201247422 六、發明說明： 【發明所屬之技術領域】 ’尤指於低化 之方法。 本發明係關於一種石墨烯薄獏轉移方法 學及機械傷害下之一種有效轉移石墨烯薄獏 【先前技術】 石墨烤薄膜之結構Μ碳原子以sp2軌域互相鍵⑼ 成六角碳環，並延伸形成如蜂巢狀之二維平面結構所: 石墨烯具有優異之光學、電學、及機械性質，且其具 有透明之特性，故可應用於透明導電層、導電複材、或軟 性電子，另外亦可應用於電容器、鋰電池電極、或 強之複合材。 多數應用石墨烯之產品大多係由數層之石墨稀薄_ 堆叠而成’而其堆疊之方式係可透過—層層之石墨稀薄膜 進行轉移而層層堆f·。目前，較佳之石墨稀薄膜轉移方法 係利用熱化學氣相沈積法，於催化金屬上形成石墨烯薄獏 後，再將附著於催化金屬上之石墨烯薄膜，以聚甲基丙烯 酸甲S曰（PMMA)黏貼後，再利用蝕刻法蝕刻其催化金屬，以 使催化金屬與附著於其上之石墨烯薄膜分離，並使石墨烯 薄膜轉移至PMMA上。接著，將目標基板與黏貼有石墨烯 4膜之PMMA壓片貼合’利用熱、uv、氣體（氫氣與氮氣） 或丙嗣，將PMMA去除，使石墨烯薄膜轉移至目標基板上， 已達到石墨稀薄膜轉移之目的0 4 201247422 上述之石墨烯薄瞑轉移 稀薄膜之轉移。然而，心石=然可以有效的進行石墨 目標基板之過程中，其需經過=:=催化金屬轉移至 械壓印之過程，因而使得 之化干浴液蝕刻以及機 ψ 〇 4* lL .V η 、缔溥膜容易產生破裂之情 發展一種有效且良率高之石墨烯薄膜轉移』 係可有效開發石墨烯薄膜更多之應用。 、 【發明内容】 本發明之主要目的俜摆 俾能於低化學傷害下，提墨稀薄膜轉移方法， 本發明之另-目的俜提…轉移品質。 俾能高效率地轉移多石墨稀薄膜轉移方法’ 為，成上述目❼，本發明係提 方法’其方法係包括：( 4專膜轉移 -第-表面、及—第火)載體，其令此載體係具有 有-第-石墨稀薄膜Γ::，且此載體之第—表面上形成 第一# 、 。又置圖案化保護層於此載體之 第-表面上；(C)圖案化 戟-之 其中此載體之圖案是對庙顯露其第一石墨稀薄膜， -石墨稀薄膜之圖荦化=圖案化保護層；（D)將設有此第 菜化载體設置於一目桿基柘μ 移除圖案化載體 一板上，以及(Ε) 上。 更，、第一石墨烯溽獏形成於目標基板 載體之材料可係為催化金屬，如鋼鎳、鐵、 石黑或…組合’較佳為鋼、錄、或其組合。 、方法係利用熱化學氣相沈積法、濺鍍法、塗 201247422 佈法，較佳為熱化學氣相沈積法，以使石墨烯薄膜形成於 載體之表面上，且可依需求而選擇形成於載體之任一表 面，而其所形成石墨烯薄膜之載體厚度並無特別限制較 佳為500-10 μηι，更佳為2〇〇_5〇 μπΐβ另外，圖案化保護層 之形成方式並無特別限制，可利用蝕刻之方法形成一圖案 化之保護層，亦可利用膠帶貼合之方式而形成。於本發明 中，較佳係利用膠帶之緊密貼合方式，以備製一圖案化保 護層。 於步驟（C)中，其載體圖案化之方式並無特別限制，可 以化學方式或物理方式進行載體之圖案化，較佳係以化學 方式進行載體之圖案化，更佳係以蝕刻法進行載體之圖案 化’、中，泫姓刻法之敍刻液係為钱刻載體之化學溶液c 而名化牟溶液係可為過硫酸鍵溶液 '氣化鐵溶液、墙酸溶 液、硫酸溶液、或其混合溶液，較佳為過硫酸銨溶液。 t述本發明之步驟（D)，其中，第一石墨烯薄膜設置於 目钻基板之方法係包括：（D丨）提供一懸浮溶液，其中此 懸浮溶液内係設置有一目標基板：（D2)將設有第一^墨烯 4膜之圖案化載體置於懸浮溶液中，使圖案化載體懸浮於 懸浮♦液上，以及（D3)移除懸浮溶液。如此使第一石墨烯 薄膜與目標載體黏貼後，再將該冑案化之載體移除，以使 第-石墨烯薄膜轉移至目標基板表面上，而完成石墨烯薄 膜轉移至目標基板之目的。 上述本發明步驟（D)之第一石墨烯薄膜設置於第一目 標基板之方法，係使具有囫案化載體之第一石墨烯薄膜懸 6 201247422 洋於懸浮溶液中，利用逐漸移除懸浮溶液之方式，使具有 圓案化載體之第一墨烯薄膜逐漸靠進懸浮溶液中之目標基 板表面。待移除懸浮溶液後，其具有圖案化載體之第—石 墨稀4膜係能黏著於目標基板之表面。最後再將該圖案化 載體移除’以完成第—石墨稀薄膜轉移於目標基板表面之 目的。 然而，其除了上述步驟（D)之第一石墨烯薄膜設置於第 =目標基板之方法外，其步驟（D)另可為·（D1)提供—懸浮 溶液’將設有第一石墨歸薄膜之圖案化載體置放於懸浮溶 液中，且該圖案化載體係懸浮於該懸浮溶液上；（D2)提昇 該圖案化載體’以自懸浮溶液中榜起第—石墨㈣膜；以 及（D3)將第-石墨稀薄膜’置放於該目標基板上。此方法 係以圖案化載體為著力. 點’可於不接觸第一石墨烯薄膜之 情，下’將具有圖案化載體之第一石墨烯薄膜由懸浮溶液 中提起’而提起之方式係可由下而上榜起。接著再將榜 起之第-石⑽薄膜黏著黏於目標基板上，以完成 薄膜附著於目標基板表面之目的=此外，將該第一石墨稀 涛膜於懸料液中榜起後m將其第—石墨稀薄膜之 至少：表面視需要而更進一步進行表面處理如電漿處 理、礼電渡處理、氫電漿處理、或雜金屬等表面處理。 上述本發明之石㈣__方*巾，其 及7T載體、及-承載板，其中，載體之第一表 = =分別形成有一第一石墨稀薄膜、以及- 潯、另外，承载板表面設置有一緩衝層； 201247422 將載體層疊於承載板上，且承載板上係依序層疊有緩衝 層、第-石墨烯薄臈、載體、以及第二石墨烯薄膜；以及： (A3)移除第二石墨烯薄膜，以顯露載體之該第二表面。 其中’承載板之材料係為一硬質地之材料，其材料於 此並無特別限制，可為玻璃板、麼克力板 '塑膠板陶究 板等’較佳為玻璃板、以及麼克力板。另外，其緩衝層之 材料係具有不易與石墨烯薄膜黏合之特性，較佳為紙張、 面紙、不織布、或其組合，更佳為面紙。 上述本發明之步驟（A)中，該載體之第一表面及第二表 面上係可形成有第一石墨烯薄膜及第二石墨烯薄膜。其 中’移除第二石墨缔薄膜之方法’係將叠有一緩衝層之承 ::上，放置形成有石墨稀薄膜之載體，已使承載板之緩 衝層上，依序層置有第一石墨一薄膜、載體、已及第二石 墨烯薄膜》其中’載體之第一石墨烯薄獏係與緩衝層接觸， 且載體之第二石墨烯薄膜係層疊至最上層。如此，使第一 石墨烯薄膜暴露於外界，以便移除。而第二石墨烯薄獏Z 移除方法並無特別限制’可為化學方法或物理方法，較佳 係以化學方法進行第二石墨稀薄膜之移除’更佳係以钱刻 法進行其第二石墨稀薄膜之移除。而其第二石墨稀薄膜之 蝕刻液係可為蝕刻碳之化學溶液，較佳為過氧化氫溶液、 ，酸溶液、氫氧化卸溶液、或其思合溶液，更佳為^氧化 虱溶液及硝酸溶液之混合。 上述本發明之步驟（A1)之後，更可包括—步驟“I 清洗第一石墨烯薄膜、及第二石墨烯薄犋。其中，青、先石 8 201247422201247422 VI. Description of the invention: [Technical field to which the invention pertains] ‘In particular, a method of miniaturization. The invention relates to a graphene thinning transfer method and an effective transfer graphene thin layer under mechanical damage. [Prior Art] The structure of a graphite baked film Μ carbon atoms are interlocked with a sp2 orbital domain (9) into a hexagonal carbon ring and extended Forming a two-dimensional planar structure such as a honeycomb: Graphene has excellent optical, electrical, and mechanical properties, and has a transparent property, so it can be applied to a transparent conductive layer, a conductive composite material, or a soft electronic device. Used in capacitors, lithium battery electrodes, or strong composites. Most of the products using graphene are made up of several layers of graphite thinner _ stacked and stacked in a permeable layer of graphite thin film to form a layer stack. At present, a preferred graphite thin film transfer method is a method for forming a graphene thin layer on a catalytic metal by a thermal chemical vapor deposition method, and then attaching a graphene film attached to the catalytic metal to polymethyl methacrylate. After the PMMA is pasted, the catalytic metal is etched by etching to separate the catalytic metal from the graphene film attached thereto and transfer the graphene film to the PMMA. Next, the target substrate is bonded to the PMMA sheet to which the graphene 4 film is adhered. 'The heat, uv, gas (hydrogen and nitrogen) or propylene is used to remove the PMMA, and the graphene film is transferred to the target substrate. The purpose of graphite thin film transfer 0 4 201247422 The above transfer of graphene thin tantalum transfer thin film. However, the core stone can be effectively carried out in the process of graphite target substrate, which needs to pass the process of =:=catalytic metal transfer to mechanical imprinting, thus making the dry bath etching and the machine 〇4* lL .V η, the ruthenium film is prone to cracking, and the development of an effective and high-yield graphene film transfer system can effectively develop more applications of graphene film. SUMMARY OF THE INVENTION The main object of the present invention is to transfer a thin film transfer method under low chemical damage, and another object of the present invention is to transfer quality.俾 高 俾 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高The carrier has a -graphite-thin film::, and the first surface of the carrier is formed on the first surface. And patterning the protective layer on the first surface of the carrier; (C) patterning the ruthenium - wherein the pattern of the carrier is to expose the first graphite thin film to the temple, - the graphite thin film is patterned = patterned a protective layer; (D) is provided with the first vegetable carrier on a plate of the one-piece rod 移除μ to remove the patterned carrier, and (Ε). Further, the material of the first graphene oxime formed on the target substrate carrier may be a catalytic metal such as steel nickel, iron, stone black or a combination of 'preferably steel, recorded, or a combination thereof. The method is formed by thermal chemical vapor deposition, sputtering, or coating 201247422, preferably by thermal chemical vapor deposition, so that the graphene film is formed on the surface of the carrier, and can be selectively formed on the surface according to requirements. The surface of the carrier is not particularly limited, and is preferably 500-10 μηι, more preferably 2〇〇_5〇μπΐβ. In addition, the pattern of the patterned protective layer is not particularly formed. Restriction, a patterned protective layer may be formed by etching, or may be formed by tape bonding. In the present invention, it is preferred to use a close fitting manner of the tape to prepare a patterned protective layer. In the step (C), the manner of patterning the carrier is not particularly limited, and the patterning of the carrier may be carried out chemically or physically, preferably by chemically patterning the carrier, and more preferably by etching. The patterning ', the middle, the 泫 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻 刻The mixed solution is preferably an ammonium persulfate solution. The method (D) of the present invention, wherein the method for disposing the first graphene film on the mesh substrate comprises: (D) providing a suspension solution, wherein the suspension solution is provided with a target substrate: (D2) The patterned carrier provided with the first siloxane 4 film is placed in a suspension solution, the patterned carrier is suspended on the suspension ♦, and (D3) the suspension solution is removed. After the first graphene film is adhered to the target carrier, the patterned carrier is removed to transfer the first-graphene film to the surface of the target substrate, thereby completing the transfer of the graphene film to the target substrate. The method for disposing the first graphene film of the step (D) of the present invention on the first target substrate is such that the first graphene film having the patterned carrier is suspended in a suspension solution, and the suspension solution is gradually removed. In this manner, the first olefin film having the rounded carrier is gradually brought into the surface of the target substrate in the suspension solution. After the suspension solution is removed, the first-stained graphite film system having the patterned carrier can adhere to the surface of the target substrate. Finally, the patterned carrier is removed to complete the transfer of the first graphite thin film to the surface of the target substrate. However, in addition to the method in which the first graphene film of the above step (D) is disposed on the first target substrate, the step (D) may further provide a suspension solution for the (D1) to be provided with the first graphite film. The patterned carrier is placed in a suspension solution, and the patterned carrier is suspended on the suspension solution; (D2) lifting the patterned carrier' to self-suspend the solution of the first-graphite (tetra) film; and (D3) A first graphite thin film is placed on the target substrate. This method is based on the patterned carrier. The point can be lifted without contacting the first graphene film, and the method of lifting the first graphene film with the patterned carrier from the suspension solution can be lifted. And on the list. Then, the first-stone (10) film of the list is adhered to the target substrate to complete the adhesion of the film to the surface of the target substrate. In addition, the first graphite thin film is listed in the suspension liquid, and then At least the surface of the graphite-thin film: the surface is further subjected to surface treatment such as plasma treatment, ritual treatment, hydrogen plasma treatment, or surface treatment such as impurity metal. The above-mentioned stone (four) __ square* towel, and the 7T carrier, and the carrier plate, wherein the first table of the carrier == respectively formed with a first graphite thin film, and - 浔, in addition, the surface of the carrier plate is provided a buffer layer; 201247422, a carrier is laminated on a carrier plate, and a buffer layer, a first-graphene thin layer, a carrier, and a second graphene film are sequentially laminated on the carrier plate; and: (A3) removing the second graphite An ene film to expose the second surface of the carrier. The material of the carrier plate is a hard material, and the material thereof is not particularly limited thereto, and may be a glass plate, a gram board, a plastic plate, a ceramic plate, etc., preferably a glass plate, and a gram force. board. Further, the material of the buffer layer has a property of being less likely to adhere to the graphene film, preferably paper, face paper, non-woven fabric, or a combination thereof, and more preferably a face paper. In the above step (A) of the present invention, the first graphene film and the second graphene film may be formed on the first surface and the second surface of the carrier. The method of 'removing the second graphite-thin film' will be stacked on a buffer layer: a carrier on which a graphite thin film is formed, and the first graphite is placed on the buffer layer of the carrier plate. A film, a carrier, and a second graphene film, wherein the first graphene thin layer of the carrier is in contact with the buffer layer, and the second graphene film of the carrier is laminated to the uppermost layer. Thus, the first graphene film is exposed to the outside for removal. The second graphene thin 貘Z removal method is not particularly limited 'may be a chemical method or a physical method, preferably a chemical method for the removal of the second graphite thin film' is better by the money engraving method Removal of two graphite thin films. The etching solution of the second graphite thin film may be a chemical solution for etching carbon, preferably a hydrogen peroxide solution, an acid solution, a hydroxide solution, or a solution thereof, and more preferably a cerium oxide solution and Mixing of nitric acid solution. After the step (A1) of the present invention, the method further includes the following steps: "I cleaning the first graphene film, and the second graphene thin layer. Among them, Qing, Xianshi 8 201247422
墨烯薄獏之目的係I 除，使石墨烯薄膜可更容、易専膜t之化學溶液以及雜質清 學反應，如電聚處理 t步的進行表面處理或化 屬、或崎反應等。理、氫電浆處理、賤鍍金 特別限制，只要能達到上、墨稀薄膜之溶液並無 :用之石，膜清洗溶液，包括：鹽酸、硫酸、 磷酸’較佳為鹽酸。 載體ΪΠ:=(Β)中’更可包括-步·):清洗 U卜風&@二：、其洗之目的係為防止載體第二表面上 面處：奋液以及雜質，以影響後續之化學反應、及表 f如㈣反應H清洗載體第二表面之化學溶 液’無特別限制，只要能達到上述清洗之目的及為本發明 所適用之石墨_膜清洗溶液，包括：鹽酸、硫酸、醋酸' 磷酸，較佳為鹽酸。 上述本發明之步驟（C)係將該載體進行圖案化，而兑中 步驟（C)之圖案化係可利用各種化學反應進行圖案化。於本 發明中，其栽體之圖案化較佳係、將具有s—石墨烯薄膜之 載體置於-#刻液中，以飯刻法進行載體之圖案化。當其 具有第-石墨㈣膜之載體進行圖案化後 = 括1案化之載體'以及圖案化保護層上之第上 膜。 第 此外γ上述步驟（C)後，更包括一步驟（C，）：表面處理 石墨烯薄膜之至少-表面。其中，該表面處理係包括·· 201247422 電漿處理、氧電漿處理、氫電漿處理、或濺鍍金屬等，如 銀金屬濺鍍。 上述本發明中，其步驟（㈡後，更可包括一步驟（F):重 複步驟（A)至步驟（E)，以於該標基板上形成複數層石墨稀薄 膜。 除了利用圖案化載體進行上述之石墨婦薄膜轉移外， 本發明另提供-種石墨烯轉移方法。而其方法係包括：⑷ 提供-載體，其中其載體具有—第—表面、及一第二表面， 且載體之第一表面上係形成有一第一石墨烯薄膜；(B)將載 體置於-載體移除溶液中以移除載體，且該第一石墨烯薄 膜係料㈣㈣㈣料± ;(⑽—料職置換載體 移除溶液n石墨稀薄膜係懸浮於懸浮溶液上；⑼分 離第一石墨稀薄膜及懸浮溶液；以及⑻將第―石墨稀薄膜 形成於一目標基板上。 /、中’載體之材質、載體移除溶液之成份内容係為蝕 刻載體之化學溶液。而該化學溶液係可為過硫酸敍溶液、 氣化鐵办液、石請溶液、硫酸溶液、或其混合溶液，較佳 為過硫酸錢溶液二而懸浮溶液之功能剌於初步清洗具有 :留之化學溶液之載體或第一石墨烯薄膜，其中，該懸浮 溶液係可為稀釋後之載體移除溶液、纟、酒精、丙嗣或去 離子水，而較佳係為去離子水。 上述本發明另一石墨烯薄膜轉移方法之步驟（A)更包 括：⑷)提供-載趙，其中載體之第一表面、及第二表面 上，分別形成有一第一石墨稀薄膜'以及一第二石墨稀薄 201247422 膜；以及⑽將載體置於一石墨稀移除溶液上宜 石墨烯層係與外界接觸，第二 '、 ^ m '烯a係與石墨稀移除溶 液接觸，以移除第二石墨稀層合 胳星古膂η妨 4步驟（Α)之方法係 將八有第-及第二之石墨烯薄膜之載體進行單一石 膜之移除，以得到僅具有第_ _ 4 、噶弟石墨烯溥臈之載體。苴中， 該石墨烯薄膜移除溶液係盥上 八 同。 上述之石墨烯薄膜移除溶液相 上述本發明之步驟（Β)之前，係更可包括 =二標記於第-石墨_膜上;且步驟_為:二上 ==浮溶液中，且透過標記以決定第-石墨烯薄 1目&基板之相對位Ρ由於本發明所提供之另一 =移方法中，其係於不具圖案化保護層之情況下進行 載體之移除’故於載體移除後，其僅會留下第一石墨歸薄 膜。然而，由於其石墨稀薄膜具有透明之特性不易以肉 眼看見’故於載體蝕刻前，係可先於其第一石墨烯 做7標記’以使第一石墨缔薄膜於載體移除後，仍可以肉 眼觀察到其位置。而該標記之方法，於不傷害第一石墨稀 :膜之情況7’皆可為本發明之第-石墨稀薄膜標記方 法’如利用筆'或油墨標記記號。 上述本發明另提供之-種石墨歸薄膜轉移方法中，1 步驟（D)可更包括：（叫將一目標基板置該懸浮溶液中；：； 及_移除懸浮溶液，以使第一石墨稀薄膜形成於目標基 板上。其中，目標基板料利用與第—石墨㈣膜間之^ 者力’於移除懸浮溶液之過程中’進行第一石墨稀薄膜之 201247422 轉移。其中，移除溶液之方法係可將m夜抽離 除了利用懸浮溶液抽離之方式，將懸浮之第卜 轉移至目標基板外’另可將第一石墨稀薄膜由懸浮溶= 撈起’以直接將其轉移至目標基板之表面上。 上述本發明另提供之一種石墨稀薄膜轉移方法，其中 步驟⑼可為步驟(D’)：自懸浮溶液令撈起第一石墨稀薄膜 後，再表面處理其撈起之第—石㈣薄膜。其中該表 理係可為電«理、氧„處理、氫錢處理、或賤鑛金 屬等。而本發明所另提供之_種石墨烯薄膜轉移方法中， ^體' 以及第-石墨㈣膜係可更進—步加以使用清洗 溶液進行清洗’以s洗帛-^㈣肖膜±之殘留化學溶 液 '雜質，使該載體、及第一石墨烯薄膜可更容易進行表 面處理。其中，該清洗溶液係同於上述之清洗溶液.。 【實施方式】 以下k藉由特定的具趙實施例說明本發明之實施方 式，熟習此技藝之人士可由本說明書所揭示之内容輕易地 了解本發明之其他優點與功效。本發明亦可藉由其他不同 的具體實施例加以施行或應用，本說明書中的各項細節亦 可基於不同觀點與應用，在不悖離本發明之精神下進行各 種修飾與變更。 實施例1 請同時參考圖丨A至圖1H。 201247422The purpose of the enamel thinning is I, so that the graphene film can be more accommodating, easy to lick the chemical solution of the film t and the impurity clearing reaction, such as electrothermal treatment t step for surface treatment or chemical, or smectic reaction. Lithium, hydrogen plasma treatment, and rhodium plating are particularly limited as long as the solution of the upper and the thin film is not used: the stone used, the membrane cleaning solution, including: hydrochloric acid, sulfuric acid, phosphoric acid, preferably hydrochloric acid. Carrier ΪΠ: = (Β) in 'more can include - step ·): cleaning U Bufeng & @二:, the purpose of washing is to prevent the second surface of the carrier: the liquid and impurities, to affect the subsequent The chemical reaction, and the chemical reaction solution of the second surface of the carrier H is not particularly limited as long as the above cleaning can be achieved and the graphite_membrane cleaning solution suitable for the present invention includes: hydrochloric acid, sulfuric acid, acetic acid. 'Phosphate, preferably hydrochloric acid. The above step (C) of the present invention is to pattern the support, and the patterning of the step (C) can be patterned by various chemical reactions. In the present invention, the patterning of the carrier is preferably carried out by placing a carrier having an s-graphene film in a -# engraving, and patterning the carrier by a meal engraving method. When the carrier having the first graphite (tetra) film is patterned, the carrier of the case 1 and the first film on the patterned protective layer are used. Further, after the above step (C) of γ, a step (C) is further included: surface-treating at least the surface of the graphene film. The surface treatment includes, for example, 201247422 plasma treatment, oxygen plasma treatment, hydrogen plasma treatment, or sputtering metal, such as silver metal sputtering. In the above invention, after the step ((2), a step (F) may be further included: the step (A) to the step (E) are repeated to form a plurality of layers of the graphite thin film on the target substrate, except that the patterned carrier is used. In addition to the above-mentioned graphite film transfer, the present invention further provides a graphene transfer method, and the method thereof comprises: (4) providing a carrier, wherein the carrier has a first surface, a second surface, and the first carrier Forming a first graphene film on the surface; (B) placing the carrier in the carrier removal solution to remove the carrier, and the first graphene film material (4) (4) (4) material ±; ((10) - replacement of the carrier In addition to the solution n graphite thin film suspended in the suspension solution; (9) separating the first graphite thin film and the suspension solution; and (8) forming the first graphite thin film on a target substrate. /, medium 'carrier material, carrier removal The chemical content of the solution is a chemical solution for etching the carrier, and the chemical solution may be a persulfate solution, a gasification solution, a solution, a sulfuric acid solution, or a mixed solution thereof, preferably a persulfate solution. The function of the suspension solution is that the preliminary cleaning has a carrier for retaining the chemical solution or the first graphene film, wherein the suspension solution can be a diluted carrier removal solution, hydrazine, alcohol, propylene or deionized water. Preferably, the step (A) of the graphene film transfer method of the present invention further comprises: (4) providing a carrier, wherein the first surface and the second surface of the carrier are respectively formed. a first graphite thin film 'and a second graphite thin 201247422 film; and (10) the carrier is placed on a graphite thinning solution, the graphene layer is in contact with the outside, the second ', ^ m 'ene a system and graphite Contacting the dilute removal solution to remove the second graphite thin layer. The method of step 4 (Α) is to remove the carrier of the graphene film of the first and second layers by a single stone film. In order to obtain a carrier having only the __4, 噶 石墨 石墨 石墨 石墨 苴 苴 苴 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨 石墨Β), before the system can include = two Recorded on the first-graphite_film; and the step_ is: two on == float solution, and the mark is passed to determine the relative position of the first-graphene thin 1 mesh &substrate; In the shifting method, the carrier is removed without a patterned protective layer. Therefore, after the carrier is removed, only the first graphite is left as a film. However, due to the transparent nature of the graphite thin film It is not easy to see with the naked eye. Therefore, before the carrier is etched, it can be marked 7 with its first graphene so that the first graphite film can be visually observed after the carrier is removed. The method of marking In the case of not damaging the first graphite thin: film, 7' can be the first-graphite thin film marking method of the present invention, such as using a pen or an ink mark. The above-mentioned invention further provides a graphite-to-film transfer method. In the first step (D), the method further includes: (locating a target substrate in the suspension solution; and removing the suspension solution to form the first graphite thin film on the target substrate. Wherein, the target substrate material is transferred to the first graphite thin film 201247422 by using the force between the first graphite (four) film and the process of removing the suspended solution. Wherein, the method of removing the solution is to remove the first graphite thin film from the suspension solution by using the suspension solution to remove the suspension from the target substrate. Transfer it directly to the surface of the target substrate. The invention further provides a graphite thin film transfer method, wherein the step (9) is the step (D'): after the first graphite thin film is picked up from the suspension solution, the first stone (four) film which is picked up is surface-treated. Wherein the characterization system may be an electric treatment, an oxygen treatment, a hydrogen treatment, a bismuth ore metal, etc. In addition, the present invention provides a graphene film transfer method, a body and a graphite film. The cleaning solution can be further cleaned and washed with a cleaning solution to remove the impurities, so that the carrier and the first graphene film can be more easily surface-treated. The cleaning solution is the same as the above-mentioned cleaning solution. [Embodiment] The following is a description of the embodiments of the present invention by a specific embodiment, and those skilled in the art can easily understand the present invention by the contents disclosed in the present specification. Other advantages and effects of the present invention may be implemented or applied by other different embodiments. The details of the present specification may also be based on different viewpoints and applications, and various modifications and modifications may be made without departing from the spirit of the invention. Change 1. Embodiment 1 Please refer to Figure A to Figure 1H at the same time. 201247422
首先，如圖丨a所示，提供一載體n，本實施例之載體 1丨為銅載體，且該鋼載體之厚度為50μιτιβ此載體π具有— 第一表面丨丨1以及第二表面η2。於混合有甲烷、氫氣之條 件中，加溫至1000。(：，且於壓力丨托耳或更低之情況下進 订石墨烯薄膜之熱化學氣相沈積法，使載體之第一表面iU 及第二表面U2上，各形成第一石墨烯薄膜丨13以及第二石 墨烯薄膜1 1 4。 接著，如圖1Β所示，提供一承載板丨2，本實施例之承 載板〗2係為一玻璃板。將該承載板12之一表面放置上一層 緩衝層13，本實施例之緩衝層η係為無塵紙。接著將上述 載體11之第一石墨烯薄膜113面向緩衝層13並置放載體Η 於緩衝層13上，並且使載體u之第二石墨烯薄膜U4與外界 接觸，其目的係用以保護該第一石墨烯薄膜113,以避免其 被後續之化學反應侵蝕。接著，設置一圖案化保護層14於 第二石墨烯薄膜114上。於本實施例中，其圖案化保護層14 係利用膠帶，於第二石墨稀薄膜】14周圍緊密貼合，以完成 其圖案化保護層1 4之設置。其中上述膠帶之緊密貼合目的 係為了避免後續化學溶液滲入並侵蝕第一石墨烯薄膜丨13。 接著，將與外界接觸之第二石墨烯薄膜114，滴上蝕刻 該第二石墨烯薄膜H4之碳蝕刻化學溶液，以完成該第二石 墨烯薄膜114之蝕刻，並且使該載體丨丨之第二表面丨12裸 露。本實施例之碳蝕刻化學溶液係為過氧化氫（h，_〇2)與硝酸 (hno3)之混合液。 201247422 如圖1 c所示，將上述完成第二石墨烯薄膜丨丨4蝕刻後之 載體丨1，延線A及A’切割，以使該載體丨1與該承載板〗2、以 及緩衝層13分離。並裸露其第一石墨烯薄膜丨丨3，如圖丨D 所示。 接著’如圖1E所示’將該載體1丨浸泡於載體蝕刻溶液 中’利用化學#刻反應將載體Η移除，以使該第一石墨稀 薄膜113與載體11分離，並裸露其第一石墨烯薄膜1丨3。本 實施例之載體蝕刻溶液係為4 %之過硫酸銨溶液 ((Nl^hSaO8)。待該載體丨丨蝕刻完成後，其第一石墨烯薄膜 113上僅剩：圖案化保護層14、及圖案化保護層丨4所對應之 圖案化載體11。 接著，將上述已蝕刻載體丨丨之第一石墨烯薄膜n 3，於 去離子水中浸泡數次，以清潔並稀釋第一石墨烯薄膜丨丨3上 所殘留之載體蝕刻溶液。如此可利於後續第一石墨烯薄膜 1]3表面之表面處理。 將上述之已蝕刻載體Η之第一石墨烯薄膜U3，利用去 離子水清洗數次後，將其懸浮於去離子水之懸浮溶液中， 如圖1F所示。接著，將一目標基板15置放於懸浮溶液中， 並將懸浮其中之第-石墨㈣膜1丨3與懸浮溶㈣之目標 基板15對準’利用逐漸抽出懸浮溶液之方式使第一石墨 烯溥膜113與目標基板15逐漸靠近貼合。 I接著，如圖1G所示，第一石墨稀薄膜U3會因逐漸減 少之懸浮溶液而沈降於目標基板15表面上。此時，由於第 一石墨稀薄膜113與目標基板15之間可能有殘留之懸浮溶 201247422 液，而使第一石墨烯薄mu3與目標基板15表面無法完整的 貼合。因此，將該附著有第一石墨烯薄膜丨丨3之目標基板15 斜放，使兩者間殘留之懸浮溶液流出，並且於此時，將與 第石墨烯薄膜1 1 3所連接之圖案化保護層丨4以及其所對 應之圖案化載體12移除，已完成第-石墨烯薄膜1⑽移於 目標基板15之目的，如圖1Η所示。 實施例2 本實施例與實施例丨大致相同，差別僅在於本實施例係 將已姓刻載體i i之第—石墨稀薄膜1】3，利用去離子水清洗 數次後’將其懸浮於去料水H㈣巾。此時，請參 考圖2A所示，將懸浮於懸浮溶液之其第一石墨烯薄膜113， 利用其圖案化㈣層及其所對應之圖案化載體η為著力 占於不接觸其上之第一石墨薄膜113情況下，榜起該第一 石墨稀薄mu，並將其轉料目標基板15上。此方法係可 更精確的將第一石墨烯薄膜U3轉移於目標基板丨5 ,已完成 第一石墨㈣膜丨丨3轉移於目標基板15之目的，請參考圖 2B ° 實施例3 請同時參考圖1B、圖⑴。本實施例與實施⑷大致相 同，差別僅在於本實施例係於載體u以及第二石墨烯薄膜 114進行_前’先以5%鹽酸（Ηα)清洗數次，以避免殘留 於載體11及第二石墨㈣膜114上之雜質影響後續之載體 11以第二石墨烯薄膜114之蝕刻效率。 201247422 另外’請在同時參考圖1 E。本實施例亦於已蝕刻載體 12之第一石墨稀薄膜1丨3上，利用5%鹽酸（HC1)清洗其第一 石墨烯濤膜1 1 3，以使後續之第-石墨烯薄膜1 13之表面處 理更加容易進行。 實施例4 本實施例與前述之實施例1大致相同’差別僅在於本實 施例係於不設置圖案化保護層14之情況下，進行第一石墨 烯薄膜Π3之轉移。 如圖2 A所不，首先，本實施例係先提供一載體1丨其 中該載體11係為銅載體，且此載體丨丨具有一第一表面、 第二表面112。將該載體丨〗於混合有甲烷、氫氣之條件中， 加/m至1 000 C，且於壓力丨托耳或更低之情況下進行第一表 面1 1 1之石墨稀薄膜之熱化學氣相沈積反應以使第一表面 111上形成第一石墨稀薄膜1丨3。 如圖2B所不’將上述之具有第一石墨烯薄膜us之載體 】1 ’浸泡於載體蝕刻化學溶液中’即4 %之過硫酸銨溶液 ((NH4)2S2〇8)’進行載體丨剩’以將第一石墨烯薄膜"3 與載體11分離。 再將漂浮於載❹刻化學溶液之第—石墨稀薄膜 113,利用去離子水多次稀釋，以稀釋成一懸浮溶液。立中， 第-石墨料膜1⑽懸浮於此懸浮溶液中。而上述之稀釋 載體敍刻化學溶液之步驟，俜用以：軎 知用以凊洗第一石墨烯薄膜113 上所殘留之載體蝕刻化學溶液。 16 201247422 接著，如圖2C、圖2D所示，將— .., 、，/± 目^基板15置放於懸 汗〉谷液中，亚使目標基板丨5對準第一 咕 田 珩石墨烯薄膜1 13，以使 第一石墨烯薄膜丨丨3貼合目標基板丨5， iπ成弟一石墨稀簿 膜1 13轉移於目標基板丨5之目的。 實施例5 本實施例與實施例4大致相同。然而，由於石墨烯薄膜 具有之透明之特性，故較難以利用肉眼進行觀察。因此本 實施例係於圖2Α時，將該第一石墨缔薄膜U3利用墨筆點上 記號，以使載體11被蝕刻後，仍可觀察出其第一石墨烯薄 膜113之位置，以利第一石墨烯薄膜U3與目標基板15之對 準。 上述實施例僅係為了方便說明而舉例而已，本發明所 主張之權利範圍自應以申請專利範圍所述為準，而非僅限 於上述實施例。 【圖式簡單說明】 圖1Α至圖1Η係本發明實施例1之石墨烯薄膜轉移流程剖面 不意圖。 圖2 Α至圖2Β係本發明實施例2之石墨烯薄膜轉移流程剖面 示意圖。 圖3 A製圖3D係本發明實施例4之石墨烯薄獏轉移流程剖面 示意圖。 【主要元件符號說明】 201247422 11載體 12承載板 13 14圖案化保護層 15目標基板 111 112第二表面 113第一石墨烯膜114 緩衝層 第一表面 第二石墨烯膜 18First, as shown in Fig. a, a carrier n is provided. The carrier 1 of the present embodiment is a copper carrier, and the thickness of the steel carrier is 50 μm τβ. The carrier π has a first surface 丨丨1 and a second surface η2. In a condition of mixing methane and hydrogen, heat to 1000. (:, and thermal chemical vapor deposition of a graphene film at a pressure or a lower pressure to form a first graphene film on the first surface iU and the second surface U2 of the carrier 13 and the second graphene film 1 14 4. Next, as shown in FIG. 1A, a carrier plate 2 is provided, and the carrier plate 2 of the embodiment is a glass plate. One surface of the carrier plate 12 is placed. A buffer layer 13, the buffer layer η of the present embodiment is a dust-free paper. Then, the first graphene film 113 of the carrier 11 faces the buffer layer 13 and the carrier is placed on the buffer layer 13, and the carrier u is second. The graphene film U4 is in contact with the outside, and is intended to protect the first graphene film 113 from being eroded by a subsequent chemical reaction. Next, a patterned protective layer 14 is disposed on the second graphene film 114. In this embodiment, the patterned protective layer 14 is closely adhered around the second graphite thin film 14 by using an adhesive tape to complete the setting of the patterned protective layer 14. The adhesive tape is closely adhered to the purpose. In order to avoid subsequent chemical solution seepage And etching and etching the first graphene film 丨 13. Next, the second graphene film 114 in contact with the outside is dropped onto the carbon etching chemical solution for etching the second graphene film H4 to complete the second graphene film 114. Etching, and exposing the second surface 丨12 of the carrier crucible. The carbon etching chemical solution of the embodiment is a mixture of hydrogen peroxide (h, _2) and nitric acid (hno3). As shown in c, the carrier 丨1 after the etching of the second graphene film 丨丨4 is completed, and the extension lines A and A' are cut so that the carrier 丨1 is separated from the carrier sheet 2 and the buffer layer 13. The first graphene film 丨丨3 is exposed, as shown in Fig. D. Then, as shown in Fig. 1E, the carrier is immersed in a carrier etching solution, and the carrier is removed by a chemical reaction. The first graphite thin film 113 is separated from the carrier 11 and the first graphene film 1丨3 is exposed. The carrier etching solution of this embodiment is a 4% ammonium persulfate solution ((Nl^hSaO8). After the carrier cerium is completed, only the first graphene film 113 remains: The layer 14 and the patterned carrier 11 corresponding to the patterned protective layer 丨 4. Next, the first graphene film n 3 of the etched carrier 丨丨 is immersed in deionized water several times to clean and dilute the first A carrier etching solution remaining on the graphene film 丨丨3. This can facilitate the surface treatment of the surface of the first graphene film 1]3. The first graphene film U3 of the above-mentioned etched carrier is deionized water. After washing several times, it is suspended in a suspension solution of deionized water, as shown in Fig. 1F. Next, a target substrate 15 is placed in a suspension solution, and the first-graphite (tetra) film suspended therein is 1 丨 3 Aligning with the target substrate 15 of the suspension solution (4) The first graphene germanium film 113 is gradually brought into close contact with the target substrate 15 by gradually withdrawing the suspension solution. I Next, as shown in Fig. 1G, the first graphite thin film U3 is deposited on the surface of the target substrate 15 by the gradually decreasing suspension solution. At this time, since the residual suspended solution 201247422 may exist between the first graphite thin film 113 and the target substrate 15, the first graphene thin mu3 may not be completely bonded to the surface of the target substrate 15. Therefore, the target substrate 15 to which the first graphene film 丨丨3 is attached is obliquely placed, and the residual suspension solution between the two is discharged, and at this time, the pattern connected to the graphene film 1 13 is patterned. The protective layer 4 and its corresponding patterned carrier 12 are removed, and the purpose of moving the first-graphene film 1 (10) to the target substrate 15 has been completed, as shown in FIG. Embodiment 2 This embodiment is substantially the same as the embodiment ,, except that the first embodiment of the present invention is a first-graph graphite thin film 1]3, which is washed several times with deionized water and then suspended. Water H (four) towel. At this time, referring to FIG. 2A, the first graphene film 113 suspended in the suspension solution is used to occupy the first layer which is not in contact with the patterned (four) layer and its corresponding patterned carrier η. In the case of the graphite film 113, the first graphite thin mu is listed and transferred onto the target substrate 15. This method can more accurately transfer the first graphene film U3 to the target substrate 丨5, and has completed the purpose of transferring the first graphite (four) film 丨丨3 to the target substrate 15, please refer to FIG. 2B. Embodiment 3 Please also refer to Figure 1B, Figure (1). This embodiment is substantially the same as the embodiment (4) except that the carrier u and the second graphene film 114 are first washed with 5% hydrochloric acid (Ηα) several times to avoid remaining in the carrier 11 and the first embodiment. The impurities on the two graphite (tetra) film 114 affect the etching efficiency of the subsequent carrier 11 with the second graphene film 114. 201247422 In addition, please refer to Figure 1 E at the same time. In this embodiment, the first graphene film 1 1 3 is also cleaned on the first graphite thin film 1丨3 of the etched carrier 12 by using 5% hydrochloric acid (HC1) to make the subsequent first-graphene film 1 13 The surface treatment is easier to carry out. [Embodiment 4] This embodiment is substantially the same as Embodiment 1 described above. The only difference is that the first embodiment is to transfer the first graphene film 3 without providing the patterned protective layer 14. As shown in Fig. 2A, firstly, in this embodiment, a carrier 1 is first provided, wherein the carrier 11 is a copper carrier, and the carrier has a first surface and a second surface 112. The carrier is kneaded in a condition of mixing methane and hydrogen, adding /m to 1 000 C, and performing the hot chemical gas of the graphite thin film of the first surface 1 1 1 under pressure or less. The phase deposition reaction causes the first graphite thin film 1丨3 to be formed on the first surface 111. As shown in FIG. 2B, the above-mentioned carrier having the first graphene film us1 is immersed in a carrier etching chemical solution, that is, 4% ammonium persulfate solution ((NH4)2S2〇8)' 'To separate the first graphene film "3 from the carrier 11. The first graphite thin film 113 floating on the engraving chemical solution is diluted with deionized water several times to be diluted into a suspension solution. In the middle, the first-graphite film 1 (10) is suspended in the suspension solution. The step of diluting the carrier to etch the chemical solution is used to: immerse the carrier etching chemical solution remaining on the first graphene film 113. 16 201247422 Next, as shown in FIG. 2C and FIG. 2D, the substrate . . . , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The olefin film 13 is formed so that the first graphene film 丨丨3 is bonded to the target substrate 丨5, and the iπ-diluted graphite film 134 is transferred to the target substrate 丨5. Embodiment 5 This embodiment is substantially the same as Embodiment 4. However, since the graphene film has a transparent property, it is difficult to observe with the naked eye. Therefore, in the embodiment of FIG. 2, the first graphite film U3 is marked with an ink pen so that the position of the first graphene film 113 can be observed after the carrier 11 is etched. A graphene film U3 is aligned with the target substrate 15. The above-described embodiments are merely examples for the convenience of the description, and the scope of the claims is intended to be limited by the scope of the claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A to Fig. 1 show a cross-sectional view of a graphene film transfer process according to a first embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing the transfer process of the graphene film of the second embodiment of the present invention. Fig. 3A is a schematic cross-sectional view showing the graphene transfer process of the fourth embodiment of the present invention. [Main component symbol description] 201247422 11 carrier 12 carrier plate 13 14 patterned protective layer 15 target substrate 111 112 second surface 113 first graphene film 114 buffer layer first surface second graphene film 18