Advanced Materials - 2015 - Park - Bismuth Based Hybrid Perovskites A3Bi2I9 A Methylammonium or Cesium For Solar Cell

15214095, 2015, 43, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201501978 by Indian Association For The, Wiley Online Library on [15/11/2022].
See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advmat.de
www.MaterialsViews.com
Bismuth Based Hybrid Perovskites A3Bi2I9 (A: Methylammonium

COMMUNICATION
or Cesium) for Solar Cell Application

Byung-Wook Park, Bertrand Philippe, Xiaoliang Zhang, Håkan Rensmo, Gerrit Boschloo,*
and Erik M. J. Johansson*
The supply of energy is one of the greatest challenges of the less toxic element. Previously it has been reported that tin (Sn)
21st century and solar energy may be an important contribu- can replace lead to form the less toxic MASnI3 perovskite,[17,18]
tion to future energy production. Today the production of and solar cells with an efficiency of over 6% was achieved.[18]
solar cells is increasing rapidly as the price for solar cells However, it was noticed that the tin perovskite was not as stable
decreases. However, to compete with fossil fuels in order to as the lead perovskite and all materials and devices processing
become a large-scale energy source, the production cost of had to be performed in nitrogen gas atmosphere to avoid the
solar cells must still be reduced. There have been significant quick degradation of the tin perovskite. Therefore it is inter-
efforts in finding new materials for solar cells, and recently a esting to find other perovskites, which may be more stable
new class of photovoltaics based on perovskite materials has for device preparation and still work in the solar cell. Among
been discovered. In the first publications it was noticed that the other perovskite materials without lead photovoltaic proper-
CH3NH3PbX3 (where X is a halide) perovskite may be used as ties have been observed in for example BiFeO3, BiFe2CrO6, and
light absorber on the nanostructured TiO2 surface in combina- BiMnO3.[19–23] While the overall power conversion efficiency of
tion with a liquid electrolyte, resulting in rather efficient solar these materials is lower than for the metal-halide perovskites,
cells.[1,2] However, the stability was poor due to the solubility of they appear to be more stable and exhibit other functionalities
the perovskite in the liquid electrolyte. It was later reported that (they are all multiferroic, i.e., ferroelectric and magnetic). These
the CH3NH3PbX3 perovskite may also be used in combination examples contain bismuth, which is much less toxic compared
with solid organic hole transport materials for highly efficient to lead.[24,25] It is therefore interesting to further investigate var-
solar cells.[3,4] Replacing or substituting part of the methylam- ious bismuth based photovoltaic materials for a lower toxicity
monium cation (CH3NH3+; MA+) with a formamidinium cation and environmental impact.
(HC(NH2)2+; FA+) or the inorganic Cesium cation (Cs+) has In this report we present the preparation of bismuth (Bi)
been shown to change the light absorption spectrum of the per- based halide perovskite with the chemical structure A3Bi2I9
ovskite, which may improve the device performance.[5] Also an for solar cells, where A is a monovalent cation. In this work
addition of Cl− in the preparation of the CH3NH3PbI3 perov- cesium (Cs+) or methylamonium cation (MA+) have been used
skite has been shown to enhance the charge diffusion length.[6] as cations in the crystal structure. These materials belong to
A tremendous increase in research on the perovskite solar the perovskite family, and the structure of these substances
cells has yielded very efficient devices[7–15] and recently over consists of metal halide octahedra layers and the voids between
20% power conversion efficiency (PCE) has been reported.[16] the layers are filled by the cations (Cs+ or MA+). Depending on
Due to the low cost of the starting materials and the simple the arrangement of the metal halide layers, it is possible to dis-
production process, perovskite photovoltaics will probably tinguish different types of A3B2×9 compounds (where A is the
have significant influence of the future solar cell market and cation, B is the metal, and X is the halide). The metal halide
this type of solar cell may also be competitive with fossil fuels. octahedra can be joined by edges or vertices, and when they are
One major disadvantage with the MAPbX3 perovskite is that completely filled the classical perovskite structure, ABX3 (for
it contains lead (Pb), which is rather toxic. An important task example, MAPbI3), results.[26] The A3Bi2I9 material consists of
is therefore to replace lead in the perovskite, with a different bioctahedral (Bi2I9)3− clusters that are surrounded by cesium
(or methylammonium) cations, and a schematic picture of the
Cs3Bi2I9 structure is shown in Figure 1. In this report we show
Dr. B.-W. Park, Dr. X. Zhang, Dr. G. Boschloo, that the A3Bi2I9 perovskites can be prepared under ambient
Dr. E. M. J. Johansson conditions and show stable properties. We investigate the light
Department of Chemistry, Ångström Laboratory absorption properties of the bismuth halide perovskites with
Uppsala University different cations and find that the light absorption and the
Box 523, SE 75120, Uppsala, Sweden
E-mail: gerrit.boschloo@kemi.uu.se; structure are affected by the cation. For the MAPbI3 perovskite
erik.johansson@kemi.uu.se it has previously been observed that Cl− may affect the mate-
Dr. B. Philippe, Prof. H. Rensmo rial and photovoltaic properties as mentioned above. In that
Department of Physics and Astronomy case the Cl− has an effect on the morphology of the material
Molecular and Condensed Matter Physics and with Cl− a longer photocharge diffusion length has been
Uppsala University
Box 516, SE 75120, Uppsala, Sweden
observed, which is very important for the photovoltaic perfor-
mance.[6] Therefore we also study how the MA3Bi2I9 may be
DOI: 10.1002/adma.201501978 affected by Cl− and it is important to investigate if any changes
6806 wileyonlinelibrary.com © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2015, 27, 6806–6813
15214095, 2015, 43, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201501978 by Indian Association For The, Wiley Online Library on [15/11/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advmat.de
COMMUNICATION
indicates a crystalline growth along the c-axis. This is rather dif-
ferent compared to bulk Cs3Bi2I9 with a polycrystalline struc-
ture (Figure 2e).
The XRD patterns for MA3Bi2I9 and MA3Bi2I9Clx thin films
(Figure 2a,b) are very similar. The crystalline phases of these
materials have previously been reported in two investigations.
Szklarz et al. determined that MA3Bi2I9 has an orthorhombic
structure and Cmcm(63) as space group, which is shown in
Figure 2c.[31] However, Jakubas and Sobczyk proposed that the
crystalline structure is hexagonal and P63/mm(194) as space
group, similar to the Cs3Bi2I9 perovskite.[32,34] The MA3Bi2I9
perovskite we obtain with the method described in this report,
agree with the results from Jakubas et al. and a comparison is
shown in Figure s2 (Supporting Information).
Comparing the XRD patterns of the MA3Bi2I9 and Cs3Bi2I9
perovskites (Figure s2 (left panel), Supporting Information), all
peaks observed are shifted, and the angle shift is increasing for
higher 2θ, which shows that the structure is affected somewhat
by the change of cations in the perovskite structure, but the
structure is still close to hexagonal crystalline phase.
There is a clear color difference for the different perovskite
materials and difference in light absorption. Comparing to
MAPbI3, the bismuth perovskites show lower light absorption
for a similar sample thickness. The absorption coefficients were
estimated to around 1 × 105 cm−1 at 450 nm for the different
bismuth perovskites. The absolute values are difficult to deter-
mine due to inhomogeneous film thicknesses, the voids in the
Figure 1. Schematic picture of the Cs3Bi2I9 structure. The unit cell is perovskite films and the filling of perovskite in the mesoporous
marked with the dark lines and the bismuth iodide octahedra are marked TiO2 layer (see SEM analysis below), however, the absorption
with a cyan color. is slightly lower compared to the absorption of MAPbI3, which
has an absorption coefficient around 2 × 105 cm−1 at 450 nm
in material properties are observed for this material, which for MAPbI3.[9] The optical bandgaps are estimated to be around
could improve the solar cell performance. The crystal structures 2.1, 2.2, and 2.4 eV for the MA3Bi2I9, Cs3Bi2I9, and MA3Bi2I9Clx
and the microscopic structures of the different bismuth perovs- samples, respectively (Figure 1f). However, the band gap energy
kites formed in the solar cells are investigated using X-ray dif- for the MA3Bi2I9Clx sample is difficult to determine and there
fraction (XRD) and scanning electron microscopy (SEM). The is also some light absorption at lower energies than the esti-
solar cells show a photovoltaic effect, and we find that the bis- mated band gap, possibly due to an inhomogeneous formation
muth perovskite with cesium cations gives the highest solar cell of the perovskite within the sample, which is also observed
performance. in the SEM analysis below. For the three samples we observe
A few basic studies on A3Bi2I9 (A: MA or Cs) have been done absorption peaks at around 3.00, 2.75, and 2.85 eV, for MA3Bi-
that report investigations of crystal structures, optical, dielectric, 2I9Clx, MA3Bi2I9, and Cs3Bi2I9, respectively (Figure s3, Sup-
and quantum physical properties.[26–35] However, no practical porting Information), and these values are 0.3–0.5 eV higher
applications, such as use in solar cells have been reported. than the exciton peak energies previously reported for MA3Bi2I9
Here, we prepared thin films of Cs3Bi2I9, MA3Bi2I9, and MA3Bi- and Cs3Bi2I9.[32,35] The Wannier–Mott exciton binding energies
2I9Clx materials using a one-step spincoating method. Briefly, in the perovskites are estimated from the optical band gaps and
an appropriate mixture of salts (MAI, CsI, BiI3, and BiCl3) was the peaks in the PL spectra (Figure 1g) and calculated to be
dissolved, spincoated, and annealed at low temperature (see the around 70–300 meV for the different perovskites. This is sim-
Experimental Section). The XRD patterns of these films are pre- ilar to the values for a layer of Cs3Bi2I9 perovskite with a thick-
sented in Figure 2. Additional XRD patterns of starting mate- ness of few hundred nanometer previously reported, but it is
rials (BiI3 and BiCl3) and a detailed comparison of MA3Bi2I9 significantly higher compared to the exciton binding energy in
and Cs3Bi2I9 perovskites are presented in the Supporting Infor- the lead halide perovskites (25–50 meV).[32,36,37] The estimated
mation. Reference patterns of polycrystalline Cs3Bi2I9 perovs- exciton binding energies of the different samples is 300 meV
kite (Figure 2e)[27–29] and MA3Bi2I9 are also shown. Cs3Bi2I9 for MA3Bi2I9Clx (grain size: 28.4 nm), 70 meV MA3Bi2I9 (grain
perovskite has a hexagonal structure and its space group is P63/ size: 29.4 nm), and 270 meV for Cs3Bi2I9 (grain size: 30.8 nm).
mmc(194);[27–29] however, this perovskite also has a monoclinic The difference may be related to quantum size effects of the
phase with space group C12/c1(15).[30] light absorbers such as in case of quantum dot solar cell mate-
For the Cs3Bi2I9 prepared in this work, the crystalline phase rials.[38] However, the grain sizes obtained from the XRD results
is in good agreement with a hexagonal phase (Figure 2d). For are rather similar, so differences in crystal growth direction and
this thin film, the preferred-orientation is at 25.16 {006}, which morphology may also be important, which therefore is further
Adv. Mater. 2015, 27, 6806–6813 © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com 6807
www.advmat.de
COMMUNICATION
Figure 2. X-ray diffraction patterns of thin A3Bi2I9 films on mesostructured-TiO2/glass substrates. a) MA3Bi2I9Clx, b) MA3Bi2I9, and d) Cs3Bi2I9. Refer-
ence XRD patterns for c) MA3Bi2I9 and e) Cs3Bi2I9 from ICSD data base for coll. code 162078, 1448. f) Tauc plots for MA3Bi2I9Clx, MA3Bi2I9, and Cs3Bi2I9
thin films g) PL spectra for the three materials.
investigated below. The SEM images of the surface of the sam- band gap and exciton energy estimated for MA3Bi2I9Clx may
ples with different perovskites are displayed in Figure 3. also be related to the nonreacted BiCl3.
For MA3Bi2I9Clx we observe particles surrounded by a more X-ray photoelectron spectroscopy using AlKα was used to
gel-like material (Figure 3a,a-1). The gel-like material can be investigate the three materials: MA3Bi2I9, MA3Bi2I9Clx, and
assigned to BiCl3, since a similar structure is observed for Cs3Bi2I9. The overview spectra and the estimated I/Bi and Cs/
the BiCl3 material (Figure s1b, Supporting Information). The Bi ratios are presented in Figure s4 and Table s1 (Supporting
particles are assigned to the perovskite crystals. The MA3Bi2I9 Information) and show that the estimated I/Bi ratio for the three
perovskite material (Figure 3b,b-1) has a structure consisting materials, 4.4, 4.7, 4.6 for Cs3Bi2I9, MA3Bi2I9, and MA3Bi2I9Clx,
of interconnected thin layers (around 50 nm thick). The SEM respectively, is in good agreement with the one suggested by the
images of Cs3Bi2I9 (Figure 3c,c-1), show hexagonal thin sheets, stoichiometry (i.e, 4.5) as well as the Cs/Bi ratio estimated to
which may agree with a crystalline growth along the c-axis be 1.6 (instead of 1.5). Regarding MA3Bi2I9Clx, chlorine could
in agreement with the XRD pattern in Figure 2d. The lower be clearly detected in the sample (Figure s4, Supporting Infor-
exciton energy and band gap energy for the MA3Bi2I9 per- mation), nevertheless, the core peak position suggested that it
ovskite compared to the MA3Bi2I9Clx sample may be related is mainly originated from remaining BiCl3 precursors in agree-
to the large difference in the material morphology observed ment with the SEM images presented in Figure 3 where two dif-
in the SEM images. The structure with interconnected layers ferent phases can be distinguished, i.e., perovskite crystals sur-
in the MA3Bi2I9 perovskite may be advantageous for forming rounded by an amorphous gel-like phase that was also observed
excitons with lower energy compared to the more particle like on the BiCl3 precursor SEM image (Figure s1b, Supporting
structure of MA3Bi2I9Clx. Also, since the SEM images indicate Information). The valence band spectra of MA3Bi2I9, MA3Bi-
that BiCl3 is present in the MA3Bi2I9Clx sample, the higher 2I9Clx, and Cs3Bi2I9 are shown in Figure 4a and compared with
www.advmat.de
COMMUNICATION
Figure 3. SEM images of the surface morphologies (top view) of the three bismuth based materials: (a and a-1) MA3Bi2I9Clx, (b and b-1) MA3Bi2I9,
and (c and c-1) Cs3Bi2I9.
Figure 4. a) Valence level spectra of the Cs3Bi2I9, MA3Bi2I9, and MA3Bi2I9Clx samples measured by XPS using AlKα in red, orange, and brown (dotted
line), respectively. As a comparison, a valence level spectrum of MAPbI3 recorded in the same conditions is presented in blue. The intensities at the
valence band peaks are set to the same intensity for simple comparison. b) Schematic drawing of the energy level diagram versus the Fermi level
using approximate energies of the valence bands estimated from XPS, and the estimated optical band gaps determined from the Tauc plot in Figure 1.
www.advmat.de
COMMUNICATION
Figure 5. a) Cross-sectional SEM images for (a-1) MA3BiI2I9Clx, (a-2) MA3Bi2I9, and (a-3) Cs3Bi2I9 based solar cell devices. b) J–V and c) IPCE curves
for solar cells using the three different materials.
the common methylammonium lead iodide (MAPbI3) per- photovoltaic device is obtained when using the Cs3Bi2I9 per-
ovskite. First of all, we can note that the three bismuth based ovskite and the photovoltaic parameters are determined as
materials have a valence band edge at similar binding energy Jsc = 2.15 mA cm−1, Voc = 0.85 V, FF = 0.60, and η = 1.09%,
versus the Fermi level, and that the spectra of MA3Bi2I9, and respectively. The best device using MA3Bi2I9 perovskite shows
MA3Bi2I9Clx overlap perfectly. As a comparison, the intersec- Jsc = 0.52 mA cm−1, Voc = 0.68 V, FF = 0.33, and η = 0.12%.
tion of a linear fit of the valence band of MAPbI3 is found at The best device using MA3Bi2I9Clx shows Jsc = 0.18 mA/cm,
lower binding energy.[39,40] Combining the optical band gap Voc = 0.04 V, FF = 0.38, and η = 0.003%. The current densities
determined above and the energies of the valence band posi- for each perovskite solar cells are confirmed by comparing the
tion versus the Fermi level obtained from X-ray photoelectron integrated current from the incident photon to current conver-
spectroscopy (XPS), a schematic energy band diagram is con- sion efficiency (IPCE) measurements in Figure 5c. The edge
structed in Figure 4b. of the IPCE spectra for MA3Bi2I9 and Cs3Bi2I9 solar cells is
Figure 5a shows the cross-sectional SEM images of the per- around 650 nm and a peak is observed in the IPCE spectrum
ovskite solar cells using the three different bismuth perovskites at the same wavelength as the exciton absorption peak for the
described above. The solar cells are constructed as follow; glass/ Cs3Bi2I9 perovskite.
fluorine-doped tin oxide (FTO)/TiO2(solid) under layer/meso- There are many possible reasons for the rather low efficiencies
scopic-TiO2 layer/perovskite/hole transport material (HTM)/Ag obtained in this early stage of investigation of these new solar
layer as shown in the cross-section SEM images in Figure 5a. cell materials, and we point out a number of different impor-
The current density–voltage (J–V) characterizations of the solar tant properties that may affect the performance. In general the
cells are shown in Figure 5b. The performances of 20 devices solar cell efficiency depends on the nonradiative recombination
of each composition were measured and the solar cells show induced by, for example, defect states in the band gap, which
rather large spread in device efficiency (see Figure S5, Sup- may seriously reduce the performance of the solar cell. Conse-
porting Information). However a clear trend between devices quently, the comparatively high PL yield for Cs3Bi2I9 perovskite
based on the different materials is observed and the best in Figure 2g suggests low losses in nonradiative recombination,
www.advmat.de
COMMUNICATION
and may therefore be related to the promising photocurrent and device. In the initial measurements performed here, we do not
voltage for the solar cell based on this material. The high PL observe any differences in hysteresis depending on the cation.
for this material may also be interesting for other optoelectronic However, the Cs3Bi2I9 based solar cell after a month shows large
applications, such as light emitting diodes or lasers. However, J–V hysteresis as mentioned above. The reason for this behavior
defect states may still be present in this material and from the is unclear, but it is possible that chemical additives may move
XPS measurements in Figure 4, there is a slightly stronger from the HTM layer to the perovskite layer. These additives as
signal in the band gap of the bismuth perovskites compared ionic organic molecules may exchange with the cation or anion
to in the band gap for the MAPbI3 sample, which therefore such as Cs+ or [Bi2I9]− in the perovskite. This possibility is pro-
indicates that there may be more band gap states in the bis- posed in the case of penetrating 4-tert-butylpyridine (TBP) into
muth perovskites. These extra band gap states may result in perovskite morphology in a previously publication.[45]
more recombination pathways and thereby lower photovoltage The stability of the perovskites and the solar cells were inves-
and photocurrent for the bismuth perovskites. To improve the tigated by measuring how the light absorption spectra and effi-
efficiency of the devices it would therefore be advantageous if ciencies changes after a month. The light absorption spectra
the band gap states can be reduced. Moreover, the efficiency only show a very small change after one month storage (in dry
depends not only on the material itself but also on the inter- air (humidity less than 10%) and in dark), which indicates that
action with the materials surrounding the photoactive material. the perovskites are rather stable (Figure s9, Supporting Infor-
For an efficient extraction of the charges, the recombination mation). The power conversion efficiency of the solar cells
of charges should be minimized at the interfaces between the show an increase during the first days and then a stable value
materials. The materials used here in combination with the per- (Figure s10, Supporting Information) (solar cells stored in dark
ovskites may not be the best materials for charge extraction and in dry air (humidity less than 10%) between the measurements).
several other materials will be tested in combination with the We can thereby conclude that the stability of these perovskites is
bismuth perovskites in our future work. All the solar cells with high and that the solar cells show no decay during a month.
the bismuth perovskites show rather rough surface of the per- In summary, we introduce low-toxic bismuth based perovs-
ovskite layers and pin holes in the perovskite layer is probably kites that could possibly replace lead based perovskites in solar
common. This may explain the large spread in efficiency for cells. The Cs3Bi2I9, MA3Bi2I9, and MA3Bi2I9Clx materials are
the devices (Figure s5, Supporting Information) and a denser prepared using a one-step spin coating method and investi-
homogeneous perovskite layer would probably results in more gated using different techniques. The MA3Bi2I9Clx, MA3Bi2I9,
efficient devices. The sample with MA3Bi2I9Clx shows particu- and Cs3Bi2I9 samples present a hexagonal crystalline phase
larly low PCE, and we suggest that it is due to the morphology and space group P63/mm(194) from XRD investigation. The
with perovskite particles surrounded by amorphous BiCl3 as light absorption spectra (UV–vis) and photoluminescence (PL)
suggested above, which may reduce the charge transport in the for the different materials are compared and some differences
material. The MA3Bi2I9Clx sample also shows low PL, which in band gap and exciton energies are observed. The Cs3Bi2I9
may be related to nonradiative recombination due to the band perovskite shows approximately five times higher PL intensity
gap states, lowering the efficiency of this solar cell. comparing with the other two perovskites. SEM of the dif-
The J–V hysteresis for the two rather high efficiency solar ferent materials shows that the morphology is different for the
cells using MA3Bi2I9 and Cs3Bi2I9 perovskites were investigated different materials, which may explain the difference in light
(Figures s6 and s7, Supporting Information). The MA3Bi2I9 absorption and PL properties. From the XPS investigation, the
based solar cell shows very small hysteresis both in the meas- valence bands binding energies of these materials are very sim-
urements on the initial day and also after a month, and a slight ilar, and the valence bands are located at slightly higher binding
increase in PCE after a month is observed possibly due to energy than the valence band of MAPbI3. For the MA3Bi2I9Clx
changes in the HTM layer (Figures s6 and s8, Supporting Infor- sample, the SEM investigation suggests that there is still BiCl3
mation). The solar cell with Cs3Bi2I9 perovskite initially showed precursor in the material, which is in agreement with the XPS
almost no hysteresis in the J–V curves at high and low scanning results. The solar cells based on the bismuth perovskites show
speeds in Figure s7a,b (Supporting Information). However, after photovoltaic properties and a photocurrent is observed for all
a month, a significant J–V hysteresis is observed and the hys- the devices. Comparing the photovoltaic results, the solar cell
teresis is particularly high at high scanning speed. This result with the Cs3Bi2I9 perovskite shows the highest performance
is significantly different from previous investigations of hyster- and a power conversion efficiency over 1% is obtained (0.6 FF,
esis in perovskite solar cells, where less hysteresis was observed 0.85 V, and 2.15 mA cm−2). This is a rather promising solar cell
at high scanning speed.[41,42] The initial low hysteresis for both performance and the bismuth perovskite may also be possible
solar cells is very similar to the results for the CsSnI3 based to utilize as dopant within the conventional lead based perovs-
solar cell previously reported.[43] After a month, we observed a kite. Based on the results presented here, we conclude that the
significantly different J–V hysteresis comparing the two solar bismuth perovskite has very promising properties for use in
cells, and the solar cell based on Cs3Bi2I9 shows an increase in optoelectronic devices and specifically in solar cells.
J–V hysteresis. According to Frost et al.,[44] various cations such
as NH4+, CH3NH3+, and CF3NH3+ show different values of the
molecule dipole moment and the rotation barrier within the
perovskite in order of NH4+ < CH3NH3+ < CF3NH3+ for hybrid Experimental Section
perovskites. The dipole moment and rotation barrier can change Perovskites Samples Fabrication: A3Bi2I9 perovskite precursors were
ferroelectric properties and the J–V hysteresis of a solar cell formed in dimethylformamide (DMF)/dimethyl sulfoxide (DMSO)
www.advmat.de
COMMUNICATION
solvent mixture (7/3 by volume). CH3NH3I was synthesized as described was dissolved in chlorobenzene and LiTFSI and tert-butylpyridine
(see ref. [3]. CsI (99.9% trace metals basis), BiI3 (purity 99%), and BiCl3 (TBP) was used as additives (0.167 g spiro-OMeTAD, 0.0298 g TBP,
(purity 99%) were purchased from Sigma Aldrich. MA3Bi2I9Clx material 0.0103 g in 1.00 mL chlorobenzene) and the solution was deposited by
was prepared from CH3NH3I (7.425 M) and BiCl3 (1.65 M) in the same spin-coating at 1500 rpm for 20 s. Finally, 150 nm thick silver electrodes
solvent. The MA3Bi2I9 perovskite was synthesized from CH3NH3I were deposited on top of devices by thermal evaporation at ≈10−6 mbar,
(2.475 M) and BiI3 (1.65 M) in the same solvent. Cs3Bi2I9 perovskite was through a shadow mask. The maximum power conversion efficiency for
synthesized from Cs (2.475 M) and BiI3 (1.65 M) in the same solvent. Cs3Bi2I9 utilized solar cell device has been obtained using oxygen doped
Mesoscopic (ms) TiO2 films were deposited on microscope glass by spiro-MeOTAD.[46]
spin coating method at 4000 rpm for 30 s. The TiO2 paste was prepared PCE: A Newport solar simulator (model 91160) giving light with AM
by diluting Dyesol paste (30NR-T, particle size ≈30 nm) with ethanol in 1.5 G spectral distribution, was calibrated using a certified reference
a 1:4 weight ratio. The ms–TiO2 coated microscope glass was annealed solar cell (Fraunhofer ISE) to an intensity of 1000 W m−2. The electrical
onto hot plate at 500 °C for 30 min. The film thickness was ≈250 nm data were recorded with a computer controlled digital source meter
(±50 nm) as determined using a Dektak3 profiler. The organic–inorganic (Keithley Model 2400) with the scan direction from the open-circuit
bismuth halide perovskite precursor solutions were coated onto TiO2/ to short-circuit at a scan rate of 100–800 mV s−1. The solar cells were
glass substrate by spin-coating method at 1500 rpm for 20 s, followed masked during the measurement with an aperture area of 0.126 cm2.
by annealing on a hot plate at 110 °C for 30 min in dry air box (relative IPCE: The IPCE spectra were recorded with a computer-controlled
humidity less than 30%). setup comprised of a xenon lamp (Spectral Products, ASB-XE-175), a
UV–Vis Spectra: To measure UV–visible–NIR transmission and monochromator (Spectral Products, CM110), and a Keithley multimeter
absorption spectra, organic–inorganic perovskite modified TiO2 (Model 2700). The setup was calibrated with a certified silicon solar
electrodes deposited on working electrode were prepared what is cell (Fraunhofer ISE) prior to the measurements. All solar cells were
mentioned above and the measurements were carried on a Cary 5000 illuminated from the working electrode side with an aperture area of
UV–vis-NIR spectrophotometer (VARIAN, Photometric accuracy is 0.126 cm2 (round type of mask) using a black mask.
<0.00025 Abs., Photometric range is 8 Abs.). The FTO glass substrate
signal was used as calibration background.
Crystallographic Properties: The perovskites deposited on TiO2/glass
substrate were investigated for crystallographic properties using X-ray Supporting Information
diffraction (XRD) with a Siemens diffractometer D5000 apparatus at
Supporting Information is available from the Wiley Online Library or
room temperature using Cu Kα radiation in time period. Diffrac plus
from the author.
XRD commander program was used to control the instrument. The
instrument was set in “detector scan” mode, and the acquisition was
done in θ−2θ mode for every 0.02° increment over the Bragg angle
range of 10°−60°. The X-ray intensity has been checked using TiO2/glass Acknowledgements
substrate before measuring perovskite samples.
Steady-State Emission Measurements: Standard steady-state emission The authors thank the Swedish Energy Agency, the ST and UP for Energy
spectra were obtained on a Fluorolog-3 instrument (Horiba Jobin Yvon) program, the Swedish Research Council (VR), the Swedish Research
equipped with double-grating excitation and emission monochromators Council FORMAS, the Göran Gustafsson Foundation, ÅForsk, and the
and a 450-W Xe lamp as a light source. The emission spectra were Knut and Alice Wallenberg Foundation. T. Edvinsson is acknowledged
corrected for the spectral sensitivity of the detection system by using a for help with illustration of the material structure. B.-W.P. thanks the
calibration file of the detector response. Front-face illumination (30° with members of the Korean Scandinavian Scientist Engineers Association
respect to the incident beam) was used to minimize inner-filter effects. A (KSSEA) and chairman Dr. Keunjae Kim for support and regards, in
filter of 510 nm wavelength has been setup front of detectors. The pump particular Taeja Kim-Björklund, former chairman in KSSEA of Sweden.
laser had setup at 450 nm in wavelength. Further thanks to Seockjeong Eom, Ambassador in Embassy of Republic
SEM: SEM was performed on a Zeiss (Gemini 1550) microscope of Korea in Sweden.
having a field emission (FE) electron source and an in-lens detector for
secondary electrons. Top view images and cross section of solar cell Received: April 24, 2015
devices were recorded using a high tension of 5 kV. Revised: August 18, 2015
XPS: XPS measurements were performed with a Scienta ESCA 300 Published online: September 29, 2015
instrument, using monochromatized AlKα radiation hν = 1486.7 eV.
The pressure in the analysis chamber was around 1 × 10−8 mbar and
the electron take off angle was 90°. Quantification was performed on
the basis of Scofield’s relative sensitivity factors. The valence spectra [1] A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, J. Am. Chem. Soc.
presented were binding energy calibrated with respect to the Fermi 2009, 131, 6050.
level as measured on a Au sample. Charging and radiation effects were [2] J. H. Im, C. Lee, J. Lee, S. Park, N. G. Park, Nanoscale 2011, 3, 4088.
examined for by measuring the specific core level repetitively and were [3] H. S. Kim, C. Lee, J. Im, K. Lee, T. Moehl, A. Marchioro, S. Moon,
found negligible for all spectra reported in the present investigation. The R. Humphry-Baker, J. Yum, J. E. Moser, M. Gratzel, N. G. Park, Sci.
energies of the valence band edge were evaluated from the experimental Rep. 2012, 2, 591.
valence levels from a linear extrapolation and define as the intersection
[4] M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakumi, H. J. Snaith,
with the baseline.
Science 2012, 338, 643.
Fabrication of Solar Cell Devices: The preparation method of perovskites
precursors are mentioned above. FTO coated glass (Pilkington TEC 15, [5] G. E. Eperon, S. D. Stranks, C. Menelaou, M. B. Johnston,
15 Ω 䊐−1) was patterned using an etching process with Zn powder and L. M. Hertz, H. J. Snaith, Energy Environ. Sci. 2014, 7, 982.
2 M HCl diluted in water. Compact TiO2 layers (thickness 30–60 nm) [6] S. D. Stranks, G. E. Eperon, G. Grancini, C. Menelaou,
were deposited on FTO substrate by spray pyrolysis on a hot plate (kept M. J. P. Alcocer, T. Leijtens, L. M. Hertz, A. Petrozza, H. J. Snaith,
at 500–550 °C). The prepared TiO2 precursor was coated by spin caster Science 2013, 342, 341.
at 4000 rpm (±30 rpm) for 20 s and annealed on hot plate at 500 °C [7] J. Burschka, N. Pellet, S. Moon, R. Humphrey-Baker, P. Gao,
for 30 min. The OIHP precursor was also deposited by spin coater at M. K. Nazeeruddin, M. Gratzel, Nature 2013, 499, 316.
1250 rpm (±25 rpm) for 20 s and annealed at 100 °C for 30–40 min in dry [8] O. Malinkiewicz, A. Yella, Y. H. Lee, G. M. Espallargas, M. Graetzel,
box and humidity was 20%–40%. The hole transporter spiro-MeOTAD M. K. Nazeeruddin, H. J. Bolink, Nat. Photon. 2014, 8, 128.
www.advmat.de
COMMUNICATION
[9] M. A. Green, A. Ho-Baillie, H. J. Snaith, Nat. Photon. 2014, 8, 506. [28] O. Lindqvist, Acta Chem. Scand. 1968, 22, 2943.
[10] J. M. Ball, M. M. Lee, A. Hey, H. Snaith, Energy Environ. Sci. 2013, [29] A. V. Arakcheeva, M. Bonin, G. Chapuis, A. I. Zaitsev, Z. Kristallogr.
6, 1739. 1999, 214, 279.
[11] J. H. Heo, S. H. Im, J. H. Noh, T. N. Mandal, C. S. Lim, J. A. Chang, [30] A. V. Arakcheeva, G. Chapuis, M. Meyer, Z. Kristallogr. 2001, 216,
Y. H. Lee, H. J. Kim, A. Sarkar, M. K. Nazeeruddin, M. Gratzel, 199.
S. I. Seok, Nat. Photon. 2013, 7, 487. [31] P. Szklarz, A. Pietraszko, R. Jakubas, G. Bator, P. Zielinski,
[12] D. Y. Liu, T. L. Kelly, Nat. Photon. 2014, 8, 133. M. Galazka, J. Phys. 2008, 20, 255221.
[13] H. P. Zhou, Q. Chen, G. Li, S. Luo, T. B. Song, H. S. Duan, [32] T. Kawai, A. Ishii, T. Kitamura, S. Shimanuki, M. Iwata, Y. Ishibashi,
Z. R. Hong, J. B. You, Y. S. Liu, Y. Yang, Science 2014, 345, 542. J. Phys. Soc. Jpn. 1996, 65, 1464.
[14] J. H. Im, I. H. Jang, N. Pellet, M. Gratzel, N. G. Park, Nat. Nano- [33] Yu. N. Ivanov, A. A. Sukhovskii, V. V. Lisin, I. P. Aleksandrova, Inorg.
technol. 2014, 9, 927. Mater. 2001, 37, 623.
[15] M. D. Xiao, F. Z. Huang, W. C. Huang, Y. Dkhissi, Y. Zhu, [34] R. Jakubas, L. Sobczyk, Phase Trans. 1990, 20, 163.
J. Etheridge, A. Gray-Weale, U. Bach, Y. B. Cheng, L. Spiccia, Angew. [35] V. F. Machulin, F. V. Motsnyi, O. M. Smolanka, G. S. Svechnikov,
Chem. Int. Ed. 2014, 53, 9898. Low Temp. Phys. 2004, 30, 964.
[16] a) N. J. Jeon, J. H. Noh, W. S. Yang, Y. C. Kim, S. Ryu, [36] V. D’innocenzo, G. Grancini, M. J. P. Alcocer, A. R. S. Kandada,
J. Seo, S. I. Seok, Nature 2015, 517, 476; b) Efficiency chart S. D. Stranks, M. M. Lee, G. Lanzani, H. J. Snaith, A. Petrozza, Nat.
of NREL, http://www.nrel.gov/ncpv/images/efficiency_chart.jpg Commun. 2014, 5, 3586.
(accessed: 2015-09-02). [37] M. Saba, M. Cadelano, D. Marongiu, F. Chen, V. Sarritzu, N. Sestu,
[17] F. Hao, C. C. Stoumpos, D. H. Cao, R. P. H. Chang, C. Figus, M. Aresti, R. Piras, A. G. Lehmann, C. Cannas, A. Musinu,
M. G. Kanatzidis, Nat. Photon. 2014, 8, 489. F. Quochi, A. Mura, G. Bongiovanni, Nat. Commun. 2014, 5, 5049.
[18] N. K. Noel, S. D. Stranks, A. Abate, C. Wehrenfennig, S. Guarnera, [38] R. W. Meulenberg, J. R. I. Lee, A. Wolcott, J. Z. Zhang,
A. A. Haghighirad, A. Sadhanala, G. E. Eperon, S. K. Pathak, L. J. Terminello, Tony van Buuren, ACS Nano 2009, 3, 325.
M. B. Johnston, A. Petrozza, L. M. Hertz, H. J. Snaith, Energy [39] R. Lindblad, N. K. Jena, B. Philippe, J. Oscarsson, D. Q. Bi,
Environ. Sci. 2014, 7, 3061. A. Lindblad, S. Mandal, B. Pal, D. D. Sarma, O. Karis, H. Siegbahn,
[19] S. Y. Yang, L. W. Martin, S. J. Byrnes, T. E. Conry, S. R. Basu, E. M. J. Johansson, M. Odelius, H. Rensmo, J. Phys. Chem. C 2015,
D. Paran, L. Reichertz, J. Ihlefeld, C. Adamo, A. Melville, Y.-H. Chu, 119, 1818.
C.-H. Yang, J. L. Musfeldt, D. G. Schlom, J. W. Ager III, R. Ramesh, [40] B. Philippe, B. W. Park, R. Lindblad, J. Oscarsson, S. Ahmadi,
Appl. Phys. Lett. 2009, 95, 062909. E. M. J. Johansson, H. Rensmo, Chem. Mater. 2015, 27, 1720.
[20] T. Choi, S. Lee, Y. J. Choi, V. Kiryukhin, S.-W. Cheong, Science 2009, [41] E. L. Unger, E. T. Hoke, C. D. Bailie, W. H. Nguyen, A. R. Bowring,
324, 63. T. Heumuller, M. G. Christoforod, M. D. McGehee, Energy Environ.
[21] J. P. Chakrabartty, R. Nechache, C. Harnagea, F. Rosei, Opt. Express Sci. 2014, 7, 3690.
2014, 22, A80. [42] W. Tress, N. Marinova, T. Moehl, S. M. Zakeeruddin, Mohammad
[22] I. Grinberg, D. V. West, M. Torres, G. Gou, D. M. Stein, L. Wu, Khaja Nazeeruddin, M. Graetzel, Energy Environ. Sci. 2015, 8,
G. Chen, E. M. Gallo, A. R. Akbashev, P. K. Davies, J. E. Spanier, 995.
A. M. Rappe, Nature 2013, 503, 509. [43] M. H. Kumar, S. Dharani, W. L. Leong, P. P. Boix, R. R. Prabhakar,
[23] R. Nechache, C. Harnagea, S. Li, L. Cardenas, W. Huang, T. Baikie, C. Shi, H. Ding, R. Ramesh, M. Asta, M. Graetzel,
J. Chakrabartty, F. Rosei, Nat. Photon. 2015, 9, 61. S. G. Mhaisalkar, N. Mathews, Adv. Mater. 2014, 26, 7122.
[24] H. Suzuki, Organobismuth Chemistry, Elsevier, Amsterdam, The [44] J. M. Frost, K. T. Butler, F. Brivio, C. H. Hendon, M. van Schilfgaarde,
Netherlands 2001. A. Walsh, Nano Lett. 2014, 14, 2584.
[25] H. Needleman, Annu. Rev. Med. 2004, 55, 209. [45] J. H. Heo, H. J. Han, D. Kim, T. K. Ahn, S. H. Im, Energy Environ.
[26] S. V. Mel’nikova, A. I. Zaítsev, Phys. Solid State 1997, 39, 1652. Sci. 2015, 8, 1602.
[27] B. Chabot, E. Parthe, Acta Crystallogr. B 1978, 34, 645. [46] Ute B. Cappel, T. Daeneke, U. Bach, Nano Lett. 2012, 12, 4925.

Advanced Materials - 2015 - Park - Bismuth Based Hybrid Perovskites A3Bi2I9 A Methylammonium or Cesium For Solar Cell

Uploaded by

Copyright:

Available Formats

You might also like

Advanced Materials - 2015 - Park - Bismuth Based Hybrid Perovskites A3Bi2I9 A Methylammonium or Cesium For Solar Cell

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Advanced Materials - 2015 - Park - Bismuth Based Hybrid Perovskites A3Bi2I9 A Methylammonium or Cesium For Solar Cell

Uploaded by

Copyright:

Available Formats

15214095, 2015, 43, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201501978 by Indian Association For The, Wiley Online Library on [15/11/2022].

Bismuth Based Hybrid Perovskites A3Bi2I9 (A: Methylammonium

or Cesium) for Solar Cell Application

You might also like