JP5697309B2 - Method for manufacturing localized plasmon resonance sensor - Google Patents
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- 238000000034 method Methods 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000010410 layer Substances 0.000 claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 49
- 239000000758 substrate Substances 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 claims description 2
- 239000010931 gold Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 18
- 238000001459 lithography Methods 0.000 description 12
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000001659 ion-beam spectroscopy Methods 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- 239000000463 material Substances 0.000 description 4
- 238000005121 nitriding Methods 0.000 description 4
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- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 4
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- 239000010409 thin film Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
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- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 238000001039 wet etching Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005256 carbonitriding Methods 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
- G01N21/553—Attenuated total reflection and using surface plasmons
- G01N21/554—Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
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Description
本発明は、局在表面プラズモン共鳴現象を利用した化学センサに関する。 The present invention relates to a chemical sensor using a localized surface plasmon resonance phenomenon.
従来、石英やガラスなど光学的に透明または半透明の誘電体基材の上に、金Ａｕや銀Ａｇといった金属の微細構造を設け、これに紫外〜近赤外の光を照射したときに起きる局在表面プラズモン共鳴（Local Surface Plasmon Resonance）現象を利用した化学センサが提案されている（特許文献１−３参照）。局在表面プラズモン共鳴は、基板表面近傍に存在する媒質との相互作用により光学特性が変化する現象であり、この光学特性の変化を用いて化学センサとする。 Conventionally, this occurs when a metal microstructure such as gold Au or silver Ag is provided on an optically transparent or translucent dielectric substrate such as quartz or glass and irradiated with ultraviolet to near infrared light. A chemical sensor utilizing a local surface plasmon resonance phenomenon has been proposed (see Patent Documents 1-3). Localized surface plasmon resonance is a phenomenon in which optical characteristics change due to an interaction with a medium existing in the vicinity of the substrate surface, and a chemical sensor is formed using the change in optical characteristics.
特許文献１には、金属微粒子を分散させたガラス基板の透過率を測定することでセンサとすることが開示されている。 Patent Document 1 discloses that a sensor is obtained by measuring the transmittance of a glass substrate in which metal fine particles are dispersed.
特許文献２には、リソグラフィ法を用いたセンサについて開示されており、このセンサは、石英基板に金属膜を形成し、ネガ型レジストを用いた電子線リソグラフィとドライエッチングを用いてナノドットアレイを形成するもので、この基板に可視〜近赤外域の光線を照射することで局在プラズモン共鳴を誘発し、これを化学センサとするものである。金属膜には厚さ５０ｎｍ（１０〜２００ｎｍ）のＡｕ膜を用いており、このＡｕ膜と石英基板の間に接着（バインダー）膜として厚さ５ｎｍのＴｉ膜層が設けられている。また、狭ピッチに配置された２〜３個のナノドットを１つのユニットとし、各ユニットを千鳥格子状に配置したことを特徴としている。 Patent Document 2 discloses a sensor using a lithography method. This sensor forms a metal film on a quartz substrate and forms a nanodot array using electron beam lithography using a negative resist and dry etching. Therefore, a localized plasmon resonance is induced by irradiating the substrate with light in the visible to near-infrared region, and this is used as a chemical sensor. An Au film having a thickness of 50 nm (10 to 200 nm) is used as the metal film, and a Ti film layer having a thickness of 5 nm is provided as an adhesive (binder) film between the Au film and the quartz substrate. Further, it is characterized in that two to three nanodots arranged at a narrow pitch are used as one unit, and each unit is arranged in a staggered pattern.
特許文献３には、特許文献２と同様にリソグラフィ法を用いて作製したセンサが開示されている。このセンサは、金属微粒子の代わりに金属薄膜に開口した基板を用いてセンサとしている。 Patent Document 3 discloses a sensor manufactured using a lithography method as in Patent Document 2. This sensor uses a substrate opened in a metal thin film instead of metal fine particles.
これらの、Ａｕ微細構造を持つセンサの局在表面プラズモン共鳴現象を透過率で表現した場合には、次の特長が見られる。
・可視域にピークを持ち、可視域〜近紫外域にディップを持つ。
・センサに接する媒質の透過率（屈折率）によってピークおよびディップの位置および強度が変化する。
・センサに接する媒質の誘電率が大きいほどピークおよびディップの位置が長波長側にシフトする（レッドシフト）。
・可視域のピークは波長５００ｎｍ〜７００ｎｍの限定された範囲に表出する。
・可視域〜近赤外域のディップの位置は微細構造の大きさと間隔に大きく左右されるとともに、基板に接する媒質の誘電率によっても大きく左右される。
When the localized surface plasmon resonance phenomenon of a sensor having an Au fine structure is expressed by transmittance, the following features can be seen.
・ It has a peak in the visible range and a dip in the visible to near-ultraviolet range.
The position and intensity of the peak and dip change depending on the transmittance (refractive index) of the medium in contact with the sensor.
As the dielectric constant of the medium in contact with the sensor increases, the peak and dip positions shift to the longer wavelength side (red shift).
-The peak in the visible region appears in a limited range of wavelengths from 500 nm to 700 nm.
The position of the dip in the visible region to the near infrared region greatly depends on the size and interval of the fine structure, and also greatly depends on the dielectric constant of the medium in contact with the substrate.
しかしながら、Ａｕ微細構造における可視〜近赤外のディップは媒質変化に対する感度が高いのにも関わらず、センサ応用の試みがあまりなされていない。センサ応用がなされていない理由の一つには、可視〜近赤外のディップの位置および強度を安定的に得ることが難しいこと、端的には特性がばらつき易いことがあげられる。このばらつきには次のものがある。
１．共鳴波長における吸収スペクトルの半値幅のばらつき。
２．共鳴波長のばらつき。
３．共鳴波長における吸収の強度のばらつき。
However, although the visible to near-infrared dip in the Au microstructure is highly sensitive to changes in the medium, there have been few attempts to apply the sensor. One of the reasons that the sensor application has not been made is that it is difficult to stably obtain the position and intensity of the visible to near-infrared dip, and that the characteristics easily vary. This variation includes the following.
1. Variation in half width of absorption spectrum at resonance wavelength.
2. Variation in resonance wavelength.
3. Variation in the intensity of absorption at the resonance wavelength.
吸収のばらつきは、特許文献３に記載されているように金属微細構造の不均一性によるものが大きい。これを解決する手段としては特許文献２および３に記載されているリソグラフィ技術の適用がある。リソグラフィ技術を適用することで、ナノドットやナノホール、ナノディスクといった微細構造を正確かつ均一に配置することが可能となる。 The variation in absorption is largely due to the non-uniformity of the metal microstructure as described in Patent Document 3. As means for solving this, there is an application of lithography techniques described in Patent Documents 2 and 3. By applying the lithography technique, it is possible to accurately and uniformly arrange fine structures such as nanodots, nanoholes, and nanodisks.
しかしながら、特許文献２および３に記載されている微細構造の作製工程は、リソグラフィにエッチング技術を組み合わせたものであり、リソグラフィ法を用いた工程では、品質が不安定で且つ製品寿命が短く、入手が困難なネガ型レジストを使用しているので実現が難しいという欠点がある。しかも、金属微細構造の上部に残ったレジストがドライエッチング工程で用いられるプラズマにより変成し、残渣を除去しきれない場合があり、センサの性能を低下させてしまう問題があった。 However, the fabrication process of the microstructure described in Patent Documents 2 and 3 is a combination of lithography and etching technology, and in the process using the lithography method, the quality is unstable and the product life is short, and it is available. However, since a negative resist that is difficult to use is used, there is a drawback that it is difficult to realize. In addition, the resist remaining on the upper part of the metal microstructure may be transformed by the plasma used in the dry etching process, and the residue may not be completely removed, thereby degrading the sensor performance.
その一方、エッチング法の代わりにリソグラフィに組み合わせる技術として、リフトオフ法がある。リフトオフ法は、リソグラフィ法で開口させたレジストの上に金属膜を蒸着などの手法で堆積し、レジストを除去することでレジスト開口部にのみ金属膜を残し、金属微細構造を作る方法である。図１はこの一例を示している。一例では、石英基板１上に設けられたクロムＣｒ層２上にポジ型の電子線レジスト３を塗布し、このレジスト３に電子線リソグラフィによってナノホールアレイ４を形成させ、次いでこの上にＡｕ膜５を蒸着させた後、レジスト３を余分なＡｕ膜５とともに除去する。これによってナノホールアレイ４内にのみＡｕが残り、Ａｕ微細構造６が作られる。以上のリフトオフ法では、入手が容易で性能寿命が長く、解像度の高いポジ型レジストを用いているため、安定した微細構造を容易に得ることができる。 On the other hand, there is a lift-off method as a technique combined with lithography instead of the etching method. The lift-off method is a method in which a metal film is deposited on a resist opened by a lithography method by a technique such as vapor deposition, and the metal film is left only in the resist opening by removing the resist to form a metal microstructure. FIG. 1 shows an example of this. In one example, a positive electron beam resist 3 is applied on a chromium Cr layer 2 provided on a quartz substrate 1, a nanohole array 4 is formed on the resist 3 by electron beam lithography, and then an Au film 5 is formed thereon. Then, the resist 3 is removed together with the excess Au film 5. As a result, Au remains only in the nanohole array 4 and an Au microstructure 6 is formed. In the lift-off method described above, since a positive resist that is easy to obtain, has a long performance life, and has a high resolution is used, a stable fine structure can be easily obtained.
リフトオフ法を用いることで微細構造を得ることができるが、この方法で作られた局在プラズモン共鳴センサでは、誘電体基板（図１中の１）と金属微細構造（図１中の６）の間に挿入される極薄い金属層（図１中の２）が、センサ特性に大きな影響を与えてしまう問題点がある。この極薄い金属層は、導電層または密着層として製造上必要となるものである。特許文献２では、金属ナノドットと石英基板との間に厚さ５ｎｍのＴｉ層を接着層（バインダー）として設けている。これにおいて、接着層ないしバインダーは密着層と同義であると考えられる。また、特許文献３では、構造物となる金属薄膜層の上に電子線レジストをコーティングし、電子線を照射し、現像することでパターンを得ているが、金属層が存在しない場合には、チャージアップ現象によってパターンが得られない。従って、石英などの不導体基板に電子線リソグラフィを適用する場合には、必ず金属等の導電層を設ける必要がある。 The microstructure can be obtained by using the lift-off method. However, in the localized plasmon resonance sensor made by this method, the dielectric substrate (1 in FIG. 1) and the metal microstructure (6 in FIG. 1) There is a problem that an extremely thin metal layer (2 in FIG. 1) inserted between the two layers greatly affects the sensor characteristics. This extremely thin metal layer is necessary for production as a conductive layer or an adhesion layer. In Patent Document 2, a Ti layer having a thickness of 5 nm is provided as an adhesive layer (binder) between metal nanodots and a quartz substrate. In this case, the adhesive layer or binder is considered to be synonymous with the adhesive layer. In Patent Document 3, a pattern is obtained by coating an electron beam resist on a metal thin film layer to be a structure, irradiating with an electron beam, and developing, but when the metal layer does not exist, A pattern cannot be obtained due to the charge-up phenomenon. Therefore, when applying electron beam lithography to a non-conductive substrate such as quartz, it is necessary to provide a conductive layer such as a metal.
対応策として、この金属層をウェットエッチングやドライエッチングといったエッチング法を用いて取り除くことが考えられる。しかしながら、ウェットエッチング法を用いた場合、ナノドット構造と基板の間の導電層が溶解し、その結果ナノドット構造が剥離してしまう問題がある。ドライエッチング法を用いた場合には、金属層を除去するのと同時にナノドット構造も削られてしまい、特性がばらつきやすくなる恐れがあった。このように、エッチング法を用いた導電層または密着層としての金属層の除去方法には限界がある。 As a countermeasure, it is conceivable to remove this metal layer by using an etching method such as wet etching or dry etching. However, when the wet etching method is used, there is a problem that the conductive layer between the nanodot structure and the substrate is dissolved, and as a result, the nanodot structure is peeled off. When the dry etching method is used, the nanodot structure is also removed at the same time as the metal layer is removed, and there is a risk that the characteristics are likely to vary. Thus, there is a limit to the method for removing the metal layer as the conductive layer or the adhesion layer using the etching method.
一方、イオンビームスパッタ法を用いることで、Ａｕ微細構造を基板上に密着層を用いずに固定することが可能となる。一般的な真空蒸着方やスパッタ法を用いた成膜方法では成膜時に成膜材料のもつ運動エネルギーが小さいためガラス基板や石英基板の上にＡｕを成膜すると容易に剥離してしまうが、これに対して、イオンビームスパッタ法ではイオンビームをターゲット材料に加速照射しており、ターゲット材より弾き飛ばされた成膜材料に高い運動エネルギーを与えることができる。この結果、成膜材料が基板に強く密着するが知られている。 On the other hand, by using the ion beam sputtering method, the Au fine structure can be fixed on the substrate without using an adhesion layer. In a general vacuum deposition method or a film formation method using a sputtering method, since the kinetic energy of the film formation material is small at the time of film formation, it is easily peeled off when Au is formed on a glass substrate or a quartz substrate. On the other hand, in the ion beam sputtering method, the target material is accelerated and irradiated with an ion beam, and high kinetic energy can be given to the film formation material blown off from the target material. As a result, it is known that the film forming material adheres strongly to the substrate.
イオンビームスパッタ法を用いたＡｕ微細構造形成の工程例を示す。電子線リソグラフィの後に、レジスト開口部の導電層をエッチング法で除去する。次にイオンビームスパッタ法でもってＡｕを堆積した後に電子線レジストを除去することで、レジスト開口部分にのみＡｕ構造が残る。イオンビームスパッタを用いることでＡｕと基板の密着性が確保されているので、レジストを除去してもＡｕ構造が基板に残る。最後にＡｕ構造間に残った導電層をエッチング法で除去することで所望のセンサ構造を得る。 The process example of Au fine structure formation using ion beam sputtering method is shown. After the electron beam lithography, the conductive layer in the resist opening is removed by an etching method. Next, after depositing Au by ion beam sputtering, the electron beam resist is removed, so that the Au structure remains only in the resist opening. Since the adhesion between Au and the substrate is secured by using ion beam sputtering, the Au structure remains on the substrate even if the resist is removed. Finally, the desired sensor structure is obtained by removing the conductive layer remaining between the Au structures by an etching method.
このように、イオンビームスパッタ法を用いることにより密着層を用いずにＡｕ微細構造を形成することができる。しかしながら、イオンビームスパッタ法は高価で特殊な装置が必要となる問題を有しており、工業化に不向きで製品が高額になってしまう欠点がある。 As described above, by using the ion beam sputtering method, an Au fine structure can be formed without using an adhesion layer. However, the ion beam sputtering method has a problem that it is expensive and requires a special apparatus, which is not suitable for industrialization and has a drawback that the product becomes expensive.
以上のとおり、リソグラフィ法を用いて局在プラズモン共鳴センサを製造する場合、従来の手法ではセンサ特性のばらつきを抑制できない、もしくは製造工程が複雑、高価になる欠点がある。 As described above, when a localized plasmon resonance sensor is manufactured by using a lithography method, there is a disadvantage that the conventional method cannot suppress variations in sensor characteristics, or the manufacturing process is complicated and expensive.
本発明は、以上のとおりの従来の欠点を解消し、金属微細構造を持つ局在プラズモン共鳴センサにおいて、リソグラフィ法による製造上必要不可欠な、誘電体基板と金属微細構造の間に挿入される導電層または密着層としての金属層を除去することなく、且つ複雑、高価な製造工程を必要とすることのない、良好な特性を持つセンサを提供することを課題としている。 The present invention eliminates the conventional drawbacks as described above, and in a localized plasmon resonance sensor having a metal microstructure, a conductive material inserted between the dielectric substrate and the metal microstructure is indispensable for manufacturing by lithography. It is an object of the present invention to provide a sensor having good characteristics without removing a metal layer as a layer or an adhesion layer and without requiring a complicated and expensive manufacturing process.
本発明は、上記課題を解決するものとして、金属微細構造を持つ局在プラズモン共鳴センサであって、誘電体基板と金属微細構造の間に設けられた導電層または密着層が誘電体化処理により誘電体層とされている、ことを特徴とする局在プラズモン共鳴センサを提供する。 In order to solve the above problems, the present invention provides a localized plasmon resonance sensor having a metal microstructure, wherein a conductive layer or an adhesion layer provided between the dielectric substrate and the metal microstructure is subjected to a dielectric treatment. Provided is a localized plasmon resonance sensor characterized by being a dielectric layer.
また、本発明は、金属微細構造を持つ局在プラズモン共鳴センサの製造方法であって、誘電体基板と金属微細構造の間に設けた導電層または密着層を誘電体化する、ことを特徴とする局在プラズモン共鳴センサ製造方法を提供する。 The present invention is also a method for manufacturing a localized plasmon resonance sensor having a metal microstructure, characterized in that a conductive layer or an adhesion layer provided between the dielectric substrate and the metal microstructure is made into a dielectric. A localized plasmon resonance sensor manufacturing method is provided.
本発明によれば、図２にその一例を示したように、誘電体基板１と金属微細構造６の間に設けられた導電層または密着層２に誘電体化処理を施して誘電体層７とすることにより、導電層または密着層２の除去処理を必要とすることなく、良好な特性を持つセンサを実現することができる。 According to the present invention, as shown in FIG. 2 as an example, the dielectric layer 7 is obtained by subjecting the conductive layer or the adhesion layer 2 provided between the dielectric substrate 1 and the metal microstructure 6 to dielectric treatment. By doing so, it is possible to realize a sensor having good characteristics without requiring the removal process of the conductive layer or the adhesion layer 2.
より具体的には、図２の例では、まず、従来と同様にして、石英基板などの誘電体基板１の上に導電層または密着層となるＣｒ、Ｔｉなどの金属あるいはＳｉなどの半導体の薄膜２を形成し、この上にスピンコート等によりレジスト層３を塗布し、レジスト層３に電子線または紫外線等の露光放射を当てるリソグラフィ法により微細開口４を均等間隔で均一に形成する。次いで、物理的蒸着法ＰＶＤもしくは化学的蒸着法ＣＶＤあるいはその他の適切な手法によりＡｕまたはＡｇなどのプラズモン共鳴を生じる金属５を堆積し、レジスト３を除去することで、微細開口４内にのみプラズモン共鳴用金属５が残り、誘電体基板１上に金属微細構造６が形成される。微細開口４つまりナノホールについては、ナノドットやナノディスクであってもよい。 More specifically, in the example of FIG. 2, first, in the same manner as in the prior art, a metal such as Cr or Ti or a semiconductor such as Si, which becomes a conductive layer or an adhesion layer, is formed on a dielectric substrate 1 such as a quartz substrate. A thin film 2 is formed, a resist layer 3 is applied thereon by spin coating or the like, and fine openings 4 are uniformly formed at equal intervals by a lithography method in which exposure radiation such as electron beams or ultraviolet rays is applied to the resist layer 3. Next, a metal 5 that causes plasmon resonance such as Au or Ag is deposited by physical vapor deposition PVD or chemical vapor deposition CVD, or other appropriate technique, and the resist 3 is removed, so that only the plasmon within the fine opening 4 is obtained. The resonance metal 5 remains, and the metal microstructure 6 is formed on the dielectric substrate 1. The fine aperture 4, that is, the nanohole, may be a nanodot or a nanodisk.
本発明ではこれに続いて、誘電体基板１と金属微細構造６の間に残っている導電層または密着層２を誘電体化するべく、酸化処理を施す。この酸化処理により、導電層または密着層２が、Ｃｒ、Ｔｉなどの金属の酸化物あるいはＳｉなどの半導体の酸化物でなる誘電体層７となる。 In the present invention, subsequently, an oxidation treatment is performed to make the conductive layer or adhesion layer 2 remaining between the dielectric substrate 1 and the metal microstructure 6 into a dielectric. By this oxidation treatment, the conductive layer or the adhesion layer 2 becomes a dielectric layer 7 made of a metal oxide such as Cr or Ti or a semiconductor oxide such as Si.
酸化処理にはたとえば加熱処理を用いることができる。加熱処理では、金属微細構造６が変形または変形しない程度の加熱を、大気中、または酸素雰囲気もしくは酸素を含むガス雰囲気において行い、導電層または密着層２を熱酸化させて酸化層つまり誘電体層７に変化させる。 具体的加熱条件は導電層または密着層としての金属ないし半導体の材料や膜厚などによって設定され、加熱温度についてはたとえば１００〜５００℃、特に２００〜３００℃が好ましく、たとえば、１ｎｍ厚のＣｒ層の場合で、３００℃、３時間の加熱を大気中で行う。この場合のセンサ特性の一例を示したものを図３に示す。図３から明らかなように、熱酸化後のセンサの方が、可視域〜近赤外域に入る波長１２００ｎｍ付近に対して透過率ディップが顕著にシャープに現れている。 For example, heat treatment can be used for the oxidation treatment. In the heat treatment, heating to such an extent that the metal microstructure 6 is not deformed or deformed is performed in the air or in an oxygen atmosphere or a gas atmosphere containing oxygen, and the conductive layer or the adhesion layer 2 is thermally oxidized to form an oxide layer, that is, a dielectric layer. Change to 7. The specific heating conditions are set according to the material or film thickness of the metal or semiconductor as the conductive layer or adhesion layer, and the heating temperature is preferably 100 to 500 ° C., particularly preferably 200 to 300 ° C., for example, a 1 nm thick Cr layer In this case, heating at 300 ° C. for 3 hours is performed in the air. An example of the sensor characteristics in this case is shown in FIG. As is clear from FIG. 3, the transmittance dip appears significantly sharper in the sensor after thermal oxidation with respect to the vicinity of a wavelength of 1200 nm that falls in the visible region to the near infrared region.
本発明において、「誘電体化」とは、完全に不導体化すなわち絶縁体に変化させることだけでなく、プラズモン共鳴現象が生じる波長域において導電性よりも誘電性が優位となる物性に変化させることを示している。 In the present invention, “dielectric” means not only completely deconducting, that is, changing to an insulator, but also changing to a physical property that is superior to conductivity in the wavelength region where the plasmon resonance phenomenon occurs. It is shown that.
この金属または半導体である導電層（または密着層）を誘電体化する方法には、上記酸化処理以外にも、窒化処理および炭化処理がある。一例としては、ＮＨ３ガスを所定の温度例えば５００℃前後で加熱分解するガス窒化処理法、あるいは、酸化と窒化を組み合わせた酸窒化処理や窒化と炭化を組み合わせた炭窒化処理などの複合的処理法を適用できる。 In addition to the oxidation treatment, there are a nitriding treatment and a carbonizing treatment as a method for making the conductive layer (or adhesion layer) made of metal or semiconductor a dielectric. As an example, a gas nitriding treatment method in which NH 3 gas is thermally decomposed at a predetermined temperature, for example, around 500 ° C., or a composite treatment method such as an oxynitriding treatment combining oxidation and nitriding, or a carbonitriding treatment combining nitriding and carbonization. Can be applied.
ところで、上述した図２の実施形態では、レジスト３を除去する処理を含めているが、レジストを一部残したまま誘電体化処理する方法も考えられる。レジストを一部残したまま加熱すると、酸素がレジスト内を拡散、透過したり、石英基板の酸素がマイグレーション（移行）したりすることで、金属層または半導体層が酸化される。この結果、工程が簡略化できるとともに、レジストが保護膜として機能するためセンサの耐摩耗性が向上する。 By the way, in the embodiment of FIG. 2 described above, the process of removing the resist 3 is included, but a method of performing a dielectric process while leaving a part of the resist is also conceivable. When the resist is heated while leaving a part of it, oxygen diffuses and permeates through the resist, or oxygen in the quartz substrate migrates, so that the metal layer or the semiconductor layer is oxidized. As a result, the process can be simplified and the wear resistance of the sensor is improved because the resist functions as a protective film.
１ 誘電体基板、石英基板
２ 導電層または密着層、金属層、クロム層、半導体層
３ レジスト層、レジスト
４ 微細開口、ナノホール
５ プラズモン共鳴用金属、Ａｕ膜
６ 金属微細構造、Ａｕ微細構造
７ 誘電体層、酸化層
DESCRIPTION OF SYMBOLS 1 Dielectric substrate, quartz substrate 2 Conductive layer or adhesion layer, metal layer, chromium layer, semiconductor layer 3 resist layer, resist 4 fine opening, nanohole 5 metal for plasmon resonance, Au film 6 metal fine structure, Au fine structure 7 dielectric Body layer, oxide layer
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