Supporting Information

Cation Diffusion Guides Hybrid Halide Perovskite Crystallization

during the Gel Stage
Lang Liu+, Yang Bai+, Xiao Zhang, Yuequn Shang, Chenyue Wang, Hao Wang, Cheng Zhu,
Chen Hu, Jiafeng Wu, Huanping Zhou, Yujing Li, Shihe Yang, Zhijun Ning, and Qi Chen*

anie_201914183_sm_miscellaneous_information.pdf
SUPPORTING INFORMATION
Experimental Procedures

Materials.
PEDOT:PSS solution (Al 4083) is purchased from Baytron. PbI 2 (99.9985%) is purchased from Alfa Aesar. Butylammonium iodide
(BAI), propylammonium iodide (PAI) and methylammonium iodide (MAI) are purchased from Dyesol. Bathocuproine (BCP), and [6,6]-
phenyl-C61-butyric acid methyl ester (PC61BM) were purchased from Xi’an Polymer Light Technology Corp.. Anhydrous N,N-
dimethylformamide (DMF 99.8%), anhydrous acetonitrile (ACN, 99.8%) and anhydrous tetrahydrofuran (THF, 99.9%) are purchased
from Sigma Aldrich. Indium tin oxide (ITO) substrates (15 Ω cm −2) are purchased from Kintec.
Preparation of perovskite precursor solutions.
Perovskite precursor solutions with concentration of 0.71M are prepared by mixing bulky ammonium iodide, MAI, and PbI2 in molar
ratio of 2:3:4 in DMF and stirred overnight in N 2 glove box. For the different gel duration sample, the perovskite recipe is the same as
BA2MA3Pb4I13, the only difference is the solvent (Table S1).
Preparation of perovskite films and solar cells.
The glass/ITO substrates are sequentially cleaned with isopropanol, acetone, distilled water and ethanol. The as-cleaned substrates
are UV-O3 treated for 20 min before use. PEDOT:PSS solution is spin-coated onto the ITO substrates at 5000 rpm for 30 s and annealed
at 150 °C for 20min. The as-prepared substrates are first preheated at desired temperatures for hot-casting.[1] Then 40 μL of perovskite
precursor solution is spin-coated at 2000 rpm for 20 s. Subsequently, the resulted film is further annealed at 80 °C for 15 min. For the
THF/ACN sample, the solvent volatilizes very fast, and even at room temperature, the film turns to brown only in 1 s. It should be noted:
to obtain a phase homogeneous film, the processing and surrounding temperature should be controlled precisely since higher
temperature lead to hybrid phases. Additionally, vacuum-flash technique[2] is helpful to remove the residual solvents as soon as possible.
PC61BM solution (30 μL, 20 mg/mL in CB) was spin-coated on the top of the perovskite film at 1500 rpm for 40 s. After that, BCP (0.8
mg/mL in isopropyl alcohol) solution was spin-coated onto PC61BM at 5000 rpm for 60 s. Finally, a 100 nm silver electrode was
deposited under a vacuum of 1 × 10−4 Pa. The effective area of the device was measured to be 0.102 cm2. The J−V curves were
measured using a Keithley 2400 source-measurement unit under AM 1.5 G illumination at 100 mW cm−2 using a SS-F5-3A (Enli tech)
solar simulator. The light intensity was calibrated using a certified silicon diode.
Characterization.
The absorption spectra were recorded by Hitachi UH4150 spectrophotometer. Steady-state photoluminescence (PL) were measured
with FLS980 with an excitation at 475 nm. The X-ray diffraction patterns were performed by Rigaku D/Max 2, 200 with Cu Kα as the X-
ray source. For the TOF-SIMS measurement (TOF-SIMS V, ION-TOF GmbH), the pulsed Cs+ primary ions (3 keV) were used for the
sputtering and a Bi+ pulsed primary ion beam for analysis (25 keV). The in situ PL spectra were collected with a USB 2000+
spectrometer (Ocean Optics) equipped with a 510 nm optical filter in an N2 glovebox, and the excited light was at 390 nm from a UV
lamp. The Grazing incidence wide angle x-ray scattering (GIWAXS) data were obtained at beamline BL14B1 of the Shanghai
Synchrotron Radiation Facility (SSRF) using X-ray with a wavelength of 0.6887 Å.

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SUPPORTING INFORMATION

Results and Discussion

As shown in Figure S1a, two dominant peaks were observed at diffraction angles of 14.12 o and 28.42o corresponding to the (111) and
(222) crystallographic planes of BA2MA3Pb4I13 respectively, which almost consistent with previous report. [1] For the UV−vis absorption
spectra (Figure S1b), there were three higher energy absorption peaks located at 573 nm, 606 nm and ∼645 nm, which could be
ascribed to the single-phase perovskites with n = 2, 3 and 4, respectively. Additionally, another lower energy absorption peak at ∼750
nm was also observed which may be assigned to the perovskite with much larger n value (close to the 3D part). This result indicated
that the film consisted of mixed perovskite phase with different n values.

a b 3.0
PA BA
2.5 n=2 PA
Absorbance (a.u.) n=3
2.0

1.5 n=4
BA
1.0
n∞
0.5

0.0
5 10 15 20 25 30 35 40 45 500 600 700 800
Wavelength (nm)
2 (degree)

Figure S1. Characterization of thin films. (a) XRD pattern and (b) optical absorbance spectra of BA 2MA3Pb4I13 and PA2MA3Pb4I13.

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SUPPORTING INFORMATION

a b
BA2MA3Pb4I13 MAPbI3
100
35
T% T%
30 80
Transmittance (%)

Transmittance (%)
25
60
20

15 40

10
20
5

0 0
400 500 600 700 800 400 500 600 700 800
Wavelength (nm) Wavelength (nm)
Figure S2 The transmittance spectrum of (a) BA2MA3Pb4I13 film and (b) MAPbI3 film.

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1.0 461 nm Gel film 1.0

458 NMP-GEL
Normalized PL (a.u.)

Normalized PL (a.u.)
0.8 0.8

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
400 450 500 550 600 400 450 500 550 600
Wavelength (nm) Wavelength (nm)
Figure S3 PL spectra of the gel film.

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SUPPORTING INFORMATION
b
1.29 DMF
Intensity (a. u.)

540

1 10 100 1000 10000

Diameter (nm)

Figure S4 Size distribution of perovskite solution determined by the dynamic light scattering measurement.

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SUPPORTING INFORMATION
Diffusion model
The concentration changes with time which corresponding to the non-steady state diffusion process. According to the Fick's Second
Law of Diffusion[3]:

C  2C
D 2
t x (1)
Where 𝑐 is the concentration of diffusing species; 𝑡 is the time; 𝐷 is diffusion coefficient and 𝑥 is the spatial coordinates.
In order to solve eq. (1), we set following conditions:
Initial conditions:

C1  C0 , x  0
t  0, 
C2  0, x  0 (2)
Boundary conditions:

C1  C0 , x  
t  0, 
C2  0, x  - (3)
For convenience, we use Boltzmann transform to solve the equation.
We set:

  x / t . (4)
Substituting eq. (4) into eq. (1), for the left side, we have:

C C  C x dC 
    3/2   
t  t  2t d 2t .
The right side of the eq. (1):

 2C  2C  2 d 2C 1
D 2  D 2 ( )  D 2 
x  x d t .
Thus eq. (1) is rewritten as:

dC d 2C
  2D 2
d d . (5)
dC

We define d ，then eq. (5) is rewritten as:

 d
 D
2 d . (6)
We obtain the solution of eq. (6):

2
  a' exp (  )
4D . (7)
dC

Substituting eq. (7) into d , we obtain:

dC 2
 a' exp (  )
d 4D .

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SUPPORTING INFORMATION
After integrating, we have:

 2
C  a'  exp (  )d  b
0
4D . (8)



We define 2 D , then eq. (8) is rewritten as:
C  a' 2 D  0 exp (2 )d  b  a  0 exp ( 2 )d  b . (9)
Combined eq. (2) with the integral of Gaussian error:


 0  exp ( 2 )d  
2 , (10)
 2  2
we have:
C  C1  a  0 e d  b , C  C2  a  0 e d  b .

a  a 
C1   b C2   b
Therefore 2 , 2 .
We find the integration constant:

 C2  C1 2
 a   
2 

b  C2  C1
 2 . (11)
Substituting eq. (11) into eq. (9), we obtain:

C1  C2 C2  C1 2 
C    0 exp( 2 )d
2 2  . (12)
Combined with eq. (2), we obtain:
x
C0 C0 2 x2 1
C  0 Dt
exp(  ) dx
2  4Dt 2 Dt . (13)
For simplicity, we consider the solutes diffuse at a constant rate r, thus t=x/r. Substitution in eq. (13) yields:

1 rx
C C rx 1 r
C  0  0  02 D
exp(  ) dx
2  4D 2 Dx . (14)
Finally, we have diffusive fluxes:

C DC0 r xr C Dr rx
J  D  exp(  ) 0  exp(  )
x 2 Dx 4D 2 x 4D . (15)

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SUPPORTING INFORMATION
Take the example of BA2MA3Pb4I13 film, C0=0.714 M. C0(MA)=0.75 C0, C0(BA)=0.5 C0. For the rate r, r=x/t. According to the TGA result
(Figure 1c), we know the as-cast gel film takes for 5 minutes to form perovskite entirely. The cross-sectional SEM image (Figure S5)
indicates the thickness of the film is around 600 nm. Thus r=x/t=2*10-9 m/s.

500 nm

Figure S5 Cross-sectional SEM images of the as-prepared perovskite film.

Diffusivity calculation
According to Eyring’s theory,[4] the diffusivity of solutes can be calculated as follow:
1/ 2
2  kT   E 
D  1/ 3   exp   
vf  2m   RT  (16)
where  is the distance between two equilibrium positions of the diffusing molecule, k is the Boltzmann constant, T is the temperature
in Kelvin, Vf is the molecular volume, m is mass of the molecule, R is the gas constant and E is the diffusion activation energy.
Herein, for convenience, we suppose the distance 2 is the same (3*10-15) for different species.[4a] To calculate the diffusivity of MA+
PA+ and BA+, we need the following parameters: m, E and Vf (Figure S6).

32 g / mol
mMA 
6.02  1023 / mol
60 g / mol
mPA 
6.02  1023 / mol
74 g / mol
mBA 
6.02  1023 / mol
v f MA  2.198  1.769  1.555  1030 m3

v f PA  4.677  2.074  1.627  1030 m3

v f BA  1.765  2.150  6.692  1030 m3

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SUPPORTING INFORMATION
Considering EBA and EPA are larger than EMA, though we can’t access the exactly E value, we can estimate approximately (for
example EMA=8000 J/mol, EBA& EPA=1~6 EMA). Finally, this diffusivity value are normalized.

MA

PA

BA

Figure S6 The length, width and height parameters of MA, PA and BA.

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SUPPORTING INFORMATION
1.35 1.0 521 Front 771
FA0.85MA0.15Pb(I0.85Br0.15)3-front
Back

Normalized PL (a.u.)
Normalized PL (a.u.)

FA0.85MA0.15Pb(I0.85Br0.15)3-back
772 784
0.90

0.5 581

0.45
614
778

0.00 0.0
500 600 700 800
500 600 700 800
Wavelength (nm)
Wavelength (nm)
Figure S7 PL spectra of the typical (FAPbI3)0.85(MAPbBr3)0.15 perovskite film.

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a b Max.

Min.

Figure S8 The in-situ PL spectrum of the film prepared at (a) 70 oC and (b) 110 oC.

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a 1.1 b 14
12
10
1.0

PCE (%)
Voc (V)

8
6
0.9 30 50
30 50 4 70 90
70 90 110 130
110 130 2

c 0.8
75
d 180
15
Fill Factor (%)

JSC (mA cm-2)

60
12

9
45 30 50 30 50
70 90 70 90
110 130
6 110 130

e 30 3
Normalized PCE (%)

100
76%
80
60
40
20
70 oC
0
0 100 200 300 400 500 600
Time (h)
Figure S9 The performance of the devices prepared at different temperatures: (a) VOC, (b) PCE, (c) FF, (d) JSC and (e) stability of the
device (under MPP tracking and continuous light irradiation with a white LED lamp, 100 mW cm−2 in a nitrogen atmosphere).

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a b
DMF 30 oC DMF 70 oC
20 20

q (nm )
q (nm )

-1
-1

15 15

z
z

10 10

5 5

0 0
0 5 10 15 20 0 5 10 15 20
-1 -1
q (nm ) q (nm )
xy xy

Figure S10 2D GIWAXS patterns of BA2MA3Pb4I13 perovskite films prepared at (a) 30 oC and (b) 70 oC.

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SUPPORTING INFORMATION
As shown in the Figure S11a&c, the crystallinity and orientation of the THF&ACN sample was very weak. However, prolongation of the
gel state duration (increase the dosage of DMAC) significantly improved the crystallinity and orientation. Thus the gel stage duration
had profound influence on the crystallinity and orientation. It should be noted that during the preparation of the THF&ACN sample, we
find the film turns to brown only in 1 s. Such an ultra-fast volatilization of a large number of solvents made the film solidified in a transient.
Under this extreme condition, although there had diffusivity difference between MA+ and BA+, there had no time to distinguish. Besides,
there was also little time to align and assemble orderly therefore the crystallinity and orientation was very poor. These results
demonstrated the significance of gel duration: only the interaction time lasted for long enough, could there be an opportunity to identify
the difference. In other words, gel was a stage for showing differences. For the THF&ACN solvent system, even there had difference,
but there had no stage to show hence no difference presented. While for the gel stage duration long enough case, the gel matrix have
enough time to distinguish and even magnified the difference. With continuous interaction between gel and ammoniums the difference
gradually embodied. Briefly, these results confirmed our assumption that the gel stage duration (as another external factor) had a great
influence on phase segregation.

a b c
3.0 THF&ACN
DMAC-150 THF&ACN
DMAC-50 20
Absorbance (a.u.)

2.5 DMAC-100
DMAC-150
Intensity (a. u.)

q (nm-1)

DMAC-100 2.0 15

1.5
z

DMAC-50 10
1.0
5
THF&ACN 0.5

0.0 0
5 10 15 20 25 30 35 40 45 500 600 700 800 0 5 10 -1 15 20
2 (degree) Wavelength (nm) q (nm )
xy

d e f DMAC-150
DMAC-50 DMAC-100
20 20 20
q (nm-1)
q (nm-1)
q (nm-1)

15 15 15
z
z

10 10 10

5 5 5

0 0 0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
qxy (nm-1) qxy (nm-1) qxy (nm-1)

Figure S11 Characterization of the films prepared by different solvents. (a) XRD pattern, (b) UV−vis absorption spectra and (c, d,
e&d) GIWAXS pattern.

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SUPPORTING INFORMATION
Table S1 The solvent recipe we used to regulate gel stage duration.
Samples Solvent THF (µL) Solvent ACN (µL) Solvent DMAC (µL)
THF&ACN 525 175 0
DMAC-50 487.5 162.5 50
DMAC-100 450 150 100
DMAC-150 412.5 137.5 150

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Supplementary Note 1.
During the hot casting process, most of the solvents are evaporated. For the following thermal annealing, the amount of residual solvent
is actually very few, and the gel stage duration is very short. In this scenario, we believe the principles of this diffusion model may still
be applicable. However, it may not be the predominant effects to determine the phase segregation during thermal annealing.

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References

1. Tsai, H.; Nie, W.; Blancon, J.-C.; Stoumpos, C. C.; Asadpour, R.; Harutyunyan, B.; Neukirch, A. J.; Verduzco, R.; Crochet, J. J.; Tretiak, S., High-efficiency
two-dimensional Ruddlesden–Popper perovskite solar cells. Nature 2016, 536, 312-316.
2. Li, X.; Bi, D.; Yi, C.; Décoppet, J.-D.; Luo, J.; Zakeeruddin, S. M.; Hagfeldt, A.; Grätzel, M., A vacuum flash–assisted solution process for high-efficiency
large-area perovskite solar cells. Science 2016, 353, 58-62.
3. Crank, J., The mathematics of diffusion. Oxford university press: 1979.
4. Steam, A. E.; Irish, E. M.; Eyring, H., A Theory of Diffusion in Liquids. The Journal of Physical Chemistry 1940, 44, 981-995.
5. Kincaid, J. F.; Eyring, H.; Stearn, A. E., The Theory of Absolute Reaction Rates and its Application to Viscosity and Diffusion in the Liquid State. Chemical
Reviews 1941, 28, 301-365.

Author Contributions

Q.C. and L.L. conceived the idea and designed the experiments. L.L. conducted most of the film fabrication and measurements. X.Z., L.L. and C.W. finished the
diffusion model. S.Y., Y.B. and C.H. performed the TOF-SIM measurement. Y.S. and Z.N. carried out the in-situ PL measurement. C.Z. and C.W. finished the
GIWAXS measurement. H.W and J.W. tested the XRD measurement. All the authors involved in the discussion for data analysis and commented on the manuscript.
L.L. wrote the first draft. Y.B., H.Z. and Q.C. revised the manuscript. L.L. and Y.B. contributed equally. Q.C. supervised the whole project.

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