Summary of the invention
Technology of the present invention is dealt with problems and is: overcome above-mentioned the deficiencies in the prior art, a kind of high-sensitivity surface plasma biochemical sensitive detector of simple and practical two-sided gaussian-shape section metal nano optical grating construction is provided.
Technical solution of the present invention is: biochemical sensitive detector for surface plasma, and its characteristics are: comprise sample test board, metal Nano structure substrate, semi-transparent semi-reflecting prism square or semi-transparent semi-reflecting lens or catoptron, polaroid, optical filter, collimating mirror, lighting fiber, collecting lens, xenon source, condenser, monochromator, photomultiplier, signal Processing digital converter, computing machine part, tested biological sample, XY scan table and turntable driving controller; Xenon source, collecting lens and lighting fiber are formed the illuminator to tested biological sample illumination; Collimating mirror, optical filter, polaroid and semi-transparent semi-reflecting prism square or semi-transparent semi-reflecting lens or catoptron are placed successively, the illumination light that illuminator is sent becomes the tested biological sample of the TM of certain wavelength coverage polarization parallel rayed, and the metal Nano structure substrate that scribbles tested biological sample is placed on the sample test board on the XY scan table; Condenser, monochromator and photomultiplier are formed detection optical system, be placed in a side of semi-transparent semi-reflecting prism square or semi-transparent semi-reflecting lens or catoptron, inject in tested biological sample and the metal Nano structure substrate after having collimated partially by the light that illuminator penetrates, produce the localization surface plasma body resonant vibration, the detection light that penetrates passes through detection optical system, received electric signal and be converted to by photomultiplier, send into the computing machine part by signal Processing and digital conversion again, detect the kind of biological sample, after having detected the tested biological sample at this place, move to the another location by computing machine part and turntable driving controller gated sweep platform again and detect, all tested biological samples that need detect have all detected on the metal Nano structure substrate.
The described illuminator of being made up of xenon source, collecting lens and lighting fiber is placed in the top, and the below is placed collimating mirror, optical filter, polaroid, semi-transparent semi-reflecting prism square or semi-transparent semi-reflecting lens or catoptron successively.
The described illuminator of being made up of xenon source, collecting lens and lighting fiber is placed in below, and the top is placed collimating mirror, optical filter, polaroid, semi-transparent semi-reflecting prism square or semi-transparent semi-reflecting lens or catoptron successively.
Described this device metal nanostructured substrate is made up of substrate and metal Nano structure diaphragm, substrate is that a height that is compressed on the metal Nano structure diaphragm reflects the transmission substance layer, its relative index of refraction is 1.55-1.85, the metal Nano structure diaphragm is a diaphragm that is made of gold copper-base alloy, the thickness of this diaphragm is 35-135nm, cycle gaussian-shape section nanometer grating structure such as all be carved with in its upper and lower surface, adopt ion beam or electronic beam photetching process to make, with the wherein some gaussian-shape channel bottoms 0 of upper surface is true origin, and the surface structure contour representation is:
The lower surface configuration contour representation is:
Λ is the grating cycle in the formula, and H is a groove depth, and ω is Gauss's groove width, t for the degree of depth of not carving (t 〉=5nm), m is the grating number, grating periods lambda=250-650nm, groove depth H=15-55nm does not carve degree of depth t=5-25nm, Gauss's groove width ω=12-80nm.
The present invention compared with prior art has the following advantages:
(1) resonance curve that obtains of sensor of the present invention peak value height not only, and peak of curve full width at half maximum value is very little, and refractive index sensitivity is big, make the quality factor that reaches very high, so sensing sensitivity also reaches very high.
(2) sensing adopts two-sided gaussian-shape cross-section structure with metal nano optical grating construction substrate, owing to be the metal grating structure of gaussian-shape section, photoetching of available electron bundle or ion beam lithography method are convenient makes.
(3) whole sensing testing apparatus structure is simple, practical, easy to adjust, and is low to environmental requirement, and the precision of sensing measurement is very high.
(4) can be coated with on the metal Nano structure substrate and put a lot of tested biological sample arrays, computerized control to move respectively and detect, thereby detection efficiency and speed height be easy to apply.
Embodiment
As shown in Figure 1, be the biochemical sensitive detector for surface plasma scantling plan of the embodiment of the invention 1.It is made up ofsample test board 1, metalNano structure substrate 2, semi-transparentsemi-reflecting prism square 4,polaroid 6,optical filter 7,collimating mirror 8,lighting fiber 9, collectinglens 10,xenon source 11,condenser 13,monochromator 14,photomultiplier 16, signal Processingdigital converter 17,computing machine part 18, testedbiological sample 19, XY scan table 20 and turntable driving controller 21.Xenonsource 11, collectinglens 10 andlighting fiber 9 are formed the illuminator to testedbiological sample 19 illuminations, and are placed in collimatingmirror 8 tops.Collimating mirror 8,optical filter 7,polaroid 6 and the semi-transparentsemi-reflecting prism square 4 that place successively the below becomes illumination light to have the TM polarization parallel light of certain wavelength coverage, and scribbles testedbiological sample 19 and metalNano structure substrate 2 by the many places that semi-transparentsemi-reflecting prism square 4 is vertically injected the below.The metalNano structure substrate 2 of testedbiological sample 19 is placed on thesample test board 1, andsample test board 1 is placed on the XY scan table 20, and XY scan table 20 positions are controlled byturntable driving controller 21 by computing machine part 18.Semi-transparentsemi-reflecting prism square 4,condenser 13,monochromator 14 andphotomultiplier 16 are formed detection optical system, are placed in a side of semi-transparentsemi-reflecting prism square 4 successively.The continuous spectrum thatxenon source 11 sends gathers light by collectinglens 10 theincident end 902 oflighting fiber 9, lightimports lighting fiber 9 into by incident end face, afterlighting fiber 9 transmission, penetrate from the exit facet of theexit end 901 oflighting fiber 9, the diverging light that optical fiber penetrates is through collimatingmirror 8 collimations, after collimated light passes throughoptical filter 7 optical filterings andpolaroid 6 polarizings, becoming wavelength coverage is the TM polarizationparallel light 5 of 450nm-950nm, vertically inject two right-angle prisms forming semi-transparentsemi-reflecting prism square 4 then, vertically inject many places from the TM polarizationparallel light 3 of prism square ejaculation and scribble testedbiological sample 19 and metalNano structure substrate 2, owing to make to have nanostructured on the metallic film top and bottom of metalNano structure substrate 2, produce the localization surface plasma body resonant vibration, its reflectedlight 12 former roads are returned and are injected semi-transparentsemi-reflecting prism square 4, and the semi-reflective surface of passing through wherein 403 reflects, penetrate from 90 ° of angular direction, injectmonochromator 14 bycondenser 13 optically focused, aftermonochromator 14 beam split,inject photomultiplier 16,photomultiplier 16 is converted to electric signal with the light signal that is detected, amplify simultaneously, handle and be converted to digital signal by signal Processingdigital converter 17 again, send intocomputing machine part 18, relatively detect certain position sample reflectance spectrum curve on the metalNano structure substrate 2 by computing machine, determine the kind of biological sample, after having detected the tested biological sample at this place, move to the another location bycomputing machine part 18 andturntable driving controller 21 control XY scan tables 20 again and detect, all testedbiological samples 19 that need detect have all detected on metalNano structure substrate 2.
As shown in Figure 1, semi-transparentsemi-reflecting prism square 4 is that the inclined-plane by 2 right-angle prisms 402 and 401 glues together mutually and forms, and wherein inclined-plane 403 is coated with the semi-transflective reflective film.Half sees through the polarized light vertically injected from thetop 5 from the below straight line and penetrates, and testedbiological sample 19 and metalNano structure substrate 2 throw light on.The detection of reflectedlight 12 that returns from the below is by the below right-angle prism 401 of semi-transparentsemi-reflecting prism square 4, and 403 semi-reflective surface reflect through the inclined-plane, and half light is with 90 ° of anglehorizontal sheaf condensers 13.
As shown in Figure 2, be another biochemical sensitive detector for surface plasma scantling plan of the embodiment of the invention 2.It bysample test board 1, metalNano structure substrate 2, semi-transparent semi-reflecting lens 4 ',polaroid 6,optical filter 7,collimating mirror 8,lighting fiber 9, collectinglens 10,xenon source 11,condenser 13,monochromator 14,photomultiplier 16, signal Processingdigital converter 17,computing machine 18, testedbiological sample 19, XY scan table 20 andturntable driving controller 21 form.Xenonsource 11, collectinglens 10 andlighting fiber 9 are formed the illuminator to testedbiological sample 19 illuminations, are placed in collimatingmirror 8 tops.Collimating mirror 8,optical filter 7,polaroid 6 and the semi-transparentsemi-reflecting lens 4 that place successively the below ' make illumination light become the TM polarization parallel light that wavelength coverage is 450nm-950nm, semi-transparent semi-reflecting lens 4 ' lower surface be a semi-transparent semi-reflective surface, place with surface level angle at 45.The metalNano structure substrate 2 that many places scribble testedbiological sample 19 is placed on thesample test board 1, andsample test board 1 is placed on the XY scan table 20, and XY scan table 20 positions are controlled byturntable driving controller 21 by computing machine 18.Semi-transparent semi-reflecting lens 4 ',condenser 13,monochromator 14 andphotomultiplier 16 form detection optical system, be placed in successively semi-transparent semi-reflecting lens 4 ' a side.Illuminator is by collimatingmirror 8, the TM polarizationparallel light 5 that sends behindoptical filter 7 and thepolaroid 6, through semi-transparent semi-reflecting lens 4 ' half sees through testedbiological sample 19 of vertical illumination and metalNano structure substrate 2, because the nanostructured on metalNano structure substrate 2 top and bottom, produce the localization surface plasma body resonant vibration, launch reflectedlight 12 former roads return directive semi-transparent semi-reflecting lens 4 ', through following semi-reflective surface reflection, half light is with 90 ° of angular directiondirective condensers 13, injectmonochromator 14 bycondenser 13 optically focused, by injectingphotomultiplier 16 aftermonochromator 14 beam split,photomultiplier 16 is converted to electric signal with the light signal that is detected, amplify simultaneously, handle and be converted to digital signal by signal Processingdigital converter 17 again, send intocomputing machine part 18, relatively detect certain position sample reflectance spectrum curve on the metalNano structure substrate 2, determine the kind of biological sample, after having detected the tested biological sample at this place, move to the another location bycomputing machine part 18 andturntable driving controller 21 control XY scan tables 20 again and detect, the testedbiological sample 19 that needs to detect on metalNano structure substrate 2 has all detected.
As shown in Figure 3, be the embodiment of theinvention 3 biochemical sensitive detector for surface plasma scantling plans.It is bysample test board 1, metalNano structure substrate 2,catoptron 4 ",polaroid 6,optical filter 7,collimating mirror 8,lighting fiber 9, collectinglens 10,xenon source 11,condenser 13,monochromator 14,photomultiplier 16, signal Processingdigital converter 17,computing machine 18, testedbiological sample 19, XY scan table 20 andturntable driving controller 21 form.Xenonsource 11, collectinglens 10 andlighting fiber 9 are formed the illuminator to testedbiological sample 19 illuminations, are placed in collimatingmirror 8 belows.Collimating mirror 8,optical filter 7 and thepolaroid 6 that place successively the top make illumination light become the TM polarizationparallel light 3 that wavelength coverage is 450nm-950nm, from the below vertical illumination." be positioned at metalNano structure substrate 2 tops, its lower surface is a reflecting surface tocatoptron 4, places with surface level angle at 45.Many places scribble the metalNano structure substrate 2 sample placed face down of testedbiological sample 19 onsample test board 1,sample test board 1 is placed on the XY scan table 20 of hollow, and XY scan table 20 is controlled byturntable driving controller 21 by computing machine part 18.One side ofcatoptron 4 ",condenser 13,monochromator 14 andphotomultiplier 16 form detection optical system, be placed incatoptron 4 successively ".Illuminator is by collimatingmirror 8, the TM polarizationparallel light 3 that sends behindoptical filter 7 and thepolaroid 6, from testedbiological sample 19 of below vertical illumination and metalNano structure substrate 2, owing on themetal nano substrate 2 film top and bottom nanostructured is arranged, produce the localization surface plasma body resonant vibration, produce transmitted light towardmirror 4 "; " reflection throughcatoptron 4, transmittedlight 12 is with 90 ° of angular directionhorizontal sheaf condensers 13, optically focused is also injectedmonochromator 14, aftermonochromator 14 beam split, injectphotomultiplier 16,photomultiplier 16 will detect light signal and be converted to electric signal, amplify simultaneously, handle and be converted to digital signal by signal Processingdigital converter 17 again, send intocomputing machine part 18, relatively detect certain position sample transmission spectrum curve on the metalNano structure substrate 2, determine the kind of biological sample, after having detected the tested biological sample of this position, move to another position that need detect bycomputing machine 18 parts andscan table controller 21 control XY scan tables 20 and detect, all testedbiological samples 19 have all detected on metalNano structure substrate 2.
As shown in Figure 4, be the local amplification profile in zoy plane of the metalNano structure substrate 2 among the embodiment of theinvention 1,embodiment 2 and the embodiment 3.It is made up ofsubstrate 201 and metal Nano structure diaphragm 202.Substrate 201 is one to be compressed on the high index of refraction transmission substance layer on the metalNano structure diaphragm 202, its refractive index is 1.55-1.85, it is the glassy layer of SF series, metalNano structure diaphragm 202 is diaphragms that are made of gold copper-base alloy, the thickness of this diaphragm is 35-135nm, cycle gaussian-shape 22 section nanometer grating structures such as all being carved with in its upper and lower surface, is true origin with the wherein some gaussian-shape channel bottoms 0 of upper surface, and its upper surface comprises the gaussian-shape structure outline and is expressed as:
Lower surface comprises the gaussian-shape structure outline and is expressed as:
In two formulas, Λ is the grating cycle, and H is a groove depth, and ω is Gauss's groove width (width whengroove depth 1/e height), and t is that (t 〉=5nm), m is the grating number to the degree of depth of not carving.In the present invention, grating periods lambda=250-650nm, groove depth H=15-55nm does not carve degree of depth t=5-25nm, Gauss's groove width ω=12-80nm.
As shown in Figure 5, be that the A of embodiment of the invention biochemical sensitive metalNano structure substrate 2 is to partial enlarged drawing.On metalNano structure diaphragm 202 pros and cons, symmetry is carved with the gaussian-shape sectiongrating nano structure 22 of a plurality of one-tenth arrays, coats testedbiological sample 19 at each above the gaussian-shape section grating nano structural area.
As shown in Figure 6, be the resonant reflection spectrum main peak sensing combined light spectrogram of the biochemical sensitive metalNano structure substrate 2 that measures of the embodiment of theinvention 1 and embodiment 2.There is shown the testedbiological sample 19 of different refractivity, resonant reflection spectrum main peak curve during the different refractivity that obtains after testing, resonant reflection spectrummain peak 26 as refractive index n=1.2 o'clock, the resonant reflection spectrummain peak 25 of refractive index n=1.3 o'clock, the resonant reflection spectrummain peak 24 of refractive index n=1.4 o'clock, the resonant reflection spectrummain peak 23 of refractive index n=1.5 o'clock.
As shown in Figure 7, be the resonance transmission spectrum main peak sensing combined light spectrogram of the biochemical sensitive metalNano structure substrate 2 that measures of the embodiment of the invention 3.There is shown the testedbiological sample 19 of different refractivity, resonance transmission spectrum main peak curve during the different refractivity that obtains after testing, resonance transmission spectrummain peak 27 as refractive index n=1.2 o'clock, the resonance transmission spectrummain peak 28 of refractive index n=1.3 o'clock, the resonance transmission spectrummain peak 29 of refractive index n=1.4 o'clock, the resonance transmission spectrummain peak 30 of refractive index n=1.5 o'clock.
Themain peak 23--30 size that spectrum is penetrated in resonance anti-(thoroughly) is with the structure of grating and different change of refractive index of tested biological sample with the position, wherein main peak size and grating cycle, groove depth are relevant with Gauss's groove width, the position of main peak is with grating cycle, groove depth, Gauss's groove width, and the increase of sample refractive index is moved to the long wave direction, the size of moving speed and peak value directly has influence on sensing sensitivity, when peak value moves big more dark more when narrow more with the sample variations in refractive index, quality factor are high more, sensing sensitivity is also high more, and the quality factor of sensor are represented with following formula:
In the formula, q is refractive index sensitivity, and FWHM is the full width at half maximum that grating anti-(thoroughly) is penetrated spectrum, full width at half maximum value of the present invention reaches 6-8nm, refractive index sensitivity reaches 300-370nm/RIU, makes the sensing quality factor reach 35-60, is better than other sensor or pick-up unit greatly.
As shown in Figure 8,computing machine part 18 of the present invention comprises Heng Guangqiangdengyuancontrol 1801,xenon lamp 1805,bus interface 1802, A/D conversion 1803, digital spectrumimage buffer storage 1806,photomultiplier power supply 1804,photomultiplier 1807 andcomputing machine 1808;Turntable driving controller 21 comprises xstep motor drive 2101 and y step motor drive 2102.Xenonlamp 1805 issues out light intensity constant light as of the present invention illumination light bybus 1802 by Heng Guangqiangdengyuancontrol 1801 controls in the instruction ofcomputing machine 1808, testedbiological sample 19 on the illumination metalnanostructured substrate 2,computing machine 1808 is bybus 1802 controls, the tested biological sample spectrum picture curve of sending here fromphotomultiplier 1807 is carried out A/D be converted to the digital spectrum image curve, and deposit digital spectrumimage buffer storage 1806 in, wait for and compare, detect the substance classes of testedbiological sample 19, after the substance classes of the tested biological sample that has detected a position,computing machine 1808 is bybus 1802 instructionscan driving governors 21, controlling and driving x stepper motor and y stepper motor, make scan table make the x direction, the y direction moves, and the other also not detected testedbiological sample 19 on the metalNano structure substrate 2 is delivered to detecting position detect.
Be illustrated in figure 9 as software control processing flow chart of the present invention.Its principle is: testing begins, each power supply such as elder generation's turn-on lamp, preset parameter, testedbiological sample 19 as metalNano structure substrate 2 is counted and the position, accuracy of detection etc., the scan table auto zero, the metalNano structure substrate 2 of then onsample test board 1, packing into, Xyturntable driving controller 21 moves to detecting position with testedbiological sample 19 automatically,computing machine 1808 instruction acquisitions are sent here byphotomultiplier 1807 and are converted the digital spectrum image to through A/D then, deposit digital spectrumimage buffer storage 1806 in, and extract anti-(thoroughly) and penetrate the spectrum peak wavelength, half-breadth high and anti-(thoroughly) penetrate rate etc. for information about, automatically compare for information about by the known species that has had in advance incomputing machine 1808 and the machine, relatively whether more identical under certain accuracy requirement, as come to the same thing, 1808 kinds of exporting and showing the testedbiological sample 19 in this position of computing machine, inequality as the result, 1808 in computing machine shows the spectrum picture curve and the original close known image ofsample 19, species or newfound species by the testedbiological sample 19 of operating personnel's interpretation, extract peak wavelength simultaneously, half-breadth is high penetrates information such as rate with anti-(thoroughly), deposit computing machine in, increase the known species that has had, the testedbiological sample 19 of on metalNano structure substrate 2 all is all detected intact like this, take off tested metalNano structure substrate 2, detection of end.