Intrinsic Electronic Structures and Optical Anisotropy of α- and β-Phase Copper Phthalocyanine Molecular Crystals

Abstract:

Electronic structures and optical anisotropy of α- and β-phase copper phthalocyanine (CuPc) molecular crystals have been systemically investigated by first-principles calculations based on Density Functional Theory (DFT). Both crystals were shown to be small gap organic semiconductors with relatively flat and dispersionless bands. The α-CuPc was a direct band gap semiconductor, whereas the β-CuPc was an indirect band gap semiconductor. The analysis of Partial Density of States (PDOS) showed that the top of valance band was mainly contributed by N 2p and C 2p states; the bottom of the conduction band was mainly contributed by N 2p, C 2p and Cu 3d states. The interband optical properties, such as the complex dielectric function, absorption coefficient and complex refractive index, showed a high degree of anisotropy that can be traced to the unique structures of these molecular crystals. The calculated dielectric function for α-CuPc in the low energy region was consistent with the experiment results proposed in the literature. These calculations provided particular interpretations on electronic structure and optical properties of α- and β-CuPc organic semiconductors that were critical to optoelectronics, which would promote the applications of these materials in semiconductor optoelectronic devices.

• Periodical: Applied Mechanics and Materials (Volume 864)
• Pages: 133-141
• DOI: https://doi.org/10.4028/www.scientific.net/AMM.864.133
• Online since: April 2017
• Authors: Xue Yan Wang, Jian Bang Zheng*, Xiao Jiang Li, Chong De Cao
• Keywords: Band Structure, Density Functional Theory (DFT), Optical Properties, PDOS, α-CuPc Molecular Crystals, β-CuPc Molecular Crystals

References

[1] M. Ghosh, N. Padma, R. Tewari, A. K. Debnath, Structural, optical, and electrical properties of in situ synthesized ZnO−CuPc nanocomposites, J. Phys. Chem. C 118 (2014) 691-699.

DOI: 10.1021/jp4059609

[2] W. Mekprasart, N. Vittayakorn, W. Pecharapa, Ball-milled CuPc/TiO2 hybrid nanocomposite and its photocatalytic degradation of aqueous Rhodamine B, Mater. Res. Bull. 47(11) (2012) 3114-3119.

DOI: 10.1016/j.materresbull.2012.08.024

[3] H. Kumar, P. Kumar, N. Chaudhary, R. Bhardwaj, S. Chand, S. C. Jain, V. Kumar, Effect of temperature on the performance of CuPc/C60 photovoltaic device, J. Phys. D: Appl. Phys. 42(1) (2009) 015102 1-7.

DOI: 10.1088/0022-3727/42/1/015102

[4] N. N. Wang, J. S. Yu, Z. L. Yuan, Y. D. Jiang, Effect of annealing copper phthalocyanine on the performance of interdigitated bulk-heterojunction organic photovoltaic cells, Eur. Phys. J. Appl. Phys. 58 (2012) 20201 1-6.

DOI: 10.1051/epjap/2012110404

[5] T. Shaymurat, Q. Tang, Y. Tong, L. Dong, Y. Liu, Gas Dielectric Transistor of CuPc Single Crystalline Nanowire for SO2 Detection Down to Sub-ppm Levels at Room Temperature, Adv. Mater. 25(16) (2013) 2269-2273.

DOI: 10.1002/adma.201204509

[6] S. Karan, B. Mallik, Nanostructured organic-inorganic photodiodes with high rectification ratio, Nanotechnol. 19(49) (2008) 495202 1-11.

DOI: 10.1088/0957-4484/19/49/495202

[7] N. Padma, Aditee Joshi, Ajay Singh, S. K. Deshpande, D. K. Aswal, S. K. Gupta, J. V. Yakhmi, NO2 sensors with room temperature operation and long term stability using copper phthalocyanine thin films, Sensors Actuat. B 143(1) (2009) 246-252.

DOI: 10.1016/j.snb.2009.07.044

[8] G. Ma, L. Guo, J. Mi, Y. Liu, S. Qian, D. Pan, Y. Huang, Femtosecond nonlinear optical response of metallophthalocyanine films, Solid. State. Commun. 118(12) (2001) 633-638.

DOI: 10.1016/s0038-1098(01)00183-1

[9] G. de la Torre, P. Vázquez, F. Agulló-López, T. Torres, Role of structural factors in the nonlinear optical properties of phthalocyanines and related compounds, Chem. Rev. 104(9) (2004) 3723-3750.

DOI: 10.1021/cr030206t

[10] W. Wu, Modelling copper-phthalocyanine/cobalt-phthalocyanine chains: towards magnetic quantum metamaterials, J. Phys.: Condens. Matter 26(29) (2014) 296002 1-5.

DOI: 10.1088/0953-8984/26/29/296002

[11] R. Murdey, N. Sato, In situ conductance measurements of copper phthalocyanine thin film growth on sapphire.

DOI: 10.1063/1.3600065

[1] J. Chem. Phys. 134(23) (2011) 234702 1-6.

[12] M. D. Pirriera, J. Puigdollers, C. Voz, M. Stella, J. Bertomeu, R. Alcubilla, Optoelectronic properties of CuPc thin films deposited at different substrate temperatures, J. Phys. D: Appl. Phys. 42(14) (2009) 145102 1-5.

DOI: 10.1088/0022-3727/42/14/145102

[13] A. Chowdhury, B. Biswas, M. K. Sanyal, B. Mallik, Organic rectifiers grown from metal phthalocyanines seeds: effects of grain growth and grain orientation on the rectification, Sci. Adv. Mater. 5(12) (2013) 1-10.

DOI: 10.1166/sam.2013.1651

[14] C. Defeyt, P. Vandenabeele, B. Gilbert, J. V. Pevenage, R. Cloots, D. Strivay, Contribution to the identification of α-, β- and ε-copper phthalocyanine blue pigments in modern artists' paints by X-ray powder diffraction, attenuated total reflectance micro-fourier transform infrared spectroscopy and micro-Raman spectroscopy, J. Raman Spectrosc. 43(11) (2012).

DOI: 10.1002/jrs.4125

[15] T. V. Basova, V. G. Kiselev, B. E. Schuster, H. Peisert, T. Chassé, Experimental and theoretical investigation of vibrational spectra of copper phthalocyanine: polarized single-crystal Raman spectra, isotope effect and DFT calculations, J. Raman Spectrosc. 40(12) (2009).

DOI: 10.1002/jrs.2375

[16] A. Hoshino, Y. Takenaka, H. Miyaji, Redetermination of the crystal structure of α-copper phthalocyanine grown on KCl, Acta Cryst. B 59 (2003) 393-403.

DOI: 10.1107/s010876810300942x

[17] O. D. Gordan, M. Friedrich, D. R. T. Zahn, The anisotropic dielectric function for copper phthalocyanine thin films, Org. Electron. 5(6) (2004) 291-297.

DOI: 10.1016/j.orgel.2004.10.001

[18] M. Fronk, B. Bräuer, G. Salvan, D. R. T. Zahn, Molecular alignment in a-CuPc films probed by reflection anisotropy spectroscopy, J. Mol. Struct. 1073 (2014) 82-86.

DOI: 10.1016/j.molstruc.2014.05.001

[19] J. Zhou, Q. Wang, Q. Sun, P. Jena, Electronic and magnetic properties of a BN sheet decorated with hydrogen and fluorine, Phys. Rev. B 81(8) (2010) 085442 1-7.

DOI: 10.1103/physrevb.81.085442

[20] C. J. Brown, Crystal structure of β-copper phthalocyanine, J. Chem. Soc. A. (1968) 2488-2493.

[21] J. P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77(18) (1996) 3865-3867; 78, 1396 (E) (1997).

DOI: 10.1103/physrevlett.78.1396

[22] L. M. Yang, P. Ravindran, P. Vajeeston, S. Svelle, M. Tilset, A quantum mechanically guided view of Cd-MOF-5 from formation energy, chemical bonding, electronic structure, and optical properties, Micropor. Mesopor. Mat. 175 (2013) 50-58.

DOI: 10.1016/j.micromeso.2013.03.020

[23] Z. Zhao, Z. Li, Z. Zou, Electronic structure and optical properties of monoclinic clinobisvanite BiVO4, Phys. Chem. Chem. Phys. 13 (2011) 4746-4753.

DOI: 10.1039/c0cp01871f

[24] L. Lozzi, S. Santucci, S. La Rosa, B. Delley, S. Picozzi, Electronic structure of crystalline copper phthalocyanine, J. Chem. Phys. 121(4) (2004) 1883-1889.

DOI: 10.1063/1.1766295

[25] J. Zhai, A. Wan, D. Yu, T. Ren, Structural, electronic, and optical properties of ordered Si1-xGexC alloys: A first principles study, J. Alloy. Compd. 632 (2015) 629-633.

DOI: 10.1016/j.jallcom.2015.01.212

[26] Q. B. Wang, C. Zhou, L. Chen, X. C. Wang, K. H. He, The optical properties of NiAs phase ZnO under pressure calculated by GGA+U method, Opt. Commun. 312 (2014) 185-191.

DOI: 10.1016/j.optcom.2013.09.035

[27] C. Lei, Z. Yang, B. Zhang, M. H. Lee, Q. Jing, Z. Chen, X. C. Huang, Y. Wang, S. Pan, M. R. S. A. Janjua, The influence of hydrogen bonding on the nonlinear optical properties of a semiorganic material NH4B [D-(+)-C4H4O5]2·H2O: a theoretical perspective, Phys. Chem. Chem. Phys. 16(37) (2014).

DOI: 10.1039/c4cp02539c

[28] X. Y. Wang, J. B. Zheng, X. J. Li, C. D. Cao, Electronic Structures and Optical Properties of β-PTCDA Based on the First-Principles Investigation, Acta Photonica Sinica, 45(6) (2016) 1-8.

[29] M. Khan, J. N. Xu, N. Chen, W. B. Cao, First principle calculations of the electronic and optical properties of pure and (Mo, N) co-doped anatase TiO2, J. Alloy. Compd. 513 (2012) 539-545.

DOI: 10.1016/j.jallcom.2011.11.002

[30] Q. B. Wang, C. Zhou, L. Chen, X. C. Wang, K. H. He, The optical properties of NiAs phase ZnO under pressure calculated by GGA+U method, Opt. Commun. 312 (2014) 185-191.

DOI: 10.1016/j.optcom.2013.09.035

[31] M. M. El-Nahass, K. F. Abd-El-Rahman, A. A. A. Darwish, Fourier-transform infrared and UV- vis spectroscopes of nickel phthalocyanine thin films, Mater. Chem. Phys. 92(1) (2005) 185-189.

DOI: 10.1016/j.matchemphys.2005.01.008

[32] W. Y. Tong, H. Y. Chen, A. B. Djurišić, A. M. C. Ng, H. Wang, S. Gwo, W. K. Chan, Infrared photoluminescence from α- and β-copper phthalocyanine nanostructures, Opt. Mater. 32(9) (2010) 924-927.

DOI: 10.1016/j.optmat.2010.01.026