CN101410478B - Group 13 nitride semiconductor particle phosphor and method for manufacturing same - Google Patents
Group 13 nitride semiconductor particle phosphor and method for manufacturing same Download PDFInfo
- Publication number
- CN101410478B CN101410478B CN2007800113756A CN200780011375A CN101410478B CN 101410478 B CN101410478 B CN 101410478B CN 2007800113756 A CN2007800113756 A CN 2007800113756A CN 200780011375 A CN200780011375 A CN 200780011375A CN 101410478 B CN101410478 B CN 101410478B
- Authority
- CN
- China
- Prior art keywords
- group
- particle
- nitride semiconductor
- nanometer crystalline
- iii nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
Abstract
Conventional semiconductor particle phosphors have low dispersibility to a medium, and since they do not exhibit red, green and blue fluorescence, white emission cannot be obtained by mixing such colors. Synthesizing steps in the conventional methods for manufacturing such semiconductor particle phosphors are complicated, and especially control of the composition and particle diameter of semiconductor particles requires accurate control in synthesizing method. A group 13 nitride semiconductor particle phosphor (10) having a high dispersibility is provided by forming nanocrystalline particles (11) including bonding of a group 13 element and a nitride atom as the semiconductor particles and by coating the nanocrystalline particles (11) with a surface modified organic compound (12) having a molecular weight of 200-500, including hetero atoms. Furthermore, a simple method for manufacturing such group 13 nitride semiconductor particle phosphor (10) is also provided.
Description
Technical field
The present invention relates to semiconductor particle phosphor and method of manufacture thereof; At length say; The present invention relates to improve the 13rd group-III nitride semiconductor particle phosphor of luminous intensity, luminous efficiency, and synthesis program is easy, synthesis yield is high the 13rd group-III nitride semiconductor particle phosphor method of manufacture.
Background technology
If known semiconductor nanocrystal particle (to call " nanometer crystalline particle " in the following text) is reduced to about the exciton Bohr radius, then can show quantum size effect.So-called quantum size effect is meant: the size decreases of material, and then wherein electronics can't free movement, and under such state, the energy of electronics is not arbitrarily but can only gets specific value.For example, size is more little, and is then short more by the light wavelength of the generation of the nanometer crystalline particle about the exciton Bohr radius.
But on the nanometer crystalline particle surface that manifests this effect, dangling bonds (not associative key) is top dog, so produced surface imperfection.Thereby; Proposed: through with the bigger semiconductor material clad nano crystal particles of energy gap ratio nano crystal particles energy gap; The technology that covers the surface imperfection of nanometer crystalline particle is (with reference to non-patent literature 1 (Yun Wei Cao and Uri Banin work (＂ Growth andProperties of Semiconductor Core/Shell Nanocrystals with InAs Cores ＂ Journalof American Chemical Society2000; 122,9692-9702) American ChemicalSociety publishes)).Particularly, proposed: the nanometer crystalline particle that will be made up of InAs is as semiconductor core, with GaAs, InP, CdSe as protection semi-conductor shell, thereby adopt semiconductor core/protection semi-conductor shell structure.
In addition, in order to improve water tolerance, optical characteristics etc., also attempted synthetic having combined amino semi-conductor ultramicron (referenced patent document 1: the spy opens the 2002-38145 communique) through organic connection residue.Patent documentation 1 spy opens the 2002-38145 communique
Non-patent literature 1Yun Wei Cao and Uri Banin work (＂ Growth and Properties ofSemiconductor Core/Shell Nanocrystals with InAs Cores ＂ Journal of AmericanChemical Society2000; 122,9692-9702) American Chemical Society publishes
Summary of the invention
Invent problem to be solved
The various semiconductor cores that coat with protection semi-conductor shell of record mainly have the emission wavelength in the near-infrared region in the non-patent literature 1.Therefore, the GaN based semiconductor light emitting element that this semiconductor core can not be used as excitation light source excites and exhibit red, green, blue fluorescence, can not the fluorescence of these colors be mixed (colour mixture) and obtains white luminous.
In addition, the semi-conductor ultramicron of patent documentation 1 record is incorporated into nanometer crystalline particle with organic connection residue, therefore, a little less than the bonding force, is not enough to protect nanometer crystalline particle fully, improve surface imperfection.In addition, organic connection residue is straight catenate, a little less than the ability of its dispersing nanometer crystal particles, and can condense, so reduce because of the defective on the nanometer crystalline particle interface causes efficient.In addition, the particle diameter of controlling nanometer crystalline particle through organic connection residue is impossible.
In view of above situation; The objective of the invention is: following the 13rd group-III nitride semiconductor particle phosphor and easy method of manufacture thereof are provided; Dispersed high, high, the good reliability of luminous efficiency of said the 13rd group-III nitride semiconductor particle phosphor; And because of having covered the surface imperfection of nanometer crystalline particle, organic cpds is able to mortise.
The method of dealing with problems
The present invention relates to nanometer crystalline particle covered the 13rd group-III nitride semiconductor particle phosphor that forms with the surface-treated organic cpds; Said nanometer crystalline particle comprises the key of the 13rd family's element and nitrogen-atoms formation, and said surface-treated organic cpds comprises heteroatoms and molecular weight is 200～500.
Here, the surface-treated organic cpds is preferably amine, is preferably tertiary amine especially.The 13rd family element coordination of the nitrogen-atoms of preferred surface modification organic cpds and nanometer crystalline particle.More preferably the surface-treated organic cpds comprises the compound more than 2 kinds.
In addition, among the present invention, the 13rd family's element of nanometer crystalline particle can be an element more than 2 kinds.
In addition, among the present invention, the particle diameter of preferred nanometer crystalline particle is below 2 times of exciton Bohr radius.
In addition; The present invention provides: the method for manufacture that covers the 13rd group-III nitride semiconductor particle phosphor that the nanometer crystalline particle comprise the key that the 13rd family's element become with nitrogen-atoms forms with the surface-treated organic cpds; Wherein, Control the particle diameter of nanometer crystalline particle through the step that resulting solution is heated, said resulting solution at least by compound with key that the 13rd family's element become with the nitrogen element, be that 200～500 surface-treated organic cpds mixes with containing heteroatoms and molecular weight.Here, can use surface-treated organic cpds more than 2 kinds.
In addition, the compound that comprises the key that the 13rd family's element become with nitrogen-atoms is preferably In compound and/or Ga compound.
Among the present invention, preferably use the solvent of hydro carbons as resulting solution.
In addition, among the present invention, the temperature of heating resulting solution is preferably 180～500 ℃.In addition, the generated time of heating resulting solution is preferably 6～72 hours.
The invention effect
The present invention provides the broad-band gap that comprises nanometer crystalline particle and surface-treated organic cpds the 13rd group-III nitride semiconductor particle phosphor.In the 13rd group-III nitride semiconductor particle phosphor of the present invention, contain heteroatoms and molecular weight and be 200～500 surface-treated organic cpds mortise on the nanometer crystalline particle surface, the surface imperfection of protection nanometer crystalline particle.In addition, isolate through molecule organic layer between the nanometer crystalline particle, do not condense between the nanometer crystalline particle, good dispersibility, processing ease when using fluor.In addition, the surface-treated organic cpds is being protected the surface of nanometer crystalline particle securely, therefore, can tolerate the deterioration that causes owing to excitation light source, and the result is that the luminous intensity of the 13rd group-III nitride semiconductor particle phosphor improves.
In addition,, in synthetic, react,, can control the particle diameter of nanometer crystalline particle through selecting the surface-treated organic cpds aptly according to the method for manufacture of the 13rd group-III nitride semiconductor particle phosphor of the present invention.In addition; Synthetic to compare step few with gas phase; And in liquid phase, carry out synthetic simultaneously; Can protect nanometer crystalline particle surface, the 13rd group-III nitride semiconductor particle phosphor through surface-treated of can 1 step synthetic surface defective few, good dispersibility, and can synthesize above-mentioned the 13rd group-III nitride semiconductor particle phosphor in a large number.
Description of drawings
Fig. 1: the synoptic diagram of the 13rd group-III nitride semiconductor particle phosphor of the present invention.
Fig. 2: show the luminous intensity of the characteristics of luminescence of representing the 13rd group-III nitride semiconductor particle phosphor and the relation between the nanometer crystalline particle particle diameter.
Fig. 3: the synoptic diagram of synthetic semiconductor particle phosphor in the comparative example 1.
Nomenclature
10: the 13 group-III nitride semiconductor particle phosphors, 11: nanometer crystalline particle, 12: surface-treated organic cpds.
Embodiment
< the 13rd group-III nitride semiconductor particle phosphor >
Below, based on Fig. 1 the structure of the 13rd group-III nitride semiconductor particle phosphor of the present invention is described.The 13rd group-III nitride semiconductor particle phosphor 10 of the present invention is to cover nanometer crystalline particle 11 and formation with surface-treated organic cpds 12.Can think:, be incorporated into the such Chemical bond of nanometer crystalline particle 10 and the two all has contribution based on the combination of physical adsorption such as the heteroatoms coordination of surface-treated organic cpds 12 for this covering.
< nanometer crystalline particle >
Nanometer crystalline particle of the present invention is the semiconductor nanocrystal particle, and it is for comprising the compound of at least a key that is become with nitrogen-atoms in the 13rd family's element (B, Al, Ga, In, T1).As nanometer crystalline particle, preferably GaN, InN, AlN, InGaN, InAlN, GaAlN, InAlGaN.
Can contain non-(meaning figure な い) impurity that have a mind to add in this nanometer crystalline particle, in addition, can also in low strength range, add wittingly among 2 family's elements (Be, Mg, Ca, Sr, Ba), Zn or the Si at least any one as doping agent.The concentration range of doping agent is particularly preferably in 1 * 10
16Cm
-3～1 * 10
21Cm
-3Between, in addition, the doping agent that preferably uses is Mg, Zn, Si.
This nanometer crystalline particle can be only by the above-mentioned single particle structure that constitutes of forming, the a kind of semiconductor core that is comprised with the semiconductor-on-insulator shell/semi-conductor shell structure also can being formed by difference.
When this nanometer crystalline particle is semiconductor core/semi-conductor shell structure, hope that semiconductor core is the semi-conductor of the little composition of band gap most, for example InN.In addition, the band gap of preferred semiconductor shell (when the semi-conductor shell is the multilayer body more than 2 layers, beginning to be called the 1st shell, the 2nd shell from interior shell-side) is bigger than semiconductor core.The semiconductor core inner casing that the semi-conductor shell might not be leaveed no choice but comprise fully in addition, can also have distribution aspect cladding thickness.
When nanometer crystalline particle of the present invention is semiconductor core/semi-conductor shell structure, carry out tem observation, confirm lattice image through the observation picture under the high magnification, can confirm the particle diameter of semiconductor core and the thickness of semi-conductor shell like this.
By X-ray diffraction mensuration result's spectral line half value Amplitude Estimation, the median size of this semiconductor core is generally 5～6nm, and it is the particulate of exciton Bohr radius below 2 times, and the thickness of semi-conductor shell is adjusted at the scope of 1～10nm.Here, if the thickness of semi-conductor shell less than 1nm, then can not fully cover the surface of semiconductor core, in addition, the effect of quantum sealing can weaken, and is therefore also not preferred.On the other hand, if when greater than 10nm, then make the semi-conductor shell equably and become difficult, defective increases, and also is undesirable on the aspect of material cost.
In the present invention, when nanometer crystalline particle was semiconductor core/semiconductor shell structure, the energy of semiconductor exciting light was absorbed by outer field semiconductor shell, then the semiconductor core transmission (migration) of being surrounded by the semiconductor shell towards periphery.Here, the particle diameter of semiconductor core is little of the degree with quantum size effect, and therefore, semiconductor core can only be taked a plurality of energy levels of dispersing, although single in some cases energy level also is possible.Be delivered to the luminous energy of semiconductor core, cause the transition between conduction band ground state level and the valence band ground state level, send the light of the wavelength suitable with its energy.
The band gap of nanometer crystalline particle (nanometer crystalline particle is a semiconductor core when being semiconductor core/semi-conductor shell structure) is preferably in the scope of 1.8～2.8eV; When using as red-emitting phosphors, preferred especially 1.85～2.5eV; When using as green-emitting phosphor, preferred especially 2.3～2.5eV; When using as blue emitting phophor, the scope of preferred especially 2.65～2.8eV.And, through adjusting the mixed crystal ratio of the 13rd family's element, decide the color of fluor.Thus, the 13rd family's element of preferred nanometer crystalline particle is more than 2 kinds.
The particle diameter of nanometer crystalline particle is preferably in the scope of 0.1nm～100nm, more preferably in the scope of 0.5nm～50nm, more preferably in the scope of 1～20nm.
When nanocrystal particle diameter (being the semiconductor core footpath when nanometer crystalline particle is semiconductor core/semi-conductor shell structure) for the exciton Bohr radius below 2 times the time, its luminous intensity obviously improves.Bohr radius representes that there is the expanded range of probability in exciton, representes with mathematical expression (1).For example, GaN is about exciton Bohr radius 3nm, and the exciton Bohr radius of InN is about 7nm.
Y=4 π ε h
2Me
2Mathematical expression (1)
Here
Y: Bohr radius
ε: specific inductivity
H: quantum of action
M: virtual mass
E: elementary electronic charge.
When using nanometer crystalline particle as fluor, the particle diameter of nanometer crystalline particle is if below 2 times of exciton Bohr radius, then because quantum size effect, and the optical band gap expansion, also preferred in this case in above-mentioned bandgap range.
< surface-treated organic cpds >
Surface-treated organic cpds of the present invention is defined as the compound that has hydrophilic radical and hydrophobic grouping in the molecule.Here, hydrophobic grouping comprises non-polar hydrocarbon, preferably contains the fatty compounds of about 10～40 carbon atoms.The preferred sfas of fatty compounds can also contain Sauerstoffatom, two key or acid amides, ester or other functional group.In addition, hydrophobic grouping can be arene residue or ester ring type compound.As the hydrophilic radical of surface-treated organic cpds, can enumerate out: nitrogen-containing functional group (nitro, amino etc.), sulfur-bearing functional group (sulfo group etc.), carboxyl, carboxamido-group, phosphino-(ホ ス Off ィ Application base), phosphine oxygen base (ホ ス Off ィ Application オ キ シ De), hydroxyl etc.
Can comprise the element beyond hydrogen, oxygen, the carbon in the molecule of surface-treated organic cpds, its molecular weight is 200～500.Hydrophilic radical and/or hydrophobic grouping can have heteroatoms, and preferably hydrophilic radical has heteroatoms at least.At this moment, polarization between heteroatoms and the hydrophobic grouping, like this, the power that the heteroatoms coordination of hydrophilic radical is attached to nanometer crystalline particle increases.In addition; Can think: contained heteroatoms, the particularly nitrogen-atoms of surface-treated organic cpds is coordinated in the 13rd family's element of nanometer crystalline particle; Like this; Not only can cover the defective that the not associative key (
do not close hand) because of the 13rd family's element on nanometer crystalline particle surface causes, can also prevent the cohesion between the nanometer crystalline particle simultaneously.In addition, can think: because the intermolecular forces of generations such as Van der Waals force, ionic linkage, hydrogen bond, the hydrophobic grouping of surface-treated organic cpds also combines with nanometer crystalline particle.Can think: this intermolecular forces is than the key a little less than the aforementioned co-ordination bond.So, formed the molecule organic layer that constitutes by the surface-treated organic cpds of clad nano crystal particles.
The molecular weight of surface-treated organic cpds of the present invention mainly changes according to the molecular weight of hydrophobic grouping.When molecular weight less than 200 the time, the hydrophobic grouping of surface-treated organic cpds is short aliphatic chain or the little aromatic series of molecular weight, the tendency of existence is: a little less than the strength of protection nanometer crystalline particle.In addition; When molecular weight greater than 500 the time; Hydrophobic grouping is long aliphatic chain or the big aromatic series of molecular weight, thereby the phenomenon that occurs is: owing to Van der Waals force power, ionic linkage, hydrogen bond etc., make that the intermolecular forces between the hydrophobic chain strengthens; Consequently there is the tendency that makes nanometer crystalline particle that weak cohesion take place in mortise between the surface-treated organic cpds.
In a word; When the molecular weight of the 13rd group-III nitride semiconductor particle phosphor 200～500 the time; Surface-treated organic cpds mortise is in the nanometer crystalline particle surface; Can protect the surface imperfection of nanometer crystalline particle, and can use above-mentioned molecule organic layer isolating between the nanometer crystalline particle.And then consequently: the 13rd group-III nitride semiconductor particle phosphor disperses and does not condense.And then, processing ease, and can protect the surface of the 13rd group-III nitride semiconductor particle phosphor securely, therefore, the deterioration that causes because of excitation light source is strong, is improved as the luminous intensity of fluor.
Surface-treated organic cpds preferred amines, said amine are to have the non-polar hydrocarbon end as hydrophobic grouping and have amino compound as hydrophilic radical.This is because can think: between heteroatoms nitrogen and hydrophobic grouping (for example fatty compounds), produce the electric polarity between nitrogen-carbon atom, the surface-treated organic cpds is attached to the nanometer crystalline particle surface securely.In addition; Nitrogen-atoms has three associative keys 1 (
closes hand), therefore can select to have the surface-treated organic cpds of 1～3 hydrophobic chain.In addition, surface-treated organic cpds preferred fat amine also can comprise aromatic amine.
In the present invention, the special preferred tertiary amine of surface-treated organic cpds.This be because: therefore tertiary amine has three hydrophobicity ends, can disperse the nanometer crystalline particle with the covering of surface-treated organic cpds well.
When the hydrophobic chain of tertiary amine all was aliphatics, the length (molecular weight) of preferred all hydrophobic chains equated.In a word, preferred such structure: with the nitrogen-atoms main shaft, and the structure of the neat broom branch appearance of leading section.The reason of doing like this is: the interval with certain is protected nanometer crystalline particle.In addition, 1 of preferred tertiary amine linearity sfas that hydrophobic chain is 5～11 of carbonatomss.
Example as preferred tertiary amine has: triamylamine, trihexylamine, three heptyl amices, trioctylamine, TNA trinonylamine, tridecylamine, three (undecyl) amine etc.
In addition, the preferred mixture of compound more than 2 kinds of surface-treated organic cpds of the present invention.This be because: have been noted that can obtain like this and use a kind of inaccessiable effect of surface-treated organic cpds, promptly protect nanometer crystalline particle securely.
The thickness of molecule organic layer of the present invention can be confirmed through the observation image of the tem observation under the high magnification.Molecule organic layer is preferably in the scope of 0.1～50nm, more preferably in the scope of 0.5～20nm, further preferably in the scope of 1～10nm.
< method of manufacture of the 13rd group element compound >
In the present invention, the 13rd group element compound is the precursor of nanometer crystalline particle, and it is the compound that comprises the key that the 13rd family's element become with nitrogen-atoms.Below; Method of manufacture with following nanometer crystalline particle precursor is that example describes, and said method has been used the Ga compound that has the key that the gallium atom become with nitrogen-atoms in the In compound that has the key that phosphide atom become with nitrogen-atoms in the molecule as the 13rd group element compound and the molecule.Through following reaction formula (1)～(3), can synthesize three (dimethylamino) indium dipolymer, three (dimethylamino) thing dipolymer and six (dimethylamino) indium gallium.
Dimethylamino lithium (リ チ ウ system ジ メ チ Le ア ミ De) and Indium-111 chloride are stirred in the normal hexane solvent, simultaneously in 5～30 ℃ of temperature of reaction, preferred 10～25 ℃ of following reactions 24～120 hours, preferred 48～72 hours.Reaction is removed the by product lithium chloride after finishing, and takes out three (dimethylamino) indium dipolymer.This reaction is shown in chemical formula (1).
2InCl
3+ 6LiN (CH
3)
2→ [In (N (CH
3)
2)
3]
2Chemical formula (1)
Adopt and use the same method, dimethylamino lithium and gallium trichloride are stirred in the normal hexane solvent, carry out the synthetic of three (dimethylamino) gallium dipolymer.This reaction is shown in chemical formula (2).
2GaCl
3+ 6LiN (CH
3)
2→ [Ga (N (CH
3)
2)
3]
2Chemical formula (2)
Then; To adopt aforesaid method synthetic three (dimethylamino) indium dipolymer and three (dimethylamino) gallium dipolymer in the normal hexane solvent, to stir; In 5～30 ℃ of synthesis temperatures, preferred 10～25 ℃ of following reactions 24～120 hours, preferred 48～72 hours, and take out six (dimethylamino) indium gallium.This reaction is shown in chemical formula (3).
1/2[In(N(CH
3)
2)
3]
2+1/2[Ga(N(CH
3)
2)
3]
2
→ [((CH
3)
2N
2In-(μ-N (CH
3)
2)
2-Ga (N (CH
3)
2)
2] chemical formula (3)
Because the dimethylamino lithium, all have hyperergy with product three (dimethylamino) indium dipolymer, three (dimethylamino) gallium dipolymer and six (dimethylamino) indium gallium, so preferably all in the non-active gas atmosphere, carry out.
< method of manufacture of the 13rd group-III nitride semiconductor particle phosphor >
< nanometer crystalline particle is the situation of single particle structure >
Six (dimethylamino) the indium gallium and three (dimethylamino) gallium dipolymer that with the total amount are the arbitrary proportion of 0.1～10 quality % are dissolved in the benzole soln as the nanometer crystalline particle precursor; Said benzole soln contains the surface-treated organic cpds (growth of the 13rd group-III nitride semiconductor particle phosphor) of 1～50 quality %; Fully stir for mixed resulting solution, react then.
This is reflected in the non-active gas atmosphere and carries out, and this resulting solution is stirred, and heating was simultaneously carried out 6～72 hours, preferred 12～48 hours under 180～500 ℃ of synthesis temperatures, preferred 280～400 ℃, accomplished reaction.Then, in order to remove organic impurity, with normal hexane and anhydrous methanol cleaning many times.In addition, in this reaction, the formation of InGaN mixed crystal nanometer crystalline particle, carry out simultaneously with the formation of the 13rd group-III nitride semiconductor particle phosphor that forms with this nanometer crystalline particle of surface-treated organic cpds covering.Thus, can access the 13rd group-III nitride semiconductor particle phosphor that comprises the InGaN mixed crystal that covers with the surface-treated organic cpds.
At this moment; If the molecular weight of surface-treated organic cpds increases in this resulting solution, InGaN mixed crystal nanometer crystalline particle is diminished, on the contrary; If the molecular weight of surface-treated organic cpds reduces, then can increase InGaN mixed crystal nanometer crystalline particle.This be considered to because: the surface-treated organic cpds also has the effect of interfacial agent.In a word; Can think: along with the molecular weight increase of surface-treated organic cpds; The length of hydrophobic grouping or spatial volume height (the high さ of か さ) increase, the surface-treated organic cpds becomes easy aggegation, accompany therewith, and nanometer crystalline particle diminishes in manufacturing processed.As the present invention,, can the particle diameter of nanometer crystalline particle be controlled at several nm～tens of nm as the surface-treated organic cpds of molecular weight 200～500 is used for the method for manufacture of the 13rd group-III nitride semiconductor particle phosphor above-mentionedly.
Among the present invention; The 13rd group element compound is dissolved in the varsol that contains the surface-treated organic cpds; Heat mixed resulting solution; Carry out the formula reaction of 1 step,, make the 13rd group-III nitride semiconductor particle phosphor that covers with the surface-treated organic cpds so again through cooling off recovering step arbitrarily.
In addition, in the present invention, the surface-treated organic cpds is identical on chemical substance with its raw material.Therefore, as the surface-treated organic cpds that uses in the manufacturing step, preferred amines, said amine be have terminal as the non-polar hydrocarbon of hydrophobic grouping, with compound as the amino of hydrophilic radical.And, in order to control particle diameter, be preferably tertiary amine especially.This be because: can select different hydrophobic grouping length or spatial volume height for tertiary amine, be easy to carry out the control of nanometer crystalline particle size.Concrete example as tertiary amine has triamylamine, trihexylamine, three heptyl amine, trioctylphosphine amine, three nonyl amine, three decyl amine, hentriacontyl amine etc.
In addition, in the present invention, the surface-treated organic cpds that uses in the manufacturing step is preferably more than 2 kinds.This be because: this fact of molecular weight size decision nanometer crystalline particle particle diameter of having utilized used surface-treated organic cpds; For example; Through mixing and the different surface-treated organic cpds more than 2 kinds of combination use molecular weight, can regulate, control the particle diameter of nanometer crystalline particle.In addition, further through the blending ratio of molecular weight different surface modification organic cpds, can control the particle diameter of nanometer crystalline particle.For example, improve the blending ratio of the bigger surface-treated organic cpds of molecular weight, the particle diameter of nanometer crystalline particle is just more little.
In addition, in the present invention, the compound solution that only is made up of carbon atom and Wasserstoffatoms is called varsol.Example as varsol has Skellysolve A, normal hexane, normal heptane, octane, pentamethylene, hexanaphthene, suberane, benzene, toluene, o-Xylol, m-xylene, p-Xylol etc.< nanometer crystalline particle is the situation of semiconductor core/semi-conductor shell structure >
At the nanometer crystalline particle that adopts the aforesaid method manufacturing and be dissolved in the varsol is in the 13rd group-III nitride semiconductor particle phosphor of single particle structure, with six (dimethylamino) indium gallium and three (dimethylamino) gallium dipolymer that adds up to 0.1～10 quality % mixing arbitrary proportion.In addition, mix the surface-treated organic cpds of 1～50 quality % simultaneously, the resulting solution for preparing is fully stirred, react then.
This is reflected in the non-active gas atmosphere and carries out, and under 180～500 ℃ of synthesis temperatures, preferred 280～400 ℃, carries out 6～72 hours, preferred 12～48 hours, heats when stirring this resulting solution.After the reaction, for removing organic impurity, with normal hexane and anhydrous methanol cleaning many times.
Through this reaction; Single particle structure with the 13rd group-III nitride semiconductor particle phosphor is that nanometer crystalline particle is a semiconductor core; Six (dimethylamino) indium gallium and three (dimethylamino) gallium dipolymer to add are material; Carry out the growth of semi-conductor shell, formed semiconductor core/semi-conductor shell structure.
In addition, in this reaction, the formation of InGaN alloy semiconductor nuclear/semi-conductor shell structural nano crystal particles, and it is covered and the formation of the 13rd group-III nitride semiconductor particle phosphor that forms, carry out simultaneously with the surface-treated organic cpds.
And, through repeating this operation, can form several layers of semi-conductor shell.
Thus, can access the 13rd group-III nitride semiconductor particle phosphor, wherein, the nanometer crystalline particle of the semiconductor core/semi-conductor shell structure that covers with the surface-treated organic cpds is made up of the InGaN mixed crystal.
Embodiment
(embodiment 1)
Use 2 kinds of surface-treated organic cpds to adopt following method to synthesize, make that the particle diameter of the 13rd group-III nitride nanometer crystalline particle is 4nm.
Synthesized six (dimethylamino) indium gallium through the reaction shown in aforesaid chemical formula (1)～(3).
And, because dimethylamino lithium and product three (dimethylamino) indium dipolymer, three (dimethylamino) gallium dipolymer and six (dimethylamino) indium gallium have hyperergy, so the reaction shown in following is all carried out in nitrogen atmosphere.
At first, 0.03 mole of weighing dimethylamino lithium and 0.01 mole of Indium-111 chloride stir it in normal hexane in glove compartment (グ ロ-Block ボ ッ Network ス), under 20 ℃ of Heating temperatures, carry out reaction in 50 hours simultaneously.After reaction finished, removing by product was lithium chloride, took out three (dimethylamino) indium dipolymer (chemical formula (1)).
Adopt identical method to synthesize three (dimethylamino) gallium dipolymer (chemical formula (2)).And 0.005 mole of aforesaid method synthetic three (dimethylamino) indium dipolymer and 0.005 mole of three (dimethylamino) gallium dipolymer are adopted in weighing, and it is stirred in normal hexane, under 20 ℃ of Heating temperatures, carry out reacting in 50 hours simultaneously.Then, take out six (dimethylamino) indium gallium (chemical formula (3)).
Then; 0.02 mole of six (dimethylamino) indium gallium and three (dimethylamino) gallium dipolymer are dissolved in the following solution for 0.03 mole; Said solution comprises three nonyl amine as the surface-treated organic cpds (molecular weight: 395.75) 25g and trioctylphosphine amine (molecular weight: the 353.67) mixture of 5g and as the benzene 200ml of solvent; The resulting solution that mixing is obtained fully stirs, and has carried out reacting (chemical formula (4)) then.
0.2[((CH
3)
2N)
2In-(μ-N(CH
3)
2)
2-Ga(N(CH
3)
2)
2]
+ 0.3 [Ga (N (CH
3)
2)
3]
2→ In
0.2Ga
0.8N chemical formula (4)
Through this reaction, the forming process of the 13rd group-III nitride semiconductor particle phosphor that the forming process of InGaN mixed crystal nanometer crystalline particle forms with covering its surface with the surface-treated organic cpds is carried out simultaneously, has formed and has used In
0.2Ga
0.8N/nN (C
9H
19)
3, nN (C
8H
17)
3(by with nN (C
9H
19)
3And nN (C
8H
17)
3The In that these 2 kinds of surface-treated organic cpds cover
0.2Ga
0.8The nanometer crystalline particle structure that N constitutes).
This is reflected under the nitrogen atmosphere and carries out, and 320 ℃ were heated 12 hours down, accomplish reaction.This adds pines for, and continues to stir this resulting solution with agitating vane.Then, for removing organic impurity, cleaned 3 times with normal hexane and anhydrous methanol.
The 13rd group-III nitride semiconductor particle phosphor nanometer crystalline particle that obtains among this embodiment is the InGaN mixed crystal; Its surface is evenly covered by 2 kinds of surface-treated organic cpds; Aggegation does not take place between the nanometer crystalline particle like this, and its size is even, dispersed high.
In addition, in the 13rd group-III nitride semiconductor particle phosphor, can the blue light emitting device that be made up of the 13rd group-III nitride be used as excitation light source, particularly can absorb the luminous of the high 405nm of external quantum efficiency efficiently.In addition, adjustment is by In
0.2Ga
0.8The In ratio of components of the nanometer crystalline particle that N constitutes makes that emission wavelength is 460nm, therefore can show blue-light-emitting.And; Use 2 kinds of surface-treated organic cpds that particle diameter is controlled; The X-ray diffraction of gained the 13rd group-III nitride semiconductor particle phosphor is measured the result: when adopting Scherrer formula (numerical expression (2)) when estimating; The median size (diameter) of the nanometer crystalline particle of estimating through the spectral line full width at half maximum be 4nm, and nanometer crystalline particle shows quantum size effect, the luminous efficiency raising.The yield of the 13rd group-III nitride semiconductor particle phosphor that obtains among this embodiment in addition, is 95%.
B=λ/Cos Θ R numerical expression (2)
Wherein
B:X ray full width at half maximum [deg],
λ: the wavelength of X ray [nm],
Θ: Bragg angle [deg],
R: particle diameter [nm].
(embodiment 2)
Adopt the method for manufacture identical with embodiment 1; Coming synthesis of nano crystal particle is that InGaN mixed crystal and nanometer crystalline particle particle diameter are the 13rd group-III nitride semiconductor particle phosphor of 5nm; Obtained the 13rd blue group-III nitride semiconductor particle phosphor, different is: use trioctylphosphine amine 30g as the surface-treated organic cpds.The 405nm's that gained the 13rd group-III nitride semiconductor particle phosphor is particularly can the efficient absorption external quantum efficiency high is luminous.In addition, the emission wavelength of nanometer crystalline particle is 475nm.
X-ray diffraction is measured the result: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating through the spectral line half value width of cloth is 5nm, and glow peak intensity is compared with traditional indium nitride semiconductor particle phosphor and brought up to about 5 times.In the method for manufacture of present embodiment; Can think: through using trioctylphosphine amine as the surface-treated organic cpds; Compare with the mixture of trioctylphosphine amine with using three nonyl amine, the power of aggegation nanometer crystalline particle precursor dies down, and InGaN mixed crystal nanometer crystalline particle increases.
(embodiment 3)
Adopt the method for manufacture identical with embodiment 1; Coming synthesis of nano crystal particle is that InGaN mixed crystal and nanometer crystalline particle particle diameter are the 13rd group-III nitride semiconductor particle phosphor of 2nm; Obtained the 13rd blue group-III nitride semiconductor particle phosphor, different is: use three nonyl amine 30g as the surface-treated organic cpds.Gained the 13rd group-III nitride semiconductor particle phosphor 405nm's that ability efficient absorption external quantum efficiency is high especially is luminous.In addition, the emission wavelength of nanometer crystalline particle is 455nm.
X-ray diffraction is measured the result: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating through the spectral line half value width of cloth be 2nm, and nanometer crystalline particle shows quantum size effect, the luminous efficiency raising.In the method for manufacture of present embodiment; Can think: through using three nonyl amine as the surface-treated organic cpds; Compare with the mixture of trioctylphosphine amine with using three nonyl amine, the power grow of aggegation nanometer crystalline particle precursor, InGaN mixed crystal nanometer crystalline particle reduces.
(embodiment 4)
Adopt the method for manufacture identical with embodiment 1; Coming synthesis of nano crystal particle is that InGaN mixed crystal and nanometer crystalline particle particle diameter are the 13rd group-III nitride semiconductor particle phosphor of 15nm; Obtained the 13rd blue group-III nitride semiconductor particle phosphor, different is: (molecular weight: 269.51) mixture of 25g is as the surface-treated organic cpds to use trioctylphosphine amine 5g and trihexylamine.The 405nm's that gained the 13rd group-III nitride semiconductor particle phosphor is particularly can the efficient absorption external quantum efficiency high is luminous.In addition, the emission wavelength of nanometer crystalline particle is 475nm.
X-ray diffraction is measured the result: when adopting the Scherrer formula to estimate; The median size (diameter) of the nanometer crystalline particle of estimating through the spectral line half value width of cloth is 15nm, and glow peak intensity is compared with traditional indium nitride semiconductor particle phosphor and brought up to about 5 times.In the method for manufacture of present embodiment; Can think: the mixture through using the little trihexylamine of trioctylphosphine amine and molecular weight is as the surface-treated organic cpds; Compare with the mixture of trioctylphosphine amine with use three nonyl amine; The power of aggegation nanometer crystalline particle precursor dies down, and InGaN mixed crystal nanometer crystalline particle increases.
(embodiment 5)
Adopt the method for manufacture identical with embodiment 1; Coming synthesis of nano crystal particle is that indium nitride, nanometer crystalline particle particle diameter are the 13rd group-III nitride semiconductor particle phosphor of 4nm; Obtained the 13rd red group-III nitride semiconductor particle phosphor, different is: using three (dimethylamino) indium dipolymer is the 13rd group element compound as the nanometer crystalline particle precursor for 0.1 mole.The 405nm's that gained the 13rd group-III nitride semiconductor particle phosphor is particularly can the efficient absorption external quantum efficiency high is luminous.In addition, the emission wavelength of nanometer crystalline particle is 610nm.
X-ray diffraction is measured the result: when adopting the Scherrer formula to estimate; The median size (diameter) of the nanometer crystalline particle of estimating through the spectral line half value width of cloth is 4nm; Nanometer crystalline particle shows quantum size effect, and glow peak intensity is compared with traditional indium nitride semiconductor particle phosphor and brought up to about 20 times.
(embodiment 6)
Adopt the method for manufacture identical with embodiment 1; Coming synthesis of nano crystal particle is that the particle diameter of gan and nanometer crystalline particle is the 13rd group-III nitride semiconductor particle phosphor of 4nm; Obtained the 13rd group-III nitride semiconductor particle phosphor, different is: using three (dimethylamino) gallium dipolymer is the 13rd group element compound as the nanometer crystalline particle precursor for 0.1 mole.
X-ray diffraction is measured the result: when adopting the Scherrer formula to estimate; The median size (diameter) of the nanometer crystalline particle of estimating through the spectral line half value width of cloth is 4nm; Nanometer crystalline particle shows quantum size effect, and glow peak intensity is compared with traditional gallium nitride semiconductor particle phosphor and brought up to about 20 times.
(embodiment 7)
Adopt the method for manufacture identical with embodiment 1, coming synthesis of nano crystal particle is that the particle diameter of InGaN mixed crystal and nanometer crystalline particle is green the 13rd group-III nitride semiconductor particle phosphor (In of 4nm
0.3Ga
0.7N/nN (C
8H
17)
3), obtained the 13rd green group-III nitride semiconductor particle phosphor (In
0.3Ga
0.7N/nN (C
9H
19)
3, nN (C
8H
17)
3), different is: using six (dimethylamino) indium gallium is the 13rd group element compound as the nanometer crystalline particle precursor for 0.02 mole with three (dimethylamino) gallium dipolymer for 0.03 mole.The 405nm's that gained the 13rd group-III nitride semiconductor particle phosphor is particularly can the efficient absorption external quantum efficiency high is luminous.The emission wavelength of the nanometer crystalline particle that is made up of InN in addition, is 520nm.
X-ray diffraction is measured the result: when adopting the Scherrer formula to estimate; The median size (diameter) of the nanometer crystalline particle of estimating through the spectral line half value width of cloth is 4nm; Nanometer crystalline particle shows quantum size effect, and glow peak intensity is compared with traditional InGaN alloy semiconductor particle phosphor and brought up to 20 times.
(embodiment 8)
Adopt the method for manufacture identical with embodiment 1, coming synthesis of nano crystal particle is that the particle diameter of InGaN mixed crystal and nanometer crystalline particle is redness the 13rd group-III nitride semiconductor particle phosphor (In of 4nm
0.5Ga
0.5N/nN (C
8H
17)
3), obtained the 13rd red group-III nitride semiconductor particle phosphor (In
0.5Ga
0.5N/nN (C
9H
19)
3, nN (C
8H
17)
3), different is: using six (dimethylamino) indium gallium is the 13rd group element compound as the nanometer crystalline particle precursor for 0.1 mole.The 405nm's that gained the 13rd group-III nitride semiconductor particle phosphor is particularly can the efficient absorption external quantum efficiency high is luminous.In addition, the emission wavelength of nanometer crystalline particle is 600nm.
X-ray diffraction is measured the result: when adopting the Scherrer formula to estimate; The median size (diameter) of the nanometer crystalline particle of estimating through the spectral line half value width of cloth is 4nm; Nanometer crystalline particle shows quantum size effect, and glow peak intensity is compared with traditional InGaN alloy semiconductor particle phosphor and brought up to about 20 times.
(comparative example 1)
At 100ml benzene (C
6H
12) the middle gallium trichloride (GaCl that mixes
3) 0.007 mole, Indium-111 chloride (InCl
3) 0.003 mole and lithium nitride (Li
3N) 0.01 mole, prepared reaction soln.Under 320 ℃ of synthesis temperatures, carry out reaction in 3 hours, carried out synthetic as the semiconductor core of nanometer crystalline particle.Reaction soln after synthetic is cooled to room temperature, as the benzole soln of semiconductor core.
Then, benzole soln, the gallium trichloride (GaCl of mixed semiconductor's nuclear in benzene 100ml
3) 0.009 mole, Indium-111 chloride (InCl
3) 0.001 mole and lithium nitride (Li
3N) 0.01 mole, under 350 ℃ of synthesis temperatures, carry out reaction in 24 hours, synthesized the semiconductor particle phosphor that coats semiconductor core/2 layers of structure of protection semi-conductor shell that semiconductor core forms with protection semi-conductor shell.
Fig. 3 has shown the structure iron of synthetic the 13rd group-III nitride semiconductor particle phosphor in the comparative example 1.
The 13rd group-III nitride semiconductor particle phosphor that obtains in this comparative example 1; Have 2 layers of structure and cover the defective that causes because of associative key not, but there is not the surface-treated organic cpds in the nanometer crystalline particle surface, therefore; The nanometer crystalline particle generation aggegation that generates, bad dispersibility.In addition, the control of the particle diameter of nanometer crystalline particle only depends on temperature of reaction and reaction times, so particle diameter control difficulty.In addition; The nanometer crystalline particle precursor does not have the key that the 13rd family's element is become with nitrogen-atoms; Therefore, be difficult to carry out the 13rd accurate family's element mixed crystal and form control realizing the emission wavelength of hoping as excitation light source by the blue light emitting device that the 13rd group-III nitride constitutes.The X-ray diffraction of gained fluor is measured the result: when adopting the Scherrer formula to estimate, the median size (diameter) of the nuclear of estimating through the spectral line half value width of cloth is 50nm, does not show quantum size effect.The yield of the 13rd group-III nitride fluor that obtains in this comparative example 1 in addition, is 50%.
Fig. 2 shows the luminous intensity of the characteristics of luminescence of representing semiconductor particle phosphor and the relation between the nanometer crystalline particle particle diameter.Transverse axis is represented the particle diameter (unit is nm) of nanometer crystalline particle, when the longitudinal axis is represented with the optical excitation of 405nm, this fluor is in luminous any luminous intensity [a.u. (arbitrary units, A.U.)] of 460nm.(a) is the luminous intensity of the 13rd group-III nitride semiconductor particle phosphor of embodiment 1 among the figure, and (b) is the luminous intensity of the 13rd group-III nitride semiconductor particle phosphor of comparative example 1 among the figure.
(c) curve among the figure for concerning between demonstration luminous intensity-nanometer crystalline particle particle diameter, can: the particle diameter of nanometer crystalline particle is below 2 times of exciton Bohr radius, and then luminous intensity obviously improves.In addition, also can be known by Fig. 2: compare with comparative example 1, little according to the exciton Bohr radius of the nanometer crystalline particle of embodiment 1, fluorescence efficiency is high.
It should be understood that embodiment disclosed herein and embodiment all are exemplary and nonrestrictive.Scope of the present invention is not to be confirmed by above-mentioned explanation, but is provided by claims, and comprises with claim and be equal to and all changes in the claim scope.
Industrial applicibility
The present invention provide have dispersiveness, the method for manufacture of the high yield of the 13rd group-III nitride semiconductor particle phosphor of medium affinity, luminous efficiency excellent function and the 13rd group-III nitride semiconductor particle phosphor.
Claims (9)
1. a group-III nitride semiconductor particle phosphor (10); The 13rd group-III nitride semiconductor particle phosphor (10) covers and forms nanometer crystalline particle (11) with surface-treated organic cpds (12); Said nanometer crystalline particle (11) comprises the key that the 13rd family's element is become with nitrogen-atoms; Said surface-treated organic cpds (12) is that molecular weight is 200～500 tertiary amine, and said surface-treated organic cpds (12) comprises the compound more than 2 kinds.
2. the 13rd group-III nitride semiconductor particle phosphor (10) of claim 1, wherein, the nitrogen-atoms of said surface-treated organic cpds (12) is coordinated on the 13rd family's element of nanometer crystalline particle (11).
3. the 13rd group-III nitride semiconductor particle phosphor (10) of claim 1, wherein, 13 family's elements of nanometer crystalline particle (11) comprise the element more than 2 kinds.
4. 13 group-III nitride semiconductor particle phosphors (10) of claim 1, wherein, the particle diameter of nanometer crystalline particle (11) is below 2 times of exciton Bohr radius.
5. the method for manufacture of a group-III nitride semiconductor particle phosphor (10); Said 13 group-III nitride semiconductor particle phosphors (10) cover the nanometer crystalline particle (11) of the key that comprises 13 family's elements and become with nitrogen-atoms with surface-treated organic cpds (12) and form
Wherein, Control the particle diameter of nanometer crystalline particle (11) through following step, said step is: at least by said 13 group element compounds that contain the key that 13 family's elements are become with the nitrogen element, with molecular weight be that 200～500 the resulting solution that mixes as the tertiary amine of surface-treated organic cpds (12) more than 2 kinds heats.
6. the method for manufacture of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 5, wherein, said the 13rd group element compound that comprises the key that the 13rd family's element become with nitrogen-atoms is In compound and/or Ga compound.
7. the method for manufacture of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 5 wherein, is used the solvent of hydro carbons as said resulting solution.
8. the method for manufacture of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 5, wherein, the temperature that said resulting solution is heated is 180～500 ℃.
9. the method for manufacture of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 5, wherein, the generated time that said resulting solution is heated is 6～72 hours.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006088668 | 2006-03-28 | ||
| JP088668/2006 | 2006-03-28 | ||
| PCT/JP2007/054171 WO2007111082A1 (en) | 2006-03-28 | 2007-03-05 | Group 13 nitride semiconductor particle phosphor and method for manufacturing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101410478A CN101410478A (en) | 2009-04-15 |
| CN101410478B true CN101410478B (en) | 2012-10-24 |
Family
ID=38541009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800113756A Expired - Fee Related CN101410478B (en) | 2006-03-28 | 2007-03-05 | Group 13 nitride semiconductor particle phosphor and method for manufacturing same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4896126B2 (en) |
| KR (1) | KR101057270B1 (en) |
| CN (1) | CN101410478B (en) |
| WO (1) | WO2007111082A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5263806B2 (en) * | 2007-07-04 | 2013-08-14 | シャープ株式会社 | Phosphor and method for producing the same |
| JP5152475B2 (en) * | 2007-07-10 | 2013-02-27 | シャープ株式会社 | III-V compound semiconductor fine particles and method for producing the same |
| KR20100071602A (en) * | 2008-12-19 | 2010-06-29 | 삼성에스디아이 주식회사 | Nano phosphors, process for preparing same and display comprising nano phosphors |
| JP5158375B2 (en) * | 2009-07-27 | 2013-03-06 | シャープ株式会社 | Semiconductor nanoparticle phosphor |
| JP2012246470A (en) * | 2011-05-31 | 2012-12-13 | Sharp Corp | Manufacturing method of semiconductor nanoparticle, and semiconductor nanoparticle, and fluorescent substance using the same |
| DE102014117764A1 (en) * | 2014-12-03 | 2016-06-09 | Osram Opto Semiconductors Gmbh | Radiation-emitting optoelectronic semiconductor component and method for its production |
| US11532767B2 (en) * | 2018-02-15 | 2022-12-20 | Osaka University | Semiconductor nanoparticles, production method thereof, and light-emitting device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595673A (en) * | 2003-09-09 | 2005-03-16 | 三星电子株式会社 | The improvement of the luminescent efficiency of semiconductor nanocrystals by surface treatment |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4404489B2 (en) * | 1998-09-18 | 2010-01-27 | マサチューセッツ インスティテュート オブ テクノロジー | Water-soluble fluorescent semiconductor nanocrystal |
| JP3835135B2 (en) | 2000-07-27 | 2006-10-18 | 三菱化学株式会社 | Semiconductor ultrafine particles formed by bonding amino groups |
| JP2002220213A (en) * | 2001-01-18 | 2002-08-09 | Sony Corp | Method for syntheszing iiib family nitrogen compound |
| FR2838241B1 (en) * | 2002-04-09 | 2004-06-25 | Commissariat Energie Atomique | LUMINESCENT MATERIALS CONSISTING OF HEART / SHELL STRUCTURE NANOCRYSTALS AND PROCESS FOR THEIR PREPARATION |
| JP2004075464A (en) * | 2002-08-20 | 2004-03-11 | Mitsubishi Chemicals Corp | Semiconductor ultrafine particle and method for producing the same |
| JP2004243507A (en) * | 2002-12-19 | 2004-09-02 | Hitachi Software Eng Co Ltd | Semiconductor nanoparticles and method of manufacture |
| JP2004307679A (en) * | 2003-04-08 | 2004-11-04 | Fuji Photo Film Co Ltd | Group 13 nitride semiconductor nanoparticle fluorescence material |
| JP5086517B2 (en) * | 2004-02-02 | 2012-11-28 | 株式会社日立ソリューションズ | Semiconductor nanoparticle manufacturing method |
| JP2006328234A (en) * | 2005-05-26 | 2006-12-07 | Sharp Corp | Manufacturing process of phosphor |
| JP4761357B2 (en) * | 2005-09-13 | 2011-08-31 | シャープ株式会社 | Semiconductor particle phosphor and method for producing the same |
-
2007
- 2007-03-05 JP JP2008506856A patent/JP4896126B2/en not_active Expired - Fee Related
- 2007-03-05 WO PCT/JP2007/054171 patent/WO2007111082A1/en active Application Filing
- 2007-03-05 CN CN2007800113756A patent/CN101410478B/en not_active Expired - Fee Related
- 2007-03-05 KR KR1020087026190A patent/KR101057270B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595673A (en) * | 2003-09-09 | 2005-03-16 | 三星电子株式会社 | The improvement of the luminescent efficiency of semiconductor nanocrystals by surface treatment |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2002-38145A 2002.02.06 |
| JP特开2004-307679A 2004.11.04 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2007111082A1 (en) | 2009-08-06 |
| WO2007111082A1 (en) | 2007-10-04 |
| JP4896126B2 (en) | 2012-03-14 |
| KR101057270B1 (en) | 2011-08-16 |
| KR20080109047A (en) | 2008-12-16 |
| CN101410478A (en) | 2009-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101161766B (en) | Nano-crystal phosphor and coated nano-crystal phosphor and preparation method thereof | |
| CN101410478B (en) | Group 13 nitride semiconductor particle phosphor and method for manufacturing same | |
| JP4936338B2 (en) | Semiconductor nanoparticle phosphor | |
| US8153022B2 (en) | Semiconductor phosphor nanoparticle | |
| EP3591026B1 (en) | Semiconductor nanoparticle, method for producing same, and light-emitting device | |
| US6780242B2 (en) | Method for manufacturing high-quality manganese-doped semiconductor nanocrystals | |
| JP4761357B2 (en) | Semiconductor particle phosphor and method for producing the same | |
| US7867556B2 (en) | Controlled preparation of nanoparticle materials | |
| JP5744468B2 (en) | Semiconductor nanoparticle phosphor | |
| TWI353376B (en) | Preparation method of quantum dot for emitting whi | |
| JP4587390B2 (en) | Semiconductor particle phosphor and method for producing the same | |
| JP2006328234A (en) | Manufacturing process of phosphor | |
| CN101307227B (en) | Group 13 nitride phosphor and method of preparing the same | |
| JP5263806B2 (en) | Phosphor and method for producing the same | |
| JP2019151832A (en) | Production method of core-shell type quantum dot dispersion, and production method of quantum dot dispersion | |
| Huang et al. | Enhancing optical properties through zinc halide precursor selection: interfacial optimization of InZnP quantum dots | |
| Yang et al. | Low-Temperature Synthesis of Highly Efficient, Deep-Red Zn-Cu-In-Se/ZnSe Fluorescence Quantum Dots |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121024 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |