CN104649233B - Controllable patterning ultrafast laser composite preparation method for metal oxide nano wires - Google Patents
Controllable patterning ultrafast laser composite preparation method for metal oxide nano wires Download PDFInfo
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Abstract
The invention discloses a controllable patterning ultrafast laser composite preparation method for metal oxide nano wires. The method comprises the following steps: (1), according to a preset pattern, irradiating the surface of a block metal by utilizing ultrafast laser to obtain a patterning micro-nano structure, namely a metal oxide nanowire precursor, on the block metal; and (2), under the oxidizing atmosphere, heating the block metal attached with the metal oxide nanowire precursor, and keeping the temperature, and cooling down, so that the metal oxide nanowires in-situ grow on the metal oxide nanowire precursor. According to the controllable patterning ultrafast laser composite preparation method for the metal oxide nano wires, by utilizing control of the ultrafast laser processing procedure on the structure distribution form of the metal surface micro-nano precursor, the control on the metal oxide nanowire distribution form can be realized; meanwhile, by virtue of the control on factors, such as the heating temperature, the heat preservation time and the oxidization atmosphere, in a thermal oxidization process, the control on the diameters, the lengths and the growth density of the metal oxide nanowires can be realized.
Description
Technical field
The invention belongs to nano material preparation and laser micro/nano manufacturing technology field, be specifically related to a kind of metal-oxide
The controllable patterned ultrafast laser composite preparation process of nano wire.
Background technology
Copper oxide (CuO) nano wire is the One, Dimensional Semiconductor Nano Materials of a kind of excellence, have special electricity, magnetics,
Physics and the chemical characteristics such as optics and catalysis, air-sensitive, at solaode, photo-detector, photocatalysis, lithium ion battery, surpass
The numerous areas such as level capacitor, feds, biology/gas sensor and super-hydrophobic/self-cleaning material all have potential
Using value, obtained the highest attention of domestic and international researchers.The controllable patterned preparation of CuO nano wire is for fully sending out
Wave its property, it is achieved its commercial application is significant.
The preparation method of existing CuO nano wire includes hydro-thermal or solvent-thermal method, sol-gel process, electrochemical method, precipitation
Hydrolyze method and solid reaction process etc..These methods are required to special chemical reaction system and complicated chemical reaction process, difficult
To realize the controllable patterned preparation of CuO nano wire.2002, the researcher of Washington, DC university [Xuchuan Jiang,
Et al., Nano Lett., 2 (2002) 1333] report a kind of thermal oxidation technology, the Copper substrate such as copper mesh, copper cash, Copper Foil are put
It is heated to 400 to 700 DEG C in oxidation atmosphere, held for some time, its superficial growth can be made to go out CuO nano-needle line structure.
This technique is without complicated chemical reaction system, and process is simple and convenient to operate, and causes the extensive attention of researchers.Afterwards
The thermal oxide growth technique of CuO nano wire has reached systematic study, has also prepared one-dimensional on the matrix such as Porous Cu, Copper thin film
CuO nano thread structure.The patterned growth of CuO nano wire also has carried out some research, such as: by photoetching or shadowmask successively
On backing material, transition layer film and Copper thin film are prepared in specific region, then can be formed only raw in specific region by thermal oxide
Long CuO nano thread structure [Xu Ningsheng, etc., (2006) CN 1843932A]；By photoetching process at Si surface formation patterning
Region, and form Copper thin film by deposition process in pattered region, then can be formed by thermal oxide and only be grown on patterning
The CuO nano thread structure [Kaili Zhang, et al., Nanotechnology, 18 (2007) 275607] in region；Via covering
Mould is in Cu paper tinsel surface electro-deposition layer of Ni coating, after removing mask, has the Cu paper tinsel of Ni coating to carry out thermal oxidation deposition, can
Formed only at CuO nano thread structure [F Mumm, the et al., Nanotechnology, 22 of the region growing not depositing Ni coating
(2011)105605].In above-mentioned thermal oxidation technology, the matrix used mostly be the Copper Foil of micro-meter scale, copper mesh, copper conductor or
Copper thin film etc., limited strength own, the CuO nano wire layer formed is also easy to ftracture, crush and peel off.A few studies is real
Show growth of one-dimensional CuO nano wire on the block copper surface of millimeter magnitude thickness, but growth course has needed the time of several days
[Y W Zhu, et al., Nanotechnology, 16 (2005) 88-92] can be completed.In addition, there will be based on thermal oxidation technology
The patterned growth of the CuO nano wire carried out, is both needed to the auxiliary of the technological means such as mask, photoetching, deposition, is patterned by formation
Growth source or the suppression source of patterning could realize, complex technical process, with high costs.Therefore, bigger of CuO nano wire
Long-pending controllable patterned preparation is still yet unresolved issue in the research of CuO nano wire.
Summary of the invention
It is an object of the invention to provide the compound preparation side of controllable patterned ultrafast laser of a kind of metal oxide nano-wire
Method, ultrafast laser is prepared the technique of surface micronano structure and thermal oxide generation metal oxide nano-wire and is combined by the method
Come, the patterning processing of ultrafast laser high efficient and flexible and the advantage of thermal oxide in-situ preparation nano wire can be played, simultaneously on microcosmic
While realizing metal oxide nano-wire growth, macroscopically it is being naturally completed the assembling of metal oxide nano-wire, is adding
Work process is simple, working (machining) efficiency is high, is a kind of controllable patterned compound system of economical and practical metal oxide nano-wire large area
Preparation Method.
The controllable patterned ultrafast laser composite preparation process of the metal oxide nano-wire that the present invention provides, including following
Step:
(1) according to the pattern being pre-designed, with the surface of ultrafast laser irradiation bulk metal, at the table of described bulk metal
Face obtains the micro nano structure of patterning, i.e. metal oxide nano-wire presoma；
(2) under oxidizing atmosphere, heating is attached with the bulk metal of described metal oxide nano-wire presoma and is incubated,
After cooling, i.e. on described metal oxide nano-wire presoma, growth in situ goes out described metal oxide nano-wire.
In above-mentioned preparation method, described metal-oxide can be CuO, Cu2O、ZnO、TiO2、MgO、Fe2O3、WO3Or WOx
Deng.
Described bulk metal can be block copper, block zinc, block titanium, block magnesium, block ferrum or block tungsten etc..
Described bulk metal is different from micron-sized metal base in prior art, such as the Copper Foil of micro-meter scale, copper mesh, copper
Wire or Copper thin film etc., the thickness of described bulk metal can be 10 μm～1cm, and concretely 1mm～3mm, 1mm or 3mm, break
Restriction to metallic matrix thickness present in thermal oxidation technology, thus improve metallic matrix to generated nano thread structure
Support strength, be conducive to the large area carrying out metal oxide nano-wire to prepare.
In above-mentioned preparation method, described method, before ultrafast laser irradiation, also includes the table removing described bulk metal
The step of the metal-oxide in face, concrete operations are as follows: the method for sand papering or mechanical grinding processing processes block by hand
Metal surface, to remove the oxide layer on metal surface, and makes it have certain glossiness, subsequently with acetone or alcohol washes
Metal surface, dries up bulk metal surface after cleaning or dries.
In above-mentioned preparation method, in step (1), meeting behind described ultrafast laser (i.e. ultra-short pulse laser) exposed material surface
Produce the ultrafast effects such as non-linear absorption, many ripples or multi-scenarios method, mutually blast, coulomb explosion, transition plasmon, formed
The mechanism of action such as ablation, induction, thus the random or arrays such as groove, pit, synapse, granule and thin rod can be formed at material surface
Arrangement, and the micron of various ways, nanometer and the micron and nanometer composite structure such as one-dimensional/multidimensional periodic corrugated structures,
It it is a kind of flexible and efficient material surface metal layer preparation means；With ultrafast laser irradiation bulk metal in the present invention
Surface, through laser ablation remove portion of material and at induced with laser under self assembly, on the surface of described bulk metal
Micro nano structure to patterning；
Described laser ablation is removed and is referred to when pulsed laser energy density exceedes the ablation threshold of material, laser action district
There is Evaporation Phenomenon in interior material surface, forms the removal of material, and removal amount depends on laser parameter；The ablation threshold of material and material
Material characteristic and Pulsed Laser Parameters such as pulse width etc. is relevant；
Described self assembly refers under the induction of ultrafast pulsed laser energy, material self occur complicated thawing, solidification,
The processes such as evaporation, deposition, these processes intersect, and form the substructure of particular form, the shape of substructure at material surface
The relative motion form that yardstick is not dependent between laser and material, and by the characteristic of material self and the character institute of pulse laser
Determine.
Above-mentioned preparation method, in step (1), utilizes ultrafast laser irradiation can realize bulk metal surface micronano forerunner
The regulation and control of body structure distribution form, can realize the regulation and control to metal oxide nano-wire distribution form further, described ultrafast sharp
Light is infrared light, visible ray or ultraviolet light, and the wavelength of described ultrafast laser can 355nm～1064nm, concretely 1064nm；
The pulse width of described ultrafast laser can be 50 femtoseconds～20 psecs, concretely 800 femtoseconds～10 psecs, 800
Femtosecond or 10 psecs；The pulse frequency of described ultrafast laser can be 1KHz～4MHz, concretely 100KHz～200KHz,
100KHz or 200KHz；The mean power of described ultrafast laser can be 1W～400W, concretely 5W～35W, 5W～18W, 15W
～35W, 5W, 15W, 18W or 35W.
Above-mentioned preparation method, in step (1), described irradiation is by following 1), 2) or 3) in by the way of carry out:
1) single-point irradiation；
2) vibration mirror scanning；
3) vibration mirror scanning coordinates with numerical control X-Y platform.
Above-mentioned preparation method, in step (1), in described single-point irradiation, irradiated area is not less than 100 μm2；
Described vibration mirror scanning can be following 1) or 2):
1) scanning pattern of described vibration mirror scanning is parallel lines, reticule or helix；The scanning room of described vibration mirror scanning
Away from being 1 μm～100 μm, concretely 10 μm～100 μm, 10 μm～40 μm, 30 μm～50 μm, 40 μm～100 μm, 10 μm,
30 μm, 40 μm, 50 μm or 100 μm；Scanning speed can be 1mm/s～10m/s, concretely 25mm/s～500mm/s, 25mm/s
～50mm/s, 50mm/s～500mm/s, 25mm/s, 50mm/s or 500mm/s；
2) scanning pattern of described vibration mirror scanning is dot matrix；The dot spacing of described vibration mirror scanning is 1 μm～100 μm, single-point
Effect umber of pulse is 1～2 × 106。
Above-mentioned preparation method, in step (1), described micro nano structure can be micrometer structure, nanostructured or micro-nano double
Yardstick composite construction；
Described micrometer structure is micron projection and/or micron pit, described micrometer structure regular distribution or random distribution；
Described micron projection can be cylindrical, cone, truncated cone-shaped or irregular contour, and its lateral dimension can be 1～100
μm, concretely 1～30 μm, 20～50 μm, 20～40 μm；Height can be 1～100 μm, concretely 20～50 μm, 30 μm or
50μm；
Described micron pit can be circular or irregular elliptic contour, such as micron hole or micron trenches, its lateral dimension
Can be 1～100 μm, concretely 1～50 μm, 10～20 μm, 10 μm, 25 μm, 30 μm or 50 μm；The degree of depth can be 1～100 μm；
Concretely 25 μm, 30 μm or 50 μm；
Described nanostructured is nanometer ripple, nano-particle or nano-particle cluster；
Described micro-nano pair of yardstick composite construction is protruding at described micron and/or self assembly in described micron pit surface
Form the composite construction after nanometer ripple, nano-particle or nano-particle cluster；
The cycle of described nanometer ripple can be 100～1000nm, the bump height of described nanometer ripple can be 10～
1000nm, the development length of described nanometer ripple can be 100nm～10 μm；
Described nano-particle can be the big of spherical, polygon or other irregular contour, described nano-particle or its cluster
I is 1～1000nm, concretely 100～500nm.
Above-mentioned preparation method, in step (2), by heating-up temperature, temperature retention time and oxidizing atmosphere in thermal oxidation technology
Etc. the regulation and control of factor, the regulation and control of the diameter to metal oxide nano-wire, length and stand density etc. can be realized；
Above-mentioned preparation method, in step (2), described oxidizing atmosphere can be oxygen, air or the mixed gas containing oxygen；
During described heating, described metal oxide nano-wire presoma is placed in heat-resisting bateau, described heat-resisting bateau
Material is quartz or aluminium sesquioxide；
During described heating, heating rate can be 1～10 DEG C/min, concretely 10 DEG C/min；The temperature of described insulation can
It is 400～600 DEG C, concretely 400 DEG C or 500 DEG C；The time of described insulation is 5min～5 days, concretely 30min～
4h, 30min～2h, 2h～4h, 30min, 2h or 4h；
Described be cooled to furnace cooling or from stove take out after force cooling.
Invention further provides the metal oxide nano-wire of the patterning that a kind of above-mentioned preparation method obtains, described
Metal oxide nano-wire bears from the surface in situ of described metal oxide nano-wire presoma, be a kind of " micro--Na-receive " across
Yardstick composite construction system, has the specific surface area that the micro nano structure of height is integrated and high, and the metal-oxide obtained is received
Rice noodle is tapered, has good original position with metallic matrix and is combined, and is advantageously implemented good partly the leading of metal oxide nano-wire
The metallic character of self excellence of bulk properties and metal-oxide integrated, the diameter of described metal oxide nano-wire can be 10～
500nm；A length of 1～50 μm.
Described metal oxide nano-wire is vertical with the surface of described metal oxide nano-wire presoma.
Due to the fact that the above technical scheme of employing, have the advantage that
1, the present invention utilizes the regulation and control of ultrafast laser course of processing precursor construction micro-nano to metal surface distribution form,
The regulation and control to metal oxide nano-wire distribution form can be realized；Meanwhile, by during to heating-up temperature in thermal oxidation technology, insulation
Between, the regulation and control of the factor such as oxidizing atmosphere, the regulation and control to metal oxide nano-wire diameter, length, stand density etc. can be realized.
2, in the present invention, the existence of the micro-nano precursor construction in metal surface has beneficially accelerates metal oxide nano-wire
Growth course, shortens metal oxide nano-wire growth required time, is the efficiently side of preparation of a kind of metal oxide nano-wire
Method.
3, method therefor of the present invention can be carried out having certain thickness bulk metal matrix surface, has broken thermal oxide work
Restriction to metallic matrix thickness present in skill, thus it is strong to the support of generated nano thread structure to improve metallic matrix
Degree, is conducive to the large area carrying out metal oxide nano-wire to prepare.
4, in the present invention, the micro-nano precursor construction of metal oxide surface is to generated in-situ metal oxide nano-wire
There is pinning effect, can effectively alleviate the problems such as the cracking of the metal oxide nano-wire layer that thermal stress causes, broken and peeling.
5, in the present invention, metal oxide nano-wire directly generates on bulk metal matrix, and via surface micronano
Precursor construction, defines good original position and is combined, be advantageously implemented the quasiconductor that metal oxide nano-wire is good with matrix
The metallic character of self excellence of characteristic and metal-oxide integrated, is expected to obtain application in fields such as photoelectric devices.
6, the present invention generates one-dimensional metallic oxide nano line on the basis of metal surface micro-nanostructure further,
Thus constituting one " micro--to receive " or " micro--Na-receive " across yardstick composite construction system, the micro nano structure with height is integrated
And high specific surface area, optimization further, regulation and control and collaborative metal surface micro-nanostructure and metal-oxide can be played
The effect of nano wire excellent properties.
7, operation of the present invention is simple and convenient to operate, it is not necessary to special chemical reaction system and complicated chemical reaction process,
It it is a kind of eco-friendly metal oxide nano-wire preparation method.
In sum, ultrafast laser is prepared surface micronano structure by the present invention and thermal oxide generates metal oxide nano
The technique of line combines, and can play the patterning processing of ultrafast laser high efficient and flexible and thermal oxide in-situ preparation nano wire simultaneously
Advantage, while realizing metal oxide nano-wire growth, receives being macroscopically naturally completed metal-oxide on microcosmic
The assembling of rice noodle, the course of processing is simple, working (machining) efficiency is high, is that a kind of economical and practical metal oxide nano-wire large area is controlled
Patterning composite preparation process.
Accompanying drawing explanation
Fig. 1 is the micro nano structure on the Cu surface prepared in embodiment 1 and the scanning of CuO nano wire born in situ
Electronic Speculum figure and transmission electron microscope picture, wherein, Fig. 1 (a) and Fig. 1 (b) is under different up-sizing, block copper surface after laser irradiation
The scanning electron microscope (SEM) photograph of the micro nano structure obtained；Fig. 1 (c) is after 400 DEG C of insulation 2h, the CuO that micro nano structure bears in situ
The scanning electron microscope (SEM) photograph of nano wire；Fig. 1 (d)～Fig. 1 (i) is respectively after 500 DEG C of insulations 1h, 2h and 4h, and micro nano structure is in situ
The scanning electron microscope (SEM) photograph of the CuO nano wire born；Fig. 1 (g1) and Fig. 1 (i1) is respectively transmission electricity corresponding for Fig. 1 (g) and Fig. 1 (i)
Mirror figure.
Fig. 2 is the micro nano structure on the Cu surface prepared in embodiment 2 and the scanning of CuO nano wire born in situ
Electronic Speculum figure, wherein, Fig. 2 (a) and Fig. 2 (b) are respectively distance between centers of tracks when being 30 μm and 38 μm, and after laser irradiation, block copper surface obtains
The scanning electron microscope (SEM) photograph of the micro nano structure arrived；Fig. 2 (c)～Fig. 2 (f) is sweeping of the CuO nano wire that bears in situ of micro nano structure
Retouch Electronic Speculum figure.
Fig. 3 is the micro nano structure on the Cu surface prepared in embodiment 3 and the scanning of CuO nano wire born in situ
Electronic Speculum figure, wherein, Fig. 3 (a) is the scanning electron microscope (SEM) photograph of the micro nano structure that block copper surface obtains, Fig. 3 (b) after laser irradiation
Scanning electron microscope (SEM) photograph for the CuO nano wire that micro nano structure bears in situ.
Fig. 4 is the micro nano structure on the Cu surface prepared in embodiment 4 and the scanning of CuO nano wire born in situ
Electronic Speculum figure, wherein, Fig. 4 (a) is the scanning electron microscope (SEM) photograph of the micro nano structure that block copper surface obtains, Fig. 4 (b) after laser irradiation
Scanning electron microscope (SEM) photograph for the CuO nano wire that micro nano structure bears in situ.
Fig. 5 is the micro nano structure on the Cu surface prepared in embodiment 5 and the scanning of CuO nano wire born in situ
Electronic Speculum figure, wherein, Fig. 5 (a) and 5 (c) are respectively distance between centers of tracks when being 50 μm and 100 μm, and after laser irradiation, block copper surface obtains
The scanning electron microscope (SEM) photograph of the micro nano structure arrived, Fig. 5 (b) and 5 (d) are respectively micro nano structure original position in above-mentioned Fig. 5 (a) and 5 (c)
The CuO nano wire scanning electron microscope (SEM) photograph born.
Fig. 6 is the micro nano structure on the Cu surface prepared in embodiment 6 and the scanning of CuO nano wire born in situ
Electronic Speculum figure, wherein, Fig. 6 (a) and Fig. 6 (b) are respectively under different up-sizing, after laser irradiation block copper surface obtain micro-
Under the scanning electron microscope (SEM) photograph of nanostructured, Fig. 6 (c) and 6 (d) the most different up-sizing, the CuO that micro nano structure bears in situ
The scanning electron microscope (SEM) photograph of nano wire.
Fig. 7 is the micro nano structure on the Cu surface prepared in embodiment 7 and the scanning of CuO nano wire born in situ
Electronic Speculum figure, wherein, Fig. 7 (a) is the scanning electron microscope (SEM) photograph of the micro nano structure that block copper surface obtains, Fig. 7 (b) after laser irradiation
～Fig. 7 (d) is the scanning electron microscope (SEM) photograph of the CuO nano wire that micro nano structure bears in situ.
Fig. 8 is the micro nano structure on the Cu surface prepared in embodiment 8 and the scanning of CuO nano wire born in situ
Electronic Speculum figure, wherein, Fig. 8 (a)～Fig. 8 (c) is respectively the micro-nano that under different distance between centers of tracks, block copper surface obtains after laser irradiation
The scanning electron microscope (SEM) photograph of rice structure, Fig. 8 (d)～Fig. 8 (f) is respectively what micro nano structure in Fig. 8 (a)～Fig. 8 (c) bore in situ
CuO nano wire scanning electron microscope (SEM) photograph, Fig. 8 (g)～Fig. 8 (i) is respectively what micro nano structure in Fig. 8 (a)～Fig. 8 (c) bore in situ
CuO nano wire scanning electron microscope (SEM) photograph.
Fig. 9 is the micro nano structure on the Cu surface prepared in embodiment 9 and the scanning of CuO nano wire born in situ
Electronic Speculum figure, wherein, Fig. 9 (a)～Fig. 9 (d) is respectively the CuO nano wire that under different up-sizing, micro nano structure bears in situ and sweeps
Retouch Electronic Speculum figure.
Figure 10 is sweeping of the micro nano structure on the Cu surface prepared in embodiment 10 and the CuO nano wire that bears in situ
Retouching Electronic Speculum figure, wherein, Figure 10 (a) is block copper surface photo after laser irradiation, Figure 10 (b), Figure 10 (d) and Figure 10 (f)
It is respectively the scanning electron microscope (SEM) photograph of the micro nano structure zones of different that block copper surface obtains after laser irradiation, Figure 10 (c) and figure
10 (e) is respectively the scanning electron microscope (SEM) photograph of the CuO nano wire that zones of different micro nano structure bears in situ, as comparison, Figure 10 (g)
Scanning electron microscope (SEM) photograph for the region without laser irradiation.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
Following embodiment realize the controllable patterned ultrafast laser of cupric oxide nano line be combined the ultimate principle of preparation be:
Ultrafast laser is utilized to prepare micro nano structure on Cu surface, as the presoma of CuO nanowire growth, at further hot oxygen
Change in processing procedure, CuO nano wire only or preferential bear in situ in Cu surface micronano precursor construction；Super by regulation and control
Relative motion between fast laser parameter and laser beam and Cu surface, can enter the pattern of Cu surface micronano structure, size
Row regulation and control, so that the presoma of CuO nanowire growth has specific patterned distribution feature, being grown in of CuO nano wire
Carry out on the presoma of patterning so that the CuO nano wire grown out also possesses patterned distribution feature, it is achieved thereby that
The controllable patterned preparation of CuO nano wire.
Embodiment 1, picosecond pulse laser prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
The controllable patterned preparation of the present embodiment CuO nano wire, comprises the steps:
(1) remove the oxide layer on block Cu surface by the mode of mechanical grinding, and make its surface reach certain fineness,
Then with alcohol washes Cu surface, after cleaning, block Cu surface is dried up or dries.
(2) selecting picosecond pulse laser, centre wavelength is 1064nm, and pulsewidth is 10 psecs, and laser beam realizes partially through galvanometer
Turning, then focus on rectangular blocks copper surface through the scene that focal length is 100mm, focused spot diameter is 30 μm, and the area of block copper is
25mm × 25mm, thickness is 3mm.
Laser parameter is: mean power is 18W, and pulse frequency is 100kHz, and laser deflection track is reticule, distance between centers of tracks
Being 10 μm, deflection speed is 25mm/s, only carries out single pass.
Fig. 1 (a) and Fig. 1 (b) is the above-mentioned scanning electron microscope of the micro nano structure that block copper surface obtains after laser irradiation
Figure, as it can be seen, obtain on the surface of block copper is the protruding feature structure with the distribution of micron pit random interval of micron, micro-
The lateral dimension of rice projection is about 1～30 μm, and height is about 30 μm, and the lateral dimension of micron pit is about 1～50 μm, and the degree of depth is about
Being 30 μm, protruding at micron and micron pit surface is coated with the nano-particle Cluster Structures of prosperity, size be about 100～
500nm。
(3) use tubular type hot plate, oxidizing atmosphere is air, and heating rate is 10 DEG C/min, holding temperature be 400 or
500 DEG C, temperature retention time is 30min～4h, and after insulation terminates, sample cools to room temperature with the furnace, takes out afterwards from heating furnace.
Fig. 1 (c) show in above-mentioned steps (2) micro nano structure obtained through picosecond laser irradiation and is incubated 2h at 400 DEG C
After scanning electron microscope (SEM) photograph, the most visible, under this heating condition, nano wire starts from the matrix of Cu surface micronano structure raw
Longer；The micro nano structure obtained through picosecond laser irradiation it is respectively in above-mentioned steps (2) 500 shown in Fig. 1 (d)～(f)
DEG C insulation 1h, the scanning electron microscope (SEM) photograph after 2h, 4h, the most visible, under this heating condition, at the matrix of Cu surface micronano structure
Upper growth in situ has gone out the nano thread structure of prosperity, and nano wire is tapered, and vertical with the matrix surface of micro nano structure, length is about
It is 1～20 μm；Fig. 1 (g)～1 (i) are the micro nano structure obtained through picosecond laser irradiation in above-mentioned steps (2), 500 DEG C of guarantors
The transmission electron microscope picture of formed nano wire after temperature 2h, it can be seen that nano wire regular shape, sharpness of border, smooth surface, directly
Footpath is less than 100nm, there is twin-plane boundary along nano wire central axis direction；Fig. 1 (g1)～1 (i1) is corresponding high-resolution-ration transmission electric-lens
Picture, therefrom also observes that twin-plane boundary feature, both sides, interface each defining well-crystallized but to be orientated different monocrystalline brilliant
Lattice.Twin-plane boundary and twin structure are lattice structure characteristic common in CuO nano-needle line, thus illustrate, in the present embodiment
The one-dimensional nano line that growth in situ goes out on the matrix of Cu surface micronano structure is CuO nano wire.
Embodiment 2, picosecond pulse laser prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
The controllable patterned preparation of the present embodiment CuO nano wire, comprises the steps:
(1) remove the oxide layer on block Cu surface by the mode of mechanical grinding, and make its surface reach certain fineness,
Then with alcohol washes Cu surface, after cleaning, block Cu surface is dried up or dries.
(2) selecting picosecond pulse laser, centre wavelength is 1064nm, and pulsewidth is 10 psecs, and laser beam realizes partially through galvanometer
Turning, then focus on rectangular blocks copper surface through the scene that focal length is 100mm, focused spot diameter is 30 μm, and the area of block copper is
25mm × 25mm, thickness is 3mm.
Laser parameter is: mean power is 18W, and pulse frequency is 100kHz, and laser deflection track is reticule, distance between centers of tracks
Being 30 μm or 38 μm, scanning speed is 500mm/s, multiple scanning 30 times.
Fig. 2 (a) and 2 (b) are respectively distance between centers of tracks when being 30 μm and 40 μm, block copper surface after picosecond pulse laser irradiation
The scanning electron microscope (SEM) photograph of the micro nano structure obtained.As it can be seen, obtain on the surface of block copper is micron projection and micron openings
The feature structure of hole period distances arrangement, the lateral dimension of micron projection is about 20～40 μm, height is about 50 μm, micron hole
Lateral dimension be about 10～20 μm, the degree of depth is about 50 μm, is coated with ripple and the granule of submicron on the surface that micron is protruding
Structure, when distance between centers of tracks is respectively 30 μm, during 38 μm, the cycle of micron projection is respectively 30 μm, 38 μm.
(3) using tubular type hot plate, oxidizing atmosphere is air, and heating rate is 1～10 DEG C/min, and holding temperature is
500 DEG C, temperature retention time is 2h, and after insulation terminates, sample cools to room temperature with the furnace, takes out afterwards from heating furnace.
After thermal oxide, the surface in situ protruding from micron bears CuO nano thread structure, and its scanning electron microscope (SEM) photograph is respectively such as figure
Shown in 2 (c) and 2 (d), and the region that the sidewall of micron projection is i.e. crossed through the direct scan process of laser, nanowire growth is more sent out
Reaching, the top nanowire growth of micron projection is in confused situation aobvious, and CuO nano wire is vertical with the sidewall of micron projection, and length is about 1
～20 μm, such as Fig. 2 (e), shown in 2 (f).
Embodiment 3, femtosecond pulse prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
The controllable patterned preparation of the present embodiment CuO nano wire, comprises the steps:
(1) remove the oxide layer on block Cu surface with grinding method, and make its surface reach certain fineness, then use
Alcohol washes Cu surface.
(2) selecting femtosecond pulse, centre wavelength is 1064nm, and pulsewidth is 800 femtoseconds, and laser beam realizes partially through galvanometer
Turning, then focus on rectangular blocks copper surface through the scene that focal length is 100mm, focused spot diameter is 30 μm.The area of block copper is
30mm × 30mm, thickness is 1mm.
Laser parameter is: mean power is 15W, and pulse frequency is 200kHz, and laser deflection track is parallel lines, distance between centers of tracks
Being 50 μm, scanning speed is 50mm/s, only carries out single pass.
Fig. 3 (a) is the above-mentioned scanning electron microscope (SEM) photograph of the micro nano structure that block copper surface obtains after laser irradiation, such as figure institute
Showing, obtain on the surface of block copper is the feature structure of micron trenches period distances arrangement, and trench cycle is 50 μm, ditch groove width
Degree is about 25 μm, and the degree of depth is about 25 μm, and the inwall at micron trenches is coated with the submicron particles Cluster Structures of prosperity.
(3) using tubular type hot plate, oxidizing atmosphere is air, and heating rate is 10 DEG C/min, and holding temperature is 500
DEG C, temperature retention time is 2h, and after insulation terminates, sample cools to room temperature with the furnace, takes out afterwards from heating furnace.
Fig. 3 (b) is micro nano structure surface sweeping Electronic Speculum figure after thermal oxide, as it can be seen, from the base of particle clusters structure
Bear CuO nano thread structure in situ on body, and CuO nano wire is only distributed in the inwall of micro meter periodic groove, hang down with inner wall surface
Directly, length is about 1～10 μm, and the flat site between groove does not has CuO nano wire to bear.
Embodiment 4, femtosecond pulse prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
Being adjusted to by laser parameter in embodiment 3 step (2): mean power is 5W, pulse frequency is 200kHz, laser
Deflected trajectory is parallel lines, and distance between centers of tracks is 50 μm, and scanning speed is 500mm/s, multiple scanning 30 times, and remaining condition is constant, real
Test result as follows:
Fig. 4 (a) is the scanning electron microscope (SEM) photograph of the micro nano structure that block copper surface obtains after laser irradiation, as seen from the figure,
Obtain on the surface of block copper is the feature structure of micron trenches period distances arrangement, and trench cycle is 50 μm, groove width
Being about 30 μm, the degree of depth is about 30 μm, and the inwall at micron trenches is coated with the ripple struction of submicron.
Fig. 4 (b) is micro nano structure surface sweeping Electronic Speculum figure after thermal oxide, as seen from the figure, from the matrix of ripple struction
Bear CuO nano thread structure in situ, and CuO nano wire is only distributed in the inwall of micro meter periodic groove, vertical with inner wall surface, long
Degree is about 1～10 μm, and the flat site between groove does not has CuO nano wire to bear.
Embodiment 5, femtosecond pulse prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
Being adjusted to by laser parameter in embodiment 3 step (2): mean power is 15W, pulse frequency is 200kHz, swashs
Light deflected trajectory is parallel lines, and distance between centers of tracks is 50 μm or 100 μm, and scanning speed is 500mm/s, multiple scanning 30 times, remaining
Part is constant, and experimental result is as follows:
Fig. 5 (a) and 5 (c) are the scanning electron microscope (SEM) photograph of the micro nano structure that block copper surface obtains after laser irradiation, by scheming
Visible, obtain on the surface of block copper is the feature structure of micron trenches period distances arrangement, and groove width is about 50 μm, deeply
Degree is about 50 μm, and the inwall at micron trenches is coated with the ripple struction of submicron, when distance between centers of tracks is respectively 50 μm, during 100 μm,
The cycle of groove is respectively 50 μm, 100 μm, and its scanning electron microscope (SEM) photograph is respectively such as Fig. 5 (a), shown in 5 (c).
Fig. 5 (b) and 5 (d) are respectively micro nano structure scanning electron microscope (SEM) photograph after thermal oxide in above-mentioned Fig. 5 (a) and 5 (c),
As seen from the figure, after thermal oxide, from the matrix of ripple struction, bear CuO nano thread structure in situ, and CuO nano wire is only distributed
In the inwall of micro meter periodic groove, vertical with inner wall surface, length is about 1～20 μm, and the flat site between groove does not has
CuO nano wire bears.
Embodiment 6, femtosecond pulse prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
Being adjusted to by laser parameter in embodiment 3 step (2): mean power is 35W, pulse frequency is 200kHz, swashs
Light deflected trajectory is reticule, and distance between centers of tracks is 30 μm, and scanning speed is 50mm/s, only carries out single pass, and remaining condition is constant,
Experimental result is as follows:
Fig. 6 (a) and Fig. 6 (b) is under different up-sizing, the micro nano structure that block copper surface obtains after laser irradiation
Scanning electron microscope (SEM) photograph, from figure (a), obtain on the surface of block copper be particle clusters period distances arrangement feature tie
Structure, the cluster cycle is about 30 μm, and the surface of each particle clusters is formed by a large amount of nanoparticle aggregates and stacking, can by Fig. 6 (b)
To find out, the size of nano-particle is about 100～1000nm.
Fig. 6 (c) and 6 (d) are under different up-sizing, and micro nano structure scanning electron microscope (SEM) photograph after thermal oxide can by figure
See, after thermal oxide, from the matrix of particle clusters structure, bear CuO nano thread structure in situ, and processed through laser scanning
Region nanowire growth the most flourishing, shown in its scanning electron microscope (SEM) photograph such as Fig. 6 (c), CuO nano wire from nano grain surface or its
Bearing in gap, length is about 1～10 μm, as shown in Fig. 6 (d).
Embodiment 7, femtosecond pulse prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
Being adjusted to by laser parameter in embodiment 3 step (2): mean power is 35W, pulse frequency is 200kHz, swashs
Light deflected trajectory is reticule, and distance between centers of tracks is 50 μm, and scanning speed is 500mm/s, multiple scanning 30 times, and remaining condition is constant,
Experimental result is as follows:
Fig. 7 (a) is the scanning electron microscope (SEM) photograph of the micro nano structure that block copper surface obtains after laser irradiation, as seen from the figure,
Obtain on the surface of block copper is the feature structure that is intervally arranged of oval shuttle shape structural cycle, and the length of shuttle is about 30 μ
M, width is about 15 μm, and the arrangement cycle is about 50 μm, is coated with ripple and the granule knot of submicron on the surface of shuttle shape structure
Structure.
Fig. 7 (b)～(d) are respectively micro nano structure scanning electron microscope (SEM) photograph after thermal oxide, as seen from the figure, through thermal oxide
After, bear CuO nano thread structure, and the sidewall of shuttle shape structure from the surface in situ of shuttle shape structure, i.e. directly sweep through laser
Retouching the region processed, nanowire growth is the most flourishing, and the top nanowire growth of shuttle shape structure is less-developed, CuO nano wire
Vertical with the sidewall of shuttle shape structure, length is about 1～20 μm.
Embodiment 8, femtosecond pulse prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
Being adjusted to by laser parameter in embodiment 3: mean power is 15W, pulse frequency is 200kHz, laser deflection rail
Mark is reticule, and distance between centers of tracks is 30 μm～50 μm, and scanning speed is 500mm/s, multiple scanning 30 times, and remaining condition is constant, real
Test result as follows:
Fig. 8 (a)～Fig. 8 (c) is respectively distance between centers of tracks 30 μm, and under 40 μm and 50 μm, after laser irradiation, block copper surface obtains
The scanning electron microscope (SEM) photograph of micro nano structure, as seen from the figure, obtain on the surface of block copper is that micron is protruding and micron hole week
The feature structure that phase is intervally arranged, the protruding width of micron is about 20～50 μm, height is about 20～50 μm, micron hole straight
Footpath is about 10 μm, the degree of depth is about 50 μm；It is coated with ripple and the grain structure of submicron on the surface that micron is protruding, works as distance between centers of tracks
Being respectively 30 μm, 40 μm, during 50 μm, the cycle of micron projection is respectively 30 μm, 40 μm, 50 μm.
Fig. 8 (d)～Fig. 8 (i) is respectively micro nano structure scanning electron microscope (SEM) photograph after thermal oxide, as seen from the figure, from micron
Protruding surface in situ bears CuO nano thread structure, and such as Fig. 8 (d), 8 (e), 8 (f) is shown, and the sidewall that micron is protruding, i.e. warp
The region that the direct scan process of laser is crossed, nanowire growth is the most flourishing, and the top nanowire growth of micron projection is in confused situation
Aobvious, CuO nano wire is vertical with the sidewall of micron projection, and length is about 1～20 μm, as shown in Fig. 8 (g), Fig. 8 (h) and Fig. 8 (i).
Embodiment 9, femtosecond pulse prepare Cu surface micronano precursor construction, and to realize CuO pattern of nanowires metaplasia long
Being adjusted to by laser parameter in embodiment 3: mean power is 15W, pulse frequency is 200kHz, laser deflection rail
Mark is helix, and distance between centers of tracks is 50 μm, and scanning speed is 500mm/s, and multiple scanning 30 times, remaining condition is constant, experimental result
As follows:
Obtain on the surface of block copper is the feature structure that is helically intervally arranged of micron trenches, the width of micron trenches
Being about 50 μm, the degree of depth is about 50 μm；After thermal oxide, bear CuO nano thread structure, nano wire in situ from the inner wall surface of groove
Vertical with the inwall of groove, length is about 1～30 μm, the inwall of groove, the region i.e. crossed, nanometer through the direct scan process of laser
Line growth is the most flourishing, and the scanning electron microscope (SEM) photograph of its different amplification is respectively such as Fig. 9 (a), Fig. 9 (b), Fig. 9 (c) and Fig. 9 (d) institute
Show.
Embodiment 10, femtosecond pulse are prepared Cu surface micronano precursor construction and are realized CuO pattern of nanowires metaplasia
Long
(1) remove the oxide layer on Cu surface with grinding method, and make its surface reach certain fineness, then use ethanol
Clean Cu surface.
(2) femtosecond pulse selected, centre wavelength is 1064nm, and pulsewidth is 800 femtoseconds, and laser beam realizes through galvanometer
Deflection, then focuses on rectangular blocks copper surface through the scene that focal length is 100mm, and focused spot diameter is 30 μm, the area of block copper
For 25mm × 25mm, thickness is 3mm.
Laser parameter is: mean power is 5W, and pulse frequency is 200kHz, and laser deflection track is
TSINGHUAUNIVERSITY font, font is internal uses reticule to fill, and filling distance between centers of tracks is 30 μm, and deflection speed is
500mm/s, multiple scanning 30 times.
(3) using tubular type hot plate, oxidizing atmosphere is air, and heating rate is 10 DEG C/min, and holding temperature is 500
DEG C, temperature retention time is 2h, and after insulation terminates, sample cools to room temperature with the furnace, takes out afterwards from heating furnace.
After thermal oxide, the region that the TSINGHUA UNIVERSITY font that Cu plate surface is lasered out is covered
Retain complete, the region crossed without laser treatment, the effect of the thermal stress owing to being formed in thermal oxidation process, there occurs peeling and
Peel off, shown in its photo such as Figure 10 (a)；Amplifying observation finds, font region defines micro nano structure, such as Figure 10 (b), Figure 10
Shown in (d) and Figure 10 (f), and CuO nano wire, nano wire and micro nano structure are born in situ from the matrix of micro nano structure
Sidewall vertical, length is about 1～10 μm, as shown in Figure 10 (c) and Figure 10 (e)；And without the region of laser treatment, surface is not
See nanowire growth, as shown in Figure 10 (g).
Claims (7)
1. a controllable patterned ultrafast laser composite preparation process for metal oxide nano-wire, comprises the following steps:
(1) according to the pattern being pre-designed, with the surface of ultrafast laser irradiation bulk metal, obtain on the surface of described bulk metal
To the micro nano structure of patterning, i.e. metal oxide nano-wire presoma；
Described metal-oxide is CuO, Cu2O、ZnO、TiO2、MgO、Fe2O3、WO3Or WOx；
Described bulk metal is block copper, block zinc, block titanium, block magnesium, block ferrum or block tungsten, the thickness of described bulk metal
Degree is 10 μm～1cm；
Described ultrafast laser is infrared light, visible ray or ultraviolet light；
The pulse width of described ultrafast laser is 50 femtoseconds～20 psecs, and pulse frequency is 1KHz～4MHz, and mean power is 1W
～400W；
(2) under oxidizing atmosphere, heating is attached with the bulk metal of described metal oxide nano-wire presoma and is incubated, cooling
After i.e. on described metal oxide nano-wire presoma growth in situ go out described metal oxide nano-wire；
During described heating, described metal oxide nano-wire presoma is placed in heat-resisting bateau, the material of described heat-resisting bateau
For quartz or aluminium sesquioxide；
During described heating, heating rate is 1～10 DEG C/min；
The temperature of described insulation is 400～600 DEG C, and the time is 5min～5 days；
Described be cooled to furnace cooling or from stove take out after force cooling.
Preparation method the most according to claim 1, it is characterised in that: described preparation method before ultrafast laser irradiation,
Also include the step removing the metal-oxide on the surface of described bulk metal.
Preparation method the most according to claim 1 and 2, it is characterised in that: in step (1), described irradiation is by following
1), 2) or 3) in mode carry out:
1) single-point irradiation；
2) vibration mirror scanning；
3) vibration mirror scanning coordinates with numerical control X-Y platform.
Preparation method the most according to claim 3, it is characterised in that: in described single-point irradiation, irradiated area is not less than 100
μm2；
Described vibration mirror scanning is following 1) or 2):
1) scanning pattern of described vibration mirror scanning is parallel lines, reticule or helix；The sweep span of described vibration mirror scanning is 1
μm～100 μm, scanning speed is 1mm/s～10m/s；
2) scanning pattern of described vibration mirror scanning is dot matrix；The dot spacing of described vibration mirror scanning is 1 μm～100 μm, single-point effect
Umber of pulse is 1～2 × 106。
Preparation method the most according to claim 4, it is characterised in that: in step (1), described micro nano structure is micron knot
Structure, nanostructured or micro-nano pair of yardstick composite construction；
Described micrometer structure is micron projection and/or micron pit, described micrometer structure regular distribution or random distribution；
Described nanostructured is the Cluster Structures of nanometer ripple, nano-particle or nano-particle；
Described micro-nano pair of yardstick composite construction is self-assembly of in and/or described micron pit surface protruding at described micron
Composite construction after nanometer ripple, nano-particle or nano-particle cluster.
6. the metal oxide nano-wire of patterning prepared by method described in any one of claim 1-5.
The metal oxide nano-wire of patterning the most according to claim 6, it is characterised in that: described metal-oxide is received
Rice noodle is tapered, a diameter of 10～500nm, a length of 1～50 μm；
Described metal oxide nano-wire is vertical with the surface of described metal oxide nano-wire presoma.
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| CN109794686A (en) * | 2019-03-19 | 2019-05-24 | 北京理工大学 | Femtosecond laser enhances thermal oxidation process and prepares multifunctional electrodes |
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| CN110136782B (en) * | 2019-05-28 | 2021-01-12 | 北京科技大学 | Construction method of metal oxide cluster structure model |
| CN112358292B (en) * | 2020-11-11 | 2023-03-10 | 武汉理工大学 | Preparation method of metal oxide ceramic with three-dimensional nanostructure |
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