• Chinese Journal of Chemical Physics
  • Vol. 33, Issue 5, 569 (2020)
Shan Sun, Hui-zhong Ma, Xiao Zhang, and Yu-chen Ma*
DOI: 10.1063/1674-0068/cjcp2001003 Cite this Article
Shan Sun, Hui-zhong Ma, Xiao Zhang, Yu-chen Ma. Direct and Indirect Excitons in Two-Dimensional Covalent Organic Frameworks[J]. Chinese Journal of Chemical Physics, 2020, 33(5): 569 Copy Citation Text show less

Abstract

Highly luminescent bulk two-dimensional covalent organic frameworks (COFs) attract much attention recently. Origin of their luminescence and their large Stokes shift is an open question. After first-principles calculations on two kinds of COFs using the GW method and Bethe-Salpeter equation, we find that monolayer COF has a direct band gap, while bulk COF is an indirect band-gap material. The calculated optical gap and optical absorption spectrum for the direct excitons of bulk COF agree with the experiment. However, the calculated energy of the indirect exciton, in which the photoelectron and the hole locate at the conduction band minimum and the valence band maximum of bulk COF respectively, is too low compared to the fluorescence spectrum in experiment. This may exclude the possible assistance of phonons in the luminescence of bulk COF. Luminescence of bulk COF might result from exciton recombination at the defects sites. The indirect band-gap character of bulk COF originates from its AA-stacked conformation. If the conformation is changed to the AB-stacked one, the band gap of COF becomes direct which may enhance the luminescence.
$ \left\{ { - \frac{1}{2}{\nabla ^2} + {V_{ps}}({\bf{r}}) + {V_H}({\bf{r}})} \right\}\psi _{n{\bf{k}}}^{QP}({\bf{r}}) + \int \Sigma \left( {{\bf{r}},{{\bf{r}}^\prime },E_{n{\bf{k}}}^{QP}} \right)\psi _{n{\bf{k}}}^{QP}\left( {{{\bf{r}}^\prime }} \right)d{{\bf{r}}^\prime } = E_{n{\bf{k}}}^Q\psi _{n{\bf{k}}}^{QP}({\bf{r}}) $ (1)

View in Article

$ \Sigma \left( {{\bf{r}},{{\bf{r}}^\prime },E} \right) = \frac{i}{2}\int {{e^{ - i\omega {0^ + }}}} G\left( {{\bf{r}},{{\bf{r}}^\prime },E - \omega } \right)W\left( {{\bf{r}},{{\bf{r}}^\prime },\omega } \right)d\omega $ (2)

View in Article

$ W\left(\mathbf{r}, \mathbf{r}^{\prime}, \omega\right)=\int \varepsilon^{-1}\left(\mathbf{r}, \mathbf{r}^{\prime \prime}, \omega\right) v\left(\mathbf{r}^{\prime \prime}, \mathbf{r}^{\prime}\right) d \mathbf{r}^{\prime \prime} $ (3)

View in Article

$ P\left( {{\bf{r}},{{\bf{r}}^\prime };\omega } \right) = 2\sum\limits_m^{occ.} {} \sum\limits_n^{unocc.} {\psi _m^*} ({\bf{r}}){\psi _n}({\bf{r}})\psi _n^*\left( {{{\bf{r}}^\prime }} \right){\psi _m}\left( {{{\bf{r}}^\prime }} \right) \times \left[ {\frac{1}{{\omega - {E_n} + {E_m}}} - \frac{1}{{\omega + {E_n} - {E_m}}}} \right] $ (4)

View in Article

$ G\left(\mathbf{r}, \mathbf{r}^{\prime} ; \omega\right)=2 \sum\limits_{i} \frac{\psi_{i}(\mathbf{r}) \psi_{i}^{*}\left(\mathbf{r}^{\prime}\right)}{\omega-E_{i}} $ (5)

View in Article

Shan Sun, Hui-zhong Ma, Xiao Zhang, Yu-chen Ma. Direct and Indirect Excitons in Two-Dimensional Covalent Organic Frameworks[J]. Chinese Journal of Chemical Physics, 2020, 33(5): 569
Download Citation