电子束退火法制备Li-N共掺杂多晶ZnO薄膜
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摘要
为研究电子束退火对Li-N共掺杂Zn O薄膜性能的影响,首先利用溶胶-凝胶旋涂法在p型Si(111)衬底上制备Li-N共掺杂的Zn O前驱膜,然后用电子束对前驱膜进行退火。退火时,电子束加速电压10 k V,退火时间5 min,聚焦束流123 m A,束流为0.7~1.9 m A,最后得到Li-N共掺杂的Zn O薄膜。XRD谱分析表明,当束流高于1.5 m A之后,薄膜为六方Zn O和立方Zn O的混合多晶薄膜,且有金属Zn生成,导致薄膜有较强的绿光发射。SEM图片分析显示,薄膜的晶粒尺寸随束流增加而增大,当束流高于1.5 m A后,晶粒尺寸变化不大,约为60 nm。光致发光(PL)谱和激光拉曼谱的分析结果证实Li、N元素已掺入Zn O晶格中,PL谱中观察到Li元素掺杂引起的紫光发射,拉曼散射光谱中观察到N替代O位的缺陷振动模式。
In order to study the performance of Li-N dual-doped Zn O thin film prepared by electron beam annealing technology,the Li-N dual-doped Zn O precursor films were prepared by sol-gel spinning method and annealed by electron beam. The accelerating voltage,focus beam current and annealing duration were fixed at 10 k V,123 m A and 5 min,respectively. The electron beam current was within the range from 0. 7 m A to 1. 9 m A. Finally,the Li-N dual-doped Zn O films were obtained. When the electron beam current is more than 1. 5 m A,the result of X-ray diffraction shows that the samples are a compound polycrystalline films of hexagonal Zn O and cubic Zn O,and the metal Zn generates in the films which contributes to the green light emission. SEM pictures show that the grain size increases with the electron beam current. There is not much change in grain size when the electron beam current is more than 1. 5 m A and it is about 60 nm. The analysis of photoluminescence( PL) and Raman spectra show that Li and N have doped in the Zn O lattice. The doped Li contributes to the purple light emission in the PL spectra and the vibration mode related to the doped N replacing O is observed in Raman scattering spectra.
In order to study the performance of Li-N dual-doped Zn O thin film prepared by electron beam annealing technology,the Li-N dual-doped Zn O precursor films were prepared by sol-gel spinning method and annealed by electron beam. The accelerating voltage,focus beam current and annealing duration were fixed at 10 k V,123 m A and 5 min,respectively. The electron beam current was within the range from 0. 7 m A to 1. 9 m A. Finally,the Li-N dual-doped Zn O films were obtained. When the electron beam current is more than 1. 5 m A,the result of X-ray diffraction shows that the samples are a compound polycrystalline films of hexagonal Zn O and cubic Zn O,and the metal Zn generates in the films which contributes to the green light emission. SEM pictures show that the grain size increases with the electron beam current. There is not much change in grain size when the electron beam current is more than 1. 5 m A and it is about 60 nm. The analysis of photoluminescence( PL) and Raman spectra show that Li and N have doped in the Zn O lattice. The doped Li contributes to the purple light emission in the PL spectra and the vibration mode related to the doped N replacing O is observed in Raman scattering spectra.
引文
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[2]MSEDDI S,TEKELI F,NJEH A,et al..Effect of initial stress on the propagation behavior of SAW in a layered piezoelectric structure of Zn O/Al2O3[J].Mech.Res.Commun.,2016,76:24-31.
[3]罗景庭,钟鑫,朱茂东,等.Zn O薄膜生长及声表面波性能研究[J].深圳大学学报理工版,2015,32(1):17-24.LUO J T,ZHONG X,ZHU M D,et al..Growth of Zn O thin film and its surface acoustic wave properties[J].J.Shenzhen Univ.Sci.Eng.,2015,32(1):17-24.(in Chinese)
[4]PALIWAL A,SHARMA A,TOMAR M,et al..Carbon monoxide(CO)optical gas sensor based on Zn O thin films[J].Sens.Actuators B:Chem.,2017,250:679-685.
[5]VITHOBA L.PATIL,SHARADRAO A,et al..Fabrication of nanostructured Zn O thin films based NO2gas sensor via SILAR technique[J].Sens.Actuators B:Chem.,2017,239:1185-1193.
[6]SHARMA V,KUMAR P,KUMAR A,et al..High-performance radiation stable Zn O/Ag/Zn O multilayer transparent conductive electrode[J].Solar Energy Mater.Solar Cells,2017,169:122-131.
[7]ZHOU J,WU X Z,XIAO D B,et al..Deposition of aluminum doped Zn O as electrode for transparent Zn O/glass surface acoustic wave devices[J].Surf.Coatings Technol.,2017,320:39-46.
[8]余长林,杨凯,余济美,等.稀土Ce掺杂对Zn O结构和光催化性能的影响[J].物理化学学报,2011,27(2):505-512.YU C L,YANG K,YU J M,et al..Effects of rare earth Ce doping on the structure and photocatalytic performance of Zn O[J].Acta Phys.Chim.Sinica,2011,27(2):505-512.(in Chinese)
[9]ANDRADE G R S,NASCIMENTO C C,LIMA Z M,et al..Star-shaped Zn O/Ag hybrid nanostructures for enhanced photocatalysis and antibacterial activity[J].Appl.Surf.Sci.,2017,399:573-582.
[10]MBAMARA U S,OLOFINJANA B,AJAYI O O,et al..Friction and wear behavior of nitrogen-doped Zn O thin films deposited via MOCVD under dry contact[J].Eng.Sci.Technol.,2016,19(2):956-963.
[11]KRMER A,ENGEL S,SANGIORGI N,et al..Zn O thin films on single carbon fibres fabricated by pulsed laser deposition(PLD)[J].Appl.Surf.Sci.,2017,399:282-287.
[12]YING M J,CHENG W,WANG X X,et al..Surface-polarity-dependent ferromagnetism in arsenic-implanted Zn O films prepared by MBE[J].Mater.Lett.,2015,144:12-14.
[13]STEFAN M,GHICA D,NISTOR S V,et al..Mn2+ions distribution in doped sol-gel deposited Zn O films[J].Appl.Surf.Sci.,2017,396:1880-1889.
[14]KIM S,KIM C H,JEONG C H,et al..Effect of energetic electron beam treatment on Ga-doped Zn O thin films[J].Cur.Appl.Phys.,2014,14(6):862-867.
[15]PARK C H,KIM S,KIM C H,et al..Effect of energetic electron beam treatment on transparent conductive Zn O thin films[J].Thin Solid Films,2013,548:263-269.
[16]MINEMOTO T,NEGAMI T,NISHIWAKI S,et al..Preparation of Zn1-xMgxO films by radio frequency magnetron sputtering[J].Thin Solid Films,2000,372(1-2):173-176.
[17]HE G H,ZHOU B H,SHEN H,et al..Photodetectors for weak-signal detection fabricated from Zn O∶(Li,N)films[J].Appl.Surf.Sci.,2017,412:554-558.
[18]ZHANG Y Z,LU J G,YE Z Z,et al..Effects of growth temperature on Li-N dual-doped p-type Zn O thin films prepared by pulsed laser deposition[J].Appl.Surf.Sci.,2008,254(7):1993-1996.
[19]王德义,高书霞,李刚,等.溶胶-凝胶法制备Li-N双掺p型Zn O薄膜的结构、光学和电学性能[J].物理化学学报,2010,59(5):3473-3480.WANG D Y,GAO S X,LI G,et al..The structure,optical and electrical properties of Li-N dual-acceptor doped p-type Zn O thin films prepared by sol-gel method[J].Acta Phys.-Chim.Sinica,2010,59(5):3473-3480.(in Chinese)
[20]ZHOU D Z,LI B,WANG H L,et al..Fabrication and electrical characterization of Li-N dual doped Zn O thin film transistor[J].Appl.Surf.Sci.,2014,305:474-476.
[21]TIAN L J,ZHOU D Z,MA Y B,et al..Effects of annealing temperature on the electrical characteristics of Li-N co-doped polycrystalline Zn O thin film transistors[J].Superlatt.Microstruct.,2017.(in Press)
[22]詹华瀚,黄斌旺,吴雅苹,等.Si(001)衬底上闪锌矿Zn O的制备与分析[J].发光学报,2010,31(2):209-213.ZHAN H H,HUANG B W,WU Y P,et al..Growth and investigation of zinc blende Zn O on Si(001)[J].Chin.J.Lumin.,2010,31(2):209-213.(in Chinese)
[23]余超,丘克强,陈启元.真空硅热还原氧化锌的热力学分析[J].物理化学学报,2011,27(6):1312-1318.YU C,QIU K Q,CHEN Q Y.Thermodynamic analysis of silicothermic reduction zinc oxide in vacuum[J].Acta Phys.Chim.Sinica,2011,27(6):1312-1318.(in Chinese)
[24]CAGLAR M,RUZGAR S.Influence of the deposition temperature on the physical properties of high electron mobility Zn O films by sol-gel process[J].J.Alloys Compd.,2015,644:101-105.
[25]NAKAGAWA T,SAKAGUCHI I,MATSUNAGA K,et al..Control of point defects and grain boundaries in advanced materials:optical properties and diffusion induced by Li doping in Zn O[J].Nuc.Instrum.Methods Phys.Res.B,2005,232:343-347.
[26]HUR T,JEEN G S,HWANG Y,et al..Photoluminescence of polycrystalline Zn O under different annealing conditions[J].J.Appl.Phys.,2003,4(9):5787-5790.
[27]林碧霞,傅竹西,廖桂红.氧化锌薄膜Zn/O比和发光性能的关系[J].发光学报,2005,26(2):225-228.LIN B X,FU ZH X,LIAO G H.Effect of Zn/O on photolum inescence of Zn O on Si[J].Chin.J.Lumin.,2005,26(2):225-228.(in Chinese)
[28]张晓松,李岚,王达健.热处理对Zn O∶Zn荧光薄膜结晶性能的影响[J].发光学报,2006,27(2):206-210.ZHANG X S,LI L,WANG D J.Crystal property of Zn O∶Zn thin film improved by post-deposition heat treatment[J].Chin.J.Lumin.,2006,27(2):206-210.(in Chinese)
[29]李万俊,孔春阳,秦国平,等.p型Zn O∶N薄膜的拉曼及光电特性研究[J].中国科学:物理学力学天文学,2012,42(8):819-826.LI W J,KONG CH Y,QIN G P,et al..The investigation on Raman,optical and electrical properties of p-type Zn O∶N film[J].Sci.Sinica Phys.,Mech.Astronom.,2012,42(8):819-826.(in Chinese)
[30]ASMAR R A,ATANAS J P,AJAKA M,et al..Characterization and Raman investigations on high-quality Zn O thin filmsfabricated by reactive electron beam evaporation[J].J.Cryst.Growth,2005,279(3):394-402.
[31]KASCHNER A,HABOECK U,STRASSBURG M,et al..Nitrogen-related local vibrational modes in Zn O∶N[J].Appl.Phys.Lett.,2002,80(11):1909-1911.
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