S与Hf/Ta/W掺杂锐钛矿相TiO_2电子结构和光学性质的第一性原理研究
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摘要
运用第一性原理密度泛函理论,计算了S单掺及S和过渡金属X(Hf、Ta、W)共掺锐钛矿相TiO_2后的电子结构和光学性质。计算结果表明,S单掺及S和X(Hf、Ta、W)共掺杂锐钛矿TiO_2后,带隙变窄,表明掺杂后的体系导电性能增强,其中Ta、W与S共掺后,费米能级穿过导带,表现出n型半导体特征;光学性质结果表明:掺杂后各体系的吸收光谱吸收带边均发生红移,S-Ta共掺和S-W共掺体系红移程度最大,并且在可见光区域出现吸收峰,S-W共掺体系的吸收峰最大,说明了该体系的光催化功能较强。各掺杂体系的反射率主峰均向低能方向移动,共掺移动幅度更大,且S-W共掺体系的反射系数在可见光区最大。各共掺体系的静态折射率依次增大,其中S-Hf共掺体系静态折射率在各体系中最小。
Using the first-principles density functional theory,electronic structure,and optical properties of X( Hf,Ta,W) and S doped Ti O2 systems were calculated. The results show that the band gap becomes narrower after S and X( Hf、Ta、W) doped in anatase Ti O2,in which the conductivity of Ta-S and W-S co-doped anatase Ti O2 are enhanced. With the Fermi level through the conduction band,the Ta-S and W-S co-doped anatase Ti O2 systems are N-type semiconductor. The results of optical properties show that the red-shift takes place in the absorption spectra of all systems after doping,there is the maximum degree of red-shift in the S-Ta co-doped and S-W co-doped systems,the absorption peaks are in the visible light region,and the absorption peaks in the S-W co-doped system is the largest peak which indicates that the system has a strong photocatalysis. The main peaks of the reflectivity of each doping system move toward low energy,the co-doping movement is greater,and the reflection coefficient of theS-W co-doped system is the largest in the visible region. The static refractive index of each co-doped system increases sequentially,and the static refractive index of the S-Hf co-doped system is the smallest in each system.
Using the first-principles density functional theory,electronic structure,and optical properties of X( Hf,Ta,W) and S doped Ti O2 systems were calculated. The results show that the band gap becomes narrower after S and X( Hf、Ta、W) doped in anatase Ti O2,in which the conductivity of Ta-S and W-S co-doped anatase Ti O2 are enhanced. With the Fermi level through the conduction band,the Ta-S and W-S co-doped anatase Ti O2 systems are N-type semiconductor. The results of optical properties show that the red-shift takes place in the absorption spectra of all systems after doping,there is the maximum degree of red-shift in the S-Ta co-doped and S-W co-doped systems,the absorption peaks are in the visible light region,and the absorption peaks in the S-W co-doped system is the largest peak which indicates that the system has a strong photocatalysis. The main peaks of the reflectivity of each doping system move toward low energy,the co-doping movement is greater,and the reflection coefficient of theS-W co-doped system is the largest in the visible region. The static refractive index of each co-doped system increases sequentially,and the static refractive index of the S-Hf co-doped system is the smallest in each system.
引文
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[22]Yang S Y,Yao L F,Chen H.A First-Principles Study on Electronic Properties of Ce/N Codoped Anatase Ti O2[J].Advanced Materials Research,2014,936:529-533.
[23]祝卓茂,卞宝安,史海峰.Effect of N and Fe co-doping on the electronic structure and optical properties of Ti O2from first-principles study[J].Journal of Semiconductors,2015,36(10):24-28.
[2]梁纪锋.掺杂锐钛矿Ti O2光学性质的第一性原理计算[D].兰州:兰州理工大学,2013,84-797.
[3]张航,马梅,彭彩云,等.稀土元素(Ce/Nd/Eu/Gd)与N共掺金红石相Ti O2的第一性原理研究[J].人工晶体学报,2017,46(2):344-351.
[4]彭丽萍,夏正才,杨昌权.金属和非金属共掺杂锐钛矿相Ti O2的第一性原理计算[J].物理学报,2012,61(12):127104-127104.
[5]曾中良.N掺杂金红石和锐钛矿的电子结构及其矿物谱学性质研究[D].北京:中国地质大学,2014.
[6]刘松翠,吕康乐,邓克俭,等.三种不同晶型二氧化钛的制备及光催化性能研究[J].影像科学与光化学,2008,38-147.
[7]Wu H C,Lin Y S,Lin S W,et al.Mechanisms of Visible Light Photocatalysis in N-Doped Anatase Ti O2with Oxygen Vacancies from GGA+U Calculations[J].International Journal of Photoenergy,2013.
[8]王渭华,冯庆.Cr-Mn掺杂锐钛矿相Ti O2的第一性原理研究[J].重庆师范大学学报自然科学版,2011,28(2):65-69.
[9]姚肖洁.锐钛矿型Ti O2晶体掺杂的第一性原理研究[D].大连:大连理工大学,2011.
[10]孙伟伟.掺杂纳米Ti O2的制备及掺杂理论的第一性原理研究[D].青岛:中国海洋大学,2011.
[11]万巍.掺杂锐钛矿相Ti O2的第一性原理计算[D].长沙:中南大学,2011.
[12]谢希德,陆栋.固体能带理论[M].复旦大学出版社,1998.
[13]刘强,程新路,李德华,等.Zr掺杂对锐钛矿型Ti O2电子结构和光学性质的影响[J].中国科学:物理学力学天文学,2001,41(1):66-70.
[14]刘芳,姜振益.第一性原理研究Eu-N共掺杂锐钛矿Ti O2光催化剂的电子和光学性质[J].物理学报,2013,62(19):165-169.
[15]张学军,柳清菊,邓曙光,等.Mn-N共掺杂对锐钛矿相Ti O2微观结构和性能的影响[J].物理学报,2011,60(8):561-570.
[16]赵冬秋.N掺杂锐钛矿Ti O2可见光催化活性的第一性原理研究[D].开封:河南大学,2011.
[17]殷春浩,朱姗姗,张永伟,李富强,赵强,刘海顺.掺杂铁系元素对Ti O2电子结构和光催化性能的影响[J].人工晶体学报,2011,40(3):662-667.
[18]付现凯,宫长伟,王家恒,焦俊荣,柴跃生.La,Ce共掺锐钛矿相Ti O2的电子结构及光学性质的第一性原理研究[J].人工晶体学报,2015,44(4):1114-1119.
[19]孙凌涛,郭朝中,伏春平,等.N,Cr共掺锐钛矿Ti O2电子结构和光学性质的第一性原理研究[J].功能材料,2015,46(23):23075-23079.
[20]方志平.第六周期过渡元素掺杂锐钛矿二氧化钛的电子结构及光学性能的第一性原理计算[D].伊宁:伊犁师范学院,2017.
[21]Sato K,Akai H,Maruyama Y,et al.Ab Initio Calculations of Electric Field Gradients Detected by Impurities on Ti O2,Al2O3,And Ca CO3[J].Hyperfine Interactions,1999,56:145.
[22]Yang S Y,Yao L F,Chen H.A First-Principles Study on Electronic Properties of Ce/N Codoped Anatase Ti O2[J].Advanced Materials Research,2014,936:529-533.
[23]祝卓茂,卞宝安,史海峰.Effect of N and Fe co-doping on the electronic structure and optical properties of Ti O2from first-principles study[J].Journal of Semiconductors,2015,36(10):24-28.