JP2009299112A - Gold nanoparticle and dispersion thereof, method for producing gold nanoparticle and nanoparticle production system - Google Patents
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000010931 gold Substances 0.000 title claims abstract description 115
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 115
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000006185 dispersion Substances 0.000 title claims description 21
- 239000002245 particle Substances 0.000 claims abstract description 48
- 238000009826 distribution Methods 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 230000001678 irradiating effect Effects 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000002679 ablation Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000000608 laser ablation Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000031700 light absorption Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010415 colloidal nanoparticle Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- -1 gold ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GCZKMPJFYKFENV-UHFFFAOYSA-K triiodogold Chemical compound I[Au](I)I GCZKMPJFYKFENV-UHFFFAOYSA-K 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
本発明は、金ナノ粒子およびその分散液、金ナノ粒子の製造方法、並びにナノ粒子製造システムに関する。 The present invention relates to a gold nanoparticle and a dispersion thereof, a method for producing a gold nanoparticle, and a nanoparticle production system.
金ナノ粒子はそのサイズがナノメートルオーダーになると表面プラズモン共鳴による光吸収、いわゆる表面プラズマ吸収が可視光から近赤外線の波長領域に観測される。特にこの吸収波長は金ナノ粒子の形態、例えば球状であればその直径、楕円形あるいはロッド状であればその長軸と短軸の比（アスペクト比）によって、可視から近赤外領域にかけて特異的な表面プラズマ吸収を持つこともよく知られている。また、これらの吸収波長は金ナノ粒子表面に吸着した分子によっても影響を受けることから、タンパク質などの生体分子を検出するバイオセンシング材料としても利用されている。 When the size of the gold nanoparticle becomes nanometer order, light absorption by surface plasmon resonance, so-called surface plasma absorption, is observed in the wavelength region from visible light to near infrared. In particular, this absorption wavelength is specific from the visible to the near-infrared region depending on the form of the gold nanoparticle, for example, the diameter if spherical, or the ratio of the major axis to the minor axis (aspect ratio) if it is elliptical or rod-shaped. It is well known that it has excellent surface plasma absorption. In addition, since these absorption wavelengths are also affected by molecules adsorbed on the gold nanoparticle surface, they are also used as biosensing materials for detecting biomolecules such as proteins.
上記のようなバイオセンシングのために利用される金ナノ粒子の中でもプラズマ吸収波長のシフトや吸光度の変化によってセンシングを行なう場合、利用される金ナノ粒子のサイズ分布がある程度狭い必要がある。これまでに、粒径分布の幅の狭い金のナノ粒子が分散した溶液は主として化学的な手法によって合成されてきた。たとえば、ヨウ化金酸イオンを含む水溶液に水酸化アルカリを加え、ヨウ化金を分解し、金微粒子を製造する際に、反応溶液中にアニオン系界面活性剤を添加することにより単分散した金微粒子を得ることを特徴とする金微粒子の製造方法が知られている（特許文献１）。また、同様な手法で、カチオン系界面活性剤（特許文献２）や両性界面活性剤（特許文献３）あるいはノニオン系界面活性剤（特許文献４）を用いる方法もある。また、１３０℃以上の高温に於いて、金属金と塩化金酸水溶液を接触反応させて、得られた塩化第一金酸水溶液を１００℃以下に冷却することによって単分散した金微粒子を得ることを特徴とする金微粒子の製造方法（特許文献５）や、同様にして得られた塩化第一金酸水溶液中にデキストリンを添加し、この水溶液を１００℃以下に冷却後１０℃〜３０℃に保持することによって単分散した金微粒子を得ることを特徴とする金微粒子の製造方法（特許文献６）等もある。 Among the gold nanoparticles used for biosensing as described above, when sensing is performed by shifting the plasma absorption wavelength or changing the absorbance, the size distribution of the gold nanoparticles used needs to be narrow to some extent. So far, solutions in which gold nanoparticles with a narrow particle size distribution are dispersed have been synthesized mainly by chemical methods. For example, when an alkali hydroxide is added to an aqueous solution containing gold iodide ion, gold iodide is decomposed, and gold fine particles are produced, monodispersed gold is added by adding an anionic surfactant into the reaction solution. A method for producing gold fine particles characterized by obtaining fine particles is known (Patent Document 1). In addition, there is a method using a cationic surfactant (Patent Document 2), an amphoteric surfactant (Patent Document 3) or a nonionic surfactant (Patent Document 4) in the same manner. Also, monodispersed gold fine particles can be obtained by contacting metal gold with an aqueous chloroauric acid solution at a high temperature of 130 ° C. or higher and cooling the resulting aqueous chloroauric acid solution to 100 ° C. or lower. Dextrin is added to a gold microparticle aqueous solution prepared in the same manner as described above (Patent Document 5), and the aqueous solution is cooled to 100 ° C. or lower. There is also a method for producing gold fine particles characterized by obtaining monodispersed gold fine particles by holding (Patent Document 6).
しかし、このような化学的手法では金のイオンを溶液中へ原料として供給する必要があるために、電離し易い金属塩を使わなければならず、常に溶液中に対イオンが存在し、さらに反応のために還元剤や界面活性剤も必要であり、これらの化学種がコロイド溶液中の不純物となることもある。従って化学法では純粋な金ナノ粒子のコロイド溶液を製造することは難しく、反応後に透析など多数の分離工程が必要になる。 However, in this chemical method, it is necessary to supply gold ions as a raw material into the solution. Therefore, it is necessary to use a metal salt that is easily ionized, and there is always a counter ion in the solution. Therefore, reducing agents and surfactants are also necessary, and these chemical species may become impurities in the colloidal solution. Therefore, it is difficult to produce a pure gold nanoparticle colloidal solution by chemical methods, and many separation steps such as dialysis are required after the reaction.
一方、化学的な合成法以外には液体中に設置した金板あるいは液体中に分散させた金粒子に強度の強いパルスレーザー光を照射して金ナノ粒子分散液を製造する、いわゆる液相レーザーアブレーション法も知られている（非特許文献１、２）。この方法の場合、液中への金ナノ粒子の原料供給はアブレーションプラズマを介してなされ、極めて純粋な金ナノ粒子分散液を製造することが出来る。しかしながら、液相レーザーアブレーション法で製造した金ナノ粒子の粒径分布の幅は比較的広く、化学法と同様に溶液中に界面活性剤を添加して粒径分布の幅を改善することは出来る（非特許論文３）もののこれが不純物となり純粋な金ナノ粒子分散液を製造することは難しいと思われてきた。
これに対して、フェムト秒の極短パルスレーザー装置を使用（非特許文献４）することで粒径分布の幅を改善することが出来ることが最近明らかとなった。しかし、フェムト秒レーザー装置は極めて高価なレーザーで、アブレーションを行うためには数十Ｊ／ｃｍ２と十分なレーザー強度が必要である。このように高いエネルギーのフェムト秒パルス光を発生するためには、極めて構造が複雑な再生増幅器も必要である等の問題点があった。
On the other hand, it has recently become clear that the width of the particle size distribution can be improved by using a femtosecond ultrashort pulse laser device (Non-Patent Document 4). However, the femtosecond laser device is an extremely expensive laser, and a sufficient laser intensity of several tens of J / cm 2 is necessary to perform ablation. In order to generate such high-energy femtosecond pulsed light, there is a problem that a regenerative amplifier having an extremely complicated structure is required.
本発明の目的は、従来技術の有する問題点を解消し、大型の装置や複雑な工程を必要としなくでも製造することができる、純度が高く粒径分布の幅の狭い金ナノ粒子およびそれらが対イオンなどの存在しない溶液中に分散した金ナノ粒子の分散液、ならびにその製造方法を提供することにある。 The object of the present invention is to solve the problems of the prior art and to produce gold nanoparticles having a high purity and a narrow particle size distribution, which can be produced without the need for a large-scale apparatus or complicated processes. An object of the present invention is to provide a dispersion of gold nanoparticles dispersed in a solution containing no counter ion or the like, and a method for producing the same.
本発明の目的を達成するために鋭意研究を進めたところ、脱イオン水あるいはアルコールなどの有機溶媒中に設置した金板に、レーザービームを高速スキャンできるビームスキャナを介してパルスレーザー光を照射する際に、レーザースポットが金板上で重ならないようにレーザービームをスキャン（走査）して照射することによって純度が高く粒径分布の幅が狭い金ナノ粒子およびそれらが対イオンなどの存在しない溶液中に分散した溶液を製造し得ることを見いだした。 As a result of diligent research to achieve the object of the present invention, a metal plate placed in an organic solvent such as deionized water or alcohol is irradiated with pulsed laser light via a beam scanner capable of scanning the laser beam at high speed. At this time, by scanning and irradiating the laser beam so that the laser spot does not overlap on the gold plate, gold nanoparticles with a high purity and a narrow particle size distribution and solutions in which they do not contain counter ions, etc. It has been found that a solution dispersed therein can be produced.
すなわち、本発明は
（１）液体中に設置した金板に、パルスレーザーをレーザースポットが前記金属板上で重ならないようにスキャンして照射し、金ナノ粒子を前記液体中に分散させることを特徴とする金ナノ粒子の製造方法、
（２）前記パルスレーザーのパルス幅が１０ｐｓ〜１００ｐｓであることを特徴とする（１）項記載の金ナノ粒子の製造方法、
（３）前記パルスレーザーが繰り返し周波１００ｋＨｚ〜４ＭＨｚ、パルス幅１０ｐｓ〜１００ｐｓ秒、１パルスあたりの強度１μＪ／ｐｕｌｓｅ以上であることを特徴とする（１）項記載の金ナノ粒子の製造方法、
（４）スポットの直径が１〜３０μｍであり、レーザーのスキャンスピードが９０ｍ／ｓｅｃ以上であることを特徴とする（１）〜（３）のいずれか１項に記載の金ナノ粒子の製造方法、
（５）（１）〜（４）のいずれか１項に記載の方法により製造された、個数基準粒径分布において全体の９９％以上が１ｎｍ以上８０ｎｍ以下にある金ナノ粒子、
（６）（１）〜（４）のいずれか１項に記載の方法により製造された、個数基準粒径分布において全体の９９％以上が１ｎｍ以上４０ｎｍ以下にある金ナノ粒子、
（７）液体中に設置した金板に、パルスレーザーをレーザースポットが前記金属板上で重ならないようにスキャンして照射して得られたことを特徴とする金ナノ粒子の分散液、および
（８）パルスレーザーを発振するレーザー手段と、該パルスレーザーのレーザースポットをターゲットに対してスキャンする光学スキャナとを備えてなり、液体中に設置したターゲットに、パルスレーザーをレーザースポットが前記ターゲット上で重ならないようにスキャンして照射し、ナノ粒子を前記液体中に分散させることを特徴とするナノ粒子製造システム
を提供するものである。
That is, the present invention (1) irradiates a gold plate placed in a liquid by irradiating a pulsed laser so that a laser spot does not overlap on the metal plate, thereby dispersing gold nanoparticles in the liquid. A method for producing gold nanoparticles,
(2) The method for producing gold nanoparticles according to (1), wherein the pulse width of the pulse laser is 10 ps to 100 ps,
(3) The method for producing gold nanoparticles according to (1), wherein the pulse laser has a repetition frequency of 100 kHz to 4 MHz, a pulse width of 10 ps to 100 ps, and an intensity per pulse of 1 μJ / pulse or more,
(4) The method for producing gold nanoparticles according to any one of (1) to (3), wherein the spot has a diameter of 1 to 30 μm and a laser scanning speed of 90 m / sec or more. ,
(5) A gold nanoparticle produced by the method according to any one of (1) to (4), wherein 99% or more of the total number in the number-based particle size distribution is 1 nm or more and 80 nm or less,
(6) Gold nanoparticles produced by the method according to any one of (1) to (4), wherein 99% or more of the total number in the number-based particle size distribution is 1 nm or more and 40 nm or less,
(7) A gold nanoparticle dispersion obtained by irradiating a gold plate placed in a liquid by irradiating a pulsed laser so that a laser spot does not overlap the metal plate, and ( 8) A laser means that oscillates a pulse laser and an optical scanner that scans the laser spot of the pulse laser with respect to the target. The laser spot is placed on the target on the target placed in the liquid. The present invention provides a nanoparticle production system characterized by scanning and irradiating so as not to overlap, and dispersing the nanoparticles in the liquid.
本発明により、小型のレーザー装置を用いた簡単な工程により、純粋で粒径分布が１ｎｍ以上４０ｎｍ以下といった幅狭い範囲にある金ナノ粒子およびその分散液を製造することができる。また、本発明の金ナノ粒子は純度が高く粒径分布の幅が狭いものとすることができる。また、本発明の金ナノ粒子分散液は不純物を含まない金コロイド溶液とすることができる。 According to the present invention, pure gold nanoparticles having a narrow particle size distribution of 1 nm to 40 nm and a dispersion thereof can be produced by a simple process using a small laser device. In addition, the gold nanoparticles of the present invention can have high purity and a narrow particle size distribution. The gold nanoparticle dispersion of the present invention can be a colloidal gold solution containing no impurities.
本発明では、液体中に設置した金板に、パルスレーザーをレーザースポットが重ならないように照射して、金ナノ粒子を前記液体中に分散させて金ナノ粒子を製造する。 In the present invention, gold nanoparticles are produced by irradiating a gold plate placed in a liquid with a pulse laser so that the laser spots do not overlap, and dispersing the gold nanoparticles in the liquid.
従来、パルスレーザーをターゲットに集光照射してアブレーションを行う場合、ターゲット上のビームスポットの位置が常に同一位置に存在した場合、アブレーションによって形成されるビームの照射痕が次第に深くなる。この場合集光レンズからスポットまでの距離が変化することによってレーザーのスポットサイズが変化し、レーザースポット下でのレーザー強度が時間と共に変化する。あるいはスポット位置がレーザー照射痕によって形成された穴の深い位置に移動し、その結果発生するプラズマプルームの形状が変化することもある。このような現象は得られるナノ粒子の粒径の均一性に影響をおよぼす。このような影響を避けるために、これまではターゲットを回転させて照射痕が深くなることをなるだけ避けてレーザーの照射条件があまり変化しない工夫がなされてきた。しかしながらこの場合も、レーザーの照射痕が重なることを避けることは難しかった。更に近年では数ＫＨｚから数ＭＨｚの高繰り返しレーザーも利用されはじめ、アブレーションの際のレーザー痕の重なりを避けることは極めて難しくなってきた。 Conventionally, when performing ablation by focusing and irradiating a pulse laser on a target, if the position of the beam spot on the target is always present at the same position, the irradiation mark of the beam formed by ablation becomes gradually deeper. In this case, the laser spot size changes as the distance from the condenser lens to the spot changes, and the laser intensity under the laser spot changes with time. Alternatively, the spot position may move to a deep position of the hole formed by the laser irradiation trace, and the resulting plasma plume may change its shape. Such a phenomenon affects the uniformity of the particle size of the obtained nanoparticles. In order to avoid such an influence, until now, a device has been devised in which the irradiation condition of the laser does not change so much by avoiding the irradiation mark from becoming deep as much as possible by rotating the target. However, in this case as well, it was difficult to avoid overlapping laser irradiation marks. Furthermore, in recent years, high repetition lasers of several KHz to several MHz have begun to be used, and it has become extremely difficult to avoid overlapping of laser marks during ablation.
これに対して本発明では、数ＭＨｚの高繰り返しレーザーにおいても高速光学スキャナを用いて、レーザーをスキャン（走査）して、脱イオン水あるいはアルコールなどの有機溶媒などの液体中に設置した金板にレーザービームを照射することでアブレーションの際のレーザーの照射痕の重なりを避けることができた。 In contrast, in the present invention, a high-speed optical scanner is used to scan a laser with a high repetition rate laser of several MHz, and the metal plate is placed in a liquid such as deionized water or an organic solvent such as alcohol. By irradiating with laser beam, it was possible to avoid overlap of laser irradiation marks during ablation.
レーザービームが重ならないようにするためには、照射レーザースポットのサイズとレーザーパルスの繰り返し周波数を適切に選択することが必要となる。ターゲット（金板）上でのレーザースポットの直径をｄ（ｍｍ）、レーザーの繰り返し周波数をｆ（Ｈｚ）、スキャンスピードをｋ（ｍｍ／ｓｅｃ）とした場合、レーザースポットが重ならないためには
ｋ＞ｄｆ （１式）
で有る必要がある。
In order to prevent the laser beams from overlapping, it is necessary to appropriately select the size of the irradiation laser spot and the repetition frequency of the laser pulse. If the laser spot diameter on the target (metal plate) is d (mm), the laser repetition frequency is f (Hz), and the scan speed is k (mm / sec), the laser spots do not overlap. > Df (1 set)
It is necessary to be in.
アブレーションにしばしば使用されるレーザーとしてＱ−スイッチＮｄ：ＹＡＧレーザーがありこの場合１ｍｍ前後のスポットサイズで、繰り返し周波数は１０Ｈｚ程度である。この場合必要となるスキャンスピードは１０ｍｍ／ｓｅｃ以上となる。
一方、数ＫＨｚから数ＭＨｚの高繰り返しレーザーの場合、アブレーションに利用されるスポットサイズは数百〜数十μｍであるが、より高速のスキャンスピードが要求される。
表１には典型的なレーザーのスポットサイズと繰り返し周波数および、スポットが重ならないために要求される最低スキャンスピードを示した。
なお、上記のスキャンスピードは、ターゲット上のレーザースポットの中心位置の移動速度と同義となる。
There is a Q-switched Nd: YAG laser as a laser often used for ablation. In this case, the spot size is about 1 mm and the repetition frequency is about 10 Hz. In this case, the necessary scanning speed is 10 mm / sec or more.
On the other hand, in the case of a high repetition laser of several KHz to several MHz, the spot size used for ablation is several hundred to several tens of μm, but a higher scanning speed is required.
Table 1 shows a typical laser spot size and repetition frequency, and the minimum scanning speed required for the spots not to overlap.
Note that the above scanning speed is synonymous with the moving speed of the center position of the laser spot on the target.
図１に本発明のナノ粒子製造システムの１例の概略図を示した。本システムでは、パルスレーザーを発振するレーザー手段１から光学スキャナ２、集光レンズ５を介して、液体７を満たしたガラスセル６中に設置したターゲット８（典型的には金板）にレーザー光４を照射する。その際、レーザーのターゲット上でのスポットが重ならないようにスキャンスピードならびに繰り返し周波数を（１式）が成り立つように制御用コンピュータ３によって調節する。また、ターゲット上のスポットが重ならないようにレーザースポットのスキャンの軌跡も制御調節する。 FIG. 1 shows a schematic diagram of an example of the nanoparticle production system of the present invention. In this system, laser light is emitted from a laser means 1 that oscillates a pulse laser to a target 8 (typically a gold plate) installed in a glass cell 6 filled with a liquid 7 via an optical scanner 2 and a condenser lens 5. 4 is irradiated. At that time, the scanning computer 3 adjusts the scanning speed and the repetition frequency so that the spots on the laser target do not overlap each other so that (1) is satisfied. Also, the laser spot scan trajectory is controlled and adjusted so that the spots on the target do not overlap.
ターゲットが設置される液体としては、水、またはアルコールやヘキサンなどの有機溶媒を使用することができ、その液体の種類はとくに制限されない。特に照射するレーザー光の波長に対して強い光吸収を有していない液体（例えば、脱イオン水やメタノール、エタノールなどのアルコール）が好ましい。
金ナノ粒子を製造する場合レーザーを照射するターゲットは公知の方法で調製された金板であれば良く、その純度は特に問わない。
As the liquid in which the target is installed, water or an organic solvent such as alcohol or hexane can be used, and the type of the liquid is not particularly limited. In particular, a liquid that does not have strong light absorption with respect to the wavelength of the laser beam to be irradiated (for example, deionized water, alcohol such as methanol or ethanol) is preferable.
When producing gold nanoparticles, the target for laser irradiation may be a gold plate prepared by a known method, and the purity is not particularly limited.
使用可能なレーザー手段はパルス光を発生できるレーザー手段であれば良く、そのパルス幅は限定されないが、好ましくは１０ｆｓ〜１０ｍｓ、さらに好ましくはましくはピコ秒（典型的には１０〜１００ｐｓ）のパルス幅を持つパルスレーザーを発振するものがよい。
レーザー光の波長は、溶液として脱イオン水を使用した場合には特に限定されないが、２００〜１０６００ｎｍが好ましい。有機溶媒を用いた場合には、有機溶媒に対して強い吸収が無い波長が好ましく、例えば、酢酸エチルでは３３５〜１０６４ｎｍがさらに好ましい。
パルスレーザーの繰り返し周波数（発振周波数）は特に限定されないが、好ましくは１００ｋＨｚ〜４ＭＨｚ、さらに好ましくは１ＭＨｚ〜４ＭＨｚ、より好ましくは１〜２ＭＨｚである。繰り返し周波数が低すぎるとナノ粒子の生成効率が低下することがあり、逆に繰り返し周波数が高すぎるとターゲット上のスポットの重なりを避けることが難しくなることがある。
The usable laser means may be any laser means capable of generating pulsed light, and the pulse width is not limited, but is preferably 10 fs to 10 ms, more preferably picosecond (typically 10 to 100 ps). It is preferable to oscillate a pulse laser having a pulse width.
The wavelength of the laser beam is not particularly limited when deionized water is used as the solution, but 200 to 10600 nm is preferable. When an organic solvent is used, a wavelength that does not strongly absorb the organic solvent is preferable. For example, 335 to 1064 nm is more preferable for ethyl acetate.
The repetition frequency (oscillation frequency) of the pulse laser is not particularly limited, but is preferably 100 kHz to 4 MHz, more preferably 1 MHz to 4 MHz, and more preferably 1 to 2 MHz. If the repetition frequency is too low, the nanoparticle generation efficiency may decrease. Conversely, if the repetition frequency is too high, it may be difficult to avoid overlapping of spots on the target.
好ましくはレーザー光を、図１に示されるように、集光レンズを介して照射するが、レーザー光の強度が十分に強い場合は集光レンズを除外することも可能である。使用する集光レンズの焦点距離は好ましくは５０ｃｍから３ｃｍであり、さらに好ましくは１０ｃｍから５ｃｍである。 Preferably, the laser light is irradiated through a condenser lens as shown in FIG. 1, but the condenser lens can be excluded if the intensity of the laser light is sufficiently high. The focal length of the condenser lens to be used is preferably 50 cm to 3 cm, and more preferably 10 cm to 5 cm.
レーザー光の照射強度はターゲット（典型的には金板）がレーザー光照射をうけてアブレーション現象が発現するに十分に足りるエネルギー密度があれば良く、１００ｋＨｚから４ＭＨｚの繰り返し周波数でピコ秒（典型的には１０〜１００ｐｓ）のパルス幅を持つパルスレーザーの場合、１パルスあたりの出力エネルギー（パルスエネルギー）としては１μＪ／ｐｕｌｓｅ以上あれば十分であり、好ましくは２μＪ／ｐｕｌｓｅから３μＪ／ｐｕｌｓｅである。スポットの直径は好ましくは３０μｍから１μｍであり、さらに好ましくは３０μｍから２０μｍである。レーザーのスキャンスピードは９０ｍ／ｓｅｃ以上が好ましく、１００〜１２０ｍ／ｓｅｃがさらに好ましい。レーザーをスキャンするために使用する光学スキャナは上記のスキャンスピードに到達すれば良く、スキャンの方式は特には問わない。 The irradiation intensity of the laser beam is sufficient if the target (typically a gold plate) has an energy density sufficient to cause the ablation phenomenon by receiving the laser beam irradiation, and it is picoseconds (typically at a repetition frequency of 100 kHz to 4 MHz). In the case of a pulse laser having a pulse width of 10 to 100 ps), it is sufficient that the output energy (pulse energy) per pulse is 1 μJ / pulse or more, preferably 2 μJ / pulse to 3 μJ / pulse. The diameter of the spot is preferably 30 μm to 1 μm, and more preferably 30 μm to 20 μm. The laser scanning speed is preferably 90 m / sec or more, and more preferably 100 to 120 m / sec. The optical scanner used to scan the laser only needs to reach the above scanning speed, and the scanning method is not particularly limited.
上記条件でのレーザー光照射後、溶液中に金ナノ粒子が分散した溶液（金ナノ粒子分散液）を得ることができる。分散液を滴下乾燥させた後、金ナノ粒子を電子顕微鏡により観察した金ナノ粒子は、個数基準粒径分布において全体の９９％以上が、好ましくは１ｎｍ以上８０ｎｍ以下であり、さらに好ましくは１ｎｍ以上６０ｎｍ以下であり、より好ましくは１ｎｍ以上４０ｎｍ以下である。 After laser light irradiation under the above conditions, a solution in which gold nanoparticles are dispersed in the solution (gold nanoparticle dispersion) can be obtained. After the dispersion is dropped and dried, the gold nanoparticles obtained by observing the gold nanoparticles with an electron microscope have a number-based particle size distribution of 99% or more, preferably 1 nm or more and 80 nm or less, more preferably 1 nm or more. It is 60 nm or less, More preferably, it is 1 nm or more and 40 nm or less.
また、上記の金ナノ粒子分散液を常法により乾燥させることで、平均粒径が小さく粒径分布の幅の狭い固体の金ナノ粒子を得ることができる。
金ナノ粒子の平均粒径は１０〜２０ｎｍが好ましく、１０〜１２ｎｍが更に好ましい。また、金ナノ粒子の粒径分布の標準偏差は７．０ｎｍ〜１５．０ｎｍが好ましく、７．０ｎｍ〜８．０ｎｍがさらに好ましい。
Further, by drying the above gold nanoparticle dispersion by a conventional method, solid gold nanoparticles having a small average particle size and a narrow particle size distribution can be obtained.
The average particle size of the gold nanoparticles is preferably 10 to 20 nm, and more preferably 10 to 12 nm. The standard deviation of the particle size distribution of the gold nanoparticles is preferably 7.0 nm to 15.0 nm, and more preferably 7.0 nm to 8.0 nm.
金ナノ粒子はそのサイズがナノメートルオーダーになると表面プラズモン共鳴による光吸収、いわゆる表面プラズマ吸収が可視光から近赤外線の波長領域に観測される。特にこの吸収波長は金ナノ粒子の形態に強く依存しており、粒径分布が狭い金ナノ粒子の場合５００から６００ｎｍの波長領域の１本の光吸収ピークとして観測される。これらの吸収波長は金ナノ粒子表面に吸着した分子によっても影響を受けることから、タンパク質などの生体分子を検出するバイオセンシング材料としても利用されている。
スポットが重ならない条件で液相レーザーアブレーションにより作製した金ナノ粒子はこのような１本の吸収ピークを有しており、また得られる金ナノ粒子分散液中には、還元剤や界面活性剤などの不純物を全く含まない金コロイド溶液を提供することが出来る。このような純粋コロイド溶液を使用すれば、金ナノ粒子表面に分子末端にＳＨ基をもつチオール化合物を容易に結合させることも出来る。
When the size of the gold nanoparticle becomes nanometer order, light absorption by surface plasmon resonance, so-called surface plasma absorption, is observed in the wavelength region from visible light to near infrared. In particular, this absorption wavelength strongly depends on the form of the gold nanoparticles, and in the case of gold nanoparticles having a narrow particle size distribution, it is observed as one light absorption peak in the wavelength region of 500 to 600 nm. Since these absorption wavelengths are also affected by molecules adsorbed on the gold nanoparticle surface, they are also used as biosensing materials for detecting biomolecules such as proteins.
Gold nanoparticles prepared by liquid phase laser ablation under conditions where the spots do not overlap have such a single absorption peak, and the resulting gold nanoparticle dispersion contains a reducing agent, surfactant, etc. It is possible to provide a colloidal gold solution that does not contain any impurities. By using such a pure colloidal solution, a thiol compound having an SH group at the molecular end can be easily bonded to the gold nanoparticle surface.
上記の態様では、ターゲットとして金板を用いた金ナノ粒子およびその分散溶液の典型的な製造方法を述べたが、ターゲットを金以外の金属板、あるいは金属酸化物ペレットにすれば白金、銀、銅、パラジウムなどの金属ナノ粒子、あるいは酸化亜鉛、酸化チタン、酸化スズ、酸化タンタル、酸化ジルコニウム、インジウムスズ酸化物などの酸化物ナノ粒子など各種のナノ粒子およびその分散溶液を同様にして調製することもできる。 In the above embodiment, a typical production method of gold nanoparticles and a dispersion thereof using a gold plate as a target has been described. However, if the target is a metal plate other than gold, or a metal oxide pellet, platinum, silver, Various kinds of nanoparticles such as metal nanoparticles such as copper and palladium, or oxide nanoparticles such as zinc oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, and indium tin oxide, and dispersions thereof are similarly prepared. You can also
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.
実施例１
図１に示した構成のシステムを用いて下記のとおり金ナノ粒子を製造した。
純度９９．５％、１０ｍｍ角、厚さ０．５ｍｍの金板８を、ガラスセル６の底に動かないようにエポキシ樹脂で固定し、１０ｍｌの脱イオン水７を加える。そこへレーザー装置１であるピコ秒ファイバーレーザー（コアレイズ（Corelase）社製、Ｘ−ＬＡＳＥ０２０）からのパルスレーザー光４（中心波長：１．０６μｍ、発振周波数：２〜４ＭＨｚ、パルス幅：２０ｐｓ）を高速光学スキャナ２および集光レンズ４を介して照射した。レーザースポット径は１３μｍとして、液体７中の金板８上に照射痕のラインが重ならないようにスキャンした。レーザーのパルスエネルギーは１．７μＪから２．９μＪの範囲で、レーザーの照射時間は２分から５０分とした。このような操作によって金ナノ粒子が分散した溶液が、液中に還元剤や界面活性剤などの化学物質を添加することなしに、極めて簡単に得られた。
Example 1
Gold nanoparticles were produced as follows using the system configured as shown in FIG.
A metal plate 8 having a purity of 99.5%, a 10 mm square and a thickness of 0.5 mm is fixed to the bottom of the glass cell 6 with an epoxy resin, and 10 ml of deionized water 7 is added. The laser device 1 is a pulse laser beam 4 (center wavelength: 1.06 μm, oscillation frequency: 2 to 4 MHz, pulse width: 20 ps) from a picosecond fiber laser (X-LASE020, manufactured by Corelase). Irradiation was performed via the high-speed optical scanner 2 and the condenser lens 4. The laser spot diameter was set to 13 μm, and scanning was performed so that the lines of irradiation marks did not overlap on the metal plate 8 in the liquid 7. The pulse energy of the laser was in the range of 1.7 μJ to 2.9 μJ, and the laser irradiation time was 2 to 50 minutes. A solution in which gold nanoparticles were dispersed by such an operation was obtained very easily without adding chemical substances such as a reducing agent and a surfactant to the liquid.
比較例１
レーザースポットが重なるスキャンスピードである２ｍ／ｓｅｃとした以外は、実施例１と同様に、金ナノ粒子を作製した。得られた金ナノ粒子の走査電子顕微鏡写真を図２にまたその粒径分布を図３に示した。図２に示すように球状のかなり大きな金ナノ粒子が数多く観察され、金ナノ粒子の粒径分布は５ｎｍから１４５ｎｍの範囲にあり、平均粒径２９．６ｎｍ、標準偏差２５．１ｎｍであった。レーザー照射条件としてスポットサイズは固定して、パルスエネルギーを変化させても、あるいはスキャンスピード並びに繰り返し周波数を、レーザーが重なる条件の範囲内で変化させても平均粒径および標準偏差は大きくは変化しなかった。さらに、液体として有機溶媒であるメタノールやエタノールあるいはアセトンや酢酸エチルなどを利用しても平均粒径および標準偏差は大きくは変化しなかった。
Comparative Example 1
Gold nanoparticles were produced in the same manner as in Example 1 except that the scanning speed at which the laser spots overlap was 2 m / sec. A scanning electron micrograph of the obtained gold nanoparticles is shown in FIG. 2 and the particle size distribution is shown in FIG. As shown in FIG. 2, a large number of spherical gold nanoparticles were observed, and the particle size distribution of the gold nanoparticles was in the range of 5 nm to 145 nm, with an average particle size of 29.6 nm and a standard deviation of 25.1 nm. Even if the spot size is fixed as the laser irradiation condition and the pulse energy is changed, or the scan speed and repetition frequency are changed within the range where the laser overlaps, the average particle size and standard deviation will change greatly. There wasn't. Furthermore, even when methanol, ethanol, acetone, ethyl acetate, or the like, which is an organic solvent, was used as the liquid, the average particle diameter and standard deviation did not change greatly.
実施例２
レーザースポットが重ならないスキャンスピードである１００ｍ／ｓｅｃで、パルスエネルギーが２．３μＪ／ｐｕｌｓｅとした以外は、実施例１と同様に、金ナノ粒子を作製した。金ナノ粒子の走査電子顕微鏡写真を図４にまたその粒径分布を図５にそれぞれ示した。図４に示すように、図２と比較して球状の巨大な金ナノ粒子の絶対数が明白に減っていることが分かる。２．３μＪ／ｐｕｌｓｅのパルスエネルギーで作製した金ナノ粒子の粒径分布は５ｎｍから６０ｎｍの範囲にあり、平均粒径１４．７ｎｍ、標準偏差８．４ｎｍであった。
Example 2
Gold nanoparticles were produced in the same manner as in Example 1 except that the scanning speed at which the laser spots did not overlap was 100 m / sec and the pulse energy was 2.3 μJ / pulse. A scanning electron micrograph of the gold nanoparticles is shown in FIG. 4 and the particle size distribution is shown in FIG. As shown in FIG. 4, it can be seen that the absolute number of gigantic spherical gold nanoparticles is clearly reduced compared to FIG. The particle size distribution of the gold nanoparticles prepared with a pulse energy of 2.3 μJ / pulse was in the range of 5 nm to 60 nm, with an average particle size of 14.7 nm and a standard deviation of 8.4 nm.
実施例３
レーザースポットが重ならないスキャンスピードである１００ｍ／ｓｅｃで、パルスエネルギーが２．９μＪ／ｐｕｌｓｅとした以外は、実施例１と同様に、金ナノ粒子を作製した。金ナノ粒子の走査電子顕微鏡写真を図６にまたその粒径分布を図７にそれぞれ示した。２．９μＪ／ｐｕｌｓｅのパルスエネルギー作製した金ナノ粒子の粒径分布は１ｎｍから７０ｎｍの範囲にあり、９９％以上の粒子が１ｎｍ〜４０ｎｍの粒径範囲にあった。さらに平均粒径１１．５ｎｍ、標準偏差７．７ｎｍであった。
Example 3
Gold nanoparticles were prepared in the same manner as in Example 1 except that the scanning speed at which the laser spots did not overlap was 100 m / sec and the pulse energy was 2.9 μJ / pulse. A scanning electron micrograph of the gold nanoparticles is shown in FIG. 6 and the particle size distribution is shown in FIG. The particle size distribution of the gold nanoparticles produced with a pulse energy of 2.9 μJ / pulse was in the range of 1 nm to 70 nm, and 99% or more of the particles were in the particle size range of 1 nm to 40 nm. Furthermore, the average particle diameter was 11.5 nm, and the standard deviation was 7.7 nm.
比較例１および実施例２および３に示されるようにレーザースポットが重ならない条件で作製した金ナノ粒子は、スポットが重なる条件で作製したものよりも平均粒径、標準偏差共に小さくなった。さらにこの傾向は脱イオン水以外の有機溶媒でさえ同様の傾向が観察された。 As shown in Comparative Example 1 and Examples 2 and 3, the gold nanoparticles prepared under the conditions where the laser spots did not overlap each other had a smaller average particle diameter and standard deviation than those prepared under the conditions where the spots overlapped. Furthermore, this tendency was observed even in organic solvents other than deionized water.
実施例４
スキャンスピード２ｍ／ｓｅｃ、繰り返し周波数３．６６ＭＨｚ、スポットサイズ１３μｍ、パルスエネルギー１．８Ｊ／ｐｕｌｓｅのレーザースポットが重なる条件、およびキャンスピード１００ｍ／ｓｅｃ、スポットサイズ１３μｍ、繰り返し周波数２．００ＭＨｚ、パルスエネルギー２．９Ｊ／ｐｕｌｓｅのスポットが重ならない条件とした以外は実施例１と同様にして金ナノ粒子分散液を得た。得られた金ナノ粒子分散液は、特別な処理をすることなく、そのままの状態で紫外−可視透過スペクトルを測定した。測定された吸収スペクトルを図８に示した。レーザーのスポットが重なる条件で作製した金ナノ粒子の光吸収スペクトル（図８中、実線で示す）は波長５３０ｎｍ付近に鋭い明瞭な吸収ピークと８００ｎｍ付近に非常にブロードな吸収ピークが観察された。一方、レーザーのスポットが重ならない条件で作製した金ナノ粒子の光吸収スペクトル（図８中、点線で示す）は波長５３０ｎｍ付近に見られる鋭い明瞭な吸収ピークだけが観測された。この鋭い明瞭な吸収ピークは粒径の小さな金ナノ粒子の表面プラズマによる吸収で、８００ｎｍ付近に見られる非常にブロードな吸収は巨大粒子によるものである。
Example 4
Scan speed 2 m / sec, repetition frequency 3.66 MHz, spot size 13 μm, conditions where laser spots with pulse energy 1.8 J / pulse overlap, and can speed 100 m / sec, spot size 13 μm, repetition frequency 2.00 MHz, pulse energy 2 A gold nanoparticle dispersion was obtained in the same manner as in Example 1 except that the spot of 9 J / pulse did not overlap. The obtained gold nanoparticle dispersion was measured for its ultraviolet-visible transmission spectrum as it was without any special treatment. The measured absorption spectrum is shown in FIG. The light absorption spectrum (shown by the solid line in FIG. 8) of the gold nanoparticles prepared under the condition where the laser spots overlap each other showed a sharp and clear absorption peak at a wavelength of about 530 nm and a very broad absorption peak at about 800 nm. On the other hand, in the light absorption spectrum (indicated by the dotted line in FIG. 8) of the gold nanoparticles prepared under the condition that the laser spots do not overlap, only a sharp and clear absorption peak observed near the wavelength of 530 nm was observed. This sharp and clear absorption peak is due to absorption of gold nanoparticles having a small particle diameter by surface plasma, and the very broad absorption observed near 800 nm is due to giant particles.
以上の実施例および比較例から、パルスレーザーのスポットの照射痕が重なるか重ならないかは、得られる金ナノ粒子の平均粒径や粒径分布に非常に大きな影響をおよぼすことが明らかになり、条件によっては平均粒径が１５ｎｍを下回り、かつ全体の９９％以上の粒子の粒径分布が１から４０ｎｍの範囲にある金ナノ粒子が作製できることができた。 From the above examples and comparative examples, it becomes clear that the irradiation marks of the pulse laser spot overlap or do not overlap, it has a very large influence on the average particle size and particle size distribution of the obtained gold nanoparticles, Depending on the conditions, it was possible to produce gold nanoparticles having an average particle size of less than 15 nm and a particle size distribution of 99% or more of the total particles in the range of 1 to 40 nm.
本発明によって作成が可能な純粋で粒径分布１から４０ｎｍの範囲にある金ナノ粒子およびその分散液はバイオ・医療応用をはじめ、自己組織化（ＳＡＭ）膜を利用した分子素子の調製にも利用できると考えられ、ナノバイオからナノエレクトロニクスの幅広いナノテクノロジーへの応用が可能である。 Gold nanoparticles having a particle size distribution in the range of 1 to 40 nm and dispersions thereof that can be prepared according to the present invention are used for bio-medical applications and for the preparation of molecular devices using self-assembled (SAM) films. It can be applied to a wide range of nanotechnology from nanobio to nanoelectronics.
１ レーザー装置
２ 光学スキャナ
３ 制御用コンピュータ
４ レーザー光
５ 集光レンズ
６ ガラスセル
７ 液体（脱イオン水）
８ ターゲット
DESCRIPTION OF SYMBOLS 1 Laser apparatus 2 Optical scanner 3 Control computer 4 Laser beam 5 Condensing lens 6 Glass cell 7 Liquid (deionized water)
8 Target
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