TW297786B - - Google Patents

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Publication number
TW297786B
TW297786B TW83108490A TW83108490A TW297786B TW 297786 B TW297786 B TW 297786B TW 83108490 A TW83108490 A TW 83108490A TW 83108490 A TW83108490 A TW 83108490A TW 297786 B TW297786 B TW 297786B
Authority
TW
Taiwan
Prior art keywords
coating
hydrogen
patent application
item
resin
Prior art date
Application number
TW83108490A
Other languages
English (en)
Original Assignee
Dow Corning
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Dow Corning filed Critical Dow Corning
Application granted granted Critical
Publication of TW297786B publication Critical patent/TW297786B/zh

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31058—After-treatment of organic layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H01L21/02134—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material comprising hydrogen silsesquioxane, e.g. HSQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Formation Of Insulating Films (AREA)
  • Silicon Compounds (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paper (AREA)

Description

第83108490號專利申請案 Φ1Γ銳昍婁你TF苜（85年3月1 A7
經濟部中夬標準局貝工消費合作杜印裝 本發明係與一種Μ氫氣來處理由氫倍半矽氧烷樹脂（H-樹脂）衍生之含SiO陶瓷塗曆之方法有關。所產生之塗層 具有儍異之性質。 此技苞已知將由H-樹脂衍生之含矽氧陶瓷塗層使用於霣 子裝置上。例如，美國專利第4,756,977號中描述了形成 此種塗層之方法，其包含K溶劑稀釋氫倍半矽氧烷，將此 溶劑施塗於基質之上，再使溶劑揮發，並於空氣中將此基 質加熱至攝氏150到1000度。然而，此專利並未提及Μ氫 氣熱處理此塗層之效果或對其罨氣性質之影響。 此技藝亦巳知，於其它環境中將Η-樹脂轉化為含Si-Ο陶 瓷。例如，歐洲專利申請案第90311008.8號中說明了 H-樹 脂於惰性氣體中之轉化。此文件亦未說明K氫氣熱處理此 塗層或對其電氣性質之影響。 如今，本發明人發規，當K氫氣處理由Η-樹脂衍生之含 Si-Ο陶瓷塗層時，此塗層之性質即可改良。 本發明提供了一種在電子基質上形成含Si-0塗層之方法 。此方法包括先將含Η-樹脂之塗層施塗於電子基質之上。 再將經塗佈之電子基質加熱至足Μ將Η-樹脂轉化為含 Si-Ο陶瓷塗$之溫度。然後將此含Si-Ο之陶瓷塗層，於足 Μ使此塗f退1火之溫度下，曝露於含籮氣之氛圍中一段時 間。’ 本發明亦與介電常數小於或等於4.5之含Si-Ο陶瓷塗層 有關。 本發明係根據於不經意之發現，即Μ氫氣熱處理由H -樹 -4 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先Μ讀背面之注意事項再填寫本頁) -裝- 線 經濟部中央梂準局貝工消費合作社印«. A7 B7 五、發明説明（2 ) 脂衍生之含Si-Ο陶瓷塗暦，印可改進此塗層之性質。例如 ，此棰熱處理可降低塗曆之介電常數，並可使其安定。再 者，此處理亦可對塗暱之物性產生有利的影W (如·吸收 水氣、破裂等）。由於在此技藝中，氪氣如何影響塗曆及 其所產生之性質仍為未知，因此，此效果令人驚異。 由於這些優點與好處，本發明所產生之塗曆於電子基質 特別有價值。這種塗暦可用作保護性塗層、雇間介罨暦 (interlevel dielectric layer)、用以製造似電晶體装 置之摻雜（doped)介霣_、用Μ製造電容器及似由容器装 置之含矽加顔料黏合_系统（pigment-loaded binder system)、多靨装置（multilayer device) 、 3-D 装置、 絕緣賴載砂（sllicon-〇n-insu丨ator)装置、超導腰塗曆、 超晶格（super lattice)装置及類似者。 此處所用之”陶瓷”一詞係指H -樹脂加熱後所得之硬質含 Si-Ο塗層。這些塗層可同時含有矽氧（Si-〇2>物質及其它 不完全不含殘碳（residule carbon)、砂酵（Si-ΟΗ)、及 /或®之似矽氧物質（如SiO, Si2〇3等）。這些塗暦亦可摻 雑®或磷。在此，”罨子基質” 一詞包括電子装置或電子線 路，如矽基裝置、鎵-砷基装置、焦點平面陣列 (focal-plane arrays)、光電装置（opto-electronic device)、光霉池（photovolatalic cell)及光學装置。 根據本發明之方法，首先將含Η-樹脂之塗曆施塗於電子 基質上。可用於本方法之Η-樹脂包括化學式為 HSi(OH)«(OR)y〇z/2之氬化矽氧烷樹脂，其中R獨立為有 —5 - 本紙張尺度遥用中國國家橾準（CNS ) A4規格（210X297公釐） ( 裝 ^ 訂* A I線 (請先閱讀背面之注•意事項再填寫本頁) 經濟部中央榡準局貝工消费合作社印裝 Α7 Β7 五、發明说明（3 ) 橢基或取代有機基，其經由氧原子與矽鍵结時可形成可水 解取代基，x=〇-2， y=0-2， z=l-3， x+y+z=3。 R 之實例包 括烷基如甲基、乙基、丙基、丁基•芳香基如苯基及烯基 如丙烯基或乙烯基。這些樹脂可為完全縮合（^5丨03/2)„或 僅部份水解（即含—些5卜0|?) ’及/或部份縮合（即含一 些SiOH)。雖然此结構式並未指出’但這些樹脂亦可因形 成或處理時各禰不同之因素’而含有少量（如小於約1〇% >之附有0至2個氤原子之砂原子’或少量之SiC鍵。再 者，若有須要，這些樹脂亦可摻入硼或磷° Μ上所述之樹脂及其製造方法已為此技®所知。例如’ 美國專利第3,615 ,272號說明了 一棰接近完全縮合Η-樹脂 (其可含矽醇多達100至300 ppm)之製造’其法包括在笨磺 酸水合物（benzenesulfonic acid hydrate)水解介質中將 三氣砂烧（trichlorosilane)水解’接著Μ水或含水确酸 洗滌所得產物樹脂。同樣地，美國專利第5,010, 159號中 描述了另一種方法，其法包括於芳磺酸水合物（3「7丨31;1_ fonic acid hyd「ate)水解介霣中將氫化矽氧焼水解Μ形 成一種樹脂·再將此樹脂輿中和劑接觸。 其它的氫化矽氧烷樹脂，如美國專利第4, 999，397號中 所描述者，在酸性、酵性水解介質中之水解焼氧基或88氧 * 矽垸而產生者，或 J Ρ - A U 〇 k a i ) Ν 〇 s . 5 9 - 1 7 8 7 4 9 、 60-8601 7及63-107122中所描述者，或任何其它相當之氯 化矽氧烷在此均可使用。 在本發明之較佳具體例中，亦可使用上述Η-樹脂之特定 -6 - 本紙張尺度適用中國國家標準（CNS ) Α4规格（210X297公釐） I I 4 I 裝 ^ 訂、 ^ I (請先閲讀背面之注意事項再填寫本頁) 經濟部中央梂準局貝工消費合作社印«. A7 B7 五、發明説明U ) 分子最部份於本申讅專利方法。在美國專利第5,063,267 號中有說明這些部份及其製備方法。此較佳部份包含其中 至少75%之聚合性成分之分子量大於1200之物霣，而更佳 部份刖包含其中至少75%之聚合性成分之分子量介於 1200及100,000間之物質。 此H -樹脂塗料物霣亦可含有其它陶瓷氧化物前驅物 (precoursor)。這些前驅物之實例包括各種金麵，如鋁、 钛、皓、钽、鈮及/或釩之化合物，及其它非金牖化合物 *如硼或磷之化合物•其可溶於溶劑之中，水解，再於相 當低溫下，以相當快速的反應速率熱解Μ形成陶瓷氧化塗 層。 上述陶瓷氧化物前驅物通常具有一或多届键结於上述金 鼷或非金鼸之可水解基，視金矚之原子價而定。只要此化 合物可溶於溶劑之中，則包含於此化合物之可水解基之數 量並不重要。同樣地*正確之可水解取代基之選擇亦不重 要*因為此取代基或將水解或熱解而鐮開系统。典型之可 水解基包括烷氣基如甲氧基、丙氧基、丁氧基、己氧基； 醮氧基如乙醯氧基；或經由氧鐽结於上述金鼸或非金鼷上 之其它有橢基，如戊二嗣酸鹽（acety丨acetonate)。特定 化合物為四戊二酮酸锆、二丁氧基二戊二嗣酸钛、三戊二 四異丁氧基汰 <tetraisobutoxy titaniuB)、 B3(OCH3)3〇3 及 P3〇CH2CH3)30。 當Η -樹脂要與上述陶瓷氧化物前驅物之一结合時，所用 之量應使最後之陶瓷塗靨含有70至99.9重量百分比的 本紙張尺度適用中國國家橾準（CNS ) Α4規格（210Χ297公釐） -------(丨裝-----„-丨訂----~丨線 (請先閱讀背面之注.意事項再填寫本頁) 經濟部中央標準局負工消費合作社印裝 A7 B7 五、發明説明（5 ) S i 0 2 〇 此Η-樹脂塗着物霣中亦可含有鉑、铑或網觸媒K增加轉 化成矽氧的速率及其程度率。通常，任何可溶之鉑、姥及 鋦化合物或錯合物均可使用。例如·一種姐合物如戊二_ 酸鉑、由美國密西根，密德蘭之道康寧公司（Dow Corning Corporation, Midland, Michigan)購得之结觸 媒RhCl3「S (CH2CH2CH2CH3)2]3、或環烷酸嗣均可使用。道 些《媒之添加蛋· Μ Η-樹脂重最為準，為5至1000 pPB(的 鉑、铑或網。 此Η -樹脂可用任何寘際之方法塗覆於所欲之基霣，但較 佳方法為使用溶於遴當溶朗|中之Η -樹脂溶液。若使用此溶 液法，可簡單地將Η-樹脂溶於或懸浮於一種溶劑或溶劑混 合物來形成此溶液。亦可於溶解時使用如攪拌及/或加熱 等各種輔肋方法來促進溶解。可用於此法之溶劑包括酵類 如乙酵或異丙酵、芳香烴如苯或甲笨、烷類如庚烷或十二 焼、嗣類、環狀二甲基聚砂饶氧類（dinethylpolysi-l〇Xanes)、酯類、乙二酵醚類等，所用之量為足以將上述 物質溶解為低固體含量即可。例如，包括足以形成〇.；!至 50%重量比溶液之上述溶劑。 述H-樹脂溶液塗覆於基霣上。在此，例如旋轉塗 佈塗佈、浸泡（dip)塗佈或流動塗佈等方法均可使 用° _著就要使溶劑揮發，可用如簡單的空氣乾燥、曝露 於大氣S境之中，或可使用真空或溫和加熱（Bnd heaU 的方法。 -8 - 本紙張尺度ii用中1|81家__ ( CNS ) (2歐297公釐） I ϋ — ( 裝 n訂 ^ I 線 (請先閱讀背面之注·意事項再填寫本頁) 經濟部中央樣準局属工消费合作社印製 A7 B7 五、發明説明（6 ) 雖然W上所述之方法主要集中在溶液法的使用·然而· 熟知此技8人士可察费到其它相當之塗佈方法（如融熔塗 佈（*elt coating))亦可用於本發明。 然後將經塗佈之霣子基質加熱至足使Η-樹胞轉化為含 Si-Ο陶瓷塗層之溫度。通常用來加熱之溫度為介於摄氏 50至1〇〇〇度之範圍内。然而，確實之溫度朗應視熱解氛圍 (pyrolysis atmosphere)、加熱時間及所欲之塗層而定。 而最佳之溫度常介於遢氐200至6 00度。 加熱通常會持續一段足Μ形成所欲之含Si-0陶瓷塗曆的 時間。通常•加熱時間為於高達6小時之範_内。小於2 小時（如0 . 1至2小時）之加热時間通常較佳。 上述加熱可於自真空至超大氣壓（superatnospheric)之 有效朦力（effective pressure)下進行•且可於有效氧化 性或非氧化性氣體環境中進行*此氣體瑁境包括空氣、 〇2、氧電獎（oxygen p丨asma)、臭氧、惰性氣贈（N2等） 、氨、胺、水氣及N20。 任何加熱方法在此均可使用，如對流爐（convective furnace)、快速熱處理（rapid heat processing)、加熱 板或輻射或微波能均可。再者，雖然加热速率非為醐鐽條 件，但較佳為雄可能快速加熱。 再將此含Si-Ο陶瓷塗層曝露於含氫氛圍中一段時間且曝 於足使塗層退火（即一成形氣體退火（forming gas a nil ea丨））之溫度下。此曜δ可於陶瓷塗層形成後立刻進行 •或也可於稍後任何時間進行。通常，此曝S係藉將所欲 -9- 本紙張尺度適用中國國家橾隼（CNS ) A4规格（210X297公嫠） (請先聞讀背面之注意項再填寫本頁) -裝
,-tT 經濟部中央橾準局員工消費合作杜印製 A7 B7 五、發明説明（7 ) 之氡氣，導人用來進行退火的小室或燃饿《(furnace)中 來完成。 此堪所用之氫氣可為任何實際可行之濃度。例如，溻度 鲔_在〇.01至100體積％均可使用。然而，灑度上限明顬 地應依所用之方法及氫氣之堪炸本質而定。通常，較佳濃 度為於1至30體積％間。但若氫氣會與空氣接觴，則應使 用小於5體積％或更低之濃度。 氫氣所用之稀釋氣體同樣無闞重要。情性氣體如氮氣、 «氣、氡氣•或反應性氣贈如空氣均可使用。然而，如K 上所述，若使用反應性氣體，氫氣之灑度必須小心監控， Μ免產生燻炸危險。 氡氣曝驀時所用之溫度亦可於相當大範園内變化。自室 溫到高達擓氏800度的溫度在此均可使用。較佳之溫度一 船介於攞Κ 200至600度之間。 氣氣暍兹所須之時間亦可於相當大範園内變化°自數分 篇到數小時的時間（如1分鐘到高達4小時）在此均可使用 。較佳之_霹時間為介於10分鐘至2小時之間。 雖然不希望被理論所牽絆，但本發明人認為（post uate )篦氣曝露可除去塗暦中之水份，並可避免上述水份再次 進入塗曆。Μ這種方式·可降低塗層介電常數（如降至 2.8至4.5範園内），並使其安定。令人特別感興趣的是 ，在1 MHz時，所得塗層之介霣常數可小於3.5 ，常小於 3.2，有時可小於3.0，且有時可小於2.8(如2.7至3.5)。 下列所附之實例可使热知此技舊人士更輕易地瞭解本發 -10- 本紙張尺度適用中國國家標準（CNS>A4规格（210X297公釐） A I裝 I 訂· I f I線 (請先閲讀背面之注*事項再填寫本頁) A7 __ B7 五、發明説明（8 ) 明° 實農丄 先將《倍半矽氧烷（依美國專利第3,615, 272號製得）以 甲基異丁基酮稀釋至18重量％。將此溶液以3000 ΓΡίπ的轉 速旋塗於4吋直徑（10.2公分）之1 isOhra-cra ，η -型矽薄Η 10秒。再將塗佈之薄片依表卜3所列之方法轉化為含 Si-Ο陶瓷。所得塗層厚度為0.3微米（Micrometer)。轉化 為陶瓷後，將樣品2暍S於40 0 C之箧氣（占氮氣之5體積 中20分鐘。表1說明氫氣對®阻性（resistivity)的影 «，表2說明氫氣對介電常数的影響，表3說明氫氣對移 動雷荷（mobile charge)的影響。 结果很明顯地，將塗層暍®於氫氣中對其電子性質有戲 刺性的效果。再者 > 正如表4中所示* Μ氫氣處理過之塗 脣•其介霣常數在實驗室環境中曝露一段時間後，仍可保 持安定，而未處理遇之塗層，其介電常數在實驗室環境中 HS葙一段時間後，刖會增大。 ( 裝 ^ 訂· 八 1 (請先閎讀背面之注-意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印装 -11 - 本紙張尺度逋用中國國家揉準（CNS ) Α4说格（210X297公釐） 五、發明説明（9 ) A7 B7 表1 -電阻性及缺陷密度（defect density) (平均值，2次迭代，2 sigma) 電阻性 抵諕 餺彳h條伴_(nhn) 缺陷/cm2 12 3 ο ο ο ο ο ο 4 4 4 氏氐氏 攝攝攝 度於氮氣中 度於氮氣中 度於氧氣中
時時時 \ \ S ο ο ο 1* 11 11 XXX 14 6 3 0 1 18 6 6 8 1 8 9 7 13 0 表2 - 1 MHz介電常敢及損耗 (平均值* 2次迭代，2 sigma) 垢諕 轉化條件 椹择 12 3 攝氐400度於氮氣中1小時 3.907 0.0156 攝氏400度於氮氣中1小時 2.968 0.0024 攝氏400度於氧氣中1小時 3.552 0.0161 表3 -移動霄荷 墙號 _仆條件 移動雷荷 12 3 ο ο ο ο ο ο 4 4 4 氏氐氏 攝攝攝 度於氮氣中 度於氮氣中 度於氧氣中 時時時 N \ \ w-w- 111 ο ο ο 11 1x IX XXX 2 7 0 112 *曝露於氫氣中 表4 -介電常黻（DK)對時間 墙號 形成時夕DK 一天後之DK 160天後少ΠΚ 1 2 7 8 0 6 9 9 3 2 4 3 7 7 8 9 3 2 4.081 2.773 -------{丨裝------—訂.----/ -線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 -12- 本紙張尺度逍用中國國家橾準（CNS ) A4規格（210X297公釐） 2077〇(j A7 B7 五、發明説明（〗〇 ) 將氫倍半矽氧烷（依美國專利第3,615,272號製得）Μ甲 基異丁基嗣稀釋至22重量％。將此溶液>乂 1500 rpm的轉速 旋_於4时直徑（10.2公分）之1〇1(^1«-(：111，11-型矽薄片上 10秒。再將經塗佈之薄Η之一於氮氣中加熱至攝氐400度 一小時W轉化為含Si-Ο陶瓷。所得塗層厚度為0.8微米。 其介雷常數為5.8 。再將經塗佈薄片曝靄於攝氏400度之 Μ氣（占氮氣之5體積中20分鐘。此時介罨常數即降至 3.8° 再將第二Η經塗佈之薄Η於氧氣中加熱至攝氏400度一 小時Κ轉化為含Si-Ο陶瓷。所得塗層厚度為約0.8微米。 其介電常数為5.0 。再將經塗佈之薄Η曝露於攝氐400度 之氫氣（占氮氣之5體積中20分鐘。此時介電常數即降 至 4. 2。 很明顯的*曝露於氫氣中對介電常數有很顯著的影響· 分別由5.8及5.0降低至3.8及4.2 。 -------f 丨裝-----：—訂----ί、丨線 (請先Μ讀背面之注•意事項苒填寫本頁) 經濟部中央揉隼局負工消費合作社印製 本紙張尺度適用中國國家揉準（CNS ) Α4規格（210Χ297公釐）

Claims (1)

  1. 第83108490號專利申請案 A8 B8 中寸由讅裒利節团你TP太（8S年3月） C8 D8 經濟部中央橾準局負工消费合作社印製 申請專利範圍 y ι]> 1. 一種在鼋子基質上形成含Si-Ο塗層之方法•其包括： 將含氫倍半矽氧烷樹脂之塗層塗佈於電子基質上； 將此經塗佈之霣子基質加熱至足κ將氫倍半矽氧烷樹 脂轉化為含Si-Ο陶瓷塗層之溫度；以及 將此含Si-Ό之陶瓷塗層曝於含氫氛圍一段時間且曝於 足Μ將此塗層退火之溫度下。 2. 根據申請專利範圔第1項之方法，其中經塗佈基質係加 熱至50至lOOOt；不超遇6小時而轉化為含Si-Ο陶瓷塗層 〇 3. 根據申請專利範圍第1項之方法，其中氫倍半矽氧烷樹 脂之聚合性部份至少75%之分子董介於1200與100,000 5 . 6 . 根據申請專利範圍第1項之方法，其中含氫倍半矽氧烷 樹脂塗層亦含有改良陶瓷氧化物前驅物，其包括含有選 自下列元素之化合物：钛、锆、鋁、钽、釩、鈮、硼及 磷•此化合物至少含有一選自烷氧基或醣氧基的可水解 取代基，且此化合物之量使矽氧塗層含0.1至30重量％ 陶瓷氧化物。 根據申請專利範圍第1項之方法，其中含氫倍半矽氧烷 樹脂塗層亦含有一鈉、錯或鋦觸媒，基於氫倍半矽氧烷 樹脂之重量，其含量為5至500 ppe。 根據申請專利範圍第1項之方法，其中經塗佈基質係於 選自空氣、氧氣、氧電漿、臭氧、惰性氣體、氨、胺、 水汽或N2〇之氛圍中加熱.而轉化為含Si-Ο陶瓷塗層。 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) Λ8 Β8 C8 D8 六、申請專利範圍 7. 根據申請專利範圃第1項之方法，其中之退火氛圍之氣 氣湄度介於1至30體積％。 8. 一種安定由氫倍半矽氧烷樹脂衍生之含Si-Ο陶瓷塗曆之 介電常數之方法，其包括： 將由氫倍半矽氧烷樹脂衍生之含Si-0陶瓷塗層曝於含 氫氛圍一段時間及曝於足Μ安定其介轚常數之溫度下。 9. 根據申請專利範圃第8項之方法，其中於1 MHz時，該 安定之介電常數值係小於3.2 。 10. 根據申請專利範圍第9項之方法，其中該含Si-〇陶瓷塗 層係用於塗層電子設備。 -----^----^ I 裝--------訂-------{ ·線 (請先閲讀背面之注意Ϋ項再填寫本頁) 經濟部中央揉準局負工消費合作社印裝 本紙張尺度適用中國國家標準（CNS ) Α4現格（210X297公嫠）
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