TWI439374B - Method of transferring a graphene film - Google Patents
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本發明係關於一種石墨烯薄膜轉移方法，尤指於低化學及機械傷害下之一種有效轉移石墨烯薄膜之方法。The invention relates to a method for transferring graphene film, in particular to a method for effectively transferring graphene film under low chemical and mechanical damage.
石墨烯薄膜之結構係由碳原子以sp2 軌域互相鍵結形成六角碳環，並延伸形成如蜂巢狀之二維平面結構所形成。The structure of the graphene film is formed by carbon atoms bonded to each other by a sp 2 orbital domain to form a hexagonal carbocyclic ring and extended to form a honeycomb-like two-dimensional planar structure.
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、或機械補強之複合材。Graphene has excellent optical, electrical, and mechanical properties, and it has transparent properties, so it can be applied to transparent conductive layers, conductive composite materials, or soft electrons. It can also be applied to capacitors, lithium battery electrodes, or mechanical reinforcement. Composite material.
多數應用石墨烯之產品大多係由數層之石墨烯薄膜所堆疊而成，而其堆疊之方式係可透過一層層之石墨烯薄膜進行轉移而層層堆疊。目前，較佳之石墨烯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膜後，再將附著於催化金屬上之石墨烯薄膜，以聚甲基丙烯酸甲酯(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薄膜之PMMA壓片貼合，利用熱、UV、氣體(氫氣與氮氣)或丙酮，將PMMA去除，使石墨烯薄膜轉移至目標基板上，已達到石墨烯薄膜轉移之目的。Most of the products using graphene are stacked by several layers of graphene films, and the stacking method is through layer-by-layer graphene film transfer and layer stacking. At present, the preferred graphene film transfer method utilizes a thermal chemical vapor deposition method to form a graphene film on a catalytic metal, and then attaches a graphene film attached to the catalytic metal to polymethyl methacrylate (PMMA). After pasting, 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 a PMMA sheet to which a graphene film is adhered, and PMMA is removed by heat, UV, gas (hydrogen and nitrogen) or acetone, and the graphene film is transferred onto the target substrate to reach graphene. The purpose of film transfer.
上述之石墨烯薄膜轉移方法雖然可以有效的進行石墨烯薄膜之轉移。然而，由於石墨烯薄膜從催化金屬轉移至目標基板之過程中，其需經過數次之化學溶液蝕刻以及機械壓印之過程，因而使得石墨烯薄膜容易產生破裂之情形。據此，發展一種有效且良率高之石墨烯薄膜轉移方法係可有效開發石墨烯薄膜更多之應用。The graphene film transfer method described above can effectively transfer the graphene film. However, since the graphene film is transferred from the catalytic metal to the target substrate, it needs to undergo several chemical solution etching and mechanical imprinting processes, thereby making the graphene film susceptible to cracking. Accordingly, the development of an effective and high yield graphene film transfer method can effectively develop more applications of graphene films.
本發明之主要目的係提供一種石墨烯薄膜轉移方法，俾能於低化學傷害下，提高石墨烯薄膜之轉移品質。The main object of the present invention is to provide a graphene film transfer method which can improve the transfer quality of a graphene film under low chemical damage.
本發明之另一目的係提供一種石墨烯薄膜轉移方法，俾能高效率地轉移多層石墨烯薄膜。Another object of the present invention is to provide a graphene film transfer method which can transfer a multilayer graphene film with high efficiency.
為達成上述目的，本發明係提供一種石墨烯薄膜轉移方法，其方法係包括：(A)提供一載體，其中此載體係具有一第一表面、及一第二表面，且此載體之第一表面上形成有一第一石墨烯薄膜；(B)設置一圖案化保護層於此載體之第二表面上；(C)圖案化此載體以顯露其第一石墨烯薄膜，其中此載體之圖案是對應於圖案化保護層；(D)將設有此第一石墨烯薄膜之圖案化載體設置於一目標基板上；以及(E)移除圖案化載體，以使其第一石墨烯薄膜形成於目標基板上。In order to achieve the above object, the present invention provides a graphene film transfer method, the method comprising: (A) providing a carrier, wherein the carrier has a first surface, and a second surface, and the carrier is first Forming a first graphene film on the surface; (B) providing a patterned protective layer on the second surface of the carrier; (C) patterning the carrier to expose the first graphene film, wherein the pattern of the carrier is Corresponding to the patterned protective layer; (D) disposing the patterned carrier provided with the first graphene film on a target substrate; and (E) removing the patterned carrier to form the first graphene film thereon On the target substrate.
其中，載體之材料可係為催化金屬，如銅、鎳、鐵、銀、或其組合，較佳為銅、鎳、或其組合。而該載體形成石墨烯薄膜之方法係利用熱化學氣相沈積法、濺鍍法、塗佈法，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 μm，更佳為200-50 μm。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。The material of the carrier may be a catalytic metal such as copper, nickel, iron, silver, or a combination thereof, preferably copper, nickel, or a combination thereof. The method for forming the graphene film by the carrier is a thermal chemical vapor deposition method, a sputtering method, a coating method, preferably a thermal chemical vapor deposition method, so that the graphene film is formed on the surface of the carrier, and The thickness of the carrier of the graphene film formed is not particularly limited, and is preferably 500 to 10 μm, more preferably 200 to 50 μm, depending on the demand. Further, the formation method of the patterned protective layer is not particularly limited, and 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.
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。其中，該蝕刻法之蝕刻液係為蝕刻載體之化學溶液。而該化學溶液係可為過硫酸銨溶液、氯化鐵溶液、磷酸溶液、硫酸溶液、或其混合溶液，較佳為過硫酸銨溶液。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. Patterning. The etching solution of the etching method is a chemical solution for etching the carrier. The chemical solution may be an ammonium persulfate solution, a ferric chloride solution, a phosphoric acid solution, a sulfuric acid solution, or a mixed solution thereof, preferably an ammonium persulfate solution.
上述本發明之步驟(D)，其中，第一石墨烯薄膜設置於一目標基板之方法係包括：(D1)提供一懸浮溶液，其中此懸浮溶液內係設置有一目標基板；(D2)將設有第一石墨烯薄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溶液上；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，再將該圖案化之載體移除，以使第一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。In the above step (D) of the present invention, the method for disposing the first graphene film on a target substrate comprises: (D1) providing a suspension solution, wherein the suspension solution is provided with a target substrate; (D2) is provided A patterned carrier having a first graphene film is placed in a suspension solution to suspend the patterned carrier on the suspension solution; 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.
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，係使具有圖案化載體之第一石墨烯薄膜懸浮於懸浮溶液中，利用逐漸移除懸浮溶液之方式，使具有圖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一石墨烯薄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，以完成第一石墨烯薄膜轉移於目標基板表面之目的。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 the suspension solution, and the method for gradually removing the suspension solution is used. The first olefin film with the patterned carrier gradually leans into the surface of the target substrate in the suspension solution. After the suspension solution is removed, the first graphene film 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 graphene film to the surface of the target substrate.
然而，其除了上述步驟(D)之第一石墨烯薄膜設置於第一目標基板之方法外，其步驟(D)另可為：(D1)提供一懸浮溶液，將設有第一石墨烯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，以自懸浮溶液中撈起第一石墨烯薄膜；以及(D3)將第一石墨烯薄膜，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況下，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撈起。接著，再將撈起之第一石墨烯薄膜黏著黏於目標基板上，以完成石墨烯薄膜附著於目標基板表面之目的。此外，將該第一石墨烯薄膜於懸浮溶液中撈起後，係可先將其第一石墨烯薄膜之至少一表面視需要而更進一步進行表面處理，如電漿處理、氧電漿處理、氫電漿處理、或濺鍍金屬等表面處理。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 be: (D1) providing a suspension solution, and the first graphene film is provided. 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 pick up the first graphene film from the suspension solution; and (D3) The first graphene film is placed on the target substrate. The method is based on the patterned carrier, and the first graphene film with the patterned carrier can be lifted from the suspension solution without contacting the first graphene film, and the lifting method can be carried out from bottom to top. Pick up. Then, the first graphene film picked up is adhered to the target substrate to complete the adhesion of the graphene film to the surface of the target substrate. In addition, after the first graphene film is picked up in the suspension solution, at least one surface of the first graphene film may be further subjected to surface treatment as needed, such as plasma treatment, oxygen plasma treatment, Surface treatment such as hydrogen plasma treatment or sputtering of metal.
上述本發明之石墨烯薄膜轉移方法中，其步驟(A)更包括：(A1)提供一載體、及一承載板，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烯薄膜、以及一第二石墨烯薄膜。另外，承載板表面設置有一緩衝層；(A2)將載體層疊於承載板上，且承載板上係依序層疊有緩衝層、第一石墨烯薄膜、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。In the above method for transferring graphene film of the present invention, the step (A) further comprises: (A1) providing a carrier and a carrier plate, wherein the first surface and the second surface of the carrier are respectively formed with a first graphite An ene film and a second graphene film. In addition, a surface of the carrier plate is provided with a buffer layer; (A2) the carrier is laminated on the carrier plate, and the buffer plate, the first graphene film, the carrier, and the second graphene film are sequentially laminated on the carrier plate; (A3) removing the second graphene film to reveal the second surface of the carrier.
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、壓克力板、塑膠板、陶瓷板等，較佳為玻璃板、以及壓克力板。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。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, an acrylic plate, a plastic plate, a ceramic plate, etc., preferably a glass plate, and an acrylic. board. Further, the material of the buffer layer has a property of being less likely to adhere to the graphene film, preferably paper, paper, non-woven fabric, or a combination thereof, and more preferably a face paper.
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，移除第二石墨烯薄膜之方法，係將疊有一緩衝層之承載板上，放置形成有石墨烯薄膜之載體，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膜係與緩衝層接觸，且載體之第二石墨烯薄膜係層疊至最上層。如此，使第二石墨烯薄膜暴露於外界，以便移除。而第二石墨烯薄膜之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烯薄膜之移除，更佳係以蝕刻法進行其第二石墨烯薄膜之移除。而其第二石墨烯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、硝酸溶液、氫氧化鉀溶液、或其混合溶液，更佳為過氧化氫溶液及硝酸溶液之混合。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. Wherein, the method for removing the second graphene film is to place a carrier having a buffer layer on the carrier plate on which the buffer layer is stacked, and the first graphite is placed on the buffer layer of the carrier plate in sequence. Film, carrier, and second graphene film. Wherein, the first graphene film of the carrier is in contact with the buffer layer, and the second graphene film of the carrier is laminated to the uppermost layer. As such, the second graphene film is exposed to the outside for removal. The method for removing the second graphene film is not particularly limited, and may be a chemical method or a physical method, preferably a chemical method for removing the second graphene film, and more preferably an etching method for the second graphite. Removal of the olefin film. The etching solution of the second graphene film may be a chemical solution for etching carbon, preferably a hydrogen peroxide solution, a nitric acid solution, a potassium hydroxide solution, or a mixed solution thereof, more preferably a hydrogen peroxide solution and a nitric acid solution. Mix of.
上述本發明之步驟(A1)之後，更可包括一步驟(A1’)：清洗第一石墨烯薄膜、及第二石墨烯薄膜。其中，清洗石墨烯薄膜之目的係要將其薄膜上之化學溶液以及雜質清除，使石墨烯薄膜可更容易地進一步的進行表面處理或化學反應，如電漿處理、氧電漿處理、氫電漿處理、濺鍍金屬、或蝕刻反應等。其中，清洗其石墨烯薄膜之溶液並無特別限制，只要能達到上述清洗之目的者，即為本發明所適用之石墨烯薄膜清洗溶液，包括：鹽酸、硫酸、醋酸、磷酸，較佳為鹽酸。After the step (A1) of the present invention described above, a step (A1') may be further included: cleaning the first graphene film and the second graphene film. Among them, the purpose of cleaning the graphene film is to remove the chemical solution and impurities on the film, so that the graphene film can be further easily subjected to surface treatment or chemical reaction, such as plasma treatment, oxygen plasma treatment, hydrogen power. Slurry treatment, sputtering metal, or etching reaction. The solution for cleaning the graphene film is not particularly limited as long as it can achieve the purpose of the above cleaning, that is, the graphene film cleaning solution suitable for the present invention, including: hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, preferably hydrochloric acid. .
上述本發明之步驟(B)中，更可包括一步驟(B’)：清洗載體之第二表面。其清洗之目的係為防止載體第二表面上之化學殘留溶液以及雜質，以影響後續之化學反應、及表面處理，如蝕刻反應。其中，清洗載體第二表面之化學溶液並無特別限制，只要能達到上述清洗之目的及為本發明所適用之石墨烯薄膜清洗溶液，包括：鹽酸、硫酸、醋酸、磷酸，較佳為鹽酸。In the above step (B) of the present invention, a step (B') may be further included: cleaning the second surface of the carrier. The purpose of cleaning is to prevent chemical residual solutions and impurities on the second surface of the carrier to affect subsequent chemical reactions, and surface treatments such as etching reactions. The chemical solution for cleaning the second surface of the carrier is not particularly limited as long as it can achieve the above cleaning purpose and the graphene film cleaning solution to which the present invention is applied, including hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, preferably hydrochloric acid.
上述本發明之步驟(C)係將該載體進行圖案化，而其中步驟(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，其載體之圖案化較佳係將具有第一石墨烯薄膜之載體置於一蝕刻液中，以蝕刻法進行載體之圖案化。當其具有第一石墨烯薄膜之載體進行圖案化後，則其載體係包括：圖案化之載體、以及圖案化保護層上之第一石墨烯薄膜。The above step (C) of the present invention is to pattern the support, and wherein the patterning of the step (C) can be patterned by various chemical reactions. In the present invention, the patterning of the carrier is preferably performed by placing the carrier having the first graphene film in an etching solution, and patterning the carrier by etching. After the carrier having the first graphene film is patterned, the carrier system includes: a patterned carrier, and a first graphene film on the patterned protective layer.
此外，上述步驟(C)後，更包括一步驟(C’)：表面處理第一石墨烯薄膜之至少一表面。其中，該表面處理係包括：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。Further, after the above step (C), a step (C') is further included: surface treating at least one surface of the first graphene film. Wherein, the surface treatment system comprises: plasma treatment, oxygen plasma treatment, hydrogen plasma treatment, or sputtering metal, such as silver metal sputtering.
上述本發明中，其步驟(E)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烯薄膜。In the above invention, after the step (E), a step (F) may be further included: the step (A) to the step (E) are repeated to form a plurality of layers of the graphene film on the target substrate.
除了利用圖案化載體進行上述之石墨烯薄膜轉移外，本發明另提供一種石墨烯轉移方法。而其方法係包括：(A)提供一載體，其中其載體具有一第一表面、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)將載體置於一載體移除溶液中以移除載體，且該第一石墨烯薄膜係懸浮於該載體移除溶液上；(C)以一懸浮溶液置換載體移除溶液，且第一石墨烯薄膜係懸浮於懸浮溶液上；(D)分離第一石墨烯薄膜及懸浮溶液；以及(E)將第一石墨烯薄膜形成於一目標基板上。In addition to performing the above-described graphene film transfer using a patterned carrier, the present invention further provides a graphene transfer method. The method comprises the following steps: (A) providing a carrier, wherein the carrier has a first surface and a second surface, and a first graphene film is formed on the first surface of the carrier; (B) the carrier is placed Removing the carrier in a carrier removal solution, and the first graphene film is suspended on the carrier removal solution; (C) replacing the carrier removal solution with a suspension solution, and suspending the first graphene film On the suspension solution; (D) separating the first graphene film and the suspension solution; and (E) forming the first graphene film on a target substrate.
其中，載體之材質、載體移除溶液之成份內容係為蝕刻載體之化學溶液。而該化學溶液係可為過硫酸銨溶液、氯化鐵溶液、磷酸溶液、硫酸溶液、或其混合溶液，較佳為過硫酸銨溶液。 而懸浮溶液之功能係用於初步清洗具有殘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、水、酒精、丙酮或去離子水，而較佳係為去離子水。Wherein, the material of the carrier and the component content of the carrier removal solution are chemical solutions for etching the carrier. The chemical solution may be an ammonium persulfate solution, a ferric chloride solution, a phosphoric acid solution, a sulfuric acid solution, or a mixed solution thereof, preferably an ammonium persulfate solution . The function of the suspension solution is for preliminarily cleaning the carrier or the first graphene film having the residual chemical solution, wherein the suspension solution may be a diluted carrier removal solution, water, alcohol, acetone or deionized water. More preferably, it is deionized water.
上述本發明另一石墨烯薄膜轉移方法之步驟(A)更包括：(A1)提供一載體，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烯薄膜、以及一第二石墨烯薄膜；以及(A2)將載體置於一石墨烯移除溶液上，其中第一石墨烯層係與外界接觸，第二石墨烯層係與石墨烯移除溶液接觸，以移除第二石墨烯層。其中，該步驟(A)之方法係將具有第一及第二之石墨烯薄膜之載體進行單一石墨烯薄膜之移除，以得到僅具有第一石墨烯薄膜之載體。其中，該石墨烯薄膜移除溶液係與上述之石墨烯薄膜移除溶液相同。The step (A) of the above graphene film transfer method of the present invention further comprises: (A1) providing a carrier, wherein the first surface and the second surface of the carrier are respectively formed with a first graphene film, and a first a graphene film; and (A2) placing the carrier on a graphene removal solution, wherein the first graphene layer is in contact with the outside, and the second graphene layer is in contact with the graphene removal solution to remove the Two graphene layers. Wherein, the method of the step (A) is to remove the carrier of the first and second graphene films by a single graphene film to obtain a carrier having only the first graphene film. Wherein, the graphene film removal solution is the same as the above graphene film removal solution.
上述本發明之步驟(B)之前，係更可包括一步驟(A’)：形成一標記於第一石墨烯薄膜上；且步驟(D)係為：將一目標基板置於懸浮溶液中，且透過標記以決定第一石墨烯薄膜與目標基板之相對位置。由於本發明所提供之另一石墨烯轉移方法中，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烯薄膜。然而，由於其石墨烯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薄膜上做一標記，以使第一石墨烯薄膜於載體移除後，仍可以肉眼觀察到其位置。而該標記之方法，於不傷害第一石墨烯薄膜之情況下，皆可為本發明之第一石墨烯薄膜標記方法，如利用筆、或油墨標記記號。Before the step (B) of the present invention, the method further comprises: a step (A'): forming a mark on the first graphene film; and the step (D) is: placing a target substrate in the suspension solution, And passing the mark to determine the relative position of the first graphene film and the target substrate. Since the other graphene transfer method provided by the present invention is carried out without removing the patterned protective layer, the carrier is removed, so that only the first graphene film is left after the carrier is removed. However, since the graphene film has a transparent property and is not easily visible to the naked eye, before the carrier is etched, a mark can be made on the first graphene film to remove the first graphene film after the carrier is removed. The position can still be observed with the naked eye. The marking method can be the first graphene film marking method of the present invention without damaging the first graphene film, such as using a pen or an ink marking mark.
上述本發明另提供之一種石墨烯薄膜轉移方法中，其步驟(D)可更包括：(D1)將一目標基板置該懸浮溶液中；以及(D2)移除懸浮溶液，以使第一石墨烯薄膜形成於目標基板上。其中，目標基板係可利用與第一石墨烯薄膜間之附著力，於移除懸浮溶液之過程中，進行第一石墨烯薄膜之轉移。其中，移除溶液之方法係可將懸浮溶液抽離。另外，除了利用懸浮溶液抽離之方式，將懸浮之第一石墨稀薄膜轉移至目標基板外，另可將第一石墨烯薄膜由懸浮溶液中撈起，以直接將其轉移至目標基板之表面上。In the above method for transferring graphene film according to the present invention, the step (D) may further comprise: (D1) placing a target substrate in the suspension solution; and (D2) removing the suspension solution to make the first graphite The olefin film is formed on the target substrate. Wherein, the target substrate can utilize the adhesion between the first graphene film and the transfer of the first graphene film during the process of removing the suspension solution. Among them, the method of removing the solution can extract the suspension solution. In addition, in addition to the suspension of the suspension solution, the suspended first graphite thin film is transferred to the target substrate, and the first graphene film can be picked up from the suspension solution to directly transfer it to the surface of the target substrate. on.
上述本發明另提供之一種石墨烯薄膜轉移方法，其中步驟(D)可為步驟(D’)：自懸浮溶液中撈起第一石墨烯薄膜後，再表面處理其撈起之第一石墨烯薄膜。其中該表面處理係可為電漿處理、氧電漿處理、氫電漿處理、或濺鍍金屬等。而本發明所另提供之一種石墨烯薄膜轉移方法中，其載體、以及第一石墨烯薄膜係可更進一步加以使用清洗溶液進行清洗，以清洗第一石墨烯薄膜上之殘留化學溶液、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。The invention further provides a graphene film transfer method, wherein the step (D) is the step (D′): picking up the first graphene film from the suspension solution, and then surface treating the first graphene film. The surface treatment system may be plasma treatment, oxygen plasma treatment, hydrogen plasma treatment, or sputtering metal. In the method for transferring a graphene film according to another aspect of the present invention, the carrier and the first graphene film may be further washed with a cleaning solution to clean residual chemical solution and impurities on the first graphene film. The carrier and the first graphene film can be more easily surface-treated. Wherein, the cleaning solution is the same as the above cleaning solution.
以下係藉由特定的具體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內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。The embodiments of the present invention are described by way of specific examples, and those skilled in the art can readily appreciate the other advantages and advantages of the present invention. The present invention may be embodied or applied in various other specific embodiments, and various modifications and changes can be made without departing from the spirit and scope of the invention.
實施例1Example 1
請同時參考圖1A至圖1H。Please refer to FIG. 1A to FIG. 1H at the same time.
首先，如圖1A所示，提供一載體11，本實施例之載體11為銅載體，且該銅載體之厚度為50 μm。此載體11具有一第一表面111以及第二表面112。於混合有甲烷、氫氣之條件中，加溫至1000℃，且於壓力1托耳或更低之情況下，進行石墨烯薄膜之熱化學氣相沈積法，使載體之第一表面111及第二表面112上，各形成第一石墨烯薄膜113以及第二石墨烯薄膜114。First, as shown in Fig. 1A, a carrier 11 is provided. The carrier 11 of this embodiment is a copper carrier, and the copper carrier has a thickness of 50 μm. This carrier 11 has a first surface 111 and a second surface 112. In the condition of mixing methane and hydrogen, heating to 1000 ° C, and at a pressure of 1 Torr or less, performing thermal chemical vapor deposition of the graphene film to make the first surface 111 of the carrier and the first On the two surfaces 112, a first graphene film 113 and a second graphene film 114 are formed.
接著，如圖1B所示，提供一承載板12，本實施例之承載板12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13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11於緩衝層13上，並且使載體11之第二石墨烯薄膜114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，於第二石墨烯薄膜114周圍緊密貼合，以完成其圖案化保護層14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113。Next, as shown in FIG. 1B, a carrier board 12 is provided. The carrier board 12 of this embodiment is a glass board. A buffer layer 13 is placed on one surface of the carrier 12, and the buffer layer 13 of the embodiment is a dust-free paper. Then, the first graphene film 113 of the carrier 11 faces the buffer layer 13 and the carrier 11 is placed on the buffer layer 13, and the second graphene film 114 of the carrier 11 is brought into contact with the outside, for the purpose of protecting the first The graphene film 113 is prevented from being attacked by subsequent chemical reactions. Next, a patterned protective layer 14 is disposed on the second graphene film 114. In the present embodiment, the patterned protective layer 14 is closely adhered around the second graphene film 114 by using an adhesive tape to complete the setting of the patterned protective layer 14. The close fitting purpose of the above tape is to prevent the subsequent chemical solution from infiltrating and eroding the first graphene film 113.
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114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11之第二表面112裸露。本實施例之碳蝕刻化學溶液係為過氧化氫(H2 O2 )與硝酸(HNO3 )之混合液。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 114 to complete the etching of the second graphene film 114, and the second of the carrier 11 is made. Surface 112 is bare. The carbon etching chemical solution of this embodiment is a mixture of hydrogen peroxide (H 2 O 2 ) and nitric acid (HNO 3 ).
如圖1C所示，將上述完成第二石墨烯薄膜114蝕刻後之載體11，延線A及A’切割，以使該載體11與該承載板12、以及緩衝層13分離。並裸露其第一石墨烯薄膜113，如圖1D所示。As shown in Fig. 1C, the carrier 11 after the etching of the second graphene film 114 is completed, and the extension lines A and A' are cut so that the carrier 11 is separated from the carrier sheet 12 and the buffer layer 13. The first graphene film 113 is exposed, as shown in FIG. 1D.
接著，如圖1E所示，將該載體11浸泡於載體蝕刻溶液中，利用化學蝕刻反應將載體11移除，以使該第一石墨烯薄膜113與載體11分離，並裸露其第一石墨烯薄膜113。本實施例之載體蝕刻溶液係為4%之過硫酸銨溶液((NH4 )2 S2 O8 )。待該載體11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14所對應之圖案化載體11。Next, as shown in FIG. 1E, the carrier 11 is immersed in a carrier etching solution, and the carrier 11 is removed by a chemical etching reaction to separate the first graphene film 113 from the carrier 11 and expose the first graphene. Film 113. The carrier etching solution of this example was a 4% ammonium persulfate solution ((NH 4 ) 2 S 2 O 8 ). After the etching of the carrier 11 is completed, only the patterned protective layer 14 and the patterned carrier 11 corresponding to the patterned protective layer 14 remain on the first graphene film 113.
接著，將上述已蝕刻載體11之第一石墨烯薄膜113，於去離子水中浸泡數次，以清潔並稀釋第一石墨烯薄膜113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113表面之表面處理。Next, the first graphene film 113 of the above-described etched carrier 11 is immersed several times in deionized water to clean and dilute the carrier etching solution remaining on the first graphene film 113. This can facilitate the surface treatment of the surface of the first graphene film 113.
將上述之已蝕刻載體11之第一石墨烯薄膜113，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，並將懸浮其中之第一石墨烯薄膜113與懸浮溶液內之目標基板15對準，利用逐漸抽出懸浮溶液之方式，使第一石墨烯薄膜113與目標基板15逐漸靠近貼合。The first graphene film 113 of the above-described etched carrier 11 was washed several times with deionized water, and then suspended in a suspension solution of deionized water, as shown in Fig. 1F. Next, a target substrate 15 is placed in the suspension solution, and the first graphene film 113 suspended therein is aligned with the target substrate 15 in the suspension solution, and the first graphene film is made by gradually withdrawing the suspension solution. 113 is gradually brought closer to the target substrate 15.
接著，如圖1G所示，第一石墨稀薄膜113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，由於第一石墨烯薄膜113與目標基板15之間可能有殘留之懸浮溶液，而使第一石墨烯薄膜113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113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，將與第一石墨烯薄膜113所連接之圖案化保護層14以及其所對應之圖案化載體12移除，已完成第一石墨烯薄膜113轉移於目標基板15之目的，如圖1H所示。Next, as shown in FIG. 1G, the first graphite thin film 113 is deposited on the surface of the target substrate 15 by the gradually decreasing suspension solution. At this time, since the residual suspension solution may exist between the first graphene film 113 and the target substrate 15, the surface of the first graphene film 113 and the target substrate 15 may not be completely bonded. Therefore, the target substrate 15 to which the first graphene film 113 is attached is laid obliquely, and the residual suspension solution between the two is discharged, and at this time, the patterned protective layer 14 connected to the first graphene film 113 is connected. And the corresponding patterned carrier 12 removal, the purpose of transferring the first graphene film 113 to the target substrate 15 has been completed, as shown in FIG. 1H.
實施例2Example 2
本實施例與實施例1大致相同，差別僅在於本實施例係將已蝕刻載體11之第一石墨烯薄膜113，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。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，利用其圖案化保護層及其所對應之圖案化載體11為著力點，於不接觸其上之第一石墨薄膜113情況下，撈起該第一石墨烯薄膜113，並將其轉移於目標基板15上。此方法係可更精確的將第一石墨烯薄膜113轉移於目標基板15，已完成第一石墨烯薄膜113轉移於目標基板15之目的，請參考圖2B。This embodiment is substantially the same as the first embodiment except that the first graphene film 113 of the carrier 11 has been etched by deionized water for several times, and then suspended in a suspension solution of deionized water. . At this time, referring to FIG. 2A, the first graphene film 113 suspended in the suspension solution is used as a force point by using the patterned protective layer and the corresponding patterned carrier 11 thereof, without contacting the first In the case of a graphite film 113, the first graphene film 113 is picked up and transferred to the target substrate 15. This method can transfer the first graphene film 113 to the target substrate 15 more accurately, and the purpose of transferring the first graphene film 113 to the target substrate 15 has been completed. Please refer to FIG. 2B.
實施例3Example 3
請同時參考圖1B、圖1C。本實施例與實施例1大致相同，差別僅在於本實施例係於載體11以及第二石墨烯薄膜114進行蝕刻前，先以5%鹽酸(HCl)清洗數次，以避免殘留於載體11及第二石墨烯薄膜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。Please refer to FIG. 1B and FIG. 1C at the same time. This embodiment is substantially the same as the first embodiment except that the carrier 11 and the second graphene film 114 are firstly washed with 5% hydrochloric acid (HCl) several times before etching to avoid remaining on the carrier 11 and The impurities on the second graphene film 114 affect the etching efficiency of the subsequent carrier 11 with the second graphene film 114.
另外，請在同時參考圖1E。本實施例亦於已蝕刻載體12之第一石墨烯薄膜113上，利用5%鹽酸(HCl)清洗其第一石墨烯薄膜113，以使後續之第一石墨烯薄膜113之表面處理更加容易進行。In addition, please refer to Figure 1E at the same time. In this embodiment, the first graphene film 113 is also cleaned on the first graphene film 113 of the carrier 12 by using 5% hydrochloric acid (HCl) to make the surface treatment of the subsequent first graphene film 113 easier. .
實施例4Example 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113之轉移。This embodiment is substantially the same as the first embodiment described above, except that the first embodiment is to transfer the first graphene film 113 without providing the patterned protective layer 14.
如圖2A所示，首先，本實施例係先提供一載體11，其中該載體11係為銅載體，且此載體11具有一第一表面111、第二表面112。將該載體11於混合有甲烷、氫氣之條件中，加溫至1000℃，且於壓力1托耳或更低之情況下進行第一表面111之石墨烯薄膜之熱化學氣相沈積反應，以使第一表面111上形成第一石墨烯薄膜113。As shown in FIG. 2A, firstly, in this embodiment, a carrier 11 is provided, wherein the carrier 11 is a copper carrier, and the carrier 11 has a first surface 111 and a second surface 112. The carrier 11 is heated to 1000 ° C in a condition of mixing methane and hydrogen, and the thermal chemical vapor deposition reaction of the graphene film of the first surface 111 is performed at a pressure of 1 Torr or less to A first graphene film 113 is formed on the first surface 111.
如圖2B所示，將上述之具有第一石墨烯薄膜113之載體11，浸泡於載體蝕刻化學溶液中，即4%之過硫酸銨溶液((NH4 )2 S2 O8 )，進行載體11蝕刻，以將第一石墨烯薄膜113與載體11分離。As shown in FIG. 2B, the carrier 11 having the first graphene film 113 is immersed in a carrier etching chemical solution, that is, a 4% ammonium persulfate solution ((NH 4 ) 2 S 2 O 8 ), and the carrier is carried out. 11 etching to separate the first graphene film 113 from the carrier 11.
再將漂浮於載體蝕刻化學溶液之第一石墨烯薄膜113，利用去離子水多次稀釋，以稀釋成一懸浮溶液。其中，第一石墨烯薄膜113係懸浮於此懸浮溶液中。而上述之稀釋載體蝕刻化學溶液之步驟，係用以清洗第一石墨烯薄膜113上所殘留之載體蝕刻化學溶液。The first graphene film 113 floating on the carrier etching chemical solution is diluted with deionized water several times to be diluted into a suspension solution. Wherein, the first graphene film 113 is suspended in the suspension solution. The step of diluting the carrier etching the chemical solution is for cleaning the carrier etching chemical solution remaining on the first graphene film 113.
接著，如圖2C、圖2D所示，將一目標基板15置放於懸浮溶液中，並使目標基板15對準第一石墨烯薄膜113，以使第一石墨烯薄膜113貼合目標基板15，並完成第一石墨烯薄膜113轉移於目標基板15之目的。Next, as shown in FIG. 2C and FIG. 2D, a target substrate 15 is placed in the suspension solution, and the target substrate 15 is aligned with the first graphene film 113 so that the first graphene film 113 is attached to the target substrate 15. And completing the purpose of transferring the first graphene film 113 to the target substrate 15.
實施例5Example 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2A時，將該第一石墨烯薄膜113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113與目標基板15之對準。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. 2A, the first graphene film 113 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 113 is aligned with the target substrate 15.
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。The above-mentioned embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the above embodiments.
11．．．載體11. . . Carrier
12．．．承載板12. . . Carrier board
13．．．緩衝層13. . . The buffer layer
14．．．圖案化保護層14. . . Patterned protective layer
15．．．目標基板15. . . Target substrate
111．．．第一表面111. . . First surface
112．．．第二表面112. . . Second surface
113．．．第一石墨烯膜113. . . First graphene film
114．．．第二石墨烯膜114. . . Second graphene film
圖1A至圖1H係本發明實施例1之石墨烯薄膜轉移流程剖面示意圖。1A to 1H are schematic cross-sectional views showing a transfer process of a graphene film according to Embodiment 1 of the present invention.
圖2A至圖2B係本發明實施例2之石墨烯薄膜轉移流程剖面示意圖。2A to 2B are schematic cross-sectional views showing a transfer process of a graphene film according to Embodiment 2 of the present invention.
圖3A製圖3D係本發明實施例4之石墨烯薄膜轉移流程剖面示意圖。3D is a cross-sectional view showing a graphene transfer process of the fourth embodiment of the present invention.
11．．．載體11. . . Carrier
12．．．承載板12. . . Carrier board
13．．．緩衝層13. . . The buffer layer
14．．．圖案化保護層14. . . Patterned protective layer
15．．．目標基板15. . . Target substrate
111．．．第一表面111. . . First surface
112．．．第二表面112. . . Second surface
113．．．第一石墨烯膜113. . . First graphene film
114．．．第二石墨烯膜114. . . Second graphene film
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| CN104582295A (en) * | 2013-10-25 | 2015-04-29 | 绿点高新科技股份有限公司 | Forming method of graphene circuit pattern and product thereof |
| TWI611461B (en) * | 2016-09-23 | 2018-01-11 | 國立成功大學 | Flexible Raman substrate and method for manufacturing the same |
| CN108910863B (en) * | 2018-06-26 | 2020-05-15 | 中科钢研节能科技有限公司 | Graphene heat-conducting film and preparation method thereof |
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