JP2009281845A - Substrate for surface reinforcing raman spectral analysis - Google Patents
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- JP2009281845A JP2009281845A JP2008133807A JP2008133807A JP2009281845A JP 2009281845 A JP2009281845 A JP 2009281845A JP 2008133807 A JP2008133807 A JP 2008133807A JP 2008133807 A JP2008133807 A JP 2008133807A JP 2009281845 A JP2009281845 A JP 2009281845A
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- 239000000758 substrate Substances 0.000 title claims abstract description 41
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 16
- 230000003014 reinforcing effect Effects 0.000 title abstract 3
- 238000010183 spectrum analysis Methods 0.000 title abstract 3
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 239000010931 gold Substances 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 17
- 239000002612 dispersion medium Substances 0.000 claims description 12
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000004611 spectroscopical analysis Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000011858 nanopowder Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 12
- 229920000178 Acrylic resin Polymers 0.000 description 11
- 239000004925 Acrylic resin Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000000609 electron-beam lithography Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007687 exposure technique Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
Description
本発明は、環境用や医療用等の高感度センサや高機能触媒等のナノ構造材料に用いるのに好適な、短時間で容易に作成でき、長時間保存及び大量生産が可能で安価な表面増強ラマン分光分析用基板の作成方法、及び、この方法により作られた表面増強ラマン分光分析用基板に関する。 The present invention is suitable for use in high-sensitivity sensors for environmental and medical use and nanostructure materials such as high-performance catalysts, and can be easily created in a short time, can be stored for a long time and mass-produced, and has an inexpensive surface. The present invention relates to a method for producing an enhanced Raman spectroscopic analysis substrate, and a surface enhanced Raman spectroscopic analysis substrate produced by this method.
ラマン分光分析は、試料にレーザを照射することにより発生するラマン散乱光を検出する分析法で、生化学物質の同定に極めて有効な分析技術である。しかし問題点として、ラマン散乱光がレーザの反射光（レイリー散乱）と比較し、極めて微弱なことが挙げられる。これを解決するのが、金属ナノ粒子表面における電場増強効果を利用した表面増強ラマン分光法である。 Raman spectroscopic analysis is an analysis method for detecting Raman scattered light generated by irradiating a sample with a laser, and is an extremely effective analysis technique for identifying biochemical substances. However, the problem is that the Raman scattered light is extremely weak compared to the reflected light of the laser (Rayleigh scattering). The solution to this is surface enhanced Raman spectroscopy using the electric field enhancement effect on the surface of metal nanoparticles.
この表面増強ラマン分光法では、ナノ粒子を持つ基板の作成が鍵となる。従来技術として、（１）銀コロイドを溶液中に分散させるもの（特許文献１、２、非特許文献１、２、３）、（２）銀ナノ粒子をガラス基板上に吸着させるもの（特許文献３）、（３）銀を電子ビームリソグラフィによりパターニングする等の方法が挙げられる。 In this surface-enhanced Raman spectroscopy, the creation of a substrate with nanoparticles is key. As conventional techniques, (1) one in which silver colloid is dispersed in a solution (patent documents 1, 2, non-patent documents 1, 2, 3), (2) silver nanoparticles are adsorbed on a glass substrate (patent documents) 3), (3) A method such as patterning silver by electron beam lithography may be used.
又、銀微粒子の露出方法として、銀薄膜の製作のために、分散剤を加えた上で銀鏡反応を行なった例が報告されている（非特許文献４）。 In addition, as a method for exposing silver fine particles, there has been reported an example in which a silver mirror reaction is performed after adding a dispersant for the production of a silver thin film (Non-patent Document 4).
表面増強ラマン分光分析基板に求められるものは、作成の容易さ、再現性、高感度である。基板は消耗品であるために、できる限り安価であることが望まれる。しかしながら、例えば（３）の電子ビームリソグラフィによる基板作成では、再現性は高いものの、基板自体が高価になってしまう。又、（１）の銀コロイドを溶液中に分散させるものや、（２）銀ナノ粒子をガラス基板上に吸着させるものは、作成に時間がかかるだけでなく長期保存ができないという問題点を有する。 What is required for a surface-enhanced Raman spectroscopic analysis substrate is ease of preparation, reproducibility, and high sensitivity. Since the substrate is a consumable item, it is desirable that it be as inexpensive as possible. However, for example, in (3) substrate production by electron beam lithography, the reproducibility is high, but the substrate itself becomes expensive. In addition, (1) the silver colloid dispersed in the solution and (2) the silver nanoparticles adsorbed on the glass substrate have problems that not only takes time but also cannot be stored for a long time. .
又、非特許文献４では、本発明で利用した銀ナノ微粒子露出技術が、銀薄膜の製作に応用されているが、表面増強ラマン分光分析用基板への応用はなかった。 In Non-Patent Document 4, although the silver nanoparticle exposure technique used in the present invention is applied to the production of a silver thin film, there is no application to a substrate for surface enhanced Raman spectroscopy.
本発明は、前記従来の問題点を解決するべくなされたもので、作成が容易で、再現性が高く、高感度で、長期保存が可能な表面増強ラマン分光分析用基板を提供可能とすることを課題とする。 The present invention has been made to solve the above-described conventional problems, and can provide a substrate for surface-enhanced Raman spectroscopic analysis that is easy to prepare, has high reproducibility, is highly sensitive, and can be stored for a long period of time. Is an issue.
本発明は、銀ナノ粒子に代表される表面増強ラマン効果を有する金属ナノ粒子を分散媒を利用して分散させてなる分散液に熱可塑性樹脂微粉末を所定の比率で分散させ、この分散液を基板上に塗布し、加熱押圧することにより分散媒を分散膜から逃散させると同時に分散膜を基板に定着させると、金属ナノ粒子が熱可塑性樹脂粉末を介して一定の間隔で分散して基板上に定着することを見出し、前記課題を解決したものである。 The present invention disperses a thermoplastic resin fine powder at a predetermined ratio in a dispersion obtained by dispersing metal nanoparticles having surface-enhanced Raman effect typified by silver nanoparticles using a dispersion medium. When the dispersion medium escapes from the dispersion film and is fixed to the substrate at the same time, the metal nanoparticles are dispersed at regular intervals through the thermoplastic resin powder. The problem has been solved by finding that it is fixed on top.
本発明は、金、銀、銅、又は白金族の金属ナノ粒子を分散媒により分散させた分散液に所望の分布密度に応じて所望比率の熱可塑性樹脂粉末を混合分散させてなる液状組成物を調整する工程と、該液状組成物を用いて基板上に塗布膜を形成する工程と、液状組成物を塗布した基板を加熱押圧して塗布膜を基板上に定着する工程からなり、基板上の塗布膜に金属ナノ粒子を分散させることを特徴とする表面増強ラマン分光分析用基板の作成方法にある。 The present invention relates to a liquid composition comprising a dispersion liquid in which gold, silver, copper, or platinum group metal nanoparticles are dispersed in a dispersion medium, and a thermoplastic resin powder having a desired ratio is mixed and dispersed in accordance with a desired distribution density. A step of forming a coating film on the substrate using the liquid composition, and a step of fixing the coating film on the substrate by heating and pressing the substrate coated with the liquid composition. In this method, a surface-enhanced Raman spectroscopic substrate is prepared by dispersing metal nanoparticles in a coating film.
ここで、樹脂粉末としては金属ナノ粒子の溶融温度以下で溶融または軟化する熱可塑性微粉末が好ましく、微粉末（１μ以下）とすることにより溶融温度を低下させることができる。分散媒としては以下の加熱押圧条件で揮発蒸散することができる溶媒が選ばれるのが好ましい。また、上記塗布膜は３〜１０μ厚で形成されるが、少ない金属ナノ粒子を有効に露出させるには薄い方が好ましい。また、加熱押圧時に幾分延伸されるのが好ましく、熱可塑性樹脂粉末から形成される。基板としてはガラス基板を使用することもできるが、分散用として使用される熱可塑性樹脂粉末と同種のものを使用するのが定着性に優れる。特に、アクリル樹脂粉末とアクリル樹脂基板を用いるのが好ましい。 Here, the resin powder is preferably a thermoplastic fine powder that melts or softens below the melting temperature of the metal nanoparticles, and the melting temperature can be lowered by using a fine powder (1 μm or less). As the dispersion medium, it is preferable to select a solvent that can be evaporated and evaporated under the following heating and pressing conditions. Moreover, although the said coating film is formed by 3-10 micrometers thickness, in order to expose few metal nanoparticles effectively, the thinner one is preferable. Further, it is preferably stretched somewhat during heating and pressing, and is formed from a thermoplastic resin powder. Although a glass substrate can be used as the substrate, it is excellent in fixability to use the same type of thermoplastic resin powder used for dispersion. In particular, it is preferable to use acrylic resin powder and an acrylic resin substrate.
本発明によれば、金属ナノ粒子を分散媒を介してより大きな粒径の熱可塑性樹脂微粉末表面に分散させ、この分散液を塗布して金属ナノ粒子が分散した薄膜を形成した基板を加熱押圧することにより、分散媒を分散膜から逃散させると同時に分散膜を基板に定着させて金属ナノ粒子を基板上に分散させているので、表面増強ラマン分光分析用基板が安価に製造することができる。しかも基板上の金属ナノ粒子は通常膜成分で覆われ、使用前にこれを研磨等で露出させるので、耐久性に優れる。また、金属ナノ粒子の凝集又は分散間隔、分散密度は金属ナノ粒子に対する熱可塑性樹脂粉末の粒径、混合比率により調整することができるので、再現性の高い基板とすることができる。 According to the present invention, metal nanoparticles are dispersed on the surface of a thermoplastic resin fine powder having a larger particle diameter through a dispersion medium, and the substrate on which a thin film in which metal nanoparticles are dispersed is formed by applying this dispersion is heated. By pressing, the dispersion medium escapes from the dispersion film, and at the same time, the dispersion film is fixed to the substrate and the metal nanoparticles are dispersed on the substrate, so that the surface enhanced Raman spectroscopic analysis substrate can be manufactured at low cost. it can. Moreover, since the metal nanoparticles on the substrate are usually covered with a film component and exposed by polishing before use, the durability is excellent. In addition, since the aggregation or dispersion interval and dispersion density of the metal nanoparticles can be adjusted by the particle size and mixing ratio of the thermoplastic resin powder with respect to the metal nanoparticles, a highly reproducible substrate can be obtained.
以下、本発明の実施形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本実施形態は、市販の銀超微粒子液（銀ナノ粒子２０〜５０ｎｍ）を用意し、これにエタノールを加えて分散媒の一部または全部をエタノールで置換し、分散媒の８０重量％以上をエタノールとする。 In this embodiment, a commercially available silver ultrafine particle liquid (silver nanoparticles 20 to 50 nm) is prepared, ethanol is added thereto, and part or all of the dispersion medium is replaced with ethanol, and 80% by weight or more of the dispersion medium is added. Ethanol.
次いで、この銀超微粒子液にアクリル樹脂微粉末（平均粒径１μｍ）を銀微粒子換算で１０００倍以上となるように加えて十分に攪拌して分散液を調製する。分散密度に応じて両者の混合比率が定められるが、銀ナノ／アクリル樹脂の重量比は１００ｐｐｍから５０００ｐｐｍが好ましい。 Next, an acrylic resin fine powder (average particle size of 1 μm) is added to the silver ultrafine particle liquid so that it becomes 1000 times or more in terms of silver fine particles, and sufficiently stirred to prepare a dispersion. Although the mixing ratio of the two is determined according to the dispersion density, the silver nano / acrylic resin weight ratio is preferably 100 ppm to 5000 ppm.
この分散液をアクリル樹脂板上に塗布し、分散媒を加熱蒸散可能で、かつアクリル樹脂粉末を膜状に成形し、しかも分散させる金属ナノ粒子を溶融しない温度を選んで加熱押圧する。本実施例の場合、８０℃前後の温度を選択し、加熱押圧すると、分散膜中のアルコールは逃散し、アクリル樹脂粉末はやや軟化または表面溶融してアクリル樹脂板上に定着される。この際銀ナノ粒子は溶融することなく、アクリル樹脂粉末表面に分散している状態でアクリル樹脂により定着される。銀ナノ粒子はアクリル樹脂粉末粒径の間隔で分散された状態で層上に形成されるアクリル膜上定着されることになるが、使用前に研磨等で露出して使用するようにすると保存性に優れるので好ましい。 The dispersion is applied onto an acrylic resin plate, and the temperature of the dispersion medium that can be evaporated by heating, the acrylic resin powder formed into a film, and the metal nanoparticles to be dispersed is not melted and pressed. In the case of this example, when a temperature of around 80 ° C. is selected and heated and pressed, the alcohol in the dispersion film escapes, and the acrylic resin powder is softened or melted on the surface to be fixed on the acrylic resin plate. At this time, the silver nanoparticles are fixed by the acrylic resin without being melted and being dispersed on the surface of the acrylic resin powder. Silver nanoparticles are fixed on the acrylic film formed on the layer in a state of being dispersed at intervals of the acrylic resin powder particle size. It is preferable because it is excellent.
本発明にかかる基板を研磨して銀ナノ粒子の表面を露出させ、使用すると、銀ナノ粒子間に熱可塑性樹脂粉末が介在することにより一定の間隔で樹脂粉末の間隙に分散し、凝集する。したがって、銀ナノ粒子の有無による測定結果により増強効果が顕著に表れ、表面増強ラマン効果が得られることになる。
When the substrate according to the present invention is polished to expose the surface of the silver nanoparticles and used, the thermoplastic resin powder intervenes between the silver nanoparticles, so that the silver nanoparticles are dispersed and aggregated in the gaps of the resin powder at regular intervals. Therefore, the enhancement effect appears remarkably according to the measurement result based on the presence or absence of silver nanoparticles, and the surface enhanced Raman effect is obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102435593A (en) * | 2011-09-15 | 2012-05-02 | 山东大学 | A preparation method of surface-enhanced Raman scattering substrate based on cationic resin |
| WO2013053598A1 (en) * | 2011-10-11 | 2013-04-18 | Evonik Degussa Gmbh | Method for producing polymer nanoparticle compounds using a nanoparticle dispersion |
| US9158107B2 (en) | 2011-10-21 | 2015-10-13 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Semiconductor device |
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2008
- 2008-05-22 JP JP2008133807A patent/JP2009281845A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102435593A (en) * | 2011-09-15 | 2012-05-02 | 山东大学 | A preparation method of surface-enhanced Raman scattering substrate based on cationic resin |
| WO2013053598A1 (en) * | 2011-10-11 | 2013-04-18 | Evonik Degussa Gmbh | Method for producing polymer nanoparticle compounds using a nanoparticle dispersion |
| US9158107B2 (en) | 2011-10-21 | 2015-10-13 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Semiconductor device |
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