Optical micro-nano antenna probes, probe components, nano-infrared spectrometers and scattering scanning near-field optical microscopes

Abstract

The present disclosure provides an optical micro-nano antenna probe, a probe assembly, a nano-infrared spectrometer, and a scattering type scanning near-field optical microscope. The optical micro-nano antenna probe includes a needle body and a composite layer, at least part of the surface of the needle body is covered by the composite layer; the composite layer includes a stacked first needle body covering layer and a second needle body covering layer, the first needle body covering layer is located between the needle body and the second needle body covering layer; the material of the first needle body covering layer includes an optical dielectric material; the material of the second needle body covering layer includes graphene. The optical micro-nano antenna probe of the present disclosure can be used as a nano-infrared spectrum probe for a nano-infrared spectrometer; it can also be used as a scattering type near-field optical microscope probe for near-field optical imaging. The optical micro-nano antenna probe of the present disclosure can be a scanning probe microscope probe that enhances the detection sensitivity of nano-infrared spectrum and near-field optical imaging.

Description

Technical Field

[0001] The invention relates to the field of sample detection, and in particular to an optical micro-nano antenna probe, a probe assembly, a nano-infrared spectrometer and a scattering-type scanning near-field optical microscope. Background Art

[0002] Nanoscale chemical structure characterization technology is one of the key technologies to reveal the relationship between the chemical structure of the material surface interface and its physical properties (mechanics, electricity, magnetism, acoustics, electrochemistry, etc.) (i.e., structure-activity relationship). Nanoscale infrared spectroscopy (nanoscale infrared, nanoIR) is one of the important means to achieve nanochemical structure characterization.

[0003] NanoIR spectroscopy technology combines infrared spectroscopy technology (which can provide "fingerprint" information of the chemical composition of samples) with scanning probe microscope (SPM, which can provide information on physical and chemical properties such as nanomechanics and electricity). By means of the interaction between focused infrared light and SPM probe-sample, the infrared spectrum of the sample in the nanometer region below the probe tip is provided, thereby obtaining information on the chemical composition of the region; further, imaging information on the spatial distribution of chemical components is obtained through scanning the probe or sample. NanoIR spectroscopy technology can be widely used in the chemical composition analysis of the surface and interface structures of samples such as polymers, organic and inorganic composite materials, biological samples, semiconductors, and nano-optical functional materials. The spatial resolution of its imaging can be better than 10 nanometers, which is much better than the spatial resolution of conventional infrared microscopes (> wavelength / 2, for example: ~5 microns, if the excitation wavelength is 10 microns).

[0004] Scattering-type scanning near-field optical microscopy (s-SNOM) is a technology that combines near-field optics and SPM technology. It modulates and demodulates the scattered light signal that varies with the tip-sample distance and extracts the near-field optical signal under the tip. s-SNOM has a wide range of applications in plasma (or phonon, exciton, magnon, etc.) polariton imaging. s-SNOM can be further combined with infrared spectroscopy to achieve nanoscale infrared spectroscopy, also known as nano-Fourier transform infrared spectroscopy (nano-FTIR), which is one of the nanoIR working modes.

[0005] The efficient interaction between light and the sample material system under the SPM tip, and the SPM probe's highly sensitive sensing of this interaction are the key to achieving highly sensitive nanoIR spectroscopy measurements, and are also the key to achieving highly sensitive s-SNOM measurements. The signal sensed by the probe can be the photoelectric field scattering signal under the tip (also called the near-field signal, corresponding to the active or passive s-SNOM measurement mode); it can also be other response signals such as the thermal expansion caused by the photoexcitation sample, the photoinduced force (Photo-induced Force) (depending on the probe working mode, it can be subdivided into contact mode AFM-IR 1,2 , PiFM in tapping mode 3 , PFIR in peak force tapping mode 4,5 wait)

[0006] In the related art, the probe used in the nano-infrared spectroscopy technology is usually a silicon-based probe with a metal coating, such as a silicon-based probe coated with a PtIr alloy coating or a silicon-based probe coated with an Au coating. Summary of the invention

[0007] The inventors have realized that the sensitivity of nano-infrared spectroscopy and the sensitivity and spatial resolution of scattering-type scanning near-field optical microscopes are directly related to the composition and structure of the probe. In particular, when the probe acts as an optical micro-nanoantenna, the probe has the ability to enhance the incident light field to the tip of the needle tip (i.e., near-field enhancement), and also has the ability to enhance the infrared light radiated by the sample in the nano-region below the needle tip (i.e., radiation enhancement), thereby significantly enhancing the sensitivity of nanoIR and s-SNOM.

[0008] The present disclosure provides an innovative SPM probe that can significantly enhance the sensitivity of nanoIR and s-SNOM. The SPM probe has the ability to effectively converge the incident infrared light field to the tip of the needle, thereby improving the sensitivity of nanoIR, and can also simultaneously enhance the ability of the sample in the nanoregion below the needle tip to radiate infrared light, thereby improving the sensitivity of s-SNOM.

[0009] In some aspects, the present disclosure provides an optical micro-nano antenna probe (e.g., an SPM probe with enhanced nanoIR and / or s-SNOM detection sensitivity), comprising a needle body and a composite layer, wherein at least a portion of the surface of the needle body is covered by the composite layer;

[0010] The composite layer comprises a first needle body covering layer and a second needle body covering layer, wherein the first needle body covering layer is located between the needle body and the second needle body covering layer;

[0011] The material of the first needle body covering layer includes dielectric materials for optics;

[0012] The material of the second needle body covering layer includes graphene.

[0013] In some embodiments, the composite layer covers the entire surface of the needle body.

[0014] In some embodiments, the first needle body covering layer is composed of a layer of optical dielectric material.

[0015] In some embodiments, the first needle body covering layer is composed of multiple optical dielectric material layers, and two adjacent optical dielectric material layers have different compositions.

[0016] In some embodiments, the first needle body covering layer is directly stacked with the second needle body covering layer. Direct stacking means that the first needle body covering layer is in direct contact with the second needle body covering layer without any intermediate layer between them.

[0017] The material of the first needle body covering layer, the material of the second needle body covering layer, and the composite layered structure are key to enhancing the sensitivity of nanoIR and s-SNOM detection. Experimental data show that the material of the first needle body covering layer and the material of the second needle body covering layer work together to unexpectedly improve the nanoIR and s-SNOM sensitivity of the probe.

[0018] In some embodiments, a periodic nanostructure is disposed on the composite layer. The nanostructure may be selected from nanoprotrusions, nanogrooves, or a combination thereof.

[0019] In some embodiments, the optical micro-nano antenna probe (eg, an SPM probe that enhances the detection sensitivity of nanoIR and / or s-SNOM) further includes an externally convex tip, which is protruded from the tip region of the composite layer.

[0020] In some embodiments, the protruding direction of the externally convex needle tip is the same as the direction pointed by the tip of the needle body.

[0021] In some embodiments, the tip of the external convex tip has a smaller radius of curvature than the tip region of the composite layer.

[0022] In some embodiments, the optical micro-nano antenna probe (eg, an SPM probe with enhanced nanoIR and / or s-SNOM detection sensitivity) further includes an inert layer that at least partially covers the non-tip region of the composite layer.

[0023] In some embodiments, the non-tip region of the composite layer refers to the region other than the tip region of the composite layer.

[0024] In some embodiments, the tip region of the composite layer refers to the apex of the composite layer tip and the region within a length L around it, where L=R-50R (eg, R-10R), and R is the radius of curvature of the composite layer tip.

[0025] In some embodiments, the optical dielectric material is selected from oxides, nitrides, carbides, hydroxides or combinations thereof of element M, and element M is selected from silicon, manganese, chromium, aluminum or combinations thereof. Based on the above technical solution, the second needle body covering layer has an improved bonding interface with the first needle body covering layer, and the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM is further improved.

[0026] In some embodiments, the optical dielectric material is selected from oxides of element M, and element M is selected from silicon, manganese, chromium, aluminum, or a combination thereof. Based on the above technical solution, the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM is further improved.

[0027] In some embodiments, the optical dielectric material is selected from nitrides of element M, and element M is selected from silicon, manganese, chromium, aluminum, or a combination thereof. Based on the above technical solution, the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM is further improved.

[0028] In some embodiments, the optical dielectric material is selected from carbides of element M, and element M is selected from silicon, manganese, chromium, aluminum, or a combination thereof. Based on the above technical solution, the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM is further improved.

[0029] In some embodiments, the optical dielectric material is selected from hydroxides of element M, and element M is selected from silicon, manganese, chromium, aluminum, or a combination thereof. Based on the above technical solution, the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM is further improved.

[0030] In some embodiments, the optical dielectric material is selected from SiC, SiO 2 、MnO、MnOOH、Mn 2 O 3 、MnO 2 , Mn 3 O 4 , Mn 2 O 5 、MnO 3 , Mn 2 O 7 , Mn 7 C 3 Cr 2 O 3or a combination thereof, with typical optical dielectric functions in references

[10] and

[14] . Based on the above technical solution, the material of the first needle body covering layer has surface properties suitable for the deposition and growth of the second needle body covering layer, so that the second needle body covering layer and the first needle body covering layer have an improved bonding interface, making the second needle body covering layer more complete and continuous, and the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM is further improved.

[0031] In some embodiments, the optical dielectric material is selected from MnO, MnOOH, MnO 2 , Mn 3 O 4 , Mn 2 O 5 、MnO 3 , Mn 2 O 7 , Mn 7 C 3 Based on the above technical solution, the material of the first needle body covering layer has surface properties suitable for the deposition of the second needle body covering layer, the second needle body covering layer has an improved bonding interface with the first needle body covering layer, the second needle body covering layer is more complete and continuous, and the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM is further improved.

[0032] In some embodiments, the optical dielectric material is Mn x O y , y / x=1~3.5. Based on the above technical solution, the material of the first needle body covering layer has surface properties suitable for the deposition of the second needle body covering layer, the second needle body covering layer has an improved bonding interface with the first needle body covering layer, the second needle body covering layer is more complete and continuous, and the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM is further improved.

[0033] In some embodiments, the optical dielectric material is MnO 2 . Based on the above technical solution, the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM has been further improved. Based on the above technical solution, the material of the first needle body covering layer has surface properties suitable for the deposition of the second needle body covering layer, the second needle body covering layer has an improved bonding interface with the first needle body covering layer, the second needle body covering layer is more complete and continuous, and the ability of the probe to enhance the detection sensitivity of nanoIR and s-SNOM has been further improved.

[0034] In some embodiments, the lateral surface of the needle body is completely covered by the composite layer.

[0035] In some embodiments, the Raman spectrum of graphene has the following characteristics: the ratio of the D peak to the G peak intensity is less than or equal to 1, for example, the ratio of the D peak to the G peak intensity is 0.01-1, for example, 0.1-0.2, for example, 0.2-0.3, for example, 0.3-0.4, for example, 0.4-0.5, for example, 0.5-0.6, for example, 0.6-0.7, for example, 0.7-0.8, for example, 0.8-0.9, for example, 0.9-1.0.

[0036] In some embodiments, the number of graphene layers is 1 to 10 layers, such as 1 to 5 layers, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 layers.

[0037] In some embodiments, the material of the needle body includes silicon, silicon nitride, silicon dioxide, or a combination thereof.

[0038] In some embodiments, the shape of the optical micro-nano antenna probe (eg, an SPM probe that enhances the detection sensitivity of nanoIR and / or s-SNOM) is conical (eg, a cone or a pyramid).

[0039] In some embodiments, the length of the optical micro-nano antenna probe (e.g., an SPM probe that enhances nanoIR and / or s-SNOM detection sensitivity) is 100 nanometers to 1000 micrometers, for example, 100 to 500 nanometers, for example, 500 to 1000 nanometers, for example, 1 to 10 micrometers, for example, 20 to 30 micrometers, for example, 40 to 50 micrometers, for example, 60 to 70 micrometers, for example, 80 to 90 micrometers, for example, 90 to 100 micrometers, for example, 500 nanometers-50 micrometers.

[0040] In some embodiments, the cross-sectional outer diameter of an optical micro-nano antenna probe (e.g., an SPM probe that enhances nanoIR and / or s-SNOM detection sensitivity) is 100 nanometers to 1000 micrometers, for example, 100 to 500 nanometers, for example, 500 to 1000 nanometers, for example, 1 to 10 micrometers, for example, 20 to 30 micrometers, for example, 40 to 50 micrometers, for example, 60 to 70 micrometers, for example, 80 to 90 micrometers, for example, 90 to 100 micrometers, for example, 500 nanometers-50 micrometers.

[0041] In some embodiments, the cross-sectional aspect ratio (ratio of length to cross-sectional radius) of an optical micro-nanoantenna probe (e.g., an SPM probe that enhances nanoIR and / or s-SNOM detection sensitivity) is 0.5-50, such as 1-25, such as 1-10, such as 2-5.

[0042] In some embodiments, the thickness of the first needle covering layer is 1 nm to 100 μm, for example 1 to 10 nm, for example 50 to 100 nm, for example 200 to 300 nm, for example 400 to 500 nm, for example 500 to 1000 nm, for example 1 to 10 μm, for example 20 to 30 μm, for example 40 to 50 μm, for example 60 to 70 μm, for example 80 to 90 μm, for example 500 nm-50 μm, for example 5 nm-2 μm.

[0043] In some embodiments, the thickness of the second needle covering layer is 0.1 nm to 100 nm, for example 0.1 to 0.5 nm, for example 0.5 to 1 nm, for example 1 to 2 nm, for example 2 to 3 nm, for example 3 to 4 nm, for example 4 to 5 nm, for example 5 to 6 nm, for example 6 to 7 nm, for example 7 to 8 nm, for example 8 to 9 nm, for example 9 to 10 nm, for example 0.3 nm to 7 nm.

[0044] In some embodiments, the radius of curvature of the tip of an optical micro-nano antenna probe (e.g., an SPM probe that enhances nanoIR and / or s-SNOM detection sensitivity) is 1 nm to 100 μm, for example, 1 to 10 nm, 20 to 30 nm, for example, 40 to 50 nm, for example, 60 to 70 nm, for example, 80 to 90 nm, for example, 100 to 200 nm, 300 to 400 nm, for example, 10 nm to 300 nm.

[0045] In some aspects, the present disclosure provides a method for preparing any of the above optical micro-nano antenna probes (e.g., an SPM probe that enhances nanoIR and / or s-SNOM detection sensitivity), comprising:

[0046] Providing a needle body;

[0047] forming a first needle body covering layer on at least a portion of the surface of the needle body;

[0048] forming a second needle body covering layer on at least a portion of the surface of the first needle body covering layer;

[0049] The material of the first needle body covering layer includes an optical dielectric material;

[0050] The material of the second needle body covering layer includes graphene.

[0051] In some embodiments, the step of forming a second needle body covering layer on at least a portion of the surface (such as the needle tip region) of the first needle body covering layer comprises the following operations:

[0052] Placing the needle body covered with the first needle body covering layer in a chamber having a graphene growth atmosphere, and forming a second needle body covering layer on the surface of the first needle body covering layer by chemical vapor deposition, wherein the material of the second needle body covering layer includes graphene;

[0053] Wherein, the optical dielectric material is selected from oxides, nitrides, carbides, hydroxides or combinations thereof of element M, and element M is selected from silicon, manganese, chromium, aluminum or combinations thereof;

[0054] The chamber is also provided with a deposition auxiliary agent, which is arranged in the upstream region or the same upstream region of the needle body covered with the first needle body covering layer. The material of the deposition auxiliary agent includes the element M 2 Oxides, hydroxides, carbides of element M 2 Same as element M.

[0055] In the above scheme, the application of the deposition auxiliary agent effectively improves the quality of the second needle body covering layer. After the deposition auxiliary agent is applied, the second needle body covering layer covers the needle body more completely, and has fewer defects and wrinkles. Without being limited by theory, the deposition auxiliary agent may provide a substance that helps the growth of the second needle body covering layer to the surface of the first needle body covering layer during the chemical vapor deposition process, so that the second needle body covering layer covers the needle body more completely, and has fewer defects and wrinkles.

[0056] In some aspects, the present disclosure provides a method for depositing a graphene layer on a surface of an optical dielectric material substrate, comprising:

[0057] Placing an optical dielectric material substrate in a chamber having a graphene growth atmosphere, and forming a graphene layer on a surface of the optical dielectric material of the substrate by chemical vapor deposition;

[0058] Wherein, the optical dielectric material is selected from oxides, nitrides, carbides, hydroxides or combinations thereof of element M, and element M is selected from silicon, manganese, chromium, aluminum or combinations thereof;

[0059] The chamber is also provided with a deposition auxiliary agent, which is arranged in the upstream region or the same upstream region of the needle body covered with the first needle body covering layer. The material of the deposition auxiliary agent includes the element M 2 Oxides, hydroxides, carbides of element M 2 Same as element M.

[0060] According to the flow direction of the airflow in the chamber and the position relative to the optical dielectric material substrate, the chamber is divided into upstream, co-streaming and downstream regions. The upstream region refers to the region that is closer to the air inlet end of the chamber than the optical dielectric material substrate along the airflow direction. The downstream region refers to the region that is farther away from the air inlet end of the chamber than the optical dielectric material substrate along the airflow direction. The co-streaming region refers to the region that is at the same distance from the optical dielectric material substrate to the air inlet end of the chamber along the airflow direction.

[0061] In some embodiments, the deposition aid is in the form of a powder or a porous body. The deposition aid in the form of a powder or a porous body has an increased specific surface area, which is beneficial for the volatilization of substances that are helpful for the growth of the second needle body covering layer.

[0062] In some embodiments, the surface area of ​​the deposition aid is more than 2 times, such as more than 5 times, such as more than 10 times, the area of ​​the optical dielectric material substrate to be deposited.

[0063] In some embodiments, the optical dielectric material includes: manganese oxide, manganese hydroxide, manganese carbide, or a mixture thereof.

[0064] In some embodiments, the material of the deposition aid includes manganese oxide, manganese hydroxide, manganese carbide, or a mixture thereof.

[0065] In some embodiments, the optical dielectric material includes: manganese dioxide; and the material of the deposition assistant includes: manganous oxide. Based on this solution, the quality of the second needle body covering layer is further improved.

[0066] In some embodiments, the graphene growth atmosphere includes: a carbon source gas and a reducing gas; optionally, also includes a carrier gas.

[0067] In some embodiments, the carbon source gas is selected from methane, ethylene, acetylene, or a combination thereof.

[0068] In some embodiments, the reducing gas is hydrogen.

[0069] In some embodiments, the carrier gas is an inert gas, such as argon.

[0070] In some embodiments, the temperature of the chemical vapor deposition method is 800-1200°C, for example 1000°C.

[0071] In some embodiments, the method of forming the first needle covering layer on the surface of the needle comprises: a physical deposition method, a chemical deposition method or a combination thereof.

[0072] In some embodiments, the method of forming the first needle body covering layer on the surface of the needle body comprises: magnetron sputtering, atomic layer deposition, thermal deposition, electrodeposition, chemical reaction generation, or a combination thereof.

[0073] In some embodiments, the method of forming the second needle covering layer on the surface of the first needle covering layer includes: chemical vapor deposition, arc discharge, epitaxial growth, or a combination thereof.

[0074] In some aspects, the present disclosure provides use of any of the above optical micro-nano antenna probes for emitting and / or receiving infrared light.

[0075] In some embodiments, the optical micro-nano antenna probe is used to emit and / or receive infrared light in the range of 300 to -270°C.

[0076] In some aspects, the present disclosure provides a probe assembly comprising

[0077] Optical micro-nano antenna probes; and

[0078] A sensing part, on which the optical micro-nano antenna probe is mounted, and the sensing part is used to conduct the signal (such as a mechanical signal, an electrical signal, a thermal signal, a magnetic signal and / or an optical signal) generated by the optical micro-nano antenna probe;

[0079] The optical micro-nano antenna probe is any one of the above items.

[0080] In some embodiments, the sensing portion is an optical fiber.

[0081] In some embodiments, the sensing portion is a microcantilever.

[0082] In some embodiments, the sensing portion is a tuning fork.

[0083] In some embodiments, the optical antenna probe is a scanning probe microscope probe, a scattering-type scanning near-field optical microscope probe, and a tip-enhanced infrared spectroscopy active probe.

[0084] In some aspects, the present disclosure provides a nano-infrared spectrometer, comprising the optical micro-nano antenna probe described in any one of the above items or the probe assembly described in any one of the above items;

[0085] Preferably, the nano-infrared spectrometer is a nano-infrared spectrometer based on a scattering-type scanning near-field optical microscope;

[0086] Preferably, the nano-infrared spectrometer is a nano-infrared spectrometer based on scanning probe microscopy to detect photothermal induced resonance of samples.

[0087] In some aspects, the present disclosure provides a scattering type scanning near-field optical microscope, comprising any one of the optical micro-nano antenna probes or any one of the probe assemblies described above. The working band of the scanning near-field optical microscope can be selected from: visible-near infrared, mid-infrared, far infrared, terahertz band, or a combination thereof.

[0088] In some embodiments, "comprising", "including" or "containing" may mean that the content is greater than zero, such as 1% or more, such as 10% or more, such as 20% or more, such as 30% or more, such as 40% or more, such as 50% or more, such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 100%. When the content is 100%, the meaning of "comprising", "including" or "containing" is equivalent to "consisting of...".

[0089] In some embodiments, % refers to % by weight.

[0090] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form an unambiguous range; and any lower limit can be combined with other lower limits to form an unambiguous range, and any upper limit can be combined with any other upper limit to form an unambiguous range. In addition, although not explicitly stated, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unambiguous range.

[0091] In the description of this article, it should be noted that, unless otherwise specified, "above" and "below" are inclusive of the number, and "several" in "one or several" means two or more.

[0092] The above summary of the invention is not intended to describe each disclosed embodiment or each implementation in the application. The following description more specifically illustrates exemplary embodiments. In many places throughout the application, guidance is provided through a series of embodiments, which can be used in various combinations. In each example, the enumeration is only used as a representative group and should not be interpreted as exhaustive.

[0093] Unless otherwise specified, the operations, steps, and tests described in this disclosure are performed at room temperature and pressure. However, the probe is not limited to use under room temperature and pressure. Known experiments show that the probe can maintain a stable morphology within the range of 300 to -270°C.

[0094] Terminology

[0095] If the following terms are used in this disclosure, they may have the following meanings.

[0096] The term "optical dielectric material" is a material with high optical transparency in the relevant wavelength region (i.e. low absorption coefficient): 1) There are optical crystals, usually single crystals, i.e. with a very wide range of microscopic order. Some of them are optically isotropic, while others exhibit pronounced anisotropic properties and birefringence, i.e. polarization-dependent refractive index. 2) Optical glasses, which have an amorphous microstructure and therefore usually have optically isotropic properties, have been used since the beginning of technical optics. 3) There are polymer materials with good transparency, which can be used in plastic optics. Many different optical properties may be relevant to the use of optical dielectric materials, such as: transparency, which is limited by residual light absorption and scattering; dispersion of the refractive index at relevant wavelengths through the wavelength dependence of the refractive index; possible anisotropic behavior and birefringence; nonlinear optical properties, such as nonlinear refractive index; thermo-optical properties, such as temperature dependence of the refractive index; thermo-mechanical properties, such as piezoelectric coefficient. In addition, there is a series of non-optical properties that may be relevant: chemical durability and resistance; density; mechanical hardness and fracture strength; ease of grinding and polishing.

[0097] The term "graphene" refers to a sp 2 A material in which hybrid connected carbon atoms are closely packed into a honeycomb lattice structure. Graphene can be selected from single-layer graphene, few-layer graphene, or a combination thereof.

[0098] The degree of defects in graphene can be determined by the following techniques: 1) Raman spectroscopy at 1350 cm -1 The D peak near represents sp 2 The out-of-plane vibration mode of hybridized carbon atoms is activated only when there are defects, and is usually used to determine the defect state of graphene; 2) High-resolution transmission electron microscopy is used to observe the lattice arrangement of graphene, and lattice distortion or lattice loss will occur at the defects; 3) Selected high-angle annular dark field imaging can be used to determine the integrity of graphene; etc.

[0099] The number of graphene layers can be determined by the following techniques: 1) Raman spectroscopy at ~1590 cm -1 The nearby G peak, sp 2 Hybridized carbon atom in-plane optical phonon E 2g The Raman spectrum is located at 2700 cm -1 The 2D peak nearby is located in the second-order Raman scattering, which is related to the inelastic scattering of two phonons with opposite momentum. The intensity ratio of the 2D peak to the G peak is greater than 2, which represents a single-layer graphene; equal intensity represents a double-layer graphene; the 2D peak intensity is less than the G peak, which represents multi-layer graphene; 3) Use a high-resolution transmission electron microscope to observe the graphene lattice and then determine the number of layers; etc.

[0100] The continuity of the graphene layer can be determined by the following techniques: 1) Using electrical methods to detect the conductivity of the probe after the surface graphene is coated; 2) Using micro-Raman spectroscopy to image the peak intensity distribution of the D peak, G peak and 2D peak to determine the uniformity (continuity) of the surface graphene quality; and so on.

[0101] The term "optical micro-nano antenna probe" refers to a probe whose tip has a radius of curvature of micrometer or nanometer size.

[0102] The term "micrometer scale" refers to 1-1000 micrometers, such as 1-10 micrometers, 3-7 micrometers, such as 5 micrometers, such as 10-100 micrometers, 30-70 micrometers, such as 50 micrometers, such as 100-1000 micrometers, such as 300-700 micrometers, such as 500 micrometers.

[0103] The term "nanoscale" refers to 0.1 to 1000 nanometers, for example 0.1 to 1 nanometer, for example 0.3 to 0.7 nanometers, for example 0.5 nanometer, for example 1 to 10 nanometers, 3 to 7 nanometers, for example 5 nanometers, for example 10 to 100 nanometers, 30 to 70 nanometers, for example 50 nanometers, for example 100 to 1000 nanometers, for example 300 to 700 nanometers, for example 500 nanometers.

[0104] The term "cantilever probe" refers to a probe assembly having a substrate, a micro-cantilever and an optical micro-nano antenna probe, wherein the optical micro-nano antenna probe is disposed on the cantilever. The micro-cantilever can be made of one or more silicon wafers or silicon nitride wafers of 100μm to 500μm long and 500nm to 5μm thick. A typical silicon micro-cantilever is about 100μm long, 10μm wide, and several microns thick. A typical substrate is made of a silicon wafer or silicon nitride wafer of about several millimeters in length and width and a sub-millimeter thickness. The probe can be used to measure various physical and chemical properties of the sample (such as nanomechanics, electricity, magnetism, acoustics, thermal, etc.).

[0105] The term "scattering type scanning near-field optical microscope" refers to a type of aperture-free near-field optical microscope with scanning function.

[0106] The term "nano-infrared spectroscopy technology" refers to the combination of infrared spectroscopy technology and scanning probe microscopy (SPM) technology, which provides infrared spectrum of samples in the nanometer region under the probe tip by means of the mechanism of action of infrared light and probe-sample or probe-sample-infrared radiation induced by external field. The measurement of nano-infrared spectrum involves the interaction of infrared light with the SPM probe-sample system, and the sensing of the interaction by the probe. In some embodiments, the sensing of the interaction by the probe can be light absorption, light scattering, temperature change, thermal expansion, photoinduced force, other responses of the material caused by the interaction of radiation, or changes in the infrared radiation of the sample due to changes in the external field.

[0107] Nano-infrared spectrometers include, for example, the following types:

[0108] 1) Nano-infrared spectrometer based on scattering-type scanning near-field microscopy (s-SNOM).

[0109] This type of microscope is also divided into two principles: active and passive. 6,7 A focused light source excites a metal or dielectric probe-sample system, and uses non-interference, homodyne interference, heterodyne interference or pseudo-heterodyne interference detection methods, and by modulating the probe-sample distance, the spectrum or single-wavelength scattering signal of the nanometer area sample under the needle tip is extracted from the total scattering signal by taking advantage of the change law of the scattered light of the needle tip-sample system with the distance between the needle tip and the sample. 8 ; Passive 9 It means that by applying non-optical external fields such as electric field, strain, thermal field, etc., the sample itself will radiate infrared light, and with the help of the enhanced scattering effect of the probe, the nano-resolution spectrum or single-wavelength scattering signal of the sample under the needle tip can be obtained. s-SNOM is suitable for nano-resolution optical and spectral imaging in various bands (including visible-infrared-terahertz bands).

[0110] 2) Nano-infrared spectrometer based on scanning probe microscopy (SPM) to detect changes in the probe-sample mechanical interaction caused by the interaction between the sample and light

[0111] That is, the pulsed laser is irradiated onto the probe-sample system, and the absorption intensity of the sample to light of different wavelengths is sensed by the forced vibration amplitude of the microcantilever probe, and then the infrared absorption spectrum of the sample in the nano-region under the needle tip is obtained by scanning the wavelength. SPM can be an atomic force microscope (AFM), and according to the difference in the AFM driving probe and the probe light response, it can be further divided into contact mode atomic force microscope-infrared spectroscopy (AFM-IR) with different working modes. 1,2 , Photoinduced force microscopy infrared spectroscopy (PiFM) 3 , Tapping AFM-IR, Peak Force Tapping Mode Infrared Spectroscopy (PFIR) 4,5 wait.

[0112] 3) Nano-infrared spectrometer for detecting other responses

[0113] Similar to the two nano-infrared spectrometers mentioned above, the nano-infrared spectrometer that detects other responses detects the response of the probe-sample under the action of infrared light or other external fields, such as: changes in photoinduced local stress, adhesion, carrier concentration, tunneling current, etc. of the sample, and changes in external fields such as electric field, magnetic field, and temperature that cause changes in thermal radiation of the sample.

[0114] The probe disclosed in the present invention can be used in any of the above-mentioned nano-infrared spectrometers, and exhibits the ability to enhance the convergence of infrared light to the bottom of the needle tip, and (or) enhance the ability to scatter the sample light signal under the needle tip to the far field.

[0115] The term "scanning probe microscope (SPM)" refers to a microscope that scans the surface morphology based on the interaction between the probe and the sample surface, and optionally measures one or more properties of the sample surface while scanning. The scanning probe microscope can be an atomic force microscope (AFM), a scanning tunneling microscope (STM), a shear force microscope (SFM), etc. SPM measures the morphology, mechanics, electricity, magnetism, electrochemistry and other physical and chemical properties of the sample surface with nano-resolution by scanning the probe or sample and using physical quantities such as interaction force or tunneling current as feedback signals through the interaction between the probe and the sample.

[0116] The term "probe-sample interaction" refers to bringing the probe tip close enough to the surface of the sample so that probe-sample interactions occur, such as attractive and / or repulsive forces, and / or various physical field-probe-sample interactions occur, such as the tip enhancing light scattering of the sample in the nano-region under its tip. The probe can be driven in a contact mode, intermittent contact / tapping mode, non-contact mode, pulsed force mode, and / or any lateral modulation mode. The interaction can be constant or periodic. The periodic interaction can be a sine wave or any arbitrary periodic waveform. Pulsed force mode and / or fast force line technology can also be used to bring the probe-sample interaction to a set point and then retract the probe.

[0117] The term "irradiation" refers to directing a radiation field onto an object (e.g., a surface of a sample, a probe needle, and / or an area of ​​probe-sample interaction). Irradiation may preferably include radiation in the infrared wavelength range. Irradiation may include any configuration of radiation sources, pulse generators, modulators, reflective elements, focusing elements, and any other radiation beam control or conditioning elements. The radiation source may be one of a variety of sources, including a thermal source or a Globar light source, a supercontinuum laser source, an optical frequency comb, a difference frequency generation, an optical parametric oscillator (OPO), a quantum cascade laser (QCL), nanosecond, picosecond and femtosecond laser systems, CO 2 A laser, a heated cantilever probe or other micro-heater, and / or any other source that produces a radiation beam. In a preferred embodiment, the light source emits an infrared laser.

[0118] The term "spectrum" refers to the measurement of one or more properties of a sample as a function of wavelength, or equivalently, as a function of wave number.

[0119] The term "optical response" refers to the result of the interaction of light with a sample. The optical response may include absorption of light, temperature increase, thermal expansion, photoinduced stress, reflection and / or scattering of light, or other responses of a material due to interaction with light.

[0120] The term "tip region" refers to the region having the smallest radius of curvature.

[0121] The references mentioned above are as follows, and the full texts of these references are cited here:

[0122] (1) Dazzi, A.; Prater, CBAFM-IR: Technology and Applications in Nanoscale Infrared Spectroscopy and Chemical Imaging. Chem. Rev. 2017, 117 (7), 5146–5173.

[0123] (2)Dazzi,A.;Prazeres,R.;Glotin,F.;Ortega,JMLocal InfraredMicrospectroscopy with Subwavelength Spatial Resolution with an Atomic ForceMicroscope Tip Used as a Photothermal Sensor.Opt.Lett.,OL 2005,30(18),2388–2390.

[0124] (3) Nowak, D.; Morrison, W.; Wickramasinghe, HK; Jahng, J.; Potma, E.; Wan, L.; Ruiz, R.; Albrecht, TR; Schmidt, K.; Frommer, J.; Sanders, DP; Park, S. Nanoscale Chemical Imaging by Photoinduced Force Microscopy. Science Advances 2016,2(3),e1501571.

[0125] (4)Wang,L.;Wang,H.;Wagner,M.;Yan,Y.;Jakob,D.S.;Xu,X.G.NanoscaleSimultaneous Chemical and Mechanical Imaging via Peak Force InfraredMicroscopy.Science Advances 2017,3(6),e1700255.

[0126] (5)Wang,H.;Janzen,E.;Wang,L.;Edgar,J.H.;Xu,X.G.Probing Mid-InfraredPhonon Polaritons in the Aqueous Phase.Nano Lett.2020,20(5),3986–3991.

[0127] (6)Ocelic,N.;Huber,A.;Hillenbrand,R.Pseudoheterodyne Detection forBackground-Free near-Field Spectroscopy.Appl.Phys.Lett.2006,89(10),101124.

[0128] (7)Hillenbrand,R.;Taubner,T.;Keilmann,F.Phonon-Enhanced Light–MatterInteraction at the Nanometre Scale.Nature 2002,418(6894),159–162.

[0129] (8) N.Quantitative Near-Field Phonon-Polariton Spectroscopy,1.Aufl.;Selected topics of semiconductor physics and technology;Verein zur des Walter Schottky Inst.der Techn.Univ.München e.V:Garching,2007.

[0130] (9)Weng,Q.;Komiyama,S.;Yang,L.;An,Z.;Chen,P.;Biehs,S.-A.;Kajihara,Y.;Lu,W.Imaging of Nonlocal Hot-Electron Energy Dissipation via ShotNoise.Science 2018,360(6390),775–778.

[0131] (10)Handbook Of Optical Constants Of Solids,Palik E(Ed),Maryland,Ap,1998.Chapter 11,Optical Properties of Nonmetallic Solids for Photon Energiesbelow the Fundamental Band Gap.

[0132] (11)M.N.Polyanskiy,"Refractive index database,"https: / / refractiveindex.info.

[0133] (12)Shah,S.I.;Zulfiqar;Khan,T.;Khan,R.;Khan,S.A.;Khattak,S.A.;Khan,G.Study of Structural,Optical and Dielectric Properties of α-MnO 2 Nanotubes(NTS).J Mater Sci:Mater Electron 2019,30(21),19199–19205.

[0134] (13)Kumar,A.;Kumar,M.;Singh,R.P.Study on Electronic,Magnetic,Opticaland Thermoelectric Properties of Manganese Oxide(MnO):DFT Based SpinPolarized Calculations.Optik 2021,241,167064.

[0135] (14)Hugel, J.; Carabatos, C. Band Structure and Optical Properties ofMnO. Solid State Communications 1986, 60(4), 369–372.

[0136] Beneficial Effects

[0137] One or more solutions of the present disclosure have one or more of the following beneficial effects:

[0138] 1. The probe disclosed in the present invention has the function of an SPM probe.

[0139] 2. The probe disclosed in the present invention can enhance the coupling efficiency between infrared light (e.g., wavelength 0.8 μm to 3000 μm, such as 0.8 μm to 1 μm, 1 μm to 10 μm, 10 μm to 100 μm or 100 μm to 3000 μm) and the probe (e.g., enhance the ability to converge infrared light to the bottom of the needle tip, that is, enhance the ability of the local optical electric field under the needle tip, enhance the infrared absorption intensity of the molecules under the needle tip, and / or enhance the ability of the needle tip to scatter infrared light).

[0140] 3. The probe disclosed in the present invention has the function of enhancing the convergence of infrared light to the needle tip, which can reduce the requirements for high-power infrared lasers, or improve the detection sensitivity at the same laser power.

[0141] 4. The probe disclosed in the present invention can be used for nano-infrared spectroscopy and optical imaging, showing a significant improvement in detection sensitivity.

[0142] 5. The probe disclosed in the present invention can also be used for some other purposes: such as measurement of luminescence properties such as nanoscale photoluminescence / electroluminescence; measurement of mechanical properties; measurement of electrical properties, etc.

[0143] 6. The preparation method of the probe disclosed in the present invention is simple and easy, has high repeatability, and is easy to mass produce.

[0144] 7. The composite layer disclosed in the present invention has high layer quality, the first needle body covering layer and the second needle body covering layer are well bonded, and the second needle body covering layer is complete, continuous, and has few defects. BRIEF DESCRIPTION OF THE DRAWINGS

[0145] Figure 1 Schematic diagram showing the products of each step when preparing cantilever probes in some embodiments;

[0146] Figure 2 A scanning electron microscope image of an optical micro-nano antenna probe of a cantilever probe of some embodiments is shown;

[0147] Figure 3 Crystalline MnO 2With some embodiments of the probe surface MnO 2 XRD patterns of layers

[0148] Figure 4 The Raman spectrum of the graphene layer of the optical micro-nano antenna probe of some embodiments is shown;

[0149] Figure 5 shows the infrared spectra of the optical micro-nano antenna probes of some embodiments;

[0150] Figure 6 A schematic diagram showing the working principle of a PFIR nano-infrared spectrometer used in some embodiments;

[0151] Figure 7 The infrared spectra obtained when the PFIR nano-infrared spectrometer used in some embodiments is equipped with different probes are shown;

[0152] Figure 8 A schematic diagram showing the working principle of an s-SNOM nano-infrared spectrometer used in some embodiments;

[0153] Fig. 9 The infrared spectra obtained when the s-SNOM nano-infrared spectrometer used in some embodiments is equipped with different probes are shown;

[0154] Fig.10 A schematic diagram showing a cantilever probe of some embodiments and a conductive performance test of the cantilever probe;

[0155] Fig.11 Showing the conductivity performance test curve of the cantilever probe of some embodiments;

[0156] Fig.12 Optical micro-nano antenna probes according to some other embodiments are shown;

[0157] Fig.13 A schematic diagram showing a chemical vapor deposition apparatus used in some embodiments when depositing a graphene layer;

[0158] Fig.14 Probe assemblies of some embodiments are shown. DETAILED DESCRIPTION

[0159] The embodiments of the present invention will be described in detail below in conjunction with the examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. If no specific conditions are specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0160] Figure 1A schematic diagram showing the intermediate products and final products of each step of the method for preparing a cantilever probe.

[0161] In a specific embodiment, the method for preparing a cantilever probe comprises the following steps:

[0162] (1) Providing a cantilever probe blank;

[0163] Figure 1 (a) shows a cantilever probe blank, which includes a cantilever 10 and a needle body 20 . The needle body 20 is disposed on one side surface of the cantilever 10 .

[0164] (2) forming a first needle body covering layer 31 on the surface of the needle body 20, and forming a first cantilever covering layer 103 on the surface 101 of the cantilever 10 on which the needle body 20 is disposed, wherein the materials of the first needle body covering layer 31 and the first cantilever covering layer 103 are optical dielectric materials;

[0165] Figure 1 (b) shows the product of step (2), the surface of the needle body 20 is covered with a first needle body covering layer 31, and the cantilever 10 is provided with a surface 101 of the needle body 20 covered with a first cantilever covering layer 103;

[0166] (3) forming a second needle body covering layer 32 on the first needle body covering layer 31, and forming a second cantilever covering layer 105 on the surface of the first cantilever covering layer 103, wherein the materials of the second needle body covering layer 32 and the second cantilever covering layer 105 each independently include graphene;

[0167] Figure 1 (c) shows the product of step (3), wherein the first needle body covering layer 31 is covered with the second needle body covering layer 32 , and the first cantilever covering layer 103 is covered with the second cantilever covering layer 105 .

[0168] (4) A reflective layer 104 is formed on the surface 102 of the cantilever 10 facing away from the needle body 20. The reflective layer may be a metal coating. The reflective layer is used to increase the reflectivity of the surface of the cantilever facing away from the needle body during detection, thereby improving the detection sensitivity.

[0169] Figure 1 (d) shows the product of step (4), where a reflective layer 104 is disposed on the surface 102 of the cantilever 10 facing away from the needle body 20 .

[0170] An optical micro-nano antenna probe according to an embodiment of the present invention is as follows: Figure 1As shown in (d). The optical micro-nano antenna probe 35 includes a needle body 20 and a composite layer 30 covering the needle body 20, the composite layer 30 includes a first needle body covering layer 31 and a second needle body covering layer 33, the second needle body covering layer 32 covers the surface of the first needle body covering layer 31, and the first needle body covering layer 31 is located between the needle body 20 and the second needle body covering layer 32. The material of the first needle body covering layer 31 includes an optical dielectric material; the material of the second needle body covering layer 32 includes graphene.

[0171] The following is a specific example to further illustrate the preparation method of a cantilever probe. Example 1 (Si@MnO 2 @Graphene)

[0172] 1) A SCANASYST-AIR probe from Bruker was provided as a cantilever probe blank. The cantilever probe blank includes a cantilever (made of silicon nitride) and a needle body (made of silicon). The cantilever extends from one side of the substrate, and the needle body is arranged on one side surface of the cantilever. The needle body is in the shape of a triangular pyramid, with a height (the distance from the tip of the needle body to the cantilever) of about 5.4 μm, and a radius of the tip of the needle body of about 10 nm.

[0173] The surface of the cantilever probe blank was cleaned by: a) acetone and anhydrous ethanol were ultrasonically treated for 5 minutes twice, and then rinsed with ultrapure water at 60°C and 25°C for 10 minutes; b) diluted HF solution (5 vol%) was soaked for 30 seconds, and then rinsed with ultrapure water for 15 minutes; c) 85°C NH 4 OH (based on 25% ammonia water): H 2 O 2 (Based on 30% mass concentration of hydrogen peroxide): H 2 O=1:2:7 (volume ratio) mixed solution for 15 minutes, then rinse with ultrapure water; d) soak in dilute HF solution for 30 seconds, then rinse with ultrapure water for 15 minutes; e) use 85℃ HCl (calculated as 37% concentrated hydrochloric acid): 2 O 2 (Based on 30% mass concentration of hydrogen peroxide): H 2 f) After washing with a mixed solution of O=1:2:7 (volume ratio) for 15 minutes, rinse with ultrapure water; f) blow dry with high-pressure high-purity argon gas and set aside.

[0174] 2) Using magnetron sputtering method, using 99.9% pure manganese dioxide (MnO 2 ) target, sputtered in a high-purity argon (99.999%) atmosphere, and covered the surface of the cantilever probe blank with a thickness of 100 nanometers. 2 layer, to obtain a layer covered with MnO 2 Layer the cantilever probe blank.

[0175] 3) The MnO-coated 2 The cantilever probe blank is further covered with a graphene layer.

[0176] Fig.13 (a) shows a schematic diagram of the chemical vapor deposition device of Example 1. The chemical vapor deposition reaction site is a tube furnace 123, which is placed horizontally and includes an air inlet end 121 and an air outlet end 122 that are arranged opposite to each other. 2 The cantilever probe blank 125 is located in the tube furnace 123, with the tip of the probe body pointing downward. 2 100 mg of a deposition aid 126 (the deposition aid in this embodiment is manganese oxide (MnO) powder) is placed 0.5 cm below the cantilever probe blank 125 of the layer.

[0177] During the chemical vapor deposition process, the composition and flow rate of the gas flow entering the tube furnace 123 are:

[0178] 99.999% pure methane, flow rate 10sccm;

[0179] 99.999% pure hydrogen, flow rate 50sccm;

[0180] 99.999% pure argon gas, flow rate 50 sccm.

[0181] During the chemical vapor deposition process, the temperature of the tube furnace was 1000°C and the deposition time was 3 minutes. After deposition, a cantilever probe covered with a composite layer was obtained, and the composite layer included MnO 2 layer and graphene layer.

[0182] 4) placing the cantilever probe covered with the composite layer obtained in step 3) in the chamber of an inductively coupled plasma etcher in a vacuum environment (10 -6 ~5×10 -6 mbar), the surface of the cantilever facing away from the needle body was cleaned to remove the graphene layer and MnO 2 layer and other impurities and contaminants, exposing the silicon nitride substrate of the cantilever.

[0183] 5) The product obtained in step 4) is placed in a vacuum coating machine, and a metal layer is plated only on the side of the cantilever that faces away from the needle body. A 10-nanometer-thick metal chromium layer is first plated on the side surface, and then a 90-nanometer-thick metal gold layer is plated. The cantilever probe of Example 1 is obtained.

[0184] Fig.10The schematic diagram of the cantilever probe of Example 1 is shown. As shown in the figure, the cantilever probe includes: a cantilever 10 and an optical micro-nano antenna probe 35 arranged on one side surface of the cantilever 10. The optical micro-nano antenna probe 35 includes a needle body 20 and a composite layer 30 covering the needle body 20, the composite layer 30 includes a first needle body covering layer 31 and a second needle body covering layer 33, the second needle body covering layer 32 covers the surface of the first needle body covering layer 31, and the first needle body covering layer 31 is located between the needle body 20 and the second needle body covering layer 32. The material of the first needle body covering layer includes MnO 2 The material of the second needle body covering layer includes graphene. The cantilever 10 includes a base 110 and a beam 120, and the beam 120 extends from one end of the base 110. The surface 101 of the cantilever provided with the optical micro-nano antenna probe is sequentially covered with a first cantilever covering layer 103 and a second cantilever covering layer 105 from the inside to the outside. The first cantilever covering layer 103 is connected to the first needle body covering layer 31, and the second cantilever covering layer 105 is connected to the second needle body covering layer 33. In this embodiment, the material of the first cantilever covering layer 103 is MnO 2 The material of the second cantilever cover layer 105 is graphene. A reflective layer is provided on the surface 102 of the cantilever facing away from the optical micro-nano antenna probe, and the reflective layer includes a chromium layer and a gold layer stacked in sequence from the inside to the outside.

[0185] Embodiments 2 to 4

[0186] The difference between Examples 2 to 4 and Example 1 is that the MnO 2 The positional relationship between the cantilever probe and the manganese oxide (MnO) powder in the tube furnace and other step parameters are the same as those in Example 1.

[0187] Fig.13 (b) shows a schematic diagram of a chemical vapor deposition apparatus of Example 2. In Example 2, the MnO 2 The cantilever probe blank 125 is placed with the needle body facing upward. 2 100 mg of deposition assistant 126 is placed 0.5 cm below the cantilever probe blank 125 of the layer.

[0188] Fig.13 (c) shows a schematic diagram of a chemical vapor deposition apparatus of Example 2. In Example 2, MnO 2 The cantilever probe 125 is placed with the needle body facing upward, covering the MnO 2 100 mg of deposition aid 126 was placed 2 cm upstream of the cantilever probe 125 .

[0189] Fig.13 (d) shows a schematic diagram of a chemical vapor deposition apparatus of Example 2. In Example 2, MnO 2 The cantilever probe 125 is placed downwardly, covering the MnO 2100 mg of deposition aid 126 was placed 2 cm upstream of the cantilever probe 125 .

[0190] Comparative Example 1

[0191] The difference between Comparative Example 1 and Example 1 is that step 3) is not performed, that is, 2 The cantilever probe blank of the layer is further covered with a graphene layer. Comparative Example 1 obtains a probe wrapped with manganese dioxide (Si@MnO 2 probe).

[0192] Comparative Example 2

[0193] Arrow TM NCPt model cantilever probe.

[0194] The cantilever probe blank includes a cantilever (made of silicon) and a conical needle body (made of silicon) arranged on one side of the cantilever. The height of the needle body is 10-15 μm, and the curvature radius of the needle body is less than 25 nanometers. The side surface of the cantilever with the needle body and the side surface facing away from the needle body are both coated with a platinum-iridium (PtIr) coating.

[0195] Comparative Example 3

[0196] NANOSENSORS TM Cantilever probe model PPP-NCSTAu.

[0197] The cantilever probe blank includes a cantilever (made of silicon nitride Si 3 N 4 ) and a conical needle body (made of silicon) arranged on one side of the cantilever. The height of the needle body is 10-15 μm, and the radius of curvature of the needle body is less than 50 nanometers. The side surface of the cantilever with the needle body and the side surface facing away from the needle body are both covered with a gold (Au) coating.

[0198] Analysis and testing

[0199] 1. Scanning electron microscopy analysis

[0200] The cantilever probe product of step (3) of Example 1 was analyzed by scanning electron microscopy using a HATACHI S-4800 microscope produced by Hitachi, Japan, with an accelerating voltage of 15KV. Figure 2 shown.

[0201] As shown in the figure, the graphene layer on the surface of the needle is relatively flat and continuous. There are no obvious structural defects or structural collapse in the photo, and the radius of curvature of the tip is no more than 100nm.

[0202] 2. XRD analysis

[0203] The intermediate product obtained in step (2) of Example 1 was subjected to X-ray diffraction analysis using a Rigaku Ultima-IV X-ray diffractometer from Rigaku Corporation of Japan.

[0204] Figure 3 Crystalline MnO 2 MnO on the probe surface 2 The XRD spectrum of the layer. Among them, the spectrum line (a) corresponds to a manganese dioxide crystal with good crystallinity; the spectrum line (b) corresponds to the intermediate product of step (2) of Example 1 (i.e., the layer covered with MnO 2 The spectral line (c) corresponds to the MnO in the XRD spectrum library. 2 Standard peak position (PDF#44-0141-MnO 2 ).

[0205] The instrument conditions for obtaining the spectrum line (a) are: voltage 35 KV, current 15 mA, slit width 10 mm, start and end angles 20-65 degrees, and scanning speed 10 degrees per minute.

[0206] The instrument conditions for obtaining the spectrum line (b) are: voltage 40 KV, current 30 mA, slit width 10 mm, start and end angles 20-65 degrees, and scanning speed 10 degrees per minute.

[0207] By comparing the spectra (a)-(c), we can see that for MnO with good crystallinity 2 The diffraction peak of the crystal (spectrum a) is very obvious in the corresponding detection band, and the peak position matches the standard peak position very well. 2 layer (spectral line b), under the conditions of larger voltage and current detection, MnO is still not detected 2 This indicates that the MnO 2 The manganese dioxide grain size in the layer is smaller or the crystallinity is lower.

[0208] 3. Raman spectroscopy analysis of optical micro-nano antenna probes

[0209] A microscopic laser Raman spectrometer (Renishaw inVia confocal Raman microscope) was used to perform Raman spectroscopy analysis on the optical micro-nano antenna probe of the cantilever probe of Example 1. The instrument parameters were set as follows: excitation wavelength 532nm, exposure time 10s, laser power 0.01mW, spot diameter 1.5μm. The Raman spectrum of the needle body surface was collected at the needle body. The Raman spectrum is as follows: Figure 4 As shown, the following information can be obtained from the figure:

[0210] (1) The characteristic peaks of graphene can be identified in the figure, including the peak at 1345.6 cm -1 The D peak is located at 1577.8cm -1 The G peak is located at 2693.2cm -1 2D peaks.

[0211] (2) The 2D peak reflecting the quality of graphene is obvious and sharp, while the D peak intensity reflecting the defects of graphene is low.

[0212] (3) The peak intensity ratio of the D peak to the G peak is 0.24, and the peak area ratio is 0.29. This ratio is relatively low, from which it can be inferred that graphene has relatively few defects.

[0213] (4) The peak intensity ratio of the 2D peak to the G peak is about 1.10, and the peak area ratio is about 2.06, from which it can be inferred that the number of graphene layers is about 2. (See Ferrari, A.C. Raman Spectroscopy as a Versatile Tool for Studying the Properties of Graphene. Nat. Nanotech. 2013, 8(4), 235-246)

[0214] 4. Analysis of infrared light absorption capability of optical micro-nano antenna probes

[0215] Raman spectroscopy was performed on the optical micro-nano antenna probe parts of the cantilever probes of Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3 using a Fourier transform infrared spectrometer (Thermo Fisher scientific Nicolet iN10). The instrument parameters were set as follows: the spectral range was 675-4000cm -1 ; Spectral resolution is 4cm -1 ; The selection area is 30×20μm. Infrared spectrum Figure 4 As shown. At 1200-4000cm -1 The average transmittance of infrared light in the wavelength range is calculated, and the results are shown in the following table:

[0216] Table 1

[0217] Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Coating <![CDATA[MnO 2 layer + graphene layer]]> <![CDATA[MnO 2 Layer]]> PtIr layer Au layer Average transmittance 3-8％ 65-70％ 75-85％ 60-68％

[0218] From the above data, it can be seen that under the same detection conditions, the probe portion of the cantilever probe of Example 1 has a much stronger ability to absorb infrared light than the probes of Comparative Examples 1 to 3. It can be inferred that the probe portion of the cantilever probe of Example 1 has a better ability to focus mid-infrared light.

[0219] 5. Infrared spectral analysis of nano-infrared spectrometer based on scanning probe microscope to detect the photothermal induced deformation of samples

[0220] The polycarbonate was subjected to nano-infrared spectroscopy analysis using a nano-infrared spectrometer based on a scanning probe microscope to detect the photothermal induced resonance of the sample. The nano-infrared spectrometer used in this embodiment includes an atomic force microscope (Bruker, Dimension Icon) and its optical-mechanical coupling components. The micrometer-scale coupling of the mid-infrared radiation beam and the AFM probe is achieved through a light guide module from a quantum cascade laser (QCL) to the AFM probe.

[0221] The schematic diagram of a typical nano-infrared spectrometer based on scanning probe microscopy to detect the photothermal induced resonance of the sample is shown below. Figure 6 As shown. The nano-infrared spectrometer includes a cantilever probe 600, an infrared light source 614, and a deflection detection system 630. The cantilever probe 600 includes a cantilever 610 and an optical micro-nano antenna probe 620. The optical micro-nano antenna probe 620 interacts with a preset area 606 of a sample 604. An infrared radiation beam 618 from an infrared light source 614 is used to irradiate a preset area 606 near the optical micro-nano antenna probe 620, and the infrared radiation beam 618 can interact with the preset area 606 and produce a detectable response. The deflection detection system 630 is an optical lever system for measuring the position, deflection, bending, and / or movement of the cantilever probe 600. In one detection, the wavelength of the infrared radiation beam 618 is tuned to the absorption band of the sample 106, and a portion of the infrared radiation beam 618 will be absorbed. The absorbed radiation can cause heating of the preset area 606, which in turn causes a temperature increase and thermal expansion of the preset area 606. The probe response is derived by measuring the deflection, oscillation, or force on the cantilever probe 600. By changing the wavelength emitted from the radiation source to a wavelength absorbed by another material component and measuring the probe response at multiple locations, the distribution of that component can be mapped. Measuring the probe response at multiple wavelengths will produce a spectrum representing the optical response of the specimen, or in certain cases an infrared absorption spectrum.

[0222] The cantilever probes of Example 1 and Comparative Example 3 were respectively configured in a nano-infrared spectrometer based on an atomic force microscope, and the polycarbonate samples were tested under the same laser power. The laser spectrum range was 1495-1965 cm -1 , spectral resolution 2cm -1 .

[0223] The infrared spectrum obtained is Figure 7 In the infrared spectra of Example 1 and Comparative Example 3, it is possible to -1The wave number position identifies the main characteristic peak of the sample (stretching vibration peak of C=O bond). In terms of intensity, the characteristic peak intensity of the nano-infrared spectrometer equipped with the probe of Example 1 is 5.23 times higher than that of the nano-infrared spectrometer equipped with the probe of Comparative Example 3.

[0224] The above experimental results indicate that the probe of Example 1 can be used for nano-infrared spectroscopy detection to obtain infrared spectroscopy data with higher sensitivity and intensity.

[0225] 6. Infrared spectrum analysis based on s-SNOM nano-infrared spectrometer

[0226] Scattering-type scanning near-field microscopy (s-SNOM) uses a focused radiation beam to excite an optical micro-nano antenna probe, and through modulation and demodulation of the needle tip and the reference mirror, the phase and amplitude of the near-field scattered light under the needle tip are extracted from the backscattered light, and single-wavelength imaging with nanoscale spatial resolution under the needle tip is obtained. At a certain point on the sample surface, scanning the wavelength can obtain a single-point infrared spectrum. If continuous light is used to illuminate the sample and the moving mirror is moved, the infrared absorption spectrum at a certain point on the surface can also be obtained.

[0227] A typical scattering scanning near-field optical microscope is as follows Figure 8 As shown. The scattering type scanning near-field optical microscope includes a light source 700, an optical micro-nano antenna probe 720, a beam splitter 724 and a detector 740. The light source 700 emits an incident light 722, and the incident light 722 is irradiated to a sample 726 near the optical micro-nano antenna probe 720 through the beam splitter 724. The scattered light (E nf ). Scattered light (E nf ) can be directed back to the beam splitter 724 and then output to the detector 740. In addition, the scattering type scanning near-field optical microscope can also be equipped with an interference system. In the interference system, the beam splitter 724 directs a portion 734 of the incident light 722 to the reference mirror 736, and a modulator 738 can be used to periodically modulate the reference phase of the reference mirror 736. A portion 734 of the incident light is reflected at the reference mirror 736 to form a reference radiation beam (E ref ), then the reference radiation beam (E ref ) is combined with the sample scattered light (E nf ) interfere with each other.

[0228] The scattering scanning near-field optical microscope used in this embodiment is the neaSNOM Microscope. For relevant information about the microscope, see Alonso-González, P.; Albella, P.; Schnell, M.; Chen, J.; Huth, F.; García-Etxarri, A.; Casanova, F.; Golmar, F.; Arzubiaga, L.; Hueso, LE; Aizpurua, J.; Hillenbrand, R. Resolving the Electromagnetic Mechanism of Surface-Enhanced Light Scattering at Single Hot Spots. Nat. Commun. 2012, 3(1), 1–7.

[0229] The cantilever probes of Example 1 and Comparative Example 2 were respectively placed in an s-SNOM nano-infrared spectrometer, and the silicon wafer was tested at the same laser power to test the ability of the probe to enhance the s-SNOM near-field signal. The light source was selected in D mode (at 1800-1850cm -1 Nearby), the optical power is 316μW. The test results are as follows:

[0230] Peak position Peak intensity Peak integrated area Example 1 <![CDATA[1839.5cm -1 ]]> 10366.9 <![CDATA[3.33×10 6 ]]> Comparative Example 2 <![CDATA[1814.7cm -1 ]]> 310.1 <![CDATA[1.53×10 5 ]]>

[0231] Fig. 9 The infrared spectrum curves obtained by the s-SNOM nano-infrared spectrometer equipped with the probes of Example 1 and Comparative Example 2 are shown. Compared with the cantilever probe of Comparative Example 2, the cantilever probe of Example 1 is used in the s-SNOM nano-infrared spectrometer, and the near-field optical signal intensity is 33.43 times that of Comparative Example 2, and the peak area is 21.76 times that of Comparative Example 2.

[0232] The above experimental results indicate that the probe of Example 1 can achieve higher sensitivity when used for nano-infrared spectroscopy detection and near-field optical measurement.

[0233] 7. Conductivity test

[0234] The conductive properties of the cantilever probe of Example 1 were tested using a semiconductor device testing probe station (Lake Shore Cryotronics, Inc, CRX-6.5K).

[0235] Conductivity test principle Fig.10As shown. The cantilever probe of Example 1 is placed in the test chamber of the CRX-6.5K probe station. The probe station is equipped with a first conductive probe 201 and a second conductive probe 102, the first conductive probe 201 contacts the graphene layer covered on the cantilever 120, and the second conductive probe 202 contacts the graphene layer covered on the substrate 110, and there is a step with a drop of 2.5μm between the substrate 110 and the cantilever 120. The distance between the first and second conductive probes (201, 202) is about 50μm. A voltage continuously varying between 1V and -1V is applied between the first and second conductive probes (201, 202) to detect the current at both ends of the probe contact.

[0236] Fig.11 The current-voltage spectrum of the reaction conductivity is shown. As shown in the figure, by applying a continuously changing voltage between 1V and -1V between the beam and the base of the graphene-coated probe to detect the current change, it is found that the current gradually decreases from 0.048A and continuously decreases to -0.049A. The above test shows that in the voltage range of 1V to -1V, the probe exhibits good conductivity similar to that of metal, which also proves that the graphene layer on the surface of the probe is completely and continuously coated.

[0237] Combined with the above analysis and test results, it can be seen that the optical micro-nano antenna probe disclosed in the present invention has one or more of the following beneficial effects:

[0238] (1) The optical micro-nano antenna probe has at least one of enhanced infrared light absorption capability, enhanced infrared light scattering capability, or enhanced infrared localized optical electric field;

[0239] (2) Optical micro-nano antenna probes are used in photothermal-induced nano-infrared spectrometers to obtain enhanced infrared signals with high sensitivity;

[0240] (3) Optical micro-nano antenna probes are used in s-SNOM nano-infrared spectrometers to obtain enhanced infrared signals with high sensitivity;

[0241] (4) The graphene layer on the surface of the optical micro-nano antenna probe has fewer defects;

[0242] (5) The graphene layer on the surface of the optical micro-nano antenna probe is complete and continuous.

[0243] (6) The optical micro-nano antenna probe has the general functions of an ordinary scanning probe.

[0244] Without being limited by theoretical limits, the above technical effects may be achieved attributable to one or more of the following features:

[0245] (1) It may be attributed to the material of the first needle body covering layer, the material of the second needle body covering layer and the composite layer structure;

[0246] (2) This may be attributed to the specific composite layer preparation process.

[0247] Fig.12 Optical micro-nano antenna probes according to some further embodiments of the present disclosure are shown.

[0248] Fig.12 (a) shows an optical micro-nano antenna probe. A periodic nanostructure 91 (such as a grating structure) is further arranged on the second needle cover layer 32 of the optical micro-nano antenna probe 35. The optical micro-nano antenna probe 35 has improved detection sensitivity.

[0249] In some embodiments, the periodic nanostructure is selected from: periodic nanoprotrusions, periodic nanogrooves, or a combination thereof.

[0250] Fig.12 (b) shows an optical micro-nano antenna probe, and the optical micro-nano antenna probe 35 also includes an outer convex needle tip 92. The outer convex needle tip 92 is convexly arranged in the area where the second needle body covering layer 32 covers the tip of the needle body 20, and the protruding direction of the outer convex needle tip 92 is the same as the direction pointed by the tip of the needle body 20. The outer convex needle tip 92 can prevent the second needle body covering layer 32 from being worn. The outer convex needle tip 92 can be made of carbon material.

[0251] In some embodiments, the outer convex needle tip 92 has a smaller radius of curvature than the area where the second needle body covering layer 32 covers the tip of the needle body 20, that is, the outer convex needle tip has a higher sharpness. Therefore, the optical micro-nano antenna probe 35 can improve the spatial resolution of various nano-physical and chemical properties.

[0252] Fig.12 (c) shows a cantilever probe, which includes a cantilever 10 and an optical micro-nano antenna probe 35 arranged on one side surface of the cantilever 10. A metal reflective layer 93 is arranged on the side surface of the cantilever 10 facing away from the optical micro-nano antenna probe 35. The optical micro-nano antenna probe has improved detection sensitivity.

[0253] Fig.12(d) shows an optical micro-nano antenna probe, which also includes an inert layer 94. The non-tip region of the second needle body covering layer 32 is covered by the inert layer 94. The non-tip region refers to the region other than the tip region of the second needle body covering layer 32. The tip region of the second needle body covering layer 32 refers to an inert layer that is, for example, non-electrically active, or, for example, non-electrochemically active. The inert layer 32 may be a polymer layer. The optical micro-nano antenna probe 35 can be used in a liquid environment, for example, for in-situ electrochemical testing in an electrode / electrolyte interface system. In the electrochemical test, since the second needle body covering layer 32 is covered with an inert layer 94 at other locations except near the tip of the needle body 20, the interference of other locations on the electrochemical reaction near the tip of the needle body 20 is reduced, thereby improving the detection accuracy. The optical micro-nano antenna probe 35 is suitable for in-situ scanning electrochemical microscopy and infrared spectroscopy testing of electrochemical reaction interfaces in a liquid environment.

[0254] Fig.14 Probe assemblies of some embodiments are shown.

[0255] Fig.14 (a) shows a probe assembly of some embodiments. The probe assembly includes a sensing portion 140 and an optical micro-nano antenna probe 145. In this embodiment, the sensing portion 140 is a tuning fork 141. The tuning fork 141 can conduct mechanical signals such as vibration.

[0256] Fig.14 (b) shows a probe assembly of some embodiments. The probe assembly includes a sensing portion 140 and an optical micro-nano antenna probe 145. In this embodiment, the sensing portion 140 is a cantilever 142. The cantilever 142 can conduct force signals, such as atomic force signals.

[0257] Fig.14 (c) shows a probe assembly of some embodiments. The probe assembly includes a sensing portion 140 and an optical micro-nano antenna probe 145. In this embodiment, the sensing portion 140 is an optical fiber 143. The optical fiber 143 can transmit optical signals.

[0258] Although some specific embodiments of the present disclosure have been described in detail by way of example, it should be understood by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the present disclosure. It should be understood by those skilled in the art that the above embodiments may be modified without departing from the scope and spirit of the present disclosure. The scope of the present disclosure is defined by the appended claims.

Claims

1. A probe assembly, comprising an optical micro-nano antenna probe and a sensing portion, The optical micro-nano antenna probe is arranged on the sensing part, and the sensing part is used to transmit the signal generated at the optical micro-nano antenna probe, and the sensing part is a micro-cantilever, an optical fiber or a tuning fork; The optical micro-nano antenna probe comprises a needle body and a composite layer, and at least a portion of the surface of the needle body is covered by the composite layer; The composite layer comprises a first needle body covering layer and a second needle body covering layer stacked together, wherein the first needle body covering layer is located between the needle body and the second needle body covering layer; The material of the first needle body covering layer includes an optical dielectric material; The material of the second needle covering layer includes graphene.

2. The probe assembly according to claim 1, wherein: The composite layer is provided with a periodic nanostructure.

3. The probe assembly according to claim 1, wherein: The optical micro-nano antenna probe further comprises an outwardly convex needle tip, and the outwardly convex needle tip is convexly arranged at the tip region of the composite layer.

4. The probe assembly according to claim 3, wherein: The optical micro-nano antenna probe has one or more of the following features: - the protruding direction of the outer convex needle tip is the same as the direction pointed by the tip of the needle body; The tip of the outer convex needle tip has a smaller radius of curvature than the tip region of the composite layer.

5. The probe assembly according to claim 1, wherein: The optical micro-nano antenna probe further includes an inert layer, which at least partially covers a non-tip region of the composite layer.

6. The probe assembly according to claim 1, wherein: The optical dielectric material is selected from oxides, nitrides, carbides, hydroxides or combinations thereof of element M, and element M is selected from silicon, manganese, chromium, aluminum or combinations thereof.

7. The probe assembly according to claim 1, wherein: The optical dielectric material is selected from SiC, SiO2, MnO, MnOOH, Mn2O3, MnO2, Mn3O4, Mn2O5, MnO3, Mn2O7, Mn7C3, Cr2O3 or a combination thereof.

8. The probe assembly according to claim 1, wherein: The optical dielectric material is selected from MnO, MnOOH, Mn2O3, MnO2, Mn3O4, Mn2O5, MnO3, Mn2O7, Mn7C3 or a combination thereof.

9. The probe assembly according to claim 1, wherein: The optical dielectric material is manganese dioxide.

10. The probe assembly according to claim 1, wherein: The lateral surface of the needle body is completely covered by the composite layer.

11. The probe assembly according to claim 1, wherein: The Raman spectrum of the graphene has the following characteristics: the ratio of the D peak to the G peak intensity is less than 1.

12. The probe assembly according to claim 1, wherein: The number of layers of the graphene is 1 to 10.

13. The probe assembly according to claim 1, wherein: The number of layers of the graphene is 1 to 5.

14. The probe assembly according to claim 1, wherein: The material of the needle body includes silicon, silicon nitride, silicon dioxide or a combination thereof.

15. The probe assembly according to claim 1, wherein: The optical micro-nano antenna probe has one or more of the following features: -The optical micro-nano antenna probe has a conical shape; -The length of the optical micro-nano antenna probe is 100 nanometers to 1000 micrometers; - the thickness of the first needle body covering layer is 1 nanometer to 100 micrometers; - the thickness of the second needle body covering layer is 0.1 nanometers to 100 nanometers; -The curvature radius of the tip of the optical micro-nano antenna probe is 1 nanometer to 100 micrometers.

16. The probe assembly according to claim 1 or 15, wherein: The optical micro-nano antenna probe has one or more of the following features: -The shape of the optical micro-nano antenna probe is a cone or a pyramid; -The length of the optical micro-nano antenna probe is 500 nanometers to 50 micrometers; - the thickness of the first needle body covering layer is 5 nanometers to 2 micrometers; - the thickness of the second needle body covering layer is 0.3 nanometers to 7 nanometers; -The curvature radius of the tip of the optical micro-nano antenna probe is 1 nanometer to 300 nanometers.

17. The probe assembly according to claim 1, wherein: The probe assembly has one or more of the following features: - A first needle covering layer is provided on one side of the micro-cantilever on which the optical micro-nano antenna probe is provided; - A second needle covering layer is provided on one side of the micro-cantilever on which the optical micro-nano antenna probe is provided; - A third needle body covering layer is covered on a surface of the micro-cantilever facing away from the optical micro-nano antenna probe, and the material of the third needle body covering layer includes metal.

18. The probe assembly according to claim 17, wherein: The metal is selected from gold, platinum, chromium, titanium, aluminum or a combination thereof.

19. A method for preparing an optical micro-nano antenna probe, wherein the optical micro-nano antenna probe is the optical micro-nano antenna probe in the probe assembly according to any one of claims 1 to 18, the method comprising: Providing a needle body; forming a first needle body covering layer on at least a portion of the surface of the needle body; forming a second needle body covering layer on at least a portion of the surface of the first needle body covering layer; The step of forming a second needle body covering layer on at least a portion of the surface of the first needle body covering layer comprises the following operations: Placing the needle body covered with the first needle body covering layer in a chamber having a graphene growth atmosphere, and forming a second needle body covering layer on the surface of the first needle body covering layer by chemical vapor deposition, wherein the material of the second needle body covering layer includes graphene; Wherein, the optical dielectric material is selected from oxides, nitrides, carbides, hydroxides or combinations thereof of element M, and element M is selected from silicon, manganese, chromium, aluminum or combinations thereof; In which, a deposition aid is also provided in the chamber, and the deposition aid is provided in the upstream area or the same upstream area of ​​the needle body covered with the first needle body covering layer. The material of the deposition aid includes oxide, hydroxide and carbide of element M2, and element M2 is the same as element M.

20. The method according to claim 19, wherein: The deposition aid is in the form of powder or porous body.

21. The method according to claim 19, wherein: The optical dielectric material includes: manganese oxide, manganese hydroxide, manganese carbide or a mixture thereof; The material of the deposition assistant includes: manganese oxide, manganese hydroxide, manganese carbide or a mixture thereof.

22. The method according to claim 19, wherein: The optical dielectric material includes: manganese dioxide; The material of the deposition assistant includes manganous oxide.

23. The method according to claim 19, wherein: The graphene growth atmosphere includes: a carbon source gas and a reducing gas.

24. The method according to claim 23, wherein: The graphene growth atmosphere also includes a carrier gas.

25. The preparation method according to claim 19, wherein The preparation method has one or more of the following characteristics: - A method for forming a first needle body covering layer on the surface of the needle body comprises: a physical deposition method, a chemical deposition method or a combination thereof; - A method for forming a first needle body covering layer on the surface of the needle body comprises: magnetron sputtering, atomic layer deposition, thermal deposition, electrodeposition, chemical reaction generation, or a combination thereof; The method of forming the second needle covering layer on the surface of the first needle covering layer comprises: chemical vapor deposition method, arc discharge method, epitaxial growth method, or a combination thereof.

26. A nano-infrared spectrometer or a scattering scanning near-field optical microscope, comprising the probe assembly according to any one of claims 1 to 18.

27. The nano-infrared spectrometer or the scattering type scanning near-field optical microscope according to claim 26, wherein: The nano-infrared spectrometer is a nano-infrared spectrometer based on a scattering type scanning near-field optical microscope.

28. The nano-infrared spectrometer or the scattering type scanning near-field optical microscope according to claim 26, wherein: The nano-infrared spectrometer is a nano-infrared spectrometer based on scanning probe microscopy to detect the photothermal induced resonance of the sample.

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