JP4009729B2 - Zinc sulfide nanostructure coated with boron nitride film and method for producing the same - Google Patents
Zinc sulfide nanostructure coated with boron nitride film and method for producing the same Download PDFInfo
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- 229910052984 zinc sulfide Inorganic materials 0.000 title claims description 74
- 239000005083 Zinc sulfide Substances 0.000 title claims description 73
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims description 73
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims description 59
- 229910052582 BN Inorganic materials 0.000 title claims description 58
- 239000002086 nanomaterial Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 18
- 230000006698 induction Effects 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000001000 micrograph Methods 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000619 electron energy-loss spectrum Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、紫外線領域の発光ダイオードやレーザー等の発光材料として利用可能な窒化ホウ素膜に覆われた硫化亜鉛ナノ構造物及びその製造方法に関する。 The present invention relates to a zinc sulfide nanostructure covered with a boron nitride film that can be used as a light emitting material such as a light emitting diode or a laser in the ultraviolet region, and a method for producing the same.
硫化亜鉛は３．７ｅＶのバンドギャップエネルギーを有する直接遷移型半導体であるため、特に青色領域の発光ダイオードやレーザーの発光材料として盛んに研究開発されている（例えば非特許文献１〜３を参照）。
ところで、半導体物質の形状寸法（サイズ）をナノメートル（ｎｍ）オーダーにすると、量子サイズ効果によって、バンドギャップエネルギーが大きくなり、例えば、硫化亜鉛をナノサイズにした構造物、すなわち、硫化亜鉛ナノ構造物は、紫外線領域のバンドギャップエネルギーを有するようになる。このため、硫化亜鉛ナノ構造物は、紫外線領域の発光ダイオードやレーザー等の発光材料として期待されている。
Since zinc sulfide is a direct transition semiconductor having a band gap energy of 3.7 eV, it has been actively researched and developed as a light emitting diode or laser light emitting material in the blue region (see, for example, Non-Patent Documents 1 to 3). .
By the way, when the shape dimension (size) of a semiconductor material is set to the nanometer (nm) order, the band gap energy increases due to the quantum size effect. For example, a structure in which zinc sulfide is nanosized, that is, a zinc sulfide nanostructure. Things come to have a band gap energy in the ultraviolet region. For this reason, zinc sulfide nanostructures are expected as light emitting materials such as light emitting diodes and lasers in the ultraviolet region.
しかしながら、ナノ構造物は、物質の体積に対する表面積の比、即ち、比表面積が極めて大きいので、必然的に化学反応性が高い。また、表面が化学反応によって変質した場合には、比表面積が極めて大きいので、構造的変形や、特性の劣化が生じやすい。
このため、デバイス作成時、あるいは実使用時において特性が劣化しやすいという課題があり、硫化亜鉛ナノ構造物も同様の課題を有している。
For this reason, there exists a subject that a characteristic tends to deteriorate at the time of device creation or actual use, and a zinc sulfide nanostructure has the same subject.
本発明は上記課題に鑑み、化学的に不活性な、すなわち、化学的安定性が高く、かつ、紫外線領域の発光ダイオードやレーザーの発光材料として使用できる硫化化亜鉛ナノ構造物を提供すること、及びその製造方法を提供することを目的とする。
化学的安定性が高い硫化亜鉛ナノ構造物を形成できれば、デバイス作製時、あるいは実使用時における特性劣化の問題を解決することができ、硫化亜鉛ナノ構造物のバンドギャップエネルギーを生かした紫外線領域の発光ダイオードやレーザーが可能になる。
In view of the above problems, the present invention provides a zinc sulfide nanostructure that is chemically inert, that is, has high chemical stability and can be used as a light emitting diode or laser light emitting material in the ultraviolet region, And it aims at providing the manufacturing method.
If zinc sulfide nanostructures with high chemical stability can be formed, the problem of characteristic deterioration during device fabrication or actual use can be solved, and in the ultraviolet region utilizing the band gap energy of zinc sulfide nanostructures. Light emitting diodes and lasers are possible.
上記目的を達成するために、本発明の窒化ホウ素で被覆された硫化亜鉛ナノ構造物は、とげ状の側枝を有する硫化亜鉛双晶ナノウィスカーが窒化ホウ素膜で被覆されていることを特徴とする。
この構成によれば、とげ状の側枝部分はナノサイズであるので、量子サイズ効果により紫外線領域のバンドギャップエネルギーを有しており、また、窒化ホウ素（ＢＮ）膜は化学的に極めて安定であり、かつ、窒化ホウ素膜のバンドギャップエネルギーが５．５ｅＶであるため紫外線領域で透明であるから、紫外線領域の発光ダイオードやレーザーの発光材料として使用できる硫化亜鉛ナノ構造物が得られる。
To achieve the above object, the zinc sulfide nanostructure coated with boron nitride according to the present invention is characterized in that zinc sulfide twinned nanowhiskers having spine-like side branches are coated with a boron nitride film. .
According to this configuration, since the spine-shaped side branch portion is nano-sized, it has a band gap energy in the ultraviolet region due to the quantum size effect, and the boron nitride (BN) film is chemically extremely stable. In addition, since the band gap energy of the boron nitride film is 5.5 eV, it is transparent in the ultraviolet region, so that a zinc sulfide nanostructure that can be used as a light emitting diode or laser light emitting material in the ultraviolet region is obtained.
また、上記の窒化ホウ素膜は結晶性窒化ホウ素膜であり、この結晶性窒化ホウ素膜は、結晶性窒化ホウ素の特定の結晶面がとげ状の側枝を有する硫化亜鉛双晶ナノウィスカーの
表面と平行な結晶配向性を有して成長している。この構成によれば、硫化亜鉛双晶ナノウィスカー表面の原子と結晶性窒化ホウ素膜の原子とが、格子レベルの規則性で結合しているので、結合力が極めて高く、従って、化学的安定性が極めて高い。
Further, the boron nitride film is a crystalline boron nitride film, and this crystalline boron nitride film is parallel to the surface of the zinc sulfide twinned nanowhisker in which a specific crystal plane of the crystalline boron nitride has a spine-shaped side branch. It grows with a good crystal orientation. According to this configuration, the atoms on the surface of zinc sulfide twinned nanowhiskers and the atoms in the crystalline boron nitride film are bonded with regularity at the lattice level, so the bonding force is extremely high, and thus chemical stability is achieved. Is extremely high.
本発明の窒化ホウ素膜で被覆された硫化亜鉛ナノ構造物の製造方法は、縦型高周波誘導加熱炉の上部と下部にそれぞれ、硫化亜鉛双晶ウィスカーを載せた窒化ホウ素円板とＢ−Ｎ−Ｏ化合物粉末を入れた坩堝を配置し、窒素ガスとアンモニアガスの混合ガスを導入しながら、Ｂ−Ｎ−Ｏ化合物の粉末を１３００〜１７５０℃の範囲で加熱してＢ−Ｎ−Ｏ化合物蒸気を発生させ、硫化亜鉛双晶ウィスカーを８５０〜９５０℃の範囲で加熱し、１〜３時間この状態を維持することによって合成することを特徴とする。
この方法によれば、硫化亜鉛双晶ナノウィスカーが再結晶化して、とげ状の側枝を有する硫化亜鉛双晶ナノウィスカーになると共に、この表面に窒化ホウ素膜が成長する。この窒化ホウ素膜は、結晶性窒化ホウ素膜であり、結晶性窒化ホウ素の特定の結晶面が、とげ
状の側枝を有する硫化亜鉛双晶ナノウィスカーの表面に平行な結晶配向性を有して成長する。
The method for producing a zinc sulfide nanostructure coated with a boron nitride film according to the present invention includes a boron nitride disc having zinc sulfide twin whiskers placed on the upper and lower portions of a vertical high frequency induction heating furnace, and BN- A crucible containing O compound powder was placed, and while introducing a mixed gas of nitrogen gas and ammonia gas, the B—N—O compound powder was heated in the range of 1300 to 1750 ° C. to obtain a B—N—O compound vapor. It is generated, by heating the zinc sulfide twins whiskers in the range of 850 to 950 ° C., characterized by synthesis by maintaining 1-3 hours this state.
According to this method, the zinc sulfide twinned nanowhiskers are recrystallized to become zinc sulfide twinned nanowhiskers having thorn-like side branches, and a boron nitride film grows on this surface. This boron nitride film is a crystalline boron nitride film, and a specific crystal plane of the crystalline boron nitride has a crystal orientation parallel to the surface of a zinc sulfide twinned nanowhisker having spine-like side branches. To do.
本発明の窒化ホウ素で被覆された硫化亜鉛ナノ構造物、及びその製造方法によれば、窒化ホウ素膜が化学的に安定であり、紫外線領域において透明であり、ナノサイズの構造を有するから、この硫化亜鉛ナノ構造物を用いれば、実使用可能な、紫外線領域の発光ダイオードやレーザーが可能になる。また、窒化ホウ素膜が結晶性窒化ホウ素であり、硫化亜鉛双晶ナノウィスカーの表面に結晶配向して成長しているので、化学的安定性が極めて高いと共に、硫化亜鉛ナノ構造物毎の特性が均一になる。 According to the zinc sulfide nanostructure coated with boron nitride of the present invention and the manufacturing method thereof, the boron nitride film is chemically stable, transparent in the ultraviolet region, and has a nano-sized structure. If zinc sulfide nanostructures are used, a light-emitting diode or laser in the ultraviolet region that can be actually used can be realized. In addition, since the boron nitride film is crystalline boron nitride and grows with crystal orientation on the surface of the zinc sulfide twinned nanowhisker, the chemical stability is extremely high and the characteristics of each zinc sulfide nanostructure are It becomes uniform.
以下、本発明を実施するための最良の形態を図面に基づき詳細に説明する。
図１は、本発明の窒化ホウ素で被覆された硫化亜鉛ナノ構造物を製造する装置の一例を示す模式図である。この装置を例に製造方法を説明する。
図において、縦型高周波誘導加熱装置１は、炉心管２の周囲に、上部誘導加熱コイル３及び下部誘導加熱コイル４を有している。硫化亜鉛双晶ウィスカー５を載せた窒化ホウ素円板６、及びＢ−Ｎ−Ｏ化合物粉末７をいれた坩堝８をそれぞれ、炉心管２の上部及び下部に配置し、それぞれ、上部誘導加熱コイル３及び下部誘導加熱コイル４で加熱する。矢印９はＢ−Ｎ−Ｏ化合物蒸気を表し、矢印１０は窒素ガスとアンモニアガスの混合ガスを表している。
Hereinafter, the best mode for carrying out the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic view showing an example of an apparatus for producing a zinc sulfide nanostructure coated with boron nitride according to the present invention. A manufacturing method will be described using this apparatus as an example.
In the figure, a vertical high-frequency induction heating apparatus 1 has an upper induction heating coil 3 and a lower induction heating coil 4 around a core tube 2. A boron nitride disc 6 on which zinc sulfide twin crystal whiskers 5 are placed, and crucibles 8 containing B—N—O compound powder 7 are arranged at the upper and lower portions of the core tube 2, respectively, and the upper induction heating coil 3, respectively. And it heats with the lower induction heating coil 4. FIG. Arrow 9 represents a B—N—O compound vapor, and arrow 10 represents a mixed gas of nitrogen gas and ammonia gas.
図１の装置を用いて窒化ホウ素で被覆された硫化亜鉛ナノ構造物を製造する方法を説明する。
初めに、硫化亜鉛双晶ウィスカー、及びＢ−Ｎ−Ｏ化合物粉末を作製しておく。
硫化亜鉛双晶ウィスカーは周知の方法で作製でき、例えば、硫化亜鉛粉末を窒素気流中で、１２００℃で約２時間加熱することにより得られる。Ｂ−Ｎ−Ｏ化合物の粉末は、例えば、後に詳細に説明するように、ホウ酸とメラミンから合成できる。
硫化亜鉛双晶ウィスカー５、及びＢ−Ｎ−Ｏ化合物７を図１に示したように配置し、上部誘導加熱コイル３で硫化亜鉛双晶ウィスカー５を加熱し、下部誘導加熱コイル４でＢ−Ｎ−Ｏ化合物粉末７を加熱してＢ−Ｎ−Ｏ化合物蒸気９を生成し、かつ、窒素ガスとアンモニアガスの混合ガス１０を流し、一定時間この状態を保持して製造する。
A method of manufacturing a zinc sulfide nanostructure coated with boron nitride using the apparatus of FIG. 1 will be described.
First, zinc sulfide twin whiskers and B—N—O compound powder are prepared.
Zinc sulfide twin whiskers can be produced by a well-known method, and can be obtained, for example, by heating zinc sulfide powder at 1200 ° C. for about 2 hours in a nitrogen stream. The powder of the B—N—O compound can be synthesized from boric acid and melamine, for example, as will be described in detail later.
The zinc sulfide twin whisker 5 and the B—N—O compound 7 are arranged as shown in FIG. 1, the zinc sulfide twin whisker 5 is heated by the upper induction heating coil 3, and the B— The N—O compound powder 7 is heated to produce a B—N—O compound vapor 9, and a mixed gas 10 of nitrogen gas and ammonia gas is allowed to flow, and this state is maintained for a certain time.
Ｂ−Ｎ−Ｏ化合物７は１３００〜１７５０℃の温度範囲で、硫化亜鉛双晶ナノウィスカー５は８５０〜９５０℃の温度範囲で加熱するのが好ましい。
Ｂ−Ｎ−Ｏ化合物と硫化亜鉛双晶ウィスカーの重量比は１０：１〜３０：１の範囲が好ましく、Ｂ−Ｎ−Ｏ化合物の硫化亜鉛双晶ウィスカーに対する重量比を３０：１よりも大きくしても、窒化ホウ素膜の成長速度は大きくならず、１０：１よりも小さくすると、硫化亜鉛双晶ウィスカーの表面全部を窒化ホウ素膜で覆うことが出来ない。
The B—N—O compound 7 is preferably heated in the temperature range of 1300 to 1750 ° C., and the zinc sulfide twinned nanowhisker 5 is preferably heated in the temperature range of 850 to 950 ° C.
The weight ratio of the B—N—O compound and the zinc sulfide twin whisker is preferably in the range of 10: 1 to 30: 1, and the weight ratio of the B—N—O compound to the zinc sulfide twin whisker is greater than 30: 1. However, the growth rate of the boron nitride film does not increase, and if it is less than 10: 1, the entire surface of the zinc sulfide twin whisker cannot be covered with the boron nitride film.
窒素ガスの流量は５００〜３０００ｃｍ3 ／ｍｉｎが好ましく、３０００ｃｍ3 ／ｍｉｎより大きくしても窒化ホウ素膜の被膜特性に変化はなく、５００ｃｍ3 ／ｍｉｎよりも流量が小さいと、硫化亜鉛双晶ナノウィスカーの全表面に均一に窒化ホウ素膜が被覆されなくなる。アンモニアガスの流量は１０〜１００ｃｍ3 ／ｍｉｎの範囲が好ましく、１００ｃｍ3 ／ｍｉｎより多く流しても窒化ホウ素膜の被膜特性に変化はなく、１０ｃｍ3 ／ｍｉｎよりも流量が少ないと、硫化亜鉛双晶ナノウィスカーの全表面に均一に窒化ホウ素膜が被覆されなくなる。 Flow rate of nitrogen gas is preferably 500~3000cm 3 / min, 3000cm 3 / be greater than min no change in the film properties of the boron nitride film, the flow rate is less than 500 cm 3 / min, zinc sulfide twin nano The entire surface of the whisker is not uniformly coated with the boron nitride film. The flow rate of the ammonia gas is preferably in the range of 10~100cm 3 / min, 100cm 3 / min even more flowed no change in the film properties of the boron nitride film, the flow rate is less than 10 cm 3 / min, zinc sulfide bi The boron nitride film is not uniformly coated on the entire surface of the crystal nanowhiskers.
Ｂ−Ｎ−Ｏ化合物の蒸気は、１３００〜１７５０℃の温度範囲で十分発生するので、１７５０℃以上に加熱する必要はなく、１３００℃よりも低いと窒化ホウ素膜を形成するための蒸気が十分に供給されない。 Since the vapor of the B—N—O compound is sufficiently generated in the temperature range of 1300 to 1750 ° C., it is not necessary to heat to 1750 ° C. or higher, and if it is lower than 1300 ° C., the vapor for forming the boron nitride film is sufficient Not supplied.
硫化亜鉛双晶ウィスカーの加熱温度は８５０〜９５０℃の温度範囲が好ましく、９５０℃よりも高いと、硫化亜鉛双晶ウィスカーが窒化ホウ素円板上から蒸発逸散してしまい、８５０℃よりも低いと、とげ状の側枝を持った硫化亜鉛双晶ナノウィスカーが形成されない。加熱時間は１〜３時間の範囲が好ましく、３時間で十分に反応が進行するので、これ以上の時間をかける必要はなく、１時間未満の場合は、窒化ホウ素膜で被膜されていない硫化亜鉛双晶ナノウィスカーの割合が増える。
生成された、窒化ホウ素膜で被覆された硫化亜鉛双晶ナノウィスカーは、肉眼では白色の粉末に見える。
The heating temperature of the zinc sulfide twin whisker is preferably in the temperature range of 850 to 950 ° C. If the temperature is higher than 950 ° C., the zinc sulfide twin whisker evaporates away from the boron nitride disc, and is lower than 850 ° C. As a result, zinc sulfide twin nanowhiskers having thorn-like side branches are not formed. The heating time is preferably in the range of 1 to 3 hours, and since the reaction proceeds sufficiently in 3 hours, it is not necessary to spend more time, and in the case of less than 1 hour, zinc sulfide not coated with a boron nitride film Increases the proportion of twin nanowhiskers.
The resulting zinc sulfide twinned nanowhiskers coated with a boron nitride film appear white powder to the naked eye.
上記の製造方法によれば、硫化亜鉛双晶ウィスカーが再結晶化して、とげ状の側枝を有する硫化亜鉛双晶ナノウィスカーになると共に、この表面に窒化ホウ素膜が成長する。この窒化ホウ素膜は結晶性窒化ホウ素膜であり、この結晶性窒化ホウ素膜は、結晶性窒化ホウ素の特定の結晶面が、とげ状の側枝を有する硫化亜鉛双晶ナノウィスカーの表面に平行な結晶配向性を有して成長する。 According to the above manufacturing method, the zinc sulfide twin whisker is recrystallized to become a zinc sulfide twin nano whisker having spine-like side branches, and a boron nitride film grows on this surface. This boron nitride film is a crystalline boron nitride film, and this crystalline boron nitride film is a crystal in which a specific crystal plane of crystalline boron nitride is parallel to the surface of a zinc sulfide twinned nanowhisker having thorn-like side branches. Grows with orientation.
次に、実施例に基づいて詳細に説明する。
初めに、Ｂ−Ｎ−Ｏ化合物を次のようにして合成した。
１０００ｃｍ3 の水に０．４モルのホウ酸を１００℃で溶解し、この溶液に０．２モルのメラミンを徐々に添加し、添加終了後、室温に冷却して２日間放置して白色粉末を沈殿させた。白色粉末を乾燥後、さらに脱水するため、空気中で５００℃、２時間加熱後、窒素中で８００℃、１時間加熱して、化学式Ｂ4 Ｎ3 Ｏ2 Ｈで表される黄色の化合物粉末を得た。さらに、この黄色化合物を空気中で６００℃、２時間焼成して酸素含有量の高い白色のＢ−Ｎ−Ｏ化合物粉末を得た。
Next, it demonstrates in detail based on an Example.
First, a B—N—O compound was synthesized as follows.
Dissolve 0.4 mol of boric acid in 1000 cm 3 of water at 100 ° C., gradually add 0.2 mol of melamine to this solution, cool to room temperature after the addition is complete, and leave it for 2 days. Precipitated. In order to further dehydrate the white powder after drying, it is heated in air at 500 ° C. for 2 hours, then in nitrogen at 800 ° C. for 1 hour, and a yellow compound powder represented by the chemical formula B 4 N 3 O 2 H Got. Further, this yellow compound was calcined in air at 600 ° C. for 2 hours to obtain a white B—N—O compound powder having a high oxygen content.
次に、硫化亜鉛双晶ウィスカーを次のようにして合成した。
アルドリッチ社製の硫化亜鉛粉末（純度９９．９９％）０．５ｇをグラファイト製のボートに入れ、このボートを抵抗加熱炉の中に設置した。抵抗加熱炉に窒素ガスを１０００ｃｍ3 ／ｍｉｎの流量で流しながら、１２００℃に２時間加熱した。抵抗加熱炉のグラファイト壁の内面に硫化亜鉛双晶ウィスカーである白色粉末が０．３ｇ堆積した。
Next, zinc sulfide twin whiskers were synthesized as follows.
0.5 g of zinc sulfide powder (purity: 99.99%) manufactured by Aldrich was placed in a graphite boat, and this boat was placed in a resistance heating furnace. While flowing nitrogen gas through the resistance heating furnace at a flow rate of 1000 cm 3 / min, heating was performed at 1200 ° C. for 2 hours. 0.3 g of white powder as zinc sulfide twin whiskers was deposited on the inner surface of the graphite wall of the resistance heating furnace.
上記方法で合成したＢ−Ｎ−Ｏ化合物粉末２ｇと硫化亜鉛双晶ウィスカー粉末０．１ｇを、図１に示したように配置した。なお、窒化ホウ素円板６とグラファイト坩堝８の距離
は１５ｃｍである。この反応系に窒素ガスを１５００ｃｍ3 ／ｍｉｎの流量で流し、アンモニアガスを５０ｃｍ3 ／ｍｉｎの流量で流しながら、Ｂ−Ｎ−Ｏ化合物７を１７００℃に、硫化亜鉛双晶ナノウィスカーを９００℃に加熱し、この状態を１．５時間継続した。その後、室温に冷却した後に、窒化ホウ素円板６上に白色の粉末が０．１ｇ堆積した。
As shown in FIG. 1, 2 g of the B—N—O compound powder synthesized by the above method and 0.1 g of zinc sulfide twinned whisker powder were arranged. The distance between the boron nitride disc 6 and the graphite crucible 8 is 15 cm. Nitrogen gas to the reaction system to flow at a flow rate of 1500 cm 3 / min, while flowing ammonia gas at a flow rate of 50 cm 3 / min, the B-N-O compound 7 to 1700 ° C., 900 ° C. The zinc sulfide twin nanowhisker And this state was continued for 1.5 hours. Thereafter, after cooling to room temperature, 0.1 g of white powder was deposited on the boron nitride disc 6.
図２に、実施例で合成した硫化亜鉛双晶ウィスカーの走査型電子顕微鏡像を示し、挿入図にその高分解能透過型電子顕微鏡像を示す。図２から、合成した硫化亜鉛双晶ナノウィスカーは、太さ１μｍ程度の棒状であること、及び挿入図から長さ方向に対して約５９°の帯角を有する双晶ウィスカーであることが分かる。 FIG. 2 shows a scanning electron microscope image of the zinc sulfide twin crystal whisker synthesized in the example, and an inset shows a high-resolution transmission electron microscope image thereof. FIG. 2 shows that the synthesized zinc sulfide twinned nanowhisker is a rod having a thickness of about 1 μm, and the inset shows a twin whisker having a band angle of about 59 ° with respect to the length direction. .
図３に、実施例で合成した白色粉末、すなわち、合成したとげ状の側枝を有する硫化亜鉛双晶ナノウィスカーの走査型電子顕微鏡像を示す。
この図から、棒状部分の太さが約３００ｎｍで、その側面から長さ約５００ｎｍのとげ状突起が張り出していることがわかる。
FIG. 3 shows a scanning electron microscope image of the white powder synthesized in Example, that is, a zinc sulfide twin nanowhisker having a synthesized spine-shaped side branch.
From this figure, it can be seen that the bar-shaped portion has a thickness of about 300 nm, and a spine-shaped protrusion having a length of about 500 nm protrudes from the side surface.
図４にとげ状部分の先端近傍の高分解能透過型電子顕微鏡像を示す。
図から、とげ状部分は、〔００１〕で示した格子面が面間隔０．６２６ｎｍで配列した単結晶であることがわかる。また、とげ状部分の表面を覆って面間隔０．３３４ｎｍの格子面が配列していることがわかる。微少領域電子線解析の結果、及び上記面間隔から、〔００１〕で示した格子面は、ｗｕｒｕｔｚｉｔｅ型硫化亜鉛の（００１）面であり、また、面間隔０．３３４ｎｍの格子面は、ｈｅｘａｇｏｎａｌ型窒化ホウ素の（００２）面であることが確認された。また、図から、とげ状部分の先端のサイズは約５ｎｍであるから、とげ状の側枝を有する硫化亜鉛双晶ナノウィスカーは、紫外線発光が可能であることがわかる。
FIG. 4 shows a high-resolution transmission electron microscope image near the tip of the barbed portion.
From the figure, it can be seen that the barbed portion is a single crystal in which lattice planes indicated by [001] are arranged with a plane spacing of 0.626 nm. It can also be seen that lattice planes with a surface spacing of 0.334 nm are arranged so as to cover the surface of the barbed portion. From the results of the microscopic region electron beam analysis and the above-mentioned plane spacing, the lattice plane indicated by [001] is the (001) plane of wurtzite type zinc sulfide, and the lattice plane with a plane spacing of 0.334 nm is a hexagonal type. It was confirmed to be the (002) plane of boron nitride. Moreover, since the size of the tip of the spine-shaped portion is about 5 nm, it can be seen that the zinc sulfide twin nanowhisker having the spine-shaped side branch can emit ultraviolet light.
図５は、とげ状部分の表面を覆う部分のＥＥＬＳ（Ｅｌｅｃｔｒｏｎ Ｅｎｅｒｇｙ Ｌｏｓｓ Ｓｐｅｃｔｒｏｍｅｔｅｒ）による測定結果を示す図であり、挿入図は、とげ状部分のＥＤＸ（Ｅｎｅｒｇｙ−Ｄｉｓｐｅｒｓｉｖｅ Ｘ−ｒａｙ Ａｎａｌｙｓｉｓ）による測定結果を示す図である。
ＥＥＬＳのスペクトルに、それぞれホウ素と窒素のＫ端に対応する１８８ｅＶと４０１ｅＶのピークが現れていることから、とげ状部分の表面を覆う物質の組成は窒化ホウ素であり、また、ＥＤＸのスペクトルから、とげ状部分の組成は硫化亜鉛であることが確認された。
FIG. 5 is a diagram showing a measurement result by EELS (Electron Energy Loss Spectrometer) of a portion covering the surface of the spine-shaped portion, and an inset is a measurement result by EDX (Energy-Dispersive X-ray Analysis) of the spinous portion. FIG.
Since 188 eV and 401 eV peaks corresponding to the K-edges of boron and nitrogen, respectively, appear in the EELS spectrum, the composition of the material covering the surface of the barbed portion is boron nitride, and from the EDX spectrum, It was confirmed that the composition of the barbed portion was zinc sulfide.
図４及び図５から、本発明の窒化ホウ素で被覆された硫化亜鉛ナノ構造物は、とげ状の側枝を有する硫化亜鉛双晶ナノウィスカーと、この表面を被覆する結晶性窒化ホウ素膜とからなり、この結晶性窒化ホウ素膜は、特定の結晶面がとげ状の側枝を有する硫化亜鉛双晶ナノウィスカーの表面と平行な結晶配向性を有して成長しており、硫化亜鉛双晶ナノウィスカーと結晶性窒化ホウ素膜の結合が極めて強固であることがわかる。 4 and 5, the zinc sulfide nanostructure coated with boron nitride according to the present invention comprises a zinc sulfide twinned nanowhisker having a spine-like side branch and a crystalline boron nitride film covering the surface. This crystalline boron nitride film is grown with a crystal orientation parallel to the surface of the zinc sulfide twin nanowhisker having a specific crystal plane having a spine-shaped side branch, It can be seen that the bonding of the crystalline boron nitride film is extremely strong.
本発明によれば、化学的安定性に優れ、紫外線領域で透明であり、かつ、ナノサイズの硫化亜鉛ナノ構造物が得られるので、例えば、この硫化亜鉛ナノ構造物を発光材料とした、紫外線領域の発光ダイオードやレーザーを製造することができる。 According to the present invention, it is excellent in chemical stability, transparent in the ultraviolet region, and nanosized zinc sulfide nanostructures can be obtained. Area light emitting diodes and lasers can be manufactured.
１ 縦型高周波誘導加熱装置
２ 炉心管
３ 誘導加熱コイル
４ 誘導加熱コイル
５ 硫化亜鉛双晶ナノウィスカー
６ 窒化ホウ素円盤
７ Ｂ−Ｎ−Ｏ化合物粉末
８ 坩堝
９ Ｂ−Ｎ−Ｏ化合物蒸気
１０ 窒素ガス及びアンモニアガスの混合ガス
DESCRIPTION OF SYMBOLS 1 Vertical type high frequency induction heating apparatus 2 Core tube 3 Induction heating coil 4 Induction heating coil 5 Zinc sulfide twin crystal nano whisker 6 Boron nitride disk 7 B—N—O compound powder 8 Crucible 9 B—N—O compound vapor 10 Nitrogen gas And mixed gas of ammonia gas
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