TWI415969B - Preparation of nanostructures - Google Patents
Preparation of nanostructures Download PDFInfo
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- TWI415969B TWI415969B TW098144459A TW98144459A TWI415969B TW I415969 B TWI415969 B TW I415969B TW 098144459 A TW098144459 A TW 098144459A TW 98144459 A TW98144459 A TW 98144459A TW I415969 B TWI415969 B TW I415969B
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 239000000523 sample Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 7
- 230000000295 complement effect Effects 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 29
- 239000002094 self assembled monolayer Substances 0.000 abstract description 7
- 239000013545 self-assembled monolayer Substances 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract 5
- 150000002894 organic compounds Chemical class 0.000 abstract 5
- 230000008021 deposition Effects 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000979 dip-pen nanolithography Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 4
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 decylamino group Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 3
- 238000004621 scanning probe microscopy Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 150000003573 thiols Chemical group 0.000 description 3
- INOAASCWQMFJQA-UHFFFAOYSA-N 16-sulfanylhexadecanoic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCS INOAASCWQMFJQA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 description 1
- UGZAJZLUKVKCBM-UHFFFAOYSA-N 6-sulfanylhexan-1-ol Chemical compound OCCCCCCS UGZAJZLUKVKCBM-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005442 molecular electronic Methods 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- NKAAEMMYHLFEFN-ZVGUSBNCSA-M sodium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Na+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O NKAAEMMYHLFEFN-ZVGUSBNCSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
- C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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Description
本發明是有關於一種奈米結構的製作方法，特別是指一種利用沾筆式奈米技術(Dip Pen Nanolithography)製作奈米結構的方法。
由於科技的蓬勃發展，相關的半導體工業製程亦隨著需求而迅速發展，元件的尺寸隨著科技的發展亦愈來愈微型化，因此如何製作微型化的電路結構，其技術發展亦越來越受到重視，而其中沾筆式奈米微影技術(Dip Pen Nanolithography，以下簡稱DPN)則為近十年來發展用以製備分子電路的微影技術之一。
DPN是利用吸附有機分子的探針與基材接觸，並利用有機分子的自組裝(self-assembled)特性在基材表面形成奈米圖案的微影技術，例如，參閱圖1，利用吸附具有硫醇官能基之有機分子2的掃描式顯微鏡(SPM)探針001在一具有一金屬層11之基材1表面移動，利用有機分子21與該金屬層11結合形成一預設圖案2，接著，以濕式蝕刻方式對該金屬層11進行蝕刻，將未吸附有機分子21的金屬層11移除，即可形成由該有機分子21與金屬111構成之金屬奈米結構圖案，此方法形成之奈米結構圖案由於經過蝕刻製程形成結構可控制尺寸與位置。
參閱圖2，另一種利用DPN方式製備奈米結構圖案的方法則是將一具有金屬層11的基材1先浸置於一含有硫醇官能基之有機分子21(例如正十二烷基硫醇，SH-(CH2
)11
-CH3
)的溶液中，利用有機分子21於該金屬層11表面形成一自組裝單分子薄膜(self-assembled monolayer，SAM)之保護膜2後，再以掃描式顯微鏡探針001將預定區域之單分子薄膜刮除，讓該部分之金屬層11的裸露出，即可在該基材1上形成如圖2所示之金屬/分子奈米級分子電路圖案，然而以此方法形成之奈米圖案，由於是藉由探針將該金屬層上預定區域之有機分子刮除，因此，露出之金屬層11的均一性較不易控制，且探針亦容易在刮除的過程中耗損。
隨著科技的發展預計元件的尺寸將縮小至分子的大小，因此分子電子學(molecular electronics)的研究亦越來愈受到重視，而如何提供更方便且可更為精確控制分子電路形成之方式，以利未來之研究發展，則為此技術領域研究者努力發展的重要目標之一。
因此，本發明之目的，即在提供一種奈米結構的製作方法。
於是，本發明一種奈米結構的製作方法包含以下五個步驟。
首先，在一奈米級探針上吸附多數第一型有機分子，其中，該等第一型有機分子的結構是SH-R1
-X1
，R1
是選自C1
~C30
的烷基，X1
是硫醇基、羥基、羧酸基、胺基，或醯胺基。
接著，準備一具有一由金屬原子構成之金屬層的基材。
然後，移動該吸附有該等第一型有機分子的探針，使該等第一型有機分子分別以其硫醇基與該金屬層之預定位置的金屬原子相結合，令該等第一型有機分子轉連結至該等金屬原子上而形成一第一圖案。
再接著，將形成有該第一圖案的基材浸到一含有多數第二型有機分子的溶液中，讓該等第二型有機分子與該金屬層其他位置的金屬原子結合而形成一與該第一圖案彼此互補的第二圖案，其中，該等第二型有機分子的結構是SH-R2
-X2
，R2
是選自C1
~C30
的烷基，X2
是甲基或鹵素取代之甲基，較佳地，該X2
是選自CH3
、CF3
、CCl3
，或CBr3
。
最後，將前述形成有該第一、二圖案之基材浸入一組成份包含第一金屬離子的化學鍍液中，讓該第一金屬離子還原、沉積在該第一型有機分子上，以完成該金屬/有機分子/金屬奈米結構的製造。
本發明之功效在於：先於金屬層上形成由不同結構的第一、二型有機分子構成且彼此互補的第一、二圖案，藉以改變金屬層的表面性質後，再以化學鍍方式選擇性沉積第一金屬於該等第一型有機分子上，形成金屬/有機分子/金屬的奈米結構，不僅製程方法簡單且可藉由第一圖案的控制而精確控制後續形成之第一金屬的形狀及位置。
有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式之一個較佳實施例的詳細說明中，將可清楚的呈現。
參閱圖3、圖4，本發明一種奈米結構的製作方法的一較佳實施例是包含以下六個步驟。
首先進行吸附步驟61，先在一掃描式顯微鏡(Scanning Probe Microscopy，SPM)探針上吸附多數第一型有機分子，更詳細的說，該步驟是將原子力顯微鏡(AFM)之探針浸置在一含有該等第一型有機分子的溶液中，讓該等第一型有機分子吸附在該探針後備用。
其中，該等第一型有機分子的結構是SH-R1
-X1
，R1
是選自C1
~C30
的烷基，X1
是選自硫醇基(SH)、羥基(OH)、羧酸基(COOH)、胺基(NH2
)，或醯胺基(CONH2
)。
較佳地，該第一型有機分子是選自11-氫硫基-十一烷基醇(11-mercaptoundcanol)、正己烷基硫醇(6-mercaptohexanol)、16-氫硫基-十六烷基羧酸(16-mercaptohexadecanoic acid，16-MHA)等具官能基之長碳鏈硫醇。
接著進行準備步驟62，準備一具有一由金屬原子構成之金屬層的基材。
具體的說，該金屬層是以濺鍍或蒸鍍等方式形成在一本體上而得到該具有金屬層的基材，該金屬層是選自金、銀、銅，及鈀，該本體是選自矽晶片(wafer)或雲母(mica)片金屬或金屬氧化物。
接著進行第一圖案形成步驟63，配合參閱圖4(a)，移動該吸附有該等第一型有機分子31的探針，使該等第一型有機分子31分別以其硫醇基與該金屬層11之預定位置的金屬原子相結合，使該等第一型有機分子31轉連結至該金屬層11上而形成一第一圖案3。
更詳細的說，該步驟是藉由AFM機台的操作，移動該吸附有第一型有機分子31的探針001在該金屬層11表面移動，使該等第一型有機分子31分別以其硫醇基與該金屬層之預定位置的金屬原子相結合，且由於該等第一型有機分子31為選自分子兩端分別具有官能基之雙官能基分子，因此，當該第一型有機分子31以硫醇基與該金屬層11反應結合形成第一圖案3時，該第一圖案3之表面性質即會因為該第一型有機分子31之X1
官能基的影響而形成一具有極性的表面。
接著進行第二圖案形成步驟64，配合參閱圖4(b)，將形成有該第一圖案3的基材1浸到一含有多數第二型有機分子41的溶液中，讓該等第二型有機分子41與該金屬層11其他位置的金屬原子結合而形成一與該第一圖案3彼此互補的第二圖案4，於本實施例中，該等第二型有機分子41的結構是SH-R2
-X2
，R2
是選自C1
~C30
的烷基，X2
是選自甲基。
較佳地，該第二型有機分子41是丙烷基硫醇(CH3
(CH2
)2
SH，1-Propanethiol，PT)、正十二烷基硫醇(CH3
(CH2
)11
SH，1-dodecanethiol)，或正十八烷基硫醇(CH3
(CH2
)17
SH，1-octadecanethiol，ODT)。
詳細的說，該步驟是將形成該第一圖案3的基材1，浸泡在含有該等第二型有機分子41的乙醇溶液約12~16小時，之後以乙醇及去離子沖洗數次，將為物理性吸附在該基材1的第二型有機分子41移除，即可在該金屬屬11上形成一由該等第二型有機分子41構成且與該第一圖案3為互補之第二圖案4，該等第二型有機分子41由於選自其中一端為硫醇官能基，另一端則為不具反應性之結構，因此，當以具有硫醇官能基之一端與該金屬層11結合形成該第二圖案4後，該第二圖案4之表面性質即會因為該第二型有機分子41的保護形成一鈍化的非極性表面，而使得該第一圖案3與該第二圖案4之表面性質產生差異。
然後進行活化步驟65，將表面形成有該第一、二圖案3、4的基材1浸入一含有第二金屬離子之活化溶液中，令該第二金屬離子選擇性吸附於該等第一型有機分子的X1
官能基上。
詳細的說，於本實施例中，該活化溶液是含有過氯酸銅的乙醇溶液，該活化溶液中的銅離子可吸附於該第一型有機分子的X1
官能基上作為成核點，以確保後續化學鍍製程的反應性。
最後進行金屬沉積步驟66，配合參閱圖4(c)，將前述經過活化溶液處理後之基材1浸入一組成份包含第一金屬離子的化學電鍍液中，並讓該第一金屬離子還原成第一金屬5沉積在該第一型有機分子31上，形成金屬/有機分子/金屬的奈米結構，以完成該奈米結構的製造。
詳細的說，於本實施例中該步驟66的化學鍍液是使用無電鍍銅液，該無電鍍銅液的製法是先將硫酸銅(CuSO4
‧5H2
O)和酒石酸氫鈉(sodium hydrogen tartrate)溶於去離子水中，以超音波震盪20分鐘後，加入氫氧化鈉將pH值調整到約12~13，最後加入體積百分比(v/v%)為2v/v%的甲醛，即得到該無電鍍銅液，接著，將該基材製入該無電鍍銅液中靜置一預定時間後，讓該銅離子還原成銅金屬沉積在該第一型有機分子之X1
官能基上，以完成本發明奈米結構的製作方法。
本發明藉由DPN方式，先將具有雙官能基團之第一型有機分子與該金屬層反應結合形成第一圖案，再以具有單官能基團之第二型有機分子形成與該第一圖案互補之第二圖案，利用該第一、二型有機分子的結構選擇，造成該第一、二圖案之表面性質差異，而得以控制以化學電鍍沉積第一金屬時，該第一金屬僅會選擇性沉積在該第一型有機分子上，不僅製程方法簡單且可藉由第一圖案的控制而精確控制後續形成之第一金屬的形狀及位置，因此可提供於製作分子電路時一個有效且方便之方法，故確實可達到本發明之目的。
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。
001．．．探針
1．．．基材
11．．．金屬層
3．．．第一圖案
31．．．第一型有機分子
4．．．第二圖案
41．．．第二型有機分子
5．．．第一金屬
61．．．吸附步驟
62．．．準備步驟
63．．．第一圖案形成步驟
64．．．第二圖案形成步驟
65．．．活化步驟
66．．．金屬沉積步驟
圖1是一示意圖，說明習知金屬/分子奈米結構；
圖2是一示意圖，說明習知金屬/分子奈米結構；
圖3是一流程圖，說明本發明奈米結構的製作方法之較佳實施例；及
圖4是一示意圖，輔助說明圖3。
61．．．吸附步驟
62．．．準備步驟
63．．．第一圖案形成步驟
64．．．第二圖案形成步驟
65．．．活化步驟
66．．．金屬沉積步驟
Claims (6)
- 一種奈米結構的製作方法，包含：(a)在一奈米級探針上吸附多數第一型有機分子，其中，該等第一型有機分子的結構是SH-R1 -X1 ，R1 是選自C1 ~C30 的烷基，X1 是硫醇基、羥基、羧酸基、胺基，或醯胺基；(b)準備一具有一由金屬原子構成之金屬層的基材；(c)移動該吸附有該等第一型有機分子的探針，使該等第一型有機分子分別以其硫醇基與該金屬層之預定位置的金屬原子相結合，使該第一型有機分子轉連結至該等金屬原子上而形成一第一圖案；(d)將形成有該第一圖案的基材浸到一含有第二型有機分子的溶液中，讓該第二型有機分子與該金屬層其他位置的金屬原子結合而形成一與該第一圖案彼此互補的第二圖案，其中，該等第二型有機分子的結構是SH-R2 -X2 ，R2 是選自C1 ~C30 的烷基，X2 是甲基或鹵素取代之甲基；及(e)將前述形成有該第一、二圖案之基材浸入一組成份包含一第一金屬離子的化學鍍液中，讓該第一金屬離子還原成一第一金屬沉積在該第一圖案上，以完成該奈米結構的製造。
- 依據申請專利範圍第1項所述之奈米結構的製作方法，其中，鹵素取代之甲基是CBr3 、CF3 ，或CCl3 。
- 依據申請專利範圍第1項所述之奈米結構的製作方法，其中，該金屬層是金、銀、銅，或鈀。
- 依據申請專利範圍第2項所述之奈米結構的製作方法，其中，該第一金屬離子是金、銀、銅，或鈀。
- 依據申請專利範圍第1項所述之奈米結構的製作方法，更包含一實施在該步驟(e)之前的步驟(f)，係將形成有該第一、二圖案的金屬層浸入一含有第二金屬離子的活化溶液中，於該第一型有機分子的X1 基團吸附供成核用之第二金屬離子。
- 依據申請專利範圍第5項所述之奈米結構的製作方法，其中，該第二金屬離子是銅、金、銀、鈀、鎳、鐵、鋁，或其中之一組合。
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| US10020807B2 (en) * | 2013-02-26 | 2018-07-10 | C3Nano Inc. | Fused metal nanostructured networks, fusing solutions with reducing agents and methods for forming metal networks |
| US11274223B2 (en) | 2013-11-22 | 2022-03-15 | C3 Nano, Inc. | Transparent conductive coatings based on metal nanowires and polymer binders, solution processing thereof, and patterning approaches |
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