CN101776573B - Silver-plated nano-fiber probe and manufacturing method thereof - Google Patents
Silver-plated nano-fiber probe and manufacturing method thereof Download PDFInfo
- Publication number
- CN101776573B CN101776573B CN2010101204525A CN201010120452A CN101776573B CN 101776573 B CN101776573 B CN 101776573B CN 2010101204525 A CN2010101204525 A CN 2010101204525A CN 201010120452 A CN201010120452 A CN 201010120452A CN 101776573 B CN101776573 B CN 101776573B
- Authority
- CN
- China
- Prior art keywords
- nano
- fiber probe
- silver
- solution
- probe
- 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
- Chemically Coating (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a silver-plated nano-fiber probe and a manufacturing method thereof, belonging to the manufacturing field of optical nano-fiber probes. The probe is manufactured from fiber substrate materials, a point structure for detecting is arranged at the front end of the probe, and a silver plating layer is covered on the surface of the point structure of the nano-fiber probe. The method of the invention can be used for manufacturing high-quality silver-plated nano-fiber probes and has low cost, and the coating can not fall off easily.
Description
Technical field
The present invention relates to the manufacturing field of optics nano-fiber probe.
Background technology
The optics nano-sensor is that a class has the miniaturization device that submicron order is popped one's head in, is used for optical detection.In nearly decades, its application has expanded to field of biology, can go deep into detecting in the individual cells.Because can carry out the real-time in-situ monitoring to biological process on unicellular level, the application of optics nano-sensor has brought revolutionary development to cell biology.
Nm probe is that whole optics nano-sensor is most important, also is the most accurate assembly, and the resolution of near field optic flying-spot microscope depends primarily on the structure and the quality of probe, comprises most advanced and sophisticated size, the thickness and the light transmissioning efficiency of sidewall coat.When the size of probe is reduced to submicron order, realize higher light transmissioning efficiency by the coat of metal that covers on its sidewall usually.
At present, have some and on nano-fiber probe, make the method for the coat of metal, for example metal vapor coating method and pitch-dark cladding process etc.Yet these method costs are higher, and coating can not be coated in the cutting-edge structure part of probe accurately, come off easily after coating is activated, make these nm probes to use in unicellular detection; Simultaneously silver coating on nano-fiber probe is not all reported on various documents.
Summary of the invention
The objective of the invention is to address the above problem and a kind of silver-plated nano-fiber probe and manufacture method thereof are provided, the high-quality silver-plated nano-fiber probe that utilizes this method to make, and this method cost is low, the coating difficult drop-off.
The technical solution adopted in the present invention is:
A kind of silver-plated nano-fiber probe, this probe is made by the optical fiber base material, and front end has a cutting-edge structure that is used to detect, and the cutting-edge structure surface coverage of described nano-fiber probe has one deck silvering.
Further, the width at described cutting-edge structure top is 50～300nm.
Further, the thickness of described silvering is 150～250nm.
A kind of manufacture method of silver-plated nano-fiber probe may further comprise the steps:
(1), utilize hot-drawing method to make nano-fiber probe with standard single mode or multimode optical fiber;
(2) nano-fiber probe is fixed in the glass capillary, immersed in the strong oxidizing property acid solution 3～5 hours, clean with pure water then, described strong oxidizing property acid solution be with percent by volume be 70%～99% sulfuric acid with percent by volume be 10%～30% hydrogen peroxide by volume for 4:6～8:2 is mixed must;
(3) glass capillary that will be fixed with nano-fiber probe immersed in the strong alkali solution 3～5 hours, clean with pure water then, described strong alkali solution contains one or more in NaOH and the potassium hydroxide, and hydroxide ion concentration is 0.5mol/L～5mol/L in the solution;
(4) to immerse mass percent be in 1%～6% the stannous chloride solution 3～20 minutes to the glass capillary that will be fixed with nano-fiber probe, thereby form stannous chloride crystal thin layer on nano-fiber probe cutting-edge structure surface, to promote the combination of silvering;
(5) use the deionized water rinsing nano-fiber probe, and dry up with nitrogen;
(6) will be fixed with in the glass capillary immersion silver ammino solution of nano-fiber probe, the adding mass percent is 2%～5% reductive agent in silver ammino solution, keep glass capillary to soak 20～150 minutes, make it that silver mirror reaction take place, nano-fiber probe cutting-edge structure surface forms one deck silvering, and the volume ratio of described silver ammino solution and reductive agent is 5:5～8:2;
(7) nano-fiber probe for preparing is placed in 20～80 ° of C ultrasound baths kept 15～60 minutes, make silvering even;
(8) use the deionized water rinsing nano-fiber probe, and dry up with nitrogen, being placed on vacuum tightness then is 1 * 10
-5Handkerchief, temperature are in the drying box of 80 ° of C～130 ° C, allow its bone dry, promptly make silver-plated nano-fiber probe.
Preferably, pure water is distilled water, reverse osmosis water or deionized water in described step (2) and (3).
Further, the silver ammino solution in the described step (6) is that mass percent is to splash into ammoniacal liquor in 1%～4% the liquor argenti nitratis ophthalmicus, up to the solution clarification that becomes colorless just.
Preferably, reductive agent is glucose solution, fructose soln, formalin or acetaldehyde solution in the described step (6).
Further, operating temperature should remain on 25 ° of C～80 ° C in the described step (6).
The present invention has the following advantages:
Utilize the inventive method can accurately silver be plated in the cutting-edge structure surface of nano-fiber probe, prevented the probe light leak, given nano-sensor splendid optical characteristics, the silver-plated nano-fiber probe that makes has the good optical characteristic, can be used for the near field optic flying-spot microscope, go deep into unicellular level bioprocess is detected in real time, and the silvering difficult drop-off; This method utilizes silver mirror reaction at fibre-optical probe cutting-edge structure electroplate simultaneously, has simplified the coating manufacture craft, effectively reduces manufacturing cost.
Description of drawings
Fig. 1 is the contrast synoptic diagram of the silver-plated front and back of nano-fiber probe;
Fig. 2 prepares the operation chart of silvering for nano-fiber probe;
Fig. 3 is the silver-plated front and back of a nano-fiber probe stereoscan photograph among the embodiment 1;
Fig. 4 is the silver-plated back of a nano-fiber probe stereoscan photograph among the embodiment 1.
Embodiment
Below in conjunction with accompanying drawing technical scheme of the present invention is further described in detail.
This probe is made by the optical fiber base material, and its front end has a cutting-edge structure that is used to detect, and the cutting-edge structure surface coverage of nano-fiber probe has one deck silvering, and the width at cutting-edge structure top is 50～300nm, and the thickness of silvering is 150～250nm.The silver-plated front and back contrast of nano-fiber probe synoptic diagram, as shown in Figure 1.
With reference to Fig. 2, the manufacture method of this silver-plated nano-fiber probe may further comprise the steps:
(1), utilize hot-drawing method to make nano-fiber probe with standard single mode or multimode optical fiber;
(2) nano-fiber probe is fixed in the glass capillary, immersed in the strong oxidizing property acid solution 3～5 hours, clean with pure water then, described strong oxidizing property acid solution is to be that 70%～99% sulfuric acid and percent by volume are that 10%～30% hydrogen peroxide is mixed for 4:6～8:2 by volume with percent by volume, and pure water is distilled water, reverse osmosis water or deionized water;
(3) glass capillary that will be fixed with nano-fiber probe immersed in the strong alkali solution 3～5 hours, clean with pure water then, described strong alkali solution contains one or more in NaOH and the potassium hydroxide, hydroxide ion concentration is 0.5mol/L～5mol/L in the solution, and pure water is distilled water, reverse osmosis water or deionized water;
(4) to immerse mass percent be in 1%～6% the stannous chloride solution 3～20 minutes to the glass capillary that will be fixed with nano-fiber probe, thereby form stannous chloride crystal thin layer on the nano-fiber probe surface, to promote the combination of silvering;
(5) use the deionized water rinsing nano-fiber probe, and dry up with nitrogen;
(6) in the environment of 25 ° of C～80 ° C, the glass capillary that is fixed with nano-fiber probe is immersed in the silver ammino solution, the adding mass percent is 2%～5% reductive agent in silver ammino solution, keep glass capillary to soak 20～150 minutes, make it that silver mirror reaction take place, the nano-fiber probe surface forms one deck silvering; The volume ratio of silver ammino solution and reductive agent is 5:5～8:2, silver ammino solution is that mass percent is to splash into ammoniacal liquor in 1%～4% the liquor argenti nitratis ophthalmicus, up to the solution clarification that becomes colorless just, reductive agent is glucose solution, fructose soln, formalin or acetaldehyde solution;
(7) nano-fiber probe for preparing is placed in 20～80 ° of C ultrasound baths kept 15～60 minutes, make silvering even;
(8) use the deionized water rinsing nano-fiber probe, and dry up with nitrogen, being placed on vacuum tightness then is 1 * 10
-5Handkerchief, temperature are in the drying box of 80 ° of C～130 ° C, allow its bone dry, promptly make silver-plated nano-fiber probe.
Embodiment 1
Make the thick silver plating nano-fiber probe of 150nm, specific operation process is as follows:
(1) utilize hot-drawing method to make nano-fiber probe standard single-mode fiber;
(2) nano-fiber probe with taper is fixed in the glass capillary, immerses in the strong oxidation acid solution 3 hours, cleans three times with distilled water then; The mixed solution that this strong oxidation acid solution is sulfuric acid and hydrogen peroxide, this mixed solution be with percent by volume be 98% the concentrated sulphuric acid and percent by volume be 30% hydrogen peroxide by volume 7:3 be mixed with and form;
(3) glass capillary that will be fixed with nano-fiber probe immersed in the sodium hydroxide solution that hydroxide ion concentration is 2mol/L 3 hours, cleaned three times with distilled water then;
(4) to immerse mass percent be in 5% the stannous chloride solution 10 minutes to the glass capillary that will be fixed with nano-fiber probe;
(5) use deionized water rinsing optical fiber, and dry up with nitrogen;
(6) with 0.2g AgNO
3Be dissolved in the 10ml deionized water, splash into ammoniacal liquor to solution and become achromaticity and clarification, make silver ammino solution, this moment, the pH value of silver ammino solution was 9.3;
(7) in 80 ° of C environment, the glass capillary immersion that is fixed with nano-fiber probe is disposed in the silver ammino solution, the adding mass percent is 4% glucose solution in silver ammino solution, to add the glucose solution volume ratio be 5:3 to silver ammino solution with institute, maintenance glass capillary immersion 120 minutes;
(8) the silver-plated nano optical fiber probe of preparation is placed in the ultrasound bath 60 ° of C and kept 30 minutes, make that the silvering of preparation is even;
(9) use deionized water rinsing optical fiber, and dry up, be placed on 120 ° of C in the vacuum drying chamber then, 1 * 10 with nitrogen
-5Kept under the condition of handkerchief vacuum tightness 24 hours, and made its bone dry, and make and be coated with the silvering that is covered with and closely be combined on the fibre-optical probe.
After testing, the surperficial silvering thickness of obtained silver-plated nano-fiber probe is about 100nm.Silver-plated front and back nano-fiber probe stereoscan photograph, as shown in Figure 3 and Figure 4.
Embodiment 2
Make the nano-fiber probe of the thick silvering of 250nm, specific operation process is as follows:
(1) utilize hot-drawing method to make nano-fiber probe standard multimode fiber;
(2) nano-fiber probe with taper is fixed in the glass capillary, immerses in the strong oxidation acid solution 5 hours, cleans four times with distilled water then; The mixed solution that this strong oxidation acid solution is sulfuric acid and hydrogen peroxide, this mixed solution are to be that 99% the concentrated sulphuric acid and percent by volume are that 10% hydrogen peroxide forms for 8:2 is mixed with by volume with percent by volume;
(3) glass capillary that will be fixed with optical fiber immersed in the potassium hydroxide solution that hydroxide ion concentration is 0.5mol/L 5 hours, cleaned three times with distilled water then;
(4) to immerse mass percent be in 3% the stannous chloride solution 20 minutes to the glass capillary that will be fixed with optical fiber;
(5) use deionized water rinsing optical fiber, and dry up with nitrogen;
(6) with 0.4g AgNO
3Be dissolved in the 10ml deionized water, splash into the clarification that becomes colorless just of ammoniacal liquor to solution, make silver ammino solution;
(7) in 25 ° of C environment, the glass capillary immersion that is fixed with optical fiber is disposed in the silver ammino solution, add mass percent and be 3.5% formalin in silver ammino solution, it is 5:5 that silver ammino solution adds the formalin volume ratio with institute, maintenance glass capillary immersion 45 minutes;
(8) the silver-plated nano optical fiber probe of preparation is placed in the ultrasound bath 80 ° of C and kept 60 minutes, make that the silvering of preparation is even;
(9) use deionized water rinsing optical fiber, and dry up, be placed on 100 ° of C in the vacuum drying chamber then, 1 * 10 with nitrogen
-5Kept under the condition of handkerchief vacuum tightness 24 hours, and made its bone dry, and make and be coated with the silvering that is covered with and closely be combined on the optical fiber probe.
Embodiment 3
Make the nano-fiber probe of the thick silvering of 200nm, specific operation process is as follows:
(1) utilize hot-drawing method to make nano-fiber probe standard single-mode fiber;
(2) nano-fiber probe with taper is fixed in the glass capillary, immerses in the strong oxidation acid solution 4 hours, cleans three times with distilled water then; The mixed solution that this strong oxidation acid solution is sulfuric acid and hydrogen peroxide, this mixed solution be with percent by volume be 70% the concentrated sulphuric acid and percent by volume be 30% hydrogen peroxide by volume 4:6 be mixed with and form;
(3) glass capillary that will be fixed with optical fiber immersed in the mixed solution of potassium hydroxide that hydroxide ion concentration is 5mol/L and NaOH 4.5 hours, cleaned three times with distilled water then;
(4) to immerse mass percent be in 5% the stannous chloride solution 20 minutes to the glass capillary that will be fixed with optical fiber;
(5) use deionized water rinsing optical fiber, and dry up with nitrogen;
(6) with 1g AgNO
3Be dissolved in the 10ml deionized water, splash into the clarification that becomes colorless just of ammoniacal liquor to solution, make silver ammino solution;
(7) in 80 ° of C environment, the glass capillary immersion that is fixed with optical fiber is disposed in the silver ammino solution, add mass percent and be 3.5% formalin in silver ammino solution, it is 5:3 that silver ammino solution adds the formalin volume ratio with institute, maintenance glass capillary immersion 60 minutes;
(8) the silver-plated nano optical fiber probe of preparation is placed in the ultrasound bath 50 ° of C and kept 15 minutes, make that the silvering of preparation is even;
(9) use deionized water rinsing optical fiber, and dry up, be placed on 130 ° of C in the vacuum drying chamber then, 1 * 10 with nitrogen
-5Kept under the condition of handkerchief vacuum tightness 24 hours, and made its bone dry, and make and be coated with the silvering that is covered with and closely be combined on the optical fiber probe.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (5)
1. silver-plated nano-fiber probe, this probe is made by the optical fiber base material, front end has a cutting-edge structure that is used to detect, the cutting-edge structure surface coverage of described nano-fiber probe has one deck silvering, the width at described cutting-edge structure top is 50～300nm, the thickness of described silvering is 150～250nm, it is characterized in that, the preparation method of this probe may further comprise the steps:
(1), utilize hot-drawing method to make nano-fiber probe with standard single mode or multimode optical fiber;
(2) nano-fiber probe is fixed in the glass capillary, immersed in the strong oxidizing property acid solution 3～5 hours, clean with pure water then, described strong oxidizing property acid solution be with percent by volume be 70%～99% sulfuric acid with percent by volume be 10%～30% hydrogen peroxide be by volume 4: 6～8: 2 mixed must;
(3) glass capillary that will be fixed with nano-fiber probe immersed in the strong alkali solution 3～5 hours, clean with pure water then, described strong alkali solution contains one or more in NaOH and the potassium hydroxide, and hydroxide ion concentration is 0.5mol/L～5mol/L in the solution;
(4) to immerse mass percent be in 1%～6% the stannous chloride solution 3～20 minutes to the glass capillary that will be fixed with nano-fiber probe, thereby form stannous chloride crystal thin layer on nano-fiber probe cutting-edge structure surface, to promote the combination of silvering;
(5) use the deionized water rinsing nano-fiber probe, and dry up with nitrogen;
(6) will be fixed with in the glass capillary immersion silver ammino solution of nano-fiber probe, the adding mass percent is 2%～5% reductive agent in silver ammino solution, keep glass capillary to soak 20～150 minutes, make it that silver mirror reaction take place, nano-fiber probe cutting-edge structure surface forms one deck silvering, and the volume ratio of described silver ammino solution and reductive agent is 5: 5～8: 2;
(7) nano-fiber probe for preparing is placed in 20～80 ℃ of ultrasound baths kept 15～60 minutes, make silvering even;
(8) use the deionized water rinsing nano-fiber probe, and dry up with nitrogen, being placed on vacuum tightness then is 1 * 10
-5Handkerchief, temperature are in 80 ℃～130 ℃ the drying box, allow its bone dry, promptly make silver-plated nano-fiber probe.
2. silver-plated nano-fiber probe according to claim 1 is characterized in that, pure water is distilled water, reverse osmosis water or deionized water in described step (2) and (3).
3. silver-plated nano-fiber probe according to claim 1 is characterized in that, the silver ammino solution in the described step (6) is that mass percent is to splash into ammoniacal liquor in 1%～4% the liquor argenti nitratis ophthalmicus, up to the solution clarification that becomes colorless just.
4. silver-plated nano-fiber probe according to claim 1 is characterized in that, reductive agent is glucose solution, fructose soln, formalin or acetaldehyde solution in the described step (6).
5. silver-plated nano-fiber probe according to claim 1 is characterized in that, operating temperature should remain on 25 ℃～80 ℃ in the described step (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101204525A CN101776573B (en) | 2010-03-09 | 2010-03-09 | Silver-plated nano-fiber probe and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101204525A CN101776573B (en) | 2010-03-09 | 2010-03-09 | Silver-plated nano-fiber probe and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101776573A CN101776573A (en) | 2010-07-14 |
| CN101776573B true CN101776573B (en) | 2011-09-07 |
Family
ID=42513089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101204525A Expired - Fee Related CN101776573B (en) | 2010-03-09 | 2010-03-09 | Silver-plated nano-fiber probe and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101776573B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874911B (en) * | 2015-05-27 | 2016-10-12 | 四川大学 | A kind of microprobe tip forming laser system of processing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1805061A (en) * | 2006-01-06 | 2006-07-19 | 华南理工大学 | Method of producing photon scanning tunneling microscope probe with optical fiber and Indium-Tin-oxide |
| CN101113953A (en) * | 2006-07-28 | 2008-01-30 | 清华大学 | Method for manufacturing optical fiber detecting probe |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01183872A (en) * | 1988-01-18 | 1989-07-21 | Nippon Telegr & Teleph Corp <Ntt> | Automatic control apparatus of optical output of semiconductor laser |
-
2010
- 2010-03-09 CN CN2010101204525A patent/CN101776573B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1805061A (en) * | 2006-01-06 | 2006-07-19 | 华南理工大学 | Method of producing photon scanning tunneling microscope probe with optical fiber and Indium-Tin-oxide |
| CN101113953A (en) * | 2006-07-28 | 2008-01-30 | 清华大学 | Method for manufacturing optical fiber detecting probe |
Non-Patent Citations (2)
| Title |
|---|
| 刘秀梅等.高效、高分辨光纤微探针的制备及检验.《光学学报》.2000,第20卷(第5期),659-665. * |
| 杨修文等.具有表面增强拉曼光谱光纤探针的研究.《辽宁师范大学学报(自然科学版)》.2007,第30卷(第3期),300-303. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101776573A (en) | 2010-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3925867B2 (en) | Method for manufacturing a silicon substrate with a porous layer | |
| Korotcenkov et al. | Silicon porosification: state of the art | |
| CN101673785B (en) | Method for preparing reflection reduction film with surface embedded type porous silicon structure of silicon base solar battery | |
| CN103675068A (en) | Bismuth nitrate oxide based solid nitrate electrode and preparation method thereof | |
| CN107937957B (en) | Preparation method of surface-enhanced Raman substrate and application of substrate in detection of animal viruses | |
| US20120326255A1 (en) | Method and device for manufacturing semiconductor devices, semiconductor device and transfer member | |
| CN103257132B (en) | Silver nanoparticle cap array surface-enhanced Raman activity substrate and preparation method thereof | |
| CN101776573B (en) | Silver-plated nano-fiber probe and manufacturing method thereof | |
| CN106711248B (en) | A method of reducing ingot casting polysilicon chip surface reflectivity | |
| CN107316917A (en) | A kind of method for the monocrystalline silicon suede structure for preparing antiradar reflectivity | |
| CN105671523B (en) | A kind of displacement reaction method for preparing silver tree branch super hydrophobic surface | |
| CN108557754B (en) | Preparation method of self-supporting metal nano-pore film | |
| CN108169299B (en) | Diamond seawater salinity sensor based on MEMS technology and manufacturing method thereof | |
| TW201041666A (en) | Process to remove metal contamination on TCO | |
| Burham et al. | Self-adjusting electrochemical etching technique for producing nanoporous silicon membrane | |
| CN102383177A (en) | Method for preparing porous silicon on silicon-on insulator (SOI) | |
| WO2006051641A1 (en) | Method for forming porous semiconductor film, light-emitting device and optical sensor | |
| CN103305890B (en) | The preparation method of the anodic oxidation aluminium formwork that three-dimensional runs through | |
| KR20130101113A (en) | Solar cell wafer and method for manufacturing same | |
| CN103866371B (en) | A kind of beryllium material electrochemistry insulation anode oxidation treatment method | |
| Mebed et al. | Fabrication, boron leaching, and electrochemical impedance spectroscopy of nanoporous P-type silicon | |
| CN103757675A (en) | Method for preparing AFM (Atomic Force Microscope) silicon tip by pulse plating of compact gold thin film in nanometer thickness | |
| CN108362678A (en) | A method of utilizing hollow Ag-Au alloys composite construction micro-nano array detection melamine | |
| CN103866316A (en) | Chemical passivation method of beryllium material | |
| CN103741178A (en) | Solution for directly electroplating surface of silicon with smooth and compact thin silver film and electroplating method |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110907 Termination date: 20120309 |