CN105621353B - A kind of large-area nano graphic method based on multi-layered anode alumina formwork - Google Patents
A kind of large-area nano graphic method based on multi-layered anode alumina formwork Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000009415 formwork Methods 0.000 title claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 25
- 230000002146 bilateral effect Effects 0.000 claims abstract description 21
- 239000002086 nanomaterial Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000000059 patterning Methods 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 239000011368 organic material Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910002601 GaN Inorganic materials 0.000 claims description 2
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 238000002061 vacuum sublimation Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 229910010271 silicon carbide Inorganic materials 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 23
- 238000006073 displacement reaction Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 22
- 229910052709 silver Inorganic materials 0.000 description 22
- 239000004332 silver Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 15
- 239000004926 polymethyl methacrylate Substances 0.000 description 15
- 239000010409 thin film Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005566 electron beam evaporation Methods 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 238000001883 metal evaporation Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 238000007743 anodising Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000609 electron-beam lithography Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- -1 Kong Zhi Footpath Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
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- 230000035515 penetration Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
- B82B3/0014—Array or network of similar nanostructural elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B1/001—Devices without movable or flexible elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
- B82B3/0019—Forming specific nanostructures without movable or flexible elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physical Vapour Deposition (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a kind of large-area nano graphic method based on multi-layered anode alumina formwork, is that first multilamellar bilateral AAO template is stacked, is transferred on target substrate；It is deposited with the material prepared needed for nanostructured again to the substrate surface for covering multilamellar AAO template；Then multilamellar AAO template is removed, that is, obtains the nano-structure array for patterning.The method of the present invention can be by the selection to different types of bilateral AAO template, by the structure of control levels AAO, relative position, the hole/wall size of levels AAO perforated membrane, relative displacement, relative rotation angle, or by way of adjusting multilamellar bilateral AAO template stacking, so as to obtain different large area（Square centimeter level）The very abundant complex pattern with nano-grade size of structure nanostructured.And this method preparation condition is simple, low cost, it is not necessary to complicated equipment, it is easy to operate, it is adaptable to scale industry application.
Description
Technical field
The invention belongs to technical field of nanometer material preparation.Aluminum dipping form is aoxidized based on multi-layered anode more particularly, to a kind of
The large-area nano graphic method of plate.
Background technology
Graphically（patterning）Technology is an important ring of micro-nano technology.In existing graphic method, photoengraving
Technology equipment needed thereby is prohibitively expensive, and is limited to the restriction of optical wavelength, its resolution 100nm following characteristics chis difficult to realize
Very little is graphical.And electron beam lithography and ion beam etching, to realize 10nm characteristic sizes, cost is equally very high.Nanometer
Although requirement of the stamping technique to equipment decrease, but the motherboard of its 10nm level makes also sufficiently expensive, and with spy
The decline of size is levied, its knockout course is difficult increasingly.
Single layered porous anodised aluminium（AAO）It is usually used in the mask plate of all kinds of depositions, 20nm or so feature chis can be prepared
Very little six square array of hemispherical/column；Its cost of manufacture is relatively low, is also easy to realize prepared by large area.But, the pattern of making is too
It is single, six square array of hemispherical/column can only be prepared；Meanwhile, its characteristic size is limited to the wall thickness of perforated membrane（20nm or so）,
It is inoperable that thinner wall will cause template strength to be reduced to.
The content of the invention
The technical problem to be solved in the present invention is for the nano patterning method such as photoetching process, EBL, FIB in prior art
It is difficult to depart from the problem of the expensive input such as ultra-clean chamber and complex device, there is provided a kind of micro-nano graphic method, specifically carries
A kind of preparation regulation and control method and its application at the graphical aspect of large-area nano for double-deck AAO templates.The method is a kind of
Without the low-cost large-area nano patterning method of ultra-clean chamber equipment, the method is by being superimposed bilayer AAO perforated membranes, and tune
Displacement and angle between control film and film, can realize that nanostructure shape and size, gap size, symmetry and cycle are adjustable；
Its gap size minimum can realize 1nm, be that a kind of easy to operate, expansibility is strong thus extremely have a kind of promising new skill
Art.
It is an object of the invention to provide a kind of large-area nano graphic method based on bilayer anode alumina formwork.
Another object of the present invention is to provide the large-area nano graphic method based on multi-layered anode alumina formwork
Preparing nano material and the application in nanostructured.
Another object of the present invention is to provide the nano material or nanostructured prepared according to said method.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of large-area nano graphic method based on multi-layered anode alumina formwork, comprises the steps：
S1. multilamellar bilateral AAO template is stacked, is transferred on target substrate；
S2. the material prepared needed for nanostructured is deposited with to the substrate surface for covering multilamellar AAO template；
S3. multilamellar AAO template is removed, that is, obtains the nano-structure array for patterning.
The method can by the selection to different types of bilateral AAO template, by control levels AAO structure and
Relative position, or by way of adjusting multilamellar bilateral AAO template stacking, so as to obtain different complicated and abundant patterns
Change nanostructured.
Such as：When bilateral AAO template used is that hole arranges the AAO templates of long-range order, finally obtained on substrate
The patterned structures for obtaining are by the structure ginseng such as the size in the hole for separately adjusting levels AAO, cycle and template thickness
Number, and the relative position of regulation and control levels AAO is realizing.The control methods of the relative position include controlling two-layer AAO
Relative rotation angle and relative displacement.Can be obtained similar to the same complicated figure of kaleidoscope by this simple mode
Case.
When bilateral AAO template used is the AAO template or the AAO for hole arrangement shortrange order that hole arranges long-range order
During template, the thickness for controlling the hole wall of upper strata AAO templates is about 10nm, just can obtain distribution density in substrate surface high
Nanostructured of the gap less than 10nm, and a big chunk gap is less than 5nm.
Used as a kind of preferred embodiment, multilamellar described in step S1 is two-layer.Specifically：
S1. two-layer bilateral AAO template is stacked, is transferred on target substrate；
S2. the material prepared needed for nanostructured is deposited with to the substrate surface for covering two-layer AAO template；
S3. two-layer AAO template is removed, that is, obtains the nano-structure array for patterning.
Wherein, the two-step anodization or nano impression that the preparation method of the AAO templates can be traditional is aided in
One-step oxidation process.
Further, since AAO templates are very thin, in order to improve the success rate of transfer, can coat one layer in AAO template surfaces has
Machine macromolecular material supporting layer, as support, is polymethyl methacrylate than more typical macromolecular material.Two-layer is carried
The AAO thin film of supporting layer is stacked and is positioned over substrate, obtains being close to substrate after then removing polymeric backing layer
The double-deck AAO templates on surface.The method for removing polymeric backing layer is mainly organic solvent dissolution method and heat resolve method.Example
Such as, when using polymethyl methacrylate, during nitrogen protection atmosphere can be placed it in, 10min is incubated i.e. at 400 DEG C
Can.Here, the diameter in the hole of two-layer AAO template, arrangement mode, cycle, template thickness be able to can also be differed with identical.
Preferably, the method for shifting described in step S1 is：One layer of high-molecular organic material is coated in AAO template surfaces to support
Multilamellar after ultra-thin bilateral AAO template shearing with high-molecular organic material supporting layer is stacked, is placed as supporting by layer
On target substrate；Then the method for passing through organic solvent or heating in an inert atmosphere removes high-molecular organic material
Support layer, leaves multilamellar AAO and is close to substrate surface.
Preferably, the high-molecular organic material supporting layer is polymethyl methacrylate or polystyrene；It is described organic
Solvent is at least one in acetone, dichloromethane or chloroform.
Preferably, the high-molecular organic material supporting layer be polymethyl methacrylate, the removing organic polymer
The method of materials for support layer is that 400～1000 DEG C are heated in nitrogen atmosphere, is incubated 10～60 minutes.
It is highly preferred that the method for removing high-molecular organic material supporting layer is that 400 DEG C are heated in nitrogen atmosphere
Insulation 10 minutes.
Preferably, substrate described in step S1 is simple glass, ito glass, FTO glass, quartz glass, silicon, sapphire, carbon
SiClx or gallium nitride.
Preferably, the method being deposited with described in step S2 is electron-beam vapor deposition method, Vacuum sublimation or magnetron sputtering method.
Preferably, material required described in step S2 can be metal.But it is not limited to metal material, or chemical combination
Thing quasiconductor or insulating material.
Preferably, the thickness of AAO templates described in step S1 is 50～1000nm；The hole of described multilamellar AAO template it is straight
Footpath, arrangement mode, cycle, template thickness be able to can also be differed with identical.
Additionally as a kind of preferable embodiment, the lower floor AAO for being adopted can be substituted with other foraminous die plates, example
Such as organic porous films.
In addition, the control of the relative rotation angle and relative position translation for levels AAO, can first prepare long-range
Orderly AAO, then random two superimposed, prepares selection of then classifying again after patterning nano material array.Double-deck AAO
During metal nano array prepared by method, if as it was previously stated, upper strata AAO wall thickness about 10nm, can obtain less than 10nm's
Gap, if 10nm gaps need not be less than, upper strata AAO wall thickness can be with thick.
According to the nanostructured that said method is prepared, also all should be within protection scope of the present invention.
The main innovation point of the present invention is to utilize multilamellar（It is double-deck）The superposition of AAO perforated membranes, can construct varied
The nano-pattern enriched such as kaleidoscope, can realize prepared by abundant nanostructured as template using it.Enable in particular to prepare
Possesses the ratio of the nano-metal particle and its high density arrays at big major diameter and extremely sharp tip.And due to the levitation effect on upper strata,
The minimal clearance of 1～5 nm is capable of achieving, this gap is present in above-specified high density array in a large number, is obtained in that great local
Electric-field enhancing, obtains all kinds of excellent and peculiar nonlinear optical/electrical effects.Importantly, utilizing this method, these are highly dense
Degree array can be obtained at low cost with large area, it is easy to accomplish scale application.
Therefore, on the premise of the flesh and blood without departing from the present invention, thinking and spirit, what those skilled in the art were done
Combination, replacement and improvement also all should be within protection scope of the present invention.The preparation of multi-layer porous AAO films is can be extended to such as,
So as to realize more applications, including：All spaces inside filling multilayer AAO, so as to obtain a kind of mesoporous metal of three-dimensional
Nanostructured, this structure may have been applied in Meta Materials.Metal Nano structure is not necessarily for another example, and multilamellar AAO can
To expand to the nanostructured of other side.With multilamellar AAO as skeleton, deposit in its inner wall surface or coat other nanometer of material
Material, so as to form loose structure.One layer of carbon is such as deposited, is used as electrode of super capacitor.
The invention has the advantages that：
（1）The present invention is by the hole to levels AAO perforated membrane/wall size, relative displacement, the regulation and control of relative rotation angle
Can realize such as a kaleidoscope of abundant nano-pattern.If using the AAO of long-range order, and upper and lower two-layer can be controlled
The relative position and relative angle of AAO, because the pore structure of AAO is nano-grade size, then can easily obtain big
Area（Square centimeter level）The very abundant complex pattern with nano-grade size of structure, as shown in Figures 1 to 3, give
Several typical patternings.If these patterns adopt EBL or FIB to prepare and take very much, area is little, and cost is very high；And
AAO templates but can be prepared with aspect fast and low-cost.
（2）The present invention passes through multilamellar（It is double-deck）AAO perforated membranes do mask, can realize that large area is highly dense by deposition or evaporation
The special-shaped nano-grain array of degree.Different from the spheroidal particle obtained by monofilm AAO perforated membranes, double-deck AAO perforated membranes are obtained
Particle aspect ratio greatly improve, tip it is especially sharp keen, for improve local electric field effect it is obvious.As shown in Figure 4 and Figure 5.
（3）The present invention is supported by lower floor's AAO perforated membranes, can be by the hole wall of upper layer film than do thinner of monolayer
Remain in that the transferability of whole template.Upper layer film has thinner hole wall and hanging two major features, can coordinate electron beam
Evaporation is deposited, and obtains nanostructured of the large area gap between 1～5 nm.As shown in Fig. 4 and Fig. 5, in nano-particle
Between gap be due to metallic vapour as substrate deposition when, be close to substrate surface lower floor AAO hold up upper strata AAO holes
The stop of wall, part metals steam bypass the bottom of hanging AAO hole walls, are smaller in size than upper strata so as to define on substrate
The extremely narrow gap of AAO pore wall thicknesses.Such small―gap suture can also produce extremely strong local electric field, and be different from granule tip or
The extremely strong local electric field that edge is formed is confined in the little space at tip or edge, and this small―gap suture local electric field can be whole
All it is distributed in gap, increases effective active area.
（4）Method of the present invention preparation condition is simple, low cost, it is not necessary to complicated equipment, it is easy to operate, it is adaptable to advise
Modelling industry application.
Description of the drawings
Fig. 1 is some the very typical examples by double-deck AAO film preparations patterned nanostructure.（a）For bilayer
The schematic three dimensional views that AAO templates are superimposed, in figure, the aperture of upper and lower two-layer AAO, pitch of holes, hole arrangement mode, template are thick
Degree is all identical, and pitch of holes is a, and two-layer template is all of Kong Junzheng pair, does not rotate against and translates, when carrying out one
It is fixed when rotating against or translating, it is possible to obtain the same pattern of complicated similar kaleidoscope.The white portion of pattern is
The substrate surface that bilayer AAO templates spill is crossed, when follow-up nano material grows, nanostructured will be formed in these regions.It is right
In upper and lower double-layer structure identical AAO, relative to lower floor AAO, by upper former（b）Do not translate,（c）To right translation a/3,（d）
To right translation a/2, a/ √ 3a are translated downwards,（e）15 ° are turned clockwise,（f）30 ° are turned clockwise,（g）Turn clockwise 45 °
The pattern for being obtained afterwards.When upper strata AAO apertures are slightly less than lower floor aperture, upper strata AAO is relative to lower floor AAO（h）Dextrorotation
Turn 30 °,（i）Do not translate and do not rotate obtained pattern.（k）When upper strata AAO apertures are about less than the 1/3 of lower floor aperture, on
Layer AAO is not translated relative to lower floor AAO and is not rotated obtained pattern.
In Fig. 2（b）It is that the parallel silver nanoparticle that electron-beam vapor deposition method is prepared on silicon chip is combined by double-deck AAO templates
Grain is schemed to the SEM of array,（a）It is the SEM figures of the corresponding double-deck AAO templates of the pattern；Two-layer AAO structure is identical, upper strata AAO phases
For lower floor AAO is shifted the distance of general a/2.
In Fig. 3（c）Be by double-deck AAO templates combine electron-beam vapor deposition method prepare on silicon chip with petal-shaped pattern
Silver nano-grain the SEM of array is schemed,（a）It is the SEM figures of the corresponding double-deck AAO templates of the pattern；Two-layer AAO structure phase
Together, upper strata AAO has turned clockwise general 30 ° relative to lower floor AAO.
Fig. 4 is the silver nano-grain for adopting bilayer AAO templates to prepare on silicon chip to two in array typical silver
Grain to TEM figure；The gap length of granule pair can more accurately be measured using TEM tests.（A, b）Shown granule is to gap point
It is not 5nm and 1nm.
Fig. 5 be using bilayer AAO templates prepare on silicon chip by the consitutional TEM of three silver nano-grains
Figure, herein referred to as " trimer ".In the trimer, three gaps are 7nm, 4nm and 3nm respectively.
Specific embodiment
The present invention, but embodiment are further illustrated below in conjunction with Figure of description and specific embodiment not to the present invention
Limit in any form.Unless stated otherwise, the reagent for adopting of the invention, method and apparatus are routinely tried for the art
Agent, method and apparatus.
Unless stated otherwise, agents useful for same of the present invention and material are commercial.
The method of the present invention can pass through the bilayer a variety of patterned nanostructures of AAO film preparations, as shown in figure 1,
Fig. 1 is some the very typical examples by double-deck AAO film preparations patterned nanostructure.In figure,（a）For double-deck AAO
The schematic three dimensional views that template is superimposed, in figure, the aperture of upper and lower two-layer AAO, pitch of holes, hole arrangement mode, template thickness be all
It is identical, pitch of holes is a, and two-layer template is all of Kong Junzheng pair, does not rotate against and translates, it is certain when carrying out
When rotating against or translating, it is possible to obtain the same pattern of complicated similar kaleidoscope.The white portion of pattern is through double
The substrate surface that layer AAO templates spill, when follow-up nano material grows, will form nanostructured in these regions.For upper
Lower double-layer structure identical AAO, relative to lower floor AAO, by upper former（b）Do not translate,（c）To right translation a/3,（d）To the right
Translation a/2, translates downwards a/ √ 3a,（e）15 ° are turned clockwise,（f）30 ° are turned clockwise,（g）Turn clockwise institute after 45 °
The pattern of acquisition.When upper strata AAO apertures are slightly less than lower floor aperture, upper strata AAO is relative to lower floor AAO（h）Turn clockwise
30 °,（i）Do not translate and do not rotate obtained pattern.（k）When upper strata AAO apertures are about less than the 1/3 of lower floor aperture, upper strata
AAO is not translated relative to lower floor AAO and is not rotated obtained pattern.
Below with specific embodiment illustrating the method for the present invention.
Embodiment 1
The present embodiment prepares silver nano-grain array, and step is as follows：
S1. two-layer identical AAO porous membrane is stacked, is fitted with clean silicon substrate.Wherein AAO porous is thin
Film be using nano impression combine anodizing prepare hole arrange long-range order bilateral porous membrane, bore dia, Kong Jian
Away from and template thickness be respectively 90nm, 100nm and 150nm, it is thin that AAO template surfaces are coated with a strata methyl methacrylate
Film is used as support.During stacking, make upper strata AAO that the length in about half hole cycle is translated relative to lower floor AAO.
S2. the silicon substrate for being coated with polymethyl methacrylate film/AAO thin film prepared in S1 has been placed on nitrogen to protect
10min is heated in the quick anneal oven of shield under conditions of 400 DEG C, the polymethyl methacrylate on AAO surfaces is completely removed,
Its SEM figure such as Fig. 2（a）It is shown.
S3. the substrate that surface is coated with double-layer porous template is put into into the sample stage in the growth chamber of electron beam evaporation instrument
On, ensure crucible of the normal of substrate plane just to placement metal evaporation sources after placement.Purity is not less than into 99.99% silver-colored material
Material is placed in crucible, and growth intracavity vacuum is less than 8 × 10-6Torr；Sedimentation rate is 0.1nm/s, and deposit thickness is 25nm；It is heavy
Product obtains silver nano-grain array, pattern such as Fig. 2 after removing foraminous die plate with adhesive tape after terminating（b）It is shown.What is obtained is phase
Mutually parallel silver nanoparticle is to array.
Embodiment 2
The present embodiment prepares silver nano-grain array, and step is as follows：
S1. two-layer identical AAO porous membrane is stacked, is fitted with clean silicon substrate.Wherein AAO porous is thin
Film be using nano impression combine anodizing prepare hole arrange long-range order bilateral porous membrane, bore dia, Kong Jian
Away from and template thickness be respectively 90nm, 100nm and 130nm, it is thin that AAO template surfaces are coated with a strata methyl methacrylate
Film is used as support.During stacking, upper strata AAO is made to rotate about 30 ° relative to lower floor AAO.
S2. the silicon substrate for being coated with polymethyl methacrylate film/AAO thin film prepared in S1 is put in acetone,
The polymethyl methacrylate on AAO surfaces is completely removed, its SEM figure such as Fig. 3（a）It is shown.
S3. the substrate that surface is coated with double-layer porous template is put into into the sample stage in the growth chamber of electron beam evaporation instrument
On, ensure crucible of the normal of substrate plane just to placement metal evaporation sources after placement.Purity is not less than into 99.99% silver-colored material
Material is placed in crucible, and growth intracavity vacuum is less than 8 × 10-6Torr；Sedimentation rate is 0.1nm/s, and deposit thickness is 20nm；It is heavy
Product obtains silver nano-grain array, pattern such as Fig. 3 after removing foraminous die plate with adhesive tape after terminating（b）It is shown.What is obtained is tool
There is the silver nano-grain array of similar petal arrangement.
Embodiment 3
The present embodiment prepares silver nano-grain array, and step is as follows：
S1. two-layer identical AAO porous membrane is stacked, with clean quartz glass substrate attaching.Wherein AAO
Porous membrane be using nano impression combine anodizing prepare hole arrange long-range order bilateral porous membrane, Kong Zhi
Footpath, pitch of holes and template thickness are respectively 90nm, 100nm and 130nm, and AAO template surfaces are coated with a strata metering system
Sour methyl ester thin film is used as support.During stacking, make upper strata AAO that the length in about half hole cycle is translated relative to lower floor AAO.
S2. the silicon substrate for being coated with polymethyl methacrylate film/AAO thin film prepared in S1 is put in acetone,
The polymethyl methacrylate on AAO surfaces is completely removed.
S3. the substrate that surface is coated with double-layer porous template is put into into the sample stage in the growth chamber of electron beam evaporation instrument
On, ensure crucible of the normal of substrate plane just to placement metal evaporation sources after placement.Purity is not less than into 99.99% silver-colored material
Material is placed in crucible, and growth intracavity vacuum is less than 8 × 10-6Torr；Sedimentation rate is 0.1nm/s, and deposit thickness is 25nm；It is heavy
Product obtains silver nano-grain to array after removing foraminous die plate with adhesive tape after terminating.The gap of each silver nano-grain centering is equal
Less than 10nm, about 5nm or so, such as Fig. 4（a）, some gaps are 1nm, such as Fig. 4（b）It is shown.
Embodiment 4
The present embodiment prepares silver nano-grain array, and step is as follows：
S1. two-layer identical AAO porous membrane is stacked, is fitted with clean silicon substrate.Wherein AAO porous is thin
Film be using nano impression combine anodizing prepare hole arrange long-range order bilateral porous membrane, bore dia, Kong Jian
Away from and template thickness be respectively 90nm, 100nm and 130nm, it is thin that AAO template surfaces are coated with a strata methyl methacrylate
Film is used as support.During stacking, upper strata AAO is made to rotate about 30 ° relative to lower floor AAO.
S2. the silicon substrate for being coated with polymethyl methacrylate film/AAO thin film prepared in S1 has been placed on nitrogen to protect
10min is heated in the quick anneal oven of shield under conditions of 400 DEG C, the polymethyl methacrylate on AAO surfaces is completely removed.
S3. the substrate that surface is coated with double-layer porous template is put into into the sample stage in the growth chamber of electron beam evaporation instrument
On, ensure crucible of the normal of substrate plane just to placement metal evaporation sources after placement.Purity is not less than into 99.99% silver-colored material
Material is placed in crucible, and growth intracavity vacuum is less than 8 × 10-6Torr；Sedimentation rate is 0.1nm/s, and deposit thickness is 25nm；It is heavy
Product obtains silver nano-grain array after removing foraminous die plate with adhesive tape after terminating.Exist in the array for being formed much by three
The structure of grain composition, referred to as " trimer ".There are three extremely narrow gaps in silver-colored Trimeric structures, as shown in figure 5, typical for one
The TEM figures of trimer, gap is in below 10nm.
Embodiment 5
The present embodiment prepares silver nano-grain array, and step is as follows：
S1. two-layer identical AAO porous membrane is stacked, is fitted with clean silicon substrate.Wherein AAO porous is thin
Film is the bilateral porous membrane that shortrange order is arranged using hole prepared by traditional two-step penetration method, bore dia, pitch of holes and
Template thickness is respectively 90nm, 100nm and 200nm, and AAO template surfaces are coated with one layer of polymethyl methacrylate film conduct
Support.
S2. the silicon substrate for being coated with polymethyl methacrylate film/AAO thin film prepared in S1 has been placed on nitrogen to protect
10min is heated in the quick anneal oven of shield under conditions of 400 DEG C, the polymethyl methacrylate on AAO surfaces is completely removed.
S3. the substrate that surface is coated with double-layer porous template is put into into the sample stage in the growth chamber of electron beam evaporation instrument
On, ensure crucible of the normal of substrate plane just to placement metal evaporation sources after placement.Purity is not less than into 99.99% silver-colored material
Material is placed in crucible, and growth intracavity vacuum is less than 8 × 10-6Torr；Sedimentation rate is 0.1nm/s, and deposit thickness is 20nm；It is heavy
Product obtains silver nano-grain array after removing foraminous die plate with adhesive tape after terminating.Have as upper and lower two-layer AAO hole is arranged as short distance
Sequence, so the pattern of the silver nano-grain array for being formed is the combination of structure shown in similar Fig. 1 b-h, every kind of pattern point
Cloth region is several square microns to tens square microns.The arrangement of pattern have no effect on silver nanoparticle to and silver-colored trimer in the middle of
The size of gap, in below 10nm, what is had is narrow to 1nm for the silver nanostructured internal clearance for being obtained.
Embodiment 6
The present embodiment prepares silver nano-grain array, and step is as follows：
S1. two-layer identical AAO porous membrane is stacked, with clean ito glass substrate attaching.Wherein AAO
Porous membrane be using nano impression combine anodizing prepare hole arrange long-range order bilateral porous membrane, Kong Zhi
Footpath, pitch of holes and template thickness are respectively 80nm, 100nm and 300nm, and AAO template surfaces are coated with strata styrene work
To support.During stacking, make upper strata AAO that the length in about half hole cycle is translated relative to lower floor AAO.
S2. the silicon substrate for being coated with polystyrene film/AAO thin film prepared in S1 is put in acetone, AAO surfaces
Polystyrene is completely removed.
S3. the substrate that surface is coated with double-layer porous template is put into into the sample stage in the growth chamber of electron beam evaporation instrument
On, ensure crucible of the normal of substrate plane just to placement metal evaporation sources after placement.Purity is not less than into 99.99% golden material
Material is placed in crucible, and growth intracavity vacuum is less than 8 × 10-6Torr；Sedimentation rate is 0.1nm/s, and deposit thickness is 25nm；It is heavy
Product obtains gold nano grain array after removing foraminous die plate with adhesive tape after terminating.
Claims (8)
1. a kind of large-area nano graphic method based on multi-layered anode alumina formwork, it is characterised in that including following step
Suddenly：
S1. two-layer bilateral AAO template is stacked, is transferred on target substrate；
S2. the material prepared needed for nanostructured is deposited with to the substrate surface for covering two-layer AAO template；
S3. two-layer AAO template is removed, that is, obtains the nano-structure array for patterning；
In preparation process, by the selection to different types of bilateral AAO template, by control levels AAO structure and
Relative position, or by way of adjusting two-layer bilateral AAO template stacking, so as to obtain different complicated and abundant patterns
Change nanostructured.
2. method according to claim 1, it is characterised in that the method shifted described in step S1 is：In AAO template surfaces
One layer of high-molecular organic material supporting layer of coating will carry the bilateral AAO template of high-molecular organic material supporting layer as support
After shearing, two is stacked together, is positioned on target substrate；Then pass through organic solvent or heat in an inert atmosphere
Method removes high-molecular organic material supporting layer, leaves two-layer AAO and is close to substrate surface.
3. method according to claim 2, it is characterised in that the high-molecular organic material supporting layer is polymethyl
Sour methyl ester or polystyrene；The organic solvent is at least one in acetone, dichloromethane or chloroform.
4. method according to claim 2, it is characterised in that the high-molecular organic material supporting layer is polymethyl
Sour methyl ester, the method for the removing high-molecular organic material supporting layer are that 400～1000 DEG C are heated in nitrogen atmosphere, insulation
10～60 minutes.
5. method according to claim 1, it is characterised in that the method being deposited with described in step S2 be electron-beam vapor deposition method,
Vacuum sublimation or magnetron sputtering method.
6. method according to claim 1, it is characterised in that substrate described in step S1 is simple glass, ito glass, FTO
Glass, quartz glass, silicon, sapphire, carborundum or gallium nitride.
7. method according to claim 1, it is characterised in that the thickness of AAO templates described in step S1 is 50～1000nm；
The lower floor AAO in two-layer bilateral AAO template described in step S1 can be substituted with organic porous films.
8. the nanostructured for being prepared according to the arbitrary methods described of claim 1～7.
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| CN108417475B (en) * | 2018-01-27 | 2020-07-03 | 安徽师范大学 | Preparation method of metal nanostructure array based on interface induced growth |
| CN109504994B (en) * | 2018-12-13 | 2020-08-21 | 上海科技大学 | Novel anodic aluminum oxide template and preparation method of nano array |
| CN111574216B (en) * | 2020-05-29 | 2021-07-23 | 河南大学 | Li1.4Al0.4Ti1.6(PO4)3 solid electrolyte compatible with lithium metal negative electrode and preparation method thereof |
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