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WO2007145088A1 - Nanoparticule semi-conductrice et son procédé de fabrication - Google Patents

Nanoparticule semi-conductrice et son procédé de fabrication Download PDF

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Publication number
WO2007145088A1
WO2007145088A1 PCT/JP2007/061179 JP2007061179W WO2007145088A1 WO 2007145088 A1 WO2007145088 A1 WO 2007145088A1 JP 2007061179 W JP2007061179 W JP 2007061179W WO 2007145088 A1 WO2007145088 A1 WO 2007145088A1
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WO
WIPO (PCT)
Prior art keywords
nanoparticles
layer
semiconductor
core
shell
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/JP2007/061179
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English (en)
Japanese (ja)
Inventor
Mitsuru Sekiguchi
Kazuya Tsukada
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.)
Konica Minolta Medical and Graphic Inc
Original Assignee
Konica Minolta Medical and Graphic Inc
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 Konica Minolta Medical and Graphic Inc filed Critical Konica Minolta Medical and Graphic Inc
Priority to JP2008521149A priority Critical patent/JPWO2007145088A1/ja
Publication of WO2007145088A1 publication Critical patent/WO2007145088A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof

Definitions

  • the present invention relates to hollow semiconductor nanoparticles and a method for producing the same.
  • Nano-sized semiconductors such as semiconductor nanoparticles and semiconductor nanorods are nanometer-sized, and thus exhibit quantum size effects such as increased band gap energy and exciton confinement effects. It is known to exhibit good optical characteristics such as light absorption characteristics and light emission characteristics. Therefore, in recent years, studies on various applications such as displays, biomedicals, and optical communication devices have been promoted as phosphors that can only be actively reported on nano-sized semiconductors.
  • an organic molecule is one of core Z shell type semiconductor nanoparticles, a Si / SiO type semi-conductor
  • the emission wavelength is determined by the size of the bandgap
  • the band gap is determined by the diameter of the core layer. Since the diameter of the core layer was determined, it was difficult to handle because large particles could not be formed.
  • the band gap is 1.12 eV, but if this is a nanoparticle with a diameter of nm, the band gap is 1.52 eV and emits light of about 830 nm, and the nanoparticle with a diameter of 4 nm is 1 It is 700 nm at 76 eV and 3.3 nm for nanoparticles with a diameter of 3.3 nm.
  • the conventional light-emitting nanoparticles are formed by the penetration.
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-172429
  • the object of the present invention is to change the emission wavelength without changing the conventional core Z-shell type nano-size.
  • the present invention provides a semiconductor nanoparticle that can be handled larger than a semiconductor particle and that has a larger light emission region and a larger amount of light emission, and a method for producing the same.
  • a semiconductor nanoparticle having a cavity at the center, having a core layer and a shell layer, and having a core layer thickness of 2 to: LOnm the core layer and the shell layer are different from each other
  • the light emission wavelength is not changed, and it is easier to handle than the conventional core Z-shell type nano-sized semiconductor particles. Particles and methods for their production can be provided.
  • FIG. 1 is a production process diagram of SiO 2 ZSiZ hollow nanoparticles with fullerene as a nucleus.
  • FIG. 2 is a production process diagram of SiO 2 ZSiZ hollow nanoparticles with carbon nanotubes as the core.
  • the present inventors have studied the above-mentioned problems, and form fullerene or carbon nanotubes as cores to form hollow core Z-shell nanoparticles that are larger than conventional ones, or fullerenes or carbon nanotubes in a later step.
  • the core Z-shell nanoparticle is enlarged, easy to handle, and the emission intensity per unit
  • the inventors have found that large nanoparticles can be obtained and have completed the present invention.
  • the present invention relates to a fullerene having a diameter of about Im having a hollow structure of about 0.7 nm with no atomic structure inside or a carbon nanotube having a hollow portion of about 0.7 to 50 nm.
  • the fullerene or carbon nanotube layer may be removed in a later step.
  • hollow core Z-shell semiconductor nanoparticles have a substantially spherical shape and a cylindrical shape, and so-called nanowires having a maximum length of several tens / zm. Includes structure.
  • the band gap of the crystal is, for example, Katsuzo Kaminishi, Electronic Device Materials, Nihon Rie Press (2002), p. 62, Hiroshi Kobayashi, Luminescence Physics, Asakura Shoten (2000) p. Indicates the value described in .108.
  • the hollow core Z-shell semiconductor nanoparticles of the present invention are obtained by growing a core layer and a shell layer using a fullerene or carbon nanotube having a hollow structure as a nucleus.
  • the average thickness of the core layer is 2 to: LOnm. Below 2 nm, the structure is a collection of atoms, and a band gap corresponding to the visible light region is generated. This is preferred, and below lOnm, the efficiency of light emission increases dramatically due to the confinement effect of exciton (one electron-hole pair). This is preferable.
  • fullerene or carbon nanotube may be removed by ashing.
  • fullerene or carbon nanotube is used as an example.
  • the core layer and the shell layer may be grown using another substance as a nucleus, and the hollow core Z shell Even after the semiconductor nanoparticles are formed, it is possible to remove the material having the hollow structure as a growth nucleus.
  • the core layer and the shell layer are formed of different crystals.
  • the crystal needs to be selected so that the band gap of the crystal forming the shell layer is larger than the band gap of the crystal forming the core layer.
  • the core Z shell is SiZSiO,
  • the hollow core Z-shell semiconductor nanoparticles of the present invention are larger than conventional core Z-shell semiconductor nanoparticles, the handling and handling of the light-emitting layer per particle is large! / Because of this, the amount of emitted light is large!
  • fullerene or carbon nanotube having a hollow interior is used for producing the hollow layer, but other structures having a hollow structure may be used.
  • Hollow structure For example, a hollow Z-shell layer is grown around the carbon black nanotubes, and the carbon black nanotubes are removed by ashing by heat treatment at about 600 ° C. But ⁇ .
  • a hollow core Z-shell semiconductor nanoparticle manufacturing method consider an example with fullerene as the core.
  • Plasma using SiH gas is placed on a C60 fullerene of lnm diameter with a hollow structure of about 0.7 nm as the core.
  • a 2-5nm Si layer is grown by CVD, and then SiH gas
  • SiO layer of about 0.5 to 20 nm is grown by plasma CVD using 4 4 and N 2 O gas
  • the oxygen remaining in the fullerene reacts with heat treatment at about 600 ° C, or the fullerene surface is partially exposed on the surface of the semiconductor nanoparticles due to defects, etc. Exposed to O plasma at about 200 ° C.
  • Ashing can be performed.
  • the combination of the core and the Z-shell of the semiconductor nanoparticles is Si / SiO, there is a possibility that Si may be oxidized.
  • the core Z shell structure forming method is si
  • ⁇ Method for Producing Hollow Core Z-Shell Semiconductor Nanoparticles with Carbon Nanotubes as the Core> As a method for producing the hollow core Z-shell semiconductor nanoparticles, for example, considering an example with carbon nanotubes as the core, a Si substrate is formed on the Si substrate. Nanoparticles that serve as catalysts such as Co are arranged, and carbon nanotubes with a hollow structure of several nanometers are grown by thermal CVD such as CH using them as nuclei.
  • a SiO layer of about 0.5 to 20 nm is grown by plasma CVD using H gas and N 2 O gas.
  • the power to realize the SiO structure by the CVD method The structure of CdSeZZnS etc.
  • C60 fullerene particles having a hollow structure of 0.7 nm are prepared. Fullerenes can be extracted from Susca by the combustion method, and are currently sold by Frontier Carbon Co., Ltd. (see Electronic Materials, January 2003, p34). In Figure 1 of the example, the particles are separated one by one, but they actually become a mass of particles!
  • fullerene 1 obtained by the above method is dissolved in an organic solvent, and is made into fine droplets by ultrasonic waves using a vaporizer 5.
  • vaporizer 5 fullerene 1 is suspended in He gas
  • fullerene 1 is introduced into the reaction chamber 4 of the CVD apparatus as He gas as a carrier.
  • a source gas, SiH, for forming a Si layer is introduced into the reaction chamber 4.
  • Reaction chamber temperature is 400 ° C
  • pressure is ITo
  • SiZ fullerene nanoparticles 3 are collected by a collector 7 by introducing them into an organic solvent together with He gas. In this way, SiZ fullerene nanoparticles 3 can be obtained.
  • SiZ fullerene nanoparticles 3 are dissolved in an organic solution and vaporized by a carburetor 5 by publishing with He. Introduce fullerene nanoparticles 3 using He gas as a carrier. Next, form a SiO layer in reaction chamber 4.
  • the reaction chamber temperature is 400
  • SiO 2 ZZZ fullerene nanoparticles 9 are formed.
  • the formed SiO 2 / Si / fullerene nanoparticles 9 are collected by a collector 7. [0032] By the above manufacturing method, SiO having a 0.7 nm hollow structure unique to fullerenes.
  • the light of m was irradiated, and the emission intensity was examined with a luminance meter. Compared to SiO ZSi nanoparticles with a Si core that emits the same red light with a diameter of about 4 nm, the emission intensity was about 7 times higher.
  • the diameter may increase in the circumferential direction, and the luminous efficiency per unit volume is considered inferior.
  • SiO ZSiZ fullerene nanoparticles 9 are dissolved in an organic solution and He
  • SiZ fullerene nanoparticles 9 are introduced using He gas as a carrier. Next, O in reaction chamber 4
  • the fullerene is sublimated inside or reacted with o remaining inside the fullerene.
  • sio 2 ZSiZ cavity nanoparticle 10 is formed. Finally, the sio 2 ZSiZ hollow nanoparticles 10 thus formed are collected by the collector 7.
  • the diameter of the child is 5 nm of the conventional SiO shell thickness
  • Co nanoparticles 23 are coated on the Si substrate 21 on which 10 nm of SiO 22 is deposited by the coating method.
  • the substrate with the carbon nanotubes 25 thus obtained is placed in the reaction chamber of the plasma CVD apparatus.
  • a SiH layer is formed in the reaction chamber
  • the reaction chamber temperature is 400 ° C and the pressure is about ITorr.
  • the temperature of the reaction chamber is kept at 400 ° C and the pressure is kept at about lOTorr.
  • a SiO layer of about 5nm is formed on the surface of the SiZ carbon nanotube nanoparticle 28.
  • the nanoparticles were irradiated with 365 nm light, and the emission intensity was examined with a luminance meter. Compared to SiO ZSi nanoparticles that emit the same red light and have a Si core diameter of about 4 nm, about 30 times per particle
  • the emission intensity was shown. This contributes si subvolumes for light emission of the nanoparticles to 34 nm 3 in Sio 2 ZSi nanoparticles, next 6200Nm 3 when the length lOOnm in nanoparticles of the present invention, are for that summer large as about 200 times .
  • the bandgap of carbon nanotubes is small in SU, the confinement effect of exciton is sufficient on one side. There is a fruit and it is thought that the luminous efficiency increased.
  • Co nanoparticles are removed by immersing the plate in a 130 ° C H 2 SO—H 2 O mixture.
  • the carbon nanotubes react with O to be CO and removed. As a result, SiO ZSiZ hollow nanoparticles 31 are formed.
  • SiO ZSiZ hollow nanoparticles having a hollow structure of 30 nm can be formed.
  • SiO ZSi nano that emits the same red light and has a Si core diameter of about 4 nm
  • the emission intensity was about 50 times per particle compared to 2 particles. This removes the carbon nanotube layer with a small band gap, and sandwiches the Si light emitting layer between the air layer and the SiO layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Led Devices (AREA)
  • Chemical Vapour Deposition (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne une nanoparticule semi-conductrice, plus grande que les nanoparticules semi-conductrices de type à centre/coque conventionnel, simple à gérer et qui possède une grande quantité d'émission due à une zone d'émission supérieure, sans changement de la longueur d'onde d'émission. L'invention concerne également un procédé de fabrication de ces nanoparticules semi-conductrices. La nanoparticule semi-conductrice possède une section creuse au centre et une couche de centre et une couche de coque. L'épaisseur de la couche du centre est de 2 à 10 nm. La couche du centre et la couche de la coque sont formées de types différents de semi-conducteurs, ainsi que d'une largeur de bande du semi-conducteur formant la couche de coque supérieure à celle d'un cristal formant la couche du centre.
PCT/JP2007/061179 2006-06-14 2007-06-01 Nanoparticule semi-conductrice et son procédé de fabrication Ceased WO2007145088A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008521149A JPWO2007145088A1 (ja) 2006-06-14 2007-06-01 半導体ナノ粒子及びその製造方法

Applications Claiming Priority (2)

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JP2006-164419 2006-06-14
JP2006164419 2006-06-14

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WO2007145088A1 true WO2007145088A1 (fr) 2007-12-21

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009116408A1 (fr) * 2008-03-17 2009-09-24 コニカミノルタエムジー株式会社 Procédé de fabrication de nanoparticules de semi-conducteur de type cœur/écorce et nanoparticules de semi-conducteur de type cœur/écorce
JP2012502461A (ja) * 2008-09-08 2012-01-26 エスエヌユー アールアンドディービー ファウンデーション 窒化物薄膜構造及びその形成方法
WO2015190257A1 (fr) * 2014-06-11 2015-12-17 コニカミノルタ株式会社 Ensemble de nanoparticules semi-conductrices et leur procédé de production

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004299011A (ja) * 2003-03-31 2004-10-28 Japan Science & Technology Agency ナノ粒子複合体をコアとしたコア・シェル構造体及びそれを構成要素とする構造体並びにそれらとそれらから調製される構造体の調製方法
JP2005074552A (ja) * 2003-08-29 2005-03-24 Japan Science & Technology Agency コア・シェル構造体からなる発光体、それを用いた分子マーカー、光記録媒体並びにそれらの調製方法
JP2005179087A (ja) * 2003-12-16 2005-07-07 National Institute For Materials Science 酸化亜鉛−酸化ガリウムナノチューブとその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004299011A (ja) * 2003-03-31 2004-10-28 Japan Science & Technology Agency ナノ粒子複合体をコアとしたコア・シェル構造体及びそれを構成要素とする構造体並びにそれらとそれらから調製される構造体の調製方法
JP2005074552A (ja) * 2003-08-29 2005-03-24 Japan Science & Technology Agency コア・シェル構造体からなる発光体、それを用いた分子マーカー、光記録媒体並びにそれらの調製方法
JP2005179087A (ja) * 2003-12-16 2005-07-07 National Institute For Materials Science 酸化亜鉛−酸化ガリウムナノチューブとその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TORIMOTO T., CSJ: THE CHEMICAL SOCIETY OF JAPAN KOEN YOKOSHU, vol. 85, no. 1, 11 March 2005 (2005-03-11), pages 213 + ABSTR. NO. 2D1-40, XP003020509 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009116408A1 (fr) * 2008-03-17 2009-09-24 コニカミノルタエムジー株式会社 Procédé de fabrication de nanoparticules de semi-conducteur de type cœur/écorce et nanoparticules de semi-conducteur de type cœur/écorce
JP2012502461A (ja) * 2008-09-08 2012-01-26 エスエヌユー アールアンドディービー ファウンデーション 窒化物薄膜構造及びその形成方法
WO2015190257A1 (fr) * 2014-06-11 2015-12-17 コニカミノルタ株式会社 Ensemble de nanoparticules semi-conductrices et leur procédé de production
JPWO2015190257A1 (ja) * 2014-06-11 2017-04-20 コニカミノルタ株式会社 半導体ナノ粒子集積体およびその製造方法

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