CN107758610A - A kind of method that orderly small size silicon nanowire array is prepared based on ion beam etching - Google Patents
A kind of method that orderly small size silicon nanowire array is prepared based on ion beam etching Download PDFInfo
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- CN107758610A CN107758610A CN201710960835.5A CN201710960835A CN107758610A CN 107758610 A CN107758610 A CN 107758610A CN 201710960835 A CN201710960835 A CN 201710960835A CN 107758610 A CN107758610 A CN 107758610A
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Abstract
The present invention is ordered into the preparation method of silicon nanowire array, belongs to Fabrication Techniques of Nano-Structure field.First individual layer polystyrene nanospheres array is obtained in Si substrate surface solid matters, then ion beam etching technology is utilized, using argon gas as working gas, ar-ion beam vertical etch polystyrene nanospheres, line is 3 ~ 10 mA, line voltage is 0.5 ~ 1.1 KV, and etch period etches the nm polystyrene nanospheres of diameter 100 under conditions of being 60 ~ 550 s, obtains the polystyrene nanospheres array mould plate of period distances.By adjusting the regulation and control of line, beam pressure and etch period realization to polystyrene nanospheres size.Then evaporation golden film and ultrasound removal polystyrene nanospheres, use metal Assisted Chemical Etching Process method to prepare ordered silicon nano-wires array of the average diameter range for 50 ~ 81 nm, the height of nano wire is controlled by etch period.The present invention is a kind of low cost, the preparation method of simple, the efficient small size Si nano-wire arrays in order of technique.
Description
Technical field
The present invention relates to a kind of method that ordered silicon nano-wires array is prepared based on ion beam etching, belong to nano material system
Standby technical field.
Background technology
Because silicon nanowires has excellent optics antireflection characteristic and sunken luminous effect, and the modification of good surface and life
Thing compatibility, has been applied in solar cell and biology sensor.The silicon nanowire array of aligned orderly and size uniform,
It is the favourable guarantee of device performance stable operation.Therefore, people prepare ordered silicon nano-wires using various templates etching silicon chip
Array.The template used now mainly has：Aluminum oxide（AAO）Template, nanometer ball template and Lithographic template.Compared to aluminum oxide
（AAO）Template and Lithographic template, nanometer ball template have the advantages of inexpensive high production.And the lithographic method of silicon chip be divided into it is dry
Method etches and wet etching.Because wet etching does not need expensive etching apparatus, favored by people.Therefore, nanosphere
Template combination wet etching method, which turns into, to be reduced ordered silicon nano-wires array production cost, simplifies technique, accelerates popularization and application
Major technique.
Nanometer ball template is the key for preparing ordered silicon nano-wires array, and it decides size and the week of silicon nanowire array
Phase.The technology of preparing of nanometer ball template mainly has plasma etching and reactive ion etching at present.Patent
（CN201210142182.7）Using plasma cleaning machine etches double-deck polystyrene nanospheres and obtained initially under an argon
Template, after annealing is then infiltrated in ferric nitrate and obtains di-iron trioxide secondary template, orderly silicon is etched after redeposited golden film
Nano-wire array.Plasma etching technology belongs to chemical reaction etching, has the advantages of etch rate is fast, but due to transverse direction
Undercutting acts on, there is also etching precision it is low the shortcomings that, be used for the polystyrene nanospheres for etching more than 500 nanometers of diameter, nothing
Method obtains small size ordered silicon nano-wires array.Plasma washing machine can only adjust etch period, can not adjust etch rate,
It is difficult to effectively control etching effect.Patent（CN200610089728.1）Using reactive ion etching technology（RIE）In oxygen atmosphere
Under prepare the polystyrene nanospheres templates of period distances, reuse silver-colored Assisted Chemical Etching Process and go out ordered silicon nano-wires battle array
Row.Reactive ion etching is that one kind combines chemical reaction etching and physical etchings method, and etching precision is carved better than plasma
Erosion technology.But when the polystyrene nanospheres of 200 nanometers of diameter are etched into 50 nanometers, due to chemical reaction etching
Horizontal undercutting, the shape of nanosphere become irregular, are unfavorable for preparing small size ordered silicon nano-wires array.In addition, reacting
In ion etching, the density and energy of reactive ion can not independent control, be unfavorable for efficiently controllable etching.
Based on above two method, preparing ordered silicon nano-wires array of the size less than 100 nanometers becomes extremely difficult.Cause
How simply this, efficiently reduce silicon nanowires size, increase etching precision, it is to prepare ordered silicon nano-wires to improve controllability
Array urgent problem, and improve ordered silicon nano-wires array performance and increase the basis of its application potentiality.
By literature search, have no and disclose report with identical of the present invention.
The content of the invention
It is an object of the invention to provide a kind of low cost, the orderly small size silicon nanowires that technique is simple, efficiently controllable
The preparation method of array.Compact arranged polystyrene nanospheres array is bombarded using ion beam etching technology, reduces nanosphere
Diameter, obtaining has the nanometer ball templates of period distances, then using metal Assisted Chemical Etching Process method, it is orderly to prepare small size
Silicon nanowire array.
The present invention uses following technical scheme：The individual layer polystyrene that 100 nanometers of diameter is first prepared in Si substrate surfaces is received
Rice ball array, the substrate for sequencing nanometer ball array is dried, is put into ion beam etching vacuum chamber.Adjustment ion beam vertically bombards
Polystyrene nanospheres array on Si substrates, that is, allow ion beam line incident direction and substrate normal angle be 0 °.With
High-purity argon gas is working gas, and base vacuum is 2.0 × 10-4 Pa ~3.0×10-4 Pa.Discharge voltage is the V of 70 V ~ 80, beam
Stream voltage is the KV of 0.5 KV ~ 1.1, and accelerating potential is the V of 100 V ~ 200, and line is the mA of 3 mA ~ 10, bombardment time be 60 s ~
Compact arranged polystyrene nanospheres array is etched under conditions of 550 s, so as to obtain the nanosphere mould of period distances
Plate；Then 20 ~ 30 nano gold layers are grown using ion sputtering process, ultrasound removes pipe/polyhenylethylene nano in tetrahydrofuran solution
Ball；Finally use hydrofluoric acid and hydrogen peroxide（Volume ratio is 4:1）Mixed solution, covered using metal inducement lithographic technique corrosion gold
Silicon under lid, form the identical ordered silicon nano-wires array of the polystyrene nanospheres size gone out with Ar Ion Beam Etching, its height
The time control etched by metal inducement.
First, in the scheme individual layer polystyrene nanospheres film preparation, concretely comprise the following steps：
（1）, selection crystal orientation for（100）Si substrates and common slide, carry out ultrasonic vibration respectively using acetone and alcohol
5 min are cleaned, with deionized water rinsing 3 times；Then substrate is put into sulfuric acid and hydrogen peroxide（Volume ratio is 4:1）Mixing it is molten
10 min are boiled in liquid, use deionized water rinsing 3 times；Finally by Si substrates in hydrofluoric acid and hydrogen peroxide（Volume ratio is 1:
10）Mixed solution in soak 30 s, with deionized water rinsing 3 times；
（2）, purchase polystyrene nanospheres be 2.5 wt%（Mass concentration）, it is a diameter of 100 nanometers, by pipe/polyhenylethylene nano
Ball solution and methanol solution are well mixed according to the ratio that volume ratio is 1: 1, then mixed by 40 microlitres using micro syringe
Close solution to drop on slide, allow mixed liquor to flow slowly into deionized water；Surfactant is added, nanosphere film forming is stable
Afterwards, deionized water is slowly excluded, obtains the compact arranged individual layer polystyrene nanospheres array of two-dimensional hexagonal on si substrates.
2nd, the nanometer ball template for there are period distances is prepared in the scheme using ion beam etching technology, is concretely comprised the following steps：
（1）, the Si substrates for being covered with polystyrene nanospheres array are put into vacuum chamber, adjustment ion beam vertically bombards Si substrates
On polystyrene nanospheres array, that is, allow ion beam line incident direction and substrate normal angle be 0 °.
（2）, treat vacuum chamber background vacuum be 2.0 × 10-4 Pa ~3.0×10-4 Pa, pour the argon gas that purity is 5N and make
For working gas, adjustment work pressure is 2.0 × 10-2 Pa~3.0×10-2 Pa；
（3）, regulation discharge voltage be the V of 70 V ~ 80, line voltage is the KV of 0.5 KV ~ 1.1, and accelerating potential is 100 V ~ 200
V, ion beam current are the mA of 3 mA ~ 10, and etch period is the s of 60 s ~ 550.
3rd, ordered silicon nano-wires array is prepared using metal Assisted Chemical Etching Process in the scheme, concretely comprised the following steps：
（1）, using ion sputtering process, deposit thickness is 20 ~ 30 nanometers of gold on the nanometer ball template for have period distances；
（2）, using be cleaned by ultrasonic instrument nanometer ball template is removed in tetrahydrofuran solution；
（3）, hydrofluoric acid and mixed solution of hydrogen peroxide etching silicon chip, prepare small size ordered silicon nano-wires array.
The present invention has following advantages compared with prior art：Ion beam etching technology belongs to physical etchings method, has
Fabulous etching resolution ratio, superfinishing fining-off can be carried out；And ion beam etching technology intermediate ion density and ion energy can be with
It is separately adjustable, it is to realize efficiently controlled etched condition.Using such scheme, received when polystyrene nanospheres diameter is reduced to 50
Meter Shi, nanosphere remain in that the spherical of rule, can prepare the ordered silicon nano-wires array of small size and size uniform, be
A kind of low cost, the method for simple, the efficient orderly small size silicon nanowire array of controllable preparation of technique.
Brief description of the drawings
The present invention is further described with the example of implementation below in conjunction with the accompanying drawings.
Fig. 1 is the scanning electron microscope diagram of the individual layer polystyrene nanospheres array of two-dimensional hexagonal solid matter；
Fig. 2 be ion beam etching after the nanometer ball template for having period distances scanning electron microscope diagram；
Fig. 3 is the scanning electron microscope diagram of the orderly small size Si nano-wire arrays obtained after metal Assisted Chemical Etching Process.
Embodiment
Embodiment 1：
（1）The typesetting of individual layer pipe/polyhenylethylene nano bead
A, select crystal orientation for（100）P-type Si substrates and slide, be cleaned by ultrasonic 3 times successively with acetone and alcohol, every time 5
Min, with deionized water rinsing 3 times；Then they are used into H2SO4:H2O2=4:1 solution boils 10 min, is rushed with deionized water
Wash 3 times；Finally by Si substrates HF:H2O=1:10 solution soaks 30 s, with deionized water rinsing 3 times；
B, by polystyrene nanospheres solution and methanol solution according to volume ratio 1:1 ratio is well mixed, then with micro note
Emitter flows slowly into 40 microlitres of mixed solutions in deionized water along slide；Surfactant is added, nanosphere film forming is stable
Afterwards, deionized water is slowly excluded, obtains the compact arranged individual layer polystyrene nanospheres array of two-dimensional hexagonal on si substrates.
(as shown in Figure 1)；
（2）Ion beam etching technology prepares the polystyrene nanospheres template for having period distances：
A, the silicon base that row there are polystyrene nanospheres is put into ion beam etching room, adjusts substrate position and ion beam incidence
Direction is vertical, and it is 3.0 × 10 to treat background vacuum-4Pa, is then filled with the argon gas of purity to intracavitary, and adjustment work pressure is 2.0
×10-2Pa；
B, at room temperature, discharge voltage is 70 V, and line voltage is 1 KV, and accelerating potential is 100 V, and ion current is 3 mA,
Etch period uses ion beam etching polystyrene nanospheres under conditions of being 550 s.
The sample detection result of the present embodiment is as shown in Figure 2.The average diameter of polystyrene nanospheres in figure reduces
For 50 nanometers, the polystyrene nanospheres template for there are period distances is obtained.
（3）Metal Assisted Chemical Etching Process prepares ordered silicon nano-wires array
A, the nanometer ball template for there are period distances is put into gold-plated film in ion sputtering instrument equipment, power is 30 mW, and vacuum is
0.1 Pa, golden film thick 20 nm of growth；
B, the nanometer ball template for being coated with golden film is put into ultrasound in tetrahydrofuran solution and removes nanosphere；
C, in HF：H2O2=4：1（Volume ratio）Mixed liquor in etch 120 s, finally remove remaining golden film, obtain in order
Si nano-wire arrays.
As shown in Figure 3, the average diameter of Si nano wires is 50 to the orderly Si nano-wire arrays that the present embodiment is prepared
Nanometer.
Embodiment 2：
Similar to Example 1, difference is that the line of ion beam etching is 3 mA, and background vacuum is 2.0 × 10-4
Pa, etch period are 300 s.The average diameter for obtaining Si nano wires is 81 nanometers.
Embodiment 3：
Similar to Example 1, difference is that the line of ion beam etching is 10 mA, and operating pressure is 3.0 × 10-2Pa,
The KV of line voltage 1.1, etch period are 60 s.The average diameter for obtaining Si nano wires is 73 nanometers.
Embodiment 4：
Similar to Example 1, difference is the V of discharge voltage 80 of ion beam etching, the KV of line voltage 0. 5, during etching
Between be 450 s, obtain Si nano wires average diameter be 75 nanometers.
Embodiment 5：
Similar to Example 1, difference is that the accelerating potential of ion beam etching is 200 V, obtains being averaged for Si nano wires
A diameter of 56 nanometers.
Embodiment 6：
Similar to Example 1, difference is the KV of line voltage 0.7 of ion beam etching, obtains the average straight of Si nano wires
Footpath is 69 nanometers.
Claims (6)
- A kind of 1. method that orderly small size silicon nanowire array is prepared based on ion beam etching, it is characterised in that：It is included in Si Solid matter polystyrene nanospheres, preparation nanometer ball template and etching silicon nano line array step on substrate；It is specific as follows：Background is true Sky is 2 × 10-4 Pa ~ 3×10-4 Pa, operating pressure are 2 × 10-2 Pa~3×10-2 Pa, discharge voltage are the V bars of 70 V ~ 80 Caused Ar ion beam currents under part, the polystyrene nanospheres of solid matter on Si substrates are etched, obtain the nanosphere mould of period distances Plate, and metal Assisted Chemical Etching Process technology is used, obtain the orderly small size silicon nanowire array that average diameter is 50 ~ 81 nm.
- A kind of 2. method that orderly small size silicon nanowire array is prepared based on ion beam etching, it is characterised in that：On Si substrates The polystyrene nanospheres of solid matter are individual layer, a diameter of 100 nm.
- 3. a kind of method that orderly small size silicon nanowire array is prepared based on ion beam etching according to claim 1, It is characterized in that：Nanometer mean diameter of a ball is 50-81 nm in the nanometer ball template of the period distances of acquisition.
- 4. a kind of method that orderly small size silicon nanowire array is prepared based on ion beam etching according to claim 1, It is characterized in that when preparing nanometer ball template on si substrates and preparing, the line incident direction of Ar ion beams and the method wire clamp of substrate Angle is 0 °.
- 5. a kind of method that orderly small size silicon nanowire array is prepared based on ion beam etching according to claim 1, It is characterized in that when preparing nanometer ball template on si substrates and preparing, Ar ion beam currents operating voltage is the KV of 0.5 KV ~ 1.1, is added Fast voltage is the V of 100 V ~ 200, and line is the mA of 3 mA ~ 10.
- 6. according to claim 1 prepare orderly small size silicon nanowires method based on ion beam etching, it is characterised in that When preparing nanometer ball template on si substrates and preparing, the Ar ion beam etching times are the s of 60 s ~ 550.
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| CN108373136A (en) * | 2018-03-14 | 2018-08-07 | 云南大学 | A kind of preparation method of the orderly polystyrene nanospheres template of non-solid matter |
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Application publication date: 20180306 |