Azam Recent Advances in Defect Passivation of Perovskite Active Layer Via PDF

Journal of Physics D: Applied Physics
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Recent Advances in Defect Passivation of Perovskite Active Layer via

Additive Engineering: A Review
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Page 1 of 24 AUTHOR SUBMITTED MANUSCRIPT - JPhysD-122489.R1
IOP Publishing Journal Title

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Journal XX (XXXX) XXXXXX https://doi.org/XXXX/XXXX
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Recent Advances in Defect
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10 Passivation of Perovskite Active Layer
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via Additive Engineering: A Review
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15 Muhammad Azam1,2,3, Kong Liu1,3, Yang Sun1, Zhijie Wang*,1, Guangxing Liang*,2,
16 Shengchun Qu*,1, Ping Fan2 and Zhanguo Wang1
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18 1 Key Laboratory of Semiconductor Materials Science, Beijing Key Laboratory of Low Dimensional
19 Semiconductor Materials and Devices, Institute of Semiconductors, Chinese Academy of Sciences,
20 Beijing, 100083, People’s Republic of China; Center of Materials Science and Optoelectronics
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21 Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
2 Shenzhen Key Laboratory of Advanced Thin Films and Applications, College of Physics and
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Optoelectronic Engineering, Shenzhen University, Shenzhen, 518060, P. R China.
23 3 These authors contributed equally
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25 E-mail: wangzj@semi.ac.cn; lgx@szu.edu.cn; qsc@semi.ac.cn
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Received xxxxxx
Accepted for publication xxxxxx
Published xxxxxx
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30 Abstract
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32 The performance and stability of Perovskite solar cells (PSCs) are mainly affected by various defects inside the perovskite
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33 active layer and the corresponding electron/hole transport layers interfaces. A lot of work has been done in progressing
34 perovskite layer passivation strategies contributing to efficient performance PSCs with improved ambient environment
35 stability. Here, the additive engineering techniques for the perovskite active layer passivation with the aim of improving
36 perovskite crystallization, reducing carrier recombination and improving device stability are reviewed. Passivation, by
37 different additives, of the active layer can improve the performance of PSCs by reducing trap states and enhance the moisture
38 stability by reducing the grain boundaries. Optimizing the ratio of PbI 2 in the perovskite precursor has been discovered to be
39 effective in passivating trap states at the grain boundaries and on the surface of the film. Non-radiative recombination trap
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centers inside the active layer can be passivated through the incorporation of additives such as organic surfactants, elemental
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iodine, and metal compounds or nanoparticles. This technique has also taken part in improving energy band alignment
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between the perovskite layer and the respective electron/hole transport layers. The present work covers most of the published
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reports on the additive engineering approach, the precursor preparation, the effect on different properties of the perovskite
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layer, the effect on device efficiency, the effect on device hysteresis and finally, the effect on device stability are presented.
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47 Keywords: Additive engineering, passivation, stability, trap states, PSCs
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52 1. Introduction
53 Metal halide organic-inorganic PSCs have gained conversion efficiency (PCE) of PSCs increased from 3.8% in
54 extraordinary research objectives in the past few years due to 2009 to 25.2% in 20194,5. According to the history of
55 their intrinsically excellent optoelectronic characteristics photovoltaic development, such quick progress has never
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such as tunable bandgap, low exciton binding energy, been observed before.
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ambipolar charge characteristic, long carrier diffusion length, The crystal structure of organic-inorganic perovskite
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long carrier lifetime, high mobility, large optical absorption based on chemical formula ABX3 architecture, where A
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coefficient1-3. Due to such remarkable properties, the power belongs to monovalent organic CH3NH3+ (MA) or
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AUTHOR SUBMITTED MANUSCRIPT - JPhysD-122489.R1 Page 2 of 24
Journal XX (XXXX) XXXXXX Author et al

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3 HC(NH2)2+ (FA) cations, and inorganic Cs+ or Rb+, whereas, generated charge carriers and device performance. Moreover,
4 B is a metal cation (i.e., Pb2+, Sn2+), and X is a halide anion we have focussed on the latest advancement in additive
5 (i.e., Cl, Br, I or their mixtures). In the early stage of engineering on improving the device stability under
6 development of this photovoltaic technology, operating conditions, as well as, under humid environment.
7 methylammonium lead iodide (MAPbI3) was observed to be The purpose was to open new aspects for the rational
8 extremely unstable in ambient environment6. Condensed and
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9 employment and design of additives to develop PSCs with an
collective efforts by research community have tremendously exceptional improvement in device efficiency and stability.
10 improved the quality and stability of perovskite materials and
11 the device durability, which lead this technology towards
We believe that our thorough discussion will give valuable
12 information to the photovoltaic community and also promote
commercialization7-9. This can be assign to the progress in (i)
13 a complete understanding of the use of additives for the
optimizing the interface engineering (ii) exploring new
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14 advancement of this technology.
device structures (iii) perovskite deposition techniques
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(responsible for the highly crystalline, uniform and compact
16 2. Defect Categories and Passivation Techniques
film) (iv) understanding the optoelectronic physics of device
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18 operation (v) defect passivation (electronic or surface defect In PSCs, the observations related to electrical instability
19 associated with perovskite active layer and interfaces of resulted from the nature of defects in these perovskite
20 electron/hole transport layers or electrode). The device materials. Thus, the defects are one of the most interesting
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21 performance mostly related to the perovskite morphology, characteristics that limit the device performance and affect
22 hence, the perovskite crystal growth mechanism plays a vital
the further advancement towards approaching the highest
23 role in device optimization10,11. Low-cost manufacturing is
possible PCE. The photo-generated carrier behavior
24 another positive aspect of PSCs, as it can be fabricated by
significantly effected by the grain boundaries (GB)
25 low-temperature solution processable technique.
properties in polycrystalline solar cells. It has been reported
26 However, the electronic trap states or surface defects can
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be readily produced within the grains, at the grain
boundaries, and on the surface of the film. It has been
reported that the possible reason behind the generation of
an that the GBs has a beneficial effect in different material
systems including lead halide perovskite, in which the charge
carriers can be easily separated by built-in potential before
30 these defects is the low formation energy of perovskite their recombination24. The most important defects category
31 materials12,13. Even though the perovskite materials have in lead halide perovskite system is the ionic point defects
32 exhibited high defect tolerance due to the shallow defect such as vacancies of Pb (VPb), MA (VMA) and I (VI) and
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33 states, these defects can alter energy level alignment of the substitutions (MAPb, MAI, PbI) obtained from DFT
34 active layer with corresponding carrier transport layers. calculations25. A number of reports indicated that these
35 Additionally, the charge collection capability adversely defects are produced due to low formation energies26, 27.
36 affected by the ion migration, as the ionic defects in Most of the defects are localized at the shallow energy levels
37 perovskite film provide the pathway for their movement,
38 surrounding the band edges and are electrically active 26,
which will result in J-V hysteresis 14-18. Therefore, to further
39 whereas, antisite and interstitial defects are located at the
enhance the device performance and improve the device
40 deep electronic levels27, which are acting as non-radiative
stability the ionic migration in the solution-processed based
41 perovskite films is a critically important subject of research.
recombination centers destructive for device performance.
42 Perovskite materials also have a huge number of dangling
The moisture instability also related to interfacial defects, as
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the completed cell contains several different hole or electron bonds on the surface, such as un-coordinated species (Pb
44 atoms or halide anions) which likely behave as defects in
transport layer etc., produced interfaces. Through these
45 PSCs28. Therefore, it is crucial to passivate these grain
defects, the oxygen or moisture molecule penetrates the
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perovskite layer and induce its degradation, which results in boundaries and surface defects.
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non-radiative recombination destructive to device A lot of work has been done to passivate the perovskite GBs,
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performance. Recently, the additive engineering approach as well as the point or surface defects within the perovskite
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50 has proven to be an effective strategy for passivating the grains29, 30. It has been proved in many reports that the PbI 2
51 perovskite surface defects or grain boundary defects and has an impurity phase in perovskite films 30-32, PbI2 has been
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52 facilitating homogeneous nucleation8,10,19-23. considered as an excellent candidate for GBs defects

53 In this review, we have focussed on surface defects passivation33. The corresponding PbI2 passivation can also be
54 passivation through additive engineering using various intentionally incorporated by using non-stoichiometric PbI2
55 organic small molecules, electron acceptors and solvents and organic halides ratio in the perovskite precursor solution.
56 additives. We have discussed precisely how these additives The effectiveness of PbI2 passivation was also studied by
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57 affect the perovskite film morphology, dynamics of photo- varying the PbI2 to MAI ratio in precursor34, 35. The excess of
58 PbI2 was also reported to be beneficial for GBs passivation in
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2

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3 double cation perovskite (FAPbI3)0.85(MAPbBr3)0.15)36. was shown reduced TiO2 nanoparticle peaks as compared to
4 Besides PbI2, organic molecules can be used as additives into the pristine film. The uniform coverage of perovskite film all
5 perovskite precursor to passivate grain boundaries, grain over the TiO2 surface and the densely formed film will
6 interior or film surfaces. The deep trap states, such as Pb-I prevent the direct contact of TiO2 and the hole transport
7 anti-site defects can be passivated by PCBM at the GBs, as layer. Recently, our group has reported a small organic
8 proved by DFT calculations29. Further, a number of molecule incorporation into mixed cation and mixed anion
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9 additives, such as inorganic nanoparticles, organic or perovskite precursor named as DRCN5T (2,20-
10 inorganic salts, small molecules, electron acceptors, QDs, [(3,3”0,3””,40-tetraoctyl[2,20:50,2”:5”,2”0:5”0,2””-
11 etc. have been reported to passivate the GBs defects and quinquethiophene]-5,5””-diyl)bis[(Z)-methylidyne(3-ethyl-4-
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modify the non-radiative recombination centers, increasing oxo-5,2-thiazolidinediylidene)]]bis-propanedinitrile).
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the device performance or stability. There are also some DRCN5T is a well-known donor material used in the organic
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efforts have been done to passivate the point defects through solar cell.45 The perovskite precursor with the composition of
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balancing the halide composition in perovskite precursor. FA0.3MA0.7Pb(I0.9Cl0.1)3 was first dissolved in DMF and
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Recently, Zohar et al. and Yang et al have successfully DRCN5T (20 mg ml-1) was dissolved in chlorobenzene.
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passivated the deep level defects through I2 vapor treatment Then the DRCN5T solution was added into perovskite
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19 and introduction of triiodide ion into perovskite precursor, precursor with different volume ratios (Figure 1(a)). We have
20 respectively37, 38. They have found that the corresponding observed the passivated film quickly turns into black
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21 treatment significantly passivates the point defects, perovskite film even at room temperature more quickly to
22 suppresses the non-radiative recombination and improved that of control film, indicating the formation of orthorhombic
23 device performance and stability. Another most famous crystal structure with good crystallization. The DRCN5T
24 approach to passivate the surface defects is the usage of molecule was successfully interacted with the perovskite
25 Lewis acids or Lewis bases to passivate the acid or base precursor as proved by (X-ray photoelectron spectroscopy)
26 traps, respectively. A number of Lewis acids or bases have XPS analysis, in which the doublet splitting of S 2p spectra
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been reported to improve the perovskite film and promote the
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perovskite crystallization kinematics 29, 39. The details about
different additives and their effects on various characteristics
was clearly observed (Figure 1(b)). Interestingly, the
incorporated film was presented an effectively suppressed
non-perovskite phase δ-FAPbI3 at 11.7ᵒ 46 (Figure 1(c)). The
30 of perovskite film, as well as how the corresponding passivation by DRCN5T prevented the formation of non-
31 additives affect the device performance and stability, have perovskite phase, which results in high performance and
32 explained in the following sections. stable devices. Moreover, both the passivated and control
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33 films present a tiny peak of PbI2 at 12.5ᵒ after annealing at
34 3. Organic Small Molecules Additives 100 ᵒC. Previously, it has been reported that the origination
35 of the PbI2 peak belongs to the partial replacement of I anion
36 3.1 Effect on Structural Properties by Cl anion 47,48 and also it has been proved that the small
37 amount of PbI2 plays a positive role in device performance48.
38 In polycrystalline solar cells, the Grain boundary (GB) Yang et al. have investigated the passivation effect of organic
39 characteristics play a critical role as they thoroughly affect molecule CH6N3+ (guanidinium (GA)) on the MAPbI3 based
40 the photogenerated carrier behavior. Some groups have PSCs43. Interestingly, GA has been thoroughly explored as
41 shown the positive effect of GBs in the perovskite material an additive for dye-sensitized solar cells (DSSCs) to improve
42 system where the charge carriers can be conveniently device performance49. It has been observed that GA cation as
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separated by built-in potential and non-radiative an additive has an influence on bias-induced ionic movement
44 recombination rate is lower40-42. However, the performances and hysteric effects because it possesses nearly zero dipoles
45 of PSCs with GBs passivation quite higher than that of moment50,51. However, the GA cannot be employed alone to
46 without passivation because the grain boundaries act as non- form a 3D perovskite structure, as it has a larger size (278
47 radiative recombination centers.28,29,34,42,43 Therefore, a lot of
48 pm) than the commonly used MA cation (217 pm).52,53
work has been done in investigating the GBs passivation Furthermore, Zhao et al. have also investigated the effect of
49 techniques for improving device performance. Poly ethylene
50 PEG on the structural properties of perovskite54. They have
glycol (PEG) consider being an effective additive in demonstrated that there were three main reasons behind the
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perovskite precursor for enhancing the performance of PSCs film quality improvement, (1) the PEG doping produced
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as reported by Su and co-workers.44 They have found that the
53 simultaneously scaffold structure, which formed complicated
precise amount of PEG incorporation into precursor could
54 long-chain molecules, behaved as a skeleton to promote the
55 tune the perovskite morphology during its formation process perovskite crystal grains, pushing it to cover entire substrate
56 by smoothly spreading it across all over the surface of the quite uniformly. The function of PEG was similar to the
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57 substrate. The XRD analysis of perovskite films with and Al2O3 scaffolds55, which distributed uniformly all over the
58 without PEG incorporation represented that the doped film
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40 Figure 1(a) Schematic representation of precursor preparation and film formation. (b) XPS spectra of S2P of control and
41 doped film (c) XRD spectra of DRCN5T incorporated and control films annealed at different temperatures. (Reproduced with
42 the permission from Reference23). (d) XRD spectra of the perovskite film with PEG molecule concentration of 40 mg ml -1 at
43
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different annealing time. (Reproduced with the permission from Reference 54) (e) Raman spectroscopy of 2-MP and PbI2-(2-
44 MP)x complex powders. (Reproduced with the permission from Reference 19)
45
46 surface in an absolutely simpler and less costly way. (2) The deep black color after 70 min of annealing, with stronger
47 hydrophilic properties of the perovskite precursor were perovskite (110) and (220) peaks (Figure 1 (d)). They
48 improved by PEG incorporation due to which the wetting observed that the intermediate phase in pristine film was
49 capability was increased and produced uniform disappeared after 70 min, while in the film with PEG,
50 morphology56. (3) The crystallization process was observed intermediate phase vanished after 90 min, which indicated
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to be slow down due to the presence of PEG in the that PEG incorporation slow down the crystallization process
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perovskite precursor, as it was examined by tracking the of perovskite film. Recently, Zhu and co-workers have been
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intermediated phase of crystal formation by XRD analysis. reported the efficient and stable chemical passivation on the
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During annealing for 30-50 min, the color of the film was MAPbI3 perovskite surface by employing bidentate
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changed from yellow to orange and the perovskite phase molecule, 2-meracaptopyridine (2-MP)19. It has been found
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57 (110) became more prominent. Surprisingly, the intermediate that the 2-MP is an efficient bidentate ligand for metal
58 perovskite phase was disappeared and the film turned into complex, due to its substantial coordination potential57,58.
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4

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3 They have observed well coordination of both nitrogen atom passivated by the lone pair electrons from N atoms in g-
4 in pyridine ring and sulfur atom in the mercapto group of 2- C3N4, therefore enhancing the electronic cloud density 54,63.
5 MP with Pb2+, which improved the adhesion and binding Tripathi and co-workers have introduced a neutral surfactant
6 strength of the passivation layer on perovskite surface. amine-based small molecule PFN-P1 into the perovskite film
7 Perovskite surface passivation was obtained by dissolving 2- to develop uniform crystallization64. They have examined
8 MP molecule in chlorobenzene and deposited it onto freshly that some molecules of PFN-P1 immediately dissolved in the
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9 spin-coated perovskite film. Further, the PL peaks of PbI2-DMF solution due to the fact that the nitrogen lone pairs
10 passivated perovskite films were blue-shifted, which could in PFN-P1 molecules strongly coordinated with Pb2+, while
11 be assigned to the trap state passivation of perovskite film by some molecules could be excluded from the film surface and
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2-MP59. They have also studied the passivation effect by behaved as surfactant to passivate the defects states at the
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monodentate counterparts of pyridine (Py) and p-toluenethiol grain boundaries. As a result, a ripple-like structure was
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(PTT) to systematically compare the effect of anchoring on obtained for PFN-P1 and PbI2 mixed film which is quite
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the passivation efficacy and durability of 2-MP. It has been different from the conventional morphology of PbI2 on
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confirmed that 2-MP passivation presented improved binding PEDOT:PSS65. The corresponding molecular incorporation
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18 strength with Pb2+ compared to Py and PTT. The destruction provided a uniform, compact, pinholes free and
19 of organic compound was initiated at 93, 73 and 209 oC for homogeneous film structure. It was proposed that the PFN-
20 Py, PTT and 2MP based complexes respectively. The P1 introduction might lead to a smooth surface and suppress
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21 distortion temperature for corresponding complexes was the irregular crystallization of the PbI2 layer and develop a
22 unproportional to their boiling point. Such a higher highly uniform crystallization. Ginger et al. have investigated
23 decomposition temperature of PbI2-(2-MP)x complex could the influence of post-deposition passivation with different
24 be assigned to highly robust binding strength between Pb 2+ Lewis bases on PL lifetime of MAPbI3 perovskite film. They
25 and 2-MP passivated molecule. Further, to study the impact have prepared the perovskite samples treated with
26 of additives on structural properties of perovskite, Raman monodentate ligands, tri-n-octylphosphine oxide (TOPO), 1-
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29
PbI2 at 75, 96, 112 and 164 cm-1were disappeared in the
spectra of PbI2-(2-MP)x complex.[Ref]. Additionally, new
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spectroscopy was carried out (Figure 1 (e)). Typical bands of octadecanethiol (ODT), and triphenylphosphine (PPh3) and
measured in nitrogen. They have obtained a highly improved
average PL lifetime of 8.82 ± 0.03 TOPO treated film, which
30 bands were observed at 159 and 205 cm -1, which could be is much larger compared to the control film (0.97 ± 0.01 μs).
31 related to Pb-S bond. [Ref] Further, in 2-MP passivated This is consistent with the reported work for untreated
32 sample, the ring modes consisting C-S stretching vibrations MAPbI3 films66,67. Importantly, they have obtained enhanced
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33 originated at 445 and 733 cm−1 in the spectra of 2-MP (PL quantum efficiency) PLQE from ∼3% for the untreated
34 molecule were redshifted to 439 and 725 cm−1, respectively, film to values as high as 35 ± 1% for the TOPO-passivated
35 which further proved the Pb-S interaction.60 In corresponding film at excitation energy which produces carrier densities
36 2-MP passivated sample, the band associated with N atom at similar to 1 sun47. The improvement in PLQE as a function
37 1261 cm-1 became extremely weak and red-shifted slightly, of excitation power could be assigned to promoting radiative
38 representing the presence of Pb-N interaction.61 Therefore, recombination, which was resulted from trap state
39 the existence of Pb-S and Pb-N interactions have proved the passivation of perovskite surface by TOPO68-70.
40 bidentate anchoring between 2-MP and perovskite, which
41 resulted in a significant increment of passivation capability. 3.2 Morphological Analysis
42
Although the crystallization kinematics of perovskite film
43
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can be substantially improved by molecular additives in Jen and co-workers have reported that a set of diammonium
44 iodides, NH3I(CH2)4NH3I, NH3I(CH2)2O(CH2)2NH3I
solution processed methods, the crystallization mechanism
45 (EDBE) and NH3I(CH2)8NH3I (C8) can passivate the
and grain size distribution of perovskite film still have room
46 perovskite surface, GBs and corresponding adjacent electro-
to be improved. Kuang et al. have been reported the
47 transport layer in fabricated PSCs 71. Surface morphology of
48 incorporation of the 2D polymeric additive into MA-based
perovskite, named as graphitic carbon nitride (g-C3N4)62. control and treated films were examined, C8-passivated film
49
They have found that the optimized concentration of g-C3N4 presented the similar morphology as that of control film,
50
beneficial for crystallinity improvement particularly the main whereas, C4 and EDBE film were shown different
51
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perovskite peaks (110) and (112) intensity were enhanced morphology with striplike and branchlike structures,
52
respectively. The huge variation in surface morphology of
53 significantly, suggesting that corresponding passivation can
54 influence the crystallization in preferred direction 9. It was corresponding films might result from the transformation of
55 observed that the Pb 4f spectra moved to lower binding 3D to 2D perovskite phase due to the large size of
56 energy by g-C3N4 addition, representing that the diammonium iodides, which tried to produce 2D hybrid
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57 undercoordinated Pb2+ ions in MAPbI3 were successfully perovskites72,73. The difference in morphology between C4,
58 EDBE, and C8 incorporated films was considered to be the
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34 Figure 2 (a, b) Surface roughness measurements (c, d) surface potential measurements of prestine and C8-treated perovskite
35 films. (Reproduced with the permission of Reference 71) (e) Grain size distributions of perovskite films with different ABS
36 concentrations (Reproduced with the permission of Reference 20) (f, g) SEM images of control and 7.5 Vol.% DRCN5T
37 incorporated films (Reproduced with the permission of Reference 23). Top-view SEM images of the perovskite films control
38 CH3NH3PbI3 (h) and (i) 0.1 wt% g-C3N4 incorporate films. (Reproduced with the permission of Reference 62)
39
40 structural difference of 2D perovskites as proved by XRD control film the surface potential at the GB was higher than
41 and absorption measurement. Researchers have been the surface grains, representing down shifting energy band at
42 reported that only C8 material has gauche conformation in GBs which result in producing electron trap states74,75. On
43 the center of the alkyl chain among all other 2D lead-halide the other hand, in treated perovskite film the difference in
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44 perovskite materials72. Compared to the C4 and EDBE surface potential at the GBs and grains was remarkably
45 material C8 has higher energy, thus, it can be concluded that reduced, representing lower energy level bending. The
46 only the middle part of its diammonium cation has to be corresponding passivations by C8 facilitate electron transport
47 converted into the gauche conformation to embed into the 2D at the GBs. The surface potential for the treated film was
48 perovskite framework. Further, to study the influence of C8 calculated as (-0.10 V) lower than that of the pristine film (-
49 on surface defects passivation they have carried out Scanning 0.34 V). Downward band bending of C8 passivated film
50 Kelvin probe microscopy (SKPM) measurements on C8- beneficial for separation of charge carriers and efficient
51
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treated and control films (Figure 2(a-d)). They calculated electron accumulation by ETL in conducted devices76. The
52 values of surface roughness were 7.99 and 5.99 nm for effect of C8 on defect passivation was further studied by
53 pristine and treated perovskite films, respectively. The lower TRPL; the average lifetime of the treated film was improved
54 roughness of passivated film indicated that C8 was helpful to 40 ns from 24 ns, indicating C8 was successfully
55 for filling the GBs and reduced the corresponding variation suppressed the non-radiative recombination. To further
56 between grain surface and GBs. Also, the control and treated evidence the surface passivation of perovskite film, the
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57 films were shown totally different surface potential. In dependence of Jsc and Voc on light intensity was studied. The
58
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6

1
2
3 higher slope (0.944) in Jsc vs I and the reduction in Voc vs I DRCN5T the morphology was remarkably improved,
4 (light intensity) slop to 1.006 kT/q were presented by treated featuring highly compact, grain boundaries/pinholes
5 film compared to the control film, indicating the lower passivation and uniform coverage with enhanced grain size
6 recombination lost and efficient extraction of electrons by (Figure 2 (f,g)). Also, the 2D polymeric g-C3N4 additive has
7 ETL29,77,78. Yang et al. have reported MAPbI3 perovskite film multiple positive functions in improving the film
8 passivation by introducing an effective additive, named as morphology, (1) Facilitate the nucleation, well-dissolved in
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9 ammonium benzenesulfonate (ABS)20. A high-quality film the perovskite precursor, produced g-C3N4/perovskite
10 was fabricated because strong coordination between ABS intermediate phase, upon Ostwald ripening during annealing
11 and PbI2 was occurred due to its multiple O-donor produced large grains84. (2) Incorporation slowed down the
12
behaviour20. Both positive and negative charge defects were crystallization process by good coordination of N atom in g-
13
passivated, as the zwitterion like ABS structures were left in C3N4 with Pb2+, which resulted in defects passivation
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the perovskite film. The uncoordinated and positively towards enhanced device performance85. (3) Suppressed non-
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charged Pb ions were neutralized due to the presence of radiative recombination with promoted charge separation and
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negatively charged phenylsulfonate group (phenyl-SOOO-) transfer due to the passivation of GBs by presented
17
18 which acts as electron donor molecule. On the other hand, conductive g-C3N4 networks. It was interesting to note that
19 negative charged trap states or MA vacancies were filled by the g-C3N4-treated perovskite film presented smooth,
20 positively charged ammonium ions (NH4+). Further, the film pinhole-free with large grain size compared to the
us
21 quality, uniformity, and ionic trap states induced charge corresponding pristine film (Figure 2(h, i)). PEG molecule
22 carrier recombination were investigated by visible PL and not only affects the structural properties of perovskite film
23 TRPL mapping techniques. The most interesting factor was but also improved the film morphology. The perovskite film
24 observed that with increasing the concentration of ABS the with polymer scaffold structure was fabricated using one-
25 quality of the film was improved with enhanced grain size step method and annealed at 105 ᵒC. The morphology of
26 (Figure 2(e)). However, on overloading the ABS perovskite film without PEG incorporation presented huge
27
28
29
concentration the morphology was distorted by producing a
flake-like structure which attributed to the interruption of
regular perovskite crystallization by ABS7. The improvement
an pinholes and uncovered conducting substrates, enhancing the
probability of short circuits. On the other hand, the film with
PEG scaffold was shown continuous and entire coverage on
30 in film morphology and the reduction in trap states by ABS the substrate. The film thickness was also varied on the same
31 passivation, reduction in carrier non-radiative recombination substrate without polymer doping, whereas, the film
32 and prolong the carrier lifetime were responsible for the thickness with polymer doping was uniform or whole
dM
33 enhancement in device PCE from 17.29% to 19.64% for MA substrate 54.
34 based devices and 20.62% for the FA/MA based devices.
35 Grätzel and co-workers have been investigated the 3.3 Effect on Device Performance
36 passivation effect in PCSs by employing the additives
37 adamantine (AD) and 1-adamantylamine (ADA)79 which is Further, we have also reviewed how molecular additive
38 available in colorless crystalline solid, insoluble in water, but affects the device performance. PEG incorporation also has
39 can be dissolved in organic non-polar solvents, having higher positive effect on the device performance. It has been found
40 melting point than hydrocarbon80. The corresponding that the device performance was quietly affected by both
41 treatment was not altering the morphology of perovskite film molecular weight and concentration of polymer scaffold.
42 The length of the polymer has an obvious effect on device
which was further proved by XRD measurements. However,
43
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the charge carrier lifetime for ADA and AD passivated films performance, which is directly related to its molecular
44 weight. Since the uniform morphology was guaranteed by
were improved compared to the reference. Hence, the
45 the formation of three-dimensional molecular networks in the
champion device with 1.5 mg/ml ADA treatment presented
46 perovskite framework, therefore the optimized molecular
remarkable improved PCE from 19.32% to 20.93% with
47 weight was 420,000 Da which produced long PEG molecules
48 enhanced Voc from 1.08 to 1.15 V. It has been proved that
small crystallite size with large grain boundaries obviously (Figure 3(a)). As the PEG in an insulating polymer, so the
49
increase the non-radiative recombination possibility which series resistance is directly related to its concentration. The
50
deteriorates the device performance81-83. Additive optimized concentration was found to be 40 mg ml -1, where
51
ce
engineering has been proven to be an effective technique for on overloading the PEG amount the adverse device
52
performance was obtained (Figure 3(b)). Therefore, the
53 passivating the grain boundaries, enhanced the grain size and
device parameters, current density (Jsc) and open circuit
54 therefore, suppressed the probability of non-radiative
55 recondition. DRCN5T has efficiently improved the voltage (Voc) were significantly improved from 17.28 to
56 morphology of the film, employed as an additive in double 19.53 mA cm-2 and 0.88 to 0.97 V respectively, for
Ac
57 cation perovskite precursor23. With a precise amount of passivated devices. It has been reported that the enhancement
58 in recombination time constant responsible for improved
59
60
7
1
2
3
4 (a) (b) (c)
5
6
7
8
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9
10
11
12
13
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15 (d) (e) (f)
16
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18
19
20
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21
22
23
24
25
26
27
28
29
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Figure 3 (a) J–V curves based on precursor solution with different PEG molecular weight (b) J–V curves based on precursor
solution with different PEG concentration (molecular weight: 20,000 Da) (c) Recombination time constant R rec .Crec (Rrec,
recombination resistance, Crec, capacitance) under different applied voltage (d) PCE distribution of perovskite solar cells with
and without PEG scaffold. (Reproduced with the permission of Reference 54) (e) J-V characteristics of devices with different
30
concentrations of DRCN5T. (Reproduced with the permission of Reference 23) (f) Steady-state photocurrent and stabilized
31
power output of the champion device with 2-MP passivation. (Reproduced with the permission of Reference 19)
32
dM
this review that the incorporation of donor molecule
33 device (Figure 3(c)). The reproducibility of device PCE with (DRCN5T) into double cation perovskite
34 polymer doping was confirmed by a statistical analysis of > (FA0.3MA0.7Pb(I0.9Cl0.1)3) was beneficial for perovskite
35 100 devices (Figure 3(d)). The device devices with 20 and 40 crystallization process, produced a uniform film with large
36 mg ml-1 PEG concentration were presented a narrow grain size and promoting the charge carrier dynamics 23.
37 performance distribution with corresponding average PCE of These results were indicated that the optimized ratio of
38
14 and 12.5%, respectively, but the devices without out PEG DRCN5T remarkably enhanced the PCE of the
39
doping were presented broader PCE distribution changing corresponding devices which could be mainly attributed to
40
from 2 to 14%. Further, C8 molecule incorporation into the improvement in Jsc and FF (Figure 3(e))). The FF mainly
41
perovskite material was successfully passivate the surface related to the perovskite layer morphology, as the DRCN5T
42
defects and suppress the non-radiative recombination at the regulated the morphology of the active layer due to which the
43
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44 grain boundaries. Due to such effective passivation by C8, device performance was influence by the molecular additive.
45 the device PCE was increased from 14.65% to 17.60% in the Furthermore, the passivation of perovskite film with small
46 planar heterojunction configuration. They have observed that molecules also beneficial for PCE stability under
47 carrier lifetime remarkably improved to 800 ns from 80 ns performance measuring conditions (Figure 3(f)).
48 when MA cation was partially replaced by GA cation. Along Photocurrent tracking under a bias of 0.97 V has proved that
49 with the improvement of perovskite morphology by GA 2-MP additive into MAPbI3 perovskite precursor
50 incorporation, the device performance was also improved to successfully passivates the defects site on the surface 19.
51
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some extent. The corresponding passivation effect by GA has Other small molecules, such as AD and ADA have also a
52 demonstrated an enhancement of Voc from 1.025 V in the positive effect on the maximum power output of PSCs,
53 reference MA-based device to 1.071 V for GA, which results control and passivated films with AD were presented
54 in an enhancement in PCE of 17.13% compared to 16.35% practically stable power output of 19.12 and 20.35 mW cm -2,
55 for the MA device. Increased carrier lifetime and reduced respectively, over the 60s tracking period 79. Interesting the
56 defect activation energy in GA incorporated devices ADA passivated device shown a small enhancement in
Ac
57 evidenced the passivation effects. As it has been discussed in power output until approaching a plateau, respective to its
58
59
60
8

1
2
3 stabilized PCE of 21.3%. The authors have concluded from
4 this power tracking analysis that the surface treatment of (a) (b)
5 triple cation perovskite films by ADA have remarkablly
6 improved the PCE by 11.4%. Furthermore, the g-C3N4-
7 treated devices were obtained a high PCE of 21.1%, with
8 improved device parameters Jsc of 23.0 mA cm-2, a Voc of
pt
9 1.16 V and a FF of 0.79, which was a 17% enhancement in
10 PCE as compared to the reference device with PCE of
11 18.0%. Further, they have also fabricated large-area PSCs by (c) (d)
12
employing g-C3N4 incorporated perovskite films. The device
13
with active area of 1 cm2 presented a PCE of 19.5%, along
cri
14
with a Jsc of 22.2 mA cm-2, a Voc of 1.14 V and a FF of 0.77.
15
Such a remarkable device performance with g-C3N4
16
treatment could be attributed to the trap state passivation,
17
18 improved film quality and emphasized GBs influenced by
19 corresponding polymeric/conductive functionalization and
20 modification86.
us
21 Figure 4 (a) PCE relative to the initial efficiency after
22 3.4 Effect on Device Stability
storage of 60 days in 30% RH air (Reproduced with the
23
The durability issue in the ambient environment is another permission of Reference 20) (b) XRD patterns of freshly
24
critical hurdle for the commercialization of the PSCs. prepared and aged perovskite films (c) Water contact-angle
25
26 Recently, it has been examined that the trap states at the film test of freshly fabricated perovskite samples. (Reproduced
27
28
29
an
surface and grain boundaries, where the molecules have great
potential of activity and migration, were accountable for
initializing the distortion of perovskite phase87. The defect
with the permission of Reference 19) (d) Stability test of
PSCs with and without passivation under continuous full-sun
illumination and maximum power point tracking in a
30 sites could be originated by the production of MA + or FA+ nitrogen atmosphere at T =30 °C (Reproduced with the
31 vacancies due to evaporation of MAI or FAI during permission of Reference 21)
32 annealing of perovskite film. Hence, the incorporation of
dM
33 different types of additive ions into perovskite precursor under such a humid environment, with the little color change
34 could be expected to have strong interaction with after storage for 5 hours, on the other hand, the un-treated
35 corresponding ionic trap states to neutralize the charges 88. MAPbI3 films were entirely degraded into a transparent film
36 Since the perovskite materials have hygroscopic and within 30 min. The UV–vis absorption was also measured
37 thermodynamically unstable nature due to which the long for the corresponding films after the humid-aging treatment.
38 term stability of this technology is one of the sever hurdle of The 2-MP passivated perovskite films were presented
39 its practical application. It has been reported that ABS-1 was stabilized its absorption profile with an onset wavelength
40 one of the best molecular additives for device performance as near 780 nm, whereas the control film was lost almost all of
41 well as for long term stability under ambient condition. The the absorption in the visible region. To further evidence the
42 PSC with ABS-1 treatment was restored 85% of its initial humid-stability of respective passivated films, the XRD
43
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efficiency after 60 days of aging in air with humidity of measurements were carried out. In the unpassivated film, the
44 ≈30% and 80% after 400 hours in air at 65% humidity, perovskite characteristic diffraction peak at 14.0 ° became
45 whereas, the control device without ABS-1 presented 52% extremely weak, further two new peaks at 8.6° and 10.5ᵒ with
46 and 50%, respectively, under the same measuring conditions high intensity were appeared, correspond to the
47 (Figure 4a). Such remarkable environmental durability of MAPbI3monohydrate phase88,90, suggesting the distortion of
48 ABS-1 treated devices could be assigned to the uniform large
49 the perovskite crystal structure (Figure 4b). Conversely, the
grains sized morphology, improved perovskite crystallinity, passivated film presented strong perovskite diffraction peak
50
and reduced defect sites, which prevented the moisture and without indication of MAPbI3 monohydrate peaks, however,
51
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oxygen penetration via susceptible sites when exposed to there was a small peak originated at 8.3ᵒ related the formation
52
ambient environment89. Furthermore, Zhu et al. have of PbI2-(2-MP)x. Such a remarkable moisture-stability could
53
reported the impact of passivation by 2-MP molecular
54 be assigned to the fact that 2-MP treatment made the
55 additive on the high moisture-stability of perovskite film by perovskite film hydrophobic and the corresponding
56 storing the films in a highly humid environment at a passivation was suppressed the possible chemical activity of
humidity of >95%19. Interestingly, the 2-MP treated
Ac
57 the perovskite film surface. The water contact angles were

58 perovskite films were presented remarkably higher stability measured to be 45 and 68 for pristine and 2-MP passivated
59
60
9

1
2
3 films, respectively, proving the formation of hydrophobic crystallization process via fractional replacement of TA +
4 perovskite film (Figure 4c). The possible mechanism behind cation with MA+ and Cl- with I-. The larger groups of TA
5 the high moisture stability might be the strong bonding and Cl responsible for steric hindrance which interrupts the
6 between 2-MP and Pb2+ ions because of bidentate anchoring. order crystal structure of MAPbI3, presenting the slight
7 As a result, the reaction between ambient moisture and the reduction in perovskite crystallization. They have also
8 perovskite crystals was successfully suppressed, resulting in observed a diffraction peak at 11ᵒ correspond to the
pt
9 efficiently enhanced energy barrier hydration reaction production of an intermediate phase between TACl and
10 pathways. Furthermore, the molecular additives also played MAPbI3 with the enhancement in TACl concentration. This
11 an important role in improving the operational stability of peak confirmed the presence of Cl in the film, as it has been
12
PSCs under the full-sun illumination in a nitrogen proved that a similar peak was observed when MACl or
13
environment. Figure 4d represented the ADA, AD-treated PbCl2 incorporated in perovskite precursor98. The absorbance
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14
and control device stability under maximum power point measurements of TACl incorporated films were further
15
tracking. The control device was lost its 28% performance of proved that the perovskite crystallization reduced due to
16
its initial value after storing 300h in continuous light larger groups of TA cation and Cl anion. TACl also affects
17
18 illumination, whereas, ADA and AD incorporated devices the charge carrier recombination mechanism which was
19 were presented exceptional efficiencies of 96% and 92% of proved by PL intensity reduction with increasing the amount
20 their initial values, respectively. It has been proved that the of TACl, leading to the reduction in nonradiative
us
21 corresponding addition of molecular additives beneficial for recombination. The corresponding additive presented dual
22 both the performance and operational stability of PSCs. functionality by passivating simultaneously positively and
23 negatively charge traps in the perovskite film 99. The
24 4. Solvents Additives positively charged (Pb2+) defects and negatively charged
25 anti-sites (Pb-I) in the polycrystalline perovskite film were
26 4.1 Effect on Structural Properties successfully passivated by the electron donor Cl- and
27
28
29
Along with molecular incorporation into perovskite
precursor, a number of reports have been also published
an electron-deficient TA+, respectively. Further,
incorporation of TU into perovskite precursor remarkably
enhanced the crystallinity of the perovskite films which
the
30 based on solvent additives in the perovskite7,10,28,91-95. Sun et evidenced by the increased (110) peak intensity up to five
31 al. have been reported the ionic additive, named as 2- orders of magnitude than the pristine film. Fu et al. have
32 pyridylthiourea into MAPbI3 perovskite precursor to reported ionic defect passivation by triiodide ions [I 3-] during
dM
33 fabricate the PSCs under ambient condition using one step solvent vapor annealing process10. It consisted of ionization
34 method92. The 2-pyridylthiourea incorporation slowed down of iodine (I2) through oxidation of IPA, and the IPA was used
35 the perovskite crystallization process via coordination of N- as an annealing solvent having [I3-] (Figure 5 (c)). The
36 donor and S-donor with PbI2, produced compact, pin-hole quality of the perovskite film was significantly improved by
37 free films with huge grain size93. Figure 5(a) presenting the the compensation of iodine vacancies with [I3-] ion in direct
38 proposed reaction process of 2-pyridylthiourea with the IPA vapor interaction. The employed strategy suppressed the
39 perovskite precursor and corresponding device structure. The charge carrier non-radiative recombination and prolonged the
40 fabrication process consisted of three steps, firstly, the desire carrier lifetime. Jen and co-workers have reported the solvent
41 ratios of MAI, PbI2 and 2-pyridylthiourea were dissolved in 1,8-diiodooctane (DIO) as additive into perovskite solution
42 DMF/DMSO mixed solvents to obtained the doped and have found that a precise amount of the corresponding
43
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precursor, secondly, during spin coating a desired amount of additive could control the crystallization of perovskite film
44 chlorobenzene was dropped on the film to speed up the and modulate the formation of film100. The authors also
45 crystallization process and obtained intermediate crystal examined that the addition of DIO could temporarily co-
46 formation, thirdly, the as-formed perovskite film was relate with Pb2+ during crystal growth. This promotes
47 transferred to hot-plate for annealing at 100 ᵒC for 60 min.
48 homogeneous nucleation and likely regulates the interfacial
Since the thiourea has S-donor and pyridine has N-donor energy positively, eventually changing the kinetics of crystal
49 species due to which 2-pyridylthiourea could strongly
50 growth. Additionally, the alkyl halide additives might take
coordinate with PbI2. Therefore, the main advantage of this part in perovskite crystallization via detached carbon–
51
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additive was to produce an intermediate perovskite phase and halogen bonds to produce extra halogen ions, while an
52
passivation grain boundaries and surface of MAPbI396,97.
53 excessively long alkyl chain length could result in steric
However, there also some ionic additives, such as obstruction for interaction with Pb2+ and an increased non-
54
55 trimethylammonium chloride (TACl) was reported to be polar nature of the additives100. There was another high
56 decreased the crystallinity of perovskite (Figure 5(b)) 7. They boiling point solvent,
Ac
57 have proposed that TACl and MAI have identical chemical

58 structures, which might take part in the perovskite
59
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1
2
3
4 (a) (b)
5
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8
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14 (c)
15
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20
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21
22
23
24
25 Figure 5 (a) Schematic representation of the reaction process from the precursor to monolithic perovskite grains and the
26 structure of corresponding perovskite solar cells. (Reproduced with the permission of Reference 92) (b) XRD spectrum of
27
28
29
an
perovskite films incorporating different concentrations of additive. (Reproduced with the permission of Reference 7) (c) XRD
patterns with different vapors treatment. (Reproduced with the permission of Reference 10)
30 named as 1-chloronaphthalene (CN), was employed as an (Figure 6(a)). The enhancement in grain size was suggesting
31 additive in the perovskite precursor to control the that the incorporation of ACN into perovskite precursor not
32 crystallization mechanism perovskite to develop high-quality only improved the morphology but also necessarily
dM
33 crystalline films101. The corresponding additive was influenced the crystallization process. The XRD
34 responsible for highly uniform, homogeneous with lower measurement of perovskite films incorporated with ACN
35 pinhole perovskite film generation compared to the pristine presented the sharp intensity perovskite peaks, suggesting the
36 film. The authors claimed that CN has one Cl atom, which corresponding solvent additive was helpful for perovskite
37 could act as soft Lewis base to interact with Pb 2+, similar to crystallization. However, on overloading the amount of ACN
38 DIO additive in perovskite precursor. Another evidence for a small peak of PbI2 was appeared, which might be related to
39 its contribution to perovskite crystallization is the high the unreacted PbI2 species in mixed solvents. Many groups
40 boiling point (259-263 oC), which significantly slowed down have been investigated that the small amount of unreacted
41 the crystallization rate of the perovskite film. PbI2 could efficiently passivate the grain boundaries and
42 improved the device performance34,47,48. The morphology
43
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4.2 Morphological Analysis and crystallization dynamics of the perovskite film weak
44 coordinated ACN additive varied in a different way
45 Furthermore, we have also reviewed how the solvents compared to the strong coordinated (DMSO) solvent
46 additives affect the morphology of perovskite film. Li et al. additive. Moreover, the optoelectronic properties of
47 have reported the incorporation of acetonitrile (ACN) into perovskite film were also affected by the addition of ACN.
48 the PbI2 solution in DMF95. They have observed that the Since the grain boundaries act as non-radiative
49 optimized ratio of ACN obviously affects the PbI 2-DMF recombination centers for charge carrier99, therefore, the
50 bonding complexes. The morphology and roughness of ACN incorporated films produced large grains with fewer
51
ce
perovskite film was remarkably influenced by the produced grain boundaries due to the lifetime of charge was
52 perovskite complexes. The entire surface coverage and remarkably improved for weak coordinated solvent
53 polyhedral-like grains with dramatically different sizes were compared to the strong one. Wang et al. have reported the
54 obtained by the variation in concentration and type of solvent incorporation of Thiourea (TU) into MAPbI 3 perovskite
55 additives (ACN or DMSO). About 3-4 times larger grain was precursor which produced Lewis-bases ligand and was
56 observed for the ACN incorporated film compared to its responsible for enhanced grain size94. Previously, it has been
Ac
57 counterpart DMSO additive with the same concentration

58 observed that the TU additive in the FAPbI3 precursor was
59
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11
1
2
3
4 (a) (b) (c)
5
6
7
8
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(d) (e)
18
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25
26
27
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29
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30
31
32 Figure 6 (a) Planer SEM images of perovskite film with ACN and DMSO incorporation. (Reproduced with the permission of
dM
33 Reference 95) (b) SEM and AFM images of perovskite film with and without TU incorporation. (Reproduced with the
34 permission of Reference 93) (c) Top and cross-sectional view of perovskite films with urea additive. (Reproduced with the
35 permission of Reference 91) (d) Dark J-V curves of (e) electron only device (g) hole only device with and without additive.
36 (Reproduced with the permission of Reference 7)
37
38 promoted to the film quality which improved the device (O=C(NH2)2) as an additive in PbI2 solution to fabricate the
39 performance102. The proper amount of TU additive was inverted PSCs using two-step spin-coating method91. For
40 remarkably increased the grain size from 200 nm to over 2 future development and commercialization of this
41 µm, which proved that TU has played a very important role photovoltaic technology the perovskite material processing
42 in nucleation and corresponding crystal growth process and device fabrication should be low cost and environment
43
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(Figure 6(b)). Since the voids on the surface and large friendly and the previous studies indicated that the employed
44 density of GBs were found to be the highly efficient routs for additive was an economical and echo-friendly105,106. They
45 ion migration103, the optimized ratio of additive was have observed that the huge PbI2 flakes were produced due to
46 successfully passivated the defects and suppressed the well coordination between urea and PbI 2 for generating
47 hysteresis in the device. They have examined the surface PbI2•O=C(NH2)2 complex, which resulted in slow down the
48 roughness of perovskite films with and without TU additive crystallization dynamics to obtained large PbI2 flakes and
49 by employing AFM measurements (Figure 6(b)). The value responsible for developing compact, uniform and large grains
50 of RMS for the optimized doped film was higher than the perovskite film (Figure 6(c)). They have found that the urea
51
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pristine film which could be curtailed for hole transferred as has played two important roles in anchoring the perovskite
52 affecting the contact area at the interface of the active layer crystallization process. (1) Arbitrated the PbI 2 film
53 and hole transporting layer. Higher roughness could result in morphology, which necessarily impacted the perovskite film
54 an enhancement in the contact area at the interface, which morphology. (2) The formed intermediate phase of
55 obviously increased the carrier transportation, but an extra CH3NH3I•PbI2•O=C(NH2)2 complex was slowed down the
56 high value of roughness resulted in low V oc and FF104. Han crystal formation process of perovskite films. It has been
Ac
57 and co-worker were the first time reported the urea found that two-step techniques for the fabrication of the
58
59
60
12

1
2
3 active layer were helpful for good nucleation of MAI at the whereas, pyridine passivation based device was present an
4 grain boundaries and defect of PbI295,107. The nucleation sites improved PCE of 16.5% (Figure 7(b)). They have also
5 of perovskite were decreased due to the larger grain size of examined the Lewis base passivation also affects the
6 PbI2 flakes, suggesting decrement in grain boundaries and stabilized power output of the devices. The planar
7 surface defects. They have concluded that the final heterojunction devices based on TiO2 and spiro-OMeTAD
8 morphology of perovskite film consisting of its grain size.
pt
9 electron and hole transport layers respectively presented the
Crystallization mechanism and film coverage on the entire stabilized power output around one half of what could be
10 surface were determined by the morphology of PbI 2108,109.
11 obtained by fast scan14. Interestingly, the stabilized power
The devices based on PbI2•O=C(NH2)2 complex were
12 out was remarkably enhanced with the pyridine and
presented remarkably improved performance from 12.75% to
13 thiophene passivation compared to the control devices. The
18.01% with an optimized ratio of urea additive. To obtained
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14 control device was presented efficiency of 13.1% via fast
the direct evidence that the solvent incorporation into
15 scan, which stabilized at 8.3% (Figure 7(c)), whereas the
perovskite precursor could passivate the surface defects,
16 thiophene-passivated device produced efficiency of 15.3%
space charge limited current (SCLC) technique was
17
employed, which could be considered to be an efficient which stabilized at 14.1% (Figure 7(d)) and for pyridine-
18
technique to quantitatively calculate the trap state treated device, 16.5% efficiency was achieved by fast scan
19
20 density1,110. The electron and hole trap state densities of the which stabilized at 15.5% (Figure 7(e)). The photocurrent
us
21 TACl passivated devices were 4.9 x 1015 and 2.94 x 1016 cm- rise time was decreased from 40 to 12 and >2 s for control,
3
22 , respectively. These values were much lower than the thiophene and pyridine passivated devices, respectively
23 corresponding values obtained from the control devices (1.98 which were well consistent with the corresponding theurtical
24 x 1016 and 3.43 x 1016 cm-3), which have proved that the results of trap filling and reduced trap state density. The
25 TACl will effectively passivate the ionic and surface defects reproducibility of PSCs also a big hurdle of its
26 (Figure 6(d-e)).
27
28
29
4.3 Effect on Device Performance
an commercialization, the solvent additive was helpful for the
reproducibility of PSCs. TACl additive based devices were
presented the narrow distribution of efficiency, presenting
superior reproducibility of devices (Figure 7(f)). They have
30 Further, we have reviewed about the effect on the device
31 performance by the incorporation of solvent additives into fabricated PSCs using a normal n-i-p structure in which ACN
32 perovskite precursor. Recently, the fabricated devices with additive perovskite film was sandwiched between TiO2
dM
33 IPA vapour passivation were presented remarkable improved nanocrystals and spiro-OMeTAD. The average PCE for
34 PCE of about 30% compared with the control devices. The pristine MAPbI3 based device was 17.43%, whereas the best
35 control device was present a Jsc of 20.14 mA cm-2, a Voc of efficiency was of 19.68% obtained for an optimized ratio of
36 1.00 V, a FF of 70% and a PCE of 14.16% (Figure 7(a)), CAN with a Voc of 1.15 V, a FF of 75.33% and a Jsc of 22.69
37 mA cm-2. The stabilized efficiency measurements at
whereas, the passivated device with optimized ratio of IPA
38 maximum power point also demonstrated that the solvent
39 vapour was showed a remarkably improved performance
with a Jsc of 22.57 mA cm-2, Voc of 1.08 V, FF of 0.76, and additive (ACN) remarkably improved the stability of the
40
41 PCE of 18.53%. This enhanced device performance could be device under working conditions. The TU additive was also
42 assigned to the improved perovskite film quality and reduced played an important role in device performance; especially
43 the Jsc was efficiently improved from 22.38 to 23.97 mA cm -2
pte
ionic point defects within the perovskite crystals, which

44 acted as non-radiative recombination centers104, with the for doped devices. This could be assigned to improved light
45 introduction IPA vapour during the annealing process. Noel absorption and charge transportation due to the large grain
46 et al. have investigated the passivation effect on crystal size. The Voc was mainly affected by the corresponding
47 position of quasi-Fermi level in the active and ETL and the
surfaces of mixed halide perovskite MAPb(I 3-xClx) by
48 ionic or surface defects non-radiative recombination in the
employing Lewis bases thiophene and pyridine28. They have
49 charge transport layers111. Precisely, the optimized ratio of
50 carried out both theoretical and device based investigation to
understand the impact of Lewis base treatments and observed TU incorporated device was presented improved device
51
ce
52 that the non-radiative recombination was significantly efficiency from 16.60% to 19.80%. Park and co-workers
53 reduced within the passivated films, particularly under a have reported the Lewis base adduct approach to fabricate
54 lower level of excitation. The performance of planar the normal structure PSCs and obtained the best cell PCE of
55 heterojunction solar cells was significantly improved by both 19.7%93. The corresponding iodine anion based adducts with
56 thiophene and pyridine treatments. The PCE of thiophene Lewis acid and oxygen based Lewis base were confirmed by
Ac
57 passivated devices were increased from 13.1 to 15.3%, infrared spectroscopy. They have presented the impact of
58
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4 (a) (b) (c)
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29
an
Figure 7 (a) J–V curves (reverse scanning direction) based on perovskite films annealed by different approaches.
(Reproduced with the permission of Reference 10) (b) J-V characteristics for the best control and the thiophene-passivated and
pyridine-passivated devices. (c) Stabilized efficiency of control, (d) thiophene-, and (e) pyridine-passivated devices,
30 measured by holding the device at its maximum power point for 120 s. (Reproduced with the permission of Reference 28) (f)
31 PCE statistical representation of control and additive based devices. (Reproduced with the permission of Reference 7)
32
dM
33 adducts on the charge carrier transport in MAPbI 3 based mobility was improved from 2.7 to 3.9 x 10 -3 cm2V-1s-1 for
34 PSCs using photoinduced charge extraction by linearly DMSO induced MAPbI3 film, which was higher than MACl-
35 increasing the voltage (photo-CELIV) measurements112. The induced perovskite film (3.2 x 10-4 cm2V-1s-1)114. The
36 comparison of the current transient of photo-CELIV for the extracted charge carriers were much higher than for adduct-
37 MAPbI3 and MAI•PbI2•DMSO layers indicated that a charge assisted devices compared to the devices without DMSO,
38 extraction CELIV peak was originated at 3 μs after applying which could be assigned to the lower charge recombination
39 increasing voltage ramp, and then current became saturated for corresponding devices. Commonly, the photo-generated
40
to the displacement current of the capacitance (jo)113. The carriers extracted by the built-in potential or recombine of its
41
42 difference in the current density could be assigned to the absence. The extracted charge carrier density was much
43 difference in the film thickness of MAPbI 3 and DMSO based higher for adduct-based devices than pristine MAPbI3 based
pte
44 film which is defined as jo = εεoA/d112. The charge carrier device, suggesting lower recombination in DMSO induced
45 samples as proved by photo-CELIV 115.
46 its initial value. Such remarkable ambient environment
47 4.4 Effect on Device Stability stability could be assigned to the enlarged grain size,
48 A number of reports have been impact of solvent additives improved crystallinity, and suppressed surface defect
49 on the ambient stability of perovskite material and states117. The quick distortion of the control solar cell
50 PSCs10,92,94,116. The long-term stability of the TU-treated performance resulted from the numerous surface defects
51
ce
perovskite film based solar cells in ambient environment developed by the small grain size. Further, Liu and co-
52 (10–20% humidity, 10–20 ᵒC temperature) was also studied. workers have investigated the effect of IPA/[I 3-] vapour
53 It has been examined that the TU-0.5 solar cells presented annealing on the long term stability of PSCs10, IPA and
54 excellent stability against humidity and temperature in the IPA/[I3-] treated film based devices were stored in an
55 ambient air (Figure 8(a)). The control device lost its ambient environment under various conditions, i.e 25 ᵒC with
56 efficiency to lower than 10% after storage for 30 days, humidity of 10-20% under continuous light illumination, a
Ac
57 whereas, the TU-treated device retained its PCE of 75% of humidity of 50% and a 70 ᵒC temperature, respectively. The
58
59
60
14
1
2
3 (a) (b) variation during the stability test (Figure 8(c)). Conversely,
4 the pristine perovskite films were exhibited a significantly
5 decreased absorption intensity in the whole absorption
6 spectrum (Figure 8d), suggesting that the grain boundaries
7 passivation by IT-M was beneficial for the ambient
8 environment stability of PSCs.
pt
9
10 (d) 5. Electron accepter Additives
(c)
11
12 5.1 Effect on Structural Properties
13
cri
14 Furthermore, we have also reviewed the electron acceptors as
15 additives into perovskite precursor, a number of reports have
16 been published based on electron acceptors
17 incorporation29,104,116-122. Recently Lu et al. have reported
18 long term stability of perovskite precursor solution by the
19 incorporation of organic acceptor molecule ITIC-Th (3,9-
Figure 8 (a) Long-term stability of solar cells for 30 d stored
20 bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-
us
in the dark in ambient air with RH: 10–20 %. (Reproduced
21 5,5,11,11-tetrakis(5-hexylthienyl)-dithieno[2,3-d:2′,3′-d′]-s-
with the permission of Reference 94) (b) Long-term stability
22 indaceno[1,2-b:5,6-b′] dithiophene)118. ITIC-Th basically
23 of IPA and IPA/[I3-] devices with a humidity of 10–20%.
related to the group of organic non-fullerene fused-ring
24 (Reproduced with the permission of Reference 10) UV–Vis
electron acceptors which have recently remarkably improved
25 absorbance spectra evolution of 0.2 mg mL -1 IT-M-assisted
the performance of organic photovoltaic 123,124. They have
26 perovskite film (c) and control perovskite film (d) after 1 h
27
28
29
and 3 h of annealing. (Reproduced with the permission of
Reference 116)
an employed mixed cation and mixed halide ion perovskite
material base on MA0.17FA0.83Pb(I0.83Br0.17)3 composition,
ITIC-Th was dissolved in the chlorobenzene and added its
device based on IPA/[I3-] treatment exhibited excellent desired concentration into perovskite precursor. It was
30 observed that α-phase of perovskite films can be achieved
stability and after 1200 hour of storage it retained 88% of its
31 from both freshly made perovskite solutions, despite
initial efficiency, while the device based on perovskite film
32
dM
treated with IPA lost its efficiency to less than 40% after 500 whether ITIC-Th is incorporated or not. However, the films
33 spin-coated from the pristine precursor solution without
34 hours of storage (Figure 8(b)). Furthermore, the IPA/[I 3-]
treatment also improved the light illumination stability, ITIC-Th aged for >12 days converted into a light yellow
35
moisture stability, and thermal stability. Since it has been color, resulting from the production of a dominant yellow
36
examined that the degradation of perovskite material begun non-perovskite phase indicating that the conventional
37
at the defect sites such as Pb or I vacancies. Therefore, the precursor solution endured from a harsh degradation over a
38
long-term storing process. Surprisingly, the samples
39 corresponding long term stability in ambient conditions
40 could be assigned to the passivation of I defects by the fabricated from ITIC-Th incorporated precursor solutions
41 IPA/[I3-] vapour annealing treatment. Yang et al. have been were continued its black perovskite phase even when the
42 reported the Lewis base method using n-type conjugated perovskite precursor were stored for a very long time of
43 small-molecule IT-M116. The corresponding incorporation of about 96 days. The fresh and aged perovskite films with and
pte
44 IT-M successfully reduced the trap states, as well as the without ITIC-Th presented different behavior as shown in
45 increased charge transport property of perovskite layer and Figure 9(a). The ITIC-Th was also played an important role
46 successfully improved the device performance to a PCE of in perovskite crystallization, the conventional perovskite film
47 20.5%, with a high fill factor of 81% and comparatively showed a non-perovskite phase located at 11.7ᵒ correspond to
48 suppressed hysteresis. Further, the molecular doping the hexagonal yellow FAPbI3 phase125, which is known to be
49 passivated the moisture-sensitive defects on the perovskite destructive for charge transportation and device performance.
50 film surface and as a result, an ambient environment and Further, the intensity of perovskite peak at 14.1 ᵒ was
51
ce
thermally stable devices were realized. The passivated device gradually decreased for the corresponding pristine precursor.
52 was retained 78% of its initial PCE after 4 hours storage in They have also observed the appearance of double peaks
53 the humidity of 80% and temperature of 85 ᵒC, while the 31.5ᵒ and 43.1ᵒ which were related to the unwanted phase
54 control device presented much less stability ( PCE decreased separation of mixed halide perovskite into Br-rich and I-rich
55 from 18.15% to 11.14%). UV–Vis absorption spectra of domains126 On the other hand, the film doped with ITIC-Th
56 respective perovskite films were also measured, the was presented strong perovskite peak even after long storage
Ac
57 absorption of IT-M treated films were show negligible time, indicating that the ITIC-Th was helpful for perovskite
58
59
60
15
1
2
3 (a) (b)
4
5
6
7
8
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9
10
11
12
13
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14 (c) (d)
15
16
17
18
19
20
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21
22
23
24
25 Figure 9 (a) Schematics of the films fabricated from the fresh and aged precursor solutions without and with ITIC-Th. (b)
26 XPS spectra in the Pb 4f region for perovskite films made from fresh precursor solutions without and with ITIC-Th.
27
28
29
an
(Reproduced with the permission of Reference 120) (c) Schematic illustration of PSCs based on CH3NH3PbI3without and with
the addition of F4TCNQ in the perovskite precursor (d) XPS spectra of passivated and control perovskite films. (Reproduced
with the permission of Reference 131)
30
31 crystallization. Additionally, the XRD peak of unwanted formed which filled the GBs and vacancies in the
32 yellow phase at 11.7° was disappeared. Hence, it was proved corresponding perovskite film. Further, the Pb 4f XPS
dM
33 that the ITIC-Th incorporation could promote the long term spectra for passivated perovskite film was shifted towards
34 stability of perovskite precursor, beneficial for the production higher binding energies, indicated the appearance of
35 of mixed cation and anion perovskite crystals by chemical interaction between F4TCNQ and Pb in perovskite
36 significantly reducing non-perovskite δ-phase and the phase precursor. Additionally, the existence of metallic Pb (at
37 separation. The perovskite films with and without ITIC-Th 136.1 and 141.1 eV) in pure perovskite film was successfully
38 incorporation was further investigated by XPS analysis. Two passivated by the corresponding additive (Figure 9 (d)).
39 satellite peaks were observed at 136.5 and 141.4 in the Metallic Pb in perovskite film responsible for the existence
40 pristine perovskite film, which could be assigned to the of iodide vacancy in perovskite crystal lattice, which plays a
41 metallic or unreacted Pb127,128, suggesting the availability of crucial role to produce non-radiative recombination centers.
42 iodine vacancies in the perovskite crystal and responsible the Interestingly, the addition of F4TCNQ into perovskite
43
pte
formation of non-radiative recombination centres11,129 precursor greatly reduced the metallic Pb, because of the
44 (Figure 9(b)). Conversely the satellite peak was remarkably passivation of defects produced by uncoordinated Pb atoms.
45 reduced in the ITIC-Th-treated perovskite film, suggesting 5.2 Morphological Analysis
46 significant passivation by good coordination between Furthermore, we have reviewed how the electron acceptor
47 unreacted Pb, Lewis base carbonyl (C=O) and cyano (C≡N) materials affect the morphology of perovskite film. Zhang et
48 in the ITIC-Th130, resulting in an enhancement in FF. Chen et
49 al. have reported pseudohalide tetrafluoroborate (BF4−)
al. have investigated the passivation effect on GBs defects additive into double cation perovskite FA0.83MA0.17Pb(IBr)38.
50
and lattice defects without morphology alteration by They have observed that the presence of NH 4BF4 in the
51
ce
employing additive engineering131. They have used p-type perovskite film significantly improved the morphology with
52
dopant named as 2,3,5,6-tetrafluoro 7,7,8,8- enlarged grain size compared with the pristine film (Figure
53
54 tetracyanoquinodimethane (F4TCNQ) as an additive into 10(a, b)), suggesting the corresponding additive promoted
55 MAPbI3 perovskite precursor (Figure 9(c)). The F4TCNQ the crystallization and helpful for the homogeneous film
56 was widely used in doping epitaxial graphene having very development. The optimized amount of NH4BF4 in the
Ac
57 low unoccupied molecular orbital energy level of -5.24 perovskite was remarkably prolonged the carrier lifetime of
58 eV132,133. Perovskite-F4TCNQ bulk heterojunction was
59
60
16
1
2
3
4 (a) (b) (e)
5
6
7
8
pt
9
10
11
12
13
cri
14
(c) (d)
15
16
17
18
19
20
us
21
22
23
24
25 Figure 10 (a) Plane-view SEM images of (FAPbI3)0.83(MAPbBr3)0.17film with a) 0%, (b) 1% NH4BF4 (c) Top SEM image of
26 pure perovskite film. (d) BHJ perovskite–0.1 wt% PCBM film. (Reproduced with the permission of Reference 121) (e) Top:
27
28
29
with the permission of Reference 119)
an
SKPM images on the perovskite film; bottom: corresponding potential curves with average potential values. (Reproduced
30 968.73 ns. The enhancement in PL lifetime could be successfully diffused into the pre-deposited PbI2:MAI film
31 attributed to the suppression of non-radiative recombination promoting a top-down PCBB-OEG gradient distribution,
32 in (FAPbI3)0.83(MAPbBr3)0.17 via NH4BF4 treatment. Wu and suggesting not only a soft-template for the production of
dM
33 co-workers have been studied a PbI2–PCBM hybrid high-quality MAPbI3 grains but also was beneficial for band
34 fabricated from a PbI2–PCBM/DMF precursor solution and alignment of multi-layer device. The surface potential of
35 the perovskite CH3NH3PbI3-PCBM film was formed by control and PCBB-OEG incorporated films were examined
36 adding an MAI/IPA solution121. The quality of the active by Kelvin probe force microscope (KPFM) and the surface
37 layer (the surface defects, grain boundaries, and smoothness potential (−114 mV) of the incorporated film was moved up
38 of the film) was the major factor for promising the PV by ≈190 mV compared that (≈303 mV) of the control film
39 performance of the cell47,134 (Figure 10(c, d)). The TRPL (Figure 10(e)). The corresponding observation indicated a
40 decay of perovskite films with additives or different suppressed potential barrier for electron transfer between
41 passivation materials presented a bi-exponential decay with a optimized doped perovskite film and PCBM. Also, the
42 fast and a slow component. Previously, it has been examined formation of an ultrathin hydrophilic PCBB-OEG layer on
43
pte
that the charge recombination in perovskite films suggests the top of doped film developed extra surface dipole,
44 that the fast decay component related to the bimolecular responsible for lowering the work function, resulting in
45 recombination of free charge carriers, and the slow one improvement in band alignment136. Additionally, the dipole
46
mainly represented the trap-assisted recombination135. moment of PCBB-OEG was aligned perpendicularly to the
47
Choline chloride has been reported to be an efficient planar perovskite film,137 which could further increase the
48
passivating material which mainly affected the slow decay built-in electric field of the device.
49
50
component due to which the recombination lifetime 5.3 Effect on Device Performance
increased from 82.3 ns to 903.4 ns. Recently, Xu et al. have To further explanation on the impact of electron acceptor
51
ce
52 been synthesized a hydrophilic fullerene derivative named as additives on charge extraction and recombination mechanism
53 [6,6]-phenyl-C61-butyric acid-(3,4,5-tris(2-(2-(2 in the operation device, we have reviewed the Nyquist plot
54 methoxyethoxy)ethoxy)ethoxy)phenyl)methanol ester obtained from impedance spectroscopy (IS) measurements.
55 (PCBB-OEG) and first they have employed it as an additive The PCBB-OEG-based device was shown an obviously
56 of second precursor solution containing MAI (in IPA lower charge transfer resistant (Rtran) of 16.89 Ω than that of
Ac
57 solvent) in the two-step deposition method119. The PCBB-

58 OEG incorporated in the second precursor solution was
59
60
17
1
2
3 (a) (b) (c)
4
5
6
7
8
pt
9
10
11
12
13 (d) (e) (f)
cri
14
15
16
17
18
19
20
us
21
22
23
24
Figure 11 (a) Nyquist plots of the ac impedance spectra of the pero-SCs based on pero-pristine and pero-0.1 films. (b) J–V
25
curves of the p-i-n planar pero-SCs based on different perovskite photoactive layers. (c) Maximal steady-state photocurrent
26
27
28
29
an
output of efficient device at the maximum power point (at 0.9 V for the device based on pero-0.1) and its corresponding
output power. (Reproduced with the permission of Reference 119) (d) Nyquist plots of the reference and champion devices (e)
J–V curves of the champion devices with different NH 4BF4 molar ratio under 1 sun illumination. (f) Steady-state current
density and PCE as a function of time for the PSC with and without 1% NH4BF4. (Reproduced with the permission of
30 Reference 8)
31 control device device (30.19 Ω), which indicated an efficient the respective devices was tested under the illumination at a
32 transfer of the electrons at the perovskite/PCBM interface constant bias of 0.90 V for 200 s (Figure 11 (c)). The
dM
33 due to the well-developed electronic coupling at interface optimized device with PCBB-OEG incorporation presented a
34 and band alignments generated from gradient distribution of photocurrent of 22.16 mA cm−2 and the corresponding PCE
35 PCBB-OEG in perovskite film (Figure 11 (a)). Additionally, was improved to 19.95% compared to that of the control
36 the PCBB-OEG-treated devices were also presented much device (16.57%). The device with 0.1 wt% PCBB-OEG
37
lower series resistance (Rs) of 14.47 Ω cm2, suggesting well additive was delivered an abrupt rising photocurrent to
38
contact between ETL and the uniform, dense-crystals maximum value during immediate light illumination. The
39
perovskite film. Due to such remarkable charge transfer corresponding higher and stable photo-current and quick
40
dynamics characteristics, the PCE of the PCBB-OEG light response in the treated device were related to the
41
incorporated device was improved to 20.2%, with a higher J sc improvement of the perovskite defects passivation and
42
43 of 23.65 mA cm−2, Voc of 1.07 V, and a high FF of 0.80. On energy level alignments in the devices. The studied results
pte
44 the other hand, the pristine device without PCBB-OEG proved that the presence of PCBB-OEG in the perovskite
45 additive was presented a Jsc of 22.97 mA cm−2, Voc of 1.04 V, film beneficial for tran-states passivation and its gradient
46 FF of 0.70 and PCE of 16.7% when measured in the reverse distribution in the precursor was responsible for the
47 scan direction (Figure 11 (b)). The improved device improvement in device performance and reduction in
48 performance could be assigned to the increment in FF, which hysteresis. The optimized amount of electron acceptor
49 could be evidenced by the more uniform grain size and additive in the perovskite film was helpful for suppression of
50 higher crystallinity of the treated perovskite film. The small charge recombination. Two types of information could be
51
ce
enhancement in Voc could be attributed to the increased built- obtained from Nyquist plot, one is transport resistance (Rtrans)
52 in electric field generated from the existence of the ultrathin and the other is recombination resistance (Rrec) at high and
53 PCBB-OEG dipole layer originated on top of the treated- low frequency region, respectively. The Rrec presented a
54 perovskite film. Theoretically, Voc was driven from the large enhancement with the incorporation of 1% NH 4BF4,
55 quasi-Fermi level splitting in the photoactive layer, and which suggested the recombination in PSCs was significantly
56 limited by the corresponding difference of work function of reduced (Figure 11 (d)). To understand the impact of additive
Ac
57 the two-electrode contacts138. Further, the PCE stability of on the device performance, they have fabricated devices
58
59
60
18

1
2
3 based on NH4BF4 perovskite films in the structure of (a) (b)
4 ITO/SnO2/perovskite/spiro-OMeTAD/MoO3/Ag. The
5 champion reference device without NH4BF4 incorporation
6 shown a PCE of 17.55% with Jsc of 23.39 mA cm−2, a Voc of
7 1.12 V, and a FF of 0.67. Conversely, the best-performing
8 device with an optimized ratio of NH4BF4 had a much-
pt
9 improved PCE of 20.16% with a Jsc of 23.38 mA cm−2, a Voc
(c)
10 of 1.15 V, and a FF of 0.75 (Figure 11(e)). The enhanced

11 device performance could be assigned to the improved
12
perovskite crystal quality, prolonged charge carrier lifetime
13
and suppression of carrier recombination by employing
cri
14
NH4BF4 as an additive in mixed cation and halide perovskite
15
precursor. The stabilized power output examination was also Figure 12 (a) Stability of the pero-SCs in ambient
16
carried out by holding the voltage at the maximum power atmosphere with 70–80% RH for 300 h. (b) The photos of
17
point. The stabilized PCE and Jsc were improved to 19.15% perovskite films stored under ambient atmosphere with 70–
18
19 and 20.82 mA cm−2, respectively, for the incorporated 80% RH for 14 d, and the images of the water droplet contact
devices compared to that of reference device with PCE of angles on the surfaces of different perovskite films.
20
(Reproduced with the permission of Reference 8) (c) Device
us
21 16.90% and Jsc of 19.20 mA cm−2 (Figure 11(f)). The long
term stability of the devices under continuous one sunlight stability measurements of aged devices with and without
22 ITIC-Th incorporation. (Reproduced with the permission of
23 illumination with and without NH4BF4 incorporation were
Reference 120)
24 also measured and the reference device was kept about
films spin-coated from perovskite precursor aged for various
25 56.7% of its initial efficiency, whereas, the treated device
time intervals. For the films fabricated from perovskite
26 was restored about 86.0% of its initial efficiency, after 300 h
27
28
29
illumination. The corresponding results indicated that the
NH4BF4 treatment beneficial for device stability under
illumination, which could be resulted from the suppressed
an precursor without ITIC-Th incorporation, the optical
absorption band-edge gradually shifted from ≈770 to ≈500
nm with the increment in aging time, indicating the
development from a typical absorption spectrum of black
30 defects in the device. It can be concluded that due to its
perovskite phase to a typical absorption spectrum of FAPbI 3
31 extraordinary photovoltaic characteristics and well-aligned
yellow-phase. Conversely, the perovskite films incorporated
32 energy levels with that of MA0.17FA0.83Pb(I0.83Br0.17)3
dM
with ITIC-Th presented sharp optical band edge and strong
33 perovskite, the existence of ITIC-Th in the perovskite film
34 light absorption similar to the films made from fresh
subsidized to improved current density and FF and therefor,
35 precursor solution. Additionally, control films without ITIC-
the PCEs of the fabricated devices were exceeded to above
36 Th doping were suffered from a high PL quenching with
19%. Furthermore, the PSCs based on the L-α-
37 prolonged the aging time. The quenching of PL peaked
phosphatidylcholine layer presented a significantly enhanced
38 represented the transition of black α-phase to the yellow δ-
performance with a Jsc of 22.7 mA cm−2, a Voc of 1.08 V, a
39 FF of 80.0%, and a PCE of 19.6% for the best device.
phase on increasing the storage time because the PL emission
40 mainly related to the α-phase. It was also observed the PL
Whereas, the pristine device with the PCBM layer was
41 shown typical performance with a Jsc of 22.5 ± 0.39 mA
peak red-shifted from 768 nm to 784 nm, indicating a
42 lowering bandgap. The corresponding variation in bandgap
cm−2, a Voc of 1.04 ± 0.02 V, a fill factor (FF) of 73.0 ±
43 could be attributed to the fact that the aged mixed perovskite
pte
2.05%, and a PCE of 17.1 ± 1.1%.

44 precursor has less MA or Br-, which have been reported to
45 5.4 Effect on Device Stability produce relatively lower bandgap138. On the other hand, the
46 The electron acceptor materials as additives into perovskite doped films were presented much lower PL quenching and
47 precursor also played an important role in device stability red-shifting. Sharp PL emission was originated for all the
48 under ambient environment119,120,122,131. The long term films (up to 96 d) and the peak shifted from 768 nm (fresh)
49 stability of the perovskite precursor was improved by to 771 nm (12 d) to 775 nm (96 d), further indicating that
50 incorporating the non-fullerene small molecule ITIC-Th. they were no variation in the composition of mixed
51
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Interestingly, the device made from 39 days aged perovskite perovskite phase fabricated from the precursor solution with
52 solution with ITIC-Th incorporation was shown a ITIC-Th regardless of the aging time. Recently, a number of
53 comparatively high efficiency of 16%, whereas, the device efforts have been devoted to enhance the operational stability
54 fabricated from 39 days aged precursor without ITIC-Th was of the PSCs using various fabrication mechanism, such as
55 shown a PCE of 1.76% (Figure 12a). Further, to examine the electron-beam-evaporated SnO2 electron transport layer139
56 stability of perovskite precursor they have carried out and fabricating bilayer spiro-OMeTAD/PbS hole extraction
Ac
57 absorption spectra and steady state PL spectra of perovskite layer have been presented to improve the device stability 140.
58
59
60
19

1
2
3 Xu and co-workers have been investigated the stability of over 25.2% in small active area devices and over 20% with a
4 PSCs by storing under an ambient environment with a 70- large active area (1 cm2), while the conventional
5 80% humidity119. They have observed that the treated device performances still have room for enhancement. To further
6 was retained about 98.4% of its initial value, whereas the improvement in device performance, the additive
7 control device was degraded to 88.1 % of its initial PCE engineering has the more possibility to enable improvement
8 (Figure 12b). The corresponding excellent stability of the
pt
9 in perovskite crystal growth and enhanced the electronic
treated device indicated that the perovskite film incorporated properties of photo-generated carriers, through the
10 with 0.1 wt% PCBB-OEG presented much higher resistance
11 to moisture in the ambient environment than that of the
considerable understanding of the role of additives upon
12 perovskite crystallization kinetics and ionic defects in the
control device. The degradation of MAPbI 3 perovskite
13 perovskite films. Most of the choices of additives have been
material based devices mainly related to the chemical
cri
14 limited to a few existing and reported materials. Finding out
decomposition in humid environment. To examined the
15 new type additives with a target (e.g., improving device
resistance against moisture by PCBB-OEG incorporation, the
16 performance and enhancing long-term stability) adjustment
control and treated films were exposed to an ambient
17
environment (Figure 12c) for different intervals of time. or by joining these existing incorporating materials with
18
After 14 days of storage in the 70-80% humidity, the color of different characteristics can thus help further increase the
19
20 pristine film was changed from black to yellow, suggesting film quality and should be the next direction for researchers.
us
21 almost whole decomposition of MAPbI3 in the control film.
22 However, for the film with 0.01 % incorporation, there was There are following critical points for further
23 some black spots, which indicate that a little improvement in research and development in the additive engineering
24 chemical stability compared to the pristine device. approach. (1) A number of additives have been reported for
25 Interestingly, there was almost no obvious color change after different defect passivation, but there is still no general rule
26 14 d for the pero-0.1 film, suggesting that the stability was for the right selection of additives, which need to be
27
28
29
remarkably increased by the incorporation of higher
concentrations of PCBBOEG in the perovskite films.
Furthermore, the hydrophobic characteristic of C60 moiety
an established. (2) Currently, there is a limitation about, how to
control the micromorphology and crystallization of
perovskite film, which need to be developed some suitable
30 was additionally protected the perovskite film from strategy. (3) it is highly recommended to produce additives
31 decomposition on contacting with the humid environment, as
with moisture resistant properties for the stability of PSCs in
32 proved by the improvement in water contact angle.
dM
33 ambient environment. (4) The relationship between stability
34 6. Conclusion and Prospective and additive still needs to be further explored. (5) It is needed
35 to understand the fundamental mechanism of the additives,
36 In this article, we have reviewed recent development in the which could beneficial for developing new insights in
37 employment of different additives on the structural, optimizing the electronic, optical and charge transport
38 optoelectronics morphological, photovoltaic and stability of characteristics of perovskite films. Conclusively, we believe
39 organic-inorganic hybrid perovskite material and the device that in near future additive engineering could develop highly
40 performance fabricated with doped perovskite precursor. A efficient and stable organic-inorganic perovskite devices for
41
number of additives have been reported, such as small commercial application.
42
43 molecules, different solvents, acceptor or donor polymers,
pte
fullerene, organic halide salts, etc. The device performance Acknowledgements

44
45 has been efficiently improved by the incorporation of
This work was financially supported by the National Key
46 additives into perovskite precursor, which could be
Research and Development Program of China (Grant No.
47 uniformly distributed at the grain boundaries, passivating the
2017YFA0206600, 2018YFE0204000), Key Research
48 defect sites in the perovskite surface and therefore reducing Program of Frontier Science, CAS (Grant No. QYZDB-
49 the non-radiative recombination. The perovskite growth SSW-LH006), National Natural Science Foundation of China
50 mechanism could be controlled by the reaction between (Contract Nos. 61674141, 51972300, 61504134 and
51
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different additives and PbI2 to form pre-crystallized 21975245), and German Research Foundation (DFG: LE
52
intermediate states. Interestingly, the additives have a 2249/5-1). Shenzhen Key Lab Fund (ZDSYS
53
54 significant effect on the crystallization kinetics of 20170228105421966). Science and Technology plan project
55 perovskites, reduced trap formation, increased the long term of Shenzhen (JCYJ20180305124340951). Z. W. appreciates
56 stability, customize the electronic structure and suppress the the support from Hundred-Talent Program (Chinese
Ac
57 device hysteresis. The device efficiency has already reached Academy of Sciences).
58
59
60
20

1
2
3 References [22] Kim J, Ho‐Baillie A, and Huang S, 2019 Solar RRL
4 3, 1800302.
5 [1] Dong Q, Fang Y, Shao Y, Mulligan P, Qiu J, Cao L, [23] Azam M, Liu K, Yue S, Sun Y, Zhang D, Hassan A,
6 and Huang J, 2015 Science 347, 967. Wang Z, Zhou H, Qu S, and Wang Z, 2019 Solar
7 [2] Stranks S D, Eperon G E, Grancini G, Menelaou C, RRL 3, 1800327.
8 Alcocer M J, Leijtens T, Herz L M, Petrozza A, and [24] Li J B, Chawla V and Clemens B M, 2012, Adv.
pt
9 Snaith H J, 2013 Science 342, 341. Mater., 24, 720.
10 [3] Xing G, Mathews N, Sun S, Lim S S, Lam Y M, [25] Ran C, Xu J, Gao W, Huang C and Dou S, 2018,
Gratzel M, Mhaisalkar S, and Sum T C, 2013
11 Chem. Soc. Rev., 47, 4581.
Science 342, 344. [26] Buin A, Pietsch P, Xu J, Voznyy O, Ip A H, Comin
12
[4] Kojima A, Teshima K, Shirai Y, and Miyasaka T, R, Sargent E H, 2014, Nano Lett. 14, 6281.
13
2009 J. Am. Chem. Soc. 131, 6050.
cri
14 [27] Buin A, Comin R, Xu J, Ip A H, Sargent E H, 2015,
[5] Best Research-Cell Efficiencies, National Renewable Chem. Mater. 27, 4405.
15 Energy Laboratory (NREL), https://www.nrel.gov/pv/
16 [28] Noel N K, Abate A, Stranks S D, Parrott E S,
(Accessed on August 2019).
Burlakov V M, Goriely A, and Snaith H J, 2014
17 [6] Yuan H, Debroye E, Janssen K, Naiki H, Steuwe C,
ACS Nano 8, 9815.
18 Lu G, Moris M, Orgiu E, Uji-i H, De Schryver F,
[29] Xu J, Buin A, Ip A H, Li W, Voznyy O, Comin R,
19 Samorì P, Hofkens J, and Roeffaers M, 2016 The J.
Yuan M, Jeon S, Ning Z, McDowell J J,
20 Phy. Chem. Lett. 7, 561.
Kanjanaboos P, Sun J P, Lan X, Quan L N, Kim D
us
21 [7] Cai F, Yan Y, Yao J, Wang P, Wang H, Gurney R
H, Hill I G, Maksymovych P, and Sargent E H,
22 S, Liu D, and Wang T, 2018 Adv. Func. Mater. 28,
2015 Nat. Commun. 6, 7081.
23 1801985.
[30] Supasai T, Rujisamphan N, Ullrich K, Chemseddine
24 [8] Zhang J, Wu S, Liu T, Zhu Z, and Jen A K Y, 2019
A, Dittrich T, 2013, Appl. Phys. Lett. 103, 183906.
25 Adv. Func. Mater., 1808833.
[31] Zhao Y and Zhu K, 2014 J. Phy. Chem. C 118,
26 [9] Zheng X, Deng Y, Chen B, Wei H, Xiao X, Fang Y,
9412.
27
28
29 [10]
Lin Y, Yu Z, Liu Y, Wang Q, and Huang J, 2018
Adv. Mater. 30, e1803428.
an
Liu T, Su P, Liu L, Wang J, Feng S, Zhang J, Xu R,
[32] Dualeh A, Tetreault N, Moehl T, Gao P,
Nazeeruddin M K, Gratzel M, 2014, Adv. Funct.
Mater. 24, 3250.
Yang H, and Fu W, 2019 J. Mater. Chem. A 7, 353.
30 [33] Wang L L, McCleese C, Kovalsky A, Zhao Y X,
[11] Lin Y, Shen L, Dai J, Deng Y, Wu Y, Bai Y, Zheng
31 Burda C, 2014, J. Am. Chem. Soc. 136, 12205.
X, Wang J, Fang Y, Wei H, Ma W, Zeng X C, Zhan
32 [34] Chen Q, Zhou H, Song T B, Luo S, Hong Z, Duan
dM
X, and Huang J, 2017 Adv. Mater. 29, 1604545.
33 [12] Wu B, Nguyen H T, Ku Z, Han G, Giovanni D,
H S, Dou L, Liu Y, and Yang Y, 2014 Nano Lett.
34 Mathews N, Fan H J, and Sum T C, 2016 Adv.
14, 4158.
35 [35] Roldan-Carmona C, Gratia P, Zimmermann I,
Energy Mater. 6, 1600551.
36 Grancini G, Gao P, Graetzel M, Nazeeruddin M K,
[13] Tress W, Correa Baena J P, Saliba M, Abate A, and
37 2015, Energy Environ. Sci. 8, 3550.
Graetzel M, 2016 Adv. Energy Mater. 6, 1600396.
38 [36] Kim Y C, Jeon N J, Noh J H, Yang W S, Seo J, Yun
[14] Snaith H J, Abate A, Ball J M, Eperon G E, Leijtens
39 J S, Ho-Baillie A, Huang S J, Green M A, Seidel J,
T, Noel N K, Stranks S D, Wang J T-W,
Ahn T K, Il Seok S, 2016, Adv. Energy Mater. 6,
40 Wojciechowski K, and Zhang W, 2014 J. Phy.
1502104.
41 Chem. Lett. 5, 1511.
[37] Zohar A, Levine I, Gupta S, Davidson O, Azulay D,
42 [15] Azpiroz J M, Mosconi E, Bisquert J, and De
Millo O, Balberg I, Hodes G, Cahen D, 2017, ACS
43
pte
Angelis F, 2015 Energy Environ. Sci. 8, 2118.

Energy Lett. 2, 2408.
44 [16] Williams S T, Rajagopal A, Chueh C-C, and Jen A
[38] Yang W S, Park B-W, Jung E H, Jeon N J, Kim Y
45 K Y, 2016 J. Phy. Chem. Lett. 7, 811.
C, Lee D U, Shin S S, Seo J, Kim E K, Noh J H,
46 [17] Manser J S, Saidaminov M I, Christians J A, Bakr O
and Seok S I, 2017 Science 356, 1376.
47 M, and Kamat P V, 2016 Acc. Chem. Res. 49, 330. [39] Abate A, Saliba M, Hollman D J, Stranks S D,
48 [18] Yuan Y and Huang J, 2016 Acc. Chem. Res. 49,
Wojciechowski K, Avolio R, Grancini G, Petrozza
49 286.
A, Snaith H J, 2014, Nano Lett. 14, 3247.
50 [19] Zhang H, Wu Y, Shen C, Li E, Yan C, Zhang W,
51 Tian H, Han L, and Zhu W H, 2019 Adv. Energy
ce
[40] Yan Y, Jiang C S, Noufi R, Wei S-H, Moutinho H

52 Mater. 9, 1803573.
R, and Al-Jassim M M, 2007 Phy. Rev. Lett. 99,
[20] Yang Y, Peng H, Liu C, Arain Z, Ding Y, Ma S, Liu
53 235504.
X, Hayat T, Alsaedi A, and Dai S, 2019 J. Mater.
54 [41] Li J B, Chawla V, and Clemens B M, 2012 Adv.
Chem. A 7, 6450.
55 Mater. 24, 720.
[21] Tavakoli M M, Yadav P, Prochowicz D, Sponseller
56 M, Osherov A, Bulović V, and Kong J, 2019 Adv.
[41] Visoly-Fisher I, Cohen S R, Gartsman K, Ruzin A,
Ac
57 Energy Mater. 9, 1803587.

and Cahen D, 2006 Adv. Func. Mater. 16, 649.
58
59
60
21

1
2
3 [42] Stewart R J, Grieco C, Larsen A V, Maier J J, and [65] Wu Y, Islam A, Yang X, Qin C, Liu J, Zhang K,
4 Asbury J B, 2016 J. Phys. Chem. Lett. 7, 1148. Peng W and Han L, 2014, Energy Environ. Sci. 7,
5 [43] De Marco N, Zhou H, Chen Q, Sun P, Liu Z, Meng 2934.
6 L, Yao E P, Liu Y, Schiffer A, and Yang Y, 2016 [66] Yamada Y, Nakamura T, Endo M, Wakamiya A,
7 Nano Lett. 16, 1009. and Kanemitsu Y, 2014 J. Am. Chem. Soc.136,
8 [44] Chang C Y, Chu C Y, Huang Y C, Huang C W, 11610.
pt
9 Chang S Y, Chen C A, Chao C Y, and Su W F, [67] Sakai N, Pathak S, Chen H-W, Haghighirad A A,
10 2015 ACS Appl. Mater. Interfaces 7, 4955. Stranks S D, Miyasaka T, and Snaith H J, 2016 J.
11 [45] Kan B, Li M, Zhang Q, Liu F, Wan X, Wang Y, Ni Mater. Chem. A 4, 4464.
12 W, Long G, Yang X, Feng H, Zuo Y, Zhang M, [68] Johnston M B and Herz L M, 2016 Acc. Chem. Res.
13 Huang F, Cao Y, Russell T P, and Chen Y, 2015 J. 49, 146.
cri
14 Am. Chem. Soc. 137, 3886. [69] Stranks S D, Burlakov V M, Leijtens T, Ball J M,
15 [46] Luo D, Zhao L, Wu J, Hu Q, Zhang Y, Xu Z, Liu Y, Goriely A, and Snaith H J, 2014 Phy. Rev. Appl. 2,
Liu T, Chen K, Yang W, Zhang W, Zhu R, and 034007.
16
Gong Q, 2017 Adv. Mater. 29. [70] D’Innocenzo V, Srimath Kandada A R, De Bastiani
17
[47] Azam M, Yue S, Xu R, Liu K, Ren K, Sun Y, Liu J, M, Gandini M, and Petrozza A, 2014 J. Am. Chem.
18
Wang Z, Qu S, lei Y, and Wang Z, 2018 J. Mater. Soc. 136, 17730.
19
Chem. A 6, 13725. [71] Zhao T, Chueh C-C, Chen Q, Rajagopal A, and Jen
20 [48] Yue S Z, Liu K, Xu R, Li M C, Azam M, Ren K, A K-Y, 2016 ACS Energy Lett. 1, 757.
us
21 Liu J, Sun Y, Wang Z J, Cao D W, Yan X H, Qu S [72] Dohner E R, Jaffe A, Bradshaw L R, and
22 C, Lei Y, and Wang Z G, 2017 Energy Environ. Karunadasa H I, 2014 J. Am. Chem. Soc.136,
23 Sci.10, 2570. 13154.
24 [49] Jeanbourquin X A, Li X, Law C, Barnes P R F, [73] Lemmerer A and Billing D G, 2012 Cryst. Eng.
25 Humphry-Baker R, Lund P, Asghar M I, and Comm. 14, 1954.
26 O’Regan B C, 2014 J. Am. Chem. Soc. 136, 7286. [74] de Quilettes D W, Vorpahl S M, Stranks S D,
27
28
29
[50]
[51]
K, 2015 J. Phy. Chem. C 119, 4694.
Giorgi G and Yamashita K, 2015 Nanotechnology
an
Giorgi G, Fujisawa J-I, Segawa H, and Yamashita
[75]
Nagaoka H, Eperon G E, Ziffer M E, Snaith H J,
and Ginger D S, 2015 Science 348, 683.
Chen Q, Zhou H, Song T-B, Luo S, Hong Z, Duan
30 26, 442001. H-S, Dou L, Liu Y, and Yang Y, 2014 Nano Lett.
31 [52] Kieslich G, Sun S, and Cheetham A K, 2014 14, 4158.
32 Chemical Science 5, 4712. [76] Zhou H, Zhang Y, Seifter J, Collins S D, Luo C,
dM
33 [53] Szafrański M and Jarek M, 2013 Cryst. Eng. Comm. Bazan G C, Nguyen T-Q, and Heeger A J, 2013
34 15, 4617. Adv. Mater. 25, 1646.
35 [54] Zhao Y, Wei J, Li H, Yan Y, Zhou W, Yu W and [77] Shao Y, Xiao Z, Bi C, Yuan Y, and Huang J, 2014
36 Zhao Q, 2016 Nat. Commun. 7, 10228. Nat. Commun. 5, 5784.
37 [55] Lee M M, Teuscher J, Miyasaka T, Murakami T N, [78] Li C-Z, Chang C-Y, Zang Y, Ju H-X, Chueh C-C,
38 and Snaith H J, 2012 Science 338, 643. Liang P-W, Cho N, Ginger D S, and Jen A K-Y,
[56] Thompson C V, 2012 Annual Rev. Mater. Res. 42, 2014 Adv. Mater. 26, 6262.
39
399. [79] Tavakoli M M, Bi D, Pan L, Hagfeldt A,
40
[57] Kato M, Omura A, Toshikawa A, Kishi S, and Zakeeruddin S M, and Grätzel M, 2018 Adv.
41
Sugimoto Y, 2002 Ang. Chem. Intern. Ed. 41, 3183. Energy Mater. 8, 1800275.
42 [58] Ghavale N, Dey S, Wadawale A, and Jain V K, [80] Nordman C E and Schmitkons D L, 1965 Acta
43
pte
2011 J. Organometallic Chem. 696, 3491. Crystallographica 18, 764.

44 [59] Li W, Zhang C, Ma Y, Liu C, Fan J, Mai Y, and [81] Huang F, Pascoe A R, Wu W Q, Ku Z, Peng Y,
45 Schropp R E I, 2018 Energy Environ. Sci.11, 286. Zhong J, Caruso R A, and Cheng Y B, 2017 Adv.
46 [60] Silva Filho J M C D, Ermakov V A, Marques F C, Mater. 29.
47 2018, Sci. Rep. 8, 1563. [82] Azam M, Yue S, Liu K, Sun Y, Liu J, Ren K, Wang
48 [61] Hassan N, Holze R, Russ, 2012, J. Electrochem. 48, Z, Qu S, and Wang Z, 2018 J. Alloys Compounds
49 401. 731, 375.
50 [62] Liao J-F, Wu W-Q, Zhong J-X, Jiang Y, Wang L, [83] Chen B, Yu Z, Liu K, Zheng X, Liu Y, Shi J,
51
ce
and Kuang D-B, 2019 J. Mater. Chem. A 7, 9025. Spronk D, Rudd P N, Holman Z and Huang J, 2019
52 [63] Qin C, Matsushima T, Klotz D, Fujihara T, and Joule 3, 177.
53 Adachi C, 2019 Adv. Science 6, 1801079. [84] Tang G, You P, Tai Q, Wu R, and Yan F, 2018
54 [64] Tripathi N, Shirai Y, Yanagida M, Karen A and Solar RRL 2, 1800066.
55 Miyano K, 2016, ACS Appl. Mater. Interfaces, 8,
56 4644. [85] Li X, Bi D, Yi C, Décoppet J-D, Luo J, Zakeeruddin
Ac
57 S M, Hagfeldt A, and Grätzel M, 2016 Science 353,

58 58.
59
60
22

1
2
3 [86] Wu W-Q, Yang Z, Rudd P N, Shao Y, Dai X, Wei [109] Wang Y, Li S, Zhang P, Liu D, Gu X, Sarvari H, Ye
4 H, Zhao J, Fang Y, Wang Q, Liu Y, Deng Y, Xiao Z, Wu J, Wang Z, and Chen Z D, 2016 Nanoscale 8,
5 X, Feng Y, and Huang J, 2019 Sci. Adv. 5, 19654.
6 eaav8925. [110] Rose A, 1955 Physical Review 97, 1538.
7 [87] Wang Q, Chen B, Liu Y, Deng Y, Bai Y, Dong Q, [111] Sun S, Salim T, Mathews N, Duchamp M,
8 and Huang J, 2017 Energy Environ. Sci.10, 516. Boothroyd C, Xing G, Sum T C, and Lam Y M,
pt
9 [88] Zheng X, Chen B, Dai J, Fang Y, Bai Y, Lin Y, Wei 2014 Energy Environ. Sci.7, 399.
10 H, Zeng Xiao C, and Huang J, 2017 Nat. Energy 2, [112] Juška G, Arlauskas K, Viliūnas M, and Kočka J,
11 17102. 2000 Phy. Rev. Lett. 84, 4946.
12 [89] Tai Q, You P, Sang H, Liu Z, Hu C, Chan H L W, [113] Juška G, Nekrašas N, Genevičius K, Stuchlik J, and
13 and Yan F, 2016 Nat. Commu. 7, 11105. Kočka J, 2004 Thin Solid Films 451-452, 290.
cri
14 [90] Christians J A, Miranda Herrera P A, and Kamat P [114] Chen Y, Peng J, Su D, Chen X, and Liang Z, 2015
15 V, 2015 J. Am. Chem. Soc. 137, 1530. ACS Appl. Mater. Interfaces 7, 4471.
[91] Han L, Cong S, Yang H, Lou Y, Wang H, Huang J, [115] Im J-H, Jang I-H, Pellet N, Grätzel M, and Park N-
16
Zhu J, Wu Y, Chen Q, Zhang B, Zhang L, and Zou G, 2014 Nat. Nanotechnology 9, 927.
17
G, 2018 Solar RRL 2, 1800054. [116] Yang G, Qin P, Fang G, and Li G, 2018 Solar RRL
18
[92] Sun M, Zhang F, Liu H, Li X, Xiao Y, and Wang S, 2, 1800055.
19
2017 J. Mater. Chem. A 5, 13448. [117] Yun J S, Kim J, Young T, Patterson R J, Kim D,
20 [93] Ahn N, Son D Y, Jang I H, Kang S M, Choi M, and Seidel J, Lim S, Green M A, Huang S, and Ho-
us
21 Park N G, 2015 J. Am. Chem. Soc. 137, 8696. Baillie A, 2018 Adv. Func. Mater. 28, 1705363.
22 [94] Wang S, Ma Z, Liu B, Wu W, Zhu Y, Ma R, and [119] Xu G, Xue R, Chen W, Zhang J, Zhang M, Chen H,
23 Wang C, 2018 Solar RRL 2, 1800034. Cui C, Li H, Li Y, and Li Y, 2018 Adv. Energy
24 [95] Li L, Chen Y, Liu Z, Chen Q, Wang X, and Zhou H, Mater. 8, 1703054.
25 2016 Adv. Mater. 28, 9862. [120] Qin M, Cao J, Zhang T, Mai J, Lau T-K, Zhou S,
26 [96] Rong Y, Venkatesan S, Guo R, Wang Y, Bao J, Li Zhou Y, Wang J, Hsu Y-J, Zhao N, Xu J, Zhan X,
27
28
29
[97]
W, Fan Z, and Yao Y, 2016 Nanoscale 8, 12892.
an
Yang S, Liu W, Zuo L, Zhang X, Ye T, Chen J, Li
C-Z, Wu G, and Chen H, 2016 J. Mater. Chem. A 4,
[121]
and Lu X, 2018 Adv. Energy Mater. 8, 1703399.
Chiang C-H and Wu C-G, 2016 Nat. Photonics 10,
196.
30 9430. [122] Bai Y, Dong Q, Shao Y, Deng Y, Wang Q, Shen L,
31 [98] Zhao Y and Zhu K, 2014 J. Phy. Chem. C 118, Wang D, Wei W, and Huang J, 2016 Nat. Commun.
32 9412. 7, 12806.
dM
33 [99] Shi D, Adinolfi V, Comin R, Yuan M, Alarousu E, [123] Lin Y, Zhao F, He Q, Huo L, Wu Y, Parker T C,
34 Buin A, Chen Y, Hoogland S, Rothenberger A, Ma W, Sun Y, Wang C, Zhu D, Heeger A J, Marder
35 Katsiev K, Losovyj Y, Zhang X, Dowben P A, S R, and Zhan X, 2016 J. Am. Chem. Soc. 138,
36 Mohammed O F, Sargent E H, and Bakr O M, 2015 4955.
37 Science 347, 519. [124] Dai S, Zhao F, Zhang Q, Lau T-K, Li T, Liu K,
38 [100] Liang P, Liao C, Chueh C, Zuo F, Williams S T, Ling Q, Wang C, Lu X, You W, and Zhan X, 2017
Xin X, Lin J and Jen A –K –Y, 2014, Adv. Mater. J. Am. Chem. Soc. 139, 1336.
39
26, 3748. [125] Saliba M, Matsui T, Seo J-Y, Domanski K, Correa-
40
[101] Song X, Wang W, Sun P, Ma W and Chen Z, 2015, Baena J-P, Nazeeruddin M K, Zakeeruddin S M,
41
Appl. Phys. Lett. 106, 33901. Tress W, Abate A, Hagfeldt A, and Grätzel M, 2016
42 [102] Lee J-W, Kim H-S, and Park N-G, 2016 Acc. Energy Environ. Sci.9, 1989.
43
pte
Chem. Res. 49, 311. [126] Hoke E T, Slotcavage D J, Dohner E R, Bowring A

44 [103] Yang W S, Park B-W, Jung E H, Jeon N J, Kim Y R, Karunadasa H I, and McGehee M D, 2015 Chem.
45 C, Lee D U, Shin S S, Seo J, Kim E K, Noh J H, Sci. 6, 613.
46 and Seok S I, 2017 Science 356, 1376. [127] Lindblad R, Bi D, Park B-w, Oscarsson J, Gorgoi
47 [104] Yu Z, Zhang L, Tian S, Zhang F, Zhang B, Niu F, M, Siegbahn H, Odelius M, Johansson E M J, and
48 Zeng P, Qu J, Rudd P N, Huang J, and Lian J, 2018 Rensmo H, 2014 J. Phys. Chem. Lett. 5, 648.
49 Adv. Energy Mater. 8, 1701659. [128] Lin M-W, Wang K-C, Wang J-H, Li M-H, Lai Y-L,
50 [105] Cai J, Zhang L, Zhou J, Qi H, Chen H, Kondo T, Ohigashi T, Kosugi N, Chen P, Wei D-H, Guo T-F,
51
ce
Chen X, and Chu B, 2007 Adv. Mater. 19, 821. and Hsu Y-J, 2016 Adv. Mater. Interfaces 3,
52 [106] Wang X L and Yang H G, 2017 App. Catalysis B: 1600135.
53 Environ. 205, 624. [129] Zhang W, Pathak S, Sakai N, Stergiopoulos T,
54 [107] Liu W, Li L, Chen M, Ding X, Wang M, Liu G, and Nayak P K, Noel N K, Haghighirad A A, Burlakov
55 Wang X, 2017 J. Alloys Compounds 697, 374. V M, deQuilettes D W, Sadhanala A, Li W, Wang
56 [108] Liu T, Hu Q, Wu J, Chen K, Zhao L, Liu F, Wang L, Ginger D S, Friend R H, and Snaith H J, 2015
Ac
57 C, Lu H, Jia S, Russell T, Zhu R, and Gong Q, 2016 Nat. Commun. 6, 10030.

58 Adv. Energy Mater. 6, 1501890.
59
60
23

1
2
3 [130] Liu K, Dai S, Meng F, Shi J, Li Y, Wu J, Meng Q, [136] Zuo L, Gu Z, Ye T, Fu W, Wu G, Li H, and Chen
4 and Zhan X, 2017 J. Mater. Chem. A 5, 21414. H, 2015 J. Am. Chem. Soc. 137, 2674.
5 [131] Liu C, Huang Z, Hu X, Meng X, Huang L, Xiong J, [137] Goh C, Scully S R, and McGehee M D, 2007 J.
6 Tan L, and Chen Y, 2018 ACS Appl. Mater. App. Phy. 101, 114503.
7 Interfaces 10, 1909. [138] Jesper Jacobsson T, Correa-Baena J-P, Pazoki M,
8 [132] Kumar A, Banerjee K, Dvorak M, Schulz F, Harju Saliba M, Schenk K, Grätzel M, and Hagfeldt A,
pt
9 A, Rinke P, and Liljeroth P, 2017 ACS Nano 11, 2016 Energy Environ. Sci.9, 1706.
10 4960. [139] Ma J, Zheng X, Lei H, Ke W, Chen C, Chen Z,
11 [133] Chen W, Chen S, Qi D C, Gao X Y, and Wee A T Yang G, and Fang G, 2017 Solar RRL 1, 1700118.
12 S, 2007 J. Am. Chem. Soc. 129, 10418. [140] Zheng X, Lei H, Yang G, Ke W, Chen Z, Chen C,
13 [134] Eperon G E, Burlakov V M, Docampo P, Goriely A, Ma J, Guo Q, Yao F, Zhang Q, Xu H, and Fang G,
cri
14 and Snaith H J, 2014 Adv. Func. Mater. 24, 151. 2017 Nano Energy 38, 1.
15 [135] Son D-Y, Lee J-W, Choi Y J, Jang I-H, Lee S, Yoo
P J, Shin H, Ahn N, Choi M, Kim D, and Park N-G,
16
2016 Nat. Energy 1, 16081.
17
18
19
20
us
21
22
23
24
25
26
27
28
29
an
30
31
32
dM
33
34
35
36
37
38
39
40
41
42
43
pte
44
45
46
47
48
49
50
51
ce
52
53
54
55
56
Ac
57
58
59
60
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IOP Publishing Journal Title

Journal XX (XXXX) XXXXXX Author et al

52 facilitating homogeneous nucleation8,10,19-23. considered as an excellent candidate for GBs defects

Journal XX (XXXX) XXXXXX Author et al

Journal XX (XXXX) XXXXXX Author et al

Journal XX (XXXX) XXXXXX Author et al

Journal XX (XXXX) XXXXXX Author et al

57 the perovskite film surface. The water contact angles were

Journal XX (XXXX) XXXXXX Author et al

57 have proposed that TACl and MAI have identical chemical

57 counterpart DMSO additive with the same concentration

Journal XX (XXXX) XXXXXX Author et al

ionic point defects within the perovskite crystals, which

57 solvent) in the two-step deposition method119. The PCBB-

Journal XX (XXXX) XXXXXX Author et al

10 of 1.15 V, and a FF of 0.75 (Figure 11(e)). The enhanced

2.05%, and a PCE of 17.1 ± 1.1%.

Journal XX (XXXX) XXXXXX Author et al

fullerene, organic halide salts, etc. The device performance Acknowledgements

Journal XX (XXXX) XXXXXX Author et al

Angelis F, 2015 Energy Environ. Sci. 8, 2118.

[40] Yan Y, Jiang C S, Noufi R, Wei S-H, Moutinho H

57 Energy Mater. 9, 1803587.

Journal XX (XXXX) XXXXXX Author et al

2011 J. Organometallic Chem. 696, 3491. Crystallographica 18, 764.

57 S M, Hagfeldt A, and Grätzel M, 2016 Science 353,

Journal XX (XXXX) XXXXXX Author et al

Chem. Res. 49, 311. [126] Hoke E T, Slotcavage D J, Dohner E R, Bowring A

57 C, Lu H, Jia S, Russell T, Zhu R, and Gong Q, 2016 Nat. Commun. 6, 10030.

Journal XX (XXXX) XXXXXX Author et al

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