WO2017126164A1 - 発光体、発光体の製造方法、及び生体物質標識剤 - Google Patents
発光体、発光体の製造方法、及び生体物質標識剤 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0065—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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Definitions
- the present invention relates to a light emitter, a method for manufacturing a light emitter, and a biological material labeling agent.
- the present invention relates to a biological material labeling agent comprising
- the near-infrared region having a wavelength of 700 to 1700 nm has high light transmissivity in a living body and is considered suitable for bioimaging technology. Particularly in the region of wavelengths of 700 to 900 nm and 1200 to 1500 nm, the light transmittance is good, and it is called “biological window”.
- I-III-VI group elements are optically active.
- Is a direct transition type semiconductor that emits light by recombination of electrons and holes by absorption of oxygen, does not contain harmful elements such as Cd, has low toxicity, and has a low environmental impact, so it is promising as a new functional material .
- Non-Patent Documents 1 to 3 and Patent Document 1 are known as prior art documents of this type of compound semiconductor.
- Non-Patent Document 1 reports light absorption and fluorescence in the ternary chalcopyrite semiconductor AgInSe 2 .
- the absorption energy of AgInSe 2 depends on the temperature, the band gap energy is 1.222 eV at a temperature of 13 K, 1.229 eV at a temperature of 100 K (same document, FIG. 1), and the emission intensity is It is described that the band gap energy peaks at about 1.175 eV (about 1055 nm in terms of wavelength), but decreases as the temperature increases, and almost no light is emitted at a temperature of 60 K (the same document). FIG. 5).
- Non-Patent Document 2 reports an optical band gap depending on the particle size of the ternary I-III-VI 2 semiconductor nanocrystal.
- the relationship between the grain size of CuInS 2 and the band gap energy is finite-depth-well effective mass approximation calculation (hereinafter referred to as “FDW-EMA method”). It is described that the calculation result approximates the experimental result (FIG. 2).
- the particle size and band gap energy are measured using the FDW-EMA method. And the emission wavelength region is predicted (the same document, FIGS. 3 and 4).
- band gap energy is about 1.5 eV (about 826.7 nm in terms of wavelength) when the particle size is 6 nm, but the band gap energy increases as the particle size becomes smaller. It is described that the band gap energy is about 3.38 eV (about 366.9 nm in terms of wavelength) when the diameter is 1 nm.
- Non-Patent Document 2 it is predicted that the emission wavelength can be varied by varying the particle size due to the quantum size effect for the seven types of compound semiconductors described above.
- Non-Patent Document 3 reports an independent composition and particle size control for In-rich Ag-In-Se nanocrystals having high fluorescence.
- Non-Patent Document 3 Ag-In-Se-based semiconductor nanoparticles are synthesized using an amide-promoted synthesis method. That is, first, heated and AgI and InI 3 to 260 ° C. dissolved in trioctylphosphine (TOP), thereby producing a Ag-In precursor solution. Next, a mixed solution in which Se and amide compound LiN (Si (CH 3 ) 3 ) 2 are dissolved in TOP is injected into the Ag-In precursor solution, reacted for 15 to 120 seconds, and then subjected to predetermined post-treatment. In this way, various Ag—In—Se-based nanoparticles blended so as to be In-rich when Ag / In is in the range of 0.1 to 0.8 are synthesized.
- TOP trioctylphosphine
- Non-Patent Document 3 a donor-accepter pair (hereinafter referred to as “DAP”) in which electrons trapped in a donor level and holes trapped in an acceptor level form a pair and recombine.
- DAP donor-accepter pair
- the quantum yield is 24% in the case of AgIn 3 Se 5 , 73% Ag—In in the case of the core-shell structure with Ag 3 In 5 Se 9 as the core part and ZnSe as the shell part.
- -Se-based nanoparticles have been obtained (Table 1, Table 1).
- Non-Patent Document 3 the Stokes shift indicating the difference between the absorption wavelength and the emission wavelength is 200 to 260 nm, the full width at half maximum at the peak wavelength of the emission intensity (FWHM (full width at half maximum); In this case, Ag-Ig-Se compound semiconductor nanoparticles having a wavelength of 180 to 260 nm are obtained (see the same document, FIG. 4). *
- Patent Document 1 discloses a first compound composed of one element of each of the I-III-VI group elements having a chalcopyrite structure, and the particles composed of the first compound have an outer diameter of 0.5.
- a phosphor having a fluorescence quantum yield of ⁇ 20.0 nm and emitting a light wave excited by excitation light is proposed to be 3.0% or more and 20.0% or less at room temperature.
- Patent Document 1 describes that Cu or Ag is included as a group I element, In or Ga is included as a group III element, and S or Se is included as a group VI element.
- Patent Document 1 a solution in which CuI and InI 3 are dissolved in oleylamine as a complexing agent is referred to as A solution, a solution in which thioacetamide as an S source is dissolved in TOP is referred to as C solution, Liquid C was mixed, and the mixed solution was aged for 24 hours or 28 days at a temperature of 25 ° C. under an argon atmosphere, and then reacted by heating at a temperature of 160 to 280 ° C. for 3 to 600 seconds.
- Cu-In-S compound semiconductors with multiple compositions with different blending ratios are synthesized.
- the aging time, the heating temperature after aging, the heating time, the wavelength of the excitation light, and the emission spectrum when the Cu / In ratio is varied are described, the peak wavelength is 650 to 700 nm, Luminous characteristics with a half-value width of about 150 nm are obtained.
- Patent Document 1 also describes an example in which Ga or Ag is added to a Cu—In—S compound, for example, AgInS 2 using Ag instead of Cu has a peak wavelength of about 750 nm, Luminous characteristics with a half-value width of about 110 nm are obtained.
- JP 2007-169605 A (Claims 1 and 6, paragraphs [0051] to [0079], FIGS. 1 to 12)
- Non-Patent Document 1 describes the emission characteristics of bulk AgInSe 2 compound semiconductors, but does not describe the emission characteristics of nanoparticles. In other words, it is considered that ultrafine nanoparticles exhibit unique characteristics different from those of bulk crystals due to the quantum size effect, but Non-Patent Document 1 evaluates the light emission characteristics of bulk crystals at extremely low temperatures. At 60 K ( ⁇ about 213 ° C.), the light emission disappeared and was not emitted at room temperature.
- Non-Patent Document 2 describes the emission spectrum profile of I-III-VI 2 compound semiconductors that express quantum size effects with ultrafine nanoparticles of 6 nm or less and predict the wavelength region of the emission wavelength. It was n’t.
- Non-Patent Document 2 describes the quantum size effect of semiconductor nanoparticles, but does not describe the profile of the emission spectrum, and does not predict the emission characteristics required in bioimaging technology. .
- Non-Patent Document 3 although the quantum yield is good, the full width at half maximum is 180 to 260 nm, the peak wavelength is gradual, and the steepness and sharpness are lacking. It is difficult to obtain a large amount of biological information.
- Non-Patent Document 3 relates to DAP emission, and the Stokes shift is as large as 200 to 260 nm, and the light absorbed electrons are transferred from the donor level to the acceptor level via the defect level derived from the crystal structure defect. It is thought that it will transition to. Therefore, it is considered that the transition from the absorption wavelength to the emission wavelength is accompanied by energy loss derived from the defect level, so that the peak wavelength is lacking in steepness and sharpness. It is difficult to emit light strongly at a wavelength.
- Patent Document 1 discloses that Cu-based compound semiconductor nanoparticles emit light in the visible light region having a wavelength of 700 nm or less, and the emission wavelength is as wide as about 150 nm. It is difficult to obtain a large number of biological information having a desired high resolution in a wavelength range where the light transmission at is good.
- the present invention has been made in view of such circumstances, and emits light strongly in the near-infrared region, can detect a large amount of biological information, and is suitable for bioimaging, and a method for manufacturing the light emitter, Another object of the present invention is to provide a biological substance labeling agent provided with this luminescent material.
- a compound semiconductor having a chalcopyrite crystal structure of Ag-In-Se system using Ag as a group I element, In as a group III element and Se as a group VI element has no toxicity as in the Cd system and is close to the bulk state. Light emission in the infrared region is possible.
- AgInS 2 using S as a group VI element has a band gap energy of 1.87 eV (660 nm in terms of wavelength) in the bulk state and emits light in the visible light region, whereas AgInSe 2 has a band gap in the bulk state.
- the energy is 1.24 eV (1000 nm in terms of wavelength), and light is emitted in the near infrared region.
- the wavelength including the “biological window” is in the near infrared region of 700 to 1400 nm even with the same composition due to the quantum size effect. It is considered possible to obtain light emitters having different peak wavelengths.
- the illuminant in order to obtain more effective biological information in the bioimaging technology, it is necessary for the illuminant to have a good resolution. For this purpose, it is desirable that the peak wavelength of the emission intensity is steep and sharp.
- the inventors of the present invention focused on the Ag—In—Se compound semiconductor from such a viewpoint and conducted extensive research.
- the peak wavelength of the emission intensity was in the range of 700 to 1400 nm by devising the manufacturing process and the like.
- a phosphor capable of suppressing the half-value width of the peak wavelength to 100 nm or less can be obtained.
- the emission spectrum near the peak wavelength is sharp and sharp in the near-infrared region, and emits light strongly, and has high resolution. It was found that a desired luminescent material suitable for a marker can be obtained.
- the present invention has been made based on such knowledge, and the phosphor according to the present invention is formed of nanoparticles made of a compound semiconductor containing an Ag component, an In component, and a Se component, and has a peak emission intensity.
- the wavelength is in the range of 700 nm to 1400 nm, and the half width of the peak wavelength is 100 nm or less.
- the peak wavelength is preferably 700 nm to 1000 nm.
- the half-value width of the peak wavelength can be suppressed to 100 nm or less in a wavelength region where the light transmittance in a living body called a “biological window” is particularly good, and a light emitter more suitable for use in bioimaging can be obtained. .
- the In component is excessively contained with respect to the stoichiometric composition.
- composition In-rich it is considered that the non-radiative deactivation process in the absorption-luminescence process is suppressed, so that it is possible to obtain better light emission characteristics.
- the blending ratio of the In component to the Ag component is preferably 1.5 to 3 in terms of molar ratio.
- the phosphor of the present invention preferably contains at least part of the absorption wavelength of 700 nm to 1000 nm.
- the compound semiconductor preferably has an average particle size of 0.1 nm to 20 nm.
- the band gap energy can be controlled only by adjusting the particle size even with the same component composition. Therefore, it is possible to obtain a plurality of light emission characteristics having different peak wavelengths of light emission intensity with the same component composition, so that various biological information can be detected.
- a method for manufacturing a light emitter according to the present invention is a method for manufacturing a light emitter using nanoparticles composed of a compound semiconductor containing an Ag component, an In component, and a Se component, the Ag compound and the In compound.
- a high boiling point solvent to prepare an Ag-In precursor solution Se powder is dissolved in a solvent to prepare an Se precursor solution, and the Ag-In precursor solution is brought to a predetermined temperature.
- heating for a predetermined reaction time at a reaction temperature higher than the predetermined temperature improves the crystallinity of the nanoparticles and suppresses the generation of defects in the nanoparticles. .
- variation in the average particle size can be suppressed, energy loss derived from defect levels can be suppressed, and light emission capable of band edge emission with a narrow half-value width and a small Stokes shift can be achieved.
- the body can be obtained with high efficiency.
- the reaction temperature is preferably 200 ° C. or higher.
- the method for producing a luminescent material of the present invention can control the absorption wavelength by adjusting the blending ratio of the Ag compound and the In compound.
- the method for producing a luminescent material of the present invention can control the peak wavelength of luminescence intensity by adjusting the predetermined reaction time.
- the method for producing a luminescent material of the present invention can control the half-value width of the peak wavelength by adjusting the reaction temperature.
- the crystallinity of the nanoparticles can be controlled by adjusting the reaction temperature in this way, and the generation of defects in the crystal structure can be controlled, the half width of the peak wavelength can be controlled.
- the high boiling point solvent contains at least one selected from octadecene, oleylamine and n-octyl ether.
- the Ag compound and the In compound are a complex having a carboxylate ion as a ligand.
- the biological material labeling agent according to the present invention is characterized by including the above-described light emitter.
- the light emitter of the present invention is formed of ultrafine particles made of a compound semiconductor containing an Ag component, an In component, and a Se component, and the peak wavelength of the emission intensity is in the range of 700 nm to 1400 nm, and the peak wavelength Since the half-value width is 100 nm or less, the emission spectrum in the vicinity of the peak wavelength in the near-infrared region is sharp, sharp, and emits strong light, and a light-emitting body with good resolution can be obtained.
- the step of preparing the Ag—In precursor solution described above, the step of preparing the Se precursor solution, the step of manufacturing the compound semiconductor, and the predetermined manufacturing of the compound semiconductor are performed. Since the step of heating at a reaction temperature higher than the temperature for a predetermined reaction time is included, the crystallinity of the nanoparticles is improved, and defect generation of the nanoparticles is suppressed. That is, the improvement in crystallinity suppresses variation in the average particle diameter, and energy loss derived from defect levels can be suppressed, and a phosphor capable of emitting band edges with a narrow half-value width and a small Stokes shift. Can be obtained with high efficiency.
- the illuminant described above since the illuminant described above is provided, the illuminant emits light so as to have a steep and sharp peak wavelength in the near-infrared region.
- Biological images can be dynamically analyzed with multiple colors, and biological material labeling agents suitable for biomarkers for bioimaging can be obtained.
- FIG. 2 is a profile showing an emission spectrum of each sample of Example 1. It is the profile which expanded the falling part of the absorption spectrum of each sample of Example 1.
- FIG. 4 is a profile showing emission spectra of Sample No. 3 and Sample No. 11 of Example 2.
- FIG. 11 is a diagram showing along with Se and diffraction profile of tetragonal AgInSe 2 is a standard sample.
- 10 is a profile showing an emission spectrum of sample number 21 in Example 3.
- 10 is a profile showing an emission spectrum of sample number 22 in Example 3.
- 10 is a profile showing an emission spectrum of sample number 23 in Example 3. It is a TEM image of the sample number 21. It is a TEM image of the sample number 22. It is a TEM image of the sample number 23.
- 6 is a graph showing an emission spectrum of Example 4.
- FIG. It is a profile which shows the relationship of the emission spectrum of a comparative example, an absorption spectrum, and Stokes shift.
- FIG. 1 is a profile schematically showing the main part of the emission spectrum of the light emitter according to the present invention, wherein the horizontal axis indicates the wavelength and the vertical axis indicates the emission intensity.
- the phosphor of the present invention is formed of nanoparticles composed of a compound semiconductor containing an Ag component, an In component, and an Se component (hereinafter referred to as “Ag—In—Se compound semiconductor”).
- the peak wavelength of the emission intensity is in the range of 700 to 1400 nm, and the full width at half maximum ⁇ H of the peak wavelength is 100 nm or less.
- Peak wavelength of luminescence intensity and luminescent material As described in the section of “Background Art”, absorption of biological constituents such as hemoglobin is large in the visible light region of less than 700 nm shorter than near infrared, When the wavelength is longer than 1700 nm, the absorption of moisture increases, so that light cannot be transmitted through the living body with high efficiency, and it is difficult to obtain desired living body information even if the light is emitted in the living body. is there.
- the light transmittance to a living body is good, and it is said that it is suitable for dynamic image analysis of living tissue using bioimaging technology.
- a wavelength range of 700 to 1400 nm is called a “biological window”, and has a good light transmittance with respect to the living body. By obtaining, it becomes possible to acquire desired biological information.
- the peak wavelength of the emission intensity is set in the range of 700 to 1400 nm, preferably 700 to 1000 nm.
- an Ag—In—Se based semiconductor compound is used as a light emitting material having a peak wavelength in the above wavelength range.
- Ag—In—Se semiconductor compounds having a chalcopyrite type crystal structure are less toxic than Cd-based materials such as CdSe and CdTe, and the emission wavelength is adjusted by forming a solid solution by adjusting the composition. Can be controlled.
- an Ag—In—S based semiconductor compound using S instead of Se for example, AgInS 2 , has a band gap energy of 1.
- the band gap energy of 87 eV (660 nm in terms of wavelength) is large and emits light in the visible light region, whereas the band gap energy of Ag—In—Se based semiconductor compounds such as AgInSe 2 is 1.24 eV (wavelength in the bulk state).
- an Ag—In—Se compound semiconductor is used as the light emitting material.
- Peak wavelength half-value width ⁇ H In order to obtain desired biological information using bioimaging technology, it is necessary to increase the resolution by causing the illuminant to emit light strongly. For this purpose, the profile in the vicinity of the peak wavelength of the emission spectrum must be sharp and sharp. is there. The steepness / sharpness of the peak wavelength can be evaluated by the wavelength width at 1 / 2P of the peak wavelength P of the emission intensity, that is, the half-value width ⁇ H.
- This half-value width ⁇ H is related to the Stokes shift S, and the relationship between the Stokes shift S and the half-value width ⁇ H will be described below.
- FIG. 2 is a profile showing the relationship between the absorption spectrum, the emission spectrum, and the Stokes shift S. *
- FIG. 2A shows absorption and emission spectrum profiles, where the horizontal axis represents the wavelength ⁇ , the left vertical axis represents the absorption coefficient ⁇ , and the right vertical axis represents the emission intensity PL. *
- FIG. 2B shows a profile of the derivative d ⁇ / d ⁇ obtained by differentiating the absorption coefficient ⁇ once with the wavelength ⁇ , where the horizontal axis is the wavelength ⁇ and the vertical axis is d ⁇ / d ⁇ .
- FIG. 2C shows a profile of the second derivative d 2 ⁇ / d ⁇ 2 obtained by differentiating the absorption coefficient ⁇ twice with the wavelength ⁇ , where the horizontal axis is wavelength ⁇ and the vertical axis is d 2 ⁇ / d ⁇ 2. It is.
- the luminescent material When photon energy is applied to the luminescent material, the luminescent material absorbs light, electrons in the valence band in the ground state are excited to the conduction band, and holes are formed in the valence band. The excited electrons are attracted to the ground state valence band where holes exist due to Coulomb force, and the electrons and holes recombine to emit light.
- a shift called Stokes shift S occurs between the absorption wavelength and the emission wavelength. .
- the defect forms various energy levels between the bands, that is, defect levels. Accordingly, it is considered that when electrons excited by absorption of light transition from the conduction band to the valence band, the electrons undergo transition through the relaxation process due to the defect level. That is, the excited electrons are accompanied by energy loss and radiatively recombine with holes at the defect level to emit light (defect light emission). As described above, since defects can take various levels between bands, the energy consumed by the transition from the conduction band to the valence band also varies. Therefore, the defect emission reflects energy loss. The emission spectrum having a large half-value width ⁇ H is obtained.
- the half-value width ⁇ H of the peak wavelength is set to 100 nm or less as described above, and thereby a high-resolution illuminant suitable for a biomarker in which energy loss is suppressed. Have gained.
- the Stokes shift S quantitatively by the difference between the minimum value M which is the tangent of the rate of change of the absorption coefficient alpha 2 order derivative d 2 alpha / d [lambda] 2 and the peak wavelength P of the emission wavelength Can be evaluated.
- the Stokes shift S is theoretically difficult to evaluate, but experimentally it is 180 nm or less, preferably 70 nm or less.
- the emission wavelength is 700 to 1400 nm, which is the window of the living body
- the Stokes shift S is small and the emission wavelength is small if the trailing edge A of the absorption wavelength is in the wavelength range of 700 to 1000 nm in the absorption spectrum. It approaches the absorption wavelength. Accordingly, both the light absorption process and the light emission process are possible in the wavelength range of 700 to 1400 nm, and excitation light emission that effectively uses the living body window can be realized.
- the peak wavelength becomes too wide, the peak wavelength forms a gentle curve and is not steep and lacks sharpness, leading to a decrease in resolution and 700 to 1400 nm. It is difficult to obtain a large amount of biological information within a range. Moreover, there is a possibility that a part of the wavelength range of the emission intensity is less than 700 nm or exceeds 1400 nm, which is not preferable.
- composition ratio of each component of the Ag—In—Se compound semiconductor is not particularly limited as long as the peak wavelength of the emission intensity is 700 to 1400 nm and the half-value width ⁇ H of the peak wavelength is 100 nm or less. However, it is preferable to contain the In component in excess of the stoichiometric composition.
- the stoichiometric composition of the Ag component and the In component is 1: 1.
- the In component at the time of manufacture is contained in excess of the stoichiometric composition, light is emitted when the excited electrons return to the ground state. It is possible to suppress the non-radiative deactivation process that is not released, and it is considered that a luminescence peak with improved intensity can be obtained.
- the In component at the time of manufacture is contained excessively more than the stoichiometric composition, impurities such as heterogeneous phases may be generated, which leads to a decrease in purity, and on the contrary, the intensity of the emission peak is increased. May decrease.
- the blending ratio of the In component to the Ag component is preferably 1.5 to 3 in terms of molar ratio.
- the average particle diameter of the Ag—In—Se compound semiconductor is not particularly limited as long as the quantum size effect is exhibited in the wavelength range of 700 to 1400 nm. Particles can be used.
- the present invention is formed of nanoparticles made of a compound semiconductor containing an Ag component, an In component, and a Se component, and (ii) the peak wavelength of the emission intensity is in the range of 700 nm to 1400 nm.
- the manufacturing method is not particularly limited as long as the three requirements of (iii) the half width ⁇ H of the peak wavelength are 100 nm or less are satisfied.
- an Ag compound containing an Ag component and an In compound containing an In component are prepared, and the compounding ratio of the Ag component and the In component after synthesis is preferably larger than the stoichiometric composition.
- the Ag compound and the In compound are weighed.
- the composition ratio of the In component to the Ag component is excessively increased, the generation of impurities such as heterogeneous phases is predicted, so that the element ratio (In / Ag) is 1.5 to 3 in terms of molar ratio. It is preferable to weigh the Ag compound and the In compound.
- the high boiling point solvent is not particularly limited as long as it has a high boiling point and is chemically stable at a high temperature.
- a high boiling point solvent is not particularly limited as long as it has a high boiling point and is chemically stable at a high temperature.
- Mixed solutions containing seeds can be used.
- Se powder is prepared, and this Se powder is dissolved in a solvent to prepare a Se precursor solution.
- the solvent is not particularly limited.
- alkylthiol such as 1-dodecanethiol and hexanethiol and alkylamine such as oleylamine
- phosphines such as tributylphosphine and trioctylphosphine may be used. it can.
- the Ag—In precursor solution is put into a container, degassed under reduced pressure, and then purged with nitrogen. Thereafter, heat treatment is performed to raise the temperature of the reaction field from room temperature to a predetermined temperature (for example, 150 ° C.).
- a predetermined temperature for example, 150 ° C.
- the Se precursor solution is injected into the Ag-In precursor solution heated to a predetermined temperature, and then further heated to a predetermined reaction temperature, and maintained at the reaction temperature for a predetermined reaction time, thereby A reactant is obtained.
- the reaction temperature is preferably higher than the predetermined temperature, for example, 200 ° C. or higher, and thereby the grain growth can be promoted moderately to such an extent that the nanoparticles do not become coarse.
- the generation of defects in the nanoparticles is suppressed, the crystallinity is improved, the variation in average particle diameter is also suppressed, the Stokes shift S is reduced, and a peak wavelength with a narrow half width ⁇ H can be obtained.
- the reaction time is not particularly limited, and can be set to 30 to 120 minutes, for example. Since the grain growth can be controlled by varying the reaction time, the average particle diameter can be adjusted. Then, by adjusting the average particle size, the emission wavelength varies due to the quantum size effect, so that the peak wavelength of the emission intensity can be controlled.
- the reaction product is allowed to cool to room temperature and then cooled, and then centrifuged to separate into a supernatant and a precipitate.
- the supernatant is recovered and the precipitate is discarded.
- a poor solvent such as methanol, ethanol, acetone, or acetonitrile is added to the supernatant to generate a precipitate, which is centrifuged again to separate and collect the precipitate.
- the operation of adding a poor solvent ⁇ centrifugation treatment ⁇ recovering the precipitate is repeated a plurality of times to produce a high-purity precipitate containing no impurities such as heterogeneous phases.
- this precipitate is dissolved by adding a nonpolar solvent such as chloroform, toluene, or hexane, whereby a dispersion solution in which Ag—In—Se compound semiconductor nanoparticles are dispersed can be prepared.
- a nonpolar solvent such as chloroform, toluene, or hexane
- a step of preparing an Ag-In precursor solution by dissolving an Ag compound and an In compound in a high boiling point solvent, and a Se precursor by dissolving Se powder in a solvent A step of producing a solution, a step of injecting the Se precursor solution into the Ag-In precursor solution in a state where the Ag-In precursor solution is heated to a predetermined temperature, and producing a mixed solution; and the mixed solution Is heated at a reaction temperature higher than the predetermined temperature for a predetermined reaction time, so that the crystallinity of the nanoparticles is improved and defect generation of the nanoparticles is suppressed.
- the improvement in crystallinity suppresses variation in the average particle diameter, and energy loss derived from defect levels can be suppressed, and light emission capable of band edge emission with a narrow half-value width ⁇ H and a small Stokes shift.
- the body can be obtained with high efficiency.
- the biological substance labeling agent includes the illuminant
- the illuminant emits light so as to have a steep and sharp peak wavelength in the near-infrared region, and thus a biological image with desired high sensitivity and multiple colors. Can be dynamically analyzed, and a biological substance labeling agent suitable for a biomarker for bioimaging can be obtained.
- the present invention is not limited to the above embodiment. It is needless to say that the above embodiment is an embodiment of the present invention and can be changed without changing the gist.
- the luminescent material of the present invention can be used as a biological material labeling agent as described above, and can also be used as a light source for exciting a label in a living body.
- a blue light emitting diode or an ultraviolet light emitting diode can be filled with the nanoparticles of the present invention, the nanoparticles of the present invention are excited by the blue light emitting diode or the ultraviolet light emitting diode to be in the near infrared region of 700 to 1400 nm. Therefore, it can be used as light for exciting the label in the living body in such a wavelength region.
- Example preparation 99% pure Ag (OCOCH 3 ) (manufactured by Nacalai Tesque) and 99.99% pure In (OCOCH 3 ) 3 (manufactured by Johnson Matthey Catalysts, trade name “Alfa Aesar”), with a purity of 99.99% Selenium powder (manufactured by High-Purity Science Laboratories), 90% pure 1-octadecene (Sigma Aldrich) and 1-dodecanethiol (Tokyo Kasei Co., Ltd.), 80-90% pure oleylamine (Across Organics) as solvent Prepared).
- this weighed product was put into a three-necked flask having an internal volume of 50 mL together with a stirrer chip, and then 8 mL of octadecene and 1 mL of 1-dodencanthiol were added as a high boiling point solvent and stirred to prepare an Ag-In precursor solution. Produced.
- Se precursor solution was prepared by dissolving 0.2 mmol of Se powder in 1 mL of 1-dodecanethiol and 1 mL of oleylamine as a solvent.
- the inside of the three-necked flask in which the Ag—In precursor solution was stored was degassed under reduced pressure, and then purged with nitrogen. Thereafter, the three-necked flask was heated with a heater, and the temperature was raised from room temperature. Then, the Se precursor solution is poured into the three-necked flask in a state where the temperature of the reaction field is 150 ° C., the temperature of the reaction field is raised to 200 ° C., and heat treatment is performed at this temperature for 30 minutes to obtain the reaction product. Obtained.
- this reaction product was air-cooled until it reached room temperature, and then centrifuged at a rotational speed of 5000 rpm for 5 minutes to separate into a supernatant and a precipitate. The supernatant was recovered, and the precipitate was discarded.
- the emission spectrum and quantum yield were measured using an absolute emission quantum yield measuring apparatus (C9920-02 manufactured by Hamamatsu Photonics) at room temperature of 25 ° C., and the half-value width of the peak wavelength was determined from the emission spectrum. Asked.
- the absorption spectrum was measured at room temperature of 25 ° C. using a spectrophotometer (U4100, manufactured by Hitachi High-Technologies Corporation).
- the Stokes shift S was calculated based on the peak wavelength of the emission intensity PL of the sample and the absorption coefficient ⁇ .
- FIG. 3 is a diagram showing the relationship between the emission spectrum, absorption spectrum, and Stokes shift of sample number 3.
- 3A shows an emission spectrum and an absorption spectrum of Sample No. 3, the horizontal axis is the wavelength ⁇ (nm), the left vertical axis is the absorption coefficient ⁇ (au), and the right vertical axis is the emission intensity PL (au). .
- FIG. 3B shows a profile diagram of the derivative obtained by differentiating the absorption coefficient ⁇ of sample number 3 once with the wavelength ⁇ , where the horizontal axis is the wavelength ⁇ (nm) and the vertical axis is the derivative d ⁇ / d ⁇ .
- FIG. 3C shows a profile diagram of the second derivative obtained by differentiating the absorption coefficient ⁇ of the sample number 3 twice with the wavelength ⁇ , the horizontal axis is the wavelength ⁇ (nm), and the vertical axis is the second derivative d 2. it is an ⁇ / d ⁇ 2.
- the difference between the peak wavelength of the emission intensity and the wavelength at which the second-order derivative d 2 ⁇ / d ⁇ 2 is minimized was calculated as Stokes shift S. That is, the Stokes shift S can be calculated based on the peak wavelength of the emission intensity PL of the sample and the absorption coefficient ⁇ .
- FIG. 4 shows the emission spectra of the samples Nos. 1 to 6, where the horizontal axis represents the wavelength ⁇ (nm) and the vertical axis represents the emission intensity PL (a.u.).
- Table 1 shows the Ag / In ratio, half-value width, Stokes shift, and quantum yield of sample numbers 1 to 6.
- Sample No. 5 had a wide half-value width of 167 nm, and a steep peak waveform could not be obtained. This seems to be because impurities such as heterogeneous phases were mixed in the sample although In was in excess of the stoichiometric composition.
- Sample Nos. 1 to 4 and 6 were able to obtain a peak wavelength with a full width at half maximum of 100 nm or less in the wavelength region of 700 to 1000 nm.
- Sample Nos. 1 and 6 have a quantum yield as low as 1.1 to 1.5% and inferior in emission intensity, but have a half-value width of 100 nm or less in a wavelength region of 700 to 1000 nm and low emission intensity. The items specified in the present invention are satisfied.
- Sample Nos. 2 to 4 having a half width of 100 nm or less have Stokes shifts of 65 to 175 nm and 180 nm or less, and it is found that a light emitter with reduced energy loss due to defect levels can be obtained. It was.
- FIG. 5 is a diagram showing the trailing edge of the absorption spectrum, where the horizontal axis is the wavelength ⁇ (nm) and the vertical axis is the absorption coefficient ⁇ (a.u.).
- the absorption wavelength shifts to the short wavelength side as the Ag / In ratio becomes smaller, that is, as the In becomes richer. Therefore, the Ag / In ratio is adjusted. It was found that the absorption edge wavelength can be adjusted.
- Sample No. 11 was prepared by the same method and procedure as Sample No. 3 of Example 1 except that the reaction time was 120 minutes.
- the emission spectrum and the quantum yield were determined by the same method and procedure as in Example 1, and the peak wavelength and the half width were determined from the emission spectrum.
- FIG. 6 is a diagram showing the emission spectrum of Sample No. 11 together with the emission spectrum of Sample No. 3, where the horizontal axis is the wavelength ⁇ (nm) and the vertical axis is the emission intensity PL (a.u.).
- Sample No. 11 had a half-width of 85 nm and a quantum yield of 12%, which was the same as that of Sample No. 3. However, as shown in FIG. The peak wavelength was about 850 nm. This is because the reaction time is 120 minutes and the reaction time is 30 minutes longer than that of the sample No. 3, which is heated for a long time. .
- the average particle diameter can be controlled by adjusting the reaction time from this example, and thereby the peak wavelength of the emission intensity can be controlled.
- FIG. 7 is a diagram showing the X-ray diffraction spectra of Sample No. 3 and Sample No. 11 together with the diffraction patterns of Se and tetragonal AgInSe 2 , where the horizontal axis is the diffraction angle 2 ⁇ (°) and the vertical axis is the X-ray intensity (au ).
- the sample was prepared by the same method and procedure as Sample No. 3 in Example 1 except that oleylamine was used instead of octadecene as the high boiling point solvent, the reaction time was 120 minutes, and the reaction times were 150 ° C., 200 ° C., and 250 ° C. Samples with numbers 21 to 23 were prepared.
- the emission spectrum was measured by the same method and procedure as in Example 1, and the peak wavelength and half width were obtained from these emission spectra.
- 11 to 13 show STEM images of sample numbers 21 to 23, respectively.
- Table 2 shows the average particle diameter Dav, standard deviation ⁇ , emission spectrum, and STEM image numbers of sample numbers 21 to 23.
- Sample No. 21 had a peak wavelength of 880 nm, but its full width at half maximum exceeded 100 nm. This is because the reaction temperature is as low as 150 ° C., so that the crystallinity is low and many defects are generated in the crystal grains, resulting in energy loss due to the defect level. As a result, the peak wavelength of the emission intensity becomes gentle and steep. It seems that the peak wavelength can no longer be obtained.
- Sample Nos. 22 and 23 have a high reaction temperature of 200 to 250 ° C., so that the crystallinity of the particles is high, the grain growth is promoted, the average particle diameter Dav is 6.1 to 8.0 nm, and the standard deviation ⁇ was 1.2 to 2.5 nm.
- the full width at half maximum was 72 to 82 nm in the wavelength range of 820 to 890 nm, and the emission intensity showed a steep curve, indicating that good emission characteristics were obtained.
- the sample number 22 had a Stokes shift of 52 nm, whereas the sample number 21 had a large Stokes shift of 200 nm.
- Sample No. 31 was prepared in the same manner and procedure as Sample No. 3 except that 95% pure n-octyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-octadecene as the high boiling point solvent, and the reaction time was 120 minutes. A sample of was prepared.
- the emission spectrum, absorption spectrum, and quantum yield are determined in the same manner and procedure as in Example 1, and the peak wavelength, half width, and absorption coefficient are determined from the emission spectrum and absorption spectrum. Further, the Stokes shift S was obtained from the peak wavelength and the absorption coefficient.
- FIG. 14 shows an emission spectrum of Sample No. 31, the vertical axis represents the emission intensity PL (a.u.), and the horizontal axis represents the wavelength ⁇ (nm).
- the peak wavelength of the emission intensity was about 830 nm, and the half width was 65 nm.
- the quantum yield was 14%
- the Stokes shift was 54 nm, and it was found that a light-emitting body having good light-emitting characteristics similar to that of Sample No. 3 was obtained even if the kind of the high-boiling solvent was changed.
- AgInS 2 using S instead of Se in AgInSe 2 was prepared, emission spectrum and absorption spectrum were measured, Stokes shift was obtained, and emission characteristics were evaluated.
- Example 2 After washing and purifying by air cooling, centrifugation, etc., the obtained ultrafine particles of AgInS 2 were dispersed in chloroform, and a comparative sample comprising an AgInS 2 nanoparticle dispersion solution Was made.
- the emission spectrum, absorption spectrum, quantum yield, half-value width, and Stokes shift were determined by the same method and procedure as in Example 1.
- FIG. 15 is a profile showing the measurement results.
- 15A shows the emission spectrum and absorption spectrum of the comparative sample, the horizontal axis is the wavelength ⁇ (nm), the left vertical axis is the absorption coefficient ⁇ (au), and the right vertical axis is the emission intensity PL ( au).
- FIG. 15B shows a profile of the derivative d ⁇ / d ⁇ of the comparative sample, where the horizontal axis is the wavelength ⁇ (nm) and the vertical axis is the derivative d ⁇ / d ⁇ .
- FIG. 15C shows the profile of the second derivative d 2 ⁇ / d ⁇ 2 of the comparative sample, where the horizontal axis is the wavelength ⁇ (nm) and the vertical axis is the second derivative d 2 ⁇ / d ⁇ 2 .
- this comparative example sample had a high quantum yield of 52%, as is clear from FIG. 15, the half-value width was about 200 nm, the emission peak was present in a wide wavelength range, and a steep emission peak was obtained. could not. Further, the Stokes shift S is as large as 351 nm, and it is considered that light emission derived from the defect level occurs.
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Abstract
Description
[背景技術]の項で述べたように、近赤外よりも波長の短い700nm未満の可視光領域ではヘモグロビン等の生体構成物質の吸収が大きく、一方、波長が1700nmを超えて長くなると水分の吸収が大きくなり、このため光が生体内を高効率で透過することができず、生体内で発光しても所望の生体情報を得るのが困難である。
バイオイメージング技術を使用して所望の生体情報を得るためには、発光体を強く発光させて分解能を高める必要があり、そのためには発光スペクトルのピーク波長近傍のプロファイルが急峻で尖鋭である必要がある。そして、ピーク波長の急峻性・尖鋭性は、発光強度のピーク波長Pの1/2Pにおける波長幅、すなわち半値幅ΔHで評価することができる。
純度99%のAg(OCOCH3)(ナカライテスク社製)及び純度99.99%のIn(OCOCH3)3(ジョンソンマッセイキャタリスト社製、商品名「Alfa Aesar」)、純度99.99%のセレン粉末(高純度科学研究所社製)、純度90%の1-オクタデセン(シグマーアルドリッチ社製)及び1-ドデカンチオール(東京化成社製)、溶媒として純度80~90%のオレイルアミン(アクロスオーガニックス社製)を用意した。
試料番号1~6の各試料について、吸収スペクトル、発光スペクトル、ピーク波長の半値幅、ストークスシフトS、及び絶対発光量子収率(以下、単に「量子収率」という。)を求めた。
Claims (14)
- Ag成分、In成分、及びSe成分を含有した化合物半導体からなるナノ粒子で形成され、
発光強度のピーク波長が、700nm~1400nmの範囲にあり、
かつ前記ピーク波長の半値幅が、100nm以下であることを特徴とする発光体。 - 前記ピーク波長が、700nm~1000nmであることを特徴とする請求項1記載の発光体。
- 前記In成分は、化学量論組成に対し過剰に含有されていることを特徴とする請求項1又は請求項2記載の発光体。
- 前記Ag成分に対する前記In成分の配合比率は、モル比換算で1.5~3であることを特徴とする請求項1乃至請求項3のいずれかに記載の発光体。
- 吸収波長が、700nm~1000nmの少なくとも一部を含むことを特徴とする請求項1乃至請求項4のいずれかに記載の発光体。
- 前記化合物半導体は、平均粒径が0.1nm~20nmであることを特徴とする請求項1乃至請求項5のいずれかに記載の発光体。
- Ag成分、In成分、及びSe成分を含有した化合物半導体からなるナノ粒子を発光体とする発光体の製造方法であって、
Ag化合物とIn化合物とを高沸点溶媒に溶解させてAg-In前駆体溶液を作製する工程と、
Se粉末を溶媒に溶解させてSe前駆体溶液を作製する工程と、
前記Ag-In前駆体溶液を所定温度に加熱した状態で前記Se前駆体溶液を前記Ag-In前駆体溶液に注入し、混合溶液を作製する工程と、
前記混合溶液を前記所定温度よりも高温の反応温度で所定の反応時間加熱する工程とを含むことを特徴とする発光体の製造方法。 - 前記反応温度は、200℃以上であることを特徴とする請求項7記載の発光体の製造方法。
- 前記Ag化合物と前記In化合物との配合比率を調整し、吸収波長を制御することを特徴とする請求項7又は請求項8記載の発光体の製造方法。
- 前記所定の反応時間を調整し、発光強度のピーク波長を制御することを特徴とする請求項7乃至請求項9のいずれかに記載の発光体の製造方法。
- 前記反応温度を調整し、ピーク波長の半値幅を制御することを特徴とする請求項7乃至請求項10のいずれかに記載の発光体の製造方法。
- 前記高沸点溶媒は、オクタデセン、オレイルアミン及びn-オクチルエーテルの中から選択された少なくとも1種を含むことを特徴とする請求項7乃至請求項11のいずれかに記載の発光体の製造方法。
- 前記Ag化合物及び前記In化合物は、カルボン酸イオンを配位子とした錯体であることを特徴とする請求項7乃至請求項12のいずれかに記載の発光体の製造方法。
- 請求項1乃至請求項6のいずれかに記載の発光体を備えていることを特徴とする生体物質標識剤。
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