evaporation34. The resulting nanocrystalline films are customary to be oriented (with the c-axis regular to the substrate airplane), homogenous, and that they display a totally finished, isostructural spin transition headquartered at TSCO = sixty three–sixty five °C (with a mild dependence upon the film thickness)34,36. Importantly, the thermal spin transition within the thin films of 1 is favourite to be noticeably abrupt, i.e. eighty% of the transition is spanned over a temperature latitude of ca. 12 °C, with a narrow (<0.5 °C-large) thermal hysteresis loop. The SCO phenomenon is accompanied by means of a drastic exchange of the optical residences of the films, in certain of the UV absorbance (Supplementary Fig. 1) as neatly as the optical reflectivity (R) on a variety of surfaces (Fig. 1b and Supplementary Fig. 2). The optical reflectivity measured at λ = 452 nm on a 200-nm-thick film of 1, deposited on precise of a gold floor, usually increases via ca. 7% as a result of the switching from the LS to the HS state, whereas it goes down on glass (−four%) and silicon (−1.5%).

Fig. 1: section-trade houses and switching persistence of the skinny films of 1.

a Molecular structure of complex 1. b Thermal evolution of the optical reflectivity (λ = 452 nm) of a 200-nm-thick film of 1 on appropriate of a gold microwire (2 mm × 2 µm × 300 nm) after 1, 104, a hundred and five, 106, and 107 thermal cycles in air triggered via Joule heating. These statistics show the tremendous edition of the reflectivity as a result of the molecular spin-state switching and exhibit the above all high resilience of the spin transition over 107 thermal cycles. Time evolution of c the applied electrical existing, d the wire temperature, and e the optical reflectivity on the wire recorded simultaneously at selected times of the thermal-cycling experiment the use of the Joule-heated microwire.

a vital and reasonably unexpected discovery with compound 1 is the existence of an incredibly high steadiness and robustness of the spin-transition properties, as well as a powerful resilience of the cloth upon prolonged thermal cycling. First, from UV absorption measurements, they demonstrated that the transition temperature, the shape, and the completeness of the thermal spin transition in the skinny films of 1 continue to be virtually unaltered over a period of greater than 1 12 months of storage in ambient air (Supplementary Fig. three). These optical measurements have also printed that the SCO homes are completely preserved after annealing the films at temperatures as excessive as 230 °C (Supplementary Fig. three). To examine the switching patience of skinny movies of 1, they first performed successive thermal cycles the use of a heating/cooling Peltier stage, while the spin-transition properties were probed via optical absorbance measurements. the usage of this time-consuming “classical” strategy, the switching properties of the movies are discovered to be preserved after greater than 10,000 thermal cycles in air (see Supplementary Fig. 1). significantly, the transition temperature shifts <0.5 °C.

to move additional, they used Joule-heated gold microwires as quick micro-heaters, to show a skinny movie of 1 to a huge number of thermal cycles (107) inside an affordable time (<14 h). These microwires, fabricated on excellent of a tumbler substrate through capacity of conventional photolithography (PL) strategies (see “strategies” section and Supplementary Fig. four), have been covered with a 200-nm-thick film of 1 and installed on a variable-temperature microscope stage to manage the temperature of the entire substrate. This latter, which differs from the exact temperature of the heating wire Twire, will be hereafter denoted “base temperature” Tb. due to their small thermal mass, these micro-wire heaters are conventional to be exceptionally wonderful for generating speedy (<µs), localized heating (T-jumps)32,37. besides, the time-resolved dimension of their electrical resistance, the use of a customized-built differential resistance dimension setup37, presents the opportunity of monitoring in situ the standard temperature rise of the wire with a sub-µs time decision (Supplementary Fig. four). For their thermal-biking test, the temperature of the wire become modulated between 50 and 88 °C with the aid of applying 200-µs-long present pulses at a frequency of 200 Hz. notice that the heating period (200 µs) became chosen long sufficient compared to the thermally activated molecular spin-state switching time (a couple of tens of nanoseconds above room temperature38), making certain that a full LS–HS–LS thermal switching cycle become accomplished for each existing pulse. At chosen times, the excitation frequency changed into reduced to 0.2 Hz to be able to list simultaneously the temporal evolution of the optical reflectivity (λ = 452 nm) on the heated microwire. As depicted in Fig. 1c–e, tremendous jumps of the reflectivity signal are followed, confirming the prevalence of the spin-state switching experience following the oscillating excitation existing. Crucially, the amplitude of the reflectivity oscillations remains comparable even after 107 cycles, demonstrating the super robustness of the spin transition in the thin movies of 1. At distinctive time intervals of the thermal-biking experiment, the reflectivity signal on the SCO-coated wire was also bought as a characteristic of the bottom temperature (Fig. 1b). Remarkably, the spin-transition curves (switching temperature, form, and amplitude) stay pretty much unchanged after more than 10 million thermal-switching hobbies.

here's the primary time that such an excellent resilience is confirmed for a SCO compound. it is essential to mention that the spin-transition properties of 1 continue to be unaltered despite a comparatively significant extent trade (ca. four.5%) upon the SCO35. indeed, as with many PCMs, the pivotal difficulty is the large transformation stress, which results in the build-up of mechanical stress and, ultimately, to fabric failure. This inherent fatigability at present constitutes a standard hurdle for the implementation of numerous PCMs and molecular switches into annoying technological applications39,forty,41. The specially high switching persistence of thin movies of 1 should doubtless arise from a mixture of structural elements. First, the molecular nature of compound 1 (with only weak intermolecular bonds) and its processing in the sort of high-purity (vacuum-deposited) thin films are without doubt essential aspects that cut the transformational stress all over the spin-state switching. most importantly, as established for shape reminiscence alloys40,42, and additionally counseled for VO243, the ordinary crystallographic compatibility of both phases seems as a key parameter to achieve excessive switching persistence. In 1, this compatibility includes the isostructural character of the transition (same orthorhombic area group Pbca within the two phases) in addition to a stated anisotropy of the transformation pressure, the structural deformation particularly taking place along the c-axis (Δc/c = +5.6%)35. This anisotropic deformation allows the crystal lattice to stronger accommodate the quantity change, through the possible formation of mismatch-free LS/HS phase boundaries all through the spin-state switching44. in spite of this, because the thin films of 1 are oriented (with the c-axis normal to the substrate), the transformation pressure is practically zero within the substrate plane45 and the spin transition as a consequence gives upward thrust to reasonably small mechanical stress in the film. while greater finished reports nonetheless deserve to be carried out on these structure–property relationships, the negligible fatigability of 1, along side its wonderful spin-transition houses, make this compound a terrific candidate for top-cycle functions, comparable to thermal imaging.

Working principles of the SCO-based surface thermometer

To show the capabilities of their SCO-based mostly thermometer, they used electron-beam lithography (EBL) to manufacture a variety of Joule-heated gold nanowires (80-µm-long, 50-nm-thick) on glass and oxidized silicon chips (see Fig. 2 and Supplementary Fig. 5). As already demonstrated32,37, their quick temporal response with their respectable all-electrical operation make these wires most useful examine benches for the construction of nanothermometry applications. The chips were entirely coated with a 200-nm-thick movie of 1, grown by means of vacuum thermal evaporation. it's essential to point out that each the deposition situations as neatly because the physical homes of the SCO skinny film are not invasive and do not regulate the average electrical and thermal performance of the gadgets (vide infra).

Fig. 2: Description of the Joule-heated gold nanowires used for nanothermometry.

a Sketch of the chips used (each and every comprising seven 80-µm-long, 50-nm-thick gold wires), and schematic illustration of a nanowire on suitable of an oxidized silicon substrate. Scanning electron microscopy (SEM) photos of b a 1-µm-vast wire and c 5 parallel 500-nm-wide wires spaced 1.5 µm aside. Scale bars, 10 µm.

whereas a thin movie exhibiting a gradual SCO enables continuous temperature monitoring33 (given that a careful thermal calibration of the measured physical residences is performed), here they indicate another strategy. Taking competencies of the abrupt persona of the thermal spin transition, they reveal that thin films of 1 will also be used as a binary sensor of the surface temperature, as a result of a colossal start of the optical reflectivity occurs at the transition temperature TSCO = 64 °C, bringing out a neatly-defined isotherm. This property can also be advantageously used to list speedy contour maps of the surface temperature distribution. As proven in Fig. 3a, reflectivity photographs of a Joule-heated nanowire on glass have been recorded by way of optical microscopy in each ON (I ≠ 0) and OFF (I = 0) states of the heating equipment at quite a few base temperatures Tb of the glass substrate, such that ΔR/R = (RON − ROFF)/ROFF photos can be obtained for every Tb. (Supplementary Fig. 6 displays a extra comprehensive series of photos.) On these photographs, two diverse areas are obviously discernible. One location, near the nanowire, where the optical reflectivity has modified following the software of the electrical latest, signaling the thermal switching into the HS state. past this region, the optical reflectivity continues to be basically unchanged. As displayed in Fig. 3a, these two areas are separated by way of an isothermal line, with an elliptical shape on glass, on which the temperature upward push is comfortably given with the aid of the difference ΔT = TSCO − Tb. Heating or cooling the chip at distinctive base temperatures makes it feasible to acquire a thermal contour map with as many isotherms as preferred (Fig. 3b). This elementary protocol seems to be extraordinarily effective for deciding on temperature gradients in a short manner, or for locating, at the start glance, the existence of hot spots on the surface (vide infra). an outstanding knowledge is that quick thermal mapping may also be executed with none thermal calibration of surface houses.

Fig. three: Contour map of the temperature distribution triggered by a Joule-heated nanowire.

The wire (80 µm × 1 µm × 50 nm) on properly of a tumbler substrate is lined with a 200-nm-thick film of 1 and Joule-heated through the software of an electrical current of 4 mA. a Optical reflectivity (λ = 452 nm) photographs ΔR/R = (RON−ROFF)/ROFF of the nanowire recorded at chosen base temperatures Tb. The dotted lines point out the position of the corresponding isotherm (TSCO = 64 °C). b Contour map of the surface temperature bought from gathering the isotherms for a number of base temperatures (ΔT = TSCO − Tb). Scale bars, 20 µm.

A more accurate formulation to investigate the native heating (as an example for each and every pixel of the CCD digicam) is in response to the evaluation of the thermal transition curves, inferred from the dimension of the optical reflectivity signal over a large range of Tb, in each ON and OFF states of the heating gadget. As shown in Fig. 4a, they applied this system to map the temperature distribution of the equal Joule-heated nanowire on glass. for instance, Fig. 4c shows normal ON-state and OFF-state transition curves got for chosen pixels of the reflectivity pictures at distinct distances from the wire. For each and every pixel, the cost of the native heating turned into conveniently deduced from the thermal shift (ΔT = TSCOOFF − TSCOON), by way of an automatic curve-fitting procedure the usage of sigmoidal features. As proven in Fig. 4a, this manner enables to map the temperature field with a micrometer spatial decision, by the way revealing a somewhat inhomogeneous heating of the nanowire. As deduced from the thermal map, the application of a current of four mA induces a regular heating of ΔTwire = forty.four ± 0.5 °C on the wire, while the temperature rise is ΔT = 5.eight ± 0.three °C at 50 µm from the middle of the wire. (Supplementary Fig. 7 shows experimental and simulated temperature maps with the corresponding go-sections for distinctive utilized electrical currents.)

Fig. 4: Thermal mapping of a Joule-heated gold nanowire on glass and silicon substrates.

a Experimental and b simulated temperature maps (ΔT) of the nanowire (80 µm × 1 µm × 50 nm) on glass, heated through the application of an electrical latest of 4 mA. The pixel measurement of the experimental map is 1 × 1 µm2. Scale bar, 20 µm. c standard ON-state (I = 4 mA) and OFF-state (I = 0) reflectivity curves measured in selected pixels, marked by means of crosses in a, at distinctive distances (x = 0, 2, 10, and 50 µm) from the wire. observe that the reflectivity sign increases with Tb on the gold wire, nonetheless it goes down on glass. solid traces are the outcomes of a curve-becoming technique the usage of a sigmoidal feature. The temperature shift between the two peaks within the corresponding derivative curves (dR/dTb vs. Tb) at once offers the usual temperature upward thrust in every pixel. d Experimental and e simulated temperature maps (ΔT) of the same nanowire on appropriate of a silicon substrate, Joule-heated via the application of an electrical present of seven mA. The pixel size of the experimental map is 0.5 × 0.5 µm2. Scale bar, 10 µm.

Following the equal system, Fig. 4d displays the temperature map (ΔT) of an analogous nanowire on good of a silicon substrate, heated by way of the utility of an electrical present of 7 mA. (See Supplementary Fig. eight for temperature maps and associated go-sections at different excitation currents.) As expected due to its high thermal conductivity, the silicon behaves as a powerful heat sink. The influence is that the heating is predominantly localized on the 1-µm-extensive wire, whereas the surrounding Si substrate undergoes basically no temperature upward push. The high thermal conductivity of silicon has also the impact of limiting the common temperature rise experienced by means of the nanowire (ΔTwire = 19.8 ± 0.6 °C at 7 mA). another enjoyable statement is the emergence of a micrometric hot spot at the connection between the wire and the gold electrode (see Fig. 4d), certainly due to a degrading electrical contact. This instance nicely illustrates the capabilities of their technique for localizing, in a simple manner, micrometric sizzling spots on digital circuits.

Our experimental outcomes were validated by way of finite-point simulations. (N.B. evaluation with different experimental strategies is not critical here as they contain an identical, or bigger, uncertainty than their method. in particular, electrical resistance measurements on the nanowires turned out to be sick-reproducible on such small wires.) Simulations have been performed the usage of material houses applied in the COMSOL software (see “methods” part). The value of the electrical resistivity of gold, which is the handiest adjustable parameter, changed into fixed from the imply electrical resistance of the nanowires measured at room temperature (Re ~ one hundred sixty Ω). As proven in Fig. 4b, e (see additionally Supplementary Figs. 7 and eight), the quantitative settlement between the simulated and experimental facts is unbelievable, each on silicon and glass substrates, for the different excitation currents used.

We took improvement from these finite-aspect simulations to examine the possible disturbance within the temperature field brought about by means of the presence of the SCO layer. below (quasi)static conditions—customarily reached inside the microsecond time scale (vide infra)—we locate that the surface temperature differs by way of <1 °C because of the presence of the SCO layer (Supplementary Fig. 9). This price is still related with the common size uncertainty. certainly, under non-thermal-equilibrium situations, the temperature change between the heating point and the thin-film surface is anticipated to be bigger. In certain, apart from the “common” warmth ability of the SCO movie, an excess warmth potential may still be additionally regarded due to the endothermic character of the LS-to-HS transition (ΔH = 40 J g−1 in 1)35, which can provide upward push to a transient thermal damping effect on microsecond time scales in adequate thick (µm range) films46. despite the fact, this effect, which turns into undetectable in films as skinny as 200 nm, can be reasonably neglected in practical thermometry applications. finally, it would be stressed out that these talents artifacts may well be reduced by means of decreasing the film thickness. during this case, the possible resulting lack of optical contrast may well be counterbalanced by way of imposing a extra sensitive (lock-in or interferometry) detection equipment and by means of deciding upon essentially the most suitable probe wavelength in the UV–Vis–NIR spectral range.

Figures of merit of their SCO-based mostly nanothermometer

the use of the above-discussed methodology, we've thoroughly assessed the achievable thermal, temporal and spatial decision, which all represent important parameters for a fully fledged thermometer.

To investigate the achievable thermal decision, they performed a sequence of measurements to investigate the temperature upward thrust in a given 1-µm-broad area of the glass substrate (within the area of the nanowire) for 3 close values of the utilized electrical present (I = three.5, 3.6, and 3.7 mA). As depicted in Fig. 5a, b, a measurable temperature shift of about 1 °C is evidenced between the ON-state curves recorded for the three values of the applied present, and temperature rises of twenty-two.three ± 0.2, 23.three ± 0.2, and 24.9 ± 0.2 °C are measured, respectively. These measurements exhibit that the detection of temperature diversifications as small as 1 °C is viable on micrometer-size areas, the usage of an easy CCD-based mostly optical detection system. in spite of everything, the usual thermal accuracy is proscribed to ca. 1 °C due to the existence of a slender (0.5 °C-huge) thermal hysteresis loop in the thin movies of 1, and since of the moderate thermal disturbance brought about by using the presence of the SCO layer on the heating factor. compared to universal thermoreflectance concepts, the presence of the SCO thin movie entails a considerable enhance of the optical contrast (ΔR/R), which suggests an greater thermal sensitivity and detection limit round TSCO. figure 5c, d illustrate, respectively, the common temperature dependence of ΔR/R measured on a glass substrate lined with a 200-nm-thick movie of 1, and the thermal evolution of the corresponding thermoreflectance coefficient κ = d(ΔR/R)/dT. far from the spin-transition temperature, the linear model of ΔR/R, which is accounted for the usual thermal expansion and associated refractive index change, coincides with a thermoreflectance coefficient of κthR = −0.036% °C−1. As proven in Fig. 5d, a gigantic increase of κ is followed due to the spin transition. The thermoreflectance coefficient reaches a maximum value of κthR+SCO = −0.35% °C−1 at the transition temperature TSCO, i.e. the temperature sensitivity is found (at optimum) 10 times stronger compared to the accepted thermoreflectance. an identical gain when it comes to thermal sensitivity become evidenced on a lot of surfaces.

Fig. 5: Temperature decision and sensitivity.

a ON-state and OFF-state thermal transition curves recorded through optical reflectivity in a 1-µm-vast area of the SCO-covered glass substrate for three close values of the utilized electrical current (I = three.5, three.6, and 3.7 mA). b geared up by-product curves (dR/dTb vs. Tb) displaying a measurable temperature shift for the ON-states. These measurements demonstrate that surface temperature variations as small as 1 °C can be unambiguously decided. c general thermal evolution of ∆R/R (λ = 452 nm) measured on a pitcher substrate covered with a 200-nm-thick movie of 1. d Thermal evolution of the corresponding thermoreflectance coefficient described as κ = d(∆R/R)/dT. at the spin-transition temperature, the thermal sensitivity is discovered one order of magnitude better compared to the commonplace thermoreflectance. crimson strong strains correspond to the most useful healthy to the records using a sigmoidal feature.

regarding the temporal decision, their thermometer is intrinsically restricted by way of the thermally induced switching dynamics of the SCO molecules. From contemporary femtosecond optical spectroscopy measurements38, they be aware of that the thermally activated spin-state switching within the skinny films of 1, ruled by using the LS ↔ HS intramolecular energy barrier, occurs inside a few tens of nanoseconds. This time scale for this reason defines the intrinsic response time of the film, in terms of optical reflectivity change, to any version of temperature. An extra prolong between the temperature upward push in the gadget and the response of the thermometer can originate from the gradual propagation of heat in the SCO layer, whose thermal diffusivity is fairly low (DT = 2.6 × 10−7 m2 s−1)47. both numerical simulations32 and ultra-quick pump-probe measurements38 have validated that the thermalization of SCO (150–300 nm thick) films, following a pointy existing step or an extremely-short laser pulse, is achieved in <1 µs. the sort of temporal resolution is sufficient for probing a big range of dynamical phenomena, reminiscent of warmth diffusion strategies or for detecting brief heating hobbies. as an instance, Fig. 6a displays the time evolution of the optical reflectivity signal (ΔR/R), measured via a gated CCD digicam the usage of a standard pump-probe strategy, on a SCO-lined gold microwire, following the injection of sharp current pulses with periods starting from 10 to a hundred µs. (Supplementary Fig. 10 suggests the linked reflectivity photos.) near the spin-transition temperature (Tb = fifty five °C), a substantial boost of the optical reflectivity is accompanied on the wire, whereas the same scan carried out at Tb = 25 °C (sufficiently removed from TSCO) handiest suggests a barely perceptible increase of the reflectivity—exceptionally for brief excitations. This example as soon as once again demonstrates the sizeable profit in terms of (thermal) sensitivity arising from the SCO phenomenon. From the temperature evolution of the optical reflectivity measured within the OFF-state (I = 0), ΔR/R statistics acquired at fifty five °C may also be transformed into ΔT values. determine 6b depicts the temperature maps (ΔT) acquired at selected instances, following the application of a 50-µs-lengthy existing pulse. These measurements illustrate the outstanding achievement of imaging the floor temperature combining µm spatial and µs temporal decision. In Fig. 6c, the time evolution of the average temperature rise measured on the wire by means of their SCO-based mostly thermometer (statistics features) is in comparison to the temperature profiles deduced from time-resolved electrical resistance measurements37 (strong traces) for the three intervals of latest pulses. As proven in Fig. 6c, the results from these two experiments are in decent contract.

Fig. 6: Temporal resolution and sensitivity.

a Time evolution of the optical reflectivity (ΔR/R) measured on a SCO-covered gold microwire (1 mm × eight µm × 300 nm) at two selected base temperatures, Tb = 55 °C and Tb = 25 °C, following the injection of sharp 10, 50, and 100-µs-long existing pulses (32 mA). At 55 °C (close to the spin-transition temperature) the reflectivity trade is amplified through the SCO phenomenon, whereas the measurements at 25 °C depict the average thermoreflectance. b Temperature maps (ΔT) deduced from the ΔR/R images at Tb = fifty five °C at selected times, following a 50-µs-lengthy existing pulse. Scale bar, forty µm. c Time evolution of the regular temperature rise of the wire measured through their SCO-based thermometer. strong strains correspond to the temperature profiles deduced from time-resolved electrical resistance measurements.

when it comes to spatial resolution, their SCO-thin-movie thermometer, in accordance with the size of the a long way-field optical reflectivity, includes a diffraction-confined, sub-µm spatial decision. This become positively proven through the measurements conducted on silicon, for which Joule heating can be well resolved on a 1-µm-huge wire (Fig. 4d). To additional examine the capabilities of their thermometer, we've additionally conducted a series of measurements on wires with in fact nanometric dimensions on silicon substrates (Supplementary Fig. 11), wherein the temperature distribution could be mapped all the way down to 500-nm lateral decision, but with a reduced sign-to-noise ratio. This spatial resolution undoubtedly surpasses that viable by using IRT (see Supplementary Fig. 12), which is still probably the most generic method of thermal imaging. To achieve even more desirable spatial decision, it is worthwhile to point out that the optical suggestions may well be additionally monitored the use of SPM concepts reminiscent of close-box scanning optical microscopy (SNOM)32. anyway, as the SCO phenomenon is also accompanied by using a concomitant alternate of the mechanical, dielectric, and magnetic residences of the fabric, other procedures can be carried out to probe the thermal spin transition, as a substitute of optical readout. among them, quantitative AFM mechanical (young’s modulus) measurements48,forty nine will also be used to probe the temperature changes in the SCO-skinny-film thermometer, providing greater spatial decision, although on the detriment of the temporal decision and ease-of-use.


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