CN1482207A - Water heat systhesis method for preparing phosphide nanometre wire - Google Patents
Water heat systhesis method for preparing phosphide nanometre wire Download PDFInfo
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- CN1482207A CN1482207A CNA031317715A CN03131771A CN1482207A CN 1482207 A CN1482207 A CN 1482207A CN A031317715 A CNA031317715 A CN A031317715A CN 03131771 A CN03131771 A CN 03131771A CN 1482207 A CN1482207 A CN 1482207A
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Abstract
The present invention relates to metal luminescent phosphide material. The hydrothermal process of preparing nano phosphide line includes: adding gallium phosphide or indium phosphide and sodium hydroxide in the molar ratio of 1 to 8 into high pressure reactor and adding water to reach sodium hydroxide concentration of 0.4 mol/L; adding cetyl trimethyl ammonium bride of 2-4 molar times the metal phosphide and n-hexanol and heptane in the amount of 0.1 time and 1/3 time the volume of water separately via stirring; adding white phosphorus in 5 molar times the phosphide and elementary iodine in 2 molar times; reaction in closed condition at 160-200 deg.c for 24-48 hr; filtering to obtain coarse product; washing wo benzene, ethanol, dilute hydrochloric acid solution and water successively and drying to obtain the product.
Description
The technical field is as follows:
the invention belongs to the technical field of hydrothermal synthesis preparation methods, and particularly relates to a preparation method of a metal phosphide luminescent material.
Secondly, background art:
the nanometer gallium phosphide and indium phosphide have wide application in light emitting diode, optical filter, super ion material and semiconductor material. The nano-wires of the material have potential application prospect as the minimum unit of electron transmission. The chemical and Physical Letters, 2003, volume 717 and page 722, reported that gallium phosphide nanowires were synthesized by vapor deposition, and the obtained product was impure. The Journal of Physical Chemistry (Journal of Physical Chemistry B, Vol.105 of 2001, 4062-. Chemical communications in the United kingdom (2564-2565 pages 2002), Advanced Materials in Germany (Advanced Materials, 1346 pages 12 of 2000), and natural Materials in the United kingdom (Nature Materials, 155-158 pages 2 of 2003) respectively report the preparation of gallium phosphide, indium phosphide nanowires or nanorods by sublimation of GaP powder, a carbon nanotube template method and a TOPO reduction method, but the reaction temperature is high, the raw Materials are not easy to obtain, the cost is high, and the mass production is difficult to realize. The Journal of the American Chemical Society, 2002, Vol.124, 13656, p.13657, reports the synthesis of gallium phosphide nanorods using metal-organic precursors, but the metal-organic precursors used in this method are very harsh, toxic, and sensitive to air; meanwhile, metal compounds of organic phosphine or phosphorus are mostly extremely toxic and sensitive to air and water, so that the expanded production is difficult. Although the solution-liquid-solid phase synthesis method of indium phosphide nano-fiber reported in the U.S. Pat. No. 270 (Science, 1995, pp.1791-1793) is ideal in terms of cost and cleanness, the obtained product has non-uniform size, which is not favorable for the application of the luminescence property of the semiconductor.
Thirdly, the invention content:
1. technical problem
The invention aims to provide a hydrothermal synthesis preparation method of phosphide nanowires in a hydrothermal system at a lower temperature and a lower pressure, so as to overcome the defects that in the existing method, a virulent metal organic compound precursor is used, the cost of raw materials and equipment is high, the particle size of a product is not uniform, and the like.
2. Technical scheme
The hydrothermal synthesis preparation method of phosphide nanowires comprises the following steps: adding metal oxide and sodium hydroxide into the high-pressure autoclave according to the molar ratio of 1: 8, wherein the metal oxide is gallium phosphide or indium phosphide, and adding water to ensure that the concentration of the sodium hydroxide reaches 0.4 mol/L; after the solid is completely dissolved, cetyl trimethyl ammonium bromide (C) with 2-4 times of molar ratio of metal oxide is added16H33(CH3)3NBr), then adding n-hexanol and heptane with the volume ratio of 30: 3: 10 to the water; after stirring evenly, white phosphorus with 5 times of molar ratio of metal oxide and elementary iodine (I) with 2 times of molar ratio are added2) Carrying out the reaction at the temperature of 160-200 ℃ for 24-48 hours under a closed condition, and filtering to obtain a crude product; and (3) sequentially washing and drying the crude product by using benzene, ethanol, 1-5mol/L dilute hydrochloric acid and water by a conventional method to obtain a product, wherein errors of all proportions and multiples are 10%. The mechanism of the invention is as follows: metal oxide (M)2O3) Generating M (OH) under the action of NaOH4 -Can be mixed with cetyl trimethyl ammonium bromide (C) as surfactant16H33(CH3)3NBr) to form an inorganic-surfactant intercalation compound, curling into a tubular micro-reactor in the subsequent reaction, and controlling the target product material generated by the reaction to grow the nano-wire.
The main reactions involved in the preparation method of the invention are as follows: (1) (2) (3)
the invention adopts cetyl trimethyl ammonium bromide (C)16H33(CH3)3NBr) as a surfactant with M (OH) produced in the reaction4 -The formation of the inorganic-surfactant intercalation compound is critical in the synthesis process.
The diameter of the nanowire can be adjusted by cetyl trimethyl ammonium bromide (C)16H33(CH3)3NBr), reaction temperature,Reaction time and other experimental parameters were varied: hexadecyl trimethyl ammonium bromide (C)16H33(CH3)3When the amount of NBr is increased, M (OH)4 -The inorganic-surfactant intercalation compound is sparsely distributed, the raw material supply of the reaction growth nanowire is insufficient, and the diameter of the nanowire is reduced; when the reaction temperature is increased, the growth of the nanowire is accelerated, and the diameter is increased; when the reaction time is prolonged, the nanowire grows completely and the diameter is increased.
Since the exciton bohr radius of indium phosphide InP is 20nm, when the diameter of the nanowire is below the exciton bohr radius (20nm), the smaller the diameter of the nanowire is, the more significant the quantum size effect is, the larger the bandwidth blue shift is, and the bandwidth (1.42-1.59eV) of the product InP nanowire can be changed with the diameter (8-20 nm). However, the exciton bohr radius of the gallium phosphide GaP is 5.5nm, the diameter of the obtained nanowire is difficult to be below the exciton bohr radius (5.5nm), so that no obvious quantum size effect exists, and the bandwidth of the product GaP nanowire cannot be changed along with the diameter of the product GaP nanowire. To prevent contamination of the reaction system with autoclave material and the introduction of impurities, autoclaves with polytetrafluoroethylene or quartz linings are generally used.
3. Advantageous effects
The metal phosphide nanowire prepared by the method has the following advantages:
the invention adopts a method of carrying out solid-liquid reaction in a hydrothermal system, so that the preparation of the metal phosphide luminescent material can be realized at a lower temperature by using conventional equipment, and the use of toxic and difficult-to-synthesize metal organic compound precursors and expensive raw materials can be avoided. The invention uses inorganic-surfactant intercalation compound as reactant and micro reactor to make the product particle size uniform. The diameter (8-20nm) and the semiconductor bandwidth (1.42-1.59eV) of the obtained indium phosphide nanowire are adjustable, and luminescent materials with different bandwidths can be prepared.
Fourthly, explanation of the attached drawings:
FIG. 1 shows the patterns obtained by XRD analysis of the products GaP and InP prepared according to the present invention;
FIG. 2A is a photograph of a product of the present invention, 10 nGaP nanowires; b is a photo of the product of the invention, 10nmInP nanowire; c is a photo and an electron diffraction pattern of the product 10nmGaP nanowire; d is a photograph and an electron diffraction pattern of the product 10nmInP nanowire;
FIG. 3A is a photoluminescence spectrum of a product of the invention, 10 nGaP nanowires; FIG. 3B is a photoluminescence spectrum of a product of the invention, 10nm InP nanowire; FIG. 3C is a photoluminescence spectrum of InP nanowires of different diameters of the product of the invention;
FIG. 4A is a photograph of a product of the present invention, 8nmInP nanowires; FIG. 4B is a photograph of a product of the present invention, 15nmInP nanowires; figure 4C is a photograph of a product of the present invention, 20nmInP nanowires.
The fifth embodiment is as follows:
example 1:
in an autoclave lined with polytetrafluoroethylene, 12mmol of NaOH and 1.5mmol of Ga were added2O3Or In2O3Then 30mL of water is added; after the solid had completely dissolved, 3mmol of cetyltrimethylammonium bromide (C) were added16H33(CH3)3NBr), 3mL of n-hexanol, 10mL of heptane; after stirring for 20 minutes, 1g of white phosphorus and 0.75g of elemental iodine (I) were added2) Sealing the autoclave, and keeping the temperature at 160 ℃ for 24 hours; washing the obtained product with benzene, alcohol, diluted hydrochloric acid (1mol/L) and water for 2 times respectively, placing in a vacuum drying oven, and drying at 60deg.C for 4 hr to obtain product powder.
The products obtained in the above examples were characterized by using a transtarget X-ray powder diffraction (XRD), a field emission scanning electron microscope (FE-SEM), a high-resolution transmission electron microscope (HRTEM), an Electron Diffraction (ED) and a photoluminescence spectrum (PL).
FIG. 1 shows the powder XRD pattern A of the product, B illustrating the GaP, InP, of the sphalerite phase of the product;
FE-SEM photograph FIG. 2A, B shows that GaP, InP of the product zincblende phase are nanowires with diameter of 10nm and length of 6 μm.
HRTEM picture and electron diffraction pattern figure 2C, D prove that GaP, InP nanometer line of products are crystallized well, grow along [111]and [111]orientation;
the photoluminescence spectra of the product are shown in fig. 3A and B, which show that the obtained material has good luminescence property, the bandwidth is 2.79eV and 1.55eV respectively, and the material is an excellent inorganic luminescent material.
Example 2:
in an autoclave lined with polytetrafluoroethylene, 12mmol of NaOH and 1.5mmol of In were added2O3Then 30mL of water is added; after the solid had completely dissolved, 6mmol of cetyltrimethylammonium bromide (C) were added16H33(CH3)3NBr), 3mL of n-hexanol, 10mL of heptane; after stirring for 20 minutes, 0.5g of white phosphorus and 0.37g of elemental iodine (I) were added2) Sealing the autoclave, and keeping the temperature at 160 ℃ for 24 hours; washing the obtained product with benzene, ethanol, diluted hydrochloric acid (1mol/L) and water for 2 times, placing in a vacuum drying oven, and drying at 60 deg.C for 4 hr to obtain product powder.
The products obtained in the above examples were characterized by means of transtarget X-ray powder diffraction (XRD), Transmission Electron Microscopy (TEM) and photoluminescence spectroscopy (PL).
The powder XRD pattern of the product was consistent with that of FIG. 1B, indicating that the product was a sphalerite phase of InP;
TEM micrograph FIG. 4A shows that the InP of the product zincblende phase is a nanowire 8nm in diameter.
The photoluminescence spectrum of the product in fig. 3C shows that the obtained material has good luminescence property, the bandwidth is 1.59eV, and the material is an excellent inorganic luminescent material.
Example 3:
in an autoclave lined with polytetrafluoroethylene, 12mmol of NaOH and 1.5mmol of In were added2O3Then 30mL of water is added; after the solid had completely dissolved, 3mmol of cetyltrimethylammonium bromide (C) were added16H33(CH3)3NBr), 3mL of n-hexanol, 10mL of heptane; after stirring for 20 minutes, 1g of white phosphorus and 0.75g of elemental iodine (I) were added2) Sealing the autoclave, and keeping the temperature at 160 ℃ for 48 hours; the obtained product is washed for 2 times by benzene, alcohol, diluted hydrochloric acid (1mol/L) and water in sequence, and then is put in vacuumDrying at 60 deg.C for 4 hr in drying oven to obtain product powder.
The products obtained in the above examples were characterized by using a transtarget X-ray powder diffraction (XRD), a field emission scanning electron microscope (FE-SEM) and a photoluminescence spectrum (PL).
The powder XRD pattern of the product was consistent with that of FIG. 1B, indicating that the product was a sphalerite phase of InP;
FE-SEM photographs figure 4B shows that InP of the product zincblende phase is a 15nm diameter nanowire.
The photoluminescence spectrum of the product in fig. 3C shows that the obtained material has good luminescence property, the bandwidth is 1.46eV, and the material is an excellent inorganic luminescent material.
Example 4:
in an autoclave lined with polytetrafluoroethylene, 12mmol of NaOH and 1.5mmol of In were added2O3Then 30mL of water is added; after the solid had completely dissolved, 3mmol of cetyltrimethylammonium bromide (C) were added16H33(CH3)3NBr), 3mL of n-hexanol, 10mL of heptane; after stirring for 20 minutes, 1g of white phosphorus and 0.75g of elemental iodine (I) were added2) Sealing the high-pressure kettle, and keeping the temperature at 200 ℃ for 24 hours; washing the obtained product with benzene, ethanol, diluted hydrochloric acid (1mol/L) and water for 2 times, placing in a vacuum drying oven, and drying at 60 deg.C for 4 hr to obtain product powder.
The products obtained in the above examples were characterized by using a transtarget X-ray powder diffraction (XRD), a field emission scanning electron microscope (FE-SEM) and a photoluminescence spectrum (PL).
The powder XRD pattern of the product was consistent with that of FIG. 1B, indicating that the product was a sphalerite phase of InP;
FE-SEM photographs fig. 4C show that InP of the product zincblende phase is a 20nm diameter nanowire.
The photoluminescence spectrum of the product in fig. 3C shows that the obtained material has good luminescence property, the bandwidth is 1.42eV, and the material is an excellent inorganic luminescent material.
The results of the above examples demonstrate that the diameter of InP nanowires (8-20nm) can be adjusted by cetyl trimethylammonium bromide (C)16H33(CH3)3NBr), reaction temperature, reaction time and other experimental parameters are changed, and the semiconductor bandwidth (1.42-1.59eV) of the obtained indium phosphide nanowire is changed along with the diameter (8-20 nm). The invention is also applicable to other metal phosphides.
Claims (2)
1. A method for preparing phosphide nanowires by hydrothermal synthesis is characterized by comprising the following steps: adding metal oxide and sodium hydroxide into the high-pressure autoclave according to the molar ratio of 1: 8, and then adding water to ensure that the concentration of the sodium hydroxide reaches 0.4 mol/L; after the solid is completely dissolved, cetyl trimethyl ammonium bromide (C) with 2-4 times of molar ratio of metal oxide is added16H33(CH3)3NBr), then adding n-hexanol and heptane with the volume ratio of 30: 3: 10 to the water; after stirring evenly, white phosphorus with 5 times of molar ratio of metal oxide and elementary iodine (I) with 2 times of molar ratio are added2) Carrying out the reaction at the temperature of 160-200 ℃ for 24-48 hours under a closed condition, and filtering to obtain a crude product; and (3) sequentially washing and drying the crude product by using benzene, ethanol, 1-5mol/L dilute hydrochloric acid and water by a conventional method to obtain a product, wherein errors of all proportions and multiples are 10%.
2. The method for preparing phosphide nanowires according to claim 1, wherein the method comprises the following steps: the metal oxide is gallium phosphide or indium phosphide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005108288A1 (en) * | 2004-05-11 | 2005-11-17 | Hunan University | Method for preparing self assembled growth silicon nano-tube by hydrothermal method |
| CN100357023C (en) * | 2005-07-28 | 2007-12-26 | 中国科学院大连化学物理研究所 | Method for preparing metal ruthenium nano-wire |
| CN113363464A (en) * | 2021-06-08 | 2021-09-07 | 广东工业大学 | Gallium-silicon-phosphorus composite negative electrode active material, lithium ion battery, and preparation method and application thereof |
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2003
- 2003-07-28 CN CN 03131771 patent/CN1203155C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005108288A1 (en) * | 2004-05-11 | 2005-11-17 | Hunan University | Method for preparing self assembled growth silicon nano-tube by hydrothermal method |
| US7544626B2 (en) | 2004-05-11 | 2009-06-09 | Hunan University | Preparation of self-assembled silicon nanotubes by hydrothermal method |
| CN100357023C (en) * | 2005-07-28 | 2007-12-26 | 中国科学院大连化学物理研究所 | Method for preparing metal ruthenium nano-wire |
| CN113363464A (en) * | 2021-06-08 | 2021-09-07 | 广东工业大学 | Gallium-silicon-phosphorus composite negative electrode active material, lithium ion battery, and preparation method and application thereof |
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