TiO_2纳米管刻蚀生长机理及其光电性能（英文）
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摘要
采用盐酸将有序排列的TiO_2纳米棒刻蚀成纳米管,并推测了生长机理。刻蚀过程中,凹陷沿棒生长方向自上而下由内而外产生,最终形成管式结构。大量纳米线围绕成具有方形空心截面的纳米管,高温下将完全分裂。TiO_2纳米管的光电转换效率远高于纳米棒,最高值(3.26%)出现在140℃刻蚀温度。纳米管比表面积增加和长度缩短分别对光电性能起到正反两方面作用。此外,煅烧导致纳米管断裂和聚集,光生载流子定向转移的难度增加,光电转换效率降低。
In this research,densely aligned TiO_2 nanorods are etched into nanotubes by hydrochloric acid,and the growth mechanism is also supposed. During the etching process,the dents appear from the top down and inside out along the growth direction of the nanorod,and finally form the tube structure. Actually,the nanotube with square hollow cross section consists of a mass of surrounded fine nanowires,which will be teared into independent ones at high temperature. When assembled into dye sensitized solar cells( DSSCs),the photoelectrical conversion efficiency of TiO_2 nanotubes is much higher than that of nanorods,and the highest value( 3. 26%) is located at the etching temperature of 140 ℃. It could be deduced that the increased specific surface area and length shortening of the nanotube play the positive and negative effect on the photoelectrical property,respectively. Furthermore,the calcination effect on the structure and photovoltaic property of TiO_2 nanotubes is also carried out. However,the fracture and aggregation of nanotubes could be observed after heating treatment,which therefore increase the difficulty of photo-induced carriers in directional transfer and also reduce the photoelectrical activity.
In this research,densely aligned TiO_2 nanorods are etched into nanotubes by hydrochloric acid,and the growth mechanism is also supposed. During the etching process,the dents appear from the top down and inside out along the growth direction of the nanorod,and finally form the tube structure. Actually,the nanotube with square hollow cross section consists of a mass of surrounded fine nanowires,which will be teared into independent ones at high temperature. When assembled into dye sensitized solar cells( DSSCs),the photoelectrical conversion efficiency of TiO_2 nanotubes is much higher than that of nanorods,and the highest value( 3. 26%) is located at the etching temperature of 140 ℃. It could be deduced that the increased specific surface area and length shortening of the nanotube play the positive and negative effect on the photoelectrical property,respectively. Furthermore,the calcination effect on the structure and photovoltaic property of TiO_2 nanotubes is also carried out. However,the fracture and aggregation of nanotubes could be observed after heating treatment,which therefore increase the difficulty of photo-induced carriers in directional transfer and also reduce the photoelectrical activity.
引文
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[2] YELLA A,LEE H W,TSAO H N,et al..Porphyrin-sensitized solar cells with cobalt (Ⅱ/Ⅲ)-based redox electrolyte exceed 12 percent efficiency [J].Science,2011,334(6056):629-634.
[3] XIN X K,HE M,HAN W,et al..Low-cost copper zinc tin sulfide counter electrodes for high-efficiency dye-sensitized solar cells [J].Angew.Chem.Int.Ed.Engl.,2011,50(49):11739-11742.
[4] 赵宇涵,李雪,关海艳,等.快速热退火处理ZnO电子传输层对聚合物太阳能电池性能的改善 [J].发光学报,2017,38(8):1063-1068.ZHAO Y H,LI X,GUAN H Y,et al..Enhanced performance of polymer solar cells using rapid thermal annealing treated ZnO electron transporting layer [J].Chin.J.Lumin.,2017,38(8):1063-1068.(in Chinese)
[5] KIM J H,KIM K P,KIM D H,et al..Electrospun ZnO nanofibers as a photoelectrode in dye-sensitized solar cells [J].J.Nanosci.Nanotechnol.,2015,15(3):2346-2350.
[6] CHEN L Y,YIN Y T.Hierarchically assembled ZnO nanoparticles on high diffusion coefficient ZnO nanowire arrays for high efficiency dye-sensitized solar cells [J].Nanoscale,2013,5(5):1777-1780.
[7] MANIKANDAN A,SARAVANAN A,ANTONY S A,et al..One-pot low temperature synthesis and characterization studies of nanocrystalline α-Fe2O3 based dye sensitized solar cells [J].J.Nanosci.Nanotechnol.,2015,15(6):4358-4366.
[8] ZHENG H D,TACHIBANA Y,KALANTAR-ZADEH K.Dye-sensitized solar cells based on WO3 [J].Langmuir,2010,26(24):19148-19152.
[9] 靳闪闪,禹益善,郝洪顺,等.SrSnO3∶Sm3+/TiO2复合光阳极的制备及其光电性能 [J].发光学报,2016,37(7):786-792.JIN S S,YU Y S,HAO H S,et al..Preparation and photoelectric performance of SrSnO3∶Sm3+/TiO2 composite photoanode [J].Chin.J.Lumin.,2016,37(7):786-792.(in Chinese)
[10] YANG H G,ZENG H C.Preparation of hollow anatase TiO2 nanospheres via Ostwald ripening [J].J.Phys.Chem.B,2004,108(11):3492-3495.
[11] 孙琼,孙先淼,李阳,等.具有阵列-簇双层结构的TiO2纳米棒的光电性能 [J].发光学报,2013,34(1):61-65.SUN Q,SUN X M,LI Y,et al..Photoelectrical properties of TiO2 nanorods with an array-cluster double-layered structure [J].Chin.J.Lumin.,2013,34(1):61-65.(in Chinese)
[12] SHANKAR K,MOR G K,PRAKASAM H E,et al..Highly-ordered TiO2 nanotube arrays up to 220 μm in length:use in water photoelectrolysis and dye-sensitized solar cells [J].Nanotechnology,2007,18(6):065707-1-11.
[13] WANG G M,WANG H Y,LING Y C,et al..Hydrogen-treated TiO2 nanowire arrays for photoelectrochemical water splitting [J].Nano Lett.,2011,11(7):3026-3033.
[14] CHEN J S,TAN Y L,LI C M,et al..Constructing hierarchical spheres from large ultrathin anatase TiO2 nanosheets with nearly 100% exposed (001) facets for fast reversible lithium storage [J].J.Am.Chem.Soc.,2010,132(17):6124-6130.
[15] WU Z B,DONG F,ZHAO W R,et al..The fabrication and characterization of novel carbon doped TiO2 nanotubes,nanowires and nanorods with high visible light photocatalytic activity [J].Nanotechnology,2009,20(23):235701-1-9.
[16] CAO C L,HU C G,WANG X,et al..UV sensor based on TiO2 nanorod arrays on FTO thin film [J].Sens.Actuators B Chem.,2011,156(1):114-119.
[17] DIEBOLD U.The surface science of titanium dioxide [J].Surf.Sci.Rep.,2003,48(5-8):53-229.
[18] BAREA E,XU X Q,GONZáLEZ-PEDRO V,et al..Origin of efficiency enhancement in Nb2O5 coated titanium dioxide nanorod based dye sensitized solar cells [J].Energy Environ.Sci.,2011,4(9):3414-3419.
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[24] WANG H,BAI Y S,WU Q,et al..Rutile TiO2 nano-branched arrays on FTO for dye-sensitized solar cells [J].Phys.Chem.Chem.Phys.,2011,13(15):7008-7013.
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[27] LIAO W P,HSU S C,LIN W H,et al..Hierarchical TiO2 nanostructured array/P3HT hybrid solar cells with interfacial modification [J].J.Phys.Chem.C,2012,116(30):15938-15945.
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[29] LV M Q,ZHENG D J,YE M D,et al..Densely aligned rutile TiO2 nanorod arrays with high surface area for efficient dye-sensitized solar cells [J].Nanoscale,2012,4(19):5872-5879.
[30] SUN X M,SUN Q,LI Y,et al..Effects of calcination treatment on the morphology,crystallinity,and photoelectric properties of all-solid-state dye-sensitized solar cells assembled by TiO2 nanorod arrays [J].Phys.Chem.Chem.Phys.,2013,15(42):18716-18720.
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[32] PAN H,QIAN J S,YU A,et al..TiO2 wedgy nanotubes array flims for photovoltaic enhancement [J].Appl.Surf.Sci.,2011,257(11):5059-5063.
[33] LI Y,SUN Q,MA S,et al..Synthesis of TiO2-SrTiO3 hetero-structured nanorod arrays and their photoelectrical performance in all-solid-state dye-sensitized solar cells [J].ECS J.Solid State Sci.,2015,4(3):Q17-Q20.
[34] SUN Q,SUN X M,LI Y,et al..Correlations between morphology and photoelectrical properties of single-crystal rutile TiO2 nanorods [J].Sci.Adv.Mater.,2013,5(9):1221-1230.