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On the Quantum Yield of Photon

Upconversion via Triplet−Triplet Annihilation
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P hoton upconversion (UC), the process of combining two

or more low-energy photons to generate a higher-energy
excited state, is of interest for applications ranging from
imaging to photodynamic therapy to solar energy conversion. Of
the available UC mechanisms, molecular upconversion through
In this Viewpoint, we propose an
updated labeling scheme for describ-
ing quantum yield in TTA-UC so as to
better facilitate communication and
Downloaded via 5.51.142.57 on March 20, 2023 at 11:19:50 (UTC).

sensitized triplet−triplet annihilation (TTA-UC) is particularly

appealing because it can be achieved with low intensity, comparisons across applications, ma-
noncoherent irradiation.1 terials, and intervening events and to
TTA-UC was first observed in the 1960s2 but largely introduce more consistency in the
remained dormant until a renaissance in the early 2000s. This
revival was facilitated, in part, by the increasing availability of
scientific literature.
new transition-metal-containing sensitizers and the recognition
that they could be used to increase both the efficiency and the
apparent anti-Stokes shift of TTA-UC.3 Subsequently, there was
an explosion of new molecules, mediums, motifs, and
applications, as well as new insight into the TTA-UC
mechanism.4−7
Unfortunately, there was, and still is, growing diversity in the
terminology for TTA-UC, including concepts as fundamental as
the upconversion quantum yield (ΦUC). Most commonly, but
not always, ΦUC describes the emission quantum yield (# of UC
photons emitted/# of photons absorbed by the sensitizer) or the
normalized yield to scale the maximum theoretical efficiency
from 50% to 100% (2 × emission quantum yield due to the two
photon nature of TTA-UC). This discussion is further
complicated by more recent applications of TTA-UC in Figure 1. Energy level diagram, mechanism, and the states/species
integrated UC solar cells8,9 and synthetic organic chemistry10,11 in TTA-UC facilitated by a molecular sensitizer (S) and annihilator
where no upconverted emission is observed but there is still an (A) pair.
upconversion quantum yield (# of UC excited states generated/
# of photons absorbed by the sensitizer). Briefly, upon light absorption, the sensitizer (S) is excited (EX
Sometimes the author’s chosen definition of ΦUC is in Figure 1) into its singlet excited state (1S*) followed by
immediately introduced. In other instances, the reader must intersystem crossing (ISC) into the triplet excited-state
diligently search the Supporting Information, or the definition is manifold (3S*). Then, sensitizer-to-annihilator (A) triplet
not given at all. This disparate terminology complicates the energy transfer (TET) results in an annihilator triplet excited-
interpretation and direct comparison between TTA-UC experi- state species (3A*). When two 3A* collide, they can annihilate
ments across different research groups. In this Viewpoint, we (TTA), with one relaxing back to its ground state and the other
propose an updated labeling scheme for describing quantum being promoted to its higher-energy singlet excited state (1A*).
yield in TTA-UC so as to better facilitate communication and Once in the upconverted, 1A* state, this molecule can undergo
comparisons across applications, materials, and intervening
events and to introduce more consistency in the scientific
literature. There is a large body of published work leading to this Received: May 26, 2020
discussion, but because of space limitations, we regret that we Accepted: June 4, 2020
cannot cite all of these works here. Published: June 22, 2020
The generally accepted mechanism for TTA-UC using a
molecular sensitizer (S) and annihilator (A) pair is presented in
Figure 1.

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsenergylett.0c01150

2322 ACS Energy Lett. 2020, 5, 2322−2326
ACS Energy Letters http://pubs.acs.org/journal/aelccp Viewpoint

nonradiative decay, radiative relaxation (EM), sensitize a Table 2. Yield Calculations for Key Steps and Processes in
different species (sen) either through trivial or nontrivial TTA-UC
mechanisms, or nonproductively back energy-transfer to the
yield equation
sensitizer molecule (ET). Singlet oxygen sensitization (OS) can
also serve as quenching processes for the 3S* and 3A* states but ΦLH =
#1S*
light harvesting
is most likely to occur for the latter because of its orders of #hνin
magnitude longer excited-state lifetime. Additionally, steps like # 3 S*
singlet sensitization,12,13 cooperative/cascading sensitiza- ISC ΦISC =
#1S*
tion,14,15 and/or singlet exciton sinks16 can readily be
incorporated into the scheme but are omitted here for clarity. 3 #3 A *
S* to 1A TET ΦTET =
Crucial to quantum yield determinations is the number of # 3 S*
photons and species (# y) involved in each step of TTA-UC. #1 A *
TTA ΦTTA =
These species are highlighted in orange in Figure 1 and #3 A *
summarized in Table 1. Using the terms in Table 1, the quantum #hνgen
A fluorescence Φf =
#1 A *
Table 1. Key States and Species That Are Generated during
#1S*
TTA-UC 1
A* to S ET ΦET =
#1 A *
label number represented #hνobs
optical outcoupling Φout =
# 1S* sensitizers in the singlet excited state #hνgen
# 3S* sensitizers in the triplet excited state
# 1A* annihilators in the singlet excited state #1 A *
UC state ΦUCs =
# 3A* annihilators in the triplet excited state #1S*
# hνin incident photons #hνgen
UC photons generated ΦUCg =
# hνgen UC photons generated #1S*
# hνobs UC photons observed #hνobs
# R′ UC sensitized species (R′ = R−; R+; R*) UC EM observed ΦUC =
#1S*
# 1O2* singlet oxygen generated
1 #R′
A* to R sen Φsen =
#1 A *
yield of any single or multistep process can be defined (Φ = # y/ #R′
ΦUCsen =
# z) with several of the most common/important shown in UC sen
#1S*
Table 2. For example, the 3S* to 1A TET yield (ΦTET) is the
#1O2
resulting number of annihilators in the triplet excited states (# O2*
1
ΦOS =
3 #1S*
A*) divided by the initial number of sensitizer triplet excited
states (# 3S*). Although not discussed in detail here, these can
also be related to the relaxation rate constants (i.e., ΦTET = rate Given the traditional and IUPAC defi-
of TET divided by the sum of all relaxation rates from 3S*).17
Experimentally we do not directly count the numbers of these nition of quantum yield (Φ = # of A/# of
species, but they can be indirectly determined using a B), we strongly encourage the com-
combination of steady-state and time-resolved spectroscopic munity to discontinue this normal-
techniques.18,19 ization practice (i.e., 2 × ΦUC), or if they
Of the quantum yields listed in Table 2, it is worth
highlighting the differences between ΦUC, ΦUCg, and ΦUCs. do, to label the result as the normalized
Here we have defined ΦUC as the measured TTA-UC emission upconversion emission efficiency (ηUC).
quantum yield. That is, the number of UC photons observed (#
hνobs) divided by the number of photons absorbed (# 1S*,
assuming higher-energy excited states, 1Sn*, undergo internal instead dependent on the sample architecture and the method of
conversion prior to ISC). Because of the two-to-one photon measurement (i.e., relative vs absolute). Output losses include
nature of TTA-UC, the maximum theoretical value of ΦUC is 0.5 waveguiding, scattering, inner filtering effects, etc. which are
or 50%. This measured value is sometimes multiplied by two or path length and sample holder dependent.22 With the
normalized to 1.0 or 100% (i.e., ΦUC or ΦUC′). Curiously, in the appropriate reference measurement, some of these losses are
singlet fission literature (SF; a one photon in, two excited states accounted for with an integrating sphere.23 Alternatively, Φout
out process) there are no instances of dividing the SF yield by can be estimated by dividing the emission quantum yield for
two. Presumably, this is because in both TTA and SF, bigger direct excitation of A in the TTA-UC architecture, but without
numbers are “better”. Nonetheless, given the traditional and sensitizer, by the fluorescence quantum yield for dilute A in a
IUPAC20 definition of quantum yield (Φ = # of A/# of B), we comparable chemical environment.
strongly encourage the community to discontinue this normal- Arguably the most literal definition of upconversion quantum
ization practice (i.e., 2 × ΦUC), or if they do, to label the result as yield is ΦUCs or the number of upconverted states generated (#
the normalized upconversion emission efficiency (ηUC). 1
A*) per the number of photons absorbed (# 1S*). ΦUCs is the
In addition to ΦUC we have defined the quantum yield of upconversion yield prior to 1A* to S energy transfer,
photons generated (ΦUCg) with the difference being the output nonradiative decay, sensitization, and output coupling losses,
coupling yield (Φout).21 The reason for this distinction is that and thus, regardless of the application (e.g., emission or
ΦUC is not necessarily intrinsic to the TTA-UC system but sensitization) it can be compared across all TTA-UC systems.
2323 https://dx.doi.org/10.1021/acsenergylett.0c01150
ACS Energy Lett. 2020, 5, 2322−2326
ACS Energy Letters http://pubs.acs.org/journal/aelccp
Table 3. Equations Relating ΦUCs, ΦUCg, ΦUC, ΦUCsen, and ΦUCsenx to Preceding Steps and the Measurable ΦUC
from stepsa
UC state ΦUCs = ΦISC ·ΦTET ·ΦTTA
UC photons ΦUCg = ΦUCs ·Φf ·(1 − ΦET)
ΦUC = ΦUCg ·Φout
UC sensitization ΦUCsen = ΦUCs ·Φsen
ΦUCsenx = ΦUCsen ·ΦLH
a
Competitive quenching by oxygen is omitted for simplicity but could be included by multiplying by (1 − ΦOS).
Also, it is worth noting that here we have defined ΦTTA as the
number of 1A* generated per 3A* (ΦTTA ≤ 0.5). TTA can also
result in higher-energy triplet excited states (i.e., 3A* + 3A* =
3
An* + 1A), but this product yield is omitted from ΦTTA because
the net process is nonproductive (2 × 3A* to 3A*) and the
resulting 3A* can return to the reaction pool to further undergo
TTA.19 TTA efficiency is sometimes partitioned into the
efficiency of generating a contact pair and a spin-statistical factor
for the fraction of contact pairs that generate a singlet ( f).24
Given the difficulty in measuring the latter, the debate regarding
the rigorousness of the spin selection rules,19,25−27 and reports
suggesting interconversion between quintet and triplet corre-
lated pairs,28−30 we argue that ΦTTA as defined here is a more
general and encompassing definition. ΦTTA can then be further
partitioned into contact pair formation efficiency (Φcp) and a
spin-fraction (f) components (ΦTTA = Φcp·f). As mentioned
above with UC, one could also report the normalized TTA
efficiency (2 × ΦTTA = ηTTA).
The yields can then be related to each other using the
equations presented in Table 3. They have been partitioned into
equating ΦUCs, ΦUCg, etc. to (1) the individual steps or (2)
experimentally measurable parameters. For the additive steps,
we simply multiply by Φy and 1 − Φy for the productive and
nonproductive processes, respectively. While conceptually
convenient, it is far more likely to use experimentally measurable
parameters (ΦUC, Φf, ΦET, Φout, and ΦLH) to calculate ΦUCs,
ΦUCg, etc. as shown in the far-right column of Table 3. However,
through a combination of both columns, important but difficult
to directly measure parameters like ΦTTA can be determined.
One caveat with these calculations is that it only assumes the
reaction pathways shown in Figure 1. Care must be taken to rule
out and/or account for other quenching mechanism like those
involving redox active species and solvent-dependent processes,
for example.31
For applications such as solar energy conversion, the
efficiency metric of interest is based not on the number of
absorbed photons (# 1S*) but instead on the number of incident
photons (# hνin). To account for this, we can include ΦLH (#
1
S*/# hνin), also known as light-harvesting efficiency or LHE, as
a multiplier to convert any of the above yields from the internal
quantum efficiency (Φy) to the external quantum efficiency
(Φyx) as exemplified for ΦUCsenx in the bottom row of Table 3.
The difference being the absorption cross section and the
spectral overlap between the light source and the sensitizer
absorption.
2324
Viewpoint
equations
from measured ΦUC
ΦUC
=
Φf ·(1 − ΦET)·Φout
ΦUC
=
Φout
measured
ΦUC
= ·Φsen
Φf ·(1 − ΦET)·Φout
ΦUC
= ·Φsen ·ΦLH
Φf ·(1 − ΦET)·Φout
The above discussion is focused on molecular sensitizers.
However, recently, inorganic materials like quantum dots32,33
and perovskite nanoparticles/thin films34,35 have emerged as
effective triplet sensitizers for TTA-UC. While a majority of the
discussion holds true for inorganic sensitizers, there are a few
distinct differences worth noting that are highlighted in Figure 2.
Figure 2. Energy level diagram, mechanism, and the states/species
in TTA-UC facilitated by an inorganic sensitizer (IS), triplet energy
relay molecule (Ar), and molecular annihilator (A). Redundant steps
from Figure 1 are deemphasized for clarity.
The first change is that because of the small energetic
difference and/or indistinguishable nature of the spin states, the
inorganic sensitizers (ISs) lack distinct 1IS* and 3IS* and that
ΦISC is likely unnecessary.36 As such, the excited state is simply
labeled here as IS*.
Second, because of their short lifetime, they typically employ a
surface bound, molecular triplet energy transfer relay (Ar) to
store a long-lived triplet state on the surface prior to TET to A in
solution (ΦTET). This adds an additional, sometimes reversible,
TET to relay step, labeled here as TETr and ΦTETr.37 Back
energy transfer can also occur from 1A* to either the triplet
sensitizer (ΦET) or the relay (ΦETr) with the former typically
being more dominant because of the broad band absorbing
nature of IS. The intense, broad absorption of IS also results in
increased losses because of inner filtering (i.e., lower Φout) which
in turn decreases ΦUC. Nonetheless, the above expressions can
readily be applied to IS systems by removing ΦISC and
multiplying by ΦTETr and 1 − ΦETr. Likewise, similar modeling
can be envisioned for thermally activated delayed fluorescence
(TADF) sensitizers where ISC becomes reversible (rISC).38
As an aside, we have three additional comments, not directly
related to quantum yield, regarding standardization in the TTA-
https://dx.doi.org/10.1021/acsenergylett.0c01150
ACS Energy Lett. 2020, 5, 2322−2326
ACS Energy Letters http://pubs.acs.org/journal/aelccp
UC literature. The first is in reporting of the “anti-Stokes shift.”
By IUPAC standards, a Stokes shift is defined by the energy
difference (in eV or cm−1) between the peak maxima of
absorption and emission of the same electronic transition.20
Because TTA-UC absorption and emission processes are not
derived from the same electronic transition, it is more
appropriately described as an apparent anti-Stokes shift.
Additionally, the magnitude of the apparent anti-Stokes shift
should be reported as the difference between the lowest energy
absorption peak of the sensitizer and emission peak of the
annihilator,39 and not the excitation wavelength. The former is
based on the intrinsic properties of the molecules and is constant
for a given sample. The latter is dictated by the excitation source,
and even for the same TTA-UC sample, this value will change
depending on the availability of excitation sources. Additionally,
the latter can be deceptive in that you can make the shift
artificially larger by using a higher-intensity laser and exciting
into a low energy absorbance shoulder.
Second is that the Ith value, the onset threshold intensity for
the maximum efficiency regime,40 should be reported in terms of
both raw source intensity (mW/cm2) and excitation density (ex
s−1 cm−2; photon flux × absorptance at λex).12 The former is
useful because it allows for direct comparisons to solar flux
available at that wavelength (vida infra) but is limited in that it is
excitation wavelength-dependent. The latter (i.e., ex s−1 cm−2)
enables a direct comparison between systems with different
light-harvesting efficiencies, excitation wavelengths, and less
than ideal overlap between laser sources and the absorption
maximum of the sensitizer.
Finally, TTA-UC activated at subsolar light f lux does not
simply mean exciting the sample with monochromatic light at
intensities <100 mW/cm2. For the AM1.5 solar spectrum, 100
mW/cm2 is the integrated intensity over the entire solar
spectrum ranging from 250 to 2500 nm. When comparing
monochromatic excitation to solar intensities, it is pivotal to only
integrate the AM1.5 solar spectrum over the sensitizer excitation
range (i.e., the fwhm of the laser or the sensitizer absorption
peak), which is typically <5 mW/cm2. In line with this point, we
strongly encourage authors to discontinue subjective and
qualitative descriptions of incident power (e.g., extremely low
power, ultralow intensity, etc.), because (1) “low power” means
very different things in solar energy conversion and photo-
dynamic therapy, for example, and (2) there are much more
quantitative ways to define these terms.
To summarize, here are the major take-home messages from
this Viewpoint:
• We propose that the TTA-UC emission quantum yield
(ΦUC) is the number of UC photons observed per the
number of photons absorbed (i.e., the traditional
definition of light emission quantum yield).
• We strongly discourage the use of the 2 × Φ UC
normalization factor, but if used, it should be clearly
indicated as the normalized TTA-UC emission efficiency
(ηUC).
• Care should be taken in noting any output coupling losses
because it is the difference between the observed (ΦUC)
and the intrinsic (ΦUCg) TTA-UC emission quantum
yield.
• Determining the yield of upconverted states (ΦUCs), prior
to relaxation, enables comparison across all TTA-UC
systems and applications.
2325
Viewpoint
• The magnitude of the apparent anti-Stokes shift should be
reported based on the difference between the emission
peak of the annihilator and lowest energy absorption peak
of the sensitizer, not the excitation wavelength.
• The Ith value should be reported in terms of both source
intensity (mW/cm2) and excitation density (ex s−1 cm−2).
• When claiming TTA-UC occurs at subsolar flux, authors
should only integrate the spectrum over the excitation
range (<5 mW/cm2) and not the entire solar spectrum
(100 mW/cm2).
• Authors should avoid qualitative descriptions of incident
light power when more quantitative descriptions are
readily available.
Yan Zhou orcid.org/0000-0002-7290-1401
Felix N. Castellano orcid.org/0000-0001-7546-8618
Timothy W. Schmidt orcid.org/0000-0001-6691-1438
Kenneth Hanson orcid.org/0000-0001-7219-7808
■
AUTHOR INFORMATION
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsenergylett.0c01150
Notes
Views expressed in this Viewpoint are those of the authors and
not necessarily the views of the ACS.
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Y.Z. and K.H. were supported by the National Science
Foundation under Grant No. DMR-1752782. F.N.C. was
supported by the U.S. Department of Energy, Office of Science,
Office of Basic Energy Sciences, under Award No. DE-
SC0011979. T.W.S. was supported by the Australian Research
Council (Centre of Excellence in Exciton Science
CE170100026).
■
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ACS Energy Lett. 2020, 5, 2322−2326