Electronic Supplementary Information
Investigation of Moisture Stability and PL
Characteristics of Terpineol-passivated Organicinorganic Hybrid Perovskite
Xin Guo,1,2 Christopher McCleese,1 Weiyin Gao,1,3 Minqiang Wang,3 Lixia Sang,4 and Clemens
Burda*,1,2
1
Department of Chemistry, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio
44106, United States.
2
Department of Materials Science and Engineering, Case Western Reserve University, 10900 Euclid
Avenue, Cleveland, Ohio 44106, United States.
3
Electronic Materials Research Laboratory, Key Laboratory of Ministry of Education, International Centers
for Dielectric Research, Xi’an Jiaotong University, Xi’an 710049, China.
4
Key Laboratory of Enhanced Heat Transfer and Energy Conservation, Ministry of Education and Key
Laboratory of Heat Transfer and Energy Conversion, Beijing Municipality, College of Environmental and
Energy Engineering, Beijing University of Technology, Beijing 100124, China.
1
1. Calculated XRD data
The XRD data for CH3NH3PbI3 were calculated using MDI Jade 6.5 and shown in Table S1-S3.
Crystal structure parameters used for the calculation of the XRD data of the cubic phase of
CH3NH3PbI3 are ρ=4.1643g/cm3, V=247.2Å3, Pm3̅m, Z = 1, Cell constant [1]: a=6.276 Å and
α=90°.
Table S1. Calculated XRD data for cubic phase of CH3NH3PbI3
Crystal structure parameters used for the tetragonal phase of MAPbI3 are ρ=4.1264g/cm3,
V=997.9Å3, I4/mcm, Z=4, cell constant [1]: a=8.8743Å, b=8.8743Å, c=12.6708, and α=β=γ=90°:
Table S2. Calculated XRD data for tetragonal phase of CH3NH3PbI3
2
Crystal structure parameters used for (CH3NH3)4PbI6·2H2O [2] are ρ=3.035g/cm3, V=1239.59Å3,
monoclinic P21/n, Z = 2, Cell constant: a=10.3937 Å, b=11.3055Å, c=10.5519 Å and β=91.298°:
Table S3. Calculated XRD data for (CH3NH3)4PbI6·2H2O
d(Å)
7.7129
7.6505
7.4881
7.3204
6.2429
6.1447
5.6528
5.2746
5.1955
4.9825
4.9656
4.78
4.7209
4.5116
4.4741
4.3768
4.3425
4.3091
4.2764
3.8565
3.8252
3.7441
3.6602
3.6352
3.6155
3.5961
3.577
3.5542
3.5489
3.5427
3.4823
3.3662
3.3577
3.354
3.3506
3.3132
3.3117
3.3082
3.269
3.2155
3.1794
3.175
3.1403
3.1215
3.0724
3.0663
3.0505
2.9858
( hkl)
( 0 1 1)
( 1 1 0)
(-1 0 1)
( 1 0 1)
(-1 1 1)
( 1 1 1)
( 0 2 0)
( 0 0 2)
( 2 0 0)
( 0 2 1)
( 1 2 0)
( 0 1 2)
( 2 1 0)
(-1 2 1)
( 1 2 1)
(-1 1 2)
(-2 1 1)
( 1 1 2)
( 2 1 1)
( 0 2 2)
( 2 2 0)
(-2 0 2)
( 2 0 2)
(-1 2 2)
(-2 2 1)
( 1 2 2)
( 2 2 1)
(-2 1 2)
( 0 3 1)
( 1 3 0)
( 2 1 2)
(-1 3 1)
( 0 1 3)
(-1 0 3)
( 1 3 1)
(-3 0 1)
( 3 1 0)
( 1 0 3)
( 3 0 1)
(-1 1 3)
(-3 1 1)
( 1 1 3)
( 3 1 1)
(-2 2 2)
( 2 2 2)
( 0 3 2)
( 2 3 0)
( 0 2 3)
2-Theta
11.463
11.557
11.809
12.08
14.175
14.403
15.664
16.795
17.052
17.787
17.848
18.547
18.781
19.661
19.827
20.273
20.434
20.595
20.754
23.043
23.234
23.745
24.297
24.467
24.602
24.737
24.871
25.033
25.072
25.116
25.559
26.456
26.524
26.554
26.582
26.888
26.899
26.929
27.258
27.72
28.041
28.081
28.398
28.573
29.039
29.098
29.252
29.9
p
4
4
2
2
4
4
2
2
2
4
4
4
4
4
4
4
4
4
4
4
4
2
2
4
4
4
4
4
4
4
4
4
4
2
4
2
4
2
2
4
4
4
4
4
4
4
4
4
2.9533
2.9515
2.9409
2.9305
2.9201
2.8845
2.8584
2.8552
2.8483
2.8325
2.8298
2.8264
2.7927
2.7778
2.7301
2.7273
2.6561
2.6443
2.6373
2.6367
2.6256
2.6106
2.5984
2.5978
2.571
2.5683
2.5675
2.5559
2.5502
2.5318
2.5062
2.5054
2.496
2.4913
2.4883
2.4861
2.4828
2.4806
2.4743
2.4694
2.4496
2.4401
2.4374
2.4285
2.4226
2.4167
2.4109
2.39
2.3852
3
( 3 2 0)
(-1 3 2)
(-2 3 1)
( 1 3 2)
( 2 3 1)
(-1 2 3)
(-3 2 1)
( 1 2 3)
(-2 1 3)
(-3 1 2)
( 3 2 1)
( 0 4 0)
( 2 1 3)
( 3 1 2)
( 0 4 1)
( 1 4 0)
(-2 3 2)
(-1 4 1)
( 0 0 4)
( 1 4 1)
( 2 3 2)
(-2 2 3)
(-3 2 2)
( 4 0 0)
( 0 3 3)
( 0 1 4)
( 2 2 3)
( 3 2 2)
( 3 3 0)
( 4 1 0)
(-1 1 4)
(-1 3 3)
(-3 0 3)
( 0 4 2)
(-3 3 1)
( 1 3 3)
( 2 4 0)
( 1 1 4)
(-4 1 1)
( 3 3 1)
( 4 1 1)
( 3 0 3)
(-3 1 3)
(-1 4 2)
(-2 4 1)
( 1 4 2)
( 2 4 1)
( 0 2 4)
( 3 1 3)
30.237
30.256
30.368
30.479
30.589
30.977
31.267
31.303
31.38
31.56
31.59
31.63
32.022
32.198
32.777
32.811
33.717
33.872
33.964
33.972
34.12
34.323
34.488
34.497
34.868
34.905
34.916
35.08
35.162
35.425
35.799
35.811
35.95
36.021
36.066
36.098
36.149
36.181
36.277
36.352
36.655
36.803
36.846
36.985
37.079
37.172
37.265
37.604
37.682
4
4
4
4
4
4
4
4
4
4
4
2
4
4
4
4
4
4
2
4
4
4
4
2
4
4
4
4
4
4
4
4
2
4
4
4
4
4
4
4
4
2
4
4
4
4
4
4
4
2. Photographs of samples
Figure S1. Photographs of perovskite film prepared by blading the paste, A) fresh perovskite film for
R.H. 30%; B) perovskite film after exposure to R.H. 30% for 70 days; C) fresh perovskite film for R.H.
50%; D) perovskite film after exposure to R.H. 50% for 70 days; E) fresh perovskite film for R.H. 70%;
F) perovskite film after exposure to R.H. 70% for 70 days;
4
3. Spin-coated sample degradation
The XRD pattern of a spin-coated sample degraded under R.H. 70% was labeled for a
comparison with the doctor bladed sample, shown in figure S2.
A
Figure S2. Photographs of perovskite film prepared by spin coating at 3000 rpm for 40s, A) stages from
fresh perovskite film to 3 days exposure R.H. 70% for 3 days; B) The XRD patterns of corresponding
perovskite films; The degraded PbI2 and hydrate phase were present in the spin-coated film after 1 day
exposure under R.H. 70% and the amount of PbI 2 phase increased significantly in the film after exposed 3
days to R.H.70%;
5
4. XRD patterns of samples
The XRD patterns of three samples under respective R.H. at the same time scales were
labeled for a comparison with the calculated XRD pattern using MDI Jade software, shown in
figure S3-S5.
Figure S3. The XRD patterns of perovskite films stored at 30, 50, 70 R. H. for 70 days. PbI2 is present
in the film under R.H. 50% and the hydrate phase exists in the film exposed to R.H.70%;
Figure S4. The XRD patterns of perovskite films stored at 30, 50, 70 R. H. for 30 days. PbI2 is present
in the film under R.H. 50% and the hydrate phase exists in the film exposed to R.H.70%;
6
Figure S5. The XRD patterns of perovskite films stored at 30, 50, 70 R. H. for 10 days. No degraded
PbI2 is observed in the film under R.H. 50% and very little amount of hydrate phase exists in the film
exposed to R.H.70%;
5. XRD patterns of perovskite paste
The XRD patterns of perovskite paste at different stirring times were shown in figure S6:
Figure S6. The XRD patterns of perovskite paste stirred for 2hrs, 4hrs, 1 and 3 days. The formation of
intermediate phase was observed in first few hours and then disappeared. After the transformation into
perovskite in 3 days, only residual PbI2 exists in the paste.
7
6. Time-resolved photoluminescence contour plot
Figure S7. Time-resolved photoluminescence contour plot of the freshly prepared perovskite film.
8
Figure S8. TRPL contour plots of perovskite films stored under RH 30%, 50%, and 70% for 3, 10, and 30
days each.
9
References
(1) T. Baikie, Y. Fang, J. M. Kadro, M. Schreyer, F. Wei, S. G. Mhaisalkar, M. Grӓtzel and
T. J. White, J. Mater. Chem. A, 2013, 1, 5628.
(2) A. Wakamiya, M. Endo, T. Sasamori, N. Tokitoh,; Y. Ogomi, S. Hayase, Y. Murata,
Chemistry Letters, 2014, 43, 711-713.
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