CN100494045C - Method for preparing micron/submicron metal ring and open-mouth metal ring - Google Patents
Method for preparing micron/submicron metal ring and open-mouth metal ring Download PDFInfo
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- CN100494045C CN100494045C CNB200710020649XA CN200710020649A CN100494045C CN 100494045 C CN100494045 C CN 100494045C CN B200710020649X A CNB200710020649X A CN B200710020649XA CN 200710020649 A CN200710020649 A CN 200710020649A CN 100494045 C CN100494045 C CN 100494045C
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- 239000002184 metal Substances 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 6
- 238000009416 shuttering Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- 239000011806 microball Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 4
- 239000000084 colloidal system Substances 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000813 microcontact printing Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Abstract
The invention discloses a preparing method of the micro/sub-micron ferrule and the open ferrule. It gets the two-dimensional colloid crystal by the self-organizing technology, then to anneal in high temperature, chemical corruption, the secondary anneal in high temperature to form the non close-packed two-dimensional structure; the polymer is filled into lattice space to form the compound film which is put in the hydrofluoric acid steam to go on the secondary corrosion and form the ring space; the surface of the compound module is spurted by metal, then to resolve the compound module to get the ferrule array structure. If the sample is dipped into the alcohol solution to make the ring space change the partiality ring space; then to spurt by metal and remove the compound module to get the open ferrule. The advance of the invention is: the structural parameter can be controlled; the inner and outer diameter of the ferrule and the open ring can be adjusted and the circle can be controlled; the single disperse character is good and the thickness is uniform; the interface is clear and the technology is simple.
Description
Technical field
The preparation method of the artificial magnetic metamaterials that the present invention relates to a kind of sequential 2 D micron/sub-micron metal ring and form by micron/sub-micron opening becket sequential 2 D array.
Background technology
Sequential 2 D micron/sub-micron metal ring and opening becket technology of preparing are technology with important application background.Because the adjustable plasmon resonance of micron/sub-micron metal ring, the electromagnetic property that the magnetic response of micron/sub-micron opening becket etc. are novel, micron/sub-micron metal ring and split ring have potential application in fields such as optics, high density storage, negative refractive index materials.The method for preparing at present micron/sub-micron metal ring and split ring mainly contains that photoetching, electron beam or ion beam etching, FIB are directly write, micro-contact printing etc., needs micro-processing technology, length consuming time and the cost height of equipment complexity mostly.
Summary of the invention
Goal of the invention: the purpose of this invention is to provide the adjustable micron/sub-micron metal ring of simple, the lower-cost parameter of a kind of technology and the preparation method of opening becket.
Technical scheme: the preparation method of micron/sub-micron metal ring of the present invention may further comprise the steps:
1, on silicon substrate, arranges micron/submicron silicon dioxide (SiO by self-organizing technique
2) microballoon, the two-dimensional colloidal crystal of acquisition high-sequential; Then a little more than SiO
2Carry out high annealing under the environment of softening temperature, make to form between microballoon and the silicon substrate firmly to be connected; Annealed sample is placed in hydrofluoric acid (HF) steam carries out suitable chemical attack, and further pass through the secondary high annealing, form the hemispherical SiO of not closed packing
2Two dimensional structure.Wherein self-organizing technique belongs to known technology, this patent can adopt applicant formerly a patent No. be the disclosed technology of ZL031319890.
2, to be filled into the silicon chip be the SiO of substrate to the chloroformic solution that will contain polymer
2In the gap of hemisphere dot matrix, concentration and volume that solution is filled in control make the polymer thickness that obtains be lower than SiO
2The microballoon height generates polymer/SiO
2Composite membrane.
3, above-mentioned organic/inorganic composite dielectric film is placed HF steam, carry out anticaustic, part is removed SiO
2Microballoon makes to occur annular space between polymer and the silica dioxide granule, obtains the polymer/SiO of porous
2Composite shuttering.
4, at the polymer/SiO of looping pit
2The complex media template surface carries out metal sputtering, removes polymer/SiO by the chemical method dissolving then
2Composite shuttering promptly obtains sequential 2 D micron/sub-micron metal ring array structure.
In technique scheme,, utilize liquid stream booster action to make thin polymer film that little moving be taken place, thereby make the annular hole of original symmetry become eccentric annular hole if in implementation step (4) before, sample is proposed behind the dipping in alcoholic solution; Has the polymer/SiO of eccentric annular hole
2The complex media template surface carries out metal sputtering, removes polymer/SiO by the chemical method dissolving then
2Behind the composite shuttering, promptly obtain artificial magnetic metamaterials by micron/sequential 2 D that sub-micron opening becket forms.
Beneficial effect: the present invention compared with prior art has following outstanding advantage:
1, structural parameters can be controlled, and the interior external diameter and the thickness of becket and split ring are adjustable, controlling cycle.The time of twice chemical attack can be regulated and control external diameter, the internal diameter of becket and split ring respectively; The thickness decision becket of splash-proofing sputtering metal and the thickness of split ring; The cycle of initial two-dimensional colloidal crystal has determined the cycle of becket and split ring.
2, the monodispersity of becket and split ring is good, and even by becket and split ring thickness that metal sputtering obtains, the interface is clear.
3, utilize metal sputtering, the metal species that can select is more.Selected metal only needs the corrosion of the mixed solution of solution of anti-HF and toluene, acetone all can.
4, technology is simple, and is less demanding to equipment, and expense is cheap.
Description of drawings
Fig. 1 is the schematic diagram of preparation process, wherein A) annealing; B) chemical attack; C) annealing; D) filled polymer polystyrene (PS); E) partial corrosion SiO
2F) partial corrosion SiO
2, immerse ethanol and also slowly pull out; G) splash-proofing sputtering metal and remove template.
Fig. 2 is the sem photograph of key step in the preparation process, wherein (A) non-close heap SiO
2(B) non-close heap hemispherical SiO
2(C) PS/SiO
2The annular foraminous die plate; (D) PS/SiO
2The open annular foraminous die plate.
Fig. 3 is the becket of preparation and the sem photograph of split ring.
The specific embodiment
Embodiment 1: selected micron/submicron silicon dioxide microsphere diameter is 1550nm (between 200nm～10 μ m all can), and institute's filled polymer is polystyrene (PS) (or other organic polymer), and the splash-proofing sputtering metal material is a gold.Sequential 2 D micron/sub-micron gold ring preparation method is:
1, not closed packing hemispherical SiO
2The preparation of oldered array.On silicon substrate, arrange SiO by self-assembling technique
2, the two-dimension single layer micro-sphere array of acquisition large tracts of land high-sequential; Through 1250 ℃ of high annealing 15min, the steam corrosion 1～3.5min of 40% HF solution obtains not closed packing SiO then
2Oldered array is seen Fig. 2 (A); Carry out 1300 ℃ of double annealing 10min again, form not closed packing hemispherical SiO
2Oldered array is seen Fig. 2 (B), and (wherein the temperature of The high temperature anneal is at 1250～1300 ℃, the time of annealing in 10～15min scope all can).
2, PS/SiO
2The preparation of annular foraminous die plate.With above-mentioned SiO
2The positive clean glass sheet that covers of sample, the centre adds one " U " shape sept and clamps, form a microchannel, the chloroformic solution of the PS of 3mg/ml is injected this microchannel, treat that solution evaporates the steam corrosion 1～2min of back with 40% HF solution fully, promptly obtain annular porous composite shuttering, see Fig. 2 (C).
3, the preparation of micron/sub-micron gold ring.At above-mentioned PS/SiO
2The gold of annular foraminous die plate surface sputtering 20～100nm thickness is removed SiO with the mixed solution of HF solution and toluene, acetone respectively then
2And PS, finally obtain evenly, the sequential 2 D micron of the non-Mi Dui of hexagonal/sub-micron gold ring array clearly, see Fig. 3 (A).Its dimensional parameters adjustable extent is: external diameter 1.3 μ m～680nm, internal diameter 510～170nm, thickness 20～100nm.
Embodiment 2: sequential 2 D micron/sub-micron gold split ring preparation: preparation process is substantially the same manner as Example 1, but is obtaining PS/SiO
2After the annular foraminous die plate, it is immersed alcoholic solution, tilt slowly to take out template then, this process makes the PS perforated membrane that small translation take place and touches SiO in the hole until border, PS hole
2, therefore obtained open annular PS/SiO
2Foraminous die plate is seen Fig. 2 (D); At sputter gold on this template and use remove template with the method for embodiment 1 after, promptly obtain sequential 2 D micron/sub-micron gold split ring array of the non-Mi Dui of hexagonal, the external boundary of opening becket is circular, and inner chamber is the U-shaped structure, see Fig. 3 (B), its dimensional parameters adjustable extent is with embodiment 1.
Claims (9)
1, a kind of preparation method of micron/sub-micron metal ring is characterized in that this method may further comprise the steps:
(1) on silicon substrate, arranges micron/submicron silicon dioxide microballoon by self-organizing technique, obtain the two-dimensional colloidal crystal of high-sequential, under the environment that is higher than the silica softening temperature, carry out high annealing then, make firmly being connected of microballoon and silicon substrate to forming; Annealed sample is placed on the chemical attack of carrying out in the hydrofluoric acid steam, and further passes through the secondary high annealing, form the hemispherical silica two dimensional structure of not closed packing;
(2) to be filled into the silicon chip be in the gap of silica hemisphere dot matrix of substrate to the chloroformic solution that will contain polymer, makes polymer thickness be lower than the silicon dioxide microsphere height, forms polymer/silica composite dielectric film;
(3) above-mentioned polymer/silica composite dielectric film is placed hydrofluoric acid steam, carry out the anticaustic dissolving and remove part silica, make to occur annular space between polymer and the silica dioxide granule;
(4) polymer/silica complex media template surface at annular hole carries out metal sputtering, removes polymer/silica composite shuttering by the chemical method dissolving then, promptly obtains sequential 2 D micron/sub-micron metal ring array structure;
Wherein in step (1), the temperature of The high temperature anneal is 1250～1300 ℃, and the time of annealing is 10～15min.
2, the preparation method of micron/sub-micron metal ring according to claim 1 is characterized in that said micron/submicron silicon dioxide diameter of micro ball is between 200nm～10 μ m in step (1).
3, the preparation method of micron/sub-micron metal ring according to claim 1 is characterized in that adopting and under the hydrofluoric acid steam ambient silica is carried out chemical attack.
4, the preparation method of micron/sub-micron metal ring according to claim 1, it is characterized in that in step (2) being filled into of being adopted in the formed complex media template is that the filler in the silica hemisphere dot matrix gap of substrate is an organic polymer with the silicon chip..
5, the preparation method of micron/sub-micron metal ring according to claim 1, the thickness that it is characterized in that splash-proofing sputtering metal is 20～100nm.
6, a kind of preparation method of micron/sub-micron opening becket is characterized in that this method may further comprise the steps:
(1) on silicon substrate, arranges micron/submicron silicon dioxide microballoon by self-organizing technique, obtain the two-dimensional colloidal crystal of high-sequential, under the environment that is higher than the silica softening temperature, carry out high annealing then, make to form between microballoon and the silicon substrate firmly to be connected; Annealed sample is placed on the chemical attack of carrying out in the hydrofluoric acid steam, and further passes through the secondary high annealing, form the hemispherical silica two dimensional structure of not closed packing;
(2) to be filled into the silicon chip be in the gap of silica hemisphere dot matrix of substrate to the chloroformic solution that will contain polymer, makes polymer thickness be lower than the silicon dioxide microsphere height, forms polymer/silica composite dielectric film;
(3) above-mentioned polymer/silica composite dielectric film is placed hydrofluoric acid steam, carry out the anticaustic dissolving and remove part silica, make to occur annular space between polymer and the silica dioxide granule;
(4) sample that step (3) is obtained proposes behind the dipping in alcoholic solution, utilizes liquid stream booster action to make thin polymer film that little moving be taken place, thereby makes the annular hole of original symmetry become eccentric annular hole; Carry out metal sputtering having the polymer of eccentric annular hole/silica complex media template surface, after removing polymer/silica composite shuttering by the chemical method dissolving then, promptly obtain artificial magnetic metamaterials by micron/sequential 2 D that sub-micron opening becket forms.
7, the preparation method of micron/sub-micron opening becket according to claim 6 is characterized in that adopting and under the hydrofluoric acid steam ambient silica is carried out chemical attack.
8, the preparation method of micron/sub-micron opening becket according to claim 6, the thickness that it is characterized in that splash-proofing sputtering metal is 20～100nm.
9, the preparation method of micron/sub-micron opening becket according to claim 6 it is characterized in that the external boundary of the opening becket of gained is circle, and inner chamber is the U-shaped structure.
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| WO2011047359A2 (en) * | 2009-10-16 | 2011-04-21 | Cornell University | Method and apparatus including nanowire structure |
| CN101746714B (en) * | 2009-12-31 | 2013-07-24 | 中国人民解放军国防科学技术大学 | Preparation method for metal nano structure array |
| CN102556952B (en) * | 2012-02-14 | 2015-01-07 | 中国人民解放军国防科学技术大学 | Metal cup-cylinder composite nano structure array and preparation method thereof |
| CN103569952B (en) * | 2013-11-12 | 2016-01-20 | 无锡英普林纳米科技有限公司 | The preparation method of one-dimensional Polymers periodic micro structure |
| CN103641059B (en) * | 2013-12-30 | 2016-03-30 | 中国人民解放军国防科学技术大学 | Metal film nano-structure array that silicon post supports and preparation method thereof |
| CN110668397A (en) * | 2019-09-16 | 2020-01-10 | 吉林师范大学 | Preparation method of highly ordered inclined nano-column |
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| CN1751983A (en) * | 2005-10-20 | 2006-03-29 | 南京大学 | Non close parked metal hollow ball shell ordered network structure material and its making method |
| CN1772463A (en) * | 2005-10-20 | 2006-05-17 | 南京大学 | Prepn of submicron/micron micro lens array on polymer surface |
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| CN1751983A (en) * | 2005-10-20 | 2006-03-29 | 南京大学 | Non close parked metal hollow ball shell ordered network structure material and its making method |
| CN1772463A (en) * | 2005-10-20 | 2006-05-17 | 南京大学 | Prepn of submicron/micron micro lens array on polymer surface |
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