CN118190899A - Raman surface-based chip enhancement multiplying power quantitative measurement device and measurement method - Google Patents
Raman surface-based chip enhancement multiplying power quantitative measurement device and measurement method Download PDFInfo
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- CN118190899A CN118190899A CN202311258206.XA CN202311258206A CN118190899A CN 118190899 A CN118190899 A CN 118190899A CN 202311258206 A CN202311258206 A CN 202311258206A CN 118190899 A CN118190899 A CN 118190899A
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- 238000001069 Raman spectroscopy Methods 0.000 description 47
- 238000005259 measurement Methods 0.000 description 43
- 230000007246 mechanism Effects 0.000 description 16
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- 238000000034 method Methods 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
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- 230000005284 excitation Effects 0.000 description 2
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- 238000001237 Raman spectrum Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
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Abstract
The invention relates to the technical field of quantitative measurement of a Raman surface-enhanced chip, in particular to a quantitative measurement device and a quantitative measurement method for the enhanced multiplying power of a Raman surface-based chip. The device comprises a first light source, a measuring camera set, a micro light spot measuring mechanism and a Raman spectrometer component, wherein a light beam is emitted through the first light source, is irradiated onto a sample on the measuring camera set with a displacement function after light splitting, the light spot formed by measuring the measuring camera set or the micro light spot measuring mechanism is subjected to comparison and quantification of the light spot size and the effective action area by adopting a plurality of comparison measuring modes, and is matched with the comparison of the number of molecules in the quantitative unit area by other auxiliary modes, and then the gain multiplying power coefficient of the Raman surface enhancement chip is calculated by combining a plurality of optical and differential scattering parameters according to the intensity of the surface enhancement Raman signal of the planar chip, the comparison of the conventional Raman signal and the number of molecules in the unit area under the same condition, so that the accuracy of the measuring result is greatly improved.
Description
Technical Field
The invention relates to the technical field of quantitative measurement of a Raman surface-enhanced chip, in particular to a quantitative measurement device and a quantitative measurement method for the enhanced multiplying power of a Raman surface-based chip.
Background
The specific value of the gain factor of the existing Raman surface enhanced chip is processed, the result is expressed by using the sample to dilute ppm or ppb times at present, and the error between the estimated result and the actual value is relatively large. Thus, it is generally seen that raman-enhanced chips are labeled with words with an enhancement factor greater than 1000000.
Based on the mechanism of generating Raman signals by interaction of light and substances, the traditional model is a qualitative measurement method for confirming results by simply using molecular number concentration as an investigation quantity, the main consideration of the method is a measurement focusing volume element calculation model, the result is usually estimated by using a needle point-like field enhancement mode, the estimation method is single, and the estimation result error is relatively large.
Disclosure of Invention
The invention provides a quantitative measurement device and a quantitative measurement method for a Raman surface-based chip enhancement multiplying power, which are used for solving the problem that in the prior art, the error of the measurement method for confirming the result by taking the concentration of molecular numbers as the investigation quantity is large in a traditional model.
In order to solve the above problems, in a first aspect, the present invention provides a raman surface-based chip enhancement ratio quantitative measurement apparatus, comprising:
The first light source is used for generating white light or laser;
the measuring camera set is arranged on one side of the second light splitting piece and is used for measuring the size of the light spot;
The micro light spot measuring mechanism is arranged on the other side of the second light splitting piece and is used for measuring the size of a micro light spot;
And the Raman spectrometer component is arranged at the lower end of the second light splitting piece and is used for detecting Raman signals generated by the sample.
In a preferred embodiment, the raman spectrometer assembly comprises a second lens, a third light splitting sheet and a raman spectrometer, wherein the second lens, the third light splitting sheet and the raman spectrometer are sequentially arranged at the lower end of the second light splitting sheet, and the third light splitting sheet is arranged between the second lens and the raman spectrometer.
In a preferred embodiment, the measuring device further includes a second light source, the second light source is disposed on one side of the third light splitting sheet, a third lens is disposed corresponding to the second light source, and the third lens is disposed between the third light splitting sheet and the second light source.
In a preferred embodiment, the measuring camera set comprises at least one measuring CCD camera and a fourth dichroic mirror, a fourth lens being arranged in correspondence of the measuring CCD camera.
According to the first aspect, in a preferred implementation manner, the measuring device further includes a first observation camera, the first observation camera is disposed at a lower end of the fourth light splitting sheet, a fifth lens is disposed corresponding to the first observation camera, and the fifth lens is disposed between the fourth light splitting sheet and the first observation camera.
According to the first aspect, in a preferred embodiment, the micro light spot measuring mechanism includes a sixth lens, a fifth beam splitter and a measuring device, the sixth lens is disposed on one side of the first beam splitter, the fifth beam splitter is disposed on one side of the sixth lens away from the first beam splitter, and the measuring device is disposed on one side of the fifth beam splitter away from the sixth lens.
In a preferred embodiment, according to the first aspect, the micro light spot measurement mechanism further includes a second observation camera, and the second observation camera is disposed at an upper end of the fifth beam splitter.
In a second aspect, the present invention further provides a measurement method suitable for the above scheme, including placing a sample on a measurement camera set, where the retroreflected light on the sample surface is split into two first beams by a first beam splitter, one first beam is directed to a second beam splitter, the other first beam is directed to a micro-spot measurement mechanism, the second beam splitter splits the first beam into two second beams, one second beam is directed to the sample, the other second beam is directed to a raman spectrometer assembly, and the raman spectrometer assembly detects raman signals generated by the sample.
The beneficial effects of the invention are as follows: the invention provides a Raman surface-based chip enhancement ratio quantitative measurement device, which comprises a first light source, a measurement camera set, a micro light spot measurement mechanism and a Raman spectrometer component, wherein a light beam generated by the first light source irradiates a sample, the measurement camera set or the micro light spot measurement mechanism is adopted to measure light spots generated by the sample, the Raman spectrometer component is adopted to measure Raman signals generated by the sample, various comparison measurement modes are adopted to conduct light spot area comparison quantification and quantitative unit area molecular number comparison, then the intensity of a chip enhancement Raman signal, the comparison of a conventional Raman signal and the unit area molecular number are conducted according to the same conditions, and then the specific ratio gain coefficient of a surface enhancement chip is calculated by integrating a plurality of optical and differential scattering parameters, so that the accuracy of a measurement result is greatly improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 shows a schematic diagram of the overall frame structure of the measuring device.
Description of main reference numerals:
100-a first light source; 110-a first lens; 120-a first light splitting sheet; 130-a second beam splitter; 200-measuring a camera set; 210-measuring a CCD camera; 220-fourth light splitting sheet; 230-a fourth lens; 300-a micro light spot measuring mechanism; 310-sixth lens; 320-fifth light splitting sheet; 330 a measuring device; 340-a second observation camera; 400-raman spectrometer assembly; 410-a second lens; 420-a third light splitting sheet; 430-raman spectrometer; 500-a second light source; 510-a third lens; 600-a first observation camera; 610-fifth lens.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
Referring to fig. 1, the present invention provides a raman surface-based chip enhancement ratio quantitative measurement apparatus (hereinafter referred to as measurement apparatus), which includes a first light source 100, a measurement camera set 200, a micro-flare measurement mechanism 300, and a raman spectrometer assembly 400, wherein the first light source 100 is used for generating white light or laser, the measurement camera set 200 and the micro-flare measurement mechanism 300 are used for measuring a flare size generated by a sample, further calculating a flare area, and the raman spectrometer assembly 400 is used for measuring a raman signal generated by the sample.
Specifically, the first light source 100 is correspondingly provided with a first lens 110, a first light splitter 120 and a second light splitter 130, the light beam generated by the first light source 100 is emitted to the first light splitter 120 after passing through the first lens 110, the micro light spot measuring mechanism 300 is arranged at one side of the first light splitter 120 away from the second light splitter 130, the measuring camera set 200 is arranged at one side of the second light splitter 130 away from the first light splitter 120, and the raman spectrometer assembly 400 is arranged at the lower end of the second light splitter 130.
It can be understood that the light beam generated by the first light source 100 passes through the first lens 110 and then is directed to the first beam splitter 120, and the first beam splitter 120 splits the light beam into two first light beams, wherein one first light beam is directed to the second beam splitter 130, and the other first light beam retroreflects in the opposite direction and is directed to the micro-flare measuring mechanism 300. The second beam splitter 130 splits the first beam into two second beams, one of the second beams irradiates the sample on the measuring camera set 200, the other second beam retroreflects the generated raman signal to the raman spectrometer assembly 400, the raman signal intensity generated by the sample is measured by the raman spectrometer assembly 400, various comparison measurement modes are adopted to conduct light spot area comparison quantification and quantitative unit area molecular number comparison, and then the chip enhancement raman signal intensity, the conventional raman signal and unit area molecular number are compared under the same conditions, and then the gain coefficient of the table enhancement chip is calculated by integrating a plurality of optical and differential scattering parameters and the like, so that the accuracy of the measurement result is greatly improved.
It should be noted that in the above-mentioned scheme, the type of the sample may be set according to the concentration, for example, a normal concentration sample may be placed on the measurement camera set 200 by using a sheet-like vessel (glass, transparent plastic, etc.), and when the concentration of the sample is extremely low, the sample may be dropped on a raman chip, and the raman chip may be placed on the measurement camera set 200.
In the device, when the numerical aperture of the lenses is different, the size of the generated light spot area is different, the light spot generated in the normal range can be measured by adopting the measuring camera set 200 (the light spot with the size of more than 5 micrometers can be measured usually limited by CCD or CMOS processing technology), and when the light spot size is smaller than the CCD pixel size, the light spot size can be quantitatively measured by adopting the micro light spot measuring mechanism 300, and then the corresponding area is calculated according to an algorithm.
According to the characteristic of the focused field light spot, the measuring device adopts a multi-grid detection program to determine the uniformity of a sample and a chip process, and multi-grid positioning wide-field microscopic imaging provides a measuring and comparing result of a next-step Raman table enhanced signal and a conventional Raman signal, so that the accuracy and reproducibility of a chip gain coefficient are ensured.
And according to the characteristics of Raman signal generation and focusing excitation volume element, further according to the quantitative measurement of the size and change of the light spot in the volume element, and simultaneously feeding back the perpendicularity of the optical axis and the physical horizontal plane of the motion displacement table. And further feeding back the accuracy of the light spot measurement result.
In the scheme, the quantitative change of the molecular number and the area change in a unit area is utilized by the measuring device, the change relation between the molecular number in an excitation surface source and a single change variable under the same condition is changed, the relative increment is measured by a controlled variable method, the quantification of a multivariable measurement feedback result is further realized according to model setting, the feedback of the measurement result is completed by matching with Raman spectrum analysis, and the accurate theoretical value of the accurate measurement result is more accurate.
Example 1
With continued reference to fig. 1, based on the above-mentioned scheme, the raman spectrometer assembly 400 includes a second lens 410, a third beam splitter 420 and a raman spectrometer 430, the second lens 410, the third beam splitter 420 and the raman spectrometer 430 are sequentially disposed at the lower end of the second beam splitter 130, and the third beam splitter 420 is disposed between the second lens 410 and the raman spectrometer 430. The second beam splitter 130 splits the first beam into two second beams, one of which is directed to the sample and the other of which passes through the second lens 410 and is directed to the raman spectrometer 430, and the light beam retroreflected on the sample is also retroreflected to the raman spectrometer 430.
Preferably, the measuring device further includes a second light source 500, the second light source 500 is disposed on one side of the third light-splitting sheet 420, a third lens 510 is disposed corresponding to the second light source 500, the second light source 500 is used for generating white light or laser, the generated light beam passes through the third lens 510 and then is emitted to the third light-splitting sheet 420, and the second light source 500 is used for illumination and monitoring reference.
Example two
With continued reference to fig. 1, on the basis of the above-mentioned scheme, the measurement camera set 200 includes a plurality of measurement CCD cameras 210 and a fourth beam splitter 220, the plurality of measurement CCD cameras 210 are respectively provided with two beam splitting sides of the fourth beam splitter 220, and each measurement CCD camera 210 is provided with a fourth lens 230, and the second light beam is split onto different measurement CCD cameras 210 after passing through the fourth beam splitter 220.
Each measurement CCD camera 210 is provided with a three-dimensional displacement mechanism, and further, the state and position of the measurement CCD camera 210 can be accurately adjusted.
Preferably, the measuring device further includes a first observation camera 600, the first observation camera 600 is disposed at the lower end of the fourth beam splitter 220, a fifth lens 610 is disposed corresponding to the first observation camera 600, the second light beam is split and then irradiated onto the first observation camera 600 through the fifth lens 610, and the first observation camera 600 is used for observing the imaging state of the light spot and can be also used for quantitative reference of the light spot size measurement.
Example III
With reference to fig. 1, on the basis of the above-mentioned scheme, the micro-spot measurement mechanism 300 includes a sixth lens 310, a fifth beam splitter 320 and a measurement device 330, wherein the sixth lens 310 is disposed at one side of the first beam splitter 120, the fifth beam splitter 320 is disposed at one side of the sixth lens 310 away from the first beam splitter 120, and the measurement device 330 is disposed at one side of the fifth beam splitter 320 away from the sixth lens 310. The first light beam passes through the sixth lens 310 and irradiates onto the fifth beam splitter 320, and the further fifth beam splitter 320 splits the light beam onto the measuring device 330, where the measuring device 330 is used to measure the size of the very small light spot in cooperation with the displacement stage or the scanning galvanometer so as to calculate the light spot area.
It should be noted that an avalanche photodiode or photomultiplier tube PMT (abbreviated as the micro-flare measuring mechanism 300) may be employed in the measuring device 330 for measuring a very small flare area that a conventional CCD or CMOS cannot measure.
Of course, the measurement device 330 may be replaced with an avalanche photomultiplier device or other PMT device.
Preferably, the measuring device further includes a second observation camera 340, the second observation camera 340 is provided with a light splitting upper end of the fifth light splitting sheet 320, the first light beam is split by the fifth light splitting sheet 320 and then irradiated onto the second observation camera 340, and the second observation camera 340 is used for observing the imaging state of the light spot. Of course, a seventh lens may be disposed corresponding to the second observation camera 340, and the seventh lens may be disposed between the fifth dichroic mirror 320 and the second observation camera 340.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (8)
1. The utility model provides a raman face base chip reinforcing multiplying power quantitative measurement device which characterized in that includes:
The first light source is used for generating white light or laser;
the measuring camera set is arranged on one side of the second light splitting piece and is used for measuring the size of the light spot;
The micro light spot measuring mechanism is arranged on the other side of the second light splitting piece and is used for measuring the size of a micro light spot;
And the Raman spectrometer component is arranged at the lower end of the second light splitting piece and is used for detecting Raman signals generated by the sample.
2. The raman face-based chip enhancement ratio quantitative measurement apparatus according to claim 1, wherein the raman spectrometer assembly comprises a second lens, a third beam splitter and a raman spectrometer, the second lens, the third beam splitter and the raman spectrometer are sequentially arranged at the lower end of the second beam splitter, and the third beam splitter is arranged between the second lens and the raman spectrometer.
3. The quantitative measurement device for the enhanced magnification of the raman surface-based chip according to claim 2, further comprising a second light source, wherein the second light source is disposed at one side of the third light splitting sheet, a third lens is disposed corresponding to the second light source, and the third lens is disposed between the third light splitting sheet and the second light source.
4. The quantitative measurement device for the enhanced magnification of the raman surface-based chip according to claim 1, wherein the measurement camera set comprises at least one measurement CCD camera and a fourth dichroic mirror, and a fourth lens is provided corresponding to the measurement CCD camera.
5. The quantitative measurement device for the enhancement rate of the raman surface-based chip according to claim 4, further comprising a first observation camera disposed at the lower end of the fourth spectroscopic plate, and a fifth lens disposed between the fourth spectroscopic plate and the first observation camera in correspondence with the first observation camera.
6. The quantitative measurement device for the enhanced magnification of the raman surface-based chip according to claim 1, wherein the micro-flare measurement mechanism comprises a sixth lens, a fifth beam splitter and measurement equipment, the sixth lens is arranged on one side of the first beam splitter, the fifth beam splitter is arranged on one side of the sixth lens away from the first beam splitter, and the measurement equipment is arranged on one side of the fifth beam splitter away from the sixth lens.
7. The quantitative measurement device for the enhanced magnification of the raman surface-based chip according to claim 6, wherein the micro-flare measuring mechanism further comprises a second observation camera, and the second observation camera is disposed at an upper end of the fifth beam splitter.
8. A measuring method applied to the quantitative measuring device of the enhanced multiplying power of the raman surface-based chip as claimed in any one of claims 1 to 7, wherein a sample is placed on a measuring camera set, a light source is divided into two first light beams through a first light splitting sheet, one first light beam is emitted to a second light splitting sheet, the other first light beam is emitted to a micro-spot measuring mechanism, the second light splitting sheet divides the emitted first light beam into two second light beams, one second light beam is emitted to the sample, the other second light beam is emitted to a raman spectrometer assembly, and the raman spectrometer assembly detects raman signals generated by the sample.
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| CN202311258206.XA CN118190899A (en) | 2023-09-27 | 2023-09-27 | Raman surface-based chip enhancement multiplying power quantitative measurement device and measurement method |
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| CN202311258206.XA CN118190899A (en) | 2023-09-27 | 2023-09-27 | Raman surface-based chip enhancement multiplying power quantitative measurement device and measurement method |
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