TWI764185B - 奈米結構體陣列 - Google Patents

奈米結構體陣列

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Publication number
TWI764185B
TWI764185B TW109121906A TW109121906A TWI764185B TW I764185 B TWI764185 B TW I764185B TW 109121906 A TW109121906 A TW 109121906A TW 109121906 A TW109121906 A TW 109121906A TW I764185 B TWI764185 B TW I764185B
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TW
Taiwan
Prior art keywords
thin film
film layer
alloys
alloy
group
Prior art date
Application number
TW109121906A
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English (en)
Other versions
TW202200488A (zh
Inventor
朱瑾
曾冠瑋
Original Assignee
國立臺灣科技大學
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Application filed by 國立臺灣科技大學 filed Critical 國立臺灣科技大學
Priority to TW109121906A priority Critical patent/TWI764185B/zh
Priority to US16/940,416 priority patent/US20210404054A1/en
Publication of TW202200488A publication Critical patent/TW202200488A/zh
Application granted granted Critical
Publication of TWI764185B publication Critical patent/TWI764185B/zh

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    • B81—MICROSTRUCTURAL TECHNOLOGY
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    • B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
    • B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

本發明係為一種形成於一基板之上之奈米結構體陣列，主要包括複數個奈米結構體，每一奈米結構體形成一容置空間，容置空間相對於基板之一端具有一開口，每一奈米結構體包括一第一薄膜層，容置空間之周圍以及底部分別由第一薄膜層之周圍部之內表面以及第一薄膜層之底部之上表面所定義，而構成第一薄膜層之材料係選自金屬、合金、氧化物、氮化物以及硫化物其中至少之一者。

Description

奈米結構體陣列
本發明係有關一種奈米結構體陣列，尤指一種由一層薄膜或多層相鄰不相同材料之薄膜所形成之奈米結構體之陣列。
奈米科技在生物醫學以及生物檢測分析科技上的應用越來越廣泛。不同的材料，其特性與應用上有所不同。以包覆方式形成之內核與外殼之結構，也會因材料之組合之不同，而改變其表面帶電特性、選擇性、催化活性等特性。藉由不同材料之選擇與設計，係可將其電性、催化、光學、磁性等性質應用於不同之功能上。習知技術以鋯(Zr)基金屬玻璃為材料所製成之奈米管陣列，用以提供作為感測元件，以感測表面附著特定目標物之特性以及光學特性。若要應用在催化、表面增強拉曼散射(SERS：Surface-Enhanced Raman Scattering)等領域上，則以鋯基金屬玻璃為材料所製成之奈米管陣列並不適合，必須以其他不同之材料來製作奈米管陣列，以符合不同應用上之需求。或是以其他不同之材料來包覆鋯基金屬玻璃或其他金屬基之金屬玻璃，藉此改變金屬玻璃之表面帶電特性、選擇性、催化活性等特性，以應用於不同之領域上。
本發明所欲解決之技術問題在於提供不同之材料或材料之組合來製作奈米管陣列，以符合不同應用上之需求。有鑑於此，發明人開 發出簡便組裝的設計，能夠避免上述的缺點，安裝方便，又具有成本低廉的優點，以兼顧使用彈性與經濟性等考量，因此遂有本發明之產生。
為解決前述問題，以達到所預期之功效，本發明提供一種形成於一基板之上之奈米結構體陣列，包括複數個奈米結構體，其中每一奈米結構體形成一容置空間，容置空間相對於基板之一端具有一開口，每一奈米結構體包括一第一薄膜層，容置空間之一周圍以及一底部係分別由第一薄膜層之一周圍部之一內表面以及第一薄膜層之一底部之一上表面所定義。藉此，形成由單一薄膜層(第一薄膜層)所構成之複數個奈米結構體，其中構成奈米結構體之材料係可選自金屬、合金、氧化物、氮化物或硫化物。藉由選擇適當材料之第一薄膜層，係可將奈米結構體陣列應用於所需之領域上。
此外，本發明更提供一種形成於一基板之上之奈米結構體陣列，包括複數個奈米結構體，其中每一奈米結構體形成一容置空間，容置空間相對於基板之一端具有一開口，每一奈米結構體包括複數層薄膜層，複數層薄膜層包括一第一薄膜層以及一第二薄膜層。容置空間之一周圍以及一底部係分別由第一薄膜層之一周圍部之一內表面以及第一薄膜層之一底部之一上表面所定義。第二薄膜層之一底部係位於介於基板與第一薄膜層之底部之間，第一薄膜層之周圍部係位於介於第二薄膜層之一周圍部與容置空間之間。藉此，形成由複數層薄膜層(包括第一薄膜層以及第二薄膜層)所構成之複數個奈米結構體，構成複數層薄膜層之材料係可選自金屬、合金、氧化物、氮化物或硫化物，其中複數層薄膜層之任兩相鄰者係由不同之材料所構成。藉由選擇適當材料組合之第一薄膜層以及第二薄膜 層，係可將奈米結構體陣列應用於所需之領域上。
於實施例時，前述之奈米結構體陣列，其中複數層薄膜層更包括一第三薄膜層，第三薄膜層係形成於介於第一薄膜層與第二薄膜層之間。藉此，形成由複數層薄膜層(包括第一薄膜層、第二薄膜層以及第三薄膜層)所構成之複數個奈米結構體，其中構成第一薄膜層以及第二薄膜層之材料係可選自金屬、合金、氧化物、氮化物或硫化物，構成第三薄膜層之材料係可選自金屬、合金、氧化物、氮化物、硫化物、碳化物或鑽石，其中複數層薄膜層之任兩相鄰者係由不同之材料所構成。藉由選擇適當材料組合之第一薄膜層、第二薄膜層以及第三薄膜層，係可將奈米結構體陣列應用於所需之領域上。
於實施例時，前述之奈米結構體陣列，其中構成第一薄膜層之材料係相同於構成第二薄膜層之材料。此時，第三薄膜層即為內核層，而第一薄膜層以及第二薄膜層則為外殼層。第一薄膜層(第二薄膜層)與第三薄膜層之特性會彼此影響。藉由選擇適當材料組合第一薄膜層(第二薄膜層)以及第三薄膜層，係可將奈米結構體陣列應用於所需之領域上。
於實施例時，前述之奈米結構體陣列，其中複數層薄膜層更包括至少一第四薄膜層，其中至少一第四薄膜層係形成於(1)介於第三薄膜層與第一薄膜層之間、(2)介於第二薄膜層與第三薄膜層之間、或(3)介於第三薄膜層與第一薄膜層之間以及介於第二薄膜層與第三薄膜層之間。藉此，形成由複數層薄膜層(包括第一薄膜層、第二薄膜層、第三薄膜層以及至少一第四薄膜層)所構成之複數個奈米結構體，其中構成第一薄膜層以及第二薄膜層之材料係可選自金屬、合金、氧化物、氮化物或硫 化物，構成第三薄膜層以及至少一第四薄膜層之任一者之材料係可選自金屬、合金、氧化物、氮化物、硫化物、碳化物或鑽石，其中複數層薄膜層之任兩相鄰者係由不同之材料所構成。藉由選擇適當材料組合之第一薄膜層、第二薄膜層、第三薄膜層以及至少一第四薄膜層，係可將奈米結構體陣列應用於所需之領域上。
於實施例時，前述之奈米結構體陣列，其中構成第三薄膜層之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金、不銹鋼、碳化矽、碳化鎢、鑽石、鎢、鎢合金以及鎢鎳硼金屬玻璃。構成第一薄膜層之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金以及不銹鋼。構成第二薄膜層之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金以及不銹鋼。構成至少一第四薄膜層之任一者之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金、不銹鋼、碳化矽、碳化鎢、鑽石、鎢、鎢合金以及鎢鎳硼金屬玻璃。
於實施例時，前述之奈米結構體陣列，其中第三薄膜層具有一厚度，係大於或等於5nm，且小於或等於1μm。第二薄膜層具有一厚度，係大於或等於5nm，且小於或等於1μm。第一薄膜層具有一厚度，係大於或等於5nm，且小於或等於1μm。
於實施例時，前述之奈米結構體陣列，其中每一奈米結構體係為一奈米管。奈米管係為一圓柱奈米管或一橢圓柱奈米管。
於實施例時，前述之奈米結構體陣列，其中每一奈米結構體具有一厚度，係大於或等於10nm，且小於或等於20μm。奈米管具有一直徑，係大於或等於100nm，且小於或等於100μm。奈米管具有一厚度以及一直 徑，厚度與直徑之比係大於或等於0.001，且小於或等於0.5。奈米管具有一高度以及一直徑，高度與直徑之比係大於或等於0.05，且小於或等於5。
此外，本發明更提供一種奈米結構體陣列之製造方法，包括以下步驟：步驟A：形成一犧牲層於一基板之上，其中構成犧牲層之材料係包括選自以下群組之至少一者：一半導體磊晶、一金屬、一合金、一氧化物以及一氮化物；步驟B：圖形化犧牲層，以提供複數個凹槽；步驟C：形成至少一薄膜層於犧牲層之一上表面以及每一複數個凹槽之一內表面；步驟D：蝕刻形成於犧牲層之上表面之上之至少一薄膜層，使犧牲層露出；以及步驟E：移除犧牲層。
為進一步了解本發明，以下舉較佳之實施例，配合圖式、圖號，將本發明之具體構成內容及其所達成的功效詳細說明如下。
1:奈米結構體陣列
10:基板
11:奈米結構體
12:犧牲層
13:凹槽
14:犧牲層之上表面
15:凹槽之內表面
2:第一薄膜層
20:第一薄膜層之底部
21:第一薄膜層之周圍部
22:第一薄膜層之底部之上表面
23:第一薄膜層之周圍部之內表面
3:第二薄膜層
30:第二薄膜層之底部
31:第二薄膜層之周圍部
4:第三薄膜層
5:容置空間
6:複數層薄膜層
7:第四薄膜層
8:至少一薄膜層
第1圖係為本發明一種奈米結構體陣列之一具體實施例之剖面示意圖。
第2圖係為本發明一種奈米結構體陣列之另一具體實施例之剖面示意圖。
第3圖係為本發明一種奈米結構體陣列之又一具體實施例之剖面示意圖。
第4圖係為本發明一種奈米結構體陣列之再一具體實施例之剖面示意圖。
第5圖係為本發明一種奈米結構體陣列之製造流程立體示意圖。
第6圖係為本發明一種奈米結構體陣列之具體實施例之掃瞄式電子顯 微鏡成像圖。
第7圖係為本發明一種奈米結構體陣列之另一具體實施例之掃瞄式電子顯微鏡成像圖。
第8圖係為本發明一種奈米結構體陣列之一具體實施例之作為載體應用之掃瞄式電子顯微鏡成像圖。
請參閱第1圖，其係為本發明一種奈米結構體陣列之一具體實施例之剖面示意圖。本發明之一奈米結構體陣列1係形成於一基板10之上。其中奈米結構體陣列1包括複數個奈米結構體11。每一個奈米結構體11形成一容置空間5。容置空間5相對於基板10之一端具有一開口。每一個奈米結構體11包括一第一薄膜層2。其中容置空間5之一周圍以及一底部係分別由第一薄膜層2之一周圍部21之一內表面23以及第一薄膜層2之一底部20之一上表面22所定義。在此實施例中，每一個奈米結構體11係為一奈米管(圓柱奈米管)。構成第一薄膜層2之材料係包括選自以下群組之至少一者：金屬、合金、氧化物、氮化物以及硫化物。在一些實施例中，金屬係包括選自以下群組之至少一者：鈹、鎂、鋁、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鎵、鍺、釔、鋯、鈮、鉬、釕、銠、鈀、銀、鎘、銦、錫、銻、鉿、鉭、鎢、鉑、金以及鉛。在一些實施例中，合金係包括選自以下群組之至少一者：鈹合金、鎂合金、鋁合金、鈦合金、釩合金、鉻合金、錳合金、鐵合金、鈷合金、鎳合金、銅合金、鋅合金、鎵合金、鍺合金、釔合金、鋯合金、鈮合金、鉬合金、釕合金、銠合金、鈀合金、銀合金、鎘合金、銦合金、錫合金、銻合金、鉿合金、鉭合金、鎢合金、鉑合金、金合金以及鉛 合金。在一些實施例中，氧化物係包括選自以下群組之至少一者：氧化鋁、二氧化鈦、氧化矽以及氧化鋅。在一些實施例中，氮化物係包括選自以下群組之至少一者：氮化矽、氮化鎵、氮化砷以及氮化鈦。在一些實施例中，硫化物係包括選自以下群組之至少一者：硫化鎘、硫化鉛以及硫化鉬。在一些較佳之實施例中，構成第一薄膜層2之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如316不銹鋼)、金、銀以及氧化鋅。藉由不同之材料之選擇，係可將奈米管應用於不同之領域上。例如，選擇以金屬或合金等材料製成之奈米管，適合應用在催化、表面增強拉曼散射、生醫應用等領域上；又例如，氧化鋁、氧化鋅可應用其光學特性、或應用於作為藥物載體等。其中奈米管具有一厚度(亦即奈米結構體11之一厚度或第一薄膜層2之一厚度)、一高度以及一直徑。在一些實施例中，奈米管之厚度係大於或等於10nm，且小於或等於20μm。在一些較佳之實施例中，奈米管之厚度係大於或等於50nm，且小於或等於500nm。奈米管之直徑係大於或等於100nm，且小於或等於100μm。在一些較佳之實施例中，奈米管之直徑係大於或等於300nm，且小於或等於20μm。奈米管之厚度與直徑之比係大於或等於0.001，且小於或等於0.5。在一些較佳之實施例中，奈米管之厚度與直徑之比係大於或等於0.01，且小於或等於0.2。奈米管之高度與直徑之比係大於或等於0.05，且小於或等於5。在一些較佳之實施例中，奈米管之高度與直徑之比係大於或等於0.1，且小於或等於2。由複數個奈米結構體11所排列而成之奈米結構體陣列1，其中複數個奈米結構體11之工作比(duty ratio)係大於或等於0.5，且小於或等於6。在一些較佳之實施例中，工作比(duty ratio)係大於或等於0.5，且小於或等於2。 在一些其他之實施例中，每一個奈米結構體11係可為其他形狀，例如橢圓柱奈米管。
請參閱第2圖，其係為本發明一種奈米結構體陣列之另一具體實施例之剖面示意圖。第2圖之實施例之主要結構係與第1圖之實施例之結構大致相同，惟，其中每一個奈米結構體11包括複數層薄膜層6，其中複數層薄膜層6包括一第二薄膜層3以及如第1圖之實施例之第一薄膜層2，複數層薄膜層6之任兩相鄰者係由不同之材料所構成，亦即構成第一薄膜層2之材料係不同於構成第二薄膜層3之材料。其中第二薄膜層3之一底部30係位於介於基板10與第一薄膜層2之底部20之間。第一薄膜層2之周圍部21係位於介於第二薄膜層3之一周圍部31與容置空間5之間。構成第二薄膜層3之材料係包括選自以下群組之至少一者：金屬、合金、氧化物、氮化物以及硫化物。在一些實施例中，金屬係包括選自以下群組之至少一者：鈹、鎂、鋁、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鎵、鍺、釔、鋯、鈮、鉬、釕、銠、鈀、銀、鎘、銦、錫、銻、鉿、鉭、鎢、鉑、金以及鉛。在一些實施例中，合金係包括選自以下群組之至少一者：鈹合金、鎂合金、鋁合金、鈦合金、釩合金、鉻合金、錳合金、鐵合金、鈷合金、鎳合金、銅合金、鋅合金、鎵合金、鍺合金、釔合金、鋯合金、鈮合金、鉬合金、釕合金、銠合金、鈀合金、銀合金、鎘合金、銦合金、錫合金、銻合金、鉿合金、鉭合金、鎢合金、鉑合金、金合金以及鉛合金。在一些實施例中，氧化物係包括選自以下群組之至少一者：氧化鋁、二氧化鈦、氧化矽以及氧化鋅。在一些實施例中，氮化物係包括選自以下群組之至少一者：氮化矽、氮化鎵、氮化砷以及氮化鈦。在一些實施例中，硫化物係包括選自以下群組之至少一 者：硫化鎘、硫化鉛以及硫化鉬。在一些較佳之實施例中，構成第一薄膜層2之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如，316不銹鋼)、金、銀以及氧化鋅；構成第二薄膜層3之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如，316不銹鋼)、金、銀以及氧化鋅。在一些實施例中，第一薄膜層2之厚度係大於或等於5nm，且小於或等於1μm；第二薄膜層3具有一厚度，第二薄膜層3之厚度係大於或等於5nm，且小於或等於1μm。奈米管之厚度(亦即第一薄膜層2之厚度加上第二薄膜層3之厚度)係大於或等於10nm，且小於或等於2μm。第一薄膜層2與第二薄膜層3之材料不同，藉由選擇兩者不同材料之組合，係可將奈米結構體陣列1應用於所需之領域上。
請參閱第3圖，其係為本發明一種奈米結構體陣列之又一具體實施例之剖面示意圖。第3圖之實施例之主要結構係與第2圖之實施例之結構大致相同，惟，其中複數層薄膜層6更包括一第三薄膜層4，第三薄膜層4係形成於介於第一薄膜層2與第二薄膜層3之間，其中複數層薄膜層6之任兩相鄰者係由不同之材料所構成，亦即構成第一薄膜層2之材料係不同於構成第三薄膜層4之材料，且構成第三薄膜層4之材料係不同於構成第二薄膜層3之材料。構成第三薄膜層4之材料係包括選自以下群組之至少一者：金屬、合金、氧化物、氮化物、硫化物、碳化物以及鑽石。在一些實施例中，構成第三薄膜層4之材料係包括選自以下群組之至少一者：金屬、合金、氧化物、氮化物以及硫化物。在一些實施例中，金屬係包括選自以下群組之至少一者：鈹、鎂、鋁、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鎵、鍺、 釔、鋯、鈮、鉬、釕、銠、鈀、銀、鎘、銦、錫、銻、鉿、鉭、鎢、鉑、金以及鉛。在一些實施例中，合金係包括選自以下群組之至少一者：鈹合金、鎂合金、鋁合金、鈦合金、釩合金、鉻合金、錳合金、鐵合金、鈷合金、鎳合金、銅合金、鋅合金、鎵合金、鍺合金、釔合金、鋯合金、鈮合金、鉬合金、釕合金、銠合金、鈀合金、銀合金、鎘合金、銦合金、錫合金、銻合金、鉿合金、鉭合金、鎢合金、鉑合金、金合金以及鉛合金。在一些實施例中，氧化物係包括選自以下群組之至少一者：氧化鋁、二氧化鈦、氧化矽以及氧化鋅。在一些實施例中，氮化物係包括選自以下群組之至少一者：氮化矽、氮化鎵、氮化砷以及氮化鈦。在一些實施例中，硫化物係包括選自以下群組之至少一者：硫化鎘、硫化鉛以及硫化鉬。在一些實施例中，碳化物係包括選自以下群組之至少一者：碳化矽、碳化鎢、碳化三鐵以及碳化鈦。在一些較佳之實施例中，構成第三薄膜層4之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如，316不銹鋼)、金、銀、氧化鋅、碳化矽、碳化鎢、鑽石、鎢、鎢合金、鎢鎳合金以及鎢鎳硼金屬玻璃。在一些實施例中，第三薄膜層4具有一厚度，第三薄膜層4之厚度係大於或等於5nm，且小於或等於1μm。第一薄膜層2之材料不同於第二薄膜層3之材料，且第二薄膜層3之材料不同於第三薄膜層4之材料，藉由選擇不同材料之組合，係可將奈米結構體陣列1應用於所需之領域上。
在一些實施例中，構成第一薄膜層2之材料係相同於構成第二薄膜層3之材料。此時，第三薄膜層4即為內核層，而第一薄膜層2以及第二薄膜層3則為外殼層。第一薄膜層2(第二薄膜層3)與第三薄膜層4之特性 會彼此影響。藉由選擇適當材料組合第一薄膜層2(第二薄膜層3)以及第三薄膜層4，係可將奈米結構體陣列1應用於所需之領域上。在又一些實施例中，構成第一薄膜層2之材料係相同於構成第二薄膜層3之材料，且其中構成第一薄膜層2之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如，316不銹鋼)、金、銀以及氧化鋅。在一些實施例中，構成第三薄膜層4之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如，316不銹鋼)、金、銀、氧化鋅、碳化矽、碳化鎢、鑽石、鎢、鎢合金、鎢鎳合金以及鎢鎳硼金屬玻璃，且構成第一薄膜層2之材料係相同於構成第二薄膜層3之材料。在另一些實施例中，構成第三薄膜層4之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如，316不銹鋼)、金、銀、氧化鋅、碳化矽、碳化鎢、鑽石、鎢、鎢合金、鎢鎳合金以及鎢鎳硼金屬玻璃，構成第一薄膜層2之材料係相同於構成第二薄膜層3之材料，且構成第一薄膜層2之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如，316不銹鋼)、金、銀以及氧化鋅。
請參閱第4圖，其係為本發明一種奈米結構體陣列之再一具體實施例之剖面示意圖。第4圖之實施例之主要結構係與第3圖之實施例之結構大致相同，惟，其中複數層薄膜層6更包括一至少一第四薄膜層7。至少一第四薄膜層7係形成於介於第一薄膜層2與第三薄膜層4之間，其中複數層薄膜層6之任兩相鄰者係由不同之材料所構成，亦即構成第一薄膜層2之材料係不同於構成至少一第四薄膜層7之材料，且構成至少一第四薄膜層7 之材料係不同於構成第三薄膜層4之材料，其中構成至少一第四薄膜層7之材料係包括選自以下群組之至少一者：金屬、合金、氧化物、氮化物、硫化物、碳化物以及鑽石。在一些實施例中，構成第四薄膜層7之材料係包括選自以下群組之至少一者：金屬、合金、氧化物、氮化物以及硫化物。在一些實施例中，金屬係包括選自以下群組之至少一者：鈹、鎂、鋁、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鎵、鍺、釔、鋯、鈮、鉬、釕、銠、鈀、銀、鎘、銦、錫、銻、鉿、鉭、鎢、鉑、金以及鉛。在一些實施例中，合金係包括選自以下群組之至少一者：鈹合金、鎂合金、鋁合金、鈦合金、釩合金、鉻合金、錳合金、鐵合金、鈷合金、鎳合金、銅合金、鋅合金、鎵合金、鍺合金、釔合金、鋯合金、鈮合金、鉬合金、釕合金、銠合金、鈀合金、銀合金、鎘合金、銦合金、錫合金、銻合金、鉿合金、鉭合金、鎢合金、鉑合金、金合金以及鉛合金。在一些實施例中，氧化物係包括選自以下群組之至少一者：氧化鋁、二氧化鈦、氧化矽以及氧化鋅。在一些實施例中，氮化物係包括選自以下群組之至少一者：氮化矽、氮化鎵、氮化砷以及氮化鈦。在一些實施例中，硫化物係包括選自以下群組之至少一者：硫化鎘、硫化鉛以及硫化鉬。在一些實施例中，碳化物係包括選自以下群組之至少一者：碳化矽、碳化鎢、碳化三鐵以及碳化鈦。在一些實施例中，構成至少一第四薄膜層7之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金(例如，718鎳合金)、不銹鋼(例如，316不銹鋼)、金、銀、氧化鋅、碳化矽、碳化鎢、鑽石、鎢、鎢合金、鎢鎳合金以及鎢鎳硼金屬玻璃。藉由選擇適當材料組合之第一薄膜層、第二薄膜層、第三薄膜層以及至少一第四薄膜層(其中複數層薄膜層6之任兩相鄰者係由不同之材 料所構成)，係可將奈米結構體陣列應用於所需之領域上。
在一些實施例中，至少一第四薄膜層7係形成於介於第二薄膜層3與第三薄膜層4之間(圖中未顯示)，其中複數層薄膜層6之任兩相鄰者係由不同之材料所構成，亦即構成第二薄膜層3之材料係不同於構成至少一第四薄膜層7之材料，且構成至少一第四薄膜層7之材料係不同於構成第三薄膜層4之材料。在另一些實施例中，至少一第四薄膜層7係形成於介於第一薄膜層2與第三薄膜層4之間，且形成於介於第二薄膜層3與第三薄膜層4之間(圖中未顯示)，其中複數層薄膜層6之任兩相鄰者係由不同之材料所構成，亦即構成第一薄膜層2之材料係不同於構成至少一第四薄膜層7之材料，構成第三薄膜層4之材料係不同於構成至少一第四薄膜層7之材料，且構成第二薄膜層3之材料係不同於構成至少一第四薄膜層7之材料。
請參閱第5圖，其係為本發明一種奈米結構體陣列之製造流程立體示意圖。本發明提供一種奈米結構體陣列之製造方法，包括以下步驟：步驟A：提供一基板10，並於基板10之上形成一犧牲層12(第5圖左上)。其中基板10係可為一矽基板。犧牲層12之材料係可為一光阻。光阻係可為一正光阻或一負光阻。光阻係以塗佈之方式形成於基板10之上。在較佳之實施例中，構成基板10之材料係為適合形成至少一薄膜層8以及犧牲層12之材料。步驟B：圖形化犧牲層12，以提供複數個凹槽13(第5圖左中)。此步驟係經由曝光以及顯影以圖形化犧牲層12，再經蝕刻以形成複數個凹槽13。步驟C：形成至少一薄膜層8於犧牲層12之一上表面14以及每一個凹槽13之一內表面15(第5圖左下)。形成之方法係為物理氣相沈積(PVD：Physical Vapor Deposition)，例如：濺鍍(Sputtering)。在一些實施例中，至少一薄膜層8係 可如第1圖之實施例，僅具有一層第一薄膜層2。當欲形成金屬或合金所構成之至少一薄膜層8時，則將金屬或合金之鈀材以濺鍍之方式形成於犧牲層12之上表面14以及每一個凹槽13之內表面15，即可形成金屬或合金材料之至少一薄膜層8。若欲形成氧化物、氮化物或硫化物所構成之至少一薄膜層8時，則需於更換相對應之鈀材，並於濺鍍過程中通入氧氣、氮氣或硫蒸氣，使氧化物、氮化物或硫化物之至少一薄膜層8形成於犧牲層12之上表面14以及每一個凹槽13之內表面15。在另一些實施例中，至少一薄膜層8亦可如第2、3、4圖之實施例，具有複數層薄膜層6；當至少一薄膜層8係如第3圖之實施例具有複數層薄膜層6時(包括第一薄膜層2、第二薄膜層3以及第三薄膜層4)，則需依序以物理氣相沈積之方式，先將第二薄膜層3形成於犧牲層12之上表面14以及每一個凹槽13之內表面15，再將第三薄膜層4形成於第二薄膜層3之一外表面，再將第一薄膜層2形成於第三薄膜層4之一外表面。步驟D：蝕刻形成於犧牲層12之上表面14之上之至少一薄膜層8，使犧牲層12露出(第5圖右上)。以及步驟E：移除犧牲層12以形成一奈米結構體陣列1(第5圖右上)，其中奈米結構體陣列1包括複數個奈米結構體11，每一個奈米結構體11形成一容置空間5，容置空間5相對於基板10之一端具有一開口。
在一些實施例中，犧牲層12係為一半導體磊晶層，係以磊晶之方式成長於基板10之上，其中基板10係為一矽基板、一半導體基板或一化合物半導體基板(例如：砷化鎵基板、碳化矽基板、磷化銦基板)。在其他一些實施例中，構成犧牲層12之材料係為金屬或合金，例如鎢化鈦(TiW)。在一些實施例中，基板10係由砷化鎵所構成，犧牲層12係由砷化鎵所構成。在一些實施例中，基板10係由磷化銦所構成，犧牲層12係由砷化銦鎵所構 成。在一些實施例中，基板10係為一矽基板，犧牲層12係由鎢化鈦所構成。
請參閱第6圖，其係為本發明一種奈米結構體陣列之具體實施例之掃瞄式電子顯微鏡成像圖。第6圖之實施例係具有與第3圖之實施例相同之結構(包括第一薄膜層2、第二薄膜層3以及第三薄膜層4)，其中第一薄膜層2以及第二薄膜層3係由相同之材料所構成。第6圖由上而下依序有五列(Row)，每一列有三張圖，每一列分別代表一種材料之組合。第一列(最上面一列)之材料組合為：第一薄膜層2以及第二薄膜層3係由青銅(Bronze)所構成，第三薄膜層4係由鎢鎳硼金屬玻璃(WNiB)所構成；其中奈米管之高度係為700nm；奈米管之直徑係為500nm。第二列之材料組合為：第一薄膜層2以及第二薄膜層3係由銅所構成，第三薄膜層4係由鎢鎳硼金屬玻璃所構成；其中奈米管之高度係為700nm；奈米管之直徑係為1μm。第三列之材料組合為：第一薄膜層2以及第二薄膜層3係由316不銹鋼所構成，第三薄膜層4係由鎢鎳硼金屬玻璃所構成；其中奈米管之高度係為700nm；奈米管之直徑係為1.5μm。第四列之材料組合為：第一薄膜層2以及第二薄膜層3係由718鎳合金所構成，第三薄膜層4係由鎢鎳硼金屬玻璃所構成；其中奈米管之高度係為2μm；奈米管之直徑係為2μm。第五列(最下面一列)之材料組合為：第一薄膜層2以及第二薄膜層3係由銀所構成，第三薄膜層4係由鎢鎳硼金屬玻璃所構成；其中奈米管之高度係為2μm；奈米管之直徑係為10μm。因此，可有許多種組合。
請參閱第7圖，其係為本發明一種奈米結構體陣列之另一具體實施例之掃瞄式電子顯微鏡成像圖。第6圖之實施例係具有與第1圖之實施例相同之結構(單一層之第一薄膜層2)，其中第一薄膜層2係由氧化鋅 (ZnO)所構成。
本發明之奈米管陣列係可應用作為載體，用以成長一些奈米結構，例如奈米粒子，奈米線等。請參閱第8圖，其係為本發明一種奈米結構體陣列之一具體實施例之作為載體應用之掃瞄式電子顯微鏡成像圖。圖中係將本發明之金屬奈米管陣列作為載體，來成長氧化鋅之奈米線。在一些實施例中，本發明之奈米管陣列可作為載體以成長金、氧化鐵等材料之奈米粒子。
以上所述乃是本發明之具體實施例及所運用之技術手段，根據本文的揭露或教導可衍生推導出許多的變更與修正，仍可視為本發明之構想所作之等效改變，其所產生之作用仍未超出說明書及圖式所涵蓋之實質精神，均應視為在本發明之技術範疇之內，合先陳明。
綜上所述，依上文所揭示之內容，本發明確可達到發明之預期目的，提供一種奈米結構體陣列，極具產業上利用之價植，爰依法提出發明專利申請。
1:奈米結構體陣列
10:基板
11:奈米結構體
2:第一薄膜層
20:第一薄膜層之底部
21:第一薄膜層之周圍部
22:第一薄膜層之底部之上表面
23:第一薄膜層之周圍部之內表面
3:第二薄膜層
30:第二薄膜層之底部
31:第二薄膜層之周圍部
4:第三薄膜層
5:容置空間
6:複數層薄膜層

Claims (11)

  1. 一種奈米結構體陣列，係形成於一基板之上，該奈米結構體陣列包括複數個奈米結構體，其中每一該奈米結構體形成一容置空間，該容置空間相對於該基板之一端具有一開口，每一該奈米結構體包括：一第一薄膜層，其中該容置空間之一周圍以及一底部係分別由該第一薄膜層之一周圍部之一內表面以及該第一薄膜層之一底部之一上表面所定義，構成該第一薄膜層之材料係包括選自以下群組之至少一者：一金屬、一合金、一氧化物、一氮化物以及一硫化物，其中該合金係包括選自以下群組之至少一者：青銅、黃銅、鎳合金、不銹鋼、鈦合金、鋁合金、鎂合金、鉬合金、鉭合金、鈮合金、鈷合金、錫合金、鋅合金、鋯合金、金合金以及銀合金，其中該金屬係包括選自以下群組之至少一者：鈹、鎂、鋁、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鎵、鍺、釔、鋯、鈮、鉬、釕、銠、鈀、銀、鎘、銦、錫、鉿、鉭、鎢、鉑、金以及鉛。
  2. 一種奈米結構體陣列，係形成於一基板之上，該奈米結構體陣列包括複數個奈米結構體，其中每一該奈米結構體形成一容置空間，該容置空間相對於該基板之一端具有一開口，每一該奈米結構體包括：複數層薄膜層，其中該複數層薄膜層之任兩相鄰者係由不同之材料所構成，該複數層薄膜層包括：一第一薄膜層，其中該容置空間之一周圍以及一底部係分別由該第一薄膜層之一周圍部之一內表面以及該第一薄膜層之一底部之一上表面所定義，構成該第一薄膜層之材料係包括選自以下群組之至少一者：一金屬、一合金、一氧化物、一氮化物以及一硫化物；以及 一第二薄膜層，其中該第二薄膜層之一底部係位於介於該基板與該第一薄膜層之該底部之間，該第一薄膜層之該周圍部係位於介於該第二薄膜層之一周圍部與該容置空間之間，構成該第二薄膜層之材料係包括選自以下群組之至少一者：一金屬、一合金、一氧化物、一氮化物以及一硫化物。
  3. 如申請專利範圍第2項所述之奈米結構體陣列，其中該複數層薄膜層更包括一第三薄膜層，該第三薄膜層係形成於介於該第一薄膜層與該第二薄膜層之間，構成該第三薄膜層之材料係包括選自以下群組之至少一者：一金屬、一合金、一氧化物、一氮化物、一硫化物、一碳化物以及鑽石。
  4. 如申請專利範圍第3項所述之奈米結構體陣列，其中構成該第三薄膜層之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金、不銹鋼、鈦合金、鋁合金、鎂合金、鉬合金、鉭合金、鈮合金、鈷合金、錫合金、鋅合金、鋯合金、金合金、銀合金、碳化矽、碳化鎢、鑽石、鎢、鎢合金以及鎢鎳硼金屬玻璃。
  5. 如申請專利範圍第2項至第4項中任一項所述之奈米結構體陣列，其中構成該第二薄膜層之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金以及不銹鋼。
  6. 如申請專利範圍第4項所述之奈米結構體陣列，其中構成該第一薄膜層之材料係相同於構成該第二薄膜層之材料。
  7. 如申請專利範圍第3項所述之奈米結構體陣列，其中構成該第一薄膜層之材料係相同於構成該第二薄膜層之材料。
  8. 如申請專利範圍第2項至第4項、第6項或第7項中任一項所述之奈米結構 體陣列，其中構成該第一薄膜層之材料係包括選自以下群組之至少一者：青銅、黃銅、鎳合金、不銹鋼、鈦合金、鋁合金、鎂合金、鉬合金、鉭合金、鈮合金、鈷合金、錫合金、鋅合金、鋯合金、金合金以及銀合金。
  9. 如申請專利範圍第3項、第4項、第6項或第7項中任一項所述之奈米結構體陣列，其中複數層薄膜層更包括至少一第四薄膜層，構成該至少一第四薄膜層之任一者之材料係包括選自以下群組之至少一者：一金屬、一合金、一氧化物、一氮化物、一硫化物、一碳化物以及鑽石，其中該至少一第四薄膜層係形成於(1)介於該第三薄膜層與該第一薄膜層之間、(2)介於該第二薄膜層與該第三薄膜層之間、或(3)介於該第三薄膜層與該第一薄膜層之間以及介於該第二薄膜層與該第三薄膜層之間。
  10. 如申請專利範圍第1項至第4項、第6項或第7項中任一項所述之奈米結構體陣列，其中每一該奈米結構體具有一厚度以及一直徑，該厚度係大於或等於10nm且小於或等於20μm，該直徑係大於或等於100nm且小於或等於100μm。
  11. 一種奈米結構體陣列之製造方法，包括以下步驟：步驟A：形成一犧牲層於一基板之上，其中該基板係為一半導體基板，構成該犧牲層之材料係包括選自以下群組之至少一者：一半導體磊晶、一金屬以及一合金；步驟B：圖形化該犧牲層，以提供複數個凹槽；步驟C：形成至少一薄膜層於該犧牲層之一上表面以及每一該複數個凹槽之一內表面，其中構成該至少一薄膜層之材料係包括選自以下群組之至少一者：一金屬、一合金、一氧化物、一氮化物以及一硫化物，其中 構成該至少一薄膜層之該合金係包括選自以下群組之至少一者：青銅、黃銅、鎳合金、不銹鋼、鈦合金、鋁合金、鎂合金、鉬合金、鉭合金、鈮合金、鈷合金、錫合金、鋅合金、鋯合金、金合金以及銀合金，其中構成該至少一薄膜層之該金屬係包括選自以下群組之至少一者：鈹、鎂、鋁、鈦、釩、鉻、錳、鐵、鈷、鎳、銅、鋅、鎵、鍺、釔、鋯、鈮、鉬、釕、銠、鈀、銀、鎘、銦、錫、鉿、鉭、鎢、鉑、金以及鉛；步驟D：蝕刻形成於該犧牲層之該上表面之上之該至少一薄膜層，使該犧牲層露出；以及步驟E：移除該犧牲層。
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TW200502158A (en) * 2002-12-21 2005-01-16 Juridical Foundation Osaka Ind Promotion Organization Nano-structure of oxides, a method of preparing the same and their use
TW200808131A (en) * 2006-05-31 2008-02-01 Gen Electric Thermoelectric nanotube arrays
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