CN103990462B - Preparation method of nickel-based catalyst nanometer film - Google Patents
Preparation method of nickel-based catalyst nanometer film Download PDFInfo
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- CN103990462B CN103990462B CN201410211474.0A CN201410211474A CN103990462B CN 103990462 B CN103990462 B CN 103990462B CN 201410211474 A CN201410211474 A CN 201410211474A CN 103990462 B CN103990462 B CN 103990462B
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Abstract
The invention discloses a preparation method of a nickel-based catalyst nanometer film. The preparation method comprises the following steps: firstly, depositing a nickel nanometer film with certain thickness on the surface of a substrate by using a magnetron sputtering technology; then placing a film sample on a three-dimensional movement platform, texturing the nickel nanometer film by using laser interference, processing the nickel nanometer film into regularly distributed patterns; finally, putting the textured film sample into a tube furnace, introducing ammonia to etch the nickel nanometer film, and finally shrinking on the surface of the nickel nanometer film to form nickel-based nanometer particles. According to the preparation method, a laser interference pattern is used for replacing a conventional photoetching mask plate, the time and cost of manufacturing the mask plate are reduced, the nickel-based film is processed by laser interference so that the uniformity of particle distribution during etching with ammonia is facilitated; through changing the interference pattern size and the introduction flow velocity of ammonia, the particle size can be controlled, and the particle size and the controllable density degree are realized.
Description
Technical field
The present invention relates to a kind of preparation method of nickel-base catalyst nano thin-film, more particularly, to a kind of particle size is controlled,
The preparation method of the nickel-base catalyst nano thin-film being evenly distributed.
Background technology
CNT is because of its peculiar structure, huge specific surface area, surface hydrophobic, adsorptivity, mechanics and electricity etc.
Characteristic, causes the concern of scholar all over the world and research, and is widely used in hydrogen storage material, information Store and life
All kinds of field such as thing medical science.Aligned carbon nanotube film is to arrange CNT axially directed, makes the arrangement of CNT
From disorderly and unsystematic to ordered arrangement, preferably play mechanics, calorifics and the electric property of CNT.
Because the draw ratio of CNT is very big, in growth course, it bends and wound form is inevitable.For
Obtain the CNT that directionality are good and pipe diameter size is evenly distributed, in three kinds of conventional carbon nano tube growth mode (electric arcs
Electric discharge is sent out, laser evaporization method and chemical vapour deposition technique) in, reaction condition is gentle, low cost because it has for chemical vapor deposition
It is widely used in preparing aligned carbon nanotube the advantages of good with controllability.Preparing aligned carbon nanotube using chemical vapor deposition
During, the size of surface catalyst granule, the uniformity of distribution have risen decisive to the quality of aligned carbon nanotube
Effect.There are the nanoscopic catalyst particles with catalysis activity that many preparation sizes are identical, be evenly distributed at present
Method, such as nanosphere etching method, photoetching process, plasma bombardment method, foraminous die plate method etc..But said method all has respective
Defect, such as to prepare catalyst film using photoetching process, though the good high cost of effect；And plasma bombardment method is applied to
Pecvd prepares aligned carbon nanotube film；Inherently one difficult problem of the preparation of porous mold.
Content of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, it is simple, high that the present invention provides one kind can carry out
Effect, the preparation method of the nickel-base catalyst nano thin-film that can achieve that the particle size that large area is processed is controlled, be evenly distributed.
Technical scheme: for achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of nickel-base catalyst nano thin-film, deposits one first with magnetron sputtering technique in substrate surface
Determine the nickel nano thin-film of thickness, form film sample；Then film sample is placed in three-dimensional mobile platform, is done using laser
Relate to the surface to nickel nano thin-film and carry out texturing processing, nickel nano thin-film is processed into the pattern of regular distribution；Finally will knit
Film sample after structureization processing is put in tube furnace, is passed through ammonia to perform etching to nickel nano thin-film, raises in tube furnace
Temperature so that nickel nano thin-film fusing, because nickel nano thin-film is different from the thermal coefficient of expansion of substrate, therefore on surface
Can be started to shrink at texture pattern for border in the presence of tension force, with the increase of etch period, nickel nano thin-film can be further
Be shrunk to Ni-based nano-particle.
In the method, process size by controlling pattern, tubular type in-furnace temperature and the etch period of laser interference
Unanimously, the nanoscale nickel-base catalyst granule being evenly distributed.
The method in the specific implementation, including early-stage preparations, the preparation of nickel catalyst agent film, nickel catalyst agent film
Laser interference texturing process and high temperature ammonia etch several steps, particularly as follows:
(1) early-stage preparations: base material is divided into after suitable size, cleans up and air-dry；
(2) preparation of nickel catalyst agent film: deposit certain thickness nickel using magnetron sputtering technique in substrate surface and receive
Rice thin film, forms film sample；
(3) the laser interference texturing of nickel catalyst agent film is processed: according to the pattern of required laser ablation, light path is entered
Row adjustment, film sample is placed in three-dimensional mobile platform, carries out texturing processing using laser interference to nickel nano thin-film,
Nickel nano thin-film is processed into the pattern of regular distribution；
(4) high temperature ammonia etching: first the film sample processing through laser interference texturing is put in quartz boat
Between position, heat up after closing, and be passed through the air that nitrogen is discharged in tube furnace, exclusion air is dry to the oxidation of film sample
Disturb；It is passed through hydrogen again and heats up, film sample is sufficiently reduced, brought with the oxide layer eliminating film sample surface
Impact；Then temperature is promoted to after etching temperature, is passed through ammonia in tube furnace, Ni-based film sample is performed etching, carve
Erosion is taken out after terminating rear furnace cooling.
In described step (1), base material is n-type silicon (100) crystal orientation polished silicon wafer.
Described step (1) specifically, base material is divided into after suitable size, successively with acetone, ethanol and go from
Sub- water carries out supersonic vibration cleaning, by the substrate cleaning up natural air drying, in order to follow-up processing.
In described step (2), the magnetron sputtering apparatus of use are k575x magnetron sputtering plating instrument.
Described step (2) is specifically, first the above-mentioned substrate cleaning up is placed on the sample stage of plated film instrument, to target chamber
Inside carries out evacuation, makes the operation vacuum of vacuum chamber reach preset value (preferably 1 × 10-4Mbar), control sputtering current (preferably
For 60ma), reach, by adjusting different sputtering times, the nickel nano thin-film preparing different-thickness, control nickel nano thin-film
Thickness is in 5～50nm.
In described step (3), the laser instrument for laser interference is pulse laser dsh-355-10.
Described step (3), specifically, being adjusted to light path according to the pattern of required laser ablation, controls laser during processing
The power of device, in 20mw～200mw, nickel nano thin-film is partitioned into uniform laser interference pattern, the nickel nano thin-film after processing
In 0.02～100 μm of the size cycle of dot matrix, longitudinal depth is film thickness.
In described step (4), the tubular type furnace apparatus of use are the temperature automatically controlled tube furnace of cvd (z) -06/60/3 model.
Described step (4) is particularly as follows: be put in quartz boat by the film sample processing through laser interference texturing first
Centre position, heats up after closing, and is passed through the air that nitrogen is discharged in tube furnace, and exclusion air is dry to the oxidation of film sample
Disturb, wherein the flow velocity of nitrogen is 100～300sccm；It is passed through hydrogen after 10min again and heats up, keep more than 600 DEG C of temperature
More than 40min is sufficiently reduced to film sample, the impact being brought with the oxide layer eliminating film sample surface；Then will
After temperature is promoted to 700～900 DEG C of etching temperature, it is passed through ammonia in tube furnace, Ni-based film sample is performed etching, its
The flow velocity of middle ammonia is 100～300sccm, and the time that is passed through is 2～20min；Etching is taken out after terminating rear furnace cooling.
Beneficial effect: the preparation method of the nickel-base catalyst nano thin-film that the present invention provides, with respect to prior art, have
Following advantage: the 1, controllable standby of particle size: nickel catalyst agent film is divided during laser interference processing
Become the unit of given size size, its size can be adjusted by the light path of laser interference, be then passed through ammonia etching,
The unified nanoscale nickel-base catalyst granule of size can be generated in substrate surface；2nd, particle distribution uniformity: by swashing
The granule of original random distribution is changed into according to the equally distributed granule of laser interference pattern, its distribution of particles interference of light etching
Density according to the controlled adjustment of laser optical path, therefore can prepare the nano-catalyst particles of different cycles arrangement, after being
The CNT of continuous highdensity qualitative growth lays the first stone；3rd, simple, the economy of particulate production: of the present invention
Magnetron sputtering, laser interference and high temperature ammonia etching process simple, covering in conventional lithography is replaced by laser interference pattern
Lamina membranacea, had not only remained the high-quality of conventional lithography but also had improved its economy.The present invention uses laser interference pattern generation in sum
For the mask plate in conventional lithography, reduce the time manufacturing mask plate and cost, Ni-based thin film is carried out add by laser interference
Work, textured Ni-based thin film contributes to the uniformity of distribution of particles during follow-up ammonia etching, and can control distribution of particles
Density, that passes through to change the size of interference figure size and ammonia is passed through the size that flow velocity can control particle size simultaneously,
Realize particle size and the controlled manufacture of density degree.
Brief description
Fig. 1 is the process chart of the present invention；
Fig. 2 is the schematic diagram of the nickel-base catalyst particle preparation of the present invention, and wherein (a) is the thin film sample after magnetron sputtering
Product, (b) is the film sample after laser interference texturing, and (c) is the film sample after high temperature ammonia etching.
Specific embodiment
Below in conjunction with the accompanying drawings the present invention is further described.
A kind of preparation method of nickel-base catalyst nano thin-film, deposits one first with magnetron sputtering technique in substrate surface
Determine the nickel nano thin-film of thickness, form film sample；Then film sample is placed in three-dimensional mobile platform, is done using laser
Relate to and texturing processing is carried out to nickel nano thin-film, nickel nano thin-film is processed into the pattern of regular distribution；Finally by texturing plus
Film sample after work is put in tube furnace, is passed through ammonia to perform etching to nickel nano thin-film, raises the temperature in tube furnace
So that the fusing of nickel nano thin-film, because nickel nano thin-film is different from the thermal coefficient of expansion of substrate, therefore capillary
Effect is lower to be started to shrink at texture pattern for border, and with the increase of etch period, nickel nano thin-film can further shrink
Become Ni-based nano-particle.In the method, processed by controlling pattern, tubular type in-furnace temperature and the etch period of laser interference
The nanoscale nickel-base catalyst granule that size is consistent, be evenly distributed.
As shown in figure 1, the invention mainly comprises early-stage preparations, the preparation of nickel catalyst agent film, nickel catalyst agent film
Laser interference texturing process and high temperature ammonia etch several steps, be described in detail below.
First, substrate carries out supersonic vibration with acetone, ethanol and deionized water successively and cleans each 5min, after will clean up
Substrate natural air drying；Then the above-mentioned substrate cleaning up is placed on the sample stage of k575x magnetron sputtering plating instrument, to target
Chamber interior carries out evacuation, makes the operation vacuum of vacuum chamber reach default 1 × 10-4Mbar, control sputtering current is 60ma, passes through
Adjust the different sputtering times nickel nano thin-film to prepare different-thickness, the most at last nickel nano film thickness control 5～
50nm；Then the sample prepared is placed in the three-dimensional mobile platform in laser interference system of processing, and is swashed according to required
The pattern of light processing is adjusted to light path, and wherein said laser instrument is pulse laser dsh-355-10, controls and swash during processing
The power of light device, in 20mw～200mw, nickel nano thin-film is split uniformly laser interference pattern, the nickel nanometer thin after processing
In 0.02～100 μm of the size cycle of film spot battle array, longitudinal depth is film thickness；Finally will process through laser interference texturing
Nickel nano thin-film sample is put in the centre position of quartz boat in the temperature automatically controlled tube furnace of cvd (z) -06/60/3, heats up after closing,
And it is passed through the air that the nitrogen that flow velocity is 100～300sccm is discharged in tube furnace, exclude the oxygen to nickel nano thin-film surface for the air
The interference changed, is passed through hydrogen again and heats up after 10min, keep 600 DEG C of temperature 40min nickel nano thin-film to be carried out sufficiently also
Impact that is former, being brought with the oxide layer eliminating nickel nano thin-film surface；Then temperature is promoted to 700～900 DEG C of etching temperature
After degree, after constant temperature, to being passed through ammonia in tube furnace, the flow velocity of ammonia is 100～300sccm, and the time that is passed through is 2～20min pair
Nickel nano thin-film sample performs etching, and etching is taken out after terminating rear furnace cooling.
In Fig. 2, (a) is the sample having deposited Ni-based thin film；B () is the thin film table processing through laser interference texturing
Face；C () is the nickel-base catalyst nano grain surface through high temperature ammonia etching.
The above be only the preferred embodiment of the present invention it should be pointed out that: for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nanoscale nickel-base catalyst granule it is characterised in that: first with magnetron sputtering technique in base
Basal surface deposits certain thickness nickel nano thin-film, forms film sample；Then film sample is placed on three-dimensional mobile platform
On, using laser interference, texturing processing is carried out to nickel nano thin-film, nickel nano thin-film is processed into the pattern of regular distribution；?
Film sample after processing texturing afterwards is put in tube furnace, is passed through ammonia to perform etching to nickel nano thin-film, rises senior executive
Temperature in formula stove makes nickel nano thin-film melt, because nickel nano thin-film is different from the thermal coefficient of expansion of substrate, therefore in table
Can be started to shrink at texture pattern for border in the presence of the tension force of face, with the increase of etch period, nickel nano thin-film can enter one
Walk is shrunk to Ni-based nano-particle.
2. nanoscale nickel-base catalyst granule according to claim 1 preparation method it is characterised in that: by control swash
The pattern of the interference of light, tubular type in-furnace temperature process with etch period that the nanoscale that size is consistent, be evenly distributed is Ni-based to urge
Catalyst particles.
3. nanoscale nickel-base catalyst granule according to claim 1 and 2 preparation method it is characterised in that: before inclusion
Phase preparation, the preparation of nickel catalyst agent film, the laser interference texturing process of nickel catalyst agent film and high temperature ammonia etching
Several steps, particularly as follows:
(1) early-stage preparations: base material is divided into after suitable size, cleans up and air-dry；
(2) preparation of nickel catalyst agent film: deposit certain thickness nickel nanometer thin in substrate surface using magnetron sputtering technique
Film, forms film sample；
(3) the laser interference texturing of nickel catalyst agent film is processed: according to the pattern of required laser ablation, light path is adjusted
Whole, film sample is placed in three-dimensional mobile platform, using laser interference, texturing processing is carried out to nickel nano thin-film, by nickel
Nano thin-film is processed into the pattern of regular distribution；
(4) high temperature ammonia etching: first the film sample processing through laser interference texturing is put in the interposition of quartz boat
Put, heat up after closing, and be passed through the air that nitrogen is discharged in tube furnace, the interference of the exclusion oxidation to film sample for the air；Again
It is passed through hydrogen and heats up, film sample is sufficiently reduced, the impact being brought with the oxide layer eliminating film sample surface；
Then temperature is promoted to after etching temperature, is passed through ammonia in tube furnace, Ni-based film sample is performed etching, etching terminates
Take out after furnace cooling afterwards.
4. nanoscale nickel-base catalyst granule according to claim 3 preparation method it is characterised in that: described step
(1), in, base material is n-type silicon (100) crystal orientation polished silicon wafer.
5. nanoscale nickel-base catalyst granule according to claim 3 preparation method it is characterised in that: described step
(2), in, the magnetron sputtering apparatus of use are k575x magnetron sputtering plating instrument.
6. nanoscale nickel-base catalyst granule according to claim 3 preparation method it is characterised in that: described step
(2) specifically, first the above-mentioned substrate cleaning up is placed on the sample stage of plated film instrument, evacuation is carried out to target chamber inside,
Make the operation vacuum of vacuum chamber reach preset value, control sputtering current, reached by the sputtering time adjusting different and prepare not
The nickel nano thin-film of stack pile, controls nickel nano film thickness in 5～50nm.
7. nanoscale nickel-base catalyst granule according to claim 3 preparation method it is characterised in that: described step
(3), in, the laser instrument for laser interference is pulse laser dsh-355-10.
8. nanoscale nickel-base catalyst granule according to claim 3 preparation method it is characterised in that: described step
(3) specifically, being adjusted to light path according to the pattern of required laser ablation, during processing control laser instrument power 20mw～
200mw, nickel nano thin-film is partitioned into uniform laser interference pattern, the size cycle of the nickel nano thin-film dot matrix after processing
0.02～100 μm, longitudinal depth is film thickness.
9. nanoscale nickel-base catalyst granule according to claim 3 preparation method it is characterised in that: described step
(4), in, the tubular type furnace apparatus of use are the temperature automatically controlled tube furnace of cvd (z) -06/60/3 model.
10. nanoscale nickel-base catalyst granule according to claim 3 preparation method it is characterised in that: described step
(4) particularly as follows: first the film sample processing through laser interference texturing to be put in the centre position of quartz boat, rise after closing
Temperature, and it is passed through the air that nitrogen is discharged in tube furnace, the interference of the exclusion oxidation to film sample for the air, the wherein flow velocity of nitrogen
For 100～300sccm；It is passed through hydrogen after 10min again and heats up, keep more than more than 600 DEG C of temperature 40min to film sample
Sufficiently reduced, the impact being brought with the oxide layer eliminating film sample surface；Then temperature is promoted to 700～900
DEG C etching temperature after, be passed through ammonia in tube furnace, Ni-based film sample performed etching, wherein the flow velocity of ammonia be 100
～300sccm, the time that is passed through is 2～20min；Etching is taken out after terminating rear furnace cooling.
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| CN105154882B (en) * | 2015-10-08 | 2018-08-21 | 华中科技大学 | A kind of preparation method of porous nickel |
| CN107365958B (en) * | 2017-07-13 | 2020-01-07 | 上海天马有机发光显示技术有限公司 | Preparation method of metal mask plate |
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| CN101916042A (en) * | 2010-07-23 | 2010-12-15 | 长春理工大学 | Multi-beam semiconductor laser interference nanoimprinting technology and system |
| CN102799063B (en) * | 2012-07-20 | 2013-11-20 | 北京科技大学 | Method for preparing photoresist template and patterned ZnO nanorod array |
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| CN101009222A (en) * | 2007-01-26 | 2007-08-01 | 北京大学 | A method for making the carbon nano tube electronic part |
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