CN103050378B - A kind of preparation method being easy to the silicon nanowire array that large area is separated - Google Patents
A kind of preparation method being easy to the silicon nanowire array that large area is separated Download PDFInfo
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- CN103050378B CN103050378B CN201210470483.2A CN201210470483A CN103050378B CN 103050378 B CN103050378 B CN 103050378B CN 201210470483 A CN201210470483 A CN 201210470483A CN 103050378 B CN103050378 B CN 103050378B
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Abstract
The invention discloses a kind of preparation method being easy to the silicon nanowire array that large area is separated, belong to nano material technology and applied technical field.First the present invention processes silicon chip, obtains the silicon chip that surface cleaning is smooth; Then silicon chip is put between two electrodes, and put into etching liquid etching reaction together with electrode, obtain the silicon nanowire array of different length; Etch terminate before 10 ~ 15min time, add electric field strength be 150 ~ 220V/cm and perpendicular to etching direction transverse electric field until reaction terminate; Finally namely obtain being easy to the silicon nanowire array of large area separation by the oxide layer that nitric acid removes the silver remained in silicon nanowire array, remove silicon chip surface with hydrofluoric acid.Present invention process is simple, favorable repeatability, flexibly controlled, cost is low; Introduce the silicon nanowire array that the preparation of additional transverse electric field is easy to be separated first, solve not easily separated in the transfer of traditional silicon nano-wire array and that the rear length of transfer is uneven problem.<!--1-->
Description
Technical field
The invention belongs to nano material technology and applied technical field, particularly a kind of preparation method being easy to the silicon nanowire array that large area is separated.
Background technology
Silicon nanowire array, with the photoelectric properties of its excellence, some surface active property and mechanical performance, in field extensive application such as opto-electronic device, transducer, electronic devices, has become one of material of main part valuable in these fields.In order to the intrinsic properties of the practical ranges and outstanding silicon nanowire array of widening silicon nanowire array, bulk silicon nano-wire array is transferred at the bottom of non-silicon-based from silicon base by the detailing requiments of many devices.People utilize contact printing technology that nano-wire array is separated from silicon base usually, but due to silicon nanowire array and base silicon substrate firmly adhesion and make to need to apply in separation process very large mechanicals efforts, but large active force inevitably can destroy order and the integrality of silicon nanowire array.In addition, because silicon nanowires fracture position is random in separation process, so be difficult to the silicon nanowire array obtaining uniform length.After this directly affects transfer silicon nanowire array with contact situation at the bottom of non-silicon-based, finally affect the performance of device.Therefore, prepare and be a kind ofly easy to be separated and the high quality silicon nano-wire array of uniform length becomes particularly important and urgent after being separated.
Summary of the invention
For solving the problem, the present invention introduces the transverse electric field perpendicular to etching direction in the process of metal nano particle catalysis etching silicon nano line, transverse electric field is utilized to accelerate the effect of lateral etching, obtain the silicon nanowire array greatly reduced with silicon base joint face, thus the high-quality realizing silicon nanowire array is separated and transfer, obtain the silicon nanowire array greatly reduced with silicon base joint face, be namely easy to the silicon nanowire array that large area is separated.
The object of the invention is to propose a kind of preparation method being easy to the silicon nanowire array that large area is separated.
Described method comprises the steps:
(1) silicon chip preliminary treatment: utilize acetone, absolute ethyl alcohol and ultra-pure deionized water ultrasonic cleaning silicon chip successively respectively, remove its surface and oil contaminant; Then silicon chip 5-8min is soaked, to remove its surface tear layer and smear layer with CP-4A solution; Use 14wt% hydrofluoric acid dips 5-6min again, to remove oxide layer; Last again with ultra-pure deionized water flushing, nitrogen dries up, and is placed in vacuum environment drying, obtains the silicon chip that surface cleaning is smooth; The resistivity of ultra-pure deionized water used must at 17 more than Ω cm;
(2) the building and prepare etching solution of extra electric field device: the electrode (graphite electrode or platinum electrode) of two pieces of length of sides much larger than the silicon chip length of side is connected with the both positive and negative polarity of constant current constant voltage power supply respectively, fix its position and keep two electrode runs parallel, the silicon chip fixed placement that then will process through step (1) is in the middle of two electrodes but discord two electrode contacts; Then prepare etching liquid, etching liquid is preheating to 25 ~ 40 DEG C in water-bath; Wherein, described etching liquid is 4.6 ~ 5mol/LHF and concentration is 0.01 ~ 0.02mol/LAgNO
3mixed solution;
(3) preparation is easy to the silicon nanowire array of separation: will impregnated in the etching liquid of 25 ~ 40 DEG C of water-baths together with two electrodes through the silicon chip of the fixing process of step (2), etching reaction 40 ~ 60min, thus the silicon nanowire array obtaining different length; Etch terminate before 10 ~ 15min time, add electric field strength be 150 ~ 220V/cm and perpendicular to etching direction transverse electric field until reaction terminate; Being preferably etch period is 45min, electric field strength 200V/cm, electric field joining day 15min;
(4) remaining silver in silicon nanowire array is removed: with 65wt% nitric acid dousing 10 ~ 15min, thoroughly remove the silver remained in silicon nanowire array, then clean with deionized water rinsing;
(5) remove the oxide layer of surface of silicon nanowires: with the hydrofluoric acid dips 5 ~ 7min of 3wt% ~ 5wt%, remove the oxide layer of silicon chip surface, and form si-h bond at surface of silicon nanowires, namely obtain the described silicon nanowire array being easy to large area separation; Clean with deionized water rinsing, dry up with nitrogen, vacuumize is preserved.
Wherein,
CP-4A solution described in step (1) is volume ratio is HF:HNO
3: absolute ethyl alcohol: H
2the mixed solution of O=3:5:3:22, wherein the mass fraction of HF is 40%, HNO
3mass fraction be 65%;
Described silicon chip is (100) orientation p-type monocrystalline silicon piece, and its resistivity is at 7 ~ 13 Ω cm;
The electrode adopted in step (2) is the uniform square-shaped electrode of thickness, and electrode spacing is 1 ~ 5cm.
Beneficial effect of the present invention is:
A kind of preparation method being easy to the silicon nanowire array that large area is separated that the present invention proposes can obtain the silicon nanowire array being easy to large-area high-quality and being separated, the introducing of extra electric field accelerates the lateral etching of metal nanoparticle, the adhesion of silicon nanowire array root and silicon base is weakened greatly, but in turn ensure that silicon nanowire array uprightly to arrange simultaneously and " paralysis paving " does not occur, substantially reduce separation force required in silicon nanowire array separation process like this, bring the advantage of silicon nanowire array uniform length simultaneously.
A kind of preparation method being easy to the silicon nanowire array that large area is separated that the present invention proposes has the advantage that technique is simple, favorable repeatability, cost are low; In addition, because extra electric field is controlled, simple and easy to get flexibly, can add at any time and withdraw from, for the silicon nanowire array being separated and shifting large-area high-quality provides brand-new visual angle and method.
Accompanying drawing explanation
Fig. 1 is the cross-section morphology figure of silicon nanowire array prepared by the embodiment of the present invention 1;
Fig. 2 is the lower surface shape appearance figure of the silicon nanowire array transferred on normal tape.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention will be further described in detail:
Embodiment 1:
(1) employing resistivity is p-type (100) single-chip of 7 ~ 13 Ω cm, each ultrasonic cleaning 10min in acetone and absolute ethyl alcohol respectively, then rinses 2 times with ultra-pure deionized water; Then soak at room temperature 5min in CP-4A solution; Be soak 5min in the hydrofluoric acid solution of 14wt% afterwards in concentration; Ultra-pure deionized water soaking flushing 5min, nitrogen dries up, and is placed in vacuumize environment;
(2) be connected with the both positive and negative polarity of constant current constant voltage power supply respectively by the electrode of two pieces of 7cm × 7cm × 3mm, fix its position with iron stand and holding electrode parallel, electrode spacing is 1.5cm; Then with concentration be 4.6 ~ 5mol/L hydrofluoric acid and 0.01 ~ 0.02mol/L liquor argenti nitratis ophthalmicus preparation etching liquid; Etching liquid is preheating to 25 DEG C in water-bath;
(3) be fixed on by silicon chip on platform that polytetrafluoroethylene makes, be immersed in the etching liquid of 25 DEG C of water-baths, when etch period arrives 30min, open constant current constant voltage source, regulation voltage, to 300V, continues to etch 15min;
(4) silicon chip being immersed concentration is 10min in the red fuming nitric acid (RFNA) of 65wt%, thoroughly removes the silver particles of silicon face remnants, then clean with deionized water rinsing;
(5) with the hydrofluoric acid dips 5min of 4wt%, remove the oxide layer of silicon chip surface, and form si-h bond at surface of silicon nanowires, namely obtain the silicon nanowire array being easy to large area separation; With ultra-pure deionized water soaking flushing 2min, dry up with nitrogen, preserve in vacuumize environment.
The cross-section morphology of obtained silicon nanowire array as shown in Figure 1, obviously can find out that from figure silicon nanowires is combined very " weakness " with silicon base, provides good condition for large area is separated.
Normal tape is attached to gently and is etched with on the side silicon face of silicon nanowire array, then to tear at leisure adhesive tape, can be observed tape surface and be covered with the uniform atrament of one deck, and silicon chip becomes grey from black, so just achieves the transfer of silicon nanowire array easily; Transfer to silicon nanowire array surface topography on normal tape as shown in Figure 2, as can be seen from the figure silicon nanowire array is transferred on normal tape by large-area high-quality.
Claims (9)
1. be easy to a preparation method for the silicon nanowire array that large area is separated, it is characterized in that, described method comprises the steps:
(1) silicon chip preliminary treatment: utilize acetone, absolute ethyl alcohol ultrasonic cleaning silicon chip successively respectively, remove its surface and oil contaminant; Then silicon chip is soaked, to remove its surface tear layer and smear layer with CP-4A solution; Use hydrofluoric acid dips again, to remove oxide layer;
(2) the building and prepare etching solution of extra electric field device: the electrode that two pieces of length of sides are greater than the silicon chip length of side is connected with the both positive and negative polarity of constant current constant voltage power supply respectively, fix its position and keep two electrode runs parallel, the silicon chip fixed placement that then will process through step (1) is in the middle of two electrodes but discord two electrode contacts; Preparation etching liquid, is preheating to 25 ~ 40 DEG C by etching liquid in water-bath; Wherein, described etching liquid is 4.6 ~ 5mol/LHF and concentration is 0.01 ~ 0.02mol/LAgNO
3mixed solution;
(3) preparation is easy to the silicon nanowire array of separation: will impregnated in the etching liquid of 25 ~ 40 DEG C of water-baths together with two electrodes through the silicon chip of the fixing process of step (2), etching direction is perpendicular to silicon base, etching reaction 40 ~ 60min, thus the silicon nanowire array obtaining different length; Etch terminate before 10 ~ 15min time, add electric field strength be 150 ~ 220V/cm and perpendicular to etching direction transverse electric field until reaction terminate;
(4) remaining silver in silicon nanowire array is removed: with nitric acid dousing 10 ~ 15min, thoroughly remove the silver remained in silicon nanowire array, then clean with deionized water rinsing;
(5) remove the oxide layer of surface of silicon nanowires: by hydrofluoric acid dips, remove the oxide layer of silicon chip surface, and form si-h bond at surface of silicon nanowires, namely obtain the described silicon nanowire array being easy to large area separation; Clean with deionized water rinsing, dry up with nitrogen, vacuumize is preserved.
2. method according to claim 1, is characterized in that, the silicon chip described in step (1) is (100) orientation p-type monocrystalline silicon piece, and its resistivity is at 7 ~ 13 Ω cm.
3. method according to claim 1, is characterized in that, the CP-4A solution described in step (1) is volume ratio is HF:HNO
3: absolute ethyl alcohol: H
2the mixed solution of O=3:5:3:22, wherein the mass fraction of HF is 40%, HNO
3mass fraction be 65%; The time using CP-4A solution to soak silicon chip is 5-8min.
4. method according to claim 1, is characterized in that, the hydrofluoric acid concentration described in step (1) is 14wt%, and soak time is 5-6min.
5. method according to claim 1, is characterized in that, step (1) finally rinses silicon chip with ultra-pure deionized water again, and nitrogen dries up, and is placed in vacuum environment drying, thus obtains the smooth silicon chip of surface cleaning; The resistivity of ultra-pure deionized water used is at 17 more than Ω cm.
6. method according to claim 1, is characterized in that, the electrode adopted in step (2) is the uniform square-shaped electrode of thickness, and electrode spacing is 1 ~ 5cm.
7. method according to claim 1, is characterized in that, the etch period described in step (3) is 45min, electric field strength 200V/cm, and the electric field joining day is 15min.
8. method according to claim 1, is characterized in that, the concentration of nitric acid described in step (4) is 65wt%.
9. method according to claim 1, is characterized in that, the hydrofluoric acid concentration described in step (5) is 3wt% ~ 5wt%, and soak time is 5 ~ 7min.
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| CN103903977A (en) * | 2014-03-20 | 2014-07-02 | 武汉新芯集成电路制造有限公司 | Etching method |
| CN104818532B (en) * | 2015-04-14 | 2018-07-27 | 杭州电子科技大学 | A method of silicon nanostructure material is prepared based on extra electric field |
| CN107193068B (en) * | 2017-06-27 | 2020-04-10 | 常州瑞丰特科技有限公司 | Method for manufacturing blazed grating by utilizing electric field to control hole distribution |
| CN107634005A (en) * | 2017-09-13 | 2018-01-26 | 云南大学 | A kind of method that silicon nanowire array is prepared based on metal Assisted Chemical Etching Process technology |
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| CN102040192A (en) * | 2009-10-20 | 2011-05-04 | 中国科学院理化技术研究所 | Method for preparing sequentially arranged bent silicon nano-wire array |
| CN102694075A (en) * | 2012-06-12 | 2012-09-26 | 东华大学 | Method of preparing inclined silicon nanowire array in electric field |
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| CN102040192A (en) * | 2009-10-20 | 2011-05-04 | 中国科学院理化技术研究所 | Method for preparing sequentially arranged bent silicon nano-wire array |
| CN102694075A (en) * | 2012-06-12 | 2012-09-26 | 东华大学 | Method of preparing inclined silicon nanowire array in electric field |
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