TWI516316B - A copper foil for graphene production, and a method for producing graphene using the same - Google Patents

Description

石墨烯製造用銅箔及使用其之石墨烯之製造方法 Copper foil for graphene production and method for producing graphene using the same

本發明係關於一種用以製造石墨烯之銅箔基材、及使用其之石墨烯之製造方法。 The present invention relates to a copper foil substrate for producing graphene, and a method for producing graphene using the same.

石墨具有堆積若干平坦排列之碳6員環之層而成之層狀結構，該單原子層~數原子層左右者被稱為石墨烯或石墨烯片。石墨烯片具有獨有之電氣、光學及機械特性，尤其是載子移動速度為高速。因此，期待石墨烯片於例如燃料電池用分隔件、透明電極、顯示元件之導電性薄膜、無汞螢光燈、複合材料、藥物遞送系統(DDS)之載體等產業界中之廣泛應用。 Graphite has a layered structure in which a plurality of flat carbon 6-membered rings are stacked, and the monoatomic layer to the atomic layer is called a graphene or graphene sheet. Graphene sheets have unique electrical, optical and mechanical properties, especially at high speeds. Therefore, graphene sheets are expected to be widely used in industries such as fuel cell separators, transparent electrodes, conductive films for display elements, mercury-free fluorescent lamps, composite materials, and carriers for drug delivery systems (DDS).

作為製造石墨烯片之方法，已知有以黏著帶剝離石墨之方法，但有所得之石墨烯片之層數並不固定，難以獲得大面積之石墨烯片，亦不適於大量生產之問題。 As a method of producing a graphene sheet, a method of peeling off graphite by an adhesive tape is known, but the number of layers of the obtained graphene sheet is not fixed, and it is difficult to obtain a large-area graphene sheet, and it is not suitable for mass production.

因此，開發出藉由在片狀之單晶石墨化金屬觸媒上接觸碳系物質後，進行熱處理而使石墨烯片成長之技術(化學氣相沈積(CVD)法)(專利文獻1)。作為該單晶石墨化金屬觸媒，記載有Ni、Cu、W等之金屬基板。 For this reason, a technique (chemical vapor deposition (CVD) method) in which a graphene sheet is grown by heat treatment after contacting a carbonaceous material on a sheet-like single crystal graphitized metal catalyst (Patent Document 1) has been developed. As the single crystal graphitized metal catalyst, a metal substrate such as Ni, Cu, or W is described.

同樣地，報告有以化學氣相沈積法在Ni或Cu之金屬箔或形成於Si基板上之銅層上將石墨烯進行製膜之技術。再者，石墨烯之製膜係以1000℃左右來進行(非專利文獻1)。 Similarly, a technique of forming graphene on a metal foil of Ni or Cu or a copper layer formed on a Si substrate by chemical vapor deposition has been reported. In addition, the film formation of graphene is performed at about 1000 ° C (Non-Patent Document 1).

專利文獻1：日本特開2009-143799號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-143799

非專利文獻1：SCIENCE Vol.324(2009)P1312-1314 Non-Patent Document 1: SCIENCE. Vol. 324 (2009) P1312-1314

然而，如專利文獻1般製造單晶之金屬基板並不容易且成本極高，又，存在難以獲得大面積之基板，進而難以獲得大面積之石墨烯片之問題。另一方面，於非專利文獻1中記載有將Cu用作基板之情況，但於Cu箔上石墨烯在短時間內不會於面方向上成長，且形成於Si基板上之Cu層藉由退火而以粗大粒之形式形成為基板。於此情形時，石墨烯之大小會被Si基板尺寸限制，製造成本亦較高。 However, it is not easy and costly to manufacture a single-crystal metal substrate as in Patent Document 1, and it is difficult to obtain a large-area substrate, and it is difficult to obtain a large-area graphene sheet. On the other hand, Non-Patent Document 1 describes a case where Cu is used as a substrate, but graphene does not grow in the surface direction on a Cu foil in a short time, and the Cu layer formed on the Si substrate is used. Annealing is formed into a substrate in the form of coarse particles. In this case, the size of the graphene is limited by the size of the Si substrate, and the manufacturing cost is also high.

亦即，本發明之目的在於提供一種能夠以低成本生產大面積之石墨烯的石墨烯製造用銅箔及使用其之石墨烯之製造方法。 That is, an object of the present invention is to provide a copper foil for producing graphene which can produce a large area of graphene at low cost, and a method for producing graphene using the same.

本發明之石墨烯製造用銅箔其壓延平行方向及壓延垂直方向之60度光澤度皆為500%以上，於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後之平均結晶粒徑為200μm以上。 The copper foil for producing graphene of the present invention has a 60 degree gloss of 500 degrees or more in the parallel direction of rolling and the vertical direction of rolling, and is heated at 1000 ° C for 1 hour in an environment containing 20% by volume or more of hydrogen and the remainder being argon. The average crystal grain size is 200 μm or more.

上述平均結晶粒徑較佳為400μm以上，更佳為900μm以上，表面之算術平均粗糙度Ra較佳為0.05μm以下。 The average crystal grain size is preferably 400 μm or more, more preferably 900 μm or more, and the arithmetic mean roughness Ra of the surface is preferably 0.05 μm or less.

又，本發明之石墨烯製造用銅箔其表面之算術平均粗糙度Ra為0.05μm以下。表面之算術平均粗糙度Ra較佳為0.03μm以下。 Moreover, the copper foil for graphene production of the present invention has an arithmetic mean roughness Ra of 0.05 μm or less on the surface. The arithmetic mean roughness Ra of the surface is preferably 0.03 μm or less.

於本發明之石墨烯製造用銅箔中，較佳為含有JIS-H3100或JIS-H3250規定之精銅、JIS-H3100或JIS- H3510規定之無氧銅、或者相對於上述精銅或上述無氧銅為0.050質量%以下之選自Sn及Ag之群中之1種以上的元素。 In the copper foil for graphene production of the present invention, it is preferable to contain refined copper, JIS-H3100 or JIS- as defined by JIS-H3100 or JIS-H3250. An oxygen-free copper or a one or more elements selected from the group consisting of Sn and Ag in an amount of 0.050% by mass or less based on the above-mentioned refined copper or the above-mentioned oxygen-free copper.

本發明之石墨烯之製造方法係使用上述石墨烯製造用銅箔，且具有下述步驟：石墨烯形成步驟：於特定之室內配置經加熱之上述石墨烯製造用銅箔，且供給含碳氣體，而於上述石墨烯製造用銅箔之表面形成石墨烯；及石墨烯轉印步驟：一面於上述石墨烯之表面積層轉印片，將上述石墨烯轉印至上述轉印片上，一面蝕刻去除上述石墨烯製造用銅箔。 The method for producing graphene according to the present invention is the use of the copper foil for graphene production described above, and the step of forming a graphene by disposing a heated copper foil for producing graphene in a specific chamber and supplying a carbon-containing gas And forming a graphene on the surface of the copper foil for graphene production; and a graphene transfer step: transferring the graphene onto the transfer sheet while transferring the graphene onto the transfer sheet The above copper foil for graphene production.

根據本發明，可獲得能夠以低成本生產大面積之石墨烯之銅箔。 According to the present invention, a copper foil capable of producing a large area of graphene at a low cost can be obtained.

以下，對本發明之實施形態之石墨烯製造用銅箔進行說明。再者，於本發明中所謂%，只要未特別限定，則表示質量%。 Hereinafter, a copper foil for graphene production according to an embodiment of the present invention will be described. In addition, in this invention, the % is a mass % unless it is not specifically limited.

<組成> <composition>

可將JIS-H3250或JIS-H3100規定之精銅(TPC)、或JIS-H3510或JIS-H3100規定之無氧銅(OFC)用作為石墨烯製造用銅箔。 Copper (TPC) specified by JIS-H3250 or JIS-H3100 or oxygen-free copper (OFC) prescribed by JIS-H3510 or JIS-H3100 can be used as the copper foil for graphene production.

又，亦可使用含有相對於該等精銅或無氧銅為0.050質量%以下之選自Sn及Ag之群中之1種以上的元素之組成。若含有上述元素，則銅箔之強度提高且具有適度之伸長率，並且可增大結晶粒徑。若上述元素之含有比例超過0.050質量%，則雖強度進一步提高，但有伸長率降低，加工性惡 化，並且結晶粒徑之成長受到抑制之情形。更佳為上述元素之含有比例為0.040質量%以下。 Further, a composition containing one or more elements selected from the group consisting of Sn and Ag in an amount of 0.050% by mass or less based on the above-mentioned fine copper or oxygen-free copper may be used. When the above elements are contained, the strength of the copper foil is improved and the elongation is moderate, and the crystal grain size can be increased. When the content ratio of the above elements exceeds 0.050% by mass, the strength is further improved, but the elongation is lowered, and the workability is bad. And the growth of crystal grain size is suppressed. More preferably, the content ratio of the above elements is 0.040% by mass or less.

再者，上述元素之含有比例之下限並無特別限制，例如可將0.0001質量%設為下限。又，例如可將0.005質量%設為下限。若上述元素之含有比例未達0.0001質量%，則由於含有比例小，故而存在難以控制其含有比例之情形。 In addition, the lower limit of the content ratio of the above elements is not particularly limited, and for example, 0.0001% by mass can be set as the lower limit. Further, for example, 0.005 mass% can be set as the lower limit. When the content ratio of the above elements is less than 0.0001% by mass, the content ratio is small, so that it is difficult to control the content ratio.

又，作為石墨烯製造用銅箔，亦可以相對於精銅或無氧銅不會對結晶粒徑造成重大影響之範圍的含有比例(例如：0.050質量%以下)來添加選自Sn、Ag、In、Ti、Zn、Zr、Fe、P、Ni、Si、Te、Cr、Nb、B及V等之群中之元素的一種以上的元素。 In addition, the copper foil for graphene production may be added to a content ratio (for example, 0.050 mass% or less) in a range in which the refined copper or the oxygen-free copper does not significantly affect the crystal grain size, and is selected from the group consisting of Sn, Ag, and One or more elements of the elements in the group of In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, B, and V.

<厚度> <thickness>

石墨烯製造用銅箔之厚度並無特別限制，一般為5~150μm。進而，為一面確保操作性，一面容易地進行後述之蝕刻去除，較佳為將銅箔之厚度設為12~50μm。若石墨烯製造用銅箔之厚度未達12μm，則容易斷裂而操作性變差，若厚度超過50μm則存在難以進行蝕刻去除之情形。 The thickness of the copper foil for producing graphene is not particularly limited and is generally 5 to 150 μm. Further, it is easy to perform etching removal described later while ensuring operability, and it is preferable to set the thickness of the copper foil to 12 to 50 μm. When the thickness of the copper foil for producing graphene is less than 12 μm, the susceptibility is deteriorated and the workability is deteriorated. If the thickness exceeds 50 μm, etching may be difficult to remove.

<60度光澤度> <60 degree gloss>

石墨烯製造用銅箔之壓延平行方向及壓延垂直方向之60度光澤度(JIS Z 8741)均為500%以上。 The copper foil for graphene production has a rolling parallel direction and a 60 degree gloss in the vertical direction of rolling (JIS Z 8741) of 500% or more.

如後所述，可知：於使用本發明之石墨烯製造用銅箔製造石墨烯後，必須自銅箔向轉印片轉印石墨烯，若銅箔表面粗糙則難以轉印，而存在石墨烯破損之情形。因此，將60度光澤度規定為表示銅箔之表面凹凸之指標。 As will be described later, after the graphene is produced by using the copper foil for graphene production of the present invention, it is necessary to transfer graphene from the copper foil to the transfer sheet, and if the surface of the copper foil is rough, it is difficult to transfer, and graphene is present. The situation of damage. Therefore, the 60-degree gloss is defined as an index indicating the surface unevenness of the copper foil.

若壓延平行方向及壓延垂直方向之60度光澤度任一者未達500%，則於轉印時石墨烯會破損。壓延平行方向及壓延垂直方向之60度光澤度的上限並無特別限制，於實用上，上限為800%左右。 If the 60-degree gloss of the rolling parallel direction and the rolling vertical direction is less than 500%, the graphene may be damaged at the time of transfer. The upper limit of the 60-degree gloss in the rolling parallel direction and the rolling vertical direction is not particularly limited, and practically, the upper limit is about 800%.

又，如上所述，為了使石墨烯易於轉印至轉印片，JIS B0601所規定之石墨烯製造用銅箔表面之算數平均粗糙度Ra較佳為0.05μm以下，更佳為Ra為0.03μm以下。Ra之下限並不需要特別規定，但認為可進行製造之銅箔表面的Ra之下限值為0.005μm或0.01μm左右。 In addition, as described above, in order to facilitate the transfer of graphene to the transfer sheet, the arithmetic mean roughness Ra of the surface of the copper foil for graphene production specified in JIS B0601 is preferably 0.05 μm or less, more preferably Ra is 0.03 μm. the following. The lower limit of Ra does not need to be specified, but it is considered that the lower limit of Ra of the surface of the copper foil which can be produced is about 0.005 μm or about 0.01 μm.

<平均結晶粒徑> <Average crystal grain size>

石墨烯製造用銅箔於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後之平均結晶粒徑為200μm以上。 The copper foil for graphene production has an average crystal grain size of 200 μm or more after heating at 1000 ° C for 1 hour in an atmosphere containing 20% by volume or more of hydrogen and the remainder being argon.

若石墨烯製造用銅箔之平均結晶粒徑小於200μm，則成為使石墨烯於石墨烯製造用銅箔之表面成長時之障礙，石墨烯變得難以於面方向上成長。可認為其係因為晶界成為石墨烯成長之障礙。石墨烯製造用銅箔之平均結晶粒徑特佳為900μm以上。 When the average crystal grain size of the copper foil for producing graphene is less than 200 μm, it becomes a hindrance when graphene is grown on the surface of the copper foil for graphene production, and it becomes difficult for graphene to grow in the surface direction. It can be considered that it is because the grain boundary becomes a barrier to the growth of graphene. The average crystal grain size of the copper foil for producing graphene is particularly preferably 900 μm or more.

再者，於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃進行1小時加熱係模仿當製造石墨烯時，將石墨烯製造用銅箔加熱至含碳氣體之分解溫度以上之條件者。 Further, heating at 1000 ° C for 1 hour in an environment containing 20% by volume or more of hydrogen and the remainder being argon is simulated. When graphene is produced, the copper foil for graphene production is heated to a temperature higher than the decomposition temperature of the carbon-containing gas. Conditioner.

又，平均結晶粒徑係藉由JIS H0501之切斷法對石墨烯製造用銅箔進行測定。 Further, the average crystal grain size was measured by a copper foil for graphene production by a cutting method of JIS H0501.

藉由使用如以上般規定之石墨烯製造用銅箔，能夠以低成本且高產率生產大面積之石墨烯。 By using the copper foil for graphene production as defined above, it is possible to produce a large area of graphene at low cost and high yield.

<石墨烯製造用銅箔之製造> <Manufacture of copper foil for graphene production>

本發明之實施形態之石墨烯製造用銅箔例如能夠以下述方式製造。首先，製造特定組成之銅鑄錠，進行熱壓延後，重複進行退火與冷壓延，而獲得壓延板。對該壓延板進行退火使其再結晶，將軋縮率設為80~99.9%(較佳為85~99.9%，更佳為90~99.9%)進行最終冷壓延至特定厚度，而獲得銅箔。 The copper foil for graphene production of the embodiment of the present invention can be produced, for example, in the following manner. First, a copper ingot of a specific composition is produced, and after hot rolling, annealing and cold rolling are repeated to obtain a rolled sheet. The rolled sheet is annealed to be recrystallized, and the rolling reduction ratio is set to 80 to 99.9% (preferably 85 to 99.9%, more preferably 90 to 99.9%) for final cold rolling to a specific thickness to obtain a copper foil. .

此處，重要的是將石墨烯製造用銅箔之60度光澤度控制在500%以上。作為此方法，將最終冷壓延之最終道次與最終冷壓延之最終道次之前一道次兩者之油膜當量均設為18000以下。 Here, it is important to control the 60-degree gloss of the copper foil for graphene production to 500% or more. As this method, the oil film equivalent of both the final pass of the final cold rolling and the final pass of the final cold rolling is set to 18,000 or less.

壓延銅箔通常於油潤滑之狀態下以高速進行加工，潤滑油膜愈薄則剪切帶變形愈容易變得顯著。此係金屬的一般共通現象。再者，剪切帶的存在對於在退火之情形時的晶粒成長而言無法說是較佳。而且，可以銅箔表面之光澤度來表示剪切帶的量或長短深度。具體而言，作為壓延時之現象，若被導入至輥與材料之間之油膜較厚，則於壓延加工表面產生油坑(凹凸)，若油膜較薄，則於材料表面處與壓延輥接觸之面積增加而限制自由變形，油坑不會發展，壓延輥之平滑之表面輪廓被轉印，形成平滑之表面。因此，作為使油膜變薄之指標，可將油膜當量設為18000以下。若油膜當量超過18000，則銅箔表面之60度光澤度 變成未達500%。 The rolled copper foil is usually processed at a high speed in an oil-lubricated state, and the thinner the lubricating oil film, the more easily the shear band is deformed. This is a general commonality of metals. Furthermore, the presence of the shear band is not preferable for grain growth in the case of annealing. Moreover, the amount of shear band or the length of the shear band can be expressed by the gloss of the surface of the copper foil. Specifically, as a phenomenon of pressure delay, if the oil film introduced between the roller and the material is thick, oil pits (concavities and convexities) are generated on the surface of the calendering process, and if the oil film is thin, contact with the calender roll at the surface of the material The area is increased to limit free deformation, the oil sump does not develop, and the smooth surface profile of the calender roll is transferred to form a smooth surface. Therefore, as an index for thinning the oil film, the oil film equivalent can be made 18,000 or less. If the oil film equivalent exceeds 18,000, the 60 degree gloss of the copper foil surface It has become less than 500%.

油膜當量係以下述式表示。 The oil film equivalent is represented by the following formula.

(油膜當量)={(壓延油黏度、40℃之動黏度；cSt)×(壓延速度；m/分鐘)}/{(材料之降伏應力；kg/mm²)×(軋入角；rad)} (oil film equivalent) = {(calendering oil viscosity, dynamic viscosity at 40 ° C; cSt) × (calendering speed; m / min)} / {(material's lodging stress; kg / mm ² ) × (rolling angle; rad) }

為了將油膜當量設為18000以下，較佳為降低壓延油黏度(40℃之動黏度)，壓延速度亦低，且軋入角(對應於軋縮量)較大。例如可列舉：藉由調整成輥直徑為250mm以下且表面粗糙度Ra_roll為0.1μm以下(較佳為0.01~0.04μm，更佳為0.01~0.02μm)之壓延輥，使用黏度為3~8cSt(較佳為3~5cSt，更佳為3~4cSt)之壓延油，壓延速度為100~500m/分鐘(較佳為200~450m/分鐘，更佳為250~400m/分鐘)，每道次之軋縮率為10~60%。又，軋入角例如為0.001~0.04rad，較佳為0.002~0.03rad，更佳為0.003~0.03rad。 In order to set the oil film equivalent to 18,000 or less, it is preferred to lower the rolling oil viscosity (dynamic viscosity at 40 ° C), the rolling speed is also low, and the rolling angle (corresponding to the rolling amount) is large. For example, a calender roll having a roll diameter of 250 mm or less and a surface roughness Ra _roll of 0.1 μm or less (preferably 0.01 to 0.04 μm, more preferably 0.01 to 0.02 μm) is used, and the viscosity is 3 to 8 cSt. (preferably 3 to 5 cSt, more preferably 3 to 4 cSt) calendering oil, calendering speed of 100 to 500 m / min (preferably 200 to 450 m / min, more preferably 250 to 400 m / min), each pass The rolling reduction rate is 10~60%. Further, the rolling angle is, for example, 0.001 to 0.04 rad, preferably 0.002 to 0.03 rad, and more preferably 0.003 to 0.03 rad.

若壓延輥之表面粗糙度Ra_roll超過0.1μm，則輥表面之凹凸被轉印，有損材料表面之平滑性。藉由於上述條件下進行壓延，可增大無油坑之表面平坦部之面積。若壓延油之黏度超過8cSt則油膜當量變大，無法獲得表面光澤，另一方面，若未達3cSt則壓延阻力變大，無法提高軋縮率。若壓延速度超過500m/分鐘，則由於導入油量增加，故而光澤度降低，另一方面，若未達100m/分鐘則無法取得充分之軋縮量，且就生產性之觀點而言不合適。 When the surface roughness Ra _{roll of the} calender _roll exceeds 0.1 μm, the unevenness of the surface of the roll is transferred, which impairs the smoothness of the surface of the material. By rolling under the above conditions, the area of the flat portion of the surface of the oil-free pit can be increased. When the viscosity of the rolling oil exceeds 8 cSt, the oil film equivalent becomes large, and surface gloss cannot be obtained. On the other hand, if it is less than 3 cSt, the rolling resistance becomes large, and the rolling reduction ratio cannot be improved. When the rolling speed exceeds 500 m/min, the amount of introduced oil increases, so that the gloss is lowered. On the other hand, if it is less than 100 m/min, a sufficient amount of shrinkage cannot be obtained, and it is not suitable from the viewpoint of productivity.

若軋縮率超過99.9%，則由於加工硬化加劇，故而變形 能力消失，無法確保最終道次之軋縮率，另一方面，若未達80%則壓延織構未發展，無法獲得表面平滑性。若軋入角超過0.04rad，則輥圓周速度與材料速度之差變大，有損材料表面之平滑性。另一方面，若未達0.002rad，則添加至壓延輥與被壓延材料間發揮潤滑作用之油之量較多，光澤降低。 If the rolling reduction exceeds 99.9%, the work hardening is intensified, so it is deformed. The ability to disappear does not ensure the final pass rate. On the other hand, if it is less than 80%, the calender texture is not developed and surface smoothness cannot be obtained. If the rolling angle exceeds 0.04 rad, the difference between the circumferential speed of the roll and the material speed becomes large, which impairs the smoothness of the surface of the material. On the other hand, if it is less than 0.002 rad, the amount of oil added to the rolling action between the calender roll and the material to be rolled is large, and the gloss is lowered.

每道次之軋縮率例如為20~40%，較佳為20~35%，更佳為25~35%。若軋縮率超過35%則剪切帶發展並產生油坑，光澤度降低。另一方面，若未達20%則由於道次數增加，故而生產性惡化。 The rolling reduction ratio per pass is, for example, 20 to 40%, preferably 20 to 35%, more preferably 25 to 35%. If the rolling reduction exceeds 35%, the shear band develops and an oil sump is generated, and the gloss is lowered. On the other hand, if it is less than 20%, the number of passes increases, and productivity is deteriorated.

又，作為將石墨烯製造用銅箔之60度光澤度控制在500%以上之其他方法，有提高最終冷壓延中之材料溫度之方法。若提高材料溫度，則會引起差排(dislocation)之恢復，而變得難以引起剪切帶變形。作為材料溫度，若會損害油之潤滑性，則銅箔再結晶之溫度變得毫無意義，故材料溫度為120℃以下、較佳為100℃以下即可。又，若材料溫度為50℃以下則幾乎無抑制剪切帶變形之效果。 Further, as another method of controlling the 60-degree gloss of the copper foil for producing a graphene to 500% or more, there is a method of increasing the temperature of the material in the final cold rolling. If the temperature of the material is increased, the recovery of the dislocation is caused, and it becomes difficult to cause the deformation of the shear band. When the lubricity of the oil is impaired as the material temperature, the temperature at which the copper foil is recrystallized becomes meaningless, so the material temperature may be 120 ° C or lower, preferably 100 ° C or lower. Further, when the material temperature is 50 ° C or less, there is almost no effect of suppressing deformation of the shear band.

藉由上述方法，可將石墨烯製造用銅箔之60度光澤度控制在500%以上。又，明白了若使銅箔之60度光澤度成為500%以上，則退火後之結晶粒徑成為200μm以上。其係被認為因為藉由控制上述油膜當量或最終冷壓延中之材料溫度，並使剪切帶變形難以產生，從而促進了退火後之結晶成長。 According to the above method, the 60-degree gloss of the copper foil for graphene production can be controlled to 500% or more. Further, it is understood that when the 60-degree gloss of the copper foil is 500% or more, the crystal grain size after annealing is 200 μm or more. It is considered that the crystal growth after annealing is promoted by controlling the temperature of the above-mentioned oil film equivalent or the temperature of the material in the final cold rolling and making the deformation of the shear band difficult.

再者，將石墨烯製造用銅箔之60度光澤度控制在500% 以上之方法並不限於上述方法。 Furthermore, the 60 degree gloss of the copper foil for graphene production is controlled at 500%. The above method is not limited to the above method.

<石墨烯之製造方法> <Method for producing graphene>

繼而，參照圖1，對本發明之實施形態之石墨烯之製造方法進行說明。 Next, a method for producing graphene according to an embodiment of the present invention will be described with reference to Fig. 1 .

首先，於室(真空室等)100內配置上述本發明之石墨烯製造用銅箔10，以加熱器104加熱石墨烯製造用銅箔10，並且對室100內進行減壓或真空處理。繼而，自氣體導入口102將含碳氣體G供給至室100內(圖1(a))。作為含碳氣體G，可列舉二氧化碳、一氧化碳、甲烷、乙烷、丙烷、乙烯、乙炔、醇等，但不限定於該等，亦可為該等中之1種或2種以上之混合氣體。又，石墨烯製造用銅箔10之加熱溫度只要設為含碳氣體G之分解溫度以上即可，例如可設為1000℃以上。又，亦可於室100內將含碳氣體G加熱至分解溫度以上，使分解氣體與石墨烯製造用銅箔10接觸。 First, the copper foil 10 for graphene production of the present invention is placed in a chamber (vacuum chamber or the like) 100, and the copper foil 10 for graphene production is heated by a heater 104, and the inside of the chamber 100 is subjected to pressure reduction or vacuum treatment. Then, the carbon-containing gas G is supplied into the chamber 100 from the gas introduction port 102 (FIG. 1(a)). Examples of the carbon-containing gas G include carbon dioxide, carbon monoxide, methane, ethane, propane, ethylene, acetylene, alcohol, and the like, but are not limited thereto, and may be one or a mixture of two or more of these. In addition, the heating temperature of the copper foil 10 for producing graphene may be equal to or higher than the decomposition temperature of the carbon-containing gas G, and may be, for example, 1000 ° C or higher. Further, the carbon-containing gas G may be heated to a temperature higher than the decomposition temperature in the chamber 100 to bring the decomposition gas into contact with the copper foil 10 for graphene production.

藉此，分解氣體(碳氣體)於石墨烯製造用銅箔10之表面形成石墨烯20(圖1(b))。 Thereby, the decomposition gas (carbon gas) forms the graphene 20 on the surface of the copper foil 10 for graphene production (FIG. 1(b)).

繼而，將石墨烯製造用銅箔10冷卻至常溫，於石墨烯20之表面積層轉印片30，將石墨烯20轉印至轉印片30上。其次，經由沉浸輥(sink roll)120將該積層體連續浸漬於蝕刻槽110，蝕刻去除石墨烯製造用銅箔10(圖1(c))。如此，可製造積層於特定之轉印片30上之石墨烯20。 Then, the copper foil 10 for graphene production is cooled to a normal temperature, and the sheet 30 is transferred onto the surface layer of the graphene 20 to transfer the graphene 20 onto the transfer sheet 30. Next, the laminated body is continuously immersed in the etching bath 110 via a sink roll 120, and the copper foil 10 for graphene production is removed by etching (FIG. 1 (c)). Thus, the graphene 20 laminated on the specific transfer sheet 30 can be produced.

進而，提拉已去除石墨烯製造用銅箔10之積層體，一面於石墨烯20之表面積層基板40，將石墨烯20轉印至基 板40上，一面剝離轉印片30，便可製造積層於基板40上之石墨烯20。 Further, the laminate of the copper foil 10 for graphene production is removed by pulling, and the graphene 20 is transferred to the substrate on the surface layer substrate 40 of the graphene 20 On the plate 40, the transfer sheet 30 is peeled off to produce the graphene 20 laminated on the substrate 40.

作為轉印片30，可使用各種樹脂片(聚乙烯、聚胺酯等聚合物片)。作為蝕刻去除石墨烯製造用銅箔10之蝕刻液，例如可使用硫酸溶液、過硫酸鈉溶液、過氧化氫、及於過硫酸鈉溶液或過氧化氫中添加有硫酸之溶液。又，作為基板40，例如可使用Si、SiC、Ni或Ni合金。 As the transfer sheet 30, various resin sheets (polymer sheets such as polyethylene or polyurethane) can be used. As the etching liquid for etching and removing the copper foil 10 for graphene production, for example, a sulfuric acid solution, a sodium persulfate solution, hydrogen peroxide, and a solution in which sulfuric acid is added to a sodium persulfate solution or hydrogen peroxide can be used. Further, as the substrate 40, for example, Si, SiC, Ni, or a Ni alloy can be used.

實施例 Example <試樣之製作> <Production of sample>

製造表1所示之組成之銅鑄錠，於以800~900℃進行熱壓延後，在300~700℃之連續退火線上將退火與冷壓延重複一次，而獲得1~2mm厚之壓延板。於600~800℃之連續退火線上對該壓延板進行退火使其再結晶，將軋縮率設為95~99.7%進行最終冷壓延至7~50μm之厚度，而獲得實施例1~17、比較例1~9之銅箔。 A copper ingot having the composition shown in Table 1 is produced, and after hot rolling at 800 to 900 ° C, annealing and cold rolling are repeated once on a continuous annealing line of 300 to 700 ° C to obtain a rolled sheet of 1 to 2 mm thick. . The rolled sheet was annealed on a continuous annealing line of 600 to 800 ° C to recrystallize, and the rolling reduction ratio was set to 95 to 99.7% for final cold rolling to a thickness of 7 to 50 μm, and Examples 1 to 17 were obtained. Copper foil of Examples 1 to 9.

此處，將最終冷壓延之最終道次與最終冷壓延之最終道次之前一道次兩者之油膜當量均調整為表1所示之值。 Here, the oil film equivalents of both the final pass of the final cold rolling and the final pass of the final cold rolling are adjusted to the values shown in Table 1.

油膜當量係以下述式表示。 The oil film equivalent is represented by the following formula.

(油膜當量)={(壓延油黏度、40℃之動黏度；cSt)×(壓延速度；m/分鐘)}/{(材料之降伏應力；kg/mm²)×(軋入角；rad)} (oil film equivalent) = {(calendering oil viscosity, dynamic viscosity at 40 ° C; cSt) × (calendering speed; m / min)} / {(material's lodging stress; kg / mm ² ) × (rolling angle; rad) }

<60度光澤度之測定> <Measurement of 60 degree gloss>

測定實施例1~17、比較例1~9之銅箔於最終冷壓延後、及於其後在含有氫20體積%以上且剩餘部分為氬之環 境中以1000℃加熱1小時後之表面的60度光澤度。 The copper foils of Examples 1 to 17 and Comparative Examples 1 to 9 were measured after the final cold rolling, and thereafter, containing 20% by volume or more of hydrogen and the remainder being a ring of argon. The 60 degree gloss of the surface after heating at 1000 ° C for 1 hour.

60度光澤度係使用根據JIS-Z8741之光澤度計(日本電色工業製造，商品名「PG-1M」)來進行測定。 The 60-degree gloss was measured using a gloss meter (manufactured by Nippon Denshoku Industries, trade name "PG-1M") according to JIS-Z8741.

<表面粗糙度(Ra、Rz、Sm)之測定> <Measurement of Surface Roughness (Ra, Rz, Sm)>

測定實施例1~17及比較例1~9之銅箔之最終冷壓延後、及於其後在含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後的表面粗糙度。 The surface roughness after the final cold rolling of the copper foils of Examples 1 to 17 and Comparative Examples 1 to 9 and after heating at 1000 ° C for 1 hour in an environment containing 20% by volume or more of hydrogen and the remainder being argon was measured. degree.

使用接觸粗糙度計(小坂研究所製造，商品名「SE-3400」)，測定根據JIS-B0601之算術平均粗糙度(Ra；μm)，油坑深度Rz係根據JIS B0601-1994而測定十點平均粗糙度。求出以測定基準長度0.8mm、評價長度4mm、截斷值0.8mm、輸送速度0.1mm/秒之條件且與壓延方向平行地改變10次測定位置之於各方向進行10次測定之值。又，凹凸的平均間隔(Sm；mm)係：求出以測定基準長度0.8mm、評價長度4mm、截斷值0.8mm、輸送速度0.1mm/秒之條件且與壓延方向平行地改變10次測定位置之10次測定之值。再者，Sm係於以輪廓曲線方式表示表面性狀之JIS B0601-2001(依據ISO4287-1997)中，被規定為凹凸之「凹凸之平均間隔」，且係指基準長度內之各凹凸之輪廓長度的平均。 The arithmetic mean roughness (Ra; μm) according to JIS-B0601 was measured using a contact roughness meter (manufactured by Otaru Research Institute, trade name "SE-3400"), and the sump depth Rz was measured according to JIS B0601-1994. Average roughness. A value obtained by measuring 10 times in each direction by measuring the reference length of 0.8 mm, the evaluation length of 4 mm, the cutoff value of 0.8 mm, the transport speed of 0.1 mm/sec, and changing the measurement position 10 times in parallel with the rolling direction was obtained. In addition, the average interval (Sm; mm) of the unevenness was obtained by measuring the reference length of 0.8 mm, the evaluation length of 4 mm, the cutoff value of 0.8 mm, and the conveying speed of 0.1 mm/sec, and changing the measurement position 10 times in parallel with the rolling direction. The value of 10 measurements. Further, Sm is defined as JIS B0601-2001 (according to ISO4287-1997) which is a surface profile, and is defined as the "average interval of the unevenness" of the unevenness, and refers to the outline length of each unevenness in the reference length. Average.

<平均結晶粒徑之測定> <Measurement of average crystal grain size>

藉由JIS H0501之切斷法來測定實施例1~17及比較例1~9之銅箔之表面的平均結晶粒徑。 The average crystal grain size of the surfaces of the copper foils of Examples 1 to 17 and Comparative Examples 1 to 9 was measured by a cutting method of JIS H0501.

<石墨烯之製造> <Manufacture of graphene>

於真空室設置各實施例之銅箔(縱橫100×100mm)，並加熱至1000℃。於真空下(壓力：0.2Torr)供給甲烷氣體至此真空室(供給氣體流量：10~100cc/min)，並以30分鐘將銅箔加熱至1000℃後，保持1小時，使石墨烯於銅箔表面成長。 The copper foil (100 x 100 mm) of each example was placed in a vacuum chamber and heated to 1000 °C. Methane gas was supplied to the vacuum chamber under vacuum (pressure: 0.2 Torr) (supply gas flow rate: 10 to 100 cc/min), and the copper foil was heated to 1000 ° C for 30 minutes, and then kept for 1 hour to make graphene in copper foil. Surface growth.

以上述條件對各實施例進行10次石墨烯之製造，以原子間力顯微鏡(AFM)來觀察銅箔表面之石墨烯的有無而進行評價。將藉由AFM而於整個表面觀察到鱗片狀之凹凸者視為製得石墨烯者，並藉由十次製造中製得石墨烯之次數以下述基準來評價產率。若評價為◎、○、或△表示於實用上沒有問題。 The graphene was produced 10 times in each of the examples under the above-described conditions, and the presence or absence of graphene on the surface of the copper foil was evaluated by an atomic force microscope (AFM). A scale-like unevenness was observed on the entire surface by AFM as a graphene, and the yield was evaluated on the basis of the following times by the number of times the graphene was produced in ten productions. If the evaluation is ◎, ○, or Δ, there is no problem in practical use.

◎：十次製造之中，製得石墨烯5次以上。 ◎: Among ten productions, graphene was produced five times or more.

○：十次製造之中，製得石墨烯4次。 ○: Among ten productions, graphene was produced four times.

△：十次製造之中，製得石墨烯3次。 △: Among ten productions, graphene was produced three times.

×：十次製造之中，製得石墨烯之次數為2次以下。 ×: The number of times the graphene was produced was ten or less in ten productions.

將所得之結果示於表1。再者，於表1中，G60_RD、G60_TD分別表示壓延平行方向及壓延垂直方向之60度光澤度。又，GS表示平均結晶粒徑。 The results obtained are shown in Table 1. Further, in Table 1, G60 _RD and G60 _TD represent the 60-degree gloss of the rolling parallel direction and the rolling vertical direction, respectively. Further, GS represents an average crystal grain size.

又，表中之實施例1~7、實施例14、實施例15、實施例17、比較例1~3、比較例7、9之「TPC」，表示JIS-H3100所規定之精銅。實施例9~12、實施例16、比較例4~6、比較例8之「OFC」表示JIS-H3100所規定之無氧銅。實施例13之TPC表示JIS-H3250所規定之精銅。實施例8之OFC表示JIS-H3510所規定之無氧銅。 Further, "TPC" of Examples 1 to 7, Example 14, Example 15, Example 17, Comparative Example 1-3, and Comparative Examples 7 and 9 in the table indicates fine copper prescribed by JIS-H3100. "OFC" of Examples 9 to 12, Example 16, Comparative Examples 4 to 6, and Comparative Example 8 indicates oxygen-free copper prescribed by JIS-H3100. The TPC of Example 13 represents the refined copper specified in JIS-H3250. The OFC of Example 8 represents oxygen-free copper as defined in JIS-H3510.

因此，比較例8之「OFC+Sn 1200ppm」表示於JIS-H3100規定之無氧銅添加有1200wtppm之Sn。 Therefore, "OFC+Sn 1200 ppm" of Comparative Example 8 indicates that 1200 wtppm of Sn was added to the oxygen-free copper specified in JIS-H3100.

由表1可知，在銅箔表面之60度光澤度為500%以上且於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後之平均結晶粒徑為200μm以上之實施例1~17之情形時，石墨烯之製造產率優異。 It can be seen from Table 1 that the average crystal grain size after heating at 1000 ° C for 1 hour in an environment containing 60% of gloss on the surface of the copper foil of 500% or more and containing 20% by volume or more of hydrogen and the remainder being argon is 200 μm or more. In the case of Examples 1 to 17, the production yield of graphene was excellent.

特別是於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後之平均結晶粒徑為900μm以上之實施例1~6、8、9、11~13、15~17之情形時，石墨烯之製造產率最優異。又，於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後之平均結晶粒徑為400~900μm之實施例7、10之情形時，與平均結晶粒徑未達400μm之實施例14相比，石墨烯之製造產率優異。 In particular, Examples 1 to 6, 8, 9, 11 to 13, and 15 to 17 have an average crystal grain size of 900 μm or more after heating at 1000 ° C for 1 hour in an environment containing 20% by volume or more of hydrogen and the remainder being argon. In the case of the graphene, the production yield of graphene is the most excellent. Further, in the case of Examples 7 and 10 in which the average crystal grain size after heating at 1000 ° C for 1 hour in an environment containing 20% by volume or more of hydrogen and the remainder being argon was 400 to 900 μm, the average crystal grain size was not reached. The production yield of graphene was superior to that of Example 14 of 400 μm.

另一方面，最終冷壓延之最終道次與最終冷壓延之最終道次的前一道次兩者之油膜當量皆超過18000，於銅箔本身之表面的60度光澤度成為未達500%之比較例1~9之情形，石墨烯之製造產率變差。又，比較例1~9之情形，於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後之平均結晶粒徑成為未達200μm，認為此係因為最終冷壓延的油膜當量過多，生成剪切帶從而晶粒之成長被抑制。 On the other hand, the oil film equivalent of both the final pass of the final cold rolling and the last pass of the final cold rolling is more than 18,000, and the 60-degree gloss on the surface of the copper foil itself is less than 500%. In the case of Examples 1 to 9, the manufacturing yield of graphene was deteriorated. Further, in the case of Comparative Examples 1 to 9, the average crystal grain size after heating at 1000 ° C for 1 hour in an environment containing 20% by volume or more of hydrogen and the remainder being argon was less than 200 μm, which was considered to be due to the final cold rolling. If the oil film equivalent is too much, a shear band is formed and the growth of crystal grains is suppressed.

10‧‧‧石墨烯製造用銅箔 10‧‧‧ Copper foil for graphene production

20‧‧‧石墨烯 20‧‧‧ Graphene

30‧‧‧轉印片 30‧‧‧Transfer film

40‧‧‧基板 40‧‧‧Substrate

100‧‧‧室 Room 100‧‧

102‧‧‧氣體導入口 102‧‧‧ gas inlet

104‧‧‧加熱器 104‧‧‧heater

110‧‧‧蝕刻槽 110‧‧‧etching trough

120‧‧‧沉浸輥 120‧‧‧ immersion roller

G‧‧‧含碳氣體 G‧‧‧Carbon-containing gas

圖1係表示本發明之實施形態之石墨烯之製造方法的步驟圖。 Fig. 1 is a flow chart showing a method of producing graphene according to an embodiment of the present invention.

10‧‧‧石墨烯製造用銅箔 10‧‧‧ Copper foil for graphene production

20‧‧‧石墨烯 20‧‧‧ Graphene

30‧‧‧轉印片 30‧‧‧Transfer film

40‧‧‧基板 40‧‧‧Substrate

100‧‧‧室 Room 100‧‧

102‧‧‧氣體導入口 102‧‧‧ gas inlet

104‧‧‧加熱器 104‧‧‧heater

110‧‧‧蝕刻槽 110‧‧‧etching trough

120‧‧‧沉浸輥 120‧‧‧ immersion roller

G‧‧‧含碳氣體 G‧‧‧Carbon-containing gas

Claims (9)

一種石墨烯製造用銅箔，其壓延平行方向及壓延垂直方向之60度光澤度皆為500%以上，於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後之平均結晶粒徑為200μm以上。 A copper foil for producing graphene, which has a gloss of 60 degrees or more in a direction parallel to the rolling direction and a vertical direction of rolling, and is heated at 1000 ° C for 1 hour in an environment containing 20% by volume or more of hydrogen and the remainder being argon. The average crystal grain size is 200 μm or more. 如申請專利範圍第1項之石墨烯製造用銅箔，其中，該平均結晶粒徑為400μm以上。 The copper foil for graphene production according to the first aspect of the invention, wherein the average crystal grain size is 400 μm or more. 如申請專利範圍第1項之石墨烯製造用銅箔，其中，該平均結晶粒徑為900μm以上。 The copper foil for graphene production according to the first aspect of the invention, wherein the average crystal grain size is 900 μm or more. 如申請專利範圍第1項之石墨烯製造用銅箔，其表面之算術平均粗糙度Ra為0.05μm以下。 The copper foil for graphene production according to the first aspect of the invention is characterized in that the arithmetic mean roughness Ra of the surface is 0.05 μm or less. 如申請專利範圍第2項之石墨烯製造用銅箔，其表面之算術平均粗糙度Ra為0.05μm以下。 The copper foil for graphene production according to the second aspect of the patent application has an arithmetic mean roughness Ra of 0.05 μm or less on the surface. 一種石墨烯製造用銅箔，其於含有氫20體積%以上且剩餘部分為氬之環境中以1000℃加熱1小時後之平均結晶粒徑為200μm以上，表面之算術平均粗糙度Ra為0.05μm以下。 A copper foil for producing graphene, which has an average crystal grain size of 200 μm or more after heating at 1000 ° C for 1 hour in an atmosphere containing 20% by volume or more of hydrogen and the remainder being argon, and an arithmetic mean roughness Ra of the surface is 0.05 μm. the following. 如申請專利範圍第6項之石墨烯製造用銅箔，其表面之算術平均粗糙度Ra為0.03μm以下。 The copper foil for graphene production according to the sixth aspect of the invention is characterized in that the arithmetic mean roughness Ra of the surface is 0.03 μm or less. 如申請專利範圍第1至7項中任一項之石墨烯製造用銅箔，其含有JIS-H3100或JIS-H3250規定之精銅、JIS-H3100或JIS-H3510規定之無氧銅、或者相對於該精銅或該無氧銅為0.050質量%以下之選自Sn及Ag之群中之1種以上的元素。 The copper foil for graphene production according to any one of claims 1 to 7, which comprises a fine copper specified by JIS-H3100 or JIS-H3250, an oxygen-free copper specified by JIS-H3100 or JIS-H3510, or a relative The refined copper or the oxygen-free copper is at least one element selected from the group consisting of Sn and Ag in an amount of 0.050% by mass or less. 一種石墨烯之製造方法，其使用有申請專利範圍第1至8項中任一項之石墨烯製造用銅箔，該方法具有下述步驟：石墨烯形成步驟：於特定之室內配置經加熱之該石墨烯製造用銅箔，且供給含碳氣體，而於該石墨烯製造用銅箔之表面形成石墨烯；及石墨烯轉印步驟：一面於該石墨烯之表面積層轉印片，將該石墨烯轉印至該轉印片上，一面蝕刻去除該石墨烯製造用銅箔。 A method for producing graphene, which comprises the copper foil for graphene production according to any one of claims 1 to 8, which has the following steps: a graphene forming step: heating in a specific chamber a copper foil for producing graphene, which is supplied with a carbon-containing gas to form graphene on the surface of the copper foil for graphene production; and a graphene transfer step of transferring the sheet onto the surface layer of the graphene layer, The graphene is transferred onto the transfer sheet, and the copper foil for producing graphene is removed by etching.