JP2006308438A - Probe used for scanning probe excitation optical measurement and method for producing the probe - Google Patents
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Abstract
【課題】 プローブ先端近接部のみからのラマン信号を検出し、高分解能を実現するために、先端部のみが励起光を散乱するようなプローブを、高いスループットで作製する。
【解決手段】 励起光に対して透明な材料で構成したプローブ基体先端に、活性光線を照射すると現像液に不溶化する屈折率の大きい物質又は金属が析出する物質をコーティングする。このコーティングしたプローブの先端部分のみに活性光線を照射し、現像する。これによって、先端部分のみに屈折率の大きい物質又は金属が担持される。
【選択図】 図１PROBLEM TO BE SOLVED: To produce a probe with a high throughput in which only a tip portion scatters excitation light in order to detect a Raman signal from only a probe tip proximity portion and realize high resolution.
A probe base tip made of a material transparent to excitation light is coated with a substance having a high refractive index or a metal depositing substance that is insoluble in a developer when irradiated with actinic rays. Only the tip of the coated probe is irradiated with actinic rays and developed. As a result, a material or metal having a large refractive index is supported only on the tip portion.
[Selection] Figure 1
Description
本発明は、走査プローブ顕微鏡等計測機器、シリコン基板のひずみ分布測定装置などにおいて、走査型プローブ励起光学測定に用いるプローブ及びそのプローブ作製方法に関する。 The present invention relates to a probe used for scanning probe excitation optical measurement in a measuring instrument such as a scanning probe microscope, a strain distribution measurement device for a silicon substrate, and the like, and a method for producing the probe.
近年、ナノ構造、ナノデバイスの分野の研究開発が急速に発展しており、これらの分野において種々の試料の特性評価のため、高い分解能をもった光学計測技術が求められている。例えば、シリコンデバイスにおいては、シリコンに入る歪みは易動度等デバイス特性に大きな影響を与えるため、試料中の歪みの空間分布を高分解能で知ることは非常に重要なことである。この歪み計測の一つの手段として従来よりラマン計測による方法が知られている。このラマン計測の原理は、ラマン信号のピーク位置は歪みに応じてシフトするため、ラマン信号のピーク位置のマッピングをとれば、歪みの分布を知ることができる、というものである。 In recent years, research and development in the fields of nanostructures and nanodevices are rapidly progressing, and optical measurement techniques with high resolution are required in these fields for the purpose of characterizing various samples. For example, in a silicon device, since strain entering silicon has a great influence on device characteristics such as mobility, it is very important to know the spatial distribution of strain in a sample with high resolution. Conventionally, a method using Raman measurement is known as one means for measuring the distortion. The principle of this Raman measurement is that the peak position of the Raman signal shifts according to the distortion, so that if the mapping of the peak position of the Raman signal is taken, the distribution of the distortion can be known.
従来、ラマン分光の分野で提案されている技術の一つに、金属のＡＦＭ（原子間力顕微鏡）探針を用いた測定がある。この方法によると、金属探針の先端の局所的な電場により、探針先端近接部のみのラマンシグナルが増強されるため、空間分解能が向上する。この方法においては、２つの金属を極小さな隙間を空けて近接させ、その間に被測定試料を設置したときに大きな増強効果が得られる。そのため、分子や超微粒子の測定においてはある程度の成果が得られているが、不透明な固体の測定には適用することができない。それは、固体においては、上記のように２つの金属の間に被測定試料をおくことが不可能なことと、金属探針から離れた位置で励起された遠視野の信号が強く、微弱な近接場の信号を覆い隠してしまうからである。 Conventionally, one of the techniques proposed in the field of Raman spectroscopy is measurement using a metal AFM (Atomic Force Microscope) probe. According to this method, the local electric field at the tip of the metal probe enhances the Raman signal only at the vicinity of the tip of the probe, so that the spatial resolution is improved. In this method, a great enhancement effect can be obtained when two metals are brought close to each other with a very small gap and a sample to be measured is placed between them. Therefore, although some results have been obtained in the measurement of molecules and ultrafine particles, it cannot be applied to the measurement of opaque solids. In solids, it is impossible to place a sample to be measured between two metals as described above, and the far field signal excited at a position away from the metal probe has a strong and weak proximity. This is because the signal of the field is obscured.
このような問題点を解決するために、本出願人は、先に、金属探針を用いた走査型プローブ励起光学測定において、遠視野の信号が近接場の信号を覆い隠してしまい、測定の空間分解能を低下させてしまう問題を解決するための出願を行った（特願２００３−３１３９０１号）。単結晶基板試料に対して、選択則により禁止される偏光方向で励起光を入射する。ここで、照射部に金属のプローブを置くと、プローブにより励起光が散乱されて偏光が解消されるために選択則が緩和されラマン散乱が活性になり、さらにプローブ先端に誘起される表面プラズモンの電場により強度も増強される。すなわち、プローブ先端近接部のみからのラマン信号を検出し、高分解能を実現する。しかしながら、全体が金属でできているプローブを用いると、プローブ先端以外の部分でも励起光が散乱されてしまい、先端部以外のところでも選択則が緩和されてしまい、空間分解能が低下する。 In order to solve such a problem, the applicant of the present invention first made a measurement with a far-field signal obscuring a near-field signal in a scanning probe excitation optical measurement using a metal probe. An application was made to solve the problem of reducing the spatial resolution (Japanese Patent Application No. 2003-313901). Excitation light is incident on the single crystal substrate sample in the polarization direction prohibited by the selection rule. Here, when a metal probe is placed on the irradiated part, the excitation light is scattered by the probe and the polarization is canceled, so the selection rule is relaxed and Raman scattering is activated, and the surface plasmon induced at the probe tip is further reduced. The strength is also increased by the electric field. That is, a Raman signal from only the probe tip proximity portion is detected, and high resolution is realized. However, when a probe made entirely of metal is used, the excitation light is scattered at portions other than the tip of the probe, and the selection rule is relaxed at portions other than the tip, thereby reducing the spatial resolution.
そこで、先端部のみが励起光を散乱するようなプローブを作製することが必要となる。その方法として、キャピラリー状の石英プローブの内部を通して原料液をプローブ先端まで輸送し、先端で反応させ銀を析出させる方法が用いられている。この方法は、２本のキャピラリーを持つ特殊な石英プローブを使わなければならず、反応の制御にも困難が伴う。また、プローブ全面に金属を蒸着した後、不要な部分をFIB（集束イオンビーム装置）で取り除く方法が知られている（特許文献１参照）が、FIBという特殊な装置を使用しなければならず、スループットも極めて低いという問題があった。
そこで、本発明は、プローブ先端近接部のみからのラマン信号を検出し、高分解能を実現するために、先端部のみが励起光を散乱するようなプローブを、高いスループットで作製することを目的としている。 Therefore, the present invention aims to produce a probe with high throughput, in which only the tip portion scatters excitation light in order to detect a Raman signal only from the probe tip proximity portion and realize high resolution. Yes.
本発明の走査型プローブ励起光学測定に用いるプローブ及びその作製方法は、励起光に対して透明な材料で構成したプローブ基体先端に、活性光線を照射すると現像液に不溶化する基体と屈折率の異なる物質又は金属が析出する物質をコーティングし、コーティングしたプローブの先端部分のみに活性光線を照射し、現像し、先端部分のみに前記屈折率の異なる物質又は金属が担持される。 The probe used in the scanning probe excitation optical measurement of the present invention and the method for producing the probe are different in refractive index from the substrate that is insoluble in the developer when irradiated with actinic rays on the tip of the probe substrate made of a material transparent to excitation light. A substance or a metal depositing substance is coated, only the tip portion of the coated probe is irradiated with actinic rays, developed, and the substance or metal having a different refractive index is supported only on the tip part.
また、本発明の走査型プローブ励起光学測定に用いるプローブ及びその作製方法は、励起光に対して透明な材料で構成したプローブ基体に、ポジ型レジストをコーティングし、コーティングしたプローブの先端部分のみに活性光線を照射し、現像によりプローブ先端部分のみのレジストを除去した後、金属微粒子を含む溶液に浸漬し、先端部分に金属微粒子を付着させることにより、先端部分に金属微粒子を担持する。 In addition, the probe used in the scanning probe excitation optical measurement of the present invention and the method for producing the probe are prepared by coating a positive resist on a probe base made of a material transparent to excitation light, and applying only to the tip of the coated probe. After irradiating actinic rays and removing the resist only at the probe tip portion by development, the tip is immersed in a solution containing metal fine particles, and the metal fine particles are attached to the tip portion, thereby supporting the metal fine particles on the tip portion.
また、本発明の走査型プローブ励起光学測定に用いるプローブ及びその作製方法は、励起光に対して透明な材料で構成したプローブ基体を、樹脂溶液に浸漬し、引き上げ、乾燥後に形成される先端部の樹脂に覆われていない部分に金属を付着した後、その他の部分の樹脂を溶媒で取り除くことによって作製される先端部分に金属を担持する。 Further, the probe used for the scanning probe excitation optical measurement of the present invention and the method for manufacturing the probe include a probe base made of a material transparent to excitation light, dipped in a resin solution, pulled up, and a tip formed after drying After the metal is attached to the part not covered with the resin, the metal is supported on the tip part produced by removing the resin of the other part with a solvent.
また、本発明の走査型プローブ励起光学測定に用いるプローブ及びその作製方法は、励起光に対して透明な材料で構成した石英ファイバー製のプローブ基体にレジストを塗布して、基体内部に光を入射することにより、光の波長よりも短い径を持つ先端部のみにレジストを残すか、或いは先端部にウィンドウを開いて、プローブ先端部のみに金属を付着させることによって先端部分に金属を担持する。 In addition, the probe used in the scanning probe excitation optical measurement according to the present invention and the method for producing the probe are prepared by applying a resist to a quartz fiber probe base made of a material transparent to the excitation light, and entering the light into the base. By doing so, the resist is left only at the tip portion having a diameter shorter than the wavelength of the light, or a window is opened at the tip portion, and the metal is attached only to the probe tip portion, thereby supporting the metal on the tip portion.
本発明によれば、プローブ先端近接部のみからのラマン信号を検出し、高分解能を実現し、先端部のみが励起光を散乱するようなプローブを、製造容易に、かつ高いスループットで作製することを可能にする。 According to the present invention, it is possible to manufacture a probe that can detect a Raman signal only from a portion near the probe tip, realize high resolution, and scatter excitation light only at the tip portion, with ease and high throughput. Enable.
先端部のみが励起光を散乱するようなプローブ（探針）を作製するためには、先端部が励起光に対して散乱能の大きな材質で構成され、それ以外の部分が散乱能の小さな材質で構成されたプローブを作製すればよい。具体的には、石英等励起光に対して透明な材料で構成したプローブの先端に金属や、プローブ基体と屈折率の異なる物質を担持させた構造を作製すればよい。 In order to produce a probe (probe) in which only the tip part scatters the excitation light, the tip part is made of a material having a large scattering ability with respect to the excitation light, and the other part is a material having a low scattering ability. What is necessary is just to produce the probe comprised by these. Specifically, a structure in which a metal or a substance having a refractive index different from that of the probe base is supported on the tip of a probe made of a material transparent to excitation light such as quartz may be manufactured.
このために、電子線や光（以下活性光線と略す）を照射すると現像液に不溶化する屈折率の異なる物質や金属が析出する物質を、プローブにコーティングし、先端部のみに活性光線を照射して、必要ならば現像し、先端部に該物質あるいはその反応生成物を担持させることにより、プローブを作製することができる。例えば、プローブ先端部分にハロゲン化銀または酸化銀をコーティングし、電子線又は光を照射することにより、先端部分のみに銀が担持されたプローブを作製することができる。 For this purpose, the probe is coated with a substance having a different refractive index or a metal depositing substance that becomes insoluble in the developer when irradiated with an electron beam or light (hereinafter abbreviated as actinic light), and only the tip is irradiated with actinic light Then, if necessary, development is performed, and the probe or the reaction product can be supported on the tip portion to produce a probe. For example, a probe in which silver is supported only on the tip portion can be produced by coating the tip portion of the probe with silver halide or silver oxide and irradiating with an electron beam or light.
先端部のみに光線を照射する方法の一つとして、エバネッセント光を利用することができる。これは、図１に示すように、石英等透明基板に光を入射する時、基板内部で全反射するように入射すると、全反射している部分では、基板内部から外部にかけてナノメートルオーダーで光がしみ出しているため、このしみ出した光にプローブ基体を当てれば、極めて狭い領域のみに光を照射することができる。この方法では、個別に光を絞る必要がないため、一度に大量のプローブに光照射を行うことができるという利点を持つ。また、プローブ先端の試料表面に接触する部分に、正確に光照射を行うことができる。この点は、作製したプローブをＡＦＭプローブとして用いる際に、極めて有用である。 Evanescent light can be used as one method of irradiating only the tip with light. As shown in FIG. 1, when light is incident on a transparent substrate such as quartz, if it is incident so as to be totally reflected inside the substrate, the light is reflected on the nanometer order from the inside of the substrate to the outside in the totally reflected portion. Therefore, if a probe base is applied to the exuded light, only a very narrow region can be irradiated with light. This method has an advantage that a large number of probes can be irradiated with light at one time because it is not necessary to squeeze light individually. In addition, it is possible to accurately irradiate the portion of the probe tip that contacts the sample surface. This point is extremely useful when the produced probe is used as an AFM probe.
また、プローブの先端に金属や、屈折率の異なる物質を担持させるために、ポジ型レジストをプローブ基体にコーティングし、先端部分のみに活性光線を照射・現像して先端部に窓を開け、その部分に金属微粒子を付着させることができる。即ち、図２に示すように、ポジ型レジストをコーティングしたプローブ先端部のみに光又は電子線（ＥＢ）を照射し（１）、現像によりプローブ先端部のみのレジストを除去した（２）後、金属微粒子を含む溶液に浸漬し、先端部に金属微粒子を付着させることにより先端部分に金属微粒子を担持したプローブを作製する。 In addition, in order to support metals and substances with different refractive indexes on the tip of the probe, a positive resist is coated on the probe base, actinic rays are irradiated and developed only on the tip, and a window is opened at the tip. Metal fine particles can be attached to the portion. That is, as shown in FIG. 2, only the probe tip coated with a positive resist is irradiated with light or an electron beam (EB) (1), and the resist only on the probe tip is removed by development (2). A probe carrying the metal fine particles at the tip is prepared by dipping in a solution containing the metal fine particles and attaching the metal fine particles to the tip.
また、先端に金属微粒子を担持させる前に、現像後レジストが除去された先端部分にのみ金属微粒子が吸着しやすい物質を付着させる（３）（４）。プローブ基体の材質は、例えば石英で、金属微粒子を含む溶液として金コロイド溶液、金属微粒子を付着させやすい物質としてアミノシランを用いることができる。この場合、金コロイド溶液に浸漬することにより（５）、金コロイドは、アミノシランを介してプローブ先端に担持される（６）。ＰＭＭＡを除去すると、金粒子が先端に担持される（７）。 In addition, before the metal fine particles are carried on the tip, a substance that easily adsorbs the metal fine particles is attached only to the tip portion from which the resist has been removed after development (3) (4). The material of the probe base is, for example, quartz, and a gold colloid solution can be used as a solution containing metal fine particles, and aminosilane can be used as a substance that easily attaches metal fine particles. In this case, the gold colloid is supported on the probe tip via aminosilane (6) by being immersed in the gold colloid solution (5). When PMMA is removed, gold particles are supported on the tip (7).
また、図３に示すように、プローブ基体をＰＭＭＡ（ポリメチルメタクリレート）等の樹脂溶液に浸漬し、ゆっくり引き上げると、鋭くとがった先端部のぬれ性は悪いため、先端部サブミクロン領域では樹脂がコーティングされない。よって、この部分にのみ金属を付着させることができる。プローブ基体を樹脂溶液に浸漬し（Ａ）、引き上げ（Ｂ）、乾燥後に形成される先端部の樹脂に覆われていない部分に金属を付着した後（Ｃ）、その他の部分の樹脂を溶媒で取り除くことによって作製される先端部に金属を担持する（Ｄ）。金属を付着させる方法として真空蒸着を用いることができ、また、金属微粒子が吸着しやすい物質を付着させてから、先端に金属微粒子を担持させることができる。樹脂としてＰＭＭＡを、金属微粒子が吸着しやすい物質としてアミノシラン、金属微粒子として金コロイドを用いることができる。 Further, as shown in FIG. 3, when the probe base is immersed in a resin solution such as PMMA (polymethylmethacrylate) and slowly pulled up, the sharply sharpened tip has poor wettability. Not coated. Therefore, metal can be attached only to this portion. Immerse the probe base in the resin solution (A), pull it up (B), attach a metal to the portion of the tip that is formed after drying that is not covered with resin (C), and then use the solvent for the other portion of the resin. A metal is carried on the tip part produced by removing (D). Vacuum deposition can be used as a method for attaching the metal, and the metal fine particles can be supported on the tip after attaching a substance that is easily adsorbed by the metal fine particles. PMMA can be used as the resin, aminosilane can be used as the substance that can easily adsorb the metal fine particles, and gold colloid can be used as the metal fine particles.
また、図４は、プローブの先端に金属を担持させる別の方法を説明する図である。図示したように、石英ファイバー製のプローブ先端部分にレジストを塗布してファイバーに光を入射すると、一般的にレジストの屈折率は石英よりも大きいため、全反射の条件が破れ、入射した光はファイバー内部から外部へ漏れ出てしまう（Ａ）。したがって、光の波長よりも短い径を持つ先端部には光は余り届かない状況となる。したがって、ポジ型のレジストを塗布しておけば、現像後、先端部のみにレジストがのこる。また、ネガ型のレジストを塗布しておくと現像後、先端部にウィンドウが開くので（Ｂ）、金属を蒸着等で堆積することにより（Ｃ）、プローブ先端部のみに金属を付着させることができる（Ｄ）。なお、図４はネガ型レジストを塗布した場合の例を示してある。 FIG. 4 is a diagram for explaining another method for supporting a metal on the tip of the probe. As shown in the figure, when a resist is applied to the tip of a quartz fiber probe and light is incident on the fiber, the refractive index of the resist is generally larger than that of quartz. Leaks from the inside of the fiber to the outside (A). Therefore, light does not reach the tip part having a diameter shorter than the wavelength of light. Therefore, if a positive resist is applied, the resist remains only at the tip after development. If a negative resist is applied, a window opens at the tip after development (B). By depositing metal by vapor deposition or the like (C), the metal can be attached only to the probe tip. Yes (D). FIG. 4 shows an example in which a negative resist is applied.
石英ファイバー製ＡＦＭプローブ（探針）基体に感光性物質としてAgClを100nm蒸着する。次に、当該プローブ基体をＡＦＭ（原子間力顕微鏡）に装着し、ＡＦＭを動作させて、石英板（透明基板）にプローブ基体を接触させる。次に、図１に示すように石英直角プリズムを用いて、アルゴンレーザーから放射される出力10mW波長364nmの紫外光を石英板に入射する。紫外光が全反射している基板表面にプローブ先端を接触させ、石英板表面にしみ出しているエバネッセント光で30分間露光する。その後、写真用の現像液（例えば、富士フイルム：スーパーフジドールＬ、還元剤）と定着液（富士フイルム：スーパーフジックス、主成分はチオ硫酸ナトリウム）にそれぞれ10分ずつ浸漬した後に純水で水洗する。電子顕微鏡で先端部分を観察したところ50nm程度の銀粒子が先端に担持されていることが観察された。 AgCl is deposited as a photosensitive material to a thickness of 100 nm on a quartz fiber AFM probe (probe) substrate. Next, the probe base is mounted on an AFM (atomic force microscope), the AFM is operated, and the probe base is brought into contact with a quartz plate (transparent substrate). Next, as shown in FIG. 1, using a quartz right angle prism, ultraviolet light emitted from an argon laser and having an output of 10 mW and a wavelength of 364 nm is incident on the quartz plate. The tip of the probe is brought into contact with the substrate surface where the ultraviolet light is totally reflected, and the substrate is exposed for 30 minutes with evanescent light that oozes out on the quartz plate surface. Then, immerse in photographic developer (for example, Fuji Film: Super Fujidol L, reducing agent) and fixer (Fuji Film: Super Fujix, the main component is sodium thiosulfate) for 10 minutes each, then rinse with pure water To do. When the tip portion was observed with an electron microscope, it was observed that silver particles of about 50 nm were supported on the tip.
石英ファイバー製ＡＦＭプローブ基体にAgClを100nm蒸着する。次に、電子線をプローブ先端部50nmの領域に1C/cm2照射した。そののち、写真用の現像液（富士フイルム：スーパーフジドールＬ）と定着液（富士フイルム：スーパーフジックス）にそれぞれ10分ずつ浸漬後純水にて水洗する。電子顕微鏡で先端部分を観察したところ50nm程度の銀粒子が先端に担持されていることが観察された。 AgCl is deposited to 100 nm on a quartz fiber AFM probe substrate. Next, 1 C / cm 2 was irradiated to the region of the probe tip 50 nm with an electron beam. After that, the film is immersed in a photographic developer (Fuji Film: Super Fuji Doll L) and a fixing solution (Fuji Film: Super Fujix) for 10 minutes each and then washed with pure water. When the tip portion was observed with an electron microscope, it was observed that silver particles of about 50 nm were supported on the tip.
石英ファイバー製ＡＦＭプローブ基体にＰＭＭＡを100nm塗布・乾燥する。次に、電子線をプローブ先端50nmの領域に0.01C/cm2照射した。メチルイソブチルケトンにて現像後、アミノシラン水溶液に５分間浸漬後、クエン酸中に直径50nm金コロイドを分散した溶液に１時間浸す。図２に示すように、金コロイドは、アミノシランを介してプローブ先端に担持される。アセトンで、ＰＭＭＡを除去した後、電子顕微鏡で先端部分を観察したところ50nmの金粒子が先端に担持されていることが観察された。 PMMA is applied to a quartz fiber AFM probe substrate to a thickness of 100 nm and dried. Next, an electron beam was irradiated to the area of the probe tip 50 nm at 0.01 C / cm 2 . After development with methyl isobutyl ketone, it is immersed in an aminosilane aqueous solution for 5 minutes, and then immersed in a solution in which a colloidal 50 nm diameter gold colloid is dispersed in citric acid for 1 hour. As shown in FIG. 2, the colloidal gold is supported on the probe tip via aminosilane. After removing PMMA with acetone, the tip portion was observed with an electron microscope, and it was observed that 50 nm gold particles were supported on the tip.
図３に示すように、石英ファイバー製ＡＦＭプローブ基体をＰＭＭＡのＭＣＡ（１−アセトキシ−２−メトキシエタン）溶液に浸し（Ａ）、ゆっくりと引き上げ乾燥する（Ｂ）。次に、イソプロピルアルコールで１分間洗浄・乾燥後、プラチナを電子ビーム加熱真空蒸着で50nm堆積する（Ｃ）。アセトンを用いて、リフトオフを行った後（Ｄ）、電子顕微鏡で先端部分を観察したところ先端部分のみにプラチナが蒸着されていることが観察された。 As shown in FIG. 3, the quartz fiber AFM probe substrate is immersed in an MCA (1-acetoxy-2-methoxyethane) solution of PMMA (A) and slowly pulled up and dried (B). Next, after washing and drying with isopropyl alcohol for 1 minute, platinum is deposited to 50 nm by electron beam heating vacuum deposition (C). After lift-off using acetone (D), the tip portion was observed with an electron microscope, and it was observed that platinum was deposited only on the tip portion.
石英ファイバー製ＡＦＭプローブ基体をＰＭＭＡのＭＣＡ溶液に浸しゆっくりと引き上げ乾燥する。次に、イソプロピルアルコールで１分間洗浄し、アミノシラン水溶液に５分間に浸漬した後、クエン酸中に分散された直径50nm金コロイドの溶液に１時間浸す。アセトンで、ＰＭＭＡを除去した後、電子顕微鏡で先端部分を観察したところ50nmの金粒子が先端に担持されていることが観察された。 The quartz fiber AFM probe substrate is immersed in an MCA solution of PMMA and slowly pulled up and dried. Next, it is washed with isopropyl alcohol for 1 minute, immersed in an aminosilane aqueous solution for 5 minutes, and then immersed in a solution of 50 nm diameter gold colloid dispersed in citric acid for 1 hour. After removing PMMA with acetone, the tip portion was observed with an electron microscope, and it was observed that 50 nm gold particles were supported on the tip.
図４に示すように、石英製ファイバーのプローブにネガ型レジストのＳＡＬ600（シップレイ社）を塗布、100℃で1分プリベーク後、パワー1mW、波長364nmのアルゴンレーザー光をファイバーに入射し、30分間露光した。115℃で1分のポストベークを行なったのち、現像液（TMAH、水酸化テトラメチルアンモニウム水溶液2.38%）で10分現像後、銀を真空蒸着で50nm堆積した。アセトンでリフトオフ後、電子顕微鏡で観察したところ、プローブ先端部直径50nm程度の領域に銀が付着していることが確認された。 As shown in Fig. 4, a negative resist SAL600 (Shipley) was applied to a quartz fiber probe, prebaked at 100 ° C for 1 minute, and then irradiated with argon laser light with a power of 1 mW and wavelength of 364 nm for 30 minutes. Exposed. After post-baking at 115 ° C. for 1 minute, after developing for 10 minutes with a developer (TMAH, tetramethylammonium hydroxide aqueous solution 2.38%), silver was deposited to 50 nm by vacuum evaporation. Observation with an electron microscope after lift-off with acetone confirmed that silver had adhered to a region having a probe tip diameter of about 50 nm.
Claims (22)
励起光に対して透明な材料で構成したプローブ基体先端にコーティングした、活性光線を照射すると現像液に不溶化するプローブ基体と異なる屈折率を持つ物質又は金属が析出する物質に、活性光線を照射し、かつ、現像することにより、プローブ基体先端部分のみに前記屈折率の異なる物質又は金属が担持されたプローブ。 In the probe used for scanning probe excitation optical measurement,
Actinic light is irradiated to a substance that has a refractive index different from that of the probe base that is coated on the tip of the probe base made of a material that is transparent to the excitation light and becomes insoluble in the developer when irradiated with active light, or a substance on which metal is deposited. And the probe by which the substance or metal from which said refractive index differs was carry | supported only by the probe base front-end | tip part by developing.
励起光に対して透明な材料で構成したプローブ基体にコーティングしたポジ型レジストを、活性光線を照射後に現像することによりレジストを除去したプローブ先端部分のみに、金属微粒子を含む溶液に浸漬することにより金属微粒子を担持したプローブ。 In the probe used for scanning probe excitation optical measurement,
By immersing a positive resist coated on a probe base made of a material transparent to excitation light in a solution containing metal fine particles only on the tip of the probe from which the resist has been removed by development after irradiation with actinic rays. Probe carrying metal fine particles.
励起光に対して透明な材料で構成したプローブ基体を、樹脂溶液に浸漬し、引き上げることにより、乾燥後に形成される先端部の樹脂に覆われていない部分に金属を付着し、かつ、その他の部分の樹脂を溶媒で取り除くことによって先端部分に金属を担持したプローブ。 In the probe used for scanning probe excitation optical measurement,
A probe base made of a material transparent to excitation light is immersed in a resin solution and pulled up to attach a metal to a portion not covered with resin at the tip formed after drying, and other A probe with a metal supported on the tip by removing the resin of the part with a solvent.
励起光に対して透明な材料で構成したプローブ基体にレジストを塗布して、基体内部に光を入射することにより、先端部のみにレジストを残して、先端部分にレジストを担持したプローブ。 In the probe used for scanning probe excitation optical measurement,
A probe in which a resist is applied to a probe base made of a material transparent to excitation light and light is incident on the inside of the base so that the resist remains only at the tip and the resist is carried on the tip.
励起光に対して透明な材料で構成したプローブ基体にレジストを塗布して、基体内部に光を入射することにより、先端部にウィンドウを開いて、プローブ先端部のみに金属を付着させることによって先端部分に金属を担持したプローブ。 In the probe used for scanning probe excitation optical measurement,
By applying a resist to the probe base made of a material transparent to the excitation light and making light incident on the inside of the base, a window is opened at the tip and the metal is attached only to the probe tip. Probe with metal on part.
励起光に対して透明な材料で構成したプローブ基体先端に、活性光線を照射すると現像液に不溶化する屈折率がプローブ基体と異なる物質又は金属が析出する物質をコーティングし、
コーティングしたプローブの先端部分のみに活性光線を照射し、
現像し、先端部分のみに前記屈折率がプローブ基体と異なる物質又は金属が担持されたプローブの作製方法。 In a method for producing a probe used for scanning probe excitation optical measurement,
The tip of the probe base made of a material that is transparent to the excitation light is coated with a substance that has a refractive index that is insoluble in the developer when irradiated with actinic light, or a substance that deposits a metal.
Irradiate only the tip of the coated probe with actinic rays,
A method for producing a probe which is developed and loaded with a substance or metal having a refractive index different from that of the probe substrate only at the tip portion.
励起光に対して透明な材料で構成したプローブ基体に、ポジ型レジストをコーティングし、
コーティングしたプローブの先端部分のみに活性光線を照射し、
現像によりプローブ先端部分のみのレジストを除去した後、金属微粒子を含む溶液に浸漬し、
先端部分に金属微粒子を付着させることにより、先端部分に金属微粒子を担持したプローブの作製方法。 In a method for producing a probe used for scanning probe excitation optical measurement,
A positive resist is coated on the probe base made of a material transparent to the excitation light,
Irradiate only the tip of the coated probe with actinic rays,
After removing the resist only at the tip of the probe by development, it is immersed in a solution containing fine metal particles,
A method for producing a probe in which metal fine particles are attached to the tip portion by attaching the metal fine particles to the tip portion.
励起光に対して透明な材料で構成したプローブ基体を、樹脂溶液に浸漬し、引き上げ、
乾燥後に形成される先端部の樹脂に覆われていない部分に金属を付着した後、その他の部分の樹脂を溶媒で取り除くことによって作製される先端部分に金属を担持したプローブの作製方法。 In a method for producing a probe used for scanning probe excitation optical measurement,
A probe base made of a material transparent to excitation light is immersed in a resin solution, pulled up,
A method for producing a probe in which a metal is supported on a tip portion produced by attaching a metal to a portion of the tip portion formed after drying that is not covered with a resin and then removing the resin in other portions with a solvent.
励起光に対して透明な材料で構成したプローブ基体にレジストを塗布し、
基体内部に光を入射することにより、先端部のみにレジストを残し、
先端部にレジストを担持したプローブの作製方法。 In a method for producing a probe used for scanning probe excitation optical measurement,
Apply a resist to the probe base made of a material transparent to the excitation light,
By making light incident inside the substrate, leaving the resist only at the tip,
A method for producing a probe carrying a resist at the tip.
励起光に対して透明な材料で構成したプローブ基体にレジストを塗布し、
基体内部に光を入射することにより、先端部にウィンドウを開き、
プローブ先端部のみに金属を付着させることによって、先端部分に金属を担持したプローブの作製方法。 In a method for producing a probe used for scanning probe excitation optical measurement,
Apply a resist to the probe base made of a material transparent to the excitation light,
By entering light inside the substrate, a window is opened at the tip,
A method for producing a probe in which a metal is supported on the tip by attaching a metal only to the tip of the probe.
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