CN1253923C - Method of preparing one dimensional semiconductor nano rod and nano-wire in water solution - Google Patents
Method of preparing one dimensional semiconductor nano rod and nano-wire in water solution Download PDFInfo
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- CN1253923C CN1253923C CN 02160269 CN02160269A CN1253923C CN 1253923 C CN1253923 C CN 1253923C CN 02160269 CN02160269 CN 02160269 CN 02160269 A CN02160269 A CN 02160269A CN 1253923 C CN1253923 C CN 1253923C
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Abstract
The present invention relates to a method for preparing a one-dimensional semiconductor nanometer rod and a nanometer line in a water solution. Water is used as a reaction medium, and a specific transition metal ion complexing agent is used as a surface ligand; IIB group soluble inorganic salt is added in the water solution of the ligand, and nitrogen is led in for removing oxygen; a sulfur source, a selenium source or a tellurium source is added and stirred for complete reaction; a solid is obtained by centrifugation, and final products can be obtained by vacuum drying. When the reaction is carried out at room temperature or the temperature below the room temperature, the products are nanometer rods with small length-diameter ratio. When the reaction is carried out at 60 to 100DEG C, the products are nanometer lines with large length-diameter ratio. When the reaction is carried out at 30 to 60DEG C, the products are the mixture of the nanometer rods and the nanometer lines. The present invention has simple technology and does not need complicated instrument equipment. The prepared material has a single crystal structure, and can be applied to the research of a physical phenomenon with a mesoscopic dimension, a solar battery of inorganic-organic composite material, a light emitting diode, nonlinear optical material, a nanometer device and microelectronics science.
Description
Technical field
The present invention relates to the preparation of monodimension nanometer material, particularly prepare the monodimension nano stick and the nano wire of II-VI semi-conducting material.
Background technology
Along with the particularly fast development of nanosecond science and technology of current science and technology, people need be to the physical phenomenon of some meso-scales, carries out deep research as the structure of nano-scale, light absorption, luminous and relevant with low-dimensional quantum size effect etc.In addition, the device microminiaturization is had higher requirement to new function material.The material synthesis technology of nanoscale beyond doubt of these problem development of restricting current.Though since the eighties in 20th century, the synthetic technology of zero-dimension nano material has developed comparatively ripely, the preparation of one dimension and quasi-one-dimensional nanometer material still is faced with huge challenge.Since discovery carbon nano-tube such as the Japanese Iijima of NEC Corporation in 1991, one dimension, quasi-one-dimensional nanometer material are paid close attention to by people in the great potential aspect Jie's sight field and the nano-device development, and the preparation research of the special semiconductor nanorods of monodimension nanometer material, nano wire etc. has also become a big focus of current nanometer technology and material science simultaneously.At present the method for preparing the semiconductor monodimension nanometer material crossed of bibliographical information has: CNT (carbon nano-tube) and porous alumina formwork method, solution-liquid phase-solid phase (SLS) are Gu growth method, nonaqueous solvents thermal synthesis, laser ablation combine growth method, Organometallic precursor in thermal decomposition method or the like in the blending surface activity with gas-liquid-(VLS).
Summary of the invention
The object of the invention provides a kind of new method for preparing II-VI family semiconductor monodimension nano stick, nano wire in the middle of the aqueous solution.This method is a raw material with inorganic salts cheap and easy to get, is reflected under the low-temperature atmosphere-pressure to carry out, and the reaction condition gentleness, technology is simple, need not complicated instrument and equipment.The one dimension semiconductor nano material of utilizing this method to prepare has six side's mono-crystalline structures; The productive rate of monodimension nanometer material is higher, and output is bigger, is applicable to batch process.Because this method is based on water solution system, than the existing method that other prepares monodimension nanometer material in the world the characteristic of environmental protection is arranged more, bright development prospect is arranged.Utilize the prepared optically active II-VI family semiconductor monodimension nanometer material that has that goes out of this method to be expected to obtain to use aspect the research in the physical phenomenon of meso-scale, novel inorganic-organic composite material solar cell and light-emitting diode, novel non-linearity optical material, novel nano-device and the microelectronics science.
Be that example describes below with CdS.
This method prepares the principle of CdS nano material, is based on Cd
2+With S
2-In the middle of the aqueous solution, generate the CdS nanocrystal by the control precipitation mode.Usually, in the middle of the aqueous solution in the presence of common stabilizer, pass through Cd
2+With S
2-The CdS nanocrystal prepared of control precipitation all be the ball shaped nano particle of zero dimension.The present invention utilizes ethylenediamine as Cd
2+Part in the middle of the aqueous solution, prepare the CdS nanometer rods and the nano wire of one dimension.Here ethylenediamine had both played and had stablized the nanocrystalline effect of CdS, obtained the CdS nanometer rods of one dimension, the effect of nano wire thereby play the nanocrystalline growth kinetics of adjusting simultaneously again.This method is a reacting precursor with water-soluble inorganic salt cheap and easy to get.Wherein the cadmium source comprises CdCl
2, CdSO
4, Cd (NO
4)
2, Cd (CH
3COO)
2, Cd (ClO
4)
2Deng.The sulphur source comprises Na
2S, (NH
4)
2S etc.Also can use H in addition
2S gas is as the sulphur source, can be the sulphur source with other water miscible sulfur-containing compound such as thiocarbamide, thioacetamide also.In the middle of the aqueous solution, add the ethylenediamine of appropriate amount during reaction earlier, add cadmium salt then, stir and make it dissolving, logical N
2Under vigorous stirring, add Na after about 20 minutes
2S allows reaction carry out under slowly at the uniform velocity stirring then, becomes obvious yellow until reaction system.
The addition of ethylenediamine is unrestricted among the present invention, can prepare the nanometer rods or the nano wire of one dimension.When but ethylenediamine concentration was too low, reaction speed is very fast, and was wayward, and the impurity of " non-one dimension " is more in the product, and it is also poor that resultant one dimension is received brilliant crystallinity.And ethylenediamine concentration is when too high, and the needed reaction time is oversize.In the concrete preparation process, need select suitable ethylenediamine concentration as the ratio in the temperature of reaction, cadmium source and sulphur source etc. different according to other reaction condition.More satisfactory ethylenediamine addition is 20-50% (percent by volume) among the present invention.
The addition in sulphur source, selenium source or tellurium source will be decided according to the dissolubility of these inorganic salts in the middle of the aqueous solution among the present invention, and along with the difference of ethylenediamine concentration, also can change with a kind of dissolubility, guarantee that the salt that adds can dissolve fully in solution every salt.Selenium source of the present invention can be sodium selenide or hydrogen selenide, and the tellurium source can be tellurium sodium or hydrotelluric acid.
The concentration that the present invention can be by regulating ethylenediamine in the aqueous solution, the concentration of conditioned reaction thing precursor, regulate Cd and the ratio of two kinds of reacting precursors of S and come that the CdS one dimension that is generated is received pattern, the size of crystalline substance and carry out regulation and control to a certain degree.
Influencing the CdS one dimension among the present invention, to receive another key factor of brilliant pattern and size be the temperature of reaction.Compare with other method of existing preparation monodimension nanometer material in the document, the needed temperature of preparation method of the present invention is much lower.In the method, when being reflected at room temperature (about 20-30 ℃) or being lower than when carrying out under the room temperature, resulting product is the less nanometer rods of draw ratio, wherein nanometer rods single armed, two arms, three arms are arranged with four arms, based on (as shown in Figure 1) of three arms.Resulting product is the bigger nano wire of draw ratio when carrying out in being reflected at 50-100 ℃ scope, this nano wire have certain flexibility, flexible, can be gathered into pencil (accompanying drawing 3).Be reflected at when carrying out between 30-50 ℃, product is the mixture of nanometer rods and nano wire.In the preparation process, reaction speed is different and different with the relative scale in S source with temperature, the concentration of ethylenediamine, the Cd source of reaction.Reaction time of the present invention is the color of product occurs in reaction system after, indicates that this reaction finishes, such as for preparation CdS nano wire, when the color of reaction system after initial white when reinforced becomes yellow, indicate that reaction finishes.Finishing the needed time of reaction does not wait by several days from several hrs.The time of long reaction makes that the CdS of preparation has good crystallinity at low temperatures, thereby does not need high annealing etc.Receive crystalline substance slowly in the growth course at CdS, the ethylenediamine molecule dynamically adsorbs, desorbs receiving brilliant surface, makes Cd and S atom also dynamically from receiving brilliant surface plus-minus, the process of " annealing " under this similar and a low temperature.
The CdS one dimension semiconductor nano material of this method preparation has six side's mono-crystalline structures (as shown in Figure 3).Utilize this method can prepare the nanometer rods of diameter in the quantum confinement scope, the nanometer rods of this yardstick can show tangible quantum size effect.
In the method, also can be with 1, the 6-hexamethylene diamine substitutes the surface ligand of ethylenediamine as preparation CdS monodimension nanometer material.
The principle that this method prepares the CdS nanocrystal is based on the central Cd of the aqueous solution
2+With S
2-The control precipitation reaction.For the semiconductor ME of some other II-VI family (M=Cd, Zn, Hg, E=S, Se, Te), because they can pass through M in the middle of the aqueous solution
2+With E
2-The control precipitation reaction and generate, so this method also is applicable to other these II-VI semiconductors except can be used for preparing the CdS one dimension semiconductor nano material.
Description of drawings
Fig. 1: transmission electron microscope (TEM) photo of the CdS monodimension nano stick of the diameter that the present invention prepares in the quantum confinement scope, reaction temperature is a room temperature.
Fig. 2: the photo of the nano wire that the present invention prepares, reaction temperature are 65 ℃.
Fig. 3: high resolution electron microscopy (HRTEM) photo of prepared CdS nanometer rods, insertion portion is the monocrystalline electron diffraction pattern of nanometer rods among the figure.
Embodiment
Embodiment one: the preparation of CdS monodimension nano stick
The first step under the room temperature, adds 100 ml waters and 50 milliliters of ethylenediamines in 250 milliliters round-bottomed flask, after solution mixes, take by weighing 0.069g (0.30mmol) and analyze pure CdCl
22/5H
2O joins in the flask, stirs to make it dissolving.
In second step, logical nitrogen is about 20 minutes in above-mentioned solution, to remove the oxygen in the solution.
In the 3rd step, take by weighing 0.216g (0.9mmol) and analyze pure Na
2S9H
2O joins in the flask under vigorous stirring, adds the back and continues vigorous stirring about 30 minutes.This moment, system was the turbid liquid of slightly lurid white.
The 4th step, mixing speed is transferred slow, the white that makes reaction proceed to system under stirring of remaining a constant speed disappear and occur significantly faint yellow till.
In the 5th step, after reaction finished, the yellow turbid liquid of gained is centrifugal, and centrifugal resulting light yellow solid was used distilled water, absolute ethanol washing successively, and vacuumize promptly gets final products after about 10 hours.The transmission electron microscope photo of products obtained therefrom as shown in Figure 1.That nanometer rods has is single armed, two arms, three arms with four arms, based on three arms, the diameter of nanometer rods is 5.5 ± 0.6nm, average aspect ratio is about 10.
Embodiment two: the preparation of CdS one-dimensional nano line
The first step under the room temperature, adds 80 ml waters and 70 milliliters of ethylenediamines in 250 milliliters round-bottomed flask, take by weighing 0.069g (0.30mmol) after solution mixes and analyze pure CdCl
22/5H
2O joins in the flask, stirs to make it dissolving.
In second step, logical nitrogen is about 20 minutes in above-mentioned solution, to remove the oxygen in the solution.
In the 3rd step, take by weighing 0.086g (0.36mmol) and analyze pure Na
2S9H
2O joins in the flask under vigorous stirring, adds the back and continues vigorous stirring about 30 minutes.This moment, system was the slightly light yellow turbid liquid of white.
The 4th step was heated to about 60 ℃ with system, transferred slow mixing speed simultaneously, till making reaction proceed to system under the condition with 60 ℃ of constant temperature of stirring that remains a constant speed tangible yellow to occur.
In the 5th step, after reaction finished, the yellow turbid liquid of gained is centrifugal, and centrifugal resulting solid was used distilled water, absolute ethanol washing successively, and vacuumize promptly gets final products after about 10 hours.The transmission electron microscope photo of products obtained therefrom as shown in Figure 2.Nano wire have certain flexibility, flexible, generally be gathered into pencil.
Embodiment three: the preparation of CdSe monodimension nano stick
The first step under the room temperature, adds 100 ml waters and 50 milliliters of ethylenediamines in 250 milliliters round-bottomed flask, after solution mixes, take by weighing 0.069g (0.30mmol) and analyze pure CdCl
22/5H
2O joins in the flask, stirs to make it dissolving.
In second step, logical nitrogen is about 20 minutes in above-mentioned solution, to remove the oxygen in the solution.
In the 3rd step, take by weighing 0.112g (0.9mmol) Na
2Se joins in the flask under vigorous stirring, adds the back and continues vigorous stirring about 30 minutes.
The 4th step, mixing speed is transferred slowly, stirring is finished until reaction remaining a constant speed.
In the 5th step, after reaction finished, reactant liquor is centrifugal, and resultant solid was used distilled water, absolute ethanol washing successively, and vacuumize promptly gets final products after about 10 hours.
Embodiment four: the preparation of CdTe monodimension nano stick
The first step under the room temperature, adds 100 ml waters and 50 milliliters of ethylenediamines in 250 milliliters round-bottomed flask, after solution mixes, take by weighing 0.069g (0.30mmol) and analyze pure CdCl
22/5H
2O joins in the flask, stirs to make it dissolving.
In second step, logical nitrogen is about 20 minutes in above-mentioned solution, to remove the oxygen in the solution.
In the 3rd step, take by weighing 0.156g (0.9mmol) Na
2Te joins in the flask under vigorous stirring, adds the back and continues vigorous stirring about 30 minutes.
The 4th step, mixing speed is transferred slowly, stirring is finished until reaction remaining a constant speed.
In the 5th step, after reaction finished, reactant liquor is centrifugal, and resultant solid was used distilled water, absolute ethanol washing successively, and vacuumize promptly gets final products after about 10 hours.
Embodiment five: the preparation of ZnSe monodimension nano stick
The first step under the room temperature, adds 100 ml waters and 50 milliliters of ethylenediamines in 250 milliliters round-bottomed flask, after solution mixes, take by weighing 0.079g (0.30mmol) and analyze pure Zn (ClO
4)
2Join in the flask, stir and make it dissolving.
In second step, logical nitrogen is about 20 minutes in above-mentioned solution, to remove the oxygen in the solution.
In the 3rd step, take by weighing 0.112g (0.9mmol) Na
2Se joins in the flask under vigorous stirring, adds the back and continues vigorous stirring about 30 minutes.
The 4th step, mixing speed is transferred slowly, remain a constant speed to stir and finish until reaction.
In the 5th step, after reaction finished, the yellow turbid liquid of gained is centrifugal, and centrifugal resulting light yellow solid was used distilled water, absolute ethanol washing successively, and vacuumize promptly gets final products after about 10 hours.
Claims (4)
1, the method for preparing one dimension semiconductor nanometer rods and nano wire in a kind of aqueous solution, with water is reaction medium, with ethylenediamine or 1, the 6-hexamethylene diamine is dissolved in the water, and adds the water-soluble inorganic salt of IIB family then and it is dissolved fully in this solution, logical nitrogen, under nitrogen atmosphere, continue to add sulphur source, selenium source or tellurium source, and it is dissolved fully, stir and make the color that occurs product in the reaction system down, the centrifugal solid that obtains gets end product after the vacuumize;
Above-mentionedly be reflected at room temperature or be lower than when carrying out under the room temperature, resulting product is a nanometer rods;
The above-mentioned 50-100 of being reflected at ℃ when carrying out, resulting product is a nano wire;
The above-mentioned 30-50 of being reflected at ℃ when carrying out, the product of gained is the mixture of nanometer rods and nano wire.
2, the method for claim 1 is characterized in that, described ethylenediamine or 1,6-diamines addition by volume percentage be 20-50%.
3, the method for claim 1 is characterized in that, described IIB family inorganic salts are the water-soluble inorganic salt of chlorate, sulfate, nitrate, acetate or perchlorate.
4, the method for claim 1 is characterized in that, described sulphur source is vulcanized sodium, ammonium sulfide, hydrogen sulfide, thiocarbamide or thioacetamide; Selenium source is sodium selenide or hydrogen selenide; The tellurium source is tellurium sodium or hydrotelluric acid.
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|---|---|---|---|
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| CN1253923C true CN1253923C (en) | 2006-04-26 |
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| CN1314593C (en) * | 2004-12-03 | 2007-05-09 | 中国科学技术大学 | Tactic zinc oxide granular one dimension mesoporous nano belt and precursor and its preparing method |
| CN1301346C (en) * | 2004-12-17 | 2007-02-21 | 南京大学 | Method for fast preparing single crystal tellurium in one dimension Nano structure from powder of fellurium |
| CN100487856C (en) * | 2005-04-29 | 2009-05-13 | 同济大学 | Method for preparing IIB group semiconductor sulfide nano-material |
| TWI342866B (en) | 2005-12-30 | 2011-06-01 | Ind Tech Res Inst | Nanowires and a method of the same |
| CN105566654B (en) * | 2016-01-28 | 2019-04-16 | 浙江省肿瘤医院 | One-dimentional structure metal organic framework compound and preparation method thereof |
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