CN112028077B - Method for forming cracks in silicon nanowires and silicon nanowire array - Google Patents
Method for forming cracks in silicon nanowires and silicon nanowire array Download PDFInfo
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- CN112028077B CN112028077B CN202010970032.XA CN202010970032A CN112028077B CN 112028077 B CN112028077 B CN 112028077B CN 202010970032 A CN202010970032 A CN 202010970032A CN 112028077 B CN112028077 B CN 112028077B
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Abstract
The invention discloses a method for forming cracks in silicon nanowires and silicon nanowire arrays, and belongs to the technical field of new materials. The invention provides a method for rapidly forming cracks in silicon nanowires and silicon nanowire arrays. The method has simple process and low cost, can be used for industrial production, can be used for peeling and transferring the silicon nanowires and the silicon nanowire arrays on a large scale, and has wide application prospect in the fields of lithium ion batteries, solar batteries and the like.
Description
Technical Field
The invention relates to a method for forming cracks in silicon nanowires and silicon nanowire arrays, and belongs to the technical field of new materials.
Background
The one-dimensional semiconductor micro-nano wire has wide application prospect in the fields of solar cells, thermoelectric devices, medical biosensors, drug delivery and the like due to the peculiar structure and physical properties. Due to the important position of silicon materials in the traditional microelectronic industry, the research on one-dimensional silicon micro-nano wires is receiving great attention. The existing silicon micro-nano preparation method mainly comprises chemical vapor deposition, oxide auxiliary growth technology and the like. These methods generally require a relatively high temperature and some complicated equipment due to the limitation of the growth mechanism, resulting in high production costs. The method for catalyzing silicon corrosion by noble metal is a top-down method capable of quickly preparing silicon micro-nanowires, and has the characteristics of low cost, high benefit, simplicity and convenience in operation, large-scale production and the like. Although metal-catalyzed etching of silicon nanowires and arrays thereof has many excellent physical and chemical properties, it is inherently integral with crystalline silicon substrates, and thus the unique properties or advantages of silicon nanowires and arrays thereof are often masked by silicon substrate properties. For example, silicon nanowires and arrays thereof supported by a silicon substrate are not suitable for direct use as anodes in lithium ion batteries because the silicon substrate undergoes large volume expansion during electrochemical cycling and shatters, causing it to quickly lose electrical contact with the collector electrode. Therefore, the silicon nanowires and the array thereof are peeled off from the crystalline silicon substrate and transferred to other flexible substrates, and the production of a mechanically strong and flexible silicon nanowire and array film thereof is receiving much attention. Shiu et al attempted to transfer silicon nanowires and arrays thereof prepared by a metal-catalyzed etching method to other substrates using polymer dipping and applying shear force to break, but this method resulted in non-uniform breaking of the silicon nanowires and arrays thereof [ s.c.shiu, s.c.hung, j.j.chao, c.f.lin, appl.surf.sci.2009,255,8566 ]. Weisse et al used a 75 c hot water bath to soak silver to catalytically etch silicon nanowires and arrays to deform the metal catalyst film, resulting in excess silver ions and uniform cracks in the silicon nanowires and arrays [ j.weisse, d.kim, c.lee, x.zheng.nano lett.2011,11,1300 ]. However, the method can only form cracks in silver-catalyzed etching of the silicon nanowires and the silicon nanowire arrays, and the soaking in a hot water bath at 75 ℃ needs to last for about 3 hours, which severely limits the application of the method.
Disclosure of Invention
The invention provides a novel method for quickly forming cracks in silicon nanowires and silicon nanowire arrays. The technology has simple process and low cost, can be used for industrial production, can be used for large-scale stripping and transferring of silver, gold and platinum catalytic etching silicon nanowires and arrays thereof, and has wide application prospect in the fields of lithium ion batteries and the like. The invention provides a method for forming cracks in silicon nanowires and a silicon nanowire array, which is characterized by comprising the following steps: the method comprises the following steps in sequence:
(1) immersing the crystal silicon wafer with the silver film deposited on the surface into a closed container containing hydrofluoric acid and hydrogen peroxide mixed aqueous solution,
processing at 20-50 ℃ for 5-120 minutes to obtain silicon nanowires and an array sample thereof, and then cleaning the sample by using deionized water; the hydrogen peroxide in the mixed aqueous solution can also be replaced by strong oxidants such as nitric acid and the like.
(2) Immersing the silicon nanowire and the array sample thereof obtained in the step (1) into deionized water containing hydrogen peroxide, treating at 20-50 ℃ for 20 seconds-2 minutes, and then cleaning with the deionized water; and hydrogen peroxide in the deionized water can be replaced by corrosive agents such as nitric acid and the like which can corrode silver.
(3) Immersing the sample obtained in the step (2) into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20-50 ℃ for 2-10 minutes to form uniform cracks in the silicon nanowires and the silicon nanowire array; the hydrogen peroxide in the mixed aqueous solution can also be replaced by strong oxidants such as nitric acid and the like.
(4) Immersing the crystal silicon wafer with the gold film deposited on the surface into a closed container containing hydrofluoric acid and hydrogen peroxide mixed aqueous solution, processing for 5-120 minutes at 20-50 ℃ to obtain silicon nanowires and an array sample thereof, and then cleaning the sample by using deionized water; or the gold film can be replaced by a platinum film, and the hydrogen peroxide in the mixed aqueous solution can be replaced by a strong oxidant such as nitric acid and the like. .
(5) Immersing the silicon nanowire obtained in the step (4) and the array sample thereof into deionized water containing hydrogen peroxide and hydrochloric acid, treating at 20-50 ℃ for 20 seconds-2 minutes, and then cleaning with the deionized water; the hydrogen peroxide and hydrochloric acid in the deionized water can be replaced by corrosive agents such as nitric acid and hydrochloric acid which can corrode gold or platinum.
(6) Immersing the sample obtained in the step (5) into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20-50 ℃ for 2-10 minutes to form uniform cracks in the silicon nanowires and the silicon nanowire array; the hydrogen peroxide in the mixed aqueous solution can also be replaced by strong oxidants such as nitric acid and the like.
The concentration range of hydrofluoric acid in the steps (1), (3), (4) and (6) is 1-10 mol/L, and the concentration range of hydrogen peroxide is 0.02-2 mol/L. The concentration range of the hydrogen peroxide in the step (2) is 0.005-2 mol/L. The concentration range of the hydrogen peroxide in the step (5) is 0.005-2 mol/L, and the concentration of the hydrochloric acid is 0.005-2 mol/L.
Drawings
FIG. 1 is a scanning electron microscope topography of a broken silicon nanowire and its array prepared on the surface of a single crystal silicon (100) according to the present invention.
Detailed Description
The invention combines metal corrosion with metal catalytic etching silicon, can quickly form uniform cracks in the silicon nanowire and the silicon nanowire array, has simple process and low cost, and can be industrially produced. The invention is further illustrated by the following examples:
example 1
And immersing the crystal silicon wafer with the silver film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20 ℃ for 30 minutes to obtain the silicon nanowire and the silicon nanowire array. And immersing the obtained silicon nanowire and array samples thereof in deionized water containing hydrogen peroxide, cleaning the silicon nanowire and array samples with the deionized water after the silicon nanowire and array samples are treated at 20 ℃ for 1 minute, and then immersing the silicon nanowire and array samples in a closed container containing mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating the silicon nanowire and array samples at 20 ℃ for 5 minutes to form cracks in the silicon nanowire and array samples.
Example 2
And immersing the crystal silicon wafer with the silver film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20 ℃ for 30 minutes to obtain the silicon nanowire and the silicon nanowire array. And immersing the obtained silicon nanowire and array samples thereof in deionized water containing nitric acid, cleaning the silicon nanowire and array samples with the deionized water after treating the silicon nanowire and array samples for 1 minute at 20 ℃, then immersing the silicon nanowire and array samples in a closed container containing mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating the silicon nanowire and array samples for 5 minutes at 20 ℃ to form cracks in the silicon nanowire and array samples.
Example 3
And immersing the crystal silicon wafer with the gold film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20 ℃ for 30 minutes to obtain the silicon nanowire and the silicon nanowire array. And immersing the obtained silicon nanowire and the array sample thereof in deionized water containing hydrogen peroxide and hydrochloric acid, cleaning the silicon nanowire and the array sample with the deionized water after treating the silicon nanowire and the array sample for 1 minute at 20 ℃, and then immersing the silicon nanowire and the array sample in a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating the silicon nanowire and the array sample for 5 minutes at 20 ℃ to form cracks in the silicon nanowire and the array.
Example 4
And immersing the crystal silicon wafer with the gold film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20 ℃ for 30 minutes to obtain the silicon nanowire and the silicon nanowire array. And immersing the obtained silicon nanowire and the array sample thereof in deionized water containing nitric acid and hydrochloric acid, cleaning the silicon nanowire and the array sample with the deionized water after treating the silicon nanowire and the array sample for 1 minute at 20 ℃, and then immersing the silicon nanowire and the array sample in a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide for 5 minutes at 20 ℃ to form cracks in the silicon nanowire and the array thereof.
Example 5
And immersing the crystal silicon wafer with the silver film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20 ℃ for 30 minutes to obtain the silicon nanowire and the silicon nanowire array. And immersing the obtained silicon nanowire and array samples thereof in deionized water containing hydrogen peroxide, treating the silicon nanowire and array samples at 20 ℃ for 30 seconds, then cleaning the silicon nanowire and array samples with the deionized water, immersing the silicon nanowire and array samples in a closed container containing mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating the silicon nanowire and array samples at 20 ℃ for 10 minutes to form cracks in the silicon nanowire and array samples.
Example 6
And immersing the crystal silicon wafer with the gold film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20 ℃ for 30 minutes to obtain the silicon nanowire and the silicon nanowire array. And immersing the obtained silicon nanowire and array samples thereof in deionized water containing nitric acid and hydrochloric acid, cleaning the silicon nanowire and array samples thereof by the deionized water after treatment at 20 ℃ for 30 seconds, then immersing the silicon nanowire and array samples thereof in a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating the silicon nanowire and array samples thereof at 20 ℃ for 10 minutes to form cracks in the silicon nanowire and array thereof.
Example 7
And immersing the crystal silicon wafer with the gold film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating for 30 minutes at 50 ℃ to obtain the silicon nanowire and the array thereof. And immersing the obtained silicon nanowire and the array sample thereof in deionized water containing nitric acid and hydrochloric acid, cleaning the silicon nanowire and the array sample with the deionized water after treating the silicon nanowire and the array sample at 50 ℃ for 30 seconds, and then immersing the silicon nanowire and the array sample in a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating the silicon nanowire and the array sample at 50 ℃ for 10 minutes to form cracks in the silicon nanowire and the array.
Example 8
And immersing the crystal silicon wafer with the platinum film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20 ℃ for 30 minutes to obtain the silicon nanowire and the array thereof. And immersing the obtained silicon nanowire and the array sample thereof in deionized water containing hydrogen peroxide and hydrochloric acid, cleaning the silicon nanowire and the array sample with the deionized water after the silicon nanowire and the array sample are treated at 50 ℃ for 2 minutes, and then immersing the silicon nanowire and the array sample in a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating the silicon nanowire and the array sample at 20 ℃ for 5 minutes to form cracks in the silicon nanowire and the array.
Claims (4)
1. A method of forming cracks in silicon nanowires and arrays thereof, characterized by:
(1) immersing the crystal silicon wafer with the silver film deposited on the surface into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, treating for 5-120 minutes at 20-50 ℃ to obtain silicon nanowires and an array sample thereof, and then cleaning the sample by using deionized water; or replacing the hydrogen peroxide in the mixed aqueous solution with nitric acid;
immersing the obtained silicon nanowire and the array sample thereof into deionized water containing hydrogen peroxide, treating at 20-50 ℃ for 20 seconds-2 minutes, and then cleaning with the deionized water; or replacing the hydrogen peroxide in the deionized water with nitric acid; immersing the treated sample into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and treating at 20-50 ℃ for 2-10 minutes to form uniform cracks in the silicon nanowires and the silicon nanowire arrays; or replacing the hydrogen peroxide in the mixed aqueous solution with nitric acid;
(2) immersing the crystal silicon wafer with the gold film deposited on the surface into a closed container containing hydrofluoric acid and hydrogen peroxide mixed aqueous solution, processing for 5-120 minutes at 20-50 ℃ to obtain silicon nanowires and an array sample thereof, and then cleaning the sample by using deionized water; or replacing the gold film with a platinum film, and replacing hydrogen peroxide in the mixed aqueous solution with nitric acid;
immersing the obtained silicon nanowire and the array sample thereof into deionized water containing hydrogen peroxide and hydrochloric acid, treating at 20-50 ℃ for 20 seconds-2 minutes, and then cleaning with the deionized water; or replacing hydrogen peroxide and hydrochloric acid in the deionized water with nitric acid and hydrochloric acid; immersing the processed silicon nanowire and the array sample thereof into a closed container containing a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, and processing at 20-50 ℃ for 2-10 minutes to form uniform cracks in the silicon nanowire and the array thereof; the hydrogen peroxide in the mixed aqueous solution can also be replaced by nitric acid.
2. The method for forming cracks in silicon nanowires and silicon nanowire arrays according to claim 1, wherein the concentration of hydrofluoric acid in the mixed aqueous solution of hydrofluoric acid and hydrogen peroxide in (1) and (2) is in the range of 1-10 mol/L, and the concentration of hydrogen peroxide is in the range of 0.02-2 mol/L.
3. A method for forming cracks in silicon nanowires and arrays thereof according to claim 1, wherein the concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution in (1) is in the range of 0.005-2 mol/L.
4. The method for forming cracks in silicon nanowires and arrays thereof as claimed in claim 1, wherein the hydrogen peroxide concentration in the mixed solution of hydrogen peroxide and hydrochloric acid in (2) is in the range of 0.005-2 mol/L and the hydrochloric acid concentration is in the range of 0.005-2 mol/L.
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