J04 GIXS

grazing incidence X-ray scattering 掠入射X射线散射

Bulk heterojunction morphology
molecular packing
phase separation

low dielectric constant of organic semiconducting materials
use the bulk heterojunction (BHJ) device structure
creates abundant donor-acceptor interfaces
efficient dissociation of strongly bounded electron-hole pairs (excitons).

crystallinity
molecular packing orientation
characteristic domain sizes
miscibility and
intercalation framework

charge transfer
transport processes

fullerene derivatives
spherical shape
isotropic charge transport
simplifying the morphology control

form amorphous clusters in the active layer
the cluster size and density

barely adjustable energy levels with
large bandgaps and low-lying lowest unoccupied molecular orbitals
(LUMO)
narrow absorption spectra

nonfullerene

great energy level tunability
broad absorption spectra

lack of electron density contrast between donor and acceptor
materials

$q=k_f-k_i$

The incident angle ${\alpha }_i$>>slightly larger than the critical angle of the probing material>>
ensure full penetration

close to the sample (about several centimeters),
the probing length scale is between ~0.01 nm and ~1 nm
(~0.1 < q < ~10 ${\stackrel{\circ }{A}}^{-1}$)
referred as grazing incidence wide-angle X-ray scattering (GIWAXS).

further away from the sample (about several meters),
the probing length scale is between ~1 nm and ~100 nm
(~0.001 < q < ~0.1 ${\stackrel{\circ }{A}}^{-1}$)
referred as grazing incidence small-angle X-ray scattering (GISAXS).

GIWAXS
molecular-scale structural information
molecular packing of organic donor and acceptor materials in the active layer
such as crystallinity, lattice constant and orientation

lamellar stacking
The stacking between backbones separated by side chains ($a$-direction)
10 to 20 $\stackrel{\circ }{A}$
lamellar peak (100) $|q|$ between ~0.3 and ~0.5 ${\stackrel{\circ }{A}}^{-1}$
side chain的距离，实际距离大，倒空间值小

$\pi$-$\pi$ stacking
The stacking between backbones in the direction of $\pi$-orbitals of conjugated rings ($b$-direction)
~4 $\stackrel{\circ }{A}$
$\pi$-$\pi$ peak (010) $|q|$ between ~1.5 to ~1.8 ${\stackrel{\circ }{A}}^{-1}$
in the orthogonal direction of the lamellar peak.
$\pi$-$\pi$堆叠的距离，实际距离小，倒空间值大

backbone ordering
The diffraction of structural ordering along the backbone direction (cdirection)
depends on the chemical structure and the resultant scattering.
rarely observed and often ignored >> lack of long-range order.

GIWAXS pattern
location and width of scattering peaks

拟合函数：高斯分布Gauss
$$y=y_0+\frac{A}{w\sqrt{\pi /2}}{e}^{-2\frac{(x-x_c{)}^2}{w^2}}$$

https://latex.91maths.com/s/?eSUyMCUzRCUyMHlfMCUyMCUyQiUyMCU1Q2ZyYWMlN0JBJTdEJTdCdyU1Q3NxcnQlN0IlNUNwaSUyRjIlN0QlN0RlJTVFJTdCLTIlNUNmcmFjJTdCKHgteF9jKSU1RTIlN0QlN0J3JTVFMiU3RCU3RA==

Crystalline Coherence Length (CCL) of lamellar, backbone and π-π peaks
of the acceptors

$\Delta q_{hkl}=FWHM$

The correlation length of this stacking：

$D_{hkl}=2\pi K/\Delta q_{hkl}$
$K=2(ln2/\pi {)}^{1/2}$ = 0.93

$q_{hkl}$ is the wave vector and $\Delta q_{hkl}$is the full width at half maximum of the scattering peak.

$q$ (lamellar or Backbone or $\pi$-$\pi$) peaks (${\stackrel{\circ }{A}}^{-1}$)
$vs$ ($d$ spacing, $\stackrel{\circ }{A}$)

$q=x_c$
$d=2\pi /q$

Refs:

https://doi.org/10.1016/j.mtnano.2019.100030
https://doi.org/10.1002/adma.201802888
\overset{\circ}{A}
Guass和Guassian
https://www.zhihu.com/question/316010845