TW546670B

TW546670B - Method for electroless deposition and patterning of a metal on a substrate

Info

Publication number: TW546670B
Application number: TW091109790A
Authority: TW
Inventors: Emmanuel Delamarche; John C Flake; Matthias Geissler; William S Graham; Roy H Magnuson
Original assignee: Ibm
Priority date: 2001-05-15
Filing date: 2002-05-10
Publication date: 2003-08-11
Also published as: KR100532515B1; WO2002093991A1; JP2004527133A; JP3808037B2; KR20030094350A

Abstract

A method for manufacturing a patterned metal layer on a substrate is provided which comprises the step of electrolessly depositing a blanket metal film of a metal onto a substrate, followed by subsequently patterning said metal layer by means of microcontact printing. The deposited metal can be overplated with another metal, which can be microcontact printed to serve as an etch mask.

Description

546670546670

發明領域本發明有關一種於基材上行金屬無電極沉積及上圖案之方法。更詳言之，本發明有關一種方法，其中組合微接觸印刷及無電極沉積之製程步驟。發明背景，習知技藝在基材上繪製金屬圖案為現代技術中一般需求且重要之製程；其應用於例如微電子及顯示器製造上。此繪圖案一般需要在基材整個表面上真空沉積金屬且使用微影蝕刻及蝕刻技術選擇性移除^金屬之真空沉積及光阻劑消耗在製造金屬結構中構成相當之成本因素，且限制了可藉使方式繪圖案之基材大小。在（絕緣）表面無電極沉積（後文稱ELD)金屬之技術可提供再基材上真空沉積金屬之替代方法（例如參見"無電極電鑛 .基礎及應用”，G.O· Mallory, J.B. Hajdu編輯；美國電鍍廠及表面拋光協會，歐蘭朵，F1，1990)。金屬如銅、銀、金、鎳、鍺及鈷之無電極沉積為廣泛用於印刷電路上製造微細金屬圖案之方法。無電極電鍍係藉自動催化之氧化還原製程進行，其中欲沉積之金屬陽離子藉可溶還原劑在欲形成之金屬圖形表面上還原，或在用以起始沉積之觸媒表面上還原。此氧化還原製成一般僅發生在可催化其之表面。非催化表面首先以金屬觸媒如鈀活化後，發生金屬化。選擇性沉積可藉使催化基材選擇性去活化獲藉觸媒使非反應性表面選擇性活化而達成。製造圖案化觸媒之數種方法為已知，大部分基於微影蝕刻技術。藉 • 6 - 本纸張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 546670 A7 B7 五、發明説明（2 金屬無電極沉積產生之圖形大小可小如〇· 1微米。微接觸印刷亦可提供使用光微影蝕刻進行金屬圖案化之替代方法。微接觸印刷（後文稱pCP)為形成具微米及次微米側向尺寸之有機單層圖案之技術。其在藉戳印至基材上印刷分子之形成某類圖案中提供實驗簡單性及彈性。迄今，大部分先前技藝仰賴長鏈烷硫醇酸酯之顯著能力而在例如金或其他金屬上形成自我組合（self-assembled)之單層。該等圖案可作用為奈米薄層阻劑而保護該支撐金屬免受適當調配之蝕刻劑之腐蝕或可選擇性放置流體在印刷圖案之親水性區域上。具有可能小於1微米之自我組合單層圖案可使用溶於乙醇之烧硫醇浴液作為”油墨’’及使用彈性體之”戮印”印刷在金屬基材上而形成。該戳印係使用光微影蝕刻術或使用其他技術如電子束微影蝕刻所製備之母模（模具）而製造。此戳印表面圖案化揭示於例如ΕΡ-Β-0 784543。FIELD OF THE INVENTION The present invention relates to a method for electrodeless deposition and patterning of metal on a substrate. More specifically, the present invention relates to a method in which the process steps of micro-contact printing and electrodeless deposition are combined. Background of the Invention, Known Techniques Drawing metal patterns on a substrate is a generally required and important process in modern technology; it is used in, for example, microelectronics and display manufacturing. This drawing pattern generally requires vacuum deposition of metal on the entire surface of the substrate and selective removal using lithographic etching and etching techniques. Vacuum deposition of metal and photoresist consumption constitute a considerable cost factor in manufacturing metal structures, and limit The pattern can be used to draw the size of the substrate. The technology of electrodeless deposition (hereinafter referred to as ELD) of metal on (insulating) surfaces can provide an alternative method for vacuum deposition of metal on substrates (see, for example, " Electroless Electroless Mining. Basics and Applications ", GO · Mallory, JB Hajdu Editor; American Electroplating Plant and Surface Polishing Association, Orlando, F1, 1990). Electrodeless deposition of metals such as copper, silver, gold, nickel, germanium, and cobalt is a widely used method for making fine metal patterns on printed circuits. Electroless plating is carried out by an autocatalytic redox process, in which the metal cations to be deposited are reduced on the surface of the metal pattern to be formed by a soluble reducing agent, or on the surface of the catalyst used to initiate deposition. This oxidation Reduction is generally made only on the surface where it can be catalyzed. Non-catalytic surfaces are first metalized after being activated with a metal catalyst such as palladium. Selective deposition can selectively deactivate the catalytic substrate to obtain non-reaction through the catalyst. This is achieved by selective activation of the surface. Several methods for making patterned catalysts are known, most of which are based on lithographic etching techniques. Borrow • 6-This paper size applies to China Standard (CNS) A4 (210X297 mm) 546670 A7 B7 V. Description of the invention (2 The size of the pattern produced by metal electrodeless deposition can be as small as 0.1 micron. Micro-contact printing can also provide the use of photolithography etching for metal Alternative method of patterning. Micro-contact printing (hereinafter referred to as pCP) is a technique for forming organic single-layer patterns with lateral dimensions of micrometer and submicrometer. It prints molecules on the substrate by stamping to form a certain type of pattern. Provides experimental simplicity and flexibility. To date, most previous techniques have relied on the remarkable ability of long-chain alkanethiolates to form self-assembled monolayers on, for example, gold or other metals. These patterns can serve as Nano-layer resists to protect the supporting metal from the corrosion of properly formulated etchant or to selectively place fluids on the hydrophilic areas of the printed pattern. Self-assembled single-layer patterns that may be less than 1 micron can be dissolved in Ethanol burning thiol bath is used as "ink" and elastomeric "stamping" is printed on a metal substrate. The stamp is by photolithography or other The technology is made by a master (mold) prepared by electron beam lithography. This stamp surface pattern is disclosed in, for example, EP-B-0 784543.

Hidber等人，”鈀膠體之微接觸印刷：藉無電極沉積銅之微米規格圖案化'Langmuir，卷12, 1996，第1375-1380頁中，揭示一種在表面上形成微米-及次微米·圖案之方法。此方法使用pCP印刷膠體，其可作為選擇性無電極沉積銅之觸媒。由聚（二甲基矽氧烷）（後文稱PDMS)製造之圖案化彈性體戳印用以遞送觸媒（以溴化四烷銨安定化且溶於曱苯之把膜體）至基材表面。在基材表面上無電極沉積銅僅發生在印刷有鈀膠體並轉移至該基材之處^藉該膠體催化之無電極沉積形成具次微米尺寸圖形之金屬結構。、本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)Hidber et al., "Microcontact Printing of Palladium Colloids: Micron-Specific Patterning of Copper by Electrodeless Deposition of Copper" 'Langmuir, Vol. 12, 1996, pp. 1375-1380, discloses a micro- and sub-micron pattern on the surface This method uses pCP printing colloid, which can be used as a catalyst for selective electrodeless copper deposition. Patterned elastomer made from poly (dimethylsiloxane) (hereinafter PDMS) is stamped for delivery A catalyst (a film stabilized with tetraalkylammonium bromide and dissolved in toluene) onto the surface of the substrate. The electrodeless deposition of copper on the surface of the substrate occurs only where the palladium colloid is printed and transferred to the substrate ^ The metal structure with sub-micron size pattern is formed by electrodeless deposition of this colloid. 、 This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm)

裝訂Binding

546670 A7546670 A7

_·23 A1揭示在基材上無電極⑽導電❹之方 =石夕使用具有壓印至基材表面上供印刷基材且在將印刷基材浸入電錢浴之無電極沉積其間沉積有金屬之基材上提供觸媒圖案之具圖案表面之戮印。因此，該兩參考文獻揭示如何組合μ(：ρ及eld。概言之，該等方式包含⑴以具有對ELD之觸媒具親和性之化^官能度使基材衍生化，（ii)以觸媒溶液油印微米圖案之pDMs^ 印，（iii)在基材上印刷該觸媒，及（iv)在該印刷觸媒圖案上 ELD金屬。簡言之，此策略可表示為"印刷及肛〇"。此策略可隨確·實印刷在歸上之物質而異，其㈣可能在基材上印刷分子以增進觸媒對基材之親和性。此變化中，印刷基材接著需浸入觸媒浴中以將觸媒加入基材印刷區域。其他變化包含以ELD之觸媒層塗佈均勻塗層及印刷分子使/已存在於該基材表面上之觸媒去活化。又另一變化可為以預觸媒層均勻塗佈基材及印刷分子至此預塗怖之基材以活化該預觸媒顆粒。_ · 23 A1 reveals that there is no electrode on the substrate ⑽ conductive square = Shi Xi uses metal that has been imprinted onto the surface of the substrate for printing substrate and the electrode is deposited by dipping the printing substrate into the electric money bath The substrate is provided with a patterned surface stamp of the catalyst pattern. Therefore, these two references disclose how to combine μ (: ρ and eld. In summary, these methods include: derivatizing the substrate with functionalities that have affinity for ELD catalysts; (ii) using The catalyst solution is imprinted with pDMs ^ printed on the micrometer pattern, (iii) the catalyst is printed on the substrate, and (iv) the ELD metal is printed on the printed catalyst pattern. In short, this strategy can be expressed as " printing and Anal 〇 ". This strategy may vary with the actual printed material, which may print molecules on the substrate to improve the affinity of the catalyst to the substrate. In this change, the printing substrate then needs to be Immerse in the catalyst bath to add the catalyst to the printed area of the substrate. Other changes include coating the ELD's catalyst layer with a uniform coating and printing molecules to deactivate / exist the catalyst on the surface of the substrate. One variation may be to uniformly coat the substrate and the printed molecules with the pre-catalyst layer to the pre-coated substrate to activate the pre-catalyst particles.

裝訂然而’該"印刷及ELD "策略及其可能之變化顯示有些嚴重缺點。首先，在ELD之觸媒及玻璃基材間提供黏著性之化學品易自我反應且無法輕易地油印至”傳統”PDMS戳印，而無法均句地轉移至基材上。PDMS為疏水性弹性體且賦予盆親水性之PDMS表面處理在此例中亦為必要。其次，ELD之典型觸媒如Pd/Sn膠體由於該等膠體在其他類溶液中一般不穩定因此以高度-酸性（一般為濃鹽酸）溶液使用。該等膠體為許多金屬之ELD之觸媒且非常具活性。其Binding However, the 'this " printing and ELD " strategy and its possible changes show some serious shortcomings. First, the chemical that provides adhesion between the ELD catalyst and the glass substrate is easily self-reactive and cannot be easily imprinted onto a "traditional" PDMS stamp, and cannot be transferred uniformly to the substrate. PDMS surface treatment in which PDMS is a hydrophobic elastomer and imparts hydrophilicity to the basin is also necessary in this case. Second, typical ELD catalysts such as Pd / Sn colloids are used as highly-acidic (generally concentrated hydrochloric acid) solutions because these colloids are generally unstable in other types of solutions. These colloids are catalysts for ELD of many metals and are very active. its

線 -8 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 546670 A7 B7Line -8-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 546670 A7 B7

對ELD特別適合但高度酸性油墨與印刷工具之相容性有問題·自油墨溢出之HC1氣體將腐钱印刷工具及戳印之金屬背版’且該等蒸氣亦具有安全性問題。除了該等缺點，迄今尚未並未鑑定出可與戳印相容之可印刷之ELD之觸媒活化劑（或去活化劑）。此排除使用達到上述’’印刷及ELD”以組合ELD及pCP之其他方式。再者’當嘗試使用”印刷及ELD”之油墨時，發生尚未解決之下列問題··如何油印該戳印？如何需使其乾燥？如何僅在一次油印中重複使用戳印？如何自戳印清洗油墨？如何在印刷期間控制及預防油墨於基材上之擴散？在無可變觸媒活性之下如何在整個大基材上均勻油印戳印及達到油墨轉移？且，重要地，如何以合理製程達到生產量以賦予，，印刷及ELD”經濟地解決降低基材上製造金屬基材成本問題？在無電極 >儿積金屬及其基材間達到良好黏著性為ELD最重要之挑戰。在沉積期間、自ELD浴移開電鍍基材期間、清洗或乾燥该新電鍍金屬期間、或隨後在加工後或裝置製造步驟期間，無電極沉積金屬在電鍍浴中將喪失其對基材之黏者性。結果，經常需要沉積物及基材間之良好黏著性且、士 4使ELD製程所有細節最適化之結果，自得自供應者之基材予以處理開始及後加工該沉積之金屬以於該材料中釋出應力。發明概述本發月之目的係提供一種在基材上行金屬無電極沉積及上圖案之方法，係組合微接觸印刷及無電極沉積之製本紙張尺度適用中國(⑽x 297公爱） 546670 A7 ____B7 五、發明説明（6 ) 金屬之局部化ELD，但替代地，沉積之金屬可與另一金屬重疊電鍍’其可微接觸印刷而作為银刻掩膜。通常，製程流程如下： 1·藉沉積觸媒而製備電絕緣表面； 2.自溶液中無電極沉積第一金屬； 3·製備供印刷之第一金屬表面，亦即退火、使用形成氣體之表面氧化物還原反應、空氣中氧化反應、清洗或經由電沉積或無電極沉積而沉積額外金屬膜及製備第二金屬表面供微接觸印刷； 4·使用可於隨後蝕刻步驟中作為蝕刻障壁之適當油墨之 μ〇Ρ使此表面圖案化；及 5·於適當溶液中蝕刻金屬或金屬膜。最簡單之可能方式包含Au之ELD步驟，在八11上^1〇?烷硫醇之自我組合單層之步驟及隨後選擇性钱刻AU2步驟。在Au基材上降低至丨微米之解析度微接觸印刷烷硫醇為確實建立之微接觸印刷之唯一應用（參見Delamarche等人，j. ?1^3.〇^111.：6，卷1〇2，1998，第 3324-3334頁）。其接著似乎對發展以Αιχ之ELD為主之策略及以硫醇印刷該沉積之au及使其蝕刻而圖案化中為最適當。此方法由於有成本、Au對基材之不良黏著力等問題，且 Ik尋求之應用而定，有半導體污染問題（在石夕中形成重組中心（牌）而由於Au原子似乎擴散入相鄰Si層）而不利。此應用中亦可使用Ag，但Ag之ELD難以控制且典型上導致膜對平滑絕緣基材之不良黏著力。Ag亦具有半導體污染問題，且 -11- 本纸張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)It is particularly suitable for ELD, but there is a problem with the compatibility of highly acidic inks with printing tools. The HC1 gas spilled from the ink will rot the printing tools and stamped metal back plates' and these vapors also have safety problems. In addition to these disadvantages, no catalyst activator (or deactivator) for printable ELD compatible with stamping has been identified to date. This excludes the use of other methods that achieve the above-mentioned "printing and ELD" to combine ELD and pCP. Furthermore, when trying to use "printing and ELD" inks, the following unresolved problems occur. · How to imprint the stamp? How? Need to make it dry? How to reuse the stamp only in a single imprint? How to clean the ink by self-printing? How to control and prevent the ink from spreading on the substrate during printing? Without variable catalyst activity Uniform imprint stamping on large substrates and ink transfer? And, importantly, how to achieve production volume in a reasonable process to give, printing, and ELD "economically solve the problem of reducing the cost of manufacturing metal substrates on substrates? Achieving good adhesion between electrodeless > cladding metals and their substrates is the most important challenge for ELD. During deposition, during removal of the electroplated substrate from the ELD bath, during the cleaning or drying of this new electroplated metal, or subsequent processing or device manufacturing steps, electrodeless deposited metal will lose its adhesion to the substrate in the electroplating bath. Person. As a result, good adhesion between the deposit and the substrate is often required, and the result of optimizing all the details of the ELD process is to start and post-process the deposited metal from the supplier's substrate for processing in the material. Relieve stress. SUMMARY OF THE INVENTION The purpose of the present month is to provide a method for depositing and patterning metal on electrodes on a substrate, which is a combination of micro-contact printing and electrodeless paper. The paper size is suitable for China (⑽x 297 public love) 546670 A7 ____B7 V. Description of the invention (6) Localized ELD of metal, but instead, the deposited metal may be plated on top of another metal, which can be printed in micro-contact to serve as a silver engraving mask. Generally, the process flow is as follows: 1. Preparing an electrically insulating surface by depositing a catalyst; 2. Depositing a first metal from the solution without an electrode; 3. Preparing a first metal surface for printing, that is, an annealed, gas-forming surface Oxide reduction reaction, oxidation reaction in air, cleaning or deposition of additional metal film through electrodeposition or electrodeless deposition and preparation of a second metal surface for micro-contact printing; 4. Use appropriate inks that can be used as etching barriers in subsequent etching steps ΜOP pattern this surface; and 5. Etch the metal or metal film in a suitable solution. The simplest possible way includes the ELD step of Au, the step of self-assembling monolayers of alkanethiol at 8-11 and the subsequent selective AU2 step. Resolution microcontact printing alkanethiol reduced to 丨 micron on Au substrate is the only application of microcontact printing that is indeed established (see Delamarche et al., J.? 1 ^ 3.〇 ^ 111 .: 6, Volume 1 〇2, 1998, pages 3324-3334). It then appears to be the most appropriate in developing an ELD-based strategy and printing the deposited au with a thiol and patterning it by etching. This method has problems such as cost, poor adhesion of Au to the substrate, and the application sought by Ik, and semiconductor pollution problems (formation of recombination centers (brands) in Shi Xi, and Au atoms seem to diffuse into neighboring Si Layer) but not. Ag can also be used in this application, but the ELD of Ag is difficult to control and typically results in poor adhesion of the film to a smooth insulating substrate. Ag also has semiconductor pollution problems, and -11- this paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm)

裝訂 546670 A7 B7 五、發明説明Binding 546670 A7 B7 V. Description of the invention

Ag易於電移動及腐蝕。Cu亦可以烷硫醇印刷且若考慮此金屬表面上存在之氧化物而有蝕刻選擇性及其相對蝕刻劑之高選擇性。至於Au及Ag,在平滑絕緣表面上電鍍之Cu膜黏著性受到限制。因此，提出另一方式，亦即第一金屬之ELD接著沉積第二金屬及印刷。由於單一ELD金屬（如Au、Ag、Cu)未提供所需性質如良好黏著力及與pCP之相容性，因此多層金屬化及印刷製程可能較佳。例如，Ni、Co或Pd(或其合金）之無電極沉積膜可使用作為第一層及第二金屬層如Cu、Ag或Au(ELD或電鍍）可使用於印刷及作為蝕刻障壁。尤其，沁及州合金（NiB、 NiP、NiWP、NiReP等）為在平滑絕緣基材上elD之優異推薦物。數種錄浴為市售’其可產生良好導電性之電錢Ni。本發明中，通常發展玻璃處理及製程而改良無電極沉積之 Ni之玻璃上之黏著性。Cu便利於電鍍、便宜、當電鍍時可與Ni相容，且其可為微接觸印刷烷硫醇之良好基材。NiB及 Cu之高導電度有助於電鍍期間於大樣品上維持均勻電流密度’其為獲得具有均勻厚度之電鍍掩膜。印刷之Cu可選擇性蝕刻而作為該底下Ni之掩膜。此Cu掩膜若需要可在製程結束時易於移除。本發明"ELD及印刷，，製程之典型流程如下： 1·自溶液中於玻璃基材上接枝對ELD之觸媒具親和性之有機層。 … 2·自溶液中於經處理玻璃上沉積均勻觸媒顆粒層及進行觸 -12- 本紙張尺度適用中國國家橾準(CNS) A4規格(210X297公釐)Ag is prone to electrical movement and corrosion. Cu can also be printed with alkanethiol and has an etch selectivity and a high selectivity to the etchant in consideration of the oxides present on the metal surface. As for Au and Ag, the adhesion of the Cu film plated on a smooth insulating surface is limited. Therefore, another method is proposed, that is, the ELD of the first metal is next deposited and printed. Since a single ELD metal (such as Au, Ag, Cu) does not provide the required properties such as good adhesion and compatibility with pCP, multilayer metallization and printing processes may be better. For example, electrodeless deposited films of Ni, Co, or Pd (or their alloys) can be used as the first and second metal layers such as Cu, Ag, or Au (ELD or electroplating). They can be used for printing and as etching barriers. In particular, Qinhezhou alloys (NiB, NiP, NiWP, NiReP, etc.) are excellent candidates for elD on smooth insulating substrates. Several kinds of recording baths are commercially available 'which can generate good electrical conductivity Ni. In the present invention, glass processing and manufacturing processes are usually developed to improve the adhesion on the glass of electrodeless Ni deposited. Cu is convenient for electroplating, cheap, compatible with Ni when electroplated, and it can be a good substrate for micro-contact printed alkanethiols. The high conductivity of NiB and Cu helps to maintain a uniform current density on large samples during electroplating ', which is to obtain a plating mask with uniform thickness. The printed Cu is selectively etched as a mask for the underlying Ni. This Cu mask can be easily removed at the end of the process if needed. The typical process of the ELD and printing process of the present invention is as follows: 1. An organic layer having an affinity for ELD catalyst is grafted on the glass substrate from the solution. … 2 · Deposit a uniform catalyst particle layer on the treated glass from the solution and perform contact -12- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

裝線五、發明説明（8 ) 3·基材浸於ELD浴中以沉積所需金屬。 4·基材較好架設在陰極框架上並浸於電化學電電鑛該犧牲之掩膜。框架接觸在其所有邊緣之金眉: 對此層分配均勾電流及避免基材：層損壞（刮傷）。展&裝置之金屬 5.掩膜藉微接觸印刷阻劑而選擇綱。 _生保護（自我組合單層 6·掩膜及無電極沉積之金屬接著選擇性移除。 7·掩膜最後整個移除。接著，提供本發明之方法㈣。亦述及此為纟一實例且本發明並非受限於其中所述之該基材、冶金、蝕刻浴、化學品等，而可使用其他基材及材料，且為熟知本技藝悉知玻璃基材（Coming #1737)於室溫下在Ν·(2•胺基乙基卜弘胺基丙基三甲氧基矽烷（後文稱EDA-Si，得自Gelest #SIA0591.0，0.250毫升於120毫升乙醇及2〇毫升水中）浸泡3 分鐘。此步驟期間，EDA黏合至玻璃上。該玻璃接著自接枝浴中移除及以水清洗及乾燥。該玻璃基材在15(rc熱板上或於烘箱中烘烤1 〇分鐘。此在對有些pd/以膠體具親和性之玻璃上產生均勻薄接枝層。經處理玻璃冷卻後健存或立即使用。玻璃基材接著浸於酸性Pd/SiT溶液（得自Fidelity ,文件 #1018 ’以濃HC1稀釋50%)中30秒在接枝玻璃上形成ELD之 -13- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 546670Installation line 5. Description of the invention (8) 3. The substrate is immersed in the ELD bath to deposit the required metal. 4. The substrate is preferably mounted on the cathode frame and immersed in the mask of the sacrificial electrode of electrochemical power. The golden eyebrows where the frame touches all its edges: the current is distributed to the layer and the substrate is avoided: the layer is damaged (scratched). Development & Device Metals 5. Mask selection by micro-contact printing resist. _Bioprotection (Self-combination single layer 6. The mask and the electrodeless metal are then selectively removed. 7. The mask is finally removed entirely. Then, the method of the present invention is provided. This is also mentioned as an example And the present invention is not limited to the substrate, metallurgy, etching bath, chemicals, etc. described herein, but other substrates and materials can be used, and glass substrates (Coming # 1737) are well known in the art. At room temperature under N · (2 · aminoethylbumonaminopropyltrimethoxysilane (hereinafter referred to as EDA-Si, obtained from Gelest # SIA0591.0, 0.250 ml in 120 ml ethanol and 20 ml water) Soak for 3 minutes. During this step, the EDA is adhered to the glass. The glass is then removed from the graft bath and washed with water and dried. The glass substrate is baked on a 150 ° C hot plate or in an oven for 1 〇 Minutes. This produces a uniformly thin graft layer on some pd / colloidally compatible glass. The treated glass is cooled or used immediately after cooling. The glass substrate is then immersed in an acidic Pd / SiT solution (from Fidelity, File # 1018 '50% dilution with concentrated HC1) for 30 seconds to form ELD on the grafted glass -13- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 546670

均勻Pd/Sn觸媒顆粒層。隨後’ Pd/Sn玻璃基材以去離子水大量清洗及浸於"加速劑" 溶液（得自Fidelity，文件#1019，以漢时】稀釋1〇%)中輝 ’接著以去離子水清洗及錢^此活化之玻璃基材放置在80 C熱板上。已述及此活化或加熱步驟為非需要在eld 可以非活化觸媒充分作用之有些例中。現在，該預加熱玻璃基材浸於NiB(Shipley，NipQsit㊣468 依建礅製備，以氨調整pH至7.2)中，在60 °C無電鍍浴，但不攪拌，而以約20-30奈米/分鐘之速率沉積NiB。ELD NiB膜厚度可藉沉積速率及浸泡時間控制。Uniform Pd / Sn catalyst particle layer. Then "Pd / Sn glass substrate was washed and immersed in " accelerator " solution (extracted from Fidelity, file # 1019, diluted 10% in Chinese) with deionized water, followed by deionized water. Cleaning and cleaning ^ The activated glass substrate was placed on a 80 C hot plate. It has been mentioned that this activation or heating step is not necessary in some cases where eld can fully function with the non-activated catalyst. Now, the pre-heated glass substrate is immersed in NiB (Shipley, NipQsit㊣468, according to Jianjian, pH adjusted to 7.2 with ammonia), without electroplating bath at 60 ° C, but without stirring, but with about 20-30 nanometer NiB was deposited at a rate of meters per minute. ELD NiB film thickness can be controlled by deposition rate and immersion time.

Ik後，在150 C熱板上放置具有薄（約5〇至4〇〇奈米）NiB膜歷時10分鐘，而改善Ni沉積及玻璃基材間之黏著性。此步驟後，使用焦磷酸銅浴於NiB沉積物上電鍍cu薄膜 (50 奈米）：1.1 克 CuS〇4 · 5h2〇，3 〇克 Ν〜ρ2〇7及 2〇〇毫克 NaHJO4溶於120毫升去離子水中。此浴之卩^[約9且在3〇c>c 使用。典型上存在於無電極沉積之NiB上之Ni之天然氧化物在電鍍前藉由將NiB-覆蓋之樣品浸於〇·3 M HC1溶液中而蝕刻及以去離子水清洗。移除Νί〇χ並非極度需要但在犯及以間提供良好黏著性。以荨電壓計型號263A(EG&G銷售）在電壓固定於-0.7至-1 .〇γ (相對Ag/AgCl參考電極）操作下進行cu電鍍，而以鑛始之鈦格栅（30 cm2，大面積之樣品需要較大電極）作為相反電極。電鍍期間追蹤電流顯示Cu沉積速―率及其厚度（對50奈米之cu 為 0· 15 cm·2)。 -14- 本纸張尺度適用中國國家榇準(CNS) A4規格(210X297公釐)After Ik, a thin (about 50 to 400 nm) NiB film was placed on a 150 C hot plate for 10 minutes, which improved the Ni deposition and the adhesion between the glass substrates. After this step, a Cu thin film (50 nm) was electroplated on the NiB deposits using a copper pyrophosphate bath: 1.1 g of CuS04 · 5h20, 30 g of N ~ ρ207 and 200 mg of NaHJO4 in 120 ml Deionized water. This bath was ^^ [about 9 and used at 30c> c. The natural oxide of Ni, which is typically present on NiB deposited without electrodes, is etched and washed with deionized water by immersing the NiB-coated sample in a 0.3 M HC1 solution before plating. Removal of Νί〇χ is not extremely needed but provides good adhesion between the offender and others. Cu voltameter model 263A (sold by EG & G) was used for cu plating at a fixed voltage of -0.7 to -1.00 (relative to Ag / AgCl reference electrode), and a titanium grid (30 cm2, Large-area samples require larger electrodes) as opposite electrodes. The tracking current during plating shows the rate of Cu deposition and its thickness (0 · 15 cm · 2 for cu of 50 nm). -14- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

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546670 五 A7 B7 、發明説明（1G )546670 Five A7 B7, invention description (1G)

Cu-覆蓋之基材浸於0·1 M HC1溶液中10秒以自表面移除氧化銅，以去離子水清洗及印刷前乾燥以確保印刷步驟期間形成均勻及密實之保護單層。現在，由PDMS(道康寧公司之Sylgard® 184)製得之微圖案化戳印首先以二十烷硫醇（ECT，由Robinson兄弟有限公司提供，文件#SV109/4)於乙醇之0.2 mM溶液上油墨，乾燥及用以印刷電鍍之銅20秒，其於接觸區域中形成單層。未印刷之Cu在室溫於0.025 M KCN溶液（於去離子水中，在pH 12緩衝）中以適當攪拌之下蝕刻（蝕刻速率約每分鐘50 奈米Cu)。此步驟期間未觀察到NiB沉積物之蝕刻。隨後，NiB於1 M H2S04中在室溫及適度攪拌下蝕刻20分鐘（蝕刻速率每分鐘5-10奈米NiB，此蝕刻速率亦隨圖案之幾何而異）。若Cu掩膜仍受該硫醇單層保護時，此蝕刻之選擇性極高；該Cu上之硫醇單層基此理由僅隨後移除。現在樣品浸於含KOH及10% H202水溶液中（pH 14)歷時20 分鐘而移除所有有機層（銅上之ECT單層及玻璃上之EDA接枝層）。存在於玻璃上NiB已蝕刻處上之Pd/Sn觸媒亦可在此步驟期間藉向下蝕刻Sn、EDA接枝及微量玻璃而蝕刻。電鍍之Cu在此步驟均一地蝕刻，但速率極低。若留在NiB間之區域需充分透光則此步驟具重要性或由於留在該等區域之有些Pd/Sn可阻斷有些光或在相鄰、鄰近NiB結構間導出某些電流則可為電絕緣。接著所有剩餘Cu於KCN之0.02ΓΜ水溶液（在pH 12緩衝）中蝕刻2分鐘。 -15- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)The Cu-covered substrate was immersed in a 0.1 M HC1 solution for 10 seconds to remove copper oxide from the surface, washed with deionized water and dried before printing to ensure that a uniform and dense protective monolayer was formed during the printing step. Now, micropatterned stamps made by PDMS (Sylgard® 184 from Dow Corning) are first eicosanethiol (ECT, provided by Robinson Brothers, Inc., document # SV109 / 4) on a 0.2 mM solution of ethanol Ink, dried and used to print electroplated copper for 20 seconds, which forms a single layer in the contact area. Unprinted Cu is etched at room temperature in a 0.025 M KCN solution (in deionized water, buffered at pH 12) with appropriate agitation (etch rate is about 50 nm Cu per minute). No etching of NiB deposits was observed during this step. Subsequently, NiB was etched in 1 M H2S04 for 20 minutes at room temperature with moderate agitation (the etch rate is 5-10 nm NiB per minute, and this etch rate also varies depending on the geometry of the pattern). If the Cu mask is still protected by the thiol monolayer, the selectivity of this etch is extremely high; the thiol monolayer on the Cu is only subsequently removed for this reason. The sample was now immersed in KOH and 10% H202 aqueous solution (pH 14) for 20 minutes to remove all organic layers (the ECT single layer on copper and the EDA grafted layer on glass). The Pd / Sn catalyst existing on the etched place of NiB on the glass can also be etched by etching down Sn, EDA graft and trace glass during this step. The electroplated Cu is uniformly etched at this step, but the rate is extremely low. This step is important if the areas left between the NiBs need to be fully transparent or some Pd / Sn left in these areas can block some light or induce some current between adjacent and adjacent NiB structures. Electrical insulation. All remaining Cu was then etched in KCN's 0.02ΓM aqueous solution (buffered at pH 12) for 2 minutes. -15- This paper size applies to China National Standard (CNS) A4 (210X 297mm)

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Claims

546670 ^ λ p p “第齒1_90號專利_請案 g 中紙暴專利範圍替換本(92年5月） C8 六、申請專利範圍— ' " 一種在基材上製造圖案化金屬層之方法，該方法包括下列步驟： a) 藉由在該基材上接枝有機層而預調節該基材； b) 在該預調節基材上沉積觸媒層； Ο藉無電極沉積技術在該觸媒層上沉積金屬層； d) 在該金屬層上沉積犧牲掩膜； e) 使用微接觸印刷在該犧牲掩膜上沉積圖案化之蝕刻保護層； f) 在該圖案化#刻保護層自由區域中蝕刻除該犧牲掩膜 :及 g)於不含該犧牲層之區域蝕刻除該無電極沉積之金屬層。 2·如申請專利範圍第1項之方法，其特徵為其又包括在步騾b)之後活化無電極沉積之該觸媒層之步驟。 3. 如申請專利範圍第1項之方法，其特徵為其又包括蝕刻除該犧牲層其餘部分。 4. 如申請專利範圍第2項之方〉去，其特徵為其〖包括姓刻除該犧牲層其餘部分。 5·如申請專利範圍第1至4項中任一項之方法，其特徵為其又包括姓刻除该接枝有機層及該觸媒層之步驟。 … 6·如申請專利範圍第1至4項中任一項之方法，其特徵有機層係N-(2-胺基乙基）-3-胺基丙基= 及 ,ϋΤΛΛ、 — Τ乳基砂$完項之方法’其特徵為沉基材浸入含觸媒顆粒之如申請專利範圍第1至4項中任一積該觸媒層之該步驟係藉由將該 7. 46546670 ^ λ pp "Patent No. 1_90_Please file g Chinese paper storm patent scope replacement (May 1992) C8 VI. Patent scope-'" A method for manufacturing a patterned metal layer on a substrate, The method includes the following steps: a) pre-adjusting the substrate by grafting an organic layer on the substrate; b) depositing a catalyst layer on the pre-adjusted substrate; Depositing a metal layer on the layer; d) depositing a sacrificial mask on the metal layer; e) depositing a patterned etch protection layer on the sacrificial mask using micro-contact printing; f) in the patterned #etched protective layer free area Etching the sacrificial mask by etching: and g) Etching the electrodeless metal layer in an area not containing the sacrificial layer. 2. If the method according to item 1 of the scope of patent application is characterized in that it is also included in step 骡b) the subsequent step of activating the catalyst layer deposited without electrodes. 3. If the method of the first scope of the patent application is applied, it is characterized by including etching the rest of the sacrificial layer. 4. If the second scope of the patent application is applied Zhi Fang>, which is characterized by including the last name The rest of the sacrificial layer. 5. The method according to any one of claims 1 to 4, which is characterized in that it further comprises a step of engraving the grafted organic layer and the catalyst layer. ... 6 · 如The method according to any one of claims 1 to 4, wherein the organic layer is characterized by N- (2-aminoethyl) -3-aminopropyl = and, ϋΤΛΛ, —Τ milk-based sand The method 'is characterized in that the substrate is immersed in the catalyst-containing particles, and the step of accumulating the catalyst layer as described in any of claims 1 to 4 of the patent application range is performed by the 7.46

溶液中而進行。 8. 如中請專利範圍第7項之方法，其特徵為該觸媒顆粒包括 Pd/Sn 〇 9. t中請專利範㈣2項之方法，其特徵為該活化步驟係藉由將咸基材浸入加速劑溶液中而進行。 L申叫專利圍第9項之万法，其特徵為該加速劑溶液括HBF4 〇 u·，申請專利範圍第1至4項中任-項之方法，其特徵為該犧牲掩膜包括銅。 12^申請專·圍第丨丨項之方法，其特徵4該犧牲掩膜電鍍法沉積者。 W申請專利範圍第！至领中任—項之方法，其特徵為該蚀呆護層係藉微圖案化戳印法印刷二十燒硫醇之自我組合單層（SAM)而塗佈者。 η如:請專·圍第13項之方法，其特徵為該微圖案化戮印為聚（二甲基矽氧烷）(PDMS)戳印。 =申請專利範圍第W項中任—項之方法，其特徵為蚀刻除孩犧牲掩膜之該步驟係&KCN/氧為主之㈣浴進行者 =申請專利範圍第…項中任_項之方法，其特徵為蚀刻除孩金屬層之該步驟係以HjO4溶液進行者。 17.2請專利第3或4項之方法，其特徵為㈣除層其餘部分之該步驟係以KCN進行者。 18·如申請專利範圍第5項之方法，其特徵絲刻除該有機声 -2 - 六、申請專利範圍 =該觸制之該”係以随及H处之水性混合物進行议如申請專利範圍第…項中任一項之方法，其特徵為該基 ^係選自玻m氧化表面、Si制2等所成之組群 2〇.如申請專利範圍第⑴項中任一項之方法，其特徵為該無電極沉積金屬層係選自Ni、NiB、Nip、Niwp、c〇、 CoWP ' CoP、Pd等所成組群者。 21·如申凊專利範圍第2〇項之方法，其特徵為沉積在該觸媒層上之該金屬層包括Ni及Β之合金。 22.如申請專利範圍第！至4項中任一項之方法，其特徵為該第一至屬層係選自Au、Cu及Ag之組群者。 23·如申請專利範圍第1至4項中任一項之方法，其特徵為該微圖案化戳印係以烷硫醇油印者。 24.如申請專利範圍第23項之方法，其特徵為該烷硫醇係二十烷硫醇者。 25·如申凊專利範圍第1至4項中任一項之方法，其特徵為該犧牲掩膜之該蝕刻係藉對該掩膜具選擇性之蝕刻劑進行者。 26·如申4專利範圍第1至4項中任一項之方法，其特徵為該金屬層係使用對該犧牲掩膜具選擇性之任何蝕刻化學品蝕刻者。 27·如申請專利範圍第！至4項中任一項之方法，其特徵為使用陰極框架電鍍該犧牲掩膜者。 28·如申凊專利範圍第27項之方法，其特徵為該框架接觸該金 8 8 8 8 A B c D t 4 546670 六、申請專利範圍屬層所有邊緣。本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)In solution. 8. The method according to item 7 of the patent, characterized in that the catalyst particles include Pd / Sn 〇 9. The method in item 2 of the patent, characterized in that the activation step is performed by applying a salty substrate Immersion is performed in an accelerator solution. The L application is called the tenth method of the patent, which is characterized in that the accelerator solution includes HBF40 u ·, and the method in any one of the first to fourth patent applications, which is characterized in that the sacrificial mask includes copper. 12 ^ Apply the method of item 丨丨 characteristic, which is characterized in 4 the sacrificial mask plating method depositor. W applies for patent scope! The method to any item in the collar is characterized in that the etch protective layer is coated by printing a self-assembled monolayer (SAM) of twenty-thiol mercaptan using a micro-patterned stamping method. η For example, please refer to the method of item 13, characterized in that the micro-patterned stamp is a poly (dimethylsiloxane) (PDMS) stamp. = Any method of item W in the scope of patent application, which is characterized in that the step of etching the sacrifice mask is performed by & KCN / oxygen-based bath performer = any item in the scope of patent application ... The method is characterized in that the step of etching away the metal layer is performed by a HjO4 solution. 17.2 The method according to item 3 or 4 of the patent, characterized in that the step of removing the rest of the layer is performed by KCN. 18 · If the method of the scope of patent application No. 5 is used, the characteristic silk engraving removes the organic sound -2-6. The scope of patent application = the touch of the "" is to discuss the scope of the patent application with the aqueous mixture at H The method according to any one of the items, characterized in that the group is selected from the group consisting of a glass oxide surface, 2 made of Si, and the like. It is characterized in that the electrodeless deposited metal layer is a group selected from the group consisting of Ni, NiB, Nip, Niwp, co, CoWP 'CoP, Pd, etc. 21. A method as claimed in claim 20 of the patent scope, which It is characterized in that the metal layer including the alloy of Ni and B is deposited on the catalyst layer. 22. The method according to any one of claims! To 4 in the patent application scope, characterized in that the first subordinate layer is selected from Groups of Au, Cu and Ag. 23. The method according to any one of claims 1 to 4, characterized in that the micropatterned stamp is imprinted with an alkanethiol. 24. If applying for a patent The method of the scope item 23 is characterized in that the alkanethiol is eicosanethiol. 25. Any one of the items 1 to 4 of the scope of the patent application The method is characterized in that the etching of the sacrificial mask is performed by an etchant that is selective to the mask. 26. The method of any one of items 1 to 4 of the patent scope of claim 4, characterized in that The metal layer is an etcher using any etching chemical that is selective to the sacrificial mask. 27. The method of any one of claims! To 4 in the scope of patent application, characterized in that the sacrificial mask is plated using a cathode frame 28. If applying the method of the 27th patent scope, it is characterized in that the frame contacts the gold 8 8 8 8 AB c D t 4 546670 6. The scope of patent application belongs to all edges of the layer. This paper standard applies to Chinese national standards (CNS) A4 size (210 X 297 mm)