CN114755213B - Monochromatic transmission light intensity calibration nondestructive testing method and equipment for SERS Raman chip sensitivity - Google Patents
Monochromatic transmission light intensity calibration nondestructive testing method and equipment for SERS Raman chip sensitivity Download PDFInfo
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- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 207
- 230000035945 sensitivity Effects 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000005540 biological transmission Effects 0.000 title claims abstract description 34
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 26
- 238000009659 non-destructive testing Methods 0.000 title abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 20
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 51
- 229910052709 silver Inorganic materials 0.000 claims description 47
- 239000004332 silver Substances 0.000 claims description 47
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 claims description 35
- 239000002105 nanoparticle Substances 0.000 claims description 28
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000001514 detection method Methods 0.000 claims description 21
- 238000003908 quality control method Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 230000001699 photocatalysis Effects 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000001237 Raman spectrum Methods 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007146 photocatalysis Methods 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
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- 239000013307 optical fiber Substances 0.000 claims description 9
- 238000000862 absorption spectrum Methods 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000003326 Quality management system Methods 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
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- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000001066 destructive effect Effects 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 description 9
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- 238000010586 diagram Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 238000000089 atomic force micrograph Methods 0.000 description 3
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- 238000011160 research Methods 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
A SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality testing method and equipment, the method is that a monochromatic light source transmission light intensity (H SP) is adopted to indirectly represent a 'H SP～HRS' calibration nondestructive quality testing technology of a calibration sample Raman peak height (H RS): firstly, selecting a group of calibration Raman chips with different sensitivities, and finding out the peak positions of extinction spectrum-SPR main peak position, -SPR secondary peak position, -other applicable monochromatic light sensitive to SPR effect in an extinction transmission spectrum curve of an ultraviolet visible light source; or finding out the three kinds of peak positions through numerical simulation; second, preferably one of the three types of peak positions, sequentially detecting H SP and H RS of the monochromatic light source of the scaled Raman chip set; thirdly, creating an H SP～HRS calibration curve; fourthly, on the monochromatic transmitted light intensity H SP～HRS calibration equipment, the nondestructive testing of the Raman chip is implemented, and the problem of nondestructive testing of the sensitivity and quality of the SERS Raman chip is solved.
Description
Technical Field
The invention relates to the field of Raman spectrum chips, in particular to a single-color transmission light intensity calibration nondestructive testing method and equipment for SERS (surface enhanced Raman scattering) Raman chip sensitivity.
Background
Currently, SERS Raman chips (Raman chips or RS chips for short) are used for detecting the sensitivity quality, a sample with higher Raman activity is selected, for example, an R6g aqueous solution with the concentration of micro-nano M/L is used as a standard sample, the sample is placed on a Raman chip and placed on a deep refrigeration-CCD Raman spectrometer sample stage, and the Raman spectrum of R6g molecules is detected and used as a reference standard for checking the sensitivity quality of the Raman chips. Because the sensitivity of the Raman chip is very high, and the Raman chip is difficult to clean after being used for detection once, the Raman chip cannot be used for the second ultra-high-sensitivity detection multiplexing. Therefore, when the Raman chip products are subjected to delivery quality inspection, the sampling inspection can be implemented in the same batch of products, and no SERS Raman chip sensitivity nondestructive detection method exists. In the industrial development of the raman chip, in order to ensure that each product is subjected to factory quality inspection, a nondestructive quality inspection method and equipment for sensitivity of the raman chip need to be developed.
Inventor Wu Shifa directs the research institute Li Yaqin to release "international conference paper for photoelectron and spectrum of Beijing nanostructures and materials, SPIE,5635:31-37", the" irregular hot spot "was found in the structural raman chip study of the first simulation of the" trimer-type silver foil/silver nanoparticle film ". The conventional hot spot SPR induces the unconventional hot spot, which is also called the induced hot spot, so that the concentration of the hot spot is increased, and the sensitivity of the trimeric type-silver foil/silver nanoparticle film Raman chip is about an order of magnitude higher than that of the silver colloid-Raman chip, and the sensitivity is shown in the attached figure-1. In 2013, wu Shifa and Pan Lujun are cooperated to guide research institute Li Dawei published paper "J.Phys.Chem.C 2013,117,6861-6871,Controlled Preparation of Uniform TiO2-Catalyzed Silver Nanoparticle Films for Surface-Enhanced Raman Scattering", to develop a trimeric type titanium dioxide SERS silver particle film Raman chip for the first time. The patent of 'a Raman chip with or without receptor titanium dioxide nano metal film and a manufacturing method' applied by Wu Shifa (ZL 2015 1 0917332.8) is authorized in 2019, and the design of optimal parameters of 'a trimeric type-silver foil/silver nanoparticle film Raman chip' for photocatalytic growth of various titanium dioxide is disclosed for the first time, and the manufacturing method of various Raman chips and the manufacturing method of control parameters in an industrial production line; the optimal parameter design of the sensitivity of the Raman chip depends on surface plasmon resonance-SPR, and is mainly related to the following three items: 1. the quasi-contact-gap of silver particles is 0-2 nm; 2. the optimal average diameter of the silver particles is coupled with the excitation wavelength; 3. the titanium dioxide film thickness is equal to or close to lambda/2 n or lambda/4 n.
In the process of controlling the production of the Raman spectrum chip, the quality of the same batch of products is difficult to ensure to have complete consistency by means of 'factory sampling inspection'. In order to develop the raman chip product into a commodity on the market, each raman chip commodity needs to be ensured to meet the requirement of a delivery quality inspection standard, so that a nondestructive quality inspection method and equipment are one of key technologies for industrial development.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a technical scheme of a SERS Raman chip monochromatic transmission light intensity calibration nondestructive testing method and equipment, solves the problem of a SERS Raman chip nondestructive quality testing technology, and provides key technology and equipment for sensitivity standardized detection of SERS Raman chip commodities and commodity delivery quality testing.
The technical scheme of the invention is as follows:
On one hand, the invention provides a SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality inspection method, which adopts monochromatic transmission light intensity (H SP) sensitive to an SPR effect to indirectly represent an 'H SP～HRS' calibration nondestructive quality inspection technology of a calibration sample Raman peak height (H RS), and specifically comprises the following steps:
Step one: selecting a group of calibration Raman chips with different sensitivities on a production line of the Raman chips to be inspected, wherein the sensitivity intervals are uniformly distributed, the span of the calibration Raman chips needs to contain the whole range-quality control limit required by qualified quality inspection standards, and the calibration Raman chip sequences with different sensitivities are marked by 'T', namely the adopted photocatalysis time of the calibration Raman chips in the silver nanoparticle film growing process;
Step two: the ultraviolet-visible light source is adopted, and the calibration Raman chip finds out the primary peak position of SPR, the secondary peak position of SPR and the monochromatic light peak position which is sensitive to the SPR effect and is suitable for calibration through an extinction-absorption spectrum-namely a transmittance spectrum experimental curve; or finding out the monochromatic light peak positions which are sensitive to the SPR effect and are suitable for calibration in the extinction spectrum of the Raman chip by a numerical simulation method without an experimental method;
Step three: selecting one of the three types of monochromatic light peak position wavelengths suitable for calibration in the second step, adopting a monochromatic light source with the selected peak position, such as a laser light source with the wavelength suitable for use, or an LED light source with a certain bandwidth or a halogen tungsten light source, constructing the Raman chip calibration nondestructive quality inspection equipment, detecting monochromatic transmission light intensity H SP of the calibration Raman chip group, and performing a T-H SP curve for calibration;
Step four: on a special Raman spectrometer for nondestructive quality testing and calibration, a calibration sample such as R6g10 -6 M/L is adopted to respectively collect Raman spectra of the calibration Raman chip, and the selected calibration Raman peak height H RS is detected to make a T-H RS curve for calibration;
Step five: on the same horizontal coordinate T, displaying T-H SP and T-H RS curves of the group of calibration Raman chips, and creating an 'H SP～HRS' calibration curve on the basis of fitting the two curves;
step six: on the H SP～HRS calibration curve, making a quality control limit according to the standard reaching range of the sensitivity quality inspection standard of the Raman chip specified by the product delivery quality inspection standard;
Step seven: and (3) placing the Raman chip product to be inspected, which is produced on the Raman chip production line in the step (I), on Raman chip calibration nondestructive quality inspection equipment constructed in the step (III), detecting the peak height H SP, and if the peak height H SP is within the standard reaching range-quality control limit established in the step (six), judging that the Raman chip is qualified, otherwise, judging that the Raman chip is unqualified.
As a further explanation of the scheme, the SERS Raman chip is an ordered silver or gold nano film structure, the SPR effect and the extinction absorption spectrum can be generated only when the SERS Raman chip is conjugated with the quality detection wavelength, and the extinction absorption spectrum and the extinction transmission spectrum of the Raman chip are complementary, so that one of the three wavelengths, namely the main SPR peak, the secondary SPR peak or other monochromatic light wavelengths sensitive to the SPR effect, is preferably selected, the height of the monochromatic transmission light intensity H SP or the transmittance is detected, and the sensitivity quality of the Raman chip is indirectly represented by utilizing the T SP～HRS calibration method to calibrate the height H RS of the Raman peak of a sample, which is the theoretical basis of the Raman chip calibration nondestructive quality detection method and equipment.
The sensitivity of the Raman chip is indirectly characterized by a T SP～HRS calibration method, and the monochromatic transmission light intensity H SP parameter is characterized in that in the extinction transmission spectrum of the Raman chip, the transmission light intensity of monochromatic wavelength which is sensitive to SPR effect, namely sensitive to the sensitivity of the Raman chip is preferable; the extinction transmission effect of the Raman chip is an anti-reflection phenomenon which is superimposed on the information background of the conventional transmission effect of the substances of the Raman chip and is generated by the existence of an SPR effect, and the anti-reflection quantity of the extinction transmission is closely related to the local SPR effect of the Raman chip and monotonically influences the H SP value.
Based on the above scheme, preferably, the raman chip is a 'trimeric type-silver foil/silver nanoparticle film' raman chip, or a gold nanoparticle film raman chip, or a gold-plated silver nanoparticle film raman chip, which is formed by photocatalytic growth of a titanium dioxide film.
Based on the above scheme, preferably, in the extinction absorption spectrum of the raman chip and the height H SP of the transmitted monochromatic light intensity of the peak position of the three extinction spectrums, the sum of three items including conventional molecular absorption, scattering loss and metal Surface Plasmon Resonance (SPR) absorption is included, wherein an "SPR absorption component" is indispensable, the "SPR extinction-absorption component" is a basis for indirectly characterizing the sensitivity quality of the raman chip to be detected through detection of H SP, and the two items of the "conventional molecular absorption and conventional elastic scattering loss" only form a background for detecting the inelastic scattering "SPR extinction-absorption" component in H SP information.
Based on the above scheme, preferably, in order to prevent oxidation of the raman chip quality inspection process in air, the detection of H SP needs to be completed in a vacuum environment or in inert gas, or in silver nitrate solution for growing silver nanoparticle films, or in ultra-pure water.
Based on the above scheme, preferably, in order to ensure the accuracy of the calibration curve of H SP～HRS, the number of calibration raman chips with the same label sensitivity T value is not less than 2, that is, the average value of the experimental values of the calibration raman chips with the same label T value is not less than two, and the number of different T values is not less than 5, which is to create the H SP and H RS values on the calibration curve of "H SP～HRS"; if the scaling Raman chips with different T values are selected, the number of T is not less than 10, namely the number of the group of scaling Raman chips for creating the H SP～HRS scaling curve is not less than 10.
Based on the above scheme, preferably, the quality control limit is formulated according to the result of the H SP～HRS calibration curve created by selecting a group of calibration Raman chips with different sensitivities on the production line of the Raman chips and the quality control factory label.
Based on the above scheme, preferably, in the raman chip quality inspection system, a semiconductor laser or an LED monochromatic light source is adopted, and under the condition of quality inspection of a "silver trimer-silver foil/silver nanoparticle film raman chip" which is empty (i.e. no sample is detected in a silver nitrate solution) and is not arranged in the detection process, the raman chip quality inspection system is displayed according to a numerical simulation result (see fig. 3): the method comprises the steps of (1) carrying out SPR sensitive monochromatic wavelength in a visible light band, adopting a 532nm wavelength semiconductor laser light source, wherein the wavelength is exactly equal to the peak position wavelength of an extinction-transmission spectrum SPR secondary peak of the quality inspection of the Raman chip, detecting the qualified dynamic range of H SP by using the wavelength (quasi-contact: gap is in the range of +3nm to-3 nm), and detecting the qualified dynamic range of H SP by using the 360nm wavelength of the peak position of the primary peak of the SPR, namely, the signal to noise ratio of H SP is doubled; the system of the 532nm narrow-band filter and the photoelectric detector is configured to detect H SP, and the cost performance is much higher than that of the system of the ultraviolet visible light source and the high-cost spectrometer; secondly, in the nondestructive quality inspection equipment, a semiconductor laser light source in a near infrared wave band of 820nm to 960nm is adopted, and a narrow-band filter and photoelectric detector system with the wavelength of the laser is adopted to detect H SP, and the Raman chip quality inspection H SP (quasi-contact: gap is in a range of +3nm to-3 nm) has the advantage of being easy to correctly distinguish whether the chip is qualified or not (see figure 3); and thirdly, a monochromatic LED light source with high cost performance is selected in the wave band which is suitable for the first and the second and has good SPR response, and a 'narrow-band filter+photoelectric detector' system for detecting H SP with the central wavelength of the LED is also effective.
Based on the scheme, preferably, an empty silver trimer-silver foil/silver nanoparticle film Raman chip is detected, in the nondestructive quality inspection equipment, a halogen tungsten light source and high-price spectrometer system is preferably configured, preferably, the sensitivity of the Raman chip is characterized by detecting H SP at the 820nm-SPR sensitive wavelength of an extinction absorption spectrum curve of the Raman chip; or a system of 'halogen tungsten lamp light source +820nm narrow-band filter + photoelectric detector' is configured, and detection H SP characterizes the sensitivity of the Raman chip.
Based on the above scheme, preferably, H SP of 'silver trimer-silver foil/silver nanoparticle film Raman chip' is detected in silver nitrate solution of the photocatalytic growth silver nanoparticle film, and scaling nondestructive detection sensitivity quality is implemented, namely, the load and medium of the Raman chip are both the silver nitrate solution, in the nondestructive quality inspection equipment, (first) an ultraviolet visible light source, namely, a deuterium halogen tungsten light source is preferably configured, the SPR main peak is near 440nm, (second) or a deuterium light source is configured, and the SPR main peak is more uv-shifted than the former; both (one) and (two) have no obvious SPR secondary peaks, and can be used for nondestructive quality inspection of the Raman chip, and a near ultraviolet visible spectrometer or a near ultraviolet narrow-band filter and photomultiplier system is adopted as a component for detecting H SP of the SPR primary peaks.
In another aspect, the present invention provides a nondestructive quality testing apparatus for use in the above method, the apparatus comprising: the center wavelength of the light source needs to cover one of the three types of monochromatic light wavelengths sensitive to the SPR effect in the second step, the detection transmitted light intensity H SP adopts a photoelectric detector system or a spectrometer system, a computer, an H SP～HRS calibration curve software insertion system and a sensitivity quality management system for indirectly representing the Raman chip to be detected, the light beam emitted by the light source passes through a self-focusing transmission optical fiber or does not pass through the optical fiber to generate a small-caliber parallel light beam, the Raman chip to be detected is vertically arranged with the parallel light beam and is placed on a bracket, and the Raman chip is in a silver nitrate solution environment for growing a silver film, or in an ultrapure water environment, or in a vacuum or inert gas environment; the periphery of the parallel light beam and the Raman chip to be inspected is provided with a dark-phase curtain or is positioned in a darkroom, the small-caliber parallel light beam is transmitted through the Raman chip and then is connected to a photoelectric detector system or a spectrometer system through another self-focusing transmission optical fiber or not through the optical fiber, H SP information of the Raman chip is received and recorded, and a computer and a H SP～HRS calibration software system and a management system are responsible for processing the H SP calibration nondestructive inspection to judge the sensitivity of the Raman chip to be inspected and display whether the sensitivity of the Raman chip in the inspection meets the requirements of factory quality inspection standards.
Drawings
Fig. 1 shows that in the raman chip simulation of the 'trimer type-silver foil/silver nanoparticle film', the phenomenon of inducing 'unconventional hot spot' is found to double the hot spot density, the electric field intensity of the conventional hot spot is doubled, and the raman spectrum enhancement can be about an order of magnitude higher than the sensitivity of the colloidal silver raman chip.
FIG. 2 is a schematic diagram of a trimer-silver foil/silver nanoparticle film Raman chip monochromatic light transmittance calibration nondestructive testing device;
Wherein, a 1-UV visible light source, or other suitable monochromatic light source sensitive to SPR effects; a 2-spectrometer system, or a photodetection system; the system comprises a 3-computer, an H SP～HRS calibration curve software insertion system and a sensitivity quality management system for indirectly characterizing the Raman chip to be tested; 4-small-caliber self-focusing transmission optical fiber; 5-parallel light beams; 6-Raman chip schematic diagram; adding ultrapure water or silver nitrate water solution into a 7-quartz glass vessel to isolate an oxygen film in the air; 8-a bracket; 9-dark-phase curtains or darkrooms.
FIG. 3 is a graph of an extinction transmittance curve for a set of calibration Raman chips, with the sensitivity of the different Raman chips labeled with different silver particle gaps "Deltaj", modeling conditions: the silver trimer-silver foil/silver nanoparticle film Raman chip model has the advantages that the distance between the centers of silver ball particles is 212nm, the diameter of the silver ball is changed by 2r when the silver ball particles grow, the silver ball gap delta is=212 nm-2r, and the gaps delta of a group of 6 piece calibration Raman chips are 27, 9,3, 1, 0 and 3 (nm) respectively.
FIG. 4 is a demonstration of the scaling relationship "H SP～HRS" established under the no-load condition of the scaled Raman chip: a group of 8 different photocatalysis times of 'trimer type-silver foil/silver nanoparticle film Raman chip',
The spectrum transmission spectrum group diagram of 8 calibration Raman chips under the light source of the halogen tungsten lamp has the most sensitive applicable monochromatic wavelength of 820nm with SPR response and the proportional relation of H SP relative transmission light intensity- (transmittance);
FIG. B.8 Raman spectrum set-up graphs of a calibration Raman chip, 1360cm -1 specific Raman spectrum peak H RS;
FIG. C.8 "H SP～HRS" scaling relationships for scaled Raman chips: "T-H SP" and "T-H RS" graphs on the same abscissa; in the figure, the dotted line portion means a known direction of the curve trend.
Graph D.8 "H SP～HR S" calibration curves for calibration Raman chips.
Fig. 5 is a demonstration of the calibration parameters for detection "H SP～HRS": h SP,HRS and AFM images of a group of 5 different photocatalysis times 'trimer type-silver foil/silver particle film Raman chip' are in place when silver nanoparticle films are produced in a photocatalysis mode, namely under the condition that silver nitrate aqueous solution isolates an air film, H SP is detected, and then H RS and an atomic force microscope image are detected;
Atomic force microscope images of different photocatalytic times of 'trimer type-silver foil/silver nanoparticle film Raman chip';
figure B. Extinction-absorption spectra and SPR main peak height H SP of different photocatalysis time 'trimer type-silver foil/silver nanoparticle film Raman chip';
Panel C. different photocatalytic times "trimer-silver foil/silver particle film Raman chip" scale samples R6g10 -6 M/L Raman spectrum and H RS.
FIG. 6 is a demonstration of the production of the "H SP～HRS" calibration relationship and the "H SP～HRS" calibration curve: a group of 5 trimerization-silver foil/silver nanoparticle film Raman chips with different photocatalysis time, under the condition of silver nitrate of growing silver film,
First step: different photocatalysis time marks 5 different sensitivity calibration Raman chips extinction-absorption SPR main peak height experimental results-T-H SP calibration relation diagrams;
And B, a second step: different photocatalysis time marks 5 different sensitivity calibration Raman chips photocatalysis time-detection R6g-10 -6 M/L Raman spectrum 1360cm -1 peak height experimental result-T-H RS calibration relation chart;
Fig. c, last step: and (3) obtaining a calibration relation diagram of 'H SP～HRS' from the results of 'T-H SPR' and 'T-H SPR', and formulating a quality control limit of H SP calibration nondestructive quality control according to the specification of standard quality control. The dashed line in the figure represents the experimentally known trend.
Detailed Description
The raman chip used in this example is a "trimer-type silver foil/silver particle film raman chip", and the characteristics and specific preparation methods thereof can be referred to in the literature: 1. patent of the invention (ZL 2015 1 091 7332.8);2、"J.Phys.Chem.C 2013,117,6861-6871,Controlled Preparation of Uniform TiO2-Catalyzed Silver Nanoparticle Films for Surface-Enhanced Raman Scattering".
Example 1
The light intensity calibration nondestructive quality inspection method for the unloaded SERS Raman chip in the air environment comprises the following specific steps:
Firstly, configuring a deep refrigeration CCD Raman spectrometer special for H SP calibration nondestructive quality inspection of a Raman chip and a Raman spectrum standard sample-R6 g-10 -6 M/L with standard concentration for nondestructive quality inspection calibration according to the H SP～HRS calibration method;
Secondly, for H SP calibration nondestructive quality inspection equipment, three components of a halogen tungsten lamp light source, a high-sensitivity spectrometer and a notebook computer are required to be purchased, and as shown in figure 2, discrete or integrated manufacturing is designed to be H SP calibration nondestructive quality inspection special equipment;
Thirdly, selecting a Raman chip for creating an H SP～HRS calibration relation and an H SP～HRS calibration curve on a production line of the Raman chip;
Fourth, the sensitivity of the calibration raman chip needs to be properly distinguished, the number of the calibration raman chip is 8, and the sensitivity quality of the calibration raman chip accords with the whole interval required by the quality control standard;
fifthly, under the light source of the halogen tungsten lamp, spectrum transmission spectrum group graphs of 8 calibration Raman chips which do not pass through the catalysis time are provided, the most sensitive applicable monochromatic wavelength with SPR response is 810nm, and the relative transmission light intensity-to-transmittance ratio relation of H SP is shown in the figure 4-A;
Step six, dripping R6g of standard concentration sample on 8 calibration Raman chips, and detecting H RS, see figure 4-B;
Seventh, processing T-H RS, T-H RS calibration relation data and H SP～HRS calibration relation curves on a notebook computer of the H SP nondestructive quality inspection equipment, wherein the calibration relation data and the calibration relation curves are shown in figures 4-C and 4-D respectively;
And eighth step, making a quality control range of a factory quality inspection standard-SP peak height. After the calibration is finished, the method can be used for nondestructive delivery quality inspection of the Raman chip, each commodity delivered is guaranteed to meet delivery standards, for example, the quality control limit is 1500-5000 according to the method of FIG. 4-D, raman chips on the same production line with the calibrated Raman chips are selected for detection, when the H SP of the Raman chips is between the quality control limit of 1500-5000 (corresponding to the maximum value of H RS), the sensitivity quality meets the delivery standards, and when the sensitivity quality does not meet the delivery standards, the sensitivity quality does not meet the delivery standards.
Example 2
The SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality inspection method under the conditions of a sample and a medium by using a silver nitrate solution comprises the following specific steps:
Firstly, configuring a deep refrigeration CCD Raman spectrometer special for H SP calibration nondestructive quality inspection of a Raman chip and a Raman spectrum standard sample with standard concentration for nondestructive quality inspection calibration, such as R6g-10 -6 M/L, according to the requirement of an H SP～HRS calibration method;
Secondly, calibrating nondestructive quality inspection equipment for H SP, namely purchasing three components of an ultraviolet visible broad spectrum light source, a high-sensitivity spectrometer and a notebook computer, wherein as shown in figure 2, discrete or integrated manufacturing is designed to be the special equipment for H SP calibration nondestructive quality inspection;
thirdly, selecting Raman chips for creating calibration relations T-H SP, T-H RS curves and H SP～HRS calibration curves on a production line of the Raman chips;
fourthly, the sensitivity of the calibration Raman chip needs to be properly distinguished, at least five kinds of sensitivity quality of the calibration Raman chip is in line with the whole interval required by the quality control standard;
Fifth, different sensitivities of the raman chip are marked with different photocatalytic times T: such as 2min, 8min, 16min, 30min, and 55min, as shown in figure 5-A; detecting extinction-absorption spectra and H SP of 5 calibration Raman chips, see figure 5-B;
Step six, dripping R6g of standard concentration sample on 5 calibration Raman chips, and detecting H RS, see figure 5-C;
Seventh, processing T-H RS, T-H RS calibration relation data and H SP～HRS calibration curves on a notebook computer of the H SP nondestructive quality inspection equipment, wherein the calibration relation data and the calibration curves are shown in figures 6-A,6-B and 6-C respectively;
And eighth step, making a quality control range of a factory quality inspection standard-SPR peak height. After the calibration is finished, the method can be used for nondestructive delivery quality inspection of the Raman chip, each commodity delivered is guaranteed to meet delivery standards, for example, the quality control limit is 1.5-2.4 according to the preparation of the figure 6-C, the Raman chip on the same production line with the calibration Raman chip is selected for detection, when H SP of the Raman chip is more than 1.5 and is lower than 2.4 which is the maximum value, the sensitivity meets the delivery standards, and HS P is less than or equal to 1.5, the Raman chip does not meet the delivery sensitivity quality standards.
Claims (9)
1. A SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality inspection method is characterized in that the method adopts monochromatic transmission light intensity H SP sensitive to an SPR effect, and indirectly characterizes H SP～HRS calibration nondestructive quality inspection technology of a calibration sample Raman peak height H RS, and specifically comprises the following steps:
Step one: selecting a group of calibration Raman chips with different sensitivities on a production line of Raman chips to be inspected, wherein the sensitivity intervals are uniformly distributed, the span of the calibration Raman chips needs to contain the whole range-quality control limit required by qualified quality inspection standards, and the calibration Raman chip sequences are marked with T, namely the photocatalysis time adopted by the calibration Raman chips in the silver nanoparticle film growing process;
Step two: the ultraviolet-visible light source is adopted, and the calibration Raman chip finds out the primary peak position, -secondary peak position, -other monochromatic light peak positions which are sensitive to the SPR effect and are suitable for calibration through extinction-absorption spectrum detection, namely a transmittance spectrum experiment curve; or finding out the primary-secondary-peak-to-SPR peak-to-other monochromatic light peak-to-SPR effect sensitive in the extinction spectrum of the calibration Raman chip by a numerical simulation method without using an experimental method;
Step three: selecting one of the primary peak position, -secondary peak position, -other monochromatic light peak positions sensitive to SPR effect and suitable for calibration, adopting a monochromatic light source of the monochromatic light peak position to construct Raman chip calibration nondestructive quality inspection equipment, detecting monochromatic transmission light intensity H SP of the calibration Raman chip group, and performing a T-H SP curve for calibration;
Step four: on a special Raman spectrometer for nondestructive quality testing and calibration, a calibration sample is adopted, raman spectra of the calibration Raman chip are collected, and the selected calibration Raman peak height H RS is detected to be used as a T-H RS curve for calibration;
Step five: on the same horizontal coordinate T, displaying T-H SP and T-H RS curves of the group of calibration Raman chips, and creating an 'H SP～HRS' calibration curve on the basis of fitting the two curves;
Step six: on the H SP～HRS calibration curve, a standard reaching range of a Raman chip sensitivity quality inspection standard specified by a product delivery quality inspection standard is formulated;
step seven: placing the Raman chip product to be inspected produced on the Raman chip production line in the step I on Raman chip calibration nondestructive quality inspection equipment constructed in the step III, detecting the peak height H SP, if the peak height H SP is within the standard-quality control limit established in the step six, then passing the Raman chip, otherwise, failing the Raman chip;
A nondestructive quality inspection apparatus for use in the method, the apparatus comprising: the central wavelength of the light source (1) needs to cover the primary peak position of SPR, the secondary peak position of SPR, or one of the primary peak position and the tertiary peak position of monochromatic light suitable for calibration which is sensitive to SPR effect, the detection transmission light intensity H SP adopts a photoelectric detector system or a spectrometer system (2), a computer, an H SP～HRS calibration curve software insertion system and a sensitivity quality management system (3) indirectly representing the Raman chip to be detected, the light beam emitted by the light source passes through a self-focusing transmission optical fiber (4) or does not pass through the optical fiber to generate a small-caliber parallel light beam (5), the Raman chip (6) to be detected is vertically arranged with the parallel light beam (5) and is placed on a bracket (8), and the Raman chip (6) is positioned in a silver nitrate solution environment of a growing silver film, or in an ultrapure water (7) environment, or in a vacuum or inert gas environment; the periphery of the parallel light beam (5) and the Raman chip (6) to be inspected is provided with a dark-phase curtain (9) or is positioned in a darkroom, the small-caliber parallel light beam is transmitted through the Raman chip (6) and then is connected to a photoelectric detector system or a spectrometer system (2) through another self-focusing transmission optical fiber (4) or not through the optical fiber, H SP information of the Raman chip (6) is received and recorded, and a computer and H SP～HRS calibration software system and a management system (3) are responsible for processing H SP calibration nondestructive inspection, judging the sensitivity of the Raman chip to be inspected and displaying whether the sensitivity of the Raman chip in the quality inspection meets the requirements of factory quality inspection standards.
2. The SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality inspection method according to claim 1, wherein the Raman chip is a trimerization type silver foil/silver nanoparticle film Raman chip, a gold nanoparticle film Raman chip or a gold-plated silver nanoparticle film Raman chip which is formed by titanium dioxide film photocatalysis.
3. The method for calibrating the single-color transmitted light intensity nondestructive quality inspection of a SERS Raman chip according to claim 1, wherein the height H SP of the transmitted single-color light intensity, which is sensitive to the SPR effect and is suitable for calibrating the single-color light peak position, comprises the sum of three items of conventional molecular absorption, scattering loss and metal surface plasmon resonance SPR extinction-absorption, wherein an SPR absorption component is indispensable, the SPR absorption component indirectly represents the basis of the sensitivity quality of the Raman chip to be measured through detection H SP, and the conventional molecular absorption and conventional elastic scattering loss components only form the background for detecting the inelastic scattering SPR extinction-absorption component in H SP information.
4. The method for performing non-destructive quality inspection on SERS Raman chips by monochromatic transmission light intensity calibration according to claim 1, wherein in order to prevent oxidation of the Raman chip in air during quality inspection, H SP is detected in a vacuum environment, or in an inert gas, or in a silver nitrate solution for growing a silver nanoparticle film, or in ultra-pure water.
5. The SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality inspection method according to claim 1 is characterized in that in order to guarantee the accuracy of an H SP～HRS calibration curve, the number of calibration Raman chips with the same marking sensitivity T value is not less than 2, namely, the values of H SP and H RS on the H SP～HRS calibration curve are created by adopting the average value of not less than two calibration Raman chip experimental values with the same marking T value, and the number of different T values is not less than 5; if the scaling Raman chips with different T values are selected, the number of T is not less than 10, namely the number of the group of scaling Raman chips for creating the H SP～HRS scaling curve is not less than 10.
6. The SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality inspection method according to claim 1, wherein the Raman chip sensitivity quality inspection standard reaching range is a quality control limit, and the quality control limit is formulated according to H SP～HRS calibration curve results created by a group of calibration Raman chips with different sensitivities selected from the Raman chip production line and the quality inspection factory label-sensitivity quality inspection standard of the Raman chip.
7. The SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality inspection method according to claim 1, wherein in the nondestructive quality inspection equipment, a semiconductor laser or an LED monochromatic light source is adopted as a light source in a Raman chip quality inspection system, under the condition of no-load silver trimer-silver foil/silver nanoparticle film Raman chip quality inspection, (one) an SPR sensitive monochromatic wavelength exists in a visible light band, a 532nm wavelength semiconductor laser light source is adopted, the wavelength is exactly the peak position wavelength of an extinction-transmission spectrum SPR secondary peak of no-load Raman chip quality inspection, and the detection of H SP signal to noise ratio and cost performance by using the wavelength is much higher than that of a configuration ultraviolet visible light source and a high-valence spectrometer system; (II) or in the nondestructive quality inspection equipment, a semiconductor laser light source in a near infrared wave band of 820nm to 960nm is adopted, and a narrow-band filter and photoelectric detector system with the wavelength of the laser is adopted to detect H SP, and the Raman chip quality inspection H SP has the advantage of being easy to correctly distinguish whether quality inspection is qualified or not; and thirdly, a monochromatic LED light source with high cost performance is selected, and a narrow-band filter and a photoelectric detector system for detecting H SP with the center wavelength of the LED are also effective.
8. The SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality control method according to claim 1, wherein the method is characterized by comprising the following steps: in the nondestructive quality inspection equipment, a halogen tungsten light source and a spectrometer system are configured, and the sensitivity of a Raman chip is characterized by detecting H SP at the sensitive wavelength of 820nm-SPR of an extinction absorption spectrum curve of the Raman chip; or a halogen tungsten lamp light source, a 820nm narrow-band filter and a photoelectric detector system are configured, and the detection H SP represents the sensitivity of the Raman chip.
9. The SERS Raman chip monochromatic transmission light intensity calibration nondestructive quality inspection method according to claim 1, wherein the method is characterized in that (A) an ultraviolet visible light source, namely a deuterium halogen tungsten lamp light source, is configured, (B) or a deuterium lamp light source is configured, and (A) and (B) both adopt a near ultraviolet visible spectrometer or a near ultraviolet narrow-band filter and photomultiplier recording system to detect H SP of an SPR main peak.
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