The transfer of graphene from metallic substrates onto application-specific substrates is usually inevitable for the applications of high-quality graphene films derived from chemical vapour deposition(CVD)approaches.C...The transfer of graphene from metallic substrates onto application-specific substrates is usually inevitable for the applications of high-quality graphene films derived from chemical vapour deposition(CVD)approaches.Commonly used to support the graphene films during the transfer,the coating of the polymer would produce the surface contaminations and hinder the industrially compatible transfer.In this work,through the thermal imidization of polyamide acid(PAA)to polyimide(PI)and tuning of the concentration of dangling chains,we achieved the ultraclean and crack-free transfer of graphene wafers with high electronic quality.The resulting contamination-free and hydrophilic surface also enabled the observed improved cell viability in a biomedical applications.By avoiding aqueous etching or the usage of strong bases,our proposed transfer method is industrially compatible for batch transfer of graphene films towards the real applications.展开更多
Vapor catalysis was recently found to play a crucial role in superclean graphene growth via chemical vapor decomposition(CVD).However,knowledge of vapor-phase catalysis is scarce,and several fundamental issues,includi...Vapor catalysis was recently found to play a crucial role in superclean graphene growth via chemical vapor decomposition(CVD).However,knowledge of vapor-phase catalysis is scarce,and several fundamental issues,including vapor compositions and their impact on graphene growth,are ambiguous.Here,by combining density functional theory(DFT)calculations,an ideal gas model,and a designed experiment,we found that the vapor was mainly composed of Cui clusters with tens of atoms.The vapor pressure was estimated to be~10^(-12)-10^(-1)1 bar under normal low-pressure CVD system(LPCVD)conditions for graphene growth,and the exposed surface area of Cui clusters in the vapor was 22-269 times that of the Cu substrate surface,highlighting the importance of vapor catalysis.DFT calculations show Cu clusters,represented by Cu17,have strong capabilities for adsorption,dehydrogenation,and decomposition of hydrocarbons.They exhibit an adsorption lifetime and reaction flux six orders of magnitude higher than those on the Cu surface,thus providing a sufficient supply of active C atoms for rapid graphene growth and improving the surface cleanliness of the synthesized graphene.Further experimental validation showed that increasing the amount of Cu vapor improved the as-synthesized graphene growth rate and surface cleanliness.This study provides a comprehensive understanding of vapor catalysis and the fundamental basis of vapor control for superclean graphene rapid growth.展开更多
Chemical vapor deposition(CVD)in conjunction with batch-to-batch manufacturing process is considered as the most promising technical route for mass-production of high-quality graphene films.To improve the space utiliz...Chemical vapor deposition(CVD)in conjunction with batch-to-batch manufacturing process is considered as the most promising technical route for mass-production of high-quality graphene films.To improve the space utilization of the CVD chamber and increase the throughput per batch,stacking of the Cu foil substrates is efficient,but suffers from the problems of adjacent fusion and the poor mass-transfer.Here,we demonstrate an efficient strategy for high-throughput and rapid growth of high-quality graphene by alternate stacking of Cu foils and porous carbon fiber paper(CFP).Relying on the unhindered mass-transfer through the pores of CFPs,full-covered high-quality graphene films on compact-stacked Cu foils were achieved within 2 min.Computational fluid dynamics(CFD)simulation and isotope labeling technique were performed to explore the gas diffusion and graphene growth process in the confined space of the Cu-CFP stacks.This work provides a feasible method for industrial production of graphene films,which may also be used for batch production of other two-dimensional materials.展开更多
Chemical vapor deposition(CVD)-grown graphene films on Cu foils,exhibiting fine scalability and high quality,are still suffering from the adverse impact of surface contamination,i.e.,amorphous carbon.Despite the recen...Chemical vapor deposition(CVD)-grown graphene films on Cu foils,exhibiting fine scalability and high quality,are still suffering from the adverse impact of surface contamination,i.e.,amorphous carbon.Despite the recent successful preparation of superclean graphene through Cu-vapor-assisted reactions,the formation mechanism of amorphous carbon remains unclear,especially with regard to the functions of substrates.Herein,we have found that the crystallographic orientations of underlying metal substrates would determine the cleanness of graphene in such a way that slower diffusion of active carbon species on asformed graphene-Cu(100)surface is the key factor that suppresses the formation of contamination.The facile synthesis of clean graphene is achieved on the meter-sized Cu(100)that is transformed from the polycrystalline Cu foils.Furthermore,a clean surface of graphene on Cu(100)ensures the reduction of transfer-related polymer residues,and enhanced optical and electrical performance,which allows for versatile applications of graphene in biosensors,functioning as flexible transparent electrodes.This work would offer a promising material platform for the fundamental investigation and create new opportunities for the advanced applications of high-quality graphene films.展开更多
Chemical vapor deposition(CVD)has emerged as a promising approach for the controlled growth of graphene films with appealing scalability,controllability,and uniformity.However,the synthesis of high-quality graphene fi...Chemical vapor deposition(CVD)has emerged as a promising approach for the controlled growth of graphene films with appealing scalability,controllability,and uniformity.However,the synthesis of high-quality graphene films still suffers from low production capacity and high energy consumption in the conventional hot-wall CVD system.In contrast,owing to the different heating mode,cold-wall CVD(CW-CVD)system exhibits promising potential for the industrial-scale production,but the quality of as-received graphene remains inferior with limited domain size and high defect density.Herein,we demonstrated an efficient method for the batch synthesis of high-quality graphene films with millimeter-sized domains based on CW-CVD system.With reduced defect density and improved properties,the as-received graphene was proven to be promising candidate material for electronics and anti-corrosion application.This study provides a new insight into the quality improvement of graphene derived from CW-CVD system,and paves a new avenue for the industrial production of high-quality graphene films for potential commercial applications.展开更多
基金supported by the National Natural Science Foundation of China(Nos.T2188101 and 52372038)the National Key Research and Development Program of China(No.2022YFA1204900)the China Postdoctoral Science Foundation(No.2023M740030).
文摘The transfer of graphene from metallic substrates onto application-specific substrates is usually inevitable for the applications of high-quality graphene films derived from chemical vapour deposition(CVD)approaches.Commonly used to support the graphene films during the transfer,the coating of the polymer would produce the surface contaminations and hinder the industrially compatible transfer.In this work,through the thermal imidization of polyamide acid(PAA)to polyimide(PI)and tuning of the concentration of dangling chains,we achieved the ultraclean and crack-free transfer of graphene wafers with high electronic quality.The resulting contamination-free and hydrophilic surface also enabled the observed improved cell viability in a biomedical applications.By avoiding aqueous etching or the usage of strong bases,our proposed transfer method is industrially compatible for batch transfer of graphene films towards the real applications.
基金supported by the National Natural Science Foundation of China(Nos.T2188101,52021006,52072042)the National Natural Science Foundation of China Youth Scientist Fund(Nos.22105006,52202033)+2 种基金Beijing National Laboratory for Molecular Science(No.BNLMS-CXTD-202001)the National Key R&D Program of China(Nos.2016YFA0200101,2016YFA0200103,2018YFA0703502)the Beijing Municipal Science&Technology Commission(Nos.Z191100000819005,Z191100000819007,Z201100008720005).
文摘Vapor catalysis was recently found to play a crucial role in superclean graphene growth via chemical vapor decomposition(CVD).However,knowledge of vapor-phase catalysis is scarce,and several fundamental issues,including vapor compositions and their impact on graphene growth,are ambiguous.Here,by combining density functional theory(DFT)calculations,an ideal gas model,and a designed experiment,we found that the vapor was mainly composed of Cui clusters with tens of atoms.The vapor pressure was estimated to be~10^(-12)-10^(-1)1 bar under normal low-pressure CVD system(LPCVD)conditions for graphene growth,and the exposed surface area of Cui clusters in the vapor was 22-269 times that of the Cu substrate surface,highlighting the importance of vapor catalysis.DFT calculations show Cu clusters,represented by Cu17,have strong capabilities for adsorption,dehydrogenation,and decomposition of hydrocarbons.They exhibit an adsorption lifetime and reaction flux six orders of magnitude higher than those on the Cu surface,thus providing a sufficient supply of active C atoms for rapid graphene growth and improving the surface cleanliness of the synthesized graphene.Further experimental validation showed that increasing the amount of Cu vapor improved the as-synthesized graphene growth rate and surface cleanliness.This study provides a comprehensive understanding of vapor catalysis and the fundamental basis of vapor control for superclean graphene rapid growth.
基金financially supported by the National Natural Science Foundation of China(Nos.T2188101 and 52021006)Beijing National Laboratory for Molecular Science(No.BNLMSCXTD-202001)+2 种基金the National Key Research and Development Program of China(Nos.2016YFA0200101,2016YFA0200103 and 2018YFA0703502)the Beijing Municipal Science&Technology Commission(Nos.Z191100000819005,Z191100000819007 and Z201100008720005)the support from Soochow University,Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province(No.KJS2122).
文摘Chemical vapor deposition(CVD)in conjunction with batch-to-batch manufacturing process is considered as the most promising technical route for mass-production of high-quality graphene films.To improve the space utilization of the CVD chamber and increase the throughput per batch,stacking of the Cu foil substrates is efficient,but suffers from the problems of adjacent fusion and the poor mass-transfer.Here,we demonstrate an efficient strategy for high-throughput and rapid growth of high-quality graphene by alternate stacking of Cu foils and porous carbon fiber paper(CFP).Relying on the unhindered mass-transfer through the pores of CFPs,full-covered high-quality graphene films on compact-stacked Cu foils were achieved within 2 min.Computational fluid dynamics(CFD)simulation and isotope labeling technique were performed to explore the gas diffusion and graphene growth process in the confined space of the Cu-CFP stacks.This work provides a feasible method for industrial production of graphene films,which may also be used for batch production of other two-dimensional materials.
基金The authors thank Beijing National Laboratory for Molecular ScienceThis work was supported by Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXTD-202001)+2 种基金This work was financially supported by the Beijing Municipal Science&Technology Commission(Nos.Z181100004818001 and Z201100008720005)the National Basic Research Program of China(No.2016YFA0200101)the National Natural Science Foundation of China(No.52072042).
文摘Chemical vapor deposition(CVD)-grown graphene films on Cu foils,exhibiting fine scalability and high quality,are still suffering from the adverse impact of surface contamination,i.e.,amorphous carbon.Despite the recent successful preparation of superclean graphene through Cu-vapor-assisted reactions,the formation mechanism of amorphous carbon remains unclear,especially with regard to the functions of substrates.Herein,we have found that the crystallographic orientations of underlying metal substrates would determine the cleanness of graphene in such a way that slower diffusion of active carbon species on asformed graphene-Cu(100)surface is the key factor that suppresses the formation of contamination.The facile synthesis of clean graphene is achieved on the meter-sized Cu(100)that is transformed from the polycrystalline Cu foils.Furthermore,a clean surface of graphene on Cu(100)ensures the reduction of transfer-related polymer residues,and enhanced optical and electrical performance,which allows for versatile applications of graphene in biosensors,functioning as flexible transparent electrodes.This work would offer a promising material platform for the fundamental investigation and create new opportunities for the advanced applications of high-quality graphene films.
基金financially supported by the National Natural Science Foundation of China(Nos.T2188101,21525310,and 52072042)the National Key R&D Program of China(No.2018YFA0703502)+1 种基金Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXTD-202001)Beijing Municipal Science&Technology Commission(Nos.Z181100004818001,Z18110300480001,Z18110300480002,Z191100000819005,Z191100000819007,and Z201100008720005)。
文摘Chemical vapor deposition(CVD)has emerged as a promising approach for the controlled growth of graphene films with appealing scalability,controllability,and uniformity.However,the synthesis of high-quality graphene films still suffers from low production capacity and high energy consumption in the conventional hot-wall CVD system.In contrast,owing to the different heating mode,cold-wall CVD(CW-CVD)system exhibits promising potential for the industrial-scale production,but the quality of as-received graphene remains inferior with limited domain size and high defect density.Herein,we demonstrated an efficient method for the batch synthesis of high-quality graphene films with millimeter-sized domains based on CW-CVD system.With reduced defect density and improved properties,the as-received graphene was proven to be promising candidate material for electronics and anti-corrosion application.This study provides a new insight into the quality improvement of graphene derived from CW-CVD system,and paves a new avenue for the industrial production of high-quality graphene films for potential commercial applications.