CN1270216C - Method for preparing nano dot array of controllable unit size using nano ball template - Google Patents
Method for preparing nano dot array of controllable unit size using nano ball template Download PDFInfo
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- CN1270216C CN1270216C CN 200410083939 CN200410083939A CN1270216C CN 1270216 C CN1270216 C CN 1270216C CN 200410083939 CN200410083939 CN 200410083939 CN 200410083939 A CN200410083939 A CN 200410083939A CN 1270216 C CN1270216 C CN 1270216C
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000011807 nanoball Substances 0.000 title abstract description 9
- 239000002096 quantum dot Substances 0.000 title abstract 6
- 230000008021 deposition Effects 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 14
- 238000001020 plasma etching Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000002077 nanosphere Substances 0.000 claims description 25
- 238000005530 etching Methods 0.000 claims description 19
- 229910005335 FePt Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 229910018979 CoPt Inorganic materials 0.000 claims description 3
- 229910002601 GaN Inorganic materials 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 239000007769 metal material Substances 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000001259 photo etching Methods 0.000 abstract description 9
- 238000003491 array Methods 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000007747 plating Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 239000011805 ball Substances 0.000 description 17
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002061 nanopillar Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000000054 nanosphere lithography Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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Abstract
The present invention discloses a method for preparing a nano dot array of controllable unit size using nano ball templates, which belongs to the technical field of nano photoetching. In the method, the size of a deposition passage in a nano ball template is controlled by plasma etching, the steps of film plating and cleaning in a nano ball photoetching technology are carried out to obtain a nano dot array of controllable unit size, wherein the density of the nano dot array is 42 G/in<2>, and the unit size is controlled from 26 to 100 nm. The method directly based on the control of the deposition passage in the template is suitable for preparing dot arrays of various materials. With the combination with the preparation technology of films of different materials, the nano ball photoetching technology improved from the method can be used for preparing nano dot arrays with different materials, controllable unit size and high density. The method can be used for preparing magnetic storages, sensors and other devices based on nano dot arrays and for optimizing the performance of devices based unit size modulation.
Description
Technical field
The invention belongs to the nanoimprinting technology field.Be particularly related to a kind of method of utilizing the nanosphere template to prepare the controlled nanometer lattice row of unit size of utilizing the size of deposition passage in the plasma etching control nanosphere template.
Background technology
Utilizing the nanosphere photoetching technique to prepare lattice array, is a kind of relative photoetching cheapness, simple method.J.C.Hulteen and R.P.V.Duyne, Deng report in " the Nanosphere lithography:A materials general fabricationprocess for periodic particle array surfaces " of document " J.Vac.Sci.Technol.A 13; 1553 (1995) ", utilization receive (little) rice ball template in the rule hole as the deposition passage, can prepare the lattice array of rule, with the dwindling and improve of ball, and the lattice array unit size reduces the density of lattice array thereupon with template.But receive at macromolecule in the high-density applications of (little) rice ball template, when high score bulbec in the template is reduced to 200nm or when following, because the obvious distortion of ball, original deposition passage blocks in the template, causes template unavailable.
C.-W.Kuo, Deng report in " the Size-andShape-Controlled Fabrication of Large-Area Periodic Nanopillar Arrays " of " the Fabricationof Size-Tunable Large-Area Periodic Sillicon Nanopillar Arrays withSub-10-nm Resolution " and " Chem.Mater.15; 2917 (2003) " of " J.Phys.Chem.B; 107; 9950 (2003) ", lattice array at different materials, carry out subsequent treatment such as selective oxidation, can realize the part of lattice array unit size is independently controlled, but the design of these class methods is subject to different materials.At present, be applicable to the array element size Control technology of various materials also not directly based on template.
C.Haginoya, M.Ishibashi and K.Koike tells about in " the Nanostructure array fabrication with a size-controllablenatural lithography " of " Appl.Phys.Lett.71; 2934 (1997) " with plasma etching the nanosphere array of individual layer is etched into discrete unit, and be applied to the preparation of hole array. be a kind of method of hole array of the controllable size that the ball in the macromolecule individual layer ball template is etched into different discrete degree, but that will destroy original deposition passage in the template, can't be used for the preparation of lattice array.
S.I.Matsushita in addition, Y.Yagi and A.Fujishima, Deng the nanosphere template of in the article of " the Sub-Microstructure Formed by Means of Reactive Ion Etchingin Multilayers of Two-Dimensional Fine-Particle Arrays " of " Chem.Lett.524 (2002) ", telling about with the plasma etching bilayer, on original template, modify out the structure and the D.-G.Choi of sub-micron, H.K.Yu, S.G.Jang, and S.-M.Yang, Deng the nanosphere template of in the article of " the Colloidal Lithographic Nanopatterning via Reactive IonEtching " of " J.Am.Chem.Soc.126; 7019 (2004) ", telling about and multilayer double-deck, on original template, modify out different graphic structures with plasma etching.These technology all are to utilize plasma etching, etch orderly, regular structure on two, multilayer polystyrene ball template.But this technology is not studied deposition passage in the template is carried out controlled expansion, and is not applied to the preparation of lattice array, is not applied to prepare the controlled nanometer lattice row of unit size yet.
In sum, also directly that (little) rice ball template is not modified at present based on receiving, applicable to high density lattice array technology of preparing various materials, that can carry out independent control to the lattice array unit size.
Summary of the invention
The purpose of this invention is to provide a kind of nanosphere template of utilizing and prepare the controlled nanometer lattice row method of unit size.Be based on the nanosphere photoetching technique, utilize the size of deposition passage in the plasma etching control nanosphere template, thereby prepare the method for the controlled high density nanometer lattice row of unit size, this method directly based on the control of deposition passage in the template, is applicable to the preparation of various material lattice arrays.It is characterized in that: utilize etching on the nanosphere template of individual layer, bilayer or multilayer, the deposition passage in the template is carried out controlled expansion, vacuum tightness is 10 in its etching storehouse
-1-10
2Pa, power 10-100W, etching time 0.1-30 minute.On template, deposit thin film by film preparing technology then, and the nanosphere template is carried out obtaining the independent controlled nanometer lattice row of regularly arranged unit size after conventional the cleaning.The density of nanometer lattice row is 42Gdot/in in lecture experiment
2, unit size is controlled at 26-100nm simultaneously.
Described nanosphere mould material is polystyrene, polybutadiene, polyisoprene, SiO
2, Ag, Au, Co or FePt.
The material of deposition thin film is Al, Cu, Au, Ag, Ti, Zn, Cr, Fe, Co, Ni, FePt, CoPt, GaN, GaAs, SiO2 or TiO2 etc. on the described template.
The invention has the beneficial effects as follows:
1. utilize etching that template is modified, carry out controlled expansion, the nanometer lattice row technology of preparing that development can independent array of controls unit size receiving the deposition passage of (little) rice in ball template.
2. obviously opened the highdensity high molecular nanometer ball template Central Plains deposition passage of sealing earlier, the application that developing high molecular nanometer sphere template prepares the high density lattice array.
3. the lattice array unit size is controlled directly based on the control to deposition passage in the template, so be applicable to the lattice array preparation of various materials.
4. the nanometer lattice row density for preparing in lecture experiment is 42G/in
2, unit size is controlled at 26-100nm simultaneously.
Description of drawings
Fig. 1 (a) is high density (bulb diameter 200nm, lattice array density 42G/in
2) polystyrene ball template figure; (b) be the polystyrene ball template figure of bulb diameter 440nm.
Fig. 2 (a) utilizes plasma etching, the diagram in the expansion templates behind the deposition passage; (b) utilize the lattice array figure that modifies the rear pattern plate preparation.
The a series of unit sizes controlled nanometer lattice row of Fig. 3 for obtaining by the control etching time.
Fig. 4 is for having expanded the double template figure of deposition passage behind plasma etching.
Fig. 5 (a) and (b) are prepared the nanometer lattice row synoptic diagram of controllable size for utilizing the size of deposition passage in the double-deck ball template of control.
Embodiment
The invention provides a kind of nanosphere template of utilizing and prepare the controlled nanometer lattice row method of unit size.Be based on the nanosphere photoetching technique, utilize the size of deposition passage in the plasma etching control nanosphere template, thereby prepare the method for the controlled high density nanometer lattice row of unit size, this method directly based on the control of deposition passage in the template, is applicable to the preparation of various material lattice arrays.When utilizing this method to control the size of deposition passage in the nanosphere template of individual layer, bilayer or multilayer, vacuum tightness is 10 in the etching storehouse
-1-10
2Pa, power 10-100W, etching time 0.1-30 minute.Then plated film in the combining nano ball photoetching technique and cleaning step obtain the controlled nanometer lattice row of unit size (as Fig. 3, Fig. 5 (a) (b) shown in).By with the combining of different materials film preparing technology, use the improved nanosphere photoetching technique of this method and can prepare high density nanometer lattice row different materials, that unit size is controlled, can be used for device preparation and performance optimization based on nanometer lattice row.The density of nanometer lattice row is 42G/in in the lecture experiment
2, unit size is controlled at 26-100nm simultaneously.Exemplifying embodiment is below further specified the present invention.
Embodiment 1
Utilize oxygen plasma etch, the deposition passage in the pipe/polyhenylethylene nano ball template (bulb diameter 200nm) of individual layer and bilayer is carried out controlled expansion.Pass through evaporation layer of metal aluminium on template then, and in toluene solvant, polystyrene spheres is dissolved, obtain regularly arranged nanometer lattice row.
Plasma etching can characterize by scanning electron microscope (SEM) the expansion of deposition passage and the preparation effect of nanometer lattice row in the template.The high-density polystyrene template can be seen the polystyrene spheres of diameter 200nm owing to there is obviously distortion from SEM photo Fig. 1 (a) before plasma etch processes, cause that original deposition passage gets clogged in the template, thereby causes template unavailable.Fig. 1 (b) is depicted as the effect that diameter 440nm polystyrene spheres is assembled into template, can see that the distortion of ball is not obvious, and the deposition passage is high-visible.
1) the deposition passage in the plasma p-poly-phenyl ethene nanosphere template carries out controlled expansion, with individual layer, double-deck pipe/polyhenylethylene nano ball template places in the plasma reaction etching machine, utilizes oxygen as etching gas, and etching time is the parameter of control deposition passage.Vacuum tightness 20Pa in the etching storehouse, power 30W, etching time 0.5-3 minute.These treatment conditions not only can be opened because of polystyrene spheres obviously is out of shape the deposition passage that blocks, and can control the size of passage.Individual layer and double template after the expansion of deposition passage are seen Fig. 2 (a) and shown in Figure 4.
2) on template, prepare film
Utilize vacuum evaporation technology, evaporation 60nm Al, Cu, Au, Ag, Ti, Zn, Cr, Fe, Co, Ni, FePt, CoPt, GaN, GaAs, SiO2 or TiO2 on template.
3) in toluene, clean the pipe/polyhenylethylene nano ball template
Metal after this step beyond polystyrene spheres and the deposition passage is cleaned, and stays the controlled nanometer lattice row of a series of unit sizes, sees Fig. 3.The nanometer lattice row unit size 43nm that wherein utilizes 1 minute template of oxygen plasma etch to prepare, density is 42G/in
2, see Fig. 2 (b).
Implementation process is similar to embodiment 1, and just the ball that template is used makes other diameters into: 0.01-10 μ m.
Implementation process is similar to embodiment 1, and what just the ball that template is used made other materials into receives (little) rice ball, as polybutadiene, polyisoprene, SiO
2, Ag, Au, Co, FePt etc.
Implementation process is similar to embodiment 1, just template is made into more than 3 layers or 3 layers.
Embodiment 5
Implementation process is similar to embodiment 1, just adopts different etching gas.Gas comprises: Ar
2, CCl
4, O
2, CF
4, Cl
2, CHF etc.
Embodiment 6
Implementation process is similar to embodiment 1, just adopts different etching sources.The etching source comprises: ion beam, electron beam etc.
Embodiment 7
Implementation process is similar to embodiment 1, and just regulating etching power respectively is 20W, 30W, 40W, 50W, 60W, 70W, 80W, 90W, 100W; Or regulating the qi flowing in the channels body branch is pressed in 10
-1Parameters such as Pa, 1Pa, 10Pa, 20Pa, 30Pa, 40Pa, 60Pa, 80Pa or 100Pa realize controlling the size of deposition passage.
Described by the foregoing description, control plasma etching condition (control etching time, power, pressure or gaseous species) is to different nanosphere mould materials, can realize the size of deposition passage in individual layer, bilayer and the multilayer template is controlled, thereby prepare the nanometer lattice row (shown in Fig. 3,5) of different size.
Claims (2)
1. one kind is utilized the nanosphere template to prepare the controlled nanometer lattice row method of unit size, on the nanosphere template of individual layer, bilayer or multilayer, utilize plasma etching, deposition passage in the template is carried out controlled expansion, on template, deposit thin film by film preparing technology then, and the nanosphere template carried out obtaining the independent controlled nanometer lattice row of regularly arranged unit size after conventional the cleaning, it is characterized in that: vacuum tightness is 10-1-102Pa in its etching storehouse, power 10-100W, etching time 0.1-30 minute; Described nanosphere mould material is polybutadiene, polyisoprene, SiO
2, Ag, Au, Co or FePt.
2. prepare the controlled nanometer lattice row method of unit size according to the described nanosphere template of utilizing of claim 1, it is characterized in that: the material of deposition thin film is that metal or Inorganic Non-metallic Materials are: Al, Cu, Au, Ag, Ti, Zn, Cr, Fe, Co, Ni, FePt, CoPt, GaN, GaAs, SiO on the described template
2Or TiO
2
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100593015C (en) * | 2005-12-09 | 2010-03-03 | 中国科学院物理研究所 | Surface nano tip array and its preparing method |
| CN100457958C (en) * | 2006-09-14 | 2009-02-04 | 电子科技大学 | Preparation method of metal oxide nano array-inverse thin film |
| CN106876261B (en) * | 2015-12-10 | 2020-05-01 | 昆山工研院新型平板显示技术中心有限公司 | Flexible conductive wire, and preparation method and application thereof |
| CN107293641B (en) * | 2017-05-05 | 2019-12-17 | 华南师范大学 | Electric control magnetic memory based on ferroelectric-ferromagnetic heterojunction and preparation method thereof |
| CN112386399B (en) * | 2019-08-12 | 2023-05-09 | 湖南早晨纳米机器人有限公司 | Nanometer surgical robot and manufacturing method thereof |
| CN111803231A (en) * | 2020-06-28 | 2020-10-23 | 深圳大学 | Bionic micro/nano antibacterial structure and manufacturing method and application thereof |
| CN112831240B (en) * | 2021-02-06 | 2021-12-28 | 北京中硅高电科技有限公司 | High-binding-force fluorine-silicon coating material and preparation method thereof |
| CN112853279A (en) * | 2021-02-06 | 2021-05-28 | 郝云霞 | Preparation method of long-acting bactericidal aluminum or aluminum alloy material |
| CN112831758A (en) * | 2021-02-06 | 2021-05-25 | 郝云霞 | Aluminum or aluminum alloy antibacterial material |
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