CN106094445A - The manufacture method of large ratio of height to width nano level metal structure - Google Patents
The manufacture method of large ratio of height to width nano level metal structure Download PDFInfo
- Publication number
- CN106094445A CN106094445A CN201610407163.0A CN201610407163A CN106094445A CN 106094445 A CN106094445 A CN 106094445A CN 201610407163 A CN201610407163 A CN 201610407163A CN 106094445 A CN106094445 A CN 106094445A
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- China
- Prior art keywords
- monocrystalline substrate
- metal structure
- width
- ratio
- photoresist
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Classifications
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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
- G03F7/2035—Exposure; Apparatus therefor simultaneous coating and exposure; using a belt mask, e.g. endless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
Abstract
The present invention provides the manufacture method of a kind of large ratio of height to width nano level metal structure, and described method includes: utilize electron beam evaporation metal material, with metal thin film patterns in the monocrystalline substrate of special parameter；Surface is formed the monocrystalline substrate of metal thin film patterns be immersed in mixed liquor and carry out catalyzed corrosion a period of time, to form the deep silicon groove of large ratio of height to width on a monocrystaline silicon substrate；With the metallic film of deep silicon trench bottom for conductive plated Seed Layer, the monocrystalline substrate with deep silicon groove is immersed in electroplate liquid and electroplates, to increase the thickness of metallic film to specified altitude assignment, to form the metal structure specifying depth-width ratio；Will be formed with specifying the monocrystalline substrate of the metal structure of depth-width ratio to be immersed in mixed liquor and carry out isotropism wet etching a period of time, to remove the monocrystal silicon between described metal structure.The depth-width ratio of the nano level metal structure that the manufacture method of the present invention makes is big.
Description
Technical field
The present invention relates to technical field of nano-processing, particularly relate to the making side of a kind of large ratio of height to width nano level metal structure
Method.
Background technology
For the phase-type diffraction optical element of high accuracy X-ray wave band, in order to obtain required position phase, it is necessary to make
Large ratio of height to width nano level metal structure.At present, in nanofabrication technique, it is mainly to utilize multilamellar adhesive process and dry etching
Technique makes large ratio of height to width nano level metal structure, i.e. utilize thicker photoresist as mask, by dry etching work
Skill carries out deep silicon etching.
During realizing the present invention, inventor finds at least to exist in prior art following technical problem:
Due to the isotropic etching of photoresist, its lateral etching precision is difficult to control so that the thickest photoresist exists
Easily occur during development that the figure caused due to developer solution tension force collapses problem；The metal formed during follow-up dry etching
The problem that structure there is also live width steepness difference.The depth-width ratio making the nano level metal structure made for above-mentioned reasons has
Limit, i.e. its depth-width ratio are difficult to more than 10.
Summary of the invention
In order to solve above-mentioned technical problem, the present invention provides the manufacture method of a kind of large ratio of height to width nano level metal structure,
The figure that can occur when avoiding photoresist developing collapse problem and the dry etching degree of depth silicon time occur live width steepness poor
Problem, and its depth-width ratio of nano level metal structure made is big.
The present invention provides the manufacture method of a kind of large ratio of height to width nano level metal structure, including:
Spin coating photoresist in the monocrystalline substrate of special parameter, and described photoresist is carried out electron beam exposure with aobvious
Shadow, to form grating mask groove in described photoresist；
Utilize electron beam evaporation metal material, to form metallic film in described grating mask groove；
Remove the photoresist of residual in described monocrystalline substrate, to form metallic film figure on described monocrystalline substrate surface
Case；
It is immersed in by hydrogen using described metallic film as catalyst, the monocrystalline substrate that surface is formed metal thin film patterns
The mixed liquor of fluoric acid, hydrogen peroxide and deionized water composition carries out catalyzed corrosion a period of time, with in described monocrystalline substrate
Form the deep silicon groove of large ratio of height to width,；
With the described metallic film of described deep silicon trench bottom for conductive plated Seed Layer, will have the monocrystal silicon lining of deep silicon groove
The end, is immersed in electroplate liquid and electroplates, and to increase the thickness of described metallic film to specified altitude assignment, specifies depth-width ratio to be formed
Metal structure；
Will be formed with specifying the monocrystalline substrate of metal structure of depth-width ratio to be immersed in be made up of Fluohydric acid., nitric acid and acetic acid
Mixed liquor carries out isotropism wet etching a period of time, to remove the monocrystal silicon between described metal structure；
Described special parameter includes the crystal orientation of monocrystal silicon, doping type and resistivity.
The manufacture method of the large ratio of height to width nano level metal structure that the embodiment of the present invention provides, compared with prior art, its
Have only to just can form very thin metal thin film patternsization on the monosilicon the metal structure of large ratio of height to width, thus do not exist
The figure caused due to developer solution tension force occurred when photoresist is the thickest collapse problem and the dry etching degree of depth silicon time line that occurs
The problem of wide steepness difference；And apply the depth-width ratio of the nano level metal structure that the manufacture method of the present invention makes big.
Accompanying drawing explanation
Fig. 1 is the flow chart of the manufacture method of large ratio of height to width nano level metal structure of the present invention；
Fig. 2 is the schematic diagram of the described metal thin film patterns in above-described embodiment.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only
It is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill
The every other embodiment that personnel are obtained under not making creative work premise, broadly falls into the scope of protection of the invention.
As it is shown in figure 1, the present invention provides the manufacture method of a kind of large ratio of height to width nano level metal structure, described method bag
Include:
Step 1) spin coating photoresist in the monocrystalline substrate of special parameter, and described photoresist is carried out electron beam exposure
With development, with in described photoresist formed grating mask groove.
Wherein, described special parameter includes the crystal orientation of monocrystal silicon, doping type and resistivity, specifically, described monocrystal silicon
Crystal orientation be<100>, described monocrystal silicon be p-type doping, the resistivity of described monocrystal silicon be more than 10cm.
Wherein, described photoresist is PMMA photoresist, and the thickness of described PMMA photoresist is 200nm.
Step 2) utilize electron beam evaporation metal material, to form metallic film in described grating mask groove.
Wherein, described metal material is gold, platinum or silver, and the thickness of described metallic film is 10nm～50nm.
Step 3) remove the photoresist of residual in described monocrystalline substrate, to form metal on described monocrystalline substrate surface
Thinfilm pattern.
Wherein, the characteristic size of described metal thin film patterns is 10nm～3 μm.
Step 4) using described metallic film as catalyst, surface is formed with the monocrystalline substrate leaching of metal thin film patterns
The mixed liquor being made up of Fluohydric acid., hydrogen peroxide and deionized water is carried out catalyzed corrosion a period of time, with at described monocrystal silicon
The deep silicon groove of large ratio of height to width is formed on substrate.
Wherein, the molar ratio of described Fluohydric acid., hydrogen peroxide and deionized water mixing is 5.9:0.3:48.
Step 5) with the described metallic film of described deep silicon trench bottom for conductive plated Seed Layer, will there is the list of deep silicon groove
Crystalline silicon substrate is immersed in electroplate liquid and electroplates, and to increase the thickness of described metallic film to specified altitude assignment, specifies height to be formed
The metal structure of wide ratio.
Wherein, the molar ratio of described Fluohydric acid., nitric acid and acetic acid mixing is 23:4:1.
Step 6) will be formed with specifying the monocrystalline substrate of the metal structure of depth-width ratio to be immersed in by Fluohydric acid., nitric acid and acetic acid
The mixed liquor of composition carries out isotropism wet etching a period of time, to remove the monocrystal silicon between described metal structure.
The manufacture method of the large ratio of height to width nano level metal structure that the embodiment of the present invention provides, compared with prior art, its
Have only to just can form very thin metal thin film patternsization on the monosilicon the metal structure of large ratio of height to width, thus do not exist
The figure caused due to developer solution tension force occurred when photoresist is the thickest collapse problem and the dry etching degree of depth silicon time line that occurs
The problem of wide steepness difference；And apply the depth-width ratio of the nano level metal structure that the manufacture method of the present invention makes big.
Below by a specific example, the present invention is described in further details.
Step 1) spin coating a layer thickness on a monocrystaline silicon substrate is the PMMA photoresist of 200nm, and to described PMMA photoetching
Glue carries out electron beam exposure and development, to form grating mask groove in described PMMA photoresist.
Wherein, the crystal orientation of described monocrystal silicon is<100>, and described monocrystal silicon is p-type doping, and the resistivity of described monocrystal silicon is big
In 10cm.
Step 2) utilize electron beam evaporation gold copper-base alloy, to form thickness in described grating mask groove for 20nm gold thin film.
Step 3) remove the PMMA photoresist of residual in described monocrystalline substrate, to be formed on described monocrystalline substrate surface
Gold thin film pattern, as in figure 2 it is shown, described gold thin film pattern is made up of multiple squares of periodic arrangement.
Wherein, the characteristic size of described gold thin film pattern is 200nm, and the most each foursquare length of side is 200nm.
Step 4) using described gold thin film as catalyst, surface is formed belong to the monocrystalline substrate of Thinfilm pattern be immersed in by
The mixed liquor of Fluohydric acid., hydrogen peroxide and deionized water composition carries out catalyzed corrosion 10 minutes, with in described monocrystalline substrate
Form the deep silicon groove that depth-width ratio is 100:1.
Wherein, the molar ratio of described Fluohydric acid., hydrogen peroxide and deionized water mixing is 5.9:0.3:48.
Step 5) with the described gold thin film of described deep silicon trench bottom for conductive plated Seed Layer, will there is the monocrystalline of deep silicon groove
Silicon substrate is immersed in gold plating bath and electroplates, and to increase the thickness of described gold thin film to specified altitude assignment, forming depth-width ratio is
The golden structure of 100:1.
Wherein, the molar ratio of described Fluohydric acid., nitric acid and acetic acid mixing is 23:4:1.
Step 6) monocrystalline substrate that will be formed with the golden structure that depth-width ratio is 100:1 is immersed in by Fluohydric acid., nitric acid and vinegar
The mixed liquor of acid composition carries out isotropism wet etching 3 minutes, to remove the monocrystal silicon between described gold structure.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any
Those familiar with the art in the technical scope that the invention discloses, the change that can readily occur in or replacement, all answer
Contain within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with scope of the claims.
Claims (7)
1. the manufacture method of a large ratio of height to width nano level metal structure, it is characterised in that including:
Spin coating photoresist in the monocrystalline substrate of special parameter, and described photoresist is carried out electron beam exposure and development, with
Grating mask groove is formed in described photoresist；
Utilize electron beam evaporation metal material, to form metallic film in described grating mask groove；
Remove the photoresist of residual in described monocrystalline substrate, to form metal thin film patterns on described monocrystalline substrate surface；
It is immersed in by hydrogen fluorine using described metallic film as catalyst, the monocrystalline substrate that surface is formed metal thin film patterns
The mixed liquor of acid, hydrogen peroxide and deionized water composition carries out catalyzed corrosion a period of time, with shape in described monocrystalline substrate
Become the deep silicon groove of large ratio of height to width,；
With the described metallic film of described deep silicon trench bottom for conductive plated Seed Layer, will have the monocrystalline substrate leaching of deep silicon groove
Electroplate liquid is electroplated, to increase the thickness of described metallic film to specified altitude assignment, to form the metal specifying depth-width ratio
Structure；
Will be formed with specifying the monocrystalline substrate of the metal structure of depth-width ratio to be immersed in the mixing being made up of Fluohydric acid., nitric acid and acetic acid
Liquid carries out isotropism wet etching a period of time, to remove the monocrystal silicon between described metal structure；
Described special parameter includes the crystal orientation of monocrystal silicon, doping type and resistivity.
Method the most according to claim 1, it is characterised in that the crystal orientation of described monocrystal silicon is<100>, described monocrystal silicon is
P-type is adulterated, and the resistivity of described monocrystal silicon is more than 10 Ω cm.
Method the most according to claim 1, it is characterised in that described photoresist is PMMA photoresist, described PMMA photoetching
The thickness of glue is 200nm.
Method the most according to claim 1, it is characterised in that described metal material is gold, platinum or silver, described metal
The thickness of thin film is 10nm～50nm.
Method the most according to claim 1, it is characterised in that rubbing of described Fluohydric acid., hydrogen peroxide and deionized water mixing
Your ratio is 5.9:0.3:48.
Method the most according to claim 1, it is characterised in that described Fluohydric acid., nitric acid and the molar ratio of acetic acid mixing
For 23:4:1.
Method the most according to claim 1, it is characterised in that the characteristic size of described metal thin film patterns is 10nm～3 μ
m。
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| CN201610407163.0A CN106094445B (en) | 2016-06-12 | 2016-06-12 | The production method of large ratio of height to width nano level metal structure |
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| CN201610407163.0A CN106094445B (en) | 2016-06-12 | 2016-06-12 | The production method of large ratio of height to width nano level metal structure |
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| CN106094445A true CN106094445A (en) | 2016-11-09 |
| CN106094445B CN106094445B (en) | 2018-11-20 |
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Cited By (7)
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| CN108018587A (en) * | 2017-12-07 | 2018-05-11 | 天津大学 | A kind of method that graphical cobalt nanowire array is prepared based on polycarbonate template method |
| CN108048882A (en) * | 2017-12-07 | 2018-05-18 | 天津大学 | A kind of method that graphical cobalt nanowire array is prepared based on anodic oxidation aluminium formwork method |
| CN109827981A (en) * | 2019-02-28 | 2019-05-31 | 中国科学院西安光学精密机械研究所 | The preparation method and grating of the ultrafast detection chip modulated grating of the full light solid of X-ray |
| CN110286432A (en) * | 2019-06-25 | 2019-09-27 | 安徽工程大学 | The preparation method of X-ray gold transmission grating |
| CN111776252A (en) * | 2020-07-06 | 2020-10-16 | 南京航空航天大学 | Laval nozzle structure-imitated guide plate functional surface and manufacturing method thereof |
| CN113582129A (en) * | 2021-07-27 | 2021-11-02 | 浙江大学 | Large-aspect-ratio probe based on metal-assisted chemical etching and manufacturing method thereof |
| CN116288374A (en) * | 2022-12-30 | 2023-06-23 | 东莞赛诺高德蚀刻科技有限公司 | Metal surface secondary processing method based on etching and electrodeposition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108018587A (en) * | 2017-12-07 | 2018-05-11 | 天津大学 | A kind of method that graphical cobalt nanowire array is prepared based on polycarbonate template method |
| CN108048882A (en) * | 2017-12-07 | 2018-05-18 | 天津大学 | A kind of method that graphical cobalt nanowire array is prepared based on anodic oxidation aluminium formwork method |
| CN109827981A (en) * | 2019-02-28 | 2019-05-31 | 中国科学院西安光学精密机械研究所 | The preparation method and grating of the ultrafast detection chip modulated grating of the full light solid of X-ray |
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| CN111776252A (en) * | 2020-07-06 | 2020-10-16 | 南京航空航天大学 | Laval nozzle structure-imitated guide plate functional surface and manufacturing method thereof |
| CN113582129A (en) * | 2021-07-27 | 2021-11-02 | 浙江大学 | Large-aspect-ratio probe based on metal-assisted chemical etching and manufacturing method thereof |
| CN113582129B (en) * | 2021-07-27 | 2024-02-02 | 浙江大学 | High-aspect-ratio probe based on metal-assisted chemical etching and manufacturing method thereof |
| CN116288374A (en) * | 2022-12-30 | 2023-06-23 | 东莞赛诺高德蚀刻科技有限公司 | Metal surface secondary processing method based on etching and electrodeposition |
| CN116288374B (en) * | 2022-12-30 | 2023-10-13 | 东莞赛诺高德蚀刻科技有限公司 | Metal surface secondary processing method based on etching and electrodeposition |
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| CN106094445B (en) | 2018-11-20 |
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