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WO2011095665A1 - Procédé et réacteur pour l'obtention de nanoparticules - Google Patents

Procédé et réacteur pour l'obtention de nanoparticules Download PDF

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Publication number
WO2011095665A1
WO2011095665A1 PCT/ES2011/070069 ES2011070069W WO2011095665A1 WO 2011095665 A1 WO2011095665 A1 WO 2011095665A1 ES 2011070069 W ES2011070069 W ES 2011070069W WO 2011095665 A1 WO2011095665 A1 WO 2011095665A1
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WO
WIPO (PCT)
Prior art keywords
plasma
nanoparticles
gas
chamber
reactor
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.)
Ceased
Application number
PCT/ES2011/070069
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English (en)
Spanish (es)
Inventor
Enric Bertran Serra
María José INESTROSA IZURIETA
Noemí AGUILÓ AGUAYO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universitat de Barcelona UB
Original Assignee
Universitat de Barcelona UB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Universitat de Barcelona UB filed Critical Universitat de Barcelona UB
Publication of WO2011095665A1 publication Critical patent/WO2011095665A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/46—Generating plasma using applied electromagnetic fields, e.g. high frequency or microwave energy
    • H05H1/4645—Radiofrequency discharges
    • H05H1/466—Radiofrequency discharges using capacitive coupling means, e.g. electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2202/00—Treatment under specific physical conditions
    • B22F2202/13—Use of plasma
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H2245/00—Applications of plasma devices
    • H05H2245/50—Production of nanostructures

Definitions

  • the present invention relates to the field of nanotechnology, in particular to the obtaining of nanoparticles, that is, of particles with a dimension smaller than approximately 100 nm.
  • the nanoparticles although having a dimension smaller than 100 nm, are in turn larger units than atoms and molecules. Depending on their size, the nanoparticles have their own characteristics, have discrete behaviors, typical of quantum physics, and have deviated properties from the laws of classical physics. The size of the nanoparticles depends on the application for which they are used.
  • Recent applications require nanoparticles of increasingly smaller sizes, which are difficult to obtain (cf. e.g. B.M. Jelencovic and A.
  • the nanoparticles have applications in many technological sectors, such as biomedicine-biotechnology, information and communication technologies, energy production and storage, materials science, food and water research, the environment, security systems, and catalysis.
  • crystalline silicon nanoparticles which have unique derived optical, electronic, chemical and biological properties, extending the applications to other technological fields (cf. eg N. O'Farrell et al., "Silicon nanoparticles:
  • nanoparticles depend on their size distribution, also called dispersion, which is often expressed as a lognormal distribution. Studies on obtaining nanoparticles are known, both in the gas / vapor phase and in the liquid phase.
  • nanoparticles obtained in the liquid phase are usually very uniform, but it is difficult to apply liquid phase procedures on an industrial scale because the production speed is very low and there are many by-products.
  • gas / steam phase processes are more appropriate on an industrial scale because the production speed is high and the purity of the product is also high. But both procedures often present difficulties in controlling the size and dispersion of nanoparticles, which is illustrated, for example, in an article by K. Kim et al. ("Generation of size and structure controlled Si nanoparticles using pulse plasma for energy devices", Thin Solid Films 2009, vol. 517, pp. 4184-41 17, where the size of the nanoparticles obtained is between 10 and 120 nm, not to mention its dispersion), and in the references cited there.
  • the present invention solves the deficiencies or limitations of the state of the art, providing a new method of obtaining nanoparticles of small sizes (up to 3 nm in diameter) and of low dispersion (less than 15%), as well as a new plasma reactor modulation specially designed for the implementation of this procedure.
  • one aspect of the present invention relates to a new plasma reactor comprising a vacuum chamber 3, provided with at least one connection 7 to a pumping unit arranged to make a vacuum.
  • This pumping unit can be composed of several pumps arranged in several pumping lines.
  • the reactor also has a plasma chamber 4, where plasma is produced, arranged to circulate the gases in a laminar regime, with at least one cathode 6 capacitively coupled with the walls of the chamber, the walls of the plasma chamber 4 being ready to act as an anode.
  • a power system that feeds the cathode 6.
  • the plasma chamber 4 is a stainless steel box with a square base.
  • the reactor also has a collection channel 5 which at one of its ends forms an extension of the plasma chamber 4 and, on the other end, communicates with the vacuum chamber 3, the walls of the collection channel 5 being also arranged for Act as anode.
  • the collection channel 5 has the same shape and section as the plasma chamber 4.
  • the reactor has at least one gas inlet 1 to the vacuum chamber 3, with an open-close valve arranged to be computer controllable; and it has at least one gas inlet 2 to the plasma chamber 4, with an open-close valve arranged to be computer controllable.
  • a computerized gas feeding system allows to control the flows of precursor gas and entrainment gas, in a synchronized manner with the plasma modulator.
  • the reactor has at least one door for nanoparticle extraction and cleaning inside.
  • the reactor comprises one or more sensors for measuring the pressure of the gases, one or more sight glasses for the ocular monitoring of obtaining the nanoparticles, and a heating system together with a device for measuring the
  • thermocouple e.g. a thermocouple
  • Another aspect of the invention relates to a process for obtaining nanoparticles using any one of the reactors described above, comprising the following steps: (i) performing the desired vacuum in the vacuum chamber 3; (ii) initiate plasma excitation and modulate it with rectangular pulses; (iii) introducing, in a substantially laminar regime, a nanoparticle precursor gas diluted in a entrainment gas,
  • the process of the present invention allows control of all the parameters involved in the process: temperature, pressure, gas flow, RF power, modulation signal and sequence of the process and its automation. This represents an advantage over other procedures for obtaining nanoparticles by plasma.
  • the precursor gas is silane, whereby silicon nanoparticles are obtained.
  • a preferred carrier gas is argon.
  • the process of the present invention can be performed at room temperature, which is an advantage over other processes in which the plasma flame heats the particles.
  • the present invention allows to obtain very small nanoparticles (with diameters of up to 3 nm), and with a very low particle size dispersion (less than 15%).
  • the shorter the pulse duration the smaller the nanoparticles obtained.
  • the quality of the synthesized nanoparticles is very high, with a high level of purity, and with a known composition and structure.
  • amorphous silicon or crystalline silicon nanoparticles can be obtained.
  • the mixture of gases eg silane and argon
  • a polymerization process followed by a nucleation process occurs.
  • the coalescence phase (which would lead to an increase in the size of the resulting particles) is avoided by entering gases into the reactor sequentially.
  • This sequencing is synchronized with the modulation of the RF signal, with pulses of duration of the order of the millisecond, so that the particles formed have time to move and stop growing, and are deposited on the walls of the collection channel 5 or on the desired substrate that has previously been introduced. It is also an advantage of the present invention the possibility of collecting the nanoparticles directly on a substrate or final device so that no subsequent manipulation of the particles occurs, thus avoiding contamination. Likewise, it is advantageous that the process hinders the oxidation of the nanoparticles.
  • the residence time in the plasma is programmable, it is possible to obtain two or more populations of particles in the same process, with different sizes.
  • the production of particles can also be combined with layers that are of the same or another material, thus producing nanoparticles in an amorphous matrix. Alloys and metal nanoparticles can also be synthesized.
  • FIG. 1 is a scheme of a plasma reactor for obtaining nanoparticles according to the invention.
  • FIG. 2 shows in detail the plasma chamber 4 and the collection channel 5 of the reactor of FIG. one .
  • FIG. 3 shows the sequences of power pulses (RF radio frequency) and the double gas input: two of argon (Ar and Ar * ) and one of silane (Si).
  • FIG. 4 shows transmission electron microscopy (TEM) images of amorphous silicon nanoparticles obtained according to the invention.
  • FIG. 5 shows a high resolution TEM image, in which crystalline planes are distinguished, and a diffraction pattern (SAED, selected electron diffraction area) with their corresponding Miller indices indicated, presenting crystalline silicon nanoparticles obtained according to the invention.
  • SAED selected electron diffraction area
  • FIG. 6 shows the size dependence of the nanoparticles
  • a low pressure and ambient temperature plasma reactor comprising a radio frequency (RF) discharge with capacitive coupling was used.
  • Said reactor was formed by four main elements: a gas management system, a vacuum equipment, a plasma chamber 4, where the nanoparticles were generated, and an RF power source with an impedance matching circuit.
  • the gases that were used to carry out the discharges were introduced into the chamber, which were argon (Ar) and silane (SiH 4 , in the abbreviated figures as Si).
  • the system consisted of various stainless steel gas lines equipped with mass flow controllers of the PID type (proportional-integral-differential), so that in each case it was possible to independently regulate the quantities of gases and, therefore, the proportion of them.
  • the vacuum equipment had two elements: a vacuum chamber 3, which contained a total volume of 108 I, and a pumping unit.
  • the connection to the pumping unit 7 is shown in FIG. one .
  • Vacuum chamber 3 was equipped with a pair of sight glasses for ocular monitoring of the process, with a main door for sample extraction and system cleaning, with various entrances with electrical passages for RF power input, with a thermocouple, with a heating system supply, with a cooling system supply, with a gas inlet 1 to the vacuum chamber 3, with a gas inlet 2 to the plasma chamber 4, and with an air inlet.
  • pressure sensors for the different ranges, namely: (i) a pressure sensor of the Pirani type based on the thermal conductivity of the gas, for primary vacuum; (ii) a capacitive type pressure sensor, for measuring the absolute pressure from 0.005 to 2 Torr (267 Pa), based on a mechanically deformable condenser; and (iii) a pressure sensor of the Penning type for high vacuum (from 10 "1 Pa to 10 " 6 Pa), based on the electrical conductivity of the ionized gas that is confined in a magnetic trap.
  • the pumping unit was composed of four vacuum pumps arranged in two independent pumping lines.
  • a first primary pumping line was formed by a mechanical vane pump of 8 m 3 / h, which allowed to reach a vacuum of 1 Pa and was used for pumping from atmospheric pressure (from air and in general from oxidizing gases) .
  • a second pumping line was composed of three pumps, namely: a turbomolecular pump of 360 l / s, which allowed a final vacuum to be reached prior to the process of the order of 10 "4 Pa; a" root “type blade pump, for high pumping flows in a viscous regime, which was used during the process for the extraction of gases from the chamber; and a mechanical pump of double stage vanes of 40 m 3 / h, located at the exit of the roots pump and the turbomolecular pump output.
  • the plasma chamber 4 (or reaction chamber) was in the center of the vacuum chamber 3 (or process chamber) and was in the shape of a stainless steel box with a square base, side equal to 20 cm and height equal to 4 cm, whereby the reaction volume was 1 .600 cm 3 .
  • the cathode 6 In the upper part of the plasma chamber 4 there was a cathode 6, while its lower part and its walls acted as an anode.
  • the cathode 6 consisted of a square of stainless steel, 20 cm x 20 cm, electrostatically shielded by its rear.
  • the cathode was connected to an RF power generator operating at 13.56 MHz and, in order to obtain a nanoparticle formation with controlled size, said plasma excitation power was modulated with rectangular pulses. Each pulse alternated a time or period of ignition (TON) with a time or period of shutdown (T 0FF ) -
  • TON time or period of ignition
  • T 0FF time or period of shutdown
  • the parameters that controlled the RF power in a nanoparticle formation process were: the ignition time of the T 0N plasma, the T 0FF plasma shutdown time, the number of cycles, the incident power and the reflected power.
  • the power reflected to the source be minimal or zero.
  • a reactive impedance matching circuit of the " ⁇ " type was inserted between the RF source and the cathode.
  • the reactor comprised two gas inlets.
  • a gas inlet 1 went directly to the vacuum chamber 3, and argon (Ar) and silane (Si) were introduced through it.
  • the other gas inlet 2 went to the plasma chamber 4, and argon was introduced through it (Ar * ).
  • the plasma chamber 4 and the substrate were subjected to cleaning, by generating about 2 min of a pure Ar plasma.
  • the nanoparticles resulting from the use of short ignition times are presented in the images, either in isolation (cf. upper part of FIG. 4), or in agglomerated form (cf. lower part of the FIG. 4).
  • T 0N ⁇ 1 s short ignition times
  • images, with which the particles were counted and measured then build histograms by size, such as those on the right sides of FIG. 4.
  • histograms were adjusted and on it the average value and the variance of the function were defined, respectively.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Nanotechnology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un procédé et un réacteur pour l'obtention de nanoparticules. On utilise le réacteur de plasma de la FIG.1 qui comprend une chambre à vide (3), une chambre à plasma (4) comportant une cathode, un canal de récupération dont les parois jouent le rôle d'anode, une entrée de gaz (1) pour la chambre à vide (3) et une entrée de gaz (2) pour la chambre à plasma (4). On obtient le vide souhaité, on provoque l'excitation du plasma et on module avec des impulsions rectangulaires, on introduit du silane dilué dans de l'argon, en synchronisant le flux du gaz d'entraînement avec la modulation du plasma de sorte que la pression totale soit constante et en dernier lieu, on récupère les nanoparticules. La présente invention permet d'obtenir des nanoparticules de petites dimensions (jusqu'à 3nm de diamètre) et à faible dispersion (moins de 15%), y compris à température ambiante, aussi bien de silane amorphe que de silicium cristallin.
PCT/ES2011/070069 2010-02-04 2011-02-03 Procédé et réacteur pour l'obtention de nanoparticules Ceased WO2011095665A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ESP201000157 2010-02-04
ES201000157A ES2363900B1 (es) 2010-02-04 2010-02-04 Procedimiento y reactor para la obtención de nanopartículas.

Publications (1)

Publication Number Publication Date
WO2011095665A1 true WO2011095665A1 (fr) 2011-08-11

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080220175A1 (en) * 2007-01-22 2008-09-11 Lorenzo Mangolini Nanoparticles wtih grafted organic molecules
US20090014423A1 (en) * 2007-07-10 2009-01-15 Xuegeng Li Concentric flow-through plasma reactor and methods therefor
US20090056628A1 (en) * 2004-06-18 2009-03-05 Uwe Kortshagen Process and apparatus for forming nanoparticles using radiofrequency plasmas
WO2010008116A2 (fr) * 2008-07-14 2010-01-21 Korea Electro Technology Research Institute Procédé et chambre de traitement au plasma couplé inductivement pour matériau cylindrique à surface tridimensionnelle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090056628A1 (en) * 2004-06-18 2009-03-05 Uwe Kortshagen Process and apparatus for forming nanoparticles using radiofrequency plasmas
US20080220175A1 (en) * 2007-01-22 2008-09-11 Lorenzo Mangolini Nanoparticles wtih grafted organic molecules
US20090014423A1 (en) * 2007-07-10 2009-01-15 Xuegeng Li Concentric flow-through plasma reactor and methods therefor
WO2010008116A2 (fr) * 2008-07-14 2010-01-21 Korea Electro Technology Research Institute Procédé et chambre de traitement au plasma couplé inductivement pour matériau cylindrique à surface tridimensionnelle

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
COSTA ET AL.: "Preparation of nanoscale amorphous silicon based powder in a square-wave-modulated rf plasma reactor.", VACUUM, vol. 45, no. 10, 1994, pages 1115 - 1117 *
VIVET F.ET AL.: "Synthesis and characterization of SiC:H ultrafine powder generated in an argon-silane-methane low-pressure radio-frequency discharge.", JOURNAL OF APPLIED PHYSICS, vol. 83, no. 12, 15 June 1998 (1998-06-15), pages 7474 - 7475, XP012044385 *

Also Published As

Publication number Publication date
ES2363900B1 (es) 2012-06-25
ES2363900A1 (es) 2011-08-18

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