CN103526288B - The method of interface interaction induction self assembly high density nano-array - Google Patents
The method of interface interaction induction self assembly high density nano-array Download PDFInfo
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- CN103526288B CN103526288B CN201310470363.7A CN201310470363A CN103526288B CN 103526288 B CN103526288 B CN 103526288B CN 201310470363 A CN201310470363 A CN 201310470363A CN 103526288 B CN103526288 B CN 103526288B
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Abstract
The method of interface interaction induction self assembly high density nano-array, belongs to technical field of nano array preparation.On substrate, deposit thickness is the mould material of 50 500nm；Will be covered with the substrate of mould material, at N2Anneal under atmosphere at 400 DEG C 2h；Then use polymer Protect edge information, directly formed the hole of a size of 10 60nm by the layer of template material on anodic oxidation substrate at substrate surface, form template；In template, deposit thickness is the nano-array material of 10 15nm；At N2Anneal under atmosphere at 400 DEG C 2h；At 200 DEG C, air is annealed 2 hours the most again；Then make in corrosive liquid and mould material is eroded.Present invention large area and economically fabricate density more than 10 in target base plate22/inch2Monolayer nanoparticle array.
Description
Technical field
The invention belongs to technical field of nano array preparation, be specifically related to be made by interface interaction induction self assembly
Method with preparation high density nano-array (NPs).
Background technology
High density nano-array is that particle diameter is less than 20nm, and interparticle distance is the densification of a few nanometer or less
Nano-array (such as dendrite, superparticle, tightly packed nano-array) has critically important at a lot of aspects
Application.Main application has the following aspects: (1) surface enhanced effect, can be used in Raman detection,
As produced the Ag nano dot with height ordered structure, it is used for detecting dyestuff by regular silver nano lattice row
R6G Raman signal, the Raman signal measured is very uniform, and repeatable, and the relative deviation of signal is only
About 13%.Meanwhile, Nano silver grain can also be used for detecting DNA, and detectable limit can reach 10-11M.
(2) magnetics aspect, by being electrodeposited in AAO template by the ferromagnetic materials such as cobalt, iron, nickel, prepares
The nano-wire array of high-sequential.Nano-array has the highest perpendicular magnetic anisotropy, can be as high density
Magnetic storage medium in order, manufactures VHD magnetic memory.(3) optics aspect, utilizes anode oxide film
Light transmission, light absorption, photoanisotropy, the metal particle such as electro-deposition Cu and Au is prepared for receiving wherein
Rice corpuscles and Al2O3Assembly system, its optical absorption measurement is shown, assembly system optical absorption band just year metal
Deposition and size and change, it is achieved thereby that the modulation on optical absorption band limit, can be applicable to the light of different-waveband
Filter.(4) the metal nanometer line beam microelectrode prepared for template with AAO, has that signal to noise ratio is low, electric urges
Change activity high, can be used not only as the positive pole of the excellent second electrode of performance requirement, also organic to some
Little molecule electrocatalytic oxidation has higher activity.(5) solar absorbing film aspect, electricity in AAO template
Deposition nickel, it is thus achieved that the absorbing film to solar selectively, this film has highly desirable selection and inhales solar energy
The property received.These application are all based on the high fine and close high-purity of nano-array, large area, the preparation skill of low cost
Art.
In order to by controlling particle size, grain spacing and three-dimensional arrangement have been developed a lot of complicated physics
And the e-beam lithography art less than 10nm of chemical preparation process, such as latest developments, focus on electronics
Beam forming, self assembly and template manufacture.But, these methods all can not meet large area, low cost simultaneously
Prepare nano-array, therefore we have invented interface interaction induction self assembly this preparation of high density nano-array
Method.
Summary of the invention
In the present invention, we have invented a kind of new manufacture method, meet large area, low cost system simultaneously
Standby high density nano-array.
The method of interface interaction induction self assembly high density nano-array, it is characterised in that comprise the following steps:
(1) on substrate, deposit thickness is the mould material of 50-500nm；Will be covered with the base of mould material
Plate, at N2Anneal under atmosphere at 400 DEG C 2h；
(2) polymer protection step (1) gained substrate edges is then used, by anodic oxidation substrate
Layer of template material directly form the hole of a size of 10-60nm at substrate surface, form template；
(3) in the template of step (2) gained, deposit thickness is the nano-array material of 10-15nm；
(4) product step (3) obtained is at N2Anneal under atmosphere at 400 DEG C 2h；Exist the most again
At 200 DEG C, air is annealed 2 hours；
(5) then make in corrosive liquid mould material is eroded.
The mould material thickness of above-mentioned use is 50-500nm, pattern hole a size of 10-60nm, preferably mould
Plate material thickness is 50-150nm, pattern hole a size of 10-20nm.
Baseplate material has: Si, SiO2, ito glass；The material manufacturing template has Al, Zr, Ti, B, Mg,
Ba, Ta, Sn, La, Pr, Ln, Nd, Gy, Tb, Eu, W, Y, Pb, Ce, Hf, Dy etc., institute's shape
The template composition become is Al2O3, ZrO2, TiO2, B2O3, MgO, BaO, TaO, SnO2, La2O3, Pr6O11,
Ln2O3, Nd2O3, Gy2O3, Tb2O3, Eu2O3, WO, Y2O3, PbO, Ce2O3, HfO2, Dy2O3Deng；Deposition is received
The material simple substance of rice array includes: Au, Ti, Ni, Cr, Co, Fe, Ag, Cu, Zn, Ge, Mn, Pt,
Y, Zr, Nb, Mo, Tc, Rh, Ru, Pd, In, Sn, Sb, Bi, Pb, Fr, Os, Re, W, Ta,
Hf, La, Dy, Pr, Nd, Gy；Metallic compound has: AuGe, CoSm, NdFeB, AlCe, GdFe,
CoLu, TbCo, DyFe, RhYb, PrPd.
When using Al as mould material, by two steps in anodic oxidation solution (oxalic acid solution of 0.3M)
Facture Al layer on different voltages (20-50V) and different temperatures (4-20 DEG C) anodic oxygen substrate
A period of time, (first step time was 10-180s；Second time is 20-600s).First after anodic oxidation,
Dissolving the surface of oxidation by soaking 2-3min the etching agent agent of 45-50 DEG C, wherein etchant solution is
1.8g CrO3The H of+7.9g 85%3PO4After then the 100ml that adds water carries out second time anodic oxidation, by substrate
On AAO be immersed in 3wt.%H3PO4Middle 30-90min, it is possible to form hole on AAO.
The present invention uses a kind of new method to prepare template, and AAO template manufacture before being different from passes through material
Interface interaction between material and AAO template controls self-assembled nanometer particle.In order to improve the metal nano of formation
The degree of crystallinity of particle (such as, Au), to carry out following annealing process: first will before corrosion process
Cover Au AAO template at 400 DEG C, N2Anneal 2 hours under atmosphere, then will cover metal on substrate
AAO template at 200 DEG C in air anneal 2 hours.We with several metals (such as Au, Ni,
Ti) proving that this process can form the nano particles array of densification, such as, the hole dimension of preparation is less than 20nm
Ultra-thin AAO template (less than 150nm).The particle diameter of these nano-arrays from 3.8 ± 1.0nm to
12.5 ± 2.9nm, mean center distance is from 3.5 ± 1.4nm to 7.9 ± 3.3nm, surface density from 5.6 ×
1011NPs/cm2To 1.5 × 1012NPs/cm2, and can be with large area manufacture (about 2cm × 3cm).This
A little nano-arrays can be slightly below several hours (examples of stable existence at a temperature of the fusing point of block materials in temperature
4h can be there is in the NPs such as Au at 800 DEG C), this is critically important to high temperature application, such as VLS mistake
Journey.Such as, fine and close thin nano wire (11.8 ± 2.6nm) can be easy to 12.5 ± 2.9nm Au
NPs obtain as growth catalyst.
The present invention has following several advantage:
(1) so far, the density of AAO pattern hole is limited in 1011/cm2, the size limitation in hole at 20nm, this
Sample also limits size and the surface density of nano-array.Our method can break through this restriction,
Large area and economically fabricate density more than 10 in target base plate22/inch2Monolayer nanoparticle array；
(2) due to the long oxidation process first that Al film is intrinsic, it is difficult to manufacturing hole size by the method for direct oxidation
Less than the orderly AAO template of 20nm, particularly those thickness AAO template less than 150nm.We
Method can overcome fracture, layering and the coming off of Al oxidizing process, do not deposit because of non-pre-deposition simultaneously
At heavy metal interlayer, thus removing barrier layer in the case of not affecting hole dimension, this is for further
Have great importance for different substrate manufactures the compact nanometer array of below 20nm.
(3) matrix material and the interface interaction of AAO template of the present invention are relied on, can be with large area (2cm × 3cm)
Produce mean particle diameter from 3.8 ± 1.0nm to 12.5 ± 2.9nm, average internal edge
Distance is from 3.5 ± 1.4nm to 7.9 ± 3.4nm, and surface density is 5.6 × 1011NPs/cm2Arrive
1.5×1012NPs/cm2NPs particle.Manufacture process includes first deposited the AAO of 150nm
The heat deposition metal level less than 10nm on the Si sheet of template.NPs array can be at slightly below metal level
At a temperature of fusing point in the case of size and internal particle are almost without change several hours of stable existence
(the such as NPs at Au can exist 4 hours at 800 DEG C).
Accompanying drawing explanation
Fig. 1 is the optical photograph of AAO template；
Wherein:
On Figure 1A: embodiment 1 intrinsic (100) Si sheet, thickness is the light of the AAO template of the Al film manufacture of 50nm
Learn photo；
On Figure 1B: embodiment 2 intrinsic (100) Si sheet, thickness is the light of the AAO template of the Al film manufacture of 100nm
Learn photo；
On Fig. 1 C: embodiment 3 intrinsic (100) Si sheet, thickness is the light of the AAO template of the Al film manufacture of 150nm
Learn photo；
On Fig. 1 D: embodiment 4 intrinsic (100) Si sheet, thickness is the light of the AAO template of the Al film manufacture of 250nm
Learn photo；
On Fig. 1 E: embodiment 5 intrinsic (100) Si sheet, thickness is the light of the AAO template of the Al film manufacture of 350nm
Learn photo；
On Fig. 1 F: embodiment 6 intrinsic (100) Si sheet, thickness is the light of the AAO template of the Al film manufacture of 500nm
Learn photo；
Fig. 1 G: deposit the AAO template of Al film manufacture thick for 150nm on embodiment 7p-type (100) Si substrate
Optical photograph；
Fig. 1 H: deposit the AAO template of Al film manufacture thick for 500nm on embodiment 8p-type (100) Si substrate
Optical photograph；
Fig. 1 I: deposit the light of the AAO template that Al film thick for 500nm manufactures on embodiment 9n-type (100) Si sheet
Learn photo；
The AAO template that Al layer thick for Fig. 1 J: embodiment 10n-type (111) Si sheet deposition 100nm manufactures
Optical photograph；
The AAO template that Al layer thick for Fig. 1 K: embodiment 11n-type (111) Si sheet deposition 150nm manufactures
Optical photograph；
Fig. 1 L: embodiment 12ITO deposition on glass thickness is the light of the AAO template that Al layer thick for 150nm manufactures
Learn photo；
Fig. 2 is AAO template SEM photograph；
Wherein: the size in Fig. 2 A: hole is 13.8 ± 2.4nm, AAO template SEM photograph；
The size in Fig. 2 B: hole is 25.2 ± 5.7nm, AAO template SEM photograph；
The size in Fig. 2 C: hole is the AAO template SEM photograph of 44.6 ± 7.7nm；
The size in Fig. 2 D: hole is the AAO template SEM photograph of 60.7 ± 7.8nm；
Fig. 3 is the SEM figure of Au nano-array, the SEM picture of the power spectrum of Au nano-array, Au nano-array；
Wherein:
Fig. 3 A, B:, bore dia thick for 100nm on embodiment 1 (100) Si sheet is heavy in the AAO template of 35nm
(template is template reaming 20-30 shown in Fig. 2 C to the Au nano-array that Au layer thick for long-pending 15nm is formed
Gained after minute)；
Fig. 3 C: the power spectrum of embodiment 13Au nano-array；
The SEM picture of the Au nano-array that Fig. 3 D: embodiment 13 is amplified；
Fig. 4: embodiment 13 deposits the Au nano-array SEM photograph that 6nm thickness Au layer is formed in AAO template；
Fig. 5 is the SEM photograph of nano-array；Wherein:
Fig. 5 A: etch away the SEM photograph of the Ni nano-array of AAO template on embodiment 14Si sheet；
The SEM photograph of the Ti nano-array of 12nm is deposited in Fig. 5 B: embodiment 14 100nm thickness AAO template.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in detail.
The present invention proposes a kind of new manufacture AAO template and manufactures the experimental technique of compact nanometer array.First,
By (the Si sheet of the different crystal orientations of doping and undoped and ito glass) on anodic oxidation different substrate
Al layer thick for 50-500nm directly forms the hole of a size of 10-60nm on surface.In this process, Al
Film is first at N2Anneal under atmosphere at 400 DEG C 2h, and uses polymer Protect edge information before oxidation.By
The difference of the color of template is caused in different substrate and different-thickness.We can find out from accompanying drawing, identical
Substrate on (intrinsic (100) Si sheet) due to Al thickness increase AAO template color from indigo plant dark-grey, grey,
Dark blue, blue, the change (Figure 1A-F) of blue-green to claret.Along with AAO thickness changes colour becomes red
Look is because light and porous Al2O3The result having an effect, i.e. more long-wave band light is by thicker AAO mould
The result of plate reflection.Meanwhile, the color of the light that AAO template reflects also depends on the type of substrate used thereof.Example
As, the AAO template of n-type (111) Si sheet demonstrates purple in Fig. 1 K, and with intrinsic (100)
Si sheet is that the AAO template of substrate then demonstrates navy blue (Fig. 1 C), although they are with the Al of same thickness
Film (150nm) manufactures.But, when Al film is sufficiently thick when, substrate below is to reflection light
Color influences the least.Such as, the when that once Al film reaching 500nm thickness, no matter they are in intrinsic,
On the Si substrate of p-type or n-type, all of AAO template just demonstrate identical claret (as
Fig. 1 F, 1H, 1I).
The present invention also proposes the preparation method of a kind of compact nanometer array, uses these templates, and we use district
Not in compact nanometer array manufacturing method before, by controlling the interface interaction shape between material and AAO template
Become self-assembled nanometer particle.We produce nano-array by the step of deposition and etching.That is, at AAO
In template, (such as bore dia is less than 150nm more than 20nm, thickness) deposition average thickness is the selected of 10nm
Metal (such as Au), and at N2Atmosphere is enclosed lower 400 DEG C and is annealed 2 hours.With mass fraction it is the most again
The H of 5%3PO4The all of Al of solution washes away2O3(keeping 45-90 minute in the solution).
The present invention prepares the method for compact nanometer array and includes manufacturing AAO template and preparing nano-array two step
Suddenly.
First, preparation AAO template specifically includes following step:
(1) in different substrate (Si in eigenstate 100 direction, p-type or the resistivity in N-shaped 100 direction
Be the Si of 0.025 Ω m, the Si in N-shaped 111 direction and ito glass) upper deposit thickness is 50-150nm's
Al (Alfa Aesar, 99.999% purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) in anodic oxidation solution (oxalic acid of 0.3M), two-step process is passed through different voltages (20-50V)
(first step time is with the Al layer a period of time on different temperatures (4-20 DEG C) anodic oxygen substrate
10-180s；Second time is 20-600s).First after anodic oxidation, by the etching agent of 45-50 DEG C
Middle immersion 2-3min dissolves the surface of oxidation.For the second time after anodic oxidation, the AAO on substrate is immersed in 3
Wt.%H3PO4Middle 30-90min, it is possible to form hole on AAO.
Secondly, prepare nano-array and specifically include following step:
(1) on substrate, thickness is less than the metal of 10nm less than deposition a layer thickness in the AAO template of 150nm
(such as, Au)；
(2) at 5wt.%H3PO4Solution soaks 60-90min, erodes AAO template as far as possible.In order to improve
The degree of crystallinity of the metal nanoparticle (such as, Au) formed, to carry out following moving back before corrosion process
Fire process: first by the AAO template of covering Au at 400 DEG C, N2Anneal 2 hours under atmosphere, then will
The AAO template covering metal on substrate is annealed 2 hours in air at 200 DEG C.
Embodiment 1
The present embodiment provides a kind of AAO template, and this template is to be 50nm's by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in eigenstate 100 direction deposit thickness be 50nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 5-10s, and voltage is 20V, and oxidizing temperature is 5-6 DEG C.First after anodic oxidation, pass through
In the etching agent of 45-50 DEG C, soak 2-3min dissolve the surface of oxidation.The second step time is 120-150s,
Voltage is 20V, and oxidizing temperature is 3-4 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 2
The present embodiment provides a kind of AAO template, and this template is for being 100nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in eigenstate 100 direction deposit thickness be 100nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 10-15s, and voltage is 25V, and oxidizing temperature is 5-6 DEG C.First after anodic oxidation, pass through
In the etching agent of 45-50 DEG C, soak 2-3min dissolve the surface of oxidation.The second step time is 150-180s,
Voltage is 25V, and oxidizing temperature is 3-4 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 3
The present embodiment provides a kind of AAO template, and this template is for being 150nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in eigenstate 100 direction deposit thickness be 150nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 60-75s, and voltage is 30V, and oxidizing temperature is 5-6 DEG C.First after anodic oxidation, pass through
In the etching agent of 45-50 DEG C, soak 2-3min dissolve the surface of oxidation.The second step time is 180-200s,
Voltage is 30V, and oxidizing temperature is 3-4 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 4
The present embodiment provides a kind of AAO template, and this template is for being 250nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in eigenstate 100 direction deposit thickness be 250nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 120-130s, and voltage is 40V, and oxidizing temperature is 10-12 DEG C.First after anodic oxidation,
The surface of oxidation is dissolved by soaking 3-5min in the etching agent of 45-50 DEG C.The second step time is
300-320s, voltage is 40V, and oxidizing temperature is 7-8 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 5
The present embodiment provides a kind of AAO template, and this template is for being 350nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in eigenstate 100 direction deposit thickness be 350nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 120-130s, and voltage is 40V, and oxidizing temperature is 8-10 DEG C.First after anodic oxidation,
The surface of oxidation is dissolved by soaking 3-5min in the etching agent of 45-50 DEG C.The second step time is
420-450s, voltage is 40V, and oxidizing temperature is 6-8 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 6
The present embodiment provides a kind of AAO template, and this template is for being 500nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in eigenstate 100 direction deposit thickness be 500nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 150-160s, and voltage is 40V, and oxidizing temperature is 8-10 DEG C.First after anodic oxidation,
The surface of oxidation is dissolved by soaking 3-5min in the etching agent of 45-50 DEG C.The second step time is
480-500s, voltage is 40V, and oxidizing temperature is 8-10 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 7
The present embodiment provides a kind of AAO template, and this template is for being 150nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in p-type 100 direction deposit thickness be 150nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 20-25s, and voltage is 20V, and oxidizing temperature is 4-5 DEG C.First after anodic oxidation, pass through
In the etching agent of 45-50 DEG C, soak 2-3min dissolve the surface of oxidation.The second step time is 120-130s,
Voltage is 20V, and oxidizing temperature is 4-5 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 8
The present embodiment provides a kind of AAO template, and this template is for being 500nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in p-type 100 direction deposit thickness be 500nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 30-40s, and voltage is 40V, and oxidizing temperature is 18-20 DEG C.First after anodic oxidation, logical
Cross the surface soaking 2-3min dissolving oxidation in the etching agent of 45-50 DEG C.The second step time is 60-90s,
Voltage is 40V, and oxidizing temperature is 18-20 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 9
The present embodiment provides a kind of AAO template, and this template is for being 500nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in N-shaped 100 direction deposit thickness be 500nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 30-40s, and voltage is 40V, and oxidizing temperature is 18-20 DEG C.First after anodic oxidation, logical
Cross the surface soaking 3-5min dissolving oxidation in the etching agent of 45-50 DEG C.The second step time is 60-90s,
Voltage is 40V, and oxidizing temperature is 18-20 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 10
The present embodiment provides a kind of AAO template, and this template is for being 100nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in N-shaped 100 direction deposit thickness be 100nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 20-25s, and voltage is 25V, and oxidizing temperature is 4-5 DEG C.First after anodic oxidation, pass through
In the etching agent of 45-50 DEG C, soak 2-3min dissolve the surface of oxidation.The second step time is 120-140s,
Voltage is 25V, and oxidizing temperature is 4-5 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 11
The present embodiment provides a kind of AAO template, and this template is for being 150nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on the Si in N-shaped 100 direction deposit thickness be 150nm Al (Alfa Aesar, 99.999%
Purity)；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 20-25s, and voltage is 25V, and oxidizing temperature is 4-5 DEG C.First after anodic oxidation, pass through
In the etching agent of 45-50 DEG C, soak 2-3min dissolve the surface of oxidation.The second step time is 180-200s,
Voltage is 25V, and oxidizing temperature is 4-5 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 12
The present embodiment provides a kind of AAO template, and this template is for being 150nm by two-step method anodic oxidation thickness
Al film gained.
Prepare this template and include following step:
(1) on ito glass, deposit thickness is the Al (Alfa Aesar, 99.999% purity) of 150nm；
(2) Si sheet N at 400 DEG C of Al will be covered2Atmosphere is annealed 2 hours；
(3) with polymer (such as PMMA) protection substrate edge；
(4) by the Al layer on two-step method anodic oxidation substrate in anodic oxidation solution (oxalic acid of 0.3M):
The first step time is 15-20s, and voltage is 20V, and oxidizing temperature is 9-10 DEG C.First after anodic oxidation, logical
Cross the surface soaking 2-3min dissolving oxidation in the etching agent of 45-50 DEG C.The second step time is 40-60s,
Voltage is 20V, and oxidizing temperature is 9-10 DEG C.
The AAO template of size uniform can be prepared by said method.
Embodiment 13
The present embodiment provides a kind of high density nano-array, and this nano-array is Au nano-array, and obtain receives
Rice array average diameter is 12.5 ± 2.9nm, and mean center distance is 7.9 ± 3.4nm, and surface density is
5.6×1011cm-2.The preparation method of this nano-array includes following several step:
Step one: in (100) direction, resistivity be that on the Si sheet of 0.025 Ω m, deposit thickness is 100nm
Thick Al (Alfa Aesar, 99.999% purity), will cover Si sheet N at 400 DEG C of Al2In atmosphere
Anneal 2 hours, and protect substrate edge with polymer (such as PMMA).At anodic oxidation solution (0.3M
Oxalic acid) in by Al layer a period of time on anodic oxidation substrate of two-step process, (first step time is
10-180s；Second time is 20-600s).First after anodic oxidation, by the solution of 45-50 DEG C
Soak 2-3min and dissolve the surface of oxidation.For the second time after anodic oxidation, the AAO on substrate is immersed in 3wt.%
H3PO4Middle 30-90min, forms hole on AAO.
Step 2: thickness is that in the AAO template of 100nm, deposition a layer thickness is the Au of 15nm on substrate；
At 5wt.%H3PO4Solution soaks 60-90min, erodes AAO template as far as possible.In order to improve the Au of formation
The degree of crystallinity of nano particle, to carry out following annealing process: first will cover Au's before corrosion process
AAO template at 400 DEG C, N2Anneal 2 hours under atmosphere, the AAO template of metal then on substrate, will be covered
At 200 DEG C, air is annealed 2 hours.
Prepare the SEM photograph of Au nano-array of gained as shown in Figure 3 A and Figure 3 B, the Au array of Fig. 3 C
Power spectrum demonstrate almost thus Al2O3The most dissolved.Fig. 3 D is the picture of the nano-array amplified, aobvious
Illustrate that some positions are the small particle of two or more, it may be possible to cause owing to Au is the thinnest at a sky
In define two or more particle.By the size of particle in statistics SEM picture, can obtain
A diameter of 30.7 ± the 6.2nm of grain (STDEV%=20%), granular center distance is 41.6 ± 15.9nm.
This with AAO pattern hole centre distance be consistent (72.8 ± 21.6nm, as shown in Figure 2 B).Surface density
It is 2.0 × 1010NPs/cm2。
In order to improve the degree of crystallinity of Au nano particle, Au nano particle is made annealing treatment by we.At AAO
The typical SEM photograph obtained after carrying out pre-anneal treatment after depositing the thick Au of 6nm in template, this micro-photograph
Sheet demonstrates that annealing is the most different with the edge of substrate from unannealed NPs edge.Obtained by statistics
SEM photograph in the size of particle and centre distance, can obtain average diameter is 12.5 ± 2.9nm, flat
All centre distance is 7.9 ± 3.4nm, and surface density is 5.6 × 1011cm-2。
Embodiment 14
The present embodiment provides a kind of high density nano-array, and this nano-array is Ni nano-array.On Si substrate
The SEM photograph intermediate pore size of the wide distribution of 15nm thickness Ni: 18nm in AAO template；Thickness: 50-100nm.
The nano-array average diameter obtained is 3.8 ± 1.0nm, and average grain spacing is 3.5 ± 1.4nm.Should
The preparation method of nano-array includes following several step:
Step one: in (100) direction, resistivity be that on the Si sheet of 0.025 Ω m, deposit thickness is 150nm
Thick Al (Alfa Aesar, 99.999% purity), will cover Si sheet N at 400 DEG C of Al2In atmosphere
Anneal 2 hours, and protect substrate edge with polymer (such as PMMA).At anodic oxidation solution (0.3M
Oxalic acid) in by Al layer a period of time on anodic oxidation substrate of two-step process, (first step time is
10-180s；Second time is 20-600s).First after anodic oxidation, by the solution of 45-50 DEG C
Soak 2-3min and dissolve the surface of oxidation.For the second time after anodic oxidation, the AAO on substrate is immersed in 3wt.%
H3PO4Middle 30-90min, forms hole on AAO.
Step 2: thickness is that in the AAO template of 150nm, deposition a layer thickness is the Ni of 15nm on substrate；
At 5wt.%H3PO4Solution soaks 60-90min, erodes AAO template as far as possible.In order to improve the Ni of formation
The degree of crystallinity of nano particle, to carry out following annealing process: first will cover Ni's before corrosion process
AAO template at 400 DEG C, N2Anneal 2 hours under atmosphere, the AAO template of metal then on substrate, will be covered
At 200 DEG C, air is annealed 2 hours.
Embodiment 15
The present embodiment provides a kind of high density nano-array, and this nano-array is Ti nano-array.On Si substrate
Ti layer thick for 15nm in AAO template is at 400 DEG C of N2In the wide-angle SEM photograph annealed 2 hours under atmosphere,
EDS explanation adheres to Ti particle in the AAO template on Si sheet really.After AAO template etches away we
Just having obtained average diameter is 8.9 ± 2.3nm, and average grain spacing is the Ti nanometer of 6.7 ± 2.6nm
Array, their surface density is up to 1.2 × 1012cm-2.The preparation method of this nano-array includes following several
Step:
Step one: in (100) direction, resistivity be that on the Si sheet of 0.025 Ω m, deposit thickness is 150nm
Thick Al (Alfa Aesar, 99.999% purity), will cover Si sheet N at 400 DEG C of Al2In atmosphere
Anneal 2 hours, and protect substrate edge with polymer (such as PMMA).At anodic oxidation solution (0.3M
Oxalic acid) in by Al layer a period of time on anodic oxidation substrate of two-step process, (first step time is
10-180s；Second time is 20-600s).First after anodic oxidation, by the solution of 45-50 DEG C
Soak 2-3min and dissolve the surface of oxidation.For the second time after anodic oxidation, the AAO on substrate is immersed in 3wt.%
H3PO4Middle 30-90min, forms hole on AAO.
Step 2: thickness is that in the AAO template of 150nm, deposition a layer thickness is the Ti of 15nm on substrate；
At 5wt.%H3PO4Solution soaks 60-90min, erodes AAO template as far as possible.In order to improve the Ti of formation
The degree of crystallinity of nano particle, to carry out following annealing process: first will cover Ti's before corrosion process
AAO template at 400 DEG C, N2Anneal 2 hours under atmosphere, the AAO template of metal then on substrate, will be covered
At 200 DEG C, air is annealed 2 hours.
Embodiment 16
The present embodiment provides a kind of high density nano-array, and this nano-array is Co nano-array.This nanometer battle array
The preparation method of row includes following several step:
Step one: in (100) direction, resistivity be that on the Si sheet of 0.025 Ω m, deposit thickness is 150nm
Thick Al (Alfa Aesar, 99.999% purity), will cover Si sheet N at 400 DEG C of Al2In atmosphere
Anneal 2 hours, and protect substrate edge with polymer (such as PMMA).At anodic oxidation solution (0.3M
Oxalic acid) in by Al layer a period of time on anodic oxidation substrate of two-step process, (first step time is
10-180s；Second time is 20-600s).First after anodic oxidation, by the solution of 45-50 DEG C
Soak 2-3min and dissolve the surface of oxidation.For the second time after anodic oxidation, the AAO on substrate is immersed in 3wt.%
H3PO4Middle 30-90min, forms hole on AAO.
Step 2: thickness is that in the AAO template of 150nm, deposition a layer thickness is the Co of 15nm on substrate；
At 5wt.%H3PO4Solution soaks 60-90min, erodes AAO template as far as possible.In order to improve the Co of formation
The degree of crystallinity of nano particle, to carry out following annealing process: first will cover Co's before corrosion process
AAO template at 400 DEG C, N2Anneal 2 hours under atmosphere, the AAO template of metal then on substrate, will be covered
At 200 DEG C, air is annealed 2 hours.
Embodiment 17
The present embodiment provides a kind of high density nano-array, and this nano-array is Fe nano-array.This nanometer battle array
The preparation method of row includes following several step:
Step one: in (100) direction, resistivity be that on the Si sheet of 0.025 Ω m, deposit thickness is 150nm
Thick Al (Alfa Aesar, 99.999% purity), will cover Si sheet N at 400 DEG C of Al2In atmosphere
Anneal 2 hours, and protect substrate edge with polymer (such as PMMA).At anodic oxidation solution (0.3M
Oxalic acid) in by Al layer a period of time on anodic oxidation substrate of two-step process, (first step time is
10-180s；Second time is 20-600s).First after anodic oxidation, by the solution of 45-50 DEG C
Soak 2-3min and dissolve the surface of oxidation.For the second time after anodic oxidation, the AAO on substrate is immersed in 3wt.%
H3PO4Middle 30-90min, forms hole on AAO.
Step 2: thickness is that in the AAO template of 150nm, deposition a layer thickness is the Fe of 15nm on substrate；
In 5wt.%NaOH solution, soak 60-90min, erode AAO template as far as possible.In order to improve formation
The degree of crystallinity of Fe nano particle, to carry out following annealing process: first will cover Fe before corrosion process
AAO template at 400 DEG C, N2Anneal 2 hours under atmosphere, the AAO mould of metal then on substrate, will be covered
Plate is annealed 2 hours in air at 200 DEG C.
Embodiment 18
The present embodiment provides a kind of high density nano-array, this nano-array be the metal simple-substances such as Ag (such as:
Cr, Cu, Zn, Ge, Mn, Pt, Y, Zr, Nb, Mo, Tc, Rh, Ru, Pd, In, Sn, Sb, Bi,
Pb, Fr, Pt, Os, Re, W, Ta, Hf, La, Dy, Pr, Nd, Gy etc.) nano-array.This nanometer
The preparation method of array includes following several step:
Step one: in (100) direction, resistivity be that on the Si sheet of 0.02 Ω 5m, deposit thickness is 150nm
Thick Al (Alfa Aesar, 99.999% purity), will cover Si sheet N at 400 DEG C of Al2In atmosphere
Anneal 2 hours, and protect substrate edge with polymer (such as PMMA).At anodic oxidation solution (0.3M
Oxalic acid) in by Al layer a period of time on anodic oxidation substrate of two-step process, (first step time is
10-180s；Second time is 20-600s).First after anodic oxidation, by the solution of 45-50 DEG C
Soak 2-3min and dissolve the surface of oxidation.For the second time after anodic oxidation, the AAO on substrate is immersed in 3wt.%
H3PO4Middle 30-90min, forms hole on AAO.
Step 2: thickness is that in the AAO template of 150nm, deposition a layer thickness is the Ag etc. of 15nm on substrate
Metal simple-substance (such as Cr, Cu, Zn, Ge, Mn, Pt, Y, Zr, Nb, Mo, Tc, Rh, Ru, Pd,
In, Sn, Sb, Bi, Pb, Fr, Pt, Os, Re, W, Ta, Hf etc.)；At 5wt.%H3PO4Or
NaOH solution is soaked 60-90min, erodes AAO template as far as possible.Receive to improve the metal simple-substance of formation
The degree of crystallinity of rice grain, to carry out following annealing process: first will cover metal list before corrosion process
The AAO template of matter at 400 DEG C, N2Anneal 2 hours under atmosphere, then will cover metal simple-substance on substrate
AAO template is annealed 2 hours in air at 200 DEG C.
Embodiment 19
The present embodiment provides a kind of high density nano-array, and this nano-array is the metallic compound (examples such as CoSm
As: AuGe, NdFeB, AlCe, GdFe, CoLu, TbCo, DyFe, RhYb, PrPd etc.) nano-array.
The preparation method of this nano-array includes following several step:
Step one: in (100) direction, resistivity be that on the Si sheet of 0.02 Ω 5m, deposit thickness is 150nm
Thick Al (Alfa Aesar, 99.999% purity), will cover Si sheet N at 400 DEG C of Al2In atmosphere
Anneal 2 hours, and protect substrate edge with polymer (such as PMMA).At anodic oxidation solution (0.3M
Oxalic acid) in by Al layer a period of time on anodic oxidation substrate of two-step process, (first step time is
10-180s；Second time is 20-600s).First after anodic oxidation, by the solution of 45-50 DEG C
Soak 2-3min and dissolve the surface of oxidation.For the second time after anodic oxidation, the AAO on substrate is immersed in 3wt.%
H3PO4Middle 30-90min, forms hole on AAO.
Step 2: thickness is that in the AAO template of 150nm, deposition a layer thickness is the CoSm of 15nm on substrate
Metallic compound (such as AuGe, NdFeB, AlCe, GdFe, CoLu, TbCo, DyFe, RhYb, PrPd)；
At 5wt.%H3PO4Or NaOH solution is soaked 60-90min, erodes AAO template as far as possible.In order to carry
The degree of crystallinity of the high metal compound nanoparticles formed, to carry out following annealed before corrosion process
Journey: first by the AAO template of covering metallic compound at 400 DEG C, N2Anneal 2 hours under atmosphere, then
The AAO template covering metallic compound on substrate is annealed 2 hours in air at 200 DEG C.
Embodiment 20
The present embodiment provides a kind of high density nano-array, and this nano-array includes the metal simple-substances such as Au, CoSm
Or metallic compound nano array (identical with material described in embodiment 1-8).Preparation process can make
By the template of different materials, it is described below.The preparation method of this nano-array includes following several step:
Step one: at SiO2Deng depositing Al on (such as ito glass, Si) substrate, Zr, Ti, B, Mg, Ba,
The elemental metals layers such as Ta, Sn, La, Pr, Ln, Nd, Gy, Tb, Eu, W, Y, Pb, Ce, Hf, Dy,
Deposit thickness is 150nm, will cover Si sheet N at 400 DEG C of A metal simple-substance layer2Atmosphere is annealed 2
Hour, and protect substrate edge with polymer (such as PMMA).At anodic oxidation solution (oxalic acid of 0.3M)
In by Al layer a period of time on anodic oxidation substrate of two-step process, (first step time is 10-180s；
Second time is 20-600s).First after anodic oxidation, by soaking 2-3min in the solution of 45-50 DEG C
Dissolve the surface of oxidation.For the second time after anodic oxidation, the template on substrate is immersed in acid or the alkali of correspondence
In solution, forming the template of different size hole, obtained template composition is respectively Al2O3, ZrO2, TiO2,
B2O3, MgO, BaO, TaO, SnO2, La2O3, Pr6O11, Ln2O3, Nd2O3, Gy2O3, Tb2O3, Eu2O3,
WO, Y2O3, PbO, Ce2O3, HfO2, Dy2O3Deng.
Step 2: on substrate thickness be 150nm metal or pottery template on deposit a layer thickness be 15nm
Metal simple-substance or the metallic compound such as Au, CoSm；Corresponding acid or aqueous slkali are soaked, as far as possible
Erode template.The degree of crystallinity of metal simple-substance or metal compound nanoparticles in order to improve formation, in corruption
Following annealing process is carried out: first will cover metal simple-substance or the AAO of metallic compound before erosion process
Template at 400 DEG C, N2Anneal 2 hours under atmosphere, then will cover metal simple-substance or metal compound on substrate
The AAO template of thing is annealed 2 hours in air at 200 DEG C.
Embodiment 21
The present embodiment provides the preparation method of a kind of high density nano-array, and this nano-array includes Au, CoSm
Deng metal simple-substance or metallic compound nano array (identical with material described in embodiment 1-8).Preparing
Journey can use the template of different materials, identical with described in embodiment 8.The preparation method of this nano-array
Including following several steps:
Step one: (such as: ito glass, SiO on the substrates such as Si2On), deposit thickness is that 150nm is thick
Al (Alfa Aesar, 99.999% purity) Zr, Ti, B, Mg, Ba, Ta, Sn, La, Pr, Ln,
The elemental metals layers such as Nd, Gy, Tb, Eu, W, Y, Pb, Ce, Hf, Dy, exist the Si sheet covering Al
N at 400 DEG C2Atmosphere is annealed 2 hours, and protects substrate edge with polymer (such as PMMA).At sun
Time in pole oxidation solution (oxalic acid of 0.3M) by one section of two-step process Al layer on anodic oxidation substrate
Between (first step time is 10-180s；Second time is 20-600s).First after anodic oxidation, pass through
In the solution of 45-50 DEG C, soak 2-3min dissolve the surface of oxidation.For the second time after anodic oxidation, by substrate
On template be immersed in correspondence acid or aqueous slkali in, formed different size hole template.
Step 2: thickness is that in the template of 150nm, deposition a layer thickness is the Au of 15nm, CoSm on substrate
Deng metal simple-substance or metallic compound；60-90min, as far as possible corrosion is soaked in corresponding acid or aqueous slkali
Fall template.The degree of crystallinity of metal simple-substance or metal compound nanoparticles in order to improve formation, was corroding
Following annealing process is carried out: first will cover metal simple-substance or the AAO template of metallic compound before journey
At 400 DEG C, N2Anneal 2 hours under atmosphere, then will cover metal simple-substance or metallic compound on substrate
AAO template is annealed 2 hours in air at 200 DEG C.
Claims (5)
1. the method for interface interaction induction self assembly high density nano-array, it is characterised in that include following step
Rapid:
(1) on substrate, deposit thickness is the mould material of 50-500nm；Will be covered with the base of mould material
Plate, at N2Anneal under atmosphere at 400 DEG C 2h；
(2) polymer protection step (1) gained substrate edges is then used, by anodic oxidation substrate
Layer of template material directly form the hole of a size of 10-60nm at substrate surface, form template；
(3) in the template of step (2) gained, deposit thickness is the nano-array material of 10-15nm；
(4) product step (3) obtained is at N2Anneal under atmosphere at 400 DEG C 2h；Exist the most again
At 200 DEG C, air is annealed 2 hours；
(5) then in corrosive liquid, mould material is eroded.
2. according to the method for claim 1, it is characterised in that mould material thickness is 50-150nm.
3. according to the method for claim 1, it is characterised in that baseplate material has: Si, SiO2Or ito glass；
Manufacture template material have Al, Zr, Ti, B, Mg, Ba, Ta, Sn, La, Pr, Ln, Nd, Gy, Tb,
Eu, W, Y, Pb, Ce, Hf or Dy, the template composition formed is Al2O3、ZrO2、TiO2、B2O3、MgO、
BaO、TaO、SnO2、La2O3、Pr6O11、Ln2O3、Nd2O3、Gy2O3、Tb2O3、Eu2O3、WO、Y2O3、PbO、
Ce2O3、HfO2Or Dy2O3。
4. according to the method for claim 1, it is characterised in that the material simple substance of deposition nano-array includes:
Au、Ti、Ni、Cr、Co、Fe、Ag、Cu、Zn、Ge、Mn、Y、Zr、Nb、Mo、Tc、Rh、Ru、
Pd, In, Sn, Sb, Bi, Pb, Fr, Pt, Os, Re, W, Ta, Hf, La, Dy, Pr, Nd or
Gy；Metallic compound has: AuGe, CoSm, NdFeB, AlCe, GdFe, CoLu, TbCo, DyFe, RhYb
Or PrPd.
5. according to the method for claim 1, it is characterised in that when using Al as mould material, at anode
By two-step process at different voltage 20-50V and different temperatures 4-20 DEG C anodic oxygen base in oxidation solution
Al layer a period of time on sheet, the first step time is 10-180s, and the second step time is 20-600s, anode
Oxidation solution is the oxalic acid solution of 0.3M.
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