TW201439359A - Method for forming large-area graphene layer on porous substrate by chemical vapor deposition process - Google Patents
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本發明是一種形成大面積石墨烯層之方法，特別是一種以化學氣相沉積程序於多孔洞基材形成大面積石墨烯層之方法。The invention is a method for forming a large-area graphene layer, in particular, a method for forming a large-area graphene layer on a porous hole substrate by a chemical vapor deposition process.
習知一種形成石墨烯之方法是使用電漿摻雜系統或射束線植入器，將碳離子植入至如金屬箔之基板中，從而使金屬箔吸收大量碳離子。隨著溫度降低，過量之碳原子使金屬箔飽和，且碳原子擴散至表面以產生石墨烯，但此方法須消耗極大之能量卻僅形成小面積之石墨烯，且擴散至金屬箔表面之石墨烯需進行轉移或轉印的步驟，才可有效使用，但在轉移或轉印的過程中，常使石墨烯破裂成為石墨烯碎片，而無法廣泛地應用於固體/液體的過濾與分離、溶質與離子的吸附、不同分子量液體的分離及不同氣體的分離。A conventional method of forming graphene is to implant carbon ions into a substrate such as a metal foil using a plasma doping system or a beamline implanter, thereby causing the metal foil to absorb a large amount of carbon ions. As the temperature decreases, excess carbon atoms saturate the metal foil and carbon atoms diffuse to the surface to produce graphene, but this method consumes a great amount of energy but forms only a small area of graphene and diffuses to the surface of the metal foil. The olefin needs to be transferred or transferred in order to be effectively used. However, in the process of transfer or transfer, graphene is often broken into graphene fragments, which cannot be widely applied to solid/liquid filtration and separation, solutes. Adsorption with ions, separation of liquids of different molecular weights, and separation of different gases.
本發明之主要目的在於藉由化學氣相沉積步驟於多孔洞基材上沉積碳層，再進行催化石墨化步驟，經由覆蓋金屬催化劑於碳層上並加熱碳層使碳層石墨化為石墨層，再經由液相剝離步驟將石墨層剝離為石墨烯層，本發明可直接於多孔洞基材上形成大面積石墨烯層，以克服先前技術所揭露在轉移或轉印的步驟中，造成石墨烯產生破裂成為石墨烯碎片而無法使用的問題，且本發明直接於多孔洞基材上形成大面積之石墨烯層，因此，可使得多孔洞基材之第一通道連通石墨烯層之第二通道，使得形成有大面積石墨烯層的多孔洞基材可運用於氣體分離、固液分離、溶液之小分子去除、海水淡化或飲用水淨化等過濾、分離或吸附程序，進而提升過濾或分離的效果。The main object of the present invention is to deposit a carbon layer on a porous hole substrate by a chemical vapor deposition step, and then perform a catalytic graphitization step, and graphitize the carbon layer into a graphite layer by covering the metal catalyst on the carbon layer and heating the carbon layer. And separating the graphite layer into a graphene layer through a liquid phase stripping step, the present invention can directly form a large-area graphene layer on the porous hole substrate to overcome the prior art disclosed in the step of transferring or transferring, causing graphite The problem that the olefin is broken into graphene fragments and cannot be used, and the present invention directly forms a large-area graphene layer on the porous hole substrate, so that the first channel of the porous hole substrate can be connected to the second of the graphene layer. The channel enables the porous hole substrate formed with a large area of graphene layer to be used for filtration, separation or adsorption processes such as gas separation, solid-liquid separation, small molecule removal of solution, seawater desalination or drinking water purification, thereby improving filtration or separation. Effect.
本發明之以化學氣相沉積程序於多孔洞基材形成大面積石墨烯層之方法包含「提供一多孔洞基材」、「化學氣相沉積步驟」、「催化石墨化步驟」及「液相剝離步驟」之步驟，首先提供一多孔洞基材，該多孔洞基材具有一第一表面、一第二表面及複數個第一通道，各該第一通道連通該第一表面及該第二表面，接著，進行一化學氣相沉積步驟，將該多孔洞基材置入一腔室中，提供一碳源氣體至該腔室並加熱該腔室，使該碳源氣體產生熱裂解成碳原子，碳原子進而於該多孔洞基材上沉積為一碳層，該碳層覆蓋該些第一通孔，接著，進行一催化石墨化步驟，將一金屬催化劑覆蓋於該碳層並對該碳層加熱，使該碳層石墨化為一石墨層，該石墨層具有一第一厚度，且該石墨層覆蓋該些第一通道，最後，進行一液相剝離步驟，以液體震盪方式使該石墨層薄化為一石墨烯層，該石墨烯層具有一第二厚度，且該石墨烯層的該第二厚度小於該石墨層之該第一厚度，該石墨烯層覆蓋該些第一通道，且該石墨烯層具有複數個第二通道及一顯露面，該些第二通道連通各該第一通道及該顯露面。The method for forming a large-area graphene layer on a porous hole substrate by a chemical vapor deposition process of the present invention comprises "providing a porous hole substrate", "chemical vapor deposition step", "catalytic graphitization step" and "liquid phase The step of the stripping step first provides a porous hole substrate having a first surface, a second surface, and a plurality of first channels, each of the first channels communicating with the first surface and the second a surface, followed by a chemical vapor deposition step of placing the porous cavity substrate into a chamber, providing a carbon source gas to the chamber and heating the chamber to thermally crack the carbon source gas into carbon An atom, a carbon atom is further deposited on the porous hole substrate as a carbon layer, the carbon layer covers the first through holes, and then a catalytic graphitization step is performed to cover a carbon catalyst on the carbon layer and Heating the carbon layer to graphitize the carbon layer into a graphite layer, the graphite layer has a first thickness, and the graphite layer covers the first channels, and finally, performing a liquid phase stripping step to make the liquid oscillating manner The graphite layer is thinned to a graphene layer having a second thickness, wherein the second thickness of the graphene layer is smaller than the first thickness of the graphite layer, the graphene layer covers the first channels, and the graphene layer And a plurality of second channels and a display surface, wherein the second channels communicate with each of the first channels and the exposed surface.
本發明藉由該化學氣相沉積步驟、該催化石墨化步驟及該液相剝離步驟直接於該多孔洞基材形成該石墨烯層，因此，可在該多孔洞基材上形成完整且大面積之該石墨烯層，藉由該多孔洞基材之該第一通道與該石墨烯層之該第二通道相連通，使得形成有大面積石墨烯層的多孔洞基材可應用於固體/液體的過濾與分離、溶質與離子的吸附、不同分子量液體的分離及不同氣體的分離，達到提升分離及純化的效果。The present invention forms the graphene layer directly on the porous hole substrate by the chemical vapor deposition step, the catalytic graphitization step and the liquid phase stripping step, and thus, a complete and large area can be formed on the porous hole substrate. The graphene layer is connected to the second channel of the graphene layer by the first channel of the porous hole substrate, so that the porous hole substrate formed with the large-area graphene layer can be applied to the solid/liquid The filtration and separation, the adsorption of solute and ions, the separation of different molecular weight liquids and the separation of different gases achieve the effect of improving separation and purification.
請參閱第1圖，為本發明之以化學氣相沉積程序於多孔洞基材形成大面積石墨烯層之方法10的流程圖，其包含「提供一多孔洞基材11」、「化學氣相沉積步驟12」、「催化石墨化步驟13」、「酸氧化步驟14」及「液相剝離步驟15」。Referring to FIG. 1 , a flow chart of a method 10 for forming a large-area graphene layer on a porous hole substrate by a chemical vapor deposition process according to the present invention includes "providing a porous hole substrate 11" and "chemical gas phase. The deposition step 12", the "catalytic graphitization step 13", the "acid oxidation step 14", and the "liquid phase stripping step 15".
請參閱第1及2圖，於「提供一多孔洞基材11」步驟中，提供一多孔洞基材100，該多孔洞基材100具有一第一表面110、一第二表面120及複數個第一通道130，各該第一通道130連通該第一表面110及該第二表面120，該多孔洞基材100選自於可耐高溫900℃以上，且與碳原子之間附著力不弱之材料，在本實施例中，該多孔洞基材100為管狀或平板狀之陶瓷基材，且各該第一通道130是由陶瓷基材之複數個孔洞(圖未繪出)相互連通形成，而各該第一通道130的寬度介於2奈米至1500奈米之間。Referring to FIGS. 1 and 2, in the step of providing a porous hole substrate 11, a porous hole substrate 100 having a first surface 110, a second surface 120, and a plurality of holes is provided. The first channel 130, each of the first channels 130 is connected to the first surface 110 and the second surface 120. The porous substrate 100 is selected from a temperature resistant to 900 ° C or higher and has a weak adhesion to carbon atoms. In the present embodiment, the porous hole substrate 100 is a tubular or flat ceramic substrate, and each of the first channels 130 is formed by a plurality of holes (not shown) of the ceramic substrate. And each of the first channels 130 has a width of between 2 nm and 1500 nm.
請參閱第1及3圖，於「化學氣相沉積步驟12」的步驟中，將該多孔洞基材100置入一腔室(圖未繪出)中，並提供一碳源氣體200於該腔室中，使該多孔洞基材100處於該碳源氣體200的氣氛環境並加熱該腔室，其中該碳源氣體200可選自純低碳數烷類氣體(甲烷、乙烷)、純低碳數烯類氣體(乙烯)或純低碳數炔類氣體(乙炔)，在本實施例中，該腔室為一石英管，該腔室係置於一高溫爐(圖未繪出)內並以該高溫爐對該腔室加熱，該加熱該腔室之溫度介於800℃至1200℃之間，在此加熱溫度範圍內該碳源氣體200方可獲得足夠之能量進行熱裂解成碳原子，碳原子進而於該多孔洞基材100上沉積為一碳層140，該碳層140覆蓋該些第一通孔130。較佳的，該碳源氣體200可選自低碳數烷類氣體、低碳數烯類氣體或低碳數炔類氣體分別與一惰性氣體(氮氣、氬氣、氦氣)混合而成，並使該碳源氣體200的流率介於100 ml/min至1000 ml/min之間，以惰性氣體作為低碳數烷類氣體、低碳數烯類氣體或低碳數炔類氣體的載流氣體，透過惰性氣體的傳輸可更有效率地使該碳源氣體200均勻地接觸該多孔洞基材100，使該碳源氣體200於該腔室中之熱裂解過程穩定，進而使該碳層140的沉積完整，較佳地，低碳數烷類氣體、低碳數烯類氣體或低碳數炔類氣體分別與該惰性氣體的混合比例介於1:1至1:5之間，若混合比例小於1:1則以惰性氣體作為載流氣體的效果不佳，而若混合比例大於1:5，低碳數烷類氣體、低碳數烯類氣體或低碳數炔類氣體則易隨著惰性氣體流動，而無法於該多孔洞基材100上形成完整之該碳層140。Referring to FIGS. 1 and 3, in the step of "Chemical Vapor Deposition Step 12", the porous hole substrate 100 is placed in a chamber (not shown) and a carbon source gas 200 is provided therein. In the chamber, the porous hole substrate 100 is placed in an atmosphere of the carbon source gas 200 and the chamber is heated, wherein the carbon source gas 200 may be selected from pure low carbon number alkane gas (methane, ethane), pure a low carbon number olefinic gas (ethylene) or a pure low carbon number acetylene gas (acetylene). In this embodiment, the chamber is a quartz tube, and the chamber is placed in a high temperature furnace (not shown). Heating and heating the chamber by the high temperature furnace, wherein the temperature of the chamber is between 800 ° C and 1200 ° C. In the heating temperature range, the carbon source gas 200 can obtain sufficient energy for thermal cracking. The carbon atoms, and the carbon atoms, are deposited on the porous hole substrate 100 as a carbon layer 140, and the carbon layer 140 covers the first through holes 130. Preferably, the carbon source gas 200 may be selected from a low carbon number alkane gas, a low carbon number olefin gas or a low carbon number acetylene gas mixed with an inert gas (nitrogen, argon, helium). And the flow rate of the carbon source gas 200 is between 100 ml/min and 1000 ml/min, and the inert gas is used as a low carbon number alkane gas, a low carbon number olefin gas or a low carbon number acetylene gas. The flow of the gas through the inert gas can more efficiently make the carbon source gas 200 uniformly contact the porous hole substrate 100, so that the thermal decomposition process of the carbon source gas 200 in the chamber is stabilized, thereby making the carbon The deposition of the layer 140 is complete. Preferably, the mixing ratio of the low carbon number alkane gas, the low carbon number olefin gas or the low carbon number acetylene gas to the inert gas is between 1:1 and 1:5. If the mixing ratio is less than 1:1, the effect of using an inert gas as a carrier gas is not good, and if the mixing ratio is greater than 1:5, a low carbon number alkane gas, a low carbon number olefin gas or a low carbon number acetylene gas is It is easy to flow with the inert gas, and it is impossible to form the complete carbon layer 140 on the porous hole substrate 100.
請參閱第1及4圖，於「催化石墨化步驟13」的步驟中，是將一金屬催化劑300覆蓋該碳層140並加熱該碳層140，使該碳層140石墨化為一石墨層150，該石墨層150具有一第一厚度D1，且該石墨層150覆蓋該些第一通道130，而該金屬催化劑300則隨著加熱而揮發，該金屬催化劑300可選自鐵鹽、鎳鹽或銅鹽，藉由該金屬催化劑300可使加熱該碳層140的溫度可由一般石墨化所需的2000℃至3000℃之間大幅降低至介於800℃至1400℃之間，在本實施例中，若加熱該碳層140之溫度低於800℃，則石墨化的能量不足，而導致該碳層140石墨化之效果不佳，使該碳層140無法完整石墨化為該石墨層150，此外，由於加熱該碳層140的溫度介於800℃至1400℃之間已可完整的將該碳層140石墨化為該石墨層150，因此，若加熱該碳層140之溫度高於1400℃則造成能量的浪費，且失去催化石墨化之本意，另外，加熱溫度於1400℃以下之高溫爐價格較低，可減少製作之成本。較佳地，該金屬催化劑300之重量百分比介於0.1 wt%至5 wt%之間，若該金屬催化劑300之重量百分比低於0.1 wt%，則催化效果不佳，需提高加熱之溫度，倘若該金屬催化劑300之重量百分比高於5 wt%，則該金屬催化劑300之金屬會殘留於該石墨層150中，且易導致該石墨層150之表面不平整，甚至增加後續「液相剝離步驟15」中薄化該石墨層150的困難。Referring to FIGS. 1 and 4, in the step of "catalyzing graphitization step 13", a metal catalyst 300 is coated on the carbon layer 140 and the carbon layer 140 is heated to graphitize the carbon layer 140 into a graphite layer 150. The graphite layer 150 has a first thickness D1, and the graphite layer 150 covers the first channels 130, and the metal catalyst 300 is volatilized with heating. The metal catalyst 300 may be selected from iron salts, nickel salts or The copper salt, by which the temperature of the carbon layer 140 can be greatly reduced from 2000 ° C to 3000 ° C required for general graphitization to between 800 ° C and 1400 ° C, in this embodiment. If the temperature of the carbon layer 140 is lower than 800 ° C, the energy of graphitization is insufficient, and the effect of graphitizing the carbon layer 140 is not good, so that the carbon layer 140 cannot be completely graphitized into the graphite layer 150. Since the temperature of the carbon layer 140 is between 800 ° C and 1400 ° C, the carbon layer 140 can be completely graphitized into the graphite layer 150. Therefore, if the temperature of the carbon layer 140 is heated to be higher than 1400 ° C, Causing waste of energy and losing the original intention of catalytic graphitization. In addition, Low price high temperature furnace at a temperature of 1400 ℃ below, can reduce the cost of production. Preferably, the weight percentage of the metal catalyst 300 is between 0.1 wt% and 5 wt%, and if the weight percentage of the metal catalyst 300 is less than 0.1 wt%, the catalytic effect is not good, and the heating temperature needs to be increased, if If the weight percentage of the metal catalyst 300 is more than 5% by weight, the metal of the metal catalyst 300 may remain in the graphite layer 150, and the surface of the graphite layer 150 may be uneven, and the subsequent "liquid phase stripping step 15 may be increased. The difficulty of thinning the graphite layer 150.
請參閱第1及5圖，於「催化石墨化步驟13」的步驟後，若有上述之金屬催化劑殘留雜質、該石墨層150表面不平整，或是有該石墨層150過厚的情況，則需進行一酸氧化步驟14，將該覆蓋有該石墨層150之多孔洞基材100置入一反應槽600中，以一強酸700對該石墨層150進行酸氧化修飾，以去除該石墨層150之雜質使該石墨層150平整，並可初步薄化該石墨層150，其中該強酸700選自於硝酸、鹽酸或硫酸，而其中硝酸之純度介於40%至70%之間，鹽酸之純度介於20%至50%之間，硫酸純度介於70%至98%之間，若該強酸700之純度過低則酸氧化修飾效果不佳，但若該強酸700之純度過高則氧化速率過快，而無法控制酸氧化修飾的時間，較佳地，本發明以加熱迴流進行酸氧化處理，以一冷凝管(圖未繪出)進行迴流，該強酸700於加熱揮發後，該強酸700之蒸氣分子在該冷凝管中冷凝後，滴落回該反應槽600中，可保持反應系統的溫度及穩定所設定之反應條件，請參閱第6圖，該酸氧化步驟14完成後，可得到表面平整之該石墨層150覆蓋於該多孔洞基材100上，以使後續「液相剝離步驟15」可順利薄化該石墨層150。Referring to FIGS. 1 and 5, after the step of "catalyzing graphitization step 13", if the metal catalyst remains as described above, the surface of the graphite layer 150 is not flat, or the graphite layer 150 is too thick, An acid oxidation step 14 is performed, and the porous hole substrate 100 covered with the graphite layer 150 is placed in a reaction tank 600, and the graphite layer 150 is acid-oxidized with a strong acid 700 to remove the graphite layer 150. The graphite layer 150 is flattened by impurities, and the graphite layer 150 is initially thinned, wherein the strong acid 700 is selected from nitric acid, hydrochloric acid or sulfuric acid, and the purity of the nitric acid is between 40% and 70%, and the purity of the hydrochloric acid is Between 20% and 50%, the purity of sulfuric acid is between 70% and 98%. If the purity of the strong acid 700 is too low, the acid oxidation modification effect is not good, but if the purity of the strong acid 700 is too high, the oxidation rate is Too fast, and the time for the acid oxidation modification cannot be controlled. Preferably, the present invention is subjected to an acid oxidation treatment by heating under reflux, and is refluxed by a condensation tube (not shown). After the strong acid 700 is volatilized by heating, the strong acid 700 is heated. After the vapor molecules are condensed in the condenser, they fall back In the reaction tank 600, the temperature of the reaction system can be maintained and the set reaction conditions can be stabilized. Referring to FIG. 6, after the acid oxidation step 14 is completed, the graphite layer 150 having a smooth surface is covered on the porous hole substrate 100. The graphite layer 150 can be smoothly thinned in the subsequent "liquid phase stripping step 15".
請參閱第1、7及8圖，於「液相剝離步驟15」的步驟中，將該多孔洞基材100置入一容置有一剝離劑400之超音波水浴震盪器500中進行超音波震盪，以液體震盪方式使該石墨層150薄化為一石墨烯層160，該石墨烯層160覆蓋該些第一通道130，該石墨烯層160具有一第二厚度D2，且該石墨烯層160的該第二厚度D2小於該石墨層150之該第一厚度D1，在本實施例中，該剝離劑400為極性非質子傳遞溶劑【N-甲基吡咯烷酮 (N-Methyl-2-pyrrolidone, NMP)】，或在其他實施例中，該剝離劑400為離子液體【1-butyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide([Bmim][Tf2N])】，藉由該剝離劑400及該超音波水浴震盪器500之物理作用可使該石墨層150薄化為數十層以下之石墨烯層160，請參閱第8及9圖，該石墨烯層160具有複數個第二通道161及一顯露面162，該些第二通道161連通各該第一通道130及該顯露面162，且該石墨烯層160之各該第二通道161的寬度介於0.7埃(A)至10埃(A)之間，由於該石墨烯層160之各該第二通道161小於該多孔洞基材100之各該第一通道130，且該多孔洞基材100之該第一通道130連通該石墨烯層160之該第二通道161，使得形成有大面積之該石墨烯層160的該多孔洞基材100可運用於氣體分離、固液分離、溶液之小分子去除、海水淡化或飲用水淨化等過濾、分離或吸附程序，進而提升過濾或分離的效果。Referring to Figures 1, 7 and 8, in the step of "liquid phase stripping step 15", the porous hole substrate 100 is placed in an ultrasonic water bath oscillator 500 containing a stripper 400 for ultrasonic vibration. The graphite layer 150 is thinned into a graphene layer 160 by a liquid oscillating manner, and the graphene layer 160 covers the first channels 130, the graphene layer 160 has a second thickness D2, and the graphene layer 160 The second thickness D2 is smaller than the first thickness D1 of the graphite layer 150. In the embodiment, the stripper 400 is a polar aprotic solvent [N-Methyl-2-pyrrolidone (NMP). Or, in other embodiments, the stripper 400 is an ionic liquid [1-butyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide ([Bmim][Tf2N])], by the stripping agent 400 and the The physical action of the ultrasonic water bath oscillator 500 can thin the graphite layer 150 into a graphene layer 160 of several tens or less layers. Referring to FIGS. 8 and 9, the graphene layer 160 has a plurality of second channels 161 and a The second channel 161 is connected to each of the first channel 130 and the exposed surface 162, and Each of the second channels 161 of the graphene layer 160 has a width of between 0.7 angstroms (A) and 10 angstroms (A), and each of the second channels 161 of the graphene layer 160 is smaller than the porous channel substrate 100. Each of the first channels 130, and the first channel 130 of the porous hole substrate 100 communicates with the second channel 161 of the graphene layer 160, so that the porous hole substrate having the large area of the graphene layer 160 is formed. 100 can be used for filtration, separation or adsorption procedures such as gas separation, solid-liquid separation, small molecule removal of solution, seawater desalination or drinking water purification, thereby improving filtration or separation.
本發明藉由該化學氣相沉積步驟12、該催化石墨化步驟13及該液相剝離步驟15直接於該多孔洞基材100形成該石墨烯層160，因此，可在該多孔洞基材100上形成完整且大面積之該石墨烯層160，藉由該多孔洞基材100之該第一通道130與該石墨烯層160之該第二通道161相連通，使得形成有大面積之該石墨烯層160的該多孔洞基材100可運用於氣體分離、固液分離、溶液之小分子去除、海水淡化或飲用水淨化等過濾、分離或吸附程序，進而提升過濾或分離的效果。The present invention forms the graphene layer 160 directly on the porous hole substrate 100 by the chemical vapor deposition step 12, the catalytic graphitization step 13 and the liquid phase stripping step 15, and thus, the porous hole substrate 100 can be Forming a complete and large area of the graphene layer 160, the first channel 130 of the porous hole substrate 100 is in communication with the second channel 161 of the graphene layer 160, so that a large area of the graphite is formed. The porous hole substrate 100 of the olefin layer 160 can be used for filtration, separation or adsorption processes of gas separation, solid-liquid separation, small molecule removal of a solution, seawater desalination or drinking water purification, thereby improving filtration or separation.
本發明之保護範圍當視後附之申請專利範圍所界定者為準，任何熟知此項技藝者，在不脫離本發明之精神和範圍內所作之任何變化與修改，均屬於本發明之保護範圍。The scope of the present invention is defined by the scope of the appended claims, and any changes and modifications made by those skilled in the art without departing from the spirit and scope of the invention are within the scope of the present invention. .
10．．．以化學氣相沉積程序於多孔洞基材形成大面積石墨烯層之方法10. . . Method for forming large-area graphene layer on porous substrate by chemical vapor deposition process
11．．．提供一多孔洞基材11. . . Providing a porous hole substrate
12．．．化學氣相沉積步驟12. . . Chemical vapor deposition step
13．．．催化石墨化步驟13. . . Catalytic graphitization step
14．．．酸氧化步驟14. . . Acid oxidation step
15．．．液相剝離步驟15. . . Liquid phase stripping step
100．．．多孔洞基材100. . . Porous hole substrate
110．．．第一表面110. . . First surface
120．．．第二表面120. . . Second surface
130．．．第一通道130. . . First channel
140．．．碳層140. . . Carbon layer
150．．．石墨層150. . . Graphite layer
160．．．石墨烯層160. . . Graphene layer
161．．．第二通道161. . . Second channel
162．．．顯露面162. . . Revealed face
200．．．碳源氣體200. . . Carbon source gas
300．．．金屬催化劑300. . . Metal catalyst
400．．．剝離劑400. . . Stripper
500．．．超音波水浴震盪器500. . . Ultrasonic water bath oscillator
600．．．反應槽600. . . Reaction tank
700．．．強酸700. . . strong acid
D1．．．第一厚度D1. . . First thickness
D2．．．第二厚度D2. . . Second thickness
第1圖：依據本發明之一實施例，一種以化學氣相沉積程序於多孔洞基材形成大面積石墨烯層之方法的流程方塊圖。第2圖：依據本發明之一實施例，一多孔洞基材之側面剖視圖。第3圖：依據本發明之一實施例，該多孔洞基材及一碳層之側面剖視圖。第4圖：依據本發明之一實施例，該多孔洞基材及一石墨層之側面剖視圖。第5圖：依據本發明之一實施例，一酸氧化步驟之示意圖。第6圖：依據本發明之一實施例，該多孔洞基材及該石墨層之側面剖視圖。第7圖：依據本發明之一實施例，一液相剝離步驟之示意圖。第8圖：依據本發明之一實施例，該多孔洞基材及一石墨烯層之側面剖視圖。第9圖：依據本發明之一實施例，該多孔洞基材及一石墨烯層之局部上視圖。1 is a flow block diagram of a method of forming a large-area graphene layer on a porous cavity substrate by a chemical vapor deposition process in accordance with an embodiment of the present invention. 2 is a side cross-sectional view of a porous hole substrate in accordance with an embodiment of the present invention. Figure 3 is a side cross-sectional view of the porous hole substrate and a carbon layer in accordance with an embodiment of the present invention. Figure 4 is a side cross-sectional view of the porous hole substrate and a graphite layer in accordance with an embodiment of the present invention. Figure 5: Schematic representation of an acid oxidation step in accordance with one embodiment of the present invention. Figure 6 is a side cross-sectional view of the porous hole substrate and the graphite layer in accordance with an embodiment of the present invention. Figure 7 is a schematic illustration of a liquid phase stripping step in accordance with one embodiment of the present invention. Figure 8 is a side cross-sectional view of the porous hole substrate and a graphene layer in accordance with an embodiment of the present invention. Figure 9 is a partial top plan view of the porous hole substrate and a graphene layer in accordance with an embodiment of the present invention.
10．．．以化學氣相沉積程序於多孔洞基材形成大面積石墨烯層之方法10. . . Method for forming large-area graphene layer on porous substrate by chemical vapor deposition process
11．．．提供一多孔洞基材11. . . Providing a porous hole substrate
12．．．化學氣相沉積步驟12. . . Chemical vapor deposition step
13．．．催化石墨化步驟13. . . Catalytic graphitization step
14．．．酸氧化步驟14. . . Acid oxidation step
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| WO2017212039A1 (en) | 2016-06-10 | 2017-12-14 | Eth Zurich | Method for making porous graphene membranes and membranes produced using the method |
| US11518142B2 (en) | 2016-06-10 | 2022-12-06 | Eth Zurich | Method for making porous graphene membranes and membranes produced using the method |
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