CN1944709A - Method for depositing continuous metal layer on capillary tube inner wall - Google Patents
Method for depositing continuous metal layer on capillary tube inner wall Download PDFInfo
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- CN1944709A CN1944709A CN 200610116337 CN200610116337A CN1944709A CN 1944709 A CN1944709 A CN 1944709A CN 200610116337 CN200610116337 CN 200610116337 CN 200610116337 A CN200610116337 A CN 200610116337A CN 1944709 A CN1944709 A CN 1944709A
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Abstract
The present invention belongs to the field of micro detecting device technology, and is especially process of depositing continuous metal layer onto inner wall of capillary tube of glass, silicon or silica. The process includes the following steps: injecting self-assembling solution into the washed and hydroxylated capillary tube of glass, silicon or silica and soaking for certain time to obtain one layer of self-assembled molecule bonded firmly to the inner surface; injecting catalyst solution and soaking for the catalyst to be adsorbed effectively to the self-assembled layer; and injecting chemical plating solution in controlled flow rate, temperature, pH value, etc to grow continuous homogeneous metal layer in controlled thickness.
Description
Technical field
The invention belongs to field of micro detecting device technology, be specifically related to a kind of method at the controlled continuous metal layer of glass, silicon or silicon-dioxide single capillary inwall deposit thickness.
Background technology
Kapillary can be used as the integral part of miniature detection system as sampling device or transmission pipeline, for the extraction of micro substance and compartment analysis provide may.Especially wherein the kapillary of making by silicon substrate or glass baseplate, because complete processing is perfect, thereby can accurately control its internal diameter yardstick and whole pattern, 3 D pore canal with this accurate typing is incorporated in the manufacturing process of miniature detection system again, can further satisfy the requirement of device volume miniaturization, function integration.
The flux analysis device that with the hollow edged electrode is detecting head has become the important on-the site analysis instrument of a class.Flux analysis is meant on the circulation path of device continuity or injects sample with pulse mode, by the control and the collection of optics, electrical signal, comes the concentration of test sample quantitatively.Its advantage is to realize continuously on-the site analysis fast, the signal to noise ratio height, dead volume is little, and signal attenuation is low, and be convenient to assembling and safeguard that a plurality of fields such as elemental substance control now have been widely used in mixing in environmental monitoring, medicine control, medical inspection, the production of silicon source.Generally speaking, the kapillary of employing below hundred microns just can reach the detection lower limit of ppb level as the analytical equipment of path.
For the flux analysis of tubular channel, the formula below its current-responsive satisfies:
i＝1.61nFC(DA/r)
2/3U
1/3＝5.48nF(Dl)
2/3CU
1/3
Wherein i is a response current intensity, and n is an amount of substance, and F is a Faraday's number, and C is a sample concentration, and D is a spread coefficient, and A is an electrode area, and r is the internal diameter of pipe, and l is the length of pipe, and U is the average-volume flow velocity.
By following formula as can be known, capillary electrode is assembled into the flux analysis device, and as the average-volume constant flow rate, it is only relevant with hollow edged electrode length to detect response current, and is irrelevant with its radius; The more important thing is that small-bore tubing shape passage will make required sample volume sharply reduce, saved the consumption of precious metals such as gold electrode simultaneously greatly.Therefore the improvement of capillary tube inner wall metal plating technology will promote the development of flux analysis to miniaturization, low cost and highly sensitive direction greatly.
Micro-fluidic chip is as a kind of emerging micro detecting device, different with the analysis and detecting instrument of routine, it is functional structures such as integrated all collections that need, pre-treatment, separation, detection on square several centimetres chip, thereby finish whole testing process in very short time at the scene, not only sensitivity and tolerance range be all not second to conventional equipment, and the sample that it consumed and detection reagent are also far much smaller.Kapillary is very important integral part in microfluidic chip structure, and conventional silica-based or glass capillary all needs to carry out interior finishing when using, and for example modifies special molecular to satisfy higher enrichment, to separate needs.And the successive metal level is as the complicated often leading step of modifying of the decorative layer of inwall, because it not only can transform inwall as conductor layer, make things convenient for the conduction of control of Electric potentials and signal, but also can greatly enrich the functional molecular kind of absorption, this is all development to some extent in fields such as medical science detection, bioseparation, DNA evaluations, therefore obtain modification technique suitable, effective capillary tube inner wall continuous metal layer and just seem particularly important.
The processing majority of traditional micro device is finished by photoetching and selective deposition coupling, such technology all can only satisfy substrate surface two dimension or accurate three-dimensional metal processing needs, direct modification for the three-dimensional tube inwall also need be finished by other deposition technique, evaporation, physical deposition methods such as sputter, generally need earlier kapillary vertically to be separated, inwall is exposed under the sedimentary environment, treat to restore back after deposition finishes, the equipment that such method needs on the one hand is very expensive, the manufacturing cost height, process-cycle is long, and complicated like this processing technology is difficult to produce in batches; On the other hand separate with reduction process in all might follow the destruction of kapillary pattern, when also having structures such as winding is arranged when the duct, just can't carry out effectively vertically separation.
And as the common processes of the surface metalation of isolator and irregular geometry, electroless plating especially wet chemistry plating has just shown special advantage.Different with the principle of electrochemical deposition, the electroless plating process is actually the process that metal ion in the plating bath is caused reduction and then carries out self catalyzed reduction, material as initiator is exactly the catalyzer of electroless plating, for kapillary, adopting the method for inner beam that the plating bath of electroless plating is flowed through along pipeline has adhered to the internal surface of catalyzer, just can obtain the metal plating of successive electroless plating.
Yet silicon, silicon-dioxide, this class stromal surface of glass often can not get effective catalyzer adsorption layer directly and a little less than the effect of catalyzer.Therefore surface modification just becomes the precondition that this class electroless plating realizes.Use the self-assembly agent to form the self-assembly layer on the surface, between this self-assembly layer and stromal surface and the catalyzer stronger chemistry or physical action are arranged, the bonding force of carrying out the settled layer of electroless plating gained so again will be greatly enhanced.For example use 3-TSL 8330 (APTMS), 3-sulfydryl propyl trimethoxy silicane silicane materials such as (MPTMS) to carry out self-assembled modified to capillary tube inner wall, the outside assembled layers of its amino or sulfydryl will have electrostatic attraction or complexing action to the particle as catalyzer, thereby can obtain the catalyst layer of successive active adsorption, further wait until the metal level that is deposited on inwall thus.
Summary of the invention
At above-mentioned capillary tube inner wall metal deposition difficulty, problem such as the metal deposition layer cohesive force is not strong on the non-conductor, for satisfying various internal diameter sizes and shape processing request capillaceous, can satisfy the processing request of kapillary independent part or array again, the present invention proposes a kind of method at the capillary tube inner wall depositing continuous metal layer.
The method that present method proposes at the capillary tube inner wall depositing continuous metal layer, be to adopt immersion self-assembly agent to carry out the technology that finishing, surface catalysis activation and continuous beam carry out electroless plating, concrete steps are as follows: injecting the resident again immersion of self-assembly solution earlier in surface cleaning and hydroxylated silicon, silicon-dioxide or glass capillary, obtain one deck self assembly molecule layer, there are bonding action in this layer molecule and internal surface, thereby can adhere to more securely; And then inject, soak catalyst solution and carry out catalytic activation, make catalyzer on the self-assembly layer of internal surface, obtain active adsorption; Inject the plating bath of electroless plating then continuously, regulate conditions such as flow velocity, temperature, pH value, the growth of whole metal level is controlled effectively, the metal level of obtain continuously evenly, thickness is adjustable.
Self-assembly agent used in the present invention comprises that 3-TSL 8330 (APTMS), 3-sulfydryl propyl trimethoxy silicane (MPTMS) are the silicane material of terminal for all kinds of of representative with amino, sulfydryl.The solvent of self-assembly liquid comprises materials such as water, alcohols or arene derivatives.Self-assembly liquid weight concentration is 0.1%-10%.Self-assembly solution drive to inject capillary cavity by flow pumps, and flow velocity is 1～10mm/s, drives behind the whole inner chamber liquid-flow intermittently 1～5min, inject for 5～20 times repeatedly, soak at room temperature is assembled, and the self-assembly time raises with concentration and shortens time range 0.5～10h.
Catalyst solution used in the present invention comprises precious metal colloidal sols such as gold and silver, platinum, palladium, also can be these metal plasma salts solutions, as Palladous chloride, chlorine palladium acid solution etc.The colloidal sol particle size range is 1～100nm, and specifically according to the control of catalyzed reaction type, the concentration range of ion salt solution is 0.5～500mM.Drive to inject capillary cavity by flow pumps, flow velocity is 1～10mm/s, drives behind the whole inner chamber liquid-flow intermittently 1～5min, 6-12 injection repeatedly, and soak at room temperature carries out catalytic activation, time range 1～10h.
Among the present invention, but metal refining comprise gold and silver, copper, nickel etc., the plating bath of electroless plating uses the standard chemical plating plating bath of each metal, the pH value is controlled at neutrality or acidity.The plating bath of electroless plating is driven by flow pumps and injects capillary cavity, and flow velocity is 0.5～5mm/s, keeps plating bath to flow, and according to the standard deposition condition, control plating speed is at 0.01～1 μ m/min under the room temperature, and depositing time is at 5～30min.
The beneficial effect of this technology is for can satisfying the processing request of different shape pipeline directly at kapillary (inside diameter ranges is 1～500 μ m) inwall metal refining, and the metal level of gained is evenly continuous, thickness is adjustable.This method not only can be carried out single processing capillaceous, also can realize the batch machining of array capillary, is metallized fast, the wet method implementations cheaply of various internal diameter capillary tube inwalls.
Description of drawings
Fig. 1. the profile scanning Electronic Speculum figure behind the capillary tube inner wall chemical gilding, upper right is the enlarged view of inwall and settled layer junction, deposit thickness is about 300nm.
Fig. 2. the sem photograph after capillary tube inner wall chemical gilding layer and kapillary are peeled off, the settled layer of gained are even successive.
Embodiment
Embodiment 1: glass capillary inwall deposited gold
The preparation of gold sol.The compound method of this colloidal sol is for being 0.5～5% HAuClO with 1mL quality volume fraction
4The aqueous solution joins in the 100mL ultrapure water and drip the aqueous solution 1mL that the quality volume fraction is 1% trisodium citrate under the successive magnetic agitation.Slowly drip the aqueous solution 1mL that contains quality volume fraction 0.07～0.09% sodium borohydride and 1% trisodium citrate then, restir is 0.5～6 hour after finishing, and promptly gets the required catalyzer that is used for catalytic activation.
Glass capillary (is formed by the drawing of vertical drawing instrument, the about 14.9 μ m of the thinnest end internal diameter) at acetone, ultrasonic cleaning 1～5min in turn in the deionized water, in dioxysulfate water (volume ratio is 7: 3) mixing solutions, carry out surface hydroxylation (10～20min), connect butt end of kapillary and water pump with connecting joint, thin end is placed in 0.5～10%APTMS (3-aminopropyl trimethoxysilane) aqueous solution, utilize the inside and outside pressure difference that produces of kapillary, can make the APTMS aqueous solution with the certain flow rate capillary tube inner wall of flowing through, behind injection solution 5-20 time, kapillary inserted take out after soaking 1～8h in this APTMS aqueous solution, fully wash the kapillary outer wall with deionized water, drive with pump, with deionized water washpipe inwall repeatedly.Same method is handled kapillary with gold sol, kapillary is immersed in the gold sol takes out behind 1～6h, flushing kapillary inside and outside wall.The kapillary of handling well is placed 0.1%～1%HAuCl
4With 0.01～0.1%NH
4In the OHHCl aqueous solution, drive Continuous Flow by flow pumps and cross kapillary, carry out electroless plating 50～500s under the room temperature.As seen plate the deposition of gold layer of having expired about 300nm by accompanying drawing 1 around capillary tube inner wall, by accompanying drawing 2, the gold layer of visible deposition was even continuously after capillary tube inner wall chemical gilding layer and kapillary were peeled off.
Embodiment 2: glass capillary inwall nickel deposited boron alloy
Self-chambering agent functional quality mark is 0.1～10% APTMS (3-aminopropyl trimethoxysilane) toluene solution, and the catalyzer working concentration is that 0.5mM～50mM catalyzer is chlorine palladium acid sodium (Na
2PdClO
4) aqueous solution.Chemical plating bath use storing solution A and reduced liquid B volume ratio are 4: 1 mixed solution, and the composition of storing solution A contains the single nickel salt that the volume mass mark is 1-50g/L, the Trisodium Citrate of 1-20g/L, the lactic acid of 1-20mL/L.Reduced liquid B is the aqueous solution of dimethylamino borine, and content is 1-10g/L, regulates pH about 7.5 with ammoniacal liquor.
Glass capillary is carried out surface hydroxylation, carry out the self-assembly of APTMS and the surface active of chlorine palladium acid sodium according to the method in the example 1.Drive the chemical plating bath Continuous Flow by flow pumps and cross kapillary, carry out electroless plating 120～600s under the room temperature.
Claims (5)
1, a kind of method at the capillary tube inner wall depositing continuous metal layer, it is characterized in that concrete steps are as follows: in surface cleaning and hydroxylated silicon, silicon-dioxide or glass capillary, injecting the resident again immersion of self-assembly solution earlier, obtaining one deck self assembly molecule layer; And then inject, soak catalyst solution and carry out catalytic activation, make catalyzer on the self-assembly layer of internal surface, obtain active adsorption; Inject the plating bath of electroless plating then continuously, regulate flow velocity, temperature, pH value, the growth of whole metal level is controlled effectively, the metal level of obtain continuously evenly, thickness is adjustable; Wherein:
Self-assembly agent in the described self-assembly solution is for being the silicane material of terminal with amino, amino, sulfydryl, and solvent is water, alcohols or arene derivatives;
Described catalyst solution is the metal-sol of gold and silver, platinum or palladium, perhaps is the ion salt solution of these metals; The particle diameter of metal-sol is 1-100nm, and the concentration of metal ion salt solution is 0.5-500mM;
But the plating bath of described electroless plating is the standard chemical plating plating bath of metal refining, and the pH value is neutral or acid, but wherein metal refining is gold and silver, copper or nickel.
2, the method at the capillary tube inner wall depositing continuous metal layer according to claim 1, it is characterized in that described self-assembly solution drives the injection capillary cavity by flow pumps, flow velocity is 1～10mm/s, drive behind the whole inner chamber liquid-flow intermittently 1～5min, inject for 5～20 times repeatedly, soak at room temperature is assembled.
3, the method at the capillary tube inner wall depositing continuous metal layer according to claim 1, it is characterized in that described catalyst solution drives the injection capillary cavity by flow pumps, flow velocity is 1～10mm/s, drive behind the whole inner chamber liquid-flow intermittently 1～5min, about 6-12 time injection repeatedly, soak at room temperature carries out catalytic activation, and the time is 1～10h.
4, the method at the capillary tube inner wall depositing continuous metal layer according to claim 1, the plating bath that it is characterized in that described electroless plating drives the injection capillary cavity by flow pumps, flow velocity is 0.5～5mm/s, keep plating bath to flow, according to the standard deposition condition, control plating speed is 0.01～1 μ m/min under the room temperature, and depositing time is 5～30min.
5, the method at the capillary tube inner wall depositing continuous metal layer according to claim 1 is characterized in that at described capillary inner diameter be 1-500 μ m.
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| CN 200610116337 CN1944709A (en) | 2006-09-21 | 2006-09-21 | Method for depositing continuous metal layer on capillary tube inner wall |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179585A (en) * | 2011-05-20 | 2011-09-14 | 南京航空航天大学 | Capillary cathode-based small-conicity micro-hole electrochemical machining device and method |
| CN102390926A (en) * | 2011-07-28 | 2012-03-28 | 东华大学 | Method for preparing glass fibre with structural colors |
| CN104746056A (en) * | 2014-12-26 | 2015-07-01 | 华中师范大学 | Method for plating silver on inner wall of quartz capillary |
| CN111420655A (en) * | 2020-04-18 | 2020-07-17 | 云南正邦科技有限公司 | Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module |
| CN111569599A (en) * | 2019-11-08 | 2020-08-25 | 杭州超钜科技有限公司 | Composite fiber type mercury capturing device and preparation method of mercury capturing composite fiber |
-
2006
- 2006-09-21 CN CN 200610116337 patent/CN1944709A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179585A (en) * | 2011-05-20 | 2011-09-14 | 南京航空航天大学 | Capillary cathode-based small-conicity micro-hole electrochemical machining device and method |
| CN102179585B (en) * | 2011-05-20 | 2012-12-12 | 南京航空航天大学 | Capillary cathode-based small-conicity micro-hole electrochemical machining device and method |
| CN102390926A (en) * | 2011-07-28 | 2012-03-28 | 东华大学 | Method for preparing glass fibre with structural colors |
| CN102390926B (en) * | 2011-07-28 | 2014-05-28 | 东华大学 | Method for preparing glass fibre with structural colors |
| CN104746056A (en) * | 2014-12-26 | 2015-07-01 | 华中师范大学 | Method for plating silver on inner wall of quartz capillary |
| CN104746056B (en) * | 2014-12-26 | 2017-10-27 | 华中师范大学 | A kind of silver-plated method of quartz capillary inwall |
| CN111569599A (en) * | 2019-11-08 | 2020-08-25 | 杭州超钜科技有限公司 | Composite fiber type mercury capturing device and preparation method of mercury capturing composite fiber |
| CN111569599B (en) * | 2019-11-08 | 2021-12-10 | 杭州超钜科技有限公司 | Composite fiber type mercury capturing device and preparation method of mercury capturing composite fiber |
| CN111420655A (en) * | 2020-04-18 | 2020-07-17 | 云南正邦科技有限公司 | Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module |
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