JP2016065805A - Base material and manufacturing method of base material - Google Patents
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Abstract
Description
本発明は、基材及び該基材の製造方法に関し、特に、ＰＭ２．５、ウィルス、花粉、菌、毒素等の身の回りの有害・危険物質を短時間で測定することができ、且つ装置を小型化・モバイル化するための分析用チップの作製に用いることができる基材及び該基材の製造方法に関するものである。 The present invention relates to a substrate and a method for producing the substrate, and in particular, can measure harmful and dangerous substances such as PM2.5, viruses, pollen, fungi, and toxins in a short time, and can reduce the size of the apparatus. The present invention relates to a base material that can be used for the production of an analysis chip for making it mobile and mobile, and a method for producing the base material.
大気中又は水中に浮遊するＰＭ２．５、ウィルス、花粉、菌、毒素等の有害・危険物質は、ヒトなどの生体の健康状態に影響を与える可能性が指摘されている。そのため、ヒトが安全で快適な生活を送るために、大気中又は水中のこれら有害・危険物質を正確に分析する必要がある。 It has been pointed out that harmful and dangerous substances such as PM2.5, viruses, pollen, fungi, and toxins floating in the air or water may affect the health of living bodies such as humans. Therefore, in order for humans to live a safe and comfortable life, it is necessary to accurately analyze these harmful and dangerous substances in the air or water.
ＰＭ２．５を分析する装置・方法としては、例えば、フィルタに捕集したＰＭ２．５をＸ線蛍光分析法により測定する方法が知られている（特許文献１参照）。しかしながら、市販されている装置は、大きい、高額である、定性定量同時計測が困難である、という問題点がある。 As an apparatus and method for analyzing PM2.5, for example, a method of measuring PM2.5 collected on a filter by X-ray fluorescence analysis is known (see Patent Document 1). However, commercially available apparatuses have problems that they are large, expensive, and difficult to perform qualitative quantitative simultaneous measurement.
また、他の有害・危険物質についても、夫々の物質に応じた分析方法が知られており、分析装置も市販されている。しかしながら、市販されている各種装置は次のような問題がある。
（１）細菌検出装置及びウィルス検出装置は、大型で装置の可搬性が低く、分析に２０〜８０分程度時間がかかり迅速な分析ができない。また、分析には４×１０3個程度の細菌又はウィルスが必要で感度が低く、更に、装置の価格も高い。
（２）有害分子検出装置は、測定時間が１０〜２０時間と長く、分析には１０-12Ｍの分子が必要で感度が低い。
（３）花粉検出装置は、大型で装置の可搬性が低く、装置の価格も高い。また、定性定量同時計測が困難である。
For other harmful and dangerous substances, analysis methods corresponding to the respective substances are known, and analyzers are also commercially available. However, various commercially available devices have the following problems.
(1) The bacteria detection device and virus detection device are large and have low portability, and it takes about 20 to 80 minutes for analysis, and rapid analysis cannot be performed. In addition, about 4 × 10 3 bacteria or viruses are required for analysis, the sensitivity is low, and the price of the apparatus is high.
(2) The harmful molecule detection apparatus has a long measurement time of 10 to 20 hours, requires 10 −12 M molecules for analysis, and has low sensitivity.
(3) The pollen detection device is large, has low portability, and is expensive. Moreover, qualitative quantitative simultaneous measurement is difficult.
ところで、昆虫の触覚は一分子単位で物質を検出することができる。分析装置においても、昆虫のように物質を一分子単位の高感度で且つ短時間で検出することができ、更に、多種類の物質を識別できることが望まれている。しかしながら、現状では、そのような分析ができる分析装置は知られていない。 By the way, insect tactile sense can detect a substance on a molecular basis. Also in an analyzer, it is desired that a substance can be detected in a single molecule unit with a high sensitivity and in a short time like an insect, and that many kinds of substances can be identified. However, at present, there is no known analyzer that can perform such analysis.
本発明は、上記従来の問題を解決するためになされた発明であり、鋭意研究を行ったところ、電子線リソグラフィ、フォトリソグラフィ、集束イオンビーム（Ｆｏｃｕｓｅｄ Ｉｏｎ Ｂｅａｍ；ＦＩＢ）等の微細加工技術を駆使することで、有害・危険物質を１分子単位で通過できる貫通孔を有した中空の筒体が基板上に形成された基材を作製できることを新たに見出した。そして、前記基材をベースとし、貫通孔の周囲に電極、中空の筒体の内部に金属蒸着層及び／又はナノワイヤ等を形成することで分析用チップを作製することができ、身の回りの有害・危険物質を捕捉、識別、検出できる可能性があることを見出した。 The present invention has been made in order to solve the above-mentioned conventional problems. As a result of extensive research, the present invention makes full use of fine processing techniques such as electron beam lithography, photolithography, and focused ion beam (FIB). Thus, it has been newly found that a base material in which a hollow cylinder having a through-hole capable of passing a harmful / dangerous substance in a unit of one molecule is formed on a substrate can be produced. Based on the base material, an analysis chip can be produced by forming an electrode around the through-hole and a metal vapor deposition layer and / or nanowire inside the hollow cylindrical body. We found that there is a possibility that dangerous substances can be captured, identified and detected.
すなわち、本発明の目的は、有害・危険物質を一分子単位の高感度で且つ短時間で検出することができ、更に、多種類の物質を識別するための有害・危険物質の分析用チップを作製するための、ベースとなる基材を提供することである。 That is, an object of the present invention is to detect harmful / dangerous substances in a single molecule unit with high sensitivity and in a short time, and to provide a chip for analyzing harmful / dangerous substances for identifying many kinds of substances. It is to provide a base material to be used as a base.
本発明は、以下に示す、基材及び該基材の製造方法に関する。 The present invention relates to a base material and a method for producing the base material described below.
（１）基板、及び一端が前記基板上に形成され他端が上方に開放している中空の筒体を含み、
前記中空の筒体には、筒体の内側と外側を貫通する貫通孔が少なくとも１以上形成され、
前記基板には、前記中空の筒体の中空部と前記基板の反対側を連通するための貫通孔が形成されていることを特徴とする基材。
（２）基板、及び一端が前記基板上に形成され他端が上方に開放している中空の筒体を含み、
前記中空の筒体には、高さの異なる位置に、筒体の内側と外側を貫通する貫通孔が少なくとも２以上形成されていることを特徴とする基材。
（３）前記中空の筒体から離れた位置に、前記中空の筒体を覆うように外郭部が形成されていることを特徴とする上記（１）又は（２）に記載の基材。
（４）前記中空の筒体と外郭部の高さが異なることを特徴とする上記（１）〜（３）の何れか一に記載の基材。
（５）前記中空の筒体に蓋が形成されていることを特徴とする上記（１）〜（４）の何れか一に記載の基材。
（６）基板上に積層した中空の筒体又は中空の筒体及び外郭部を形成するための材料の中に充填材を閉じ込める工程、
前記材料の表面に、中空の筒体又は中空の筒体及び外郭部に相当する部分にフォトレジストを形成する工程、
前記フォトレジストが形成されていない部分の前記材料を、前記基板までエッチングする工程、
前記材料の中に閉じ込まれた充填材、及び前記材料の表面のフォトレジストを除去する工程、
を含むことを特徴とする貫通孔を有する中空の筒体を基板上に形成した基材の製造方法。
（７）前記基板上に積層した中空の筒体又は中空の筒体及び外郭部を形成するための材料の中に充填材を閉じ込める工程が、
前記基板上に中空の筒体又は中空の筒体及び外郭部を形成する材料を積層する工程、
前記材料をエッチングして形成した孔に充填材を充填する工程、及び、
前記充填材を充填した後に、中空の筒体又は中空の筒体及び外郭部を形成する材料を積層する工程、
を少なくとも１回以上含む、
ことを特徴とする上記（６）に記載の製造方法。
（８）基板上に、中空の筒体を形成するための材料を堆積して中空の筒体を形成する工程、
前記中空の筒体に貫通孔を形成する工程、
を含むことを特徴とする貫通孔を有する中空の筒体を基板上に形成した基材の製造方法。
（９）前記中空の筒体に貫通孔を形成する工程の後に、
前記中空の筒体から離れた位置に前記中空の筒体を覆うように外郭部を形成する工程、
を含むことを特徴とする上記（８）に記載の製造方法。
（１０）基板上に、中空の筒体を形成するための材料を堆積して中空の筒体を形成する工程、
前記中空の筒体から離れた位置に前記中空の筒体を覆うように外郭部を形成する工程、
前記中空の筒体に貫通孔を形成する工程、
を含むことを特徴とする貫通孔を有する中空の筒体を基板上に形成した基材の製造方法。
（１１）前記基板に貫通孔を形成する工程を更に含むことを特徴とする上記（６）〜（１０）の何れか一に記載の製造方法。
(1) including a substrate and a hollow cylinder having one end formed on the substrate and the other end opened upward;
The hollow cylinder is formed with at least one or more through holes penetrating the inside and outside of the cylinder,
The substrate is characterized in that a through hole for communicating the hollow portion of the hollow cylindrical body and the opposite side of the substrate is formed in the substrate.
(2) including a substrate and a hollow cylinder having one end formed on the substrate and the other end opened upward;
The hollow cylindrical body has at least two or more through holes penetrating the inner side and the outer side of the cylindrical body at positions having different heights.
(3) The base material according to (1) or (2), wherein an outer portion is formed at a position away from the hollow cylinder so as to cover the hollow cylinder.
(4) The substrate according to any one of (1) to (3) above, wherein the hollow cylindrical body and the outer shell have different heights.
(5) The substrate according to any one of (1) to (4), wherein a lid is formed on the hollow cylindrical body.
(6) A process of confining a filler in a hollow cylinder or a material for forming a hollow cylinder and an outer shell laminated on a substrate,
A step of forming a photoresist on the surface of the material in a portion corresponding to a hollow cylinder or a hollow cylinder and an outer shell;
Etching the portion of the material where the photoresist is not formed to the substrate;
Removing the filler confined in the material and the photoresist on the surface of the material;
The manufacturing method of the base material which formed the hollow cylinder which has a through-hole characterized by including on a board | substrate.
(7) The step of confining the filler in the hollow cylinder or the material for forming the hollow cylinder and the outer shell laminated on the substrate,
A step of laminating a material that forms a hollow cylinder or a hollow cylinder and an outer portion on the substrate;
Filling a hole formed by etching the material with a filler; and
A step of laminating a material for forming a hollow cylinder or a hollow cylinder and an outer shell after filling the filler;
Including at least once,
The manufacturing method as described in said (6) characterized by the above-mentioned.
(8) A step of depositing a material for forming a hollow cylinder on the substrate to form a hollow cylinder;
Forming a through hole in the hollow cylinder,
The manufacturing method of the base material which formed the hollow cylinder which has a through-hole characterized by including on a board | substrate.
(9) After the step of forming a through hole in the hollow cylinder,
Forming an outer shell so as to cover the hollow cylinder at a position away from the hollow cylinder;
The manufacturing method as described in said (8) characterized by including.
(10) A step of depositing a material for forming a hollow cylinder on the substrate to form a hollow cylinder;
Forming an outer shell so as to cover the hollow cylinder at a position away from the hollow cylinder;
Forming a through hole in the hollow cylinder,
The manufacturing method of the base material which formed the hollow cylinder which has a through-hole characterized by including on a board | substrate.
(11) The manufacturing method according to any one of (6) to (10), further including a step of forming a through hole in the substrate.
本発明の基材は、電子線リソグラフィ、フォトリソグラフィ、集束イオンビーム（Ｆｏｃｕｓｅｄ Ｉｏｎ Ｂｅａｍ；ＦＩＢ）等の微細加工技術を駆使することで、任意の大きさ、個数及び位置に貫通孔を有し、内径の大きさも任意である中空の筒体を基板上に形成することができる。そして、貫通孔を通過する有害・危険物質を測定することで有害・危険物質のサイズを測定し、中空の筒体の内側に形成した金属蒸着層やナノワイヤで有害・危険物質を濃縮・識別できる可能性がある。したがって、本発明の基材をベースとすることで、有害・危険物質を一分子単位の高感度で且つ短時間で検出することができ、更に、多種類の物質を識別できる分析用チップの提供が可能となる。 The substrate of the present invention has through holes in any size, number and position by making full use of microfabrication technology such as electron beam lithography, photolithography, and focused ion beam (FIB). A hollow cylinder having an arbitrary inner diameter can be formed on the substrate. The size of harmful and dangerous substances can be measured by measuring the harmful and dangerous substances passing through the through hole, and the hazardous and dangerous substances can be concentrated and identified by the metal vapor deposition layer and nanowire formed inside the hollow cylinder. there is a possibility. Therefore, by using the base material of the present invention as a base, it is possible to detect harmful / dangerous substances in a single molecule unit with high sensitivity and in a short time, and further provide an analysis chip that can identify many kinds of substances. Is possible.
以下に、本発明の基材及び該基材の製造方法について詳しく説明する。 Below, the base material of this invention and the manufacturing method of this base material are demonstrated in detail.
図１は、本発明の基材１の第１実施形態を示している。本発明の基材１は、基板２、基板２上に形成された中空の筒体（以下、「筒体」と記載することがある。）３を含んでいる。筒体３の一端は基板２上に形成され他端は上方に開放しており、筒体３には筒体の内側と外側を貫通する貫通孔３１が少なくとも１以上形成されている。１枚の基板２上に形成する筒体３の数は特に制限はない。間隔を詰め過ぎると、分析用チップとする場合の回路配線が複雑となり、間隔をあけすぎると分析効率が低くなるので、分析目的に応じて適宜調整すればよい。 FIG. 1 shows a first embodiment of a substrate 1 of the present invention. The base material 1 of the present invention includes a substrate 2 and a hollow cylinder (hereinafter sometimes referred to as “cylinder”) 3 formed on the substrate 2. One end of the cylindrical body 3 is formed on the substrate 2 and the other end is opened upward, and the cylindrical body 3 is formed with at least one or more through holes 31 penetrating the inner side and the outer side of the cylindrical body. The number of the cylinders 3 formed on one substrate 2 is not particularly limited. If the interval is too small, circuit wiring in the case of an analysis chip becomes complicated, and if the interval is too large, the analysis efficiency decreases. Therefore, it may be appropriately adjusted according to the purpose of analysis.
本発明の基材１は、後述する微細加工技術を用いた製造工程で製造することから、基板２、筒体３は、半導体製造技術の分野で一般的に用いられている絶縁性の材料であれば特に制限は無い。基材２の材料としては、例えば、Ｓｉ、Ｇｅ、Ｓｅ、Ｔｅ、ＧａＡｓ、ＧａＰ、ＧａＮ、ＩｎＳｂ、ＩｎＰ等が挙げられる。また、筒体３の材料としては、例えば、ＳｉＯ2、Ｓｉ3Ｎ4、ＢＰＳＧ、ＳｉＯＮ等が挙げられる。 Since the base material 1 of the present invention is manufactured by a manufacturing process using a microfabrication technique described later, the substrate 2 and the cylinder 3 are made of an insulating material generally used in the field of semiconductor manufacturing technology. If there is no particular limitation. Examples of the material of the base material 2 include Si, Ge, Se, Te, GaAs, GaP, GaN, InSb, and InP. The material of the cylindrical body 3, for example, SiO 2, Si 3 N 4 , BPSG, SiON , and the like.
図２は、図１に示す基材１のＡ−Ａ’断面図であって、基板２と筒体３の構造、及び基材１をベースに分析用チップを作製した場合の使用形態を示している。基板２には、筒体３の内側の中空部３２と基板２の反対側を連通するための貫通孔２１が形成されている。そのため、中空部３２に入ったサンプル液５を基材１の外部に排出することができ、中空部３２内には、下流方向へのサンプル液５の流れができる。したがって、図２に示すように、上方からサンプル液５を投入すると、サンプル液５中の物質４を筒体３の外側から貫通孔３１を通過させることができ、貫通孔３１を流れるイオン電流を計測することで、物質４のサイズを識別することができる。なお、図２では、サンプル液５を上方から投入する例を示しているが、サンプル液５は、基板２上に堆積するよう投入してもよく、筒体３を形成する間隔により適宜調整すればよい。また、中空部３２に直接侵入する物質４を少なくし、貫通孔３１を通過する物質４を多くするため、必要に応じて、中空部３２の上方の開口部分に蓋をしてもよい。当該蓋は、例えば、シリコン等で作製したシートを載せればよい。勿論、蓋は前記の例に限定されず、樹脂を充填する等、中空部３２の開口部分に蓋をすることができれば特に制限は無い。なお、本発明において、「蓋」は、中空部３２の開口部分を完全に塞いで密封状態にするのみでなく、開口部分の一部を塞ぐことも含む意味である。 FIG. 2 is a cross-sectional view taken along the line AA ′ of the base material 1 shown in FIG. 1, and shows the structure of the substrate 2 and the cylindrical body 3 and the mode of use when an analysis chip is produced based on the base material 1. ing. The substrate 2 is formed with a through hole 21 for communicating the hollow portion 32 inside the cylindrical body 3 with the opposite side of the substrate 2. Therefore, the sample liquid 5 that has entered the hollow portion 32 can be discharged to the outside of the substrate 1, and the sample liquid 5 can flow in the downstream direction in the hollow portion 32. Therefore, as shown in FIG. 2, when the sample liquid 5 is introduced from above, the substance 4 in the sample liquid 5 can be passed through the through hole 31 from the outside of the cylindrical body 3, and the ionic current flowing through the through hole 31 is reduced. By measuring, the size of the substance 4 can be identified. Although FIG. 2 shows an example in which the sample liquid 5 is introduced from above, the sample liquid 5 may be introduced so as to be deposited on the substrate 2 and is appropriately adjusted depending on the interval at which the cylindrical body 3 is formed. That's fine. Further, in order to reduce the amount of the substance 4 that directly enters the hollow portion 32 and increase the amount of the substance 4 that passes through the through hole 31, a lid may be provided on the opening portion above the hollow portion 32 as necessary. For example, a sheet made of silicon or the like may be placed on the lid. Of course, the lid is not limited to the above example, and there is no particular limitation as long as the lid can be covered at the opening of the hollow portion 32 such as filling with resin. In the present invention, the “lid” means not only that the opening portion of the hollow portion 32 is completely closed and sealed, but also that the opening portion is partially closed.
筒体３の内部には、例えば、Ｐｔ、Ａｕ、Ａｇ、Ａｇ／ＡｇＣｌ等の金属蒸着層３３を形成してイオン電流を検出することで物質４を検出することができる。また、ナノワイヤ３４を形成することで、物質４を捕捉・濃縮することができ、物質４が生体細胞の場合は、破砕したりすることもできる。 The substance 4 can be detected by forming a metal vapor deposition layer 33 of Pt, Au, Ag, Ag / AgCl or the like inside the cylindrical body 3 and detecting an ionic current. In addition, by forming the nanowire 34, the substance 4 can be captured and concentrated. When the substance 4 is a living cell, it can be crushed.
ナノワイヤは、金、プラチナ、アルミ、銅、鉄、コバルト、銀、錫、インジウム、亜鉛、ガリウム等の触媒を筒体３の内面に蒸着し、ＳｉＯ2、Ｌｉ2Ｏ、ＭｇＯ、Ａｌ2Ｏ3、ＣａＯ、ＴｉＯ2、Ｍｎ2Ｏ3、Ｆｅ2Ｏ3、ＣｏＯ、ＮｉＯ、ＣｕＯ、ＺｎＯ、Ｇａ2Ｏ3、ＳｒＯ、Ｉｎ2Ｏ3、ＳｎＯ2、Ｓｍ2Ｏ3、ＥｕＯ等の材料を用い、パルスレーザーデポジション、ＶＬＳ（Ｖａｐｏｒ−Ｌｉｑｕｉｄ−Ｓｏｌｉｄ）法等の物理蒸着法でナノワイヤを形成すればよい。また、必要に応じて、ＳｉＯ2、ＴｉＯ2等を用い、スパッタリング、ＥＢ蒸着、ＰＶＤ、ＡＬＤ等の一般的な蒸着法により、形成したナノワイヤの周囲に被覆層を形成してもよい。 Nanowires deposited gold, platinum, aluminum, copper, iron, cobalt, silver, tin, indium, zinc, the catalyst inner surface of the cylindrical body 3 such as gallium, SiO 2, Li 2 O, MgO, Al 2 O 3 , CaO, TiO 2, Mn 2 O 3, Fe 2 O 3, CoO, NiO, CuO, ZnO, Ga 2 O 3, SrO, in 2 O 3, SnO 2, Sm 2 O 3, a material such as EuO using Nanowires may be formed by physical vapor deposition such as pulse laser deposition or VLS (Vapor-Liquid-Solid). Further, if necessary, a coating layer may be formed around the formed nanowires by using a general vapor deposition method such as sputtering, EB vapor deposition, PVD, or ALD using SiO 2 , TiO 2 or the like.
また、基板２に形成した貫通孔２１を挟むように電極を形成することで、物質４が通過する際のイオン電流やトンネル電流を計測することができ、分子サイズや分子構造を識別することができる。 Further, by forming electrodes so as to sandwich the through-hole 21 formed in the substrate 2, ion current and tunnel current when the substance 4 passes can be measured, and molecular size and molecular structure can be identified. it can.
図２に示す実施形態の場合、物質４は上方から筒体３の中空部３２に入り、基板２の貫通孔２１から流出する。そのため、金属蒸着層３３やナノワイヤ３４等の分析手段を筒体３の内面に形成するためには、貫通孔３１と貫通孔２１の距離が長い方が好ましい。したがって、貫通孔３１は、筒体３の中間部より上方（基板２と離れる方向）に形成することが好ましく、１／４より上方に形成することがより好ましく、破損しない強度を維持できる範囲内で筒体３の上方端部近傍に形成することが特に好ましい。なお、一つの筒体３に形成する貫通孔３１は、一つでも複数であってもよい。複数形成する場合は、基板２からの距離が同じ位置に貫通孔３１を形成してもよいし、基板２からの距離が異なる位置に貫通孔３１を形成してもよい。また、貫通孔３１の大きさは、同じであっても異なっていてもよい。更に、各々の筒体３に形成する貫通孔３１の大きさ、個数及び位置は同じであってもよいし、異なっていてもよい。 In the case of the embodiment shown in FIG. 2, the substance 4 enters the hollow portion 32 of the cylindrical body 3 from above and flows out from the through hole 21 of the substrate 2. Therefore, in order to form analysis means such as the metal vapor deposition layer 33 and the nanowire 34 on the inner surface of the cylindrical body 3, it is preferable that the distance between the through hole 31 and the through hole 21 is long. Accordingly, the through hole 31 is preferably formed above the middle part of the cylindrical body 3 (in the direction away from the substrate 2), more preferably formed above ¼, and within a range in which strength that does not break can be maintained. It is particularly preferable to form near the upper end of the cylindrical body 3. In addition, the through-hole 31 formed in the one cylinder 3 may be one or more. In the case of forming a plurality, the through holes 31 may be formed at the same distance from the substrate 2 or the through holes 31 may be formed at different positions from the substrate 2. Moreover, the size of the through hole 31 may be the same or different. Further, the size, number and position of the through holes 31 formed in each cylinder 3 may be the same or different.
貫通孔３１の大きさは、物質４が通過することで物質４のサイズの分析ができれば特に制限は無いが、イオン電流は物質４が通過する際の貫通孔３１内の溶液の体積変化を測定することから、分析対象物質４が通過できる大きさで、可能な限り小さくすることが好ましい。例えば、空気中のＰＭ２．５の直径は約２．５μｍであるので、貫通孔３１の直径は３μｍ程度の大きさであればよい。また、スギ花粉の直径は約２０〜４０μｍ、ヒノキ花粉の直径は２８μｍ〜４５μｍ程度と言われているので、貫通孔３１の直径は約５０μｍ程度であればよい。勿論、上記の数値は目安であって、物質４がさらに大きな場合は、貫通孔３１の直径を１００μ、１５０μｍ、２００μｍ等、物質４のサイズに応じて大きくしてもよい。貫通孔３１の直径は、後述する製造工程において、筒体３を形成する材料をエッチングする深さで調整することができる。一方、貫通孔３１の直径の下限は、エッチングした箇所に充填する充填材の分子レベルの大きさまで小さくすることができるが、貫通孔３１の直径が小さすぎると、高圧をかけないとサンプル溶液５が貫通孔３１及び貫通孔２１を通過せず、基材１が電気的に破壊される恐れがある。そのため、分析対象である物質４のサイズよりは大きく、且つ、１００ｎｍ以上が好ましく、５００ｎｍ以上がより好ましく、１μｍ以上が特に好ましい。また、筒体３の厚さに関しても、厚さが薄いほど貫通孔３１の体積が少なくなり、検出感度が向上することから、強度を考慮しながら可能な限り薄くすることが望ましい。 The size of the through hole 31 is not particularly limited as long as the size of the substance 4 can be analyzed by passing the substance 4, but the ion current measures the volume change of the solution in the through hole 31 when the substance 4 passes. Therefore, it is preferable to make the analysis target substance 4 as small as possible so that the analysis target substance 4 can pass therethrough. For example, since the diameter of PM2.5 in the air is about 2.5 μm, the diameter of the through hole 31 may be about 3 μm. Moreover, since the diameter of the cedar pollen is about 20 to 40 μm and the diameter of the cypress pollen is said to be about 28 μm to 45 μm, the diameter of the through hole 31 may be about 50 μm. Of course, the above numerical values are only a guide, and when the substance 4 is larger, the diameter of the through-hole 31 may be increased according to the size of the substance 4 such as 100 μm, 150 μm, 200 μm. The diameter of the through-hole 31 can be adjusted with the depth which etches the material which forms the cylinder 3 in the manufacturing process mentioned later. On the other hand, the lower limit of the diameter of the through hole 31 can be reduced to the molecular level of the filler to be filled in the etched portion. However, if the diameter of the through hole 31 is too small, the sample solution 5 must be subjected to high pressure. May not pass through the through-hole 31 and the through-hole 21, and the base material 1 may be electrically destroyed. Therefore, it is larger than the size of the substance 4 to be analyzed, and is preferably 100 nm or more, more preferably 500 nm or more, and particularly preferably 1 μm or more. Further, regarding the thickness of the cylindrical body 3, the thinner the thickness, the smaller the volume of the through hole 31 and the detection sensitivity is improved. Therefore, it is desirable to make it as thin as possible in consideration of strength.
筒体３の高さは、上記の金属蒸着層３３、ナノワイヤ３４等の分析手段を、貫通孔３１と基板２の間に形成できる長さがあれば特に制限は無いが、長すぎると破損し易くなることから、分析手段を形成できる範囲内で可能な限り短くすることが好ましい。 The height of the cylindrical body 3 is not particularly limited as long as the analysis means such as the metal vapor deposition layer 33 and the nanowire 34 can be formed between the through hole 31 and the substrate 2. Since it becomes easy, it is preferable to shorten as much as possible within the range which can form an analysis means.
基板２に形成する貫通孔２１の直径は、筒体３の貫通孔３１と同じでよい。また、基板２の厚さも、筒体３の厚さと同様に薄い方が好ましいことから、製造が可能で強度が維持できる範囲内の厚さとすればよい。 The diameter of the through hole 21 formed in the substrate 2 may be the same as that of the through hole 31 of the cylindrical body 3. Moreover, since it is preferable that the thickness of the substrate 2 is as thin as the thickness of the cylindrical body 3, the thickness may be set within a range in which the manufacturing is possible and the strength can be maintained.
中空部３２の直径は、貫通孔３１を通過した物質４が通過することから、少なくとも、貫通孔３１の直径以上である必要がある。一方、貫通孔３１の直径に対する中空部３２の直径が大きくなり過ぎると、サンプル液５を上方から投入する場合、貫通孔３１を通過せず直接直中空部３２に入る物質４が多くなることから、中空部３２の直径は、貫通孔３１の１０倍程度が好ましく、５倍程度がより好ましく、２倍程度が特に好ましい。 The diameter of the hollow portion 32 needs to be at least equal to or larger than the diameter of the through hole 31 because the substance 4 that has passed through the through hole 31 passes therethrough. On the other hand, if the diameter of the hollow portion 32 with respect to the diameter of the through hole 31 becomes too large, the amount of the substance 4 that directly enters the direct hollow portion 32 without passing through the through hole 31 increases when the sample liquid 5 is introduced from above. The diameter of the hollow portion 32 is preferably about 10 times that of the through hole 31, more preferably about 5 times, and particularly preferably about 2 times.
なお、上記のとおり、サンプル液５を基板２から堆積するように投入する場合は、貫通孔３１は中空部３２の先端より基板２側に形成されているので、貫通孔３１を通って中空部３２に入る物質４が多くなる。その場合、中空部３２の直径は、貫通孔３１の直径とは関係なく設定すればよく、上記の貫通孔３１の１０倍より更に大きくてもよい。また、中空部３２の開口部分に蓋をする場合も、同様に、中空部３２の直径は貫通孔３１の１０倍より更に大きくてもよい。 As described above, when the sample liquid 5 is poured so as to be deposited from the substrate 2, since the through hole 31 is formed on the substrate 2 side from the tip of the hollow portion 32, the hollow portion passes through the through hole 31. The number of substances 4 entering 32 increases. In that case, the diameter of the hollow portion 32 may be set regardless of the diameter of the through hole 31, and may be larger than 10 times the through hole 31. Similarly, when the opening portion of the hollow portion 32 is covered, the diameter of the hollow portion 32 may be larger than 10 times that of the through hole 31.
貫通孔３１及び貫通孔２１に形成する電極は、基材１を作製後、フォトリソグラフィ等の手段により形成すればよい。または、プリンター等により形成してもよい。 The through holes 31 and the electrodes formed in the through holes 21 may be formed by means such as photolithography after the substrate 1 is manufactured. Alternatively, it may be formed by a printer or the like.
図３は、本発明の基材１の第２実施形態を示す図である。図３に示す第２実施形態では、基板２に貫通孔を形成せず、筒体３の基板２に近い部分にサンプル液５の排出用の貫通孔３５を形成している。サンプル液５を上方から投入する場合、サンプル液５を中空部３２中で下流方向に流すことができればよいことから、基板２の貫通孔２１に代え、筒体３の基板２に近い部分に貫通孔３５を形成することで、同等の機能を達成することができる。貫通孔３１と貫通孔３５の間に、金属の蒸着層３３やナノワイヤ３４等の分析手段を形成することから、貫通孔３５と貫通孔３１は可能な限り、離して形成することが望ましい。第２実施形態の場合は、貫通孔３５は後述する製造工程中の充填材の塗布の位置を調整することで簡単に作製することができ、貫通孔２１を別途作製する手順が不要である。第２実施形態は、貫通孔２１に代え貫通孔３５を形成した以外は、第１実施形態と同様でよい。 FIG. 3 is a view showing a second embodiment of the substrate 1 of the present invention. In the second embodiment shown in FIG. 3, no through hole is formed in the substrate 2, and a through hole 35 for discharging the sample solution 5 is formed in a portion of the cylindrical body 3 close to the substrate 2. When the sample liquid 5 is introduced from above, it is only necessary that the sample liquid 5 can flow in the downstream direction in the hollow portion 32. By forming the hole 35, an equivalent function can be achieved. Since the analyzing means such as the metal vapor deposition layer 33 and the nanowire 34 is formed between the through hole 31 and the through hole 35, it is desirable to form the through hole 35 and the through hole 31 as far apart as possible. In the case of the second embodiment, the through hole 35 can be easily manufactured by adjusting the position of application of the filler during the manufacturing process described later, and a procedure for separately manufacturing the through hole 21 is not necessary. The second embodiment may be the same as the first embodiment except that the through hole 35 is formed instead of the through hole 21.
図４は、本発明の基材１の第３実施形態を示す図である。図４に示す第３実施形態では、第１実施形態又は第２実施形態の基材１の筒体３から離れた位置に、筒体３を覆うように外郭部６が形成されている。外郭部６は後述する製造工程で、フォトレジストの形状を変え、筒体３の周りをエッチングすることで中空部３２と同時に形成することができる。外郭部６を形成することで、分析手段が形成されている筒体３を保護することができる。また、フォトレジストの形状を変え、エッチングの手順を変えることで、筒体３の高さと比較して、外郭部６の高さを低くすることも、高くすることもできる。筒体３の外側と外郭部６の内側の距離は、物質４が入る大きさ以上であれば特に制限は無い。 FIG. 4 is a diagram showing a third embodiment of the substrate 1 of the present invention. In 3rd Embodiment shown in FIG. 4, the outer part 6 is formed so that the cylinder 3 may be covered in the position away from the cylinder 3 of the base material 1 of 1st Embodiment or 2nd Embodiment. The outer shell 6 can be formed at the same time as the hollow portion 32 by changing the shape of the photoresist and etching around the cylindrical body 3 in the manufacturing process described later. By forming the outer shell 6, the cylindrical body 3 on which the analysis means is formed can be protected. Further, by changing the shape of the photoresist and changing the etching procedure, the height of the outer shell 6 can be made lower or higher than the height of the cylindrical body 3. The distance between the outer side of the cylindrical body 3 and the inner side of the outer shell 6 is not particularly limited as long as it is larger than the size in which the substance 4 can enter.
図５は、基材１の製造工程の一例を示す図であって、筒体３の基板２に近い部分に貫通孔３５を２か所、上端に近い部分に貫通孔３１を２か所、及び外郭部６を形成する例を示している。
（１）基板２の上に、筒体３及び外郭部６を形成する材料７を化学蒸着で塗布する。
（２）ポジ型フォトレジスト８をスピンコータで塗布する。
（３）貫通孔３５を形成する個所に光が照射するように、フォトマスクを用いて露光・現像処理し、貫通孔３５を形成する部分のポジ型フォトレジスト８を除去する。
（４）貫通孔３５の直径に相当する深さとなるようにエッチングする。
（５）エッチングした箇所に充填材８１を充填する。
（６）材料７を化学蒸着で塗布して、貫通孔３５を形成する部分の充填材８１を材料７中に閉じ込める。
（７）上記（２）〜（６）の手順を繰り返し、貫通孔を形成したい箇所に充填材８１を閉じ込める。次いで、材料７の表面にポジ型フォトレジスト８を塗布し、露光・現像処理により、筒体３及び外郭部６に相当する部分はポジ型フォトレジスト８を残し、それ以外のポジ型フォトレジスト８を除去する。
（８）ポジ型フォトレジスト８が形成されていない部分を基板２に到達するまでエッチングする。
（９）ポジ型フォトレジスト８及び充填材８１を除去することで貫通孔３１及び貫通孔３５を形成した筒体３及び外郭部６を形成する。
FIG. 5 is a diagram illustrating an example of a manufacturing process of the base material 1, and includes two through holes 35 in a portion near the substrate 2 of the cylindrical body 3 and two through holes 31 in a portion near the upper end. And the example which forms the outer shell part 6 is shown.
(1) A material 7 for forming the cylindrical body 3 and the outer shell 6 is applied on the substrate 2 by chemical vapor deposition.
(2) A positive photoresist 8 is applied by a spin coater.
(3) Exposure / development processing is performed using a photomask so that light is irradiated to a portion where the through hole 35 is to be formed, and the positive photoresist 8 in the portion where the through hole 35 is to be formed is removed.
(4) Etching is performed to a depth corresponding to the diameter of the through hole 35.
(5) The filler 81 is filled in the etched portion.
(6) The material 7 is applied by chemical vapor deposition, and the portion of the filler 81 that forms the through hole 35 is confined in the material 7.
(7) The procedures (2) to (6) are repeated, and the filler 81 is confined in a place where a through hole is to be formed. Next, a positive photoresist 8 is applied to the surface of the material 7, and exposure / development processes leave the positive photoresist 8 at portions corresponding to the cylindrical body 3 and the outer shell 6, and the other positive photoresist 8. Remove.
(8) The portion where the positive photoresist 8 is not formed is etched until it reaches the substrate 2.
(9) By removing the positive photoresist 8 and the filler 81, the cylindrical body 3 and the outer portion 6 in which the through hole 31 and the through hole 35 are formed are formed.
なお、図４に示す第３実施形態の基材１を製造する場合は、貫通孔３５に相当する充填材８１を材料７に閉じ込める工程を省略し、上記工程（９）の後に、基板２の反対側から貫通孔２１を形成すればよい。貫通孔２１は、以下に示すウエットエッチングで形成することができる。
（ｉ）基板２の裏面に、貫通孔２１の大きさに応じた開口部を持ったメタルマスクを用いて、クロム蒸着を行う。
（ｉｉ）ＲＩＥ−１０ＮＲ−ＮＰを用いて、裏面の酸化膜をエッチングする。
（ｉｉｉ）裏面のみをＫＯＨ溶液に漬けて、ウエットエッチングを行う。
In addition, when manufacturing the base material 1 of 3rd Embodiment shown in FIG. 4, the process of confining the filler 81 equivalent to the through-hole 35 in the material 7 is abbreviate | omitted, and the board | substrate 2 of the board | substrate 2 is skipped after the said process (9). The through hole 21 may be formed from the opposite side. The through hole 21 can be formed by wet etching as described below.
(I) Chromium vapor deposition is performed using a metal mask having an opening corresponding to the size of the through hole 21 on the back surface of the substrate 2.
(Ii) The oxide film on the back surface is etched using RIE-10NR-NP.
(Iii) Only the back surface is immersed in a KOH solution and wet etching is performed.
基材１の微細な貫通孔２１、３５や中空部３２等にサンプル液５が流れやすくするために、作製した基材１は親水化処理をしてもよい。親水化処理方法としては、プラズマ処理、界面活性剤処理、ＰＶＰ（ポリビニルピロリドン）処理、光触媒等が挙げられ、例えば、基材１の表面を１０〜３０秒間プラズマ処理することで、表面に水酸基を導入することができる。 In order to make the sample liquid 5 easily flow into the fine through holes 21 and 35 and the hollow portion 32 of the base material 1, the produced base material 1 may be subjected to a hydrophilic treatment. Examples of the hydrophilic treatment method include plasma treatment, surfactant treatment, PVP (polyvinylpyrrolidone) treatment, photocatalyst and the like. For example, the surface of the substrate 1 is subjected to plasma treatment for 10 to 30 seconds, whereby hydroxyl groups are formed on the surface. Can be introduced.
また、材料７、ポジ型フォトレジスト８の塗布・積層方法も上記の例に限定されず、半導体製造分野で一般的に用いられている方法であれば特に制限は無い。また、充填材８１としては、最終的に閉じ込めた場所から溶剤等を用いて除去できるものであれば特に制限は無い。例えば、樹脂や金属等が挙げられるが、充填材８１としてポジ型フォトレジスト８を用いると、工程（９）で表面に残留しているポジ型フォトレジスト８の除去と同じ工程で充填材８１を除去できるので、製造工程の簡略化の観点から望ましい。 Also, the method for applying and laminating the material 7 and the positive photoresist 8 is not limited to the above example, and there is no particular limitation as long as it is a method generally used in the semiconductor manufacturing field. Further, the filler 81 is not particularly limited as long as it can be removed from the finally confined place using a solvent or the like. For example, resin or metal can be used. When positive photoresist 8 is used as filler 81, filler 81 is removed in the same step as the removal of positive photoresist 8 remaining on the surface in step (9). This is desirable from the viewpoint of simplifying the manufacturing process.
ポジ型フォトレジスト８としては、ＴＳＭＲ Ｖ５０、ＰＭＥＲ等、半導体製造分野で一般的に使用されているものであれば特に制限はない。また、ポジ型に代え、ネガティブ型のフォトレジストを用いてもよく、ＳＵ−８、ＫＭＰＲ等、半導体製造分野で一般的に使用されているものであれば特に制限はない。フォトレジストの除去液は、ジメチルホルムアミドとアセトン等、半導体分野で一般的な除去液であれば特に制限はない。 The positive photoresist 8 is not particularly limited as long as it is generally used in the semiconductor manufacturing field, such as TSMR V50, PMER. In addition, a negative type photoresist may be used instead of the positive type, and there is no particular limitation as long as it is generally used in the semiconductor manufacturing field, such as SU-8 and KMPR. The photoresist removal solution is not particularly limited as long as it is a common removal solution in the semiconductor field, such as dimethylformamide and acetone.
図５に示した基材１の製造工程は、微細加工技術を利用してエッチング及び塗布を繰り返し、基板２上に多数の筒体３、外郭部６を同時に形成する方法であるが、基板２上に筒体３、外郭部６を堆積し、筒体３の任意の箇所に貫通孔を形成することで基材を製造することもできる。 The manufacturing process of the base material 1 shown in FIG. 5 is a method in which etching and coating are repeated using a microfabrication technique to form a large number of cylindrical bodies 3 and outer portions 6 on the substrate 2 at the same time. The base material can also be manufactured by depositing the cylindrical body 3 and the outer shell 6 on the top and forming a through hole at an arbitrary position of the cylindrical body 3.
図６は、筒体３及び外郭部６を作製する他の製造工程を示す図である。図６に示す製造工程では、
（１）オルトケイ酸テトラエチル（ＴＥＯＳ）、タングステン、カーボン、白金等の材料を、ガスインジェクション装置、液体金属イオン源等９を用いて基板２上に堆積して筒体３を形成する。
（２）ヘリウムイオン顕微鏡、ガリウムイオン等の集束イオンビーム（Ｆｏｃｕｓｅｄ Ｉｏｎ Ｂｅａｍ；ＦＩＢ）１０を用いて、筒体３の任意の箇所に貫通孔３１を形成する。
（３）前記（１）と同様の材料及び手順で外郭部６を堆積する。なお、筒体３には既に貫通孔３１が形成されているので、外郭部６の高さは筒体３より高くしてもよい。
FIG. 6 is a diagram showing another manufacturing process for producing the cylindrical body 3 and the outer shell 6. In the manufacturing process shown in FIG.
(1) A cylinder 3 is formed by depositing a material such as tetraethyl orthosilicate (TEOS), tungsten, carbon, or platinum on the substrate 2 using a gas injection device, a liquid metal ion source 9 or the like.
(2) A through-hole 31 is formed at an arbitrary position of the cylindrical body 3 using a focused ion beam (FIB) 10 such as a helium ion microscope or gallium ion.
(3) The outer portion 6 is deposited by the same material and procedure as in (1) above. In addition, since the through-hole 31 has already been formed in the cylinder 3, the height of the outer shell 6 may be higher than that of the cylinder 3.
図７は、図６に示す製造工程を一部変更した例を示している。図７に示す製造工程では、図６の工程の（２）と（３）の順番を変えている。なお、図７に示す製造工程の場合、工程（３）で筒体３に貫通孔３１を形成するため、工程（２）において、外郭部６は筒体３より低くすることが好ましい。 FIG. 7 shows an example in which the manufacturing process shown in FIG. 6 is partially changed. In the manufacturing process shown in FIG. 7, the order of (2) and (3) in the process of FIG. 6 is changed. In the case of the manufacturing process shown in FIG. 7, since the through hole 31 is formed in the cylindrical body 3 in the process (3), the outer portion 6 is preferably made lower than the cylindrical body 3 in the process (2).
図５に示す製造工程では、貫通孔３１（３５）を形成する位置及び大きさが同じである筒体３を一度に大量に製造する場合に有用である。一方、図６及び７に示す製造方法は、貫通孔３１（３５）の位置及び大きさを、筒体３毎に任意の場所に形成することができる。したがって、一つの基板２上の筒体３毎に異なる微粒子を検出する場合に有用である。 The manufacturing process shown in FIG. 5 is useful when a large number of cylindrical bodies 3 having the same position and size for forming the through holes 31 (35) are manufactured at a time. On the other hand, in the manufacturing method shown in FIGS. 6 and 7, the position and size of the through hole 31 (35) can be formed at any place for each cylindrical body 3. Therefore, it is useful when different particles are detected for each cylinder 3 on one substrate 2.
以下に実施例を掲げ、本発明を具体的に説明するが、この実施例は単に本発明の説明のため、その具体的な態様の参考のために提供されているものである。これらの例示は本発明の特定の具体的な態様を説明するためのものであるが、本願で開示する発明の範囲を限定したり、あるいは制限することを表すものではない。 The present invention will be described in detail with reference to the following examples, which are provided merely for the purpose of illustrating the present invention and for reference to specific embodiments thereof. These exemplifications are for explaining specific specific embodiments of the present invention, but are not intended to limit or limit the scope of the invention disclosed in the present application.
＜実施例１＞
以下の手順により、基材１を作製した。
先ず、基板２の前処理として、厚さ３００μｍのＢｅａｒ−Ｓｉを、ＵＶ−１（Ｓａｍｃｏ社製）を用い、オゾン洗浄（３００℃、１５分）を行った。
（１）次に、ＰＤ−２００ＳＴＰ（Ｓａｍｃｏ社製）を用い、ＴＥＯＳ １２ｓｃｃｍ、Ｏ２ ４００ｓｃｃｍ、１５０Ｗ、４０Ｐａ、２００℃の条件で、ＳｉＯ2を約２．４μｍ積層した。
（２）ポジ型フォトレジスト８（ＺＥＰ−５２０Ａ：Ａ７＝１：１）を、スピンコータ（５０００ｒｐｍ、９０秒）により塗布した。塗布後は、ホットプレートで１８０℃、３分、ベークした。
（３）ＥＬＴ−１００Ｔ（Ｅｌｉｏｎｉｘｓ社製）を用い、貫通孔３１を形成する個所に光が照射するように、フォトマスクを用いて露光した。露光後は、ＺＥＤ−Ｎ５０を用いて室温で９０秒現像した。次いで、ＳＶＣ−７００ＬＲＦ（サンユー電子製）を用い、５０Ｗ、０．２Ｐａ、Ａｒ ８ｓｃｃｍの条件でＣｒの金属マスクを行い、ＤＭＦを用いてリフトオフを行った。
（４）ＲＩＥ−１０ＮＲ−ＮＰを用いて、ＣＦ４ １５ｓｃｃｍ、２００Ｗ，１０Ｐａの条件で、深さが約２μｍとなるようにＳｉＯ2をエッチングした。
（５）エッチングした部分に、スピンコータ―（３０００ｒｐｍ、６０秒）を用いて、ＴＳＭＲ−Ｖ５０ＥＬを充填した。充填後、ホットプレートで、１１０℃、３分、ベークした。次いで、反応性イオンエッチング装置（ＲＩＥ−１０ＮＲ−ＮＰ）を用いて、Ｏ2 １６ｓｃｃｍ、２０Ｐａ、５０Ｗ、３分の条件で、材料表面のＴＳＭＲ−Ｖ５０ＥＬを除去した。
（６）上記（１）と同様の手順で、ＳｉＯ2を約２．４μｍ塗布した。
（７）上記（２）〜（６）の手順を２回以上繰り返した。次いで、ポジ型フォトレジストとしてＺＥＰ−５２０原液を用いた以外は、上記（２）と同様の手順でレジストの塗布を行った。次いで、上記（３）と同様の手順で、筒体３及び外郭部６以外の部分のレジストを除去した。
（８）上記（４）と同様の手順で、基板２に到達するまでＳｉＯ2のエッチングを行った。
（９）アセトンを用いて、ＳｉＯ2表面及びＳｉＯ2中のポジ型フォトレジストを除去し、純水で洗浄した。
<Example 1>
The base material 1 was produced according to the following procedure.
First, as a pretreatment of the substrate 2, 300 μm-thick Bear-Si was subjected to ozone cleaning (300 ° C., 15 minutes) using UV-1 (Samco).
(1) Next, using PD-200STP (Samco), about 2.4 μm of SiO 2 was laminated under the conditions of TEOS 12 sccm, O 2 400 sccm, 150 W, 40 Pa, 200 ° C.
(2) A positive photoresist 8 (ZEP-520A: A7 = 1: 1) was applied by a spin coater (5000 rpm, 90 seconds). After coating, it was baked on a hot plate at 180 ° C. for 3 minutes.
(3) Using ELT-100T (manufactured by Elionix), exposure was performed using a photomask so that light was irradiated to the portions where the through holes 31 were to be formed. After exposure, development was performed at room temperature for 90 seconds using ZED-N50. Next, using SVC-700LRF (manufactured by Sanyu Denshi), a Cr metal mask was formed under conditions of 50 W, 0.2 Pa, Ar 8 sccm, and lift-off was performed using DMF.
(4) Using RIE-10NR-NP, SiO 2 was etched to a depth of about 2 μm under the conditions of CF 4 15 sccm, 200 W, 10 Pa.
(5) The etched portion was filled with TSMR-V50EL using a spin coater (3000 rpm, 60 seconds). After filling, it was baked on a hot plate at 110 ° C. for 3 minutes. Next, TSMR-V50EL on the surface of the material was removed using a reactive ion etching apparatus (RIE-10NR-NP) under conditions of O 2 16 sccm, 20 Pa, 50 W for 3 minutes.
(6) About 2.4 μm of SiO 2 was applied in the same procedure as in (1) above.
(7) The above procedures (2) to (6) were repeated twice or more. Subsequently, the resist was applied in the same procedure as (2) except that the ZEP-520 stock solution was used as a positive photoresist. Subsequently, resists other than the cylindrical body 3 and the outer shell 6 were removed by the same procedure as the above (3).
(8) Etching of SiO 2 was performed until reaching the substrate 2 in the same procedure as in (4) above.
(9) Using acetone, the SiO 2 surface and the positive photoresist in SiO 2 were removed and washed with pure water.
図８（１）は実施例１で作製した基材１の電子顕微鏡写真で、図６（２）は図６（１）を拡大した写真である。作製した基材１の筒体３の外径は約５μｍ、内径は２．５μｍであった。外郭部６の外径は１０μｍ、内径は約７．５μｍであった。また、隣接する筒体３の中心間距離は、約４０μｍであった。筒体３及び外郭部６の高さは約５０μｍであった。なお、写真からは明らかではないが、貫通孔３１の直径は約２．４μｍであった。 FIG. 8 (1) is an electron micrograph of the substrate 1 produced in Example 1, and FIG. 6 (2) is an enlarged photograph of FIG. 6 (1). The cylindrical body 3 of the produced base material 1 had an outer diameter of about 5 μm and an inner diameter of 2.5 μm. The outer diameter of the outer shell 6 was 10 μm, and the inner diameter was about 7.5 μm. Further, the distance between the centers of the adjacent cylinders 3 was about 40 μm. The height of the cylindrical body 3 and the outer shell 6 was about 50 μm. Although not clear from the photograph, the diameter of the through hole 31 was about 2.4 μm.
＜実施例２＞
実施例１とは異なる以下の手順で基材１を作製した。
（１）ＴＥＯＳを、ガスインジェクション装置（Ｏｘｆｏｒｄ Ｉｎｓｔｒｕｍｅｎｔｓ，Ｉｎｃ．；ネオンガスを使用）を用い基板２上に塗布することで、基板２上にＳｉＯ2で作製された筒体３及び外郭部６を形成した。なお、外郭部６の高さは、筒体３より低くなるように形成した。
（２）ヘリウムイオン顕微鏡（ＯＲＩＯＮ ＮａｎｏＦａｂ；Ｃａｒｌ ＺｅｉｓｓＭｉｃｒｏｓｃｏｐｙ，Ｉｎｃ．）を用い、上記（１）で作製した筒体３に貫通孔３１を形成した。
<Example 2>
Substrate 1 was produced by the following procedure different from Example 1.
(1) TEOS is applied onto the substrate 2 using a gas injection device (Oxford Instruments, Inc .; using neon gas), thereby forming the cylindrical body 3 and the outer shell portion 6 made of SiO 2 on the substrate 2. did. Note that the height of the outer shell 6 was formed to be lower than that of the cylinder 3.
(2) The through-hole 31 was formed in the cylinder 3 produced by said (1) using the helium ion microscope (ORIN NanoFab; Carl Zeiss Microscopy, Inc.).
図９は実施例２で作製した基材１の電子顕微鏡写真で、貫通孔３１の直径は約１３ｎｍであった。 FIG. 9 is an electron micrograph of the substrate 1 produced in Example 2. The diameter of the through hole 31 was about 13 nm.
本発明の基材１は、任意の大きさ、個数及び位置に貫通孔を形成し、内径の大きさも任意である中空の筒体を、基板上に複数形成することができる。そして、貫通孔を通過する微粒子を測定することで微粒子のサイズを測定し、中空の筒体の内側に形成した金属蒸着層やナノワイヤで微粒子を濃縮・識別できる可能性がある。したがって、本発明の基材１を用いて有害・危険物質を分析するチップを作製することで、身の回りの有害・危険物質をスマホ等の身近な機器に組み込める可能性があるので、安全・安心社会を実現するための機器の開発に有用である。
The base material 1 of the present invention can form a plurality of hollow cylinders having through-holes in any size, number and position, and an arbitrary inner diameter on the substrate. Then, the size of the fine particles passing through the through holes is measured to measure the size of the fine particles, and there is a possibility that the fine particles can be concentrated and identified by a metal vapor deposition layer or nanowire formed inside the hollow cylinder. Therefore, by creating a chip that analyzes hazardous and dangerous substances using the base material 1 of the present invention, there is a possibility that harmful and dangerous substances around us may be incorporated into familiar devices such as smartphones. This is useful for the development of equipment to achieve the above.
Claims (11)
前記中空の筒体には、筒体の内側と外側を貫通する貫通孔が少なくとも１以上形成され、
前記基板には、前記中空の筒体の中空部と前記基板の反対側を連通するための貫通孔が形成されていることを特徴とする基材。 A substrate, and a hollow cylinder having one end formed on the substrate and the other end opened upward;
The hollow cylinder is formed with at least one or more through holes penetrating the inside and outside of the cylinder,
The substrate is characterized in that a through hole for communicating the hollow portion of the hollow cylindrical body and the opposite side of the substrate is formed in the substrate.
前記中空の筒体には、高さの異なる位置に、筒体の内側と外側を貫通する貫通孔が少なくとも２以上形成されていることを特徴とする基材。 A substrate, and a hollow cylinder having one end formed on the substrate and the other end opened upward;
The hollow cylindrical body has at least two or more through holes penetrating the inner side and the outer side of the cylindrical body at positions having different heights.
前記材料の表面に、中空の筒体又は中空の筒体及び外郭部に相当する部分にフォトレジストを形成する工程、
前記フォトレジストが形成されていない部分の前記材料を、前記基板までエッチングする工程、
前記材料の中に閉じ込まれた充填材、及び前記材料の表面のフォトレジストを除去する工程、
を含むことを特徴とする貫通孔を有する中空の筒体を基板上に形成した基材の製造方法。 A process of confining a filler in a hollow cylinder or a material for forming a hollow cylinder and an outer shell laminated on a substrate;
A step of forming a photoresist on the surface of the material in a portion corresponding to a hollow cylinder or a hollow cylinder and an outer shell;
Etching the portion of the material where the photoresist is not formed to the substrate;
Removing the filler confined in the material and the photoresist on the surface of the material;
The manufacturing method of the base material which formed the hollow cylinder which has a through-hole characterized by including on a board | substrate.
前記基板上に中空の筒体又は中空の筒体及び外郭部を形成する材料を積層する工程、
前記材料をエッチングして形成した孔に充填材を充填する工程、及び、
前記充填材を充填した後に、中空の筒体又は中空の筒体及び外郭部を形成する材料を積層する工程、
を少なくとも１回以上含む、
ことを特徴とする請求項６に記載の製造方法。 The step of confining a filler in a material for forming a hollow cylinder or a hollow cylinder and an outer shell laminated on the substrate,
A step of laminating a material that forms a hollow cylinder or a hollow cylinder and an outer portion on the substrate;
Filling a hole formed by etching the material with a filler; and
A step of laminating a material for forming a hollow cylinder or a hollow cylinder and an outer shell after filling the filler;
Including at least once,
The manufacturing method according to claim 6.
前記中空の筒体に貫通孔を形成する工程、
を含むことを特徴とする貫通孔を有する中空の筒体を基板上に形成した基材の製造方法。 A step of depositing a material for forming a hollow cylinder on the substrate to form a hollow cylinder;
Forming a through hole in the hollow cylinder,
The manufacturing method of the base material which formed the hollow cylinder which has a through-hole characterized by including on a board | substrate.
前記中空の筒体から離れた位置に前記中空の筒体を覆うように外郭部を形成する工程、
を含むことを特徴とする請求項８に記載の製造方法。 After the step of forming a through hole in the hollow cylinder,
Forming an outer shell so as to cover the hollow cylinder at a position away from the hollow cylinder;
The manufacturing method of Claim 8 characterized by the above-mentioned.
前記中空の筒体から離れた位置に前記中空の筒体を覆うように外郭部を形成する工程、
前記中空の筒体に貫通孔を形成する工程、
を含むことを特徴とする貫通孔を有する中空の筒体を基板上に形成した基材の製造方法。 A step of depositing a material for forming a hollow cylinder on the substrate to form a hollow cylinder;
Forming an outer shell so as to cover the hollow cylinder at a position away from the hollow cylinder;
Forming a through hole in the hollow cylinder,
The manufacturing method of the base material which formed the hollow cylinder which has a through-hole characterized by including on a board | substrate.
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