n-Si,believed as a promising photoanode candidate,has suffered from sluggish oxygen evolution reaction(OER)kinetics and poor chemical stability when exposed to aqueous electrolyte.Herein,CoO_(x)/Ni:CoOOH bilayers were...n-Si,believed as a promising photoanode candidate,has suffered from sluggish oxygen evolution reaction(OER)kinetics and poor chemical stability when exposed to aqueous electrolyte.Herein,CoO_(x)/Ni:CoOOH bilayers were successfully deposited on n-Si substrate by atomic layer-deposition(ALD)and photoassisted electrochemical deposition(PED)for stabilizing and catalyzing photoelectrochemical(PEC)water oxidation.In comparison to the n-Si/CoO_(x)photoanode as reference,the prepared n-Si/CoO_(x)/Ni:CoOOH photoanode upon the optimized PED process presents a much improved PEC performance for water splitting,with the onset potential cathodically shifted to~1.03 V vs.reversible hydrogen electrode(RHE)and the photocurrent density much increased to 20 mA cm^(−2)at 1.23 V vs.RHE.It is revealed that the introduction of Ni dopants increases the work functions of the deposited Ni:CoOOH overlayers,which gives rise to the upward band bending weakened at the n-Si/CoO_(x)/Ni:CoOOH cascading interface while strengthened at the Ni:CoOOH/electrolyte interface(with the band bending shifted from downward to upward),contributing to the decreased and the increased driving forces for charge transfer at the interfaces,respectively.Then,the balanced driving forces at the interfaces would endow the n-Si/CoO_(x)/Ni:CoOOH photoanode with the best PEC performance.Moreover,PED has been evidenced superior to ED to dope Ni into CoOOH with the formed overlayer effectively catalyzing and stabilizing PEC water splitting.展开更多
Large roughness and structure disorder in ferroelectric ultrathin Langmuir-Blodgett(LB)film results in severe space scatter in electrical,ferroelectric and piezoelectric characteristics,thus limiting the nanoscale res...Large roughness and structure disorder in ferroelectric ultrathin Langmuir-Blodgett(LB)film results in severe space scatter in electrical,ferroelectric and piezoelectric characteristics,thus limiting the nanoscale research and reliability of nano-devices.However,no effective method aiming at large-area uniform organic ferroelectric LB film has ever been reported to date.Herein,we present a facile hot-pressing strategy to prepare relatively large-area poly(vinylidene fluoride)(PVDF)LB film with ultra-smooth surface root mean square(RMS)roughness is 0.3 nm in a 30μm×30μm area comparable to that of metal substrate,which maximized the potential of LB technique to control thickness distribution.More importantly,compared with traditionally annealed LB film,the hot-pressed LB film manifests significantly improved structure uniformity,less fluctuation in ferroelectric characteristics and higher dielectric and piezoelectric responses,owing to the uniform dipole orientation and higher crystalline quality.Besides,different surface charge relaxation behaviors are investigated and the underlying mechanisms are explained in the light of the interplay of surface charge and polarization charge in the case of nanoscale non-uniform switching.We believe that our work not only presents a novel strategy to endow PVDF LB film with unprecedented reliability and improved performance as a competitive candidate for future ferroelectric tunnel junctions(FTJs)and nano electro mechanical systems(NEMS),but also reveals an attracting coupling effect between the surface potential distribution and nanoscale non-uniform switching behavior,which is crucial for the understanding of local transport characterization modulated by band structure,bit signal stability for data-storage application and the related surface charge research,such as charge gradient microscopy(CGM)based on the collection of surface charge on the biased ferroelectric domains.展开更多
基金supported by the National Key Research and Development Program of China (2018YFB1502003)the National Natural Science Foundation of China (21875183)+3 种基金the Natural Science Basic Research Program of Shaanxi Province (2019JCW-10)the National Program for the Support of Top-notch Young Professionalsthe Fundamental Research Funds for the Central UniversitiesThe Youth Innovation Team of Shaanxi Universities
文摘n-Si,believed as a promising photoanode candidate,has suffered from sluggish oxygen evolution reaction(OER)kinetics and poor chemical stability when exposed to aqueous electrolyte.Herein,CoO_(x)/Ni:CoOOH bilayers were successfully deposited on n-Si substrate by atomic layer-deposition(ALD)and photoassisted electrochemical deposition(PED)for stabilizing and catalyzing photoelectrochemical(PEC)water oxidation.In comparison to the n-Si/CoO_(x)photoanode as reference,the prepared n-Si/CoO_(x)/Ni:CoOOH photoanode upon the optimized PED process presents a much improved PEC performance for water splitting,with the onset potential cathodically shifted to~1.03 V vs.reversible hydrogen electrode(RHE)and the photocurrent density much increased to 20 mA cm^(−2)at 1.23 V vs.RHE.It is revealed that the introduction of Ni dopants increases the work functions of the deposited Ni:CoOOH overlayers,which gives rise to the upward band bending weakened at the n-Si/CoO_(x)/Ni:CoOOH cascading interface while strengthened at the Ni:CoOOH/electrolyte interface(with the band bending shifted from downward to upward),contributing to the decreased and the increased driving forces for charge transfer at the interfaces,respectively.Then,the balanced driving forces at the interfaces would endow the n-Si/CoO_(x)/Ni:CoOOH photoanode with the best PEC performance.Moreover,PED has been evidenced superior to ED to dope Ni into CoOOH with the formed overlayer effectively catalyzing and stabilizing PEC water splitting.
基金supported by the National Natural Science Foundation of China(51625202)the National Key Research&Development Program of China(2017YFB0701603)。
文摘Large roughness and structure disorder in ferroelectric ultrathin Langmuir-Blodgett(LB)film results in severe space scatter in electrical,ferroelectric and piezoelectric characteristics,thus limiting the nanoscale research and reliability of nano-devices.However,no effective method aiming at large-area uniform organic ferroelectric LB film has ever been reported to date.Herein,we present a facile hot-pressing strategy to prepare relatively large-area poly(vinylidene fluoride)(PVDF)LB film with ultra-smooth surface root mean square(RMS)roughness is 0.3 nm in a 30μm×30μm area comparable to that of metal substrate,which maximized the potential of LB technique to control thickness distribution.More importantly,compared with traditionally annealed LB film,the hot-pressed LB film manifests significantly improved structure uniformity,less fluctuation in ferroelectric characteristics and higher dielectric and piezoelectric responses,owing to the uniform dipole orientation and higher crystalline quality.Besides,different surface charge relaxation behaviors are investigated and the underlying mechanisms are explained in the light of the interplay of surface charge and polarization charge in the case of nanoscale non-uniform switching.We believe that our work not only presents a novel strategy to endow PVDF LB film with unprecedented reliability and improved performance as a competitive candidate for future ferroelectric tunnel junctions(FTJs)and nano electro mechanical systems(NEMS),but also reveals an attracting coupling effect between the surface potential distribution and nanoscale non-uniform switching behavior,which is crucial for the understanding of local transport characterization modulated by band structure,bit signal stability for data-storage application and the related surface charge research,such as charge gradient microscopy(CGM)based on the collection of surface charge on the biased ferroelectric domains.
