EP2948778A1 - Microscope having a multimode local probe, tip-enhanced raman microscope, and method for controlling the distance between the local probe and the sample - Google Patents
Microscope having a multimode local probe, tip-enhanced raman microscope, and method for controlling the distance between the local probe and the sampleInfo
- Publication number
- EP2948778A1 EP2948778A1 EP14703140.5A EP14703140A EP2948778A1 EP 2948778 A1 EP2948778 A1 EP 2948778A1 EP 14703140 A EP14703140 A EP 14703140A EP 2948778 A1 EP2948778 A1 EP 2948778A1
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- EP
- European Patent Office
- Prior art keywords
- tip
- sample
- distance
- microscope
- signal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q10/00—Scanning or positioning arrangements, i.e. arrangements for actively controlling the movement or position of the probe
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/02—Details
- G01J3/06—Scanning arrangements arrangements for order-selection
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
- G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q10/00—Scanning or positioning arrangements, i.e. arrangements for actively controlling the movement or position of the probe
- G01Q10/04—Fine scanning or positioning
- G01Q10/045—Self-actuating probes, i.e. wherein the actuating means for driving are part of the probe itself, e.g. piezoelectric means on a cantilever probe
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q20/00—Monitoring the movement or position of the probe
- G01Q20/04—Self-detecting probes, i.e. wherein the probe itself generates a signal representative of its position, e.g. piezoelectric gauge
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q30/00—Auxiliary means serving to assist or improve the scanning probe techniques or apparatus, e.g. display or data processing devices
- G01Q30/02—Non-SPM analysing devices, e.g. SEM [Scanning Electron Microscope], spectrometer or optical microscope
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q40/00—Calibration, e.g. of probes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
- G01Q60/02—Multiple-type SPM, i.e. involving more than one SPM techniques
- G01Q60/04—STM [Scanning Tunnelling Microscopy] combined with AFM [Atomic Force Microscopy]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
- G01Q60/10—STM [Scanning Tunnelling Microscopy] or apparatus therefor, e.g. STM probes
- G01Q60/16—Probes, their manufacture, or their related instrumentation, e.g. holders
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
- G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
- G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
- G01Q60/26—Friction force microscopy
Definitions
- the present invention generally relates to the field of local probe microscopy.
- Local probe microscopy or peak scanning microscopy, is based on the measurement of a physical quantity when scanning a tip at a very short distance from the surface of a sample.
- Local probe microscopy provides an image of the surface topography of a sample with a spatial resolution greater than the resolution of an optical microscope.
- AFM Atomic Force Microscopy
- STM Scanning Tunneling Microscope
- SFM Shear-Force Microscopy
- a tunneling microscope has an electrically conductive tip that collects the tunnel-generated electrical current when the tip is brought at a very short distance (between 0 and 5 nm) from the surface of a conductive sample.
- a STM generally comprises tunnel current control means based on nano-movement between the sample and the tip along the Z axis of the tip using a piezoelectric ceramic, the Z axis being generally transverse to the surface of the sample. The value of the positioning performed along the Z axis to control the tunnel current as a function of a scan of the XY tip is then representative of the evolution of the surface relief of the sample.
- Tunneling microscopy provides a surface topography image of sub-nanometric resolution.
- An STM requires a conductive tip, usually metal, nickel or tungsten. The application of the STM is, however, limited to conducting samples.
- Atomic Force Microscopy is based on the use of the repulsion and attraction forces between the atoms of the sample surface and the atoms of the nanoscale end of the tip.
- An atomic force microscope generally comprises a lever supporting a tip of silicon or silicon nitride, optionally covered with a metal deposit. Conventionally, the displacement of the tip is observed by measuring the deviation of a laser beam reflected on the lever of the tip. The distance between the end of the tip and the surface of the sample is controlled by a very fine detection of the attraction and repulsion regimes, so as to avoid contact between the tip and the surface.
- An AFM makes it possible to observe any type of sample.
- a friction force microscope comprises a resonant or vibrating local probe, generally comprising a piezoelectric oscillator (or resonator, generally in the form of tuning fork) in quartz on which is fixed a fine tip. Excited to its resonance frequency f 0 (between 15 and 30 kHz) by the application of an electrical signal to its terminals or by mechanical excitation, the resonator induces a vibration of the small amplitude peak ( ⁇ 1 nm) transversely to the Z axis of the tip.
- f 0 between 15 and 30 kHz
- the imaging mode consists of scanning the tip parallel to the surface of the sample and measuring the amplitude of the current resulting from the excitation, itself proportional to the amplitude of mechanical oscillation of the branches of the resonator.
- a tapered optical fiber or a metal tip Different types of tips are used for SFM: a tapered optical fiber or a metal tip.
- One of the limitations of friction force microscopy is that the distance between the tip and the surface of the sample is generally unknown, this distance usually being between twenty and a hundred nm. This distance is generally estimated by detecting the moment of contact between the tip and the sample, inducing the destruction of the end of the tip, which affects the spatial resolution.
- a friction force microscope makes it possible to map the surface topography of any type of sample, but provides a topography image with a spatial resolution in the relatively degraded XY plane because of oscillations of the tip.
- microscopes said to multimode local probe, which combine different modes of operation of local probe microscopy.
- this device does not make it possible to avoid contact between the tip and the surface of the sample and to precisely calibrate the distance between the end of the tip and the surface of the sample for a distance of less than 20 nm. , because of a quasi-total damping of the amplitude of oscillation of the branches of the tuning fork.
- a third electrode electrically connects the tip to a current-voltage converter for measuring the tunnel current between the tip and the surface of the sample covered with a thin layer of gold or diamond.
- This microscope makes it possible to independently measure the tunneling current and the lateral shear force at the same point on the surface of the sample.
- this configuration has the effect of drastically degrade the quality factor of the tuning fork (by a factor of ten) which reduces the sensitivity of the microscope in the friction force regime. There is thus a stiffening of the system which affects the regulation of the tip-sample distance, especially for a distance of less than twenty nanometers.
- near-field microscopy can be advantageously coupled to different analysis techniques.
- the Tip Enhanced Raman Spectroscopy (TERS) technique or nanoRaman, involves the coupling of a Raman spectroscopy apparatus with a local probe microscope equipped with a metal tip. noble or covered with a noble metal. An exaltation of the Raman signal emitted locally at a point on the surface of a sample is observed when the Raman spectrometer excitation laser beam is focused on the tip of the microscope tip in the near field approaching a few nanometers from the surface. of the sample, due to a local amplification of the electromagnetic field.
- TMS Tip Enhanced Raman Spectroscopy
- the tip-to-sample distance is usually regulated by an AFM, but the topographic resolution is then degraded given the layer of metal deposited on the tip, or thanks to a STM, but the need to regulate on the tunnel current only allows the TERS analysis of conductive samples. This makes the TERS technique very difficult to implement.
- a first difficulty is to bring the tip of the surface of the sample to a very small distance of a few nanometers only. Another difficulty is to control this very small distance when scanning the tip. Yet another difficulty is to avoid contact between the end of the tip and the surface of the sample, any contact is likely to damage the nanometer end of the tip.
- TERS Raman spectroscopy operating with a friction force type local probe to precisely control and calibrate the distance between the tip end and the surface of a sample in the distance range between 0 and about twenty nm, and preferably less than 10 nm, without involving contact between the end of the tip and the surface.
- One of the aims of the invention is to provide a multimode microscope with a local probe in which the distance between the end of the tip and the surface of the sample can be enslaved, in particular for a small distance, less than a few tens of nanometers.
- Another object of the invention is to propose a Raman spectroscopy apparatus exalted by a peak effect at a very small and regulated distance between the end of the tip and the surface of the sample.
- Yet another object of the invention is to provide a method of calibrating the distance between the end of a microscope tip with a local probe, in particular by friction force, and the surface of a sample, when this distance is between 0 and 10nm.
- the object of the present invention is to overcome the disadvantages of the local probe microscopes of the prior art and more particularly proposes a multimode local probe microscope comprising a resonator (preferably a quartz tuning fork) comprising a first input electrode and a second output electrode disposed on the resonator, excitation means adapted to generate a mechanical resonance in the resonator (the tuning fork), a metal or metallized tip having a nano-sized end, the tip being fixed on the resonator, means relative displacement between the resonator and a sample adapted to approach the end of the tip at a distance Z between 0 and 100 nm from the surface of the sample.
- a resonator preferably a quartz tuning fork
- said metal tip is electrically connected to said second output electrode, said second output electrode forming a common electrical contact point for collecting on the one hand a first electrical signal relating to frictional forces between the end of the tip and the surface of the sample and secondly, a second electrical signal relating to a tunnel current between the end of the tip and the surface of the sample
- the microscope comprises amplification means electrically connected at said second an output electrode, said amplification means being adapted to simultaneously amplify the first signal relating to the friction forces and the second signal relating to the tunnel current, processing means adapted to separately process the first signal relating to the forces of friction and secondly the second signal relating to the tunnel current, and control means adapted to regulate the distance Z between the end of the tip and the surface of the sample, in a first mode, according to the first signal representative of the frictional forces and respectively, in a second mode, as a function of the second signal relative to the tunnel current.
- the device makes it possible to regulate the distance Z between 0 and several tens of nanometers, while avoiding a mechanical contact between the end of the tip and the surface of the sample.
- the local probe microscope of the invention can simultaneously measure the frictional forces and the tunnel current, and can operate in a multi-mode mode: in a first mode, the friction forces are measured, while regulating the distance point -sample on the tunnel current; in another mode, the tunnel current is measured while regulating the tip-to-sample distance on the measurement of the frictional forces.
- the configuration of the local probe avoids connecting the metal or metallized tip to an external conductor wire to collect a signal representative of the frictional forces which makes the local probe less sensitive to external disturbances and makes it possible to maintain the quality factor of the resonator at a high value.
- the collection and amplification at the same summation point of a tunnel current signal and a signal representative of the frictional forces thus make it possible to improve the signal-to-noise ratio of these two signals.
- the multimode local probe microscope comprises:
- common amplification means of the two signals comprising a low noise preamplifier for simultaneously amplifying the current resulting from the excitation of the resonator and the tunnel current;
- the processing means comprise active or passive electronic filtering means connected to the second electrode, said filtering means being adapted to separate on the one hand the first signal relating to the frictional forces and on the other hand the second signal relating to the tunnel current as a function of their respective frequencies for subsequent control processing;
- the microscope comprises scanning means (in XY) of the tip relative to the surface of the sample;
- the tuning-fork quartz resonator (or resonant fork) having a first branch and a second branch, the first input electrode being disposed on the first branch and the second output being disposed on the second branch.
- the filtering means comprise a low-pass filter having a cut-off frequency at 10 kHz relative to the tunnel current, and a band-pass filter for passing a signal around f 0 relative to the friction and / or shear forces.
- the invention also relates to a peak-enhanced Raman microscope comprising a multimode local probe microscope according to an embodiment described, said Raman microscope comprising a Raman spectrometer, means for focusing an excitation laser beam on the end of the Raman microscope. the tip of the microscope, and means for detecting a Raman scattering signal generated by the sample in the vicinity of said tip.
- the peak-enhanced Raman microscope comprises means for triggering the detection of the Raman scattering signal and synchronization means connected on the one hand to the triggering means of the detection and on the other hand to the means regulating the distance Z between the tip and the sample, so as to synchronize said means for triggering the detection of the Raman scattering signal and said regulating means when approaching the tip at a distance ⁇ 0 - ⁇ predetermined.
- the invention also relates to a method for calibrating the distance Z between the surface of a sample and the end of the tip of a multimode local probe microscope according to one of the described embodiments, said calibration method comprising the following steps:
- said reference distance is greater than zero and less than or equal to 10 nm and preferably less than 5 nanometers.
- This calibration is performed on a conductive sample, then is transferable to any other type of semiconductor or insulating sample (such as glass).
- the local probe microscope comprises means for measuring a variation of at least one parameter of the resonator during the XY scan of said tip and processing means adapted to extract from said variation an image representative of the topography of the surface of the sample resolved spatially in XY.
- said measuring means also comprise means for measuring a tunnel current between the end of the tip and a point on the surface of a sample, when said tip end is placed at a non-zero distance to avoid any damage to said tip.
- the amplification means comprise a low noise preamplifier.
- the invention will find a particularly advantageous application in peak-excited Raman spectroscopy, in which a local probe microscope is coupled to a Raman spectrometer for Raman spectrometry measurements with nanoscale spatial resolution.
- the present invention also relates to the features which will emerge in the course of the description which follows and which will have to be considered individually or in all their technically possible combinations.
- FIG. 1 represents the electronic diagram of a tuning fork-type probe of a friction force and tunnel current detection microscope according to the prior art
- FIG. 2 diagrammatically represents a perspective view of a tuning fork-shaped probe of a friction force microscope according to one embodiment of the invention
- FIG. 3A represents the resonance amplitude of the resonator, in an exemplary embodiment of the invention, before compensation;
- FIG. 3B represents the resonance amplitude the resonator, after compensation;
- Figure 3C shows the corresponding phase of the resonator;
- FIG. 4 schematically represents the frequency distribution of signals respectively representative of a tunnel current and of a quartz resonator
- FIG. 5A represents an electronic diagram of a resonant local probe device according to a preferred embodiment of the invention
- Fig. 5B shows an electronic schematic of a resonant local probe device according to an alternative of the embodiment of Fig. 5A;
- FIG. 6 schematically represents a local probe of a multiple microscope according to the invention, operating on the detection of the friction forces and the tunnel current, at different distances from the surface of a sample;
- FIGS. 7A and 7B schematically represent the spatial resolution of a Raman spectrometry measurement when a local probe tip is located respectively in a far-field (7A) and in a near-field (7B) for a nano-Raman or TERS measurement ;
- FIG. 8 represents a timing diagram for controlling the tip-to-sample distance, in particular for measurements of the TERS type
- FIG. 9 illustrates an example of nano-Raman or TERS measurements for two different distances between the end of the tip and the surface of a sample.
- FIG. 1 schematically represents a probe of a friction type type local probe microscope, according to the prior art and its amplification electronic circuits, in a configuration where it is desired to capture a current (emission current of field or tunnel current) between the end of the tip and the surface of the sample.
- the probe shown here comprises a resonator 1 having a tuning fork shape which comprises a first branch 10 and a second branch January 1.
- the resonator 1 is a quartz crystal resonator analogous to a quartz resonator used in watchmaking.
- the probe comprises a metal point 4, for example gold, fixed on one of the branches 1 1 of the tuning fork so that a tapered end of the tip protrudes from the end of the branch 1 1, about a few tenths of a millimeter along the direction Z.
- a function generator 19 makes it possible to electrically excite the resonator 1 in the vicinity of its resonant frequency so that the branches of the tuning fork vibrate in the XY plane.
- a sample 5 rests on a conductive sample holder 7.
- a voltage source 20 makes it possible to apply a DC voltage to the sample 5.
- the probe comprises a first electrode 8 disposed on the first branch 10 and a second electrode 9 disposed on the second branch 1 1.
- the first electrode 8 and the second electrode 9 are electrically connected to an electronic circuit 12.
- the electronic circuit 12 makes it possible to amplify and convert into electric voltage the current resulting from the excitation of the resonator at its resonant frequency.
- the signal 13 at the output of the converter 12 can then be processed by an electronic system to extract signals (amplitude and phase) representative of the friction and / or shear forces between the probe 1 and the surface of the sample 5, when the probe is close to the surface of the sample 5.
- the tip 4 bonded to the branch 1 1 without electrical contact with the electrode 9, is connected to another electrical contact 14.
- An electric wire 15 connects the contact electrical 14 of the tip 4 to another amplification electronic circuit 17 can amplify a tunnel current that can be collected between the tip 4 and the sample 5 and provide a signal 18 at the output of the electronic circuit 17.
- the device of the prior art shown in FIG. 1 makes it possible, ideally under vacuum pressure conditions, to measure the tunnel current between the end of the tip 4 of the vibrating probe 1 and a polarized sample.
- the quality factor of a vibrating probe as shown in FIG. 1 is strongly degraded by the addition to the metal point of an electrical contact 14 and an additional wire. for the detection of the tunnel current, due to a stiffening of the probe and a greater mechanical dissymmetry of the resonator.
- a local probe microscope as shown in Figure 1 shows degraded results in friction force mode and is sensitive to ambient electromagnetic radiation.
- a second observation forming part of the present invention is that the device shown in FIG. 1 comprises two distinct pre-amplification electronic circuits 12 and 17.
- the probe of the prior art consisting of the resonator 1 and the tip 4 comprises three distinct electrical contacts: the first electrode 8, the second electrode 9 and the electrical contact point 14 on the tip 4.
- FIG. 2 diagrammatically represents a perspective view of a probe comprising a tuning fork resonator 1 according to one embodiment of the invention.
- the probe comprises a tuning fork, preferably made of quartz, a first electrode 8 being disposed on the first branch 10 and a second electrode 9, or output electrode being arranged on the second branch January 1.
- a tapered metal (or metallized) tip 4 is attached to the second leg 1 1 of the tuning fork.
- the tip 4 is for example glued to the second branch January 1, so that its tapered end protrudes from the end of the second branch a few tens to a few hundred microns.
- the tip 4 is formed or covered with a noble metal, preferably formed of a gold or silver wire.
- the tip 4 is in electrical contact with the second electrode 9 of the tuning fork.
- the tip 4 is not connected by a conductive wire to another electronic circuit, which avoids unsymmetrically increasing the probe and stiffening the vibrating probe, and thus retains an excellent quality factor for the tuning fork.
- the local probe shown in Figure 2 is particularly compact.
- FIG. 3A shows the amplitude resonance spectrum as a function of the frequency f (Hz) for a resonator mounted with a tip glued to the output electrode 9. For frequencies above the resonance frequency, the appearance is observed antiresonance resulting from parasitic capacitance.
- electronic compensation means for example a variable parallel capacitance, are added at the summation point of the circuit. electronic signal processing (see Figure 5A).
- Figures 3B-3C show the resonance spectrum after compensation (Fig. 3B amplitude spectrum and Fig. 3C in-phase spectrum respectively) of the resonator thus obtained. It is observed that the quality factor Q (ratio of the resonance frequency f 0 and the width at half the resonance) is not degraded, unlike a probe of the prior art as shown in FIG. .
- the second electrode 9 of the probe as shown in FIG. 2 simultaneously collects the tunneling current and a current resulting from the oscillation of the resonator, unlike a probe as represented in FIG. 1 in which these currents are collected. respectively on separate contact points.
- FIG. 5A shows an electronic schematic of a resonant local probe device according to a preferred embodiment of the invention.
- a voltage source 19 is connected to the electrodes 8 and 9 to excite the probe 1 in the vicinity of its resonance frequency (f 0 -25 kHz).
- a conductive line 21 makes it possible to transmit the excitation reference frequency to a synchronous detection system 27 ("lock-in").
- a sample 5 is based on a sample holder 7.
- a voltage source 20 makes it possible to apply a DC bias voltage of a few mV to some V, preferably fixed, to the sample 5.
- a preamplifier 25 (low-noise current / voltage converter and its resistor 26) is connected directly via a conductive line 22 to the output electrode 9 electrically connected to the metal point 4.
- a filter 34 for example a low-pass filter and a filter 33, for example a bandpass, are arranged at the output of the preamplifier 25. At the output of the filter 34, a signal representative of the filtered tunnel effect current of the 25 kHz signal is obtained. .
- the electronic circuit 28 comprises a digital acquisition card, comprising an internal real-time processor as well as high-resolution analog-digital (A / D or ADC) and digital-to-analog (N / A or DAC) converters.
- the electronic circuit 28 is driven by the computer 29 and provides respectively a first signal representative of the amplitude of the vibrating probe on a first output 41, a second signal representative of the phase of the vibrating probe on a second output 42 and a third signal representative of a current tunnel effect on a third output 43. All these signals are transmitted to a computer to build an image during a scan. Each of these three signals 41, 42, 43 may be chosen as variable for regulating the position of the tip 4 above the sample.
- a device based on the diagram of FIG. 5A thus makes it possible to manufacture a multi-mode microscope that can operate either in friction force mode, or in tunnel mode, or in a mode combining friction force and tunnel current, these two tools not interfering with each other.
- the electronic diagram of FIG. 5A makes it possible to simultaneously amplify the small signals of the tunnel current (between a few pA and nA) and the resonator by using a single preamplifier 25.
- the summing point of the amplifier is located before the preamplifier 25. , on the conductive line 22.
- This electronic device robust to ambient interference, can optionally add to this summation point an electronic circuit for compensating the antiresonance of the resonator, and possible compensation of the interference due to 50 Hz.
- the electronic circuit can be integrated closer to the local probe, directly into a so-called active multimode microscope head, to limit interference noise.
- the electronics of FIG. control controlling these nano-movements 30 may be connected to one of the three outputs 41, 42, 43 for regulation on one of the signals from the vibrating probe (amplitude or phase) or the tunnel current and a measurement of the other signal depending on the scanning of the probe on the surface of the sample.
- the device of FIG. 5A is based on the use of a single common electronic circuit connected to only two points of electrical contacts 8, 9 on the probe 1.
- a multimode microscope with local probe operating on the simultaneous detection on the one hand shear-force forces and on the other hand the tunnel current and on a distance control based on one or the other of these signals.
- the multi-mode local probe microscope of the invention can operate at atmospheric temperature and pressure.
- FIG. 5B represents an electronic diagram of a resonant local probe device according to an alternative embodiment of the invention, the same reference signs representing the same elements as in FIG. 5A.
- a conductive line 22 connects the output electrode 9 to a first filter 23 and a second filter 24.
- the first filter 23 is a bandpass filter centered around the frequency of the oscillator, for example at 25 kHz.
- the second filter 24 is a low-pass filter at the output of which is obtained a signal representative of the filtered tunnel current of the 25 kHz signal.
- the filters 23, 24 allow a decoupling of the respective bandwidths of the relative signals on the one hand to the vibrating probe and on the other hand to the tunnel current.
- a preamplifier 25 (low-noise current / voltage converter and its resistor 26) makes it possible to amplify a signal representative of the tunneling current between the tip 4 and the polarized sample 5, when the sample 5 is conductive or semiconductor.
- a real-time electronic circuit 28 comprising a digital acquisition card (internal real-time processor as well as high-resolution analog-digital (A / D or ADC) and digital-to-analog (D / A or DAC) converters) driven by a computer 29, provides respectively a first signal representative of the amplitude of the vibrating probe on a first output 41, a second signal representative of the phase of the vibrating probe on a second output 42 and a third signal representative of a current effect-tunnel on a third exit 43.
- FIG. 6 diagrammatically represents a local probe of a multimode microscope according to the invention, as described with reference to FIG. 2. It is sought to regulate the distance Z between the end of tip 4 and the surface of the sample 5 in real time.
- the main difficulty lies in the fact that the regulation distance Z 0 is not precisely known in shear-force mode. However, in some applications, particularly in peak-excited Raman spectroscopy, it is desired to bring the distance Z to a distance of less than or equal to about 5 nm to regulate precisely at this same distance, avoiding any contact between the end of the tip. 4 and the surface of the sample 5, even though the tip is vibrating in the XY plane.
- the device described in connection with FIGS. 2 and 5A makes it possible to simultaneously measure the signals of the friction force microscope (Shear-Force mode) and the tunnel current (STM mode) and to choose from regulate the position of the tip on the detection of friction forces and simultaneously view the tunnel current or vice versa.
- the calibration process comprises the following steps:
- a distance Z tun n ei by measuring the tunnel current on a reference conductive sample (selected from reference samples of different types: metallic, doped semiconductor, conductive glass);
- This regulation is then operational on any other sample of the same nature as the selected reference sample.
- the tunnel current calibration is performed on a conductive sample at a distance of a few nanometers for which a tunnel current is detected.
- a reference torque corresponding to a distance z.sub.z that is nonzero and a tunnel current l 0 is known .
- the reference amplitude value corresponding to this calibrated distance z tunn ei can then be used on another non-conductive sample (of the same nature as the selected reference sample), thus to enslave in Shear-Force mode the tip to a distance z tunn ei known with respect to the reference distance z 0 .
- FIGS. 7A-7B show the end of a probe tip 4 of a multimode local probe microscope as described with reference to FIGS. 2 and 5A, in the TERS application.
- An excitation laser beam 50 is focused on the surface of the sample 5.
- the end of the tip is at a distance Z from the surface of the sample greater than a few tens of nanometers, the detection the Raman signal is then called in the far field.
- the laser beam incident on the surface of the sample generates a Raman Si scattering signal.
- the spatial resolution Ri of a measurement of the Raman Si spectrometry signal is determined by the spatial extent of the laser beam 50 on the surface of the sample.
- This spatial resolution Ri is typically of the order of the wavelength of the laser beam.
- the tip 4 is approximated at a non-zero distance z 0 , corresponding to the near field.
- the laser excitation beam 50 generates in addition to the signal Si, an amplified Raman scattering signal S 2 in the vicinity of the end of the tip and the local surface of the sample.
- the Raman Si and S 2 spectrometry signals are superimposed and are detected simultaneously. However, it is observed that the intensity of the Raman S 2 signal in the near field is much greater than the intensity of the Raman Si signal in the far field.
- the Raman signal detected when the tip 4 approximated at a distance z 0 is therefore essentially representative of the surface of the sample locally around the end of the tip, on a surface of dimension R 2 .
- This phenomenon corresponds to the TERS effect of Raman exaltation by peak effect, which makes it possible to obtain a Raman signal of sub-nanometric spatial resolution.
- the tip of the microscope is a tip of noble metal, gold or silver.
- the device and method of the invention allow, by controlling tip-to-sample distance at an extremely small distance, to combine a friction force microscope with a Raman spectrometer to perform peak-exalted Raman spectroscopy measurements at a single point. controlled and low distance, which was out of reach of the previous devices without damaging the tip or the sample.
- the exaltation effect of the Raman signal is exponential as a function of the inverse of the distance Z: the smaller the distance Z, the higher the intensity of the Raman signal S 2 .
- An increase in the Raman signal of three orders of magnitude is observed when the distance between the end of the tip is between 1 and 30 nm.
- This exaltation of the Raman signal in the near field therefore requires a control extremely pushed the distance between a vibrating local probe and the surface of a sample.
- This control requires not only to approach the tip at a very small distance, but also to regulate this distance during the transverse vibration movements of the vibrating probe and while avoiding a destructive contact between the tip and the sample.
- Figure 8 schematically shows a timing chart for recording a nano-Raman signal.
- the sample-tip distance is slaved to a calibrated distance Z 0 by virtue of the calibration described in the invention, for example 30 nm .
- a second period T2 or At we exert a shift - ⁇ to bring the tip to a small but non-zero distance from the surface of the sample (- ⁇ is equal to -25, -20, -10 or -5 nm , for example).
- FIG. 9 represents the intensity of two Raman spectra of the same sample as a function of the wave number ⁇ (cm -1 ) respectively for two distances Z.
- a first spectrum Si is obtained for a regulation distance equal to Z 0 30 nm and a second spectrum S2 is obtained for a distance equal to Z 0 - ⁇ (15 nm). It is observed in the second spectrum S2 of the Raman emission lines characteristic of the probed molecules that do not appear on the first spectrum Si .
- This result illustrates the effect of exaltation of the Raman signal in the near field, when the tip is approached at a very small distance, but not zero, from the surface of the sample.
- the invention proposes a multimode local probe microscope which allows simultaneous measurements in friction force (Shear-force) and tunnel mode (STM) mode, the operation of one not affecting the other, at temperature and atmospheric pressure.
- This microscope has only two electrical contact points on the probe and preferably only one common preamplifier in a single electronic circuit comprising active or passive filters.
- This multimode local probe microscope makes it possible to very precisely regulate and calibrate the working distance between the tip and the surface of the sample, in particular for a very short distance, of the order of a few nanometers. This operation makes it possible to very effectively combine such a resonant local probe microscope with a Raman spectrometer, for the acquisition of spectrometry measurements. Raman exalted by tip.
- the amplification factor of the TERS Raman signal increases inversely with the decrease of the Z-distance, which makes it possible to obtain Raman TERS measurements presenting both unprecedented sensitivity and spatial resolution.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1350637A FR3001294B1 (en) | 2013-01-24 | 2013-01-24 | MULTIMODE LOCAL PROBE MICROSCOPE, RAMAN EXTENDED RAMAN MICROSCOPE AND METHOD FOR CONTROLLING THE DISTANCE BETWEEN THE LOCAL PROBE AND THE SAMPLE |
PCT/FR2014/050058 WO2014114860A1 (en) | 2013-01-24 | 2014-01-13 | Microscope having a multimode local probe, tip-enhanced raman microscope, and method for controlling the distance between the local probe and the sample |
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EP2948778A1 true EP2948778A1 (en) | 2015-12-02 |
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EP14703140.5A Withdrawn EP2948778A1 (en) | 2013-01-24 | 2014-01-13 | Microscope having a multimode local probe, tip-enhanced raman microscope, and method for controlling the distance between the local probe and the sample |
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US (1) | US9366694B2 (en) |
EP (1) | EP2948778A1 (en) |
JP (1) | JP6184521B2 (en) |
FR (1) | FR3001294B1 (en) |
WO (1) | WO2014114860A1 (en) |
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CN116699180A (en) | 2015-02-26 | 2023-09-05 | 沙朗特有限责任公司 | System and method for manufacturing a probe for a nanoelectromechanical system |
KR102097351B1 (en) | 2015-02-26 | 2020-04-06 | 살렌트, 엘엘씨 | Multiple integrated tips scanning probe microscope |
US10866273B2 (en) | 2016-03-09 | 2020-12-15 | Xallent, LLC | Functional prober chip |
US9616470B1 (en) * | 2016-09-13 | 2017-04-11 | International Business Machines Corporation | Cleaning of nanostructures |
US10663484B2 (en) | 2018-02-14 | 2020-05-26 | Xallent, LLC | Multiple integrated tips scanning probe microscope with pre-alignment components |
CN108970652B (en) * | 2018-05-24 | 2019-08-13 | 华中科技大学 | A kind of optical fibre embedded micro flow chip and detection device based on SERS detection |
CN109929748A (en) * | 2019-03-08 | 2019-06-25 | 东南大学 | The instrument platform of DNA sequencing is realized based on pinpoint enhanced Raman scattering spectrum technology |
KR102252266B1 (en) * | 2020-02-12 | 2021-05-14 | 서울대학교산학협력단 | rheometer |
CN111896776B (en) * | 2020-06-30 | 2021-10-22 | 中山大学 | Atomic force microscope probe and manufacturing method thereof |
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NL9301617A (en) * | 1993-09-17 | 1995-04-18 | Stichting Katholieke Univ | Measuring device for measuring the intensity and / or polarization of electromagnetic radiation, for determining physical properties of a preparation and for reading information from a storage medium. |
US5948972A (en) * | 1994-12-22 | 1999-09-07 | Kla-Tencor Corporation | Dual stage instrument for scanning a specimen |
JPH0989911A (en) * | 1995-09-22 | 1997-04-04 | Kared Karei & Mires Heines G Burgerrihen Rechts Mbh | Compound-oscillator scanning imager |
JPH10213749A (en) * | 1997-01-30 | 1998-08-11 | Canon Inc | Surface observing method by scanning type probe microscope |
JPH10267942A (en) * | 1997-03-26 | 1998-10-09 | Shimadzu Corp | Scanning probe microscope |
JP3671687B2 (en) * | 1998-08-28 | 2005-07-13 | 森 勇蔵 | Ultra-short pulse high voltage generator for scanning probe microscope |
JP4111867B2 (en) * | 2003-05-16 | 2008-07-02 | 日本電子株式会社 | Scanning probe microscope |
JP5504418B2 (en) * | 2008-07-07 | 2014-05-28 | 株式会社東芝 | Plasmon evaluation method and plasmon evaluation apparatus |
JP5270280B2 (en) * | 2008-09-19 | 2013-08-21 | 独立行政法人科学技術振興機構 | Signal light measurement system for near-field optical microscope |
JP5306015B2 (en) * | 2009-02-23 | 2013-10-02 | 株式会社堀場製作所 | Scanning probe microscope probe and scanning probe microscope |
JP5246667B2 (en) * | 2009-06-12 | 2013-07-24 | 独立行政法人理化学研究所 | Ultraviolet near-field optical microscopy and tip-enhanced Raman spectroscopy |
JP5298264B2 (en) * | 2010-03-23 | 2013-09-25 | 国立大学法人 筑波大学 | Heterodyne beat probe scanning probe tunneling microscope and method for measuring minute signal superimposed on tunneling current by this |
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2013
- 2013-01-24 FR FR1350637A patent/FR3001294B1/en not_active Expired - Fee Related
-
2014
- 2014-01-13 EP EP14703140.5A patent/EP2948778A1/en not_active Withdrawn
- 2014-01-13 WO PCT/FR2014/050058 patent/WO2014114860A1/en active Application Filing
- 2014-01-13 US US14/761,726 patent/US9366694B2/en not_active Expired - Fee Related
- 2014-01-13 JP JP2015554226A patent/JP6184521B2/en not_active Expired - Fee Related
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FR3001294A1 (en) | 2014-07-25 |
JP6184521B2 (en) | 2017-08-23 |
JP2016505144A (en) | 2016-02-18 |
US9366694B2 (en) | 2016-06-14 |
FR3001294B1 (en) | 2015-03-20 |
US20160003866A1 (en) | 2016-01-07 |
WO2014114860A1 (en) | 2014-07-31 |
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