CN113862638B - Cold plasma gas phase preparation method of tin dioxide nano particles - Google Patents
Cold plasma gas phase preparation method of tin dioxide nano particles Download PDFInfo
- Publication number
- CN113862638B CN113862638B CN202111036429.2A CN202111036429A CN113862638B CN 113862638 B CN113862638 B CN 113862638B CN 202111036429 A CN202111036429 A CN 202111036429A CN 113862638 B CN113862638 B CN 113862638B
- Authority
- CN
- China
- Prior art keywords
- tin
- plasma
- nano particles
- dioxide nano
- tin dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 89
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000005495 cold plasma Effects 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 33
- 239000012159 carrier gas Substances 0.000 claims abstract description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 50
- 229910052786 argon Inorganic materials 0.000 claims description 25
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 11
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910006404 SnO 2 Inorganic materials 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 238000003917 TEM image Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 101100112111 Caenorhabditis elegans cand-1 gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4418—Methods for making free-standing articles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
Abstract
The invention discloses a cold plasma gas phase preparation method of tin dioxide nano particles, and relates to the field of new materials. The invention provides a cold plasma gas phase preparation method of tin dioxide nano particles, which is characterized by comprising the following steps of: sequentially introducing inert gas, oxygen and a tin-containing compound into the plasma cavity to obtain the tin dioxide nano particles; wherein, the tin-containing compound is introduced into the plasma reaction cavity through carrier gas; the mixed gas is excited using a radio frequency source. SnO prepared by the invention 2 The crystallinity of the nano particles is adjustable from amorphous state to crystalline state, the size is smaller and can reach below 5nm, the size distribution is more uniform, and the standard deviation of the size is less than 20% of the average size.
Description
Technical Field
The invention relates to the field of new materials, in particular to a cold plasma gas phase preparation method of tin dioxide nano particles.
Background
Tin dioxide (SnO) 2 ) The semiconductor material is a direct band gap semiconductor material with a wide forbidden band (3.6 eV) and an N type, has good electron transmission capability and visible light transmission capability, and has very wide application in the fields of gas sensitive materials, photocatalysis, lithium ion batteries, solar batteries (Nature 2021,590,587-593) and the like.
It is well known that ultrafine micronization of materials, in particular of very small size<5 nm) nanoparticles, and the unique surface effect and small-size effect of the nanoparticles, can endow materials with new properties and applications. Many techniques have been proposed and used for SnO 2 Nanoparticle synthesis, however, these methods all suffer from some inherent problems. Conventional solid phase methods such as mechanical ball milling and the like are difficult to obtain<100 nm, ultra-fine nano particles of uniform size. The liquid phase preparation method such as hydrothermal method (Cryst. Growth Des.2013,13,4,1685-1693), sol-gel method (Physica B2021,613,412987) can obtain nanometer particles with smaller sizeThe crystallinity and purity of the nanoparticles are difficult to control effectively, and the yield is not high. Vapor phase preparation methods such as Chemical Vapor Deposition (CVD) and the like are suitable for the preparation of SnO 2 Thin film materials, but free-standing nanoparticle materials with extremely small grain sizes are not available. These technical disadvantages limit SnO 2 The application of the nano particles in the fields of semiconductor devices and energy sources.
Disclosure of Invention
Based on this, the object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a cold plasma gas phase preparation method of tin dioxide nanoparticles.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a cold plasma gas phase preparation method of tin dioxide nano particles comprises the following steps: sequentially introducing inert gas, oxygen and a tin-containing compound into the plasma cavity to obtain the tin dioxide nano particles; wherein, the tin-containing compound is introduced into the reaction plasma cavity through carrier gas; the mixed gas is excited using a radio frequency source.
The invention uses the radio frequency source to excite the mixed gas to generate plasma, and the high-energy electrons in the plasma bombard gas source molecules to lead the tin-containing compound reaction source to generate decomposition reaction to generate SnO 2 Nanoparticles of SnO 2 The nano particles are carried out of the plasma cavity by the air flow for separation and collection. In the invention, the tin-containing reaction source, oxygen and the inert gas are continuously introduced, and the SnO is formed by 2 The nano particles are continuously generated and carried out by the air flow for separation and collection. Under the action of plasma, the tin-containing reaction source and oxygen of the invention obtain higher temperature and higher reactivity, and the decomposition reaction generates charged negative ion groups which play a key role in the nucleation of nano particles, and the negative ions or the ion groups collide with each other to gather, promote the nucleation and growth, and form SnO 2 And (3) nanoparticles. SnO preparation using the method 2 When the nano particles are used, the reaction is carried out in an inert gas atmosphere, so that the introduction of other impurities and the formation of SnO are avoided 2 The nanoparticles have very high purity.
In cold conditionInside the plasma, the electrons have very small mass and are easily accelerated to very high speeds by the electric field. High-speed moving electrons and SnO 2 The nanoparticles collide causing the particles to become negatively charged. The electrostatic repulsive force between the nano particles can effectively prevent the combination and agglomeration, and SnO with narrower size distribution is obtained 2 And (3) nanoparticles. In the cold plasma, electrons moving at high speed can negatively charge the inner wall of the reaction cavity when colliding with the inner wall of the reaction cavity to form an electric field pointing to the inner wall of the cavity to block SnO 2 The diffusion of the nanoparticles to the inner wall of the cavity yields high yields. Inside the cold plasma, nanoparticle surface electron-ion recombination and surface chemistry release a large amount of heat, which causes the temperature of the nanoparticle to rise sharply, promoting nanoparticle crystallization. The chemical reaction process and energy release in the plasma can be controlled by regulating and controlling the power of the radio frequency source, thereby regulating and controlling the obtained SnO 2 Crystalline forms of nanoparticles.
Preferably, the inert gas is capable of generating plasma under the excitation of a radio frequency source and is not compatible with SnO 2 A gas in which the nanoparticles react, wherein the tin-containing compound is a gaseous tin-containing compound at 50 ℃ or less; further preferably, the inert gas is at least one of helium and argon; the tin-containing compound is tin tetrachloride and the carrier gas is argon. The tin-containing reaction source is preferably tin tetrachloride because tin tetrachloride has higher vapor pressure at room temperature and lower cost.
Preferably, the tin-containing compound is continuously introduced into the plasma cavity through carrier gas for reaction; continuously introducing the tin-containing compound into a plasma cavity through the carrier gas for reaction by using a volume flow meter, wherein the volume flow of the carrier gas is 10-500 sccm; the volume flow of the carrier gas is 10-500sccm, the volume flow of the oxygen is 10-100sccm, and the volume flow of the inert gas is 100-1000sccm; sccm represents 1 cubic centimeter per minute at 0℃and 1 standard atmospheric pressure.
The flow rate of the inert gas affects the SnO 2 Size of the nanoparticle. Controlling inert gasesThe concentration distribution of raw materials or products in the reaction area can be changed by the flow of the reaction gas, and finally the SnO is controlled 2 Size and properties of nanoparticles. The flow rate of carrier gas and oxygen of a tin reaction source is increased, and the SnO in unit time can be improved 2 The yield of nanoparticles, but the flow rate is too high, requiring a significant increase in the power of the plasma.
Preferably, the purity of the inert gas, oxygen and the tin-containing compound is more than or equal to 99.99 percent. The purity of the gas used in the invention is at least 99.99%, so as to improve the purity of the product.
Preferably, when amorphous tin dioxide nano-particles are obtained, the power of the radio frequency source is 50-100W, and when crystalline tin dioxide nano-particles are obtained, the power of the radio frequency source is 100-500W.
The invention can obtain crystalline and amorphous SnO by controlling the plasma power 2 And (3) nanoparticles. By increasing the power of the radio frequency source, the rate of the decomposition reaction can be increased, so that the yield of the nano particles is increased, but the increase of the power is more severe to the equipment, the power of the radio frequency source is preferably below 500W, and at the moment, the inner diameter of the plasma cavity is 23mm, and the wall thickness is 1mm.
Preferably, the pressure in the plasma chamber is 100-500Pa. The pressure in the plasma cavity is related to the gas flow and the pumping speed of the system, snO 2 The nanoparticle generation reaction time can be regulated by the intra-cavity air pressure.
In addition, the invention provides the tin dioxide nano-particles prepared by the cold plasma gas phase preparation method of the tin dioxide nano-particles.
Preferably, the particle size of the tin dioxide nano-particles is 1-10nm. SnO of the present invention 2 The size of the nanoparticle is directly related to the residence time (t) of the nanoparticle in the plasma. t has the following relation with the reaction pressure (P), the gas flow rate (F) and the plasma length (L): t ≡ (P
The invention adjusts the reaction cavity by controlling the flow of inert gas, oxygen and tin reaction source carrier gas and a vacuum pumpThe medium pressure can regulate and control the obtained SnO 2 Size of the nanoparticle.
Compared with the prior art, the invention has the beneficial effects that: (1) SnO (SnO) 2 The size of the nano particles is smaller and can reach below 5nm, the size distribution is more uniform, and the standard deviation of the size can reach less than 20% of the average size; (2) SnO (SnO) 2 The crystallinity of the nano particles is controllable and can be adjusted from amorphous state to crystalline state; and (3) the production process is simple, the period is short, and the yield is high.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of crystalline tin dioxide nanoparticles prepared in example 1;
FIG. 2 is an X-ray diffraction (XRD) pattern of crystalline tin dioxide nanoparticles prepared in example 2;
FIG. 3 is an X-ray diffraction (XRD) pattern of amorphous tin dioxide nanoparticles prepared in example 3;
FIG. 4 is a Transmission Electron Micrograph (TEM) of the nanoparticles prepared in example 2;
FIG. 5 is a size distribution diagram of nanoparticles prepared in example 2;
FIG. 6 is a size distribution diagram of nanoparticles prepared in example 4;
FIG. 7 is a size distribution diagram of nanoparticles prepared in example 5;
FIG. 8 is a Transmission Electron Micrograph (TEM) of the nanoparticles prepared according to comparative example 2;
fig. 9 is an X-ray diffraction (XRD) pattern of the nanoparticle prepared in comparative example 2.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
The cold plasma gas phase preparation method of the tin dioxide nano-particles is provided with examples 1-5, and the preparation method of the specific examples 1-5 is as follows:
example 1
The invention discloses a cold plasma gas phase preparation method of tin dioxide nano particles, which comprises the following steps:
(1) Starting a vacuum pump, purging the plasma cavity and the gas path by nitrogen, and vacuumizing to reduce the pressure in the plasma system to about 1Pa;
(2) Argon is introduced into the plasma cavity, and the flow rate of the argon is 450sccm; turning on a radio frequency source, adjusting the power to 500W, and generating argon plasma;
(3) Introducing O from the inner tube of the air inlet pipeline into the plasma cavity 2 ，O 2 Continuously introducing tin tetrachloride into the plasma cavity through carrier gas with the volume flow of 50sccm, wherein the volume flow of the carrier gas is 50sccm;
(4) Controlling the air pressure in the plasma cavity at 200Pa, adjusting a radio frequency source matching box to enable the load power and the loading power to be completely matched, and collecting and obtaining the tin dioxide nano particles.
Example 2
The invention discloses a cold plasma gas phase preparation method of tin dioxide nano particles, which comprises the following steps:
(1) Starting a vacuum pump, purging the plasma cavity and the gas path by nitrogen, and vacuumizing to reduce the pressure in the plasma system to about 1Pa;
(2) Argon is introduced into the plasma cavity, and the flow rate of the argon is 450sccm; turning on a radio frequency source, adjusting the power to 200W, and generating argon plasma;
(3) Introducing O from the inner tube of the air inlet pipeline into the plasma cavity 2 ，O 2 Continuously introducing tin tetrachloride into the plasma cavity through carrier gas with the volume flow of 50sccm, wherein the volume flow of the carrier gas is 50sccm;
(4) Controlling the air pressure in the plasma cavity at 200Pa, adjusting a radio frequency source matching box to enable the load power and the loading power to be completely matched, and collecting and obtaining the tin dioxide nano particles.
Example 3
The invention discloses a cold plasma gas phase preparation method of tin dioxide nano particles, which comprises the following steps:
(1) Starting a vacuum pump, purging the plasma cavity and the gas path by nitrogen, and vacuumizing to reduce the pressure in the plasma system to about 1Pa;
(2) Argon is introduced into the plasma cavity, and the flow rate of the argon is 450sccm; turning on a radio frequency source, adjusting the power to 50W, and generating argon plasma;
(3) Introducing O from the inner tube of the air inlet pipeline into the plasma cavity 2 ，O 2 Continuously introducing tin tetrachloride into the plasma cavity through carrier gas with the volume flow of 50sccm, wherein the volume flow of the carrier gas is 50sccm;
(4) Controlling the air pressure in the plasma cavity at 200Pa, adjusting a radio frequency source matching box to enable the load power and the loading power to be completely matched, and collecting and obtaining the tin dioxide nano particles.
Example 4
(1) Starting a vacuum pump, purging the plasma cavity and the gas path by nitrogen, and vacuumizing to reduce the pressure in the plasma system to about 1Pa;
(2) Argon is introduced into the plasma cavity, and the flow rate of the argon is 1000sccm; turning on a radio frequency source, adjusting the power to 200W, and generating argon plasma;
(3) Introducing O from the inner tube of the air inlet pipeline into the plasma cavity 2 ，O 2 Continuously introducing tin tetrachloride into the plasma cavity through carrier gas with the volume flow of 100sccm and the volume flow of carrier gas of 500sccm;
(4) Controlling the air pressure in the plasma cavity at 500Pa, adjusting a radio frequency source matching box to enable the load power and the loading power to be completely matched, and collecting and obtaining the tin dioxide nano particles.
Example 5
The invention discloses a cold plasma gas phase preparation method of tin dioxide nano particles, which comprises the following steps:
(1) Starting a vacuum pump, purging the plasma cavity and the gas path by nitrogen, and vacuumizing to reduce the pressure in the plasma system to about 1Pa;
(2) Argon is introduced into the plasma cavity, and the flow rate of the argon is 100sccm; turning on a radio frequency source, adjusting the power to 200W, and generating argon plasma;
(3) Introducing O from the inner tube of the air inlet pipeline into the plasma cavity 2 ，O 2 The volume flow rate of (2) is 10sccm,continuously introducing tin tetrachloride into the plasma cavity through carrier gas, wherein the volume flow of the carrier gas is 10sccm;
(4) Controlling the air pressure in the plasma cavity at 100Pa, adjusting a radio frequency source matching box to enable the load power and the loading power to be completely matched, and collecting and obtaining the tin dioxide nano particles.
Meanwhile, the cold plasma gas phase preparation method of the tin dioxide nano-particles is provided with comparative examples 1-2, and the preparation method of specific examples 1-2 is as follows:
comparative example 1
(1) Starting a vacuum pump, purging the plasma cavity and the gas path by nitrogen, and vacuumizing to reduce the pressure in the plasma system to about 1Pa;
(2) Argon is introduced into the plasma cavity, and the flow rate of the argon is 450sccm; turning on a radio frequency source, adjusting the power to 30W, and generating argon plasma;
(3) Introducing O from the inner tube of the air inlet pipeline into the plasma cavity 2 ，O 2 Continuously introducing tin tetrachloride into the plasma cavity through carrier gas with the volume flow of 50sccm, wherein the volume flow of the carrier gas is 50sccm;
(4) And controlling the air pressure in the plasma cavity at 200Pa, adjusting a radio frequency source matching box to enable the load power and the load power to be completely matched, and obtaining the tin dioxide nano particles without generating products and collecting the tin dioxide nano particles.
Comparative example 2
(1) Starting a vacuum pump, purging the plasma cavity and the gas path by nitrogen, and vacuumizing to reduce the pressure in the plasma system to about 1Pa;
(2) Argon is introduced into the plasma cavity, and the flow rate of the argon is 450sccm; turning on a radio frequency source, adjusting the power to 200W, and generating argon plasma;
(3) Introducing O from the inner tube of the air inlet pipeline into the plasma cavity 2 ，O 2 Continuously introducing tin tetrachloride into the plasma cavity through carrier gas with the volume flow of 5sccm and the volume flow of carrier gas of 50sccm;
(4) Controlling the air pressure in the plasma cavity at 200Pa, adjusting a radio frequency source matching box to enable the load power to be completely matched with the load power, and collecting the product which is not the tin dioxide nano particles.
The X-ray diffraction (XRD) pattern of the crystalline tin dioxide nano-particles prepared in the embodiment 1 of the invention is shown in figure 1; the X-ray diffraction (XRD) pattern of the crystalline tin dioxide nano-particles prepared in the embodiment 2 of the invention is shown in figure 2; the X-ray diffraction (XRD) pattern of the amorphous tin dioxide nano-particles prepared in the embodiment 3 of the invention is shown in figure 3;
FIG. 4 is a Transmission Electron Micrograph (TEM) of the nanoparticles prepared in example 2; FIG. 5 is a size distribution diagram of nanoparticles prepared in example 2, with an average size of 4.5nm and a standard deviation of 0.9nm of the size distribution, which is 20% of the average size; FIG. 6 is a size distribution diagram of nanoparticles prepared in example 4, with an average size of 8.5nm and a standard deviation of 1.9nm for the size distribution of 22% of the average size; FIG. 7 is a size distribution diagram of nanoparticles prepared in example 5, with an average size of 2.8nm and a standard deviation of 0.6nm for the size distribution, which is 21% of the average size;
FIG. 8 is a Transmission Electron Micrograph (TEM) of the nanoparticles prepared according to comparative example 2; fig. 9 is an X-ray diffraction (XRD) pattern of the nanoparticle prepared in comparative example 2. As can be seen from fig. 8 and 9, the final collected product of the preparation method of comparative example 2 is not tin dioxide nanoparticles.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (3)
1. The cold plasma gas phase preparation method of the tin dioxide nano particles is characterized by comprising the following steps of: sequentially introducing inert gas, oxygen and a tin-containing compound into the plasma cavity to obtain the tin dioxide nano particles; wherein, the tin-containing compound is introduced into the plasma reaction cavity through carrier gas; the mixed gas is excited by using a radio frequency source;
the tin-containing compound is continuously introduced into the plasma cavity through carrier gas for reaction; the volume flow of the carrier gas is 10-500sccm, the volume flow of the oxygen is 10-100sccm, and the volume flow of the inert gas is 100-1000sccm;
the pressure in the plasma cavity is 100-500Pa;
when amorphous tin dioxide nano particles are obtained, the power of the radio frequency source is 50-100W;
when crystalline tin dioxide nano particles are obtained, the power of the radio frequency source is 100-500W;
the particle size of the tin dioxide nano particles is 1-10nm.
2. The cold plasma gas phase preparation method of tin dioxide nanoparticles as claimed in claim 1, wherein the inert gas is at least one of helium and argon; the tin-containing compound is tin tetrachloride and the carrier gas is argon.
3. The method for preparing tin dioxide nano particles by cold plasma gas phase according to claim 1, wherein the purity of the inert gas, oxygen and the tin-containing compound is more than or equal to 99.99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111036429.2A CN113862638B (en) | 2021-09-03 | 2021-09-03 | Cold plasma gas phase preparation method of tin dioxide nano particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111036429.2A CN113862638B (en) | 2021-09-03 | 2021-09-03 | Cold plasma gas phase preparation method of tin dioxide nano particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113862638A CN113862638A (en) | 2021-12-31 |
| CN113862638B true CN113862638B (en) | 2024-01-26 |
Family
ID=78989505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111036429.2A Active CN113862638B (en) | 2021-09-03 | 2021-09-03 | Cold plasma gas phase preparation method of tin dioxide nano particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113862638B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613123A (en) * | 2013-12-13 | 2014-03-05 | 青岛大学 | Method for preparing monodisperse stannic oxide nanocrystalline particles |
-
2021
- 2021-09-03 CN CN202111036429.2A patent/CN113862638B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613123A (en) * | 2013-12-13 | 2014-03-05 | 青岛大学 | Method for preparing monodisperse stannic oxide nanocrystalline particles |
Non-Patent Citations (2)
| Title |
|---|
| 张志勇 等."MOPECVD法制备超微颗粒SnO2薄膜".《西北大学学报(自然科学版)》.2000,第30卷(第3期),第185-188页. * |
| 陈祖耀 等."低温等离子体化学法制备SnO2超微粒子粉末".《硅酸盐学报》.1986,第14卷(第3期),第326-331页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113862638A (en) | 2021-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shen et al. | Direct synthesis of ZnO nanoparticles by a solution-free mechanochemical reaction | |
| EP3802418B1 (en) | Methods for forming carbon nanostructured materials | |
| JP5105372B2 (en) | Boron nitride spherical nanoparticles and production method thereof | |
| CN109809372B (en) | Method for preparing single-layer tungsten diselenide nanobelt based on space confinement strategy | |
| i Cabarrocas et al. | Synthesis of silicon nanocrystals in silane plasmas for nanoelectronics and large area electronic devices | |
| Kumar et al. | Synthesis and characterization of nano silicon and titanium nitride powders using atmospheric microwave plasma technique | |
| JP2019524612A (en) | Boron nitride nanomaterial, its production method and application | |
| CN106698437A (en) | Method for preparing spherical nanometer silicon by virtue of thermal plasma method | |
| CN109161844B (en) | Boron-carbon-nitrogen film enveloping high-orientation boron nitride nanocrystalline and preparation method thereof | |
| Shimada et al. | Synthesis of Gallium Nitride Nanoparticles by Microwave Plasma‐Enhanced CVD | |
| JP5587423B2 (en) | Method and apparatus for depositing nanostructured thin layers with controlled morphology and nanostructures | |
| CN113862638B (en) | Cold plasma gas phase preparation method of tin dioxide nano particles | |
| CN110616414A (en) | Method for preparing two-dimensional BiOBr film | |
| Mohammad et al. | Nanomaterials synthesis routes | |
| Juangsa et al. | Synthesis of Nanostructured Silicon Nanoparticles for Anodes of Li-Ion Battery | |
| CN108842142B (en) | Film composed of micron-sized pentagonal stannous oxide and preparation method thereof | |
| KR102082685B1 (en) | Apparatus for Production of Metal Alloy and Method for Production of Metal alloy using the same | |
| Shi et al. | Morphology and growth mechanism of novel zinc oxide nanostructures synthesized by a carbon thermal evaporation process | |
| CN111593318A (en) | Diamond nanocrystalline/nitrogen-doped silicon carbide interface phase n-type semiconductor composite film and preparation method thereof | |
| Lee et al. | Structural evolution of indium hydroxide powders prepared by a precipitation method | |
| CN115341272B (en) | Preparation method of millimeter-level two-dimensional topological material bismuth selenide monocrystal | |
| CN114671437B (en) | Preparation method of low-oxygen-content superfine amorphous silicon carbide nanoparticles | |
| Yang et al. | High efficiency preparation, structure and properties of silicon nano-crystals by induction plasma method | |
| Sivkov et al. | Study of particles of plasma dynamic synthesis product in the Ti-O system by high-resolution transmission electron microscopy | |
| Choi et al. | Synthesis of Bimetallic Nanoparticles and Their Application to Growth of Multiwalled Carbon Nanotube Forest |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |