25 March 2015 Interface structure between titania and perovskite materials observed by quartz crystal microbalance system
Author Affiliations +
J. of Photonics for Energy, 5(1), 057410 (2015). doi:10.1117/1.JPE.5.057410
Adsorption of PbI2 onto a titania layer was monitored by a quartz crystal microbalance system in solution. The amount of PbI2 adsorbed on the titania layer increased with an increase in the PbI2 concentration in dimethylformamide (DMF). However, PbI2 remained after being rinsed with DMF, suggesting that PbI2 is rigidly bonded to the surface of the titania. The x-ray photoelectron spectroscopy measurement of PbI2 adsorbed on the titania substrate showed that the Pb compound has a composition of PbI0.33, not PbI2, suggesting that part of the Pb-I reacts with the HO-Ti moieties of titania to form Pb-O-Ti linkages. Trap density as measured by the thermally stimulated current method decreased after PbI2 passivation. Perovskite solar cells consisting of porous titania passivated with PbI2 had a higher efficiency than those without the passivation. It was concluded that PbI2 passivation of porous titania surfaces is one of the crucial approaches for enhancing the efficiency of perovskite solar cells with a scaffold layer of porous titania.
Nakayashiki, Daisuke, Ogomi, and Hayase: Interface structure between titania and perovskite materials observed by quartz crystal microbalance system



The certified efficiency of perovskite solar cells with a size of 0.1cm2 is now 17.8% (Ref. 1) and comes close to the 20.4% efficiency of polycrystalline Si solar cells. Therefore, perovskite solar cells are expected to be one of the important types of solar cells in the next generation printable solar cells. Perovskite solar cells contain CH3NH3PbI3 (Perov Pb) as the light harvesting layer. The Perov Pb layer is prepared by spin-coating the mixture of PbCl2 (or PbI2) and CH3NH3I (MAI) onto a TiO2 nanoporous layer (scaffold layer); this process is known as a one-step synthesis.3 The Perov Pb can also be prepared with a two-step synthesis, where the PbI2 layer is fabricated on a porous titania layer (scaffold layer) and the sample is dipped in the MAI solution in dimethylformamide (DMF). The MAI is diffused in the PbI2 layer to make the perovskite structures.4 It has been reported that the two-step process has the advantage of a higher efficiency over the one-step process.4 In this report, we focus on the two-step process. When the perovskite layer is exposed to light, the perovskite is excited and electrons are injected into the titania layer or are carried by the perovskite itself.5,6,9 The surface of the porous titania affects the electron collection as well as the crystal growth of the perovskite crystals.1011.12 For example, we have reported that the electron trap density of the perovskite/titania layer is decreased by passivating the surface of the titania.10,12 In addition, the crystal size of the perovskite becomes larger when the titania surface is passivated with amino acid hydroiodic acid (HI) salt.11 The interface between titania and the perovskite crystal is crucial for understanding the photoconversion; however, the interface has not been discussed in detail. Previously, dye adsorption for dye-sensitized solar cells has been discussed using a quartz crystal microbalance (QCM) measurement.13,14 We now discuss the interface structure of the titania/perovskite layer by monitoring the PbI2 adsorption on the titania layer employing the QCM measurement.



PbI2 and CH3NH3I were prepared in the same way as has been reported in previous works.1011.12 Figure 1 shows the QCM system (Meywafosus Co. LTD) employed in this experiment. The titania (anatase) compact layer (500 nm) was prepared on a Au QCM sensor by atomic layer deposition (ALD) (Sunable ALD R200 Basic, Picosun) using TiCl4 and water as the precursor. The chamber temperature was kept at 300°C (1000 cycles, 50 nm thickness), followed by annealing the sample at 450°C for 30 min. The titania compact layers had an anatase structure. The titania/Au sensor was placed at position B in Fig. 1. The PbI2 solution in the DMF (0.2 to 5 mM) was put into container A, and the solution was passed over the titania/QCM sensor B. The flow rate was 0.5μL/s and the temperature was kept at 25°C. The amount of PbI2 adsorbed on the titania compact layer was monitored with a frequency shift according to the following Sauerbrey equation:15


where ΔF is the frequency change, F0 is the sensor frequency, Δm is the change of weight, A is the sensor area, μ is the shearing stress (2.947×1010kgms), and ρ is the density (2648kg/m3).

Fig. 1

Quartz crystal microbalance measurement apparatus for measuring PbI2 adsorption on titania surface.


The perovskite solar cell was prepared in the same way as in our previous reports.1011.12 F-doped SnO2 layered glass (FTO glass, Nippon Sheet Glass Co. Ltd.) was patterned using Zn and a 6 M HCl aqueous solution. On this patterned FTO glass, titanium diisopropoxide bis(acetylacetonate) solution in ethanol was sprayed at 300°C to prepare the compact titania layers. A porous titania layer was fabricated by spin-coating titania paste (PST-18NR, JGC Catalysts and Chemicals Ltd.) in ethanol (titaniapasteethanol=12.5 weight ratio), followed by heating the substrate at 550°C for 30 min. The one-step preparation process for perovskite solar cells is as follows: MAI and PbI2 were mixed in a 11 molar ratio to prepare a 40% solution of perovskite in N,N-dimethylformamide (DMF) and the mixture was spin-coated on the substrate. The substrate was heated at 100°C for 45 min, followed by spin-coating a mixture of 55 mM of tert-butylpyridine, 9 mM of lithium bis(trifluoromethylsyfonyl)imide salt, and 68 mM of 2,2’,7,7’- tetrakis[N,N-di (4-methoxy phenyl) amino]—9,9’- spirobifluorene (spiro). Finally, Ag and Au electrodes were fabricated with a vacuum deposition method (ALS Tech E-299).

The two-step preparation process for perovskite solar cells is as follows: 1 M solution of PbI2 in N,N’-dimethylformamide (DMF) was spin-coated, followed by baking at 70°C for 30 min. After that, the sample was dipped in a 10mg/ml solution of MAI in 2-propanol for 30 s. After rinsing, the sample was heated at 70°C for 30 min. On the sample, spiro and electrode were prepared in the same way as in the one-step preparation. The photovoltaic performance of the cells was evaluated using an AM 1.5G 100mW/cm2 irradiance solar simulator (CEP-2000, Bunkoukeiki Inc.) and a 0.4×0.4cm2 mask on a cell of size 0.5×0.5cm2.

The thermally stimulated current (TSC) was measured using a TS-FETT apparatus (Rigaku) in the same way as described in our previous reports.16 At a low temperature (180°C), traps were filled with electrons by exposing the substrate to ultraviolet light. As the temperature of the sample increased, these electrons were released from the trap sites. These electrons are detected as a TSC. The TSC at a higher temperature is the result of electrons released from deeper traps and the TSC at a lower temperature is associated with electrons released from shallow traps. The trap depths and trap densities are calculated using the temperature and the current density at that temperature by Eqs. (2) and (3), respectively.16,17


where Et is the trap depth, k is the Boltzmann constant, Tm is the temperature (K), β is the programing rate (K/s), and ln is the natural logarithm


where N is the trap density, dI/dt is the current/unit time, e is the elementary charge, n is the volume (thickness×gap), and P is the porosity.


Results and Discussion

Figure 2 shows the relationship between the adsorption time and the PbI2 adsorption density on a compact titania layer. The PbI2 solution was introduced to the sensor surface at point A in Fig. 2. The weight of the compact layer increased with time, demonstrating that PbI2 was adsorbed on the compact titania layer. At point B in Fig. 2, the surface was rinsed by introducing DMF onto the sensor surface. The adsorption curve showed a sharp drop and remained at a constant value after that. The curve was explained as follows. The amount of PbI2 adsorbed on the compact titania layer increased with time and the uptake speed gradually decreased. Weakly adsorbed PbI2 was washed away upon rinsing with DMF and strongly adsorbed PbI2 remained on the titania surface.

Fig. 2

Relationship between PbI2 adsorption density on titania and the adsorption time.


The saturated (maximum) PbI2 adsorption density increased with an increase in the PbI2 concentration and reached a constant value as shown in Fig. 3, suggesting that PbI2 was adsorbed on all the adsorption sites. A, B, and C are explained later (Table 1). Supposing that the diameter of PbI2 is 0.558 to 0.954 nm, the surface area occupied by one PbI2 molecule is calculated to be 2.45 to 7.15×1015cm2. If all surfaces were covered with PbI2, the adsorption density of PbI2 could be calculated to be 107 to 313ng/cm2. The experimentally determined saturated adsorption density was 150 to 200ng/cm2 as shown in Fig. 3. The experimentally estimated adsorption density was roughly coincident with the calculated value.

Fig. 3

Relationship between saturated PbI2 adsorption density and PbI2 concentration in dimethyl formamide (DMF).


Table 1

Photovoltaic performances for solar cells consisting of CH3NH3PbI3.

JSC (mA/cm2)VOC (V)Fill factorPCE (%)
One-step (1)8.450.780.442.91
Two-step (5)14.840.840.597.33

The x-ray photoelectron spectroscopy (XPS) of PbI2 adsorbed on the titania layer is shown in Fig. 4. In Fig. 4(b), the 616 eV peak is assigned to I3d, and both the 135 and 137 eV peaks are assigned to Pb4f, as estimated from the data base shown in Fig. 4(a). The ratio of Pb:I of PbI2 adsorbed on the titania layer was estimated from the comparison of the peak intensity of a PbI2 thin film prepared on a glass substrate and was determined to be PbI=10.03. This suggested that PbI2 is bonded on the titania surface by a Pb-O-Ti linkage as shown in Fig. 5. It is probable that Ti-OH moieties on a titania layer react with Pb-I to form Ti-O-Pb and HI, namely; the negatively charged O of Ti-O attacks the positively charged Pb nucleophilically to form Ti-O-Pb.

Fig. 4

X-ray photoelectron spectroscopy (XPS) spectra of Pb adsorbed on titania: (a) reference, (b) PbI2 solution was coated on compact titania layer and the substrate was rinsed with DMF, (c) compact titania only for the reference.


Fig. 5

Expected reaction of PbI2 and titania.


The Pb4f signals of XPS for a Perov Pb bulk layer and a PbI2 bulk layer were observed at 135.6 and 135.7 eV, respectively, as shown in Fig. 6. After the bulk layer of the Perov Pb layer and the bulk layer of PbI2 on the titania layer were washed away, the titania surface was analyzed by XPS. The peak assigned to Pb4f was observed for the rinsed PbI2/titania surface at 136.4 eV, which was slightly shifted to a higher bonding energy than that of bulk PbI2 (135.7 eV). This is consistent with previous reports that the metals of an oxide metal have higher XPS bonding energies than that of the corresponding halides. The rinsed Perov Pb/titania surface also has the same XPS peak (136.4 eV) as the rinsed PbI2/titania layer. This suggests that Ti-O-Pb linkages are also formed at the titania/Perov Pb interfaces as well as at the titania/PbI2 interfaces. Perov Pb crystals may grow from the Pb-O-Ti surfaces.

Fig. 6

XPS Pb4f signal of Pb adsorbed on titania surface.


In order to examine the surface passivation effects on solar cell performance, the surface of the porous titania was treated with dilute PbI2 solutions with various concentrations, such as 0.2, 1, and 5 mM. The different concentrations correspond to points A, B, and C in Fig. 3, where 150 to 200, 100 to 125, and 75ng/cm2 of PbI2 were absorbed on the porous titania surface. After the surface treatment of the titania layer with a PbI2 dilute solution, the mixed solution of PbI2 and MAI was spin-coated on the porous titania layer to form a perovskite layer (Perov Pb). The photovoltaic performances for these solar cells are summarized in Table 1, in which the performance for a Perov Pb solar cell without any surface pretreatment is also included. It is observed that the photovoltaic performances, namely, Jsc and Voc, increased with an increase in the concentration of PbI2 passivation from 0.2 to 5 mM as shown in A, B, and C in Fig. 3. These results demonstrate that the photovoltaic performances are improved by controlling the titania–perovskite interfaces (passivation effect).

For our experimental conditions, the two-step preparation method showed higher photovoltaic performances (7.33%) than the one-step preparation method (2.91%) as shown in Table 1. In the two-step preparation method, the PbI2 layer is directly fabricated on the porous titania layer by using a 1 M solution of PbI2 (a much higher concentration) before MAI is introduced to the PbI2 layer. Therefore, the interface between the PbI2 and the porous titania layer was well passivated by the Ti-O-Pb bond formation.

Two possible mechanisms have been proposed for electron collection. One explanation is that electrons are collected through the nanoporous titania, which is a mechanism similar to that of dye-sensitized solar cells.4 The other explanation is that electrons are directly collected by the Perov Pb layers.5 For a Perov Pb solar cell consisting of porous titania, both processes may occur simultaneously. In Perov solar cells consisting of porous titania layer, electrons would be collected by both of porous titania layer and Perob Pb layer.16 Since these traps become charge recombination centers, the trap density must be low.1819. Figure 7 shows the electron trap distribution for the titania porous layer, the titania/PbI2 layer, and the titania/PbI2 rinsed with DMF solution. The trap density of porous titania at 4.2eV was 1016/cm3 and the trap density decreased to 1012 and 1011 after the porous titania surface was passivated with PbI2. Even after the surface was rinsed with the DMF solution, a low trap density was maintained, demonstrating that the titania surface was passivated with Ti-O-Pb linkages by PbI2.

Fig. 7

Trap distributions of TiO2 passivated with and without PbI2: (a) titania only, (b) porous titania passivated with PbI2, (c) PbI2/poroustitania after being rinsed with DMF.




The interface structure between titania and a Perov Pb layer was examined by QCM, XPS, and thermally stimulated currents. It was concluded that the interface was made by Ti-O-Pb, which passivates the surface trap of nanoporous titania. The photovoltaic performances were improved after the passivation.


This work was supported by Funding Program for the World–Leading Innovative R&D on Science and Technology (FIRST program headed by Professor Hiroshi Segawa).



M. A. Green et al., “Solar cell efficiency tables (Version 45),” Prog. Photovolt: Res. Appl. 22, 701–710 (2014).PPHOED1062-7995http://dx.doi.org/10.1002/pip.2573Google Scholar


J. H. Noh et al., “Chemical management for colorful, efficient, and stable inorganic–organic hybrid nanostructured solar cells,” Nano Lett. 13, 1764–1769 (2013).NALEFD1530-6984http://dx.doi.org/10.1021/nl400349bGoogle Scholar


H.-S. Kim et al., “Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%,” Sci. Rep. 2, 591 (2012).SRCEC32045-2322http://dx.doi.org/10.1038/srep00591Google Scholar


J. Burschka et al., “Sequential deposition as a route to high-performance perovskite-sensitized solar cells,” Nature 499, 316–319 (2013).NATUAS0028-0836http://dx.doi.org/10.1038/nature12340Google Scholar


M. M. Lee et al., “Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites,” Science 338, 643–647 (2012).SCIEAS0036-8075http://dx.doi.org/10.1126/science.1228604Google Scholar


J. M. Ball et al., “Low-temperature processed mesosuperstructured to thin-film perovskite solar cells,” Energy Environ. Sci. 6, 1739–1743 (2013).1754-5692http://dx.doi.org/10.1039/c3ee40810hGoogle Scholar


D. Liu and T. L. Kelly, “Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques,” Nat. Photonics 8, 133–138 (2013).1749-4885http://dx.doi.org/10.1038/nphoton.2013.342Google Scholar


H. J. Snaith, “Perovskites: the emergence of a new era for low-cost, high-efficiency solar cells,” J. Phys. Chem. Lett. 4, 3623–3630 (2013).1948-7185http://dx.doi.org/10.1021/jz4020162Google Scholar


M. Liu, M. B. Johnston and H. J. Snaith, “Efficient planar heterojunction perovskite solar cells by vapour deposition,” Nature 501, 395–398 (2013).NATUAS0028-0836http://dx.doi.org/10.1038/nature12509Google Scholar


Y. Ogomi et al., “Control of charge dynamics through a charge-separation interface for all-solid perovskite-sensitized solar cells,” ChemPhysChem. 15, 1062–1069 (2014).CPCHFT1439-4235http://dx.doi.org/10.1002/cphc.201301153Google Scholar


Y. Ogomi et al., “All-solid perovskite solar cells with HOCO-R-NH3+I- anchor-group inserted between porous titania and perovskite,” J. Phys. Chem. 118, 16651–16659 (2014).JPCHAX0022-3654http://dx.doi.org/10.1021/jp412627nGoogle Scholar


Q. Shen et al., “Charge transfer and recombination at the metal oxide/CH3NH3PbClI2/spiro-OMeTAD interfaces: uncovering the detailed mechanism behind high efficiency solar cells,” ChemPhysChem. 15, 1062–1069 (2014).CPCHFT1439-4235http://dx.doi.org/10.1002/cphc.201301153Google Scholar


H. A. Harms et al., “In situ investigation of dye adsorption on TiO2 films using a quartz crystal microbalance with a dissipation technique,” Phys. Chem. Chem. Phys. 14, 9037–9040 (2012).PPCPFQ1463-9076http://dx.doi.org/10.1039/c2cp41268cGoogle Scholar


H. A. Harms et al., “In-situ investigation of adsorption of dye and coadsorbates on TiO2 films using QCM-D fluorescence and AFM techniques,” Proc. SPIE 8811, 88110C (2013).PSISDG0277-786Xhttp://dx.doi.org/10.1117/12.2024194Google Scholar


K. K. Kanazawa and J. G. Gordon, “Frequency of a quartz microbalance in contact with liquid,” Anal. Chem. 57, 1770–1777 (1985).ANCHAM0003-2700http://dx.doi.org/10.1021/ac00285a062Google Scholar


Y. Noma et al., “Surface state passivation effect for nanoporous TiO2 electrode evaluated by thermally stimulated current and application to all-solid state dye-sensitized solar cells,” Jpn. J. Appl. Phys. 47, 505 (2008).JJAPA50021-4922http://dx.doi.org/10.1143/JJAP.47.505Google Scholar


A. Opanowicz and P. Petrucha, “Heating-rate method for determination of kinetic parameters from thermally stimulated conductivity and luminescence,” J. Appl. Phys. 93, 957–967 (2003).JAPIAU0021-8979http://dx.doi.org/10.1063/1.1530713Google Scholar


A. Kay and M. Grätzel, “Dye-sensitized core–shell nanocrystals: improved efficiency of mesoporous tin oxide electrodes coated with a thin layer of an insulating oxide,” Chem. Mater. 14, 2930–2935 (2002).CMATEX0897-4756http://dx.doi.org/10.1021/cm0115968Google Scholar


Y. Diamant et al., “Core–shell nanoporous electrode for dye sensitized solar cells: the effect of shell characteristics on the electronic properties of the electrode,” Coord. Chem. Rev. 248, 1271–1276 (2004).CCHRAM0010-8545http://dx.doi.org/10.1016/j.ccr.2004.03.003Google Scholar


E. Palomares et al., “Control of charge recombination dynamics in dye sensitized solar cells by the use of conformally deposited metal oxide blocking layers,” J. Am. Chem. Soc. 125, 475–482 (2003).JACSAT0002-7863http://dx.doi.org/10.1021/ja027945wGoogle Scholar


F. Fabregat-Santiago et al., “Electron transport and recombination in solid-state dye solar cell with spiro-OMeTAD as hole conductor,” J. Am. Chem. Soc. 131, 558–562 (2009).JACSAT0002-7863http://dx.doi.org/10.1021/ja805850qGoogle Scholar


F. Fabregat-Santiago et al., “The origin of slow electron recombination processes in dye-sensitized solar cells with alumina barrier coatings,” J. Appl. Phys. 96, 6903–6907 (2004).JAPIAU0021-8979http://dx.doi.org/10.1063/1.1812588Google Scholar


Y. Ogomi et al., “Ru dye uptake under pressurized CO2 improvement of photovoltaic performances for dye-sensitized solar cells,” J. Electrochem. Soc. 153, A2294–A2297 (2006).JESOAN0013-4651http://dx.doi.org/10.1149/1.2358927Google Scholar


Shuzi Hayase graduated from Osaka University in 1978 and received his PhD from Osaka University in 1983. He was with the R&D Center at Toshiba from 1978 to 2000, during which he engaged in the development of ULSI lithography. He was with the polysilane research group of the Robert West group at the University of Wisconsin from 1988 to 1990. He has been a professor at the Kyushu Institute of Technology (National Institute) since 2001. His research interest is printable solar cells and their materials.

Biographies of the other authors are not available.

Soya Nakayashiki, Hirotani Daisuke, Yuhei Ogomi, Shuzi Hayase, "Interface structure between titania and perovskite materials observed by quartz crystal microbalance system," Journal of Photonics for Energy 5(1), 057410 (25 March 2015). http://dx.doi.org/10.1117/1.JPE.5.057410


Solar cells






Back to Top