CN105223185A - A kind of evaluation method of Raman spectrum fast detector - Google Patents
A kind of evaluation method of Raman spectrum fast detector Download PDFInfo
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- CN105223185A CN105223185A CN201510759772.8A CN201510759772A CN105223185A CN 105223185 A CN105223185 A CN 105223185A CN 201510759772 A CN201510759772 A CN 201510759772A CN 105223185 A CN105223185 A CN 105223185A
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Abstract
The invention provides a kind of evaluation method of Raman spectrum fast detector, comprise the steps: 1, determine that instrument to be evaluated is Raman spectrum fast detector, and determine the evaluating of this Raman spectrum fast detector, this evaluating comprises the accuracy of Raman shift, the repeatability of Raman shift, the repeatability of raman spectrum strength, sensitivity and detection time, and described sensitivity comprises signal to noise ratio (S/N ratio) and detection limit; 2, the accuracy of described Raman shift is evaluated; 3, the repeatability of described Raman shift is evaluated; Meanwhile, the repeatability of described raman spectrum strength is evaluated; 4, described signal to noise ratio (S/N ratio) is evaluated; 5, described detection limit is evaluated; Meanwhile, to evaluating described detection time; 6, evaluation result is drawn.The present invention is that the mode combined with physical method and chemical method is evaluated Raman spectrum fast detector, can the performance index of thoroughly evaluating Raman spectrum fast detector.
Description
Technical field
The present invention relates to instrument evaluation standardization areas, particularly relate to a kind of evaluation method of Raman spectrum fast detector.
Background technology
Raman spectroscopy analyzes one of various molecular structure and the most important spectral technique differentiating substance classes, take Raman spectroscopy as the Raman spectrum fast detector of core be the instrument adopting Raman spectrum principle to carry out field quick detection, this instrument is by kit (instrument that enhancing matrix need be adopted to carry out sample measurement comprises this kit), excitation source, scattered light collection system, beam splitting system, detection system, control to form with data handling system and standard diagram database, towards rapid and convenient Site Detection demand, there is miniaturization, low cost, the features such as high-sensitivity detection can be realized in conjunction with enhancing module, and its application of easily extensible, the food security be widely used in, environmental science, the field quick detection in the fields such as public safety.
But there is no the comprehensive evaluation for Raman spectrum fast detector and Product Level standard at present.Therefore, the quality of the Raman spectrum fast detector on market is uneven, and has the much follow-up technological development of the product needed of part just can complete detection, cannot detect fast, cause certain influence to its promotion and application.For this reason, need evaluation and the product standard of setting up Raman spectrometer, make Raman spectrum fast detector be easy to promote and obtain widespread use.
Summary of the invention
The technical problem to be solved in the present invention, be the evaluation method that a kind of Raman spectrum fast detector is provided, Raman spectrum fast detector for field quick detection is Appraising subject, strengthen matrix agent box to comprising, the detector of spectra database carries out method and the standard of the overall evaluation, facilitate applying and the standardization of evaluation method and standardization of Raman spectrum fast detector.
The present invention is achieved in that a kind of evaluation method of Raman spectrum fast detector, comprises the steps:
Step 1, determine that instrument to be evaluated is Raman spectrum fast detector, and determine the evaluating of this Raman spectrum fast detector, simultaneously, specification according to described Raman spectrum fast detector arranges corresponding optimum controlling condition, this evaluating comprises the accuracy of Raman shift, the repeatability of Raman shift, the repeatability of raman spectrum strength, sensitivity and detection time, and described sensitivity comprises signal to noise ratio (S/N ratio) and detection limit;
Step 2, evaluate the accuracy of described Raman shift, the evaluation procedure of the accuracy of this Raman shift is as follows:
Polystyrene standard sample is placed in the focal position of the signal acquisition probe of described Raman spectrum fast detector or the sample cell of described Raman spectrum fast detector, under this optimum controlling condition, measure the Raman spectrum of described polystyrene standard sample, Gaussian function fitting is utilized to obtain the Raman shift values of raman spectra, duplicate measurements 3 times, calculate the difference of the respective value in the Raman shift values of each each raman spectra measured and normalized Raman shift value respectively, take out respectively and measure 3 maximum differences obtained 3 times, get the accuracy of the maximal value in 3 maximum differences as described Raman shift again,
Step 3, evaluate the repeatability of described Raman shift, the evaluation procedure of the repeatability of this Raman shift is as follows:
Polystyrene standard sample is placed in the focal position of the signal acquisition probe of described Raman spectrum fast detector or the sample cell of described Raman spectrum fast detector, under this optimum controlling condition, the Raman spectrum of duplicate measurements 6 polystyrene standard sample again, Gaussian function fitting is utilized to obtain the Raman shift values of 6 groups of raman spectras and the numerical value of raman spectrum strength, and record Raman shift values and the raman spectrum strength change of this raman spectra, in the Raman shift values of the raman spectra recorded for 6 times, the difference of maximum difference and minimal difference is the repeated △ S of Raman shift,
, evaluate the repeatability of described raman spectrum strength, the evaluation procedure of the repeatability of this raman spectrum strength is as follows meanwhile:
The numerical value of the raman spectrum strength recorded 6 times substitutes into Bessel Formula and calculates its relative standard deviation, and be the repeatability of raman spectrum strength, computing formula is as follows:
In formula: δ
irepresent the repeatability of raman spectrum strength, its unit is %; I
irepresent the numerical value of i-th raman spectrum strength;
represent the mean value of 6 raman spectrum strength; N is the number of times representing measurement;
Step 4, evaluate described signal to noise ratio (S/N ratio), the evaluation procedure of this signal to noise ratio (S/N ratio) is as follows:
Direct irradiation sample is carried out to the Raman spectrum fast detector detected, check the signal to noise ratio (S/N ratio) of this Raman spectrum fast detector; By Laser Focusing on the surface processing clean monocrystalline silicon, under the optimum controlling condition of this Raman spectrum fast detector, test its Raman spectrum, record is positioned at 940cm
-1± 4cm
-1the intensity of the silicon raman spectra in scope and be positioned at 600cm
-1~ 800cm
-1baseline noise intensity in scope, repeat above-mentioned steps 3 times, what record is positioned at 940cm at every turn
-1± 4cm
-1the intensity of the silicon raman spectra in scope and be positioned at 600cm
-1~ 800cm
-1baseline noise intensity ratio in scope is the signal to noise ratio (S/N ratio) of this measurement, gets the signal to noise ratio (S/N ratio) of maximal value as this Raman spectrum fast detector of 3 signal to noise ratio (S/N ratio)s;
Step 5, evaluate described detection limit, the evaluation procedure of this detection limit is as follows:
Strengthening for adopting the Raman spectrum fast detector that matrix carries out sample measurement, checking the detection limit of this Raman spectrum fast detector; According to the method preparation object standard solution of the object measurement that this Raman spectrum fast detector is set up, 10 times of the object detection limit that the concentration of this object standard solution is this Raman spectrum fast detector institute nominal, and the matched reagent box using this Raman spectrum fast detector to provide processes the object standard solution after preparation, and carry out 11 mensuration respectively, and record the concentration indicating value measured for each time;
The concentration indicating value that 11 times are measured is carried out detection limit calculating, and computing formula is as follows:
DL＝(2S/I)×c
In formula: DL represents minimal detectable concentration, its unit is mg/L; I represents the mean value of 11 object standard solution measurements; S represents the standard deviation of 11 object standard solution measured values; C represents the concentration of object standard solution, and its unit is mg/L;
, evaluate described detection time, the evaluation procedure of this detection time is as follows meanwhile:
At least add up during this object standard solution is measured for 11 times the detection time of measuring for 1 time, and calculate its maximal value; Step 2, step 3, step 4 and step 5 do not have sequencing;
Step 6, draw evaluation result:
The accuracy of requirement 1, described Raman shift is no more than 4cm
-1;
The repeatability of requirement 2, described Raman shift is no more than 1cm
-1;
The repeatability of requirement 3, described raman spectrum strength is not more than 5%;
Require 4, direct irradiation sample carried out to the Raman spectrum fast detector that detects, measure monocrystalline silicon and be positioned at 940cm
-1± 4cm
-1the intensity of the silicon raman spectra in scope is high-visible, and signal to noise ratio (S/N ratio) is not less than 3:1;
Requiring 5, strengthening for adopting the Raman spectrum fast detector that matrix carries out sample detection, the detection limit of respective objects thing standard solution meets the limitation requirement of Raman spectrum fast detector nominal;
The maximal value of the detection time of requirement 6, this object standard solution is not more than 20min;
If reach above requirement simultaneously, then illustrate that the technical feature of described Raman spectrum fast detector meets the requirement detecting targets anticipate; Otherwise, illustrate that the technical feature of described Raman spectrum fast detector does not meet the requirement detecting targets anticipate.
Further, the optimum controlling condition of described Raman spectrum fast detector comprises the optimum value of optical maser wavelength, the optimum value of spectral range, the optimum value of laser peak power, the optimum value of integral time, the optimum value of cumulative frequency and the optimum value of preheating time.
Tool of the present invention has the following advantages:
1, propose the standard of Raman spectrum fast detector, namely define, require, test method, inspection rule, mark, packaging, transport and storage etc.;
2, the method will promote applying and the standardization of assessment technique and standardization of Raman spectrum fast detector;
3, propose based on the evaluation criterion of Raman spectrum fast detector, the spectrometer of this Raman spectrum fast detector and the use of Contrast agent box should meet quick, the requirement easily of object measuring process, examining report can be provided in 20min, realize direct, the effective evaluation of the object detection perform of the Raman spectrum fast detector to field quick detection;
4, (evaluate wave number accuracy with polystyrene with physical method, wave number is repeated, spectral intensity is repeated, signal to noise ratio (S/N ratio) with the direct surveying instrument of monocrystalline silicon second order peak evaluation) and chemical method (to adopt strengthen instrument that matrix carries out sample detection adopt detect object and carry out the evaluation of detection limit) technical requirement such as the mode that combines is repeated to the displacement accuracy of Raman spectrum fast detector, displacement repeatability, spectral intensity, measurement sensistivity evaluates, can the performance index of thoroughly evaluating Raman spectrum fast detector;
5, adopt nontoxic polystyrene as wave number accuracy, wave number repeatability, the standard substance of spectral intensity Repeatability checking, to human non-toxic's evil in operating process, environmentally safe;
6, define with the index of opening the global index that Raman spectrum fast detector measures object, the i.e. requirement of measurement sensistivity: to evaluating with the signal to noise ratio (S/N ratio) at monocrystalline silicon second order peak by the instrument that detects of direct irradiation sample, the instrument that matrix carries out object detection is strengthened, to comprising the entirety of kit to promise to undertake that the detection limit measuring object is evaluated for adopting; There is the features such as evaluation is quick, standard model good stability, guarantee science and the comparability of evaluation method.
Accompanying drawing explanation
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is the flowchart of the evaluation method of a kind of Raman spectrum fast detector of the present invention.
Fig. 2 is the Raman spectrogram (three groups of data) of the polystyrene test of the evaluation method of a kind of Raman spectrum fast detector of the present invention.
Fig. 3 is the Raman spectrogram (six groups of data) of the polystyrene test of the evaluation method of a kind of Raman spectrum fast detector of the present invention.
Fig. 4 is the silicon chip Raman spectrogram (signal to noise ratio (S/N ratio) test) of the evaluation method of a kind of Raman spectrum fast detector of the present invention.
Fig. 5 is the rhodamine B sample Raman spectrogram of the evaluation method of a kind of Raman spectrum fast detector of the present invention.
Fig. 6 is the basic orange II test Raman spectrogram of the evaluation method of a kind of Raman spectrum fast detector of the present invention.
Embodiment
For making the present invention become apparent, below with a preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
Raman spectrum fast detector should have the basic demands such as the convenience of use, mobility, detection be quick.Therefore, should define from the angle of the actual use of instrument the quick instrument of Raman spectrum, mainly refer to and directly can carry out Quick Measurement to sample, and result is provided in 20min, without the need to more than 4 hours can be used continuously when external power supply, easy to carry, the mobile Raman spectrum detector without the need to recalibrating.Corresponding, its relevant technical indicator is specified and requirement from the angle detected fast.
As shown in Figure 1, the evaluation method of a kind of Raman spectrum fast detector of the present invention, comprises the steps:
Step 1, determine that instrument to be evaluated is Raman spectrum fast detector, and determine the evaluating of this Raman spectrum fast detector, simultaneously, (optimum controlling condition of the Raman spectrum fast detector of certain model comprises the optimum value of optical maser wavelength, the optimum value of spectral range, the optimum value of laser peak power, the optimum value of integral time, the optimum value of cumulative frequency and the optimum value of preheating time, is specifically set to: optical maser wavelength: 785nm, spectral range: 100cm to arrange corresponding optimum controlling condition according to the specification of described Raman spectrum fast detector
-1-2500cm
-1, laser peak power: 100mW, integral time: 1s, cumulative frequency: 1 time, preheating time: 30min), this evaluating comprises the accuracy of Raman shift, the repeatability of Raman shift, the repeatability of raman spectrum strength, sensitivity and detection time, and described sensitivity comprises signal to noise ratio (S/N ratio) and detection limit;
Step 2, evaluate the accuracy of described Raman shift, the evaluation procedure of the accuracy of this Raman shift is as follows:
Polystyrene standard sample is placed in the focal position of the signal acquisition probe of described Raman spectrum fast detector or the sample cell of described Raman spectrum fast detector, under this optimum controlling condition, measure the Raman spectrum of described polystyrene standard sample, Gaussian function fitting is utilized to obtain the Raman shift values of raman spectra, duplicate measurements 3 times, calculate the difference of the respective value in the Raman shift values of each each raman spectra measured and normalized Raman shift value respectively, take out respectively and measure 3 maximum differences obtained 3 times, get the accuracy of the maximal value in 3 maximum differences as described Raman shift again,
Normalized Raman shift value includes the Raman shift values of 11 raman spectras, is respectively: 620.9cm
-1, 795.8cm
-1, 1001.4cm
-1, 1031.8cm
-1, 1155.3cm
-1, 1450.5cm
-1, 1583.1cm
-1, 1602.3cm
-1, 2852.4cm
-1, 2904.5cm
-1and 3054.3cm
-1; , test a part or four corner that the data recorded are normalized Raman shift values;
The Raman shift values of each raman spectra measured for the 1st time is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, calculate the Raman shift values (620.33cm of this raman spectra respectively
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1) with normalized Raman shift value in respective value (620.9cm
-1, 795.8cm
-1, 1001.4cm
-1, 1155.3cm
-1, 1583.1cm
-1) difference, difference is respectively: 0.57cm
-1, 3.51cm
-1, 2.7cm
-1, 1.56cm
-1, 3.5cm
-1, its maximum difference is 3.51cm
-1;
The Raman shift values of each raman spectra measured for the 2nd time is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, calculate the Raman shift values (620.33cm of this raman spectra respectively
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1) with normalized Raman shift value in respective value (620.9cm
-1, 795.8cm
-1, 1001.4cm
-1, 1155.3cm
-1, 1583.1cm
-1) difference, difference is respectively: 0.57cm
-1, 3.51cm
-1, 2.7cm
-1, 1.56cm
-1, 3.5cm
-1, its maximum difference is 3.51cm
-1;
The Raman shift values of each raman spectra measured for the 3rd time is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, calculate the Raman shift values (620.33cm of this raman spectra respectively
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1) with normalized Raman shift value in respective value (620.9cm
-1, 795.8cm
-1, 1001.4cm
-1, 1155.3cm
-1, 1583.1cm
-1) difference, difference is respectively: 0.57cm
-1, 3.51cm
-1, 2.70cm
-1, 1.56cm
-1, 3.5cm
-1, its maximum difference is 3.51cm
-1;
Three displacement measurement values are as shown in following table (table 1):
Table 1:
| For the first time | For the second time | For the third time |
| 620.33cm -1 | 620.33cm -1 | 620.33cm -1 |
| 792.29cm -1 | 792.29cm -1 | 792.29cm -1 |
| 998.70cm -1 | 998.70cm -1 | 998.70cm -1 |
| 1153.74cm -1 | 1153.74cm -1 | 1153.74cm -1 |
| 1579.60cm -1 | 1579.60cm -1 | 1579.60 |
As shown in Figure 2, the maximal value of 3 maximum differences is 3.51cm to the Raman spectrogram (three groups of data) of its polystyrene test
-1, therefore get 3.51cm
-1as the accuracy of described Raman shift;
Step 3, evaluate the repeatability of described Raman shift, the evaluation procedure of the repeatability of this Raman shift is as follows:
Polystyrene standard sample is placed in the focal position of the signal acquisition probe of described Raman spectrum fast detector or the sample cell of described Raman spectrum fast detector, under this optimum controlling condition, the Raman spectrum of duplicate measurements 6 polystyrene standard sample again, Gaussian function fitting is utilized to obtain the Raman shift values of 6 groups of raman spectras and the numerical value of raman spectrum strength, and record Raman shift values and the raman spectrum strength change of this raman spectra, in the Raman shift values of the raman spectra recorded for 6 times, the difference of maximum difference and minimal difference is the repeated △ S of Raman shift,
The Raman shift values of each raman spectra measured for the 1st time is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, the numerical value of raman spectrum strength is 1337,3372,28504,2866,2524;
The Raman shift values of each raman spectra measured for the 2nd time is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, the numerical value of raman spectrum strength is 1304,3347,28469,2848,2524;
The Raman shift values of each raman spectra measured for the 3rd time is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, the numerical value of raman spectrum strength is 1290,3347,28469,2812,2514;
The Raman shift values of each raman spectra that the 4th is measured is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, the numerical value of raman spectrum strength is 1290,3332,28445,2805,2497;
The Raman shift values of each raman spectra that the 5th is measured is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, the numerical value of raman spectrum strength is 1272,3332,28379,2794,2490;
The Raman shift values of each raman spectra measured for the 6th time is respectively: 620.33cm
-1, 792.29cm
-1, 998.70cm
-1, 1153.74cm
-1, 1579.60cm
-1, the numerical value of raman spectrum strength is 1258,3302,28336,2756,2483;
Six displacement measurement values are as shown in following table (table 2):
Table 2:
| For the first time | For the second time | For the third time | 4th time | 5th time | 6th time |
| 620.33cm -1 | 620.33cm -1 | 620.33cm -1 | 620.33cm -1 | 620.33cm -1 | 620.33cm -1 |
| 792.29cm -1 | 792.29cm -1 | 792.29cm -1 | 792.29cm -1 | 792.29cm -1 | 792.29cm -1 |
| 998.70cm -1 | 998.70cm -1 | 998.70cm -1 | 998.70cm -1 | 998.70cm -1 | 998.70cm -1 |
| 1153.74cm -1 | 1153.74cm -1 | 1153.74cm -1 | 1153.74cm -1 | 1153.74cm -1 | 1153.74cm -1 |
| 1579.60cm -1 | 1579.60cm -1 | 1579.60cm -1 | 1579.60cm -1 | 1579.60cm -1 | 1579.60cm -1 |
In the Raman shift values of the raman spectra recorded for 6 times, maximum difference is 0cm
-1, minimal difference is 0cm
-1, the difference of its maxima and minima is 0cm
-1, then the repeated △ S=0cm of Raman shift
-1, the Raman spectrogram (six groups of data) of its polystyrene test as shown in Figure 3;
Six strength test values are as shown in following table (table 3):
Table 3:
| For the first time | For the second time | For the third time | 4th time | 5th time | 6th time |
| 1337 | 1304 | 1290 | 1290 | 1272 | 1258 |
| 3372 | 3347 | 3347 | 3332 | 3332 | 3302 |
| 28504 | 28469 | 28469 | 28445 | 28379 | 28336 |
| 2866 | 2848 | 2812 | 2805 | 2794 | 2756 |
| 2524 | 2524 | 2514 | 2497 | 2490 | 2483 |
, evaluate the repeatability of described raman spectrum strength, the evaluation procedure of the repeatability of this raman spectrum strength is as follows meanwhile:
The numerical value of the raman spectrum strength that 6 times record in step 3 is substituted into Bessel Formula and calculates its relative standard deviation, be the repeatability of raman spectrum strength, computing formula is as follows:
In formula: δ
irepresent the repeatability of raman spectrum strength, its unit is %; I
irepresent the numerical value of i-th raman spectrum strength; I represents the mean value of 6 raman spectrum strength; N is the number of times representing measurement;
Can calculate according to formula: 620.33cm
-1the repeatability of place's raman spectrum strength: δ
i=2.1%, 792.29cm
-1the repeatability of place's raman spectrum strength: δ
i=0.69%, 998.70cm
-1the repeatability of place's raman spectrum strength: δ
i=0.22%, 1153.74cm
-1the repeatability of place's raman spectrum strength: δ
i=1.3%, 1579.60cm
-1the repeatability of place's raman spectrum strength: δ
i=0.7%;
If a Raman spectrum fast detector both can detect by direct irradiation sample, also can detect by reagents box, then the signal to noise ratio (S/N ratio) of this Raman spectrum fast detector and detection limit were all tested; If Raman spectrum fast detector only direct irradiation sample detects, then the signal to noise ratio (S/N ratio) of this Raman spectrum fast detector is tested; If Raman spectrum fast detector only reagents box detects, then the detection limit of this Raman spectrum fast detector is all tested;
Step 4, evaluate described signal to noise ratio (S/N ratio), the evaluation procedure of this signal to noise ratio (S/N ratio) is as follows:
By Laser Focusing on the surface processing clean monocrystalline silicon, under the optimum controlling condition of this Raman spectrum fast detector, test its Raman spectrum, record is positioned at 940cm
-1± 4cm
-1the intensity of the silicon raman spectra in scope and be positioned at 600cm
-1~ 800cm
-1baseline noise intensity in scope, repeat above-mentioned steps 3 times, what record is positioned at 940cm at every turn
-1± 4cm
-1the intensity of the silicon raman spectra in scope and be positioned at 600cm
-1~ 800cm
-1baseline noise intensity ratio in scope is the signal to noise ratio (S/N ratio) of this measurement, gets the signal to noise ratio (S/N ratio) of maximal value as this Raman spectrum fast detector of 3 signal to noise ratio (S/N ratio)s;
Three signal to noise ratio (S/N ratio) tests are as shown in following table (table 4):
Table 4:
The maximal value of 3 signal to noise ratio (S/N ratio)s is 17.5, then the signal to noise ratio (S/N ratio) of this Raman spectrum fast detector is 17.50, and the silicon chip Raman spectrogram (three groups of data) of its signal to noise ratio (S/N ratio) test as shown in Figure 4;
Step 5, evaluate described detection limit, the evaluation procedure of this detection limit is as follows:
Strengthening for adopting the Raman spectrum fast detector that matrix carries out sample measurement, checking the detection limit of this Raman spectrum fast detector; According to the method preparation object standard solution of the object measurement that this Raman spectrum fast detector is set up, 10 times of the object detection limit that the concentration of this object standard solution is this Raman spectrum fast detector institute nominal, and the matched reagent box using this Raman spectrum fast detector to provide processes the object standard solution after preparation, and carry out 11 mensuration respectively, and record the concentration indicating value measured for each time;
The concentration indicating value that 11 times are measured is carried out detection limit calculating, and computing formula is as follows:
DL＝(2S/I)×c
In formula: DL represents minimal detectable concentration, its unit is mg/L; I represents the mean value of 11 object standard solution measurements; S represents the standard deviation of 11 object standard solution measured values; C represents the concentration of object standard solution, and its unit is mg/L;
, evaluate described detection time, the evaluation procedure of this detection time is as follows meanwhile:
At least add up during this object standard solution is measured for 11 times the detection time of measuring for 1 time, and calculate its maximal value;
If object standard solution is rhodamine B standard solution, according to the supporting detection method of this Raman spectrum fast detector instructions, to pipette in 1mg/L rhodamine B standard solution 200 μ L and 200 μ L nanoparticles solution to sample hose with pipettor and mix, in 25s ~ 30s, detect the Raman spectrum of rhodamine B standard solution, and record is positioned at 1642cm
-1± 2cm
-1the intensity of the raman spectra in scope, repeat above-mentioned steps 11 times, and the intensity of the raman spectra recorded is carried out detection limit calculating, computing formula is as follows:
DL＝(2S/I)×c
In formula: DL represents minimal detectable concentration (detection limit of rhodamine B standard solution), and its unit is mg/L; I represents the mean value of the intensity of the raman spectra measured for 11 times; S represents the standard deviation of the intensity of the raman spectra measured for 11 times; C represents the concentration of rhodamine B standard solution, and its unit is mg/L;
Rhodamine B experiment (spectrum peak position: 1641cm
-1) as shown in following table (table 5):
Table 5:
Standard deviation S=217.42 of intensity of raman spectra calculate the mean value I=6441.63 of the intensity of the raman spectra that 11 times are measured, measuring for 11 times, and the concentration c=1mg/L of rhodamine B standard solution, can draw the detection limit DL=0.067mg/L ≈ 0.1mg/L of rhodamine B standard solution according to formula, its rhodamine B sample Raman spectrogram (11 groups of data) as shown in Figure 5;
If object standard solution is basic orange II, then basic orange II experiment (spectrum peak position: 482cm
-1) as shown in following table (table 6):
Table 6:
Calculate the mean value I=3250.63 of the intensity of the raman spectra that 11 times are measured, standard deviation S=163.88 of the intensity of the raman spectra measured for 11 times, and the concentration c=10mg/L of basic orange II solution, can draw the detection limit DL=1mg/L of basic orange II according to formula, its basic orange II test Raman spectrogram (11 groups of data) as shown in Figure 6;
Meanwhile, at least add up during rhodamine B standard solution is measured for 11 times the detection time of measuring for 1 time, and at least add up during basic orange II standard solution is measured for 11 times the detection time of measuring for 1 time; Step 2, step 3, step 4 and step 5 do not have sequencing;
Step 6, draw evaluation result:
The accuracy of requirement 1, described Raman shift is no more than 4cm
-1;
The repeatability of requirement 2, described Raman shift is no more than 1cm
-1;
The repeatability of requirement 3, described raman spectrum strength is not more than 5%;
Require 4, direct irradiation sample carried out to the Raman spectrum fast detector that detects, measure monocrystalline silicon and be positioned at 940cm
-1± 4cm
-1the intensity of the silicon raman spectra in scope is high-visible, and signal to noise ratio (S/N ratio) is not less than 3:1;
Requiring 5, strengthening for adopting the Raman spectrum fast detector that matrix carries out sample detection, the detection limit of respective objects thing standard solution meets the limitation requirement of Raman spectrum fast detector nominal;
The maximal value of the detection time of requirement 6, this object standard solution (rhodamine B standard solution and basic orange II standard solution) is not more than 20min;
If reach above requirement simultaneously, then illustrate that the technical feature of described Raman spectrum fast detector meets the requirement detecting targets anticipate; Otherwise, illustrate that the technical feature of described Raman spectrum fast detector does not meet the requirement detecting targets anticipate.
Experimentally known, the accuracy of described Raman shift is 3.51cm
-1, described Raman shift repeatability be 0cm
-1, described raman spectrum strength repeatability be 2.1%, direct irradiation sample carried out to the Raman spectrum fast detector that detects, measure monocrystalline silicon and be positioned at 940cm
-1± 4cm
-1the intensity of the silicon raman spectra in scope is high-visible, and signal to noise ratio (S/N ratio) be 17.5, the detection limit DL=0.067mg/L ≈ 0.1mg/L of rhodamine B standard solution, the detection limit DL=1mg/L of basic orange II, be all less than the detection limit of instrument nominal; Therefore illustrate that the technical feature of described Raman spectrum fast detector meets the requirement detecting targets anticipate.
Although the foregoing describe the specific embodiment of the present invention; but be familiar with those skilled in the art to be to be understood that; specific embodiment described by us is illustrative; instead of for the restriction to scope of the present invention; those of ordinary skill in the art, in the modification of the equivalence done according to spirit of the present invention and change, should be encompassed in scope that claim of the present invention protects.
Claims (2)
1. an evaluation method for Raman spectrum fast detector, is characterized in that: comprise the steps:
Step 1, determine that instrument to be evaluated is Raman spectrum fast detector, and determine the evaluating of this Raman spectrum fast detector, simultaneously, specification according to described Raman spectrum fast detector arranges corresponding optimum controlling condition, this evaluating comprises the accuracy of Raman shift, the repeatability of Raman shift, the repeatability of raman spectrum strength, sensitivity and detection time, and described sensitivity comprises signal to noise ratio (S/N ratio) and detection limit;
Step 2, evaluate the accuracy of described Raman shift, the evaluation procedure of the accuracy of this Raman shift is as follows:
Polystyrene standard sample is placed in the focal position of the signal acquisition probe of described Raman spectrum fast detector or the sample cell of described Raman spectrum fast detector, under this optimum controlling condition, measure the Raman spectrum of described polystyrene standard sample, Gaussian function fitting is utilized to obtain the Raman shift values of raman spectra, duplicate measurements 3 times, calculate the difference of the respective value in the Raman shift values of each each raman spectra measured and normalized Raman shift value respectively, take out respectively and measure 3 maximum differences obtained 3 times, get the accuracy of the maximal value in 3 maximum differences as described Raman shift again,
Step 3, evaluate the repeatability of described Raman shift, the evaluation procedure of the repeatability of this Raman shift is as follows:
Polystyrene standard sample is placed in the focal position of the signal acquisition probe of described Raman spectrum fast detector or the sample cell of described Raman spectrum fast detector, under this optimum controlling condition, the Raman spectrum of duplicate measurements 6 polystyrene standard sample again, Gaussian function fitting is utilized to obtain the Raman shift values of 6 groups of raman spectras and the numerical value of raman spectrum strength, and record Raman shift values and the raman spectrum strength change of this raman spectra, in the Raman shift values of the raman spectra recorded for 6 times, the difference of maximum difference and minimal difference is the repeated △ S of Raman shift,
, evaluate the repeatability of described raman spectrum strength, the evaluation procedure of the repeatability of this raman spectrum strength is as follows meanwhile:
The numerical value of the raman spectrum strength recorded 6 times substitutes into Bessel Formula and calculates its relative standard deviation, and be the repeatability of raman spectrum strength, computing formula is as follows:
In formula: δ
irepresent the repeatability of raman spectrum strength, its unit is %; I
irepresent the numerical value of i-th raman spectrum strength;
represent the mean value of 6 raman spectrum strength; N is the number of times representing measurement;
Step 4, evaluate described signal to noise ratio (S/N ratio), the evaluation procedure of this signal to noise ratio (S/N ratio) is as follows:
Direct irradiation sample is carried out to the Raman spectrum fast detector detected, check the signal to noise ratio (S/N ratio) of this Raman spectrum fast detector; By Laser Focusing on the surface processing clean monocrystalline silicon, under the optimum controlling condition of this Raman spectrum fast detector, test its Raman spectrum, record is positioned at 940cm
-1± 4cm
-1the intensity of the silicon raman spectra in scope and be positioned at 600cm
-1~ 800cm
-1baseline noise intensity in scope, repeat above-mentioned steps 3 times, what record is positioned at 940cm at every turn
-1± 4cm
-1the intensity of the silicon raman spectra in scope and be positioned at 600cm
-1~ 800cm
-1baseline noise intensity ratio in scope is the signal to noise ratio (S/N ratio) of this measurement, gets the signal to noise ratio (S/N ratio) of maximal value as this Raman spectrum fast detector of 3 signal to noise ratio (S/N ratio)s;
Step 5, evaluate described detection limit, the evaluation procedure of this detection limit is as follows:
Strengthening for adopting the Raman spectrum fast detector that matrix carries out sample measurement, checking the detection limit of this Raman spectrum fast detector; According to the method preparation object standard solution of the object measurement that this Raman spectrum fast detector is set up, 10 times of the object detection limit that the concentration of this object standard solution is this Raman spectrum fast detector institute nominal, and the matched reagent box using this Raman spectrum fast detector to provide processes the object standard solution after preparation, and carry out 11 mensuration respectively, and record the concentration indicating value measured for each time;
The concentration indicating value that 11 times are measured is carried out detection limit calculating, and computing formula is as follows:
DL＝(2S/I)×c
In formula: DL represents minimal detectable concentration, its unit is mg/L; I represents the mean value of 11 object standard solution measurements; S represents the standard deviation of 11 object standard solution measured values; C represents the concentration of object standard solution, and its unit is mg/L;
, evaluate described detection time, the evaluation procedure of this detection time is as follows meanwhile:
At least add up during this object standard solution is measured for 11 times the detection time of measuring for 1 time, and calculate its maximal value; Step 2, step 3, step 4 and step 5 do not have sequencing;
Step 6, draw evaluation result:
The accuracy of requirement 1, described Raman shift is no more than 4cm
-1;
The repeatability of requirement 2, described Raman shift is no more than 1cm
-1;
The repeatability of requirement 3, described raman spectrum strength is not more than 5%;
Require 4, direct irradiation sample carried out to the Raman spectrum fast detector that detects, measure monocrystalline silicon and be positioned at 940cm
-1± 4cm
-1the intensity of the silicon raman spectra in scope is high-visible, and signal to noise ratio (S/N ratio) is not less than 3:1;
Requiring 5, strengthening for adopting the Raman spectrum fast detector that matrix carries out sample detection, the detection limit of respective objects thing standard solution meets the limitation requirement of Raman spectrum fast detector nominal;
The maximal value of the detection time of requirement 6, this object standard solution is not more than 20min;
If the testing result of Raman spectrum fast detector reaches above requirement simultaneously, then illustrate that the technical feature of described Raman spectrum fast detector meets the requirement detecting targets anticipate; Otherwise, illustrate that the technical feature of described Raman spectrum fast detector does not meet the requirement detecting targets anticipate.
2. the evaluation method of a kind of Raman spectrum fast detector as claimed in claim 1, is characterized in that: the optimum controlling condition of described Raman spectrum fast detector comprises the optimum value of optical maser wavelength, the optimum value of spectral range, the optimum value of laser peak power, the optimum value of integral time, the optimum value of cumulative frequency and the optimum value of preheating time.
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