CN103979487B - Method for preparing doping porous silicon ball - Google Patents
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- CN103979487B CN103979487B CN201410243087.5A CN201410243087A CN103979487B CN 103979487 B CN103979487 B CN 103979487B CN 201410243087 A CN201410243087 A CN 201410243087A CN 103979487 B CN103979487 B CN 103979487B
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Abstract
The invention discloses a method for preparing a doping porous silicon ball. The method includes the steps that a silicon ball with certain doping content is selected, after being washed by hydrofluoric acid, the silicon ball is immersed in solutions formed by nitrate and hydrofluoric acid, after ultrasonic processing is carried out, the silicon ball is immersed in solutions prepared by the hydrofluoric acid and oxidizing agents and reacts at a certain temperature for a certain time period, then the silicon ball is washed in a centrifugal mode, and ultimately the nano porous silicon ball is prepared after nitric acid washing and other post-processing procedures. The best variety and the best concentration of reaction solutions, the optimum proportion of components, the best reaction temperature, the best reaction time, best ultrasonic frequency and best ultrasonic processing time are screened out through a large quantity of experiments. According to the whole preparation method, process design is reasonable, operability is high, production cost is low, production efficiency is high, and large-scale industrial production can be achieved. According to the high-purity doping porous silicon ball prepared in the method, the shapes of holes are regular, the holes are uniformly distributed and honeycomb-shaped, the shape of the silicon ball is regular, and the method can be widely used in the field of lithium batteries, solar batteries, semi-conductors, sensors and the like.
Description
Technical field
The present invention relates to a kind of preparation field of porous silica material, be specifically related to a kind of silicon ball utilizing doping, under uniform temperature and reaction time, prepared the method for the cellular porous silicon ball of structure-controllable by the chemical etching solution of certain proportioning.
Background technology
Porous silica material has unique photoelectric characteristic, and large specific area makes it can be applied to the fields such as various detector, biosensor, photoelectric nano apparatus, energy storage material, and the negative material especially as lithium battery receives much concern in recent years.Compared with traditional negative material, silicon has the theoretical specific capacity (4200mAh/g) of superelevation and lower de-lithium current potential (<0.5V), when charging, difficulty causes surface to analyse lithium, security performance is better, and current silicon becomes one of potential selection of richness of lithium ion battery carbon back negative pole upgrading.But silicon is that self electrical conductivity is lower as lithium ion battery negative material shortcoming, there is the Swelling and contraction of more than 300% in volume in electrochemistry cyclic process, the mechanicals efforts of generation can be made material efflorescence gradually, cause structure collapses, cause cycle performance of battery greatly to reduce.So by silicon materials nanometer, improve micro-structural, improve electric conductivity be all highly effective method.Nano-porous structure wherein can effectively buffer volumes expand, and improves starting efficiency, cyclical stability and high rate performance.
In raising electric conductivity, main employing prepares silicon metal or Si-C composite material material.It take silicon alloy powder as the method that porous silicon particulate prepared by raw material that patent CN103165874A discloses a kind of.Patent CN103247792A discloses a kind of preparation method of nanoporous aluminosilicate alloy material.Patent CN102683649 discloses a kind of carbon method for coating of the nano silica fume for the preparation of cathode of lithium battery.Patent CN101973517A discloses a kind of method of low doped porous silicon nanowire array.Bibliographical information passes through B
2o
3doped silicon ball (Scalable preparation of porous silicon nanoparticles and their application for lithium-ion battery anodes, Mingyuan Ge, Jiepeng Rong, et al, Nano Research2013,6 (3): 174 – 181) prepare porous silicon and embody good performance as on lithium battery silicium cathode material.At present involved porous silicon ball preparation mainly refers to the preparation of silica spheres, with monocrystalline or polysilicon ball for matrix prepares porous silicon ball, particularly adopts the silicon ball of different levels of doping to prepare porous silicon ball as matrix, does not also have report.
Summary of the invention
Goal of the invention: the object of the invention is for the deficiencies in the prior art, a kind of preparation method of the porous silicon ball that adulterates is provided, the method utilizes the silicon ball of different doping contents to be raw material, electrochemical etching is used to prepare the porous silicon ball of different electrical conductivity, to meet the different application demand on photoelectric nano device.The method has that preparation technology's flow scheme design is reasonable, and do not need complex device, productive rate is high, can the advantage such as suitability for industrialized production.
Technical scheme: in order to realize above technical purpose, the technical scheme that the present invention takes is:
Adulterate the preparation method of porous silicon ball, and it comprises the steps:
(1) the silicon ball of appropriate doping is measured, by hydrofluoric acid clean;
(2) eccentric cleaning;
(3) silicon ball is placed in certain density nitrate, solution that hydrofluoric acid is prepared according to a certain volume, at room temperature react after ultrasonic process;
(4) eccentric cleaning;
(5) silicon ball is placed in certain density hydrofluoric acid, solution that oxidant is prepared according to a certain volume reacts;
(6) eccentric cleaning;
(7) then clean with nitric acid;
(8) namely eccentric cleaning obtains doping porous silicon ball.
Preferably, in technical scheme of the present invention, the silicon ball of the doping that step (1) uses can be obtained by following two kinds of methods: the first, be with the monocrystalline of different levels of doping or polycrystal silicon ingot, silicon rod for raw material, prepared by pulse discharge method; The second after silicon ball is formed, utilizes various forms of doped source to carry out diffusion obtain different levels of doping.Doped source is the doped chemicals such as phosphorus (P), arsenic (As), antimony (Sb), boron (B), aluminium (Al), gallium (Ga), indium (In), the size range of doped silicon ball is 0.1 ~ 50 μm, doped source total concentration 1 × 10
14~ 1 × 10
21atoms/cm
3.Particularly preferably first method obtains doped silicon ball.
Pulse discharge method prepares article " Apractical approach on producing Silicon nanoparticles through spark erosion using high speed small hole EDM " (the Applied Mechanics and Materials of technical process in Zhang Wei, Wang Wei, flood tax etc. of doped silicon ball, 2012), detailed elaboration has all been done in the preparation method of a kind of shock wave of patent of invention nano particle of assisting ultrashort pulse to discharge to contribute etc. of Wang Wei, Zhang Wei, flood and device (patent publication No. CN102744477A).The concentration of the doping of element in silicon ball can adjust according to the concentration of raw material silicon ingot or silicon rod, and concentration of dopant atoms can 1 × 10
14~ 1 × 10
21atoms/cm
3between select.The preparation of the silicon ball of different size can realize by adopting different machined parameters controlled discharge energy, and the size of silicon ball is preferably 0.1 ~ 30 μm, and size becomes normal distribution, and concentration degree is greater than 90%.Machined parameters scope is open-circuit voltage 80 ~ 100V; Peak point current 2 ~ 20A; Pulsewidth 1 ~ 100 μ s; Dutycycle 1:10 ~ 10:1, working solution is deionized water, kerosene or saponification liquor etc., and preferred deionized water, electrode is copper, molybdenum etc.
The particle size range of the doped silicon ball described in step of the present invention (1) is 0.1 ~ 30 μm, and be monocrystalline or polysilicon ball, doped source is phosphorus, arsenic, antimony, boron, aluminium, gallium, indium, doped source total concentration 1 × 10
14~ 1 × 10
21atoms/cm
3.
Preferably, the preparation method of above-described doping porous silicon ball, in step (1), the hydrofluoric acid concentration that cleaning adopts is 1% ~ 20%, room temperature cleaning 5 ~ 30 minutes.The oxide layer of silicon face is removed by this step.
Preferably, the preparation method of above-described doping porous silicon ball, centrifugal rotational speed when described step (2), step (4), step (6) and step (8) eccentric cleaning is 3000 ~ 6000 revs/min, cleaning adopts deionized water, rinses 3 ~ 5 times.The eccentric cleaning step that the present invention adopts effectively can remove on the one hand the residual of acid in previous step or reaction solution, and particularly in step (4) and step (6), add washed with de-ionized water step, interruptible price reacts the effect carried out.
Preferably, the preparation method of above-described doping porous silicon ball, in described step (3), nitrate is ferric nitrate, silver nitrate or for ferric nitrate and mixture of silver nitrate, concentration is 5 ~ 40mmol/L, hydrofluoric acid concentration is 2 ~ 8mol/L, and the nitrate of above-mentioned concentration and hydrofluoric acid are 1:5 ~ 5:1 mixing by volume, and be 20 ~ 120KHz in frequency, time is carry out ultrasonic aid in treatment under parameter in 1 ~ 5 minute, finally at room temperature react, the reaction time is 3 ~ 30 minutes.Silicon ball is placed in after in corrosive liquid, and silicon atom and the metal ion of silicon ball surface react, and metal ion is reduced into granular metallic atom, and metal defines hole pattern masterplate at silicon face, for the continuation corrosion of second step is prepared.Ultrasonic wave added contribute to silicon ball dispersion, by the control treatment time, control reaction process, for the uniformity of hole and the integrality of silicon ball all most important.
Preferably, the preparation method of above-described doping porous silicon ball, in described step (5), hydrofluoric acid concentration is 2 ~ 8mol/L, oxidant is hydrogen peroxide, nitric acid or the mixture such as hydrogen peroxide and nitric acid, volumetric concentration 1% ~ 5%, and the volume ratio of the hydrofluoric acid of above-mentioned concentration and oxidant is 1:5 ~ 2:1, be 40 ~ 80 DEG C of reactions in temperature, the reaction time is 0.5 ~ 3 hour.After first step silicon face defines hole pattern, carry out continuation corrosion by the reaction of second step, relative first step reaction second step suitably can control the carrying out reacted by the consumption of controlled oxidization agent, prevent reaction from causing silicon ball fractured too soon.By regulating the preferred concentration of oxidant and controlling the object that the reaction time plays the corrosion depth controlling porous silicon.
Preferably, the preparation method of above-described doping porous silicon ball, in described step (7), the volumetric concentration of aqueous solution of nitric acid is 5% ~ 50%.This step can remove the metal attachment on silicon ball top layer.
Preferably, the preparation method of above-described doping porous silicon ball, step (1) is in step (8), and the volume ratio of silicon ball and reactant liquor or cleaning solution is≤1:2.
The present invention is in metal sedimentation chemistry etching and prepare on the basis of nano-structure porous silicon and nano wire based on silicon chip, with the silicon ball of doping for raw material, the composition of chemical etching corrosive agent is filtered out by great many of experiments, volume ratio and concentration, the optimal processing parameters such as reaction time, reaction temperature, supersonic frequency and time, compared to existing technology, can prepare pattern uniform, the porous silicon of the three-dimensional alveolate texture of perforate continuously of continuous print, and aperture and hole wall size range can reach 2 ~ 500nm.
And it should be noted that: the doping porous silicon ball that technique provided by the invention prepares can ensure as spherical silicon grain, and the technical bottleneck problem such as the integrality of spherical silicon grain is very good, can overcome prior art easily broken, imperfect.
In the technical scheme provided of the present invention, in step (5), after the concentration of hydrofluoric acid is selected, by the accelerated reaction process that the concentration increasing oxidant can be suitable, and the degree of depth of surface etch can be deepened, and hole density also can increase, therefore by the concentration of adjustment oxidant, the doping porous silicon ball of different demand can be prepared, be applicable to different field, there is extraordinary industrial value.
Beneficial effect: compared to the prior art the preparation method of doping porous silicon ball provided by the invention, has the following advantages:
1, the preparation method of this doping porous silicon ball provided by the invention, the pioneering doped silicon ball of different levels of doping that adopts is as the process program of matrix material preparation doping porous silicon ball.By the regulation and control to raw-material doping content, can realize the controlled synthesis of doping porous silicon ball, process operability is strong, with low cost, and output is high, is suitable for industrialized production.
2, the preparation method of doping porous silicon ball provided by the invention, filtered out by great many of experiments, the composition of best chemical etching corrosive agent, the volume ratio of reaction reagent and concrete concentration, reaction time, reaction temperature, the optimal processing parameters such as the frequency of ultrasonic wave added and time, the bottleneck problem using chemical etching to prepare different levels of doping nano-structure porous silicon ball can be solved, based on the loose structure of doped silicon ball, with the electric conductivity that they are different, own structural characteristics, great specific area, novel photoelectric properties can widen the range of application of nano-pore structure on photoelectric nano device greatly.
3, the doping porous silicon ball for preparing of the present invention, can ensure as spherical silicon grain, and the integrality of spherical silicon grain is very good, prior art can be overcome easily broken, the technical bottleneck problem such as imperfect, and the highly purified doping porous silicon ball that the present invention prepares, hole shape rule, arranges evenly, in cellular, spherical regular, lithium battery, solar cell, semiconductor and sensor field can be widely used in.
4, technical scheme provided by the invention, can be according to actual needs, after the concentration of hydrofluoric acid is selected, by the accelerated reaction process that the concentration increasing oxidant can be suitable, and the degree of depth of surface etch can be deepened, and hole density also can increase, therefore by the concentration of adjustment oxidant, the doping porous silicon ball of respective demand can be prepared, be applicable to different field, there is extraordinary industrial value.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure of the porous silicon ball that the present invention prepares.
Fig. 2 is ESEM (SEM) figure of the porous silicon ball that the present invention prepares.
Detailed description of the invention
Below illustrating, the present invention will be described for specific embodiment.It is pointed out that following examples only for the invention will be further described, do not represent protection scope of the present invention, the nonessential amendment that other people carry out according to prompting of the present invention and adjustment, still belong to protection scope of the present invention.
Embodiment 1
The present embodiment provides a kind of method utilizing doped silicon ball to prepare nano-structure porous silicon, and when employing doped silicon ball is as raw material, use chemical etching to prepare nano-structure porous silicon, concrete steps are as follows:
1) boron doping concentration is selected to be 5.09 × 10
19atoms/cm
3the p type single crystal silicon foundry alloy of (electrical conductivity 0.002 ~ 0.0025 Ω cm) is as raw material, and adopt pulse discharge method processing, machined parameters is: open-circuit voltage 100V; Peak point current 5A; Pulsewidth 50 μ s; Dutycycle 1:2, working solution is deionized water, and electrode is copper electrode.Doped silicon ball is collected in processing, and silicon ball particle size range is 0.1 ~ 2 μm, and size concentrates on 1 μm, and concentration degree is greater than 90%.
2) 10g silicon ball is measured as matrix material;
3) carry out chemical solution cleans to silicon ball surface, solution is 5% hydrofluoric acid solution, and scavenging period is 15Min, room temperature;
4) by centrifugal for the silicon ball after above-mentioned cleaning, centrifugal rotational speed, at 3000 ~ 6000 turns, adopts washed with de-ionized water, repeatedly carries out 3 ~ 5 times;
5) first step reaction solution is prepared, preparation 20mmol/L silver nitrate, the hydrofluoric acid of 5mol/L, the ratio mixed preparing being 2:1 according to volume ratio goes out reaction solution, according to silicon ball: reaction solution volume ratio is that silicon ball is placed in solution by the ratio of 1:3, the ultrasonic process of 80KHz was reacted under room temperature after 3 minutes, and the reaction time is 8 minutes;
6) by centrifugal for above-mentioned reacted silicon ball, centrifugal rotational speed, at 3000 ~ 6000 turns, adopts washed with de-ionized water, repeatedly carries out 3 ~ 5 times;
7) second step reaction solution is prepared, the hydrofluoric acid of preparation 5mol/L, the ratio mixed preparing that volumetric concentration 2% hydrogen peroxide is 1:1 according to volume ratio goes out second step reaction solution, according to silicon ball: reaction solution volume ratio is that silicon ball is placed in solution by the ratio of 1:3, be 40 ~ 80 DEG C of reactions in temperature, the reaction time is 1 hour.
8) by centrifugal for above-mentioned reacted silicon ball, centrifugal rotational speed, at 3000 ~ 6000 turns, adopts washed with de-ionized water, repeatedly carries out 3 ~ 5 times;
9) get the silicon ball nitric acid after cleaning to clean, the concentration of nitric acid is 10%, soaks 20 minutes;
10) by centrifugal for the silicon ball after above-mentioned nitric acid treatment, centrifugal rotational speed, at 3000 ~ 6000 turns, adopts washed with de-ionized water, repeatedly carries out 3 ~ 5 times.
11) oven dry is collected, test, for subsequent use.
Carry out performance test to the porous silicon ball prepared, the content that ICP-OES shows the boron of porous silicon ball is about 4.5 × 10
19atoms/cm
3, substantially identical with foundry alloy content, as depicted in figs. 1 and 2, it is uniform for preparing porous silicon pattern, continuous print honeycombed spherical structure, and aperture and hole wall are of a size of 50 ~ 100nm, silicon purity more than 99%.
Embodiment 2
The present embodiment provides a kind of method utilizing doped silicon ball to prepare nano-structure porous silicon, and when employing doped silicon ball is as raw material, use chemical etching to prepare nano-structure porous silicon, concrete steps are as follows:
1) phosphorus doping density is selected to be 2.02 × 10
15atoms/cm
3the n type single crystal silicon ingot of (electrical conductivity 1 ~ 3 Ω cm) is as raw material, and adopt pulse discharge method processing, machined parameters is: open-circuit voltage 150V; Peak point current 10A; Pulsewidth 100 μ s; Dutycycle 1:5, working solution is deionized water, and electrode is copper electrode.Doped silicon ball is collected in processing, and silicon ball particle size range is 1 ~ 10 μm, and size concentrates on 5 μm, and concentration degree is greater than 90%.
2) 10g silicon ball is measured as matrix material;
3) carry out chemical solution cleans to silicon ball surface, solution is 10% hydrofluoric acid solution, and under room temperature, scavenging period is 15Min;
4) by centrifugal for the silicon ball after above-mentioned cleaning, centrifugal rotational speed, at 3000 ~ 6000 turns, adopts washed with de-ionized water, repeatedly carries out 3 ~ 5 times;
5) first step reaction solution is prepared, preparation 20mmol/L silver nitrate, the hydrofluoric acid of 4.6mol/L, the ratio mixed preparing being 4:1 according to volume ratio goes out reaction solution, according to silicon ball: reaction solution volume ratio is that silicon ball is placed in solution by the ratio of 1:3, the ultrasonic process of 40KHz was reacted under room temperature after 5 minutes, and the reaction time is 10 minutes;
6) by centrifugal for above-mentioned reacted silicon ball, centrifugal rotational speed, at 3000 ~ 6000 turns, adopts washed with de-ionized water, repeatedly carries out 3 ~ 5 times;
7) second step reaction solution is prepared, the hydrofluoric acid of preparation 5mol/L, the ratio mixed preparing that 3% hydrogen peroxide is 1:2 according to volume ratio goes out second step reaction solution, according to silicon ball: reaction solution volume ratio is that silicon ball is placed in solution by the ratio of 1:3, be 40 ~ 80 DEG C of reactions in temperature, the reaction time is 2 hours.
8) by centrifugal for above-mentioned reacted silicon ball, centrifugal rotational speed, at 3000 ~ 6000 turns, adopts washed with de-ionized water, repeatedly carries out 3 ~ 5 times;
9) get the silicon ball nitric acid after cleaning to clean, the concentration of nitric acid is 30%, soaks 20 minutes;
10) by centrifugal for the silicon ball after above-mentioned nitric acid treatment, centrifugal rotational speed, at 3000 ~ 6000 turns, adopts washed with de-ionized water, repeatedly carries out 3 ~ 5 times.
11) oven dry is collected, test, for subsequent use.
Carry out performance test to the porous silicon ball prepared, ICP-OES shows the content about 2 × 10 of the phosphorus of porous silicon ball
15atoms/cm
3, substantially identical with content of raw material, it is uniform for preparing porous silicon pattern, continuous print honeycombed spherical structure, and aperture and hole wall size are about 100 ~ 200nm, silicon purity more than 99%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. adulterate the preparation method of porous silicon ball, it is characterized in that, comprise the steps:
(1) the silicon ball of appropriate doping is measured, by hydrofluoric acid clean;
(2) eccentric cleaning;
(3) silicon ball is placed in certain density nitrate, solution that hydrofluoric acid is prepared according to a certain volume, at room temperature react after ultrasonic process;
(4) eccentric cleaning;
(5) silicon ball is placed in certain density hydrofluoric acid, solution that oxidant is prepared according to a certain volume reacts;
(6) eccentric cleaning;
(7) then clean with nitric acid;
(8) namely eccentric cleaning obtains doping porous silicon ball;
In described step (3), nitrate is ferric nitrate, silver nitrate or for ferric nitrate and mixture of silver nitrate, concentration is 5 ~ 40mmol/L, hydrofluoric acid concentration is 2 ~ 8mol/L, and the nitrate of above-mentioned concentration and hydrofluoric acid are 1:5 ~ 5:1 mixing by volume, at room temperature react, the reaction time is 3 ~ 30 minutes, ultrasonic frequency is 20 ~ 120KHz, and sonication treatment time is 1 ~ 5 minute;
In described step (5), hydrofluoric acid concentration is 2 ~ 8mol/L, oxidant is the mixture of hydrogen peroxide, nitric acid or hydrogen peroxide and nitric acid, volumetric concentration 1% ~ 5%, and the hydrofluoric acid of above-mentioned concentration and oxidant are 1:5 ~ 2:1 mixing by volume, be 40 ~ 80 DEG C of reactions in temperature, the reaction time is 0.5 ~ 3 hour.
2. the preparation method of doping porous silicon ball according to claim 1, it is characterized in that: the particle size range of the silicon ball of the doping described in step (1) is 0.1 ~ 30 μm, for monocrystalline or polysilicon ball, doped source is phosphorus, arsenic, antimony, boron, aluminium, gallium, indium, doped source total concentration 1 × 10
14~ 1 × 10
21atoms/cm
3.
3. the preparation method of doping porous silicon ball according to claim 1, is characterized in that: in step (1), and the hydrofluoric acid concentration that cleaning adopts is 1% ~ 20%, room temperature cleaning 5 ~ 30 minutes.
4. the preparation method of doping porous silicon ball according to claim 1, it is characterized in that: centrifugal rotational speed when described step (2), step (4) and step (6) eccentric cleaning is 3000 ~ 6000 revs/min, cleaning adopts deionized water, rinses 3 ~ 5 times.
5. the preparation method of doping porous silicon ball according to claim 1, is characterized in that: in described step (7), and the volumetric concentration of aqueous solution of nitric acid is 5% ~ 50%.
6. the preparation method of the doping porous silicon ball according to any one of claim 1 to 5, is characterized in that: step (1) is in step (8), and the volume ratio of silicon ball and reactant liquor or cleaning solution is≤1:2.
7. the preparation method of doping porous silicon ball according to claim 6, is characterized in that: the porous silicon ball pattern that step (8) prepares is even, and the three-dimensional alveolate texture continuously in continuous print, aperture is 2 ~ 500nm.
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| CN106058167A (en) * | 2016-02-03 | 2016-10-26 | 万向A二三***有限公司 | Porous silicon-based alloy composite |
| CN106744971A (en) * | 2016-12-15 | 2017-05-31 | 盐城工学院 | The preparation method and preparation facilities of a kind of three-D nano-porous silicon |
| CN107572531A (en) * | 2017-10-19 | 2018-01-12 | 贵州大学 | A kind of porous silicon preparation method |
| CN109768062B (en) * | 2019-01-11 | 2021-02-02 | 惠科股份有限公司 | X-ray detector and display device with same |
| WO2020143483A1 (en) | 2019-01-11 | 2020-07-16 | 惠科股份有限公司 | X-ray detector, method for manufacturing an x-ray detector, and medical equipment |
| CN110165158B (en) * | 2019-04-23 | 2021-02-09 | 南京卓胜自动化设备有限公司 | Preparation method of silicon-copper composite nanowire |
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