TWI432595B - 基板塗層及其形成方法 - Google Patents

基板塗層及其形成方法 Download PDF

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TWI432595B
TWI432595B TW099113912A TW99113912A TWI432595B TW I432595 B TWI432595 B TW I432595B TW 099113912 A TW099113912 A TW 099113912A TW 99113912 A TW99113912 A TW 99113912A TW I432595 B TWI432595 B TW I432595B
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layer
carbon
coating
substrate
diamond
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Winston Chan
Kit Ling Ng
Xin Chao Duan
Po Ching Chan
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Winsky Technology Ltd
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Priority to US13/046,487 priority patent/US8852746B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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    • 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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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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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
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
    • 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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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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Description

基板塗層及其形成方法
本發明關於一種塗層。更特定來說，本發明關於一種易清潔之基板塗層。
電子產品逐漸成為現代生活中不可或缺的一環，除了不斷推陳出新的諸多功能，外觀也成為消費者選購的重要考量之一。常見的電子產品外殼包含有金屬外殼、鏡面、及鋼琴烤漆等等，但是不論哪一種外殼一旦沾滿指紋，外觀勢必大打折扣。因此需要一種易於清潔之塗層使得指紋不易留在外殼上，即便留在外殼上也可輕易地去除。
易於清潔之塗層主要成分是具有抗水性(hydrophobic)及抗油性(oleophobic)的高分子量有機化合物，其傳統形成方法有兩種，一種是溶膠凝膠法(sol-gel)，另一種是化學氣相沉積(CVD)。
由於塗層厚度相當薄，溶膠凝膠法只能用潑灑或浸泡的方式處理，因此不適用於大面積的製程(例如1平方米)，即便在小面積的製程中(例如0.1m*0.1m)也容易在邊緣處產生淚痕。
使用化學氣相沉積所形成的塗層之附著性較差，並且在塗層的化學成分上有許多限制。舉例來說，高分子化有機化合物在揮發的過程中很容易就被分解了，因此不適用於化學氣相沉積。此外，使用化學氣相沉積還具有化學成分分佈的均勻度較差的缺點。因此，極為需要一種適用於大面積、多種基板與廣泛化學成分之易清潔塗層。
本發明之一實施例提供一種基板塗層，包含：一第一層，其用於附著於一基板上，該第一層之成分至少包含矽含量豐富之碳，其中矽含量約等於或大於碳含量；及一第二層，其附著於該第一層上，該第二層之成分至少包含摻雜氟之類鑽石碳。
本發明之另一實施例提供一種形成塗層之方法，包含：於一基板上形成一第一層，該第一層之成分至少包含矽含量豐富之碳，其中矽含量約等於或大於碳含量；及於該第一層上形成一第二層，該第二層之成分至少包含摻雜氟之類鑽石碳。
依據本發明之一較佳實施例，第一層及第二層係以電漿輔助式化學氣相沈積之製程形成於該基板上。
本發明所使用的摻雜氟之類鑽石碳可達到易清潔之功能，並且提供一堅硬防刮且平滑之表面。矽含量豐富之碳可作為第二層與基板間之應力匹配介面，依據基板之性質調整矽與碳之比例使塗層的附著性更佳且不易脫落。此外，本發明所使用的電漿輔助式化學氣相沈積可產生非常薄且厚度均勻的透光塗層。
為了使本發明的前述和其他目的、特徵和優點更易於理解，下文詳細描述伴有圖式的較佳實施例。
圖1為本發明中一較佳實施例之基板塗層。基板2上方之層4至少包含矽含量豐富之碳，其中矽含量約等於或大於碳含量。層4上方之層6至少包含摻雜氟之類鑽石碳。矽含量豐富之碳在基板2與層6之間提供一應力匹配介面，使層6不易因應力而碎裂。隨著基板2之材質不同，必須調整層4中矽與碳之比例來完成應力匹配。
在本案之一實施例中，層4及層6係利用電漿輔助式化學氣相沈積之製程依序形成於基板2上，由於電漿輔助式化學氣相沈積係為習知技術，故不在此詳述其實施方法。但是，將電漿輔助式化學氣相沈積應用於本發明可更精確地控制塗層之厚度，並且不論在大面積(如1m*1m)或小面積(如0.01m*0.01m)上都可以達到較佳平整度。由於電漿輔助式化學氣相沈積可產生非常薄(可小於100nm)且厚度均勻的塗層，故本發明之塗層可透光，故可廣泛應用於各種電器產品上，例如手機及筆記型電腦等。此外，使用電漿輔助式化學氣相沈積，可輕易控制層4中矽與碳之比例及層6中氟與碳之比例。再者，相較於使用傳統化學氣相沈積在類鑽石碳中摻雜氟十分困難，如果使用電漿輔助式化學氣相沈積，即便在商業利用上也可輕易地控制化合物分解之情形。
在另一實施例中，本發明可在以電漿輔助式化學氣相沈積方法沈積矽含量豐富之碳及摻雜氟之類鑽石碳之過程中，藉由注入氧氣、氮氣、氬氣或氦氣，在進入反應腔室前與反應氣體(例如含矽、碳及/或氟之氣體)混和，以便於更精準地控制矽含量豐富之碳層及摻雜氟之類鑽石碳層之組成。在一較佳實施例中，操作壓力大約維持在0.1Torr，沈積速度大約1nm/min至500nm/min之間。
在沈積摻雜氟之類鑽石碳的過程，可調整電漿輔助式化學氣相沈積設備的偏壓，使達到更高含量的類鑽石碳，進而得到更好的防刮傷能力。此外，在沈積過程調整氟含量，使達到更高含量的氟-碳，並藉由微調氟含量，得到所需要的疏油性及疏水性之效果。
在本發明之較佳實施例中，基板之材質可為玻璃、不銹鋼、鎂合金、陶瓷、鋁或鋁合金。層4中矽與碳之比例約介於1：1至20：1之間。當基板之材質為玻璃時，層4中矽與碳之比例約介於3：1至15：1之間；當基板之材質為不銹鋼時，層4中矽與碳之比例約介於1：1至3：1之間；當基板之材質為鎂合金時，層4中矽與碳之比例約介於2：1至10：1之間；當基板之材質為鋁或鋁合金時，層4中矽與碳之比例約介於3：1至15：1之間；當基板之材質為陶瓷時，層4中矽與碳之比例約介於3：1至15：1之間。
氟化之長鏈碳可提供易於清潔之功能，因此，本案之一較佳實施例利用摻雜氟之類鑽石碳達到易於清潔之功能。此外，氟也可以使表面平滑，而類鑽石碳提供一堅硬表面，使塗層表面不易留下刮痕。依據本發明之實施例，層6中氟與碳之比例可介於約1：0.5至1：100之間，而其較佳實施範圍落在約1：10至1：80之間。
圖2之左半邊顯示使用本發明之基板塗層所留下之指紋，右半邊則為未使用本發明基板塗層所留下之指紋。圖3係顯示圖2之基板經擦拭後之情形。由圖2及圖3可發現使用本發明之基板塗層較不容易留下指紋，且一經擦拭就不留痕跡。相較之下，未使用基板塗層之對照組較容易留下指紋，即便擦拭後仍然會留下人手上的油脂。
表1更進一步顯示本發明之基板塗層通過的多種測試，以佐證本發明之優點。
綜上所述，本發明所使用的摻雜氟之類鑽石碳可達到易於清潔之功能，且提供一堅硬、耐磨、防刮且平滑之表面。矽含量豐富之碳可調整第二層與多種基板間之應力匹配，使塗層的附著性更佳且不易脫落。此外，本發明使用電漿輔助式化學氣相沈積，故可產生非常薄(可小於100nm)且厚度均勻的透光塗層。再者，使用電漿輔助式化學氣相沈積更可輕易控制化合物分解之情形。因此，本發明不僅提供一種優良之基板塗層，更提供一種適合商業上利用之形成塗層之方法。
雖然本發明之技術內容與特徵係如上所述，然於本發明之技術領域具有通常知識者仍可在不悖離本發明之教導與揭露下進行許多變化與修改。因此，本發明之範疇並非限定於已揭露之實施例而係包含不悖離本發明之其他變化與修改，其係如下列申請專利範圍所涵蓋之範疇。
2．．．基板
4及6．．．層
圖1為本發明中一較佳實施例之基板塗層。
圖2之左半邊顯示使用本發明之基板塗層所留下之指紋，右半邊則為未使用本發明基板塗層所留下之指紋。
圖3係顯示圖2之基板經擦拭後之情形。
2．．．基板
4及6．．．層

Claims (18)

  1. 一種基板塗層，包含：一第一層，其用於附著於一基板上，該第一層之成分至少包含矽含量豐富之碳，其中矽含量約等於或大於碳含量，其中該第一層中矽對碳的一比例約在2：1至20：1之間；及一第二層，其附著於該第一層上，該第二層之成分至少包含摻雜氟之類鑽石碳。
  2. 如請求項1之塗層，其中該第一層中矽與碳之比例約在3：1至20：1之間。
  3. 如請求項1之塗層，其中該第一層作為該第二層與該基板之一應力匹配介面。
  4. 如請求項1之塗層，其中該摻雜氟之類鑽石碳中氟與碳之比例實質上落在約1：0.5至1：100之範圍內。
  5. 如請求項1之塗層，其中該摻雜氟之類鑽石碳中氟與碳之比例實質上落在約1：10至1：80之範圍內。
  6. 如請求項1之塗層，其中該第一層及第二層係以電漿輔助式化學氣相沈積之製程形成於該基板上。
  7. 如請求項1之塗層，其中第一層及第二層之厚度實質上各小於約100nm。
  8. 如請求項1之塗層，其中該基板係由玻璃、不銹鋼、鎂合金、陶瓷、鋁或鋁合金形成。
  9. 一種形成塗層之方法，包含：於一基板上形成一第一層，該第一層之成分至少包含 矽含量豐富之碳，其中矽含量約等於或大於碳含量，其中該第一層中矽對碳的一比例約在2：1至20：1之間；及於該第一層上形成一第二層，該第二層之成分至少包含摻雜氟之類鑽石碳。
  10. 如請求項9之方法，其中該第一層中矽與碳之比例約在3：1至20：1之間。
  11. 如請求項9之方法，其中該第一層作為該第二層與該基板之一應力匹配介面。
  12. 如請求項9之方法，其中該摻雜氟之類鑽石碳中氟與碳之比例實質上落在約1：0.5至1：100之範圍內。
  13. 如請求項9之方法，其中該摻雜氟之類鑽石碳中氟與碳之比例實質上落在約1：10至1：80之範圍內。
  14. 如請求項9之方法，其中形成該第一層及第二層之步驟係以電漿輔助式化學氣相沈積之製程所形成。
  15. 如請求項9之方法，其中該基板係由玻璃、不銹鋼、鎂合金、陶瓷、鋁或鋁合金形成。
  16. 如請求項14之方法，其中操作壓力約在0.1Torr，且沈積速度約在1nm/min至500nm/min之間。
  17. 如請求項14之方法，更包含調整電漿輔助化學氣相沈積設備的偏壓之步驟。
  18. 如請求項14之方法，更包含注入氧氣、氮氣、氬氣或氦氣以與一反應氣體混合之步驟。
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