CN103990462A - Preparation method of nickel-based catalyst nanometer film - Google Patents
Preparation method of nickel-based catalyst nanometer film Download PDFInfo
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- CN103990462A CN103990462A CN201410211474.0A CN201410211474A CN103990462A CN 103990462 A CN103990462 A CN 103990462A CN 201410211474 A CN201410211474 A CN 201410211474A CN 103990462 A CN103990462 A CN 103990462A
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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, relate in particular to that a kind of particle size is controlled, the preparation method of the nickel-base catalyst nano thin-film that is evenly distributed.
Background technology
CNT is because of characteristics such as its peculiar structure, huge specific area, surface hydrophobic, adsorptivity, mechanics and electricity, cause scholar's all over the world concern and research, and be widely used in all kinds of fields such as hydrogen storage material, information storage and biomedicine.Aligned carbon nanotube film is that CNT is aligned vertically, makes the arrangement of CNT from disorderly and unsystematic to ordered arrangement, better brings into play mechanics, calorifics and the electric property of CNT.
Because the draw ratio of CNT is very large, in growth course, it bends inevitable with wound form.In order to obtain the CNT that directionality is good and pipe diameter size is evenly distributed, in three kinds of conventional carbon nano tube growth modes (arc discharge is sent out, laser evaporation method and chemical vapour deposition technique), chemical vapour deposition (CVD) is widely used in preparing aligned carbon nanotube because it has the advantages such as the low and controllability of reaction condition gentleness, cost is good.Prepare in the process of aligned carbon nanotube in use chemical vapour deposition (CVD), the size of surface catalyst particle, the uniformity of distribution have played conclusive effect to the quality of aligned carbon nanotube.Have at present that many preparation size sizes are identical, the method for the nm-class catalyst particle with catalytic activity that is evenly distributed, as nanosphere etching method, photoetching process, plasma bombardment method, foraminous die plate method etc.But said method all has defect separately, as adopted photoetching process to carry out Kaolinite Preparation of Catalyst film, though the good cost of effect is high; And being applicable to PECVD, plasma bombardment method prepares aligned carbon nanotube film; The preparation of porous mold itself is exactly a difficult problem.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides and a kind ofly can carry out that simple, efficient, can to realize large area processing particle size is controlled, the preparation method of the nickel-base catalyst nano thin-film that is evenly distributed.
Technical scheme: for achieving the above object, the technical solution used in the present invention is:
A preparation method for nickel-base catalyst nano thin-film, first utilizes magnetron sputtering technique to deposit certain thickness nickel nano thin-film at substrate surface, forms film sample; Then film sample is placed on three-dimensional mobile platform, utilizes laser interference to carry out texturing processing to the surface of nickel nano thin-film, nickel nano thin-film is processed into the pattern of regular distribution; Finally the film sample after texturing processing is put into tube furnace, pass into ammonia so that nickel nano thin-film is carried out to etching, temperature in rising tube furnace can make the fusing of nickel nano thin-film, because nickel nano thin-film is different from the thermal coefficient of expansion of substrate, therefore under capillary effect, can start taking texture pattern as border to shrink, along with the increase of etch period, nickel nano thin-film can further be shrunk to Ni-based nano particle.
In the method, process with etch period the nanoscale nickel-base catalyst particle that size is consistent, be evenly distributed by controlling temperature in the pattern, tube furnace of laser interference.
The method in the specific implementation, comprises the preparation of early-stage preparations, nickel-base catalyst film, laser interference texturing processing and the several steps of high temperature ammonia etching of nickel-base catalyst film, is specially:
(1) early-stage preparations: base material is divided into after suitable size, cleans up also air-dry;
(2) preparation of nickel-base catalyst film: utilize magnetron sputtering technique to deposit certain thickness nickel nano thin-film at substrate surface, form film sample;
(3) the laser interference texturing processing of nickel-base catalyst film: light path is adjusted according to the pattern of required laser ablation, film sample is placed on three-dimensional mobile platform, utilize laser interference to carry out texturing processing to nickel nano thin-film, nickel nano thin-film is processed into the pattern of regular distribution;
(4) high temperature ammonia etching: first, by be put in the centre position of quartz boat through the film sample of laser interference texturing processing, heat up after sealing, and pass into the air in nitrogen discharge tube furnace, the interference of the oxidation of deaeration to film sample; Pass into again hydrogen and heat up, film sample is reduced fully, the impact bringing to eliminate the oxide layer on film sample surface; Then by temperature increase to etching temperature, to passing into ammonia in tube furnace, Ni-based film sample is carried out to etching, after etching finishes with the cooling rear taking-up of stove.
In described step (1), base material is N-type silicon (100) crystal orientation polished silicon wafer.
Described step (1) is specially, and base material is divided into after suitable size, carries out ultrasonic vibration cleaning successively by acetone, alcohol and deionized water, by the substrate natural air drying cleaning up, so that follow-up processing.
In described step (2), the magnetron sputtering apparatus of use is K575X magnetron sputtering plating instrument.
Described step (2) is specially, and first the above-mentioned substrate cleaning up is placed on the sample stage of plated film instrument, and target chamber inside is vacuumized, and makes the operation vacuum of vacuum chamber reach preset value and (is preferably 1 × 10
-4mbar), control sputtering current (being preferably 60mA), prepare the nickel nano thin-film of different-thickness by regulating different sputtering times to reach, control nickel nano film thickness at 5～50nm.
In described step (3), be pulse laser DSH-355-10 for the laser instrument of laser interference.
Described step (3) is specially, according to the pattern of required laser ablation, light path is adjusted, when processing, control the power of laser instrument at 20mw～200mw, nickel nano thin-film is partitioned into uniform laser interference pattern, size cycle 0.02～100 μ m of the nickel nano thin-film dot matrix after processing, longitudinally the degree of depth is film thickness.
In described step (4), the tube furnace equipment of use is the temperature automatically controlled tube furnace of CVD (Z)-06/60/3 model.
Described step (4) is specially: first will be put in the centre position of quartz boat through the film sample of laser interference texturing processing, after sealing, heat up, and pass into nitrogen and discharge the air in tube furnace, the interference of the oxidation of deaeration to film sample, wherein the flow velocity of nitrogen is 100～300sccm; After 10min, pass into again hydrogen and heat up, keeping more than 600 DEG C of above temperature 40min film sample being reduced fully, the impact bringing to eliminate the oxide layer on film sample surface; Then by after the etching temperature of temperature increase to 700～900 DEG C, to passing into ammonia in tube furnace, Ni-based film sample is carried out to etching, wherein the flow velocity of ammonia is 100～300sccm, and the time of passing into is 2～20min; After etching finishes with the cooling rear taking-up of stove.
Beneficial effect: the preparation method of nickel-base catalyst nano thin-film provided by the invention, with respect to prior art, tool has the following advantages: 1, the controlled preparation of particle size size: nickel-base catalyst film is divided into the unit of given size size in the process of laser interference processing, its size can be adjusted by the light path of laser interference, then pass into ammonia etching, can generate the unified nanoscale nickel-base catalyst particle of size at substrate surface; 2, even particle distribution: the particle of original random distribution is become according to the equally distributed particle of laser interference pattern by laser interference etching, its distribution of particles density can be according to the controlled adjustment of laser optical path, therefore can prepare the nanocatalyst particle that different cycles is arranged, for the CNT of follow-up highdensity qualitative growth lays the first stone; 3, simple, the economy of particle preparation process: magnetron sputtering of the present invention, laser interference and high temperature ammonia etching process are simple, replace the mask plate in conventional lithography by laser interference pattern, not only retained the high-quality of conventional lithography but also improve its economy.The present invention uses laser interference pattern to replace the mask plate in conventional lithography in sum, reduce time and the cost of manufacturing mask plate, by laser interference, Ni-based film is processed, the uniformity of distribution of particles when textured Ni-based film contributes to follow-up ammonia etching, and can control the density of distribution of particles, by changing the size that passes into flow velocity and can control particle size of the size of interference figure size and ammonia, realize the controlled manufacture of particle size and density degree simultaneously.
Brief description of the drawings
Fig. 1 is process chart of the present invention;
Fig. 2 is schematic diagram prepared by nickel-base catalyst particle of the present invention, wherein (a) is the film sample after magnetron sputtering, (b) being the film sample after laser interference texturing, is (c) film sample after high temperature ammonia etching.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is further described.
A preparation method for nickel-base catalyst nano thin-film, first utilizes magnetron sputtering technique to deposit certain thickness nickel nano thin-film at substrate surface, forms film sample; Then film sample is placed on three-dimensional mobile platform, utilizes laser interference to carry out texturing processing to nickel nano thin-film, nickel nano thin-film is processed into the pattern of regular distribution; Finally the film sample after texturing processing is put into tube furnace, pass into ammonia so that nickel nano thin-film is carried out to etching, temperature in rising tube furnace can make the fusing of nickel nano thin-film, because nickel nano thin-film is different from the thermal coefficient of expansion of substrate, therefore under capillary effect, can start taking texture pattern as border to shrink, along with the increase of etch period, nickel nano thin-film can further be shrunk to Ni-based nano particle.In the method, process with etch period the nanoscale nickel-base catalyst particle that size is consistent, be evenly distributed by controlling temperature in the pattern, tube furnace of laser interference.
As shown in Figure 1, the present invention mainly comprises the preparation of early-stage preparations, nickel-base catalyst film, laser interference texturing processing and the several steps of high temperature ammonia etching of nickel-base catalyst film, specifically describes as follows.
First, substrate is carried out ultrasonic vibration by acetone, alcohol and deionized water successively and is cleaned each 5min, after by the substrate natural air drying cleaning up; Then the above-mentioned substrate cleaning up is placed on the sample stage of K575X magnetron sputtering plating instrument, target chamber inside is vacuumized, make the operation vacuum of vacuum chamber reach default 1 × 10
-4mbar, control sputtering current is 60mA, by regulating different sputtering times to prepare the nickel nano thin-film of different-thickness, nickel nano film thickness is controlled at 5～50nm the most at last; Then the sample of preparing is placed on the three-dimensional mobile platform in laser interference system of processing, and according to the pattern of required Laser Processing, light path is adjusted, wherein said laser instrument is pulse laser DSH-355-10, when processing, control the power of laser instrument at 20mw～200mw, nickel nano thin-film is divided into uniform laser interference pattern, size cycle 0.02～100 μ m of the nickel nano thin-film dot matrix after processing, longitudinally the degree of depth is film thickness; Finally the centre position of quartz boat in the temperature automatically controlled tube furnace of CVD (Z)-06/60/3 will be put in through the nickel nano thin-film sample of laser interference texturing processing, after sealing, heat up, and to pass into flow velocity be that the nitrogen of 100～300sccm is discharged the air in tube furnace, the interference of the oxidation of deaeration to nickel nano thin-film surface, after 10min, pass into again hydrogen and heat up, keep the temperature 40min of 600 DEG C to reduce fully to nickel nano thin-film, the impact bringing to eliminate the oxide layer on nickel nano thin-film surface; Then by after the etching temperature of temperature increase to 700～900 DEG C, after constant temperature, to passing into ammonia in tube furnace, the flow velocity of ammonia is 100～300sccm, and the time of passing into is that 2～20min carries out etching to nickel nano thin-film sample, after etching finishes with the cooling rear taking-up of stove.
In Fig. 2, (a) be the sample of nickel deposited base film; (b) be the film surface through laser interference texturing processing; (c) be the nickel-base catalyst nano grain surface through high temperature ammonia etching.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for nickel-base catalyst nano thin-film, is characterized in that: first utilize magnetron sputtering technique to deposit certain thickness nickel nano thin-film at substrate surface, form film sample; Then film sample is placed on three-dimensional mobile platform, utilizes laser interference to carry out texturing processing to nickel nano thin-film, nickel nano thin-film is processed into the pattern of regular distribution; Finally the film sample after texturing processing is put into tube furnace, pass into ammonia so that nickel nano thin-film is carried out to etching, temperature in rising tube furnace can make the fusing of nickel nano thin-film, because nickel nano thin-film is different from the thermal coefficient of expansion of substrate, therefore under capillary effect, can start taking texture pattern as border to shrink, along with the increase of etch period, nickel nano thin-film can further be shrunk to Ni-based nano particle.
2. the preparation method of nickel-base catalyst nano thin-film according to claim 1, is characterized in that: process with etch period the nanoscale nickel-base catalyst particle that size is consistent, be evenly distributed by controlling temperature in the pattern, tube furnace of laser interference.
3. the preparation method of nickel-base catalyst nano thin-film according to claim 1 and 2, it is characterized in that: comprise the preparation of early-stage preparations, nickel-base catalyst film, laser interference texturing processing and the several steps of high temperature ammonia etching of nickel-base catalyst film, be specially:
(1) early-stage preparations: base material is divided into after suitable size, cleans up also air-dry;
(2) preparation of nickel-base catalyst film: utilize magnetron sputtering technique to deposit certain thickness nickel nano thin-film at substrate surface, form film sample;
(3) the laser interference texturing processing of nickel-base catalyst film: light path is adjusted according to the pattern of required laser ablation, film sample is placed on three-dimensional mobile platform, utilize laser interference to carry out texturing processing to nickel nano thin-film, nickel nano thin-film is processed into the pattern of regular distribution;
(4) high temperature ammonia etching: first, by be put in the centre position of quartz boat through the film sample of laser interference texturing processing, heat up after sealing, and pass into the air in nitrogen discharge tube furnace, the interference of the oxidation of deaeration to film sample; Pass into again hydrogen and heat up, film sample is reduced fully, the impact bringing to eliminate the oxide layer on film sample surface; Then by temperature increase to etching temperature, to passing into ammonia in tube furnace, Ni-based film sample is carried out to etching, after etching finishes with the cooling rear taking-up of stove.
4. the preparation method of nickel-base catalyst nano thin-film according to claim 3, is characterized in that: in described step (1), base material is N-type silicon (100) crystal orientation polished silicon wafer.
5. the preparation method of nickel-base catalyst nano thin-film according to claim 3, is characterized in that: in described step (2), the magnetron sputtering apparatus of use is K575X magnetron sputtering plating instrument.
6. the preparation method of nickel-base catalyst nano thin-film according to claim 3, it is characterized in that: described step (2) is specially, first the above-mentioned substrate cleaning up is placed on the sample stage of plated film instrument, target chamber inside is vacuumized, make the operation vacuum of vacuum chamber reach preset value, control sputtering current, prepare the nickel nano thin-film of different-thickness by regulating different sputtering times to reach, control nickel nano film thickness at 5～50nm.
7. the preparation method of nickel-base catalyst nano thin-film according to claim 3, is characterized in that: in described step (3), be pulse laser DSH-355-10 for the laser instrument of laser interference.
8. the preparation method of nickel-base catalyst nano thin-film according to claim 3, it is characterized in that: described step (3) is specially, according to the pattern of required laser ablation, light path is adjusted, when processing, control the power of laser instrument at 20mw～200mw, nickel nano thin-film is partitioned into uniform laser interference pattern, size cycle 0.02～100 μ m of the nickel nano thin-film dot matrix after processing, longitudinally the degree of depth is film thickness.
9. the preparation method of nickel-base catalyst nano thin-film according to claim 3, is characterized in that: in described step (4), the tube furnace equipment of use is the temperature automatically controlled tube furnace of CVD (Z)-06/60/3 model.
10. the preparation method of nickel-base catalyst nano thin-film according to claim 3, it is characterized in that: described step (4) is specially: first will be put in the centre position of quartz boat through the film sample of laser interference texturing processing, after sealing, heat up, and pass into nitrogen and discharge the air in tube furnace, the interference of the oxidation of deaeration to film sample, wherein the flow velocity of nitrogen is 100～300sccm; After 10min, pass into again hydrogen and heat up, keeping more than 600 DEG C of above temperature 40min film sample being reduced fully, the impact bringing to eliminate the oxide layer on film sample surface; Then by after the etching temperature of temperature increase to 700～900 DEG C, to passing into ammonia in tube furnace, Ni-based film sample is carried out to etching, wherein the flow velocity of ammonia is 100～300sccm, and the time of passing into is 2～20min; After etching finishes with the cooling rear taking-up of stove.
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| CN105154882A (en) * | 2015-10-08 | 2015-12-16 | 华中科技大学 | Preparation method for porous nickel |
| CN107365958A (en) * | 2017-07-13 | 2017-11-21 | 上海天马有机发光显示技术有限公司 | The preparation method of metal mask plate |
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