TW201213898A - Fiber probe and detecting system having same - Google Patents

Abstract

The disclosure relates to a fiber probe. The fiber probe includes a fiber and a carbon nanotube composite film. The carbon nanotube composite film can include a carbon nanotube film structure and a plurality of metallic particles. The carbon nanotube film structure can be located on an end of the fiber. The carbon nanotube film structure can include a plurality of carbon nanotubes. The metallic particles can be located on surfaces of the carbon nanotubes.

Description

201213898 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a fiber optic probe and a sensing system having the same. [Prior Art 3 [0002] A sensing system composed of a surface-enhanced Raman scattering technique and an optical fiber combination has potential application value in chemical, biological, and environmental monitoring due to its flexible portability. Previous sensing systems included a fiber optic probe that was formed by physically or electrochemically depositing silver particles at a probe end of a conventional fiber optic. The physical or electrochemical method includes an electric ore, a steaming bell or a sputtered honey or the like. The fiber optic probe undergoes plasmon resonance absorption on the surface of the captured metal particles under the excitation of the incident optical field, so that the local electromagnetic field between the particles is enhanced, thereby causing the Raman signal of the molecules adsorbed on the probe to be enhanced. [0003] The silver particles in the fiber optic probe are directly plated on the surface of the detecting end to form an integral structure with the detecting end. When the skein particles are to be removed, the structure of the detecting end is usually destroyed, thereby destroying the structure. The structure of the fiber Ο. Therefore, when the silver iridium is damaged to render the fiber optic probe inoperable, the fiber optic probe is difficult to reuse because the silver particles are difficult to remove. SUMMARY OF THE INVENTION It is necessary to provide a fiber optic probe having high sensitivity and reusable fiber and a sensing system having the fiber optic probe. A fiber optic probe comprising an optical fiber and a carbon nanotube composite film. The nano-tube composite membrane comprises a carbon nanotube membrane structure and a plurality of metal particles. The carbon carbon film structure is disposed on the outer surface of one end of the fiber, the nemesis 099131440 Form No. A0101 Page 3 of 36 0992055105-0 [0005] 201213898 The carbon tube membrane structure comprises a plurality of carbon nanotubes. The plurality of metal particles are disposed on the surface of the plurality of carbon nanotubes. A fiber optic probe includes an optical fiber, a carbon nanotube film structure, and a metal layer. The fiber includes a probe end. The carbon nanotube membrane structure is disposed on an outer surface of the probe end of the optical fiber. The carbon nanotube membrane structure includes a plurality of carbon nanotube membranes. The metal layer is disposed on a surface of the carbon nanotube film structure, and the metal layer is composed of a plurality of metal particles. A sensing system includes a transmitting module, a fiber optic probe, and a receiving module. The transmitting module emits a light beam to the filled fiber optic probe. The fiber optic probe scatters a beam of light emitted by the transmitting module at an end of the fiber optic probe to form scattered light, and transmits the scattered light to the receiving module. The receiving module collects scattered light scattered from the fiber optic probe to form a Raman spectral feature map. The fiber optic probe includes

A fiber and a carbon nanotube composite film. The carbon nanotube composite membrane comprises a carbon nanotube membrane structure and a plurality of metal particles. According to the nano-charcoal structure, the Dilu membrane structure is disposed on the outer surface of one end of the fiber, and the nano-woven tube is combined with a number of carbon nanotubes. The plurality of metal particles are disposed in a plurality of nanometers * wood $ carbon tube table

[0008] The carbon nanotube film is structurally formed with a film of the carbon nanotube film structure without being directly plated on the end of the fiber. Therefore, when the ya particles are damaged or contaminated by adsorption of the sample to be fresh, α removes the metal particles 2 in a manner other than the carbon nanotube composite film, thereby destroying the structure of the optical fiber, thereby enabling the optical fiber to be reused. 099131440 [Embodiment] Form No. Α0101 Page 4/36 pages °"2〇551〇5.〇201213898 - The present invention provides a sensing system including a transmitting cymbal, a fiber optic probe and a Receive module. The bird mask _] the transmitting module emits to the fiber optic probe - the beam illuminates a -sample to be tested adsorbed on the fiber optic probe to form a scattered light of the sample to be tested at the fiber optic probe. The light beam is a strong light source having a small frequency and having a solid and a frequency, such as argon ions. Preferably, it is longer in the coded nanometer ~514.5 nm. It is preferably green light with a wavelength of 514.5 nm, and the green light of 514 5 nm has a large scattered light intensity at the same power. More scattered light can be formed from the pair. The Qing (four) county collects the scattered light of the Langshu domain to detect the Raman spectral feature of the sample to be tested. Specifically, the received module can be directly connected to the domain probe. The receiving mode 2 is a multi-channel photon detection device such as a digital detector, such as a photomultiplier tube. The vibration mode of the molecule or functional group of the sample to be tested and its corresponding bifurcation functional group can be read from the Raman spectral characteristic map. The sample to be tested may be a solid sample (such as a sample powder, a solid particle to which a sample is adsorbed, etc.), a liquid sample (such as a droplet of an internally dissolved sample component, a molten sample, etc.) or a gaseous sample. When the sample to be tested is in a gaseous state, the detecting end of the fiber optic probe can be directly placed in the environment in which the gaseous sample is located. 'The vapor molecules of the sample to be tested are greater than ten in the air. 0. I. When the sample to be tested is a solid sample dissimilar sample, the detecting end of the fiber optic probe is generally in direct contact with the sample to be tested. When the sample to be tested is a JUH sample or a liquid sample 099131440, Form No. A0101 0992055105-0, page 5 / page 36, 201213898, the detection end of the fiber optic probe may also be close to the sample to be tested, at this time, The sample to be tested has a certain degree of volatility, has its vapor around it and the content of the vapor molecules of the sample to be tested in the air is greater than one part per billion. [0013] The fiber optic probe includes an optical fiber and a carbon nanotube composite film disposed on an outer surface of one end of the optical fiber. [0014] The optical fiber may select a single mode fiber or a multimode fiber. The optical fiber includes a detecting end and a detecting end, and the detecting end and the detecting end are opposite ends of the optical fiber. The shape of the detecting end is not limited. Preferably, the detecting end is a cylinder. The detecting end is optically connected to the receiving module for transmitting data in the optical fiber to the receiving module. The carbon nanotube composite membrane is disposed on an outer surface of the detecting end of the optical fiber. Preferably, the carbon nanotube composite membrane completely covers the outer surface of the detecting end. [0015] The carbon nanotube composite membrane comprises a carbon nanotube membrane structure and a metal layer disposed on a surface of the carbon nanotube membrane structure. [0016] The carbon nanotube film structure includes a plurality of carbon nanotubes formed on a surface of the detecting end. The plurality of carbon nanotubes may be substantially perpendicular to the surface of the probe end to form an array of carbon nanotubes. The plurality of carbon nanotubes may also be at an angle to the surface of the probe end. The plurality of carbon nanotubes may also be substantially parallel to the surface of the probe end, i.e., the plurality of carbon nanotubes are substantially parallel to the surface of the carbon nanotube membrane structure. Preferably, the plurality of carbon nanotubes are connected by Van der Waals attract-i v e f o r c e to form a self-supporting structure. The so-called "self-supporting" means that the carbon nanotube film structure does not need to be disposed on a substrate surface, 099131440 Form No. A0101 Page 6 of 36 0992055105-0 201213898 Also, the moon has its own specific shape. Because of the self-supporting smear, a large number of carbon nanotubes in the 冓 冓 相互 相互 相互 相互 相互 相互 相互 相互 相互 相互 相互 相互 相互 相互 凡 凡 凡 凡 凡 凡 凡 凡 凡 凡 凡 凡 ° ° ° ° ° ° ° ° ° ° ° [0018] When the carbon nanotube membrane structure is a self-supporting structure, the carbon nanotube membrane is a membrane-like structure formed by at least one nanometer carbon film, when the carbon nanotube When the structure comprises a plurality of carbon nanotube membranes, the plurality of carbon nanotube membranes are stacked, and the phase _ nanocarbon (four) is combined by van der Waals force. Referring to FIG. 1 , the carbon nanotube film can be a carbon nanotube flocculation membrane, and the 75-meter carbon nanotube flocculation membrane is a self-supporting naphthalene obtained by flocculation treatment of a nano tube. The carbon nanotube film ◊ The carbon nanotube film comprises a carbon nanotube intertwined and uniformly distributed. The length of the carbon nanotubes is greater than i0 micrometers, and Ο is preferably from 200 micrometers to 900 micrometers so that the nanotubes are entangled with each other. The carbon nanotubes are attracted to each other by van der Waals forces to form a network structure. Because of this, the carbon nanotubes in the self-supporting carbon nanotube flocculation film are attracted to each other and entangled by van der Waals force, so that the carbon nanotube film has a specific shape and forms a self-supporting shape. structure. The carbon nanotube flocculation membrane is isotropic. The carbon nanotubes in the carbon nanotube film are uniformly distributed and randomly arranged to form a large number of gaps or micropores having a size ranging from 1 nm to 500 nm. The gap or micropores can increase the specific surface area of the carbon nanotube membrane and adsorb more samples to be tested. The carbon nanotube film can be a carbon nanotube hard film, and the nano carbon tube pressure film is obtained by arbitrarily recycling a carbon nanotube array with a self-supporting 099131440 Form No. A0101 Page 7 / Total 36 pages 0992055105-0 [0019] 201213898 Sexual carbon nanotube film. The carbon nanotube barrier film comprises a carbon nanotubes uniformly distributed, and the carbon nanotubes are preferentially oriented in the same direction or in different directions. The carbon nanotubes in the na[iota] tube are partially overlapped with each other and are closely attracted to each other by van der Waals force, so that the carbon nanotube film has a good flexibility and can be twisted into Any shape without breaking. And because the carbon nanotubes of the carbon nanotubes of the county are attracted to each other, they are closely combined, so that the carbon nanotubes are a self-supporting structure. The carbon nanotubes of the carbon nanotubes are formed at an angle with the surface of the growth substrate forming the array of carbon nanotubes, wherein no angle is greater than or equal to 0 degrees and less than or equal to 15 degrees. In the pressure on the array of carbon nanotubes f, the greater the pressure, the smaller the angle. Preferably, the carbon nanotubes of the carbon nanotubes are arranged parallel to the growth substrate. (4) The membrane is obtained by obstructing the pressure-carbon nanotube array, and the nanocarbon in the carbon nanotube (four) membrane has different arrangement forms depending on the manner of rolling. Specifically, the carbon nanotubes can be arranged in disorder; please refer to FIG. 2 'When the hair is made in different directions', the carbon nanotubes are preferentially oriented in different directions, and the carbon nanotubes are fixed along the same direction. The direction of the preferred orientation extends. The length of the carbon nanotubes (four) of the carbon nanotubes ^ is greater than 50 micro-seeking. The area of the 玄I Xuan Nai carbon tube is basically the same as the size of the carbon nanotube array. The thickness of the carbon nanotube film is related to the height of the carbon nanotube array and the pressure at which the pressure is impeded, and can be between 1 and 10 μm. It can be understood that the smaller the height of the carbon nanotube array is, the smaller the pressure applied is, the larger the thickness of the prepared carbon nanotube tube waste film; on the contrary, the smaller the height of the carbon nanotube array, the more the applied pressure Large, then prepared carbon nanotubes under pressure 099131440 Form No. A0101 No. 8 1 / Total 36 pages 0992055105-0 201213898 Membrane, the smaller the thickness of the 1 nanocarbon among the adjacent = have a certain _, From the ^ nanocarbon tube barrier _ medium I 2 size between 1 nm to 5GG nm gap or micropores. The gate (four) micropores can increase the sample of the nanocarbon 24 to be more than the sample. Long and attached [0021]

The carbon nanotube film may be a nano-material, and the film is composed of a plurality of carbon nanotubes, and some of the ten-characteristics are too broken, and "冓." The general direction of the majority of the na[iota] in the direction of the length of the carbon nanotubes is substantially the same direction. The majority of the nanocarbon (4) extends in the direction of the base. . m [0022] Further, the carbon nanotubes are connected end to end by van der Waals force. Specifically, each of the carbon nanotubes in the majority of the carbon nanotubes that extend in the same direction in the same direction is connected to the inner tube in the extending direction by the van der Waals. Of course, there are a few nanocarbons in the carbon nanotube film that deviate from the extending direction. These carbon nanotubes do not form an obvious extension of the overall orientation of most of the carbon carbon in the carbon nanotube film. influences. The self-supporting carbon nanotube film does not require a large-area carrier support, and as long as the support force is provided on both sides, it can be suspended in the whole to maintain its own film state, that is, the carbon nanotube film is placed (or When fixed on two undulating bodies arranged at a certain distance, the carbon nanotube film located between the two supports can be suspended to maintain its own membranous state. The self-supporting is mainly realized by the presence of continuous 099131440 form number Α0101 page 9/36 pages 0992055105-0 201213898 carbon nanotubes extending through the end of the van der Waals force. Specifically, the plurality of carbon nanotubes extending substantially in the same direction in the carbon nanotube film are not absolutely linear and may be appropriately bent; or are not completely aligned in the extending direction, and may be appropriately deviated from the extending direction. . Therefore, it is not possible to exclude partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes extending substantially in the same direction. Specifically, the carbon nanotube film comprises a plurality of continuous and aligned carbon nanotube segments. The plurality of carbon nanotube segments are connected end to end by van der Waals force. Each carbon nanotube segment consists of a plurality of carbon nanotubes that are parallel to each other. The carbon nanotube segments have any length, thickness, uniformity, and shape. The carbon nanotube film has good light transmittance and the visible light transmittance can reach more than 75%. [0023] When the carbon nanotube film structure comprises a plurality of carbon nanotube film, the plurality of carbon nanotube films are laminated to form a layered structure. The thickness of the layered structure is not limited, and the adjacent carbon nanotube film is bonded by van der Waals force. Preferably, the layered structure comprises a carbon nanotube film having a layer number of less than or equal to 10 layers, so that the number of carbon nanotubes per unit area is small, and the Raman light intensity of the carbon nanotube itself is made strong. It is kept in a small range, thereby reducing the Raman peak intensity of the carbon nanotubes in the Raman spectrum. In this embodiment, the layered structure comprises a number of layers of the carbon nanotube film of less than or equal to 4 layers, so that the layered structure has a transmittance of more than 40%. The carbon nanotubes in the adjacent carbon nanotube film in the layered structure have an intersection angle α between the α and the α is greater than 0 degrees and less than or equal to 90 degrees. When the carbon nanotubes in the adjacent carbon nanotube film have an intersection angle α, the carbon nanotubes in the composite carbon nanotube film are interwoven to form a network structure. The mechanical properties of the carbon nanotube membrane structure are increased. It can be understood that when 099131440 Form No. Α0101 Page 10 / Total 36 Page 0992055105-0 201213898 The adjacent nano carbon 2 sample to be tested is a solution, the network structure is easy to make the solution attached to the surface of the carbon tube Droplet formation - (d) Dispersed solution film / easy to detect. At the same time, the "node" of the carbon nanotubes forming the network structure adheres to each other, and the adsorption of the sample is better, and more samples to be adsorbed can be adsorbed. In the embodiment, the carbon nanotube membrane structure is adsorbed. Including two layers: the carbon carbon is laminated, and the angle α between the carbon nanotubes in the adjacent carbon nanotube film is substantially equal to 90 degrees, that is, the extension of the carbon nanotubes in the tube film. The direction is roughly vertical

_] The metal layer is provided with a surface (or a surface) or two opposite surfaces. The metal layer can be formed by forming a metal material by electron beam plating or electron beam sputtering on the surface of the 'carbon nanotube film structure. A quartz crystal oscillator can be used to monitor the thickness of the metal layer. The metal material includes a transition metal or a noble metal, and preferably, the material of the metal includes one or more of gold, silver, copper, and palladium. The thickness of the metal layer is between approximately 45 nanometers and approximately 45 nanometers. [0025] Microscopically, the metal layer is disposed in the carbon nanotube film structure. . 'S 〆

a plurality of metal particles on the outer surface or a portion of the outer surface of the carbon nanotube. It can be understood that the carbon nanotubes exposed on the surface of the carbon nanotube membrane structure are provided with more metal particles on the outer surface thereof. The metal particles are quasi-spherical. It is to be noted that the maximum one-dimensional dimension of the metal particles extends substantially along the tube wall of the carbon nanotubes due to the non-wetting of the surface of the metal and the carbon nanotubes. Therefore, the diameter of the metal particles and the thickness of the vapor-deposited metal layer are not numerically corresponding to each other' and are slightly larger than the thickness of the metal layer. However, the thicker the thickness of the metal layer, the larger the particle size of the metal particles. For example, when the thickness of the gold layer is approximately 1 nm to 50 099131440, the form number Α0101 page 11 / total 36 苋 0992055105-0 201213898 nanometer 'the particle size of the metal particles in the metal layer is 5 Nano to 50 nm. The interparticle spacing between the plurality of metal particles is generally between 1 nm and 15 nm. That is, the plurality of metal particles are spaced apart to form a plurality of gaps between the plurality of metal particles, the gap having a distance of substantially between 1 nm and 15 nm. In this embodiment, the interparticle distance is between about 2 nm and 5 nm, and the particle size of the metal particles is between about 18 nm and 22 nm. Of course, it is not excluded that a very small portion, such as a metal particle having a particle size of more than 50 nm or less than 5 nm, does not exclude a very small portion, such as a particle spacing of more than 15 nm. The carbon nanotube composite film may further include a buffer layer disposed between the carbon nanotube film structure and the metal layer. The buffer layer may be formed before the metal layer is formed on the surface of the carbon nanotube film structure. The buffer layer has a thickness of between about 10 nm and about 1 nm. Preferably, the buffer layer has a thickness of between about 15 nm and 30 nm. Microscopically, the buffer layer covers part or all of the surface of the carbon nanotube membrane in the carbon nanotube membrane structure. At this time, the metal layer is disposed at the retardation layer away from the nanocarbon. The surface of the tubular membrane structure, rather than being disposed directly on the surface of the carbon nanotube. The buffer layer isolates the metal particles from the carbon nanotubes and prevents electron transfer between the metal particles and the carbon nanotubes. At the same time, by providing the buffer layer, the metal particles have a relatively uniform deposition surface, and the metal particles are evenly distributed in all directions, so that the uniformity of the radius of curvature of the metal particles is better, thereby making the metal particles closer. The spherical shape increases the electromagnetic field enhancement coefficient and the Raman enhancement coefficient of the fiber optic probe. It can be understood that when the carbon nanotube composite film does not include a buffer layer, the metal particles are directly disposed on the carbon nanotubes along the 099131440 form number A0101 page 12 / 36 pages 0992055105-0 201213898 nano carbon The long axis radius of the tube growth direction is large. The material of the buffer layer includes an inorganic oxide material such as cerium oxide or magnesium oxide. [0027] The preparation method of the carbon nanotube composite membrane is not limited as long as a plurality of metal particles capable of enhancing the Raman signal can be formed on the surface of the carbon nanotube membrane structure. For example, the carbon nanotube composite film can be formed by first forming the carbon nanotube film structure on the outer surface of the detecting end, and then forming a plurality of metal particles on the surface of the carbon nanotube film structure. . When the carbon nanotube film structure is a non-self-supporting structure, it may be formed on the outer surface of the detecting end by coating, in-situ growth or the like. When the carbon nanotube film structure is a self-supporting structure, the carbon nanotube composite film may be directly disposed on the outer surface of the detecting end of the fiber optic probe by winding or adhesion. When the carbon nanotube composite membrane is wound at least two turns at the detecting end, a plurality of layers of carbon nanotube composite membranes are disposed on the detecting end. When the carbon nanotube composite membrane is wound one turn at the detecting end, only one layer of the carbon nanotube composite membrane is disposed on the detecting end. The carbon nanotube composite film may be attached to the detecting end only by van der Waals force, or may be bonded to the detecting end by a bonding agent. Specifically, since the carbon nanotube composite membrane includes a plurality of carbon nanotubes having a large specific surface area and a very small size, the carbon nanotube composite membrane may have a large specific surface area, and at this time, the nanometer The carbon tube composite film can directly adhere to the outer surface of the detecting end by its own adhesion. [0028] Compared with the conventional fiber optic probe, the fiber optic probe of the present invention is prepared by forming a carbon nanotube composite film on the outer surface of the detecting end, and the method is relatively simple, and the outer surface of the fiber optic probe need not be roughened. The outer surface of the detecting end can be a smooth surface. In the invention of 099131440 Form No. A0101, page 13 / 36 pages 0992055105-0 201213898 in the fiber 4 wood, the metal particles are formed on the carbon nanotube film structure, and the catching end forms an integral structure, and The carbon nanotube film junction and the probe 4 are two structures that are relatively independent. Therefore, when it is necessary to remove the metal particles from the surface of the optical fiber, it is only necessary to erase the entire carbon nanotube composite film by using a rubber or lens paper to prevent the structure of the optical fiber from being destroyed. It will be appreciated that since the carbon nanotube composite membrane already has a plurality of densely packed metal particles, the carbon nanotube composite membrane itself can be regarded as a flexible Raman scattering substrate. Therefore, when preparing the domain probe, it is equivalent to providing a flexible Raman scattering substrate at the detecting end. The light transmittance of the substrate is excellent, that is, the light transmittance A of the carbon nanotube composite film is 40% ·> [0029]

When the sensing system is in operation, the detecting end of the fiber optic probe protrudes into a sample to be tested or is placed in an environment of a vapor molecule having a sample to be tested, and the carbon nanotube composite film is used to adsorb a large amount of Test sample molecules. When the transmitting module emits a light beam to the carbon nanotube composite film, photons in the light beam will collide with the sample molecules to be tested adsorbed in the carbon nanotube composite film. The photon collides with the molecule to be tested, and the momentum changes, thereby changing the direction of the photon and scattering to the square. When the photon collides, it also exchanges energy with the sample molecule to change the energy or frequency of the photon, so that the photon has to be Test the molecular structure information of the sample. That is, after the beam collides with the sample molecule to be tested, scattered light having information about the molecular structure of the sample to be tested is formed. Part of the scattered light is transmitted to the detecting end via the total reflection of the optical fiber and transmitted to the receiving module via the detecting end. The receiving module can obtain a Raman spectrum of the sample to be tested by processing the received scattered light. 099131440 Form No. A0101 Page 14 / Total 36 Page 0992055105-0 201213898 [0030] From the working process of the sensing system, the light beam emitted by the emission module can be directly irradiated to the carbon nanotube In the composite film, the light beam is input from the detecting end to the optical fiber and is irradiated to the Nexai tube composite film via the optical fiber. When the light beam is irradiated to the carbon nanotube composite film via the optical fiber, the sensing system may further include a light processing module, and the light beam emitted by the transmitting module passes through the light processing module After the treatment, it is transferred to the carbon nanotube composite medium via the optical fiber. The scattered light is transmitted from the optical fiber to the optical processing module, and then processed by the optical processing module and transmitted to the receiving module. That is, the light processing block is mainly used to provide and coordinate the light paths of the light beam and the scattered light. [0031] The metal particles in the fiber optic probe are disposed on the carbon nanotube film structure instead of being disposed directly on the detecting end of the optical fiber, so that the outer surface of the detecting end of the optical fiber may be smooth. The surface does not need to be roughened. When it is necessary to remove the metal pellets, it is only necessary to remove the Naicai composite film which is wound or disposed at the detecting end, and the structure of the optical fiber is not damaged, so that the optical fiber can be reused. Further, the carbon nanotube membrane structure i consists of a plurality of carbon nanotubes having a small size and a large specific surface area, and has a large specific surface area, thereby being capable of adsorbing more molecules of the sample to be tested. Moreover, since the carbon nanotube membrane structure has a large specific surface area, the metal particles can be densely arranged on the carbon nanotube structure and form a plurality of smaller particle spacings. Since the particle diameter of the metal particles is small and the interval between adjacent metal particles is small, the particle diameter of the metal particles and the interval between adjacent metal particles are relatively uniform. In the outside world, the photoelectric field excites τ, and the metal surface emits 099131440. Form No. Α0101 Page 15/36 pages 0992055105-0 201213898 The plasmon resonance absorption causes the local electromagnetic field between the particles to be enhanced, resulting in the Raman of the molecule to be tested. The signal is enhanced to increase the sensitivity of the fiber optic probe. [0036] [0036] The sensing system of the present invention will be described in detail below with reference to the accompanying drawings and by way of specific embodiments.

Referring to FIG. 4, the sensing system 1 includes a transmitting module 丨〇, a receiving module 20, and a fiber optic probe 30. The transmitting module 10 and the receiving module 2 are respectively disposed at two ends of the fiber optic probe 30. The end of the fiber optic probe 3 伸 extends into a sample to be tested 200.

The transmitting module 10 emits H to the field #head 3() to illuminate the illuminating sample 2 (10) on the absorbing surface, and the surface fiber ray to form the scattered light of the sample 2GG to be tested. The scattered light is transmitted to the receiving die via the illuminating probe 30, and the touch module analyzes the scattered light to obtain a Raman spectrum of the sample to be tested from the Raman spectral characteristic map. The vibration mode of the sample to be tested (4) and its corresponding molecular or official _ can be read. — B——and referring to FIG. 5, the fiber optic probe 3Q includes a fiber-optic carbon tube composite film 32 (pulsing the hemp, not raising the I and then scattering the substrate). The optical fiber 31 includes a detecting end 311 and a detecting end 312. The shape of the detecting end is not limited. In the present embodiment, the detecting end 3n is a circle, and the diameter of the cone is gradually decreasing in a direction away from the fiber optic probe 3 () to the carbon nanotube composite film. 32 is wound around the surface of the detecting end. The carbon nanotube composite film 32 and the detecting end 311 can be combined only by the form bat No. A0101, page 16 / 36 pages 0992055105-0 201213898 ❹ Ο [0037] Agent and other ways to bond. Referring to FIG. 6, the carbon nanotube composite film 32 includes a carbon nanotube film structure 321 and a metal layer 322. The metal layer 322 is disposed on a surface of the nanotube film structure 321. The metal layer 322 is disposed on a surface of the carbon nanotube film structure 3 21 away from the detecting end 311. Of course, the metal layer 322 may also be disposed on the surface of the carbon nanotube film structure 321 near the probe end 311 or at the same time on the opposite surfaces of the carbon nanotube film structure 321 . Referring to FIG. 7 'in the present embodiment, the carbon nanotube film structure 321 includes at least two layers of carbon nanotube film and the extending direction of the carbon nanotubes in the adjacent carbon nanotube film. Roughly vertical. The carbon nanotube membrane structure 321 is defined as a carbon nanotube substrate. Referring to Fig. 8 and Fig. 9, the material of the metal layer 322 is silver selected to have a thickness of approximately 5 nm, and the metal particles constituting the metal layer 322 have a particle diameter of approximately 20 nm or so. The carbon nanotube composite membrane 32 is defined as a silver-nano carbon nanotube substrate. Referring to FIG. 10, FIG. 11 and FIG. 12, the carbon nanotube composite flag 32 may further include a buffer layer 323. The material of the buffer layer 323 is selected to be a dioxide dioxide, and the thickness is approximately 20 nm. about. The carbon nanotube composite membrane 32 is defined as a silver-buffer layer-nanocarbon nanotube substrate. Referring to FIGS. 13 and 14, the carbon nanotube substrate, the silver-carbon nanotube substrate, and the silver-buffer layer-carbon nanotube substrate are respectively disposed on the outer surfaces of the detecting ends 311 of the three fibers 31. The detection end 311 is respectively inserted into a 2.5×10 3 mole per liter aqueous pyridine solution and a 1〇-6 mole per liter rhodamine ethanol solution, and the Raman spectrum characteristic diagram of the hydrazine aqueous solution and the rhod A Raman spectrum characteristic diagram of a clear ethanol solution. [0038] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to the law. 099131440 Form No. Α0101 Page 17/36 Page 0992055105-0 201213898. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. [0040] [0040] [0044] [0044] [0044] [0044] [0046] [0046] [0048] [0050] [0050] [0051] 099131440 FIG. 1 is a Scanning electron micrograph of a carbon nanotube film. Figure 2 is a scanning electron micrograph of a carbon nanotube rolled film. Figure 3 is a scanning electron micrograph of a carbon nanotube film. 4 is a schematic structural view of a sensing system. FIG. 5 is a partially enlarged schematic structural view of the sensing system of FIG. 4. FIG. Fig. 6 is a schematic view showing the structure of a carbon nanotube composite membrane. Figure 7 is a scanning electron micrograph of a carbon nanotube substrate. Figure 8 is a transmission electron micrograph of a silver-nanocarbon tube substrate. Figure 9 is a high resolution transmission electron micrograph of the silver-nanocarbon nanotube substrate of Figure 8. Fig. 10 is a schematic view showing the structure of another carbon nanotube composite membrane. Figure 11 is a transmission electron micrograph of a silver-buffer layer-nanocarbon nanotube substrate. Figure 12 is a high resolution transmission electron micrograph of the silver-buffer layer-nanocarbon nanotube substrate of Figure 11. FIG. 13 is a view showing the carbon nanotube substrate of FIG. 7 , the silver-nanocarbon tube substrate of FIG. 8 , and the silver-buffer layer-nanocarbon tube substrate of FIG. 11 respectively in the sensing system of FIG. 4 . A Raman spectral characteristic diagram obtained when 2. 5 x 1 0_3 mole per liter of the aqueous pyridine solution was detected. Form No. A0101 Page 18/36 Page 0992055105-0 201213898 [0052] FIG. 14 is a view showing the carbon nanotube base [0053] of FIG. 7 and the silver of FIG. 8 respectively in the sensing system of FIG. - Raman spectral characteristics obtained when the carbon nanotube substrate and the silver-buffer layer-carbon nanotube substrate of Fig. 11 were detected in a solution of 1 〇 6 moles per liter of rhodamine ethanol. [Main component symbol description] Sensing system: 10 0 [0054] Transmitter module: 10 [0055] Receiver module: 20 C [0056] Fiber optic probe: 30 [0057] Fiber: 31 [0058] Probe: 311 [0059] End to be tested: 312 [0060] Nano carbon tube composite membrane: 32 [0061] Nano carbon tube membrane structure: 321 ❹ [0062] Metal layer: 322 [0063] Buffer layer: 323 [0064] Sample to be tested: 200 099131440 Form No. A0101 Page 19 of 36 0992055105-0

Claims (1)

201213898 VII. Patent application scope: 1. A fiber optic probe comprising an optical fiber, wherein the optical fiber probe further comprises a carbon nanotube composite film disposed on an outer surface of one end of the optical fiber, the carbon nanotube composite film The method comprises: a carbon nanotube membrane structure, the carbon nanotube membrane structure comprises a plurality of carbon nanotubes: and a plurality of metal particles disposed on the surface of the plurality of carbon nanotubes 〇2. The fiber optic probe of the invention, wherein the optical fiber has a detecting end, and the carbon nanotube composite film is disposed on an outer surface of the detecting end. 3. The fiber optic probe of claim 1, wherein the outer surface of the detecting end is a smooth surface. 4. The fiber optic probe of claim 2, wherein the carbon nanotube composite membrane covers the probe end. 5. The fiber optic probe of claim 4, wherein the carbon nanotube composite film is bonded to an outer surface of the detecting end by a bonding agent. 6. The fiber optic probe of claim 2, wherein the plurality of carbon nanotubes are substantially perpendicular to an outer surface of the probe end. 7. The fiber optic probe of claim 2, wherein the plurality of carbon nanotubes are substantially parallel to the surface of the carbon nanotube film, and the adjacent carbon nanotubes are bonded by van der Waals force. 8. The fiber optic probe of claim 7, wherein the carbon nanotube film composite film is a self-supporting structure, and the carbon nanotube film composite film is directly wound around an outer surface of the detecting end. . </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The plurality of metal particles are adsorbed on the surface of the carbon nanotubes in the carbon nanotube film structure by van der Waals force. 1〇. If you apply for a patent scope! The fiber optic probe of the present invention, wherein the nanotube film structure comprises at least a layer of carbon nanotubes, wherein the carbon nanotubes in the carbon nanotube film extend substantially in a preferred orientation in the same direction, In the carbon nanotube film, most of the carbon nanotubes in the same direction extend in the same direction, and the carbon nanotubes are connected in the (four) direction. The fiber optic probe of claim 1, wherein the carbon nanotube film structure comprises at least two layers of carbon nanotube film laminates. 12. The fiber optic probe of claim 1, wherein the number of layers of the carbon nanotube film in the carbon nanotube film structure is less than or equal to four layers. 13. The fiber optic probe of claim η, wherein the carbon nanotubes in the adjacent carbon nanotube film extend substantially perpendicularly. 14. For example, the scope of patent application! The fiber optic probe of the present invention, wherein the particle distance between the plurality of metal particles disposed on the surface of the carbon nanotube is between 1 and 15 nm. 15 as claimed in claim J. The fiber optic probe, wherein the metal particles have a particle size of between 5 nm and 50 nm. 16 fiber optic probes, comprising: an optical fiber, comprising: a detecting end, wherein the optical fiber probe further comprises: a carbon nanotube film structure, the carbon nanotube film structure being disposed at a detecting end of the optical fiber The outer surface, the nanocarbon (four) structure comprises a plurality of carbon nanotubes; a metal layer 'material is disposed on the surface of the nanocarbon structure'. The metal layer is composed of a plurality of metal particles. The fiber optic probe of claim 16, wherein the fiber 0992055105-0 Form No. A0101 Page 21 of 36 17138138 The probe further includes a buffer layer disposed on the nanocarbon Between the tubular membrane structure and the metal layer. 18. The fiber optic probe of claim 16, wherein the carbon nanotube film structure and the metal layer form a carbon nanotube composite film, and the carbon nanotube composite film is flexible. The Raman scattering substrate, the nanometer; 5 carbon tube composite film has a light transmittance of 40 ° /» or more. The fiber optic probe of claim 16, wherein the metal layer has a thickness of between 1 nm and 50 nm. a sensing system comprising a transmitting module, a fiber optic probe and a receiving module; the transmitting module transmitting a light beam to the fiber optic probe; the fiber optic probe transmitting the light beam emitted by the transmitting module The end of the fiber optic probe is scattered to form scattered light 'and the scattered light is transmitted to the receiving module; #A The receiving module collects scattered light scattered from the fiber optic probe to form a Raman spectral feature The improvement is that the fiber optic probe comprises a fiber-optic carbon nanotube composite membrane comprising a carbon nanotube membrane structure and a plurality of metal particles, and the carbon nanotube membrane structure is arranged On the surface of one end of the fiber, the carbon nanotube film structure entrains a plurality of carbon nanotubes, and the plurality of metal particles are disposed on the surface of the plurality of carbon nanotubes. 099131440 Form No. A0101 Page 22 of 36 0992055105-0