镉掺杂氧化亚铜薄膜的制备及其光电性能
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摘要
采用一步水热法制备镉掺杂的Cu_2O薄膜(Cd/Cu_2O),分别探讨了制备过程中CuSO_4浓度、NaOH浓度、反应时间、反应温度和CdSO_4浓度对Cu_2O和Cd/Cu_2O薄膜光电性能的影响。结果表明,当反应釜中CuSO_4浓度为0.114 2 mol/L、NaOH浓度为0.028 6 mol/L、反应时间为8 h、反应温度为90℃、CdSO_4浓度分别为0 mol/L和0.571 4μmol/L时,可在基底Cu片上分别获得光电压为0.366 7 V的Cu_2O样品和光电压为0.460 2 V的Cd/Cu_2O薄膜样品。紫外可见吸收光谱(UV-Vis)、X射线衍射(XRD)图谱、扫描电子显微镜(SEM)和能谱仪(EDS)表征结果显示,Cu_2O的禁带宽度为2.1 eV,而Cd/Cu_2O的禁带宽度最小达到1.8 eV;Cd/Cu_2O的择优生长面为(111)面,其衍射峰强度比Cu_2O明显增强; Cd/Cu_2O样品表面与Cu_2O对比变得光滑,粒径由Cu_2O的1.0～3.0μm减小到Cd/Cu_2O的0.3～0.9μm。
Cu_2O thin films were prepared by the one-step hydrothermal method.The effects of reaction conditions,such as the concentration of CuSO_4(cCuSO_4),concentration of NaOH(cNaOH),reaction time,reaction temperature and concentration of CdSO_4 on the photoelectric properties of the Cu_2O and Cd/Cu_2O thin films were discussed.The results show that when the copper sheet is inserted into the reactor and placed in the oven at 90 ℃ for 8 h,cCuSO_4 in the reactor is 0.114 2 mol/L,cNaOHis 0.028 6 mol/L,the concentration of CdSO_4 is 0 mol/L or 0.571 4 μmol/L,the Cu_2O thin films with the highest photovoltage of 0.366 7 V and the Cd/Cu_2O thin films with the highest photovoltage of 0.460 2 V are obtained respectively.The characterization results of the Ultraviolet-visible spectroscopy(UV-Vis),X-ray diffraction(XRD) spectrum,energy dispersive spectrometer(EDS) and scanning electron microscope(SEM) indicate that the bandgap of Cu_2O is 2.1 eV,while that of Cd/Cu_2O is at least 1.8 eV.The preferred growth surface of Cd/Cu_2O is(111) plane,and its diffraction peak intensity is obviously stronger than that of Cu_2O.The surface of Cd/Cu_2O sample is smoother than that of Cu_2O,and the particle size is reduced from 1.0-3.0 μm for Cu_2O to 0.3-0.9 μm for Cd/Cu_2O.
Cu_2O thin films were prepared by the one-step hydrothermal method.The effects of reaction conditions,such as the concentration of CuSO_4(cCuSO_4),concentration of NaOH(cNaOH),reaction time,reaction temperature and concentration of CdSO_4 on the photoelectric properties of the Cu_2O and Cd/Cu_2O thin films were discussed.The results show that when the copper sheet is inserted into the reactor and placed in the oven at 90 ℃ for 8 h,cCuSO_4 in the reactor is 0.114 2 mol/L,cNaOHis 0.028 6 mol/L,the concentration of CdSO_4 is 0 mol/L or 0.571 4 μmol/L,the Cu_2O thin films with the highest photovoltage of 0.366 7 V and the Cd/Cu_2O thin films with the highest photovoltage of 0.460 2 V are obtained respectively.The characterization results of the Ultraviolet-visible spectroscopy(UV-Vis),X-ray diffraction(XRD) spectrum,energy dispersive spectrometer(EDS) and scanning electron microscope(SEM) indicate that the bandgap of Cu_2O is 2.1 eV,while that of Cd/Cu_2O is at least 1.8 eV.The preferred growth surface of Cd/Cu_2O is(111) plane,and its diffraction peak intensity is obviously stronger than that of Cu_2O.The surface of Cd/Cu_2O sample is smoother than that of Cu_2O,and the particle size is reduced from 1.0-3.0 μm for Cu_2O to 0.3-0.9 μm for Cd/Cu_2O.
引文
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[3]NG C H B,FAN W Y.Shape evolution of Cu2O nanostructures via kinetic and thermodynamic controlled growth[J].Journal of Physical Chemistry B,2006,110(42):20801-20807.
[4]NISHI Y,MIYATA T,MINAMI T.Electrochemically deposited Cu2O thin films on thermally oxidized Cu2O sheets for solar cell applications[J].Solar Energy Materials&Solar Cells,2016,155:405-410.
[5]MUSSELMAN K P,WISNET A,IZA D C,et al.Strong efficiency improvements in ultra-low-cost inorganic nanowire solar cells[J].Advanced Materials,2010,22(35):E254-E258.
[6]CHEN L C.Review of preparation and optoelectronic characteristics of Cu2O-based solar cells with nanostructure[J].Materials Science in Semiconductor Processing,2013,16(5):1172-1185.
[7]HUANG L,PENG F,YU H,et al.Preparation of cuprous oxides with different sizes and their behaviors of adsorption,visible-light driven photocatalysis and photocorrosion[J].Solid State Sciences,2009,11(1):129-138.
[8]LI H L,LEI Y G,HUANG Y,et al.Photocatalytic reduction of carbon dioxide to methanol by Cu2O/Si C nanocrystallite under visible light irradiation[J].Journal of Natural Gas Chemistry,2011,20(2):145-150..
[9]RESENDE J,JIMNEZ C,NGUYEN N D,et al.Magnesium-doped cuprous oxide(Mg∶Cu2O)thin films as a transparent p-type semiconductor[J].Physica Status Solidi,2016,213(9):2296-2302.
[10]GEORGIEVA V,RISTOV M.Electrodeposited cuprous oxide on indium tin oxide for solar applications[J].Solar Energy Materials&Solar Cells,2002,73(1):67-73.
[11]SUN F,GUO Y P,SONG W B,et al.Morphological control of Cu2O micro-nanostructure film by electrodeposition[J].Journal of Crystal Growth,2007,304(2):425-429.
[12]LUO S L,LI Y,YANG L X,et al.Low-temperature,facile fabrication of ultrafine Cu2O networks by anodization on Ti O2nanotube arrays[J].Semiconductor Science&Technology,2012,27(10):105010-1-105010-7.
[13]WANG H M,LU Z F,LU D Z,et al.A surfactant-free solvothermal synthesis of Cu2O microcrystals and their photocatalytic activity[J].Water Science&Technology,2016,73(10):2379-2385.
[14]LI X S,COLOMBO L,RUOFF R.Synthesis of graphene films on copper foils by chemical vapor deposition[J].Advanced Materials,2016,28(29):6247-6252.
[15]MARTNEZ-RUIZ A,MORENO M G,TAKEUCHI N.First principles calculations of the electronic properties of bulk Cu2O,clean and doped with Ag,Ni,and Zn[J].Solid State Sciences,2003,5(2):291-295.
[16]李洪婧,马春雨,李帅,等.沉积温度对N掺杂Cu2O薄膜生长及光学特性的影响[J].功能材料,2011,42(10):1881-1885.LI H J,MA C Y,LI S,et al.Effects of deposition temperature on the growth behavior of and optical properties N-doped Cu2O films[J].Journal of Functional Materials,2011,42(10):1881-1885(in Chinese).
[17]LAI G Z,WU Y W,LIN L M,et al.Low resistivity of N-doped Cu2O thin films deposited by RF-magnetron sputtering[J].Applied Surface Science,2013,285:755-758.
[18]SHARMA D,UPADHYAY S,SATSANGI V R,et al.Ni-doped Cu2O thin films for solar-hydrogen generation:experiments and first-principles analysis[J].Advanced Science Letters,2016,22(4):780-784.
[19]HENG B J,XIAO T,TAO W,et al.Zn doping-induced shape evolution of microcrystals:the case of cuprous oxide[J].Crystal Growth&Design,2012,12(8):3998-4005.
[20]JAYATHILAKA K M D C,JAYASINGHE A M R,SUMANASEKARA G U,et al.Effect of chlorine doping on electrodeposited cuprous oxide thin films on Ti substrates[J].Physica Status Solidi(B),2015,252(6):1300-1305.
[21]JIANG Y Y,LI Y,WANG D Y,et al.Photovoltaic performance of an alternating cold-hot method deposited Cd Se thin films[J].IET Micro&Nano Letters,2017,12(6):391-395.
[22]JIANG Y Y,LI Y,GAO Y P,et al.Photoelectric properties of Cu2O thin films prepared by room-temperature water bath[J].Materials Research Express,2017,4(3):036404-1-036404-10.
[23]CETIN A,OKUTAN M,ICELLI O,et al.Electrical and optical properties of chalcedony and striped chalcedony[J].Vacuum,2013,97:75-80.
[24]HOLZWARTH U,GIBSON N.The Scherrer equation versus the″Debye-Scherrer equation″[J].Nature Nanotechnology,2011,6(9):534.
[25]SONG X H,WANG M Q,SHI Y H,et al.In situ hydrothermal growth of Cd Se(S)nanocrystals on mesoporous Ti O2,films for quantum dot-sensitized solar cells[J].Electrochimica Acta,2012,81:260-267.