WO2013146872A1 - Structure de type assemblage de nanoparticules semi-conductrices - Google Patents

Structure de type assemblage de nanoparticules semi-conductrices Download PDF

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WO2013146872A1
WO2013146872A1 PCT/JP2013/058984 JP2013058984W WO2013146872A1 WO 2013146872 A1 WO2013146872 A1 WO 2013146872A1 JP 2013058984 W JP2013058984 W JP 2013058984W WO 2013146872 A1 WO2013146872 A1 WO 2013146872A1
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semiconductor
semiconductor nanoparticles
nanoparticles
semiconductor nanoparticle
nanoparticle
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PCT/JP2013/058984
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English (en)
Japanese (ja)
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満 関口
敬三 高野
高橋　優
中野　寧
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コニカミノルタ株式会社
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Priority to JP2014501123A priority Critical patent/JP5556973B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors

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  • the present invention relates to a semiconductor nanoparticle integrated structure having high emission luminance.
  • fluorescent dyes have been used as phosphors.
  • fluorescent dyes are organic materials, and there has been a problem that the luminance decreases when irradiated with excitation light for a long time, that is, the light resistance is poor.
  • the current trend is to apply semiconductor nanoparticles having a simple structure with an inorganic material, which have no problem of light resistance, to this field.
  • the semiconductor nanoparticles are such that when the semiconductor particles are reduced to a nano size, the band gap becomes smaller than that of the bulk and the quantum effect is strengthened, resulting in fluorescence.
  • materials such as II-VI group semiconductor nanoparticles, CdSe, CdTe, III-V group semiconductor nanoparticles, InP, GaP, I-III-VI group CuInS 2 and the like have been developed.
  • these materials are used as a core, and a shell such as ZnS having a larger band gap is formed on the outer side to improve the electron confinement effect and increase the luminous efficiency of the semiconductor nanoparticles themselves. Things have been done.
  • Non-Patent Document 1 a method for increasing the luminance per particle by integrating semiconductor nanoparticles to form giant particles of 50 to 1000 nm.
  • One method for producing such giant particles is a method of encapsulating semiconductor nanoparticles in silica beads using a hydrolysis reaction of a silica precursor based on the Stober method (see Non-Patent Document 1).
  • Non-Patent Document 2 has attempted to encapsulate CdSe / ZnS semiconductor nanoparticles in silica beads by reacting with tetraethylorthosilicate (TEOS) in the presence of tri-n-octylphosphine oxide (TOPO). It is disclosed.
  • TEOS tetraethylorthosilicate
  • TOPO tri-n-octylphosphine oxide
  • Non-Patent Document 3 discloses poly (allylamine hydrochloride) (PAH) and poly (sodium 4-styrenesulfonate) (PSS) as a method of laminating CdTe on the surface of silica colloidal crystal beads.
  • PAH poly (allylamine hydrochloride)
  • PSS poly (sodium 4-styrenesulfonate)
  • a method of alternately laminating a PAH / PSS / PAH laminated body made of) and layers made of CdTe is disclosed.
  • the invention described in Non-Patent Document 3 intends to increase the emission intensity by utilizing the high porosity and high surface area to volume ratio of silica colloidal crystal beads.
  • FIG. 2 shows the absorption of nanoparticles constituting a CdSe / ZnS semiconductor nanoparticle assembly widely used as a core / shell type semiconductor nanoparticle assembly. An emission spectrum is shown. As shown in FIG.
  • the present invention has been made in view of the above problems, and an object of the present invention is to obtain a high-brightness semiconductor nanoparticle integrated structure in which a decrease in luminance is small even when semiconductor nanoparticles are integrated.
  • the first semiconductor nanoparticles are: The semiconductor nanoparticle integrated structure according to [1], wherein the first semiconductor nanoparticle has a band gap that is equal to or greater than the half-value width of the emission peak wavelength of the first semiconductor nanoparticle and smaller than the second semiconductor nanoparticle.
  • the first semiconductor nanoparticles include The semiconductor nanoparticle integrated structure according to [1] or [2], which has an emission peak wavelength longer than that of the second semiconductor nanoparticle.
  • the difference between the emission peak wavelength of the first semiconductor nanoparticles and the emission peak wavelength of the second semiconductor nanoparticles is equal to or greater than the half-value width of the emission peak wavelength of the first semiconductor nanoparticles.
  • the core portion and the shell portion constituting the first semiconductor nanoparticles are each made of the same material as the core portion and the shell portion constituting the second semiconductor nanoparticles, and The semiconductor nanoparticle integrated structure according to [5], wherein the core part constituting the first semiconductor nanoparticles has a larger volume average diameter than the core part constituting the second semiconductor nanoparticles.
  • the difference between the volume average diameter of the core part constituting the first semiconductor nanoparticles and the volume average diameter of the core part constituting the second semiconductor nanoparticles is:
  • the semiconductor nanoparticle integrated structure according to [6] which is equal to or more than the half-value width of the emission peak wavelength of the core portion constituting the first semiconductor nanoparticle.
  • FIG. 6 is a cross-sectional view illustrating a manufacturing process of the semiconductor nanoparticle integrated structure shown in Example 1.
  • FIG. 6 is a cross-sectional view illustrating a manufacturing process of a semiconductor nanoparticle integrated structure shown in Example 2.
  • FIG. It is a figure which shows the relationship of the band gap of two types of core-shell type semiconductor nanoparticles which comprise the semiconductor nanoparticle integrated structure of an Example description. It is a figure which shows the definition of the core diameter in the core-shell type semiconductor nanoparticle which comprises the semiconductor nanoparticle integrated structure of an Example description.
  • a semiconductor nanoparticle integrated structure 10 includes: An internal structure in which a plurality of first semiconductor nanoparticles 11 are integrated; An external structure formed by integrating a plurality of second semiconductor nanoparticles 14 covering the internal structure, The first semiconductor nanoparticles 11 have a smaller band gap than the second semiconductor nanoparticles 14.
  • the present invention is characterized in that the first semiconductor nanoparticle 11 has a smaller band gap than the second semiconductor nanoparticle 14 in order to minimize concentration quenching of fluorescence emitted from the semiconductor nanoparticle.
  • the semiconductor nanoparticle assembly structure 10 includes two semiconductor nanoparticles having different band gaps, that is, a first semiconductor nanoparticle 11 and a second semiconductor nanoparticle 14.
  • the first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14 constituting the semiconductor nanoparticle integrated structure 10 are “nanoparticles arranged inside the integrated body” and “outside the integrated body”, respectively.
  • Nanoparticles ”.
  • the band gaps of the first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14 are: They are 2.30eV and 2.53eV respectively.
  • photons emitted from the first semiconductor nanoparticles 11 existing inside are energy of 2.30 eV, and energy that can be absorbed by the second semiconductor nanoparticles 14 present outside. Since it is smaller than 2.53 eV, the fluorescence from the first semiconductor nanoparticles 11 can be efficiently extracted outside without being absorbed by the second semiconductor nanoparticles 14.
  • the problem is how much difference is provided between the band gap of the first semiconductor nanoparticles 11 and the band gap of the second semiconductor nanoparticles 14, but the absorption spectrum is shorter than the peak wavelength. Therefore, it is considered effective to shift the band gap by half the width (FWHM: full peak width at half the peak value, that is, full width at half maximum) in terms of emission spectrum. That is, in the present invention, the first semiconductor nanoparticles 11 may have a band gap that is smaller than the second semiconductor nanoparticles 14 by a portion corresponding to the half-value width of the emission peak wavelength of the first semiconductor nanoparticles 11 or more. preferable.
  • the emission peak wavelength of the first semiconductor nanoparticles 11 is greater than the emission peak wavelength of the first semiconductor nanoparticles 11 compared to the emission peak wavelength of the second semiconductor nanoparticles 14. It is preferable that it is longer than the half-value width.
  • the second semiconductor nanoparticles 14 need only have an emission peak wavelength that is smaller than the emission peak wavelength of the first semiconductor nanoparticles 11 by the half-value width thereof.
  • the emission wavelength tends to become longer as the particle size increases.
  • the semiconductor nanoparticles are core-shell semiconductor nanoparticles
  • the emission wavelength tends to increase as the diameter of the core portion (core diameter) increases. This tendency is also confirmed from the relationship between the core diameter and the emission wavelength of the CdSe / ZnS semiconductor nanoparticles shown in FIG.
  • the band gap tends to decrease as the particle size increases.
  • the semiconductor nanoparticles are core-shell semiconductor nanoparticles, There is a tendency to decrease as the core diameter increases.
  • the first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14 are formed of the same semiconductor, the first semiconductor nanoparticles 11 have a smaller band gap than the second semiconductor nanoparticles 14.
  • the average diameter of the first semiconductor nanoparticles 11 may be selected so as to be larger than the average diameter of the second semiconductor nanoparticles 14.
  • the core portion and the shell portion constituting the first semiconductor nanoparticles 11 are the second
  • the core portion constituting the first semiconductor nanoparticle 11 constitutes the second semiconductor nanoparticle 14.
  • the average diameter is larger than that of the core portion.
  • “average diameter” refers to a volume average diameter unless otherwise specified.
  • the second semiconductor nanoparticles 14 need only have a light emission peak wavelength that is smaller than the light emission peak wavelength of the first semiconductor nanoparticles 11 by the half width. What is necessary is just to change the particle size of the 2nd semiconductor nanoparticle 14 according to it.
  • the second semiconductor nanoparticle 14 corresponds to the emission peak wavelength of the first semiconductor nanoparticle 11.
  • the core diameter of the second semiconductor nanoparticles 14 may be set so that the emission peak wavelength is smaller by the half width.
  • the difference between the average diameter of the core part constituting the first semiconductor nanoparticles 11 and the average diameter of the core part constituting the second semiconductor nanoparticles 14 constitutes the first semiconductor nanoparticles 11. This is equal to or greater than the half-value width of the emission peak wavelength of the core portion.
  • the core diameter of the second semiconductor nanoparticles 14 is set in this way if there is a characteristic curve as exemplified in FIG.
  • the emission peak wavelength of the first semiconductor nanoparticles 11 is 540 nm
  • the core size is 3.7 nm from FIG.
  • the difference between the band gap of the second semiconductor nanoparticles 14 and the band gap of the first semiconductor nanoparticles 11 may be the half width at the emission peak of the first semiconductor nanoparticles 11.
  • the two emission peaks do not overlap and the emission wavelength region is widened, which is disadvantageous in terms of detection. Therefore, based on a simplified model, the range in which the emission peak of the first semiconductor nanoparticles 11 and the emission peak of the second semiconductor nanoparticles 14 can overlap is examined.
  • the emission peak of the first semiconductor nanoparticles 11 and the emission peak of the second semiconductor nanoparticles 14 have center wavelengths of ⁇ 11 and ⁇ 14 , respectively, and have the same peak height and peak width. And both have a peak shape (standard deviation ⁇ with respect to peak broadening) following a normal distribution.
  • the emission peak of the first semiconductor nanoparticle 11 is 99.7% of the peak distributed within the range of 3 ⁇ on one side from the center wavelength, that is, within the range of the wavelength ⁇ 11 ⁇ 3 ⁇ .
  • 99.7% of the peak is distributed within the wavelength range of ⁇ 14 ⁇ 3 ⁇ .
  • the wavelength of the first semiconductor nanoparticles 11 is between ⁇ 11 ⁇ 3 ⁇ and the wavelength of the second semiconductor nanoparticles 14 is between ⁇ 14 ⁇ 3 ⁇ .
  • there is an overlapping portion that is, the distance between the peaks ( ⁇ 11 ⁇ 14 ) and the standard deviation ⁇ of the peak width have a relationship satisfying the following formula (1a).
  • the first semiconductor nanoparticle 11 has a light emission peak wavelength of the first semiconductor nanoparticle 11 as compared with the second semiconductor nanoparticle 14.
  • the first semiconductor nanoparticles 11 have a band gap that is smaller than the half-value width of the first semiconductor nanoparticles 11, that is, the emission peak wavelength of the first semiconductor nanoparticles 11 is larger than the emission peak wavelength of the second semiconductor nanoparticles 14. Is longer than the half-value width of the emission peak wavelength (that is, F H ⁇ ( ⁇ 11 ⁇ 14 ) is satisfied), the distance between the peaks ( ⁇ 11 ⁇ 14 ) is generally expressed by the following formula ( The relationship represented by 2) is preferred.
  • the first semiconductor nanoparticle is equal to or larger than the half-value width of the emission peak wavelength of the first semiconductor nanoparticle than the second semiconductor nanoparticle.
  • the semiconductor nanoparticles constituting the semiconductor nanoparticle integrated structure 10 of the present invention are both the first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14 in the semiconductor nanoparticle integrated structure 10 from the outside. It has the role of emitting fluorescence in the process of being excited by receiving given energy and returning from the excited state to the ground state.
  • the first semiconductor nanoparticles 11 have a smaller band gap than the second semiconductor nanoparticles 14.
  • the semiconductor constituting the semiconductor nanoparticles used in the present invention is preferably a semiconductor having a band gap that causes fluorescence emission from the visible region to the near infrared region, and specifically, a range of 200 to 700 nm. When excited by ultraviolet to visible light having an inner wavelength, it preferably emits visible to near infrared light having a wavelength in the range of 400 to 900 nm.
  • inorganic semiconductors of II-VI group, III-V group, III-VI group, IV group, IV-VI group and I-III-VI group are preferably used.
  • III-V group inorganic semiconductors AlN, AlP, AlAs, GaN, GaP, GaAs, InN, InP, InAs, InGaP and InGaAs are suitable examples of III-VI group inorganic semiconductors, and Al 2 Se 3 is a suitable example of group IV inorganic semiconductors.
  • PbS, PbSe, and PbTe are preferable examples of inorganic semiconductors of Si, Ge, and IV-VI
  • CuInS 2 is preferable as a preferable example of inorganic semiconductors of the I-III-VI group.
  • the semiconductor nanoparticles used in the present invention may have a uniform structure as a whole in both the first semiconductor nanoparticles 1 and the second semiconductor nanoparticles 4, or two or more different constituent components may be used. You may have a structure, or you may have a structure where the composition of a component changes continuously with a position.
  • Core-shell type semiconductor nanoparticles As the semiconductor nanoparticles constituting the present invention, it is desirable to use semiconductor nanoparticles having a core / shell structure, that is, core-shell type semiconductor nanoparticles.
  • the core-shell type is a particle containing a semiconductor material to be described later, and is a particle having a multiple structure composed of a core part (core part) and a shell part (covering part) covering the core part. Usually, it is approximately 20 nm or less.
  • Core portion also referred to as “core particle”
  • Materials for forming the core portion include Si, Ge, InN, InP, GaAs, AlSe, CdSe, AlAs, GaP, ZnTe, CdTe, InAs, and CuInS 2
  • a semiconductor such as the above or a raw material for forming these can be used.
  • InP, CdTe, CdSe, and CuInS 2 are particularly preferably used.
  • the average particle size of the core portion (“core particle”) according to the present invention is preferably 0.5 to 15 nm.
  • II-VI group, III-V group, and IV group inorganic semiconductors can be used as a material for forming the shell portion according to the present invention.
  • a semiconductor having a larger band gap than each core-forming inorganic material such as Si, Ge, InN, InP, GaAs, AlSe, CdSe, AlAs, GaP, ZnTe, CdTe, InAs, etc. Is preferred.
  • ZnS is applied as a shell to InP, CdTe, CdSe, CuInS 2 .
  • 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, or the semiconductor nanoparticle without the shell portion. It may be.
  • the average particle size of the core / shell structure semiconductor nanoparticle according to the present invention is preferably 1 to 20 nm.
  • the internal structure is formed by integrating the plurality of first semiconductor nanoparticles 11, and the external structure is integrated with the plurality of second semiconductor nanoparticles 14. Do it.
  • the semiconductor nanoparticle integrated structure 10 has a structure as shown in FIG.
  • the internal structure has a form of a semiconductor nanoparticle assembly 12 in which a plurality of first semiconductor nanoparticles 11 are integrated while being encapsulated by a matrix 17.
  • stacked is formed as an external structure so that the surface of this semiconductor nanoparticle integrated body 12 may be covered.
  • the matrix 17 has a role as a binder for fixing the accumulated first semiconductor nanoparticles 11, and silica, polymelamine, polystyrene, or the like is preferably used as the material thereof.
  • the semiconductor nanoparticle assembly 12 preferably has an average diameter of about 30 to 500 nm, and preferably contains as many first semiconductor nanoparticles 11 as possible so that the particles do not touch each other. .
  • the semiconductor nanoparticle integrated structure 10 has a structure as shown in FIG.
  • the internal structure includes a support core structure 16 that does not include semiconductor nanoparticles therein, and a plurality of first semiconductor nanoparticles so as to cover the surface of the support core structure 16.
  • 11 has a form in which a first semiconductor nanoparticle integrated layer formed by integrating 11 is formed.
  • stacked is formed as an external structure so that the surface of this internal structure may be covered.
  • the support core structure 16 has a role as a base for forming the first semiconductor nanoparticle integrated layer and the second semiconductor nanoparticle integrated layer, and ensures a high surface area to volume ratio. It has the role of increasing the emission intensity.
  • a dielectric such as silica particles, or a polymer such as polymelamine or polystyrene is preferably used.
  • the support core structure 16 preferably has an average diameter of about 30 to 500 nm.
  • the semiconductor nanoparticle integrated structure 10 of the present invention has one internal structure and one external structure, but the present invention covers this external structure.
  • the semiconductor nanoparticle integrated structure 10 of the present invention may have a plurality of external structures by further forming the second external structure formed by integrating semiconductor nanoparticles.
  • the semiconductor nanoparticles constituting the second external structure may be the second semiconductor nanoparticles 14 or a third semiconductor having a larger band gap than the second semiconductor nanoparticles 14.
  • Nanoparticles may be used. Therefore, the semiconductor nanoparticle integrated structure 10 of the present invention is configured so that the band gap of the constituent semiconductor nanoparticles gradually increases from the inside toward the outside, in other words, the emission peak of the constituent semiconductor nanoparticles from the inside toward the outside.
  • the external structure may be laminated so that the wavelength is gradually shortened.
  • the internal structure and these external structures are composed of core-shell type semiconductor nanoparticles having the same constituent semiconductor material
  • the external structure is configured so that the core diameter of the constituent semiconductor nanoparticles decreases from the inside toward the outside.
  • the body may be laminated.
  • the semiconductor nanoparticle integrated structure 10 of the present invention preferably has an average diameter in the range of 50 to 1000 nm.
  • the support core structure 16 and the first semiconductor nanoparticle assembly A bonding layer 13 may be provided between the stacked layers. The presence of such a bonding layer 13 is preferable because the bonding between the inner structure and the outer structure and the bonding between the support core structure 16 and the first semiconductor nanoparticle integrated layer are strengthened.
  • a bonding layer 13 for example, a PAH / PSS / PAH layer in which PAH (polyallylamine hydrochloride) and PSS (polysodium 4-styrene sulfonate) are laminated in the order of PAH, PSS, and PAH is preferably used. Can be used.
  • the semiconductor nanoparticle integrated structure 10 of the present invention is used for the purpose of introducing a functional group used for bonding with other molecules, for the purpose of improving hydrophilicity, or for the semiconductor nanoparticle.
  • a surface layer 15 may be further provided on the outermost periphery. Therefore, such a surface layer 15 may have a functional group such as a carboxyl group, an amino group, or a hydroxyl group.
  • a hydrophilic layer having a carboxyl group can be provided as the surface layer 15 by providing a layer made of PAA (polyacrylic acid) via a PAH / PSS / PAH layer.
  • the semiconductor nanoparticle integrated structure 10 which concerns on this invention can be manufactured using a conventionally well-known method.
  • a liquid phase method can be suitably used as a method for producing the first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14 constituting the semiconductor nanoparticle integrated structure 10.
  • each semiconductor constituting these semiconductor nanoparticles is obtained by chemically reacting a corresponding semiconductor precursor in an appropriate solvent.
  • the production method based on the liquid phase method include a precipitation method, 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 10-310770 A). No., JP 2000-104058 A, etc.).
  • the production method includes a step of reducing the semiconductor precursor by a reduction reaction. It is also preferable that there is.
  • an embodiment having a step of performing the reaction of the semiconductor precursor in the presence of a surfactant is preferable.
  • the formed first semiconductor nanoparticles 11 and second semiconductor nanoparticles 14 (and the core portion constituting these semiconductor nanoparticles, if applicable) do not inadvertently aggregate during the reaction process.
  • An embodiment having a step performed in the presence of a stabilizer such as tri-n-octylphosphine oxide (TOPO) is preferable.
  • the semiconductor precursor used in the present invention is a compound containing an element used as the semiconductor material, for example if the semiconductor is Si, and the like SiCl 4 as semiconductor precursor.
  • Other semiconductor precursors include InCl 3 , P (SiMe 3 ) 3 , ZnMe 2 , CdMe 2 , GeCl 4 , tributylphosphine selenium and the like.
  • the reaction temperature for introducing the semiconductor precursor from the semiconductor precursor to the required semiconductor is not particularly limited as long as it is not lower than the boiling point of the semiconductor precursor and not higher than the boiling point of the solvent, but is preferably in the range of 70 to 110 ° C.
  • the reducing agent for reducing the semiconductor precursor various conventionally known reducing agents can be selected and used according to the reaction conditions.
  • lithium aluminum hydride LiAlH 4
  • sodium borohydride NaBH 4
  • sodium bis (2-methoxyethoxy) aluminum hydride trihydride
  • trihydride sec- Preferred are reducing agents such as lithium (butyl) boron (LiBH (sec-C 4 H 9 ) 3 ), potassium tri (sec-butyl) borohydride, lithium triethylborohydride.
  • lithium aluminum hydride (LiAlH 4 ) is preferable because of its reducing power.
  • solvent Various known solvents can be used as the solvent for dispersing the semiconductor precursor. Alcohols such as ethyl alcohol, sec-butyl alcohol and t-butyl alcohol, and hydrocarbon solvents such as toluene, decane and hexane are used. It is preferable to use it. In the present invention, a hydrophobic solvent such as toluene is particularly preferable as the dispersion solvent.
  • surfactant As the surfactant, various conventionally known surfactants can be used, and anionic, nonionic, cationic, and amphoteric surfactants are included. Of these, tetrabutylammonium chloride, bromide or hexafluorophosphate, tetraoctylammonium bromide (TOAB), or tributylhexadecylphosphonium bromide, which are quaternary ammonium salt systems, are preferred. Tetraoctyl ammonium bromide is particularly preferable.
  • the reaction by the liquid phase method varies greatly depending on the state of the compound containing the solvent in the liquid.
  • special care must be taken.
  • the size and state of the reverse micelle serving as a reaction field vary depending on the concentration and type of the surfactant, so that the conditions under which nanoparticles are formed are limited. Therefore, it is necessary to appropriately combine the surfactant and the solvent.
  • a gas phase method may be used as a method for producing the first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14.
  • the opposing raw material semiconductor is evaporated by the first high temperature plasma generated between the electrodes, and in the second high temperature plasma generated by electrodeless discharge in a reduced pressure atmosphere.
  • a method of separating and removing nanoparticles from an anode made of a raw material semiconductor by electrochemical etching for example, see Japanese Patent Application Laid-Open No. 2003-515459).
  • a method of synthesizing a powder containing particles by reacting a raw material gas in a gas phase in a low pressure state is also preferably used.
  • the semiconductor nanoparticle can also be purchased by designating the light emission wavelength. In the embodiment described later, a case of purchasing is shown.
  • Integration of Semiconductor Nanoparticles the semiconductor nanoparticles (that is, the first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14) are integrated when the semiconductor nanoparticle integrated structure 10 is constructed. There is a need to.
  • the obtained first semiconductor nanoparticles 11 are integrated by an appropriate method to thereby obtain an internal structure.
  • the obtained second semiconductor nanoparticles 14 are applied to the surface of the internal assembly by an appropriate method.
  • An external structure can be formed by stacking.
  • an assembly in which the plurality of first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14 are in contact with each other is directly used as an internal structure and an external structure without constructing a matrix. Each may be used.
  • the first semiconductor nanoparticles 11 and the second semiconductor nanoparticles 14 are aggregated by an appropriate method to form an aggregate precursor once.
  • the internal structure and the external structure are respectively constructed by forming a matrix on the integrated body precursor by a method such as the liquid phase method.
  • the “aggregate precursor” refers to an aggregate in which a plurality of semiconductor nanoparticles are gathered in contact with each other.
  • the external structure it may be formed directly on the surface of the internal structure, but from the viewpoint of strengthening the bond between the external structure and the internal structure, first, the surface of the internal structure is formed. It is preferable to construct the external layer on the surface of the bonding layer 13 after the coupling layer 13 is constructed by a conventionally known appropriate method.
  • a method for manufacturing the semiconductor nanoparticle integrated structure 10 according to the first preferred embodiment will be described.
  • silica can be suitably used as the material constituting the matrix 17, and in that case, the Stover method based on the method described in Non-Patent Document 1 can be used to construct the matrix 17 made of silica.
  • the method described in Non-Patent Document 2 can be cited.
  • CdSe / ZnS semiconductor nanoparticles are dispersed in a TOPO toluene solution.
  • TEOS is added to this solution to silanize the semiconductor nanoparticles.
  • a silica sphere of about 50 nm containing about 20 semiconductor particles is obtained as the semiconductor nanoparticle aggregate 12.
  • This silica sphere corresponds to the semiconductor nanoparticle silica aggregate in the semiconductor nanoparticle assembly structure 10 according to the first preferred embodiment.
  • a second semiconductor nanoparticle integrated layer in which semiconductor nanoparticles having a larger band gap than the first semiconductor nanoparticles 11 integrated inside (that is, the second semiconductor nanoparticles 14) are integrated on the outside.
  • the external structure can be constructed by a conventionally known appropriate method, but in this example, a growth method called Layer-by-Layer method can be suitably used.
  • a specific method for constructing such a second semiconductor nanoparticle integrated layer for example, the method described in Non-Patent Document 3 can be cited.
  • PAH polyallylamine hydrochloride
  • PSS polysodium 4-styrenesulfonate
  • the silica spheres prepared above are treated with a piranha solution (30% H 2 O 2 + 70% H 2 SO 4 ) to charge the silica spheres negatively.
  • a piranha solution (30% H 2 O 2 + 70% H 2 SO 4 ) to charge the silica spheres negatively.
  • PAH polyallylamine hydrochloride
  • PSS polysodium 4-styrene sulfonate
  • PAA polyacrylic acid
  • a PAH / PSS / PAA solution is sequentially added to the negatively charged silica spheres to form a PAH / PSS / PAH layer as a bonding layer 13 on the silica spheres. Let it be the body.
  • the silica intermediate structure is dispersed in an aqueous solution of CdSe / ZnS semiconductor nanoparticles capped with mercaptopropionic acid, so that CdSe / with a band gap larger than that of the first semiconductor nanoparticles 11 accumulated on the inner side.
  • a second semiconductor nanoparticle integrated layer in which ZnS is integrated can be formed as an external structure.
  • the CdSe / ZnS semiconductor nanoparticles used at this stage are CdSe / ZnS semiconductor nanoparticles having a larger band gap than the CdSe / ZnS semiconductor nanoparticles used as the first semiconductor nanoparticles 11.
  • the semiconductor nanoparticle integrated structure 10 is formed by the Stover method for the inside of the semiconductor nanointegrated body and the layer by layer method for the outside. It is not limited to such a method, You may carry out by another method.
  • the semiconductor nanoparticle assembly structure 10 is formed with the above-described second semiconductor nanoparticle assembly layer on the surface of the support core structure 16 made of a suitable material such as silica and not containing semiconductor nanoparticles.
  • a first semiconductor nanoparticle assembly layer in which a plurality of first semiconductor nanoparticles 11 are integrated is formed by a method similar to that used to construct an internal structure, and then its surface.
  • an external structure including a second semiconductor nanoparticle integrated layer in which a plurality of second semiconductor nanoparticles 14 having a larger band gap than the first semiconductor nanoparticles 11 are integrated (see FIG.
  • a layer-by-layer method can be suitably used for the first semiconductor nanoparticle integrated layer and the second semiconductor nanoparticle integrated layer.
  • the bonding layer 13 such as a PAH / PSS / PAH layer by the same method as described above.
  • the semiconductor nanoparticle is integrated on the surface of the external structure formed as mentioned above.
  • Two external structures may be further formed.
  • the semiconductor nanoparticles constituting the second external structure may be the second semiconductor nanoparticles 14 or a third semiconductor having a larger band gap than the second semiconductor nanoparticles 14.
  • Nanoparticles may be used.
  • Such a second external structure can also be formed by a method similar to that of the external structure. Specifically, a new PAH / PSS / PAH layer is formed on the surface of the external structure formed by the above method by sequentially forming a PAH layer, a PSS layer, and a PAH layer. Thus, a series of steps of dispersing in the aqueous solution in which the semiconductor nanoparticles as the raw material of the second external structure are dispersed may be repeated.
  • the semiconductor nanoparticle integrated structure 10 obtained in this way may be used as it is, or may be further subjected to surface treatment to form a surface layer 15 such as a hydrophilic layer.
  • the formation of the surface layer 15 can be performed using an appropriate conventionally known method as in the case of the external structure. For example, after forming the PAH / PSS / PAH layer, the required surface layer 15 can be formed.
  • a hydrophilic layer is formed as the surface layer 15, the formation of the PAH layer, the formation of the PSS layer, and the formation of the PAH layer are performed on the outermost peripheral portion of the semiconductor nanoparticle integrated structure where the surface layer 15 is not yet formed.
  • a new PAH / PSS / PAH layer can be formed by sequentially performing the formation, and then a PAA layer can be formed by further performing a PAA treatment, whereby semiconductor nanoparticles having a carboxyl group on the surface
  • the integrated structure 10 can be obtained.
  • the semiconductor nanoparticle integrated structure 10 of the present invention is not particularly limited in its application, but can be suitably used for the application of a biomaterial labeling agent.
  • the biological substance labeling agent according to the present invention has a structure in which the semiconductor nanoparticle assembly structure 10 is bonded to a molecular labeling substance via an organic molecule.
  • the biological substance labeling agent according to the present invention by adding the biological substance labeling agent according to the present invention to a living cell or living body having a target (tracking) substance, it binds or adsorbs to the target substance, and the conjugate or adsorbent is excited at a predetermined wavelength.
  • fluorescence dynamic imaging of the target (tracking) substance can be performed.
  • the biomaterial labeling agent according to the present invention can be used for bioimaging methods (technical means for visualizing biomolecules constituting the biomaterial and dynamic phenomena thereof).
  • Hydrophilization treatment of the semiconductor nanoparticle assembly The surface of the semiconductor nanoparticle assembly structure 10 described above is generally hydrophobic in a state where the surface treatment has not yet been performed, and thus is used, for example, as a biological material labeling agent. In this case, there are problems such as poor water dispersibility and aggregation of semiconductor nanoparticle aggregates. Therefore, it is preferable to perform a hydrophilic treatment on the surface of the semiconductor nanoparticle assembly structure 10 to obtain a hydrophilic semiconductor nanoparticle assembly structure.
  • hydrophilic treatment method for example, a method of chemically and / or physically binding a surface modifier to the surface of the semiconductor nanoparticle assembly structure 10 after removing the lipophilic component attached to the surface with pyridine or the like.
  • a surface modifier those having a carboxyl group / amino group as a hydrophilic group are preferably used, and specific examples include mercaptopropionic acid, mercaptoundecanoic acid, aminopropanethiol and the like.
  • 10 ⁇ 5 g of Ge / GeO 2 type nanoparticles are dispersed in 10 ml of pure water in which 0.2 g of mercaptoundecanoic acid is dissolved, and stirred at 40 ° C. for 10 minutes to treat the surface of the shell.
  • the surface of the shell of the inorganic nanoparticles can be modified with a carboxyl group.
  • the biological substance labeling agent according to the present invention is obtained by binding the hydrophilic semiconductor nanoparticle assembly structure obtained as described above, a molecular labeling substance and an organic molecule.
  • the biological substance labeling agent according to the present invention can label a biological substance by specifically binding and / or reacting with the target biological substance.
  • the molecular labeling substance examples include nucleotide chains, antibodies, antigens, sugar chains, and cyclodextrins.
  • an antibody drug such as trastuzumab
  • the biological substance labeling agent according to the present invention confirms whether a cancer marker such as HER2 recognized by such an antibody drug is present in a tissue section or the like. Can be used for tissue staining.
  • the hydrophilic semiconductor nanoparticle integrated structure and the molecular labeling substance are bound by an organic molecule.
  • the organic molecule is not particularly limited as long as it is capable of binding the semiconductor nanoparticle aggregate and the molecular labeling substance.
  • the form of the bond is not particularly limited, and examples thereof include a covalent bond, an ionic bond, a hydrogen bond, a coordinate bond, physical adsorption, and chemical adsorption.
  • a bond having a strong bonding force such as a covalent bond is preferable from the viewpoint of bond stability.
  • the semiconductor nanoparticle integrated structure 10 is hydrophilized with mercaptoundecanoic acid
  • avidin and biotin can be used as organic molecules.
  • the carboxyl group of the hydrophilic semiconductor nanoparticle integrated structure is preferably covalently bonded to avidin, and the avidin is further selectively bonded to biotin, and biotin is further bonded to the molecular labeling substance, thereby Become.
  • Example 1 The semiconductor nanoparticle integrated structure according to Example 1 will be described with reference to FIG.
  • the present Example 1 comprises an internal structure in the state in which one of two semiconductor nanoparticles having different band gap energies is encapsulated in a semiconductor nanoparticle silica aggregate 2 as the semiconductor nanoparticle aggregate 12.
  • the external structure formed by integrating the other semiconductor nanoparticles is shown so as to cover the semiconductor nanoparticle silica aggregate 2.
  • the CdSe / ZnS particles may be synthesized as described in the above section “Mode for Carrying Out the Invention”, but in this Example 1, those purchased from Evident Technology Co. can be used.
  • the wavelength can be selected from 490, 520, 540, 560, 580, 600, 620 nm.
  • a CdSe / ZnS semiconductor nanoparticle having an emission wavelength of 540 nm is integrated as the first semiconductor nanoparticle 1 to construct a semiconductor nanoparticle silica aggregate 2.
  • 490 nm CdSe / ZnS semiconductor nanoparticles are integrated as the second semiconductor nanoparticles 4 to construct an external structure.
  • the semiconductor nanoparticle silica aggregate 2 is formed with reference to Non-Patent Document 2.
  • the obtained semiconductor nanoparticles are dispersed in a TOPO 0.1M (mol / L) toluene solution, stirred for about 15 hours, and the surface of CdSe / ZnS semiconductor nanoparticles is silanized using TEOS (tetraethoxysilane). Add ethanol, H 2 O, and ammonia, and reflux at 100 ° C. for 1 hour.
  • TEOS tetraethoxysilane
  • the ratio of the semiconductor particles, TEOS, toluene, ethanol, H 2 O, and NH 3 is 1,2.8 ⁇ 10 4 , 5.87 ⁇ 10 6 , 1.07 ⁇ 10 8 , 7.9 ⁇ as molar ratios, respectively. 10 7 and 7.17 ⁇ 10 5 . Finally, it was centrifuged for 30 minutes and dispersed again in H 2 O. As a result, a semiconductor nanoparticle silica aggregate 2 having a particle size of about 50 nm and containing about 20 CdSe / ZnS particles is formed.
  • CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm as the second semiconductor nanoparticles 4 are further accumulated outside the semiconductor nanoparticle silica aggregate 2 using the layer-by-layer method.
  • Non-Patent Document 3 it can be performed with reference to Non-Patent Document 3. That is, the semiconductor nanoparticle silica aggregate 2 prepared above is treated with a piranha solution (30% H 2 O 2 + 70% H 2 SO 4 ) to be negatively charged. Next, prepare 1 mg / mL PAH (polyallylamine hydrochloride), PSS (polysodium 4-styrenesulfonate) and PAA (polyacrylic acid) in 0.5 mol / L NaCl solution. . First, a PAH solution is added to 0.5 mL per about 100 negatively charged semiconductor nanoparticle silica aggregates 2, absorbed for 20 minutes, and then washed with water four times to form a PAH layer on the surface.
  • PAH polyallylamine hydrochloride
  • PSS polysodium 4-styrenesulfonate
  • PAA polyacrylic acid
  • the PSS layer and the PAH layer are formed by performing the same processing for the PSS and PAH, respectively.
  • a PAH / PSS / PAH layer (hereinafter referred to as a PAH / PSS / PAH layer) 3 that functions as the bonding layer 13 is formed on the semiconductor nanoparticle silica aggregate 2.
  • the second semiconductor nanoparticle 4 (CdSe / ZnS semiconductor nanoparticle having an emission wavelength of 490 nm) obtained by capping the semiconductor nanoparticle silica aggregate formed with the PAH / PSS / PAH layer 3 with 0.8 mmol / L of mercaptopropionic acid.
  • the semiconductor nanoparticle integrated structure formed by forming the external structure in which the semiconductor nanoparticles 4 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm) 2 are integrated can be obtained.
  • the second semiconductor nanoparticles 4 In order to stack a plurality of layers of the second semiconductor nanoparticles 4 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm), formation of a PAH layer, formation of a PSS layer, and After a new PAH / PSS / PAH layer is formed by sequentially forming a PAH layer, the second semiconductor nanoparticles 4 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm) are dispersed again in an aqueous solution. What is necessary is just to repeat a series of processes to disperse
  • a PAH layer, a PSS layer, and a PAH layer are sequentially formed on the outermost periphery of the semiconductor nanoparticle assembly structure in the same manner. From the above, PAA treatment is further performed, and then carboxyl groups are introduced.
  • Example 2 A semiconductor nanoparticle integrated structure according to Example 2 will be described with reference to FIG.
  • Example 2 shows an embodiment in which silica particles 6 are further included as the support core structure 16 in addition to the two semiconductor nanoparticle-containing layers having different band gap energies.
  • the semiconductor particle-containing layer formed on the outer side of the silica particle 6 includes two types of semiconductor nanoparticle-containing layers having different band gap energies, that is, a first semiconductor nanoparticle integrated layer and a second semiconductor nanoparticle. It differs from the invention described in Non-Patent Document 3 in that it is a layer composed of two layers with an integrated layer.
  • CdSe / ZnS particles for example, those purchased from Evident Technology can be used.
  • the wavelength can be selected from 490, 520, 540, 560, 580, 600, 620 nm.
  • CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 540 nm (half-value width at emission peak: 30 nm) are integrated as the first semiconductor nanoparticles 1 to obtain an internal structure.
  • the first semiconductor nanoparticle integrated layer constituting the body is constructed, and 490 nm CdSe / ZnS semiconductor nanoparticles are integrated as the second semiconductor nanoparticle 4 by the layer-by-layer method to form the second external structure.
  • Build a semiconductor nanoparticle integrated layer is
  • silica particles 6 (60 nm diameter) dispersed in water available from Corefront Corporation or the like can be used.
  • CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 540 nm as the first semiconductor nanoparticles 1 are accumulated outside the silica particles 6 using a layer-by-layer method.
  • Non-Patent Document 3 it can be carried out with reference to Non-Patent Document 3, as in Example 1. That is, the silica particles 6 are treated with a piranha solution (30% H 2 O 2 + 70% H 2 SO 4 ) to be negatively charged. Next, prepare 1 mg / mL PAH (polyallylamine hydrochloride), PSS (polysodium 4-styrenesulfonate) and PAA (polyacrylic acid) in 0.5 mol / L NaCl solution. . First, 0.5 mL of the PAH solution is added per about 100 negatively charged silica particles, absorbed for 20 minutes, and then washed with water four times to form a PAH layer on the surface of the silica particles 6.
  • PAH polyallylamine hydrochloride
  • PSS polysodium 4-styrenesulfonate
  • PAA polyacrylic acid
  • the PSS layer and the PAH layer are formed by performing the same processing for the PSS and PAH, respectively.
  • the PAH / PSS / PAH layer 3 that functions as the bonding layer 13 is formed on the silica particles 6.
  • the first semiconductor nanoparticles 1 CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 540 nm
  • the silica particles on which the PAH / PSS / PAH layer 3 was formed were capped with 0.8 mmol / L of mercaptopropionic acid were dispersed.
  • a silica intermediate structure in which an internal structure in which the first semiconductor nanoparticles 1 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 540 nm) are integrated on silica particles is formed by dispersing in 0.2 mL of an aqueous solution. You can get a body.
  • a PAH layer, a PSS layer, and a PAH layer are formed on the silica intermediate structure.
  • the first semiconductor nanoparticles 1 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 540 nm) are dispersed again in an aqueous solution. What is necessary is just to repeat a series of processes.
  • CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm as the second semiconductor nanoparticles 4 are further accumulated outside the silica intermediate structure using the layer-by-layer method.
  • about 100 silica intermediate structures prepared above were added 0.5 mL of PAH solution prepared by the same method as in Example 1 and absorbed for 20 minutes.
  • a PAH layer is formed on the surface of the structure.
  • the PSS layer and the PAH layer are formed by performing the same processing for the PSS and PAH, respectively. By these operations, the PAH / PSS / PAH layer 3 is formed on the silica intermediate structure.
  • second semiconductor nanoparticles 4 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm) in which the silica intermediate structure on which the PAH / PSS / PAH layer 3 is formed are capped with 0.8 mmol / L of mercaptopropionic acid are applied.
  • the second semiconductor nanoparticles 4 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm) having a larger band gap than the semiconductor nanoparticles 1 constituting the internal structure are obtained.
  • a semiconductor nanoparticle integrated structure formed by forming an integrated external structure can be obtained.
  • the second semiconductor nanoparticles 4 In order to stack a plurality of layers of the second semiconductor nanoparticles 4 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm), formation of a PAH layer, formation of a PSS layer, and After a new PAH / PSS / PAH layer is formed by sequentially forming a PAH layer, the second semiconductor nanoparticles 4 (CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 490 nm) are dispersed again in an aqueous solution. What is necessary is just to repeat a series of processes to disperse
  • the PAH layer, the PSS layer, and the PAH layer are sequentially formed on the outermost periphery of the semiconductor nanoparticle assembly structure in the same manner.
  • PAA treatment is further performed to introduce a carboxyl group.
  • a hydrophilic layer is formed as the surface layer 5.
  • Example 1 Example except that the second semiconductor nanoparticles 4 constituting the external structure are the same CdSe / ZnS semiconductor nanoparticles having an emission wavelength of 540 nm as the first semiconductor nanoparticles 1 constituting the internal structure. In the same manner as in No. 2, a semiconductor nanoparticle integrated structure was obtained.
  • Table 1 shows data on the semiconductor nanoparticles constituting the semiconductor nanoparticle integrated structure obtained in Example 2 and Comparative Example 1.
  • the relationship between the band gaps of the two types of core-shell type semiconductor nanoparticles constituting the semiconductor nanoparticle integrated structure described in the examples is shown in FIG. 8, and the core-shell type constituting the obtained semiconductor nanoparticle integrated structure is shown in FIG.
  • the definition of the core diameter in the semiconductor nanoparticles is shown in FIG.
  • the particle diameters (volume average diameter) of the first semiconductor nanoparticles 1, the second semiconductor nanoparticles 4, and the semiconductor nanoparticle integrated structure are determined by a dynamic light scattering method (MalvernvInstruments, Zetasizer Nano). Using S), the particle size distribution was measured immediately after the production of semiconductor nanoparticles or aggregates (before aggregation). The average particle diameter (volume average diameter) was the particle diameter at the peak (center) position of the particle size distribution.
  • Table 2 shows the emission wavelength and fluorescence intensity of the semiconductor nanoparticle integrated structure obtained in Example 2 and Comparative Example 1.

Abstract

L'objet de la présente invention est d'obtenir une structure de type assemblage de nanoparticules semi-conductrices ayant une luminance élevée, qui est supprimée par décroissement de la luminance même si les nanoparticules semi-conductrices sont assemblées. Une structure de type assemblage de nanoparticules semi-conductrices selon la présente invention comprend une structure intérieure qui est obtenue par assemblage d'une pluralité de premières nanoparticules semi-conductrices et une structure extérieure qui est obtenue par assemblage d'une pluralité de secondes nanoparticules semi-conductrices. Les premières nanoparticules semi-conductrices ont une bande interdite plus petite que celle des secondes nanoparticules semi-conductrices.
PCT/JP2013/058984 2012-03-29 2013-03-27 Structure de type assemblage de nanoparticules semi-conductrices WO2013146872A1 (fr)

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US10927294B2 (en) 2019-06-20 2021-02-23 Nanosys, Inc. Bright silver based quaternary nanostructures
US11360250B1 (en) 2021-04-01 2022-06-14 Nanosys, Inc. Stable AIGS films
US11407940B2 (en) 2020-12-22 2022-08-09 Nanosys, Inc. Films comprising bright silver based quaternary nanostructures
US11926776B2 (en) 2020-12-22 2024-03-12 Shoei Chemical Inc. Films comprising bright silver based quaternary nanostructures

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US10927294B2 (en) 2019-06-20 2021-02-23 Nanosys, Inc. Bright silver based quaternary nanostructures
US11970646B2 (en) 2019-06-20 2024-04-30 Shoei Chemical Inc. Bright silver based quaternary nanostructures
US11407940B2 (en) 2020-12-22 2022-08-09 Nanosys, Inc. Films comprising bright silver based quaternary nanostructures
US11926776B2 (en) 2020-12-22 2024-03-12 Shoei Chemical Inc. Films comprising bright silver based quaternary nanostructures
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