PEDOT：PSS聚合物的结构及电子特性的第一性原理计算
|
摘要
聚合物导电性的发现使导电聚合物成为了活跃的研究和应用领域,其中PEDOT/PSS(聚乙撑二氧噻吩／聚对苯乙烯磺酸)因为它的环境稳定性和高的电导率在近二十年受到了广泛关注,成为导电聚合物领域研究的热点之一。
PEDOT/PSS具有环境稳定性好,导电性好,容易成膜,透光性好,合成简单等一系列优点。这使其在抗静电剂,电化学器件,发光器件等领域有着很好的应用。
量子力学第一性原理(First-Principles)计算(即从头算)只采用5个基本物理常数：电子质量、电子电量、普郎克常数、光速和玻耳兹曼常数(m。、e、h、c、kB)来解薛定谔(Schrodinger)方程。
建立于R.Hohenberg和W.Kohn关于非均匀电子气理论基础上的密度泛函理论,在固体和分子电子结构和总能量计算中取得了很大的成功,成为多粒子体系能带理论研究的重要方法。
利用基于密度泛函理论第一性原理的VASP (Vienna Ab-initio Simulation Package)和基于含时密度泛函理论的octopus两大程序包,主要做了如下工作：
1、计算得到了本征PEDOT稳定的分子结构,掺杂氢离子后的分子结构以及掺入电子后的分子结构。
2、分析得出本征、掺杂氢离子以及掺入电子三种情况下的PEDOT分子的空间电荷密度。发现氧化掺杂(即掺入氢离子)使主链失去电子,形成正极化子；而掺入电子则会使主链形成负极化子。
3、分析得出了本征、掺杂氢离子以及掺入电子三种情况下的PEDOT分子的能级分布,发现掺杂后的分子能级出现了新的能级,称之为极化能级。
4、计算得出本征、掺杂氢离子以及掺入电子三种情况下的PEDOT分子吸收光谱图。
The discovery of conductivity of polymers have made conductive polymer become active research and applications field.In this field, PEDOT/PSS has been attracting interests in the past 20 years because of its good stability and high conductivity and PEDOT/PSS has become the hot spots in the field of conductive polymer.
PEDOT/PSS has a series of advantages such as good stability, high conductivity, easy filming, good transparency and easily synthesized. These advantages make PEDOT/PSS have a very good application in anti-static agent, electrochemical devices, optical devices and other fields.
The calculation of first principles is a method which is a way to solve the equations of Schrodinger and only five fundamental physical constants (electronics quality、electronic charge、Planck constant、the speed of light and Boltzmann) are used in this calculation process.
DFT(Density Functional Theory),based on the non-uniform electron gas theory established by R. Hohenberg and W. Kohn, gains great success on the calculation of molecular electronic structure and total energy and it becomes a important method of many-particle system energy band theory.
Based on VASP(Vienna Ab-initio Simulation Package) which is based on based on DFT(Density Functional Theory) and first principles and octopus which is based on TDDFT(time dependent density functional theory),some work has been done on this paper.
1、The molecular structure of the intrinsic、the hydrogen ion-doped and the electron-doped was calculated.
2、The space charge density about the intrinsic、the hydrogen ion-doped and the electron-doped was calculated. Positive polaron appears in the main chain of hydrogen ion-doped PEDOT and negative polaron appears in the electron-doped PEDOT.
3、The energy levels about the intrinsi、the hydrogen ion-doped and the electron-doped was calculated. Some new energy levels are found and they are polarization energy levels.
4、The absorption spectra about the intrinsic、the hydrogen ion-doped and the electron-doped PEDOT was calculated.
PEDOT/PSS具有环境稳定性好,导电性好,容易成膜,透光性好,合成简单等一系列优点。这使其在抗静电剂,电化学器件,发光器件等领域有着很好的应用。
量子力学第一性原理(First-Principles)计算(即从头算)只采用5个基本物理常数：电子质量、电子电量、普郎克常数、光速和玻耳兹曼常数(m。、e、h、c、kB)来解薛定谔(Schrodinger)方程。
建立于R.Hohenberg和W.Kohn关于非均匀电子气理论基础上的密度泛函理论,在固体和分子电子结构和总能量计算中取得了很大的成功,成为多粒子体系能带理论研究的重要方法。
利用基于密度泛函理论第一性原理的VASP (Vienna Ab-initio Simulation Package)和基于含时密度泛函理论的octopus两大程序包,主要做了如下工作：
1、计算得到了本征PEDOT稳定的分子结构,掺杂氢离子后的分子结构以及掺入电子后的分子结构。
2、分析得出本征、掺杂氢离子以及掺入电子三种情况下的PEDOT分子的空间电荷密度。发现氧化掺杂(即掺入氢离子)使主链失去电子,形成正极化子；而掺入电子则会使主链形成负极化子。
3、分析得出了本征、掺杂氢离子以及掺入电子三种情况下的PEDOT分子的能级分布,发现掺杂后的分子能级出现了新的能级,称之为极化能级。
4、计算得出本征、掺杂氢离子以及掺入电子三种情况下的PEDOT分子吸收光谱图。
The discovery of conductivity of polymers have made conductive polymer become active research and applications field.In this field, PEDOT/PSS has been attracting interests in the past 20 years because of its good stability and high conductivity and PEDOT/PSS has become the hot spots in the field of conductive polymer.
PEDOT/PSS has a series of advantages such as good stability, high conductivity, easy filming, good transparency and easily synthesized. These advantages make PEDOT/PSS have a very good application in anti-static agent, electrochemical devices, optical devices and other fields.
The calculation of first principles is a method which is a way to solve the equations of Schrodinger and only five fundamental physical constants (electronics quality、electronic charge、Planck constant、the speed of light and Boltzmann) are used in this calculation process.
DFT(Density Functional Theory),based on the non-uniform electron gas theory established by R. Hohenberg and W. Kohn, gains great success on the calculation of molecular electronic structure and total energy and it becomes a important method of many-particle system energy band theory.
Based on VASP(Vienna Ab-initio Simulation Package) which is based on based on DFT(Density Functional Theory) and first principles and octopus which is based on TDDFT(time dependent density functional theory),some work has been done on this paper.
1、The molecular structure of the intrinsic、the hydrogen ion-doped and the electron-doped was calculated.
2、The space charge density about the intrinsic、the hydrogen ion-doped and the electron-doped was calculated. Positive polaron appears in the main chain of hydrogen ion-doped PEDOT and negative polaron appears in the electron-doped PEDOT.
3、The energy levels about the intrinsi、the hydrogen ion-doped and the electron-doped was calculated. Some new energy levels are found and they are polarization energy levels.
4、The absorption spectra about the intrinsic、the hydrogen ion-doped and the electron-doped PEDOT was calculated.
引文
[1]L.Guo,S.Yang,C.Yang,P.J.Wang,W.Ge, and GK.L.Wong,Appl.Phys.Lett.76(2000)2901.
[2]C.L.Yang,J.N.Wang,W.K.Ge,L.Gun,S.H.Yang,and D.Z.Shell, J.Appl.Phys,90(2001)4489.
[3]杜续生,导电聚合物的合成及其性质的研究,2001年6月,第5-6页
[4]李玉真,许景坤,导电聚(3,4二氧乙基噻吩)应用研究进展,2007年3月,第25-27页
[5]K.E.Aasmundtveit,et al.Synth Met,1999,101:56
[6]MIAOXIANG CHEN,PROCEEDINGS OF THE IEEE,93 (2005) 1339
[7]Born M and Huang K Dynamical Theory of Crystal Lattices.Oxford:Oxford University Press,1954
[8]Hartree D.R.,Proc.Cam.PhiL.Soc.,1928,24,89.
[9]ock V z.,Phys.,1930,61,249.
[10]Hohenberg P. and Kohn w.,Phys.Rev.,1964,136,B864.
[11]Kohn W and Sham L.J., Phys.Rev,1965,140,A1133.
[12]Thomas H., Proc.Cam.PhiL.Soc.1927,23,542.
[13]Fermi E., Accad.Naz.Lincei,1927,6,602.
[14]Herring C., Phys.Rev.1940,57,119
[15]Herring C. and Hill A.G, Phys.Rev.1940,58,152.
[16]Hamann D.R., Schlllter M. and Chiang C., Phys.Rev.Lett,1979,43,1494.
[17]F.Bloch 1933 Z.Physik81 1561
[18]Runge E,Gross E.K.U.1984 Phys.Rev.Lett.52 997
[19]W.Kohn,L.J.Sham,1965 Phys.Rev.140 A1133
[20]W.P.Su J.R.Schrieffer and A.J.Heeger, Phys.Rev.Lett42,1698(1979); Phys.Rev.B22, 2099(1980)
[21]D.K.Campbell and A.R.Bishop, Phys.Rev.B24,4859(1981)
[22]K.Fesseret al. Phys.Rev.B27,4804(1983)
[23]Xie S J, Mei L M, Lin D L. Transition between bipolaron and polaron states in doped heterocycle polymers.Phys Rev B,1994,50:13364-13370
[24]孙鑫,低维凝聚态物理的进展(2),1986年3月,第25-33页
[25]戴兢陶,徐景坤,杨平,杜玉扣,江龙,导电高分子PEDOT/PSS保护银纳米颗粒的制备与表征,感光科学与光化学,第23卷第5期,2005年9月
[26]谢希德,陆栋,固体能带论(Energy Band Theory of Solids),复口.大学出版社
[27]黄昆原著,韩汝琦改编,固体物理学,高等教育出版社
[28]Lavanya M. Ramaniah Mauro Boero, Structural, electronic, and optical properties of the diindenoperylene molecule from firstprinciples density-functional theory, PHYSICAL REVIEW A 74,042505_2006
[29]Leif A.A. Pettersson*, Soumyadeb Ghosh, Olle Ingan ∈as, Optical anisotropy in thin films of poly(3,4-ethylenedioxythiophene)-poly(4-styrenesulfonate), Organic Electronics 3 (2002) 143-148
[2]C.L.Yang,J.N.Wang,W.K.Ge,L.Gun,S.H.Yang,and D.Z.Shell, J.Appl.Phys,90(2001)4489.
[3]杜续生,导电聚合物的合成及其性质的研究,2001年6月,第5-6页
[4]李玉真,许景坤,导电聚(3,4二氧乙基噻吩)应用研究进展,2007年3月,第25-27页
[5]K.E.Aasmundtveit,et al.Synth Met,1999,101:56
[6]MIAOXIANG CHEN,PROCEEDINGS OF THE IEEE,93 (2005) 1339
[7]Born M and Huang K Dynamical Theory of Crystal Lattices.Oxford:Oxford University Press,1954
[8]Hartree D.R.,Proc.Cam.PhiL.Soc.,1928,24,89.
[9]ock V z.,Phys.,1930,61,249.
[10]Hohenberg P. and Kohn w.,Phys.Rev.,1964,136,B864.
[11]Kohn W and Sham L.J., Phys.Rev,1965,140,A1133.
[12]Thomas H., Proc.Cam.PhiL.Soc.1927,23,542.
[13]Fermi E., Accad.Naz.Lincei,1927,6,602.
[14]Herring C., Phys.Rev.1940,57,119
[15]Herring C. and Hill A.G, Phys.Rev.1940,58,152.
[16]Hamann D.R., Schlllter M. and Chiang C., Phys.Rev.Lett,1979,43,1494.
[17]F.Bloch 1933 Z.Physik81 1561
[18]Runge E,Gross E.K.U.1984 Phys.Rev.Lett.52 997
[19]W.Kohn,L.J.Sham,1965 Phys.Rev.140 A1133
[20]W.P.Su J.R.Schrieffer and A.J.Heeger, Phys.Rev.Lett42,1698(1979); Phys.Rev.B22, 2099(1980)
[21]D.K.Campbell and A.R.Bishop, Phys.Rev.B24,4859(1981)
[22]K.Fesseret al. Phys.Rev.B27,4804(1983)
[23]Xie S J, Mei L M, Lin D L. Transition between bipolaron and polaron states in doped heterocycle polymers.Phys Rev B,1994,50:13364-13370
[24]孙鑫,低维凝聚态物理的进展(2),1986年3月,第25-33页
[25]戴兢陶,徐景坤,杨平,杜玉扣,江龙,导电高分子PEDOT/PSS保护银纳米颗粒的制备与表征,感光科学与光化学,第23卷第5期,2005年9月
[26]谢希德,陆栋,固体能带论(Energy Band Theory of Solids),复口.大学出版社
[27]黄昆原著,韩汝琦改编,固体物理学,高等教育出版社
[28]Lavanya M. Ramaniah Mauro Boero, Structural, electronic, and optical properties of the diindenoperylene molecule from firstprinciples density-functional theory, PHYSICAL REVIEW A 74,042505_2006
[29]Leif A.A. Pettersson*, Soumyadeb Ghosh, Olle Ingan ∈as, Optical anisotropy in thin films of poly(3,4-ethylenedioxythiophene)-poly(4-styrenesulfonate), Organic Electronics 3 (2002) 143-148
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |