JP5500543B2 - Zinc sulfide nanobelts, UV detection sensors, and methods for producing them - Google Patents
Zinc sulfide nanobelts, UV detection sensors, and methods for producing them Download PDFInfo
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- JP5500543B2 JP5500543B2 JP2009274154A JP2009274154A JP5500543B2 JP 5500543 B2 JP5500543 B2 JP 5500543B2 JP 2009274154 A JP2009274154 A JP 2009274154A JP 2009274154 A JP2009274154 A JP 2009274154A JP 5500543 B2 JP5500543 B2 JP 5500543B2
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- 239000005083 Zinc sulfide Substances 0.000 title claims description 92
- 229910052984 zinc sulfide Inorganic materials 0.000 title claims description 91
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims description 91
- 239000002127 nanobelt Substances 0.000 title claims description 86
- 238000000825 ultraviolet detection Methods 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 26
- 239000010931 gold Substances 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052737 gold Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 238000000206 photolithography Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 229910052786 argon Inorganic materials 0.000 description 18
- 238000005136 cathodoluminescence Methods 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 208000000453 Skin Neoplasms Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 206010042496 Sunburn Diseases 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 201000000849 skin cancer Diseases 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Luminescent Compositions (AREA)
- Light Receiving Elements (AREA)
Description
本発明は、ベルト状に結晶化した硫化亜鉛ナノベルト及びその製造法、並びにこの硫化亜鉛ナノベルトを用いた紫外線検知センサー及びその製造法に関する。 The present invention relates to a zinc sulfide nanobelt crystallized in a belt shape and a method for producing the same, and an ultraviolet detection sensor using the zinc sulfide nanobelt and a method for producing the same.
紫外線が皮膚に当たると日焼けや皮膚がんを引き起こしやすい。そこで、その危険度を把握するためには、まず、紫外線の量を計測することが重要であり、紫外線を検知する材料や検知器の開発が強く要求されている。
近年、紫外線検出器として酸化亜鉛ナノロッド／ポリフルオレンを用いたハイブリッドフォトダイオードが検討されており、これは紫外領域において、可視光領域の１０００倍の感度を示すことが報告されている（たとえば、非特許文献１参照）。
しかし、酸化亜鉛結晶体は、３７０ｎｍ以下の紫外域での発光ピークを有するものがなかったり、あるいは可視光領域に強い発光ピークが共存したりするので、３７０ｎｍ以下の紫外域に発光ピークを有し、可視光領域では強い発光ピークを有しない結晶体があれば、更に高い感度の紫外線量検出器の提供が可能となるものと期待されている。
When UV rays hit the skin, they tend to cause sunburn and skin cancer. Therefore, in order to grasp the degree of risk, it is important to first measure the amount of ultraviolet rays, and there is a strong demand for the development of materials and detectors that detect ultraviolet rays.
In recent years, hybrid photodiodes using zinc oxide nanorods / polyfluorene as an ultraviolet detector have been studied, and this has been reported to show 1000 times higher sensitivity in the ultraviolet region than in the visible light region (for example, Patent Document 1).
However, none of the zinc oxide crystals have a light emission peak in the ultraviolet region of 370 nm or less, or a strong light emission peak coexists in the visible light region, and thus has a light emission peak in the ultraviolet region of 370 nm or less. If there is a crystal body that does not have a strong emission peak in the visible light region, it is expected that an ultraviolet light amount detector with higher sensitivity can be provided.
硫化亜鉛ナノベルトに関しては、従来、ＢＮＯ化合物粉末と炭素の混合物並びに硫化亜鉛粉末を離して配置し、窒素ガス／水蒸気の還元雰囲気気流中で、１６００℃および１１００℃にそれぞれ加熱する方法（たとえば、非特許文献２参照）、硫化亜鉛粉末と炭素粉末ならびに硫黄粉を不活性ガス（アルゴンガス）気流中で１１００℃に加熱する方法（たとえば、非特許文献３参照）、硫化亜鉛ナノ粒子を酸素の存在しない状態でアルゴンガス気流中において１１００℃に加熱して、シリコン基板上に堆積させる方法（たとえば、非特許文献４参照）、高純度硫化亜鉛粉末を５％水素を含むアルゴンガス気流中で１０００℃に加熱して金薄膜付きシリコン基板に堆積させる方法（たとえば、非特許文献５参照）、硫化亜鉛粉末をアルゴンガス気流中で９７０℃に加熱して、７５０〜８００℃に維持された金薄膜付きサファイア基板上に堆積させる方法（たとえば、非特許文献６参照）などにより製造されている。 With respect to zinc sulfide nanobelts, conventionally, a mixture of BNO compound powder and carbon and zinc sulfide powder are disposed separately and heated to 1600 ° C. and 1100 ° C. in a nitrogen gas / water vapor reducing atmosphere, respectively (for example, non- Patent Document 2), a method of heating zinc sulfide powder, carbon powder and sulfur powder to 1100 ° C. in an inert gas (argon gas) stream (for example, see Non-Patent Document 3), presence of oxygen in zinc sulfide nanoparticles Without heating, the method is heated to 1100 ° C. in an argon gas stream and deposited on a silicon substrate (see, for example, Non-Patent Document 4). High purity zinc sulfide powder is 1000 ° C. in an argon gas stream containing 5% hydrogen. (E.g., see Non-Patent Document 5), zinc sulfide powder with argon gas By heating in the flow to 970 ° C., a method of depositing a gold thin film-sapphire substrate is maintained at 750 to 800 ° C. (e.g., see non-patent document 6) is manufactured by like.
本発明は、日焼けや皮膚がんを起こしやすい紫外線を、感度よく検知する材料及びこれを用いた紫外線検知器を提供することであり、あるいは、それらの製造法を提供することを目的とする。 An object of the present invention is to provide a material capable of sensitively detecting ultraviolet rays that are likely to cause sunburn and skin cancer, and an ultraviolet detector using the same, or an object of the present invention.
〔発明の要約〕
本発明者らは、前記非特許文献６における硫化亜鉛ナノベルトの製造方法を種々検討している過程で、ある改良された条件、すなわち、硫化亜鉛粉末の蒸発時の昇温速度を従来よりも緩慢にした条件で製造した硫化亜鉛ナノベルトは、陰極線ルミネッセンスによる発光ピークが紫外域の３３７ｎｍ付近に特徴的に存在すると共に、可視域の発光ピークは前記紫外域の発光ピークに比べ低い硫化亜鉛ナノベルト（すなわち、従来知られていない特性を有する硫化亜鉛ナノベルト）が得られることを見出し、本発明を完成するに至った。
[Summary of the Invention]
In the process of variously examining the method for producing a zinc sulfide nanobelt in Non-Patent Document 6, the present inventors have made a certain improved condition, that is, the heating rate during evaporation of zinc sulfide powder slower than before. The zinc sulfide nanobelt manufactured under the above conditions has a characteristic emission peak due to cathodoluminescence in the vicinity of 337 nm in the ultraviolet region, and the emission peak in the visible region is lower than the emission peak in the ultraviolet region (that is, The present inventors have found that a zinc sulfide nanobelt having properties not conventionally known can be obtained, and have completed the present invention.
すなわち、本発明（第１の発明）は、陰極線ルミネッセンスによる発光ピークが紫外域に特徴的に存在する「ベルト状に単結晶化した硫化亜鉛ナノベルト」を提供する。
ここで、ナノベルトとは、厚みがｎｍオーダー（通常は１００ｎｍ以下）で、幅／厚の比が５以上の大きさをもち、長さは幅よりも大きいベルト状若しくはリボン状物を意味する。
That is, the present invention (the first invention) provides a “belt-shaped zinc sulfide nanobelt” in which an emission peak due to cathodoluminescence is characteristically present in the ultraviolet region.
Here, the nanobelt means a belt-like or ribbon-like material having a thickness of the order of nm (usually 100 nm or less), a width / thickness ratio of 5 or more, and a length larger than the width.
また、本発明（第２の発明）は、上記「ベルト状に単結晶化した硫化亜鉛ナノベルト」の製造法、すなわち、次のステップを含む硫化亜鉛ナノベルト製造法も提供する。
（１）筒状加熱炉の中央部に硫化亜鉛粉末を置き、その下流側に金薄膜付きシリコン基板を置く。
（２）前記加熱炉中の酸素が除去されるまで、その加熱炉中へ、所定の流速で不活性ガスを導入する。
（３）不活性ガスを所定の流速で導入しながら、前記加熱炉を１７±５℃／ｍｉｎの昇温速度で室温から１０００〜１２００℃まで昇温させたのち、その温度で一定時間保つ。
（４）放冷後、金薄膜付きシリコン基板上に堆積した堆積物（目的物；ベルト状に単結晶化した硫化亜鉛ナノベルト）を回収する。
The present invention (second invention) also provides a method for producing the above-mentioned “zinc sulfide nanobelt monocrystallized in a belt shape”, that is, a method for producing zinc sulfide nanobelts including the following steps.
(1) A zinc sulfide powder is placed at the center of a cylindrical heating furnace, and a silicon substrate with a gold thin film is placed downstream thereof.
(2) An inert gas is introduced into the heating furnace at a predetermined flow rate until oxygen in the heating furnace is removed.
(3) While introducing the inert gas at a predetermined flow rate, the heating furnace is heated from room temperature to 1000 to 1200 ° C. at a temperature rising rate of 17 ± 5 ° C./min, and then kept at that temperature for a certain time.
(4) After standing to cool, the deposit (target object; zinc sulfide nanobelt single-crystallized in a belt shape) deposited on the silicon substrate with the gold thin film is collected.
また、本発明（第３の発明）は、紫外光を受けて、その光の強さに応じた強さの電気を発生する光電変換部材を有する紫外線検知センサーであって、その光電変換部材として上記硫化亜鉛ナノベルトが用いられている紫外線検知センサー、も提供する。 Moreover, this invention (3rd invention) is an ultraviolet detection sensor which has a photoelectric conversion member which generate | occur | produces the electricity of the intensity | strength according to the intensity of the light which receives ultraviolet light, Comprising: An ultraviolet detection sensor using the zinc sulfide nanobelt is also provided.
上記紫外線検知センサーは、例えば、以下の（ａ）〜（ｃ）を含んで構成される紫外線検知センサーである。
（ａ）絶縁層に覆われたＳｉ基板、
（ｂ）前記絶縁層上に置かれた上記本発明の硫化亜鉛ナノベルト、及び
（ｃ）前記硫化亜鉛ナノベルトの上に形成された２つの分離された金属電極。
The ultraviolet detection sensor is, for example, an ultraviolet detection sensor including the following (a) to (c).
(A) a Si substrate covered with an insulating layer;
(B) the zinc sulfide nanobelt of the present invention placed on the insulating layer, and (c) two separated metal electrodes formed on the zinc sulfide nanobelt.
このような紫外線検知センサーは、以下の（ｉ）及び（ｉｉ）のステップを経た製造法（第４の発明）により製造できる。
（ｉ） 絶縁層で覆われたＳｉ基板上に、上記本発明の硫化亜鉛ナノベルトを分散させる；
（ｉｉ）光リソグラフィーを用いて前記Ｓｉ基板上にレジストパターンを形成し、金属電極用の金属材料を前記Ｓｉ基板及び前記レジストパターン上に電子ビームデポジションし、その後にリフトオフプロセスを行うことにより、前記ナノベルトの上に金属電極をパターン形成する。
Such an ultraviolet detection sensor can be manufactured by a manufacturing method (fourth invention) through the following steps (i) and (ii).
(I) Dispersing the zinc sulfide nanobelt of the present invention on a Si substrate covered with an insulating layer;
(Ii) forming a resist pattern on the Si substrate using photolithography, depositing a metal material for a metal electrode on the Si substrate and the resist pattern, and then performing a lift-off process; A metal electrode is patterned on the nanobelt.
本発明の硫化亜鉛ナノベルトは、陰極線ルミネッセンスによる発光ピークが紫外域に（すなわち、３３７ｎｍ付近に）特徴的に存在し、可視域の発光ピークは前記紫外域に存在する発光ピークに比べ低い。このような陰極線ルミネッセンススペクトルを有する硫化亜鉛ナノベルトは今までに知られておらず、新規な特性を有する硫化亜鉛ナノベルトである。
本発明の硫化亜鉛ナノベルト製造法により、上記本発明の硫化亜鉛ナノベルトを再現性よく製造できる。
本発明の紫外線検知センサーは、陰極線ルミネッセンスによる発光ピークが紫外域の３３７ｎｍ付近に特徴的に存在し、可視域の発光ピークは前記紫外域の発光ピークに比べ低い「ベルト状に単結晶化した硫化亜鉛ナノベルト」を光電変換部材として用いているので、可視光に鈍感で（ｂｌｉｎｄ）、紫外光にのみ反応し、これを感度よく検知できる。
本発明の紫外線検知センサー製造法により、上記紫外線検知センサーを容易に製造できる。
In the zinc sulfide nanobelt of the present invention, the emission peak due to cathodoluminescence is characteristically present in the ultraviolet region (that is, in the vicinity of 337 nm), and the emission peak in the visible region is lower than the emission peak existing in the ultraviolet region. A zinc sulfide nanobelt having such a cathodoluminescence spectrum has not been known so far, and is a zinc sulfide nanobelt having novel characteristics.
By the zinc sulfide nanobelt manufacturing method of the present invention, the zinc sulfide nanobelt of the present invention can be manufactured with good reproducibility.
The ultraviolet detection sensor of the present invention has a characteristic emission peak due to cathodoluminescence in the vicinity of 337 nm in the ultraviolet region, and the emission peak in the visible region is lower than the emission peak in the ultraviolet region. Since the “zinc nanobelt” is used as a photoelectric conversion member, it is insensitive to visible light (blind), reacts only to ultraviolet light, and can be detected with high sensitivity.
According to the method for producing an ultraviolet detection sensor of the present invention, the ultraviolet detection sensor can be easily produced.
〔発明の更に詳しい説明〕
先ず、本発明の「ベルト状に単結晶化した硫化亜鉛ナノベルト」の製造法を説明する。製造工程は、上述したように、次のステップ（１）〜（４）を含む。
（１）加熱炉にセットした筒状加熱管の中央部に硫化亜鉛粉末を置き、その下流側に金薄膜付きシリコン基板を置く。
（２）前記筒状加熱管中の酸素が除去されるまで、その筒状加熱管中へ、不活性ガスを導入する。
（３）不活性ガスを所定の流速で導入しながら、加熱炉を１７±５℃／ｍｉｎの昇温速度で室温から１０００〜１２００℃まで昇温させたのち、その温度で一定時間保つ。
（４）放冷後、金薄膜付きシリコン基板上に堆積した堆積物を回収する。
[Detailed description of the invention]
First, a method for producing “a zinc sulfide nanobelt monocrystallized in a belt shape” of the present invention will be described. As described above, the manufacturing process includes the following steps (1) to (4).
(1) A zinc sulfide powder is placed at the center of a cylindrical heating tube set in a heating furnace, and a silicon substrate with a gold thin film is placed downstream thereof.
(2) An inert gas is introduced into the cylindrical heating tube until oxygen in the cylindrical heating tube is removed.
(3) While introducing the inert gas at a predetermined flow rate, the heating furnace is heated from room temperature to 1000 to 1200 ° C. at a temperature rising rate of 17 ± 5 ° C./min, and then kept at that temperature for a certain time.
(4) Collect the deposit deposited on the silicon substrate with the gold thin film after cooling.
ここで、筒状加熱管としては、内径２０ｍｍ〜５０ｍｍ程度、長さ１００ｃｍ〜１５０ｃｍ程度の石英管が好ましく、これを加熱炉の中にセットして用いる。加熱炉は縦型（垂直方向）としてもよいが、通常は取り扱いやすさの点から横型（水平方向）が好ましく、また、加熱炉の有効加熱部の長さは上記筒状加熱管よりも短い約５０ｃｍ程度のものが通常用いられる。
用いる硫化亜鉛粉末の純度は好ましくは９９％以上のもの、更に好ましくは９９．９％以上のものとする。純度が低いと、結晶中に欠陥が生じやすくなるからである。
Here, as the cylindrical heating tube, a quartz tube having an inner diameter of about 20 mm to 50 mm and a length of about 100 cm to 150 cm is preferable, and this is set and used in a heating furnace. Although the heating furnace may be a vertical type (vertical direction), the horizontal type (horizontal direction) is usually preferable from the viewpoint of ease of handling, and the length of the effective heating portion of the heating furnace is shorter than the cylindrical heating tube. About 50 cm is usually used.
The purity of the zinc sulfide powder used is preferably 99% or more, more preferably 99.9% or more. This is because if the purity is low, defects are likely to occur in the crystal.
用いる不活性ガスとしては、アルゴン、ヘリウム、窒素ガス等の不活性ガスが用いられるが、酸素不含の点及びコストの点からアルゴンが好ましく用いられる。
工程（２）における加熱炉中への不活性ガス（通常はアルゴン）の導入は、加熱炉中における酸素の除去を主目的としている。そのためには、比較的多量の不活性ガス／アルゴンを長時間流す必要がある。例えば、内径５．５ｃｍ、長さ４５ｃｍの加熱炉を使用した場合には、５００ｓｃｃｍを越える流量（線速度として２１ｃｍ／ｍｉｎを越える速度）が好ましい。線速度２１ｃｍ／ｍｉｎ未満の流速では、加熱炉中に酸素が残存したり、酸素を除去する時間が長くなり生産効率が悪くなる。不活性ガス／アルゴンの導入を線速度２１ｃｍ／ｍｉｎ以上の流速で行えば、処理時間は３時間で十分である。
As the inert gas to be used, an inert gas such as argon, helium, or nitrogen gas is used, but argon is preferably used from the viewpoint of not containing oxygen and cost.
The introduction of the inert gas (usually argon) into the heating furnace in the step (2) is mainly aimed at removing oxygen in the heating furnace. This requires a relatively large amount of inert gas / argon to flow for a long time. For example, when a heating furnace having an inner diameter of 5.5 cm and a length of 45 cm is used, a flow rate exceeding 500 sccm (a linear velocity exceeding 21 cm / min) is preferable. If the linear velocity is less than 21 cm / min, oxygen remains in the heating furnace or the time for removing oxygen becomes longer, resulting in poor production efficiency. If the inert gas / argon is introduced at a flow rate of 21 cm / min or higher, a treatment time of 3 hours is sufficient.
加熱炉中の酸素が完全に除去された後、不活性ガス／アルゴンを流したまま、加熱炉を、好ましくは１７±５℃／ｍｉｎ、更に好ましくは１７±２℃／ｍｉｎの昇温速度で、１０００〜１２００℃の温度範囲になるまで加熱する。ここで、１２００℃を越えて加熱すると硫化亜鉛の昇華温度よりもずっと高温であるため蒸発速度が早すぎて良質の単結晶が生成されない。１０００℃よりも低い温度ではほとんど昇華せず生産効率が悪くなる。 After the oxygen in the heating furnace is completely removed, the heating furnace is preferably heated at a rate of temperature increase of 17 ± 5 ° C./min, more preferably 17 ± 2 ° C./min, with an inert gas / argon flowing. Heat to 1000-1200 ° C. Here, when the temperature exceeds 1200 ° C., the temperature is much higher than the sublimation temperature of zinc sulfide, and thus the evaporation rate is too fast to produce a good quality single crystal. At a temperature lower than 1000 ° C., there is almost no sublimation and the production efficiency is deteriorated.
また、工程（３）における、加熱炉の加熱を開始してからの不活性ガス／アルゴンの供給は、外部からの酸素の侵入防止とキャリアガスとしての役目であるので、その流量（流速）は工程（２）における不活性ガス／アルゴンの流量（流速）よりも低い、線速度として２〜２０ｃｍ／ｍｉｎの流速が好ましい。２０ｃｍ／ｍｉｎを越える流速であると、下流に設けた金薄膜（触媒作用を有する）付きシリコン基板への生成物の堆積量が減る傾向となる。２ｃｍ／ｍｉｎよりも少ない流速では酸素が混入する恐れがある。
加熱炉が１０００〜１２００℃の温度に達したら、引き続いて同じ流量（流速）の不活性ガス／アルゴンを流したまま、その温度を一定時間、例えば、１０分〜５０分間維持する。
その後、不活性ガス／アルゴンの供給（導入）及び加熱炉の加熱を止め、放冷する。金薄膜付きシリコン基板に目的物（ベルト状に単結晶化した硫化亜鉛ナノベルト）が堆積しているので、これを回収する。
In addition, in the step (3), the supply of the inert gas / argon after starting the heating of the heating furnace serves to prevent the entry of oxygen from the outside and serves as a carrier gas. A flow rate of 2 to 20 cm / min is preferable as the linear velocity, which is lower than the flow rate (flow rate) of the inert gas / argon in the step (2). When the flow rate exceeds 20 cm / min, the amount of product deposited on a silicon substrate with a gold thin film (having a catalytic action) provided downstream tends to decrease. At a flow rate lower than 2 cm / min, oxygen may be mixed.
When the heating furnace reaches a temperature of 1000 to 1200 ° C., the temperature is maintained for a certain period of time, for example, 10 minutes to 50 minutes with the same flow rate (flow rate) of the inert gas / argon continuously flowing.
Thereafter, the supply (introduction) of the inert gas / argon and the heating of the heating furnace are stopped and allowed to cool. Since the object (zinc sulfide nanobelt single-crystallized in a belt shape) is deposited on the silicon substrate with the gold thin film, it is collected.
このようにして、本発明の陰極線ルミネッセンスによる発光ピークが紫外域に特徴的に存在する「ベルト状に単結晶化した硫化亜鉛ナノベルト」が得られる。陰極線ルミネッセンスによる前記紫外域の発光ピークは、通常は、３３７ｎｍ付近（３３７±４ｎｍ）に存在している。また、可視域の発光ピークは、通常は、５５０ｎｍ付近（５５０±１０ｎｍ）に存在するが、その発光ピーク前記紫外域の発光ピークに比べ低く幅広い。 Thus, a “belt-shaped zinc sulfide nanobelt” in which the emission peak due to cathodoluminescence of the present invention is characteristically present in the ultraviolet region is obtained. The emission peak in the ultraviolet region due to cathodoluminescence usually exists in the vicinity of 337 nm (337 ± 4 nm). In addition, the emission peak in the visible region usually exists in the vicinity of 550 nm (550 ± 10 nm), but the emission peak is lower and wider than the emission peak in the ultraviolet region.
製造条件、例えば、加熱炉の室温から１０００〜１２００℃（到達最高温度）への昇温速度、到達最高温度、到達最高温度での維持時間、不活性ガス／アルゴンの流速等により、得られる硫化亜鉛ナノベルトの形態は多少変動するが、代表的な硫化亜鉛ナノベルトとして、長さが１５〜１００μｍ、幅１００ｎｍ〜５μｍ、厚さ１０ｎｍ〜５０ｎｍのものが得られる。 Sulfurization obtained depending on the production conditions, for example, the heating rate from the room temperature of the heating furnace to 1000 to 1200 ° C. (maximum temperature reached), the maximum temperature reached, the maintenance time at the maximum temperature reached, the inert gas / argon flow rate, etc. The form of the zinc nanobelt varies somewhat, but a typical zinc sulfide nanobelt having a length of 15 to 100 μm, a width of 100 nm to 5 μm, and a thickness of 10 nm to 50 nm is obtained.
得られた硫化亜鉛ナノベルトは、これを光電変換部材とする紫外線検知センサーに利用できる。この紫外線検知センサーは、既に述べたように、通常は、以下の（ａ）〜（ｃ）、すなわち、
（ａ）絶縁層に覆われたＳｉ基板、
（ｂ）前記絶縁層上に置かれた本発明の硫化亜鉛ナノベルト、及び
（ｃ）前記硫化亜鉛ナノベルトの上に形成された２つの分離された金属電極、
を含んで構成される。
ここで、２つの分離された金属電極間を渡し掛けるように置かれる硫化亜鉛ナノベルトの本数は一本とすることもできるが、感度及びレスポンスの安定性を高めるためには複数本が好ましい。また、２つの分離された金属電極間の間隔（距離）は、１μｍ〜１００μｍとすることができ、また、一つの金属電極の幅及び奥行は各々５０μｍ〜５００μｍとすることができるが、いずれも小さいよりも大きいほど感度及び安定性が高い傾向になる。
The obtained zinc sulfide nanobelt can be used for an ultraviolet detection sensor using this as a photoelectric conversion member. As described above, this ultraviolet ray detection sensor is usually the following (a) to (c), that is,
(A) a Si substrate covered with an insulating layer;
(B) the zinc sulfide nanobelt of the present invention placed on the insulating layer, and (c) two separate metal electrodes formed on the zinc sulfide nanobelt,
It is comprised including.
Here, the number of zinc sulfide nanobelts placed between two separated metal electrodes can be one, but a plurality of zinc sulfide nanobelts are preferable in order to improve sensitivity and stability of response. In addition, the distance (distance) between two separated metal electrodes can be 1 μm to 100 μm, and the width and depth of one metal electrode can be 50 μm to 500 μm, respectively, Larger than smaller tend to have higher sensitivity and stability.
用いるＳｉ基板としては、シリコン単結晶を約１ｍｍの厚みに切断したシリコンウエハが好ましく用いられ、また、それを覆う絶縁層としてはシリコンウエハを熱酸化して得られる二酸化珪素（ＳｉＯ２）膜が好ましく用いられる。前記ＳｉＯ２膜の代わりに、Ａｌ２Ｏ３膜等の絶縁膜を用いることもできる。
このとき、ＳｉＯ２膜やＡｌ２Ｏ３膜の厚みは、好ましくは、２００ｎｍから６００ｎｍの範囲である。
As a Si substrate to be used, a silicon wafer obtained by cutting a silicon single crystal into a thickness of about 1 mm is preferably used. As an insulating layer covering the silicon substrate, a silicon dioxide (SiO 2 ) film obtained by thermally oxidizing a silicon wafer is used. Preferably used. Instead of the SiO 2 film, an insulating film such as an Al 2 O 3 film can be used.
At this time, the thickness of the SiO 2 film or Al 2 O 3 film is preferably in the range of 200 nm to 600 nm.
用いる電極は、好ましくは、Ｃｒの層がＡｕの層の下に設けられたＡｕ／Ｃｒ構成とする。Ｃｒ層は、硫化亜鉛ナノベルトとの接着性を高めるために設けるものであり、そのＣｒ層の厚さは好ましくは５ｎｍから１５ｎｍの範囲である。また、Ａｕの層の厚さは好ましくは５０ｎｍから１５０ｎｍの範囲である。 The electrode to be used preferably has an Au / Cr structure in which a Cr layer is provided under the Au layer. The Cr layer is provided in order to enhance adhesion with the zinc sulfide nanobelt, and the thickness of the Cr layer is preferably in the range of 5 nm to 15 nm. The thickness of the Au layer is preferably in the range of 50 nm to 150 nm.
上記紫外線検知センサーは、先に述べたように、次の（ｉ）及び（ｉｉ）のステップを経て製造できる。
（ｉ）絶縁層で覆われたＳｉ基板上に、上記本発明の硫化亜鉛ナノベルトを分散させる；
（ｉｉ）光リソグラフィーを用いて前記Ｓｉ基板上にレジストパターンを形成し、金属電極用の金属材料を前記Ｓｉ基板及び前記レジストパターン上に電子ビームデポジションし、その後にリフトオフプロセスを行うことにより、前記ナノベルトの上に金属電極をパターン形成する。
具体的には、実施例で更に詳しく説明する。
As described above, the ultraviolet detection sensor can be manufactured through the following steps (i) and (ii).
(I) The zinc sulfide nanobelt of the present invention is dispersed on a Si substrate covered with an insulating layer;
(Ii) forming a resist pattern on the Si substrate using photolithography, depositing a metal material for a metal electrode on the Si substrate and the resist pattern, and then performing a lift-off process; A metal electrode is patterned on the nanobelt.
Specifically, this will be described in more detail in Examples.
＜実施例１＞
（１）硫化亜鉛ナノベルトの調製
純度９９．９９％、粒子径１０μｍ以下の硫化亜鉛粉末（アルドリッチ社製）を入れたアルミナボートを内径３６ｍｍ（管の断面積は１０．２ｃｍ２）、長さ１５０ｃｍの石英管を有する横型電気炉（有効加熱部の長さ：４５ｃｍ）の中央部に配置した。厚さ３ｎｍの金薄膜付きのシリコンウエハ（２ｍｍ×６ｍｍ）を前記アルミナボートから１０ｍｍ下流側に設置した。炉内の酸素を徹底的に除去するために、初めに流量５００ｓｃｃｍ（線速度としては４９ｃｍ／ｍｉｎ）のアルゴンガスを３時間流した。次に、アルゴンガスの流量を１００ｓｃｃｍ（線速度としては９．８ｃｍ／ｍｉｎ）に絞り、電気炉の温度を１時間かけて１１００℃まで上げ（昇温速度は１７．８℃／ｍｉｎ）、この温度に３０分間保った。その後、電気炉を室温まで冷却した。金薄膜付きのシリコンウエハ上に白色のウール状生成物が堆積していた。
<Example 1>
(1) Preparation of Zinc Sulfide Nanobelt An alumina boat filled with zinc sulfide powder (manufactured by Aldrich) having a purity of 99.99% and a particle diameter of 10 μm or less is 36 mm in inner diameter (the cross-sectional area of the tube is 10.2 cm 2 ) and 150 cm in length Was placed in the center of a horizontal electric furnace (effective heating part length: 45 cm) having a quartz tube. A silicon wafer (2 mm × 6 mm) with a gold thin film having a thickness of 3 nm was placed 10 mm downstream from the alumina boat. In order to thoroughly remove oxygen in the furnace, argon gas having a flow rate of 500 sccm (linear velocity: 49 cm / min) was first flowed for 3 hours. Next, the flow rate of argon gas is reduced to 100 sccm (linear speed is 9.8 cm / min), and the temperature of the electric furnace is increased to 1100 ° C. over 1 hour (temperature increase rate is 17.8 ° C./min). The temperature was kept for 30 minutes. Thereafter, the electric furnace was cooled to room temperature. A white wool-like product was deposited on a silicon wafer with a gold thin film.
（２）得られた硫化亜鉛ナノベルトの分析・評価
図１ａ、ｂに生成した白色ウール状物質の走査型電子顕微鏡像を示した。図１ａの像からは、硫化亜鉛ナノベルトは１００μｍ程度の長さを有することが分かり、また、図１ｂの像からはその先端が細くなっていることが分かる。
(2) Analysis / evaluation of the obtained zinc sulfide nanobelt FIGS. 1a and 1b show scanning electron microscope images of the white wool-like substance produced. From the image of FIG. 1a, it can be seen that the zinc sulfide nanobelt has a length of about 100 μm, and from the image of FIG. 1b, it can be seen that the tip is thin.
図２ａは、白色ウール状物質の透過型電子顕微鏡像である。図２ａ及び図示しない他の像から、得られた硫化亜鉛ナノベルトの幅は２００ｎｍから１μｍまでの範囲にあることが分かった。また、図２ｂにこの白色ウール状物質のエネルギー分散型Ｘ線分析の結果を示したが、亜鉛と硫黄のシグナルが現れており、その化学組成は純粋な硫化亜鉛であることが分かる。なお、この図に現れている銅のシグナルは試料を取り付ける際に用いた銅グリッドに由来するものである。 FIG. 2a is a transmission electron microscope image of a white wool-like substance. From FIG. 2a and other images not shown, it was found that the width of the obtained zinc sulfide nanobelts was in the range of 200 nm to 1 μm. FIG. 2b shows the result of energy dispersive X-ray analysis of this white wool-like substance. Zinc and sulfur signals appear, indicating that the chemical composition is pure zinc sulfide. In addition, the copper signal appearing in this figure is derived from the copper grid used when attaching the sample.
得られた硫化亜鉛ナノベルトの陰極線ルミネッセンススペクトルの測定結果を図３ａに示した。この図から、波長３３７ｎｍにおける強い発光ピークと共に波長５５０ｎｍに弱い発光ピークを有することが分かる。得られた硫化亜鉛ナノベルトの種々の位置における陰極線ルミネッセンススペクトルの測定結果を図３ｂに示した。この図から、硫化亜鉛ナノベルトのどの位置においてもスペクトルはほとんど同じ波長と強度を有し、ほぼ均質であることが裏付けられた。 The measurement result of the cathode ray luminescence spectrum of the obtained zinc sulfide nanobelt is shown in FIG. 3a. This figure shows that it has a weak emission peak at a wavelength of 550 nm as well as a strong emission peak at a wavelength of 337 nm. The measurement results of the cathodoluminescence spectrum at various positions of the obtained zinc sulfide nanobelt are shown in FIG. 3b. From this figure, it was confirmed that the spectrum has almost the same wavelength and intensity at almost every position of the zinc sulfide nanobelt and is almost homogeneous.
（３）紫外線検知センサーの作製
先に得られた硫化亜鉛ナノベルトを、厚さ３００ｎｍの熱酸化した二酸化珪素膜の付いたシリコンウエハ（基板）の上に載せ、フォトマスクを置いてレジストパターンを形成したのち、金属電極用のクロム及び金を前記Ｓｉ基板及び前記レジストパターン上に電子ビームデポジションし、その後にリフトオフプロセスを行うことにより、前記硫化亜鉛ナノベルトの上に金／クロム（１００ｎｍ／１０ｎｍ）電極のパターンを形成し、紫外線検知センサーを作製した（図４）。
(3) Fabrication of UV detection sensor Zinc sulfide nanobelt obtained above is placed on a silicon wafer (substrate) with a 300 nm thick thermally oxidized silicon dioxide film, and a photomask is placed to form a resist pattern. After that, chromium and gold for metal electrodes are electron beam deposited on the Si substrate and the resist pattern, and then a lift-off process is performed, whereby gold / chromium (100 nm / 10 nm) is formed on the zinc sulfide nanobelt. An electrode pattern was formed to produce an ultraviolet detection sensor (FIG. 4).
図４ａは、紫外線検知素子アレイの光学顕微鏡像であり、図４ｂは、硫化亜鉛ナノベルトを用いた紫外線検知センサーの構造を示す概念図（斜視図）である。図４ｂに示すように、紫外線検知センサーは下側よりシリコンウエハ、二酸化珪素膜、硫化亜鉛ナノベルト、金／クロム電極からなる構成である。また、図４ｃ及び図示しない他の走査型電子顕微鏡像から、硫化亜鉛ナノベルトの厚さは約２０ｎｍ、幅は約４００ｎｍであった。また、二つの電極間の距離は約４μｍである。 FIG. 4A is an optical microscope image of the ultraviolet detection element array, and FIG. 4B is a conceptual diagram (perspective view) showing the structure of an ultraviolet detection sensor using a zinc sulfide nanobelt. As shown in FIG. 4b, the ultraviolet detection sensor is composed of a silicon wafer, a silicon dioxide film, a zinc sulfide nanobelt, and a gold / chrome electrode from the lower side. Further, from FIG. 4c and other scanning electron microscope images not shown, the thickness of the zinc sulfide nanobelt was about 20 nm and the width was about 400 nm. The distance between the two electrodes is about 4 μm.
（４）紫外線検知センサーの評価
５００Ｗのキセノンランプを用いて、３２０ｎｍから６３０ｎｍまでの異なった波長の光を照射して電流−電圧特性を測定した。図４ｄは、波長６００ｎｍの光を照射した場合、及び波長３２０ｎｍの光を照射した場合での電流−電圧特性曲線である。この図から、３２０ｎｍの紫外光照射で電流が流れ、６００ｎｍの可視光照射では電流がほとんど流れないことが分かる。
(4) Evaluation of UV detection sensor Using a 500 W xenon lamp, light of different wavelengths from 320 nm to 630 nm was irradiated to measure current-voltage characteristics. FIG. 4d is a current-voltage characteristic curve when irradiated with light having a wavelength of 600 nm and when irradiated with light having a wavelength of 320 nm. From this figure, it can be seen that current flows when irradiated with ultraviolet light of 320 nm, and hardly flows when irradiated with visible light of 600 nm.
また、上記紫外線検知センサーに１０Ｖの電圧を印加しつつ、各波長の光を照射したときに流れる電流を測定し規格化したものを、図５ａに示した。この結果から、４００ｎｍ以上の可視光領域と３００ｎｍ付近の紫外光領域とでは、感度でおよそ３桁の違いがあることが分かる。すなわち、本発明の紫外線検知センサーは、（可視光領域の光には反応せずに）紫外領域及び短波長域の光のみを感知することが分かる。
図５ｂに、波長３２０ｎｍの紫外光をオン、オフさせたときに発生した電流を測定した結果を示した。表１は、その測定結果を元に、それぞれのＯＮ時、ＯＦＦ時の電流値を示した。波長３２０ｎｍの紫外線が当たっていると電流が流れ、その紫外線が当たらないと電流が流れないことが確認できた。ただ、波長３２０ｎｍの紫外線が当たっているときの電流値がやや不安定であった。
FIG. 5a shows a standardized measurement of the current that flows when light of each wavelength is irradiated while applying a voltage of 10 V to the ultraviolet detection sensor. From this result, it can be seen that there is a difference of about 3 digits in sensitivity between the visible light region of 400 nm or more and the ultraviolet light region near 300 nm. That is, it can be seen that the ultraviolet detection sensor of the present invention senses only light in the ultraviolet region and short wavelength region (without reacting to light in the visible light region).
FIG. 5b shows the results of measuring the current generated when ultraviolet light having a wavelength of 320 nm is turned on and off. Table 1 shows the current values at ON and OFF times based on the measurement results. It was confirmed that an electric current flowed when the ultraviolet ray having a wavelength of 320 nm was hit, and an electric current did not flow if the ultraviolet ray was not hit. However, the current value when the ultraviolet ray having a wavelength of 320 nm was hit was somewhat unstable.
＜実施例２＞
（ｉ）硫化亜鉛ナノベルトの調製・評価
実施例１と同様に操作して、金薄膜付きのシリコンウエハ上に白色のウール状生成物を得た。得られた硫化亜鉛ナノベルトは典型的には約１μｍ幅から約２μｍ幅（厚みは２０〜４０ｎｍ）であった。
また、電気炉の温度を１時間かけて室温から１１００℃までに上げるときに、アルゴンガス流量の１００ｓｃｃｍから５０ｓｃｃｍへの切換えを５分ごとに繰り返し行なうと、図６ｃに示すようなノコギリ状の硫化亜鉛ナノベルトが得られた。
（ｉｉ）紫外線検知センサーの作製・評価
図６は、一つの電極の幅が１０μｍ、二つの電極間の距離は２μｍの３種類（ａ、ｂ、ｃ）の紫外線検知センサーで、左側は光学顕微鏡像、中央が電流（Ｉ）−電圧（Ｖ）特性曲線、右側が３２０ｎｍの波長の光をオン、オフさせたときの光電流を測定した結果である。また、ａは一本の（幅１〜２μｍの）硫化亜鉛ナノベルトを電極間にほぼ直交するように渡し掛け、ｂは一本の（幅１〜２μｍの）硫化亜鉛ナノベルトを電極間に斜めに渡し掛け、ｃでは（幅１〜２μｍの）ノコギリ状の硫化亜鉛ナノベルトを電極間に渡し掛けたものである。これら３種類の紫外線検知センサー間で大きな特性の差は認められなかった。しかし、実施例１で作製した紫外線検知センサー（図４、５）に比べて、電流−電圧特性曲線の傾斜が大きく、また、３２０ｎｍの波長の光をオン、オフさせたときの光電流値も大きく、感度が高いことが分かる。これは、光に晒される硫化亜鉛ナノベルトの表面積が大きいためと推定している。
<Example 2>
(I) Preparation and Evaluation of Zinc Sulfide Nanobelt A white wool product was obtained on a silicon wafer with a gold thin film by operating in the same manner as in Example 1. The obtained zinc sulfide nanobelts were typically about 1 μm to about 2 μm wide (thickness 20-40 nm).
Further, when the temperature of the electric furnace is raised from room temperature to 1100 ° C. over 1 hour, if the argon gas flow rate is repeatedly switched from 100 sccm to 50 sccm every 5 minutes, a sawtooth sulfidation as shown in FIG. A zinc nanobelt was obtained.
(Ii) Fabrication and Evaluation of Ultraviolet Detection Sensor FIG. 6 shows three types (a, b, c) of ultraviolet detection sensors in which the width of one electrode is 10 μm and the distance between the two electrodes is 2 μm, and the left side is an optical microscope. An image, the center is a current (I) -voltage (V) characteristic curve, and the right side is a result of measuring a photocurrent when light having a wavelength of 320 nm is turned on and off. Further, a passes a single zinc sulfide nanobelt (with a width of 1 to 2 μm) so as to be substantially orthogonal between the electrodes, and b denotes a single zinc sulfide nanobelt (with a width of 1 to 2 μm) slanted between the electrodes. In c, a saw-shaped zinc sulfide nanobelt (with a width of 1 to 2 μm) is passed between the electrodes. There was no significant difference in characteristics between these three types of UV detection sensors. However, the slope of the current-voltage characteristic curve is larger than that of the ultraviolet detection sensor (FIGS. 4 and 5) produced in Example 1, and the photocurrent value when light having a wavelength of 320 nm is turned on and off is also obtained. It can be seen that it is large and has high sensitivity. This is presumably because the surface area of the zinc sulfide nanobelt exposed to light is large.
＜実施例３＞
紫外線検知センサーの作製・評価
硫化亜鉛ナノベルトとしては先の実施例２で得られた約１μｍ幅から約２μｍ幅（厚みは２０〜４０ｎｍ）の直線状の硫化亜鉛ナノベルトを用いた。距離が約５０μｍの二つの電極間に一本の（幅１〜２μｍの）硫化亜鉛ナノベルトを渡して紫外線検知センサーとした。図７ａは低倍率ＳＥＭ像、図７ｂが電流−電圧特性曲線、図７ｃが３２０ｎｍの波長の光をオン、オフさせたときの光電流を測定した結果である。図７ｂ及び図７ｃから分かるように、電流−電圧特性曲線の傾斜は図６に比べて大きく、また、３２０ｎｍの波長の光をオン、オフさせたときの光電流値も図６に比べて大きく、更に感度が高まっていることが分かる。
<Example 3>
Production and Evaluation of Ultraviolet Detection Sensor As the zinc sulfide nanobelt, a linear zinc sulfide nanobelt having a width of about 1 μm to about 2 μm (thickness: 20 to 40 nm) obtained in Example 2 was used. A single (2 to 2 μm wide) zinc sulfide nanobelt was passed between two electrodes having a distance of about 50 μm to form an ultraviolet detection sensor. 7a is a low-magnification SEM image, FIG. 7b is a current-voltage characteristic curve, and FIG. 7c is a result of measuring photocurrent when light having a wavelength of 320 nm is turned on and off. As can be seen from FIGS. 7b and 7c, the slope of the current-voltage characteristic curve is larger than that of FIG. 6, and the photocurrent value when light having a wavelength of 320 nm is turned on / off is also larger than that of FIG. It can be seen that the sensitivity is further increased.
＜実施例４＞
紫外線検知センサーの作製・評価
硫化亜鉛ナノベルトとしては先の実施例２で得られた約１μｍ幅から約２μｍ幅（厚みは２０〜４０ｎｍ）の直線状の硫化亜鉛ナノベルトを用いた。距離が狭いところで約２〜３μｍ、大きいところでの約５０μｍの二つの電極間に、複数本の硫化亜鉛ナノベルトを電極間に渡し掛し、（ａ、ｂ）２種類の紫外線検知センサーを作製した（ただし、ａの場合よりもｂの場合のほうが渡し掛けた硫化亜鉛ナノベルトの本数は多い）。図８は各々の紫外線検知センサーで、左側は低倍率ＳＥＭ像、中央が電流−電圧特性曲線、右側が３２０ｎｍの波長の光をオン、オフさせたときの光電流を測定した結果である。この図から、渡し掛けた硫化亜鉛ナノベルトの本数が多いほど、電流−電圧特性曲線の傾斜が大きく、また、３２０ｎｍの波長の光をオン、オフさせたときの光電流値も大きく、したがって感度が高いことが分かる。
また、この図８ｂを、実施例１の図５ｂと比べると、紫外線検知感度は約５０倍高まり、また、３２０ｎｍの波長の光をオン、オフさせたときのレスポンスも非常に安定となったことが分かる。
<Example 4>
Production and Evaluation of Ultraviolet Detection Sensor As the zinc sulfide nanobelt, a linear zinc sulfide nanobelt having a width of about 1 μm to about 2 μm (thickness: 20 to 40 nm) obtained in Example 2 was used. A plurality of zinc sulfide nanobelts were passed between two electrodes having a distance of about 2 to 3 μm at a small distance and about 50 μm at a large distance, and (a, b) two types of ultraviolet detection sensors were produced ( However, the number of zinc sulfide nanobelts passed in the case of b is larger than that of a). FIG. 8 shows the results of measuring the photocurrent when each ultraviolet ray detection sensor has a low-magnification SEM image on the left side, a current-voltage characteristic curve on the center, and light having a wavelength of 320 nm on and off on the right side. From this figure, the greater the number of zinc sulfide nanobelts passed, the greater the slope of the current-voltage characteristic curve, and the greater the photocurrent value when turning on and off light with a wavelength of 320 nm. I understand that it is expensive.
Further, comparing FIG. 8b with FIG. 5b of Example 1, the ultraviolet detection sensitivity was increased by about 50 times, and the response when turning on and off the light with a wavelength of 320 nm was very stable. I understand.
Claims (13)
（１）加熱炉にセットした筒状加熱管の中央部に硫化亜鉛粉末を置き、その下流側に金薄膜付きシリコン基板を置く。
（２）前記筒状加熱管中の酸素が除去されるまで、その筒状加熱管中へ、不活性ガスを導入する。
（３）不活性ガスを所定の流速で導入しながら、加熱炉を１７±５℃／ｍｉｎの昇温速度で室温から１０００〜１２００℃まで昇温させたのち、その温度で一定時間保つ。
（４）放冷後、金薄膜付きシリコン基板上に堆積した堆積物を回収する。 With emission peak due to the cathode ray luminescence exists in the ultraviolet range, emission peak existing in the visible range is lower than the emission peak existing in the ultraviolet region, in the preparation of zinc sulphide nanobelts which a single crystal like a belt, following Manufacturing method including the following steps:
(1) A zinc sulfide powder is placed at the center of a cylindrical heating tube set in a heating furnace, and a silicon substrate with a gold thin film is placed downstream thereof.
(2) An inert gas is introduced into the cylindrical heating tube until oxygen in the cylindrical heating tube is removed.
(3) While introducing the inert gas at a predetermined flow rate, the heating furnace is heated from room temperature to 1000 to 1200 ° C. at a temperature rising rate of 17 ± 5 ° C./min, and then kept at that temperature for a certain time.
(4) Collect the deposit deposited on the silicon substrate with the gold thin film after cooling.
（ａ）絶縁層に覆われたＳｉ基板、
（ｂ）前記絶縁層上に置かれた請求項１〜４のいずれかの硫化亜鉛ナノベルト、及び
（ｃ）前記硫化亜鉛ナノベルトの上に形成された２つの分離された金属電極。 The ultraviolet detection sensor comprised including the following (a)-(c).
(A) a Si substrate covered with an insulating layer;
(B) the zinc sulfide nanobelt of any of claims 1 to 4 placed on the insulating layer, and (c) two separated metal electrodes formed on the zinc sulfide nanobelt.
（ｉ）絶縁層で覆われたＳｉ基板上に、請求項１〜４のいずれかの硫化亜鉛ナノベルトを分散させる；
（ｉｉ）光リソグラフィーを用いて前記Ｓｉ基板上にレジストパターンを形成し、金属電極用の金属材料を前記Ｓｉ基板及び前記レジストパターン上に電子ビームデポジションし、その後にリフトオフプロセスを行うことにより、前記ナノベルトの上に金属電極をパターン形成する
The manufacturing method of the ultraviolet detection sensor which has the following steps (i) and (ii).
(I) Dispersing the zinc sulfide nanobelts according to claim 1 on a Si substrate covered with an insulating layer;
(Ii) forming a resist pattern on the Si substrate using photolithography, depositing a metal material for a metal electrode on the Si substrate and the resist pattern, and then performing a lift-off process; Pattern metal electrodes on the nanobelts
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