GROUP-III NITRIDE SEMICONDUCTOR NANOPARTICLES AND PRODUCTION METHOD THEREOF
20220098480 · 2022-03-31
Assignee
Inventors
- Takuya KAZAMA (Tokyo, JP)
- Wataru TAMURA (Tokyo, JP)
- Yasuyuki MIYAKE (Tokyo, JP)
- Takayuki Omori (Tokyo, JP)
- Atsushi MURAMATSU (Miyagi, JP)
- Kiyoshi KANIE (Miyagi, JP)
Cpc classification
C01B21/0602
CHEMISTRY; METALLURGY
C01P2004/82
CHEMISTRY; METALLURGY
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
C01P2002/76
CHEMISTRY; METALLURGY
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
C01P2004/16
CHEMISTRY; METALLURGY
C01P2002/74
CHEMISTRY; METALLURGY
C01P2002/77
CHEMISTRY; METALLURGY
C01P2002/78
CHEMISTRY; METALLURGY
C01P2004/24
CHEMISTRY; METALLURGY
C01P2004/64
CHEMISTRY; METALLURGY
International classification
C01B21/06
CHEMISTRY; METALLURGY
Abstract
Provided are group-III nitride nanoparticles that prevent the piezoelectric field caused by strains on the nanoparticles, achieving good luminous efficiency. The group-III nitride nanoparticle represented by Al.sub.xGa.sub.yIn.sub.zN (0≤x, y, z≤1) incorporating two crystal structures; a wurtzite structure and a zincblende structure, in a single particle. As another example, the group-III nitride nanoparticle has a core-shell structure with a core and a shell, in which the particle constituting the core contains two crystal structures; the wurtzite structure and the zincblende structure, in the particle. Nanoparticles containing the two crystal structures can be produced by using a phosphorus-containing solvent as a reaction solvent, and the mixture ratio of the two crystal structures, (wurtzite structure)/(zincblende structure), is 20/80 or higher.
Claims
1. A group-III nitride semiconductor nanoparticle represented by Al.sub.xGa.sub.yIn.sub.zN (0≤x, y, z≤1), comprising two crystal structures; a wurtzite structure and a zincblende structure, in a single particle.
2. A group-III nitride semiconductor nanoparticle having a core-shell structure formed of a core and a shell, wherein a particle constituting the core comprises two crystal structures; a wurtzite structure and a zincblende structure within the particle.
3. The group-III nitride semiconductor nanoparticle according to claim 2, wherein the core and the shell have different lattice constants.
4. The group-III nitride semiconductor nanoparticle according to claim 2, having shape anisotropy.
5. The group-III nitride semiconductor nanoparticle according to claim 4, having any of the following shapes; an elliptical shape, a rod-like shape, and a disk-like shape.
6. The group-III nitride semiconductor nanoparticle according to claim 1, wherein the particle comprising the two crystal structures within the particle has the ratio of the zincblende structure at 25% or higher based on XRD diffraction intensity.
7. The group-III nitride semiconductor nanoparticle according to claim 6, wherein the particle comprising the two crystal structures within the particle has the ratio of the zincblende structure at 30% or higher based on the XRD diffraction intensity.
8. The group-III nitride semiconductor nanoparticle according to claim 1, having shape anisotropy.
9. A production method of group-III nitride semiconductor nanoparticles, using group-Ill nitride materials and a solvent, for synthesis of a group-Ill nitride by pyrolysis, wherein the production method uses a phosphorus-containing solvent as the solvent.
10. The production method of the group-III nitride semiconductor nanoparticles according to claim 9, wherein the phosphorus-containing solvent contains either of trioctylphosphine and trioctylphosphine oxide.
11. The group-III nitride semiconductor nanoparticle according to claim 2, wherein the particle comprising the two crystal structures within the particle has the ratio of the zincblende structure at 25% or higher based on XRD diffraction intensity.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0015]
[0016]
[0017]
[0018]
[0019]
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] There will now be described embodiments of group-III nitride nanoparticles and a production method thereof according to the present invention. The group-III nitride nanoparticle of the present invention is represented by In.sub.xGa.sub.yAl.sub.zN (0≤x, y, z≤1), and one particle incorporates two crystal structures of a wurtzite structure and a zincblende structure in a mixed manner. Since these two crystal structures are coexistent within one particle, strain is less likely to occur under various conditions such as the composition and the shape which tend to give strain to the lattice of the hexagonal, so that high luminous efficiency can be achieved. The state where the two crystal structures are coexistent (incorporated in a mixed manner) within the particle may be calculated, for example, from precision structure analysis such as Rietveld method, or from the intensity ratio between (110) and (103) of the X-ray diffraction pattern.
[0021] The Rietveld method is a technique to calculate quantitative values such as lattice constants by fitting the whole diffraction pattern with the least squares method, and a mixture ratio can be calculated from the ratio between the calculated lattice constants, and lattice constant of the wurtzite structure/lattice constant of the zincblende structure. Measurement according to the Rietveld method was performed using the software for crystal structural analysis (TOPAS) available from Bruker.
[0022] As shown in
[0023] Furthermore, the X-ray diffraction patterns are measured for a large number of sets of group-III nitride nanoparticles of the present invention, and there is calculated the ratio R of the intensity ratio X1 of the measurement target (a mixed system of crystal structures) to the intensity ratio XO of (110) and (103) of wurtzite. This allows calculation of the ratio of zincblende in the mixed system, along with calculating the mixture ratio:
R=(X1/XO)×100
Mixture ratio=R:(100−R)
[0024] The ratio of the wurtzite structure is preferably 10% or higher, more preferably 20% or higher, and still more preferably 30% or higher. With around 10% of wurtzite, it is impossible to obtain a superior luminous brightness compared with the nitride nanoparticles having the wurtzite structure alone. On the other hand, the ratio of the zincblende structure is preferably 50% or less. By making the ratio of the zincblende structure which is a metastable phase, less than half, the crystal structure of the group-III nitride nanoparticles can be kept stable.
[0025] The group-III nitride nanoparticles of the present invention incorporate two crystal structures in a mixed manner within a particle, and thus it is possible to prevent the strain received in the growth plane direction of the crystal, enabling reduction of the piezoelectric field generated when subjected to the strain. There are following two main factors, when divided broadly, which provide strain to the group-III nitride nanoparticles. One of the factors is the shape of the nanoparticle. For example, in the case of a single particle, an elliptical particle as shown in
[0026] The other factor is the lattice mismatch between the core and the shell, caused by the combination of materials in the core-shell structured nanoparticle. In the case of Type 1 quantum dot, a combination of the core and shell is made such that the shell has a larger energy gap relative to the energy gap of the core particle.
[0027] The group-III nitride nanoparticle of the present invention features that the core particle contains the zincblende structure having good symmetry at a predetermined ratio within the particle. Therefore, it is possible to prevent the strain caused by those factors above, thereby increasing the luminous efficiency as compared to the particle having the wurtzite structure alone.
[0028] The composition of the group-III nitride nanoparticle is similar to that of conventional group-III nitride, and it may contain any binary nitride such as InN, GaN, AlN, or a ternary nitride represented by In.sub.xGa.sub.yAl.sub.zN (where each of x, y, and z is between or equal to 0 and 1, and satisfy x+y+z=1).
[0029] Among the compositions as described above, in the case of the core-shell type nanoparticle having the structure where the core is covered with the shell, this type of particle has a combination of the compositions to form the core and the shell where the energy gap of the shell is larger than the energy gap of the core particle. As shown in
[0030] The composition of the materials of the core and shell may be adjusted considering the lattice matching between them. Also for the lattice matching, a combination of compositions having near lattice constants in the graph of
[0031] There will now be described an example of a production method of the group-III nitride nanoparticles of the present invention. The group-III nitride nanoparticles of the present invention can basically be produced by chemical synthesis according to a conventional thermal decomposition method (pyrolysis method), and group-III materials and nitrogen materials are reacted at a high temperature together with a predetermined solvent. However, in the conventional chemical synthesis, materials such as tetradecylbenzene, 1-octadecene, trioctylphosphine, diphenyl ether, and benzene may be used as the solvent, but in the present invention, it is preferable to use the phosphorus-containing solvent in order to incorporate the two crystal structures in the particle in a mixed manner. As the solvent of the phosphorus-containing system, materials such as trioctylphosphine (TOP) and trioctylphosphine oxide may be used, and particularly, TOP is preferable.
[0032] The solvent may be 100% of phosphorus-containing solvent, or a mixture with the general synthetic solvent described above may be used. However, as the proportion of the phosphorus-containing solvent is larger in the solvent used in the reaction, the ratio of the zincblende structure can be increased. When the proportion of the phosphorus-containing solvent is 100%, the ratio of the zincblende structure may be increased to nearly 40%.
[0033] When the group-III materials and the nitrogen materials are synthesized into the group-III nitrides by a chemical reaction, precursors are first formed, and then a nucleation and a crystal growth step proceed to form crystal particles. It is conceivable that the presence of phosphorus of the group V being the same group as nitrogen, in the reaction system at the time of the precursor formation, changes the covalent bonding property of the group-III-V bond, whereby the interatomic distance is changed and this causes partial generation of the zincblende structure.
[0034] For the points other than above, conventional production methods can be employed. For example, first the temperature of the materials is raised to around 140° C. to 150° C. at a predetermined temperature rise rate, and reacting the materials for a predetermined time, thereby forming the precursors. Then, the temperature is raised to higher temperature, e.g., around 300° C. to 400° C., and the reaction is advanced to grow the crystals. By controlling this reaction time, the particle diameter of the produced nanoparticles can be controlled.
[0035] After particles are generated, centrifugation and centrifugal washing using the solvent such as ethanol are performed to collect nanoparticles. If necessary, a process of imparting dispersibility to the nanoparticles may be performed.
[0036] In the case of the core-shell structure, a phosphorus-containing solvent is used to produce the core particle in which crystal structures are coexistent, and then synthesis is performed in the same manner as the core particle, using the core particle, the shell materials, and the solvent. As the solvent for the shell synthesis, the aforementioned general reaction solvent can be used. Thus, it is possible to obtain a nitride nanoparticle having the core-shell structure where the shell covers around the core particle containing the crystal structures mixed therein.
[0037] As the group-III materials, materials used in general chemical synthesis can be used, for example, a group-III halide such as indium iodide may be used. It is also possible to use organic materials such as trimethylate and triethylate. As the nitrogen materials, there may be used materials such as ammonia, a metal azide compound, a metal nitride, an amine, and a metal amide. In particular, metallic amides such as sodium amide and lithium amide are preferable.
[0038] Since a chemical stoichiometric amount determines the amounts of the group-III materials used for the core and the shell, it is sufficient to use the amounts that form a designated composition. An equivalent or more amount of the nitrogen material relative to the group-III materials is used to obtain the group-III nitride of the intended composition. When the amount of nitrogen (V) material is increased excessively (e.g., V/III=40) and the reaction temperature is set to a high temperature of around 400° C., the shape of the core particle can be made to be elliptical. As for the shell, the amount of nitrogen material (e.g., V/III=40) may be made excessive or high temperature for reaction (during the precursor formation or crystal growth) may be set to around 400° C., thereby controlling the shape of core-shell particle and providing a rod-shaped particle or a disk-shaped particle.
EXAMPLES
[0039] There will now be described examples of synthetic methods of the group-III nitride semiconductor nanoparticles according to the present invention. In the following examples, Parr Instrument 4740 was used as a synthetic vessel, and MS-ESB (available from AS ONE Corporation) was used as a heater. This product is a combination of a mantle heater and a stirrer. The synthesis was performed by charging a solvent and materials into an inner cylinder with a lid made of platinum, and placing the inner cylinder in the synthetic vessel, within a glove box where oxygen and moisture concentration was controlled to be 1 ppm or less.
[0040] The analysis of the crystal structures in each Example, especially the mixture ratio between the zincblende structure and the wurtzite structure, was calculated from quantification according to precise structure analysis such as the Rietveld method and the intensity ratio between (110) and (103) of XRD (X-ray diffraction) pattern.
Example 1 (InGaN Particles)
[0041] As an indium material, 53.5 mg (0.108 mmol) of indium iodide (Aldrich product 99.998%) was used, as a gallium material, 194.6 mg (0.432 mmol) of gallium iodide (Aldrich product 99.99%) was used, and as a nitrogen material, 987.6 mg (43.20 mmol) of lithium amide (Aldrich product 97%) was used. As a solvent, 6 ml of trioctylphosphine (TOP) (Sigma Aldrich product 97%) was used.
[0042] Those materials and the solvent were filled in the inner cylinder, and the inner cylinder was placed in the synthetic vessel. Then the synthetic vessel was set in the mantle heater and the temperature was raised to 150° C. at a temperature rise rate of 5° C./min. Solid-phase precursors were formed by the reaction for five minutes, at the temperature ranging from 140° C. to 160° C. Here, in order to uniformly react lithium amide having low solubility in the solvent, stirring was performed with a stirrer bar. The stirring speed was set at 600 rpm. Thereafter, the synthetic vessel was heated to 400° C., and the synthesis was allowed to proceed for one hour. After the synthesis, the vessel was cooled in cold water to rapidly stop the reaction.
[0043] After completion of the synthesis, ethanol was added to the synthesized solution, and centrifugation was performed by ultracentrifugation. A supernatant substance after the centrifugation was removed, then ethanol was added again, and centrifugation was performed. After those steps were carried out three times, hexane was added and further centrifugation was performed. Then, finally, centrifugal washing was performed with ethanol to collect particles. The condition of the centrifugation was set at 28000 rpm×30 min.
[0044] Thus collected particles were measured using the XRD, XRF (X-ray fluorescence), and TEM to evaluate the crystal structure and a particle size, and so on.
Examples 2, 3, and Comparative Example 1
[0045] The solvent to be charged into the reaction vessel (inner cylinder) was made different from the solvent TOP (trioctylphosphine) used in Example 1 as follows, and except that, under the same conditions as Example 1, the nitride particles were synthesized and collected in the same manner as in Example 1.
Comparative Example 1: DPE (Diphenyl Ether)
Example 2: TDB (Tetradecylbenzene)
Example 3: Mixed Solvent of DPE and TOP (DPE:TOP=1:1)
[0046]
[0047] In addition, luminous intensity of Examples 1 to 3 and Comparative Example 1 was measured using a spectrofluorometer, with the excitation wavelength of 365 nm.
Example 4 (InGaN Core/GaN Shell)
[0048] As the indium material, 53.5 mg (0.108 mmol) of indium iodide (Aldrich product 99.998%) was used, as the gallium material, 194.6 mg (0.432 mmol) of gallium iodide (Aldrich product 99.99%) was used, and as the nitrogen material, 246.9 mg (10.80 mmol) of lithium amide (Aldrich product 97%) was used. As the solvent, 6 ml of trioctylphosphine (Sigma Aldrich product 97%) was used.
[0049] After filling the aforementioned materials and solvent into the inner cylinder and placing the inner cylinder in the synthetic vessel, synthesis was performed under the same conditions as in Example 1 except that the synthesis temperature was 350° C., then centrifugation and centrifugal washing were performed, and particles were collected. The composition of this particle was In.sub.0.2Ga.sub.0.8N, and the particle size was about 5 nm. The mixture ratio of the wurtzite structure and the zincblende structure calculated from the XRD diffraction pattern, similar to Example 1, was (wurtzite structure):(zincblende structure)=68:32.
[0050] Subsequently, the synthesized InGaN nanoparticle was used as the core particle, and then a GaN shell was synthesized. As the materials of the shell, 243.2 mg (0.540 mmol) of gallium iodide (Aldrich product 99.99%) was used as the gallium material, 246.9 mg (10.80 mmol) of lithium amide (Aldrich product 97%) was used as the nitrogen material, and 6 ml of diphenyl ether (Sigma Aldrich product 99%) was used as the solvent.
[0051] These shell materials and solvent, and 25.0 mg (0.27 mmol) of InGaN core particles were filled in the inner cylinder, and the inner cylinder was placed in the synthetic vessel. Then the synthetic vessel was set in the mantle heater, and the temperature was raised to 150° C. at a temperature rise rate of 5° C./min. After the reaction for five minutes, at the temperature ranging from 140° C. to 160° C. at the stirring speed of 600 rpm, solid-phase precursors were formed. Thereafter, the synthetic vessel was heated up to 350° C., and after synthesis was performed for one hour, the vessel was cooled with cold water in order to rapidly stop the reaction. After completion of the synthesis, centrifugation and centrifugal washing using ethanol were performed to collect particles, in the same manner as in the particle collection procedure of Example 1. This resulted in obtainment of the core-shell particles, having InGaN as the core and GaN as the shell.
Example 5 (GaN Core/AlGaN Shell)
[0052] The composition of the core and the shell was made different, and the core-shell structured nitride nanoparticles were produced as in Example 4.
[0053] For the core materials, 243.2 mg (0.540 mmol) of gallium iodide (Aldrich product 99.99%) was used as the gallium material, and 246.9 mg (10.80 mmol) of lithium amide (Aldrich product 97%) was used as the nitrogen material. As in Example 4, 6 ml of trioctylphosphine (Sigma Aldrich product 97%) was used as the solvent, and synthesis was performed in the same manner as in Example 4, and the GaN core particles were collected.
[0054] The mixture ratio of the wurtzite structure and the zincblende structure in the core particle was; (wurtzite structure):(zincblende structure)=65:35.
[0055] Here, 22.6 mg (0.27 mmol) of the GaN core particles were used, 110.1 mg (0.27 mmol) of aluminum iodide (Aldrich product 99.999%) was used as an aluminum material, 121.6 mg (0.270 mmol) of gallium iodide (Aldrich product 99.99%) was used as the gallium material, 246.9 mg (10.80 mmol) of lithium amide (Aldrich product 97%) was used as the nitrogen material, and 6 ml of diphenyl ether (Sigma Aldrich product 99%) was used as the solvent, whereby Al.sub.0.5Ga.sub.0.5N shell was formed on the GaN core particle in the same manner as in Example 4, and then the particles were collected.
Examples 6 and 7
[0056] The composition of the shell was made different, and nitride nanoparticles having the core-shell structure were produced in the same manner as Example 4 (Example 6: InGaN core/AlInN shell, and Example 7: InGaN core/InGaN shell).
[0057] In Example 6, in order to form Al.sub.0.8In.sub.0.2N shell, 176.1 mg (0.432 mmol) of aluminum iodide (Aldrich product 99.999%) was used as the aluminum material, 53.5 mg (0.108 mmol) of indium iodide (Aldrich product 99.998%) was used as the indium material, and 246.9 mg (10.80 mmol) of lithium amide (Aldrich product 97%) was used as the nitrogen material.
[0058] In Example 7, in order to form In.sub.0.1Ga.sub.0.9N shell, 176.1 mg (0.054 mmol) of indium iodide (Aldrich product 99.998%) was used as the indium material, 53.5 mg (0.486 mmol) of gallium iodide (Aldrich product 99.99%) was used as the gallium material, and 246.9 mg (10.80 mmol) of lithium amide (Aldrich product 97%) was used as the nitrogen material.
[0059] In both Examples above, In.sub.0.2Ga.sub.0.8N core particles were synthesized as in Example 4, and after 25.0 mg (0.270 mmol) of the InGaN core particles were charged into the inner cylinders, respectively with the aforementioned shell materials, and 6 ml of diphenyl ether (Sigma Aldrich product 99%) as the solvent, each of the inner cylinders was placed in the synthetic vessel. Then, the shells were synthesized in the same conditions as in Example 4. Then, there was obtained the particle with the AlInN shell (Example 6) formed onto the InGaN core particle, or the particle with the InGaN shell (Example 7) formed onto the InGaN core particle.
Example 8 (Rod)
[0060] Using the InGaN core particles (25.0 mg (0.27 mmol) of In.sub.0.2Ga.sub.0.8N core particles) that were synthesized in the same manner as in Example 4, GaN shells were synthesized. The ratio of the group-III (Ga) and the Group V (nitrogen) used in synthesis were made different, and rod-shaped shells were synthesized.
[0061] That is, 243.2 mg (0.540 mmol) of gallium iodide (Aldrich product 99.99%) was used as the gallium material, and 987.6 mg (43.20 mmol) of lithium amide (Aldrich product 97%) was used as the nitrogen material. As the solvent, 6 ml of diphenyl ether (Sigma Aldrich 99%) was used. After completion of the synthesis, centrifugation and centrifugal washing were performed in the same manner as in Example 4, and particles were collected.
Example 9 (Disk)
[0062] Using the InGaN core particles synthesized as in Example 4, disk-shaped shells were synthesized by controlling the synthesis temperature of the shell.
[0063] In the present Example, the core composition and the shell composition were the same as in Example 4, and upon synthesizing the shell, the synthesis was carried out for one hour at the temperature raised to 400° C. after the formation of the precursors, though it was 350° C. in Example 4. Except that, the conditions were the same as in Example 4, and the core-shell particles with the GaN shells formed on the InGaN core particles were obtained.
[0064] According to Examples as described above, it was confirmed that there were produced the group-III nitride nanoparticles in which two crystal structures; the wurtzite structure and the zincblende structure, were coexistent in the particle. It was also confirmed that the shape of the particle could be controlled, by controlling the ratio (V/III) between the group-III materials and the nitrogen materials used for synthesis and/or the reaction temperature, thereby realizing production of the group-III nitride nanoparticles in the shape such as the elliptical shape and the rod shape.