CN1256274C

CN1256274C - Nano phosphide semconductor material hydrothermal synthesis preparing method

Info

Publication number: CN1256274C
Application number: CN 02138423
Authority: CN
Inventors: 谢毅; 高善民; 陆俊
Original assignee: University of Science and Technology of China USTC
Current assignee: University of Science and Technology of China USTC
Priority date: 2002-10-10
Filing date: 2002-10-10
Publication date: 2006-05-17
Anticipated expiration: 2022-10-10
Also published as: CN1488573A

Abstract

The present invention relates to a hydrothermal synthesis preparing method of nanometer phosphide semconductor materials, which is characterized in that IIIA metal oxide is dissolved in water solution of sodium hydroxide or potassium hydroxide, the quality percentage concentration of the sodium hydroxide is 20 to 30%, simple substance white phosphorus which excesses 0.3 to 2 times according to a stoichiometric ratio is added, and simple substance iodine is added; then the mixture reacts at temperature of 120 to 200 DEG C in a sealed autoclave for 8 to 20 hours, and finally, products are washed and dried. The method of the present invention avoids the shortage that the existing method uses danger reagents of organic solvent, metal organic compounds, etc. The present invention has the advantages of easy acquisition of raw material, convenient operation, mild condition and high yield, and the present invention is suitable for mass production.

Description

The hydro-thermal synthetic preparation method of nm phosphide semiconductor material

Technical field:

The invention belongs to the technology of preparing of nm phosphide semiconductor material, particularly relate to hydro-thermal synthetic preparation method.

Background technology:

According to U.S.'s " materials chemistry " (Chemistry of Materials) 1994 the 6th volumes 82-86 page or leaf report, nm phosphide adopt usually metal organic precursor thing and organic phosphine or phosphorus the common prepared in reaction of metallic compound and but the used metal organic precursor thing synthesis condition of this method is very harsh, severe toxicity, and extremely responsive to air; Simultaneously, the metallic compound of organic phosphine or phosphorus is severe toxicity and to air and its sensitivity of water electrode mostly, be difficult to realize produces in batches.

U.S.'s " inorganic chemistry " (Inorganic Chemistry) 1993 the 32nd volumes 2745-2752 page or leaf and the 33rd volume 5693-5700 page or leaf have been reported solid phase permutoid reaction (Solid State Metathesis; be called for short SSM) the synthetic IIIA family of method phosphide semiconductor material; but need under high temperature (500-1000 ℃) and specific atmosphere protection, carry out; the product particle is big; and because of by products such as its product and alkali metal halide at high temperature form sintered compact; be difficult to separate and obtain the higher product of purity; be not suitable for lot production; generally, only be used for fundamental research not as the preparation method.

Summary of the invention:

The hydro-thermal synthetic preparation method that the invention provides a kind of nm phosphide semiconductor material is to overcome the above-mentioned shortcoming that existing metal organic precursor thing preparation method and SSM method exist.

The hydro-thermal synthetic preparation method of nm phosphide semiconductor material of the present invention, it is characterized in that: the IIIA family metal oxide is dissolved in the aqueous solution that mass percentage concentration is 20～30% sodium hydroxide or potassium hydroxide, add simple substance white phosphorus doubly by the excessive 0.3-2 of stoichiometric ratio, add iodine again, then in the autoclave of sealing, in 120-200 ℃ of thermotonus 8-20 hour, carry out the washing and the drying of product at last.

Described IIIA family metal oxide comprises aluminium sesquioxide, Gallium trioxide or indium trioxide.

The principal reaction that relates among the preparation method of the present invention has:

(I)

(II)

(III)

M=Al wherein, Ga, In; N=K, Na.

Adopt the inventive method to prepare the nm phosphide semiconductor material, the adding of iodine is one of successful key.If the adding of no iodine, but, only can produce a little P H by the disproportionation reaction of white phosphorus in alkaline solution ₃Gas makes the productive rate of reaction very low, is unsuitable for producing in batches; After adding iodine, following reaction has taken place:

(IV)

The PH that the existence of iodine not only makes reaction produce ₃The amount of gas increases, and the H of reaction generation ₃PO ₄Can continue following circulating reaction to take place with white phosphorus:

(V)

(VI)

Like this, under the excessive situation of white phosphorus, can set up above-mentioned circulating reaction, thereby produce a large amount of PH ₃Gas carries out reaction (III) fully, generates the nm phosphide semiconductor material.

In reaction process, temperature of reaction and reaction times are all influential to reaction result.If temperature of reaction is lower than 120 ℃, no matter how long, reaction all can not take place; If temperature of reaction is higher than 200 ℃, then have other side reaction and take place, the actual nm phosphide semiconductor material productive rate that generates greatly reduces, and does not have practical significance.Therefore the temperature range that can react is 120 ℃-200 ℃, and the reaction times is 8-20 hour.Lower temperature of reaction then needs the long reaction times, otherwise higher temperature of reaction then can shorten the reaction times.

For avoiding the influence of reaction vessel material to product purity, described autoclave is preferably selected for use and is had liner, and its inner lining material can be chosen from tetrafluoroethylene, platinum, gold or silver, generally selects tetrafluoroethylene for use.

The method that the present invention prepares the nm phosphide semiconductor material has following advantage:

In water solution system, carry out the method for solid-liquid reaction because the present invention adopts, thereby can under the temperature lower, realize the preparation of nm phosphide semiconductor material and can avoid palpus to adopt the condition and the too big defective of product particle of high vacuum or specific protective atmosphere than SSM method; The present invention adopt metal oxide and alkaline solution, elemental phosphorous and iodine in aqueous phase system direct reaction and nm phosphide, avoid using costliness, severe toxicity, be difficult to synthetic organometallics presoma, raw material is cheap, be easy to get, and it is relatively stable to air, thereby preparation technology is simple, be easy to amplify and produce in batches, cost is lower; Adopt the inventive method, productive rate is higher, can reach more than 90%; The inventive method is because by product can be removed by washing, and product purity is higher; Because realization response at a lower temperature, the products therefrom particle diameter is less, and generally at 8-10nm, maximum is no more than 15nm; And the size-grade distribution homogeneous, have tangible quantum size effect, can be used as the material that further carries out the quantum device assembling.

Description of drawings:

Fig. 1 is projection electron microscope (TEM) photo of the gallium phosphide nano material of employing the inventive method preparation;

Fig. 2 is the TEM photo of the indium phosphide nano material of embodiment of the invention preparation;

Fig. 3 embodiment of the invention prepares X-ray diffraction (XRD) figure of product, curve 1 wherein is X-ray diffraction (XRD) figure of gallium phosphide, curve 2 is the XRD figure of indium phosphide, wherein X-coordinate is a test angle, ordinate zou is a relative intensity, from left to right three diffraction peaks are respectively (111) of the gallium phosphide and the indium phosphide of zincblende lattce structure, (220) and (311) diffraction peak among the figure;

Fig. 4 is the absorption spectrum and the fluorescence spectrum of the gallium phosphide nano material of present method preparation;

Fig. 5 is the absorption spectrum and the fluorescence spectrum of the indium phosphide nano material of present method preparation.

Embodiment:

Embodiment 1. preparation nanometer gallium phosphides

In being lined with the autoclave of tetrafluoroethylene, the adding mass percentage concentration is 20% KOH solution and the pulverous Ga of 1g ₂O ₃, add again by the excessive 2 times white phosphorus of stoichiometric ratio, add 2g simple substance I2 then, sealing autoclave was in 150 ℃ of following constant temperature 12 hours; Products therefrom places vacuum drying oven with distillation washing 2 times, 80 ℃ of dryings 4 hours, promptly obtains 0.98 gram grey powder (theoretical yield is 1.074 grams).Equally, reacted 20 hours, 10 hours, 8 hours and 6 hours at 120 ℃, 160 ℃, 180 ℃ and 200 ℃ respectively, all obtain same result.

Adopt TEM and XRD that the product that present embodiment prepares is carried out analysis and characterization.Fig. 1 is the TEM photo of present embodiment product, and the curve 1 among Fig. 3 is the XRD test pattern of present embodiment product, proves that product is a gallium phosphide, and the median size of powder is less than 10nm, and particle is sphere.The productive rate of product gallium phosphide powder can reach more than 90%.Fig. 4 is the absorption spectrum and the fluorescence spectrum of present embodiment product, shows tangible quantum size effect.

The result of above analysis and characterization proves that the present embodiment products therefrom is the nanometer gallium phosphide.

Embodiment 2. preparation nanometer indium phosphides

In being lined with the autoclave of tetrafluoroethylene, add the NaOH solution and the Powdered In of 1g of mass percent concentration 30% ₂O ₃, add white phosphorus again by stoichiometric ratio excessive 30%, add 2g simple substance I2 then, sealing autoclave was in 150 ℃ of following constant temperature 12 hours; Products therefrom places vacuum drying oven with distillation washing 2 times, 80 ℃ of dryings 4 hours, obtains 0.96 gram dark gray powder (theoretical yield is 1.05 grams).Under the identical situation of other condition, change into respectively at 120 ℃, 160 ℃, 180 ℃ and 200 ℃ and reacting 20 hours, 10 hours, 8 hours and 6 hours, all can obtain same result.

Adopt TEM and XRD that product is carried out analysis and characterization.Fig. 2 is the TEM photo of present embodiment product, and the curve 2 among Fig. 3 is the XRD figure of present embodiment product, proves that product is an indium phosphide, and the median size of powder is less than 15nm, and particle is sphere.The productive rate of product indium phosphide powder can reach more than 90%.Fig. 5 is the absorption spectrum and the fluorescence spectrum of present embodiment product, shows tangible quantum size effect.

The result of above analysis and characterization proves that the present embodiment products therefrom is the nanometer indium phosphide.

Claims

1, a kind of hydro-thermal synthetic preparation method of nm phosphide semiconductor material, it is characterized in that: the IIIA family metal oxide is dissolved in the aqueous solution that mass percentage concentration is 20～30% sodium hydroxide or potassium hydroxide, add simple substance white phosphorus doubly by the excessive 0.3-2 of stoichiometric ratio, add iodine again, then in the autoclave of sealing, in 120-200 ℃ of thermotonus 8-20 hour, carry out the washing and the drying of product at last.

2, the hydro-thermal synthetic preparation method of nm phosphide semiconductor material according to claim 1 is characterised in that described IIIA family metal oxide comprises aluminium sesquioxide, Gallium trioxide or indium trioxide.