CN109243662B - The preparation method of hanging thick golden zone plate lens without substrate supports - Google Patents
The preparation method of hanging thick golden zone plate lens without substrate supports Download PDFInfo
- Publication number
- CN109243662B CN109243662B CN201811075983.XA CN201811075983A CN109243662B CN 109243662 B CN109243662 B CN 109243662B CN 201811075983 A CN201811075983 A CN 201811075983A CN 109243662 B CN109243662 B CN 109243662B
- Authority
- CN
- China
- Prior art keywords
- zone plate
- etching
- photoresist
- preparation
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 52
- 239000010931 gold Substances 0.000 claims abstract description 52
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000004528 spin coating Methods 0.000 claims abstract description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 18
- 238000000609 electron-beam lithography Methods 0.000 claims abstract description 13
- 238000009713 electroplating Methods 0.000 claims abstract description 10
- 238000000992 sputter etching Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000002210 silicon-based material Substances 0.000 claims description 15
- 238000002207 thermal evaporation Methods 0.000 claims description 14
- 238000001039 wet etching Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000001020 plasma etching Methods 0.000 claims description 8
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- 238000001259 photo etching Methods 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 238000005240 physical vapour deposition Methods 0.000 claims description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 4
- 238000002161 passivation Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims 1
- 238000003384 imaging method Methods 0.000 abstract description 7
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 230000000873 masking effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
- G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
- G21K1/06—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators
- G21K1/065—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating using diffraction, refraction or reflection, e.g. monochromators using refraction, e.g. Tomie lenses
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Micromachines (AREA)
Abstract
The invention belongs to inductively coupled plasma etching technical field, the preparation method of the hanging thick golden zone plate lens of specially a kind of no substrate supports.Its step includes: spin coating HSQ photoresist on a si substrate, the design configuration of zone plate lens is formed on a photoresist as the etching masking layer of zone plate silicon template using the method for electron beam lithography, then the zone plate silicon template that deep reaction ion etching forms large ratio of height to width is carried out in inductively coupled plasma etching system, and golden electroplating technique is combined to be electroplated in silicon template with certain thickness gold, it finally removes residual photoresist exposure mask and removes silicon structure remaining in substrate silicon and Au zone plate, to obtain the hanging golden zone plate of the large ratio of height to width applied to hard x-ray imaging field.The method of the present invention controllability is good, process stabilizing, and is suitable for the preparation of the metal structure of large ratio of height to width.
Description
Technical field
The invention belongs to inductively coupled plasma etching technical field, specially a kind of silicon substrate hollow out gold zone plate is saturating
The preparation method of mirror.
Background technique
Key focus and image-forming component of the Fresnel zone plate as synchrotron radiation X-ray whole audience imaging system, manufacture
It is horizontal that the progress of technology will directly influence X-ray microtechnic.In order to realize the imaging of high quality, zone plate absorber gold knot
The thickness of structure is usually tens microns of orders of magnitude.Thicker wavestrip chip architecture is needed for high X-ray energy, such thickness is used
To ensure the attenuation length of hard X ray.
For the technology of preparing of X-ray zone plate, the penetration capacity of electronics is limited and the approach effect of electron beam lithography
Limit its attainable depth-width ratio of institute.There is result of study to show that electron beam lithography production focuses 100 nm of 9keV X-ray
Its depth-width ratio limit of zone plate is 20.The zone plate made with electron beam lithography, thickness is substantially at 2 μm or less.
Solve the effective way of this problem first is that formed the template that there is certain thickness structure as zone plate from
And improve the thickness of zone plate.Due to silicon process technology maturation, it is suitable for the template of zone plate.
The method forms zone plate using inductively coupled plasma etching system and in conjunction with deep reaction ion etching
Silicon template, and electroplating technology is combined to prepare the hanging golden zone plate lens of no substrate supports, it may be implemented 200 ~ 300 nm points
Resolution, the hanging golden zone plate of 3 ~ 5 μ m-thicks.4 μ m thicks can be extrapolated according to attenuation length of the X-ray in Au material
Self-supporting Au zone plate can be used for the x-ray imaging of 20 keV, this has broken the imaging bottleneck of hard X ray.Hard X ray is compared
Grenz ray penetration power is stronger, can carry out the imaging of thick sample, and grenz ray is only applicable to sample surfaces imaging.
This technique is applicable not only to the preparation of X-ray focusing and image-forming component, can be also used for photon screen, laser target, light
Collimation lens etc. needs the field of large ratio of height to width silicon structure.
Summary of the invention
It is an object of the invention to propose it is a kind of simple, conveniently, high-precision production have large ratio of height to width without substrate supports
Hanging golden zone plate lens method.
The preparation method of the hanging golden zone plate lens of no substrate supports proposed by the present invention, is by electron beam lithography skill
Art, inductively coupled plasma etching and electroplating technology combine, and making has the outstanding without substrate supports of large ratio of height to width
Empty gold zone plate lens structure, the specific steps are as follows:
(1) spin coating HSQ photoresist on a silicon substrate, it is saturating to form zone plate using the method for electron beam lithography on a photoresist
The photoetching offset plate figure of mirror;
(2) deep reaction ion etching is carried out in inductively coupled plasma etching system, forms the wavestrip of large ratio of height to width
Piece silicon template;General depth-width ratio > 30:1, such as depth-width ratio are 30:1--60:1;
(3) metal conducting layer is prepared on the sample that step (2) obtains, material is Cr/Au composite membrane, as seed
Layer;
(4) Si is grown in the sample reverse side that step (3) obtains3N4Diaphragm;
(5) the sample front and back sides spin coating PMMA photoresist for obtaining step (4), then progress overlay mark exposure, and
Open zone plate window in front;
(6) sample obtained to step (5) carries out plating Au;
(7) one Cr/Au composite membrane is grown using thermal evaporation to the sample reverse side that step (6) obtains, is marked as gold;
(8) the sample acetone obtained to step (7) removes front and back sides photoresist;
(9) sample reverse side step (8) obtained spin coating PMMA photoresist again, then wavestrip is formed in reverse side optics alignment
Piece light passing window;
(10) sample obtained to step (9) is exposed with the zone plate light passing window of reactive ion etching removal reverse side
Si3N4Diaphragm, and remove reverse side photoresist with acetone;
(11) KOH solution wet etching removes substrate silicon materials;
(12) HF solution wet etching removes HSQ remnants' exposure mask, then carries out inductively coupled plasma body quarter in front again
Etching off is except the silicon materials in zone plate gap.
In step (1) of the present invention, photoresist is HSQ photoresist, with a thickness of the nm of 300 nm ~ 600.And it toasts and is allowed to hard
Change, baking temperature is between 150 DEG C ~ 180 DEG C, and the time is in the min of 10 min ~ 30.
In step (2) of the present invention, the deep reaction ion etching is using Bosch etching method;Bosch work is directed to when etching
Skill is regulated and controled: by passivation gas C4F8Be added in etch step and control lateral etching, by inaction period and etching period when
Between respectively reduce to 3-5s and 5-8 s, to guarantee low sidewall roughness;
Fixed following technological parameter: coil power 600W, pole plate power 20W, 25 DEG C of bottom crown cooling temperature, passivation
C in period4F8Gas flow is 85 sccm and air pressure is 19 mtorr, the SF in etching period6Gas flow is 175
Sccm and air pressure are 35 mtorr, and etch and be fixed on 1 min, 30 s total time, carry out tracing analysis, find optimised process
Parameter area makes the thickness of zone plate silicon template be increased to 4 μm.
In step (3) of the present invention, the seed layer is prepared using the method for thermal evaporation or physical vapor deposition, material
For Cr/Au composite membrane, Cr is with a thickness of 5 nm ~ 15 nm, Au with a thickness of the nm of 5 nm ~ 15.
In step (4) of the present invention, Si3N4Diaphragm is grown using PECVD, with a thickness of the nm of 100 nm ~ 300.
In step (5) of the present invention, the photoresist of spin coating is PMMA, with a thickness of the nm of 300 nm ~ 400.Front windowing is circle
Shape, diameter are the mm of 4 mm ~ 6.
In step (6) of the present invention, plated material is gold, and current density when plating is in 0.3 A/dm2~ 1A/dm2, voltage
For 10-21V, electroplating time is the min of 10 min ~ 30.Plating metal with a thickness of 3 μm ~ 5 μm.
In step (7) of the present invention, gold label is prepared using the method for thermal evaporation or physical vapor deposition, material Cr/
Au composite membrane, Cr is with a thickness of 5 nm ~ 15 nm, Au with a thickness of the nm of 100 nm ~ 110.
In step (9) of the present invention, the photoresist of spin coating is PMMA, with a thickness of the nm of 300 nm ~ 400.Reverse side opens light window
For circle, diameter is 85 μm ~ 120 μm, this window size makes the wave of etching exposing obtained by KOH wet etching angle calculation
Strap periphery guarantees have the gold of 5 μm ~ 15 μm of width to make peripheral support.
In step (10) of the present invention, the etching gas used in the RIE etching process of silicon nitride is CHF3And O2Mixing
Gas, CHF3Gas flow is 40 sccm ~ 60 sccm, O2Gas flow be the sccm of 5 sccm ~ 15, power be 200 W ~
300 W, time are the min of 1 min ~ 3.
Using KOH solution that substrate silicon material etch is clean in step (11) of the present invention, etching time is the h of 11 h ~ 14.
In step (12) of the present invention, remove the remaining HSQ photoresist exposure mask of sample after plating, minimizing technology is wet process quarter
Erosion, such as HF solution.Silicon materials in the removal zone plate gap of front using dry etching, using inductive coupling etc. from
Daughter etching removal.
The method of the present invention can be divided into four parts:
First part, i.e. step (1), form etch mask: spin coating photoresist on a silicon substrate utilizes electron beam lithography
Method forms the photoetching offset plate figure of zone plate lens on a photoresist;This figure is by the exposure mask as subsequent etch step.Tool
Body includes: one layer of HSQ photoresist of spin coating on a silicon substrate, with a thickness of the nm of 300 nm ~ 600, carries out front baking;HSQ light will be had
The substrate of photoresist is exposed under electron beam lithography machine;Develop to figure after exposure;
Second part, i.e. step (2), form deep silicon template: carrying out in inductively coupled plasma etching system deep anti-
Ion etching is answered to form the zone plate silicon template of large ratio of height to width, deep reaction ion etching therein is using Bosch technique;
Part III, i.e. step (3) arrive step (6), and the transfer of nano graph: first preparing one layer of metal conducting layer, as
Seed layer, preparation method are thermal evaporation or physical vapor deposition, and material is Cr/Au composite membrane, and thickness is respectively 5 nm ~ 15
nm/5 nm~15 nm;This layer of seed layer and silicon substrate adhesiveness are good, prepare for subsequent plating Au;Wavestrip gate is opened in front
The pattern transfer of silicon template is the figure of Au zone plate by the mouth Au that then electroplating thickness is 3 μm ~ 5 μm;
Part IV, i.e. step (7) arrive step (12), remove residual photoresist exposure mask and silicon removal: for it is electroplated
Sample afterwards is engraved in reverse side windowing using set, removes the Si of exposing3N4Diaphragm and KOH remove substrate silicon materials;Then exist
HF solution uses inductively coupled plasma etching to remove the silicon in zone plate gap after removing remnants HSQ photoresist exposure mask.
In the present invention, the structure of this hanging golden zone plate does not need diaphragm support figure, supports wave using reinforcing rib structure
Strap annulus is hanging to ensure.Wherein, reinforcing rib is the radiation vertical element that each ring is connected along radial direction.For designed
The outermost ring width of 300 nm, diameter be 40 μm of zone plate, reinforcing rib number is 24, and width is 300 nm.
The number of area size and reinforcing rib that hanging fastness is reserved by alignment in control electroplating technology and width come
Control, by guaranteeing hanging fastness with external support inside zone plate.The zone plate of 2 microns or more thickness is not available electricity
Beamlet photoetching making, and the hard X ray that the hanging golden zone plate of this 4 micron thickness can be used for 20 keV focuses.
The method of the present invention controllability is good, process stabilizing, and is suitable for the preparation of the metal structure of large ratio of height to width.
The concrete operations process of the method for the present invention is as follows
(1) monocrystalline substrate is selected, substrate is cleaned;
(2) the HSQ photoresist that spin coating a layer thickness is the nm of 300 nm ~ 600 on substrate, carries out front baking processing;
(3) it selects suitable dosage to be exposed processing under electron beam lithography machine, develops to figure after exposure, shape
At the photoetching offset plate figure of zone plate lens;
(4) zone plate of large ratio of height to width is formed using Bosch etching technics in inductively coupled plasma etching system
Silicon template;
(5) one layer of metal conducting layer is prepared on obtained sample, as seed layer;
(6) Si is grown in sample reverse side3N4Diaphragm;
(7) then spin coating photoresist in sample front and back sides is subjected to front baking processing;
(8) it carries out overlay mark exposure and zone plate window is opened in front;
(9) plating Au is carried out to sample;Reverse side is using thermal evaporation growth layer of Au as gold label;
(10) remove front and back sides photoresist with acetone;
(11) reverse side spin coating photoresist again;
(12) zone plate light passing window is formed in reverse side optics alignment;
(13) Si that the zone plate light passing window of reactive ion etching removal reverse side exposes3N4Diaphragm;
(14) remove reverse side photoresist with acetone;
(15) KOH solution wet etching removes substrate silicon materials;
(16) HF solution wet etching removes HSQ remnants' exposure mask;
(17) silicon materials in inductively coupled plasma etching removal zone plate gap are carried out in front.
Detailed description of the invention
Fig. 1 is designed zone plate geometric graph and photoetching alignment mark figure.
Fig. 2 to Figure 18 is respectively corresponded in embodiment 1 in 17 steps according to the sequence of the above-mentioned making step of the present invention
The sectional view (reflect sample structure change situation) of 17 sample structures.
Fig. 2 corresponds to step 1: cleaning monocrystalline substrate.
Fig. 3 corresponds to step 2: spin coating HSQ photoresist on substrate.
Fig. 4 corresponds to the mask pattern for formation of developing after step 3:EBL exposes.
Fig. 5 corresponds to step 4: the large ratio of height to width silicon template formed after etching.
Fig. 6 corresponds to step 5: one layer of Cr/Au seed layer of thermal evaporation.
Fig. 7 corresponds to step 6: sample reverse side grows Si3N4Diaphragm.
Fig. 8 corresponds to step 7: front and back sides spin coating photoresist.
Fig. 9 corresponds to step 8: carrying out overlay mark exposure and zone plate window is opened in front.
Figure 10 corresponds to step 9: certain thickness Au is electroplated, reverse side is using thermal evaporation growth layer of Au as gold label.
Figure 11 corresponds to step 10: acetone removes front and back sides photoresist.
Figure 12 corresponds to step 11: reverse side spin coating photoresist again.
Figure 13 corresponds to step 12: forming zone plate light passing window in reverse side optics alignment.
Figure 14 corresponds to step 13: reactive ion etching removes the Si that reverse side exposes3N4Diaphragm.
Figure 15 corresponds to step 14: acetone removes reverse side photoresist.
Figure 16 corresponds to step 15:KOH solution wet etching removal substrate silicon materials.
Figure 17 corresponds to step 16:HF solution wet etching removal HSQ remnants' exposure mask.
Figure 18 corresponds to step 17: front carries out the silicon materials in inductively coupled plasma etching removal zone plate gap.
Figure 19 is the hanging golden zone plate schematic diagram that the present invention is realized.
Specific embodiment
Implementation of the invention is further described by way of example with reference to the accompanying drawing, but the present invention is not limited only to reality
Example.All technological parameters in embodiment have carried out simple change, belong within the scope of the present invention.
Embodiment 1: the hanging golden zone plate lens without substrate supports of large ratio of height to width are prepared:
(1)<100>crystal orientation is selected, resistivity is the n type single crystal silicon substrate of 1 ~ 10 Ω cm and cleans up substrate.
Silicon wafer is put into acetone first and is impregnated, this process combines ultrasonic treatment 10min.Then silicon substrate film is put into aqueous isopropanol
Taking-up dries up substrate slice with nitrogen gun after 5 min of middle infiltration, as a result as shown in Figure 2;
(2) the HSQ electron beam resist of 375 nm of spin coating thickness again after spin coating HMDS adhesion layer on a silicon substrate, and
It toasts 10 min in 180 DEG C of baking ovens to be allowed to harden, as a result as shown in Figure 3;
(3) sample is exposed processing under electron beam lithography machine, exposure dose is 1700 μ C/cm2;
(4) TMAH/H for being 1:2.5 in the volume ratio that temperature is 50 DEG C23 min that develop in O mixed solution are later in H2O
30 s of middle fixing, as a result as shown in Figure 4;
(5) it is formed after HSQ exposure mask, is formed in inductively coupled plasma etching system using Bosch etching technics
The zone plate silicon template of large ratio of height to width.The time of inaction period and etching period is respectively 4 s and 5 s, lower pole in etching technics
Plate cooling temperature is 25 DEG C, C4F8Gas flow is 85sccm and air pressure is 19 mtorr, and the air pressure in etching period is 35
Mtorr, and also joined in etching period the C of 85sccm4F8, respectively 400 W and 35 of coil power and pole plate power
W, SF6Gas flow is 150 sccm, and etch period is 9 min, and the zone plate silicon template thickness of etching is 4.1 μm, outer ring width
Degree is 220 nm.It is as shown in Figure 5 to etch result;
(6) the Cr/Au composite membrane that a layer thickness is respectively the nm of 5 nm/15 is deposited using thermal evaporation, as metallic conduction
Layer, as a result as shown in Figure 6;
(7) Si is grown using PECVD3N4Diaphragm, with a thickness of 100 nm, as a result as shown in Figure 7;
(8) front and back sides spin coating with a thickness of 300 nm PMMA photoresist, and in 180 DEG C of baking ovens toast 1h be allowed to harden,
As a result as shown in Figure 8;
(9) it carries out overlay mark exposure and zone plate window is opened in front, window is circle, and diameter is 4 mm, zone plate
In window center position, as a result as shown in Figure 9;
(10) plating Au is carried out to sample, electroplating voltage is 50 V, in 0.5 A/dm23 min are electroplated under current density, then
In 0.75 A/dm23 min are electroplated under current density, be electroplated Au with a thickness of 1.2 μm.Again in reverse side using thermal evaporation growth one
Layer Au is Cr/Au composite membrane as gold label, material, and thickness is respectively the nm of 5 nm/100;The results are shown in Figure 10;
(11) remove front and back sides photoresist with acetone;As a result as shown in figure 11;
(12) reverse side again spin coating with a thickness of 300 nm PMMA photoresist, and in 180 DEG C of baking ovens toast 1h be allowed to hard
Change, as a result as shown in figure 12;
(13) zone plate light passing window is formed in reverse side optics alignment again, window is circle, and diameter, which is 100 μm, to be made to etch
The zone plate periphery of exposing guarantees have the gold of 10 μm of width to make peripheral support.As a result as shown in figure 13;
(14) Si that the zone plate light passing window of reactive ion etching removal reverse side exposes3N4Diaphragm;The etching gas of use
For CHF3And O2Mixed gas, CHF3Gas flow is 50 sccm, O2Gas flow is 12sccm, and power is 300 W, when
Between be 1 min30 s.As a result as shown in figure 14;
(15) remove reverse side photoresist with acetone;As a result as shown in figure 15;
(16) it is carried out at 80 DEG C using the KOH solution (KOH of 500 g, the water of 1200 ml, 200 ml ethyl alcohol) of 30 %
Wet etching, 13 h of corrosion remove the substrate silicon materials of 500 μ m thicks.As a result as shown in figure 16;
(17) HF solution wet etching removes HSQ remnants' exposure mask, as a result as shown in figure 17;
(18) silicon materials in inductively coupled plasma etching removal zone plate gap are carried out in front;As a result such as Figure 18
It is shown.
Embodiment 2: the preparation of the silicon nanometer column template applied to photon sieve with high height-width ratio:
The main distinction of this embodiment and upper example is: this HSQ photoresist mask pattern is round dot matrix.In addition,
The parameter used in the part steps also have it is a little it is different in addition to, other are identical as precedent.
(1)<100>crystal orientation is selected, resistivity is the n type single crystal silicon substrate of 1 ~ 10 Ω cm and cleans up substrate.
Silicon wafer is put into acetone first and is impregnated, this process combines ultrasonic treatment 10min.Then silicon substrate film is put into aqueous isopropanol
Taking-up dries up substrate slice with nitrogen gun after 5 min of middle infiltration, as a result as shown in Figure 2;
(2) the HSQ electron beam resist of 430 nm of spin coating thickness again after spin coating HMDS adhesion layer on a silicon substrate, and
It toasts 10 min in 180 DEG C of baking ovens to be allowed to harden, as a result as shown in Figure 3;
(3) sample is exposed processing under electron beam lithography machine, exposure dose is 3000 μ C/cm2;
(4) TMAH/H for being 1:2.5 in the volume ratio that temperature is 50 DEG C21 min that develops in O mixed solution is later in H2O
30 s of middle fixing, as a result as shown in Figure 4;
(5) it is formed after HSQ exposure mask, is formed in inductively coupled plasma etching system using Bosch etching technics
The silicon nanometer column template of large ratio of height to width.The time of inaction period and etching period is respectively 4 s and 5 s, lower pole in etching technics
Plate cooling temperature is 25 DEG C, C4F8Gas flow is 85sccm and air pressure is 19 mtorr, and the air pressure in etching period is 35
Mtorr, and also joined in etching period the C of 85sccm4F8, respectively 400 W and 35 of coil power and pole plate power
W, SF6Gas flow is 150 sccm, and etch period is 25 min, and the silicon stem height of etching is 13.3 μm.Etch result such as
Shown in Fig. 5;
(6) the Cr/Au composite membrane that a layer thickness is respectively the nm of 5 nm/15 is deposited using thermal evaporation, as metallic conduction
Layer, as a result as shown in Figure 6;
(7) Si is grown using PECVD3N4Diaphragm, with a thickness of 100 nm, as a result as shown in Figure 7;
(8) front and back sides spin coating with a thickness of 300 nm PMMA photoresist, and in 180 DEG C of baking ovens toast 1h be allowed to harden,
As a result as shown in Figure 8;
(9) it carries out overlay mark exposure and photon screen window is opened in front, window is circle, and diameter is 4 mm, photon screen
In window center position, as a result as shown in Figure 9;
(10) plating Au is carried out to sample, electroplating voltage is 50 V, in 0.5 A/dm23 min are electroplated under current density, then
In 0.75 A/dm23 min are electroplated under current density, be electroplated Au with a thickness of 1.2 μm.Again in reverse side using thermal evaporation growth one
Layer Au is Cr/Au composite membrane as gold label, material, and thickness is respectively the nm of 5 nm/100;The results are shown in Figure 10;
(11) remove front and back sides photoresist with acetone;As a result as shown in figure 11;
(12) reverse side again spin coating with a thickness of 300 nm PMMA photoresist, and in 180 DEG C of baking ovens toast 1h be allowed to hard
Change, as a result as shown in figure 12;
(13) photon screen light passing window is formed in reverse side optics alignment again, window is circle, and diameter, which is 100 μm, to be made to etch
The photon screen periphery of exposing guarantees have the gold of 10 μm of width to make peripheral support.As a result as shown in figure 13;
(14) Si that the light passing window of reactive ion etching removal reverse side exposes3N4Diaphragm;The etching gas used is CHF3
And O2Mixed gas, CHF3Gas flow is 50 sccm, O2Gas flow is 12sccm, and power is 300 W, time 1
min30 s.As a result as shown in figure 14;
(15) remove reverse side photoresist with acetone;As a result as shown in figure 15;
(16) it is carried out at 80 DEG C using the KOH solution (KOH of 500 g, the water of 1200 ml, 200 ml ethyl alcohol) of 30 %
Wet etching, 13 h of corrosion remove the substrate silicon materials of 500 μ m thicks;As a result as shown in figure 16;
(17) HF solution wet etching removes HSQ remnants' exposure mask, as a result as shown in figure 17;
(18) silicon materials in inductively coupled plasma etching removal photon screen gap are carried out in front.As a result such as Figure 18
It is shown.
Claims (10)
1. a kind of preparation method of the hanging thick golden zone plate lens of no substrate supports, which is characterized in that specific step is as follows:
(1) spin coating HSQ photoresist on a silicon substrate, forms zone plate lens using the method for electron beam lithography on a photoresist
Photoetching offset plate figure;
(2) deep reaction ion etching is carried out in inductively coupled plasma etching system, forms the zone plate silicon of large ratio of height to width
Template;Depth-width ratio > 30:1;
(3) metal conducting layer is prepared on the sample that step (2) obtains, material is Cr/Au composite membrane, as seed layer;
(4) Si is grown in the sample reverse side that step (3) obtains3N4Diaphragm;
(5) the sample front and back sides spin coating PMMA photoresist for obtaining step (4) then carries out overlay mark exposure, and in front
Open zone plate window;
(6) sample obtained to step (5) carries out plating Au;
(7) one Cr/Au composite membrane is grown using thermal evaporation to the sample reverse side that step (6) obtains, is marked as gold;
(8) the sample acetone obtained to step (7) removes front and back sides photoresist;
(9) sample reverse side step (8) obtained spin coating PMMA photoresist again, then in reverse side optics alignment to form zone plate logical
Light window;
(10) sample that step (9) is obtained, the Si exposed with the zone plate light passing window of reactive ion etching removal reverse side3N4
Diaphragm, and remove reverse side photoresist with acetone;
(11) KOH solution wet etching removes substrate silicon materials;
(12) HF solution wet etching removes HSQ remnants' exposure mask, then carries out inductively coupled plasma etching in front again and goes
Except the silicon materials in zone plate gap.
2. preparation method according to claim 1, which is characterized in that in step (1), HSQ photoresist is with a thickness of 300
nm~600 nm;And toast and be allowed to harden, baking temperature is 150 DEG C to 180 DEG C, and the time is the min of 10 min ~ 30.
3. preparation method according to claim 1, which is characterized in that in step (2), the deep reaction ion etching is
Using Bosch etching method;Regulated and controled when etching for Bosch technique: by passivation gas C4F8It is added in etch step and controls
Lateral etching respectively reduces the time of inaction period and etching period to 3-5s and 5-8 s, to guarantee that low sidewall is coarse
Degree.
4. preparation method according to claim 1, which is characterized in that seed layer described in step (3) utilizes thermal evaporation
Or prepared by the method for physical vapor deposition, in Cr/Au composite membrane, Cr is with a thickness of 5 nm ~ 15 nm, Au with a thickness of 5 nm ~ 15
nm。
5. preparation method according to claim 1, which is characterized in that in step (4), Si3N4Diaphragm is raw using PECVD
It is long, with a thickness of the nm of 100 nm ~ 300.
6. preparation method according to claim 1, which is characterized in that in step (5), PMMA photoresist with a thickness of 300
nm~400 nm;Front windowing is circle, and diameter is the mm of 4 mm ~ 6.
7. preparation method according to claim 1, which is characterized in that in step (6), current density when plating is 0.3
A/dm2~ 1A/dm2, voltage is 10 V ~ 21V, and electroplating time is the min of 10 min ~ 30;Electroplating gold with a thickness of 3 μm ~ 5 μm.
8. preparation method according to claim 1, which is characterized in that in step (7), gold label utilizes thermal evaporation or object
Prepared by the method for managing vapor deposition, in Cr/Au composite membrane, Cr is with a thickness of 5 nm ~ 15 nm, Au with a thickness of 100 nm ~ 110
nm。
9. preparation method according to claim 1, which is characterized in that in step (9), PMMA photoresist is with a thickness of 300
nm~400 nm;Reverse side opens light window as circle, and diameter is 85 μm ~ 120 μm, this window size is by KOH wet etching angle
Gained is calculated, the zone plate periphery for exposing etching guarantees have the gold of 5 μm ~ 15 μm of width to make peripheral support.
10. preparation method according to claim 1, which is characterized in that in step (10), in Si3N4RIE etching process
The middle etching gas used is CHF3And O2Mixed gas, CHF3Gas flow is 40 sccm ~ 60 sccm, O2Gas flow
For the sccm of 5 sccm ~ 15, power is the W of 200 W ~ 300, and the time is the min of 1 min ~ 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811075983.XA CN109243662B (en) | 2018-09-14 | 2018-09-14 | The preparation method of hanging thick golden zone plate lens without substrate supports |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811075983.XA CN109243662B (en) | 2018-09-14 | 2018-09-14 | The preparation method of hanging thick golden zone plate lens without substrate supports |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109243662A CN109243662A (en) | 2019-01-18 |
CN109243662B true CN109243662B (en) | 2019-12-03 |
Family
ID=65058528
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811075983.XA Expired - Fee Related CN109243662B (en) | 2018-09-14 | 2018-09-14 | The preparation method of hanging thick golden zone plate lens without substrate supports |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109243662B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111175861B (en) * | 2020-01-17 | 2021-06-15 | 中国科学院长春光学精密机械与物理研究所 | Design and preparation method of multi-focal-length curved fly-eye lens |
CN113151801B (en) * | 2021-03-03 | 2022-12-27 | 电子科技大学 | Preparation method of self-supporting suspended carbon film |
CN113707357B (en) * | 2021-07-08 | 2024-05-17 | 湖南大学 | Preparation method of high-aspect-ratio zone plate |
CN113793714A (en) * | 2021-07-28 | 2021-12-14 | 湖南大学 | Preparation method for large-area soft X-ray zone plate |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR910006164B1 (en) * | 1987-03-18 | 1991-08-16 | 가부시키가이샤 도시바 | Making method and there device of thin film |
WO2011000622A1 (en) * | 2009-06-30 | 2011-01-06 | Asml Netherlands B.V. | Spectral purity filter, lithographic apparatus, and method for manufacturing a spectral purity filter |
CN102466832B (en) * | 2010-11-12 | 2013-09-11 | 中国科学院微电子研究所 | Method for manufacturing photon sieve with high height-width ratio |
-
2018
- 2018-09-14 CN CN201811075983.XA patent/CN109243662B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN109243662A (en) | 2019-01-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109243662B (en) | The preparation method of hanging thick golden zone plate lens without substrate supports | |
TWI288116B (en) | Method of manufacturing a LIGA mold by backside exposure | |
CN101677231B (en) | Method of producing surface acoustic wave devices by exposing X-rays | |
JP2010144250A (en) | Method for forming microscopic structure on substrate | |
CN110970147B (en) | High-resolution hard X-ray tungsten/gold Fresnel zone plate and preparation method thereof | |
US11803121B2 (en) | Method for manufacturing a horology component | |
CN112885951B (en) | Porous superconductive niobium nitride nanowire and preparation method thereof | |
CN104465337A (en) | Method for manufacturing metal nanometer slit through PMMA/NEB double-layer glue | |
CN109116454B (en) | Method for preparing grating | |
CN102608687A (en) | Large height-width ratio photon sieve and preparation method thereof | |
CN109087837B (en) | Preparation method of streak camera photocathode | |
Chen et al. | Fabrication of high-aspect-ratio Fresnel zone plates by e-beam lithography and electroplating | |
CN108242398A (en) | Method for Forming Complex Curved Surface on Wafer Surface | |
US11960205B2 (en) | Method for manufacturing a horology component | |
JP2001100395A (en) | Mask for exposure and method for manufacturing the same | |
JPH0689847A (en) | X-ray mask structure and its manufacture, x-ray exposure using the structure, and device manufactured by using the structure | |
CN102495526B (en) | Optical exposing method, and method for applying optical exposure in preparation of silicon material vertical hollow structure | |
CN102466832B (en) | Method for manufacturing photon sieve with high height-width ratio | |
CN115520833A (en) | Multistage micro-nano structure and preparation method and application thereof | |
RU2421833C2 (en) | Metal mesh structure and method of making said structure | |
CN103303860A (en) | Method for generating 0-50nm of random-height nano step on surface of Si | |
CN104319098B (en) | The preparation method of interdigital capacitor and the method for forming adjacent evaporation pattern | |
CN101734619B (en) | Method for preparing material with highly gradient surface micronano structure | |
Pil-Ali et al. | A novel multi-layer grating structure for X-ray phase-contrast imaging | |
JPH0795506B2 (en) | Method for manufacturing mask for X-ray exposure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191203 |