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Page 1 of 22 Journal of Materials Chemistry A
top valance band, increasing the valence band width 3, 10. As the neighbor in the
elemental periodic table, the Bi3+ cation has similar electron configuration to Pb2+
(5d106s26p0) and thus can have the similarly large relativistic effects and strong
hybridization of 6s states with the anion p states in the valence band11, so the Bi related
compound semiconductors may also possess superior carrier mobility. Furthermore, Bi
is a non-toxic and environment-friendly element. As a result, the search of candidate
solar cell materials in the Bi based compounds attracts more and more attention 11-13.
Bi2S3 has a band gap around 1.3-1.45 eV 14, close to the optimal bandgap for the
light-absorber material in the single-junction solar cells 15, 16, and very high optical
absorption coefficient, >104 cm−1 for λ < 780 nm and >105 cm−1 for λ < 500 nm.
Therefore Bi2S3 attracted intensive attention as a photovoltaic material in the past
decade 17-26, e.g., as the sensitizer in the dye-sensitized TiO2 solar cells (replacing the
expensive Ruthenium dye) 22, 23, light absorber material 26, counter electrode in the
CdSe quantum dot-sensitized solar cells 24, active layer in the organic/inorganic bulk
heterojunction (BHJ) solar cells (blending Bi2S3 and polymers) 27, 28, n-type electron
acceptor in the p-PbS/n-Bi2S3 nano-heterojunction and polymer/nanocrystal
heterojunction solar cells 17, 25, 29.
However, the absolute power-conversion efficiency (PCE) of the Bi2S3 based solar
cells is still low relative to the commercialized Si, CdTe, Cu(In,Ga)Se2 or perovskite
CH3NH3PbI3 solar cells. The reason depends on the specific roles of Bi2S3 in these solar
cells, e.g., a short lifetime and diffusion length of minority carriers is detrimental if it
is used as the light-absorber or sensitizer, and low n-type conductivity is detrimental if
used as the electron acceptor. Since the intrinsic defects and extrinsic dopants influence
both the minority carrier lifetime and electrical conductivity significantly, a
systematical study on the possible defects and dopants is critically important for
understanding the current low efficiency of Bi2S3 based solar cells.
Motivated by the optimization of the thermoelectric performance, Chmielowski et al.
studied four intrinsic defects (S and Bi vacancy, SBi and BiS antisites), finding that S
vacancy and BiS antisite make Bi2S3 weakly n-type. However, other possible defects
such as S and Bi interstitials were neglected and their influences are still unknown 30.
Doping Bi2S3 using extrinsic elements including Cu, Ag, Sb, Si, Ge and Cl had been
tried experimentally 31-35, but their influence on the electrical conductivity is still not
clear. Chmielowski et al. studied the Si, Ge, Sn, Hf and Cl doping theoretically, but
none of them leads to p-type conductivity 30. Therefore, a clear understanding on how
the intrinsic defects and extrinsic dopants influence the carrier lifetime, electrical
Page 3 of 22 Journal of Materials Chemistry A
carrier lifetime, which should be an important reason for the current low efficiency of
the Bi2S3 based solar cells. The doping of in Bi2S3 by extrinsic elements such as Cu, Br
and Cl makes the materials even more n-type and only the Pb doping makes it weakly
p-type. Based on this, we propose that the surface region of n-type Bi2S3 nanocrystals
in the p-PbS/n-Bi2S3 nano-heterojunction solar cells may be type-inverted to p-type due
to the Pb doping, with a buried p-n junction formed in the Bi2S3 nanocrystals, which
provides a new explanation to the observed longer carrier lifetime and higher efficiency
29
. With a relatively low conduction band and high n-type conductivity, Cu, Br and Cl
doped Bi2S3 may be an ideal n-type electron acceptor or counter electrode material,
while its performance as the light-absorber or sensitizer material is intrinsically limited.
For example, the formation of PbS (with a calculated formation energy -0.91 eV/f. u.)
should be avoided, so the highest possible μPb is -0.24 eV at Bi-rich condition (μBi =
0, μS = −0.67 eV), and -0.91 eV under the S-rich condition (μBi = −1.00 eV, μS =
0 ). With these chemical potential requirements satisfied, there will be no leftover of
the secondary compounds such as PbS in the Pb-doped Bi2S3 samples.
After the range of the elemental chemical potentials are determined by these
requirements, we can now calculate the formation energy ∆Hf (α, q) as a function of
the electron Fermi level (as shown in Figs. 2, 5 and 7). The transition energy level
ϵ(q⁄q′ ) is defined as the Fermi level at which the formation energies of the defect α in
the charge state q and q’ are equal, i.e., the Fermi level at the cross points in Figs. 2, 5
and 7. It can be calculated as,
ϵ(q⁄q′ ) = [∆Hf (α, q) − ∆Hf (α, q′ )]/(q − q′ ) (5)
where q′ and q are different charge states, and ∆Hf (α, q) and ∆Hf (α, q′ ) are given
by Eq. (1).38 When the Fermi level is located at the transition energy levels of a defect,
the defect can accept (or donate) electrons to get ionized to the negatively (positively)
charged state.
The total energy and electronic eigenstates are calculated using the density functional
theory 39, 40 (DFT) methods as implemented in the VASP code 41, with the local density
approximation42 (LDA) to the exchange correlation functional. The cutoff energy for
the plane-wave basis is 400 eV. Since Bi is a heavy element, the spin-orbit coupling
(SOC) is considered in our calculations. To calculate the formation energy of a defect,
a 60 atom supercell and a Γ point centered 4×4×4 k-point mesh were used. For a charged
defect, a uniform background charge is added to keep the global charge neutrality of
the periodic supercell, and the Makov–Payne correction is included to account for the
interaction between the image charges. Since LDA tends to underestimate the band gap
(usually underestimates the CBM energy and overestimates the VBM energy), we
corrected our calculated formation energies by correcting the band edge energies 43, 44.
The correction to the band edge energies are determined by comparing the band edge
energies from the LDA and hybrid functional (HSE45) calculations. Test calculations
showed that the corrected formation energies agree well with the formation energies
calculated directly using the hybrid functional 44.
Page 5 of 22 Journal of Materials Chemistry A
The crystal structure of Bi2S3 is orthorhombic with a space group Pbnm and has 20
atoms in the primitive cell. As shown in Fig. 1, the crystal structure of Bi2S3 can be
sites, e.g., the Bi vacancy has two different Bi sites, VBi1 and VBi2, which are both
studied, and the results are reported for the site that has the lowest formation energy.
For the interstitial defects (dopants), there are many possible interstitial sites in the
lattice. We constructed six different interstitial sites, among which the lowest-energy
sites for the cation and anion interstitials are shown in Fig. 1.
Figure 1. The crystal structure of a 60-atom Bi2S3 supercell, with the yellow balls
showing the S anions and the purple balls showing the Bi cations. The most stable
interstitial sites for the cations (in blue) and anions (in red) are also shown.
3. Intrinsic Defects
To study the properties of intrinsic defects in Bi2S3, we calculated their formation
energies as a function of the Fermi level under (a) Bi-rich and S-poor and (b) Bi-poor
and S-rich conditions, as plotted in Fig. 2 where the slope of a line shows the charge
state of a defect. According to Eq. (1), the positive slope of a line means that the defect
is a donor and can donate electrons to get ionized to a positively charged state, while
the negative slope means the defect is an acceptor and can accept electrons to get
Journal of Materials Chemistry A Page 6 of 22
Unexpectedly most of the intrinsic defects act as the donor defects, even the anion
interstitial Si, which is usually an acceptor in compound semiconductors46, acts as a
donor. Only VBi and BiS can be acceptor, but their acceptor levels are both very deep
(high), close to the conduction band minimum (CBM) level, so they cannot get ionized
effectively and generate free hole carriers. The absence of effective acceptor defects
indicates that the undoped Bi2S3 cannot show p-type conductivity.
As Fig. 2 shows, whether under the Bi-rich and S-poor or under the Bi-poor and S-
rich condition, the donor defects such as VS and Si have much lower formation energies
and thus higher concentration than the acceptor defects, so the undoped Bi2S3 should
exhibit intrinsic n-type conductivity. This is consistent with the experimental
observation of the n-type conductivity 47-51. Furthermore, since the formation energies
of the donor defects decrease to negative as the Fermi level is close to the VBM level
(0), they will form spontaneously if the material is doped to p-type and thus pin the
Fermi level at the middle of the bandgap, so a high hole concentration (thus high p-type
conductivity) is thermodynamically impossible in Bi2S3.
Under the Bi-rich and S-poor condition, the neutral sulfur vacancy (VS) has the lowest
formation energy, only 0.89 eV (when the Fermi level is at CBM) as shown in Fig. 2.
Page 7 of 22 Journal of Materials Chemistry A
deep level in the bandgap. This deep level results from the Bi dangling bond, and is
thus composed mainly of the Bi 6p states, localized near the broken Bi-S bond. Because
the S anion is small while Bi cation is large, the neighboring Bi cations get closer and
have Bi 6p+Bi 6p hybridization after the S is removed, which pushes the bonding state,
(0/2+) level, downward.
Figure 3. Calculated transition (ionization) energy levels of intrinsic point defects in the
bandgap of Bi2S3.
Among all the defects, BiS antisite (Bi replacing S) has the second lowest formation
energy, always lower than 1.6 eV. It is abnormal that an antisite defect has such a low
formation energy, since the cation-substitute-anion or anion-substitute-cation antisites
usually have high formation energies in three-dimensional covalent semiconductors
such as CdTe and Cu2ZnSnSe4.44, 54 This abnormal behavior of BiS results from the
quasi-one-dimensional structure of Bi2S3, which has more tolerance to the antisite
defects than three-dimensional covalent semiconductor. As shown by the calculated
Journal of Materials Chemistry A Page 8 of 22
Under the Bi-poor and S-rich condition, VS and BiS increase their formation energy
significantly, while SBi and Si have formation energies decreased to lower than 1.5 eV,
becoming the dominant defects, as shown in Fig. 2. The formation energy for neutral Si
is only 0.84 eV, and it acts as a donor defect, which is quite abnormal because the anion
interstitial is usually an acceptor defect in compound semiconductors such as in ZnS
and ZnO 52, 53. Fig. 4 shows the atomic structure around the S interstitial. As we can see,
the interstitial S not only bonds with the neighboring Bi (Bi-S bond length 2.67 Å), but
also bonds with a neighboring S (S-S bond length 2.06 Å), which is similar to the split-
anion interstitials in other compounds semiconductors 8, 55. The p-p hybridization
between the two S atoms decreases its energy, thus making Si the dominant defect.
Furthermore, the S 3p+S 3p hybridization pushes one anti-bonding state upward,
producing an occupied (0/2+) donor level in the band gap, about 0.6 eV above VBM as
shown in Fig. 3.
Neutral SBi has a formation energy slightly lower than 1.4 eV. Compared to Si, it is a
relatively shallow donor, with the (0/+) level about 0.1 eV below CBM. When an S
atom replaces a Bi atom, a large structural relaxation happens too, with a 2.06 Å S-S
bond formed (as shown in Fig. 4 for the +2 charged Si) and the strong S 3p+S 3p
hybridization pushes one anti-bonding state upward, producing the localized but
shallow (0/+) donor level near CBM.
Page 9 of 22 Journal of Materials Chemistry A
As we can see, the formation of S-S bonds makes the anion interstitial Si and anion-
substitute-cation antisite SBi become donor defects, which is abnormal because they are
usually acceptor defects52, 53. For the same reason, the cation vacancy VBi becomes a
donor defect in Bi2S3. As shown in Fig. 4, an S-S bond is also formed near the +1
charged VBi after relaxation, and the strong S 3p+S 3p hybridization pushes the
occupied bonding states downward into the valence band while the unoccupied anti-
bonding states upward to close to the CBM, which decreases the total energy
significantly and stabilizes the +1 charged donor state of VBi. This is the case when the
Fermi level is lower than 1.1 eV. However, when the Fermi level is high and the anti-
bonding states are occupied by four electrons (VBi becomes -3 charged and thus an
Journal of Materials Chemistry A Page 10 of 22
acceptor), the S 3p+S 3p hybridization cannot decrease the total energy DOI: theView Article Online
and10.1039/C6TA10377D
formation of the S-S bond is energetically not favorable. The transition from the +1
charged donor state to -3 charged acceptor state happens at the Fermi level 1.1 eV above
VBM (0.3 eV below CBM), corresponding to the (3-/+) level as shown in Fig. 3.
bandgap, the photovoltaic efficiency of the Bi-poor and S-rich Bi2S3 samples is also
limited. Therefore the intrinsic Bi2S3 should not be an ideal photovoltaic absorber
materials no matter synthesized under a Bi-rich, S-poor or a Bi-poor, S-rich condition.
4.1 Pb doping
When Pb is doped into Bi2S3, it tends to occupy the PbBi and Pbi sites. Their formation
energy dependence on the Fermi level is plotted in Fig. 5. Overall PbBi has lower
formation energy than Pbi, which indicates that PbBi is easier to form than Pbi. This can
be understood considering that Pb2+ has large ionic radius and the ionic radius disparity
between Bi3+ and Pb2+ is small.
The PbBi substitution is an acceptor with the (-/+) ionization energy level 0.51 eV
above VBM, as shown in Fig. 7. When Pb replaces Bi in the lattice, the Bi-S bonds are
replaced by Pb-S bonds. Because the Pb 6s levels are higher in energy than the Bi 6s
levels, the hybridization between Pb 6s states and S 3p states is stronger than that
between Bi 6s and S 3p, pushing the acceptor level up relative to the top valance bands
(which are mainly the antibonding states of the Bi 6s and S 3p hybridization), and thus
producing a deep level in the gap. In contrast, the Pbi interstitial is a donor with the
(+/2+) ionization level 0.25 eV below CBM. This deep level is composed mainly of the
Pb 6p and Bi 6p orbitals, because a Pb-Bi bond is formed around the Pbi interstitial and
the hybridization between Pb 6p states and the Bi 6p states pushes the donor levels
Page 11 of 22 Journal of Materials Chemistry A
Figure 5. Calculated formation energies of PbBi and Pbi as a function of Fermi levels
under (a) Bi-rich and (b) S-rich conditions. The formation energies of the intrinsic
defects are also included in order to show the competition between intrinsic and
extrinsic defects.
Under the Bi-rich and S-poor condition, the most favorable doping site PbBi has a
formation energy lower than 1.1 eV, but it is not as low as those of the intrinsic donor
defects such as VS (see Fig. 5), so the Pb doping cannot make the Bi2S3 sample p-type.
The competition between the PbBi acceptor and the Vs donor sets the Fermi level
located above the middle of the band gap, about 0.5 eV below the CBM level, i.e., the
sample is weakly n-type under this condition.
Under the Bi-poor and S-rich condition, PbBi decreases its formation energy
significantly, making its formation energy even lower than those of the lowest-energy
intrinsic defects such as Si and SBi. (when the Fermi level is high). The competition
between the acceptor PbBi and the donor Si and SBi sets the Fermi level located below
the middle of the band gap, about 0.5 eV above the VBM level, so the sample becomes
weakly p-type. However, it should be noted that the Fermi level is still quite high, so
the hole concentration is still low.
calculated formation energies for these dopants at different sites are plotted inDOI:
Fig. 6,View Article Online
10.1039/C6TA10377D
and their ionization (transition) energy levels in the bandgap are plotted in Fig. 7.
We discuss the results about the F, Cl, Br and I doping first. They all prefer
The ionization energy levels of the FS, ClS, BrS and IS donors are all resonant in the
conduction band, with no impurity levels in the bandgap, indicating that these dopants
are all ionized and generate free electron carriers once they are doped into the Bi 2S3
lattice. Since their formation energies are only 0.2-0.5 eV under the Bi-rich, S-poor
condition and 0.5-0.8 eV under the Bi-poor, S-rich condition (when Fermi level is at
CBM), their concentration (solubility) can be very high in the Bi2S3 lattice. Therefore
very high concentration of electron carriers may be achieved in Bi2S3 through Cl, Br, F
and I doping.
Figure 6. Calculated formation energies of F, Cl, Br, I, Cu, and Ag dopants at different
sites, as a function of Fermi levels under (a) Bi-rich and (b) S-rich conditions.
Page 13 of 22 Journal of Materials Chemistry A
Although the Fi, Cli, Bri and Ii interstitials have higher formation energies (lower
concentration) in Bi2S3, they all show an abnormal trend, i.e., they prefer acting as
donors when the Fermi level is low, in contract with the anion interstitials in many other
semiconductors which usually act as acceptors46, 52, 53. This abnormal trend is similar to
that of the intrinsic S interstitial which acts also as a donor. When these interstitials act
as donors, they all undergo dramatic structural distortion. As shown in Fig. 8, the +1
charged Ii forms two I-S bonds with the neighboring S atoms. Bri actually takes the
place of one S atom and displaces the S atom to an interstitial site, thus splitting into
BrS and Si (with an S-S bond formed near the Si, as discussed in Section 3). Because of
the formation of S-I and S-S bonds, the p-p hybridization pushes the partially occupied
antibonding state (the donor level) to close to CBM for Ii and into the conduction band
for Bri, so the (0/+) transition energy level of Ii is close to CBM, and that of Bri is
resonant in the conduction band (absent in the bandgap). Therefore, only in a very small
Fermi level range close to the CBM level, Ii can be stable in its neutral state, and in the
other range Ii is ionized to the +1 charged donor state. Bri is always ionized to the +1
charged donor state in the whole Fermi level range.
Journal of Materials Chemistry A Page 14 of 22
and Cl doping increases only the electron carrier concentration and does not cause highView Article Online
DOI: 10.1039/C6TA10377D
concentration of recombination centers, we predict that Br and Cl doping should be a
good choice for improving the n-type conductivity and photovoltaic performance of
Bi2S3. Since the formation energy of ClS and BrS can be very low under the Bi-rich, S-
The effect of Cu and Ag doping is similar to that of F, Br and I doping, although the
favorable doping site is different. Cu and Ag dopants prefer the interstitial sites (Cu i,
Published on 23 February 2017. Downloaded by University of Newcastle on 23/02/2017 22:34:05.
Agi), rather than substituting the cation Bi (CuBi, AgBi), with formation energies at the
substitution sites much higher than those of the interstitial sites. The formation energies
of Cui and Agi are only 0.2 and 0.8 eV respectively under the Bi-rich, S-poor condition,
and 0.7 and 0.8 eV under the Bi-poor, S-rich condition (when the Fermi level is close
to CBM). They both act as the donors, with the ionization energy levels resonant in the
conduction band, so these interstitial dopants all generate free electron carriers once
they are doped into Bi2S3.
Considering their low formation energies and resonant donor levels, we predict that
Cu and Ag doping can also make the Bi2S3 sample highly n-type and push the Fermi
level upward. Especially under the Bi-rich, S-poor condition, Cu doping can produce
very high concentration of electron carriers and pin the Fermi level close to CBM.
When the Fermi level is determined to be close to CBM (n-type) by Cui and Agi, CuBi
and AgBi both act as acceptors, and their ionization energy levels are deep in the
bandgap. Their formation energies can be low (concentration can be high) in n-type
Bi2S3 sample under the Bi-poor, S-rich condition, but is very low (concentration can be
very low) under the Bi-rich, S-poor condition. So a Bi-rich, S-poor condition should be
better for increasing the n-type conductivity through Cu or Ag doping and meanwhile
suppressing the formation of recombination centers.
Journal of Materials Chemistry A Page 16 of 22
Figure 9. The band edge positions (relative to the vacuum level) of different
photovoltaic semiconductors, collected from Ref. 56-63. Note that the band edge position
and band gaps depend on the morphology of these semiconductors.
Summarizing the effect of the F, Cl, Br, I, Cu and Ag doping, we can see that these
dopants all prefer acting as donors and producing electron carriers in Bi2S3. This seems
to be similar to the case of the intrinsic defects, where most of them act as donors and
make Bi2S3 intrinsically n-type. The favorability of the n-type conductivity may result
from the low conduction band edge position of Bi2S3, which is 4.27 eV below the
vacuum level 17. According to the doping limit rule 46, 64, it is easier to dope a
semiconductor to n-type if its conduction band is low and it is difficult to dope it to p-
type if its valence band is low. As shown in Fig. 9, both the conduction and valence
band edges of Bi2S3 are low compared to other photovoltaic semiconductors, so the
favorability of the n-type conductivity can be understood.
5. Discussion
The calculated results showed that Pb doping in Bi2S3 is unique among all the dopant
elements that we studied, because it can make the intrinsically n-type Bi2S3 type-
inverted into p-type. Therefore a p-n junction may be formed between the Pb-doped
Bi2S3 and undoped Bi2S3. Interestingly, Rath et al. realized an over threefold efficiency
increase in the p-PbS/n-Bi2S3 nano-heterojunction solar cell with a 3-absorber-layer
structure (120 nm PbS quantum dots layer, 180 nm PbS/Bi2S3 blend nanocomposite
layer and 40 nm Bi2S3 nanocrystals layer), relative to the conventional bilayer
heterojunction solar cell (210 nm PbS quantum dots and 120 nm Bi2S3 nanocrystals) 29.
Page 17 of 22 Journal of Materials Chemistry A
The explanation to the increased efficiency is the more efficient charge separation andView Article Online
DOI: 10.1039/C6TA10377D
transport in the nano-heterojunction structure, with the recombination in the n-Bi2S3
largely suppressed since the photo-generated holes in the PbS quantum dots and
PbS/Bi2S3 nanocomposite layers are repelled from the n-type Bi2S3 layer by the built-
and cannot be suppressed. Our current calculations show that the Pb doping is unique
in Bi2S3 and can make the semiconductor weakly p-type. During the fabrication of the
p-PbS/n-Bi2S3 nano-heterojunction solar cell, some of the Pb atoms may be doped into
the surface layer of the n-type Bi2S3 nanocrystals, with the surface layer type-inverted
into weakly p-type, then a buried p-n junction may be formed in the Bi2S3 layer, which
can facilitate the electron-hole separation and thus increase the carrier lifetime as well
as the photovoltaic efficiency. If this new explanation based on our dopant calculations
is correct, the efficiency increase should be not so obvious if the PbS layer is replaced
by other materials free of Pb (since many other elements cannot dope Bi2S3 to p-type).
We call for future experimental investigation.
Bi2S3 plays different roles in a series of solar cells, such as the sensitizer in the dye-
sensitized TiO2 solar cells 22, 23, light absorber material 26, counter electrode in CdSe
quantum dot-sensitized solar cells 24, the active layer in the organic/inorganic bulk
heterojunction (BHJ) solar cells 27, 28, n-type electron acceptor in p-PbS/n-Bi2S3
heterojunction solar cells 17, 25, 29. With the calculated properties of defects and dopants,
we can analyze the performance of Bi2S3 in these solar cells. Firstly, because of the high
concentration of deep-level intrinsic defects (serious non-radiative recombination), the
performance of the solar cells using Bi2S3 as the light absorber, sensitizer or active layer
should be limited. On the other hand, the quasi-one-dimensional structure of Bi2S3
indicates that the electron or hole carriers may have a large effective mass and thus a
poor mobility along the direction perpendicular to the (Bi4S6)n ribbons, which limits the
diffusion length of minority carriers. This is another limitation to the application of
Bi2S3 as a light absorber, sensitizer or active layer, resulting from the electronic
dimensionality as introduced by Xiao et al.4, and indicates that the orientation control
of Bi2S3 is necessary for these applications.
Secondly, although most of the intrinsic defects are donors, their formation energies
are not very low and thus the concentration is not very high, so the n-type conductivity
of undoped Bi2S3 and its performance as the n-type electron acceptor or counter
electrode is also limited. Cl, Br and Cu doping can increase the n-type conductivity
dramatically, especially under the Bi-rich condition. Meanwhile, the deep-level
recombination centers (mainly the compensating acceptors) are suppressed under the
Bi-rich condition. Therefore, we predict that good performance may be achieved using
the Cl, Br and Cu doped Bi2S3 synthesized under the Bi-rich condition as the electron
acceptor or counter electrode.
Journal of Materials Chemistry A Page 18 of 22
6. Conclusions
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A series of intrinsic point defects and dopants in Bi2S3 solar cell are studied using
first-principles calculations. Most of the intrinsic defects in Bi2S3 including even Si are
found to be donor defects, explaining the observed n-type conductivity and also limiting
the p-type doping. Significant structural distortion with the formation of S-S bonds
makes Si, SBi and VBi (which are usually acceptor defects in other semiconductors)
become donors in Bi2S3. No matter under Bi-rich or Bi-poor condition, there are a high
concentration of deep level defects (BiS, VS, or SBi, Si), so the minority carrier lifetime
and photovoltaic efficiency of solar cells using Bi2S3 as the light absorber is limited.
Most of dopant elements such as Cu, Br and Cl make Bi2S3 more n-type, except Pb
which makes it weakly p-type. Based on this, we propose that the surface region of n-
type Bi2S3 nanocrystals in p-PbS/n-Bi2S3 nano-heterojunction solar cells may be type-
inverted into p-type due to the Pb doping, with a buried p-n junction formed in the Bi2S3
nanocrystals, which provides a new explanation to the observed longer carrier lifetime
and higher efficiency. Considering its relatively low conduction band and high n-type
conductivity, we predict that the Cu, Br and Cl doped Bi2S3 may be an ideal n-type
electron acceptor or counter electrode material, especially under the Bi-rich condition,
while its performance as the light-absorber or sensitizer material is intrinsically limited.
Acknowledgements
This work was supported by National Natural Science Foundation of China (NSFC)
under grant No. 61574059, Shanghai Rising-Star Program (14QA1401500), Shu-
Guang program (15SG20), National Key Research and Development Program of China
(2016YFB0700700) and CC of ECNU. This research was supported in part by an
appointment to the Higher Education Research Experience for Faculty at Oak Ridge
National Laboratory Program.
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View Article Online
DOI: 10.1039/C6TA10377D
Table of Contents
First-principles calculations show that the photovoltaic efficiency of the solar cells
using Bi2S3 as the light absorber is intrinsically limited by its point defects, while Cu,
Br and Cl doped Bi2S3 may be ideal n-type electron acceptor or counter electrode
material.