CN109941959A - A kind of production method of the coaxial annulus nanostructure of column - Google Patents
A kind of production method of the coaxial annulus nanostructure of column Download PDFInfo
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- CN109941959A CN109941959A CN201910092384.7A CN201910092384A CN109941959A CN 109941959 A CN109941959 A CN 109941959A CN 201910092384 A CN201910092384 A CN 201910092384A CN 109941959 A CN109941959 A CN 109941959A
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Abstract
The present invention provides a kind of production method of the coaxial annulus nanostructure of column, the process including forming pattern etching layer in substrate surface；Pattern etching layer is handled, in the process that substrate surface forms the coaxial annulus nanostructure of column；Using the coaxial annulus nanostructure of the column of substrate surface as exposure mask, substrate is performed etching, the process that structure is transferred to substrate, and removes substrate surface structure.This method rapidly and efficiently, can large area preparation；Low in cost, freedom of processing is high.
Description
Technical field
The invention belongs to micro nano structure preparation fields, and in particular to a kind of production side of the coaxial annulus nanostructure of column
Method.
Background technique
Nanotechnology is when previous big research hotspot, and it is special that various nanostructures show many novel physics
Property, it is considered having great application potential in numerous areas such as optics, material, biology, the energy and medicine.Column is coaxially received
Rice structure is that a kind of special nanostructure may be used to form special nanocomposite optical resonant cavity after especially metallizing,
It can be applied to the occasions such as refractive index sensing, surface Raman enhancement, nano laser.This kind of column co-axial nano structure dimension is often
In the magnitude of tens nanometer to several microns.When outer diameter is when within 1 micron, preparation has very high want to processing technology
It asks.In general, preparing this kind of nanoscale coaxial columnar structure mainly takes focused-ion-beam lithography (FIB), electron beam exposure
(EBL), the techniques such as nano impression, first two mode process equipment is extremely expensive and is all made of the processing method of point by point scanning, when
Efficiency is extremely low when sample area is big；Although and nano impression can large area prepare co-axial nano structure, the system of its template
It is standby to also need to realize using FIB, EBL etc. costly and inefficient technique, and template can not be changed once preparing and completing, and make
The freedom degree for obtaining subsequent nano impression substantially reduces.It is, thus, sought for one kind can low cost, large area preparation column it is coaxial
The method of nanostructure.
Summary of the invention
The present invention provides a kind of production method of coaxial annulus nanostructure of column, this method rapidly and efficiently, can large area
Preparation, low in cost, (such as internal-and external diameter, period is big for each dimensional parameters of the coaxial annulus nanostructure of column during the preparation process
It is small etc.) higher freedom of processing may be implemented.
The present invention solves above-mentioned technical problem, is achieved through the following technical solutions:
A kind of production method of the coaxial annulus nanostructure of column, comprising:
In the process that substrate surface forms pattern etching layer；
Pattern etching layer is handled, in the process that substrate surface forms the coaxial annulus nanostructure of column；
Using the coaxial annulus nanostructure of the column of substrate surface as exposure mask, substrate is performed etching, structure is transferred to base
Bottom, and the process for removing substrate surface structure.
In the present invention, substrate is semiconductor or insulator.Preferably, the substrate is silicon base, silica substrate.
In the present invention, pattern etching layer is in substrate surface by being followed successively by organic solvent-resistant corrosion layer, Yi Beiyou from the bottom up
Solvent corrosion layer and material protection layer are constituted.
Further, organic solvent-resistant corrosion layer is photoresist SU8 layers, is easily positive photoresist Ar-P- by organic solvent corrosion layer
3740 layers.
The material protection layer is titanium layer or silicon dioxide layer, and material protection layer is with a thickness of 10-30nm.Preferably, material
Protective layer is titanium layer.
In the present invention, organic solvent-resistant corrosion layer and the method realization for easily being passed through coating by organic solvent corrosion layer, material
Protective layer is realized by physical deposition methods.
In the present invention, pattern etching layer is handled the following steps are included: being patterned into pattern etching layer surface
There is the first mask layer of radius r circular hole；Material protection layer in etched features etch layer, then etch easily by organic solvent corrosion layer
It is easily R by organic solvent corrosion layer and organic solvent-resistant corrosion layer etching radius with organic solvent-resistant corrosion layer, and R is greater than
R exposes substrate；The second mask layer of radius r circle is patterned on the surface for exposing substrate；It removes in pattern etching layer
It is easy by organic solvent corrosion layer, material protection layer and the first mask layer, retain organic solvent-resistant corrosion layer, in substrate table
Face forms the coaxial annulus nanostructure of column.
In the present invention, pass through in the first mask layer that pattern etching layer surface is patterned into radius r circular hole with lower section
Formula obtains: arranging one layer of nanosphere by self-assembling method in pattern etching layer surface, handles nanosphere, so that nanometer
The radius of a ball is r, plates etching mask layer by physical deposition methods, then remove nanosphere, obtains in pattern etching layer surface formation figure
Case is the first mask layer for having radius r circular hole.
Further, self-assembling method is gas-liquid interface self-assembling method or vertical sedimentation method.
Nanosphere is polystyrene nanospheres or silica nanosphere.
Nanosphere carries out processing as using the argon (Ar) of inductively coupled plasma etching (ICP) technique or plasma cleaner
Ion etch process performs etching nanosphere.
Further, the operating power of plasma cleaner Ar is 150W-500W, in reaction chamber pressure be 200 ±
The flow of 70mtorr, Ar are 72sccm.
In the present invention, removal nanosphere is removed using corrosive liquid or supersonic cleaning machine.
In the present invention, pass through physical deposition in the second mask layer that the surface for exposing substrate is patterned into radius r circle
Method is plated etching mask layer and is obtained.
In the present invention, physical deposition methods include electron beam evaporation, thermal evaporation, magnetron sputtering.
In the present invention, etching mask layer is aluminium layer, layers of chrome, silicon dioxide layer or aluminum oxide layer.Preferably, described
Etching mask layer is aluminium layer.
Further, the aluminium layer uses electron beam evaporation plating, and rate is
It is material protection layer in etched features etch layer, easily rotten by organic solvent corrosion layer and organic solvent-resistant in the present invention
It loses layer and uses dry etching technology.
Further, the material protection layer exposed is etched away, easily by organic solvent corrosion layer and organic solvent-resistant corrosion
Layer uses inductively coupled plasma etching (ICP).
In the present invention, remove easy by organic solvent corrosion layer, material protection layer and the first exposure mask in pattern etching layer
Layer is handled using corrosive liquid.
Further, it removes easy by organic solvent corrosion layer, material protection layer and the first exposure mask in pattern etching layer
Layer uses corrosive liquid for acetone.
In the present invention, etching substrate is handled using dry etching technology.
Further, etching substrate uses inductively coupled plasma etching (ICP).
In the present invention, removal substrate surface structure is removed using corrosive liquid.
Further, the corrosive liquid that removal substrate surface structure uses is Piranha solution.
In the present invention, the depth H of the coaxial annulus nanostructure of column is in 10-3000nm, the inner ring radius r of annulus
100-1000nm, gap d (d=R-r) is in 10nm-450nm.
The invention has the following advantages:
(1) the present invention is based on the group technology that the modes such as nanometer bead self-assembling method combination plated film and etching are formed,
Technical process involved in this method, the methods of the self assembly of nanometer bead, plated film all have can rapidly and efficiently, large area preparation
Advantage, so as to realize than traditional the methods of FIB, EBL have the effect of it is more economical, more efficient；While and nano impression
It compares, this method does not need expensive fining template, and cost is lower；
It (2), can be by adjusting each technological parameter side during the present invention production coaxial annulus nanostructure of column
Just each dimensional parameters (such as internal-and external diameter, period size) for controlling resulting column co-axial nano structure are higher to realize
Freedom of processing；
(3) the coaxial annulus nanostructure of column that the present invention makes is a kind of special nanostructure, is especially metallized
Later, it may be used to form special nanocomposite optical resonant cavity, can be applied to refractive index sensing, surface Raman enhancement, nanometer and swash
The occasions such as light device.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the coaxial annulus nanostructure of column of the present invention；
Fig. 2 is the production flow diagram of the coaxial annulus nanostructure of column of the present invention；
Fig. 3 is the electron microscope that the coaxial annulus nanostructure of column of the present invention amplifies 5k times；
Fig. 4 is the electron microscope that column of the present invention coaxial annulus nanostructure section amplifies 10k times.
Specific embodiment
The technical solution that the present invention will be described in detail combined with specific embodiments below, so that those skilled in the art are best understood from
With implementation technical solution of the present invention.
Embodiment 1
The production method of the coaxial annulus nanostructure of Fig. 1-column shown in Fig. 2 comprising following steps:
(1) successively coated film materials A and thin-film material B on a silicon substrate, wherein thin-film material A is organic solvent-resistant
The photoresist SU8 of corrosion, thin-film material B are the positive photoresist Ar-P-3740 easily corroded by organic solvent；And in the upper surface material B
On with physical deposition methods plate layer of material C, material C is the titanium with a thickness of 30nm, such as Fig. 2 a.
(2) substrate surface after step (1) arranges the polystyrene that one layer of diameter is 1um by the method for self assembly
(PS) bead, such as Fig. 2 b, the size of the small ball's diameter will determine the period size of final column co-axial nano structure herein, or work as
When control self assembling process makes bead in random distribution, the column co-axial nano structure of random arrangement may finally be obtained.
(3) by the argon of plasma cleaner (Ar) ion etch process, by polystyrene (PS) bead, its diameter is decreased to
Suitably sized, which determines annulus inner ring radius (r) size of the coaxial annulus nanostructure of final column, such as Fig. 2 c.This
In embodiment, the diameter of polystyrene (PS) bead is reduced to 640nm, and the operating power of plasma cleaner Ar is 500W,
Pressure is 200 ± 70mtorr in reaction chamber, and the flow of Ar is 72sccm, time 14min.
(4) electron beam evaporation plating is used in step (3) sample surface, rate isLayer of material D is plated, material D is thick
Degree is the metallic aluminium of 30nm, such as Fig. 2 d.
(5) print is placed in supersonic cleaning machine and removes polystyrene (PS) bead (stripping technology), such as Fig. 2 e.
(6) and pass through inductively coupled plasma etching (ICP) technique for exposed material C titanium, thin-film material A photoresist
SU8 and thin-film material B positive photoresist Ar-P-3740 are etched away, and the degree of etching thin-film material A and thin-film material B finally determines column
The annulus outer ring radius (R) of coaxial annulus nanostructure, such as Fig. 2 f.In the present embodiment, the radius R for etching thin-film material A and B is equal
For 470nm.It etches Ti and uses C4F8And SF6Mixed gas uses O2Photoresist is removed as reaction gas.The technique of etching is joined
Number such as table 1:
1 inductively coupled plasma etching of table (ICP) etches Ti and removes the technological parameter of photoresist
The time that Ti is etched in the present embodiment is 50s, and the time for etching photoresist is 35s.
(7) sample surfaces after step (6) reuse electron beam evaporation plating and layer of material D are deposited on etched print
With a thickness of the metallic aluminium of 30nm, such as Fig. 2 g.
(8) material B positive photoresist Ar-P-3740, material C titanium layer and the material D aluminium of rear surface will be handled through step (7) with acetone
Layer removes, and is left materials A photoresist SU8 and material D aluminium layer in substrate surface, such as Fig. 2 h.
(9) structure is transferred to substrate with inductively coupled plasma etching (ICP) in step (8) resulting sample, according to
Process requirements etch corresponding depth H, such as Fig. 2 i.In the present embodiment, H 950nm, inductively coupled plasma etching (ICP) is adopted
Use C4F8And SF6Mixed gas is as reaction gas, etch process parameters such as table 2.
The technological parameter of 2 inductively coupled plasma etching of table (ICP) etching base silicon
The time that base silicon is etched in the present embodiment is 55s.
(10) the remaining materials A photoresist SU8 of step (9) and the material D aluminium layer Piranha solution (7 (concentrated sulfuric acid of volume ratio
(98%)) it: 3 (hydrogen peroxide (32%))) removes, the coaxial annulus nanostructure of column is finally obtained, such as Fig. 2 j and Fig. 2 k.
As Figure 3-Figure 4, the depth H of the finally obtained column co-axial nano structure of the present embodiment is 950nm, relief width
Degree d is 150nm, and inner ring radius is 320nm.
Embodiment 2
The production method of the coaxial annulus nanostructure of the column of the present embodiment difference from example 1 is that, substrate
For silica substrate.Inductively coupled plasma etching (ICP) etching silicon dioxide substrate uses C4F8With He mixed gas conduct
Reaction gas.Specific etch process parameters such as table 3:
The technological parameter of 3 inductively coupled plasma etching of table (ICP) etching substrate silica
The time that substrate silica is etched in the present embodiment is 190s.
The above embodiment is only for illustrating the present invention, and protection scope of the present invention is not intended to be limited to the above implementation
Example.The purpose of the present invention can be achieved according to the above present disclosure in person of an ordinary skill in the technical field, appoints
What is fallen within the scope of protection of the present invention based on the improvement and deformation made on the basis of present inventive concept, is specifically protected model
It encloses and is subject to what claims were recorded.
Claims (10)
1. a kind of production method of the coaxial annulus nanostructure of column, which comprises the following steps:
In the process that substrate surface forms pattern etching layer；
Pattern etching layer is handled, in the process that substrate surface forms the coaxial annulus nanostructure of column；
Using the coaxial annulus nanostructure of the column of substrate surface as exposure mask, substrate is performed etching, structure is transferred to substrate, and
The process for removing substrate surface structure.
2. the production method of the coaxial annulus nanostructure of column according to claim 1, which is characterized in that the figure is carved
Lose layer substrate surface by being followed successively by organic solvent-resistant corrosion layer from the bottom up, easily by organic solvent corrosion layer and material protection layer
It constitutes.
3. the production method of the coaxial annulus nanostructure of column according to claim 2, which is characterized in that described resistance to organic
Solvent corrosion layer is photoresist SU8 layers, and described is easily positive photoresist Ar-P-3740 by organic solvent corrosion layer；The material protection layer
For titanium layer or silicon dioxide layer.
4. the production method of the coaxial annulus nanostructure of column according to claim 2, which is characterized in that pattern etching
Layer is handled the following steps are included: being patterned into the first mask layer of radius r circular hole in pattern etching layer surface；Etching
Material protection layer in pattern etching layer, then etch easily by organic solvent corrosion layer and organic solvent-resistant corrosion layer, it is easily organic
Solvent corrosion layer and organic solvent-resistant corrosion layer etching radius are R, and R is greater than r, exposes substrate；Exposing substrate
Surface is patterned into the second mask layer of radius r circle；It removes easy by organic solvent corrosion layer, material guarantor in pattern etching layer
Sheath and the first mask layer retain organic solvent-resistant corrosion layer, form the coaxial annulus nanostructure of column in substrate surface.
5. the production method of the coaxial annulus nanostructure of column according to claim 4, which is characterized in that in pattern etching
The first mask layer that layer surface is patterned into radius r circular hole obtains in the following manner: passing through in pattern etching layer surface
Self-assembling method arranges one layer of nanosphere, handles nanosphere, so that the nanometer radius of a ball is r, is plated by physical deposition methods
Etching mask layer, then nanosphere is removed, it obtains being patterned into the first exposure mask of radius r circular hole in pattern etching layer surface
Layer.
6. the production method of the coaxial annulus nanostructure of column according to claim 4, which is characterized in that exposing base
The second mask layer that the surface at bottom is patterned into radius r circle plates etching mask layer by physical deposition methods and obtains.
7. the production method of the coaxial annulus nanostructure of column according to claim 5 or 6, which is characterized in that the quarter
Erosion mask layer is aluminium layer, layers of chrome, silicon dioxide layer or aluminum oxide layer.
8. the production method of the coaxial annulus nanostructure of column according to claim 5, which is characterized in that the nanosphere
For polystyrene nanospheres or silica nanosphere；Nanosphere carries out processing as using inductively coupled plasma etching (ICP)
Argon (Ar) ion etch process of technique or plasma cleaner performs etching nanosphere.
9. the production method of the coaxial annulus nanostructure of column according to claim 4, which is characterized in that etched features are carved
Lose material protection layer in layer, easily by organic solvent corrosion layer and organic solvent-resistant corrosion layer using dry etching technology；Etch base
Bottom is handled using dry etching technology；Remove it is easy by organic solvent corrosion layer, material protection layer in pattern etching layer, with
And first mask layer handled using corrosive liquid；Substrate surface structure is removed to remove using corrosive liquid.
10. the production method of the coaxial annulus nanostructure of column according to claim 1, which is characterized in that the column
The depth H of coaxial annulus nanostructure is in 10-3000nm, and the inner ring radius r of annulus is 100-1000nm, and gap d is in 10nm-
450nm。
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