CN102233424B - Silver nano superstructure array, and preparation method and application thereof - Google Patents
Silver nano superstructure array, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102233424B CN102233424B CN 201010171537 CN201010171537A CN102233424B CN 102233424 B CN102233424 B CN 102233424B CN 201010171537 CN201010171537 CN 201010171537 CN 201010171537 A CN201010171537 A CN 201010171537A CN 102233424 B CN102233424 B CN 102233424B
- Authority
- CN
- China
- Prior art keywords
- superstructure
- silver nanoparticle
- silver
- array
- cysteine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention provides a silver nano superstructure array. The silver nano superstructure array is arranged on the surface of a substrate. The invention also provides a preparation method for the silver nano superstructure array. The preparation method comprises the following steps of: putting a patterned silicon wafer into a silver ion-cysteine complexing solution with the pH value of 10.0 to 11.0; and culturing the patterned silicon wafer at the temperature of between 4 and 45 DEG C for 1 to 3 days to obtain the silver nano superstructure array. The invention further provides application of the silver nano superstructure array to surface enhanced Raman spectrum (SERS) detection and solar batteries. The silver nano superstructure array prepared by the method has high sensitivity and highly uniform SERS detection effect.
Description
Technical field
The present invention relates to a kind of silver nanoparticle superstructure array, and preparation method and the purposes of this silver nanoparticle superstructure array, the chemical material field belonged to.
Background technology
Caused electromagnetism strengthens (that is: physics strengthens) because surperficial local plasmon excimer is excited to be adsorbed on the compound of roughening metal surface, and the cluster on the rough surface and the molecule that adsorbs on it constitute the active site (that is: chemistry strengthens) that Raman strengthens, the two effect makes determined Raman scattering produce great enhancement effect, and its enhancer can reach 10
3-10
7Found that the metal that can produce SERS (the English SERS of abbreviation) has a few metals such as Ag, Au, Cu and Pt, wherein enhancement effect the best of Ag.This technology has selectively good and highly sensitive advantage, and the actual detected limit can reach 10
-12The gram level.Can be used for trace and explication de texte and the detection of material, be the important tool of research surface and interface process, is the advantageous methods of the close compound of qualitative evaluation chemical constitution.There are huge using value and prospect in the analyzing and testing field relevant at environment, biology etc.
At present, the method that detects substrate for the preparation of SERS mainly contains two classes, and a class is the micro-processing technology from top to bottom in conjunction with vapour deposition process; Another kind of is to be the self-assembling technique from bottom to top of representative with the solution synthetic method.The former has accurate surperficial positioning accuracy and complex surfaces patterning ability on large scale, but relatively poor for the effective ad hoc structure control on the small scale; The latter can carry out effective ad hoc structure control as required on small scale for the former, and realize the large-scale low-cost preparation easily, but relatively poor aspect the order control on large scale.
For this reason, be conceived to prepare the demand of high accuracy high reliability SERS detection system, require the preparation method on a plurality of (or all) yardsticks, to control the structure of noble metal system and the order of arrangement realization simple and effective.
Summary of the invention
Unless otherwise indicated, " superstructure " herein refers to such an extent that be multiple dimensioned order structure, and namely the construction unit on a plurality of (or all) yardsticks from the macroscopic view to the microcosmic is all arranged in an orderly manner in this structure.
One object of the present invention is to provide a kind of silver nanoparticle superstructure array, the silver nanoparticle superstructure array that accurate orientation and location are arranged in the substrate surface preparation, because this silver nanoparticle superstructure array accurate orientation and location on substrate surface is so this system has the SERS effect of highly sensitive and high homogeneous.
Another object of the present invention is to provide the preparation method of silver nanoparticle superstructure array of the present invention.
A further object of the present invention is to provide the purposes of silver nanoparticle superstructure array of the present invention.
One aspect of the present invention provides a kind of silver nanoparticle superstructure array, and described silver nanoparticle superstructure array is the silver nanoparticle superstructure array on the substrate surface.
Preferably, described silver nanoparticle superstructure array is made up of one dimension item chain silver nanoparticle superstructure lines or one-dimensional rod-like silver nanoparticle superstructure lines.
Preferably, described one dimension item chain silver nanoparticle superstructure lines are made up of silver nanoparticle superstructure ball.
More preferably, described silver nanoparticle superstructure ball or one-dimensional rod-like silver nanoparticle superstructure lines are made up of Nano silver grain respectively.
Again preferably, the width of described one-dimensional rod-like silver nanoparticle superstructure lines and one dimension item chain silver nanoparticle superstructure lines is 150-450nm.
Again preferably, described width is 250-350nm.
Most preferably, described width is 300nm.
Preferably, the diameter of described Nano silver grain is 10-20nm.
More preferably, the diameter of described Nano silver grain is 12-18nm.
Most preferably, the diameter of described Nano silver grain is 15nm.
Preferably, described substrate is silicon or plating silicon base.
The present invention also provides a kind of preparation method of silver nanoparticle superstructure array of the present invention on the other hand, this method is: a. places the substrate of patterning silver ion-cysteine complex solution of pH 10.0-11.0, b. then cultivated 1-3 days at 4-45 ℃, obtain described silver nanoparticle superstructure array.
Preferably, cultivated 1.5-2.5 days at 30-40 ℃.
Most preferably, cultivated 2 days at 37 ℃.
Preferably, before described step a, also use the hydrofluoric acid of 30-50% volumetric concentration to flood 0.5-2 hour the substrate of patterning.
Preferably, also with the substrate of patterning with the hydrofluoric acid dipping of 40% volumetric concentration 1 hour.
The silver nanoparticle superstructure that obtains without the pretreated patterned substrate of hydrofluoric acid surface of the present invention is formed silver nanoparticle superstructure ball by Nano silver grain successively, form one dimension item chain silver nanoparticle superstructure lines by silver nanoparticle superstructure ball, form silver nanoparticle superstructure array by one dimension item chain silver nanoparticle superstructure lines.
The silver nanoparticle superstructure that obtains through the pretreated patterned substrate of hydrofluoric acid surface of the present invention is formed one-dimensional rod-like silver nanoparticle superstructure lines by Nano silver grain successively, forms silver nanoparticle superstructure array by one-dimensional rod-like silver nanoparticle superstructure lines.Be that one dimension item chain silver nanoparticle superstructure lines or one-dimensional rod-like silver nanoparticle superstructure lines all have good using value, wherein, item chain silver nanoparticle superstructure lines are suitable for discontinuous focus SERS and detect, and bar-shaped silver nanoparticle superstructure lines are suitable for continuous focus SERS and detect.
Preferably, in described method, described complex solution is the complex solution of soluble silver salt and cysteine.
More preferably, described complex solution be pH 10.0-11.0 1) silver nitrate or silver perchlorate and 2) complex solution of cysteine.
Most preferably, described complex solution is the silver perchlorate of pH 10.4 and the complex solution of cysteine.
Preferably, in described method, the concentration of the silver ion in described silver ion-cysteine complex solution is 0.05-0.50mM, and the concentration of cysteine is 0.10-0.80mM.
More preferably, the concentration of described silver ion is 0.10-0.20mM, and the concentration of cysteine is 0.20-0.30mM.
Most preferably, the concentration of described silver ion is 0.15mM, and the concentration of cysteine is 0.25mM.
Preferably, the silicon chip of described patterning prepares by the following method:
A. at first according to pattern, at the silicon chip gluing electron beam exposure of cleaning and develop;
B. the silicon chip after will developing carries out reactive ion beam etching (RIBE);
C. the silicon chip after the etching is removed photoresist, obtain the silicon chip of described patterning.
Preferably, in described step c, the silicon chip after adopting acetone to etching removes photoresist.
Preferably, in described step a, with just hindering the agent gluing.
It is more preferably, described that just to hinder agent be polymethyl methacrylate.
Preferably, in described step a, the electron beam that produces with ESEM, scanning transmission electron microscope exposes.The English that the English of ESEM abbreviates SEM, scanning transmission electron microscope as abbreviates STEM as.
Preferably, be that 1: 3 methylisobutylketone and the mixed solution of isopropyl alcohol develop with volume ratio.
Preferably, in described step b, adopt sulfur hexafluoride gas to carry out etching, the current density of ion beam is 10-50sccm, and ion energy is 50-100W.
More preferably, the current density of described ion beam is 20-40sccm, and ion energy is 60-90W.
Most preferably, the current density of described ion beam is 25-35sccm, and ion energy is 75-85W.
Further aspect of the present invention also provides the purposes of silver nanoparticle superstructure array of the present invention in SERS detects.
Further aspect of the present invention also provides the purposes of silver nanoparticle superstructure array of the present invention in solar cell.
The silver nanoparticle superstructure array that the present invention prepares has from nanoscale to hundred micron and the multiple dimensioned classification order of surface orientation on the large scale more.The silver nanoparticle superstructure array that the present invention prepares has the SERS effect of highly sensitive and high homogeneous, and p-aminophenyl thiophenol (a kind of SERS probe molecule commonly used) detectability that its SERS detects can reach 10
-10M.
When the support base of the silver nanoparticle superstructure array for preparing as the present invention is monocrystalline silicon piece, can use in area of solar cell, and because silicon chip surface has the silver nanoparticle superstructure array of accurate orientation and location, so be conducive to the enhancing of surface plasma body resonant vibration, be conducive to strengthen the electricity conversion of solar cell.
The prepared silver nanoparticle superstructure of the present invention array has desirable stability at normal temperatures and pressures.
The silver nanoparticle superstructure array of accurate orientation of the present invention and location, the orderly noble metal superstructure of this multiple dimensioned classification, because the orderly array structure of patterned surface so be fit to make integrated chip, has huge using value at micro integrated SERS detection range.
Method of the present invention is at micro-processing technology and self-assembling technique advantage and deficiency separately from top to bottom from bottom to top, electron beam exposure and reactive ion beam etching (RIBE) patterned surface technology are combined with the auxiliary self-assembling technique of silver ion-cysteine complexing from bottom to top, give full play to two kinds of methods advantage separately, realized having the simple and effective preparation in the orderly noble metal nano superstructure of surface orientation classification of the high position precision on the large scale and the effective ad hoc structure control on small scale.
The present invention is directed to current SERS and detect the deficiency that exists in the substrate preparation method, for example the effective ad hoc structure control of micro-processing technology on small scale from top to bottom is relatively poor, the relatively poor defective of the positioning accuracy of self-assembling technique on large scale is developed a kind of simple and effective method that can control structure and the arrangement realization order of noble metal silver system on whole yardsticks from bottom to top.
The invention provides complexing auxiliary and electron beam exposure and the combination of reactive ion beam etching (RIBE) patterned surface of a kind of cysteine and silver ion, 4-45 ℃ of very gentle class physiology low energy consumption condition, preferred 30-40 ℃, most preferably 37 ℃ have the silver nanoparticle superstructure array of accurate orientation and location and the preparation method of this array in the substrate surface preparation.The present invention has realized the technical scheme of the orderly silver nanoparticle superstructure of the multiple dimensioned classification of the surface orientation array simple and effective preparation on the large scale more, be the method for utilizing and electron beam exposure and reactive ion beam etching (RIBE) patterned surface combination auxiliary based on the complexing of cysteine and silver ion, simultaneously in small scale and the structure of large scale scope control silver nanoparticle superstructure array system and the order of arrangement.
Preparation method's of the present invention beneficial effect is:
(1) preparation condition of the present invention is very gentle class physiology low energy consumption condition alkalescent pH10.4,4-45 ℃, preferred 30-40 ℃, most preferably cultivated 1-3 days for 37 ℃, preferred 1.5-2.5 days, most preferably obtained described substrate surface silver nanoparticle superstructure array in 2 days, this preparation method is conducive to reduce the energy resource consumption in the preparation of product process.
(2) preparation method is the combination of the complexing of cysteine and silver ion auxiliary and electron beam exposure and reactive ion beam etching (RIBE) patterned surface, and is easy and efficient.
Description of drawings
Fig. 1 represents SEM picture of large image scale (Figure 1A) and the local enlarged image (Figure 1B) on the patterning silicon chip surface that process step (1)-(4) of the embodiment of the invention 1 obtain.Pattern is 1 * 10 line array, the about 100 μ m of line length, the about 1 μ m of live width, the about 10 μ m of distance between centers of tracks.
Fig. 2 represents the scanning electron microscope image (Fig. 2 A-C) without the pretreated silicon chip surface one dimension of hydrofluoric acid item chain silver nanoparticle superstructure lines that process step (1)-(10) of the embodiment of the invention 1 obtain; The scanning electron microscope image (Fig. 2 D-F) through the pretreated silicon chip surface one-dimensional rod-like of 40% hydrofluoric acid silver nanoparticle superstructure lines that process step (1)-(10) of the embodiment of the invention 2 obtain.
Fig. 3 represents the scanning electron microscope image without the orderly silver nanoparticle superstructure array of the pretreated patterning silicon chip surface classification of hydrofluoric acid that process step (1)-(10) of the embodiment of the invention 1 obtain, wherein Fig. 3 A represents silver nanoparticle superstructure array, Fig. 3 B represents one dimension item chain silver nanoparticle superstructure lines, Fig. 3 C represents silver nanoparticle superstructure ball, and Fig. 3 D represents Nano silver grain.
The partial sweep electron microscope image of the silicon chip surface silver nanoparticle superstructure array of Fig. 4 A presentation graphs 3, and the X ray energy dispersion spectral element analysis result in the last constituency 1 of Fig. 4 B presentation graphs 4A, Fig. 4 C presentation graphs 4A goes up the X ray energy dispersion spectral element analysis result in constituency 2.By the comparison of Fig. 4 B and Fig. 4 C, as can be seen Fig. 4 B with respect to Fig. 4 C many spectrogram of silver element, show that the silver nanoparticle superstructure strictly has been limited in pattered region.
Fig. 5 represents the SERS result of the different sampled points of silicon chip surface silver nanoparticle superstructure array of the embodiment of the invention 1, and (Fig. 5 A) is the result of blank silicon chip surface sampled point; (Fig. 5 B) is the result of five stochastical sampling points on the silver-colored sodium rice superstructure array; (Fig. 5 C) is the relevant position of five stochastical sampling points of Fig. 5 B.The high sensitivity that detects for SERS from the relatively more visible silver nanoparticle superstructure of the result of Fig. 5 A and Fig. 5 B is necessary indispensable.Has high homogeneity from the SERS effect of visible this silicon chip surface silver nanoparticle superstructure array of the comparison of Fig. 5 B.
The specific embodiment
Following examples only are used for explanation the present invention, and are not used in restriction the present invention.
Embodiment 1
Silicon chip in the present embodiment is available from mirror section instrument technology Co., Ltd in Beijing, and trade name is monocrystalline silicon piece, and article number is P556359.
The preparation of the silicon chip surface silver nanoparticle superstructure array of being formed by one dimension item chain silver nanoparticle superstructure lines.
The commercialization polished silicon slice cuts into the small pieces of 1.5cm * 1.5cm during (1) with P＜100〉type 4 with scribing machine.
(2) with the silicon chip of well cutting with acetone, ethanol and secondary water ultrasonic cleaning successively 5 minutes, dry up with nitrogen after removing surface contaminant.
(3) (rubberized material is polymethyl methacrylate clean silicon chip to be carried out gluing successively according to pre-designed line array pattern in ultra-clean chamber, glue-spread is that 1-2 μ m is thick), silicon chip behind the gluing is exposed under the SEM electron beam, control the scanning coil of instruments such as pattern generator and D/A converting circuit driving SEM during exposure by computer system, thereby make the break-make of electron beam deflection and control bundle lock, by the nano graph generation systems standard sample of photo is carried out IMAQ and scanning field correction again, cooperate precise positioning work table to realize splicing and the alignment of exposure field, develop after finishing exposure, the used developer that develops is that methylisobutylketone and isopropyl alcohol are the mixed solution that is made at 1: 3 according to volume ratio again.
(4) band glue patterning silicon chip is handled with reactive ion beam etching (RIBE).Used ion beam is sulfur hexafluoride (SF
6) fluorine ion that gas (pressure is 3Pa) produces through ionization, the current density of ion beam is 30sccm, ion energy is 80W.The ion beam that cold-cathode source produces bombards etching (30s) by drawing the control of accelerating system and averager to substrate surface, removes (silica) oxide layer of expose portion silicon chip surface.
(5) processing of will removing photoresist through the band glue patterning silicon chip that reactive ion beam etching (RIBE) is handled, the described inorganic agent that removes photoresist is acetone.
(6) L type cysteine is mixed with the aqueous solution that 150mL concentration is 0.25mM.
(7) silver perchlorate is added form silver ion-cysteine complex solution in the cysteine aqueous solution (ultimate density of silver perchlorate is 0.15mM, and the ultimate density of cysteine is 0.25mM.)。
(8) silver ion-cysteine complex solution is adjusted to clarification pH 10.4 with the sodium hydrate aqueous solution of 2M.
(9) will immerse in silver ion-cysteine complex solution through electron beam exposure and the good patterning silicon chip of reactive ion beam etching (RIBE) preliminary treatment, and put into 37 ℃ of electrothermostats then and cultivated 2 days.
(10) silicon chip after cultivating is taken out, wash repeatedly through secondary water and dry up with nitrogen after removing remained on surface solution, obtain the silicon chip surface silver nanoparticle superstructure array of being formed by one dimension item chain silver nanoparticle superstructure lines.
The preparation of the silicon chip surface silver nanoparticle superstructure array of being formed by one-dimensional rod-like silver nanoparticle hyperline bar.
Step (1)-(8) are with embodiment 1
(9) will through electron beam exposure and the good patterning silicon chip of reactive ion beam etching (RIBE) preliminary treatment flood 1 hour in the hydrofluoric acid of volumetric concentration 40% after, immerse again in silver ion-cysteine complex solution, and put into 37 ℃ of electrothermostats then and cultivated 2 days.
(10) silicon chip after cultivating is taken out, wash repeatedly through secondary water and dry up with nitrogen after removing remained on surface solution, obtain the silicon chip surface silver nanoparticle superstructure array of being formed by one-dimensional rod-like silver nanoparticle superstructure lines.
Embodiment 1 step (1)-(4) are through electron beam exposure and the pretreated silicon chip surface of reactive ion beam etching (RIBE) patterned surface, as shown in Figure 1.Process step (1)-(10) of embodiment 1 obtain without the pretreated silicon chip surface one dimension of hydrofluoric acid item chain silver nanoparticle superstructure lines, shown in Fig. 2 A-C; What process step (1)-(10) of embodiment 2 obtained floods pretreated silicon chip surface one-dimensional rod-like silver nanoparticle superstructure lines through 40% hydrofluoric acid, shown in Fig. 2 D-E.Without the patterning silicon chip surface classification orderly silver nanoparticle superstructure array (comprising Nano silver grain, silver nanoparticle superstructure ball, one dimension item chain silver nanoparticle superstructure lines and silver nanoparticle superstructure array from bottom to top successively) of hydrofluoric acid impregnation process, as shown in Figure 3.The different constituencies of silicon chip surface silver nanoparticle superstructure array and corresponding X ray energy dispersion spectral element analysis result, as shown in Figure 4.The SERS result of the different sampled points of silicon chip surface silver nanoparticle superstructure array, as shown in Figure 5.
Embodiment 3
SERS detects
(1) p-aminophenyl thiophenol (English be called for short PATP) is dissolved in to be made into concentration in the mixed solvent of 1: 1 first alcohol and water of volume ratio be 10
-10The solution of M.
(2) be 10 with 100 μ L concentration
-10The PATP solution of M adds in the special SERS sample cell, and the silicon chip with silver nanoparticle superstructure array with embodiment 1 preparation immerses then, carries out SERS signal collection (laser 633nm; The about 2mW of power; Time for exposure 10s), the result shows that the PATP detectability of this silicon chip surface silver nanoparticle superstructure array can reach 10
-10M.
Comparative example 1
The SERS of vapour deposition process preparation detects substrate: people such as the Norris of Univ Minnesota-Twin Cities USA have at first carried out patterned process to silicon chip surface by focused ion beam technology, utilize gas phase deposition technology to form silver-colored film at the silicon chip surface of patterning then, turn over the silver-colored film that membrane technology has obtained having patterned array by epoxy resin at last.This silver film has good SERS and strengthens effect, is that the enhancer of SERS probe molecule has reached 1.4 * 10 with the benzenethiol
7This research work is published on the 325th phase " science " magazine.Compare with this work, strengthen under the prerequisite of effect at the preparation of patterned surface silver nanoparticle superstructure and the SERS that realize same level, method provided by the present invention need not vapour deposition, so have easier preparation flow and lower power consumption of polymer processing.
Comparative example 2
The SERS of solution synthetic method preparation detects substrate: Xu's red magnitude people of Inst. of Physics, CAS has synthesized silver nanoparticle superstructure ball with silver nitrate and PVP in the aqueous solution, then silver nanoparticle superstructure ball is spin-coated at random silicon chip surface and obtains SERS detection substrate.This substrate has good SERS and strengthens effect, is that the detectability of SERS probe molecule has reached 10 with isothiocyano-malachite green
-10M.This research work is published on the 21st phase " advanced material " magazine.But it is random distribution that this system SERS detects on-chip silver nanoparticle superstructure ball, does not realize further arranging in order.Strengthen at same level SERS under the prerequisite of effect, silicon chip surface silver nanoparticle superstructure array provided by the present invention has from nanoscale to hundred micron and the multiple dimensioned classification order of surface orientation on the large scale more, and this will improve accuracy, reappearance and micro integrated that SERS detects substrate greatly.
Claims (34)
1. silver nanoparticle superstructure array, it is characterized in that, described silver nanoparticle superstructure array is the silver nanoparticle superstructure array on the substrate surface, and described silver nanoparticle superstructure array is made up of one dimension item chain silver nanoparticle superstructure lines or one-dimensional rod-like silver nanoparticle superstructure lines; The width of described one-dimensional rod-like silver nanoparticle superstructure lines and one dimension item chain silver nanoparticle superstructure lines is 150-450nm.
2. silver nanoparticle superstructure array according to claim 1 is characterized in that, described one dimension item chain silver nanoparticle superstructure lines are made up of silver nanoparticle superstructure ball.
3. silver nanoparticle superstructure array according to claim 2 is characterized in that, described silver nanoparticle superstructure ball or one-dimensional rod-like silver nanoparticle superstructure lines are made up of Nano silver grain respectively.
4. according to each described silver nanoparticle superstructure array among the claim 1-3, it is characterized in that described width is 250-350nm.
5. according to each described silver nanoparticle superstructure array among the claim 1-3, it is characterized in that described width is 300nm.
6. according to claim 2 or 3 described silver nanoparticle superstructure arrays, it is characterized in that the diameter of described silver nanoparticle superstructure ball is 150-450nm.
7. according to claim 2 or 3 described silver nanoparticle superstructure arrays, it is characterized in that the diameter of described silver nanoparticle superstructure ball is 250-350nm.
8. according to claim 2 or 3 described silver nanoparticle superstructure arrays, it is characterized in that the diameter of described silver nanoparticle superstructure ball is 300nm.
9. silver nanoparticle superstructure array according to claim 3 is characterized in that, the diameter of described Nano silver grain is 10-20nm.
10. silver nanoparticle superstructure array according to claim 3 is characterized in that, the diameter of described Nano silver grain is 12-18nm.
11. silver nanoparticle superstructure array according to claim 3 is characterized in that the diameter of described Nano silver grain is 15nm.
12., it is characterized in that described substrate is silicon or plating silicon base according to each described silver nanoparticle superstructure array among the claim 1-3.
13. method for preparing each described silver nanoparticle superstructure array among the claim 1-12, it is characterized in that, this method is: a. places the substrate of patterning silver ion-cysteine complex solution of pH10.0-11.0, b. then cultivated 1-3 days at 4-45 ℃, obtain described silver nanoparticle superstructure array.
14. method according to claim 13 is characterized in that, step b cultivated 1.5-2.5 days at 30-40 ℃, obtained described silver nanoparticle superstructure array.
15. method according to claim 13 is characterized in that, step b cultivated 2 days at 37 ℃, obtained described silver nanoparticle superstructure array.
16. according to each described method among the claim 13-15, it is characterized in that, before described step a, also use the hydrofluoric acid of 30-50% volumetric concentration to flood 0.5-2 hour the substrate of patterning.
17. method according to claim 16 is characterized in that, with the substrate of patterning with the hydrofluoric acid dipping of 40% volumetric concentration 1 hour.
18., it is characterized in that in described method, described complex solution is the complex solution of soluble silver salt and cysteine according to each described method among the claim 13-15.
19. according to each described method among the claim 13-15, it is characterized in that, in described method, described complex solution be pH10.0-11.0 1) silver nitrate or silver perchlorate and 2) complex solution of cysteine.
20., it is characterized in that in described method, described complex solution is the silver perchlorate of pH10.4 and the complex solution of cysteine according to each described method among the claim 13-15.
21., it is characterized in that in described method, the concentration of the silver ion in described silver ion-cysteine complex solution is 0.05-0.50mM according to each described method among the claim 13-15, the concentration of cysteine is 0.10-0.80mM.
22., it is characterized in that in described method, the concentration of the silver ion in described silver ion-cysteine complex solution is 0.10-0.20mM according to each described method among the claim 13-15, the concentration of cysteine is 0.20-0.30mM.
23., it is characterized in that in described method, the concentration of the silver ion in described silver ion-cysteine complex solution is 0.15mM according to each described method among the claim 13-15, the concentration of cysteine is 0.25mM.
24. according to each described method among the claim 13-15, it is characterized in that the substrate of described patterning prepares by the following method:
A. at first according to pattern, gluing, electron beam exposure and develop on the silicon chip of cleaning;
B. the silicon chip after will developing carries out reactive ion beam etching (RIBE);
C. the silicon chip after the etching is removed photoresist, obtain the substrate of described patterning.
25. method according to claim 24 is characterized in that, in described step c, removes photoresist with the silicon chip of acetone after to etching.
26. method according to claim 24 is characterized in that, in described step a, with just hindering the agent gluing.
27. method according to claim 26 is characterized in that, described just to hinder agent be polymethyl methacrylate.
28. method according to claim 24 is characterized in that, in described step a, the electron beam that produces with ESEM exposes.
29. method according to claim 24 is characterized in that, in described step a, is that the methylisobutylketone of 1:3 and the mixed solution of isopropyl alcohol develop with volume ratio.
30. method according to claim 24 is characterized in that, in described step b, adopts sulfur hexafluoride gas to carry out etching, the current density of ion beam is 10-50sccm, and ion energy is 50-100W.
31. method according to claim 24 is characterized in that, in described step b, adopts sulfur hexafluoride gas to carry out etching, the current density of ion beam is 20-40sccm, and ion energy is 60-90W.
32. method according to claim 24 is characterized in that, in described step b, adopts sulfur hexafluoride gas to carry out etching, the current density of ion beam is 25-35sccm, and ion energy is 75-85W.
33. the purposes of each described silver nanoparticle superstructure array in SERS detects among the claim 1-12.
34. the purposes of each described silver nanoparticle superstructure array in solar cell among the claim 1-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010171537 CN102233424B (en) | 2010-05-07 | 2010-05-07 | Silver nano superstructure array, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010171537 CN102233424B (en) | 2010-05-07 | 2010-05-07 | Silver nano superstructure array, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102233424A CN102233424A (en) | 2011-11-09 |
| CN102233424B true CN102233424B (en) | 2013-08-07 |
Family
ID=44884816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010171537 Expired - Fee Related CN102233424B (en) | 2010-05-07 | 2010-05-07 | Silver nano superstructure array, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102233424B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423808A (en) * | 2011-12-14 | 2012-04-25 | 天津工业大学 | Quick high concentration synthesizing method of silver nanometer line |
| CN103820826A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院合肥物质科学研究院 | Preparation method for shape-controllable silver nanosheet assembly structure array and application of shape-controllable silver nanosheet assembly structure array |
| CN103111621B (en) * | 2013-03-06 | 2014-08-27 | 中国科学院合肥物质科学研究院 | Preparation method for silver nanoparticle chain |
| CN104625088B (en) * | 2015-03-20 | 2017-02-01 | 广东工业大学 | Environment-friendly synthesis method of 1D chain structure nano particles |
| CN105469848B (en) * | 2015-12-30 | 2017-11-24 | 安徽师范大学 | The constructing system and method for atom cooling two-dimensional nano local light |
| CN106770180B (en) * | 2017-02-23 | 2019-10-11 | 国家纳米科学中心 | A kind of preparation method of surface-enhanced Raman substrate |
| CN107235471B (en) * | 2017-04-20 | 2019-06-14 | 广东工业大学 | A kind of surface enhanced Raman scattering substrate and its preparation method and application |
| CN108982464A (en) * | 2018-04-17 | 2018-12-11 | 中国科学院合肥物质科学研究院 | A kind of high distribution density nano gap oldered array and the preparation method and application thereof |
| CN114373825A (en) * | 2022-01-10 | 2022-04-19 | 深圳迈塔兰斯科技有限公司 | Heterojunction device based on two-dimensional material, photoelectric detector comprising heterojunction device and method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709789A (en) * | 2005-06-24 | 2005-12-21 | 清华大学 | Method for preparing silver monocrystal nano line array in cm-level length |
| CN1709790A (en) * | 2005-06-24 | 2005-12-21 | 清华大学 | Method for preparing monocrystal silver nano line array with square cm order area |
| CN101172573A (en) * | 2006-11-01 | 2008-05-07 | 国家纳米技术与工程研究院 | Silver nano-grain array mould plate and preparation method thereof |
| CN101281133A (en) * | 2008-05-12 | 2008-10-08 | 中国科学院合肥智能机械研究所 | Preparation of surface reinforced Raman active substrate of large area micro-nano dendritical structure array |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8568871B2 (en) * | 2007-10-29 | 2013-10-29 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Portland State University | Mono-layer and multi-layer nanowire networks |
-
2010
- 2010-05-07 CN CN 201010171537 patent/CN102233424B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709789A (en) * | 2005-06-24 | 2005-12-21 | 清华大学 | Method for preparing silver monocrystal nano line array in cm-level length |
| CN1709790A (en) * | 2005-06-24 | 2005-12-21 | 清华大学 | Method for preparing monocrystal silver nano line array with square cm order area |
| CN101172573A (en) * | 2006-11-01 | 2008-05-07 | 国家纳米技术与工程研究院 | Silver nano-grain array mould plate and preparation method thereof |
| CN101281133A (en) * | 2008-05-12 | 2008-10-08 | 中国科学院合肥智能机械研究所 | Preparation of surface reinforced Raman active substrate of large area micro-nano dendritical structure array |
Non-Patent Citations (4)
| Title |
|---|
| Highly Surface-roughened Flower-like Silver Nanoparticles for Extremely Sensitive Substreats of Surface-enhanced Raman Scattering;Hongyan Liang 等;《Advanced Materials》;20090915;第21卷(第45期);4614-4618 * |
| Hongyan Liang 等.Highly Surface-roughened Flower-like Silver Nanoparticles for Extremely Sensitive Substreats of Surface-enhanced Raman Scattering.《Advanced Materials》.2009,第21卷(第45期),4614-4618. |
| Prashant Nagpal 等.Ultrasmooth Patterned Metals for Plasmonics and Metamaterials.《Science》.2009,第325卷(第5940期),594-597. |
| Ultrasmooth Patterned Metals for Plasmonics and Metamaterials;Prashant Nagpal 等;《Science》;20090731;第325卷(第5940期);594-597 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102233424A (en) | 2011-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102233424B (en) | Silver nano superstructure array, and preparation method and application thereof | |
| CN104251853A (en) | Method for detecting perchlorate radical in water by using surface enhanced Raman scattering technology | |
| CN102311095B (en) | Method for preparing multistage metal micro-nanostructures inside micro fluidic chip | |
| CN101281133B (en) | Preparation of surface reinforced Raman active substrate of large area micro-nano dendritical structure array | |
| CN101113953B (en) | Method for manufacturing optical fiber detecting probe | |
| CN105241864A (en) | Laser-induce self-assembly method for preparing high-sensitivity optical fiber SERS probe | |
| Wu et al. | Structural characterization of nickel oxide nanowires by X-ray absorption near-edge structure spectroscopy | |
| CN107101988A (en) | A kind of high density nanometer pinpoint array of golden film covering and its application | |
| CN106814128A (en) | A kind of method of utilization Mass Spectrometer Method excretion body small molecule metabolites | |
| CN107488661A (en) | A kind of nucleic acid nano structure and its preparation method and application | |
| CN109865541A (en) | A kind of scanning electron microscope home position Electrochemical Detection chip and preparation method thereof | |
| CN104911667A (en) | Preparation method of novel multilayer composite noble metal nanopore array SERS substrate with honeycomb-shaped array structure | |
| Wang et al. | Selective extraction and preconcentration of trace lead (II) in medicinal plant-based ionic liquid hollow fiber liquid phase microextraction system using dicyclohexyl-18-crown-6 as membrane carrier | |
| CN106093004A (en) | Super-hydrophobic molecule enrichment concentrates chip and its preparation method and application | |
| CN104237202B (en) | A kind of silicon nano-array substrate and preparation method thereof, application | |
| CN116840154A (en) | System and method for detecting heavy metal elements in aqueous solution by enhancing LIBS (laser induced breakdown spectroscopy) signals | |
| CN105784668A (en) | Hand-written surface-enhanced Raman scattering substrate, and preparation method and application thereof | |
| CN102838082A (en) | Method for preparing micro-nano structure on material surface based on laser interference photolithography | |
| CN101358941A (en) | Double-face nanometer band electrode array integration sensor capable of being cut and method for manufacturing same | |
| Yusuf et al. | Optimized deep reactive-ion etching of nanostructured black silicon for high-contrast optical alignment marks | |
| Sowlat et al. | Development and field evaluation of an online monitor for near-continuous measurement of iron, manganese, and chromium in coarse airborne particulate matter (PM) | |
| Xu et al. | Femtosecond laser ablated pyramidal fiber taper-SERS probe with laser-induced silver nanostructures | |
| CN102954956A (en) | Enhanced Raman spectroscopy test piece device and test piece manufacturing method | |
| CN109975270A (en) | A kind of silver nano flower-like periodic array SERS substrate and preparation method thereof | |
| Wang et al. | An effective surface-enhanced Raman scattering template based on gold nanoparticle/silicon nanowire arrays |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130807 Termination date: 20160507 |