CN101410478A - 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
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- CN101410478A CN101410478A CNA2007800113756A CN200780011375A CN101410478A CN 101410478 A CN101410478 A CN 101410478A CN A2007800113756 A CNA2007800113756 A CN A2007800113756A CN 200780011375 A CN200780011375 A CN 200780011375A CN 101410478 A CN101410478 A CN 101410478A
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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 manufacture method thereof, in detail, 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 manufacture method.
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 electronics wherein 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: by using 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 Society 2000,122,9692-9702) American ChemicalSociety publishes)).Particularly, proposed: the nanometer crystalline particle that will be made 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 the synthetic semi-conductor ultramicron (refer to Patent Document 1: the spy opens the 2002-38145 communique) that combines amino by organic connection residue.
Patent documentation 1 spy opens the 2002-38145 communique
Non-patent literature 1 Yun Wei Cao and Uri Banin work (" Growth and Properties ofSemiconductor Core/Shell Nanocrystals with InAs Cores " Journal of AmericanChemical Society 2000,122,9692-9702) 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 shows redness, green, blue fluorescence, the fluorescence of these colors can not 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 by 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 manufacture method thereof are provided, dispersed high, high, the good reliability of luminous efficiency of described the 13rd group-III nitride semiconductor particle phosphor, and because of having covered the surface imperfection of nanometer crystalline particle, organic compound is able to mortise.
The method of dealing with problems
The present invention relates to nanometer crystalline particle be covered the 13rd group-III nitride semiconductor particle phosphor that forms with the surface modification organic compound, described nanometer crystalline particle comprises the key of the 13rd family's element and nitrogen-atoms formation, and described surface modification organic compound comprises heteroatoms and molecular weight is 200～500.
Here, the surface modification organic compound is preferably amine, is preferably tertiary amine especially.The 13rd family element coordination of the nitrogen-atoms of preferred surface modification organic compound and nanometer crystalline particle.More preferably the surface modification organic compound 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 invention provides: the manufacture method that covers the 13rd group-III nitride semiconductor particle phosphor that the nanometer crystalline particle comprise the key that the 13 family's element become with nitrogen-atoms forms with the surface modification organic compound, wherein, control the particle diameter of nanometer crystalline particle by the step that resulting solution is heated, described resulting solution at least by compound with key that the 13rd family's element become with the nitrogen element, be that 200～500 surface modification organic compound mixes with containing heteroatoms and molecular weight.Here, can use surface modification organic compound 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 invention provides broad-band gap the 13rd group-III nitride semiconductor particle phosphor that comprises nanometer crystalline particle and surface modification organic compound.In the 13rd group-III nitride semiconductor particle phosphor of the present invention, contain heteroatoms and molecular weight and be 200～500 surface modification organic compound mortise on the nanometer crystalline particle surface, the surface imperfection of protection nanometer crystalline particle.In addition, isolate by molecule organic layer between the nanometer crystalline particle, do not condense between the nanometer crystalline particle, favorable dispersity, processing ease when using fluor.In addition, the surface modification organic compound 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 by selecting the surface modification organic compound aptly according to the manufacture method 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 the nanometer crystalline particle surface; can 1 the 13rd group-III nitride semiconductor particle phosphor through surface modification of few, the favorable dispersity of step synthetic surface defective, 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 modification organic compound.
Embodiment
＜the 13 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 modification organic compound 12.Can think:, be incorporated into the such Chemical bond of nanometer crystalline particle 10 and in conjunction with the two contribution arranged all based on physical adsorption such as the heteroatoms coordination of surface modification organic compound 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, Tl).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, preferably the doping agent that uses is Mg, Zn, Si.
This nanometer crystalline particle can be only by the above-mentioned single particle structure that constitutes of forming, also the a kind of semiconductor core that is comprised with the semiconductor-on-insulator shell/semi-conductor shell structure can being formed by difference.
When this nanometer crystalline particle is semiconductor core/semi-conductor shell structure, wish 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 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 by 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 the spectral line half value Amplitude Estimation of X-ray diffraction measurement result, 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.Herein, 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/semi-conductor shell structure, the energy of semi-conductor exciting light was absorbed by outer field semi-conductor shell, and the semiconductor core that is surrounded by the semi-conductor shell towards periphery transmits (Move and moves then).Herein, 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, by 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 represents that there is the expanded range of probability in exciton, with mathematical expression (1) expression.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)
Herein
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 modification organic compound 〉
Surface modification organic compound 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 saturated fatty acid 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 modification organic compound, can list: nitrogen-containing functional group (nitro, amino etc.), sulfur-bearing functional group (sulfo group etc.), carboxyl, amide group, phosphino-(ホ ス Off イ ソ yl), phosphine oxygen base (ホ ス Off イ ソ オ キ ッ De), hydroxyl etc.
Can comprise hydrogen, oxygen, carbon element in addition in the molecule of surface modification organic compound, 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 modification organic compound is coordinated in the 13rd family's element of nanometer crystalline particle, like this, the not associative key (Wei Knot that not only can cover because of the 13rd family's element on nanometer crystalline particle surface closes hand) defective that 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 modification organic compound also combines with nanometer crystalline particle.Can think: this intermolecular forces is than the key a little less than the aforementioned coordinate bond.So, formed the molecule organic layer that constitutes by the surface modification organic compound of clad nano crystal particles.
The molecular weight of surface modification organic compound 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 modification organic compound 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 the intermolecular forces between the hydrophobic chain strengthen, consequently there is the tendency that makes nanometer crystalline particle that weak cohesion take place in mortise between the surface modification organic compound.
In a word; when the molecular weight of the 13rd group-III nitride semiconductor particle phosphor 200～500 the time; surface modification organic compound mortise is in the nanometer crystalline particle surface; can protect the surface imperfection of nanometer crystalline particle, and can will isolate between the nanometer crystalline particle with above-mentioned molecule organic layer.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 modification organic compound preferred amines, described amine are to have the non-polar hydrocarbon end as hydrophobic grouping and have amino compound as hydrophilic radical.This is because can think: produce the electric polarity between nitrogen-carbon atom between heteroatoms nitrogen and hydrophobic grouping (for example fatty compounds), the surface modification organic compound is attached to the nanometer crystalline particle surface securely.In addition, nitrogen-atoms has three associative key (Knot to close hand), therefore can select to have the surface modification organic compound of 1～3 hydrophobic chain.In addition, surface modification organic compound preferred fat amine also can comprise aromatic amine.
In the present invention, the special preferred tertiary amine of surface modification organic compound.This be because: therefore tertiary amine has three hydrophobicity ends, can disperse the nanometer crystalline particle that covers with the surface modification organic compound 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 sample of leading section.The reason of doing like this is: with certain interval nanometer crystalline particle is protected.In addition, 1 of preferred tertiary amine linearity saturated fatty acid 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 modification organic compound of the present invention.This be because: have been noted that can obtain like this and use a kind of inaccessiable effect of surface modification organic compound, promptly protect nanometer crystalline particle securely.
The thickness of molecule organic layer of the present invention can be confirmed by 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.
The manufacture method of＜the 13 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, manufacture method with following nanometer crystalline particle precursor is that example describes, and described 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.By following chemical equation (1)～(3), can synthesize three (dimethylamino) indium dipolymer, three (dimethylamino) thing dipolymer and six (dimethylamino) indium gallium.
Dimethylamino lithium (リ チ ウ system ヅ 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.
The manufacture method of＜the 13 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, described benzole soln contains the surface modification organic compound (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 ℃, finished reaction.Then, in order to remove organic impurity, clean for several times with normal hexane and anhydrous methanol.In addition, in this reaction, the formation of InGaN mixed crystal nanometer crystalline particle, the formation of the 13rd group-III nitride semiconductor particle phosphor that forms is carried out simultaneously with covering this nanometer crystalline particle with the surface modification organic compound.Thus, can access the 13rd group-III nitride semiconductor particle phosphor that comprises the InGaN mixed crystal that covers with the surface modification organic compound.
At this moment, if the molecular weight of surface modification organic compound increases in this resulting solution, InGaN mixed crystal nanometer crystalline particle is diminished, on the contrary, if the molecular weight of surface modification organic compound reduces, then can increase InGaN mixed crystal nanometer crystalline particle.This be considered to because: the surface modification organic compound also has the effect of interfacial agent.In a word, can think: along with the molecular weight increase of surface modification organic compound, the length of hydrophobic grouping or spatial volume height (the high さ of か さ) increase, the surface modification organic compound becomes easy aggegation, accompany therewith, and nanometer crystalline particle diminishes in manufacturing processed.As the present invention,, the particle diameter of nanometer crystalline particle can be controlled at several nm～tens of nm as the surface modification organic compound of molecular weight 200～500 is used for the manufacture method 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 modification organic compound, heat mixed resulting solution, carry out the formula reaction of 1 step, through cooling off recycling step arbitrarily, make the 13rd group-III nitride semiconductor particle phosphor that covers with the surface modification organic compound so again.
In addition, in the present invention, the surface modification organic compound is identical on chemical substance with its raw material.Therefore, as the surface modification organic compound that uses in the manufacturing step, preferred amines, described amine be have non-polar hydrocarbon end as 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 modification organic compound 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 modification organic compound, for example, by mixing and being used in combination the different surface modification organic compound more than 2 kinds of molecular weight, can regulate, control the particle diameter of nanometer crystalline particle.In addition, further by the blending ratio of the different surface modification organic compound of molecular weight, can control the particle diameter of nanometer crystalline particle.For example, improve the blending ratio of the bigger surface modification organic compound 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 of carbon atom and hydrogen atom 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 modification organic compound 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 carries out 6～72 hours, preferred 12～48 hours under 180～500 ℃ of synthesis temperatures, preferred 280～400 ℃, heats when stirring this resulting solution.After the reaction,, clean for several times with normal hexane and anhydrous methanol for removing organic impurity.
By 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 with interpolation 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 modification organic compound.
And, by 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 modification organic compound is made of the InGaN mixed crystal.
Embodiment
(embodiment 1)
Use 2 kinds of surface modification organic compound 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 by 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 reaction shown below is all carried out in nitrogen atmosphere.
At first, 0.03 mole of weighing dimethylamino lithium and Indium-111 chloride are 0.01 mole in glove compartment (グ ロ one Block ボ Star Network ス), and it is stirred in normal hexane, carry out reaction in 50 hours simultaneously under 20 ℃ of Heating temperatures.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 0.005 mole of aforesaid method synthetic three (dimethylamino) indium dipolymer and three (dimethylamino) gallium dipolymer is adopted in weighing, and it is stirred in normal hexane, carries out reacting in 50 hours simultaneously under 20 ℃ of Heating temperatures.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, described solution comprises three nonyl amine as the surface modification organic compound (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)
By 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 cover its surface with the surface modification organic compound 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 using nN (C
9H
19)
3And nN (C
8H
17)
3The In that these 2 kinds of surface modification organic compound 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, finish 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 modification organic compound, 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, the blue light emitting device that is made of the 13rd group-III nitride can be used as excitation light source, particularly can absorb the luminous of the high 405nm of external quantum efficiency efficiently.In addition, adjust 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 modification organic compound that particle diameter is controlled, the X-ray diffraction measurement result of gained the 13rd group-III nitride semiconductor particle phosphor is: when adopting Scherrer formula (numerical expression (2)) when estimating, the median size (diameter) of the nanometer crystalline particle of estimating by the spectral line full width at half maximum is 4nm, nanometer crystalline particle shows quantum size effect, and luminous efficiency improves.In addition, the yield of the 13rd group-III nitride semiconductor particle phosphor that obtains among this embodiment 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 manufacture method 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 modification organic compound.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.
The X-ray diffraction measurement result is: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating by 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 manufacture method of present embodiment, can think: by using trioctylphosphine amine as the surface modification organic compound, 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 manufacture method 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 modification organic compound.Gained the 13rd group-III nitride semiconductor particle phosphor 405nm's that energy efficient absorption external quantum efficiency is high especially is luminous.In addition, the emission wavelength of nanometer crystalline particle is 455nm.
The X-ray diffraction measurement result is: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating by the spectral line half value width of cloth be 2nm, and nanometer crystalline particle shows quantum size effect, the luminous efficiency raising.In the manufacture method of present embodiment, can think: by using three nonyl amine as the surface modification organic compound, 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 manufacture method 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 modification organic compound 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.
The X-ray diffraction measurement result is: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating by 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 manufacture method of present embodiment, can think: the mixture by using the little trihexylamine of trioctylphosphine amine and molecular weight is as the surface modification organic compound, 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 manufacture method 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.
The X-ray diffraction measurement result is: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating by 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 manufacture method 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.
The X-ray diffraction measurement result is: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating by 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 manufacture method 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.In addition, the emission wavelength of the nanometer crystalline particle that is made of InN is 520nm.
The X-ray diffraction measurement result is: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating by 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 manufacture method 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.
The X-ray diffraction measurement result is: when adopting the Scherrer formula to estimate, the median size (diameter) of the nanometer crystalline particle of estimating by 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 of the semiconductor core/2 layers of structure of protection semi-conductor shell that form with protection semi-conductor shell coating semiconductor core.
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 modification organic compound 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 wishing as excitation light source by the blue light emitting device that the 13rd group-III nitride constitutes.The X-ray diffraction measurement result of gained fluor is: when adopting the Scherrer formula to estimate, the median size (diameter) of the nuclear of estimating by the spectral line half value width of cloth is 50nm, does not show quantum size effect.In addition, the yield of the 13rd group-III nitride fluor that obtains in this comparative example 1 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 optical excitation with 405nm, this fluor is in luminous any luminous intensity [a.u. (arbitrary units, arbitrary unit)] 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, by Fig. 2 also as can be known: compare with comparative example 1, little according to the exciton Bohr radius of the nanometer crystalline particle of embodiment 1, the fluorescence efficiency height.
It should be understood that embodiment disclosed herein and embodiment all are exemplary and nonrestrictive.Scope of the present invention is not to be determined 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 invention provides have dispersiveness, the 13rd family of function that medium compatibility, luminous efficiency are good The height of nitride semiconductor particle phosphor and the 13rd group-III nitride semiconductor particle phosphor is received The manufacture method of rate.
Claims (13)
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 modification organic compound (12), described nanometer crystalline particle (11) comprises the key that the 13rd family's element is become with nitrogen-atoms, and described surface modification organic compound (12) comprises heteroatoms and molecular weight is 200～500.
2. the 13rd group-III nitride semiconductor particle phosphor (10) of claim 1, wherein, described surface modification organic compound (12) is an amine.
3. the 13rd group-III nitride semiconductor particle phosphor (10) of claim 2, wherein, described surface modification organic compound (12) is a tertiary amine.
4. the 13rd group-III nitride semiconductor particle phosphor (10) of claim 2, wherein, the nitrogen-atoms of described surface modification organic compound (12) is coordinated on the 13rd family's element of nanometer crystalline particle (11).
5. the 13rd group-III nitride semiconductor particle phosphor (10) of claim 1, wherein, described surface modification organic compound (12) comprises the compound more than 2 kinds.
6. 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.
7. 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.
8. the manufacture method of a group-III nitride semiconductor particle phosphor (10), described 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 modification organic compound (12) and form
Wherein, control the particle diameter of nanometer crystalline particle (11) by following step, described step is: at least by described 13 group element compounds that contain the key that 13 family's elements are become with the nitrogen element, be that the resulting solution that 200～500 surface modification organic compound (12) mixes heats with containing heteroatoms and molecular weight.
9. the manufacture method of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 8 wherein, is used the surface modification organic compound (12) more than 2 kinds.
10. the manufacture method of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 8, wherein, described 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.
11. the manufacture method of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 8 wherein, is used the solvent of hydro carbons as described resulting solution.
12. the manufacture method of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 8, wherein, the temperature that described resulting solution is heated is 180～500 ℃.
13. the manufacture method of the 13rd group-III nitride semiconductor particle phosphor (10) of claim 8, wherein, the generated time that described resulting solution is heated is 6～72 hours.
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| JP088668/2006 | 2006-03-28 | ||
| JP2006088668 | 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 |
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| JP (1) | JP4896126B2 (en) |
| KR (1) | KR101057270B1 (en) |
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| CN107004747A (en) * | 2014-12-03 | 2017-08-01 | 欧司朗光电半导体有限公司 | Launch the optoelectronic semiconductor component and its manufacture method of radiation |
| CN111801298A (en) * | 2018-02-15 | 2020-10-20 | 国立大学法人大阪大学 | Semiconductor nanoparticles, method for producing same, and light-emitting device |
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| 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 |
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| 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 |
| KR100796122B1 (en) * | 2003-09-09 | 2008-01-21 | 삼성전자주식회사 | Improvement of Quantum Efficiency by Surface Treatment of Compound Semiconductor Nanocrystals |
| 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 |
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| CN107004747A (en) * | 2014-12-03 | 2017-08-01 | 欧司朗光电半导体有限公司 | Launch the optoelectronic semiconductor component and its manufacture method of radiation |
| CN111801298A (en) * | 2018-02-15 | 2020-10-20 | 国立大学法人大阪大学 | Semiconductor nanoparticles, method for producing same, and light-emitting device |
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| KR20080109047A (en) | 2008-12-16 |
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| KR101057270B1 (en) | 2011-08-16 |
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