1. Field of the Invention
The present invention relates to a phosphor and a production process thereof, more particularly, to a phosphor which generates near infrared fluorescent light from visible light, and a production process thereof, and even more particularly, to a phosphor containing semiconductor nanoparticles capable of carrying out modification, staining and so on of bio-related substances, a phosphor for a semiconductor light source used in illumination, displays and so on, and a production process thereof.
2. Description of the Related Art
When a semiconductor is reduced in size to the nanometer order, quantum size effects appear, and the energy band gap increases accompanying a reduction in the number of atoms. Semiconductor fluorescent nanoparticles comprised of a semiconductor of the nanometer order emit fluorescent light equivalent to the band gap energy of the semiconductor. The fluorescent color of CdSe nanoparticles of group II and VI semiconductors can be adjusted as desired within the range of about 500 to 700 nm by adjusting the particle diameter as a result of utilizing quantum size effects, and extensive research has been conducted on these nanoparticles due to their highly fluorescent properties (Published Japanese Translation of PCT Application No. 2003-524147).
Because they are inorganic semiconductors, they have been suggested to have the potential for use as fluorescent materials of fluorescent tags for biochemical analyses, illumination, displays and so on due to being more stable than organic pigments. Nanoparticles which generate fluorescence of visible light at room temperature have also been developed with group III and V semiconductors, silicon and germanium. Moreover, chalcopyrite compounds are semiconductor compounds which have been suggested to be used as absorbers and so on.
However, since the toxicity of Cd and Se presents a considerable environmental risk during production and use, and since group III and V semiconductors and silicon and other group IV semiconductors, which have comparatively low toxicity and generate fluorescence in the visible light range, demonstrate a high degree of covalent bonding, thereby requiring a complex processes during production thereof, it is difficult to deploy these semiconductors in a wide range of industrial applications. Therefore, the inventors of the present invention conducted extensive research activities for the purpose of creating novel semiconductor fluorescent nanoparticles composed of lowly toxic elements. During this research, attention was focused on a compound having a chalcopyrite structure similar to the physical properties of CdSe, and particularly CuInS2, as a target material, and this compound was then compounded with ZnS and other group II and VI compounds followed by evaluation of fluorescence characteristics, thereby leading to completion of the present invention.
In consideration of this technical background, the present invention achieves the following objects.
An object of the present invention is to provide a lowly toxic phosphor and a production process thereof.
An other object of the present invention is to provide a phosphor resulting obtained by synthesizing a compound having a chalcopyrite structure and compounding with a group II and VI compound such as ZnS, and a production process thereof.
Still another object of the present invention is to provide a compound obtained by synthesizing a compound having a chalcopyrite structure and compounding with a group III and V compound, and a production process thereof.
The present invention employs the following means to achieve the above-mentioned objects.
[Phosphor]
A phosphor of the present invention provides a phosphor comprising a first compound composed of elements of groups I, III and VI having a chalcopyrite structure, or composite particles or composite compound containing the first compound. The particle diameter of the first compound, or the composite particles or composite compound, is 0.5 to 20.0 nm.
The composite compound is a compound other than the first compound, is composed of elements of groups II and VI or groups III and V, forms a solid solution with the first compound, and is preferably a compound which forms a band gap.
In addition, the composite particles or composite compound contains a second compound other than the first compound composed of group II and VI or group III and V elements and having a band gap larger than the band gap of the first compound, and the lattice mismatch ratio between the lattice constant of the first compound and the lattice constant of the second compound is preferably 5% or less.
The first compound is composed of the elements of copper (Cu), indium (In) and sulfur (S), the second compound is zinc sulfide (ZnS), the composite particles or composite compound is preferably produced from raw materials in which A is 0.5 to 5.0 and B is 0.5 to 5.0 for a composite ratio (feed ratio) of the zinc (Zn), copper (Cu), indium (In) and sulfur (S) of the raw materials of 1:A:B:4. Furthermore, the composite ratio does not refer to the composite ratio of the phosphor, but rather to the feed ratio (moles) of the raw materials.
The first compound is composed of the elements of silver (Ag), indium (In) and sulfur (S), the second compound is zinc sulfide (ZnS), and the composite particles or composite compound is preferably produced from raw materials in which A is 0.5 to 5.0 and B is 0.5 to 5.0 for a composite ratio (feed ratio) of zinc (Zn), silver (Ag), indium (In) and sulfur (S) of 1:A:B:4.
Moreover, the first compound preferably has a quantum efficiency of emission of light waves following excitation by excitation light of 0.1% to 10.0% at room temperature. The fluorescence emitted by the first compound consists of light waves having a wavelength of 550 to 800 nm.
[Phosphor Production Process]
The phosphor production process of the present invention comprises mixing a first solution, in which a raw material salt of a plurality of types of elements composing a compound having a chalcopyrite structure is dissolved and mixed in a solution to which has been added a complexing agent which coordinates to the plurality of types of elements, and a second solution in which a chalcogenite compound has been dissolved, and heat-treating the mixture under predetermined heating conditions.
Examples of compounds which can be used for the chalcogenite compound include metal salts of zinc, cadmium, magnesium, manganese, nickel, copper, lead, sulfur and so on with dithiocarbaminates such as dimethyldithiocarbaminate, diethyldithiocarbaminate or dihexyldithiocarbaminate, xanthogenic acids such as hexadecylxanthogenic acid or dodecylxanthogenic acid, trithiocarbonates such as hexadecyltrithiocarbonate or dodecyltrithiocarbonate or dithiophosphoric acids such as hexadecyldithiophosphoric acid or dodecyldithiophosphoric acid, thioacetoamides, alkyl thiols, thiourea and derivatives thereof, and compounds which generate chalcogens such as sulfur, selenium or tellurium as a result of being decomposed by heating, such as trioctylphosphine selenide and trioctylphosphine telluride.
The predetermined conditions preferably consist of mixing the first solution and the second solution, and heat-treating the mixture at a temperature of 70 to 350° C. In addition, the predetermined conditions preferably consist of mixing the first solution and the second solution, and heat-treating the mixture for 1 second to 30 hours. The predetermined conditions also preferably consist of mixing the first solution and the second solution in a micro-reactor having a flow channel of 50 μm to 5 mm, followed by reacting by heating. Moreover, the sulfur compound is preferably zinc sulfide (ZnS).
The first solution is preferably a solution obtained by dissolving and mixing copper (I) or a copper (II) salt and an indium (III) salt in a solution containing a complexing agent which coordinates copper (I) and indium (III). The phosphor is produced from raw materials in which A is 0.5 to 5.0 and B is 0.5 to 5.0 for a composite ratio (feed ratio) of the zinc (Zn), copper (Cu), indium (In) and sulfur (S) of 1:A:B:4.
The first solution is preferably a solution obtained by dissolving and mixing a silver (I) salt and an indium (III) salt in a solution containing a complexing agent which coordinates silver (I) and indium (III). The phosphor is produced from raw materials in which A is 0.5 to 5.0 and B is 0.5 to 5.0 for a composite ratio (feed ratio) of the zinc (Zn), silver (Ag), indium (In) and sulfur (S) of 1:A:B:4.
Although the first compound in the form of a compound having a chalcopyrite structure composed of elements of groups I, III and VI may be any such typically known compound, it is particularly preferably a compound containing one or more types of elements among Cu and Ag as group I elements, among In, Ga and Al as group III elements, and among S, Se and Te as group VI elements, respectively.
Although the mixing ratio of the chalcopyrite compound and the compound to be compounded therewith can be varied as desired within a range that allows the formation of a solid solution or composite structure, the mixing ratio is preferably such that the compound to be compounded is compounded at a molar ratio of 0.05 to 3.00, and preferably 0.1 to 3.0, based on a group I element of the chalcopyrite compound. The phosphor described above may be spherical or spindle-shaped.
The following effects are demonstrated by the present invention.
A phosphor of the present invention, and a production process thereof, are able to provide a lowly toxic, semiconductor nanoparticle phosphor since the phosphor is a compound comprising elements of groups I, III and VI having a chalcopyrite structure, which is considered to have low toxicity, or composite particles or composite compound containing the compound, and these composite particles or the composite compound contains elements of groups II and VI or groups III and V.
In addition, a product which demonstrates near ultra violet fluorescence from visible light can be obtained by changing the phosphor synthesis conditions.
The following indicates an Example 1 of producing a phosphor of the present invention. Preparation of the reaction solutions used in this research was entirely carried out in an argon atmosphere using argon gas. Copper (I) iodide and indium (III) iodide were respectively dissolved in a complexing agent in the form of oleyl amine followed by mixing using octadecene as a solvent to obtain Solution A. Zinc diethyldithiocarbaminate was dissolved in trioctylphosphine followed by mixing with octadecene to obtain Solution C. Solutions A and C were then mixed and heated for a predetermined amount of time at 160 to 280° C. The resulting product was diluted with toluene followed by measurement of absorption and fluorescence spectra. The measurement results were then graphed.
The graph of
The quantum yield indicating the proportion of photons emitted by fluorescence relative to the number of photons of excitation light absorbed by each of the phosphors of the graph of
A=log(I/I0) (1)
The Cu/Zn ratio (molar ratio) in the reaction solution of Example 1, the Cu/Zn ratio (molar ratio) in the product, and the average particle diameter of the product were determined and shown in Table 2.
The product of Example 1 was measured by X-ray diffraction, and those results are shown in the chart of
Next, Example 2 shows a different example of the production of a phosphor of the present invention. Example 2 is basically the same as Example 1, and differences between the two are described below. The composite ratio of the phosphor raw materials as Zn:Cu:In:S is 1.0:0.8:0.8:4.0. The results of measuring the characteristics of the formed phosphor were graphed. The optical absorbance of the phosphor for each of the plots in
Fluorescence intensity is plotted on the horizontal axis of the graph of
Example 3 shows an example of producing a phosphor of the present invention. The production process of Example 3 is basically the same as the previously described Examples 1 and 2, and the differences there between are described below. Copper (I) iodide and indium (III) iodide were respectively dissolved in a complexing agent in the form of dodecyl amine followed by mixing using octadecene as a solvent to obtain Solution A. The concentration of copper (Cu) at this time was 0.1 mmol, that of indium (In) was 0.1 mmol, the amount of dodecyl amine was 2 ml, and the amount of octadecene was 5 ml.
Zinc diethyldithiocarbaminate was dissolved in trioctylphosphine to obtain Solution C. The concentration of zinc (Zn) at this time was 0.13 mmol, that of sulfur (S) was 0.26 mmol, and the amount of trioctylphosphine was 7 ml. Solution A and Solution C were mixed with a mixer followed by heating for a predetermined amount of time at a temperature of 160 to 240° C. in a micro-reactor. The results of measuring the formed phosphor were graphed.
The graph of
Example 4 shows another example of producing a phosphor of the present invention. The production process of Example 4 is basically the same as the previously described Example 1, and only the differences there between are described below. Acetic acid and indium acetate were respectively dissolved in a complexing agent in the form of oleyl amine followed by mixing using octadecene as a solvent to obtain Solution A. Zinc diethyldithiocarbaminate was dissolved in trioctylphosphine followed by mixing with octadecene to obtain Solution C.
Solution A and Solution C were then mixed and heated for a predetermined amount of time at 160 to 280° C. The resulting product was diluted with toluene followed by measurement of the absorption and fluorescent spectra. The measurement results were then graphed and shown in
Example 5 shows another example of producing a phosphor of the present invention. The production process of Example 5 is basically the same as the previously described Example 1, and only the differences there between are described below. Gallium iodide, copper iodide and indium iodide were respectively dissolved in a complexing agent in the form of oleyl amine followed by mixing using octadecene as a solvent to obtain Solution A. Zinc diethyldithiocarbaminate was dissolved in trioctylphosphine followed by mixing with octadecene to obtain Solution C.
Solution A and Solution C were then mixed and heated for a predetermined amount of time at 200° C. The resulting product was diluted with toluene followed by measurement of the absorption and fluorescent spectra. The maximum value of the absorption wavelength and the maximum value of the fluorescence wavelength were read from the measurement results and then graphed and shown in
The synthesis temperatures were as indicated in the graph of
Example 6 shows another example of producing a phosphor of the present invention. The production process of Example 6 is basically the same as the previously described Example 1, and only the differences there between are described below. Zinc bis-diethyldithiocarbaminate was added to the product obtained by the same process as described in the above-mentioned Example 1 using the raw materials of Zn, Cu, In and S in the ratio of 1.0:1.0:1.0:4.0 in Example 1, followed by heating for 5 minutes at 200° C. to synthesize composite particles having a ZnS shell. The fluorescence intensity of the resulting ZnS composite structure particles was measured. The excitation wavelength during measurement was 340 nm.
Example 7 shows an example of producing a phosphor of the present invention. Synthesis was carried out using trioctylphosphine selenide as a selenium source, octadecene as a solvent and oleylamine as a complexing agent. Zinc acetate, copper (II) acetate and indium iodide were completely dissolved in oleyl amine and mixed with octadecene followed by mixing with trioctylphosphine selenide dissolved in trioctylphosphine. This solution was then heated for 5 minutes at a temperature of 220° C. to obtain a product. The resulting product generated fluorescent light having a fluorescence wavelength of 600 nm as a result of optical excitation at 400 nm.
Example 8 shows an example of producing a phosphor of the present invention. Synthesis was carried out using thioacetoamide as a sulfur source, and dodecanethiol as a solvent and complexing agent. Copper iodide and indium iodide were completely dissolved in the dodecanethiol followed by the addition of thioacetoamide and heating for 22 hours at a temperature of 100° C. to obtain a product. The fluorescence spectrum of the resulting product is shown in
The present invention is used advantageously in the following fields.
A phosphor of the present invention can be used as a phosphor containing semiconductor nanoparticles capable of carrying out modification, staining and so on of bio-related substances. A phosphor containing nanoparticles of the present invention exhibits various fluorescence of 450 to 800 nm as a result of monochromatic excitation, and the nanoparticles demonstrate high stability. Consequently, in addition to applications as a fluorescent reagent for biomolecular analyses typically used at present in biochemical research and diagnostics, a phosphor of the present invention can be expected to be used in a wide range of other applications, including as a fluorescent tag for observation of the kinetics of biomolecules and as a fluorescent tag for simultaneous analysis of multiple types of molecules.
Moreover, since this nanoparticle phosphor is composed of lowly toxic elements and enables fluorescent color to be controlled as desired over a range of 450 to 800 nm corresponding to the range of visible light to near infrared light, it can be used as an optical material over an extremely wide range, including as a phosphor used in EL displays, plasma displays and field emission displays, as a phosphor for light-emitting diodes and as a phosphor for use in lasers. In addition, it can also be used as a semiconductor light source for illumination.
Number | Date | Country | Kind |
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2004-210548 | Jul 2004 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP2005/013185 | 7/15/2005 | WO | 00 | 3/4/2008 |