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WO2008032618A1 - Nanoparticule semi-conductrice et procédé de production correspondant - Google Patents

Nanoparticule semi-conductrice et procédé de production correspondant Download PDF

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Publication number
WO2008032618A1
WO2008032618A1 PCT/JP2007/067279 JP2007067279W WO2008032618A1 WO 2008032618 A1 WO2008032618 A1 WO 2008032618A1 JP 2007067279 W JP2007067279 W JP 2007067279W WO 2008032618 A1 WO2008032618 A1 WO 2008032618A1
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WO
WIPO (PCT)
Prior art keywords
semiconductor
nanoparticles
semiconductor nanoparticles
core
nanoparticle
Prior art date
Application number
PCT/JP2007/067279
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English (en)
Japanese (ja)
Inventor
Kazuyoshi Goan
Kazuya Tsukada
Hideki Hoshino
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 JP2008534301A priority Critical patent/JP5131195B2/ja
Publication of WO2008032618A1 publication Critical patent/WO2008032618A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2054—Light-sensitive devices comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to semiconductor nanoparticles and a method for producing the same. More specifically, the present invention relates to a semiconductor nanoparticle having optical properties converted from an indirect transition type to a direct transition type and an increased quantum yield as a light emitting device, and a method for producing the same.
  • nanostructure crystals have attracted attention in II-VI group semiconductors such as ultrafine particles such as Si and Ge, and porous silicon.
  • the nanostructure crystal refers to a crystal grain having a nano-order particle size of about! ⁇ LOOnm, and is generally abbreviated as “nanoparticle” or “nanocrystal”.
  • semiconductors can be classified into two types according to the bandgap format.
  • the direct transition type (direct type: gallium arsenide, etc.) with simple light absorption and emission
  • the indirect transition type indirect type: silicon, etc.
  • crystalline silicon is an indirect transition type semiconductor with a band gap of 1. leV, and hydrogenated amorphous silicon varies depending on the hydrogen content, from 1.5 to 1.5; 1.7 eV! It is a direct transition type semiconductor with a band gap of /.
  • Solar cells made of amorphous silicon show an output voltage about 0.2-0.3% higher than crystalline silicon because of the deep band gap, whereas crystalline silicon is an indirect transition type.
  • the optical characteristics are poor and there are disadvantageous aspects in the manufacture of light emitting elements and the like.
  • nano-semiconductor particles are used as a light-emitting element, it is preferable to use Si, Ge, etc., which are low in raw material cost and have no concern about toxicity, as a semiconductor material component.
  • Si, Ge, etc. which are low in raw material cost and have no concern about toxicity, as a semiconductor material component.
  • semiconductors consisting of components are often indirect transition type, and the quantum yield is extremely low as a light emitting device material! It becomes a problem in practical use.
  • Patent Document 1 JP-A-5-82837
  • Patent Document 2 Japanese Patent Laid-Open No. 7-79050
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-303983
  • the present invention has been made in view of the above problems, and a solution to the problem is to convert the optical properties of semiconductor nanoparticles as a light emitting device material into an indirect transition type force direct transition type, and to obtain a quantum yield. It is providing the semiconductor nanoparticle which improved, and its manufacturing method.
  • a semiconductor nanoparticle and a method for producing the same in which the optical property of the semiconductor nanoparticle as a light emitting device material is converted from an indirect transition type to a direct transition type and the quantum yield is improved. Can be provided.
  • the semiconductor nanoparticles of the present invention are surface-modified semiconductor nanoparticles having an average particle diameter of 2 to 50 nm, and a tangential gradient force obtained by Tauc plot for the semiconductor nanoparticles. It is characterized in that it is 2 to 5 times the inclination of the tangent for Balta having the same chemical composition as the core of the particle.
  • the core part of the semiconductor nanoparticles of the present invention referred to herein means the center part of the nanoparticles whose surface has been modified, and is in agreement with the semiconductor nanoparticles before modification.
  • One semiconductor nanoparticle of the present invention is made of a semiconductor material and has an average particle diameter of 2 to 50 nm.
  • the tangential tilt force obtained by the Tauc plot for the semiconductor nanoparticles is a surface modified semiconductor nanoparticle of the same chemical composition as the core (semiconductor nanoparticle before modification) of the semiconductor nanoparticle. It is characterized by being 2 to 5 times the slope of the tangent to the crystal.
  • One of the preferred embodiments of the semiconductor nanoparticles of the present invention has a core / shell structure in which the semiconductor nanoparticles are composed of a core portion made of a semiconductor material and a shell portion (shell layer) covering the core portion.
  • So-called core / shell type semiconductor nanoparticles having an average particle diameter of 2 to 50 nm and a tangential gradient force obtained by Tauc plot for core / shell type semiconductor nanoparticles having a modified surface
  • the semiconductor nanoparticles It is characterized in that it is 2 to 5 times the inclination of the tangent line for a Balta crystal having the same chemical composition as the core part.
  • the "Tauc plot” is a method for obtaining an optical band gap from an electron spectrum generally used for amorphous semiconductors.
  • the relationship between absorbance and photon energy is expressed by the following equation.
  • ⁇ is the absorbance
  • ⁇ is the photon energy
  • ⁇ is the optical band gap
  • the horizontal axis represents photon energy
  • the vertical axis represents the square root of the product of absorbance and photon energy
  • a tangent line is drawn. The intersection of this tangent and the horizontal axis is the optical band gap (written by Tatsuo Shimizu “Amorphous Semiconductor”, Baifukan (1994) ⁇ ⁇ 201).
  • the "Balta crystal” here refers to a collection of particle crystals having a particle size of 1 Hm or more.
  • Average particle size refers to the cumulative 50% volume particle size measured by the laser scattering method.
  • the difference in slope between the tangent line obtained by Tauc plot and the linear approximation line is 5% for Balta crystals having the same composition as the core part of the semiconductor nanoparticles. Is preferably within.
  • the “linear approximation straight line” is the straight line obtained when linear approximation is performed for values in the range lower than the contact point between the Tauc plot and the obtained tangent line.
  • the Tauc plot of the indirect transition Balta crystal is almost straight, so the difference in slope between the tangent and the linear approximation line is within 5%.
  • the Balta crystal having the same composition as the core part of the semiconductor nanoparticles is used.
  • the core part of the core / shell type semiconductor nanoparticles is used.
  • the band gap is 0.2 to 1.5 eV higher than the band gap obtained by Tauc plot.
  • the core part of the semiconductor nanoparticle of the present invention or the semiconductor nanoparticle having a core / shell structure can be formed using various known semiconductor materials.
  • Examples of semiconductor materials used for the core include MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaTe, ZnS, ZnSe, ZnTe, CdS, CdSe,
  • a particularly preferable semiconductor material is Si or Ge.
  • the average particle size of the core part according to the present invention is preferably 1 to 40 nm in order to achieve the effect of the invention! More preferred! / ⁇ is 2-30nm.
  • the "average particle size" of the core according to the present invention refers to an accumulated 50% volume particle size measured by a laser scattering method.
  • the shell portion according to the present invention is a core / shell type semiconductor nanoparticle according to the present invention!
  • the shell portion according to the present invention may not completely cover the entire surface of the core particle as long as the core particle is not partially exposed to cause a harmful effect.
  • the semiconductor material used for the shell portion various known semiconductor materials can be used.
  • the column include ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaS, GaN, GaP, GaAs, GaSb, In As, InN, InP, InSb, AlAs, A1N, A1P, AlSb, or a mixture thereof can be used.
  • the semiconductor material is SiO or ZnS.
  • the production method of the liquid phase method includes a precipitation method such as a coprecipitation method, a sol-gel method, a uniform precipitation method, and a reduction method.
  • a precipitation method such as a coprecipitation method, a sol-gel method, a uniform precipitation method, and a reduction method.
  • the reverse micelle method, the supercritical hydrothermal synthesis method, and the like are also excellent methods for producing nanoparticles (for example, JP 2002-322468, JP 2005-239775, JP 10-10). (See 310770, JP 2000-104058, etc.).
  • the manufacturing method of the vapor phase method includes (1) a second high temperature generated by electrodeless discharge in a reduced-pressure atmosphere by evaporating the opposing raw material semiconductor by the first high-temperature plasma generated between the electrodes.
  • a laser ablation method for example, see Japanese Patent Application Laid-Open No. 2004-356163.
  • a method of synthesizing powder containing particles by reacting a raw material gas in a gas phase in a low pressure state is also preferably used.
  • the method for producing semiconductor nanoparticles or core / shell type semiconductor nanoparticles according to the present invention is preferably a production method in which core particles are produced by a liquid phase method, and then the particles are coated with a shell material.
  • the surface treatment of the semiconductor nanoparticles is performed in a gas atmosphere such as an oxygen atmosphere, an argon atmosphere, a nitrogen atmosphere, or a nitrogen + hydrogen atmosphere. It is necessary to optimize the conditions in order to satisfy the conditions of the tangential slope obtained by the Tauc plot.
  • TOAB tetraoctyl ammonium bromide
  • the particle size of the silicon nanoparticles can be adjusted by the ratio of SiCl and TOAB.
  • SiCl TOAB average particle size
  • Si nanoparticles d 1 100 2nm
  • the Si nanoparticles a to d are dispersed in a colloidal silica containing silicon dioxide (PL-3 manufactured by Fuso Chemical Industry Co., Ltd.) and potassium hydroxide mixed with pure water to adjust the liquid volume to 1500 ml.
  • a colloidal silica containing silicon dioxide PL-3 manufactured by Fuso Chemical Industry Co., Ltd.
  • potassium hydroxide mixed with pure water to adjust the liquid volume to 1500 ml.
  • the dispersion was allowed to stay at 200 ° C for 5 minutes using a spray pyrolysis apparatus to cover the SiO shell layer, and powders of Si / SiO core / shell nanoparticles A to D were obtained. .
  • the obtained Si nanoparticles a to d and Si / SiO core / shell nanoparticles A to D coated with a shell layer on each were subjected to the following conditions: oxygen atmosphere, argon atmosphere, nitrogen atmosphere, nitrogen + 1% hydrogen atmosphere. Instead, the surface of the nanoparticles was modified at 900 ° C. for 10 minutes in a spray pyrolysis apparatus.
  • FIG. 1 shows an example of a Tauc plot. 1 is a Tauc plot of a Si Balta crystal, and 2 is a Tauc plot of a sample whose surface was modified by heat-treating Si nanoparticle c in a nitrogen atmosphere, each showing its tangent line.
  • Fluorescence quantum yield A fluorescence spectrum generated by irradiating the obtained sample with excitation light having a wavelength of 350 nm was measured. The quantum yield is obtained by comparing the molar absorption coefficient obtained from the absorption spectrum of the sample, the wavenumber integral value of the fluorescence spectrum, and the refractive index of the solvent with a standard substance (rhodamine B, anthracene, etc.) with a known quantum yield. It was.
  • ⁇ ⁇ is the refractive index of the solvent of the standard material
  • ⁇ cd is the absorbance of the sample
  • F is the integral of the wave number of the standard material
  • n is the refractive index of the solvent of the standard material
  • ⁇ cd is This is the absorbance of the standard substance.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Luminescent Compositions (AREA)
  • Silicon Compounds (AREA)

Abstract

Cette invention concerne une nanoparticule semi-conductrice qui permet non seulement de modifier les propriétés optiques d'une nanoparticule semi-conductrice, telle qu'un matériau pour dispositif électroluminescent, d'un type de transition indirecte vers un type de transition directe, mais aussi d'obtenir un rendement quantique. Cette invention concerne également un procédé permettant de produire une telle nanoparticule. La nanoparticule semi-conductrice consiste en une nanoparticule dont le diamètre moyen est compris entre 2 et 50 nm et dont la surface est modifiée, cette nanoparticule se caractérise par un gradient tangentiel obtenu par un schéma Tauc par rapport à la nanoparticule semi-conductrice comprise entre 2 et 5 fois le gradient tangentiel du cristal en vrac de la même composition chimique que celle de la portion noyau de la nanoparticule semi-conductrice.
PCT/JP2007/067279 2006-09-15 2007-09-05 Nanoparticule semi-conductrice et procédé de production correspondant WO2008032618A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008534301A JP5131195B2 (ja) 2006-09-15 2007-09-05 半導体ナノ粒子とその製造方法

Applications Claiming Priority (2)

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JP2006250712 2006-09-15
JP2006-250712 2006-09-15

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WO2008032618A1 true WO2008032618A1 (fr) 2008-03-20

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009280766A (ja) * 2008-05-26 2009-12-03 Sharp Corp インク組成物
JP2014135405A (ja) * 2013-01-11 2014-07-24 Shimadzu Corp 半導体物質の光学的バンドギャップの算出方法及び算出装置
JP5686096B2 (ja) * 2009-05-08 2015-03-18 コニカミノルタ株式会社 量子ドット内包シリカナノ粒子、その製造方法、およびそれを用いた生体物質標識剤

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2005101601A (ja) * 2003-09-09 2005-04-14 Samsung Electronics Co Ltd 半導体ナノ結晶の表面処理による量子効率の向上
JP2006508012A (ja) * 2002-08-13 2006-03-09 マサチューセッツ・インスティテュート・オブ・テクノロジー 半導体ナノクリスタルヘテロ構造体
JP2006176859A (ja) * 2004-12-24 2006-07-06 Canon Anelva Corp シリコンナノ結晶構造体の作製方法
WO2007034657A1 (fr) * 2005-09-22 2007-03-29 Konica Minolta Medical & Graphic, Inc. Matériau fluorescent finement particulaire et son procédé de production
JP2007106832A (ja) * 2005-10-12 2007-04-26 Konica Minolta Medical & Graphic Inc 蛍光体の製造方法及びその方法によって製造された蛍光体
WO2007086267A1 (fr) * 2006-01-27 2007-08-02 Konica Minolta Medical & Graphic, Inc. Nanoparticule semi-conductrice présentant une structure noyau/enveloppe et son procédé de fabrication

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2006508012A (ja) * 2002-08-13 2006-03-09 マサチューセッツ・インスティテュート・オブ・テクノロジー 半導体ナノクリスタルヘテロ構造体
JP2005101601A (ja) * 2003-09-09 2005-04-14 Samsung Electronics Co Ltd 半導体ナノ結晶の表面処理による量子効率の向上
JP2006176859A (ja) * 2004-12-24 2006-07-06 Canon Anelva Corp シリコンナノ結晶構造体の作製方法
WO2007034657A1 (fr) * 2005-09-22 2007-03-29 Konica Minolta Medical & Graphic, Inc. Matériau fluorescent finement particulaire et son procédé de production
JP2007106832A (ja) * 2005-10-12 2007-04-26 Konica Minolta Medical & Graphic Inc 蛍光体の製造方法及びその方法によって製造された蛍光体
WO2007086267A1 (fr) * 2006-01-27 2007-08-02 Konica Minolta Medical & Graphic, Inc. Nanoparticule semi-conductrice présentant une structure noyau/enveloppe et son procédé de fabrication

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009280766A (ja) * 2008-05-26 2009-12-03 Sharp Corp インク組成物
JP5686096B2 (ja) * 2009-05-08 2015-03-18 コニカミノルタ株式会社 量子ドット内包シリカナノ粒子、その製造方法、およびそれを用いた生体物質標識剤
US9023659B2 (en) 2009-05-08 2015-05-05 Konica Minolta Medical & Graphic, Inc. Silica nanoparticle embedding quantum dots, preparation method thereof and biosubstance labeling agent by use thereof
JP2014135405A (ja) * 2013-01-11 2014-07-24 Shimadzu Corp 半導体物質の光学的バンドギャップの算出方法及び算出装置

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Publication number Publication date
JPWO2008032618A1 (ja) 2010-01-21
JP5131195B2 (ja) 2013-01-30

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