CN102827610A - Preparation method for silicon-based nano-hybrid material - Google Patents
Preparation method for silicon-based nano-hybrid material Download PDFInfo
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- CN102827610A CN102827610A CN2011101575962A CN201110157596A CN102827610A CN 102827610 A CN102827610 A CN 102827610A CN 2011101575962 A CN2011101575962 A CN 2011101575962A CN 201110157596 A CN201110157596 A CN 201110157596A CN 102827610 A CN102827610 A CN 102827610A
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Abstract
The invention discloses a preparation method for a silicon-based nano-hybrid material. The method employs monocrystalline silicon nanowires, tellurium hydrides of alkali metals, cadmium source compounds and carboxyl-containing water-soluble sulphydryl compounds as raw materials for preparing the silicon-based nano-hybrid material. The silicon-based nano-hybrid material is prepared by a microwave radiation method which comprises the steps of bonding C=O bonds of the water-soluble sulfhydryl compounds with Si-H bonds on the surfaces of the monocrystalline silicon nanowires; bonding Ca2+ in crystal nucleus and sulphydryl groups of the water-soluble sulfhydryl compounds through S-Cd bonds, thereby obtaining crystal nucleus-modified silicon nanowires; and thus the silicon-based nano-hybrid material is obtained after crystal nucleus growth. The silicon-based nano-hybrid material has relatively high fluorescent intensity because CdTe quantum dots have strong luminescent characteristics. Experimental results show that luminescent efficiency of the prepared quantum dot-modified silicon nanowires is 10-35%; and diameters of the quantum dots are 50 nanometers.
Description
Technical field
The present invention relates to technical field of nano material, more particularly, relate to a kind of silicon-base nanometer hybrid preparation methods.
Background technology
Nano-hybrid material is nano material (L.H.Yu, C.D.Zangmeister, the J.G.Kushmerick that is combined by the nano material of multiple different structure such as nano particle, nano wire and nanotube etc.; Phys.Rev.Lett.2007; 98,206803.S.Mann, Nature Mater.2009; 8,781-792.; J.E.Macdonald, S.M.Bar, L.Houben, I.Popov, U.Banin, Nature Mater.2010,9,810-815.).Nano-hybrid material can prepare according to following method: the nano material that will have difference in functionality, different structure combines; Thereby obtain having the nano-hybrid material (D.J.Maxwell of complex function; J.R.Taylor, S.M.Nie, J.Am.Chem.Soc.2002; 124,9606-9612.; A.Wada, S.Tamaru, M.Ikeda, I.Hamachi, J.Am.Chem.Soc.2009,131,5321-5330.; X.H.Peng, J.Y.Chen, J.A.Misewich, S.S.Wong, Chem.Soc.Rev.2009,38,1076-1098.).
On the other hand, the silicon-based nano material is owing to have strong interest and broad research (L.Pavesi, the L.D.Negro that unique optical property, electrical properties and chemical have obtained scientist; C.Mazzoleni, G.Franzo, F.Priolo; Nature 2000,408,440-444.; D.D.D.Ma, C.S.Lee, F.C.K.Au, S.Y.Tong, S.T.Lee, Science 2003,299,1874-1877.; F.Patolsky, B.P.Timko, G.H.Yu, Y.Fang, A.B.Greytak, G.F.Zheng, C.M.Lieber, Science 2006,313,1100-1104.).
Therefore, the silicon-base nanometer hybrid material is owing to have the advantage of two aspects of nano-hybrid material and silicon-based nano material, thereby obtained extensive studies.As the representative of silicon-base nanometer hybrid material, the silicon nanowires of metal nanoparticles such as finishing gold and silver, platinum has been widely used in every field (M.Lv, S.Su such as solar cell, catalysis, chemistry, biosensor; Y.He, Q.Huang, W.B.Hu; D.Li, C.H.Fan, S.T.Lee; Adv.Mater.2010,22,5463-5467.; Y.He, C.H.Fan, S.T.Lee, Nano Today 2010,5,282-295.).
But the kind of silicon-base nanometer hybrid material is more single at present, and the fluorescence intensity of the silicon nanowires of the finishing metal nanoparticle of prior art for preparing is lower, thereby has limited silicon-base nanometer hybrid Development of Materials and application.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of silicon-base nanometer hybrid preparation methods, prepares the silicon nanowires of the fluorescence quantum modification with higher fluorescence intensity.
The present invention provides a kind of silicon-base nanometer hybrid preparation methods, may further comprise the steps:
Alkali-metal hydrogen telluride thing, cadmium source compound and carboxylic water-soluble sulfhydryl compound are mixed in water, obtain the quantum dot precursor solution;
Monocrystalline silicon nano line is mixed with said quantum dot precursor solution, obtain mixing solutions;
Utilize microwave radiation that said mixing solutions is heated, obtain the silicon-base nanometer hybrid material after the reaction.
Preferably, said alkali-metal hydrogen telluride thing prepares as follows:
Alkali-metal hydroborate and tellurium powder are placed water, 0～30 ℃ of reaction down, obtain alkali-metal hydrogen telluride thing then.
Preferably, said alkali-metal hydrogen telluride thing is sodium hydrogen telluride or hydrogen telluride potassium.
Preferably, said cadmium source compound is Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium iodate, Cadmium Sulphate, cadmium hydroxide or cadmium carbonate.
Preferably, said water-soluble sulfhydryl compound is Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine or Gelucystine.
Preferably, cadmium, water-soluble sulfhydryl compound and HTe
-Mol ratio be 1: (1.5～5): (0.3～0.7).
Preferably, said monocrystalline silicon nano line prepares as follows:
Silicon single crystal wafer is placed Silver Nitrate and hydrofluoric mixing solutions, obtain monocrystalline silicon nano line after the reaction.
Preferably, said microwave radiation temperature is 80～160 ℃.
Preferably, said microwave irradiation power is 15W～1000W.
Preferably, the said reaction times is 3 minutes～1 hour.
The present invention provides a kind of silicon-base nanometer hybrid preparation methods, is raw material with monocrystalline silicon nano line, alkali-metal hydrogen telluride thing, cadmium source compound and carboxylic water-soluble sulfhydryl compound, prepares the silicon-base nanometer hybrid material.In the preparation process of silicon-base nanometer hybrid material, Cd
2+And Te
2-Form the nucleus of CdTe quantum dot through Ostwald nucleus slaking mechanism.Because all there are a large amount of Si-H keys in the inside of monocrystalline silicon nano line and surface; Therefore; The present invention adopts the method for microwave radiation, the Si-H key of the C=O key in the said water-soluble sulfhydryl compound with the monocrystalline silicon nano line surface combined, and with the Cd in the said nucleus
2+Combine through the S-Cd key with the sulfydryl in the said water-soluble sulfhydryl compound, thereby obtain the silicon nanowires that nucleus is modified, obtain the silicon nanowires that the CdTe quantum dot is modified behind the nucleus growth, i.e. the silicon-base nanometer hybrid material.Because the CdTe quantum dot has the strong characteristics of luminescence, so the silicon-base nanometer hybrid material of the present invention's preparation has higher fluorescence intensity.In addition, the silicon nanowires of the CdTe quantum dot modification of the present invention's preparation has enriched the kind of silicon-base nanometer hybrid material.Experimental result shows that the luminous efficiency of the silicon nanowires that the quantum dot of the present invention's preparation is modified is 10～35%, and lateral size of dots is 50 nanometers.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the ESEM picture of the silicon-base nanometer hybrid material of the embodiment of the invention 1 preparation;
Fig. 2 is the transmission electron microscope picture of the silicon-base nanometer hybrid material of the embodiment of the invention 1 preparation;
Fig. 3 is the ultraviolet-fluorescence spectrum of the silicon-base nanometer hybrid material of the embodiment of the invention 1 preparation.
Embodiment
The invention discloses a kind of silicon-base nanometer hybrid preparation methods, may further comprise the steps:
Alkali-metal hydrogen telluride thing, cadmium source compound, carboxylic water-soluble sulfhydryl compound are mixed in water, obtain the quantum dot precursor solution;
Monocrystalline silicon nano line is mixed with said quantum dot precursor solution, obtain mixing solutions;
Utilize microwave radiation that said mixing solutions is heated, obtain the silicon-base nanometer hybrid material after the reaction.
Among the present invention, said alkali-metal hydrogen telluride thing is preferably according to following method preparation: alkali-metal hydroborate and tellurium powder are placed water, 0～30 ℃ of reaction down, obtain alkali-metal hydrogen telluride thing then.In above-mentioned preparation process, redox reaction has taken place in said alkali-metal hydroborate and tellurium powder, thereby has generated alkali-metal hydrogen telluride thing.Said temperature of reaction is preferably 5～25 ℃, more preferably 10～20 ℃.The mol ratio of said alkali-metal hydroborate and tellurium powder is preferably (1.5～5): 1, more preferably (2～5): 1, most preferably be (2.5～4): 1.Above-mentioned temperature of reaction is preferably 5～25 ℃, more preferably 10～20 ℃.The said reaction times is preferably 7～30 hours, more preferably 9～25 hours, most preferably is 12～20 hours.Wherein, said alkali-metal hydrogen telluride thing is preferably sodium hydrogen telluride or hydrogen telluride potassium.
Said cadmium source compound includes but not limited to the oxide compound of cadmium salt, cadmium or the oxyhydroxide of cadmium, is preferably Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium iodate, Cadmium Sulphate, cadmium hydroxide or cadmium carbonate.In said quantum dot precursor solution, the volumetric molar concentration of said cadmium source compound is preferably 0.0005～0.1mol/L, and more preferably 0.005～0.1mol/L most preferably is 0.05～0.1mol/L.Water-soluble sulfhydryl compound described in the present invention is preferably Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine or Gelucystine.
According to the present invention; Said with alkali-metal hydrogen telluride thing, cadmium source compound, carboxylic water-soluble sulfhydryl compound in water, mix obtain the quantum dot precursor solution specifically can for: the cadmium source compound is mixed with carboxylic water-soluble sulfhydryl compound solution; Regulate pH value to 7～13 then; Feed nitrogen,, obtain the quantum dot precursor solution fully mixing with alkali-metal hydrogen telluride thing under the agitation condition.
Among the present invention, cadmium, water-soluble sulfhydryl compound and HTe
-Mol ratio be preferably 1: (1.5～5): (0.3～0.7), more preferably 1: (2～5): (0.4～0.7) most preferably is 1: (2～4): (0.4～0.6).Monocrystalline silicon nano line can adopt method preparation well known to those skilled in the art among the present invention; The preferred hydrogen fluoride auxiliary etch method that adopts prepares; Be specially: silicon single crystal wafer is placed Silver Nitrate and hydrofluoric mixing solutions, obtain monocrystalline silicon nano line after the reaction.The volumetric molar concentration of said silver nitrate solution is 0.1～1M, is preferably 0.5～1M; The mass concentration of said hydrogen fluoride solution is 10～40%, is preferably 15～35%.Said Silver Nitrate and hydrogen fluoride volume ratio are preferably 1: (0.01～0.5), more preferably 1: (0.05～0.5).The said reaction times is preferably 2 minutes～and 1 hour, more preferably 10 minutes～1 hour, most preferably be 20 minutes～40 minutes.It is the n type silicon wafer of 0.01～20 Ω * cm that said silicon wafer is preferably p type silicon wafer or the resistivity that resistivity is 0.01～20 Ω * cm, and wherein, resistivity is relevant with the quality of the nano wire for preparing.
According to the present invention, said silicon single crystal wafer is placed Silver Nitrate and hydrofluoric mixing solutions after, preferred slowly vibration certain hour, thus it is fully reacted.According to principle of electrochemical reaction, silver ions at first is reduced to silver nano-grain by the Si-H key of silicon single crystal wafer surface, thereby is further formed monocrystalline silicon nano line array by the hydrogen fluoride etching then.In addition, the present invention also preferably includes: utilize and ultrasonicly can get off monocrystalline silicon nano line is ultrasonic from silicon chip, and spinning, the monocrystalline silicon nano line with preparation is scattered in the aqueous solution of 0.5～5ml then, obtains the nano wire precursor solution.The present invention also can adopt said nano wire precursor solution and said quantum dot precursor solution blended mode are obtained mixing solutions.
In addition, the present invention also preferably includes: said silicon single crystal wafer is placed the acetone soln ultrasonic cleaning, utilize water to clean and be placed in the mixing solutions of the vitriol oil and ydrogen peroxide 50, clear water cleans, and obtains clean silicon chip; Place hydrogen fluoride solution to react said clean silicon chip then.The mass concentration of said hydrogen fluoride solution is 10～40%, is preferably 15～35%.The said vitriol oil and ydrogen peroxide 50 volume ratio are preferably 1: (0.1～0.8), more preferably 1: (0.2～0.6).In the above-mentioned treating processes; The vitriol oil and ydrogen peroxide 50 are used to remove the pollution impurity on said silicon single crystal wafer surface; But, form zone of oxidation on the silicon single crystal wafer surface, therefore because the vitriol oil and ydrogen peroxide 50 have strong oxidation; The preferred just said clean silicon chip of the present invention places hydrogen fluoride solution to react, and removes the zone of oxidation that covers silicon face.
Said microwave radiation temperature is preferably 80～160 ℃, more preferably 90～150 ℃, most preferably is 100～140 ℃.Said microwave irradiation power is preferably 15W～1000W, and more preferably 50W～800W most preferably is 200W～500.The said reaction times is preferably 3 minutes～and 1 hour, more preferably 10～50 minutes, most preferably be 20～40 minutes.
In the preparation process of silicon-base nanometer hybrid material, Cd in the quantum dot precursor solution
2+Ion and Te
2-Ion forms the nucleus of CdTe quantum dot through Ostwald nucleus slaking mechanism.And; Because all there are a large amount of Si-H keys in the inside of monocrystalline silicon nano line and surface; Therefore, compared with prior art, the present invention adopts the method for microwave radiation; The Si-H key of C=O key in the said water-soluble sulfhydryl compound with the monocrystalline silicon nano line surface combined, and with the Cd in the said nucleus
2+Combine through the S-Cd key with the sulfydryl in the said water-soluble sulfhydryl compound, thereby obtain the monocrystalline silicon nano line that nucleus is modified, obtain the monocrystalline silicon nano line that the CdTe quantum dot is modified behind the nucleus growth, i.e. the silicon-base nanometer hybrid material.Because the CdTe quantum dot has the strong characteristics of luminescence, so the silicon-base nanometer hybrid material of the present invention's preparation has higher fluorescence intensity, and in addition, the silicon nanowires that the CdTe quantum dot of the present invention's preparation is modified has enriched the kind of silicon-base nanometer hybrid material.In the said step that obtains the silicon-base nanometer hybrid material, according to quantum size effect,, can increase the quantum spot size, thereby prepare yellow fluorescence silicon nanowires and red fluorescence silicon nanowires etc. through the proper extension reaction times.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
Embodiment 1
Step (1) preparation silicon nanowires
With reaction area is 2cm
2, specific conductivity is that the p type silicon single crystal wafer of 5 Ω adds an amount of acetone; For following ultrasonic cleaning 10 minutes, with ultrapure water flushing 3 times, more said silicon wafer being put into the 20ml volume ratio was 3: 1 98% vitriol oil and 30% hydrogen peroxide mixed solution at 40Hz power; Soak and take out silicon wafer after 30 minutes; And have ultrapure water to wash again 3 times, and put it into again in 5% hydrogen fluoride solution and soaked 20 minutes, obtain the clean silicon wafer of surface coverage Si-H key;
It is 1: 1 0.005M Silver Nitrate and 10% hydrogen fluoride mixing solutions 3 minutes that said clean silicon wafer is put into the 20ml volume ratio; Put into volume ratio after the taking-up again and be 1: 1 10% hydrogen fluoride and the reaction of 1% hydrogen peroxide mixed solution 10 minutes, obtain silicon nanowire array;
Said silicon nanowire array is ultrasonic 30 minutes down at 60Hz power,, more said deposition is scattered in the 0.5ml ultrapure water, promptly obtain the silicon nanowires precursor solution at the collecting precipitation after 15 minutes of spinning under the 6000rpm/min condition;
Step (2) preparation quantum dot precursor solution
With 30.9 milligrams of NaBH
4Solid and 42.5 milligrams of Te powder are put in the little flask, add 1 ml water then, obtain NaHTe solution in reaction under 18 degrees centigrade after 10 hours;
With 6 milligrams of CdCl
2Be dissolved in 20 ml waters, add 0.008 milliliter of Thiovanic acid then, regulate pH to 9, inject the NaHTe solution of 0.06 milliliter of above-mentioned preparation then, obtain the quantum dot precursor solution with the NaOH solution of 0.5 mol;
Step (3) is modified the silicon nanowires that fluorescence quantum is modified
The silicon nanowires precursor solution that step (1) is prepared adds in the quantum dot precursor solution of step (2) preparation, stirs, and obtains mixing solutions;
Said mixing solutions is carried out carry out microwave radiation heating, and microwave power is 120W, and Heating temperature is 150 ℃, and the reaction times is 5min, obtains the silicon nanowires that fluorescence quantum is modified.
The silicon nanowires ultra-sonic dispersion that the fluorescence quantum of above-mentioned preparation is modified is tested in ethanol, and its luminous efficiency is 35%, and lateral size of dots is 80 nanometers, and silicon nanowires length is 800 nanometers.
Embodiment 2
Step (1) preparation silicon nanowires
With reaction area is 3cm
2, specific conductivity is that the p type silicon wafer of 0.05 Ω adds an amount of acetone; For following ultrasonic cleaning 15 minutes, with ultrapure water flushing 3 times, again silicon wafer being put into the 20ml volume ratio was 4: 1 98% vitriol oil and 30% hydrogen peroxide mixed solution at 60Hz power; Soak and take out silicon wafer after 30 minutes; And have ultrapure water to wash again 3 times, and put it into again in 5% hydrogen fluoride solution and soaked 20 minutes, obtain the clean silicon wafer of surface coverage Si-H key;
It is that 1: 0.8 0.005M Silver Nitrate and 10% hydrogen fluoride mixing solutions soaked 3 minutes that said clean silicon wafer is put into the 20ml volume ratio; Put into volume ratio after the taking-up again and be 1: 1 10% hydrogen fluoride and the reaction of 1% hydrogen peroxide mixed solution 8 minutes, obtain silicon nanowire array;
Said silicon nanowire array is ultrasonic 30 minutes down at 60Hz power,, more said deposition is scattered in the 0.5ml ultrapure water, obtain the silicon nanowires precursor solution at the collecting precipitation after 15 minutes of spinning under the 8000rpm/min condition;
Step (2) preparation quantum dot precursor solution
With 40 milligrams of NaBH
4Solid and 45.6 milligrams of Te powder are put in the little flask, add 1 ml water then, obtain NaHTe solution in reaction under 10 degrees centigrade after 12 hours;
With 4.2 milligrams of CdCl
2Be dissolved in 20 ml waters, add 0.006 milliliter of Thiovanic acid, regulate pH to 8.4, inject 0.04 milliliter of NaHTe solution then, obtain the quantum dot precursor solution with the NaOH solution of 0.5 mol;
Step (3) is modified the fluorescence silicon nanowires
The silicon nanowires precursor solution that step (1) is prepared adds in the quantum dot precursor solution of preparation in the step (2), stirs, and obtains mixing solutions;
Said mixing solutions is carried out carry out microwave radiation heating, and microwave power is 80W, and Heating temperature is 130 ℃, and the reaction times is 10min, obtains the silicon nanowires that fluorescence quantum is modified.
The silicon nanowires ultra-sonic dispersion that the fluorescence quantum of above-mentioned preparation is modified is tested in ethanol, and its luminous efficiency is 20%, and lateral size of dots is 50 nanometers, and silicon nanowires length is 1000 nanometers.
Embodiment 3
Step (1) preparation silicon nanowires
With reaction area is 3.5cm
2, specific conductivity is that the n type silicon wafer of 5 Ω adds an amount of acetone; For following ultrasonic cleaning 12 minutes, with ultrapure water flushing 3 times, again silicon wafer being put into the 15ml volume ratio was 3.5: 1 98% vitriol oil and 30% hydrogen peroxide mixed solution at 100Hz power; Soak and take out silicon wafer after 35 minutes; And have ultrapure water to wash again 3 times, and put it into again in 5% hydrogen fluoride solution and soaked 20 minutes, obtain the clean silicon wafer of surface coverage Si-H key;
It is 1: 1.2 0.005M Silver Nitrate and 10% hydrogen fluoride mixing solutions 5 minutes that said clean silicon wafer is put into the 20ml volume ratio; Put into volume ratio after the taking-up again and be 1: 1.3 10% hydrogen fluoride and the reaction of 1% hydrogen peroxide mixed solution 6 minutes, obtain silicon nanowire array;
Said silicon nanowire array is ultrasonic 20 minutes down at 100Hz power,, more said deposition is scattered in the 1ml ultrapure water promptly to obtain the silicon nanowires precursor solution at the collecting precipitation after 20 minutes of spinning under the 7000rpm/min condition;
Step (2) preparation quantum dot precursor solution
With 37 milligrams of KBH
4Solid and 30.2 milligrams of Te powder are put in the little flask, add 1 ml water, obtain KHTe solution in reaction under 0 degree centigrade after 24 hours;
With 3.7 milligrams of CdCl
2Be dissolved in 10 ml waters, add 0.005 milliliter of Thiovanic acid, regulate pH to 8.0, inject 0.03 milliliter of KHTe solution, obtain the quantum dot precursor solution with the NaOH solution of 0.5 mol;
Step (3) is modified the fluorescence silicon nanowires
The silicon nanowires solution of preparation in the step (1) is added in the quantum dot precursor solution of preparation in the step (2), stir, obtain mixing solutions;
Said mixing solutions is carried out carry out microwave radiation heating, and microwave power is 60W, and temperature of reaction is 120 ℃, and the reaction times is 20min, obtains the silicon nanowires that fluorescence quantum is modified.
The silicon nanowires ultra-sonic dispersion that the fluorescence quantum of above-mentioned preparation is modified is tested in ethanol, and its luminous efficiency is 35%, and lateral size of dots is 100 nanometers, and silicon nanowires length is 1500 nanometers.
Embodiment 4
Step (1) preparation silicon nanowires
With reaction area is 2.5cm
2, specific conductivity is that the n type silicon wafer of 0.02 Ω adds an amount of acetone; For following ultrasonic cleaning 18 minutes, with ultrapure water flushing 3 times, again silicon wafer being put into the 20ml volume ratio was 2.5: 1 98% vitriol oil and 30% hydrogen peroxide mixed solution at 80Hz power; Soak and take out silicon wafer after 30 minutes; And have ultrapure water to wash again 3 times, and put it into again in 5% hydrogen fluoride solution and soaked 20 minutes, obtain the clean silicon wafer of surface coverage Si-H key;
It is 1: 1 0.005M Silver Nitrate and 10% hydrogen fluoride mixing solutions 5 minutes that said clean silicon wafer is put into the 20ml volume ratio; Put into volume ratio after the taking-up and be 1: 1.5 10% hydrogen fluoride and the reaction of 1% hydrogen peroxide mixed solution 10 minutes, obtain silicon nanowire array;
Said silicon nanowire array is ultrasonic 30 minutes down at 100Hz power,, more said deposition is scattered in the 0.6ml ultrapure water, obtain the silicon nanowires precursor solution at the collecting precipitation after 30 minutes of spinning under the 9000rpm/min condition;
Step (2) preparation quantum dot precursor solution
With 32 milligrams of KBH
4Solid and 27.8 milligrams of Te powder are put in the little flask, add 1 ml water, obtain KHTe solution in reaction under 5 degrees centigrade after 16 hours;
With 3.8 milligrams of CdCl
2Be dissolved in 20 ml waters, add 0.015 milliliter of Thiovanic acid, regulate pH to 8.2, inject 0.02 milliliter of KHTe solution, obtain the quantum dot precursor solution with the NaOH solution of 0.5 mol;
Step (3) is modified the fluorescence silicon nanowires
In the quantum dot precursor solution that the silicon nanowires precursor solution adding step (2) that step (1) is prepared prepares, stir, obtain mixing solutions;
Said mixing solutions is carried out carry out microwave radiation heating, and microwave power is 70W, and temperature of reaction is 160 ℃, and the reaction times is 8min, obtains the silicon nanowires that fluorescence quantum is modified.
The silicon nanowires ultra-sonic dispersion that the fluorescence quantum of above-mentioned preparation is modified is tested in ethanol, and its luminous efficiency is 32%, and lateral size of dots is 95 nanometers, and silicon nanowires length is 1800 nanometers.
Embodiment 5
Step (1) preparation silicon nanowires
With reaction area is 1cm
2, specific conductivity is that the p type silicon wafer of 10 Ω adds an amount of acetone; For following ultrasonic cleaning 15 minutes, with ultrapure water flushing 3 times, again silicon wafer being put into the 20ml volume ratio was 3: 1 98% vitriol oil and 30% hydrogen peroxide mixed solution at 80Hz power; Soak and take out silicon wafer after 30 minutes; And have ultrapure water to wash again 3 times, and put it into again in 5% hydrogen fluoride solution and soaked 20 minutes, obtain the clean silicon wafer of surface coverage Si-H key;
It is that 1: 1.3 0.005M Silver Nitrate and 10% hydrogen fluoride mixing solutions soaked 3 minutes that said clean silicon wafer is put into the 20ml volume ratio; Put into volume ratio after the taking-up again and be 1: 1.1 10% hydrogen fluoride and the reaction of 1% hydrogen peroxide mixed solution 10 minutes, obtain silicon nanowire array;
Is ultrasonic 20 minutes down with said silicon nanowire array at 90Hz power, and 15 minutes collecting precipitations of spinning under the 6000rpm/min condition are scattered in the 0.3ml ultrapure water with said deposition again, obtain the silicon nanowires precursor solution.
Step (2) preparation quantum dot precursor solution
With 35.5 milligrams of NaBH
4Solid and 47.6 milligrams of Te powder are put in the little flask, add 1.5 ml waters, obtain NaHTe solution in reaction under 20 degrees centigrade after 6 hours;
With 2.3 milligrams of CdCl
2Be dissolved in 10 ml waters, add 0.007 milliliter of Thiovanic acid, regulate pH to 7.8, inject 0.025 milliliter of NaHTe solution, obtain the quantum dot precursor solution with the NaOH solution of 0.5 mol;
Step (3) is modified the fluorescence silicon nanowires
The silicon nanowires precursor solution that step (1) is prepared adds in the quantum dot precursor solution of preparation in the step (2), stirs, and obtains mixing solutions;
Said mixing solutions is carried out carry out microwave radiation heating, and microwave power is 60W, and temperature of reaction is 100 ℃, and the reaction times is 20min, obtains the silicon nanowires that fluorescence quantum is modified.
The silicon nanowires ultra-sonic dispersion that the fluorescence quantum of above-mentioned preparation is modified is tested in ethanol, and its luminous efficiency is 25%, and lateral size of dots is 70 nanometers, and silicon nanowires length is 1200 nanometers.
Embodiment 6
Step (1) preparation silicon nanowires
With reaction area is 2.5cm
2, specific conductivity is that the n type silicon wafer of 5 Ω adds an amount of acetone; For following ultrasonic cleaning 15 minutes, with ultrapure water flushing 3 times, again silicon wafer being put into the 25ml volume ratio was 3.6: 1 98% vitriol oil and 30% hydrogen peroxide mixed solution at 80Hz power; Soak and take out silicon wafer after 30 minutes; And have ultrapure water to wash again 3 times, and put it into again in 5% hydrogen fluoride solution and soaked 20 minutes, obtain the clean silicon wafer of surface coverage Si-H key;
It is that 1: 1 0.005M Silver Nitrate and 10% hydrogen fluoride mixing solutions soaked 3 minutes that said clean silicon wafer is put into the 20ml volume ratio; Put into volume ratio after the taking-up again and be 1: 1 10% hydrogen fluoride and the reaction of 1% hydrogen peroxide mixed solution 25 minutes, obtain silicon nanowire array;
Is ultrasonic 30 minutes down with said silicon nanowire array at 100Hz power, and 25 minutes collecting precipitations of spinning under the 8000rpm/min condition are scattered in the 1ml ultrapure water with said deposition again, obtain the silicon nanowires precursor solution;
Step (2) preparation quantum dot precursor solution
With 31 milligrams of NaBH
4Solid and 42.8 milligrams of Te powder are put in the little flask, add 1 ml water, obtain NaHTe solution in reaction under 25 degrees centigrade after 7 hours;
With 3.4 milligrams of CdCl
2Be dissolved in 15 ml waters, add 0.011 milliliter of Thiovanic acid, regulate pH to 8.1, inject 0.036 milliliter of NaHTe solution, obtain the quantum dot precursor solution with the NaOH solution of 0.5 mol;
(3) modify the fluorescence silicon nanowires
The silicon nanowires solution of step (1) preparation is added in the quantum dot precursor solution of step (2) preparation, stir, obtain mixing solutions;
Said mixing solutions is carried out carry out microwave radiation heating, microwave power 100W, temperature of reaction is 150 ℃, the reaction times is 5min, obtains the fluorescence silicon nanowires.
The silicon nanowires ultra-sonic dispersion that the fluorescence quantum of above-mentioned preparation is modified is tested in ethanol, and its luminous efficiency is 33%, and lateral size of dots is 50 nanometers, and silicon nanowires length is 500 nanometers.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. silicon-base nanometer hybrid preparation methods may further comprise the steps:
Alkali-metal hydrogen telluride thing, cadmium source compound and carboxylic water-soluble sulfhydryl compound are mixed in water, obtain the quantum dot precursor solution;
Monocrystalline silicon nano line is mixed with said quantum dot precursor solution, obtain mixing solutions;
Utilize microwave radiation that said mixing solutions is heated, obtain the silicon-base nanometer hybrid material after the reaction.
2. preparation method according to claim 1 is characterized in that, said alkali-metal hydrogen telluride thing prepares as follows:
Alkali-metal hydroborate and tellurium powder are placed water, 0～30 ℃ of reaction down, obtain alkali-metal hydrogen telluride thing then.
3. preparation method according to claim 1 is characterized in that, said alkali-metal hydrogen telluride thing is sodium hydrogen telluride or hydrogen telluride potassium.
4. preparation method according to claim 1 is characterized in that, said cadmium source compound is Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium iodate, Cadmium Sulphate, cadmium hydroxide or cadmium carbonate.
5. preparation method according to claim 1 is characterized in that, said water-soluble sulfhydryl compound is Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine or Gelucystine.
6. preparation method according to claim 1 is characterized in that, the mol ratio of cadmium, water-soluble sulfhydryl compound and HTe-is 1: (1.5～5): (0.3～0.7).
7. preparation method according to claim 1 is characterized in that, said monocrystalline silicon nano line prepares as follows:
Silicon single crystal wafer is placed Silver Nitrate and hydrofluoric mixing solutions, obtain monocrystalline silicon nano line after the reaction.
8. preparation method according to claim 1 is characterized in that, said microwave radiation temperature is 80～160 ℃.
9. preparation method according to claim 1 is characterized in that, said microwave irradiation power is 15W～1000W.
10. preparation method according to claim 1 is characterized in that, the said reaction times is 3 minutes～1 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103194221A (en) * | 2013-04-25 | 2013-07-10 | 苏州大学 | Method for preparing water-soluble fluorescent silicon nanoparticle by utilizing microwave radiation |
| CN103545400A (en) * | 2013-09-27 | 2014-01-29 | 上海师范大学 | Si nanometer rod/QDs (quantum dots) composite effective silica-based solar cell and manufacturing method thereof |
| CN109897630A (en) * | 2019-04-17 | 2019-06-18 | 中国科学院理化技术研究所 | A kind of nano wire, preparation method, the Ratio-type fluorescence chemical sensor comprising the nano wire and application |
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| 刘安华等: "《含硅有机/无机纳米杂化材料》", 《功能材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194221A (en) * | 2013-04-25 | 2013-07-10 | 苏州大学 | Method for preparing water-soluble fluorescent silicon nanoparticle by utilizing microwave radiation |
| CN103194221B (en) * | 2013-04-25 | 2014-10-22 | 苏州大学 | Method for preparing water-soluble fluorescent silicon nanoparticle by utilizing microwave radiation |
| CN103545400A (en) * | 2013-09-27 | 2014-01-29 | 上海师范大学 | Si nanometer rod/QDs (quantum dots) composite effective silica-based solar cell and manufacturing method thereof |
| CN103545400B (en) * | 2013-09-27 | 2016-03-30 | 上海师范大学 | Si nano rod/QDs comprehensive silicon based solar battery sheet and preparation method thereof |
| CN109897630A (en) * | 2019-04-17 | 2019-06-18 | 中国科学院理化技术研究所 | A kind of nano wire, preparation method, the Ratio-type fluorescence chemical sensor comprising the nano wire and application |
| CN109897630B (en) * | 2019-04-17 | 2021-12-14 | 中国科学院理化技术研究所 | Nanowire, preparation method thereof, ratio type fluorescence chemical sensor containing nanowire and application |
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