CN102424356B - Device and method for preparing metal nanoparticle microarray chip - Google Patents
Device and method for preparing metal nanoparticle microarray chip Download PDFInfo
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- CN102424356B CN102424356B CN201110378204.5A CN201110378204A CN102424356B CN 102424356 B CN102424356 B CN 102424356B CN 201110378204 A CN201110378204 A CN 201110378204A CN 102424356 B CN102424356 B CN 102424356B
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Abstract
The invention discloses a device and a method for preparing a metal nanoparticle microarray chip. The preparation method comprises a laser, an electric control switch, a spatial filter, a beam shaping system, a reflector, a focusing objective lens, a specimen holder, a precision electric control three-dimensional displacement platform and an observation screen; and the preparation method comprises the following steps of: preparing a composite sol containing metal nanoparticles and a polymer material; spin-coating the composite sol on a substrate; drying and curing to obtain a composite colloid film containing the metal nanoparticles; and performing laser etching on a sample consisting of the composite colloid film and the substrate under the preparation device to obtain the metal nanoparticle microarray chip. The metal nanoparticle microarray chip prepared by the method has uniformly distributed dot matrix patterns, metal nanoparticle microarray units are clear in profile and regular in shape, and the size and distribution of unit dots are easy to control and regulate; and the method has the advantages of simple process, low cost and suitability for promotion.
Description
Technical field
The present invention relates to a kind of micro-nano process technology, especially relate to a kind of preparation facilities and method of metal nanoparticle microarray chip.
Background technology
In recent years, nano material has unique physical and chemical performance because of it, and has significant application value in fields such as optical, electrical, catalysis, storage, medical treatment and sensings, thereby causes numerous scientific workers' research interest.So far, people have prepared the nano material of different morphologies and structure, as polystyrene nanospheres, gold nano bar, silicon nanowires, CNT and nanometer zinc oxide disc etc.Along with scientific and technical progress, minute manufacturing technology is from the synthetic and property representation of nano material, develops into people and can utilize nano material to carry out Design and manufacture to have according to the wish of oneself the micro-nano structure device of certain function.
At present, prepare micro-nano structure device and mainly contain two kinds of methods: the first is to utilize the weak non-covalent bond less with directionality, as hydrogen bond, Robert Van de Walle key and weak ionic bond synergy, atom, lewis' acid are assembled into specific micro/nano structure.This method is simple and convenient, but controllability and repeated aspect have much room for improvement; The second is by methods such as photoetching, electron beam lithography, reactive ion etching, focused-ion-beam lithography, nano impression, electrochemical deposition, vacuum evaporations, prepares specific micro/nano structure.These methods can be prepared the micro/nano structure that precision is high, pattern is complicated, but need complicated and expensive micro-nano process equipment, and length consuming time, cost are high, prepare area little, can not carry out large-scale production.Some achievements are obtained although people prepare at micro-nano structure device aspect many, but still can not meet and realize extensive, high efficiency, prepare requirement, the therefore preparation method of a kind of micro/nano structure simple to operate, with low cost of necessary development cheaply.
On the other hand, laser direct-writing technology is a kind of development novel micro-processing technology rapidly, it directly exposes laser beam or ablation to sample surfaces after specific optical shaping system, is realized at sample surfaces and is formed required embossment profile by the movement of computer control sample stage.This technology belongs to once shaping technology, without complicated subsequent treatment process, has the plurality of advantages such as cost is low, the process-cycle is short, use is flexible, environmental requirement is low, aspect the making of microelectronics, integrated optics, MEMS etc., has obtained extensive use.Therefore the preparation that, utilizes laser direct-writing technology to carry out metal nanoparticle microarray chip has important development prospect.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of easy and simple to handle, with low cost, and efficiency is high, reproducible, can realize preparation facilities and the method for the metal nanoparticle microarray chip of large-scale production.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation facilities of metal nanoparticle microarray chip, it is characterized in that comprising laser instrument, electric-controlled switch, spatial filter, beam shaping system, speculum, focusing objective len, specimen holder, accurate automatically controlled three-D displacement platform and film viewing screen, described electric-controlled switch is for controlling the opening and closure of laser beam of described laser instrument transmitting, described spatial filter mainly by be arranged at the first diaphragm between the light incident side of described laser instrument and described beam shaping system and be arranged at described in light exit side and the described speculum of beam shaping system between the second diaphragm form, described specimen holder is connected with the automatically controlled three-D displacement platform of described precision, sample on described specimen holder is between described focusing objective len and described film viewing screen, by described specimen holder, the upper and lower displacement on the automatically controlled three-D displacement platform of described precision realizes position coarse adjustment to sample on described specimen holder, sample on described specimen holder by the fine tuning of the automatically controlled three-D displacement of described precision position of platform after focal plane in described focusing objective len, the laser beam of the laser instrument transmitting described in when described electric-controlled switch is opened incides on described speculum by the first described diaphragm, described beam shaping system and the second described diaphragm, the laser direct-writing point that the laser beam of described speculum reflection is irradiated to sample by described focusing objective len is upper, and in the time that the diffraction pattern on described film viewing screen is stablized, this laser direct-writing point has completed laser direct-writing.
Described laser instrument adopts low-power laser; The pore size of the first described diaphragm and the second described diaphragm is all adjustable, and minimum-value aperture size is 0.5mm, and maximum aperture size is 4mm; The multiple that expands of described beam shaping system is 4; The reflectivity of described speculum is 0.95; The multiplication factor of described focusing objective len is 10～100 times.
Described electric-controlled switch be arranged at described laser instrument, described the first diaphragm, described beam shaping system, described the second diaphragm, described speculum and described focusing objective len arbitrarily between the two.
The automatically controlled three-D displacement platform of described precision is mainly made up of X-direction moving assembly, Y direction moving assembly and Z-direction moving assembly, and described X-direction moving assembly, described Y direction moving assembly and described Z-direction moving assembly all adopt manual fine setting shifter or electronic fine setting shifter.
A preparation method for metal nanoparticle microarray chip, is characterized in that comprising the following steps:
1. preparing average grain diameter is the metal nanoparticle particle of 1～20nm;
2. by step 1. prepared metal nanoparticle uniform particles be scattered in organic solvent, being prepared into concentration is the metal nanoparticle particle colloidal sols of 20～100mg/ml;
3. choose polymeric material, and polymeric material is dissolved in organic solvent completely, be prepared into the polymer sol that concentration is 20～100mg/ml;
4. press volume ratio hybrid metal nano particle particle colloidal sols and the polymer sol of 1:1～1:4, then by the complex sol stirring, ultrasonic processing obtains the dispersion of metal nanoparticle uniform particles;
5. adopt spin-coating method that complex sol is spun on substrate base, then obtain by insulating box baking-curing the composite colloid film that thickness is 200～6000nm;
6. first select the preparation facilities laser instrument used of metal nanoparticle microarray chip, determine the multiplication factor of the preparation facilities of metal nanoparticle microarray chip focusing objective len used, connect laser power supply and open the preparation facilities electric-controlled switch used of metal nanoparticle microarray chip, then the sample of composite colloid film and substrate base composition is fixed on the preparation facilities of metal nanoparticle microarray chip specimen holder used, specimen holder is fixed on the preparation facilities of the metal nanoparticle microarray chip automatically controlled three-D displacement platform of precision used and adjusts the position of specimen holder on the automatically controlled three-D displacement platform of precision and realize the coarse adjustment of sample position in Z-direction, then adjust the Z-direction moving assembly of accurate automatically controlled three-D displacement platform, make the focal plane of the preparation facilities of sample in metal nanoparticle microarray chip focusing objective len used, after this close electric-controlled switch, adjust the X-direction moving assembly of accurate automatically controlled three-D displacement platform, Y direction moving assembly is realized sample location, position in the horizontal direction, again open electric-controlled switch and watch the diffraction pattern on the preparation facilities of metal nanoparticle microarray chip film viewing screen used, in the time that diffraction pattern is stablized, determined sample a laser direct-writing point laser direct-writing and close electric-controlled switch, repeat again to adjust the X-direction moving assembly of accurate automatically controlled three-D displacement platform, Y direction moving assembly completes the laser direct-writing of all laser direct-writing points of sample, obtain metal nanoparticle microarray chip.
Described step
prepared metal nanoparticle particle is golden nanometer particle particle or Nano silver grain particle or nano platinum particle particle.
The organic solvent that the organic solvent that described step is selected in 2. and described step are selected in is 3. identical, and described organic solvent is for the step described in polymeric material and the dispersion of dissolving described step and 3. adopting
prepared metal nanoparticle particle.
2. the organic solvent in 3. adopts any in toluene, dimethylbenzene, chloroform, carrene, cyclohexane to described step with described step; The polymeric material of described step in 3. adopts any in polystyrene, polymethyl methacrylate, polypropylene, Merlon.
The mixing time of described step in is 4. 2～3 hours; The time of ultrasonic processing is 20～80 minutes; The substrate base of described step in 5. adopts glass substrate, quartz substrate, ITO(tin indium oxide) any in glass substrate; On substrate base, setting spin coating rotating speed when spin coating complex sol is 800～1500rpm, and the spin coating time is 20～60 seconds; While utilizing insulating box baking, setting baking temperature is 60～100 degree, and baking time is 2～6 hours.
Described step
the wavelength of the laser beam of the laser instrument transmitting of middle selection, should according to described step 1. the RESONANCE ABSORPTION wavelength of prepared metal nanoparticle particle determine, the power output of the laser instrument polymeric material that described step adopts in 3. that can gasify after being focused according to laser beam decides; Described step
in the enlargement ratio of focusing objective len select according to the live width of actual design pattern.
Compared with prior art, the invention has the advantages that:
1) apparatus of the present invention realize the coarse adjustment of the position that is placed in the sample on specimen holder by adjusting the position of specimen holder on the automatically controlled three-D displacement platform of precision, realize again the fine tuning of the position of sample in conjunction with the adjusting of accurate automatically controlled three-D displacement platform, make the focal plane of sample in focusing objective len, the laser beam of laser instrument transmitting is by the first diaphragm like this, beam shaping system, the second diaphragm, speculum, after focusing objective len, be irradiated on sample sample is carried out to laser direct-writing, and the location that can realize laser direct-writing point on sample by adjusting the position of accurate automatically controlled three-D displacement platform, prepare metal nanoparticle microarray chip.Apparatus of the present invention are not only simple in structure, easy to operate, and reproducible, can realize large-scale production.
2) first the inventive method prepares the complex sol that contains metal nanoparticle particle, it comprises the metal nanoparticle particle colloidal sols being dispersed in organic solvent is evenly mixed in proper volume ratio with specific polymeric material colloidal sol, then adopt the method for spin-coating, obtain the composite colloid film sample of containing metal nano particle particle by drying, solidifying, finally this sample is placed in and under laser direct writing system, carries out laser ablation and obtain metal nanoparticle microarray chip.Utilize the dot matrix pattern of the metal nanoparticle microarray chip that the inventive method prepares to be evenly distributed, the clear-cut of metal nanoparticle microarray unit, regular shape, the size of unit spot and distribution be easy to control and adjust, and the inventive method technique simple, with low cost, be easy to promote.
3) the inventive method adopts organic polymer material as filmogen, has raw material wide material sources, cheap advantage.
4) the inventive method only need be utilized low power laser just can carry out laser direct-writing to composite colloid film and obtain metal nanoparticle microarray chip, therefore effectively reduces plant maintenance and cost of upkeep.
5) position of the automatically controlled three-D displacement platform of the precision control composite colloid film in the preparation facilities of the inventive method employing metal nanoparticle microarray chip, can realize the preparation of complex pattern.
6) the automatically controlled three-D displacement platform of precision that the inventive method adopts can be by computer programming control, and therefore laser direct-writing process can realize automation control, can effectively increase work efficiency and realize high-repetition-rate, is easy to promote and large-scale production.
7) in the process of preparation complex sol, by changing the volume ratio of metal nanoparticle particle colloidal sols and polymer sol, can effectively control the distribution of metal nanoparticle particle in composite colloid film, prepare structural integrity, interface metal nanoparticle microarray chip clearly.
Accompanying drawing explanation
Fig. 1 is the structural representation of the preparation facilities of metal nanoparticle microarray chip of the present invention;
Fig. 2 is the electron scanning micrograph of the gold nano grain micro-array chip prepared of embodiment bis-;
Fig. 3 is the electron scanning micrograph of the gold nano grain micro-array chip prepared of embodiment tri-;
Fig. 4 is the electron scanning micrograph of the gold nano grain micro-array chip prepared of embodiment tetra-.
The specific embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in detail.
Embodiment mono-:
The preparation facilities of a kind of metal nanoparticle microarray chip that the present embodiment proposes, as shown in Figure 1, it mainly comprises laser instrument 11, spatial filter, beam shaping system 13, electric-controlled switch 14, speculum 15, focusing objective len 16, specimen holder 17, accurate automatically controlled three-D displacement platform 18 and film viewing screen 19, electric-controlled switch 14 is opened and closure for the laser beam controlling laser instrument 11 and launch, spatial filter is mainly made up of the second diaphragm 122 that is arranged at the first diaphragm 121 between laser instrument 11 and the light incident side of beam shaping system 13 and be arranged between light exit side and the speculum 15 of beam shaping system 13, specimen holder 17 is connected with accurate automatically controlled three-D displacement platform 18, sample 173 on specimen holder 17 is between focusing objective len 16 and film viewing screen 19, by specimen holder 17, the upper and lower displacement on the automatically controlled three-D displacement platform 18 of precision realizes position coarse adjustment to sample 173 on specimen holder 17, sample 173 on specimen holder 17 by the fine tuning of accurate automatically controlled three-D displacement platform 18 after focal plane in focusing objective len 16, the laser beam that when electric-controlled switch 14 is opened, laser instrument 11 is launched incides on speculum 15 by the first diaphragm 121, beam shaping system 13 and the second diaphragm 122, the laser direct-writing point that the laser beam that speculum 15 reflects is irradiated to sample 173 by focusing objective len 16 is upper, and in the time that the diffraction pattern on film viewing screen 19 is stablized, this laser direct-writing point has completed laser direct-writing.
In this specific embodiment, laser instrument 11 is selected low-power laser, as semiconductor laser, solid-state blue laser and semiconductor pumped solid ultraviolet laser etc., in actual application, select which kind of laser instrument should meet: the wavelength of the laser beam of the laser instrument transmitting of selection should be determined according to the RESONANCE ABSORPTION wavelength of preparing metal nanoparticle microarray chip metal nanoparticle particle used, after the power output of laser instrument should be focused according to laser beam, can decide for metal nanoparticle microarray chip polymeric material used by vaporizing system; The first diaphragm 121 and the second diaphragm 122 are selected all adjustable diaphragms of pore size, and minimum-value aperture size is all elected 0.5mm as, and maximum aperture size is all elected 4mm as; The multiple that expands of beam shaping system 13 is elected 4 times as; The reflectivity of speculum 15 elects 0.95 as; The multiplication factor of focusing objective len 16 is elected 10～100 times as, in actual application, in the time of the multiplication factor of selective focus object lens 16, should select according to the live width of actual design pattern.
In this specific embodiment, electric-controlled switch 14 be arranged at laser instrument 11, the first diaphragm 121, beam shaping system 13, the second diaphragm 122, speculum 15 and focusing objective len 16 arbitrarily between the two, electric-controlled switch 14 in Fig. 1 is arranged between the light exit side and the second diaphragm 122 of beam shaping system 13, can be determined voluntarily by user the position of electric-controlled switch 14 in actual application.
In this specific embodiment, sample 173 is fixed on fixed form on specimen holder 17 and can adopts the fixed form of existing any maturation, and the present embodiment is fixed on sample 173 on specimen holder 17 by holding screw 171; The fixed form of specimen holder 17 and accurate automatically controlled three-D displacement platform 18 also can adopt the fixed form of existing any maturation, as a guide rail 184 can be set on the platform of the automatically controlled three-D displacement platform 18 of precision, by existing securing member 172, specimen holder 17 is fixed on guide rail 184, in the time need carrying out coarse adjustment to the position of sample, loosening securing member 172 makes specimen holder 17 just can realize at guide rail 184 top offsets, after coarse adjustment finishes, tightening fastener parts 172.
In this specific embodiment, accurate automatically controlled three-D displacement platform 18 is mainly made up of X-direction moving assembly 181, Y direction moving assembly 182 and Z-direction moving assembly 183, X-direction moving assembly 181, Y direction moving assembly 182 and Z-direction moving assembly 183 adopt manual fine-tuning shifter or electronic fine setting shifter, while adopting electronic fine setting shifter, electronic fine setting shifter is connected with computer, realizes the fine tuning of the position of sample 173 by the displacement of the electronic fine setting shifter of computer control.
Embodiment bis-:
The present embodiment has proposed the method that preparation facilities described in a kind of embodiment of utilization mono-is prepared gold nano grain micro-array chip, and it mainly comprises the following steps:
In this specific embodiment, the preparation process of golden nanometer particle particle is as follows: 1) take the four octyl group ammonium bromide chip solids of 1.5g, four octyl group ammonium bromides are dissolved in completely in the toluene solvant of 80ml for subsequent use; 2) take the three water gold chloride powder of 0.31g, three water gold chloride powder are dissolved in the deionized water of 20ml and obtain the yellow aqueous solution, then the yellow aqueous solution is joined by process 1) obtain containing in the toluene solution of four octyl group ammonium bromides, at room temperature vigorous stirring ultrasonication 3 minutes, until the yellow aqueous solution becomes colourlessly, then removes the aqueous solution of lower floor; 3) by process 2) add the positive hexyl mercaptan 0.36g taking with subtraction in the solution that obtains, under room temperature, stir 10 minutes; 4) take 0.38g sodium borohydride powder, sodium borohydride powder is dissolved in the deionized water of 20ml, after fully dissolving, equably this aqueous solution is added drop-wise to by process 3) in the solution that obtains, vigorous stirring 30 minutes in the situation that of ice-water bath, at room temperature stir again after 3 hours, after removing lower aqueous solution, the dark solution on upper strata is transferred in Rotary Evaporators, controlled temperature below 50 degrees Celsius, evaporation dark solution is to 10ml left and right; 5) by process 4) add the ethanol of 400ml in the solution that obtains, through Rotary Evaporators, this solution is evaporated to 10ml left and right; 6) repeating 2 times adopts and process 5) identical operation operates to the last time solution obtaining and processes; 7) to process 6) add the deionized water of 200ml in the dark solution that obtains, through Rotary Evaporators by this solution evaporate to dryness; 8) repeating 2 times adopts and process 7) identical operation operates to the last time powder obtaining and processes, and evaporate to dryness obtains black powder, and this black powder is golden nanometer particle particle, and gross mass is about 800mg, and average grain diameter is 10nm.
2. by step
in the golden nanometer particle particle of the 800mg that makes be dispersed in completely in the toluene of 10ml, being prepared into concentration is the golden nanometer particle particle colloidal sols of 80mg/ml.
3. take polystyrene 0.5g, add the toluene solvant of 10ml and be placed on magnetic stirring apparatus and stir 2.5 hours, until polystyrene dissolves completely, obtaining concentration is the polystyrene colloidal sol of 50mg/ml.
4. the polystyrene colloidal sol 1ml that the golden nanometer particle particle colloidal sols 1ml that is 80mg/ml by the concentration measuring and concentration are 50mg/ml mixes, and obtains by stirring and ultrasonic processing the complex sol that golden nanometer particle uniform particles is disperseed.At this, mixing time is 2.5 hours, and the ultrasonic processing time is 80 minutes.
5. the complex sol that adopts spin-coating method that 4. step is obtained is spun on quartz substrate, and is placed in baking-curing in insulating box, and on quartz substrate, forming thickness is the composite colloid film of 4 μ m, as sample.At this, setting spin coating rotating speed is 1200rpm, and the spin coating time is 40 seconds; Baking temperature is 80 degree, and baking time is 4 hours.
6. first select the preparation facilities laser instrument 11 used of metal nanoparticle microarray chip, at this, select semiconductor laser, the wavelength of its emitting laser light beam is 532nm, it adopts continuous wave output mode and power output is 35mw, and the numerical aperture of the preparation facilities of definite metal nanoparticle microarray chip focusing objective len 16 used be 0.4 and multiplication factor be 25 times, connect laser instrument 11 power supplys and open the preparation facilities electric-controlled switch 14 used of metal nanoparticle microarray chip, then the sample 173 of composite colloid film and substrate base composition is fixed on the preparation facilities of metal nanoparticle microarray chip specimen holder 17 used, the coarse adjustment of sample 173 position in Z-direction is realized in the position of adjusting on the guide rail 184 of specimen holder on the automatically controlled three-D displacement platform 18 of the preparation facilities of metal nanoparticle microarray chip precision used, then adjust the Z-direction moving assembly 183 of accurate automatically controlled three-D displacement platform, make the focal plane of the preparation facilities of sample 173 in metal nanoparticle microarray chip focusing objective len 16 used, after this close electric-controlled switch 14, adjust the X-direction moving assembly 181 of accurate automatically controlled three-D displacement platform, Y direction moving assembly 182 is realized sample location, position in the horizontal direction, again open electric-controlled switch 14 and watch the diffraction pattern on the preparation facilities of metal nanoparticle microarray chip film viewing screen 19 used, in the time that diffraction pattern is stablized, determined sample 173 a laser direct-writing point laser direct-writing and close electric-controlled switch 14, repeat again to adjust the X-direction moving assembly 181 of accurate automatically controlled three-D displacement platform, Y direction moving assembly 182 completes the laser direct-writing of all laser direct-writing points of sample 173, obtain metal nanoparticle microarray chip.
In this specific embodiment, the detailed process of composite colloid film being carried out to laser direct-writing is: 1) open the power supply of laser instrument 11, after half an hour, laser instrument is stablized Output of laser, 2) close electric-controlled switch 14, with holding screw 171 fixed samples 173, adjust securing member 172 and make sample 173 Range Focusing object lens 16 for 1cm left and right, 3) adjust X-direction moving assembly 181 and Y direction moving assembly 182, make the edge of laser beam irradiation at sample 173, open electric-controlled switch 14, adjust Z-direction moving assembly 183, sample 173 is moved along Z-direction, at the focal plane place through focusing objective len 16, laser beam is directly write formation circular hole on sample 173, in this process, after the laser diffraction annulus occurring on film viewing screen 19 can occur first to cave in outer gush or elder generation outside the phenomenon of caving in after gushing, oppositely regulate Z-direction moving assembly 183, when annulus by gush outward transfer to cave in or transfer to by caving in outside while gushing, interpret sample 173 is the focal plane in focusing objective len 16 just in time, 4) close electric-controlled switch 14, adjust X-direction moving assembly 181 and Y direction moving assembly 182, on sample 173, choose the starting point of location reference point as laser direct-writing pattern, 5) open electric-controlled switch 14, the location reference point on laser beam irradiation sample 173, watches the variation of the diffraction pattern on film viewing screen 19, and after diffraction pattern is stable, the laser direct-writing of this point completes, 6) close electric-controlled switch 14, adjust X-direction moving assembly 181 and Y direction moving assembly 182, choose the position of next laser direct-writing point, 7) according to the design of micro-array chip, repeatedly repetitive process 5) and process 6), until the whole making of pattern are complete, obtain gold nano grain micro-array chip.
Fig. 2 has provided the electron scanning micrograph of the gold nano grain micro-array chip that the present embodiment prepares.As can be seen from Figure 2, the dot matrix pattern of this gold nano grain micro-array chip is evenly distributed, the clear-cut of each gold nano grain microarray unit, regular shape, inner and outer ring edge is step-like, interior ring diameter is 5 μ m, and outer ring diameter is 12 μ m, the golden nanometer particle particle in interior ring be evenly distributed
.
Embodiment tri-:
Step in the preparation method of the gold nano grain micro-array chip of the present embodiment
to step 3. and step 5. to 6. with the preparation method of the gold nano grain micro-array chip described in embodiment bis-in step
to step 3. and step 5. to 6. identical, in the present embodiment, the volume proportion of complex sol and embodiment's bis-is different, step is 4. not identical.4. the step of the present embodiment is: the polystyrene colloidal sol 2ml that the golden nanometer particle particle colloidal sols 1ml that is 80mg/ml by the concentration measuring and concentration are 50mg/ml mixes, and obtains by stirring and ultrasonic processing the complex sol that golden nanometer particle uniform particles is disperseed.
Fig. 3 has provided the electron scanning micrograph of the gold nano grain micro-array chip that the present embodiment prepares.As can be seen from Figure 3, the dot matrix pattern of this gold nano grain micro-array chip is evenly distributed, the clear-cut of gold nano grain microarray unit, and regular shape, inner and outer ring edge is step-like, and interior ring diameter is 8 μ m, and outer ring diameter is 13 μ
m,golden nanometer particle particle in interior ring is evenly distributed.
Embodiment tetra-:
Step in the preparation method of the gold nano grain micro-array chip of the present embodiment
to step 3. and step 5. to 6. with the preparation method of the gold nano grain micro-array chip described in embodiment bis-in step
to step 3. and step 5. to 6. identical, in the present embodiment, the volume proportion of complex sol and embodiment's bis-is different, step is 4. not identical.4. the step of the present embodiment is: the polystyrene colloidal sol 4ml that the golden nanometer particle particle colloidal sols 1ml that is 80mg/ml by the concentration measuring and concentration are 50mg/ml mixes, and obtains by stirring and ultrasonic processing the complex sol that golden nanometer particle uniform particles is disperseed.
Fig. 4 has provided the electron scanning micrograph of the gold nano grain micro-array chip that the present embodiment prepares.As can be seen from Figure 4, the dot matrix pattern of gold nano grain micro-array chip is evenly distributed, the outer shroud clear-cut of gold nano grain microarray unit, and the smooth of the edge protuberance, diameter is 15 μ m, and middle part is pit shape, and diameter is 5 μ m.
Embodiment five:
The preparation method of a kind of silver nano-grain micro-array chip that the present embodiment proposes, it mainly comprises the following steps:
the lipophile Nano silver grain particle 500mg that preparation average grain diameter is 20nm.
2. by step
in the Nano silver grain particle that makes be dispersed in completely in the chloroform of 10ml, being prepared into concentration is the Nano silver grain particle colloidal sols of 50mg/ml.
3. take polymethyl methacrylate (PMMA) 0.4g, add the chloroform of 10ml and be placed on magnetic stirring apparatus and stir 2 hours, until PMMA dissolves completely, obtaining concentration is the PMMA colloidal sol of 40mg/ml.
4. the PMMA colloidal sol 2ml that the Nano silver grain particle colloidal sols 1ml that is 50mg/ml by the concentration measuring and concentration are 40mg/ml mixes, and obtains by stirring and ultrasonic processing the complex sol that Nano silver grain uniform particles is disperseed.At this, mixing time is 3 hours, and the ultrasonic processing time is 40 minutes.
5. the complex sol that adopts spin-coating method that 4. step is obtained is spun on glass substrate substrate, and is placed in baking-curing in insulating box, and on glass substrate substrate, forming thickness is the composite colloid film of 6 μ m, as sample.At this, setting spin coating rotating speed is 900rpm, and the spin coating time is 30 seconds; Baking temperature is 90 degree, and baking time is 3 hours.
6. the preparation facilities that the preparation of the preparation of the silver nano-grain micro-array chip of the present embodiment and the gold nano grain micro-array chip of embodiment bis-adopts is basic identical, difference is only that the laser instrument 11 of the present embodiment selects the solid-state blue laser of continuous wave output, the wavelength of the laser beam of its transmitting is 457nm, and power output is 100mw.
Embodiment six:
The preparation method of a kind of Pt nanoparticle micro-array chip that the present embodiment proposes, it mainly comprises the following steps:
the lipophile nano platinum particle particle 400mg that preparation average grain diameter is 5nm.
2. by step
in the nano platinum particle particle that makes be dissolved in completely in the carrene of 5ml, being prepared into concentration is the nano platinum particle particle colloidal sols of 80mg/ml.
3. take Merlon 0.2g, add the carrene of 10ml and be placed on magnetic stirring apparatus and stir 2.5 hours, until Merlon dissolves completely, obtaining concentration is the Merlon colloidal sol of 20mg/ml.
4. the Merlon colloidal sol 2ml that the nano platinum particle particle colloidal sols 1ml that is 80mg/ml by the concentration measuring and concentration are 20mg/ml mixes, and obtains by stirring and ultrasonic processing the complex sol that nano platinum particle uniform particles is disperseed.At this, mixing time is 2 hours, and the ultrasonic processing time is 60 minutes.
5. the complex sol that adopts spin-coating method that 4. step is obtained is spun on ito glass substrate base, and is placed in baking-curing in insulating box, and on ito glass substrate base, forming thickness is the composite colloid film of 3 μ m, as sample.At this, setting spin coating rotating speed is 1500rpm, and the spin coating time is 60 seconds; Baking temperature is 100 degree, and baking time is 4 hours.
6. the preparation facilities that the preparation of the preparation of the Pt nanoparticle micro-array chip of the present embodiment and the gold nano grain micro-array chip of embodiment bis-adopts is basic identical, difference is only the semiconductor pumped solid ultraviolet laser that the laser instrument 11 of the present embodiment is continuous wave output, the wavelength of the laser beam of its transmitting is 266nm, and power output is 50mw.
Except the above-mentioned specific embodiment providing two is to six, user can select according to actual conditions the occurrence of parameters; User also can select dimethylbenzene or cyclohexane etc. in the time selecting organic solvent, as long as guarantee that the organic solvent of selecting during organic solvent that step selects in 2. and step are is 3. identical, and selected organic solvent can dissolving step 3. in 1. prepared metal nanoparticle particle of the polymeric material of employing and dispersion steps; User also can select the polymeric materials such as polypropylene in the time of selective polymer material; The wavelength of the laser beam of the laser instrument transmitting that user selects should according to step 1. the RESONANCE ABSORPTION wavelength of prepared metal nanoparticle particle determine, the polymeric material can gasification step after the power output of laser instrument should be focused according to laser beam adopting in 3. decides; When the enlargement ratio of user's selective focus object lens, should select according to the live width of actual design pattern.
Claims (10)
1. the preparation facilities of a metal nanoparticle microarray chip, it is characterized in that comprising laser instrument, electric-controlled switch, spatial filter, beam shaping system, speculum, focusing objective len, specimen holder, accurate automatically controlled three-D displacement platform and film viewing screen, described electric-controlled switch is for controlling the opening and closure of laser beam of described laser instrument transmitting, described spatial filter mainly by be arranged at the first diaphragm between the light incident side of described laser instrument and described beam shaping system and be arranged at described in light exit side and the described speculum of beam shaping system between the second diaphragm form, described specimen holder is connected with the automatically controlled three-D displacement platform of described precision, sample on described specimen holder is between described focusing objective len and described film viewing screen, by described specimen holder, the upper and lower displacement on the automatically controlled three-D displacement platform of described precision realizes position coarse adjustment to sample on described specimen holder, sample on described specimen holder by the fine tuning of the automatically controlled three-D displacement of described precision position of platform after focal plane in described focusing objective len, the laser beam of the laser instrument transmitting described in when described electric-controlled switch is opened incides on described speculum by the first described diaphragm, described beam shaping system and the second described diaphragm, the laser direct-writing point that the laser beam of described speculum reflection is irradiated to sample by described focusing objective len is upper, and in the time that the diffraction pattern on described film viewing screen is stablized, this laser direct-writing point has completed laser direct-writing.
2. the preparation facilities of a kind of metal nanoparticle microarray chip according to claim 1, is characterized in that described laser instrument adopts low-power laser; The pore size of the first described diaphragm and the second described diaphragm is all adjustable, and minimum-value aperture size is 0.5mm, and maximum aperture size is 4mm; The multiple that expands of described beam shaping system is 4; The reflectivity of described speculum is 0.95; The multiplication factor of described focusing objective len is 10～100 times.
3. the preparation facilities of a kind of metal nanoparticle microarray chip according to claim 1 and 2, it is characterized in that described electric-controlled switch be arranged at described laser instrument, described the first diaphragm, described beam shaping system, described the second diaphragm, described speculum and described focusing objective len arbitrarily between the two.
4. the preparation facilities of a kind of metal nanoparticle microarray chip according to claim 3, it is characterized in that the described automatically controlled three-D displacement platform of precision is mainly made up of X-direction moving assembly, Y direction moving assembly and Z-direction moving assembly, described X-direction moving assembly, described Y direction moving assembly and described Z-direction moving assembly all adopt manual fine setting shifter or electronic fine setting shifter.
5. a preparation method for metal nanoparticle microarray chip, is characterized in that comprising the following steps:
1. preparing average grain diameter is the metal nanoparticle particle of 1～20nm;
2. by step 1. prepared metal nanoparticle uniform particles be scattered in organic solvent, being prepared into concentration is the metal nanoparticle particle colloidal sols of 20～100mg/ml;
3. choose polymeric material, and polymeric material is dissolved in organic solvent completely, be prepared into the polymer sol that concentration is 20～100mg/ml;
4. press volume ratio hybrid metal nano particle particle colloidal sols and the polymer sol of 1:1～1:4, then by the complex sol stirring, ultrasonic processing obtains the dispersion of metal nanoparticle uniform particles;
5. adopt spin-coating method that complex sol is spun on substrate base, then obtain by insulating box baking-curing the composite colloid film that thickness is 200～6000nm;
6. first select the preparation facilities laser instrument used of metal nanoparticle microarray chip, determine the multiplication factor of the preparation facilities of metal nanoparticle microarray chip focusing objective len used, connect laser power supply and open the preparation facilities electric-controlled switch used of metal nanoparticle microarray chip, then the sample of composite colloid film and substrate base composition is fixed on the preparation facilities of metal nanoparticle microarray chip specimen holder used, specimen holder is fixed on the preparation facilities of the metal nanoparticle microarray chip automatically controlled three-D displacement platform of precision used and adjusts the position of specimen holder on the automatically controlled three-D displacement platform of precision and realize the coarse adjustment of sample position in Z-direction, then adjust the Z-direction moving assembly of accurate automatically controlled three-D displacement platform, make the focal plane of the preparation facilities of sample in metal nanoparticle microarray chip focusing objective len used, after this close electric-controlled switch, adjust the X-direction moving assembly of accurate automatically controlled three-D displacement platform, Y direction moving assembly is realized sample location, position in the horizontal direction, again open electric-controlled switch and watch the diffraction pattern on the preparation facilities of metal nanoparticle microarray chip film viewing screen used, in the time that diffraction pattern is stablized, determined sample a laser direct-writing point laser direct-writing and close electric-controlled switch, repeat again to adjust the X-direction moving assembly of accurate automatically controlled three-D displacement platform, Y direction moving assembly completes the laser direct-writing of all laser direct-writing points of sample, obtain metal nanoparticle microarray chip.
6. the preparation method of a kind of metal nanoparticle microarray chip according to claim 5, it is characterized in that described step 1. prepared metal nanoparticle particle be golden nanometer particle particle or Nano silver grain particle or nano platinum particle particle.
7. according to the preparation method of a kind of metal nanoparticle microarray chip described in claim 5 or 6, it is characterized in that the organic solvent of selecting during the organic solvent selected during described step 2. and described step are is 3. identical, described organic solvent is for 1. prepared metal nanoparticle particle of the polymeric material that dissolves described step and 3. adopts and step described in dispersion.
8. the preparation method of a kind of metal nanoparticle microarray chip according to claim 7, is characterized in that 2. the organic solvent in 3. adopts any in toluene, dimethylbenzene, chloroform, carrene, cyclohexane to described step with described step; The polymeric material of described step in 3. adopts any in polystyrene, polymethyl methacrylate, polypropylene, Merlon.
9. the preparation method of a kind of metal nanoparticle microarray chip according to claim 8, is characterized in that the mixing time during described step is 4. 2～3 hours; The time of ultrasonic processing is 20～80 minutes; The substrate base of described step in 5. adopts glass substrate or quartz substrate; On substrate base, setting spin coating rotating speed when spin coating complex sol is 800～1500rpm, and the spin coating time is 20～60 seconds; While utilizing insulating box baking, setting baking temperature is 60～100 degree, and baking time is 2～6 hours.
10. the preparation method of a kind of metal nanoparticle microarray chip according to claim 9, it is characterized in that the wavelength of the laser beam of the laser instrument transmitting of selecting during described step 6., should according to described step 1. the RESONANCE ABSORPTION wavelength of prepared metal nanoparticle particle determine, the power output of the laser instrument polymeric material that described step adopts in 3. that can gasify after being focused according to laser beam decides; The enlargement ratio of the focusing objective len of described step in is 6. selected according to the live width of actual design pattern.
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| CN109987580B (en) * | 2019-04-16 | 2020-02-11 | 中国科学院微电子研究所 | Preparation method of nano forest structure and regulation and control method of nano forest structure |
| CN111001939B (en) * | 2019-11-28 | 2021-11-19 | 长春理工大学 | Method for processing multiple nano patterns by femtosecond laser |
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