Luminescent converter of solar light into electrical energy. Review
We review a status of the research on conversion of solar energy into electricity by using the systems that split the solar spectrum with a set of luminescent concentrators. Influence of the luminophore choice (rare-earth elements, dyes, or semiconductor quantum dots) and their characteristics as we...
Збережено в:
| Дата: | 2016 |
|---|---|
| Автори: | , , , , , |
| Формат: | Стаття |
| Мова: | English |
| Опубліковано: |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2016
|
| Назва видання: | Semiconductor Physics Quantum Electronics & Optoelectronics |
| Онлайн доступ: | https://nasplib.isofts.kiev.ua/handle/123456789/121584 |
| Теги: |
Додати тег
Немає тегів, Будьте першим, хто поставить тег для цього запису!
|
| Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Цитувати: | Luminescent converter of solar light into electrical energy. Review / M.R. Kulish, V.P. Kostylyov, A.V. Sachenko, I.O. Sokolovskyi, D.V. Khomenko, A.I. Shkrebtii // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2016. — Т. 19, № 3. — С. 229-247. — Бібліогр.: 50 назв. — англ. |
Репозитарії
Digital Library of Periodicals of National Academy of Sciences of Ukraine| id |
nasplib_isofts_kiev_ua-123456789-121584 |
|---|---|
| record_format |
dspace |
| spelling |
nasplib_isofts_kiev_ua-123456789-1215842025-02-09T22:23:02Z Luminescent converter of solar light into electrical energy. Review Kulish, M.R. Kostylyov, V.P. Sachenko, A.V. Sokolovskyi, I.O. Khomenko, D.V. Shkrebtii, A.I. We review a status of the research on conversion of solar energy into electricity by using the systems that split the solar spectrum with a set of luminescent concentrators. Influence of the luminophore choice (rare-earth elements, dyes, or semiconductor quantum dots) and their characteristics as well as the luminescence quantum losses, when the light quanta travel inside the optical waveguide formed by the luminescent concentrator, were analyzed. The methods to minimize these losses, including optimal converter design, were discussed. The choice of design with stacked luminescent concentrators was demonstrated. The design of the stacked luminescent concentrators with optimized parameters of the transparent matrix and semiconductor quantum dots was investigated. 2016 Article Luminescent converter of solar light into electrical energy. Review / M.R. Kulish, V.P. Kostylyov, A.V. Sachenko, I.O. Sokolovskyi, D.V. Khomenko, A.I. Shkrebtii // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2016. — Т. 19, № 3. — С. 229-247. — Бібліогр.: 50 назв. — англ. 1560-8034 DOI: 10.15407/spqeo19.03.229 PACS 88.40.jm, 88.40.jp https://nasplib.isofts.kiev.ua/handle/123456789/121584 en Semiconductor Physics Quantum Electronics & Optoelectronics application/pdf Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| institution |
Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| collection |
DSpace DC |
| language |
English |
| description |
We review a status of the research on conversion of solar energy into electricity by using the systems that split the solar spectrum with a set of luminescent concentrators. Influence of the luminophore choice (rare-earth elements, dyes, or semiconductor quantum dots) and their characteristics as well as the luminescence quantum losses, when the light quanta travel inside the optical waveguide formed by the luminescent concentrator, were analyzed. The methods to minimize these losses, including optimal converter design, were discussed. The choice of design with stacked luminescent concentrators was demonstrated. The design of the stacked luminescent concentrators with optimized parameters of the transparent matrix and semiconductor quantum dots was investigated. |
| format |
Article |
| author |
Kulish, M.R. Kostylyov, V.P. Sachenko, A.V. Sokolovskyi, I.O. Khomenko, D.V. Shkrebtii, A.I. |
| spellingShingle |
Kulish, M.R. Kostylyov, V.P. Sachenko, A.V. Sokolovskyi, I.O. Khomenko, D.V. Shkrebtii, A.I. Luminescent converter of solar light into electrical energy. Review Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Kulish, M.R. Kostylyov, V.P. Sachenko, A.V. Sokolovskyi, I.O. Khomenko, D.V. Shkrebtii, A.I. |
| author_sort |
Kulish, M.R. |
| title |
Luminescent converter of solar light into electrical energy. Review |
| title_short |
Luminescent converter of solar light into electrical energy. Review |
| title_full |
Luminescent converter of solar light into electrical energy. Review |
| title_fullStr |
Luminescent converter of solar light into electrical energy. Review |
| title_full_unstemmed |
Luminescent converter of solar light into electrical energy. Review |
| title_sort |
luminescent converter of solar light into electrical energy. review |
| publisher |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| publishDate |
2016 |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/121584 |
| citation_txt |
Luminescent converter of solar light into electrical energy. Review / M.R. Kulish, V.P. Kostylyov, A.V. Sachenko, I.O. Sokolovskyi, D.V. Khomenko, A.I. Shkrebtii // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2016. — Т. 19, № 3. — С. 229-247. — Бібліогр.: 50 назв. — англ. |
| series |
Semiconductor Physics Quantum Electronics & Optoelectronics |
| work_keys_str_mv |
AT kulishmr luminescentconverterofsolarlightintoelectricalenergyreview AT kostylyovvp luminescentconverterofsolarlightintoelectricalenergyreview AT sachenkoav luminescentconverterofsolarlightintoelectricalenergyreview AT sokolovskyiio luminescentconverterofsolarlightintoelectricalenergyreview AT khomenkodv luminescentconverterofsolarlightintoelectricalenergyreview AT shkrebtiiai luminescentconverterofsolarlightintoelectricalenergyreview |
| first_indexed |
2025-12-01T09:25:25Z |
| last_indexed |
2025-12-01T09:25:25Z |
| _version_ |
1850297422634287104 |
| fulltext |
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
229
PACS 88.40.jm, 88.40.jp
Luminescent converter of solar light into electrical energy.
Review
M.R. Kulish1*, V.P. Kostylyov1, A.V. Sachenko1, I.O. Sokolovskyi1, D.V. Khomenko1, A.I. Shkrebtii2
1V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,
41, prospect Nauky, 03028 Kyiv, Ukraine
2University of Ontario, Institute of Technology,
Simcoe Street 2000 N, Oshawa, ON, L1H 7K4, Canada
*Corresponding author e-mail: n_kulish@yahoo.com
Abstract. We review a status of the research on conversion of solar energy into
electricity by using the systems that split the solar spectrum with a set of luminescent
concentrators. Influence of the luminophore choice (rare-earth elements, dyes, or
semiconductor quantum dots) and their characteristics as well as the luminescence
quantum losses, when the light quanta travel inside the optical waveguide formed by the
luminescent concentrator, were analyzed. The methods to minimize these losses,
including optimal converter design, were discussed. The choice of design with stacked
luminescent concentrators was demonstrated. The design of the stacked luminescent
concentrators with optimized parameters of the transparent matrix and semiconductor
quantum dots was investigated.
Keywords: luminescence, luminophore, solar cells, efficiency, concentrator.
Manuscript received 05.04.16; revised version received 12.07.16; accepted for
publication 13.09.16; published online 04.10.16.
1. Introduction
Current researches on power generation by using
photovoltaics are often aimed at single p-n-junction
silicon solar panels. These panels, however, cannot
utilize the total energy of sunlight (see Fig. 1 [1]). The
bandgap of semiconductor material determines the
fundamental limit, which defines how much energy of
the sunlight can be converted into electrical energy.
Thus, when the energy of photons is less than the
semiconductor bandgap, they are not absorbed. In a Si
cell, these losses can be as high as 19% (Fig. 1). For the
photons with the energy above the gap, their excess
energy (hν – Eg), where hν is the photon energy and Eg –
bandgap, is converted into heat, and therefore it is also
lost (the so-called thermalization losses). In the Si solar
cell, these losses can reach 33% (Fig. 1). A part of
photogenerated carriers are lost during their separation
by the p-n-junction, these losses can reach 15% (Fig. 1).
Only 33% of the photons in the solar spectrum are
available to be converted into electrical energy. As a
result of the above losses, the theoretically attainable
efficiency of the silicon solar cells cannot exceed 30%
[2]. The maximum efficiency achieved experimentally is
around 25% for AM1.5 [3].
The solar cell efficiency increase can be achieved
by concentrating the photons incident on the input
surface of the cell. When the light concentration equals
to 92 suns, the single junction solar cell efficiency η
reaches 27.6% [3].
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
230
Fig. 1. Minimum losses for a silicon solar cell (bandgap of
1.1 eV) and where they occur in the solar spectrum (top line).
These are the losses accounted for in the Shockley–Queisser
limit and represent the upper limit for the single-junction solar
cells made of bulk crystalline semiconductors. Thermalization
represents the largest loss in this formalism, and it increases for
the blue portions of the solar spectrum. See the text for an
explanation of each loss [1].
A significant increase in the efficiency of sunlight
conversion into electricity can be achieved by splitting
the solar spectrum on spectral bands; each of them sends
the light to a separate cell zone. There are two options
for implementing this concept. In the first case, materials
with a one p-n-junction are stacked in such a manner that
the cell zone with the lowest bandgap is at the bottom
and material with the highest bandgap is at the top. In
particular, for such a structure with three p-n-junctions
(Ga0.5In0.5P/GaAs/In0.3Ga0.7As) under AM1.5 conditions,
the maximum efficiency for the non-concentrated light
reaches 33.8%, and for the 81-sun concentration the
efficiency η = 38.9% [4]. In [5], the record efficiency
η = 44.7% has been reported in the structure with four
p-n-junctions at 297 suns for AM1.5 conditions. In the
technical realization of these structures the main
difficulties are caused by the need to match the
semiconductor lattice constants of the stacked
semiconductors. For the second concept, the solar cells
with different spectral sensitivity are placed laterally
using a dispersion element that splits sunlight into bands.
A prism, diffraction grating or set of interferential filters
can be used as the dispersion element. Each solar cell is
illuminated with a corresponding band of sunlight [6].
The maximum value η = 43% under AM1.5 has been
achieved by splitting the solar spectrum into three bands
and each band illuminates cell with multiple junctions.
The first light band is transformed into electrical energy
by two GaInP/GaAs p-n-junctions, the second band
irradiates Si cell, the third one illuminates
GaInAsP/GaInAs stack [7]. These structures can
efficiently convert sunlight to electricity only at the
normal incidence onto the photoconverter surface, and
they cannot convert diffuse light into electrical energy.
This is the main disadvantage of such structures. To
maximize the efficiency of these photoconverters, the
tracking systems, which orient the panel to achieve the
normal incidence onto the surface of the panel, are
required.
The above disadvantages are not inherent to the
Light Converter structures with Luminescence
Concentrator (LCLC). LCLC operation is based on four
mechanisms: (1) absorption of the light by the
luminophore particles, (2) luminophore emission of the
photons with energies lower than those of the absorbed
photons, (3) transport of the fluorescent photons in a
peculiar optical waveguide to the input surface of the
solar cell, and (4) converting light into electricity by the
solar cell. The advantages of such converters are the
possibility of light concentrating at the input of the
surface solar cells, the possibility of converting the
scattered light into electrical energy, while the tracking
systems for the solar panel orientation toward the sun is
not required. In majority of the articles estimate the
maximum efficiency ηc of the luminescent solar
concentrator (LSC), it is done for the concentrator doped
certain luminophore (mainly certain dye) (see, e.g.,
[8, 9]). For the structure of a fluorescent concentrator
doped with two dyes, the maximum efficiency achieved
experimentally ηc = 7.1% [10]. The relatively low value
of ηc is a consequence of the low efficiency of LSC,
although it was theoretically shown that the quantum
efficiency ηq of luminescent concentrators can be close
to unity (according to [11] the maximum value
ηq = 99.7%), since the number of the light quanta
absorbed by the luminophore should be equal to the
number of fluorescent quanta.
Experimental LSC low efficiencies (less than ten
percent) are caused by the fact that only a part of
sunlight is able to create luminescent quanta, and there
are luminescent quanta losses in the concentrator. There
are two ways to improve LCLC efficiency. 1) Minimize
all possible losses of the quanta in the LSC with its
efficiency close to unit and to match the spectral
luminescence band with that of maximum efficiency of
the solar cell. 2) Form a stack of the LSC and achieve
the current matching between the solar cells, which
creates a peculiar photoconverter with luminescent
splitter of the solar spectrum.
The purpose of this work is to find ways of forming
stacked LSC, attached to each LSC solar cells. To
achieve it, we have to: 1) determine the optimal number
of stacked concentrators, 2) minimize the loss of light in
each LSC plate and in stacked LSC, 3) determine the
design of each plate in LSC and of the whole stacked
LSC.
To attain this result, we consistently considered:
1) principle of LSC operation and identified all types of
light quanta losses as well as the ways to minimize them,
2) analyzed the luminophore properties and determined
the type of the optimal luminophore, 3) properties of the
matrix LSC and found optimal geometry of both the
individual LSC matrix and stacked LSCs.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
231
Fig. 2. Illustration of LCLC operation.
2. Luminescent photoconverter
As a luminescent photoconverter, we mean stacked
concentrators with the solar cells, attached to each
concentrator (Fig. 2). For example, we demonstrate the
principles of such photoconverter operation by using
three stacked LSCs. The luminophore located at the top
LSC plate absorbs only the high energy part of the solar
spectrum. As a result of absorption, luminophore
molecules transfer to the excited state. Transition of the
molecules to the ground state is accompanied by
emission of luminescent photons in a narrow energy
band. These photons propagate in the plate as in a
peculiar optical waveguide and eventually get
transferred to the lateral side of the plate, which is the
input surface of the solar cells. The solar cells convert
energy of the luminescent quanta into the electrical one.
Light and fluorescent quanta that are not absorbed by the
highest concentrator pass into the second LSC plate.
There, luminophore molecules absorb less energetic part
of the solar spectrum and emit luminescent quanta in the
second narrow luminescence band. Luminescence
quanta in the optical waveguide are transmitted to the
input of solar cells attached to the middle LSC plate and
are converted into the electrical energy. The rest of the
solar spectrum (not absorbed in the upper concentrators)
reaches the bottom LSC plate, where the luminescent
molecules absorb the remaining solar quanta and emit
the luminescent quanta in a narrow band. Fluorescent
photons transferred to the solar cell are converted into
the electrical energy again.
It should be noted that such stacked LSC are the
splitter of the solar spectrum into a set of spectral bands.
If each input area of the LSC plate is much larger than
the area of end faces with the solar cell attached, the
ratio of these areas determines the value of the light
concentration. Therefore, the ideal LSC is
simultaneously the concentrator of the solar energy and
the solar spectrum splitter. To estimate the maximum
possible efficiency of such photoconverter, we have to
determine the losses both in the stacked LSC and in solar
cells, as well as identify ways to minimize these losses.
Next, one has to simulate the real and idealized
fluorescent phototransducer. Let’s start with the losses in
a separate LSC.
3. Losses of the luminescent quanta in LSC
We consider first a luminescent concentrator as a plate
(in the simplest case of the rectangular shape)
transparent to the sunlight and doped with a luminophore
(consisting of rare-earth ions, or dyes, or quantum dots)
with no solar cells attached to plate (see Fig. 3). Sunlight
incident on the input surface plate is denoted as (1),
small part of it (2) is reflected from the plate and lost.
Another part of the photons passes through the plate
without absorption (3) and is lost. Part of the photons is
absorbed by absorption centers (4) of the plate and is
emitted by the fluorescent centers (5). Each luminescent
center radiates photons in all directions (6). If the
absorption and luminescence spectra overlap, the
fluorescent photons can be reabsorbed (7) and excite the
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
232
Fig. 3. Cross-section of the luminescent solar concentrator with a schematic representation of the loss of sunlight photons. Light
that enters the LSC is absorbed by luminescent centers. Each luminescent center emits photons in all directions. Fluorescent
photons that emit under angle smaller than the critical one leave the matrix. These photons are concentrated in the cones marked
by the heavy lines. Fluorescent photons that are emitted at an angle larger than the critical one, spread into the optical waveguide.
They can be reabsorbed either directly or after total internal reflection and surface transport to the input solar cells face.
luminescent centers that generate quanta of
luminescence. The part of luminescent photons that are
spread at the angles below the critical angle βC (8) leaves
the plate. Those photons that are spread at angles above
the critical one βC (9) are reflected from the surface of
the plate and travel inside the optical waveguide to the
end surfaces. When the refractive indices of the plate
and solar cell are different, the part of photons is
reflected back into the waveguide (10). At all the stages
of interaction of the light inside the plate, light quanta
can be additionally lost.
3.1. Reflection losses
The intensity of light Itran passing through the front
surface of the concentrator is
( ) 01 IRItran −= , (1)
where R is the reflection coefficient, I0 – intensity of the
incident light on the front surface of the plate. The value
of the losses of light in this case is ηtran = I0R. When the
incident light is normal to the plate, then the reflection
coefficient R can be estimated by the formula
2
1)(
1)()( ⎟⎟
⎠
⎞
⎜⎜
⎝
⎛
+λ
−λ
=λ
n
nR , (2)
where n(λ) is the refractive index of the material of the
plate.
To reduce the reflection losses, one can either
manufacture the plates using low refractive index
material or apply deposit an antireflecting film onto the
front surface of the plate. However, as it will be shown
below, the use of the antireflecting film is inappropriate.
3.2. Transmission losses
These losses are caused by the limited absorption band
of the luminophore. Reduction of these losses can be
achieved by using as much as possible LSCs in the stack
and by setting high luminophore concentrations, which
absorb all sunlight. Detailed analysis of the properties of
luminophore will be made below.
3.3. Luminescence quantum yield
In the concentrators, luminophore converts sunlight of
particular spectral range into narrow luminescence band
by luminescent centers that are uniformly distributed
inside the plate. Luminophore emits photons in a lower
energy region as compared to the absorption spectrum
range. This process is characterized by the luminescence
quantum yield (ηL), which is a ratio of the concentration
of the emitted photons NL to the concentration of the
absorbed photons Nα.
aLL NN /=η . (3)
It is necessary that in each concentrator the ηL
value is close to unity.
Energy of the fluorescent photons usually differs
from the energy of absorbed photons. The energy losses
are caused by the Stokes shift, can be approximately
characterized by ηst, equal to
ab
L
st h
h
νΔ
νΔ
=η , (4)
where ΔhνL = ΔhνL max – ΔhνL min is the width of the
luminescence band at the 0.1 level, hνL max and hνL min are
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
233
the maximum and minimum energies of the
luminescence quanta at 0.1 level, Δhνab = Δhνab max –
Δhνab min is the bandwidth of the light absorption by
luminophore, hνab max and hνab min are the maximum and
minimum energies of the quanta absorbed by the
luminophore. The energy losses can be minimized by
narrowing the fluorescent band as much as possible and
by simultaneously increasing the absorption bands in a
maximum possible manner.
4. Luminophores
The properties of luminophores determine substantially
the efficiency of solar concentrator. When analyzing
perspectives of using luminophores for doping
concentrator plates, the following criteria have to be
used [12]:
1. Absorption band should be broad and not striped to
fully use solar energy containing in that band.
2. Luminophore absorption coefficient should be high
enough for complete absorption of photons.
3. Luminescence band must be narrow as compared to
the absorption band. It is desirable that the distance
between the bands was the maximum possible.
4. The quantum yield of luminescence must be high,
ideally close to unity, and temperature independent.
5. The overlap of the absorption and luminescence
spectra should be minimal. Ideally, the spectra
should be completely non-overlapping, that is the
self-absorption of luminescence can be neglected.
6. The luminophore emission band must coincide with
the area of the maximum external quantum yield of
the solar cell.
7. Photostability should be kept unchanged for a long
time, ideally within 30-50 years, which is close to
the lifespan of solar panels.
8. Thermal resistance should be high, preferably
above 400 K.
9. The cost and toxicity of the luminophores should
be minimal.
An analysis of the luminophores properties is
necessary to decide which ones are the best suited to
satisfy the above criteria. In the analysis, provided
below, the known luminophores are divided into three
following groups: (1) rare earth atoms, (2) organic dyes
and (3) quantum dots.
4.1. Rare-earth atoms and complexes
Ions of the rare-earth lanthanides group elements can be
used as the luminophore in fluorescent concentrators.
This includes atoms of such metals as erbium (Er),
neodymium (Nd), samarium (Sm), europium (Eu),
praseodymium (Pr), terbium (Tb), holmium (Ho),
thulium (Tm), and ytterbium (Yb) as well as the atoms
of transition metals such as chromium (Cr), titanium
(Ti), vanadium (V) associated with the relevant
complex. In the trivalent form, the lanthanides basically
are stable. Ions of the lanthanides group have the
electron configuration [Xe]4fn5s25p6, where n varies
from 0 to 14. Partially filled 4f inner shell is responsible
for the characteristic optical properties of the
lanthanides. The number of configurations for the n
electrons averaged over 4f orbitals is numerous. They
determine the energy spectrum of the rare-earth
elements, known as Dike diagram (Fig. 4) [13]. A
characteristic feature of the energy spectrum of these
metal ions is their discrete nature (Fig. 4). As the result,
both the absorption and luminescence spectra of the ions
are narrow-band, see, e.g., the absorption and emission
spectra of Nd3+ ions (Fig. 5) [14]. As shown in Fig. 5,
the absorption spectrum of Nd3+ ions contain numerous
peaks in the 300…900-nm range, which correspond to
the transitions from 4I9/2 ground state of the ion to
different excited states.
The emission spectrum contains three peaks with
the maxima at 880, 1064 and 1330 nm (not shown in the
figure) with 75% of emissions originating from the main
peak at 1064 nm. The emission goes from the 4F3/2
excited state. Narrow-band absorption and luminescence
spectra are typical for all rare-earth elements (see, e.g.,
[9, 15-17]).
The main advantages of the matrices doped with
rare-earth elements are as follows: 1) high internal
quantum yield of luminescence, close to 70…100% [14],
which also includes transitions in the infrared region;
2) Stokes shift of the luminescence is large (see, e.g.,
Fig. 5). Due to this, the reabsorption can be neglected;
3) band of the luminescence is narrow; 4) photostability
of rare-earth elements is high. These parameters remain
unchanged over hundreds of years.
The main disadvantages of the matrix doped with
metal ions are as follows: 1) Absorption bands of the
rare-earth ions are numerous and narrow. 2) The
absorption coefficient is low, so the thickness of the
matrix doped with rare-earth elements should be
significant, and high concentrations of rare-earth
elements should be used for doping. This often leads to
concentration quenching of the luminescence.
3) Correlation of the appropriate absorption band of the
rare-earth ions with the range of maximum solar cells
efficiency is difficult to achieve. 4) Technology of the
matrix synthesis with rare-earth ions and transition
metals are complex and expensive. 5) Selection of the
ions of rare-earth metals is limited.
To achieve the maximum efficiency of solar energy
conversion into the electrical energy, a rare-earth doped
plate that completely absorbs the light from the
corresponding spectral range is required. One way to
implement this is to dope the plate with several rare-
earth ions such as, for example, Nd or Yb [14].
However, in this case, the absorption spectrum contains
regions with low absorption coefficients.
Expanding the absorption spectrum can also be
achieved through formation of complexes of rare-earth
ions or transition metal atoms. Usually such a complex
contains rare-earth ion (which serves as an acceptor)
related energetically with other metal ion or rare-earth
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
234
Fig. 4. Energy-level digram for RE3+ ions doped into the crystal LaCl3 (after Dieke [13]). The first axis on the left represents the
emitted photon wavelength from a given multiplet to the ground state only. The second axis on the left represents the energy
(cm−1) of the 2S+1LJ level [13].
metal or transition metal ion (it serves as a donor).
Typically, the acceptor is surrounded by the organic
ligand. One example of such complex is shown in
Fig. 6a [18, 19]. The light is absorbed by both the ligand
and the rare-earth ion. The energy absorbed by the donor
is not emitted but rather is non-radiatively transferred to
the acceptor. As a result, the absorption spectrum of the
complex becomes wider as compared to the absorption
spectrum of the rare-earth elements (see Fig. 6b). For the
efficient energy transfer from the donor to the acceptor,
the maximum overlap of these absorption spectra is
required.
Depending on the design, the energy transfer in the
complex occurs through the dipole-dipole mechanism
(so-called Förster mechanism [20], the energy is usually
transferred from a single metal ion to another) or by the
energy exchange mechanism by Dexter [21]. Structures
of different types of ligands and complexes are described
in many papers (see, e.g., [22]). According to the authors
of [23], the complex Eu (TTA) 3dpbt absorbs only 7.6%
of the solar spectrum. Note that, in the field of
transparency of the absorption spectrum of the ligand
complexes, there are narrow absorption bands that are
representative for rare-earth elements.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
235
Fig. 5. Absorption (solid) and emission (dashed) spectra of
NdF3 [14].
a)
b)
Fig. 6. The molecular structure of Eu (TTA) 3phen complex
(a) [18] and (b) absorption and luminescence spectra of such
complex systems [22].
4.2. Organic dyes
The number of different organic dyes is huge. The
absorption and luminescence spectra of most dyes lie in
the visible and near infrared region [24, 25]. This is
demonstrated in Fig. 7, which shows the absorption and
luminescence spectra of several dyes [14]. Typical for
the absorption spectra is that they are striped, and a
significant overlap of the absorption and luminescence
spectra occurs. The extent of the absorption bands of
individual organic dyes is around 100 nm (Fig. 7) and
usually covers from 10 to 15% of the area of the visible
spectrum [12]. Therefore, to absorb the maximum
number of photons, mixing the several dyes is necessary,
which in many cases leads to the luminescence
quenching.
a)
b)
Fig. 7. Visible (a) and near infrared (b) dye absorption and
emission spectra (normalized) [14].
When the several dyes are inserted into the plate,
the set of absorption spectra forms a broad absorption
band. Short-wave photons transfer solar energy to the
dye through cascade that generates photons with longer
wavelengths. In this case, the efficiency of the
luminescence concentrator is determined by the
luminescence quantum yield of the dye that generates
light in the long-wave range of the spectrum.
Luminescence quantum efficiency depends on the
wavelength of the emission of dyes (Fig. 8). Fig. 8
shows that the longer the wavelength, the lower the
quantum yield is. Dyes with the quantum yield of
luminescence φ ≈ 1 emit in the range below 600 nm.
From 600 to 700 nm quantum yield dyes averages to
φ ≈ 0.6, from 700 to 800 nm, it drops to φ ≈ 0.4 and
beyond 800 nm range the quantum yield is reduced to its
minimum φ ≈ 0.2 [12]).
Dyes degrade and have a limited lifetime. The
investigation of Violett 570 dye [12] has demonstrated
that the intensity of luminescence PMMA doped dye
samples is reduced to 50% from its initial value after
exposure for two years. Incidentally, the value of the
degradation is strongly dependent on the base polymer
and exposure conditions. Obviously, the lifetime of
organic dyes is much less than 20 years, during which
the initial power of silicon solar modules is reduced to
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
236
Fig. 8. Quantum yield of the dye as a function of the emission wavelength [12].
80% [26]. To convert solar energy into electricity, high
chemical stability of the luminophore to ultraviolet
exposure is required. However, under UV irradiation
dyes decompose, and, to prevent degradation of dyes, a
filter that eliminates the ultraviolet photons is necessary.
Therefore, the advantages of using dyes include:
1) A large number of different dyes available allows to
find the one which luminescence band is in the desired
spectral range. 2) The internal quantum yield is high and
usually reaches 90…100% for dyes that emit photons in
the visible range of the solar spectrum. 3) Transparent
polymer plates (such as, e.g., PMMA) can be easily
doped with organic dyes.
The main disadvantages of dyes are:
1) Concentration quenching the luminescence prevents
using high concentration of the dye in the transparent
matrix. 2) The light absorption in the dyes occurs in
bands of limited width. 3) Most of the dyes are not
sufficiently stable, and particularly strong degradation of
their properties takes place under the ultraviolet light. 4)
A significant overlap of the absorption and luminescence
spectra causes significant losses of luminescence
quantum due to their reabsorption. 5) The plate doped
with the dyes must have a significant thickness to
maximize light absorption. 6) The dyes have a low
luminescence quantum yield in the infrared range.
4.3. Quantum dots
Quantum dots (QDs) are nanocrystalline particles with
their size comparable or less than the Mott exciton
diameter. The size of semiconductor QD nanoparticles
lies typically in the range of 1 to 20 nm. In these QDs,
the energy of electrons and holes are quantized. This
results in formation of the large number of quantized
levels in the allowed band of energies (Fig. 9 [27, 28]).
In the case of strong quantization, when r < αe, αh (here r
is the radius of the nanoparticles, αe and αh are the Bohr
radius of electron and hole, respectively) the quantized
energy levels are:
henl
he
nl mkE ,
2
,
2,
, 2h= , (5)
where rk nlnl ,, ϕ= , l is the orbital quantum number,
n = 1,2,3, ... – radial quantum number, φl,n – universal
series of numbers equal to the serial number of the root
of Bessel functions (Table 1 [29]). The value φl,n does
not depend of r.
The absorption spectrum of the nanocrystals
originates from transitions between the size-quantized
levels of electrons and holes with the same quantum
numbers n and l (Fig. 9). In this case, the absorption
coefficient K depends on the photon energy as [30]:
∑ ⎟
⎠
⎞
⎜
⎝
⎛ξ
μ
+= −
nl
nl
nl r
rP
k
lAK
,
2/3
,2
,
2)12(
h
, (6)
where the constant A is proportional to the square of the
matrix element module, ( )hehe mmmm +=μ is the
reduced effective mass, ( ) 2
,
2
, 2 nlgnl kEh h−νμ=ξ ,
rk nlnl ,, ϕ= , gE – bandgap of bulk material, r –
average radius of nanocrystals, ( )rrP is the size
distribution function of nanocrystals.
Table 1. Roots of the Bessel functions φl, n [30].
l
n
1 2 3 4
0 3.142 6.283 9.425 12.566
1 4.493 7.725 10.904 14.066
2 5.764 9.095 12.323
3 6.988 10.417 13.698
4 8.183 11.705
5 9.356 12.967
6 10.513 14.207
7 11.657
8 12.791
9 13.916
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
237
Fig. 9. The energy spectrum of QD (left) and transitions that
form absorption and luminescence spectra (right). Eg0 is the
bandgap of the bulk semiconductor; A and L are transitions
that are involved in the absorption and emission of light.
Note that the absorption spectrum of a separate
quantum dot contains narrow delta-shaped bands. Due to
variation in size of nanocrystals the delta-shaped
absorption bands are spread and start overlapping, thus
forming a continuous absorption spectrum. Such
distribution is typical for any nanocrystal synthesis
technology, including the nanocrystals that can be
purchased [31]. A typical nanoparticle absorption
spectrum is shown in Fig. 10 [32, 33]. According to
Fig. 10, changing the size and type of semiconductor
nanoparticles allows to control the energy position of the
absorption spectrum of quantum dots. It is also seen that
apart of some oscillations due to dimensional
quantization, quantum dots absorption spectrum
resembles spectrum of the bulk semiconductors. Position
of the energy absorption bands in nanoparticles can be
described by the relation
,2)(2)(
)()(
22
,
22
, rmrm
absEEEabsEh
hnlenl
vol
g
h
q
e
q
vol
g
abs
ϕ+ϕ+
+=++=ν
hh
(7)
where )(absEvol
g is the bulk semiconductor bandgap,
e
qE and h
qE are the size quantization energy of electron
and hole, respectively, me and mh are the effective mass
of electron and hole, respectively, r is the radius of
nanoparticles, φl,n – constant (for the lowest quantum
level φl,n = 3.14). Therefore, changing the semiconductor
type and QD size, it is always possible to fit the
luminescence energy band to the maximum sensitivity of
photoconductor.
Luminescence spectra (Fig. 10) are due to electron
transition from the lowest electron quantization level to
the highest quantization level of hole (Fig. 9). The
fluorescent band width is determined by the spread of
nanoparticles sizes. Energy position of the luminescence
peak can be estimated as follows:
eh
h
q
e
q
PL
g
PL
ev EEEEh −++=ν (8)
reEhh eh
PL
ev
abs
0
2 48.1 πεε==ν−ν (9)
where ε and ε0 are the permittivity of semiconductor and
electric constant of vacuum, respectively. According to
(6), narrowing the nanoparticle size distribution results
in narrowing the luminescence band. Properly choosing
the average QD size r leads to reduction of the overlap
of the absorption and luminescence spectra, which
allows reabsorption to be negligible.
a)
b)
Fig. 10. а) Typical absorption and photoluminescence (PL)
spectra of CdSe quantum dots. The thick line represents
absorption and photoluminescence spectra of the quantum dots
with the mean diameter of 4.3±0.4 nm. The dashed line shows
absorption and photoluminescence spectrum from the 3.1±0.3-
nm quantum dots. It is clear that the absorption spectrum shifts
to the shorter wavelengths for smaller quantum dots [32].
b) Absorption (solid line) and PL (dotted line) spectra at 298 K
for colloidal ensembles of InP QDs with different mean
diameters. All QD colloidal samples were photoexcited at
2.48 eV [33].
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
238
Currently, the results of researches on the single
fluorescent quantum dots are available (see, e.g., [34-
36]). Specifically, the half-width lines luminescence of
the CdSe/ZnS core/shell quantum dots by various
estimates [34-36] are within the range from 1.5 to
4.4 GHz or 6.2 to 0.18 μeV. In particular, choosing the
optimal synthesis technology of PbSe nanoparticles,
their luminescence quantum yield can exceed 80% [37].
We have to note that apart from the exciton bands,
the impurity luminescence bands can be present due to
presence of the impurity atoms in the bulk of quantum
dots or their own defects. By choosing the optimal
synthesis technology, one can achieve dominance of the
exciton luminescence bands. On the other hand, coating
of the quantum dot with shells of the wide gap
semiconductor materials followed by deposition of a
surface-active layer of organic coating can provide
surface passivation of dangling bonds. This alleviates the
influence of the non-radiative recombination and
prevents coagulation of the quantum dots.
The advantages of QD based luminophores are [38]:
1) Crystalline semiconductor QDs of nanometer size
degrade less than organic dyes and their properties
can be kept constant throughout the decades.
2) High fluorescence quantum yield in QDs remains at
the room temperature. If full passivation of the QD
surface is achieved, the internal quantum yield of
quantum dots luminescence can be close to unity.
3) The absorption edge of QDs can be adjusted by
selecting their diameter.
4) The width of the absorption spectra of QD is large,
and it also covers the UV region.
5) When the defects in the bulk and on the surface of
the quantum dots are minimized, the exciton band
luminescence prevail and radiation in other bands
can be ignored. The width of the luminescence
spectrum is defined by the QD size distribution,
which in turn can be optimized by selecting proper
synthesis conditions. Reducing the QD size
distribution results in narrowing the width of the
exciton luminescence bands. In the absence of such
size distribution, the delta-function like band
luminescence is expected.
6) The separation of the absorption band and the
luminescence bands can be controlled by changing
the diameter of the quantum dots. This allows
minimizing the reabsorption influence on the
efficiency of solar photovoltaics.
7) The emission wavelength of QDs can be adjusted
to ensure the maximum sensitivity of the
photoconductor.
Disadvantages of luminophores with quantum dots
include:
1) Quantum yield of QD is somewhat smaller in
comparison with organic dyes.
2) QDs are substantially more expensive as compared
to dyes.
3) The overlap of absorption and emission in many
QDs is still not negligible.
4) The presence of water and oxygen ions affects on
properties of solutions of quantum dots.
5) The toxicity of the QD elements (such as, e.g., lead
and cadmium in CdS and PbS QDs) has to be
considered.
In conclusion: if QDs with high quantum efficiency
(> 0.99) can be inserted in the suitable transparent
media, the LSC high efficiency will be achieved.
4.4. Selecting luminophore
To facilitate the choice of the optimal type of
luminophores, their comparative characteristics are
shown in Table 2. The data presented in this table
suggest that preference should be given to the
fluorescent quantum dots since this type luminophore
allows achieving the maximum efficiency in converting
solar energy into electricity.
5. Photon transport losses
For the luminescent photoconverter to work efficiently, it
is necessary to minimize losses of quantum luminescence
during their transfer from luminophore to the solar cell.
These losses are associated with: (1) reabsorption due to
overlapping luminescent and absorption bands, (2) due to
a possible presence of the surface roughness hub, (3) the
presence of the Stokes shift, (4) leakage of the fluorescent
photons from the matrix, (5) with the reflection of the
light on the input surface of the solar cell. Here, we
analyze these losses in details.
Table 2. Properties of luminophores.
Parameter Rare-earth
atoms Dye Quantum dot
The shape of
the absorption
spectrum
Set of
narrow lines
(line width
< 5.10 nm)
Absorption
band width of
~300…650 nm
Great extend
The shape of
the spectrum of
luminescence
One or more
line widths
of < 5 nm
Luminescence
band width of
~100 nm
Wide band
~50 nm (with
a standard
synthesis
technology).
Luminescence
quantum yield
Low
~30…40%
for
> 800 nm.
~100% in the
visible spectrum
< 40% for
> 800 nm.
More than
80%
Reabsorption Absent Large
Significant at
standard
synthesis
technology
Spectral
agreement with
solar cell
Difficult to
implement
Easily to
implement
Easily to
implement
Stability
properties
Sustains over
hundreds of
years
Sustains for
several years
Sustains for
several
decades
The cost of
manufacturing
technology
High Low Medium
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
239
Fig. 11. Illustration of a narrow-band interferential filter. Luminescence photons contained within the cone escape through the
upper surface of the plate and are reflected back to the plate, pass through the plate and escape through the bottom surface.
5.1. Reabsorption [9, 14, 39]
In dyes and quantum dots (with a large spread of the
nanocrystal sizes), there is overlap of absorption and
luminescence spectra, which causes the reabsorption of
the luminescence quanta. At each act of reabsorption and
appropriate reradiation, a part of photons is lost and this
results in decrease of the quantum yield. Relation between
the number of reabsorption and reradiation acts j and the
quantum efficiency losses as a result of this process is
( ) j
ra L
η=η − , (10)
where Lη is the luminescence quantum yield. For
example, if Lη = 0.95, after 5 reabsorption-reradiation
acts (j = 5) ra−η = 0.77.
Therefore, only when the overlap of the absorption
and luminescence spectra is not available, we can
neglect the losses of the luminescence quanta caused by
the reabsorption and reradiation processes.
5.2. The losses due to leakage
Each luminescent center emits photons isotropically.
Among all the angles that the fluorescent photons are
distributed, there is a critical angle Ñβ , equals to the
angle of the total internal reflection
( )msÑ nnarcsin=β , (11)
where ns and nm are the index of refraction outside the
plate and of the concentrator plate material, respectively.
If the plate is surrounded by air, then ns = 1.
If propagation angles of the luminescence photons
Ñβ>β , then due to the total internal reflection the
photons are back into the hub plate. After a several
reflections from the concentrator surfaces, the photons
reach the input surface of the solar cell without losses,
i.e., the fluorescent photons propagate in the plate as in
an optical waveguide. Total internal reflection defines
waveguide properties of the plate luminescence
concentrator. However, in very thin plates as a result of
interference luminescence quenching can occur.
Description of the plane wave propagating inside an
infinite waveguide layer can be found in many
monographs (see, e.g., [41, 42]).
The energy of the photons that reach the solar cell
is converted into the electrical energy. Thus, the
concentrator can be considered as a transformer of the
broadband short-wave light into a narrow spectral
interval, energy location of which coincides with the
range of maximum sensitivity of the solar cell. It also
serves as a concentrator for collecting the light that falls
onto a large area of LSC input and sends it to a much
smaller area of the solar cell. In fact, the main
characteristic of the fluorescent photoconverter is the
efficiency LSCη of conversion of the energy of solar
photons into electrical energy.
If the angles of propagating luminescence photons
Ñβ<β , the luminescent quanta leave the concentrator
(see Fig. 3). The amount of these losses can be estimated
using the formula [14]
n
n
w
12 −
=η . (12)
Specifically for plates with a refractive index
n = 1.5, which are doped with luminophore, the
luminescence quanta that escape through the cone
towards the top of the concentrator plate is ~12.5%. The
same number of the luminescence photons leaves the
plate through its bottom surface.
The total internal reflection is a process without
loss of luminescent photons. However, the surface of the
luminescent concentrator is not perfect. The presence of
roughness on the surface causes the light scattering,
which also contributes to the losses. Also, a
contamination of the plate can seriously affect the
efficiency of the light waveguide.
The easiest way to reduce the leakage losses is to
use a filter that reflects escaping light back to the plate
solar concentrator (Fig. 11), thus reuse this light.
Reflection coefficient of the filter should be close to
100%, however it should reflect the fluorescent photons
in the plate and transmit the incoming photons of the
lower and larger energy light quanta (Fig. 12). The
multilayer interferential filters can be used for this, and
when using these filters one has to consider the
following issues.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
240
Fig. 13. Transmission spectra for various angles of incidence (in glass) of a right-handed cholesteric liquid crystals (CLC)
stacked on the top of the left-handed CLC. The pitch varies linearly from 437 up to 520 nm in the right-handed material and from
429 up to 521 nm in the left-handed material, respectively. Dashed lines indicate the experimental data, solid lines indicate
simulated results (taken from [42]).
Fig. 12. Сalculated reflection spectrum of an optimized Rugate
filter. This filter shows only a single reflectance peak and very
low reflection otherwise [9].
1) Luminescence quanta propagating in the
concentrator plate at larger than critical angles can
be reflected from the face and back surface of the
plate rather (hundreds of times) before they reach
the surface of solar cell.
2) The reflection bandwidth and its energy position
depend on the angle of incidence (Fig. 13 [42]). To
minimize the losses of fluorescent photons caused
by the light falling onto the surface of the filter at
different angles the refractive index of the plate
material should be as high as possible.
3) Since the coefficient of reflection for the
interference filter is always slightly less than unity,
if the reflection coefficient is 99%, the percentage
of photons which are left behind, for example, 100
reflections should be 0.99100 = 0.36, which is 36%.
If reflection of the fluorescent quanta is due to the
total internal reflection, 100% of the reflected
photons remain. This means that between the plate
and interference filter an air gap is required.
4) We have also to remember that the rays reflected by
the filter propagate in plate under the same angles,
under which they come out of the plate. This means,
if it has only the upper interference filter, then all
light propagating within the cone passes through the
plate. In the presence of filters located on face and
back surface of the plate, fluorescent photons within
the cone are completely lost due to absorption in the
matrix (in the absence of reabsorption).
5) The losses increase significantly when reabsorption
is available, because after each act of absorption
there is lost 25% of fluorescent quanta emitted
inside the cone towards the face and back surfaces
of the plate.
Therefore, to minimize leakage losses, reflector
should be separated from the plate luminescent
concentrator, and not put it directly on the surface of the
plate luminescent concentrator. Light, which comes out
from the back surface, should be used to excite the
luminophore in the plate, which is located under this
plate.
5.3. Losses due to reflection of the input surface of the
solar cell
In the luminescent concentrator, the solar cells are
optically related with the concentrator. If the fluorescent
quanta fall onto the solar cell face, a part of them is
reflected from the cell face. To reduce these losses, the
incoming surface of cells is made as a set of small
pyramids, and the antireflecting layer is deposited on the
surface of pyramids, it is usually silicon oxide. As a
result, the losses caused by reflection become negligible.
5.4. Losses due to the light absorption in the material
plate
The plate concentrator should satisfy the following
requirements [12]:
1. To be transparent to light of AM0 and AM1.5
spectra, that is to have close to 100% optical
transparency in the visible and near infrared regions.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
241
2. To allow doping of the plate, which provides
absorption of all light quanta in the required
spectral range Kd ≥ 5.
3. Doping the plate with luminophore should not
reduce the internal quantum yield of luminescence.
It should be maximized (preferably equal to unity).
4. To be chemically stable, ideally inert.
5. To have sufficient flexibility, i.e., the ability to
easily form plate of a given shape.
6. To be mechanically robust, the big plate of
luminescent concentrator should withstand its own
weight.
7. The matrix photostability must be high and not
change significantly over 20…25 years, i.e., during
the warranty period of solar panels.
8. To have a high resistance to atmospheric influences
(temperature fluctuations, wind, oxidation), ideally
within 20…30 years, i.e., during the solar cells
lifespan.
9. To have a low density of the plate material,
preferably < 1 g/cm3, so that the plate of
100 cm×100 cm×1 cm dimension has the weight
< 10 kg.
10. To be cost-efficient.
11. To have zero toxicity.
12. To have a high refractive index, required disclosure
to minimize light leakage from the cone.
13. Additional requirements for photovoltaic LC
matrix for space application are the stability of
matrices with respect to the radiation damage.
Most of these requirements are met by silica, glass,
and transparent organic plastics. The following
properties of silica are attractive for the matrix. This
material is transparent within the spectral region
0.2…3 mm (Fig. 14 [43]). The absorption coefficient of
the silica plates in this spectral region is very small. For
example when λ = 1 μm K =1·10–5 сm–1 [45]. The
melting point of silica is 1730 °C [44].
Another material that can be used to manufacture
the plate concentrator is glass. Among all glasses [45],
the most promising is borosilicate glass, particularly
N-BK7 type of the glass. The range of transmission for
this glass is shown in Fig. 15 [46]. The absorption
coefficient of this glass within the spectral range 370 to
1500 nm is less than 0.01 cm–1 [45]. Borosilicate glass
melting temperature depends on the composition and lies
in the range 1200…1500 °C [47].
Optically transparent polymers can be also used to
produce fluorescent concentrator plates. They are:
polymethyl methacrylate (PMMA), polyvinyl chloride
(PVC), polyethylene terephthalate (PET), and
polycarbonate (PC). Fig. 16 shows the transmission
range of some of these materials. It can be seen that the
difference between the transmission spectra of these
materials is negligible. However, in experimental
researches of the properties of luminescent concentrators
polymethyl methacrylate (organic glass) is mainly used.
It shows the average value of the absorption coefficient
of organic glass in the visible spectrum, which is about
0.001 cm–1. The mixture of luminophore (rare-earth
atoms, dyes, quantum dots) with monomer PMMA can
be polymerized at the temperatures of 140 °C < T <
170 °C [48]. These temperatures do not affect the
properties of organic dyes and the shell quantum dots.
So, among all the materials suitable for
manufacturing plate concentrator, preference should be
given to organic glass.
Fig. 14. The transmission spectrum of silica [43].
Fig. 15. The range of internal transmittance for the N-BK7
glass (taken from [46]).
Fig. 16. Transmission spectra of various plastic plates
(thickness of 2 mm). Various plastic materials: polymethyl
methacrylate (PMMA), polyvinyl chloride (PVC),
polyethylene terephthalate (PET), and polycarbonate (PC) −
were analyzed, and their transmission spectra are shown in this
figure. It was found that the transmittance differs depending on
material [48].
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
242
Fig. 18. The schematic distribution of fluorescent photons, used to calculate the geometric dimensions of the concentrator.
6. Design of fluorescent photoconductor
Consideration of the fluorescent concentrator design
includes selection of the geometric dimensions of the
plate concentrator, analysis of manufacture technology
suitable to form the stacked concentrators and attaching
the solar cells to the fluorescent concentrator, in
particular electrical connection of solar cells.
6.1. Influence of collector geometry
In the research of the fluorescent concentrator properties,
the plates are often made in shape of a quadrangle,
although they can be made in various shapes: triangle,
square, semi-circle [12]. The shape of the plate
influences on the uniformity of illumination of the end
surfaces. Best lighting uniformity at the end can be
achieved with a circular form since the light is
completely symmetrical. Assuming that the efficiency of
the solar cells has its highest value when they are made
of monocrystalline materials and have the form of plates,
the best compromise is to manufacture the concentrator
plates in the form of hexagonal prisms (Fig. 17).
Fig. 17. Possible shape of luminescent concentrators with
attached solar cells
The plate thickness should be chosen to fully
absorb the light by luminophore, it is sufficient when
Kd = 5. We assume that the light is fully absorbed by the
luminophore with K = 10 cm–1, and in this case, d =
0.5 cm. Typically, the plate thickness is within the range
of 0.2…0.5 cm and the sheet material (PMMA) can be
easily formed with this thickness. Too thin plates are not
strong enough to support the LSC. Conversely, a thicker
sheet will increase the weight of the LSC, which is also
not desirable. Therefore, we further assume that d =
0.5 cm.
In the absence of reabsorption, other geometric
concentrator dimensions define the absorption
coefficient of the matrix and the maximum part of
luminescent photons. For example, we define the
geometric parameters of the rectangular hub based on
PMMA.
Consider that the luminescent center is located in
the lower corner of the plate (Fig. 18). The longest path
is inherent to the beam originating from this center for
the angle equal to the angle Ñβ of the total internal
reflection. If on this path the loss of luminescence quanta
caused by light absorption in the matrix does not exceed
10%, then by the end of the path 90% of the quantum
luminescence will be available.
It means that in the PMMA plate with the
absorption coefficient 0.001 cm–1 in the visible spectral
region, the longest path for the luminescent photons
should not exceed ≈ 2300 cm. At the wavelength of
900 nm, the absorption coefficient in plexiglas is
0.05 cm–1. In this case, the maximum length of the
luminescence quantum propagation should not exceed
46 cm. Then, one can calculate the length LS and area SS
of the side face. For the plates with the absorption
coefficient Km = 0.001 сm–1 and Km = 0.05 сm–1, the
calculated LS values are equal to 1430 and 28.6 cm,
accordingly, and SS equals to 715 and 14.2 cm2. Finally,
we find the correspondent entrance area that equals to
4293184 and 818 cm2. Finally, we calculate the
maximum gain, which equals to 6004 and 57,
respectively.
6.2. The design of the stacked photoconverter
Fig. 19 shows one of the possible stacked concentrator
designs. The structure is a combination of interference
filters and fluorescent concentrators with the solar cells
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
243
attached to the plate. The thickness of the plates and
filters should be such to avoid deformation due to its
own weight. The air space should be present between the
filters and plates,. First, it is necessary to implement the
total internal reflection of the luminescence photons
emitted and then transported to the solar cell. Second,
the filter returns luminescent quanta that escape the cone
in the plate. To minimize the losses, the reflection
coefficient of the filter should be close to 100%. Third,
the filter transmittance must be also close to 100% for
the rest of sunlight. Since the above values cannot be
100%, a part of the luminescent quanta is lost.
Reduction of the above losses can only be achieved
using the narrow band luminescence and, therefore,
narrow band reflection filter. It means that preference
should be given to luminophore with a narrow
bandwidth of luminescence and wide spectral range,
within which light quanta are completely absorbed by
the luminophore. Only quantum dots with minimal sizes
can satisfy this requirement.
The disadvantage of the filters is the dependence of
the energy position of the reflection band on the angle of
incidence of the sunlight onto plate. It means that to form
the plates, it is necessary to choose materials with the
highest refractive index, which decreases the aperture of
the escape cone. Another negative factor is that the
tracking systems of the sun position are necessary.
Fig. 19. Schematic diagram of the stacked photoconverter
design.
The second concentrator is attached to the first one,
and the design elements are repeated. The third last
concentrator is attached to the second one with the
number of the same design elements. The last plate is
different, since it contains the attached lens or non-
imaging concentrator and solar cell.
One can use any glue or adhesive to attach the filter
to the plate. Information about the properties of the glue
and adhesives can be found, for example, in the
monograph [49]. To attach the solar cell to the plate, one
can use any glue, which is transparent in the visible and
infrared regions. Information about the properties of this
glue one can found, for example, in the monograph [50].
In the spectral band 320 to 2700 nm, Canadian balsam is
often used as optically transparent adhesive. If Canadian
balsam is 0.01-mm thick, then its transmission exceeds
99% [50].
Fig. 20 shows evolution of the light in the photo-
converter. At the top of stacked fluorescent concentrators,
the filter is placed. Let normally incident sunlight (for the
sake of being specific, AM1.5) illuminates the plate. The
filter reflects luminescent quanta (Fig. 20-1), which are
emitted by the luminophore of first concentrator in a
narrow band. The filter reflection coefficient should be
close to 100%. Transparence in a low and a high energy
bands should be close to 100%.
Light that passes through the first filter (Fig. 20-2)
enters to the first plate (for certainty, plate of PMMA).
High-energy light is absorbed by the luminophore that
generates luminescent quanta in the narrow band.
Approximately 82.5% of the luminescence quanta is
transported to solar cells attached to the first
concentrator plate (Fig. 20-3).
To avoid the losses of light during its transport to
the cells the gap should introduced between the filter and
plate. Approximately 12.5% of fluorescent photons
propagates toward the filter that reflects it back to the
plate. The photons passing through the plate without
absorption travel toward the second filter. In the same
direction, 12.5% of fluorescent photons travels, which
are emitted in the first plate within the critical cone
(Fig. 20-4).
Next, on the second filter 12.5% fluorescent
photons falls, which are emitted by quantum dots in the
first plate as well as rest sunlight. The second filter
reflects light in a narrow spectral range (Fig. 20-5),
which is emitted in the luminescence band of
luminophore of a second plate. Approximately 87.5% of
fluorescent quanta are transported to solar cells attached
to the plates of the second plate (Fig. 20-6). The
fluorescent photons out of the second plate and rest
sunlight photons fall onto the third interference filter
(Fig. 20-7). This filter reflects luminescent quanta
contained in the third plate (Fig. 20-8). Approximately
87.5% of fluorescent quanta are transported to solar cells
attached to the third plate (Fig. 20-9). Rest of fluorescent
photons goes out of the third plate (Fig. 20-9), and the
rest of sunlight is transported by non-imaging
concentrator directed to the solar cell (Fig. 20-10).
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
244
Fig. 20. Evolution of light in its distribution inside solar cells with fluorescent concentrators.
7. Discussion
The main purpose of this work is to predict the
properties of the solar cells with the fluorescent
concentrators and to identify the factors, the
implementation of which ensures maximum efficiency
of converting solar energy into electricity. When
considering the properties of solar cells, we explicitly or
implicitly supposed that they can convert into electrical
energy both photons of light directly falling onto the
concentrator and the photons of the scattered light. It is
also considered that for such solar cells the tracking
system is not required.
The key features are photoconverter stacked
fluorescent concentrators is that it can use the entire
spectrum of solar radiation, which spectrally fits the
solar cells. In this case, we have a freedom in choosing
the material to produce solar cells, and more freedom in
joining the cells.
Usage of the stacked plates can reduce the
temperature of the solar cell, since the thermal load
occurs in plates, not in the cells. It results in increase of
the efficiency of the solar cells.
To minimize the losses caused by leakage, one has
to use the interference filters that effectively reflect the
flow of escaping fluorescent photons and at the same
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
245
time are transparent for direct sunlight. Sunlight falls
onto the filter under large angles to this filter, which
requires the tracking systems. Besides, with the presence
of filters, the ability to use the diffuse light scattered in
all directions from the clouds, trees, variety facilities is
lost. Impossibility to use scattered light by filtering
systems and need to expend the energy for managing
systems following the sun indicate inappropriate
development of solar cells with fluorescent concentrators
with the band-pass filters introduced to them.
8. Conclusions
Our comparison of the properties of materials suitable
for making plates for luminescent concentrators allows
us to give a preference to silica, and in assessing the real
values of the efficiency – to polymethyl methacrylate.
From a comparison of the properties of such
luminophores as ions of rare-earth metals, dyes,
semiconductor quantum dots, we can conclude that for
the doped concentrator plates the use of the quantum-
dimensional nanocrystals is most appropriate.
Inability to use ambient diffuse light to convert its
energy into electrical energy and the need to use extra
energy for the tracking systems allow us to conclude that
the use of the luminescent solar concentrators with the
interference filters are not justified.
References
1. O. Semonin, J.M. Luther and M.C. Beard, Multiple
exciton generation in a quantum dot solar cell // 26
March 2012, SPIE Newsroom. DOI:
10.1117/2.1201203.004146
2. W. Shockley and H.J. Queisser, Detailed balance
limit of efficiency of p-n junction solar cells // J.
Appl. Phys. 32(3), p. 510-519 (1961).
3. M.A. Green, K. Emery, Y. Hishikawa, W. Warta
and E.D. Dunlop, Solar cell efficiency tables
(version 43) // Prog. Photovolt.: Res. Appl. 22(1),
p. 1-9 (2014).
4. J.F Geisz, S. Kurtz, M.W. Wanlass, J.S. Ward,
A. Duda, D.J. Friedman, J.M. Olson, W.E.
McMahon, T.E. Moriarty, J.T. Kiehl, High-
efficiency GaInP/GaAs/InGaAs triple-junction
solar cells grown inverted with a metamorphic
bottom junction // Appl. Phys. Lett. 91, No.2, р.
023502 (2007).
5. L. Mearian, New solar cell sets world record,
focusing the power of 297 suns // News
September 26, 2013 03:53 PM ET;
http://www.computerworld.com/article/2597774/
emerging-technology/new-solar-cell-sets-world-
record-focusing-the-power-of-297-suns.html; Mark
Osborne, Quadruple III-V bonded CPV cell hits
44.7% record conversion efficiency // 24
September 2013, 16:12 In News, Thin Film, III-V;
http://www.pv-tech.org/news/quadruple_iii_v_bon-
ded_cpv_cell_hits_44.7_record_conversion_effi-
ciency
6. A.V. Sachenko, M.R. Kulish, I.O. Sokolovskyi, V.P.
Kostylyov, Lateral multijunction photovoltaic cells //
Semiconductor Physics, Quantum Electronics &
Optoelectronics, 16, No.1, p. 1-17 (2013).
7. M.A. Green and A. Ho-Baillie, Forty three per cent
composite split-spectrum concentrator solar cell
efficiency // Prog. Photovolt.: Res. Appl. 18, p. 42-
47 (2010).
8. Lo Chin Kim, Simulation and construction of
luminescent solar concentrator // A master thesis
submitted to the Department of Electrical and
Electronic Engineering, Faculty of Engineering and
Science, University Tunku Abdul Rahman, in
partial fulfillment of the requirements for the
degree of Master of Engineering Science,
November 2011, р. 1-262.
9. J.C. Goldschmidt, Novel solar cell concepts //
Dissertation zur Erlangung des akademischen
Grades des Doktors der Naturwissenschaften (Dr.
rer. nat.) an der Universität Konstanz Fachbereich
Physik, Fraunhofer Institut für Solare
Energiesysteme (ISE), Freiburg, September 2009,
р. 1-280.
10. L.H. Slooff, E.E. Bende, A.R. Burgers, T. Budel,
M. Pravettoni, R.P. Kenny, E.D. Dunlop,
A. Buechtemann, A luminescent solar concentrator
with 7.1% power conversion efficiency // Physica
Status Solidi (RRL), 2(6), p. 257-259 (2008).
11. J. Gutmann, M. Peters, B. Bläsi, M. Hermle,
A. Gombert, H. Zappe, J.C. Goldschmidt,
Electromagnetic simulations of a photonic
luminescent solar concentrator // Opt. Exp. 20, No.
S2, p. A157-A167 (2012).
12. T.J.J. Meyer, Photon Transport in Fluorescent
Solar Collectors // Doctoral Thesis, University of
Southampton, School of Engineering Sciences,
2010.
13. G. Dieke, Spectra and Energy Levels of Rare Earth
Ions in Crystals. Interscience Publ., New York,
1968.
14. L.R. Wilson, Luminescent Solar Concentrators:
A Study of Optical Properties, Re-absorption and
Device Optimization // Doctor of Philosophy.
Department of Mechanical Engineering School of
Engineering & Physical Sciences, Heriot-Watt
University, Edinburgh EH14 4AS, United
Kingdom, May 2010.
15. A.K. Gupta and S.K. Ujjwal, Optical absorption
spectra of rare earth elements with amino acid in
different solvents // Adv. in Appl. Sci. Res. 4(3),
p. 33-38 (2013).
16. A.K. Gupta, and S.K. Ujjwal, Absorption spectra of
praseodymium with amino acid // Res. J. Phys. Sci.
1(4), p. 7-10 (May 2013).
17. R. Van Deun, P. Fias, P. Nockemann, K. Van
Hecke, L. Van Meervelt, and K. Binnemans,
Visible-light-sensitized near-infrared luminescence
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
246
from rare-earth complexes of the 9-hydro-
xyphenalen-1-one ligand // Inorg. Chem. 45,
p.10416-10418 (2006).
18. K. Binnemans, P. Lenaerts, K. Driesen and
C. Gorller-Walrand, A luminescent tris(2-
thenoyltrifluoroacetonato)europium(III) complex
covalently linked to a 1,10-phenan-
throlinefunctionalised sol–gel glass // J. Mater.
Chem. 14, p. 191-195 (2004).
19. X. Zhang, S. Wen, S. Hu, L. Zhang, L. Li,
Electrospinning preparation and luminescence
properties of Eu(TTA)3phen/polystyrene
composite nanofibers // J. Rare Earths, 28, No. 3,
p. 333-339 (June 2010).
20. T. Förster, Intermolecular energy migration and
fluorescence // Ann. Phys. 2, p. 55-75 (1948).
21. D.L. Dexter, Theory of optical properties of
imperfections in nonmetals // Solid State Phys. 6
(Eds. F. Seitz and D. Turnbull), p. 353-411 (1958),
Academic Press.
22. J.-C.G. Bünzli, S.V. Eliseeva, Lanthanide NIR
luminescence for telecommunications, bioanalyses
and solar. Review // J. Rare Earths, 28, No. 6,
p. 824-842 (Dec. 2010).
23. J.-C.G. Bünzli and A.-S. Chauvin, Lanthanides in
solar energy conversion. In: Handbook on the
Physics and Chemistry of Rare Earths, Eds. J.-
C.G. Bünzli and V.K. Pecharsky, Vol. 44.
Amsterdam, The Netherlands, 2014, p. 169-281.
24. J.S. Batchelder, The luminescent solar concentrator
// Thesis for the degree doctor of philosophy.
California Institute of Technology, Pasadena,
California, 1982, p. 1-287.
25. Catalogue of Active Laser Media Based on
Solutions of Organic Dyes and Related
Compounds, Ed. V.I. Stepanov. Institute of Physics
of Academy of Sciences of Byelorussian SSR,
Minsk, 1977 (in Russian).
26. Mono Crystalline Silicon PV Module SF-125×125-
72-M/L/D // Zhejiang Sunflower Light Energy
Science & Technology Co. Ltd. www.sunowe.com;
Monocrystalline Silicon Solar Module // Eoplly
New Energy Technology Co., Ltd www.eoplly.com;
Supplementary Warranties Applicable to Bosch
Solar c-Si Series of Photovoltaic Modules Supplied
by Robert Bosch (Australia) Pty Ltd in Australia
after 1st January 2012 // www.bosch-
solarenergy.com.au.
27. N.R. Kulish, V.P. Kunets, M.P. Lisitsa,
N.I. Malysh, Evolution of absorption spectra when
transferring from bulk to quantum-sized crystals
CdSXSe1-X // Ukrainskii Fizicheskii Zhurnal, 37,
№8, p. 1141-1146 (1992), in Russian.
28. N.R. Kulish, V.P. Kunets, M.P. Lisitsa, Optical
properties of quasi-zero-dimensional CdSXSe1-X
crystallites grown in a glass matrix // Opt. Eng. 34,
No. 4, p. 1054-1071 (1995).
29. S. Flügge, Practical Quantum Mechanics.
Springer-Verlag, Berlin – Heidelberg, 1999.
30. A.L. Efros and A.L. Efros, Interband light
absorption in semiconductor sphere // Fizika
tekhnika poluprovodnikov, 16(7), p. 1209-1214
(1982), in Russian.
31. Nanomaterials and related products catalogue &
price-list // PlasmaChem. Surface and Nano-
Technology, 2014, p. 1-48.
32. A. Irman, Modification of Spontaneous Emission
of Quantum Dots by Photonic Crystals //
Graduation Thesis 11 November 2003. Complex
Photonic Systems (COPS) Group MESA+ Institute
Faculty of Science and Technology University of
Twente, Enschede, The Netherlands. P. 1-48.
33. O.I. Mićic, H.M. Cheong, H. Fu, A. Zunger,
J.R. Sprague, A. Mascarenhas, and A.J. Nozik,
Size-dependent spectroscopy of InP quantum dots
// J. Phys. Chem. B, 101, p. 4904-4912 (1997).
34. S.A. Blanton, M.A. Hines, P. Guyot-Sionnest,
Photoluminescence wandering in single CdSe
nanocrystals // Appl. Phys. Lett. 69(25), p. 3905-
3907 (1996).
35. A.P. Alivisatos, Electrical studies of
semiconductor-nanocrystal colloids // MRS
Bulletin, 23, Issue 2, p. 18-23 (1998).
36. M.J. Fernée, C. Sinito, Y. Louyer, P. Tamarat and
B. Lounis, The ultimate limit to the emission
linewidth of single nanocrystals // Nanotechnology,
24, 465703 (5p.) (2013).
37. H. Du, C. Chen, R. Krishnan, T.D. Krauss,
J.M. Harbold, F.W. Wise, M.G. Thomas, and
J. Silcox, Optical properties of colloidal PbSe
nanocrystals // Nano Lett. 2, No. 11, p. 1321-1324
(2002).
38. B. Norton, P.C. Eames, T.K. Mallick, Ming Jun
Huang, S.J. McCormack, J.D. Mondol,
Y.G. Yohanis, Enhancing the performance of
building integrated photovoltaics // Solar Energy,
85, p. 1629-1664 (2011).
39. S. Peeters, Reabsorption Losses in Luminescent
Solar Concentrators // Masterproef ingediend tot
het behalen van de academische graad van Master
in de ingenieurswetenschappen: fotonica
Academiejaar 2010-2011. P. 1-72.
40. N.J. Cronin, Microwave and Optical Waveguides.
CRC Press, 1995.
41. R.R.A. Syms and J.R. Cozens, Optical Guided
Waves and Devices. McGraw-Hill, 1992.
42. D.K.G. de Boer, D.J. Broer, M.G. Debije, W. Keur,
A. Meijerink, C.R. Ronda, and P.P.C. Verbunt,
Progress in phosphors and filters for luminescent
solar concentrators // Opt. Exp. 20, No. S3,
p. A395-А405 (2012).
43. International Crystal Laboratories. Optics &
Spectroscopy Supplies & Accessories. Tel. (973)
478-8944. Fax. (973) 478-4201.
44. Fused Silica (FS) // Del Mar Ventures. 4119
Twilight Ridge, San Diego, CA 92130, tel: (858)
876-3133, fax: (858) 630-2376, optics@sciner.com,
http://www.sciner.com/Opticsland.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 3. P. 229-247.
doi: 10.15407/spqeo19.03.229
© 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
247
45. Optical glass/ Data sheet // Schott North America,
Inc. Advanced Optics. 400 York Avenue Duryea,
PA 18642 USA/ info.optics@us.schott.com;
www.us.schott.com.
46. TIE-35: Transmittance of optical glass // October
2005. Optics for Devices SCHOTT North America,
Inc. 400 York Avenue Duryea, PA 18642 USA,
E-mail: sgt@us.schott.com; www.us.schott.com/
optics_devices
47. H. Cao, J.W. Adams and P.D. Kalb, Low
Temperature Glasses for Hanford Tank Wastes //
Annual Report. FY 1995. Environmental Sciences
Department Brookhaven National Laboratory
Brookhaven Science Associates Upton, Long
Island New York, 11973, Under Contract No. DE-
AC02-98CH10886 with the UNITED STATES
DEPARTMENT OF ENERGY.
48. Measurement of Optical Characteristic of Plastic by
UH4150 Spectrophotometer. An example of High
Throughput measurements in the UV, Visible and
Near-Infrared Regions // Hitachi High-
Technologies Corporation.
49. D.W. Swanson, J.J. Licari, Adhesives Technology for
Electronic Applications – Materials, Processing,
Reliability. Materials and Processes for Electronic
Applications. Elsevier Science, August 2005.
50. Handbook for designer of optical-and-mechanical
devices / V.А. Panov, M.Ia. Kruger, V.V. Kulagin
et al. Mashinostroenie, Leningrad, 1980 (in
Russian).
|