Energy Reviews 1 (2022) 100003

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Energy Reviews
journal homepage: www.journals.elsevier.com/energy-reviews

Short Review Article

Photon energy loss and management in perovskite solar cells

Yutian Lei a, Yongfang Li b, c, Zhiwen Jin a, *
a
School of Physical Science and Technology & Key Laboratory for Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, Lanzhou, 730000,
China
b
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, PR
China
c
Laboratory of Advanced Optoelectronic Materials, Suzhou Key Laboratory of Novel Semiconductor-optoelectronics Materials and Devices, College of Chemistry, Chemical
Engineering and Materials Science, Soochow University, Suzhou, 215123 PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The power conversion efficiency (PCE) of perovskite solar cells (PSCs) has increased rapidly to 25.7% in 2022.
Energy loss There is growing curiosity about whether it will increase further up to the PCE limit. Understanding the funda-
Photon management mental energy loss mechanism and targeted treatment is the crux to step forward, especially the definite and
Light harvesting
management of photons in PSCs. Here, we first briefly review the main modes of photon energy loss in PSCs and
Perovskite solar cells
illustrate the significance of photon recycling. Next, historical research trials to overcome these loss mechanisms
in PSCs are highlighted, including the application of anti-reflection coatings, plasmonic strategies, and the
adoption of upconversion and downconversion materials. Finally, we make a brief summary and prospect about
strategies that can help to improve photon management in the future.

1. Introduction undergo multiple absorption and emission events before escaping. That
is, photons are reabsorbed by the semiconductor itself through radiative
Perovskite solar cells (PSCs) have made unprecedented break- recombination emission, a phenomenon known as photon recycling
throughs in the past few years, achieving a certification power conver- [19–21]. During steady-state operation, photon recycling can increase
sion efficiency (PCE) of 25.7% [1]. The tremendous improvement in the the charge carrier density within the photoactive layers [22–24].
PCE of PSCs makes it a promising next-generation photovoltaic tech- Therefore, it is crucial to skillfully regulate the action path of photons,
nology [2–5]. Meanwhile, researchers are still wondering whether they ensuring the occurrence of light capture and self-absorption phenomena
can further improve its efficiency, thus approaching the theoretical limit. as much as possible to improve device performance.
However, recent improvements in PCE are extremely slow and frus- Fortunately, historical research experiments have made fruitful con-
trating. Of course, this is unavoidable as the gap between reality and tributions to overcoming the fundamental photon energy loss in PSCs.
theory narrows. Therefore, it is difficult to further improve PCE without a For example, for reflections and unwanted parasitic processes, the anti-
directional strategy and precise improvement target [6–9]. reflection coating on the top glass cover of PSCs can bring better light
Before designing strategies, it is necessary to revisit the fundamental transmission and reduce glare; the interaction between light and matter
factors that limit the theoretical ceiling. Considering the energy source in can be realized by texturing the interior with controlled micro/nanoarray
solar cells, the basic process from light to photon should be a crucial link [25]. Meanwhile, the plasmonic nanostructure is used as a secondary
in energy conversion [10–13]. The principal energy loss in the conver- light source to enhance the light trap in the perovskite layer and the
sion of solar energy into electricity fundamentally originates from the carrier transport layer, improving the generation of carriers [26]. For the
non-absorption of low-energy photons ascribed to Shockley-Queisser underutilized reality of the spectrum, the unique energy level structure
limits and thermalization losses of high-energy photons [14–16]. produced by the 4fn inner shell structure of the trivalent rare earth ions
Furthermore, the nanoscale film-induced interference phenomenon leads provides a variety of options for efficient light harvesting of
to a wavelength-dependent optical field distribution on the device. Thus up-conversion and down-conversion [27,28].
the optical absorption exhibits selectivity on common PSCs [17,18]. In this review, we highlight the sources of light loss in PSCs, and
From the perspective of photophysics, photons inside the active layer can summarize the corresponding mitigation measures in a targeted manner,

* Corresponding author.
E-mail address: jinzw@lzu.edu.cn (Z. Jin).

https://doi.org/10.1016/j.enrev.2022.100003
Received 4 August 2022; Received in revised form 12 August 2022; Accepted 14 August 2022
2772-9702/© 2022 The Authors. Published by Elsevier Ltd on behalf of Shenzhen City Clean Energy Research Institute, Shenzhen University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Y. Lei et al. Energy Reviews 1 (2022) 100003

including the application of anti-reflection coatings, plasmonic strate- absorption properties [37,38]. Ideally, photons will continue to undergo
gies, and means to broaden spectral utilization. Finally, we conclude by reabsorption/reemission events until they adjust to escape conditions,
providing an outlook and suggesting future research directions. where the emission angle is smaller than the escape cone, called photon
recycling (Fig. 1d) [39]. In this way, photon recycling increases the
2. Light utilization and loss in PSCs effective density of carriers within the absorber layer, resulting in more
significant quasi-Fermi level splitting. In a solar cell featuring external
PSCs are devices that realize photoelectric conversion, and the utili- contacts, the photon recycling increases the VOC and hence the PCE [40,
zation of sunlight is the key factor that affects the performance of the 41]. More precisely, the voltage gain corresponding to an increase in
devices. The light loss will seriously affect the absorption capacity of photon absorption can be expressed as a function of the photon con-
solar cells to sunlight, directly determine the short-circuit current (JSC) of centration ratio C [42].
devices, and indirectly affect the open-circuit voltage (VOC) through the  
concentration of carriers in devices. KB T
ΔV ¼ lnðCÞ (1)
Energy losses in solar cells intuitively originate from two components: q
low-energy photons cannot be absorbed, and high-energy photons cannot In this, kB, T, and q, are the Boltzmann constant, absolute tempera-
be effectively utilized (Fig. 1a). For the former, low-energy photons are ture, and elementary charge respectively. Considering the effect of
not energetic enough to excite effective electron-hole pair generation in photon recycling more directly, equation (1) can be rewritten as:
the active layer [29,30]. As we know, AM 1.5G sunlight extends over a
 
wide range of useable wavelengths of 280–2500 nm (~ 0.5–4.4 eV). For PR KB T

ΔVOC ¼ ln 4n2 (2)
the best-performing ~1.5 eV bandgap perovskites, the corresponding q
PSCs can utilize incident photons in the 300–800 nm region, while failing
In this, n is the refractive index of the absorber. When only radiative
to use them effectively in the 775 nm–2500 nm sunlight region, sug-
recombination is considered, the maximum path length enhancement of
gesting that a significant portion of the energy over the near-infrared
light is 4n2. Thus, it is reliable to manipulate device performance by
(NIR) region cannot be utilized by the most recognized perovskite
managing photon recycling, which has two main aspects: increasing the
layers [31–33]. The underutilization of high-energy photons is mainly
probability of events (controlling the radiative recombination of the
related to hot carriers and optical losses. A high-energy photon can only
device); and ensuring that as many as possible photons are recovered
produce one electron-hole pair, and when photons with energy exceeding
(optical design increases the refractive index of the absorbing material)
the perovskite band gap are absorbed, the excess energy is usually lost as
(Fig. 1e) [19].
phonon emission. For optical losses, there are mainly parasitic absorption
By identifying the source of energy loss in the device and clarifying
caused by transparent conductive oxides with non-zero extinction co-
the photophysical mechanisms that affect the PV parameters, it is crucial
efficients, reflections caused by the difference in refractive index be-
for us to accurately design appropriate strategies to further advance the
tween semiconductor materials and air, and reflections from metal
performance of PSCs. In this part, we summarize several key mechanisms
electrodes (Fig. 1b and c) [34–36].
of energy loss in devices and provide directions for the elaboration of
In addition, from the point of view of photophysics, the interaction
corresponding measures in the next part.
process between photon and carrier is not single. Under normal condi-
tions, only part of the carriers generated by incident photons in the
3. Optical management for enhanced light harvesting in PSCs
photoactive layer can be collected by the charge collecting layer.
Considering the carriers thermodynamic process, carriers that are not
Facilitating light harvesting in PSCs with the help of optical design is
extracted at the electrode can be removed by radiation or non-radiation
the key to boosting their performance to the theoretical limit. In this
combination. Here, if we only consider radiation recombination, the
section, we summarize several advanced optical management
emitted photons may be reabsorbed and reemitted according to their

Fig. 1. Optical energy loss in PSCs: (a) Energy loss

occurring in the PSCs. Different colors represent
different energy loss mechanisms; (b) Spectral ab-
sorption of each layer in the PSCs. Reproduced with
permission [29]. Copyright 2018, Elsevier Inc Publi-
cations; (c) JSC and optical losses determined. Repro-
duced with permission [33]. Copyright 2018,
Wiley-VCH Publications; (d) Schematics of photon
recycling mechanism and photon recycling effect ob-
tained under an open-circuit condition at steady state;
(e) The three technologies required to implement
photon recycling in PSCs. Reproduced with permis-
sion [42]. Copyright 2018, Springer-Verlag Publica-
tions. (For interpretation of the references to color in
this figure legend, the reader is referred to the Web
version of this article.)

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Y. Lei et al. Energy Reviews 1 (2022) 100003

approaches. It mainly includes the application of anti-reflection coatings, also worth considering. The specific surface area and aspect ratio have
the design of plasmonic nanostructures, and the broadening of spectral significant regulatory effects on the antireflective and hydrophobic
absorption. properties of the material. It has been reported that patterned
anti-reflection coatings can better exert the effect of light utilization
3.1. Implement anti-reflection coating compared to flat surfaces. For example, Hanbin et al. used the texture
PDMS antireflection film prepared by chemical etching to reduce the
For rigid glass-based PSCs, according to Snell's law, 4% of the normal total reflection of solar cells from 8.7% to 3.2%, and the corresponding
incident light is reflected to the glass surface due to the difference in device current increased from 19.91 to 23.29 mA/cm2 (Fig. 2d and e)
dielectric absorption coefficient and the presence of metal electrodes, [51].
and 1% of the transmitted light is directly absorbed by the glass. In Additionally, the cone surface texture can be used to capture light
addition, there is a 4% reflection at the glass-air interface, so only about between the transparent conductive oxide and the buffer layer, allowing
91% of the light gets through the glass into the active layer. more inci- light to scatter to the device over a wide angular range, thus increasing
dent light is lost if the illumination angle is considered [20]. Therefore, the effective path length in the PSCs. However, it should be noted that
using an anti-reflective coating on the substrate can effectively manipu- this method is difficult to control because of geometric reasons, that is,
late incident light, reducing reflection and allowing more light to be the texture undulation exceeds the thickness of the absorbance film and
captured by the device. In addition, it can also show good transmittance increases the recombination of carriers in the interface region (Fig. 2f–h)
through multiple light scattering even under inclined irradiation. For [52].
example, as shown in Fig. 2a and b, the design of a reflective layer be-
tween FTO and TiO2 can significantly transfer the absorption at the 3.2. Plasmonic strategies
interface to the perovskite active layer [43].
In order to design an anti-reflection coating that is perfectly coupled The plasmonic effect refers to the trapping and manipulating of light
to the device, it should be able to provide excellent broadband across the based on localized surface plasmon resonance (LSPR) of metal nano-
entire wavelength region of the perovskite material, low polarization structures. As shown in Fig. 3a, LSPR induces strong surface polarization
sensitivity and compatible protection [44,45]. The last point is that the of nanostructures, resulting in strong enhancement of electromagnetic
material should be superhydrophobic, preventing water droplets from fields (“near-field enhancement”) and radiating electromagnetic waves
accumulating on it and degrading the device's performance. In PSCs, a (“far-field scattering”) at the micro-scale. It can also transfer trapped
common strategy is to introduce a transparent structure in the front energy into adjacent semiconductor systems through non-radiative
section of the glass to scatter incident light into the active layer and relaxation. In addition, the plasmon energy is also being extracted into
reduce reflection at the air/glass interface [46,47]. Strictly speaking, the surrounding medium by hot electron relaxation (decays into electron-
considering the thick-dependent properties of wavelength, this hole pairs) [53,54]. Based on these, the plasmonic structure in solar cells
anti-reflective coating is composed of a stack of ultra-thin transparent can provide three ways to enhance the light absorption capacity of the
layers with a refractive index ranging from that of the glass (nglass 1.5) active layer without requiring strict optical thickness: i) increasing light
to that of the air (nair  1.0) [48,49]. Materials that satisfy these re- scattering, ii) light concentration using particle plasmons, and iii) Light
quirements include MgF, NaF and PDMS. However, the disadvantage of trapping by the excitation of surface plasmon polaritons at the metal/-
this method is that it only suppresses the reflection at the glass/air semiconductor interface (Fig. 3b) [21]. In fact, the most intriguing
interface without introducing additional light into the device, and there property of plasmonic is its capacity to both enhance light absorption and
are only a few materials that meet the applicable conditions. improve charge transport through energy transfer.
Therefore, the researchers developed anti-reflective coatings with For i) process, when metal nanoparticles are embedded in the inter-
structural properties, such as biomimetic moth-eye, nanocone arrays, and face between two different media, the light is preferentially scattered to
invertedpyramids (Fig. 2c). The various forms of rough microstructure the medium with a larger dielectric constant. The scattered light will
make the light transmission between the substrate of the device and air obtain angular diffusion in the dielectric, thus effectively increasing the
meet the gradient refractive index and promote the absorption of diffuse optical path length. For example, embedding plasmonic nanoparticles
light [50]. In addition, the morphology of the microstructure pattern is between the charge transport layer and the active layer is a common

Fig. 2. Application of antireflection layer in PSCs:

(a) Schematic illustration of the perovskite photovol-
taic cell with the antireflection layer; (b) The spatial
distribution of the light-absorption density with the
antireflection layer/m-TiO2/CH3NH3PbI3 architecture
for with and without. Reproduced with permission
[43]. Copyright 2017, Wiley-VCH Publications; (c)
ITO/glass substrate and dmoth-eye PDMS film/ITO/-
glass substrate. Reproduced with permission [50].
Copyright 2018, Springer-Verlag Publications; (d)
Schematic diagram of the fabrication procedure for
the inverted PDMS layers; (e) Transmissive photon
number flux on bare glass and PDMS substrates.
Reproduced with permission [51]. Copyright 2018,
Wiley-VCH Publications; (f) Schematic of the light
path within the perovskite films grown on a modu-
lated textured surface substrate; (g) Images of FTO
and modulated textured surface-FTO substrates; (h)
The simulated absorption distribution of 600 nm
wavelength incident light within the films based on
FTO and modulated textured surface-FTO substrates,
respectively. Reproduced with permission [52].
Copyright 2022, Elsevier Inc Publications.

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Y. Lei et al. Energy Reviews 1 (2022) 100003

Fig. 3. Application of plasmonic nanostructures in

PSCs: (a) Schematic illustration of plasmon enhance-
ment mechanisms of radiative effects. Reproduced
with permission [53]. Copyright 2016, The Royal
Society of Chemistry; (b) Plasmonic light-trapping
geometries for thin-film solar cells. Reproduced with
permission [21]. Copyright 2010, Nature Publishing
Group; (c) Mechanism of light scattering within the
PSC modified with Au NOs; simulated electric field
intensity profile of the TiO2 film without and with Au
NOs under an incident wavelength of 723 nm.
Reproduced with permission [55]. Copyright 2021,
American Chemical Society Publications; (d) The
calculated distribution of localized electric field in-
tensity around different metal nanostructures at their
plasmonic resonance wavelengths. Reproduced with
permission [57]. Copyright 2018, Elsevier Inc Publi-
cations; (e) Schematic illustration of the plasmonic
enhanced PSCs with different morphology metal
electrodes: grating structure (left), bioinspired
moth-eye nanostructures (right). Reproduced with
permission. Copyright 2017, Wiley-VCH Publications
[58].

strategy in PSCs. As shown in Fig. 3c, the plasmonic metal nanoparticles incident solar spectrum, failing most of the sunlight to participate in the
between TiO2 and perovskite can generate a stronger local field, which is photoelectric conversion process of the PSCs. Therefore, how to effec-
beneficial to enhance the light-harvesting ability of the perovskite layer tively utilize the wide spectrum energy of the solar spectrum, including
[55]. UV and NIR bands, is an essential topic in solar cell research. It has been
In process ii), metal nano-plasma particles can be used as sub- found that the introduction of up/down conversion luminescent mate-
wavelength antennas to induce coupling between the near field of plasma rials into solar cells can carry out quantum integration and pruning of the
and the absorbent layer, thus increasing its effective absorption cross- solar spectrum, converting NIR and UV light to the high-efficiency area of
section. Specifically, the strong local field enhancement near metal solar cells, which can improve the JSC and efficiency of devices.
nanoparticles is used to increase the absorption of surrounding photo-
active materials [56]. Here, tuning the localized electromagnetic field 3.3.1. Downconversion strategies
strength around the plasmonic structure is the key to its performance. Perovskite material has the strongest absorption capacity in the ul-
Hence its size and shape are critical. It has been shown that attractively traviolet region, and its absorption coefficient can reach 105 cm1.
induced dipoles are more likely to form in regions with sharp geometric However, the UV region not only contributes nothing to the efficiency of
shapes, increasing the density of polarization vectors (Fig. 3d) [57]. the device but also leads to the degradation of the active layer [60].
Therefore, much stronger electromagnetic fields can be obtained around Therefore, a downconversion strategy to re-emit photons from absorbed
malformed nanostructures than conventional metal nanostructures. high-energy light (typically in the 300–500 nm range) at lower energies
In the above two mechanisms, LSPR is mainly generated between the (e.g., visible light) is a reliable way to enhance the efficiency and improve
introduced metal nanoparticles and the semiconductor in the device. the stability of PSCs (Fig. 4a) [61]. Various types of downconversion
While in process iii), through the design of the back metal electrode, the materials have been investigated for this purpose, such as lanthanide rare
sunlight is coupled into the surface plasmon polaritons mode at the earth materials, luminescent quantum dots, organic molecules. Here, we
metal/semiconductor interface and the photon mode propagating in the mainly introduce common downconversion materials and their behavior
semiconductor plate plane, that is, light guiding and light trapping are in PSCs.
realized simultaneously. As shown in Fig. 3e, the self-enhanced absorp-
tion effect of the perovskite layer caused by surface plasmon polaritons ➢ Lanthanide rare earth materials. Trivalent lanthanide ions are
excited by the corrugated metal back electrode can lead to a 20% broad candidates for efficient spectral transitions because of their
improvement in device performance compared to the flat electrode [58]. superior energy level structure known as the Dieke diagram, and their
In addition, plasma nanostructures can promote light recycling in intense emission based on inra-4f-4f transitions. Yb3þ ions are usually
PSCs. From the view of photophysics, the high polarizability of metal used as activators because the emitted photons have high luminous
nanoparticles increases the probability of exciton radiation in the active quantum efficiency in the wavelength range of 750–1100 nm. The
layer. Meanwhile, the change of exciton radiation geometry due to the sensitizers Ce3þ, Eu3þ, Tb3þ, Tm3þ, Pr3þ, Er3þ, etc., have large ab-
presence of a strong dipole leads to an increase in radiation reabsorption. sorption cross-sections caused by 4f-4f and 4f-5d transitions, making
In other words, the radiative path of exciton decay can be deflected them have strong excitation bands at 300–500 nm. Fig. 4b shows the
through nearby metal nanoparticles, that is, effectively increasing the down-conversion principle based on a single rare-earth ion I or two
path of light and thus making reabsorption more likely, giving the photon rare-earth ions I and II, where I is a wide band-gap sensitized ion that
energy multiple opportunities to generate current [59]. In conclusion, can absorb high-energy photons, and II is an activator ion that can
plasma effects based on metal nanostructures are widely used in light accept the energy of I. [62].
capture and manipulation, which can maximize the coupling of light to
the active layer and design the structure, shape, and size of nanoparticles For example, Jin and co-workers used light-emitting materials of Eu3þ
with the capacity to tune charge transfer. doped TiO2 to successfully construct a downconverting ETL in PSCs. The
results show that when the device is running, visible light can be directly
3.3. Broaden the available spectrum utilized by the perovskite active layer. The corresponding part of high-
energy UV light is first converted into low-energy photons by the
The energy loss in PSCs is related to the incomplete utilization of the down-conversion material and finally absorbed by the active layer, thus

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Y. Lei et al. Energy Reviews 1 (2022) 100003

Fig. 4. Application of downconversion nano-

particles in PSCs: (a) Mechanism of downconversion
in solar cells; (b) The schematic diagram and principle
down-conversion luminescence. Reproduced with
permission [62]. Copyright 2022, IOP Publishing; (c)
Suitable energy level matching of downconverted
nanoparticles in PSCs. Reproduced with permission
[63]. Copyright 2017, American Chemical Society
Publications; (d) Energy band gap alignment diagram
of CsPbCl3:0.1Mn QDs; (e) Solar spectrum (black
curve), emission spectrum of CsPbCl3:0.1Mn (blue
curve) after 365 nm excitation, excitation spectrum
(green curve) monitored by 590 nm, and absorption
spectrum (red curve) of CsPbCl3:0.1Mn QDs. Repro-
duced with permission [12]. Copyright 2017, Amer-
ican Chemical Society Publications; (f) The structure
of NITZ molecule with its photophysical mechanism.
Reproduced with permission [68]. Copyright 2018,
Elsevier Inc Publications. (For interpretation of the
references to color in this figure legend, the reader is
referred to the Web version of this article.)

improving the JSC and protecting the perovskite layer in the corre- does not affect PCE during testing and helps to improve device sta-
sponding device from UV damage, as shown in Fig. 4c [63]. In addition, bility [68].
rare earth downconversion materials are often applied to the active layer
and the external functional layer. The basic principle and conversion Meanwhile, specific functional groups can be introduced into organic
mechanism are essentially similar, and will not be repeated here [64]. molecules to endow them with certain physical and chemical properties,
making them both capable of converting UV light and improving inter-
➢ Luminescent quantum dots (QDs). Semiconductor QDs are also facial defects. More recently, Cheng et al. designed and introduced small
down-conversion materials with tunable luminescence properties, molecule 2,5-bis(perfluorophenyl)thiazolo [5,4-d]thiazole (PFP2TTz) to
which have certain advantages over traditional rare-earth-based construct high-performance PSCs. The results show that PFP2TTz is a
luminescent materials in terms of luminous efficiency and color kind of bi-functional additive. The fluorine and nitrogen groups con-
tunability. In particular, halide perovskite QDs are not easily affected tained in PFP2TTz can complexate with Pb2þ in perovskite to improve the
by oxygen and moisture, showing very high photoluminescence crystal quality. In addition, it can also be used as a fluorescent resonance
quantum yields of up to 90% [65]. In the application of modified energy transfer agent to produce fluorescence overlapping with perov-
PSCs, transition metal ions (Mn2þ, Bi3þ) and rare earth ions (Yb3þ, skite absorption spectrum by absorbing light at 300–500 nm [32]. In
Ce3þ) are usually doped into the lattice of perovskite quantum dots to conclusion, downconversion materials have received extensive attention
regulate their optical properties. As shown in Fig. 4d and e, Wang in PSCs due to the advantages of convertible UV light to enhance ab-
et al. spin-coated 0.1 M Mn-doped CsPbCl3 QDs onto a glass substrate. sorption and alleviate device UV degradation.
CsPbCl3:Mn QDs exhibit strong absorption spectra in the UV region
and can convert UV light into visible light with a quantum efficiency 3.3.2. Upconversion strategies
of 60%, which perfectly agrees with the absorption spectrum of PSCs. As mentioned earlier, the wavelength of sunlight ranges from UV to
This is essentially by virtue of the 4T1-6A1 transition attributed to NIR (280–2500 nm), whereas PSCs can only absorb short-wavelength
Mn2þ ions. The exciton partially excited by the host CsPbCl3 QDs photons below 800 nm. As shown in Fig. 5a, most photons in NIR and
conduction band is transferred to the excited state of Mn2þ, resulting IR regions are not generating energy, resulting in a spectral loss of 44%
in emission at 590 nm. Similarly, some carbon QDs and graphene QDs [69]. If this part of the energy is fully utilized, it will greatly benefit the
have also been used as downconversion materials, and these materials PCE of PSCs. A feasible method is introducing upconversion materials to
have the same conversion mechanism, but differ in compatibility with convert and utilize NIR light. Upconversion luminescence is essentially
perovskite materials and perovskite spectra [12]. an anti-Stockes effect, in which the emitted energy is greater than the
➢ Organic molecules. Organic molecules have a variety of tunable absorbed energy [70]. In this process, the sensitizer first absorbs one or
optical and electrical properties due to their variable highest occupied more photons and then is excited to its excited state. By the way, the
molecular orbital (HOMO) and lowest unoccupied molecular orbital energy is transferred to the emitter, which is excited to the intermediate
(LUMO) levels and molecular structure. These molecules are solution excited state level, and the sensitizer non-radiatively transitions back to
processable with low-cost deposition. Organic molecules as down- the ground state. The second sensitizer then absorbs the photon, excites it
conversion materials mainly rely on intermolecular energy transfer to a higher excited state level by energy transfer, and releases a higher
caused by the resonance between the excited state and the ground energy photon from this excited state (Fig. 5b) [25]. In this way,
state [66,67]. As shown in the Fig. 4f, S-tetrazine (NITZ) was intro- low-energy NIR light is converted into higher-energy visible light. Here,
duced by Gheno et al. to modulate UV light in PSCs. NITZ as a we mainly introduce several upconversion materials that are classically
downconversion layer showed favorable optical characteristics, with used in PSCs.
excitation the UV region and light emission in the visible region. The
maximum excitation of NITZ molecules is at 350 nm, while the ➢ NaYF4 system. NaYF4 is found to be a suitable upconversion host for
maximum emission (excitation at 350 nm) is at 580 nm, which is the the following reasons: (i) it has the lowest phonon energy, which is
ideal location because it is where the perovskite active layer absorbs conducive to providing a suitable crystal field and reducing the
the most light and produces the most. This photoluminescence is probability of non-radiative transitions; (ii) in the visible range, the
caused by the π→π* transition, and emission is caused by the n→π* absorption of light is weak and the reflectivity is low, which ensures
transition. The device is encapsulated with a NITZ-coated film that perfect optical transmission [71,72]. Therefore, the star host material
is NaYF4 and the dopant is a pair of rare earth ions such as Yb3þ/Er3þ,

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Y. Lei et al. Energy Reviews 1 (2022) 100003

Fig. 5. Application of upconversion nanoparticles

in PSCs: (a) AM 1.5G spectrum shows the fraction
response by PSCs; (b) Schematic illustration of the
excitation and emission in upconversion materials; (c)
Upconversion enhanced PSCs with IR806-β-NaYF4:Yb
nanoparticles located in perovskite layer. Reproduced
with permission [73]. Copyright 2017, Elsevier Inc
Publications; (d) Schematic diagram of NaYF4 shell
structure and energy level transfer. Reproduced with
permission [75]. Copyright 2017, Elsevier Inc Publi-
cations; (e) Fabrication process of mCu2-XS@-
SiO2@Er2O3 nanocomposites and their application in
PSCs. Reproduced with permission [76]. Copyright
2017, The Royal Society of Chemistry.

Yb3þ/Ho3þ, and Yb3þ/Tm3þ. In this system, one acts as a sensitizer Cu2-XS has excess free carriers, which leads to plasmons that expand
(Yb3þ) that absorbs NIR light, and the other acts as an emitter (Er3þ, the absorption in the NIR band. This improvement of the upconver-
Ho3þ and Tm3þ) that emits visible photons. Tao et al. reported that sion efficiency of rare earth oxides by the LSPR effect is obviously
NaYF4: Yb3þ/Er3þ nanocrystals could trap near infrared from 800 nm fascinating. However, it is necessary to clarify the physical mecha-
to 1000 nm and emit visible light from 500 nm to 700 nm. After nism of LSPR to enhance the photoluminescence properties and
introducing it into MAPbI3 perovskite precursor, the corresponding improve the upconversion efficiency of lanthanide oxides through
device performance is improved from 13.52% to 17.49% (Fig. 5c) chemical composition regulation, and thus to design more universal
[73]. components and expand the application in PSCs.

In addition, some other rare earth fluorides have also been reported to This section mainly describe several upconversion materials
be used as upconversion materials, such as KLaF4, BaYF5, Li(Gd,Y)F4, etc. commonly used in PSCs. It is an effective way to improve the photovol-
Due to the differences in crystal structure among these host materials, the taic performance of solar cells by using upconversion materials to extend
location and symmetry of lanthanide ion incorporation will be different, the absorption spectrum to the NIR part. However, at present, the
thus affecting the upconversion efficiency. However, the overall trans- commonly used upconversion materials mainly contain rare earth ele-
formation mechanism is the same and will not be explained in detail ments, which greatly increases the cost of preparation. Moreover, the
here. The concern is that during the energy transfer process, nano- resources of rare earth elements are limited, so similar materials with low
particles with smaller volumes and larger specific surface areas are easily cost, larger potential, and abundant reserves should be developed.
affected by the luminescence quenching center to cause quenching
phenomenon, resulting in energy loss [74]. Therefore, it is necessary to 4. Summary and prospects
design the material structure properly. For example, it has been found
that the core-shell structure can effectively alleviate the luminescence In summary, the sources of energy loss in PSCs have been clearly and
quenching of upconversion nanoparticles due to surface effects and accurately understood, and some mitigation measures of corresponding
quantum size effects. (Fig. 5d) [75]. photon management have been widely used. In this mini-review, we
describe the optical loss due to the band gap of intrinsic perovskite ma-
➢ Lanthanide oxide system. The lanthanide oxides have high up- terials and incomplete photon cycling due to photophysical processes in
conversion efficiency and better performance at high temperatures devices. Accordingly, we also summarize some characteristic optical
and large doping amounts. Especially combined with plasmon Cu2-XS management measures, including optical anti-reflection coating, plas-
components, lanthanide oxides can effectively reduce the threshold monic strategy, and absorption spectrum broadening (up/down-conver-
power of up-conversion and prolong the absorption spectrum, thus sion strategies). These advanced methods have indeed contributed to
effectively improving the conversion efficiency. Zhou et al. have improving PSCs performance in the past. However, for the PCE of PSCs to
applied the semiconductor plasmons mCu2-XS@SiO2@Er2O3 nano- truly catch up to the theoretical limit, the following ideas may be
composites in PSCs and improved the PCE by ~10% (from 16.2% to instructive:
17.8%) (Fig. 5e) [76]. This is because, as a plasma semiconductor,

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Y. Lei et al. Energy Reviews 1 (2022) 100003

➢ Exploiting the Potential of Photon Recycling Acknowledgments

The main benefit of photon recycling applied to PSCs is the VOC in- This work was funded by the National Natural Science Foundation of
crease, achieved by increasing quasi-Fermi level splitting (Δμ) within the China (52073131), the Fundamental Research Funds for the Central
active layer through the reabsorption of radiation-emitted photons. This Universities (lzujbky-2021-ct15).
means that photo-induced carriers recombine radiatively, rather than
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