CN105241862A - Surface-enhanced Raman scattering substrate with pin holes in its surface and preparation method - Google Patents
Surface-enhanced Raman scattering substrate with pin holes in its surface and preparation method Download PDFInfo
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- CN105241862A CN105241862A CN201510608664.0A CN201510608664A CN105241862A CN 105241862 A CN105241862 A CN 105241862A CN 201510608664 A CN201510608664 A CN 201510608664A CN 105241862 A CN105241862 A CN 105241862A
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- 239000000758 substrate Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052709 silver Inorganic materials 0.000 claims abstract description 50
- 239000004332 silver Substances 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 239000002073 nanorod Substances 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001069 Raman spectroscopy Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 23
- 230000008021 deposition Effects 0.000 claims description 21
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 17
- 238000005566 electron beam evaporation Methods 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010894 electron beam technology Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000002985 plastic film Substances 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 12
- 238000001514 detection method Methods 0.000 abstract description 10
- 238000000231 atomic layer deposition Methods 0.000 abstract description 4
- 238000011895 specific detection Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 2
- 239000002344 surface layer Substances 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 11
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- -1 30mM) Chemical compound 0.000 description 5
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010946 fine silver Substances 0.000 description 4
- 238000012113 quantitative test Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention especially relates to a surface-enhanced Raman scattering substrate with pin holes in its surface and a preparation method, belonging to the technical field of detection of trace substances. According to the invention, a silver nanorod array film is prepared by using an inclined growth process; and then a layer of an alumina film with pin holes is uniformly deposited on the surface of the silver nanorod array film by using low-temperature atomic layer deposition technology, and an obtained sliver-alumina composite nanostructure with pin holes in its surface is used as the surface-enhanced Raman scattering substrate. The method can adjust the parameters of the low-temperature atomic layer deposition technology to control the proportion of the pin holes in the alumina film; an ultrathin oxide layer of the alumina film ensures good surface-enhanced Raman scattering activity of the substrate; and interior silver nanorods are isolated from the outside, so chemical stability of the substrate is greatly improved. Moreover, the alumina film and silver surface layers in the pin holes can both adsorb specific detection molecules; and the substrate is applicable to detection of a plurality of chemical substances, expands the application scope of surface-enhanced Raman scattering and has wide application prospects.
Description
Technical field
The invention belongs to trace materials detection technique field, particularly a kind of surface has surface-enhanced Raman effects substrate and the preparation method of pin hole.
Background technology
Surface-enhanced Raman effects is used for the trace detection of chemistry, biomolecule, has the advantages such as nondestructive analysis, highly sensitive, detection time is short, expense is low, applicability is strong.The method needs to utilize the noble metals such as gold, silver to prepare the surface-enhanced Raman effects substrate with high sensitivity, poor chemical stability due to metal Nano structure, the adsorptive power to some detection molecules are not strong simultaneously, greatly limit the development of surface enhanced Raman technique.
The present invention is by low temperature ald technology, there is at silver nanostructured surface deposition one deck the ultrathin alumina film of pin hole, and by regulating the parameter of low temperature ald technology can the needle hole ratio of controlled oxidization aluminium film, the chemical stability of the substrate obtained and applicability have very large lifting, extend the sensing range of surface-enhanced Raman effects.Because ultra-thin oxide layer can not the surface-enhanced Raman signals of strong attenuation Silver nanorod, substrate has good surface reinforced Raman active; Metal core and external environment are also isolated by oxide layer, significantly improve the chemical stability of substrate; Meanwhile, all adsorbable specific detection molecules in silver-colored top layer in aluminium oxide top layer and pin hole, this substrate can be used for the detection of number of chemical material, extends the range of application of surface-enhanced Raman effects.
Summary of the invention
The object of this invention is to provide the surface-enhanced Raman effects substrate that a kind of surface has the silver-alumina composite nanostructured of pin hole, and utilize low temperature ald method (AtomicLayerDeposition, ALD) to prepare the method for silver-alumina composite nanostructured substrate.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of surface has the surface-enhanced Raman effects substrate of pin hole: the aluminum oxide film at Silver nanorod array film surface uniform deposition one deck with pin hole, and needle hole ratio is controlled, obtains surface and there is the silver-alumina composite nanostructured of pin hole as surface-enhanced Raman effects substrate.
Further, described Silver nanorod array film is oblique rod array film or the straight rod array film of cylinder, and Silver nanorod length is 400nm ~ 700nm, and the surface of described aluminum oxide film has pin hole, thickness is less than 1nm.
Further, the surface area that described needle hole ratio refers to the silver of not oxidized aluminium plastic film covering accounts for the long-pending ratio of whole surface-enhanced Raman effects substrate surface; The scope of needle hole ratio is 16% ~ 5%.
The preparation method of surface-enhanced Raman effects substrate as above: utilize inclination growing method, at deposition on substrate argent, obtains Silver nanorod array film; Utilize low temperature ald technology to have the aluminum oxide film of pin hole at Silver nanorod array film surface uniform deposition one deck, obtain surface and there is the silver-alumina composite nanostructured of pin hole as surface-enhanced Raman effects substrate.
Further, the step utilizing inclination growing method to prepare Silver nanorod array film is: at room temperature, is fixed on by substrate on the sample stage of electron beam evaporation deposition machine; Employing argent is target, and it is 3 × 10 that electron beam evaporation deposition machine chamber is evacuated to vacuum tightness
-5pa ~ 8 × 10
-5pa; Adjustment electron beam incident angle is 85 ° ~ 88 °, and makes sample stage static or rotate with the speed of 6rpm ~ 10rpm, and the substrate of sample stage grows Silver nanorod array film.
Further, when utilizing low temperature ald deposition techniques to have the aluminum oxide film of pin hole, put in the middle part of ald reaction cavity by previously prepared good Silver nanorod array film, cavity temperature is 50 DEG C ~ 70 DEG C; Using trimethyl aluminium and water as precursors, alternately pass in reaction cavity, flow is 20sccm, and regulated the needle hole ratio of aluminum oxide film by the time that passes into changing two kinds of presomas, trimethyl aluminium and water pass into 2 ~ 80ms and 1 ~ 40ms respectively.
Further, along with the amount passing into trimethyl aluminium and water increases, needle hole ratio declines, and the scope of needle hole ratio is 16% ~ 5%.
The invention has the beneficial effects as follows: the ultrathin alumina film at Silver nanorod array film surface uniform deposition one deck by low temperature ald technology with pin hole, and the needle hole ratio by regulating ald parameter to carry out controlled oxidization aluminium film.Because ultra-thin oxide layer can not the surface-enhanced Raman signals of strong attenuation Silver nanorod, substrate has good surface reinforced Raman active; Metal core and external environment are also isolated by oxide layer, significantly improve the chemical stability of substrate; Meanwhile, all adsorbable specific detection molecules in silver-colored top layer in aluminium oxide top layer and pin hole, this substrate can be used for the detection of number of chemical material, extends the range of application of this surface enhanced Raman substrate.
Accompanying drawing explanation
In Fig. 1, Fig. 1 a is the scanning electron microscope (SEM) photograph that the surface of preparing in embodiment 1 has the silver-alumina composite nanostructured substrate of pin hole, Fig. 1 b is the transmission electron microscope picture of single Silver nanorod, Fig. 1 c is the high-resolution-ration transmission electric-lens figure of the aluminum oxide film having pin hole, Fig. 1 d is silver-alumina composite nanostructured substrate detection 1 × 10 with surface prepared by trimethyl aluminium and the water of different content with pin hole
-2the Raman spectrogram of M acridine gained.
In Fig. 2, Fig. 2 a, 2c, 2e are respectively the oblique rod array film of silver nanoparticle of preparation in embodiment 2 at sodium chloride (NaCl, 30mM), hydrogen peroxide (H
2o
2, 2.2%) and sodium cyanide (NaCN, 50ppb) solution in soak the scanning electron microscope (SEM) photograph after 3h, 0.5h and 3h; Fig. 2 b, 2d, 2f are respectively has the silver-alumina composite nanostructured substrate of pin hole at sodium chloride (NaCl, 30mM), hydrogen peroxide (H by the surface of preparation in embodiment 2
2o
2, 2.2%) and sodium cyanide (NaCN, 50ppb) solution in soak the scanning electron microscope (SEM) photograph after 3h, 0.5h and 3h.
In Fig. 3, silver-alumina composite nanostructured substrate that the surface of preparation in embodiment 3 has pin hole is used for detecting trace sodium cyanide and 2 by Fig. 3 a, Fig. 3 c respectively, the Raman spectrum line chart obtained during 6-pyridinedicarboxylic acid, Fig. 3 b, Fig. 3 d are correspondingly the quantitative test figure to raman scattering intensity-molecular conecentration relation.
Embodiment
Below in conjunction with accompanying drawing 1 ~ 3 and embodiment, the present invention is illustrated.Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1
1. by silicon chip or glass substrate acetone, alcohol, deionized water order ultrasonic cleaning drying;
2. pretreated substrate is fixed on the sample stage of electron beam evaporation deposition machine;
3. at room temperature, employing argent is target, and the chamber of electron beam evaporation deposition machine being evacuated to vacuum tightness is 3 × 10
-5pa;
4. adjusting the incident angle of electron beam to 85 °, and make sample stage static, is the oblique rod array film of silver nanoparticle of 700nm in the substrate surface thereof growing nano-rod length of sample stage;
5. by low temperature ald method, heating cavity to 70 DEG C, the flow controlling trimethyl aluminium and water is 20sccm, by regulating the needle hole ratio of the time that the passes into controlled oxidization aluminium film of trimethyl aluminium and water, the time that passes into of trimethyl aluminium is respectively 2ms, 5ms, 10ms, 20ms, 40ms, 80ms, the time that passes into of water is correspondingly followed successively by 1ms, 2ms, 5ms, 10ms, 20ms, 40ms, there is at silver nanoparticle oblique rod array film surface uniform deposition one deck the aluminum oxide film of pin hole, obtain silver-alumina composite nanostructured that surface has pin hole, as surface-enhanced Raman effects substrate.
Fig. 1 a is the scanning electron microscope (SEM) photograph of the silver-alumina composite nanostructured substrate with surface prepared by the ald that trimethyl aluminium and water pass into 20ms and 10ms respectively with pin hole, Fig. 1 b is the transmission electron microscope picture of single Silver nanorod, and Fig. 1 c is the high-resolution-ration transmission electric-lens figure of the aluminum oxide film having pin hole.Because the temperature of reaction of ald is lower, the pattern of Silver nanorod is not destroyed, and can see that pellumina is very thin, and even coated with silver nanometer rods, its thickness is about 0.7nm.
Fig. 1 d is silver-alumina composite nanostructured substrate detection 1 × 10 with surface prepared by trimethyl aluminium and the water of different content with pin hole
-2the Raman spectrogram of M acridine gained.Wherein uncoatedAg represents the oblique rod array film of fine silver nanometer, the surface prepared by ald that 2-1 expression trimethyl aluminium and water pass into 2ms and 1ms respectively has the silver-alumina composite nanostructured substrate of pin hole, the surface prepared by ald that 5-2 expression trimethyl aluminium and water pass into 5ms and 2ms respectively has the silver-alumina composite nanostructured substrate of pin hole, the surface prepared by ald that 10-5 expression trimethyl aluminium and water pass into 10ms and 5ms respectively has the silver-alumina composite nanostructured substrate of pin hole, the surface prepared by ald that 20-10 expression trimethyl aluminium and water pass into 20ms and 10ms respectively has the silver-alumina composite nanostructured substrate of pin hole, the surface prepared by ald that 40-20 expression trimethyl aluminium and water pass into 40ms and 20ms respectively has the silver-alumina composite nanostructured substrate of pin hole, the surface prepared by ald that 80-40 expression trimethyl aluminium and water pass into 80ms and 40ms respectively has the silver-alumina composite nanostructured substrate of pin hole.
Because acridine only can be adsorbed on silver surface, and not and form chemical bond between aluminium oxide, the adsorbable more acridine of the oblique rod array film of fine silver nanometer, the Raman spectrum obtained is strong; Surface has the silver surface absorption acridine of surface-enhanced Raman effects substrate by exposing in pin hole of pin hole, and adsorption site is less, and the Raman spectrum obtained is weak.There is at the oblique rod array film of fine silver nanometer and surface according to acridine the 1043cm of the surface-enhanced Raman effects substrate of pin hole
-1the intensity rate of raman characteristic peak, can draw the needle hole ratio (surface area of the silver of not oxidized aluminium plastic film covering accounts for the long-pending ratio of whole surface-enhanced Raman effects substrate surface) of different base.Along with the amount passing into trimethyl aluminium and water increases, needle hole ratio declines, and can realize the adjustment to needle hole ratio 16% ~ 5%.
Embodiment 2
1. by silicon chip or glass substrate acetone, alcohol, deionized water order ultrasonic cleaning drying;
2. pretreated substrate is fixed on the sample stage of electron beam evaporation deposition machine;
3. at room temperature, employing argent is target, and the chamber of electron beam evaporation deposition machine being evacuated to vacuum tightness is 5 × 10
-5pa;
4. adjusting the incident angle of electron beam to 86 °, and sample stage is rotated with the speed of 6rpm, is the oblique rod array film of silver nanoparticle of 600nm in the substrate surface thereof growing nano-rod length of sample stage;
5. by low temperature ald method, heating cavity to 60 DEG C, the flow controlling trimethyl aluminium and water is 20sccm, the time of passing into is respectively 10ms and 5ms, there is at silver nanoparticle oblique rod array film surface uniform deposition one deck the aluminum oxide film of pin hole, obtain silver-alumina composite nanostructured that surface has pin hole, as surface-enhanced Raman effects substrate;
6. oblique for the silver nanoparticle prepared in step 4-5 rod array film and surface had the silver-alumina composite nanostructured substrate of pin hole at sodium chloride (NaCl, 30mM), hydrogen peroxide (H
2o
2, 2.2%) and sodium cyanide (NaCN, 50ppb) solution in soak 3h, 0.5h and 3h respectively, and observe its pattern change.
In Fig. 2, Fig. 2 a, 2c, 2e are respectively the oblique rod array film of silver nanoparticle of preparation in embodiment 2 at sodium chloride (NaCl, 30mM), hydrogen peroxide (H
2o
2, 2.2%) and sodium cyanide (NaCN, 50ppb) solution in soak the scanning electron microscope (SEM) photograph after 3h, 0.5h and 3h; Fig. 2 b, 2d, 2f are respectively has the silver-alumina composite nanostructured substrate of pin hole at sodium chloride (NaCl, 30mM), hydrogen peroxide (H by the surface of preparation in embodiment 2
2o
2, 2.2%) and sodium cyanide (NaCN, 50ppb) solution in soak the scanning electron microscope (SEM) photograph after 3h, 0.5h and 3h.Wherein uncoatedAgNRs represents the oblique rod array film of fine silver nanometer, AgNRsAl
2o
3presentation surface has the silver-alumina composite nanostructured substrate of pin hole.
Because sodium chloride, hydrogen peroxide and sodium cyanide solution all have corrosivity, the oblique rod array film of silver nanoparticle is corroded very soon, and pattern there occurs great variety (Fig. 2 a, 2c, 2e), and substrate poor stability, is unfavorable for that surface-enhanced Raman detects; And surface has the silver-alumina composite nanostructured substrate of pin hole, the even coated with silver nanometer rods of aluminum oxide film on its surface, and pin hole quantity is few, effectively the Silver nanorod of inside and bad border, the external world can be isolated, its nanostructured is kept stable (Fig. 2 b, 2d, 2f).
Embodiment 3
1. by silicon chip substrate or glass substrate acetone, alcohol, deionized water order ultrasonic cleaning drying;
2. pretreated substrate is fixed on the sample stage of electron beam evaporation deposition machine;
3. at room temperature, employing argent is target, and the chamber of electron beam evaporation deposition machine is evacuated to 8 × 10
-5the high vacuum of Pa;
4. adjusting the incident angle of electron beam to 88 °, and sample stage is rotated with the speed of 10rpm, is the straight rod array film of silver nanoparticle cylinder of 400nm in the substrate surface thereof growing nano-rod length of sample stage;
5. by low temperature ald method, heating cavity to 50 DEG C, the flow controlling trimethyl aluminium and water is 20sccm, the time of passing into is respectively 80ms and 40ms, there is at silver nanoparticle cylinder straight rod array film surface uniform deposition one deck the aluminum oxide film of pin hole, obtain silver-alumina composite nanostructured that surface has pin hole;
6. silver step 5 prepared-alumina composite nanostructured substrate, as surface enhanced Raman substrate, detects sodium cyanide solution (1ppb-100ppb) and 2, the 6-pyridinedicarboxylic acid solution (1 × 10 of variable concentrations
-8m-1 × 10
-4m).
In Fig. 3, silver-alumina composite nanostructured substrate that the surface of preparation in embodiment 3 has pin hole is used for detecting trace sodium cyanide and 2 by Fig. 3 a, Fig. 3 c respectively, the Raman spectrum line chart obtained during 6-pyridinedicarboxylic acid, Fig. 3 b, Fig. 3 d are correspondingly the quantitative test figure to raman scattering intensity-molecular conecentration relation.
Sodium cyanide only can be adsorbed on silver surface, and can not and aluminium oxide between form chemical bond, surface has the silver surface absorption nacn of silver-alumina composite nanostructured substrate by exposing in pin hole of pin hole, obtain Surface enhanced raman spectroscopy, and can be used for the quantitative test of raman scattering intensity-sodium cyanide concentration relation; 2,6-pyridinedicarboxylic acid not only can be adsorbed on silver surface, also chemical bond can be formed with aluminium oxide, therefore the surface silver-alumina composite nanostructured substrate with pin hole adsorbs 2 by silver surface, the aluminum oxide film surface exposed in pin hole simultaneously, 6-pyridinedicarboxylic acid, obtains Surface enhanced raman spectroscopy, and the detectable concentration limit is low, and can be used for the quantitative test of raman scattering intensity-2,6-pyridinedicarboxylic acid concentration relationship.
Claims (7)
1. a surface has the surface-enhanced Raman effects substrate of pin hole, it is characterized in that, there is at Silver nanorod array film surface uniform deposition one deck the aluminum oxide film of pin hole, and needle hole ratio is controlled, obtain silver-alumina composite nanostructured that surface has pin hole, as surface-enhanced Raman effects substrate.
2. surface-enhanced Raman effects substrate according to claim 1, it is characterized in that, described Silver nanorod array film is oblique rod array film or the straight rod array film of cylinder, and Silver nanorod length is 400nm ~ 700nm, and the surface of described aluminum oxide film has pin hole, thickness is less than 1nm.
3. surface-enhanced Raman effects substrate according to claim 1, is characterized in that, the surface area that described needle hole ratio refers to the silver of not oxidized aluminium plastic film covering accounts for the long-pending ratio of whole surface-enhanced Raman effects substrate surface; The scope of needle hole ratio is 16% ~ 5%.
4. a preparation method for the surface-enhanced Raman effects substrate according to claim 1-3 any one, is characterized in that, utilizes inclination growing method, at deposition on substrate argent, obtains Silver nanorod array film; Utilize low temperature ald technology to have the aluminum oxide film of pin hole at Silver nanorod array film surface uniform deposition one deck, obtain silver-alumina composite nanostructured that surface has pin hole, as surface-enhanced Raman effects substrate.
5. preparation method according to claim 4, is characterized in that, the step utilizing inclination growing method to prepare Silver nanorod array film is: at room temperature, is fixed on by substrate on the sample stage of electron beam evaporation deposition machine; Employing argent is target, and it is 3 × 10 that electron beam evaporation deposition machine chamber is evacuated to vacuum tightness
-5pa ~ 8 × 10
-5pa; Adjustment electron beam incident angle is 85 ° ~ 88 °, and makes sample stage static or rotate with the speed of 6rpm ~ 10rpm, and the substrate of sample stage grows Silver nanorod array film.
6. preparation method according to claim 4, it is characterized in that, when utilizing low temperature ald deposition techniques to have the aluminum oxide film of pin hole, put in the middle part of ald reaction cavity by previously prepared good Silver nanorod array film, cavity temperature is 50 DEG C ~ 70 DEG C; Using trimethyl aluminium and water as precursors, alternately pass in reaction cavity, flow is 20sccm, and regulated the needle hole ratio of aluminum oxide film by the time that passes into changing two kinds of presomas, trimethyl aluminium and water pass into 2 ~ 80ms and 1 ~ 40ms respectively.
7. preparation method according to claim 6, is characterized in that, along with the amount passing into trimethyl aluminium and water increases, needle hole ratio declines, and the scope of needle hole ratio is 16% ~ 5%.
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| CN108680556A (en) * | 2018-05-14 | 2018-10-19 | 清华大学 | A kind of silver aluminium solid solution nanorod surfaces enhancing Raman substrate and preparation method thereof |
| CN109161849A (en) * | 2018-07-19 | 2019-01-08 | 西安交通大学 | A kind of ordered porous array and preparation method thereof of silver tantalum composite material building |
| CN111896521A (en) * | 2020-08-06 | 2020-11-06 | 中国电子科技集团公司第四十六研究所 | Method for detecting coverage rate of large-area continuous thin film of transition metal sulfide |
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