Next Article in Journal
Corrosion Protection of N80 Steel in Hydrochloric Acid Medium Using Mixed C15H15NO and Na2WO4 Inhibitors
Next Article in Special Issue
Enhancement for Potential-Induced Degradation Resistance of Crystalline Silicon Solar Cells via Anti-Reflection Coating by Industrial PECVD Methods
Previous Article in Journal
Microstructure and Corrosion Characterization of Cr Film on Carburized CSS-42L Aerospace Bearing Steel by Filtered Cathodic Vacuum Arc Deposition
Previous Article in Special Issue
Electroplating of Semiconductor Materials for Applications in Large Area Electronics: A Review
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Coatings
Volume 8
Issue 9
10.3390/coatings8090314
coatings-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Facile Solution Spin-Coating SnO2 Thin Film Covering Cracks of TiO2 Hole Blocking Layer for Perovskite Solar Cells

by
Haiyan Ren
,
Xiaoping Zou
*,
Jin Cheng
,
Tao Ling
,
Xiao Bai
and
Dan Chen
Research Center for Sensor Technology, Beijing Key Laboratory for Sensor, Ministry of Education Key Laboratory for Modern Measurement and Control Technology, School of Applied Sciences, Jianxiangqiao Campus, Beijing Information Science & Technology University, Beijing 100101, China
*
Author to whom correspondence should be addressed.
Coatings 2018, 8(9), 314; https://doi.org/10.3390/coatings8090314
Submission received: 4 August 2018 / Revised: 28 August 2018 / Accepted: 3 September 2018 / Published: 6 September 2018
(This article belongs to the Special Issue Advanced Thin Film Materials for Photovoltaic Applications)
Browse Figures
Versions Notes

Abstract

The hole blocking layer plays an important role in suppressing recombination of holes and electrons between the perovskite layer and fluorine-doped tin oxide (FTO). Morphological defects, such as cracks, at the compact TiO2 hole blocking layer due to rough FTO surface seriously affect performance of perovskite solar cells (PSCs). Herein, we employ a simple spin-coating SnO2 thin film solution to cover cracks of TiO2 hole blocking layer for PSCs. The experiment results indicate that the TiO2/SnO2 complementary composite hole blocking layer could eliminate the serious electrical current leakage existing inside the device, extremely reducing interface defects and hysteresis. Furthermore, a high efficiency of 13.52% was achieved for the device, which is the highest efficiency ever recorded in PSCs with spongy carbon film deposited on a separated FTO-substrate as composite counter electrode under one sun illumination.

Graphical Abstract

1. Introduction

Currently, perovskite solar cells (PSCs) have been recognized as the most promising alternatives to conventional silicon solar cells due to high conversion efficiency, low manufacturing cost, and simple process [1,2,3,4,5,6,7]. As for typical planar heterojunction PSCs composed of working electrode (cathode)/hole blocking layer/perovskite layer/electron blocking layer/counter electrode (anode), the hole blocking layer plays an important role in extracting electrons from the perovskite layer and, as well as, suppressing recombination of holes and electrons between the perovskite layer and FTO [8,9,10,11]. A uniform, pinhole-free and well electrically conductive hole blocking layer is highly demanded for well performed planar heterojunction PSCs [8,12]. Liao et al. found that the pinholes on the surface of the single SnO2 hole blocking layer coating on the rough FTO substrate were still hard to eliminate. Therefore, radio-frequency magnetron sputtering TiO2 fully covered the surface of the FTO electrode, thus passivating the FTO surface defects and reducing the recombination, finally utilizing TiO2/SnO2 bilayer as hole blocking layer to improve device performance [8,13]. Furthermore, TiO2 compact layer has commonly been used as the hole blocking layer in the planar heterojunction PSCs. Since the spin-coating process formed a highly irregular thick TiO2 layer on top of the rough FTO layer, the pinholes appeared on the surface of the TiO2 hole blocking layer, so that the perovskite light-absorber layer directly contacted the FTO layer, resulting in recombination of holes and electrons between the perovskite light-absorber layer and FTO layer. Though uniform and pinhole-free compact TiO2 layers were prepared using atomic layer deposition to improve device performance, the atomic layer deposition method had the disadvantage of including a low crystallinity of thin film due to the low deposition temperature [14]. However, Choi et al. mitigated the influence of the morphological defects (such as an irregular film thickness and poor physical contact between the TiO2 and the FTO layers) at the TiO2 interface due to a rough FTO by implementing a TiO2 hole blocking layer based on the anodization method [15]. Though the research by Choi et al. mitigated the influence of the morphological defects, the preparation technology was very complicated. Up to now, several research groups have developed carbon counter electrodes to reduce the costs of perovskite devices [16,17,18]. In our research group, previously, the PSC based on sponge carbon/FTO composite counter electrode obtained the power conversion efficiency of 10.7% [19].
In this work, we employ TiO2/SnO2 complementary composite layer prepared by facile solution spin-coating SnO2 on compact TiO2-coated rough FTO as the hole blocking layer for planar heterojunction PSCs to solve morphological defects, such as cracks, at the compact TiO2 hole blocking layer due to rough FTO surface. However, due to TiO2 hole blocking layer has relative lower electron mobility, leading to unbalanced carrier transport in the device, thus regular planar structure PSC usually has a strong hysteresis behavior [20]. Meanwhile, SnO2 is currently recognized as the promising hole blocking layer substitution for the conventional TiO2 due to high electron mobility, low conduction band minimum, and low-temperature preparation [20,21,22,23,24,25]. Grätzel et al. and co-workers reported planar PSCs with efficiencies close to 21% using a simple, solution-processed technological approach for depositing SnO2 layers [26]. Thereby, we obtained the modified hole blocking layer thin film without cracks through solution spin-coating SnO2 on compact TiO2-coated rough FTO at 3000 rpm. Correspondingly, this TiO2/SnO2 thin film and component optimization of perovskite precursor solution contributed to the formation of high-quality perovskite thin films (such as high crystallinity, large grain size, low defect density, and good flatness). Notably, the largest size of individual perovskite grain reached 2.67 μm. Therefore, PSC based on the TiO2/SnO2 complementary composite hole blocking layer achieved high power conversion efficiencies (PCE) of 13.52% in size of 0.2 cm2 under absolute ambient condition, which is the highest efficiency ever recorded in PSCs with such spongy carbon/FTO composite counter electrode. These improvements indicate that the TiO2/SnO2 complementary composite hole blocking layer could eliminate the serious electrical current leakage existing inside the device and reduce interface defects.

2. Materials and Methods

2.1. Materials

Fluorine-doped SnO2 (FTO) substrates were obtained from Yingkou Opv Tech New Energy Co., Ltd. (Yingkou, China, 7–8 Ω/square, 2.2 mm in thickness, 1.5 × 1.5 cm2 in specification). N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) were purchased from Sa’en Chemical Technology (Shanghai, China) Co., Ltd. Acidic titanium dioxide solution (bl-TiO2) was purchased from Shanghai MaterWin New Materials Co., Ltd. (Shanghai, China, product code of MTW-CL-H-002, commodity name of HH-TiOx, colorless and transparent in appearance, 99.98% in purity). The SnO2 colloid precursor (Cas No. 18282-10-5) was obtained from Alfa Aesar (Shanghai, China, tin (IV) oxide, 15% in H2O colloidal dispersion). Before use, the particles were diluted by deionized water to 3%. Lead(II) Iodide (PbI2, Cas No. 10101-63-0, yellow crystalline powder in appearance, purity >99.99%), Methylammonium iodide (CH3NH3I, MAI, Cas No. 14965-49-2, white powder in appearance, purity ≥99.5%), Formamidinium Iodide (HC(NH2)2I, FAI, Cas No. 879643-71-7, white powder in appearance, purity ≥99.5%), Methylammonium Bromide (CH3NH3Br, MABr, Cas No. 6876-37-5, white powder in appearance, purity ≥99.5%), Methylammonium Chloride (CH3NH3Cl, MACl, Cas No. 593-51-1, white powder in appearance, purity ≥99.5%), and commercial 2,2’,7,7’-tetrakis-(N,N-dip-methoxyphenylamine)-9,9’-spirobifluorene solution (Spiro-OMeTAD, Cas No. 207739-72-8, yellow powder in appearance, purity ≥99.5%) were purchased from Xi’an Polymer Light Technology Corp. (Xi’an, China).

2.2. Device Fabrication

The surface treatment of the FTO for complete coverage before deposition of any film which affect severely the film deposition and properties. Malviya et al. demonstrated that rigorous cleaning process yielded clean FTO surface, and rigorous cleaning of the substrates prior to the hematite deposition was crucial for achieving highly reproducible results [27]. In order to ensure the quality of the subsequent film deposition, we thoroughly cleaned the FTO glass substrate before proceeding to the next step. FTO substrate was firstly wiped using a mixed solution of detergent and deionized water. The resultant FTO substrates were ultrasonically cleaned with glass water (deionized water: acetone: 2-propanol = 1:1:1) and ethanol for 20 min, separately. The FTO glasses were dried with dryer for 30 min and then cleaned with ultraviolet ozone for 10 min. Compact TiO2 layer was deposited on the cleaned FTO substrate by spin-coating an acidic titanium dioxide solution at 2000 rpm for 60 s. The substrate was annealed on a hotplate at 100 °C for 10 min, and then sintered in muffle furnace at 500 °C for 30 min. For TiO2/SnO2 complementary composite hole blocking layer based devices, due to the hydrophobicity of the TiO2 thin film layer and the complete aqueous solution of the SnO2 precursor solution, the FTO/TiO2 substrates were firstly cleaned by ultraviolet ozone for 10 min in order to form a hydrophilic group on the surface of the film. Then the SnO2 functional layer was prepared by spin-coating 3 wt % SnO2 precursor solution on the compact TiO2-coated FTO substrate for 30 s at 2000, 3000, and 4000 rpm, respectively [23]. Subsequently, the FTO/TiO2/SnO2 based substrates were dried on a hotplate at 150 °C for 30 min, and then cleaned by ultraviolet ozone for 10 min again to improve its hydrophilicity.
The perovskite thin film was deposited by a two-step spin-coating method [19]. Firstly, the prepared FTO/TiO2/SnO2 substrates were preheated on a hotplate at 70 °C. The precursor solution of PbI2 was prepared by dissolving 0.5993 g PbI2 powder in 1 mL mixture of DMF/DMSO (0.95:0.05 of volume ratio), and then spin-coated on the preheated FTO/TiO2/SnO2 substrates at 1500 rpm for 30 s. After that, the doped FAI precursor solution was prepared by mixing 60 mg FAI and 6 mg MABr and 6 mg MACl in 1 mL isopropanol, and then spin-coated on the PbI2 layer at 1300 rpm for 30 s. In order to obtain a high-quality perovskite light-absorber layer, the spin-coated substrates were annealed on a hotplate at 150 °C for 15 min under ambient condition. The electron blocking layer was deposited on top of the perovskite layer by 3000 rpm for 30 s using Spiro-OMeTAD solution.
Finally, some cleaned FTO glasses were used as substrates to collect soot of a burning candle as spongy carbon counter electrodes. The spongy carbon/FTO composite counter electrode was then pressed on the Spiro-OMeTAD layers of uncompleted devices. The whole process is carried out in air condition with a relative humidity of 10%–20% at room temperature. The entire preparation process was described in Scheme 1.

2.3. Characterization

X-ray diffraction (XRD) data from samples of perovskite films deposited on FTO/TiO2/SnO2 substrates were collected using an X-ray diffractometer (D8 Focus, Bruker, Dresden, Germany). The morphology of the perovskite films were measured using a scanning electron microscope (SEM) (SIGMA, Zeiss, Jena, Germany). The photo-current density–voltage (J–V) characteristics were measured under simulated standard air-mass AM 1.5 sunlight with using a solar simulator (Sol 3A, Oriel, Newport, RI, USA). All the measurements of the PSCs were performed under ambient atmosphere at room temperature without encapsulation.

3. Results and Discussion

Figure 1 shows the top-view SEM images of the bare FTO glass substrate (Figure 1a) and 3D roughness reconstruction of bare FTO glass (Figure 1f). As we can see, the surface of the bare FTO is very rough which corresponds to Sa (arithmetic-mean-height) of 74 nm. Many cracks (marked with a red square in Figure 1b) are observed on the surface of TiO2 thin film. Figure 1c is the enlarged SEM surface image of the red square (in Figure 1b), however, the bottom FTO can be seen through the cracks, which will cause a large number of photocarriers to be recombination and seriously affect the performance of the PSC device. As shown in the cross-sectional SEM image (Figure 1d), the poor uniformity of TiO2 thin film and the obvious fracture (marked with a red circle in Figure 1d) which was due to surface roughness of FTO, reveals that the bare FTO surface was exposed and could form direct contact with the perovskite layer, resulting in serious recombination of holes and electrons between the perovskite layer and FTO, in agreement with the results obtained with top-view SEM images (Figure 1b,c). The cross-sectional SEM image of bare FTO layer is shown in Figure 1e, we can find that the surface of bare FTO layer was very rough due to the presence of sharp peaks. Even some peaks and valleys reached a height of ~200 nm. However, as can be seen from Figure 1d, the spin-coating process formed a highly irregular thick TiO2 layer due to overfilling the valleys on the rough FTO surface with TiO2. The average thickness of single-layer TiO2 compact layer was ~100 nm, which indicated some FTO peaks higher than 100 nm could not be covered, leading to the appearance of cracks in single-layer TiO2 thin films. This is consistent with the observation from SEM images (Figure 1b,c) of the hole blocking layer thin films prepared with single-layer TiO2 compact layer deposited on rough FTO substrates. The PSC devices based on single-layer TiO2 hole blocking layer and double-layer TiO2 hole blocking layer are named as device R1 and device R2, respectively. Table 1 shows the summary of J–V characteristics of device R1 and device R2 from reverse scan. As we can see, device R1 achieved low power conversion efficiency of 4.63% due to the presence of cracks. Compared with the device R1, the performance of the device R2 was improved. Huang et al. reported a facile dip-coating route to sequentially prepare a dense sol-gel-derived titanium dioxide (TiO2) hole blocking layer and a smooth organolead halide perovskite film for pseudo-planar heterojunction perovskite solar cells [28]. Masood et al. used a scalable and low-cost dip coating method to prepare uniform and ultra-thin (5−50 nm) compact TiO2 films on FTO glass substrates [29]. Though the dip-coating process does not require any complicated equipment and greatly minimizes the waste of source materials, enabling fast and easy production of uniform thin films, the method is not the same as our spin coating process.
Figure 2 presents the top-view SEM images of SnO2 thin films deposited on compact TiO2-coated rough FTO for 30 s at 2000 rpm (Figure 2a,b), 3000 rpm (Figure 2c,d), and 4000 rpm (Figure 2e,f), respectively. As shown in Figure 2a,b, the cracks on the surface of the TiO2/SnO2 thin film were obviously filled with SnO2 crystal grains. Due to the rotational speed being too low, a thick SnO2 thin film formed. Thus, many cracks appeared on the surface of the SnO2 thin film. Jiang et al. demonstrated a dense, pinhole-free film formed by spin coating SnO2 nanoparticles solution onto glass/Indium-Tin Oxide (ITO) substrate at 3000 rpm [23]. However, in our experiment, as shown in Figure 2c,d, modified TiO2/SnO2 thin film without visible cracks through solution spin-coating SnO2 on compact TiO2-coated rough FTO at 3000 rpm formed, and is flat, uniform, and dense, which indicates the TiO2/SnO2 complementary composite hole blocking layer is able to fully cover the rough surface of the FTO electrode. Choi et al. demonstrated the TiO2 film was so too thin that pinholes were observed in the TiO2 layer, and electrons in the FTO layer easily recombined with holes due to the lack of hole blocking [15]. However, in our experiment, as the rotating speed increased to 4000 rpm, the bare FTO was exposed from a few large cracks in Figure 2e,f, which indicated that the thickness of the functional layer of SnO2 was thinner due to the excessive spin-coating speed, and coverage of FTO/TiO2 based substrate is incomplete. This result suggests that the direct contact between bare FTO and the perovskite light-absorber layer can cause the recombination of holes and electrons, leading to the degradation of device performance. It is consistent with the results obtained with summary of photovoltaic parameters with the J–V characteristics from reverse scan of the PSC devices based on TiO2/SnO2 complementary composite hole blocking layer.
However, the reasons for formation of cracks are different under high speed (4000 rpm) and low speed (2000 rpm), presented in detail in Figure 3. Figure 3 presents schematics for formation process of SnO2 thin films at different rotational speed. Compared with situations of other rotational speed, the SnO2 thin film from 2000 rpm was thicker, and the total amount of solution in the film was more. The solvent volatilization rate is lower during the spin coating process of 30 s, so that the solution film of SnO2 was formed. During the annealing process of the solution film at 150 °C for 30 min, the solvent evaporated and the solution film contracted in the thickness direction, resulting in the exposure of the sharp peak of substrate, thus forming the cracks, as shown as Figure 3, corresponding to the SEM images (Figure 2a,b).
For the SnO2 film from 3000 rpm, the solvent volatilized rate was more than the situation of SnO2 film from 2000 rpm during the spin coating of 30 s, and the film itself was relatively thinner, thus forming a semi-solid/semi-liquid film after finishing the spin coating. In particular, the SnO2 film at the location of the sharp peak of substrate almost became solid, thus preserving the shape at the location of the sharp peak, as shown as Figure 3, corresponding to the SEM images (Figure 2c,d).
In the process of spin-coating at 4000 rpm, the solvent volatilization was very fast, and the whole SnO2 film was very thin and the total amount of solvent was very little, so the solid SnO2 film had been formed after 30 s spin coating. It is worth noting that at the position of the sharp peak of substrate, the SnO2 film was so thin that the ability to withstand strain of the film was very weak, resulting in a crack after annealing at 150 °C, as shown as Figure 3, corresponding to the SEM images (Figure 2e,f).
In addition, the film from spin coating at high speed was thinner than the one at low speed, and the film from spin coating at high speed was rougher than the one at low speed. Light trapping is a technique to improve optical absorption in the active layer of a solar cell. The rough surface can act as a light trapping structure to enhance the absorption perovskite solar cell [30,31,32,33]. However, the feature size here (<74 nm) is far less than the effective trapping sizes mentioned by previous research groups (~300 nm [30], ~6 μm [31] and ~800 nm [32]), so that the TiO2/SnO2 thin film with lower roughness is not the main reason for the efficiency drop.
Figure 4 presents the cross-sectional SEM images of the TiO2/SnO2 complementary composite hole blocking layer with SnO2 spin-coated on compact TiO2-coated FTO at 3000 rpm, which indicated the formation of modified TiO2/SnO2 film without visible breakages. As shown in Figure 4a, the entire film of TiO2/SnO2 complementary composite hole blocking layer was uniform in thickness and completely covered. Compared with single-layer TiO2 hole blocking layer thin film, the SnO2 thin film spin-coated on compact TiO2-coated rough FTO exhibited a flatter surface. Notably, as shown in Figure 4b, the TiO2/SnO2 complementary composite hole blocking layer also has good coverage at the protrusions of the underlying substrate and no breakage or large bulging in the protrusions could be observed. This is consistent with the observation from top-view SEM images of SnO2 films deposited on compact TiO2-coated rough FTO at 3000 rpm (Figure 2c,d).
Figure 5 shows schematic illustration for the solution spin-coating process of TiO2/SnO2 complementary composite hole blocking layer. As we can see, the surface of the bare FTO was very rough due to the presence of sharp peaks (Figure 5a), corresponding to the SEM image (Figure 1e). As shown in Figure 5b, the spin-coating process formed a highly irregular thick TiO2 layer due to overfilling the valleys on the rough FTO surface with TiO2, resulting in many cracks appearing on the surface of TiO2, and the bare FTO surface was exposed, corresponding to the SEM images (Figure 1b–d). However, as can be seen from Figure 5c, the cracks were absent from the surface of SnO2 thin film deposited on compact TiO2-coated rough FTO at 3000 rpm and the SnO2 thin film fully covered the surface of the FTO electrode, corresponding to the SEM images (Figure 2c,d). Meanwhile, the SnO2 thin film is flat, uniform, and dense, corresponding to the SEM images (Figure 4). This result suggests that the modified TiO2/SnO2 complementary composite hole blocking layer is beneficial to suppressing recombination of holes and electrons between the perovskite layer and FTO and enhances the performance of devices.
XRD data of the SnO2 thin film deposited on FTO/TiO2 substrate were collected in Figure 6. Each of the marked peak positions in the figure (Figure 6) corresponded to the (110), (101), (200), (211), (310), (301) crystal planes of the SnO2 crystal, which was in consistent with the results of the previous report [23] about XRD pattern of the SnO2 material, indicating SnO2 thin film composite counter electrodes had been successfully deposited on the FTO/TiO2 substrate.
Figure 7 presents top-view SEM images (Figure 7a,b) and cross-sectional SEM image (Figure 7c) of perovskite thin films deposited on TiO2/SnO2 of solution spin-coating SnO2 on compact TiO2-coated rough FTO at 3000 rpm, respectively. From Figure 7a,b, it can be seen that the entire perovskite film was high-quality and quite uniform free of cracks. However, high-quality perovskite film is essential for the performance of planar PSCs, as it can avoid the direct contact of hole blocking layer and electron blocking layer [20]. It is worth noting that the individual grain size of perovskite crystals was especially large, and the largest grain size reached a rare 2.67 μm. Furthermore, due to the passivation of the doping, the grain boundary was too smooth, which reduced defects of grain boundaries in the perovskite film to a great extent. From the cross-sectional SEM image (Figure 7c), it can be found that the entire perovskite film was composed of single layer of large grains and uniformly dense, which is coincident with the morphology of the film on the top-view SEM images (Figure 7a,b).
Figure 8 displays the XRD pattern of the perovskite thin film deposited on FTO/TiO2/SnO2 substrate in the case of spin-coating SnO2 at 3000 rpm. Obviously, the XRD pattern presents strong and sharp (101) and (200) diffraction peaks at 14.02° and 28.32°, demonstrating the good crystallinity of perovskite film, which is consistent with the SEM results (Figure 7) of the large-grain-size perovskite film. The perovskite grains of good crystallinity effectively enhance the efficiency of injection of photo-carriers of the perovskite light-absorber layer into the hole blocking layer and electron blocking layer, thereby further improving the overall performance of the PSC device.
Figure 9 shows energy bandgap diagram for TiO2/SnO2 based PSC, the shift of conduction band is not the main reason for the efficiency drop [34].
Figure 10 shows the J–V curves from reverse scan (RS) and forward scan (FS) for the PSC devices based on TiO2/SnO2 complementary composite hole blocking layer under different SnO2 spin-coating speeds, measured under simulated sunlight with intensity of 100 mW cm−2 (AM 1.5 G). Obviously, when the SnO2 spin-coating speed was 3000 rpm, the RS and FS curves of the device basically coincided and the hysteresis phenomenon basically disappeared, which matches the thin film morphology seen from the top-view SEM images (Figure 7a,b). When the SnO2 spin-coating speeds were 2000 and 4000 rpm, a SnO2 functional layer that was wither too thick or too thin could not match well with the TiO2 compact layer to form modified TiO2/SnO2 complementary composite hole blocking layer. This led directly to a drop in the optoelectronic performance of the device. The presence of cracks also caused serious electrical current leakage existing inside the device, resulting the PSC devices under these two processes having different degrees of hysteresis.
Table 2 shows summary of J–V characteristics from RS of the PSC devices based on TiO2/SnO2 complementary composite hole blocking layer under different SnO2 spin-coating speeds. The best cell based on TiO2/SnO2 complementary composite hole blocking layer under the SnO2 spin-coating speed of 3000 rpm obtained a PEC of 13.52% corresponding to a Jsc of 22.48 mA cm−2, a Voc of 1.01 V and a FF of 59.51. Although this efficiency is not the highest in PSCs, it is the highest efficiency ever recorded in PSCs with such spongy carbon/FTO composite counter electrode, and furthermore, the preparation techniques of high-quality perovskite thin films and the cheap spongy carbon/FTO composite counter electrode under absolute ambient condition are beneficial for large-scale applications and commercialization. At the same time, since the problem of the defect at the interface between the hole blocking layer and the perovskite light-absorber layer was solved, the hysteresis phenomenon of the entire device was well solved.

4. Conclusions

In summary, we optimized a rotational speed of spin-coating SnO2 at 3000 rpm to cover the cracks of compact TiO2-coated on rough FTO. Using composite layered TiO2/SnO2 can reduce hysteresis behavior due to an effectively suppressed recombination of holes and electrons between the perovskite layer and FTO. Meanwhile, as a result, we achieved high-quality perovskite thin films and high efficiency of 13.52% for devices with spongy carbon/FTO composite counter electrode. This work highlights the preparation process of modified hole blocking layer in PSC and has a certain reference significance for perovskite based opto-electronic devices.

Author Contributions

Conceptualization, X.B.; Methodology, X.Z.; Validation, D.C.; Investigation, H.R.; Data Curation, J.C.; Writing-Original Draft Preparation, H.R.; Writing-Review & Editing, T.L.; Visualization, H.R.; Supervision, X.Z.

Funding

This research was funded by Project of Natural Science Foundation of China (No. 61875186), Project of Natural Science Foundation of Beijing (No. Z160002), Opened Fund of the State Key Laboratory on Integrated Optoelectronics (No. IOSKL2016KF19), and Beijing Key Laboratory for Sensors of BISTU (No. KF20181077203).

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Snaith, H.J. Perovskites: The emergence of a new Era for low-cost, high-efficiency solar cells. J. Phys. Chem. Lett. 2013, 4, 3623–3630. [Google Scholar] [CrossRef]
  2. Park, N.G. Organometal perovskite light absorbers toward a 20% efficiency low-cost solid-state mesoscopic solar cell. J. Phys. Chem. Lett. 2013, 4, 2423–2429. [Google Scholar] [CrossRef]
  3. Green, M.A.; Ho-Baillie, A.; Snaith, H.J. The emergence of perovskite solar cells. Nat. Photonics 2014, 8, 506–514. [Google Scholar] [CrossRef]
  4. Grätzel, M. The light and shade of perovskite solar cells. Nat. Mater. 2014, 13, 838–842. [Google Scholar] [CrossRef] [PubMed]
  5. Abdi-Jalebi, M.; Pazoki, M.; Philippe, B.; Dar, M.I.; Alsari, M.; Sadhanala, A.; Diyitini, G.; Imani, R.; Lilliu, S.; Kullgren, J.; et al. Dedoping of lead halide perovskites incorporating monovalent cations. ACS Nano 2018, 12, 7301–7311. [Google Scholar] [CrossRef] [PubMed]
  6. Alsari, M.; Bikondoa, O.; Bishop, J.; Abdi-Jalebi, M.; Ozer, L.Y.; Hampton, M.; Thompson, P.; Horantner, M.T.; Mahesh, S.; Greenland, C.; et al. In situ simultaneous photovoltaic and structural evolution of perovskite solar cells during film formation. Energy Environ. Sci. 2018, 11, 383–393. [Google Scholar] [CrossRef]
  7. Alsari, M.; Pearson, A.J.; Wang, J.T.W.; Wang, Z.P.; Montisci, A.; Greenham, N.C.; Snaith, H.J.; Lilliu, S.; Friend, H. Degradation kinetics of inverted perovskite solar cells. Sci. Rep. 2018, 8, 5977. [Google Scholar] [CrossRef] [PubMed]
  8. Liu, Z.Y.; Sun, B.; Liu, X.Y.; Han, J.H.; Ye, H.B.; Tu, Y.X.; Chen, C.; Shi, T.L.; Lang, Z.R.; Liao, G.L. 15% efficient carbon based planar-heterojunction perovskite solar cells using TiO2/SnO2 bilayer as electron transport layer. J. Mater. Chem. A 2018, 6, 7409–7419. [Google Scholar] [CrossRef]
  9. Ren, Z.Q.; Wang, N.; Zhu, M.H.; Li, X.; Qi, J.Y. A NH4F interface passivation strategy to produce air-processed high-performance planar perovskite solar cells. Electrochim. Acta 2018, 282, 653–661. [Google Scholar] [CrossRef]
  10. Li, X.; Yang, J.Y.; Jiang, Q.H.; Lai, H.; Li, S.P.; Xin, J.W.; Chu, W.J.; Hou, J.D. Low-temperature solution-processed znse electron transport layer for efficient planar perovskite solar cells with negligible hysteresis and improved photostability. ACS Nano 2018, 12, 5605–5614. [Google Scholar] [CrossRef] [PubMed]
  11. Ma, J.J.; Yang, G.; Qin, M.C.; Zheng, X.L.; Lei, H.W.; Chen, C.; Chen, Z.L.; Guo, Y.X.; Han, H.W.; Zhao, X.Z.; et al. MgO nanoparticle modified anode for highly efficient SnO2-based planar perovskite solar cells. Adv. Sci. 2017, 4, 1700031. [Google Scholar] [CrossRef] [PubMed]
  12. Wu, Y.Z.; Yang, X.D.; Chen, H.; Zhang, K.; Qin, C.J.; Liu, J.; Peng, W.Q.; Islam, A.; Bi, E.B.; Ye, F.; et al. Highly compact TiO2 layer for efficient hole-blocking in perovskite solar cells. Appl. Phys. Express 2014, 7, 052301. [Google Scholar] [CrossRef]
  13. Liu, Y.; Peng, Q.; Zhou, Z.P.; Yang, G. Effects of substrate temperature on properties of transparent conductive Ta-doped TiO2 films deposited by radio-frequency magnetron sputtering. Chin. Phys. Lett. 2018, 35, 048101. [Google Scholar] [CrossRef]
  14. Duong, T.T.; Kim, Y.J.; Eom, J.H.; Choi, J.S.; Le, A.T.; Yoon, S.G. Enhancement of solar cell efficiency using perovskite dyes deposited via a two-step process. RSC Adv. 2015, 5, 33515–33523. [Google Scholar] [CrossRef]
  15. Choi, J.; Song, S.; Horantner, M.T.; Snaith, H.J.; Park, T. Well-defined nanostructured, single-crystalline TiO2 electron transport layer for efficient planar perovskite solar cells. ACS Nano 2016, 10, 6029–6036. [Google Scholar] [CrossRef] [PubMed]
  16. Zhang, N.; Guo, Y.; Yin, X.; He, M.; Zou, X. Spongy carbon film deposited on a separated substrate as counter electrode for perovskite-based solar cell. Mater. Lett. 2016, 182, 248–252. [Google Scholar] [CrossRef]
  17. Mei, A.; Li, X.; Liu, L.; Ku, Z.; Liu, T.; Rong, Y.G.; Xu, M.; Hu, M.; Chen, J.; Yang, Y.; et al. A hole-conductor-free, fully printable mesoscopic perovskite solar cell with high stability. Science 2014, 345, 295–298. [Google Scholar] [CrossRef] [PubMed]
  18. Habisreutinger, S.N.; Leijtens, T.; Eperon, G.E.; Stranks, S.D.; Nicholas, R.J.; Snaith, H.J. Carbon nanotube/polymer composites as a highly stable hole collection layer in perovskite solar cells. Nano Lett. 2014, 14, 5561–5568. [Google Scholar] [CrossRef] [PubMed]
  19. Ling, T.; Zou, X.P.; Cheng, J.; Bai, X.; Ren, H.Y.; Chen, D. Modified sequential deposition route through localized-liquid-liquid-diffusion for improved perovskite multi-crystalline thin films with micrometer-scaled grains for solar cells. Nanomaterials 2018, 8, 416. [Google Scholar] [CrossRef] [PubMed]
  20. Wu, C.C.; Huang, Z.R.; He, Y.H.; Luo, W.; Ting, H.K.; Li, T.Y.; Sun, W.H.; Zhang, Q.H.; Chen, Z.J.; Xiao, L.X. TiO2/SnOxCly double layer for highly efficient planar perovskite solar cells. Org. Electron. 2017, 50, 485–490. [Google Scholar] [CrossRef]
  21. Ke, W.J.; Fang, G.J.; Liu, Q.; Xiong, L.B.; Qin, P.L.; Tao, H.; Wang, J.; Lei, W.H.; Li, B.R.; Wan, J.W.; et al. Low-temperature solution-processed tin oxide as an alternative electron transporting layer for efficient perovskite solar cells. J. Am. Chem. Soc. 2015, 137, 6730–6733. [Google Scholar] [CrossRef] [PubMed]
  22. Song, J.X.; Zheng, E.Q.; Bian, J.; Wang, X.F.; Tian, W.J.; Sanehira, Y.; Miyasaka, T. Low-temperature SnO2-based electron selective contact for efficient and stable perovskite solar cells. J. Mater. Chem. A 2015, 3, 10837–10844. [Google Scholar] [CrossRef]
  23. Jiang, Q.; Zhang, L.Q.; Wang, H.L.; Yang, X.L.; Meng, J.H.; Liu, H.; Yin, Z.G.; Wu, J.L.; Zang, X.W.; You, J.B. Enhanced electron extraction using SnO2 for high-efficiency planar-structure HC(NH2)2PbI3-based perovskite solar cells. Nat. Energy 2017, 2, 16177. [Google Scholar] [CrossRef]
  24. Baena, J.P.C.; Steier, L.; Tress, W.; Saliba, M.; Neutzner, S.; Matsui, T.; Giordano, F.; Jacobsson, T.J.; Kandada, A.R.S.; Zakeeruddin, S.M.; et al. Highly efficient planar perovskite solar cells through band alignment engineering. Energy Environ. Sci. 2015, 8, 2928–2934. [Google Scholar] [CrossRef]
  25. Chen, J.Y.; Chueh, C.C.; Zhu, Z.L.; Chen, W.C.; Jen, A.K.Y. Low-temperature electrodeposited crystalline SnO2 as an efficient electron transporting layer for conventional perovskite solar cells. Sol. Energy Mater. Sol. Cells 2017, 164, 47–55. [Google Scholar] [CrossRef]
  26. Anaraki, E.H.; Kermanpur, A.; Steier, L.; Domanski, K.; Matsui, T.; Tress, W.; Saliba, M.; Abate, A.; Grätzel, M.; Hagfeldt, A.; et al. Highly efficient and stable planar perovskite solar cells by solution-processed tin oxide. Energy Environ. Sci. 2016, 9, 3128–3134. [Google Scholar] [CrossRef]
  27. Malviya, K.D.; Dotan, H.; Yoon, K.R.; Kim, I.D.; Rothschild, A. Rigorous substrate cleaning process for reproducible thin film hematite (alpha-Fe2O3) photoanodes. J. Mater. Res. 2016, 31, 1565–1573. [Google Scholar] [CrossRef]
  28. Huang, L.K.; Li, C.; Sun, X.X.; Xu, R.; Du, Y.Y.; Ni, J.; Cai, H.K.; Li, J.; Hu, Z.Y.; Zhang, J.J. Efficient and hysteresis-less pseudo-planar heterojunction perovskite solar cells fabricated by a facile and solution-saving one-step dip-coating method. Org. Electron. 2017, 40, 13–23. [Google Scholar] [CrossRef]
  29. Masood, M.T.; Weinberger, C.; Sarfraz, J.; Rosqvist, E.; Sanden, S.; Sandberg, O.J.; Vivo, P.; Hashmi, G.; Lund, P.D.; Osterbacka, R.; et al. Impact of film thickness of ultrathin dip-coated compact TiO2 layers on the performance of mesoscopic perovskite solar cells. ACS Appl. Mater. Interfaces 2017, 9, 17906–17913. [Google Scholar] [CrossRef] [PubMed]
  30. Du, Q.G.; Shen, G.S.; John, S. Light-trapping in perovskite solar cells. AIP Adv. 2016, 6, 065002. [Google Scholar] [CrossRef]
  31. Iftiquar, S.M.; Yi, J.S. Numerical simulation and light trapping in perovskite solar cell. J. Photonics Energy 2016, 6, 025507. [Google Scholar] [CrossRef]
  32. Peer, A.; Biswas, R.; Park, J.M.; Shinar, R.; Shinar, J. Light management in perovskite solar cells and organic LEDs with microlens arrays. Opt. Express 2017, 25, 10704–10709. [Google Scholar] [CrossRef] [PubMed]
  33. Bhattacharya, J.; Peer, A.; Joshi, P.H.; Biswas, R.; Dalal, V.L. Blue photon management by inhouse grown ZnO:Al cathode for enhanced photostability in polymer solar cells. Sol. Energy Mater. Sol. Cells 2018, 179, 95–101. [Google Scholar] [CrossRef]
  34. Lee, Y.H.; Paek, S.; Cho, K.T.; Oveisi, E.; Gao, P.; Lee, S.; Park, J.S.; Zhang, Y.; Humphry-Baker, R.; Asiri, A.M.; et al. Enhanced charge collection with passivation of the tin oxide layer in planar perovskite solar cells. J. Mater. Chem. A 2017, 5, 12729–12734. [Google Scholar] [CrossRef]
Coatings 08 00314 sch001
Scheme 1. The entire process of the device fabrication.
Scheme 1. The entire process of the device fabrication.
Coatings 08 00314 sch001
Coatings 08 00314 g001
Figure 1. SEM images: (a) Top-view SEM image of bare FTO glass; (b,c) Top-view SEM image of TiO2 film; (d) Cross-sectional SEM image of TiO2 film; (e) Cross-sectional SEM image of bare FTO glass; (f) Top-view SEM image of 3D roughness reconstruction of bare FTO glass.
Figure 1. SEM images: (a) Top-view SEM image of bare FTO glass; (b,c) Top-view SEM image of TiO2 film; (d) Cross-sectional SEM image of TiO2 film; (e) Cross-sectional SEM image of bare FTO glass; (f) Top-view SEM image of 3D roughness reconstruction of bare FTO glass.
Coatings 08 00314 g001
Coatings 08 00314 g002
Figure 2. Top-view SEM images of SnO2 thin films deposited on compact TiO2-coated rough FTO at different spin-coating speeds for 30 s: (a,b) 2000 rpm; (c,d) 3000 rpm; (e,f) 4000 rpm.
Figure 2. Top-view SEM images of SnO2 thin films deposited on compact TiO2-coated rough FTO at different spin-coating speeds for 30 s: (a,b) 2000 rpm; (c,d) 3000 rpm; (e,f) 4000 rpm.
Coatings 08 00314 g002
Coatings 08 00314 g003
Figure 3. Schematics for formation of SnO2 thin films at different rotational speed.
Figure 3. Schematics for formation of SnO2 thin films at different rotational speed.
Coatings 08 00314 g003
Coatings 08 00314 g004
Figure 4. Cross-sectional SEM images of the TiO2/SnO2 complementary composite hole blocking layer with SnO2 spin-coated on compact TiO2-coated rough FTO at 3000 rpm: (a) Smaller magnification; (b) Larger magnification.
Figure 4. Cross-sectional SEM images of the TiO2/SnO2 complementary composite hole blocking layer with SnO2 spin-coated on compact TiO2-coated rough FTO at 3000 rpm: (a) Smaller magnification; (b) Larger magnification.
Coatings 08 00314 g004
Coatings 08 00314 g005
Figure 5. Schematic illustration for the solution spin-coating process of TiO2/SnO2 complementary composite hole blocking layer: (a) The bare FTO substrate; (b) TiO2 thin film deposited on rough FTO substrate; (c) SnO2 thin film deposited on compact TiO2-coated rough FTO at 3000 rpm.
Figure 5. Schematic illustration for the solution spin-coating process of TiO2/SnO2 complementary composite hole blocking layer: (a) The bare FTO substrate; (b) TiO2 thin film deposited on rough FTO substrate; (c) SnO2 thin film deposited on compact TiO2-coated rough FTO at 3000 rpm.
Coatings 08 00314 g005
Coatings 08 00314 g006
Figure 6. XRD pattern of SnO2 thin film deposited on FTO/TiO2 substrate.
Figure 6. XRD pattern of SnO2 thin film deposited on FTO/TiO2 substrate.
Coatings 08 00314 g006
Coatings 08 00314 g007
Figure 7. SEM images: (a,b) Top-view SEM images of FTO/TiO2/SnO2/perovskite; (c) Cross-sectional SEM image of FTO/TiO2/SnO2/perovskite.
Figure 7. SEM images: (a,b) Top-view SEM images of FTO/TiO2/SnO2/perovskite; (c) Cross-sectional SEM image of FTO/TiO2/SnO2/perovskite.
Coatings 08 00314 g007
Coatings 08 00314 g008
Figure 8. XRD pattern of the perovskite thin film deposited on FTO/TiO2/SnO2 substrate in the case of spin-coating SnO2 at 3000 rpm.
Figure 8. XRD pattern of the perovskite thin film deposited on FTO/TiO2/SnO2 substrate in the case of spin-coating SnO2 at 3000 rpm.
Coatings 08 00314 g008
Coatings 08 00314 g009
Figure 9. Energy bandgap diagram for TiO2/SnO2 based perovskite solar cells.
Figure 9. Energy bandgap diagram for TiO2/SnO2 based perovskite solar cells.
Coatings 08 00314 g009
Coatings 08 00314 g010
Figure 10. The J–V curves from reverse scan (RS) and forward scan (FS) for the PSC devices based on TiO2/SnO2 complementary composite hole blocking layer under different SnO2 spin-coating speeds, measured under simulated sunlight with intensity of 100 mW cm−2 (AM 1.5 G).
Figure 10. The J–V curves from reverse scan (RS) and forward scan (FS) for the PSC devices based on TiO2/SnO2 complementary composite hole blocking layer under different SnO2 spin-coating speeds, measured under simulated sunlight with intensity of 100 mW cm−2 (AM 1.5 G).
Coatings 08 00314 g010
Table 1. Summary of J–V characteristics of device R1 and device R2 from reverse scan.
Table 1. Summary of J–V characteristics of device R1 and device R2 from reverse scan.
DevicesNaJscb (mA/cm2)Vocc (V)FF dPCE e (%)
R1113.130.8641.094.63
R2218.260.9754.709.66
Notes: a Number of TiO2 spin-coating layers; b Short-circuit photocurrent density; c Open-circuit voltage; d Fill factor; e Power conversion efficiency.
Table 2. Summary of J–V characteristics from reverse scan of the PSC devices based on TiO2/SnO2 complementary composite hole blocking layer under different SnO2 spin-coating speeds.
Table 2. Summary of J–V characteristics from reverse scan of the PSC devices based on TiO2/SnO2 complementary composite hole blocking layer under different SnO2 spin-coating speeds.
RSSC a (rpm)Jscb (mA/cm2)Vocc (V)FF dPCE e (%)
200018.740.7661.958.81
300022.481.0159.5113.52
400015.560.8752.227.10
Notes: a Rotating speed of spin-coating SnO2; b Short-circuit photocurrent density; c Open-circuit voltage; d Fill factor; e Power conversion efficiency.

Share and Cite

MDPI and ACS Style

Ren, H.; Zou, X.; Cheng, J.; Ling, T.; Bai, X.; Chen, D. Facile Solution Spin-Coating SnO2 Thin Film Covering Cracks of TiO2 Hole Blocking Layer for Perovskite Solar Cells. Coatings 2018, 8, 314. https://doi.org/10.3390/coatings8090314

AMA Style

Ren H, Zou X, Cheng J, Ling T, Bai X, Chen D. Facile Solution Spin-Coating SnO2 Thin Film Covering Cracks of TiO2 Hole Blocking Layer for Perovskite Solar Cells. Coatings. 2018; 8(9):314. https://doi.org/10.3390/coatings8090314

Chicago/Turabian Style

Ren, Haiyan, Xiaoping Zou, Jin Cheng, Tao Ling, Xiao Bai, and Dan Chen. 2018. "Facile Solution Spin-Coating SnO2 Thin Film Covering Cracks of TiO2 Hole Blocking Layer for Perovskite Solar Cells" Coatings 8, no. 9: 314. https://doi.org/10.3390/coatings8090314

APA Style

Ren, H., Zou, X., Cheng, J., Ling, T., Bai, X., & Chen, D. (2018). Facile Solution Spin-Coating SnO2 Thin Film Covering Cracks of TiO2 Hole Blocking Layer for Perovskite Solar Cells. Coatings, 8(9), 314. https://doi.org/10.3390/coatings8090314

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop