The preparation method of ordered silicon nano-wires
Technical field
The invention belongs to the nano-device manufacturing process technology field, be specifically related to a kind of preparation method of preface silicon nanowires.
Technical background
Silicon nanowires and array thereof are accurate one dimension semiconductor photoelectricity information materials, in fieldtron, Monoelectron memory device, light-detecting device, feds, nanosensor device and high efficiency light-emitting device and integrated technology, have potential application.The preparation method of silicon nanowires mainly contains: thermal chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), low-pressure chemical vapor deposition (LPCVD), laser ablation deposition (LAD), thermal evaporation, electron beam evaporation (EBE), solution method and hydrothermal method etc.The growth mechanism of silicon nanowires mainly contains: gas-liquid-solid (VLS), gas-solid (VS) Gu, gas-solid-(VSS) Gu, solid-liquid-(SLS) etc.Though much human based on crystalline gas-liquid-solid (VLS) Gu growth mechanism or solid-liquid-(SLS) growth mechanism synthetic Si nano wire on the nano particle of iron, cobalt, nickel, gold, copper etc.; The Si nano wire of traditional method preparation is in diameter, length and all have bigger dispersiveness and randomness in shape, can't array and will use catalyzer.Realize the diameter of Si nano wire and the ordering of length controlled and arrangement, the anodic oxidation aluminium formwork method is a kind of feasible method.The hole of anodic oxidation aluminium formwork is the hexagonal cylindricality perpendicular to face, is in order to be arranged in parallel, and the aperture can be regulated in 1~400nm scope, and the degree of depth also can be regulated through changing anodizing time.Someone once attempted utilizing electron beam evaporation (EBE) and anodised aluminium (AAO) template to combine the preparation silicon nanowires, still, did not obtain ideal results.Major cause has two: the first, and when utilizing electron beam evaporation, the Siliciumatom energy that is evaporated is big inadequately, and is abundant inadequately in the motion on anodic oxidation aluminium formwork surface, and the silicon that enters into the template hole is seldom.Carry out along with sedimentary, Siliciumatom stops up the aperture of template live, and stops Siliciumatom to continue in the hole of template, to fill.The result has only the silicon of very small amount to be filled in the hole of template, can't in hole, form silicon nanowires; The second, the composite package of silicon and anodic oxidation aluminium formwork directly is put in the acid solution corrodes.Because the percent crystallinity of the silicon fiml of electron beam evaporation preparation is not high, physical strength is not enough.Along with the corrosion of anodic oxidation aluminium formwork, silicon fiml also is broken into many small shredss gradually, even cannot from solution, take out.
Because the silicon nanowires of general method preparation is in diameter, length and all have bigger dispersiveness and randomness in shape, all brings great difficulty to studying its photoelectric characteristic and device application.Therefore, in patented technology, propose a kind of method for preparing diameter and length controlled and arrange orderly silicon nanowires and have important theory value and practical significance with the integrated aspect of silicon based opto-electronics aspect preparing at nano-device.
Summary of the invention
For solving the above-mentioned defective that prior art exists, the objective of the invention is to propose a kind of method for preparing ordered silicon nano-wires, utilize this method can prepare diameter and length controlled and arrange orderly silicon nanowires.The preparation process is simple and easy to do, can access big area, diameter and length controlled and arrange orderly silicon nanowires.
To achieve these goals, the technical scheme of the present invention's employing is: a kind of ordered silicon nano-wires preparation method, its characteristic comprises the steps:
(1) cleaning of high purity aluminium flake and electrochemical etching;
(2) adopt the two-step anodization legal system to be equipped with anodic oxidation aluminium formwork;
(3) with the anodic oxidation aluminium formwork be substrate, adopt pulsed laser deposition technique to prepare the composite package of silicon and anodised aluminium;
(4) composite package is taken out from reaction chamber after, at the silicon fiml surface coating, glue erodes anodic oxidation aluminium formwork with hydrochloric acid soln after doing fully, ionized water is cleaned and is dried, and so just prepares consistent size, is evenly distributed on the silicon nanowires on the silicon fiml.
Said high purity aluminium flake cleans in ultrasonic cleaner with acetone, and said electrochemical etching is in volume ratio is the mixed solution of 1/2~1/10 perchloric acid and absolute ethyl alcohol, to carry out electrochemical etching, and the time is 5min~10min, and polishing voltage is 10V~18V.
Said two-step anodization method is for to use electrolytic solution to carry out anodic oxidation as the oxalic acid solution of 0.1mol/L~0.5mol/L, and voltage is 10V~40V, and temperature is no more than 10 ℃; First anodizing time is 10min~15min, soaks 5min~20min with chromic acid then, removes the disordering part in the zone of oxidation that first anodic oxidation produces; Then carry out two-step anodization, condition is with first anodised identical, and the time is 20min~40min; Before pulsed laser deposition; With the NaOH solution reaming 10s~20s of anodic oxidation aluminium formwork, use deionized water drip washing clean then, earlier with subsequent use after the drier with 0.1mol/L~1mol/L.
Said with pulsed laser deposition deposited silicon film on the face of anodic oxidation aluminium formwork perforate; Said deposition is divided into two stages and carries out; First stage; Pulse-repetition frequency and pulse energy through the adjustment laser apparatus make sedimentation rate smaller, let silicon be filled in the hole of anodic oxidation aluminium formwork as far as possible; Second stage makes sedimentation rate bigger through pulse-repetition frequency and the pulse energy of adjusting laser apparatus, and to improve the speed of growth of silicon fiml, said pulse laser adopts the KrF excimer laser, and the background vacuum will reach 10
-6More than the Pa magnitude, silicon target is a silicon chip, source-cardinal distance 3~5cm, and pressure is 10 during the reaction beginning
-5Pa magnitude, underlayer temperature are 300 ℃~700 ℃, and during deposition, substrate wants rotation to guarantee the even of silicon film thickness.
Said gluing is at the modified acroleic acid ester gum of surfaces coated one deck acid-fast alkali-proof of silicon fiml or the glue of other acid-fast alkali-proof, can strengthen the physical strength of silicon fiml after glue is done, and guarantees that silicon fiml can not break after removing anodic oxidation aluminium formwork; Said etch is removed anodic oxidation aluminium formwork, and corrosion process must thoroughly be removed anodic oxidation aluminium formwork clean, and the silicon fiml after the corrosion is pulled out, and cleans with deionized water and dries, and just obtains being evenly distributed on the silicon nanowires on the silicon fiml.
The diameter of said silicon nanowires equates that with the aperture of anodic oxidation aluminium formwork the distribution of silicon nanowires is the same with the distribution in anodic oxidation aluminium formwork hole.
Adopt the beneficial effect of technique scheme: because the growth of anodised aluminium has self-organization and the symmetric long-range order of hexagonal; Its hole is parallel to each other; Be evenly distributed; And perpendicular to substrate surface, aperture, porosity and hole depth can the controls very easily through changing preparation condition.With the anodised aluminium is template, can prepare the regularly arranged nano material array of large-scale self-organizing growth, and this research to nano science has very important meaning.Pulsed laser deposition technique utilizes the plasma body that interaction produced of laser beam and target on substrate, to deposit film forming; Can be at the film and the multilayer complex films of lower temperature deposit complicated ingredient; Because the transient energy density of pulse laser is bigger, the particle energy in the plasma body of generation is bigger.In addition, pulsed laser deposition technique has also that processing compatibility is good, flexibility is strong, the sedimentation rate advantages of higher, and pulsed laser deposition technique and anodic oxidation aluminium formwork method are combined, and can prepare the composite package of silicon and anodic oxidation aluminium formwork.Because silicon growth is on anodic oxidation aluminium formwork foraminous face; The part siliceous deposits is in the hole of anodic oxidation aluminium formwork; Form a kind of structure of inlaying each other, anodic oxidation aluminium formwork is removed just can obtain diameter and length controlled and arrange orderly silicon nanowires.For removing the anodic oxidation aluminium formwork of composite package, can select for use hydrochloric acid soln to carry out chemical corrosion.Because hydrochloric acid and anodic oxidation reactive aluminum, and do not react with silicon.Before corrosion treatment, need there be the one side of silicon fiml to be coated with the glue of one deck acid-fast alkali-proof at composite package, glue carries out corrosion treatment after doing again.Because glue can be strengthened the physical strength of silicon fiml, guarantee that silicon fiml can not break after removing anodic oxidation aluminium formwork.According to above-mentioned processing condition; Adopt the two-step anodization method to prepare high-quality anodic oxidation aluminium formwork; Utilize sem to test; The stereoscan photograph that obtains anodic oxidation aluminium formwork can be found out: the about 70nm of the diameter in hole, and hole depth reaches 700nm, and the direction in hole is vertical with template surface.Anodic oxidation aluminium formwork is eroded the silicon nanowires that just obtains being distributed in the silicon fiml surface with hydrochloric acid soln; Utilize sem to test; Obtain shown in the stereoscan photograph of silicon nanowires sample: the about 70nm of the diameter of silicon nanowires; The length of silicon nanowires is about 100nm, the area density 10 of silicon nanowires
11/ cm
2, silicon nanowires is evenly distributed on the silicon fiml, the direction of silicon nanowires and the Surface Vertical of film, and the diameter of silicon nanowires is identical everywhere with length.Therefore, the silicon nanowires that is distributed on the silicon fiml can be successfully prepared in the combination of pulsed laser deposition and anodic oxidation aluminium formwork method, and need not use any catalyzer.Because the growth of anodised aluminium has self-organization and the symmetric long-range order of hexagonal, its hole is parallel to each other, is evenly distributed, perpendicular to substrate surface.And the shape and size of silicon nanowires are by the decision of the shape and size in the hole of anodic oxidation aluminium formwork, so the silicon nanowires of this method preparation also has the characteristics of " be parallel to each other, be evenly distributed, perpendicular to substrate surface ".Silicon chip through selecting different sorts and different levels of doping can obtain the silicon nanowires of different sorts and different levels of doping as the target of pulsed laser deposition.
Description of drawings
Below in conjunction with accompanying drawing specific embodiment of the present invention is done further detailed explanation.
Fig. 1 is silicon and anodised aluminum compound film side structure synoptic diagram.
Fig. 2 is the front scan electromicroscopic photograph of anodic oxidation aluminium formwork.
Fig. 3 is the side stereoscan photograph of anodic oxidation aluminium formwork.
Fig. 4 adopts the stereoscan photograph of the ordered silicon nano-wires of the inventive method preparation.
Embodiment
A kind of ordered silicon nano-wires preparation method, its characteristic comprises the steps:
(1) at first; Purity is cleaned 10min at 99.99% high purity aluminium flake with acetone in ultrasonic cleaner; To remove the grease on surface; Be to carry out electrochemical etching in 1/2~1/10 perchloric acid and the absolute ethyl alcohol mixed solution in volume ratio then, the time is 5min~10min, and polishing voltage is 10V~20V.Preferably be employed in volume ratio and be in 1: 4 the mixed solution of perchloric acid and absolute ethyl alcohol and carry out electrochemical etching 10min, polishing voltage is 20V.
(2) use electrolytic solution to carry out anodic oxidation as the oxalic acid solution of 0.1mol/L~0.5mol/L; Voltage is 10V~40V; Temperature is no more than 10 ℃; First anodizing time is 10min~15min, soaks 5min~20min with chromic acid then, removes the disordering part in the zone of oxidation that first anodic oxidation produces.The preferred oxalic acid solution of 0.3mol/L that adopts carries out anodic oxidation, and voltage is 40V, and first anodizing time is 15min, and chromic acid soaks and is 15min; Then carry out two-step anodization, condition is with first anodised identical, and the time is 20min~40min, and preferred oxidization time is for being 30min.This moment, the aperture of porous aluminum was about 30nm~40nm, and pitch-row is about 50nm~100nm, and thickness is about 500nm~1000nm.Adopt the aperture of the anodised aluminium of preferred parameter preparation to be about 40nm, pitch-row is about 80nm, and hole depth is about 700nm.With the NaOH reaming 10s~20s of the anodised aluminium for preparing with 0.1mol/L~1mol/L, after the reaming, the aperture is about 50nm~100nm.Preferably select the NaOH solution reaming of 0.5mol/L for use, the aperture is about 70nm, cleans with deionized water immediately after the reaming and dries, and so just obtains like Fig. 2, the high-quality anodic oxidation aluminium formwork shown in 3.
(3) send the anodic oxidation aluminium formwork for preparing to Vakuumkammer, with pulsed laser deposition deposited silicon film on the face of anodic oxidation aluminium formwork perforate.The KrF excimer laser that laser apparatus adopts Germany to produce, wavelength is 248nm, and pulsewidth is 10ns, and pulsed laser energy is 250mJ, and focal area is 4mm
2, energy density 6J/cm
2, used vacuum apparatus is produced by Shenyang Scientific Instrument Development Centre, Chinese Academy of Sciences, and maximum vacuum is 2 * 10
-8Pa, the N that selects for use Luoyang monocrystalline silicon piece factory to produce<100>Silicon chip, resistivity 5-8.5 Ω cm.Silicon target can be selected the silicon chip of different doping types and different levels of doping as required for use, can obtain the silicon nanowires of different sorts and different levels of doping.Source-cardinal distance 3~5cm, pressure is 10 during the reaction beginning
-5Pa magnitude, underlayer temperature are 300 ℃~700 ℃, and preferred temperature is 500 ℃, during deposition, and substrate PM rotation 10 circles, target PM rotation 9 circles guarantee the even of silicon film thickness.For guaranteeing that silicon can be filled in the hole of anodic oxidation aluminium formwork, deposit that being divided into two stages carries out.First stage makes sedimentation rate smaller through pulse-repetition frequency and the pulse energy of adjusting laser apparatus, laser repetition rate 5Hz, and pulse energy 250mJ plays 5 group pulses, and every group of 1000 pulses let silicon be filled in the hole of anodic oxidation aluminium formwork as far as possible; Second stage makes sedimentation rate bigger through pulse-repetition frequency and the pulse energy of adjusting laser apparatus, with the speed of growth of raising silicon fiml, and laser repetition rate 10Hz, pulse energy 250mJ plays 95 group pulses, every group of 1000 pulses.The silicon as shown in Figure 1 and the anodic oxidation aluminium formwork that under this condition, obtain are inlayed the composite package that forms each other.
(4) composite package is taken out from reaction chamber after, at the modified acroleic acid ester gum of surfaces coated one deck acid-fast alkali-proof of silicon fiml, can strengthen the physical strength of silicon fiml after glue is done, guarantee that silicon fiml can not break after removing anodic oxidation aluminium formwork.Glue erodes anodic oxidation aluminium formwork with hydrochloric acid soln after doing fully, and the concentration difference of hydrochloric acid soln can cause corrosion speed different with etching time, and corrosion process must thoroughly guarantee anodic oxidation aluminium formwork is removed clean.Silicon fiml after the corrosion is pulled out, clean with deionized water and dry, just obtain the silicon nanowires on the silicon fiml that is evenly distributed on as shown in Figure 4.