Patent Grant
8298506
This invention relates to titanium dioxide particles doped with a rare earth element. More particularly, the present invention relates to titanium dioxide particles containing a rare earth element substituting at the titanium sites of a titanium dioxide lattice.
Titanium dioxide is being widely utilized for pigments, cosmetics such as UV creams, photocatalysts, solar cells and so on. It is also being broadly studied. Particularly, nano particles of titanium dioxide are attracting attention because of having various potential applications. Novel techniques relating to titanium dioxide include inserting europium ions (Eu3+) among nano sheets of titanium oxide to prepare a light emitting material that emits red light attributable to Eu3+ (see, inter alia, Non-Patent Document 1).
Another technique relating to titanium dioxide is a method of manufacturing ceramic powder directly from a mixture or the reaction product of a metal compound and an alkoxide by way of a thermal plasma process (see, inter alia, Patent Document 1).
According to known technique of the above cited Non-Patent Document 1, nano sheets of titanium oxide is irradiated with light to excite electrons in a valence band (VB) to move to a conduction band (CD). Electrons that are excited to move to the conduction band are not relaxed to move back directly to the valence band but trapped temporarily in a defect level. Later, such electrons move to the excitation level of Eu3+ without being recombined with holes in the valence band. As a result, it becomes possible to take out fluorescence attributable to Eu3+.
Such a move of energy from nano sheets of titanium oxide to Eu3+ takes place effectively when the energy level of the defect level of the nano sheets of titanium oxide is slightly higher than that of Eu3+ in an excited state. Since it is only necessary to excite nano sheets of titanium oxide that is a host compound in order to take out fluorescence attributable to rare earth ions, it is possible to use light of a wavelength that is absorbed by the nano sheets of titanium oxide.
On the other hand, Patent Document 1 describes a method of manufacturing ceramic powder, using (I) a metal compound other than alkoxide having one or more than one metal elements, (II) an alkoxide having one or more than one metal elements, a mixture of (I) and (I) and/or the reaction product of (I) and (II), by way of a thermal plasma process. With such a thermal plasma process, it is possible to obtain ceramic powder without using sintering and crushing steps.
With the technique described in Patent Document 1, it is possible to manufacture highly crystalline ceramic powder by using a precursor obtained by mixing (I) and (II) or causing them to react with each other as starting material.
However, with the technique described in the above cited Non-Patent Document 1, it is not possible to take out fluorescence attributable to terbium ions (Tb3+) because the energy level of the defect level of nano sheets of titanium oxide is lower than that of Tb3+ in an excited state when terbium ions (Tb3+) are inserted into nano sheets of titanium oxide.
In other words, the above technique has a drawback that it can only take out fluorescence attributable to limited rare earth ions that can satisfy the above energy structure by inserting rare earth ions into nano sheets of titanium oxide.
While the technique described in the above-cited Patent Document 1 is suited for manufacturing multi-composite particles, it is not suited for manufacturing titanium dioxide particles doped with an impurity.
More specifically, an organic solvent or water is used when mixing (I) and (II) and the mixture solution is a slurry solution where (I) or (II) is partly precipitated. This means that, when a rare earth compound and a titanium alkoxide are selected for (I) and (II) respectively, the obtained titanium oxide particles can be those of a composite oxide of titanium and a rare earth element or of titanium oxide and a rare earth oxide and not those where the rare earth element is substituted at the titanium sites in the titanium oxide lattice.
Energy can hardly move from a host compound to a rare earth element in particles of any of such composite oxides and composite matters and hence it is difficult to highly efficiently take out fluorescence attributable to a rare earth element.
Therefore, it is the object of the present invention to provide titanium dioxide particles, more particularly, titanium dioxide particles where a rare earth element is substituted at the titanium sites from which it is possible to highly efficiently take out fluorescence attributable to the rare earth element and also a method of manufacturing such titanium dioxide particles.
According to the present invention, the above object is achieved by providing a method of manufacturing titanium dioxide particles doped with a rare earth element, comprising: a step of preparing a liquid precursor containing a titanium source and a rare earth metal source, the doping ratio of the rare earth element in the liquid precursor being within a range not less than 0 at % and not more than 5.0 at %; a step of generating thermal plasma; and a step of providing the liquid precursor into the thermal plasma.
The doping ratio of the rare earth element in the liquid precursor may be within a range not less than 0 at % and not more than 0.5 at %.
The titanium source may be a titanium alkoxide chelate complex and the rare earth metal source may be a rare earth metal compound chelate complex.
The titanium alkoxide chelate complex may contain a titanium alkoxide selected from a group of titanium ethoxide, titanium propoxide and titanium butoxide and an organic solvent selected from a group of diethanolamine, triethanolamine and acetylacetone and the rare earth metal compound chelate complex may contain a rare earth metal non-alkoxide selected from a group of rare earth nitrates, rare earth chlorides, rare earth sulfates and rare earth acetates, citric acid or ethylenediaminetetraacetate and ammonia or a rare earth metal alkoxide selected from a group of rare earth metal ethoxides, rare earth metal propoxides and rare earth metal butoxides and an organic solvent selected from a group of diethanolamine, triethanolamine and acetylacetone.
The titanium source may be a titanium trichloride solution and the rare earth metal source may be a rare earth metal alkoxide.
The rare earth metal alkoxide may be selected from a group of rare earth metal ethoxides, rare earth metal propoxides and rare earth metal butoxides.
The rare earth element may be selected from a group of cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium.
When the rare earth metal compound chelate complex contains a rare earth metal non-alkoxide selected from a group of rare earth nitrates, rare earth chlorides, rare earth sulfates and rare earth acetates, citric acid or ethylenediaminetetraacetate and ammonia, the preparation process further includes: a step of mixing the rare earth metal non-alkoxide and the citric acid or ethylenediaminetetraacetate; a step next to the mixing step of mixing the ammonia; and a step next to the mixing step of mixing the titanium alkoxide chelate complex.
The step of mixing ammonia may be so conducted as to make the pH of the rare earth metal compound chelate complex equal to 9.0.
The generating step may be conducted to generate oxygen-containing thermal plasma by means of a plasma generation system selected from a group of an RF induction plasma system, a DC arc plasma system, a DC RF hybrid plasma system and a microwave induction plasma system.
The providing step may be conducted to atomize the liquid precursor.
In titanium dioxide particles doped with a rare earth element according to the present invention, the doping ratio of the rare earth element is within a range not less than 0 at % and not more than 5.0 at % and the rare earth element is substituted for titanium atoms in the unit lattice of titanium dioxide so that the titanium dioxide particles emit light attributable to the rare earth element when the titanium dioxide particles are irradiated with light having the absorption wavelength of titanium dioxide in order to achieve the object.
The doping ratio of the rare earth element is within a range not less than 0 at % and not more than 0.5 at %.
The particle diameter of the titanium dioxide particles may be within a range not less than 5 nm and not more than 100 nm.
The rare earth element may be selected from a group of cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium.
The titanium dioxide particles may contain anatase titanium dioxide particles and rutile titanium dioxide particles.
The content ratio of the anatase titanium dioxide particles relative to the titanium dioxide particles may be within a range not less than 0 wt % and less than 100 wt %.
The emission of light attributable to the rare earth element may be produced by irradiating the titanium dioxide particles with light exceeding the absorption wavelength of titanium dioxide and capable of exciting the rare earth element.
In titanium dioxide particles doped with a rare earth element according to the present invention, the doping ratio of the rare earth element is within a range not less than 0 at % and not more than 5.0 at %, preferably within a range not less than 0 at % and not more than 0.5 at %. The rare earth element is reliably substituted for the titanium atoms in the unit lattice of titanium dioxide when the doping ratio is within the above-defined range.
As the titanium dioxide particles are irradiated with light having the absorption wavelength of titanium dioxide, energy moves highly efficiently from the titanium dioxide to the rare earth element because the rare earth element exists at the titanium sites in the unit lattice of titanium dioxide. Then, as a result, the titanium dioxide particles can emit light attributable to the rare earth element.
A method of manufacturing titanium dioxide particles doped with a rare earth element according to the present invention comprises: a step of preparing a liquid precursor containing a titanium source and a rare earth metal source; a step of generating thermal plasma; and a step of providing the liquid precursor into the thermal plasma.
As liquid sources are used respectively for the titanium source and the rare earth metal source, it is possible to mix titanium and the rare earth without precipitation. Additionally, since the doping ratio of the rare earth element in the liquid precursor is within a range not less than 0 at % and not more than 5.0 at %, it is possible not only to efficiently control the doping ratio but also substituting the rare earth element at the titanium sites.
Before describing embodiments of the present invention, the principle underlying the present invention will be described below.
The steps of the manufacturing method will be described by referring to the plasma reactor 200 in
Step S110: A liquid precursor containing a titanium source and a rare earth metal source is prepared.
Both the titanium source and the rare earth metal source are solutions. The doping ratio of the rare earth element in the liquid precursor is regulated so as to be within a range not less than 0 at % and not more than 5.0 at %. With the above-cited doping ratio, it is possible to substitute the rare earth element for all the titanium sites in the titanium dioxide lattice and the crystal structure of titanium dioxide can be maintained.
For example, a report on doping gadolinium oxide, which is similar to titanium dioxide, with a rare earth element (Eu) up to 14 at % and a report on doping yttrium oxide with a rare earth element (Tb) up to 6 at % are known. Preferably, the doping ratio of the rare earth element in the liquid precursor is not less than 0 at % and not more than 0.5 at %. The process of substitution proceeds without problem without specifying any particular manufacturing conditions when the content ratio of the rare earth element is within the above range.
As will be described hereinafter, the intensity of emitted light attributable to the rare earth element (rare earth ions) tends to fall when the rare earth element is doped beyond 5.0 at % so that it is desirable that the content ratio of the rare earth element is not more than 5.0 at %.
The expression “doping of a rare earth element” as used in this specification refers to that the rare earth element is substituted for part of the titanium at the titanium sites of a titanium dioxide lattice and it should be noted that any composite particles of titanium dioxide and the rare earth element are not contained there.
Step S120: Thermal plasma 270 is generated in the chamber 210 of the plasma reactor 200.
The pressure in the chamber 210 is adjusted to a range between 10 and 760 Torr by means of the vacuum pump 260. The power supply source 220 generates plasma by means of a frequency of 0.2 MHz to 50 MHz and RF power of 5 KW to 500 KW. Thermal plasma 270 is generated from gas that contains O2 (oxygen gas) and may typically be Ar/O2 thermal plasma generated from a mixture gas of O2 and Ar supplied from the sheath 240. The power supply source 220 may be selected from a group of an RE induction plasma system, a DC arc plasma system, a DC RF hybrid plasma system and a microwave induction plasma system.
Step S130: The liquid precursor prepared in Step S110 is supplied to the thermal plasma 270. The liquid precursor may be supplied to the chamber 210 by way of an atomizing probe 230. At this time, the liquid precursor may be supplied to the chamber 210 with Ar or O2 carrier gas. As a result, the liquid precursor turns into mist. Since such a misty liquid precursor can be supplied continuously to the thermal plasma 270, it is possible to produce uniform high quality powder. The front end of the atomizing probe 230 is arranged so as to be held in contact with the thermal plasma 270 generated by the power supply source 220. As a matter of course, the liquid precursor may be directly exposed to the thermal plasma 270.
The misty liquid precursor exposed to the thermal plasma 270 is decomposed at high temperature. The decomposed liquid precursor gives rise to a chemical reaction when it is cooled. Then, as a result, stable titanium dioxide particles are produced. Such a reaction process can easily be conceivable to those skilled in the art by analogy. The obtained titanium dioxide particles are collected by way of the chamber 210 and the filter 250.
The starting material does not precipitate in the liquid precursor and is mixed well when liquid is used to supply the starting material and limit the doping ratio of the rare earth element to the above-described range. Then, as a result, it is possible to obtain titanium dioxide particles where the rare earth element is substituted at the titanium sites. The particle diameter of the obtained titanium dioxide particles can be within a range between 5 nm and 100 nm as a result of using a thermal plasma process. Thus, it is possible to obtain titanium dioxide particles having a desired particle diameter by controlling the manufacturing process.
Since the rare earth element is located at the titanium sites, the relationship between the energy level of titanium dioxide and that of rare earth element ions, which is described earlier by referring to
Now, embodiments of the present invention will be described below by referring to the accompanying drawings.
(Embodiment 1)
Since the steps in
Step S310: A mixture containing a titanium alkoxide chelate complex and a rare earth metal compound chelate complex is prepared. The titanium alkoxide chelate complex and the rare earth metal compound chelate complex respectively operate as a titanium source and a rare earth metal source. Both such a titanium alkoxide chelate complex and such a rare earth metal compound chelate complex are liquid. The doping ratio of the rare earth element in the liquid precursor is adjusted to be within a range not less than 0 at % and not more than 5.0 at %.
More particularly, Step S310 may be either Step S310A or Step S310B.
Step S310A: A liquid precursor containing a titanium alkoxide chelate complex, which by turn contains a titanium alkoxide that operates as titanium source and an organic solvent, and a rare earth metal compound chelate complex, which by turn contains a rare earth metal non-alkoxide and citric acid or ethylenediaminetetraacetate (EDTA) and ammonia as rare earth metal source, is prepared.
The titanium alkoxide is selected from a group of titanium ethoxide, titanium propoxide and titanium butoxide. The organic solvent is selected from a group of diethanolamine, triethanolamine and acetylacetone. The above-described organic solvent can operate to stably hold the titanium alkoxide in the solution without precipitation.
The rare earth metal non-alkoxide is selected from a group of rare earth nitrates, rare earth chlorides, rare earth metal sulfates and rare earth acetates. Citric acid or EDTA can operate to stably hold the rare earth metal non-alkoxide in the solution without precipitation.
The rare earth element is selected from a group of cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium. Such a rare earth element can be substituted for the titanium in the titanium dioxide lattice and emit light due to the atom size and the electron configuration thereof.
Ammonia operates to prevent citric acid or EDTA from hydrolyzing the titanium alkoxide by turning the rare earth metal compound chelate complex that contains citric acid or EDTA, which is acidic, alkaline. Preferably, ammonia is mixed so as to make the pH of the rare earth metal compound chelate complex equal to 9.0.
More specifically, firstly the rare earth metal non-alkoxide and citric acid or EDTA, which is acidic, are mixed with each other. As a result, the rare earth metal non-alkoxide is prevented from precipitating. Then, ammonia is mixed with the mixture solution to produce a rare earth metal compound chelate complex. As a result, the pH of the rare earth metal compound chelate complex is adjusted and the complex becomes alkaline. Thereafter, the rare earth metal compound chelate complex whose pH has been adjusted is mixed with a titanium alkoxide chelate complex that contains titanium alkoxide and an organic solvent to prepare a liquid precursor. As the mixings are conducted in the above-described order, the rare earth metal non-alkoxide and the titanium alkoxide are prevented from precipitating and additionally the titanium alkoxide is prevented from hydrolyzing.
The liquid precursor prepared in this way does not give rise to any precipitation because of the effect of the organic solvent and citric acid or EDTA and the titanium alkoxide chelate complex and the rare earth metal compound chelate complex can be mixed well in it. It should be noted here that, as a result of intensive research efforts, the inventors of the present invention found a combination of an organic solvent and citric acid or EDTA that operates to stably hold both the titanium alkoxide and the rare earth metal non-alkoxide and mixes them well.
Step S310B: A liquid precursor containing a titanium alkoxide chelate complex, which by turn contains a titanium alkoxide that operates as titanium source and an organic solvent, and a rare earth metal compound chelate complex, which by turn contains a rare earth metal alkoxide that operates as rare earth metal source and an organic solvent, is prepared.
In this case, again, as in Step S310A, the titanium alkoxide is selected from a group of titanium ethoxide, titanium propoxide and titanium butoxide. The organic solvent is selected from a group of diethanolamine, triethanolamine and acetylacetone.
The rare earth metal alkoxide is selected from a group of rare earth metal ethoxides, rare earth metal propoxides and rare earth metal butoxides. The organic solvent is selected from a group of diethanolamine, triethanolamine and acetylacetone as in the case of the titanium alkoxide chelate complex. In this case again, the organic solvent selected from the above group can operate to stably hold the rare earth metal alkoxide in the solution without precipitation.
The rare earth element is selected from a group of cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium.
The titanium alkoxide chelate complex and the rare earth metal compound chelate complex can be mixed with each other well without precipitating due to the effect of the organic solvent in the liquid precursor that is prepared in this way. It should be noted here that, as a result of intensive research efforts, the inventors of the present invention found a combination of organic solvents that operates to stably hold both the titanium alkoxide and the rare earth metal alkoxide and mixes them well. It is not necessary to adjust the pH in Step S310B.
The following steps may be same as Step S120 and Step S130 described above by referring to
When the doping ratio of the rare earth element in the liquid precursor is adjusted within a range not less than 0 at % and not more than 0.5 at %, it is possible to obtain titanium dioxide particles doped with a rare earth element with ease because the manufacturing process does not need to be subjected to a number of restrictions including conditions for generating thermal plasma 270.
(Embodiment 2)
Since the steps in
Step S410: A mixture containing a titanium trichloride solution and a rare earth metal alkoxide is prepared. The titanium trichloride solution and the rare earth metal alkoxide respectively operate as a titanium source and a rare earth metal source. Both such a titanium trichloride solution and such a rare earth metal alkoxide are liquid. The doping ratio of the rare earth element in the liquid precursor is adjusted to be within a range not less than 0 at % and not more than 5.0 at %.
The rare earth metal alkoxide is selected from a group of rare earth metal ethoxides, rare earth metal propoxides and rare earth metal butoxides. The rare earth element is selected from a group of cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and ytterbium.
The titanium trichloride solution is more stable and more easily handleable if compared with the titanium alkoxide of Embodiment 1. Therefore, Embodiment 2 provides an advantage that the precursor solution thereof can be prepared easier than Embodiment 1.
The following steps may be same as Step S120 and Step S130 described above by referring to
As described above for Embodiment 1, when the doping ratio of the rare earth element in the liquid precursor is adjusted within a range not less than 0 at % and not more than 0.5 at % in Step S410, it is possible to obtain titanium dioxide particles doped with a rare earth element with ease because the manufacturing process does not need to be subjected to a number of restrictions including conditions for generating thermal plasma 270.
Now, the present invention will be described further by way of examples, although it should be noted that the present invention is by no means limited to the examples.
Specimens of titanium dioxide particles (hereinafter referred to as Er—TiO2) doped with erbium to different doping ratios were manufactured from respective liquid precursors, each containing a titanium alkoxide chelate complex, which by turn contains titanium butoxide as titanium alkoxide and diethanolamine as organic solvent for stabilizing titanium butoxide, and a rare earth metal compound chelate complex, which by turn contains erbium nitrate as rare earth metal non-alkoxide and citric acid.
Referring to
Each of the liquid precursors contained a titanium alkoxide chelate complex by turn containing 0.1 mol of titanium butoxide and 0.4 mol of diethanolamine, a rare earth metal non-alkoxide chelate complex by turn containing erbium nitrate to a predetermined ratio (erbirum doping ratios of the specimens: 0.25 at %, 0.5 at %, 1.0 at % and 3.0 at %) and citric acid and 20 ml of distilled water. Citric acid and erbium nitrate were mixed to show a mol ratio of 1:1.
Each of the liquid precursors obtained in this way was then supplied to the center of thermal plasma 270 (
The produced titanium dioxide particles were collected from the lateral wall of the stainless-steel-made reactor 210 and the filter 250 as specimens. The specimens of collected titanium dioxide particles are referred to respectively as 0.25 at % Er—TiO2 (Ex1-1), 0.5 at % Er—TiO2 (Ex1-2), 1.0 at % Er—TiO2 (Ex1-3) and 3.0 at % Er—TiO2 (Ex1-4) to indicate the erbium doping ratios.
The structures of Ex1-1 through Ex1-4 were analyzed by means of an X-ray diffractometer (Model Philips PW1800: tradename, available from Philips Research Laboratories, Holland). The operating conditions of the X-ray diffractometer included an acceleration voltage using Cu—Kα rays of 40 kV, an electric current of 50 mA and a scanning rate of 0.15°/2θ·min. For the purpose of simplicity, the results obtained for Ex1-1, Ex1-2 and Ex1-4 are shown in
The surface of Ex1-4 was observed through a scanning electron microscope (FE-SEM, Model S-500: tradename, available from Hitachi, Japan).
The crystal sizes (particle diameters) of the specimens were determined by means of the Scherrer's formula, using the diffraction peaks of the (101) face that indicates the anatase type and the (110) face that indicates the rutile type obtained from
The cathode luminescence of Ex1-4 was measured by means of a scanning electron microscope (FE-SEM, Model S-4000SE: tradename, available from Hitachi, Japan) that was mounted by a cathode luminescence system.
The cathode luminescence measuring conditions included an accelerating voltage of 20 kV and a wavelength range between 1,100 nm and 1,600 nm. For the purpose of comparison, the results obtained for erbium oxide are also shown in
From the X-ray diffraction patterns, a peak of Er2Ti2O7 of pyrochlore phase was detected from each of Ex1-3 (not shown in
While it is theoretically possible to dope up to 5.0 at %, it may be safe to assume that rare earth ions were deposited when the content ratio of the rare earth element exceeded 0.5 at % because the manufacturing process was not optimized. However, it was found that it is possible to obtain titanium dioxide particles doped with a rare earth element with ease without providing a special manufacturing process when the content ratio is not less than 0 at % and not more than 0.5 at %.
Additionally, a peak of the (101) face that indicates anatase titanium dioxide and a peak of the (110) face that indicates rutile titanium dioxide were detected in each of the X-ray diffraction patterns of Ex1-1 through Ex1-4. From the above, it was found that the obtained titanium dioxide particles of each of the specimens were a mixture of anatase titanium dioxide and rutile titanium dioxide.
Still additionally, it was also found the ratio of the peak intensity of the (101) face to that of the (110) face changes as a function of the doping ratio of Er ions. This will be described in greater detail hereinafter by referring to
From
From the above finding, it was found that the doping ratio at the feed-in time is maintained by a manufacturing method according to the present invention.
formula (1):
Er2O3+3/2TiTix→2Er′Ti+V0{umlaut over ( )}+3/2TiO2 (1),
where TiTix is Ti located at a Ti site and Er′Ti is Er located at a Ti site, whereas V0{umlaut over ( )} represents an oxygen hole. It is known that rutile titanium dioxide has a capacity for generating oxygen holes greater than anatase titanium dioxide. In other words, rutile titanium dioxide is generated with priority as Er3+ is dissolved in titanium dioxide to produce oxygen holes.
More specifically, both the basic structure of rutile titanium dioxide and that of anatase titanium dioxide are a series of oxygen octahedrons, in each of which a titanium atom is surrounded by six oxygen atoms. The number of linked edge sharing oxygen octahedrons is 2 in rutile titanium dioxide, whereas that of linked edge sharing oxygen octahedrons is 4 in anatase titanium dioxide.
As oxygen atoms of oxygen octahedrons are drawn out to produce oxygen holes in anatase titanium dioxide where the number of linked edge sharing oxygen octahedrons is greater than in rutile titanium dioxide, the repulsive energy between the positive ions (Ti4+ in this case) located at the centers of two oxygen octahedrons becomes greater than in rutile titanium dioxide. Then, as a result, the crystal structure of anatase titanium dioxide becomes instable so that rutile titanium dioxide is generated with priority as a result.
While it was found that, while Er3+ ions are deposited as pyrochlore phase when the Er3+ concentration exceeds 0.5 at % from
This suggests that Er3+ ions are dissolved in rutile titanium dioxide at the time when cores are generated for titanium dioxide nano particles so that it is possible to substitute Er3+ more for titanium dioxide particles beyond 0.5 at % without generating a pyrochlore phase by optimizing the manufacturing process. More specifically, it is possible to suppress the generation of a pyrochlore phase by improving the cooling rate of a plasma downstream section. Then, as a result, it is possible to obtain titanium dioxide particles doped with Er3+ maximally to 5 at %.
Anatase titanium dioxide can be utilized as photocatalyst. On the other hand, rutile titanium dioxide has a refractive index and shows double refraction that are greater than anatase titanium dioxide so that it is expected to be used as host materials and find optical applications in the field of photonic crystals. Thus, it is possible to manufacture titanium dioxide particles having a phase composition doped with a rare earth element according to the user application with ease.
The particle diameter of the rutile titanium dioxide in the obtained titanium dioxide particles was not less than 60 nm and it was found that the particle diameter grows up to 90 nm as the Er3+ concentration increases. The particle diameter of the anatase titanium dioxide in the obtained titanium dioxide particles was constantly about 35 nm regardless of the Er3+ concentration.
Now, the obtained results are summarily shown in Table 2 below.
From the above, the emission of light observed at about 1,530 nm was not attributable to free erbium oxide locally existing in titanium dioxide particles but attributable to Er3+ substituted at the titanium sites of titanium dioxide. In other words, the substitution was successful.
Specimens of titanium dioxide particles (hereinafter referred to as Eu—TiO2) doped with europium to different doping ratios were manufactured from respective liquid precursors, each containing a titanium alkoxide chelate complex, which by turn contains titanium tetra-n-butoxide (TTBO) as titanium alkoxide and diethanolamine as organic solvent for stabilizing TTBO, and a rare earth metal compound chelate complex, which by turn contains europium nitrate as rare earth metal non-alkoxide, citric acid and ammonia.
Each of the liquid precursors contained a titanium alkoxide chelate complex by turn containing 0.1 mol of TTBO and 0.4 mol of diethanolamine, a rare earth metal non-alkoxide chelate complex by turn containing europium nitrate to predetermined ratio (europium doping ratios of the specimens: 0.05 at %, 0.1 at %, 0.2 at %, 0.3 at %, 0.5 at %, 0.75 at % 1.0 at %, 2.0 at %, 3.0 at % and 5.0 at %), citric acid and ammonia and 20 ml of distilled water. Citric acid and europium nitrate were mixed to show a mol ratio of 1:1.
Since citric acid can hydrolyze TTBO in the presence of diethanolamine, the pH of the rare earth metal compound chelate complex was adjusted to about 9.0 for each of the specimens by adding ammonia after mixing europium nitrate and citric acid. A 25% ammonia solution (3 mL) was used for the adjustment of pH. Thereafter, europium nitrate was mixed with the rare earth metal compound chelate complex of each of the specimens whose pH had been adjusted to obtain the corresponding liquid precursor.
Table 3 below shows the manufacturing apparatus and the manufacturing conditions of this example, which will not be explained further because they are same as those of Example 1 except the O2 flow rate of the precursor solution doped with europium to the ratio of 0.5 at % was changed from 10 to 90 L/min (more specifically, 10, 30, 40, 50, 70 and 90 L/min).
The produced titanium dioxide particles were collected from the lateral wall of the stainless-steel-made reactor 210 (
The specimens of collected titanium dioxide particles are referred to respectively as 0.05 at % Eu—TiO2 (Ex2-1), 0.1 at % Eu—TiO2 (Ex2-2), 0.2 at % Eu—TiO2 (Ex2-3), 0.3 at % Eu—TiO2 (Ex2-4), 0.5 at % Eu—TiO2 (Ex2-5), 0.75 at % Eu—TiO2 (Ex2-6), 1.0 at % Eu—TiO2 (Ex2-7), 2.0 at % Eu—TiO2 (Ex2-8), 3.0 at % Eu—TiO2 (Ex2-9) and 5.0 at % Eu—TiO2 (Ex2-10) to indicate the europium doping ratios.
The structures of Ex2-1 through Ex2-10 were analyzed by means of an instrument similar to the one used in Example 1 under similar operating conditions. For the purpose of simplicity, the results obtained for Ex2-5, Ex2-7, Ex2-9 and Ex2-10 and those obtained for non-doped titanium dioxide for purpose of comparison are shown in
The crystal sizes (particle diameters) of the specimens were determined by means of the Scherrer's formula, using the diffraction peaks of the (101) face that indicates the anatase type and the (110) face that indicates the rutile type obtained from
Additionally, the content ratios of the anatase titanium dioxide and rutile titanium dioxide in the obtained titanium dioxide particles of the specimens were determined by means of the Spurr and Myers's formula as in Example 1. The results are shown in
As for the conditions of the observation, the specimens were analyzed with a resolution of 1 cm−1, using Ar+ laser (wavelength: 514.5 nm; power; 50 mW) as the excitation light. The obtained results are shown for Ex2-1, Ex2-2, Ex2-4, Ex2-7, Ex2-9 and Ex2-10 in
The UV-visible diffusion/reflection spectrums of Ex2-1 through Ex2-10 were observed by means of a visible-UV absorption spectrometer (Jasco V-570: tradename, available from JASCO, Japan).
The observation wavelength was within a range between 200 nm and 800 nm. The results obtained for Ex2-1, Ex2-5 and Ex2-10 and also those obtained for non-doped titanium dioxide and Eu2Ti2O7 of pyrochlore phase for the purpose of comparison are shown in FIG. 13 and will be described in detail below.
The excitation spectrum and the emission spectrum of the specimens of Ex2-5 were observed by means of a fluorescence spectrophotometer (F-4500: tradename, available from Hitachi, Japan). The obtained results are shown in
The photoluminescence spectrum was observed for Ex2-1 through Ex2-10 by means of a photoluminescence spectrometer (Renishaw plc, UK). The photoluminescence was observed for Ex2-1 through Ex2-10 by means of a He—Cd laser (wavelength 325 nm) for excitation light.
The results obtained for Ex2-5 and Ex2-10, and also those obtained for non-doped titanium dioxide and Eu2Ti2O7 of pyrochlore phase, which were observed for the purpose of comparison are shown in
As in Example 1, the peak (222) of Eu2Ti2O7 of pyrochlore phase was detected from the X-ray diffraction patterns for Ex2-7, Ex2-9 and Ex2-10 that were doped with Eu beyond 0.5 at %. However, it is possible to dope up to 5.0 at % by optimizing the manufacturing process.
Additionally, as in Example 1, a peak of the (101) face that indicates anatase titanium dioxide and a peak of the (110) face that indicates rutile titanium dioxide were detected in each of the X-ray diffraction patterns. From the above, it was found that the obtained titanium dioxide particles of each of the specimens were a mixture of anatase titanium dioxide and rutile titanium dioxide.
Still additionally, it was also found the ratio of the peak intensity of the (101) face to that of the (110) face changes as a function of the doping ratio of Eu ions. This will be described in greater detail hereinafter by referring to
More specifically, the content ratio of rutile titanium dioxide was 22 wt % in non-doped titanium dioxide and increased to 52 wt % when doped with Eu3+ to a concentration of 5 at %. This means that it is possible to control the content ratio of anatase titanium dioxide to rutile titanium dioxide by controlling the manufacturing condition.
The fact that the content ratio of rutile titanium dioxide increases without saturation as the Eu3+ concentration increases as in Example 1 suggests that Eu ions can be substituted by optimizing the manufacturing process.
The particle diameter of the rutile titanium dioxide in the obtained titanium dioxide particles was not less than 60 nm and it was found that the particle diameter grows up to 90 nm as the Eu3+ concentration increases. The particle diameter of the anatase titanium dioxide in the titanium dioxide particles was constantly between 30 nm and 35 nm regardless of the Eu3+ concentration.
Table 4 below summarily shows the above results.
Eu2Ti2O7 showed a diffused weak Raman scattering within a range between 100 cm−1 and 800 cm−1. On the other hand, all the specimens of titanium dioxide doped with Eu3+ (Ex2-1 through Ex2-10) showed a characteristic peak.
More specifically, the scatterings at 146 cm−1 (Eg mode), 200 cm−1 (Eg mode), 401 cm−1 (Blg mode), 519 cm−1 (Blg mode) and 641 cm−1 (Eg mode) agreed with those of anatase titanium dioxide, where the scatterings at 449 cm−1 (Eg mode) and 614 cm−1 (Alg mode) agreed with those of rutile titanium dioxide.
The scattering at 143 cm−1 (Blg mode) of rutile titanium dioxide did not show any overlapping with the scattering at 146 cm−1 (Eg mode) of anatase titanium dioxide.
The peak intensity of the Eg mode (449 cm−1) and that of the Alg mode (614 cm−1) of rutile titanium dioxide increased as the Eu3+ concentration increased. This fact agrees with that the content ratio of rutile titanium dioxide increases as the Eu3+ concentration increases as pointed out above by referring to
All the spectrums had an absorption band at about 405 nm. It was confirmed that the absorption band corresponds to a band gap of about 3.06 eV, which is same as the band gap of titanium dioxide.
On the other hand, Eu2Ti2O7 showed additional absorptions at 395 nm, 416 nm, 467 nm and 538 nm. These correspond to the inner shell transition 4f→4f of Eu3+.
Meanwhile, none of Ex2-1, Ex2-5 and Ex2-10 showed peaks that correspond to the inner shell transition 4f→4f of Eu3+. This is because none of the specimens contain Eu3+ to such an extent that allows the peaks of Eu3+ to be detected and the transition process that causes the absorption of Eu3+ 395 nm that shows the highest intensity was quenched by the large absorption (about 405 nm) of titanium dioxide.
Referring to
The spectrum (a) showed peaks at 360 nm, 416 nm, 467 nm and 538 nm. The peaks of 416 nm, 467 nm and 538 nm out of the four peaks agreed with the peaks of the pyroclore phase of the UV-visible absorption spectrum described above by referring to
In other words, the three peaks correspond respectively to the 7F0,1→5D3, 7F0,1→5D2 and 7F0,1→5D1 transitions of Eu3+. The peak of 360 nm in the spectrum (a) agreed with the absorption band of non-doped titanium dioxide described above by referring to
From these, it was shown that Eu3+ was efficiently excited by way of the titanium dioxide host lattice. Note that, although the right-hand skirt of the peak of 360 nm partly overlaps the peak of 416 nm, it does not completely overlap the latter peak.
The spectrum (b) is the photoluminescence spectrum that is observed when non-doped titanium dioxide is excited with light of wavelength not higher than 360 nm (wavelength equal to 360 nm here). The spectrum (b) did not show any characteristic peak.
The spectrum (d) is the photoluminescence spectrum that is observed when Ex2-5 is excited with light of wavelength not higher than 360 nm (wavelength equal to 360 nm here). Unlike the spectrum (b), it showed peaks attributable to Eu3+ within a wavelength range between 590 nm and 720 nm.
More particularly, the peaks of the spectrum (d) agree with the 5D0→7Fj (j=1 through 4) transitions of electrons of excited Eu3+.
These peaks can be visually identified as pure red. They are very sharp and show a high intensity. A light emitting material that shows such a clear red can be, for instance, effectively applied to white LEDs.
The spectrum (c) is the photoluminescence spectrum that is observed when Ex2-5 is excited with light having a wavelength greater than the absorption edge of non-doped titanium dioxide (>450 nm) (wavelength equal to 457 nm here).
Again, the spectrum (c) showed peaks attributable to Eu3+ within a wavelength range between 590 nm and 720 nm.
Thus, it is possible to take out emitted light attributable to a rare earth element by irradiating titanium dioxide particles with light of a wavelength that can excite rare earth elements (wavelength equal to 457 nm here).
However, the peak intensities of the spectrum (c) are smaller that those of the spectrum (d) and the peaks were broader than those of the spectrum (d). From this fact, it was found that titanium dioxide particles that are doped with a rare earth element according to the present invention can easily give rise to a move of energy from the host titanium dioxide to rare earth ions.
From above, it was also found that europium-doped titanium dioxide according to the present invention can easily excite Eu3+ by means of light having the absorption wavelength of titanium dioxide to make it possible to take out emitted light attributable to Eu3+.
This fact suggests that the local environment of Eu3+ in Eu2-5 and in Eu2-10 differs from that of Eu3+ in Eu2O3 and Eu2Ti2O7. In other words, the radiation from Ex2-5 and Ex2-10 are not attributable to Eu2O3 and Eu2Ti2O7 but to Eu3+ substituted for titanium at part of the titanium sites in the titanium dioxide lattice.
A peak similar to a peak attributable to Eu2Ti2O7 was observed at 612 nm in the spectrum of Eu2-10. As described above by referring to
The spectrum of Eu2-5 showed the peaks of 5D0→7Fj (j=1 through 4). It is known that 5D0→7F1 rays (599 nm, three Stark splits) are produced from a magnetic dipole transition.
On the other hand, it is known that 5D0→7F2 rays (617 nm, five Stark dissociations) are produced from an electric dipole transition. A magnetic dipole transition can take place while an electric dipole transition is suppressed. An electric dipole transition can take place only when Eu3+ is not at the center of inversion but occupies lattice positions and is influenced by local symmetry.
As seen from the spectrum of Ex2-5 in
It is well known that the relative intensity ratio of the 5D0→7F1 transition to the 5D0→7F2 transition is highly sensitive to the local symmetry of Eu3+. In Example 2, the intensity ratio of the 5D0→7F2 transition (617 nm) to the 5D0→7F1 transition (599 nm) is constant and equal to about 9.7 in each of Ex2-1 through Ex2-10.
This fact suggests that the local environment of Eu3+ in each of the specimens is such that it is located at the lattice position (or titanium sites) in the TiO2 host lattice.
The light emission intensity due to the 5D0→7F2 transition (617 nm) of each of Ex2-1 through Ex2-10 was normalized by the light emission intensity of Ex2-5 on the basis of
The luminance increased as the Eu3+ concentration increased up to 0.5 at % and then remained at a constant level beyond 0.5 at %. This is because Eu3+ that contributes to emission light (or Eu3+ located at titanium sites in the TiO2 host lattice) is deposited as pyrochlore phase when the Eu3+ concentration exceeds 0.5 at % as described above by referring to
Since the luminance increases in proportion to the concentration of Eu3+ substituted at titanium sites, it is possible to obtain a light emitting material showing a more desirable luminance level if it is possible to dope Eu3+ ions up to 5.0 at % by optimizing the manufacturing process.
As described above in detail by way of examples and drawings, the present invention succeeded in producing titanium dioxide in which a rare earth element is substituted at titanium sites in the titanium dioxide crystal lattice thereof to a predetermined level and hence titanium dioxide doped with a rare earth element. Thus, as a result, the present invention succeeded in producing a fluorescence emitting substance from which fluorescence can be highly efficiently taken out by means of a rare earth element. Namely, the applicability of the present invention is very high in many industrial fields as pointed out below.
Titanium dioxide particles doped with a rare earth element is described above in detail. It has been found that a rare earth element can be substituted with ease at titanium sites in a TiO2 host lattice without requiring any complex manufacturing process within a concentration range between 0 and 0.5 at %. It is also possible to substitute up to 5.0 at % by optimizing the manufacturing process.
Additionally, it is possible to take out light emitted from titanium dioxide particles doped with a rare earth element that is attributable to rare earth ions simply by irradiating them with light having the absorption wavelength of titanium dioxide. Thus, it is possible to utilize titanium dioxide particles doped with a rare earth element as light emitting material by exploiting this light emitting characteristic. Light emitting materials in the form of nano particles can find applications in the field of light emitting devices that can be used in white LEDs, plasma displays, optical amplifiers, micro lasers, television screens, lighting equipment and so on.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-177077 | Jun 2005 | JP | national |
This is a divisional application of Ser. No. 11/922,342 filed on Dec. 17, 2007, which is patented as U.S. Pat. No. 8,062,621, which claims the priority of Japanese Patent Application No. 2005-177077 filed on Jun. 17, 2007, the content of which is incorporated.
| Number | Date | Country |
|---|---|---|
| 2005-105213 | Apr 2005 | JP |
| Number | Date | Country | |
|---|---|---|---|
| 20110311818 A1 | Dec 2011 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11922342 | US | |
| Child | 13137063 | US |
