CN106647187A - Preparation method of small-period array structure - Google Patents
Preparation method of small-period array structure Download PDFInfo
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- CN106647187A CN106647187A CN201710029268.1A CN201710029268A CN106647187A CN 106647187 A CN106647187 A CN 106647187A CN 201710029268 A CN201710029268 A CN 201710029268A CN 106647187 A CN106647187 A CN 106647187A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
- G03F7/203—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure comprising an imagewise exposure to electromagnetic radiation or corpuscular radiation
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The invention discloses a preparation method of a small-period array structure and relates to the technical field of two-dimensional micro-nano devices. The preparation method is used for preparing the small-period array structure on a substrate, and comprises the following steps: step 1, spin-coating photoresist on the substrate; step 2, scanning an exposed pattern on the photoresist through adopting an electron beam photoetching process, so as to obtain a photoresist pattern, wherein an exposed step length of the electron beam photoetching process is a large step length so as to guarantee that the photoresist between two electron beam spots is not exposed; step 3, transferring the photoresist pattern onto the substrate, so as to obtain a sample; step 4, putting the sample into photoresist removing liquid to obtain the small-period array structure on the substrate. By adopting the preparation method disclosed by the invention, the step length and dosage of electron beam exposure are controlled, and a small-period array pattern is formed on an electron beam exposure region in a process of scanning on the large-area pattern; the preparation method has the characteristics of rapidness in preparation, good controllability, low cost, capability of preparing in a large area and the like.
Description
Technical field
The present invention relates to two-dimentional micro-nano device technical field, more particularly to a kind of preparation of minor cycle nano array structure
Method
Background technology
With the development of electronic device and optics, the nano array structure of minor cycle is more and more used
In the device for being used.For example in optical material, the dimension of the response frequency of optics Meta Materials and metamaterial structure used with
Cycle is directly related.The response frequency of optics Meta Materials is higher, and its corresponding Meta Materials dimension and cycle will be less, if will
The Meta Materials of visible light wave range are obtained, structural cycle needs control below 500 nanometers.It is less when electronic device is made
The integrated level that electronic device is provided is higher.And it is current to integrated level requirement more and more higher, there are various sides in prior art
Formula improving integrated level, such as by preparing three-dimensional electronic device to increase the integrated level in short transverse, by advanced
Equipment reduces characteristic size of device etc..
The realization of generally minor cycle structure is obtained by traditional e-beam lithography or extreme ultraviolet technique
's.Although these approach can greatly reduce the characteristic size of device or structure, these methods there is also some problems, example
Such as e-beam lithography, when minor cycle array is prepared, speed is too slow, and extreme ultraviolet equipment is relatively expensive etc..And with
The continuous expansion of minor cycle topology requirement, process above can not meet the demand of present scientific research and processing.
The content of the invention
It is an object of the invention to provide a kind of preparation method of new minor cycle array structure.
Especially, the invention provides a kind of preparation method of minor cycle array structure, for preparing Xiao Zhou on substrate
Phase array structure, including：
Step one：The spin coating photoresist on substrate；
Step 2：E-beam lithography scan exposure figure is adopted on the photoresist, photoetching offset plate figure is obtained, its
In, the step-length of the e-beam lithography exposure is big step-length, will not be exposed with the photoresist ensured between two beam spots
Light；
Step 3：The photoetching offset plate figure is transferred on the substrate, sample is obtained；
Step 4：The sample is placed in glue, the minor cycle array structure on the substrate is obtained.
Further, the substrate in the step one is silicon substrate, silicon dioxide substrates, Sapphire Substrate or is putting down
The arbitrary plane substrate with thin-film material being processed on face；
Preferably, the substrate is grown silicon nitride film, silicon dioxide film or silicon carbide film on the silicon substrate substrate.
Further, the photoresist in the step one is positive glue or negative glue；
Preferably, the positive glue is polymethyl methacrylate；
Preferably, the negative glue is hydrogen silicon silsequioxane.
Further, exposure figure is single figure or complex figure in the step 2, wherein, complex figure is two
Or the dislocation of multiple figures is overlapped.
Further, the step-length of the exposure of the e-beam lithography in the step 2 is 100nm～500nm, is exposed
Dosage is adjustable, by the cycle of minor cycle array structure described in the step size controlling of adjustment exposure, by adjusting exposure dose control
The radius of the single figure.
Further, it is that the photoetching offset plate figure is transferred on the substrate using depositing operation in the step 3；
Preferably, the depositing operation is thermal evaporation process, electron-beam deposition methods or pulse laser deposition process.
Further, the depositing operation material therefor is metal material, dielectric material or semi-conducting material；
Preferably, the metal material is gold, silver or chromium；
Preferably, the dielectric material is tin indium oxide or aluminum oxide；
Preferably, the semi-conducting material is zinc oxide or gallium nitride.
Further, it is characterised in that be to be transferred to the photoetching offset plate figure using etching technics in the step 3
On the substrate；
Preferably, the etching technics is ion beam etching, plasma etching or wet etching.
Further, it is described to remove glue to remove glue acetone or removing glue DMA.
Using the preparation method of the present invention, controlled using the step-length and dosage of electron beam exposure technique, in large area pattern
Exposure area becomes the nano-pillar of minor cycle during upper scanning.And can be by control step-length and dosage precise control nano-array
Cycle and radius, using exposure figure dislocation overlap realize multiexposure, multiple exposure, precision is higher compared with traditional alignment process,
The nano graph of complexity can be formed, is a kind of very flexible preparation method.
Description of the drawings
Describe some specific embodiments of the present invention in detail by way of example, and not by way of limitation with reference to the accompanying drawings hereinafter.
Identical reference denotes same or similar part or part in accompanying drawing.It should be appreciated by those skilled in the art that these
What accompanying drawing was not necessarily drawn to scale.In accompanying drawing：
Fig. 1 is the flow chart of the preparation method of the minor cycle array structure of one embodiment of the invention；
Fig. 2 is the flow chart of the preparation method of the minor cycle array structure of another embodiment of the present invention；
Fig. 3 is the signal of the minor cycle nano array structure when the step-length of electron beam exposure is more than the diameter of single figure
Property plan；
Fig. 4 is the signal of the minor cycle nano array structure when the step-length of electron beam exposure is less than the diameter of single figure
Property plan；
Fig. 5 is cycle the sweeping for the minor cycle nano array structure of 150nm for adopting the preparation method of the present invention to prepare
Retouch electron micrograph；
Fig. 6 is cycle the sweeping for the minor cycle nano array structure of 450nm for adopting the preparation method of the present invention to prepare
Retouch electron micrograph.
Specific embodiment
Fig. 1 is the flow chart of the preparation method of the minor cycle array structure of one embodiment of the invention.As shown in figure 1, a kind of
The preparation method of minor cycle array structure, including：
Step one：Spin coating photoresist 1 on the substrate 2.
Substrate 2 used in step one can be for silicon substrate, silicon dioxide substrates or Sapphire Substrate, or in institute
Grown silicon nitride film, silicon dioxide film or silicon carbide film on silicon substrate substrate are stated, the band being processed in the plane is can also be
There is the arbitrary plane substrate of thin-film material.
Photoresist 1 used in step one is positive glue or negative glue.Photoresist can soon occur Jing after illumination in exposure region
Reaction so that the physical property of this material, particularly dissolubility, affinity etc. occur significant change, at Jing appropriate solvent
Reason, dissolves soluble part, obtains required figure.Form insoluble material after illumination is negative glue；Conversely, being to some solvents
Insoluble, soluble substance is become Jing after illumination is positive glue.Wherein, positive glue can be polymethyl methacrylate (PMMA)
Can be that hydrogen silicon silsequioxane (HSQ) and PMMA add modified adhesive (ZEP) of phenyl ring etc. Deng, negative glue.
Step 2：The photoetching process scan exposure figure of electron beam 3 is adopted on photoresist 1, photoetching offset plate figure is obtained, its
In, the step-length of the photoetching process of electron beam 3 exposure is big step-length, will not be exposed with the photoresist 1 ensured between two beam spots.
Exposure figure is single figure or complex figure in step 2, wherein, complex figure is single for two or more
The dislocation of figure is overlapped.
The step-length of the exposure of the photoetching process of electron beam 3 in step 2 is 100nm～500nm, and exposure dose is adjustable, passes through
The cycle of minor cycle array structure described in the step size controlling of adjustment exposure, by the radius for adjusting the single figure of exposure dose control
R。
Fig. 3 is the signal of the minor cycle nano array structure when the step-length of the exposure of electron beam 3 is more than single pattern diameter
Property plan.As shown in figure 3, the graphic structure prepared is single graphic structure.Fig. 4 is when the step-length of the exposure of electron beam 3 is little
The schematic plan view of minor cycle nano array structure when single pattern diameter.
In step 2, step-length L exposed using e-beam lithography is controlled with dosage, is scanned on large area pattern
When the exposure area of electron beam 3 become minor cycle array structure.The preparation method can be by control e-beam lithography exposure
Step-length L and electron beam 3 exposure dose precise control minor cycle array cycle and the radius R of single figure, using single
The dislocation of figure is overlapped realizes multiexposure, multiple exposure, forms complex figure.
Step 3：Photoetching offset plate figure is transferred on substrate 2, sample is obtained；
In step 3, photoetching offset plate figure transfer has different implementation methods.As shown in figure 1, being using heavy in step 3
Product technique is transferred to photoetching offset plate figure on substrate 2.Material 4 is carried out using depositing operation to deposit.The material 4 is by depositing work
Skill deposits to substrate surface and forms sedimentary, obtains sample.The depositing operation can be thermal evaporation process, electron beam deposition work
Skill or pulse laser deposition process etc..Depending on the thickness L1 of sedimentary can be according to actual conditions.Material used in depositing operation
Can be metal material, dielectric material or semi-conducting material.Wherein, the metal material can be gold, silver or chromium etc., be given an account of
Material can be ITO or aluminum oxide etc., and the semi-conducting material can be zinc oxide or gallium nitride etc..
Step 4：The sample that step 3 is obtained is placed in glue, minor cycle nano-array knot is obtained on the substrate 2
Structure.
The different correspondences of photoresist 1 it is different remove glue.Glue is gone to be removing photoresist for hydrogen silicon silsequioxane (HSQ)
Liquid acetone or ZEP's removes glue DMAC N,N' dimethyl acetamide.
This preparation method has that to prepare quick, controllability good, inexpensive and can large area the features such as prepare.This method and biography
The alignment process of system compares that precision is higher, can form the nano-scale pattern of complexity, is a kind of very flexible preparation method.
Fig. 2 is the flow chart of the preparation method of the minor cycle array structure of another embodiment of the present invention.In Fig. 2 embodiment with
The difference of embodiment in Fig. 1 is, is that substrate 2 is performed etching using etching technics in Fig. 2 three the step of embodiment, part
The substrate 2 for not covering photoresist 1 is etched, with certain etching depth L2.Above-mentioned etching technics can for ion beam etching,
The technique such as plasma etching or wet etching.Depending on etching depth L2 can be according to actual conditions.
Different materials can select corresponding structure transfer process.
Fig. 5 is the minor cycle nano array structure for adopting cycle for preparing of preparation method of the present invention for 150 nanometers
Electron scanning micrograph.By following steps, you can prepare minor cycle nano array structure as shown in Figure 5：
Step one：The spin coating electron beam resist PMMA on finished product silicon substrate, rotating speed 4000r/min, are finally placed in 180 DEG C
1min is toasted on hot plate.
Step 2：Exposed on the sample that step one is obtained using electron beam exposure technique, the step-length of electron beam exposure sets
150nm is set to, 100 μm are scanned2Rectangular area.
Step 3：The sample that step 2 is obtained is placed in the solution of methyl iso-butyl ketone (MIBK) (MIBK), development obtains photoetching
Glue pattern, using thermal evaporation process gold 60nm is deposited；
Step 4：The sample that step 3 is obtained is placed in acetone, is soaked 4 hours, gently blow away the metal of sample surfaces,
Pull sample out and dried up with nitrogen, obtain the golden array structure that the cycle is 150nm.
Fig. 6 is the minor cycle nano array structure for adopting cycle for preparing of preparation method of the present invention for 450 nanometers
Electron scanning micrograph.By following steps, you can prepare minor cycle nano array structure as shown in Figure 6：
Step one：There are spin coating electron beam resist ZEP on the silicon substrate of 300nm silica, rotating speed 4000r/ in growth
Min, is subsequently placed on 180 DEG C of hot plates and toasts 1min.
Step 2：Exposed on the sample that step one is obtained using big step-length electron beam exposure technique, electron beam exposure
Step-length is set to 300nm, scans 100 μm2Rectangular area three times, the original position of three exposures constitutes an equilateral triangle
Type, the length of side is 100nm.
Step 3：The sample that step 2 is obtained is placed in butyl acetate, development obtains photoetching offset plate figure, using electron beam
Evaporation technology deposits nickel 30nm.
Step 4：The sample that step 3 is obtained is placed in acetone, is soaked 4 hours, gently blow away the metal of sample surfaces,
Pull sample out and dried up with nitrogen, obtain the nickel array structure that the cycle is 300nm.
So far, although those skilled in the art will appreciate that detailed herein illustrate and describe multiple showing for the present invention
Example property embodiment, but, without departing from the spirit and scope of the present invention, still can be direct according to present disclosure
It is determined that or deriving many other variations or modifications for meeting the principle of the invention.Therefore, the scope of the present invention is understood that and recognizes
It is set to and covers all these other variations or modifications.
Claims (9)
1. a kind of preparation method of minor cycle array structure, including：
Step one：The spin coating photoresist on substrate；
Step 2：E-beam lithography scan exposure figure is adopted on the photoresist, photoetching offset plate figure is obtained, wherein,
The step-length of the e-beam lithography exposure is big step-length, will not be exposed with the photoresist ensured between two beam spots；
Step 3：The photoetching offset plate figure is transferred on the substrate, sample is obtained；
Step 4：The sample is placed in glue, the minor cycle array structure on the substrate is obtained.
2. preparation method according to claim 1, it is characterised in that the substrate in the step one be silicon substrate,
Silicon dioxide substrates, Sapphire Substrate or the arbitrary plane substrate with thin-film material being processed in the plane；
Preferably, the substrate is grown silicon nitride film, silicon dioxide film or silicon carbide film on the silicon substrate substrate.
3. preparation method according to claim 1 and 2, it is characterised in that the photoresist in the step one is for just
Glue or negative glue；
Preferably, the positive glue is polymethyl methacrylate；
Preferably, the negative glue is hydrogen silicon silsequioxane.
4. the preparation method according to any one of claim 1-3, it is characterised in that the exposure figure in the step 2
For single figure or complex figure, wherein, the complex figure is that the dislocation of two or more single figures is overlapped.
5. the preparation method according to any one of claim 1-4, it is characterised in that the electron beam light in the step 2
The step-length of the exposure of carving technology is 100nm～500nm, and exposure dose is adjustable, by Xiao Zhou described in the step size controlling of adjustment exposure
The cycle of phase array structure, by the radius for adjusting single figure described in exposure dose control.
6. the preparation method according to any one of claim 1-5, it is characterised in that be using deposition in the step 3
Technique is transferred to the photoetching offset plate figure on the substrate；
Preferably, the depositing operation is thermal evaporation process, electron-beam deposition methods or pulse laser deposition process.
7. preparation method according to claim 6, it is characterised in that the depositing operation material therefor be metal material,
Dielectric material or semi-conducting material；
Preferably, the metal material is gold, silver or chromium；
Preferably, the dielectric material is tin indium oxide or aluminum oxide；
Preferably, the semi-conducting material is zinc oxide or gallium nitride.
8. the preparation method according to any one of claim 1-5, it is characterised in that be using etching in the step 3
Technique is transferred to the photoetching offset plate figure on the substrate；
Preferably, the etching technics is ion beam etching, plasma etching or wet etching.
9. the preparation method according to any one of claim 1～8, it is characterised in that described to remove glue to remove glue third
Ketone removes glue DMAC N,N' dimethyl acetamide.
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| CN201710029268.1A CN106647187A (en) | 2017-01-16 | 2017-01-16 | Preparation method of small-period array structure |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750253A (en) * | 2019-01-10 | 2019-05-14 | 金华伏安光电科技有限公司 | A kind of preparation method tilting structure |
| CN109904153A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院物理研究所 | The side wall assistant preparation method of multiple 3-D nano, structure |
| CN111929277A (en) * | 2020-06-03 | 2020-11-13 | 中国科学院苏州生物医学工程技术研究所 | One-dimensional assembly of noble metal nanoparticles with adjustable spacing and application of assembly in nano sensor |
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| US20080036986A1 (en) * | 2006-08-11 | 2008-02-14 | Elpida Memory, Inc. | Photomask, method and apparatus that uses the same, photomask pattern production method, pattern formation method, and semiconductor device |
| CN101916038A (en) * | 2010-07-15 | 2010-12-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for processing round arrays by electronic beam photo-etching |
| US8133427B2 (en) * | 2007-09-28 | 2012-03-13 | Hitachi, Ltd. | Photo nanoimprint lithography |
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2017
- 2017-01-16 CN CN201710029268.1A patent/CN106647187A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080036986A1 (en) * | 2006-08-11 | 2008-02-14 | Elpida Memory, Inc. | Photomask, method and apparatus that uses the same, photomask pattern production method, pattern formation method, and semiconductor device |
| US8133427B2 (en) * | 2007-09-28 | 2012-03-13 | Hitachi, Ltd. | Photo nanoimprint lithography |
| CN101916038A (en) * | 2010-07-15 | 2010-12-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for processing round arrays by electronic beam photo-etching |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109904153A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院物理研究所 | The side wall assistant preparation method of multiple 3-D nano, structure |
| CN109750253A (en) * | 2019-01-10 | 2019-05-14 | 金华伏安光电科技有限公司 | A kind of preparation method tilting structure |
| CN111929277A (en) * | 2020-06-03 | 2020-11-13 | 中国科学院苏州生物医学工程技术研究所 | One-dimensional assembly of noble metal nanoparticles with adjustable spacing and application of assembly in nano sensor |
| CN111929277B (en) * | 2020-06-03 | 2021-06-01 | 中国科学院苏州生物医学工程技术研究所 | One-dimensional assembly of noble metal nanoparticles with adjustable spacing and application of assembly in nano sensor |
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