CN109795975A - A kind of metal micro-/ nano linear array and preparation method thereof - Google Patents
A kind of metal micro-/ nano linear array and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
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- 239000010949 copper Substances 0.000 claims description 12
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- 239000010941 cobalt Substances 0.000 claims description 2
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Abstract
The invention belongs to technical field of micro and nano fabrication, and in particular to a kind of metal micro-/ nano linear array and preparation method thereof.The metal micro-/ nano linear array includes supporting layer sheet metal and the metal micro-/ nano line that is erected on the sheet metal.The metal micro-/ nano linear array has big depth-to-width ratio, and the thickness of the diameter of the metal micro-/ nano line, height and sheet metal can be controlled accurately;Metal micro-/ nano line is directly erected on sheet metal, between each other without intersecting and being overlapped, improves specific surface area and recycling rate of waterused;The metal micro-/ nano linear array can be applied to prepare big depth-to-width ratio, nano-device flexible.The preparation method is to have the material of preferably rigidity and etching stability as substrate, it is ensured that the problems such as collapsing is less prone in etching process obtains the micro-/ nano linear array of high-aspect-ratio;In addition, this method can be by controlling etch period, the accurate height for controlling micro-/ nano line.
Description
Technical field
The invention belongs to technical field of micro and nano fabrication, and in particular to a kind of metal micro-/ nano linear array and preparation method thereof.
Background technique
The metal micro-/ nano line of bigger serface possesses excellent physicochemical property, and especially surface area is big, is catalysis in metal
In the case where agent, catalytic efficiency can be greatly improved;In addition, being shown after metal micro-/ nano line carrying active substance on surface
Excellent fake capacitance electrode performance, there is fairly good development prospect in current collector of super capacitor device.
Currently, preparing metal micro-/ nano line is usually chemical method synthesis and growth, obtained metal micro-/ nano line exists
The disadvantages of pattern is uncontrollable, reusing is poor, and the micro-/ nano line arrangement rule being prepared using micro-nano technology technology
Then, reusing is preferable, becomes one of the hot spot for preparing the research of metal micro-/ nano line.
In the prior art, in periodical literature " preparing 200nm period gold self-supporting transmission grating based on nanometer embossing ",
A kind of preparation method of high density golden light grid is disclosed, vapor deposition forms Au electrode layer in advance on silicon wafer, by imprinting, etching shape
At optical grating construction, then the gold being reduced is deposited on to progress microplating in the golden film exposed obtain grating, but passes through the system
The depth-to-width ratio for the optical grating construction that Preparation Method obtains is less than 5:1, and glue-line is easy to appear collapsing in etching process, not can be carried out
The preparation of big depth-to-width ratio metal grating.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcome it is in the prior art cannot obtain high-aspect-ratio it is micro-/
The defects of nano wire, to provide a kind of metal micro-/ nano linear array and preparation method thereof.
In order to solve the above technical problems, the present invention provides the following technical scheme that
The present invention provides a kind of metal micro-/ nano linear array, including supporting layer sheet metal and it is erected at the support
Metal micro-/ nano line on layer sheet metal;
Wherein, the ratio between the height and diameter of the micro-/ nano line is (5-20): 1.
The diameter of the metal micro-/ nano line is 200nm-5 μm, is highly 1 μm -50 μm.
The thickness of the supporting layer sheet metal is greater than 5 μm.
The present invention provides a kind of preparation methods of metal micro-/ nano linear array, include the following steps,
The preparation of micro-/ nano deep-hole structures: existed using nanometer embossing preparation coining glue hole battle array or photoetching micro & nano technology
Photoresist hole battle array is prepared on substrate material, then performs etching to obtain micro-/ nano deep-hole structures using etching technics;
The preparation of micro-/ nano linear array: in the plating metal on surface conductive layer of the micro-/ nano deep-hole structures, then with it
Electro-deposition is carried out as cathode, removal substrate material is reacted with corrosive solution, obtains metal micro-/ nano linear array.
The diameter of coining glue hole battle array is 200nm-2 μm;The diameter of photoresist hole battle array is 2 μm -5 μm.
The etch rate is 0.1-0.2 μm/s.
The substrate material can be silicon wafer, silicon nitride or gallium nitride.
When the substrate material is silicon wafer, etching gas SF6, protective gas C4F8。
The metal conducting layer is with a thickness of 10-30nm.
Select the techniques such as physical vaporous deposition in the plating metal on surface conductive layer of the micro-/ nano deep-hole structures;Plated film
It is in the process to keep thicknesses of layers uniform, it is preferred that can be used and turn depositing process;
Wherein, physical vaporous deposition can be electron beam evaporation plating, magnetron sputtering, arc-plasma plating, ion film plating,
Molecular beam epitaxy etc..
The current density of the electro-deposition is 0.5-3A/dm2;Time is 12-24h.
The material of the metal conducting layer is nickel, copper, gold, silver, palladium, iron or cobalt;
Electroplate liquid used in the electrodeposition process is the salting liquid of above-mentioned metal conducting layer metal.
Corrosive solution used is strong base solution in the preparation step of the micro-/ nano linear array, and the reaction temperature is
50-80 DEG C, reaction time 12-18h.
Technical solution of the present invention has the advantages that
1. metal micro-/ nano linear array provided by the invention, including metal micro-/ nano line and supporting layer sheet metal, institute
State being erected on sheet metal for metal micro-/ nano line rule.The metal micro-/ nano linear array have high-aspect-ratio, up to 20:
1;And the thickness of the diameter of the metal micro-/ nano line, height and sheet metal can be controlled accurately;Metal micro-/ nano line is direct
It is erected on sheet metal, between each other without intersecting and being overlapped, improves specific surface area, high-aspect-ratio micro-nano rice noodles provide one
Kind big surface area, be applied to battery afflux liquid, current collector of super capacitor, in terms of have to improve and handed over medium
Mutual ability;The metal micro-/ nano linear array can be applied to prepare big depth-to-width ratio, nano-device flexible, and in practice
Recycling rate of waterused is higher.
Metal micro-/ nano linear array provided by the invention, the diameter of the metal micro-/ nano line are 200nm-5 μm, height
It is 1 μm -50 μm.The micro-/ nano linear diameter and depth-to-width ratio range are big, can meet the nano-device of different requirements;The branch
The thickness of layer sheet metal is supportted at 5 μm or more, support micro-/ nano line is can be very good, so that it is erected at supporting layer and be not in down
The phenomenon that collapsing.
2. the preparation method of metal micro-/ nano linear array provided by the invention, including (1) are prepared using nanometer embossing
Coining glue hole battle array or photoetching micro & nano technology prepare photoresist hole battle array on substrate material, are then performed etching using etching technics
To micro-/ nano deep-hole structures;(2) in the plating metal on surface conductive layer of the micro-/ nano deep-hole structures, then using it as cathode
Electro-deposition is carried out, removal substrate material is reacted with corrosive solution, obtains metal micro-/ nano linear array.The preparation method is logical
Control etch period is crossed, the height of micro-/ nano line can be accurately controlled;With the photo mask board of different-diameter and nano impression mould
The photoresist or ultraviolet cured adhesive hole battle array structure of different-diameter can be prepared in plate, and then controls the diameter of micro-/ nano line.
3. the diameter of the preparation method of metal micro-/ nano linear array provided by the invention, coining glue hole battle array is
200nm-2μm;The diameter of photoresist hole battle array is 2 μm -5 μm.It is required to select different preparation processes, Ke Yijing according to different sizes
The really diameter and height of control micro-/ nano line.It is 0.1-0.2 μm/s, the nano-pillar in etching process by control etch rate
The homogeneity for being less prone to collapsing and nano-pillar is preferable.
4. the preparation method of metal micro-/ nano linear array provided by the invention, the substrate material can be silicon wafer, silicon nitride
Or gallium nitride, to have the material of preferably rigidity and etching stability as substrate, it is ensured that be less prone in etching process
The problems such as collapsing, obtains the micro-/ nano linear array of high-aspect-ratio.The metal conducting layer is heavy carrying out electricity with a thickness of 10-30nm
When product micro-/ nano cable architecture can be formed effectively by metal deposit to metal conducting layer.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is that the photoetching micro-nano technology technology of the present invention of embodiment 1 prepares metal micro line flow chart;
Fig. 2 is that the stamping technique of the present invention of embodiment 2 prepares metal nanometer line flow chart;
Fig. 3 is silicon micron deep hole microscopic appearance figure prepared by embodiment 1;Wherein, left figure is silicon deep hole plan view;Right figure is
Silicon deep hole sectional view;
Fig. 4 is nickel micro wire electron microscope prepared by embodiment 1;
Fig. 5 is silicon nanometer deep hole microscopic appearance figure prepared by embodiment 2;
Appended drawing reference:
1- photoresist, 2- substrate material, 3- photo mask board, 4- metal layer, 5- metal, 6- array of metal lines, 7- nanometers
Impression block.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
Embodiment 1
A kind of method that photoetching micro-nano technology technology prepares nickel micron linear array is present embodiments provided, as shown in Figure 1, being
The flow chart of the present embodiment method, the specific steps are as follows:
The preparation of silicon micron deep hole: ordinary silicon chip spin coating photoresist, rate 4000r/min, time 40s, film forming thickness 1.5
μm.2 μm of diameter are taken, 6 μm of Lithographic template of period carries out photoetching, obtains 2 μm of diameter, 6 μm of the period of photoresist hole.With photoresist
Deep silicon etching (north China wound HSE200 moldeed depth silicon etching machine), etching gas SF are carried out for exposure mask6, protective gas C4F8, carve
Erosion rate is 0.2 μm/s, etch period 120s, and etching depth is 20 μm, removes body structure surface within 5 minutes using acetone ultrasound
Photoresist obtains silicon micron deep hole, as shown in Figure 3.
The preparation of metallic nickel micro wire: being deposited one layer of metallic nickel in deep hole silicon face using electron beam evaporation, with a thickness of
20nm is electroplated using it as cathode, electroplate liquid NiCl2Aqueous solution, current density 0.5A/dm2, time 12h;It will be electric
The silicon wafer plated, which is put into 2mol/L KOH solution, removes silicon, and reaction time 18h, 50 DEG C of reaction temperature, obtained nickel sheet is repeatedly
It is rinsed with deionized water, is then dried with nitrogen, be put into 60 DEG C of vacuum ovens and dry 10h to get the nickel micron of proper alignment
Line, as shown in Figure 4.
From fig. 4, it can be seen that micro wire high unity, there is no collapse silicon wafer during the preparation process.
After tested, the sheet metal of micron linear array manufactured in the present embodiment with a thickness of 20 μm, the diameter of micro wire is 2
μm, it is highly 20 μm, depth-to-width ratio 10:1.
Embodiment 2
A kind of method that nanometer embossing prepares nickel nano-wire array is present embodiments provided, as shown in Fig. 2, being this reality
Apply the flow chart of a method, the specific steps are as follows:
The preparation of silicon nanometer deep hole: ordinary silicon chip spin coating ultraviolet light solidified imprinting glue, rate 2000r/min, time 40s,
Film forming thickness 150nm takes diameter 500nm, and the PDMS soft template of period 1000nm is imprinted, and after ultraviolet light solidification, is formed straight
The coining glue hole of diameter 500nm, period 1000nm are etched using sense coupling machine (ULVAC CE300I) and are removed
Remnant layer.Deep silicon etching, etching gas SF are carried out as exposure mask to imprint glue6, protective gas C4F8, etch rate is 0.2 μ
M/s, etch period 60s, etching depth are 10 μm.Silicon nanometer deep hole is obtained, as shown in Figure 5.
The preparation of metal nickel nano-line: being deposited one layer of metallic nickel in deep hole silicon face using electron beam evaporation, with a thickness of
15nm is electroplated using it as cathode, electroplate liquid NiCl2Aqueous solution, current density 0.5A/dm2, the time is for 24 hours;It will be electric
The silicon wafer plated, which is put into 2mol/L KOH solution, removes silicon and coining glue, and reaction time 15h, is obtained by 70 DEG C of reaction temperature
Nickel sheet is rinsed with deionized water repeatedly, is then dried with nitrogen, and is put into 60 DEG C of vacuum ovens dry 10h to get proper alignment
Nickel nano wire.
During the preparation process, there is no collapse silicon wafer.
After tested, the sheet metal of nano-wire array manufactured in the present embodiment with a thickness of 15 μm, the diameter of nano wire is
500nm is highly 10 μm, depth-to-width ratio 20:1.
Embodiment 3
A kind of method that photoetching micro-nano technology technology prepares copper micron linear array is present embodiments provided, specific steps are such as
Under:
The preparation of silicon micron deep hole: ordinary silicon chip spin coating photoresist, rate 3000r/min, time 40s, film forming thickness 1.8
μm.5 μm of diameter are taken, 10 μm of Lithographic template of period carries out photoetching, obtains 5 μm of diameter, 10 μm of the period of photoresist hole.With photoetching
Glue is that exposure mask carries out deep silicon etching, etching gas SF6, protective gas C4F8, etch rate is 0.15 μm/s, etch period
For 400s, etching depth is 40 μm, using the photoresist of 5 minutes removal body structure surfaces of acetone ultrasound, obtains silicon micron deep hole.
The preparation of metallic copper micro wire: being deposited one layer of metallic copper in deep hole silicon face using electron beam evaporation, with a thickness of
25nm is electroplated using it as cathode, electroplate liquid CuSO4Aqueous solution, current density 2A/dm2, time 18h;It will plating
Good silicon wafer, which is put into 2mol/L NaOH solution, removes silicon, and reaction time 12h, 70 DEG C of reaction temperature, obtained copper sheet is used repeatedly
Deionized water is rinsed, and is then dried with nitrogen, and is put into 60 DEG C of vacuum ovens and is dried 10h to get the copper micro wire of proper alignment.
During the preparation process, there is no collapse silicon wafer.
After tested, the present embodiment prepare the sheet metal of micron linear array with a thickness of 30 μm, the diameter of micro wire is 5 μ
M is highly 40 μm, depth-to-width ratio 8:1.
Embodiment 4
Present embodiments provide a kind of method that nanometer embossing prepares silver nano line array, the specific steps are as follows:
The preparation of silicon nanometer deep hole: ordinary silicon chip spin coating ultraviolet light solidified imprinting glue, rate 2000r/min, time 50s,
Film forming thickness 180nm takes diameter 300nm, and the PDMS soft template of period 600nm is imprinted, and after ultraviolet light solidification, forms diameter
Remnant layer is removed using sense coupling machine engraving etching off in the coining glue hole of 300nm, period 600nm.It is to imprint glue
Exposure mask performs etching, etching gas SF6, protective gas C4F8, etch rate is 0.1 μm/s, etch period 60s, etching
Depth is 5 μm, obtains silicon nanometer deep hole.
The preparation of metal silver nanowires: plating one layer of metallic silver in deep hole silicon face using magnetron sputtering technique, with a thickness of
18nm is electroplated using it as cathode, and electroplate liquid is AgCl aqueous solution, current density 0.8A/dm2, time 12h;It will be electric
The silicon plated, which is put into 2mol/L KOH solution, removes silicon and coining glue, reaction time 15h, and 70 DEG C of reaction temperature, obtained silver
Piece is rinsed with deionized water repeatedly, is then dried with nitrogen, and is put into 60 DEG C of vacuum ovens dry 10h to get proper alignment
Silver nanowires.
During the preparation process, there is no collapse silicon.
After tested, the sheet metal of nano-wire array manufactured in the present embodiment with a thickness of 12 μm, the diameter of nano wire is
300nm is highly 5 μm, depth-to-width ratio 50:3.
Embodiment 5
A kind of method that photoetching micro-nano technology technology prepares copper micron linear array is present embodiments provided, specific steps are such as
Under:
The preparation of GaN microns of deep holes: substrate material GaN spin coating photoresist, rate 4000r/min, time 40s, at film thickness
1.5 μm of degree.3 μm of diameter are taken, 10 μm of photo mask board of period carries out photoetching, obtains 3 μm of diameter, 10 μm of photoresist of period
Hole.It is performed etching by exposure mask of photoresist, etching gas Cl2And BCl3, etch rate is 0.1 μm/s, and etch period is
210s, etching depth are 20 μm, using the photoresist of 5 minutes removal body structure surfaces of acetone ultrasound, obtain a micron deep hole.
The preparation of metallic copper micro wire: being deposited one layer of metallic copper on the surface deep hole GaN using electron beam evaporation, with a thickness of
30nm is electroplated using it as cathode, electroplate liquid CuSO4Aqueous solution, current density 1.5A/dm2, time 18h;It will be electric
The GaN plated, which is put into 2mol/L NaOH solution, removes GaN, and reaction time 18h, 80 DEG C of reaction temperature, obtained copper sheet is repeatedly
It is rinsed with deionized water, is then dried with nitrogen, be put into 60 DEG C of vacuum ovens and dry 10h to get the copper micron of proper alignment
Line.
During the preparation process, there is no collapse GaN.
After tested, the sheet metal of micron linear array manufactured in the present embodiment with a thickness of 25 μm, the diameter of micro wire is 3
μm, it is highly 20 μm, depth-to-width ratio 20:3.
Embodiment 6
Present embodiments provide a kind of method that stamping technique prepares nickel micron linear array, the specific steps are as follows:
The preparation of silicon micron deep hole: ordinary silicon chip spin coating ultraviolet light solidified imprinting glue, rate 1000r/min, time 40s,
2 μm of film forming thickness, 2 μm of diameter are taken, 4 μm of the period of PDMS soft template is imprinted, and after ultraviolet light solidification, forms 2 μm of diameter, week
4 μm of phase of coining glue hole etches removal remnant layer using sense coupling machine (ULVAC CE300I).With coining
Glue is that exposure mask carries out deep silicon etching, etching gas SF6, protective gas C4F8, etch rate is 0.1 μm/s, and etch period is
120s, etching depth are 10 μm, obtain silicon micron deep hole.
The preparation of metallic nickel micro wire: being deposited one layer of metallic nickel in deep hole silicon face using electron beam evaporation, with a thickness of
13nm is electroplated using it as cathode, electroplate liquid NiCl2Aqueous solution, current density 1.5A/dm2, time 13h;It will be electric
The silicon wafer plated, which is put into 2mol/L KOH solution, removes silicon and coining glue, and reaction time 15h, is obtained by 70 DEG C of reaction temperature
Nickel sheet is rinsed with deionized water repeatedly, is then dried with nitrogen, and is put into 60 DEG C of vacuum ovens dry 10h to get proper alignment
Nickel micro wire.
During the preparation process, there is no collapse silicon wafer.
After tested, the sheet metal of micron linear array manufactured in the present embodiment with a thickness of 18 μm, the diameter of micro wire is 2
μm, it is highly 10 μm, depth-to-width ratio 5:1.
Comparative example 1
This comparative example provides a kind of preparation method of high linear density golden light grid, specific as follows:
Deposited by electron beam evaporation successively plates the Au of the Cr and 20nm of 5nm as microplating on the silicon wafer Jing Guo cleaning treatment
Electrode layer, then the successively polymethyl methacrylate (PMMA) of spin coating 250nm and the nano impression uv-curable glue of 150nm,
Homemade nanometer pressure is put into after being compressed with the transparent nano coining quartz template with 200nm period, the optical grating construction of 100nm thickness
In print machine, the pressure for applying several atmospheric pressure is completely forced into template in uv-curable glue, carries out uv-exposure.It is ultraviolet to upper layer
Solidification glue, which is fully cured, moves back removing template, is transferred to the grating pattern in template in nano impression uv-curable glue;React from
The double-deck glue is performed etching respectively in sub- etching machine, prepares macromolecule grating.First use CHF3And O2Remaining nanometer pressure is etched
Ultra-violet curing glue-line is printed, then uses O2Etched it is PMMA layers remaining, expose electrode layer, prepare about 350nm macromolecule raster pattern
Case;Then carry out microplating, be reduced out gold will be deposited in the golden film that grating blank space exposes, finally with chlorobenzene,
Acetone soln is cleaned by ultrasonic the double-deck plastic structure, obtains the grating for the gold that the period is 200nm.
It is observed that during the test, PMMA layers there is collapsing phenomenon.
After tested, the height of the grating of this comparative example preparation is 350nm, diameter 100nm, depth-to-width ratio 3.5:1.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or
It changes still within the protection scope of the invention.
Claims (11)
1. a kind of metal micro-/ nano linear array, which is characterized in that including supporting layer sheet metal and be erected at the supporting layer gold
Belong to the metal micro-/ nano line on thin slice;
Wherein, the ratio between the height and diameter of the micro-/ nano line is (5-20): 1.
2. metal micro-/ nano linear array according to claim 1, which is characterized in that the diameter of the metal micro-/ nano line
It is 200nm-5 μm, is highly 1 μm -50 μm;
The thickness of the supporting layer sheet metal is at 5 μm or more.
3. a kind of preparation method of metal micro-/ nano linear array, which is characterized in that include the following steps,
The preparation of micro-/ nano deep-hole structures: using nanometer embossing preparation coining glue hole battle array or photoetching micro & nano technology in substrate
Photoresist hole battle array is prepared on material, then performs etching to obtain micro-/ nano deep-hole structures using etching technics;
The preparation of micro-/ nano linear array: in the plating metal on surface conductive layer of the micro-/ nano deep-hole structures, then using its as
Cathode carries out electro-deposition, and removal substrate material is reacted with corrosive solution, obtains metal micro-/ nano linear array.
4. the preparation method of metal micro-/ nano linear array according to claim 3, which is characterized in that the coining glue hole
The diameter of battle array is 200nm-2 μm;The diameter of photoresist hole battle array is 2 μm -5 μm.
5. the preparation method of metal micro-/ nano linear array according to claim 3, which is characterized in that the etch rate
For 0.1-0.2 μm/s.
6. the preparation method of metal micro-/ nano linear array according to claim 3, which is characterized in that the substrate material
It can be silicon wafer or gallium nitride.
7. the preparation method of metal micro-/ nano linear array according to claim 3, which is characterized in that the metallic conduction
Layer is with a thickness of 10-30nm.
8. the preparation method of metal micro-/ nano linear array according to claim 3, which is characterized in that select physical vapor
Plating metal on surface conductive layer of the sedimentation in the micro-/ nano deep-hole structures.
9. the preparation method of metal micro-/ nano linear array according to claim 3, which is characterized in that the electro-deposition
Current density is 0.5-3A/dm2;Time is 12-24h.
10. the preparation method of metal micro-/ nano linear array according to claim 3, which is characterized in that the metallic conduction
The material of layer is nickel, copper, gold, silver, palladium, iron or cobalt;
Electroplate liquid used in the electrodeposition process is the salting liquid of above-mentioned metal conducting layer metal.
11. according to the preparation method of the described in any item metal micro-/ nano linear arrays of claim 3-10, which is characterized in that institute
Stating corrosive solution used in the preparation step of micro-/ nano linear array is strong base solution, and the reaction temperature is 50-80 DEG C, instead
It is 12-18h between seasonable.
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