Molecular control of energy transfer is an attractive proposition because it allows chemists to synthetically tweak various kinetic and thermodynamic factors. In this Perspective, we examine energy transfer between semiconductor nanocrystals (NCs) and π-conjugated molecules, focusing on the transmitter ligand at the organic–inorganic interface. Efficient transfer of triplet excitons across this interface allows photons to be directed for effective use of the entire solar spectrum. For example, a photon upconversion system composed of semiconductor NCs as sensitizers, bound organic ligands as transmitters, and molecular annihilators has the advantage of large, tunable absorption cross sections across the visible and near-infrared wavelengths. This may allow the near-infrared photons to be harnessed for photovoltaics and photocatalysis. Here we summarize the progress in this recently reported hybrid upconversion platform and point out the challenges. Since triplet energy transfer (TET) from NC donors to molecular transmitters is one of the bottlenecks, emphasis is on the design of transmitters in terms of molecular energetics, photophysics, binding affinity, stability, and energy offsets with respect to the NC donor. Increasing the efficiency of TET in this hybrid platform will increase both the up- and down-conversion quantum yields, potentially exceeding the Shockley–Queisser limit for photovoltaics and photocatalysis.

AbstractA sub-monolayer CdS shell on PbS quantum dots (QDs) enhances triplet energy transfer (TET) by suppressing competitive charge transfer from QDs to molecules. The CdS shell increases the linear photon upconversion quantum yield (QY) from 3.5 % for PbS QDs to 5.0 % for PbS/CdS QDs when functionalized with a tetracene acceptor, 5-CT. While transient absorption spectroscopy reveals that both PbS and PbS/CdS QDs show the formation of the 5-CT triplet (with rates of 5.91±0.60 ns−1 and 1.03±0.09 ns−1 respectively), ultrafast hole transfer occurs only from PbS QDs to 5-CT. Although the CdS shell decreases the TET rate, it enhances TET efficiency from 60.3±6.1 % to 71.8±6.2 % by suppressing hole transfer. Furthermore, the CdS shell prolongs the lifetime of the 5-CT triplet and thus enhances TET from 5-CT to the rubrene emitter, further bolstering the upconverison QY.

AbstractA sub-monolayer CdS shell on PbS quantum dots (QDs) enhances triplet energy transfer (TET) by suppressing competitive charge transfer from QDs to molecules. The CdS shell increases the linear photon upconversion quantum yield (QY) from 3.5 % for PbS QDs to 5.0 % for PbS/CdS QDs when functionalized with a tetracene acceptor, 5-CT. While transient absorption spectroscopy reveals that both PbS and PbS/CdS QDs show the formation of the 5-CT triplet (with rates of 5.91±0.60 ns−1 and 1.03±0.09 ns−1 respectively), ultrafast hole transfer occurs only from PbS QDs to 5-CT. Although the CdS shell decreases the TET rate, it enhances TET efficiency from 60.3±6.1 % to 71.8±6.2 % by suppressing hole transfer. Furthermore, the CdS shell prolongs the lifetime of the 5-CT triplet and thus enhances TET from 5-CT to the rubrene emitter, further bolstering the upconverison QY.

Triplet excitons are key players in multi-excitonic processes like singlet fission and triplet–triplet annihilation based photon upconversion, which may be useful in next-generation photovoltaic devices, photocatalysis and bioimaging. Here, we present an overview of experimental and theoretical work on triplet energy transfer, with a focus on triplet transport in thin films. We start with the theory describing Dexter-mediated triplet energy transfer and the fundamental parameters controlling this process. Then we summarize current experimental methods used to measure the triplet exciton diffusion length. Finally, the use of hierarchically ordered structures to improve the triplet diffusion length is presented, before concluding with an outlook on the remaining challenges.

Herein we report the first example of nanocrystal (NC) sensitized triplet–triplet annihilation based photon upconversion from the visible to ultraviolet (vis-to-UV). Many photocatalyzed reactions, such as water splitting, require UV photons in order to function efficiently. Upconversion is one possible means of extending the usable range of photons into the visible. Vis-to-UV upconversion is achieved with CdS/ZnS core–shell NCs as the sensitizer and 2,5-diphenyloxazole (PPO) as annihilator and emitter. The ZnS shell was crucial in order to achieve any appreciable upconversion. From time resolved photoluminescence and transient absorption measurements we conclude that the ZnS shell affects the NC and triplet energy transfer (TET) from NC to PPO in two distinct ways. Upon ZnS growth the surface traps are passivated thus increasing the TET. The shell, however, also acts as a tunneling barrier for TET, reducing the efficiency. This leads to an optimal shell thickness where the upconversion quantum yield (Φ′UC) is maximized. Here the maximum Φ′UC was determined to be 5.2 ± 0.5% for 4 monolayers of ZnS shell on CdS NCs.

The effect of isomeric substitutions on the transmitter for triplet energy transfer (TET) between nanocrystal (NC) donor and molecular acceptor is investigated. Each isomeric acceptor is expected to bind in a unique orientation with respect to the NC donor. We see that this orbital overlap drastically affects the transmission of triplets. Here, two functional groups, the carboxylic acid and dithiocarbamate, were varied between the 1-, 2- and 9-positions of the anthracene ring to give three ACA and three ADTC isomers. These six anthracene isomers served as transmitters for triplets between CdSe NC sensitizers and 9,10-diphenylanthracene annihilators for photon upconversion. The photon upconversion quantum yield (QY) is the highest for 9-ACA (12%), lowest for 9-ADTC (0.1%), around 3% for both 1-ACA and 1-ADTC, and about 1% for the 2-isomers. These trends in QYs are reflected in the rates of TET given by ultrafast transient absorption spectroscopy where a maximum of 3.8 × 107 s−1 for 9-ACA was measured. Molecular excited state energy levels were measured both in solution and polymer hosts to correlate structure to TET. This work confirms that anthracene excited states levels are very sensitive to molecular substitution, which in combination with orbital overlap, critically affect Dexter-based TET.

Third generation photovoltaics are inexpensive modules that promise power conversion efficiencies exceeding the thermodynamic Shockley–Queisser limit, perhaps by using up- or down-converters, intermediate band solar cells, tandem cells, hot carrier devices, or multiexciton generation. Here, we report the efficient upconversion of infrared to visible light at excitation densities below the solar flux. Colloidally synthesized core–shell lead sulfide–cadmium sulfide nanocrystals in combination with tetracene derivatives absorb near-infrared light and emit visible light at 560 nm with an upconversion quantum yield (QY) of 8.4 ± 1.0%, which is a factor of 4 lower than the maximum upconversion QY possible. This is achieved with 808 nm cw excitation at 3.2 mW/cm2, approximately three times lower than the available solar flux. The molecular and nanocrystal engineering here paves the way toward utilizing this hybrid upconversion platform in photovoltaics, photodetectors and photocatalysis.Keywords: acene; core−shell semiconductor quantum dots; Dexter transfer; NIR upconversion; solar; triplets;

We designed and synthesized a tetracene derivative 4-(tetracen-5-yl)benzoic acid (CPT) as a transmitter ligand used in PbS/PbSe nanocrystal (NC) sensitized upconversion of near infrared (NIR) photons. Under optimal conditions, comparing CPT functionalized NCs with unfunctionalized NCs as sensitizers, the upconversion quantum yield (QY) was enhanced 81 times for 2.9 nm PbS NCs from 0.021% to 1.7%, and 11 times for 2.5 nm PbSe NCs from 0.20% to 2.1%. The surface density of CPT controls the solubility of functionalized NCs and the upconversion QY. By increasing the concentration of CPT in the ligand exchange solution, the number of CPT ligand per NC increases. The upconversion QY is maximized at a transmitter density of 1.2 nm−2 for 2.9 nm PbS, and 0.32 nm−2 for 2.5 nm PbSe. Additional transmitter ligands inhibit photon upconversion due to triplet–triplet annihilation (TTA) between two neighboring CPT molecules on the NC surface. 2.1% is the highest reported QY for TTA-based photon upconversion in the NIR with the use of earth-abundant materials.

We investigate triplet energy transfer (TET) across variable-length aromatic oligo-p-phenylene and aliphatic bridges in a covalently linked CdSe nanocrystal (NC)–bridge–anthracene hybrid system. Photon upconversion measurements in saturated 9,10-diphenylanthracene hexane solutions under air-free conditions at room temperature provided the steady-state rate of TET (ket) across this interface. For flexible transmitters, ket is similar for different lengths of aliphatic bridges, suggesting that the ligands bend backward. For the rigid phenylene spacer, triplet sensitization of anthracene transmitter molecules by CdSe NCs shows a strong distance dependence, with a Dexter damping coefficient of 0.43 ± 0.07 Å–1. The anthracene transmitter bound closest to the NC surface gave the highest quantum yield of 14.3% for the conversion of green to violet light, the current record for a hybrid platform.

The ability to upconvert two low energy photons into one high energy photon has potential applications in solar energy, biological imaging, and data storage. In this Letter, CdSe and PbSe semiconductor nanocrystals are combined with molecular emitters (diphenylanthracene and rubrene) to upconvert photons in both the visible and the near-infrared spectral regions. Absorption of low energy photons by the nanocrystals is followed by energy transfer to the molecular triplet states, which then undergo triplet–triplet annihilation to create high energy singlet states that emit upconverted light. By using conjugated organic ligands on the CdSe nanocrystals to form an energy cascade, the upconversion process could be enhanced by up to 3 orders of magnitude. The use of different combinations of nanocrystals and emitters shows that this platform has great flexibility in the choice of both excitation and emission wavelengths.

We investigate the parameters affecting the upconversion of visible light in a hybrid organic–inorganic system based on CdSe nanocrystal (NC) sensitizers, 9-anthracene carboxylic acid (9-ACA) transmitter, and diphenylanthracene (DPA) annihilator. Seven wurtzite CdSe NCs ranging in photoluminescence quantum yield (PLQY) from 2.0% to 11%, and in diameter from 2.7 to 5.1 nm, were used in combination with the 9-ACA and DPA molecules. Using 2.7 nm diameter CdSe NCs, we show that the upconversion quantum yield has a quadratic to linear dependence on NC sensitizer concentration. Additionally, upconversion efficiency correlates positively with 9-ACA surface coverage on CdSe NCs and NC PLQY but negatively with particle size. This work clearly illustrates the path toward designing nanocrystal–molecule combinations with high upconversion efficiency that have potential applications in the fields of bioimaging, solar energy conversion, and data storage.

We study ligand exchange between the carboxylic acid group and 5.0 nm oleic-acid capped CdS nanocrystals (NCs) using fluorescence resonance energy transfer (FRET). This is the first measurement of the initial binding events between cadmium chalcogenide NCs and carboxylic acid groups. The binding behavior can be described as an interaction between a ligand with single binding group and a substrate with multiple, identical binding sites. Assuming Poissonian binding statistics, our model fits both steady-state and time-resolved photoluminescence (SSPL and TRPL, respectively) data well. A modified Langmuir isotherm reveals that a CdS nanoparticle has an average of 3.0 new carboxylic acid ligands and binding constant, Ka, of 3.4 × 105 M–1.

We report control of the density of isolated, single functional groups in homogeneously mixed trichloroalkyl silanes on various silica surfaces. The functional groups are covalently bound to a silane derived from the Rink resin. This Rink-silane is reactive to any nucleophile. Control over the density of functional groups is achieved by diluting the immersion solution containing the Rink-silane with an inert silane, octadecyltrichlorsilane. The isolated nature of the functional groups is confirmed by the stochastic blinking of fluorescent single boron-dipyrromethane dyes imaged in total internal reflection geometry. The robust character of silane monolayers allows facile covalent binding and cleavage of molecular species from silica surfaces as well as general synthetic transformations to be conducted. This is shown by the covalent attachment and then cleavage of a naphthalene chromophore. This low-cost and scalable platform has great potential for use in sensing, molecular electronics, semiconductor processing, and the investigation of fundamental processes in catalysis and the kinetics of molecular association.

Herein we report the first example of nanocrystal (NC) sensitized triplet–triplet annihilation based photon upconversion from the visible to ultraviolet (vis-to-UV). Many photocatalyzed reactions, such as water splitting, require UV photons in order to function efficiently. Upconversion is one possible means of extending the usable range of photons into the visible. Vis-to-UV upconversion is achieved with CdS/ZnS core–shell NCs as the sensitizer and 2,5-diphenyloxazole (PPO) as annihilator and emitter. The ZnS shell was crucial in order to achieve any appreciable upconversion. From time resolved photoluminescence and transient absorption measurements we conclude that the ZnS shell affects the NC and triplet energy transfer (TET) from NC to PPO in two distinct ways. Upon ZnS growth the surface traps are passivated thus increasing the TET. The shell, however, also acts as a tunneling barrier for TET, reducing the efficiency. This leads to an optimal shell thickness where the upconversion quantum yield (Φ′UC) is maximized. Here the maximum Φ′UC was determined to be 5.2 ± 0.5% for 4 monolayers of ZnS shell on CdS NCs.

We designed and synthesized a tetracene derivative 4-(tetracen-5-yl)benzoic acid (CPT) as a transmitter ligand used in PbS/PbSe nanocrystal (NC) sensitized upconversion of near infrared (NIR) photons. Under optimal conditions, comparing CPT functionalized NCs with unfunctionalized NCs as sensitizers, the upconversion quantum yield (QY) was enhanced 81 times for 2.9 nm PbS NCs from 0.021% to 1.7%, and 11 times for 2.5 nm PbSe NCs from 0.20% to 2.1%. The surface density of CPT controls the solubility of functionalized NCs and the upconversion QY. By increasing the concentration of CPT in the ligand exchange solution, the number of CPT ligand per NC increases. The upconversion QY is maximized at a transmitter density of 1.2 nm−2 for 2.9 nm PbS, and 0.32 nm−2 for 2.5 nm PbSe. Additional transmitter ligands inhibit photon upconversion due to triplet–triplet annihilation (TTA) between two neighboring CPT molecules on the NC surface. 2.1% is the highest reported QY for TTA-based photon upconversion in the NIR with the use of earth-abundant materials.

Triplet excitons are key players in multi-excitonic processes like singlet fission and triplet–triplet annihilation based photon upconversion, which may be useful in next-generation photovoltaic devices, photocatalysis and bioimaging. Here, we present an overview of experimental and theoretical work on triplet energy transfer, with a focus on triplet transport in thin films. We start with the theory describing Dexter-mediated triplet energy transfer and the fundamental parameters controlling this process. Then we summarize current experimental methods used to measure the triplet exciton diffusion length. Finally, the use of hierarchically ordered structures to improve the triplet diffusion length is presented, before concluding with an outlook on the remaining challenges.

The effect of isomeric substitutions on the transmitter for triplet energy transfer (TET) between nanocrystal (NC) donor and molecular acceptor is investigated. Each isomeric acceptor is expected to bind in a unique orientation with respect to the NC donor. We see that this orbital overlap drastically affects the transmission of triplets. Here, two functional groups, the carboxylic acid and dithiocarbamate, were varied between the 1-, 2- and 9-positions of the anthracene ring to give three ACA and three ADTC isomers. These six anthracene isomers served as transmitters for triplets between CdSe NC sensitizers and 9,10-diphenylanthracene annihilators for photon upconversion. The photon upconversion quantum yield (QY) is the highest for 9-ACA (12%), lowest for 9-ADTC (0.1%), around 3% for both 1-ACA and 1-ADTC, and about 1% for the 2-isomers. These trends in QYs are reflected in the rates of TET given by ultrafast transient absorption spectroscopy where a maximum of 3.8 × 107 s−1 for 9-ACA was measured. Molecular excited state energy levels were measured both in solution and polymer hosts to correlate structure to TET. This work confirms that anthracene excited states levels are very sensitive to molecular substitution, which in combination with orbital overlap, critically affect Dexter-based TET.