TWI752326B - A graphene device, graphene transfer device and manufacturing method thereof - Google Patents
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本發明關於一種二維材料及其製造方法,尤其是指一種石墨烯裝置、石墨烯移轉裝置及其製造方法。 The present invention relates to a two-dimensional material and a manufacturing method thereof, in particular to a graphene device, a graphene transfer device and a manufacturing method thereof.
石墨烯因為具有良好的電子、機械及化學等特性,在可撓性電子的應用上具有極大的應用潛力。但是,要將石墨烯製備成具有足夠規模和質量應用的透明導電膜,仍然在合成、轉移和摻雜上都缺乏有效率的方法,而使目前的應用受到阻礙。 Because of its good electronic, mechanical and chemical properties, graphene has great application potential in the application of flexible electronics. However, to prepare graphene into transparent conductive films with sufficient scale and quality for application, there is still a lack of efficient methods for synthesis, transfer, and doping, which hinders current applications.
傳統的透明電極使用銦錫氧化物(ITO)並常用於太陽能電池,觸摸傳感器和平板顯示器,ITO的薄層電阻小於100Ω□-1,光學透明度達到90%。相比之下,生長在石墨烯上的最佳薄層電阻為通過化學氣相沉積(CVD)生長在鎳的基底上,為280Ω□-1,並且只有公分等級的面積大小。CVD的成長方式,需要一個能夠承受接近溫度1,000℃的基板,以及可以被移除的金屬催化劑層。因此,這些是直接使用石墨烯的主要障礙。所以將石墨烯轉移到異質基板上是必不可少的。目前透過將石墨烯生長在大型柔性銅箔上,並搭配輥壓的捲對捲生產方法可以達到最 大化生產的規模,然而要能轉移出大面積、高度均勻性且無雜質殘留的石墨烯薄膜,仍然是目前遇到的最大挑戰。 Traditional transparent electrodes use indium tin oxide (ITO) and are commonly used in solar cells, touch sensors and flat panel displays. ITO has a sheet resistance of less than 100Ω□ -1 and an optical transparency of 90%. In contrast, the optimal sheet resistance for graphene grown on a nickel substrate by chemical vapor deposition (CVD) is 280Ω□ -1 and is only a centimeter-scale area. The CVD method of growth requires a substrate that can withstand temperatures approaching 1,000°C, and a metal catalyst layer that can be removed. Therefore, these are the main obstacles to the direct use of graphene. So it is essential to transfer graphene onto heterogeneous substrates. At present, the scale of production can be maximized by growing graphene on large flexible copper foils and using a roll-to-roll production method with roll pressing. However, it is necessary to transfer graphene films with large areas, high uniformity and no residual impurities , is still the biggest challenge encountered so far.
本發明提出一種可以大面積轉移石墨烯的裝置及方法,此技術所轉印之wafer級晶圓基板可以製造出大面積、高度均勻性且無雜質殘留的石墨烯薄膜,並應用於半導體元件、高功率元件、高頻元件、微波元件以及高靈敏度生物感測器......等。 The present invention provides a device and method for transferring graphene in a large area. The wafer-level wafer substrate transferred by this technology can produce a graphene film with a large area, high uniformity and no residue of impurities, and is applied to semiconductor elements, High-power components, high-frequency components, microwave components, and high-sensitivity biosensors...etc.
本發明解決的技術問題為提出了一種大面積石墨烯裝置及其製作方法,利用多層不同物理特性的高分子薄膜結構作為石墨烯轉印時的支撐材料,同時結合可調控各種參數的連續性生產設備,以創新之製程方法達到將四吋wafer級或以上之大面積石墨烯轉印至目標基板的技術開發,轉印後薄膜表面潔淨度提升7~10%,薄膜完整性提升15~18%,並能夠達到大面積的表面完整性及表面潔淨度,且具有較低的平均片電阻,可從實驗室研發階段導入工業化製程,以提供未來科技應用之需求。 The technical problem solved by the present invention is to propose a large-area graphene device and a manufacturing method thereof, which utilizes a multilayered polymer film structure with different physical properties as a support material during graphene transfer, and combines continuous production that can control various parameters. The equipment uses an innovative process method to achieve the technology development of transferring large-area graphene of four-inch wafer level or above to the target substrate. After transfer, the surface cleanliness of the film is improved by 7~10%, and the film integrity is improved by 15~18% , and can achieve large-area surface integrity and surface cleanliness, and has a low average sheet resistance, which can be introduced into industrial processes from the laboratory research and development stage to meet the needs of future technology applications.
本發明提出一種石墨烯移轉裝置,包括一移轉基板,該移轉基板上有一石墨烯層,該石墨烯層上有一轉印複合層,其中該石墨烯層和該轉印複合層間的附著力小於該石墨烯層和該移轉基板表面間的附著力。 The present invention provides a graphene transfer device, comprising a transfer substrate, a graphene layer on the transfer substrate, a transfer composite layer on the graphene layer, wherein the graphene layer and the transfer composite layer are attached The force is less than the adhesion between the graphene layer and the transfer substrate surface.
進一步,其中該轉印複合層包括一應力緩衝層和一支撐層,該應力緩衝層位於該石墨烯層和該支撐層之間,其中該支撐層和該應力緩衝層間的附著力小於該應力緩衝層和該石墨烯層間的附著力。 Further, wherein the transfer composite layer comprises a stress buffer layer and a support layer, the stress buffer layer is located between the graphene layer and the support layer, wherein the adhesion between the support layer and the stress buffer layer is smaller than the stress buffer layer the adhesion between the layer and the graphene layer.
進一步,該應力緩衝層和該支撐層間具有一第一正向應力,該應力緩衝層和該石墨烯層間具有一第二正向應力,其中該第二正向應力大於該第一正向應力。 Further, a first normal stress exists between the stress buffer layer and the support layer, and a second normal stress exists between the stress buffer layer and the graphene layer, wherein the second normal stress is greater than the first normal stress.
進一步,該應力緩衝層和該支撐層間具有一第一剪應力,該應力緩衝層和該石墨烯層間具有一第二剪應力,其中該第一剪應力大於該第二剪應力。 Further, a first shear stress exists between the stress buffer layer and the support layer, and a second shear stress exists between the stress buffer layer and the graphene layer, wherein the first shear stress is greater than the second shear stress.
本發明提出一種大面積石墨烯移轉裝置的方法,包括下列步驟:提供一金屬基材;成長一石墨烯層於該金屬基材的表面上;塗佈一轉印複合層於該石墨烯層上;去除該金屬基材,得到一轉印複合層/石墨烯層結構;將該結構置於一移轉基板上,形成該大面積石墨烯移轉裝置。 The present invention provides a method for a large-area graphene transfer device, comprising the following steps: providing a metal substrate; growing a graphene layer on the surface of the metal substrate; coating a transfer transfer composite layer on the graphene layer removing the metal substrate to obtain a transfer composite layer/graphene layer structure; placing the structure on a transfer substrate to form the large-area graphene transfer device.
本發明提出一種大面積石墨烯移轉裝置的方法,包括下列步驟:提供一金屬基材;成長一石墨烯層於該金屬基材的表面上;塗佈一應力緩衝層於該石墨烯層上;塗佈一支撐層於該應力緩衝層上;去除該金屬基材,得到一支撐層/應力緩衝層/石墨烯層結構;將該結構置於一移轉基板上,形成該大面積石墨烯移轉裝置。 The present invention provides a method for a large-area graphene transfer device, comprising the following steps: providing a metal substrate; growing a graphene layer on the surface of the metal substrate; coating a stress buffer layer on the graphene layer Coating a support layer on this stress buffer layer; Remove this metal base material to obtain a support layer/stress buffer layer/graphene layer structure; This structure is placed on a transfer substrate to form this large area graphene transfer device.
進一步,在塗佈該支撐層於該應力緩衝層上後,還包括一施加能量的步驟。 Further, after coating the support layer on the stress buffer layer, a step of applying energy is also included.
本發明提出一種大面積石墨烯裝置,包括一移轉基板,該移轉基板上有一石墨烯層,其中該石墨烯層的面積可以介於4吋至18吋晶圓。 The present invention provides a large-area graphene device, comprising a transfer substrate with a graphene layer on the transfer substrate, wherein the area of the graphene layer can be between 4 inches and 18 inches of wafers.
本發明提出一種大面積石墨烯裝置,包括一移轉基板,該移轉基板上有一石墨烯層,其中該石墨烯層的面積可以介於50至40,000平方公分的長條形面積,其中長寬介於1至200公分之間。 The present invention proposes a large-area graphene device, comprising a transfer substrate with a graphene layer on the transfer substrate, wherein the area of the graphene layer can be between 50 and 40,000 square centimeters in a long strip area, wherein the length and width are Between 1 and 200 cm.
進一步,包括一石墨烯元件區和一石墨烯間隔區,其中該石墨烯元件區佔該石墨烯層的面積大於90%。 Further, it includes a graphene element region and a graphene spacer region, wherein the graphene element region accounts for more than 90% of the area of the graphene layer.
進一步,還包括一保護層,該應力保護層佔該石墨烯層的面積小於10%。 Further, a protective layer is also included, and the stress protective layer accounts for less than 10% of the area of the graphene layer.
進一步,其拉曼光譜的量測值ID/IG<0.25以及I2D/IG為>2的面積佔全部的面積92%以上。 Furthermore, the area where the measured value of the Raman spectrum I D / IG <0.25 and I 2D / IG >2 accounts for more than 92% of the total area.
本發明提出一種製造大面積石墨烯裝置的方法,包括下列步驟:提供一金屬基材;成長一石墨烯層於該金屬基材的表面上;塗佈一轉印複合層於該石墨烯層上;去除該金屬基材,得到一轉印複合層/石墨烯層結構;將該結構置於一移轉基板上,形成具轉印複合層/石墨烯層/移轉基板結構的一大面積石墨烯移轉裝置;降低該轉印複合層和該石墨烯層間分子的附著力;將該轉印複合層進行剝離,得到該大面積石墨烯裝置。 The present invention provides a method for manufacturing a large-area graphene device, comprising the following steps: providing a metal substrate; growing a graphene layer on the surface of the metal substrate; coating a transfer transfer composite layer on the graphene layer Removing this metal base material to obtain a transfer composite layer/graphene layer structure; This structure is placed on a transfer substrate to form a large area of graphite with transfer transfer composite layer/graphene layer/transfer substrate structure A graphene transfer device; reducing the adhesion between the transfer composite layer and the graphene layer; peeling off the transfer composite layer to obtain the large-area graphene device.
本發明提出一種製造大面積石墨烯裝置的方法,包括下列步驟:提供一金屬基材;成長一石墨烯層於該金屬基材的表面上;塗佈一應力緩衝層於該石墨烯層上;塗佈一支撐層於該應力緩衝層上;去除該金屬基材,得到一支撐層/應力緩衝層/石墨烯層結構;將該結構置於一移轉基板上,形成具支撐層/應力緩衝層/石墨烯層/移轉基板結構的一大面積石墨烯移轉裝置;降低該支撐層和該應力緩衝層間分子的附著力;去除該支撐層;降低該應力緩衝層和該石墨烯層間分子的附著力;將該應力緩衝層進行剝離,得到該大面積石墨烯裝置。 The present invention provides a method for manufacturing a large-area graphene device, comprising the following steps: providing a metal substrate; growing a graphene layer on the surface of the metal substrate; coating a stress buffer layer on the graphene layer; Coating a support layer on the stress buffer layer; removing the metal substrate to obtain a support layer/stress buffer layer/graphene layer structure; placing the structure on a transfer substrate to form a support layer/stress buffer A large area graphene transfer device of layer/graphene layer/transfer substrate structure; reduce the adhesion of the molecules between the support layer and the stress buffer layer; remove the support layer; reduce the stress buffer layer and the molecules between the graphene layers the adhesion; peel off the stress buffer layer to obtain the large-area graphene device.
本發明提出一種製造大面積石墨烯裝置的方法,包括下列步驟:提供一金屬基材;成長一石墨烯層於該金屬基材的表面上;塗佈一應力緩衝層於該石墨烯層上;塗佈一支撐層於該應力緩衝層上;去除該金屬基材,得到一支撐層/應力緩衝層/石墨烯層結構;將該結構置於一移轉 基板上,形成具支撐層/應力緩衝層/石墨烯層/移轉基板結構的一大面積石墨烯移轉裝置;降低該支撐層和該應力緩衝層間分子的附著力;去除該支撐層,降低該應力緩衝層和該石墨烯層間分子的附著力;將部份應力緩衝層進行剝離後,得到該大面積石墨烯裝置。 The present invention provides a method for manufacturing a large-area graphene device, comprising the following steps: providing a metal substrate; growing a graphene layer on the surface of the metal substrate; coating a stress buffer layer on the graphene layer; Coating a support layer on the stress buffer layer; removing the metal substrate to obtain a support layer/stress buffer layer/graphene layer structure; placing the structure in a transfer On the substrate, form a large-area graphene transfer device with a support layer/stress buffer layer/graphene layer/transfer substrate structure; reduce the adhesion of the molecules between the support layer and the stress buffer layer; remove the support layer, reduce Adhesion of molecules between the stress buffer layer and the graphene layer; after peeling off part of the stress buffer layer, the large-area graphene device is obtained.
1:石墨烯移轉裝置 1: Graphene transfer device
11、31、41:移轉基板 11, 31, 41: Transfer substrate
13、33、43:石墨烯層 13, 33, 43: Graphene layers
15:轉印複合層 15: Transfer composite layer
151:應力緩衝層 151: Stress buffer layer
153:支撐層 153: Support Layer
331、431:石墨烯元件區 331, 431: Graphene element area
333、433:石墨烯間隔區 333, 433: Graphene spacers
451:保護層 451: Protective Layer
S11-S15:步驟 S11-S15: Steps
2、3、4:石墨烯裝置 2, 3, 4: Graphene devices
AA’:剖面線 AA’: hatch
PN:正向力 PN: normal force
PS:側向力 PS: Lateral force
σss:第一正向應力 σ ss : first normal stress
σgs:第二正向應力 σ gs : second normal stress
τss:第一剪應力 τ ss : first shear stress
τgs:第二剪應力 τ gs : second shear stress
圖1為本發明一實施方式之石墨烯移轉裝置的示意圖。 FIG. 1 is a schematic diagram of a graphene transfer device according to an embodiment of the present invention.
圖2為本發明一實施方式之石墨烯移轉裝置的製作方法流程圖。 2 is a flow chart of a method for manufacturing a graphene transfer device according to an embodiment of the present invention.
圖3為本發明一實施方式之石墨烯裝置的示意圖。 3 is a schematic diagram of a graphene device according to an embodiment of the present invention.
圖4為本發明另一實施方式之石墨烯裝置的示意圖。 4 is a schematic diagram of a graphene device according to another embodiment of the present invention.
圖5為本發明又一實施方式之石墨烯裝置的上視圖。 FIG. 5 is a top view of a graphene device according to another embodiment of the present invention.
圖6為圖5石墨烯裝置沿AA’剖面線的側視圖。 FIG. 6 is a side view of the graphene device of FIG. 5 along section line AA'.
圖7為本發明石墨烯移轉裝置的受力示意圖。 FIG. 7 is a schematic diagram of the force of the graphene transfer device of the present invention.
圖8為圖7石墨烯移轉裝置中應力緩衝層的應力分佈示意圖。 FIG. 8 is a schematic diagram of the stress distribution of the stress buffer layer in the graphene transfer device of FIG. 7 .
以下將結合具體實施例對本發明內容進一步的詳細描述,接下來的詳細說明及附圖,皆是為了能進一步說明本發明達到預定目的所採取的方式、手段及功效。然而,關於實施例中之說明僅為闡釋本發明之技術內容及其目的功效,圖中的尺寸、比例皆為說明目的,而非用以直接限制本發明。 The content of the present invention will be further described in detail below with reference to specific embodiments. The following detailed description and accompanying drawings are all for the purpose of further illustrating the ways, means and effects adopted by the present invention to achieve the predetermined purpose. However, the descriptions in the embodiments are only to illustrate the technical content of the present invention and its purpose and functions, and the dimensions and ratios in the figures are for illustrative purposes, rather than directly limiting the present invention.
請參考圖1所示,為本發明之石墨烯移轉裝置1的示意圖,石墨烯移轉裝置1,包括一移轉基板11,移轉基板11上置有一石墨烯層13,石
墨烯層13上有一轉印複合層15。在將石墨烯層13轉印至移轉基板11時,所述轉印複合層15具有支撐的功能,以及具有應力緩衝的功能,以防止石墨烯層13在移轉的過程中受到外力損害,可以達到轉移出大面積、高度均勻性且無雜質殘留的石墨烯薄膜。
Please refer to FIG. 1 , which is a schematic diagram of a
請參考圖2所示,為上述石墨烯移轉裝置1的製作方法流程圖,包括下列步驟,步驟S11:提供一金屬基材,包括但不限於銅、鎳、鈷等金屬材料;步驟S12:成長石墨烯層13於金屬基材的表面上,石墨烯層13成長的方式包括但不限於包含機械剝離法(mechanical exfoliation)、氧化還原石墨烯之方法(reduced graphene oxide)、液相剝離法(liquid phase exfoliation)、磊晶成長法(epitaxial growth)、化學氣相沉積法(chemical vapor deposition,CVD)、電化學剝離法(electrochemical exfoliation)等;步驟S13:塗佈一轉印複合層15於石墨烯層13上,於空氣中風乾或加熱或照光以形成固態膜層,加強石墨烯層13與轉印複合層15的附著力,形成一轉印複合層15/石墨烯層13/金屬基材的層狀結構,步驟S14:再將上述層狀結構的金屬基材去除,得到轉印複合層15/石墨烯層13的結構,步驟S15:再將上述結構置於移轉基板11上,形成具有轉印複合層15/石墨烯層13/移轉基板11的石墨烯移轉裝置1。
Please refer to FIG. 2, which is a flow chart of the manufacturing method of the above-mentioned
上述轉印複合層15包括一應力緩衝層151和一支撐層153,先將應力緩衝層151塗佈於石墨烯層13上,於空氣中風乾或加熱或照光以形成固態膜層,以加強石墨烯層13與應力緩衝層151的附著力,應力緩衝層151的材料可以包括高分子材料,例如但不限於:聚甲基丙烯酸甲酯(PMMA,Poly(methyl methacrylate))、聚苯乙烯(PS,Polystyrene)、
聚乳酸(PLA,Polylactic Acid)、光阻(PR,photoresist)、松香(Rosin)、聚乙烯醇(PVA,Polyvinyl alcohol)、聚二甲基矽氧烷(PDMS,Polydimethylsiloxane)等;接著再塗佈支撐層153於應力緩衝層151上,於空氣中風乾或加熱或照光以形成固態膜層,加強應力緩衝層151與支撐層153的附著力,支撐層153的材料可以包括高分子材料,例如但不限於:聚甲基丙烯酸甲酯(PMMA,Poly(methyl methacrylate)、聚對苯二甲酸乙二酯(PET,Polyethylene Terephthalate)、聚醯亞胺(PI,Polyimide)、熱解膠帶(TRT,thermal release tape)、聚乳酸(PLA,Polylactic Acid)、光阻(PR,photoresist)、聚乙烯(PE,Polyethylene)、聚二甲基矽氧烷(PDMS,Polydimethylsiloxane)、乙烯/醋酸乙烯酯共聚物(EVA,Polyethylene vinylacetate)、蠟(Wax)、聚對二甲苯(parylene)等。
The above-mentioned
應力緩衝層151和一支撐層153的貼合,可以透過施加壓力增加支撐層153和應力緩衝層151的貼合力,施加壓加的方式,例如但不限於利用捲對捲滾壓裝置,將支撐層153和應力緩衝層151進行滾壓的動作,亦可包括平板熱壓、真空貼合等。接著再去除金屬基材,得到支撐層153/應力緩衝層151/石墨烯層13的結構,並以去離子水清潔,氮氣吹乾表面;再將上述結構置於移轉基板1上,形成具有支撐層153/應力緩衝層151/石墨烯層13/移轉基板11多層結構的石墨烯移轉裝置1。
The bonding of the
上述去除金屬基材的步驟,可以使用直接機械剝離的方式。在本發明其它的實施方式中,金屬基材可以先使用一脫層(Decoupling)製程弱化並分離石墨烯與金屬基材作用,例如進行一氧化步驟,氧化已成長石墨烯層13的金屬基材,使石墨烯層13和金屬基材間形成氧化金屬層,
可弱化石墨稀層13與金屬基材之間的鍵結力,此時可以使用直接機械剝離的方式去除金屬基材,或是於氧化步驟之後再使用電化學步驟,通過施加偏壓的方式,進行電化學插層反應,使氧化金屬層再還原成金屬基材以更加弱化石墨稀層13與金屬基材之間的鍵結力,達成更有效之剝離效果,此外,脫層方法不受限上述,亦包含化學分子藉由擴散進行插層弱化。
The above-mentioned step of removing the metal substrate can be carried out by means of direct mechanical peeling. In other embodiments of the present invention, the metal substrate can be weakened and separated by a decoupling process, for example, an oxidation step is performed to oxidize the metal substrate on which the
得到上述石墨烯移轉裝置1後,進行一轉印複合層15去除的步驟,以得到石墨烯裝置2,如圖3所示,石墨烯裝置2為包括石墨烯層13/移轉基板11的雙層結構。進行轉印複合層15去除的動作,方法包括先將支撐層153進行剝離的動作,留下應力緩衝層151/石墨烯層13/移轉基板11的三層結構,再將上述三層結構利用浸泡於溶劑中、照光裂解、加熱揮發將應力緩衝層151清洗乾淨,溶劑可以例如但不限於丙酮(Acetone),並以異丙醇(2-Propanol)沖洗乾淨,最後以氮氣吹乾即得到石墨烯裝置2。石墨烯裝置2中,石墨烯層13可以披覆的面積約為4吋、6吋、8吋、12吋、16吋-18吋晶圓片,及/或可以披覆的面積為50、100、200、400、800、1,000平方公分至40,000平方公分的長方形面積,寬度和長度分別介於1、5、10、50、100公分以上至200公分。
After obtaining the above-mentioned
支撐層153和應力緩衝層151間的附著力小於應力緩衝層151和石墨烯層13間的附著力,支撐層153剝離的方式可以用直接物理方式剝離,在另一實施方式中,剝離時可以使用加熱剝離,加熱剝離的整體電性較未加熱的好,加熱剝離可以從未加熱的整體平均片電阻可以降低80%,因為加熱剝離有較少的結構缺陷。在拉曼光譜的量測部分,加熱
剝離後石墨烯層13的ID/IG比整體平均落在0.1-0.25左右,I2D/IG比則加熱剝離後平均落在1-2左右。I2D/IG=2可以代表石墨烯層13為單層石墨稀、I2D/IG=1為雙層石墨稀、I2D/IG=0.5為三層石墨稀。本實施方式中,石墨烯層13的拉曼光譜量測值,ID/IG比<0.25,I2D/IG比>0.5的面積佔全部的面積達92%以上。
The adhesion between the
應力緩衝層151和石墨烯層13間的附著力小於石墨烯層13和移轉基板11間的附著力,應力緩衝層151才易於脫離石墨烯層13。上述轉印複合層15去除的動作,包括調變各層間附著能的步驟,透過調整支撐層153和應力緩衝層151間的附著力大小,以及應力緩衝層151和石墨烯層13接觸的分子間的附著能大小,進而控制剝離步驟後石墨烯層13的完整度。降低附著能易於分離,可以得到大面積且高完整度的石墨烯層13。調整附著能的方式例如,在應力緩衝層151去除時,可以增加適當能量與壓力,如加熱升溫、微波或光能加熱、特定光波照射或甚組合等,壓力可為熱壓等,使和石墨烯層13接觸的分子附著能降低,所以可乾淨且輕易移除。在其它實施方式中,使用如溶劑完全溶解、昇華、融化且於表面形成超疏水性,可聚為液滴而吹氣或拖曳而去除等。在其它實施方式中,可以透過增加應力緩衝層151和石墨烯層13接觸的分子間的附著能,進而達到擇選性去除石墨烯層13的目的。上述透過對分子間的附著能的改變,進而達到擇選性去除的目的,可以理解的,其方法可以包括例用奈米壓印(模具)TRT可以選擇性接觸,透過壓力使附著能改變,在其它實施方式中,可以透過而選擇性的能量照射,也可以達到改變分子間的附著能的目的。
The adhesive force between the
上述轉印複合層15的塗佈方式,不同旋轉塗佈轉速對應的薄膜厚度不相同,隨者轉速的提升薄膜厚度也跟著變薄,但在一定轉速後,厚度就趨於穩定。當薄膜變薄,其轉印後石墨稀層13電性會變差,其原因為薄膜變薄,應力緩衝的效果就變差,在進行滾壓時,石墨烯層13受應力影響而造成破損。
In the above-mentioned coating method of the
請參考圖4所示,為本發明另一實施方式中的石墨烯裝置3的示意圖。石墨烯裝置3,包括石墨烯元件區331和石墨烯間隔區333,透過調變石墨烯層13和轉印複合層15間分子的附著能,可以達到圖樣化石墨烯層13的目的。石墨烯層13和轉印複合層15間的附著力大於石墨烯層13和移轉基板11間的附著力時,石墨烯層13和轉印複合層15會一同被去除,得到石墨烯間隔區333;石墨烯層13和轉印複合層15間的附著力小於石墨烯層13和移轉基板11間的附著力時,可以僅將印複合層15去除,得到石墨烯元件區331。石墨烯層13的面積可以披覆的面積約為4吋、6吋、8吋、12吋、16吋-18吋晶圓片,及/或可以披覆的面積為50、100、200、400、800、1,000平方公分-40,000平方公分的長方形面積,寬度和長度分別介於1、5、10、50、100公分以上至200公分。石墨烯元件區331佔石墨烯層33的面積大於90%。
Please refer to FIG. 4 , which is a schematic diagram of a
請參考圖5和圖6所示,為本發明另一實施方式中的石墨烯裝置4的示意圖。石墨烯裝置4為石墨烯層43/移轉基板41的雙層結構。圖5為石墨烯裝置4的上視圖,圖6為圖5沿AA’剖面線的側視圖。石墨烯層43包括石墨烯元件區431和石墨烯間隔區433,石墨烯層43的面積可以披覆的面積約為4吋、6吋、8吋、12吋、16吋-18吋晶圓片,及/或可以披覆
的面積為50、100、200、400、800、1,000平方公分-40,000平方公分的長方形面積,寬度和長度分別介於1、5、10、50、100公分以上至200公分。石墨烯元件區431佔石墨烯層43的面積大於90%。請再參考圖5和圖6所示,透過調變石墨烯層43和應力緩衝層(圖未示)間分子的附著能,可以達到圖樣化石墨烯層43的目的。石墨烯層43和應力緩衝層間的附著力大於石墨烯層43和移轉基板41間的附著力時,石墨烯層43和應力緩衝層會一同被去除,得到石墨烯間隔區433;石墨烯層43和應力緩衝層間的附著力小於石墨烯層13和移轉基板11間的附著力時,當應力緩衝層去除後,會獲得部分殘留及不殘留區,殘留的應力緩衝層會形成保護層451於石墨烯層43,其中保護層451佔石墨烯層43的面積小於10%。不殘留區得到石墨烯元件區431。
Please refer to FIG. 5 and FIG. 6 , which are schematic diagrams of a
上述調變分子間的附著力以達到不同的石墨烯層43披覆區域,可以再進行半導體製程選擇性地在石墨烯元件區331或石墨烯間隔區333或在石墨烯元件區331和石墨烯間隔區333交界區往上堆疊材料以製作元件,產生透過底層石墨烯傳輸或非傳輸或異質接面功能。並可利用保護層451做為電性傳輸阻障層或是結構襯墊或是犧牲層,而在基板上利用半導體製程往上推疊材料以製作元件。
The above-mentioned modulation of the intermolecular adhesion force to achieve
請參考圖7所示,為本發明實施方式中石墨烯移轉裝置1的受力示意圖,將石墨烯層13轉印至移轉基板11時,所述轉印複合層15具有支撐的功能,以及具有應力緩衝的功能,以防止石墨烯層13在移轉的過程中受到外力損害。在轉印過程中,會受到正向力PN以及側向力PS的作用。圖8所示為石墨烯移轉裝置1中應力緩衝層151的應力分佈示意圖,應力緩衝層151和支撐層153間朝向應力緩衝層151具有一第一正向應力σss,應力緩衝層151和石墨烯層13間朝向應力緩衝層151具有一第二正向
應力σgs,其中第二正向應力σgs大於第一正向應力σss。應力緩衝層151和支撐層153間具有一第一剪應力τss,應力緩衝層151和石墨烯層13間具有一第二剪應力τgs,其中第一剪應力τss大於第二剪應力τgs。
Please refer to FIG. 7, which is a schematic diagram of the force of the
使用本發明所揭露之利用多層不同物理特性的高分子薄膜結構作為石墨烯轉印時的轉印複合層,同時結合可調控各種參數的連續性生產設備,以創新之製程方法達到將4吋晶圓級或以上之大面積石墨烯轉印至目標基板的技術開發,轉印後薄膜表面潔淨度提升7~10%,薄膜完整性提升9~12%,並能夠提供大面積的表面完整性及表面潔淨度,且具有較低的平均片電阻,可從實驗室研發階段導入工業化製程,以提供未來科技應用之需求。 Using the multi-layered polymer film structure with different physical properties disclosed in the present invention as the transfer composite layer during graphene transfer, and combined with continuous production equipment that can control various parameters, an innovative process method is used to achieve 4-inch wafers. The technology development of transferring large-area graphene of circular grade or above to the target substrate, after transfer, the surface cleanliness of the film is improved by 7~10%, and the film integrity is improved by 9~12%, and it can provide large-area surface integrity and Surface cleanliness and low average sheet resistance can be introduced into industrial processes from the laboratory R&D stage to meet the needs of future technology applications.
1:石墨烯移轉裝置 1: Graphene transfer device
11:移轉基板 11: Transfer the substrate
13:石墨烯層 13: Graphene layer
15:轉印複合層 15: Transfer composite layer
151:應力緩衝層 151: Stress buffer layer
153:支撐層 153: Support Layer
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