WO2007145089A1 - Particule semi-conductrice à trois couches - Google Patents

Particule semi-conductrice à trois couches Download PDF

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Publication number
WO2007145089A1
WO2007145089A1 PCT/JP2007/061180 JP2007061180W WO2007145089A1 WO 2007145089 A1 WO2007145089 A1 WO 2007145089A1 JP 2007061180 W JP2007061180 W JP 2007061180W WO 2007145089 A1 WO2007145089 A1 WO 2007145089A1
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WO
WIPO (PCT)
Prior art keywords
layer
shell
particles
core
sio
Prior art date
Application number
PCT/JP2007/061180
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English (en)
Japanese (ja)
Inventor
Mitsuru Sekiguchi
Kazuya Tsukada
Original Assignee
Konica Minolta Medical & 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 & Graphic, Inc. filed Critical Konica Minolta Medical & Graphic, Inc.
Priority to JP2008521150A priority Critical patent/JPWO2007145089A1/ja
Publication of WO2007145089A1 publication Critical patent/WO2007145089A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/08—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to a three-layer semiconductor particle.
  • 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 optical characteristics such as excellent 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.
  • organic molecules are placed on the surface of si / sio type semiconductor nanoparticles, which are one of the core Z shell type semiconductor nanoparticles.
  • Bound biological substance labeling agents have been studied (for example, see Patent Document 1) o
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-172429
  • the emission wavelength is determined by the size of the band gap
  • the band gap is determined by the diameter of the core layer. Since the diameter was determined and large particles could not be formed, it was difficult to handle.
  • the band gap is 1.12 eV.
  • the band gap is 1.52 eV and emits about 830 nm, and the 4 nm diameter is 1.76 eV and 700 nm. 3.
  • leV is 600nm.
  • the present invention provides three-layer type semiconductor particles that are easier to handle than the conventional core Z-shell type nano-sized semiconductor particles without changing the emission wavelength, and have a larger light emission amount due to the larger emission region. The purpose is to do.
  • the present invention has been made in view of the above-mentioned problems, and the object of the present invention is to handle larger than conventional core Z-shell nano-sized semiconductor particles without changing the emission wavelength.
  • the object is to provide a three-layer semiconductor particle that is easy and has a large emission region and a large emission amount.
  • semiconductor particles are composed of three material layers: a core, a first shell, and a second shell.
  • the first shell is the light emitting layer, and the thickness is in the range of 2 to 10 nm. The thickness is such that the quantum effect is manifested by exciton confinement.
  • the core and the second shell use a material having a band gap larger than that of the semiconductor layer of the first shell, thereby ensuring the exciton confinement effect and ensuring the light emission characteristics of the first shell.
  • the core layer is a nucleus of the three-layer semiconductor particle of the present invention, and the size can be freely changed from several nm to several mm. This makes it possible to control the overall size of the three-layer semiconductor particles as the phosphor.
  • the thickness of the second shell is arbitrary. To ensure the light extraction effect from the first shell, a thickness of about 0.5 to 20 nm is preferred.
  • the present invention provides a core Z, a first shell Z, a second shell type three-layer semiconductor particle, and a first shell having a core portion having a large band gap and a second shell having a thickness of 2 to 10 nm.
  • Light emission by quantum size effect is achieved by sandwiching the semiconductor layer, and the size of the core Z-shell type nanoparticles is increased by deciding the size of the whole particle by the diameter of the core part. It has been found that nanoparticles having a high per unit emission intensity can be obtained.
  • the three-layer semiconductor particle of the present invention uses a material containing C in the second shell layer, for example, a SiOC film containing a CH group, to thereby form an organic molecule.
  • a material containing C in the second shell layer for example, a SiOC film containing a CH group
  • [0009] having a core layer, a first shell layer, and a second shell layer, wherein the thickness of the first shell layer between the core layer and the second shell layer is 2 to: LOnm
  • the band gap of the material forming the second shell layer and the core layer is larger than the band gap of the semiconductor forming the first shell layer.
  • the first shell layer is made of Si
  • the second shell layer and the core layer are made of SiO.
  • the emission wavelength is not changed, and it is easier to handle than the conventional core Z-shell type nano-sized semiconductor particles, and the three-layer type has a larger light emission amount due to a larger light emitting region.
  • Semiconductor particles can be provided.
  • the three-layer semiconductor particles of the present invention have excellent light emission characteristics such as a large particle size and easy handling, and a large light emission amount.
  • FIG. 1 is a production process diagram of SiO 2 ZSiZSiO 3 layer semiconductor particles of the present invention.
  • FIG. 2 is a production process diagram of SiOCZSiZSiO three-layer semiconductor particles of the present invention.
  • FIG. 3 is a production process diagram of GaAsZGaPZGaAs three-layer semiconductor nanowire particles of the present invention.
  • FIG. 4 is a production process diagram of ZnSZCdSeZZnS three-layer semiconductor particles of the present invention.
  • GaAsZGaP nanowire particles 9 GaAs shell layer
  • the shape of the three-layered semiconductor particles is either a sphere or an ellipse, or a cylinder, and includes a so-called nanowire structure whose length reaches a maximum of several tens / zm. .
  • 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. Values shown in 108 are shown.
  • the three-layer semiconductor particles of the present invention have a core layer, a first shell layer, and a second shell layer, and the first shell layer between the core layer and the second shell layer.
  • the thickness of the first shell layer is in the range of 2 to: LOnm. More preferably, it is 2-5 nm.
  • the thickness force of the first shell layer is 2 nm or more, a structure in which atoms are assembled is formed, and a band gap necessary for light emission can be formed, which is preferable.
  • it is less than lOnm, the confinement effect of excitons (electron-hole pairs) appears, and it is preferable because it is a region where the luminous efficiency is rapidly improved.
  • the three-layer semiconductor particles of the present invention form, for example, core particles having a diameter of several nanometers, and a semiconductor layer having a band gap smaller than that of the core layer and having a first shell layer of 2 to 1 Onm. After that, a second material having a band gap larger than that of the first shell layer is grown to a thickness of 0.5 to 20 nm.
  • the average thickness of the first shell layer is preferably in the range of 2-5 nm. Exceeding the lower limit of the above range results in a structure in which atoms are assembled, and a band gap corresponding to the visible light region is generated. This is preferable because it is a region where the confinement effect of the hole pair) appears remarkably and the luminous efficiency improves rapidly.
  • the core layer Z, the first shell layer, and the second shell layer are each formed of a different material. It is necessary to select the material so that the band gap of the material forming the core layer and the second shell layer is larger than the band gap of the crystal forming the first shell layer.
  • core layer Z first shell layer Z second shell layer is SiO 2 / Si / SiO, Si
  • the three-layer type semiconductor particles of the present invention are larger in size than conventional core Z-shell type semiconductor nanoparticles, so that the volume of the light-emitting layer contained in each particle is large because of handling and the amount of emitted light. The characteristic that is large is obtained.
  • Si does not emit light by m size particles, but if / z m size SiO 2 / Si / SiO particles are made by this method, the Si layer is nano-sized.
  • Si semiconductor particles mu m size emission.
  • pixels are in units of 100 / zm, and ⁇ m-sized particles are easier to handle for use in such places.
  • nanowires are used as the core layer, wire-shaped three-layer semiconductor particles can be obtained. Even in this case, the three-layer semiconductor particles of the present invention are larger in size than the conventional core Z-shell semiconductor nanoparticles, and thus the volume of the light-emitting layer included in each particle is large. The characteristic that the light emission amount is large is obtained.
  • the second shell In a three-layer semiconductor particle in which the core is made of SiO and the first shell is made of Si, the second shell
  • the second shell layer has Si in the Si-O network with CH groups.
  • the band gap of SiOC film is between 9. OeV for SiO and 3.3 eV for SiC
  • Lectin and peptide can be bound, and lectin selectively adsorbs to cancer cells Therefore, when exposed to ultraviolet light, SiO / Si / SiOC 3 adsorbed on cancer cells via lectins
  • the layer semiconductor particles fluoresce and can be a marker for the affected area.
  • a 50 nm diameter SiO core particle 1 is prepared.
  • the particles of SiO are (J. L. Gole
  • the SiO core particles 1 are mixed with an organic solution (IPA (isopropyl alcohol, etc.)
  • IPA isopropyl alcohol, etc.
  • a raw material gas, SiH, is introduced.
  • Reaction chamber temperature is 400 ° C
  • pressure is 1 X 1
  • SiO ZSi particles 3 are mixed with an organic solution (IPA (isopropyl alcohol).
  • IPA isopropyl alcohol
  • reaction chamber 4 vaporized in the vaporizer 5b, and introduced into the reaction chamber 4b of the CVD apparatus, and He gas as a carrier. Next, reaction chamber 4
  • the temperature of the reaction chamber is kept at 400 ° C and the pressure is kept at about 10 X 1. 33322 X 10 2 Pa.
  • SiO shell layer 8 of about 5 nm was grown on the surface. In this way SiO / Si / SiO grains
  • SiO 2 / Si / SiO particles 9 could be formed.
  • the emission intensity was about 100 times per unit.
  • Embodiment 2 as a second embodiment will be described with reference to FIG.
  • SiO core particles 1 having a diameter of 50 nm were prepared.
  • Example 2 2 ZSi particles 3 are the same as in Example 1 up to obtaining.
  • SiOC seal layer 10 having a degree of growth was grown.
  • SiO ZSiZSiOC particles 11 are formed.
  • ZSiZSiOC particles 11 are collected by the collector 7b '.
  • SiO 2 ZZiZSiOC particles could be formed.
  • SiO 2 ZSiZSiOC particles were irradiated with 365 nm light, and the luminance intensity was measured with a luminance meter. I investigated. SiZSiO nanoparticles that emit the same red light and have a Si core diameter of about 4 nm
  • the emission intensity was about 100 times per unit. This is because the volume of Si having a quantum effect is increased for the same reason as described in Example 1.
  • the SiOC film fabricated as the second shell this time has a CH group in the Si-O network.
  • the band gap is 5 to 6 eV between 9 ⁇ OeV for SiO and 3.3 ⁇ eV for SiC.
  • this SiOC has a CH group, by oxidizing it to a COOH group,
  • the lectin and peptide can be bonded, and the lectin is selectively adsorbed to the cancer cells, when exposed to ultraviolet light, the SiO / Si / SiOC 3 layer adsorbed to the cancer cells via the lectin
  • the semiconductor particles fluoresce and can be a marker for the affected area.
  • Embodiment 3 which is a third embodiment will be described with reference to FIG.
  • Au nanoparticles 24 are coated on a Si substrate 21 on which 10 nm of SiO 22 is deposited by a coating method.
  • a GaAs nanowire 25 having a diameter of 20 nm and a length of 1 m is formed using the catalyst as a catalyst.
  • the substrate to which the GaAs nanowires 25 thus obtained are attached is placed in the reaction chamber 20 of the CVD apparatus.
  • source gases, Ga (CH) and PH, for forming the GaP shell layer 27 as the first shell layer are introduced into the reaction chamber.
  • a GaP shell layer 27 is grown on the GaAs nanowire by the CVD reaction. At this time, the thickness of the GaP shell layer 27 can be adjusted to about 2 to 5 nm by adjusting the amount of gas and the reaction time.
  • the GaP layer is also deposited on the substrate, but it is not the essence of the discussion here.
  • source gases, Ga (CH 3) 2 and AsH, for forming the GaAs shell layer 29 are introduced as a second shell layer into the reaction chamber of the same CVD apparatus. Temperature of reaction chamber
  • the temperature is maintained at 700 ° C and a pressure of about 10 X 1. 33322 X 10 2 Pa.
  • a GaAs shell layer 29 is grown on the GaAsZGaP nanowire particle 28 by the CVD reaction. in this way As a result, GaAsZGaPZGaAs nanowire particles 30 were obtained.
  • Figure 4 shows the literature (C. Sarigiannidis et al., Mat. Res. Soc. Symp. Proc. Vol. 7
  • the ZnS core particles 40 thus obtained are dispersed in an organic solution (IPA (isopropyl alcohol, etc.), and published with He, so Vaporize and introduce ZnS core particles 40 into the reaction chamber 47b of Jet Reactor using He gas as a carrier, then mix 5 vol% of H Se into H and introduce 50 sccm from the upper tube.
  • IPA isopropyl alcohol, etc.
  • a CdSe shell layer 43 having a thickness of 3 nm was formed around the element 40, and ZnSZCdSe particles 44 were formed and collected by a collector 41b.
  • the emission wavelength is not changed and is larger than the conventional core Z-shell type nano-sized semiconductor particles. It is easy to handle, providing a large light emitting region, large amount of light emission, and providing three-layer semiconductor particles.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Luminescent Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne une particule semi-conductrice à trois couches, 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 grande zone électroluminescente, sans changement de la longueur d'onde d'émission. La particule semi-conductrice à trois couches est munie d'une couche de centre, d'une première couche de coque et d'une seconde couche de coque. L'épaisseur de la première couche de coque entre la couche de centre et la seconde couche de coque est comprise entre 2 et 10 nm. Les largeurs de bande des matériaux formant la seconde couche de coque et la couche de centre sont supérieures à celle d'un semi-conducteur formant la première couche de coque.
PCT/JP2007/061180 2006-06-14 2007-06-01 Particule semi-conductrice à trois couches WO2007145089A1 (fr)

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JP2008521150A JPWO2007145089A1 (ja) 2006-06-14 2007-06-01 ３層型半導体粒子

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JP2006164420 2006-06-14
JP2006-164420 2006-06-14

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008090814A1 (fr) * 2007-01-22 2008-07-31 Konica Minolta Medical & Graphic, Inc. Nanoparticule de semi-conducteur de type cœur/écorce et son procédé de fabrication
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
JP2009249507A (ja) * 2008-04-07 2009-10-29 Konica Minolta Medical & Graphic Inc 希土類元素ドープ蛍光体ナノ粒子、それを用いた生体物質標識剤
JP2010106119A (ja) * 2008-10-29 2010-05-13 Sharp Corp 半導体ナノ粒子蛍光体
JP2015191908A (ja) * 2014-03-27 2015-11-02 京セラ株式会社 量子ドット，光電変換層，光電変換装置
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

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JPH05224261A (ja) * 1992-02-10 1993-09-03 Canon Inc 非線形光学材料及びその製造方法
JP2005172429A (ja) * 2003-12-05 2005-06-30 Sony Corp 生体物質蛍光標識剤及び生体物質蛍光標識方法、並びにバイオアッセイ方法及び装置
EP1666562A2 (fr) * 2004-11-11 2006-06-07 Samsung Electronics Co., Ltd. Nanocristaux fusionné et méthode de leur préparation
JP2007077010A (ja) * 2005-09-12 2007-03-29 Samsung Electro Mech Co Ltd 多層シェルナノ結晶及びその製造方法
WO2007086188A1 (fr) * 2006-01-30 2007-08-02 Konica Minolta Medical & Graphic, Inc. Nanoparticule semi-conductrice triple couche et nanotige semi-conductrice triple couche

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JPH05224261A (ja) * 1992-02-10 1993-09-03 Canon Inc 非線形光学材料及びその製造方法
JP2005172429A (ja) * 2003-12-05 2005-06-30 Sony Corp 生体物質蛍光標識剤及び生体物質蛍光標識方法、並びにバイオアッセイ方法及び装置
EP1666562A2 (fr) * 2004-11-11 2006-06-07 Samsung Electronics Co., Ltd. Nanocristaux fusionné et méthode de leur préparation
JP2007077010A (ja) * 2005-09-12 2007-03-29 Samsung Electro Mech Co Ltd 多層シェルナノ結晶及びその製造方法
WO2007086188A1 (fr) * 2006-01-30 2007-08-02 Konica Minolta Medical & Graphic, Inc. Nanoparticule semi-conductrice triple couche et nanotige semi-conductrice triple couche

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008090814A1 (fr) * 2007-01-22 2008-07-31 Konica Minolta Medical & Graphic, Inc. Nanoparticule de semi-conducteur de type cœur/écorce et son procédé de fabrication
JP5151993B2 (ja) * 2007-01-22 2013-02-27 コニカミノルタエムジー株式会社 コア／シェル型半導体ナノ粒子とその製造方法
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
JP2009249507A (ja) * 2008-04-07 2009-10-29 Konica Minolta Medical & Graphic Inc 希土類元素ドープ蛍光体ナノ粒子、それを用いた生体物質標識剤
JP2010106119A (ja) * 2008-10-29 2010-05-13 Sharp Corp 半導体ナノ粒子蛍光体
JP2015191908A (ja) * 2014-03-27 2015-11-02 京セラ株式会社 量子ドット，光電変換層，光電変換装置
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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