Robert Younts

Influence of mono versus bis-electron-donor ancillary ligands in heteroleptic Ru(II) bipyridyl complexes on electron injection from the first excited singlet and triplet states in dye-sensitized solar cells

A novel heteroleptic Ru(II) bipyridyl complex (HD-1-mono) was molecularly designed with a mono-carbazole ancillary ligand, synthesized and characterized for DSCs. The aim was to systematically study the influence of mono (HD-1-mono) versus bis-carbazole ancillary ligand (NCSU-10) on molar absorptivity, light harvesting efficiency (LHE), ground and excited state oxidation potentials, incident-photon-to-current conversion efficiency (IPCE), electron injection from the first excited singlet and triplet states, short-circuit photocurrent density (Jsc), and total solar-to-electric conversion efficiency (η) for DSCs. This study showed that HD-1-mono exhibited slightly lower Voc but greater Jsc compared to NCSU-10. Though HD-1-mono showed lower extinction coefficient than NCSU-10, interestingly, it was found that the decrease in molar extinction coefficient of HD-1-mono is not directly related to the short-circuit photocurrent density (Jsc). For example, HD-1-mono showed a higher Jsc of 21.4 mA cm−2 without the presence of any additives. However, under optimized conditions, HD-1-mono showed a Jsc of 19.76 mA cm−2, Voc of 0.68 V, and (%η) of 9.33 compared to a Jsc of 19.58 mA cm−2, Voc of 0.71 and (%η) of 10.19 for NCSU-10, where N719 achieved a Jsc of 16.85 mA cm−2, Voc of 0.749 V and (%η) of 9.33 under the same experimental device conditions. Impedance results for HD-1-mono showed a shorter recombination time as compared to N719 and NCSU-10, which justify its lower Voc. Femtosecond transient absorption spectroscopy results elucidated that electron injection from the first triplet state is 63% more efficient for HD-1-mono than that of NCSU-10.

Efficient Generation of Long‐Lived Triplet Excitons in 2D Hybrid Perovskite

Triplet excitons form in quasi-2D hybrid inorganic-organic perovskites and diffuse over 100 nm before radiating with >11% photoluminescence quantum efficiency (PLQE) at low temperatures.

Charge Generation Dynamics in Efficient All-Polymer Solar Cells: Influence of Polymer Packing and Morphology.

All-polymer solar cells exhibit rapid progress in power conversion efficiency (PCE) from 2 to 7.7% over the past few years. While this improvement is primarily attributed to efficient charge transport and balanced mobility between the carriers, not much is known about the charge generation dynamics in these systems. Here we measured exciton relaxation and charge separation dynamics using ultrafast spectroscopy in polymer/polymer blends with different molecular packing and morphology. These measurements indicate that preferential face-on configuration with intermixed nanomorphology increases the charge generation efficiency. In fact, there is a direct quantitative correlation between the free charge population in the ultrafast time scales and the external quantum efficiency, suggesting not only the transport but also charge generation is key for the design of high performance all polymer solar cells.

Impact of the photo-induced degradation of electron acceptors on the photophysics, charge transport and device performance of all-polymer and fullerene–polymer solar cells

The photodegeneration of polymer solar cells (PSCs) based on polymer donors and fullerene acceptors limits their lifetime and reliability. Here, we demonstrate that replacing fullerene acceptors with naphthalenediimide (NDI)-based n-type polymers can significantly enhance the photo-stability of PSCs. As a model system, we compared the photo-stabilities of all-polymer solar cells (all-PSCs) and fullerene-based PSCs (fullerene-PSCs) using the same polymer donor (PBDTTTPD) exposed to one sunlight illumination. We observed a remarkable contrast in their photo-stabilities. After 4 days of irradiation, the performance of the fullerene-PSCs dropped by 50%, whereas the performance of the all-PSCs remained stable. The detailed analysis of charge dynamics measured by femtosecond transient absorption spectroscopy and space charge limited current measurements shows significant reduction in interfacial charge transfer and charge carrier mobility, which correlates with the loss in JSC and FF of the fullerene-PSCs under solar illumination. By contrast, for the all-PSCs, the ultrafast dynamics and charge mobility remained consistent after illumination. The NDI-based copolymer had high stability under light exposure, whereas the photo-induced dimerization of phenyl-C61-butyric acid methyl ester (PCBM) acceptors was responsible for the photo-degradation of fullerene-PSCs.

Lowest energy Frenkel and charge transfer exciton intermixing in one-dimensional copper phthalocyanine molecular lattice

We report the results of the combined experimental and theoretical studies of the low-lying exciton states in crystalline copper phthalocyanine. We derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer exciton state and compare it with temperature dependent optical absorption spectra measured experimentally, to obtain the parameters of the Frenkel-charge-transfer exciton intermixing. The two Frenkel exciton states are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the charge transfer exciton, showing the coupling constant 0.17 eV which agrees with earlier experimental measurements. These results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines.

Impact of highly crystalline, isoindigo-based small-molecular additives for enhancing the performance of all-polymer solar cells

We have developed a simple yet versatile approach for enhancing the performance of all-polymer solar cells (all-PSCs) using a highly crystalline small-molecular additive, 6,6′-dithiopheneisoindigo (DTI). The DTI additive in a blend of PTB7-Th donor and P(NDI2HD-T) acceptor enhances the power conversion efficiency of all-PSCs from 5.9 to 6.8%. Based on the analyses of the electrical, optical, and structural properties of all-PSCs, it is suggested that DTI additives promote tighter π–π packing and larger sizes of crystalline domains. Such morphological changes of the PTB7-Th:P(NDI2HD-T) blend films upon the addition of DTI enhance the exciton lifetime and diffusion length, which are proved by static and femtosecond-transient absorption spectroscopies and time-resolved photoluminescence. As a result of improved exciton dissociation probability and charge transport, the short-circuit current density of all-PSCs is greatly increased. Importantly, we also show that the DTI additive can be applied to other all-PSC systems with different polymer donors and naphthalene diimide (NDI)-based polymer acceptors, where the efficiencies of all-PSCs are enhanced by 10–20%.

Monitoring Charge Separation Processes in Quasi-One-Dimensional Organic Crystalline Structures

We perform the transient absorption spectroscopy experiments to investigate the dynamics of the low-energy collective electron-hole excitations in α-copper phthalocyanine thin films. The results are interpreted in terms of the third-order nonlinear polarization response function. It is found that, initially excited in the molecular plane, the intramolecular Frenkel exciton polarization reorients with time to align along the molecular chain direction to form coupled Frenkel-charge-transfer exciton states, the eigenstates of the one-dimensional periodic molecular lattice. The process pinpoints the direction of the charge separation in α-copper phthalocyanine and similar organic molecular structures. Being able to observe and monitor such processes is important both for understanding the physical principles of organic thin film solar energy conversion device operation and for the development of organic optoelectronics in general.

The Role of FRET in Non-Fullerene Organic Solar Cells: Implications for Molecular Design

Non-fullerene acceptors (NFAs) have been demonstrated to be promising candidates for highly efficient organic photovoltaic (OPV) devices. The tunability of absorption characteristics of NFAs can be used to make OPVs with complementary donor-acceptor absorption to cover a broad range of the solar spectrum. However, both charge transfer from donor to acceptor moieties and energy (energy) transfer from high-bandgap to low-bandgap materials are possible in such structures. Here, we show that when charge transfer and exciton transfer processes are both present, the coexistence of excitons in both domains can cause a loss mechanism. Charge separation of excitons in a low-bandgap material is hindered due to exciton population in the larger bandgap acceptor domains. Our results further show that excitons in low-bandgap material should have a relatively long lifetime compared to the transfer time of excitons from higher bandgap material in order to contribute to the charge separation. These observations provide significant guidance for design and development of new materials in OPV applications.

Polymer non-fullerene solar cells of vastly different efficiencies for minor side-chain modification: impact of charge transfer, carrier lifetime, morphology and mobility

The performance of the highly efficient PBDB-T : ITIC system with 11.25% power conversion efficiency is degraded significantly to 4.35% when ITIC is blended with a version of PBDB, dubbed PBDB-O, which has only a minor side-chain modification. We explored the reasons for this difference and investigated the impact of morphology, molecular packing and mobility on carrier lifetime and performance. We employed transient absorption spectroscopy to investigate the hole and electron carrier dynamics in each of the blends and observed significant differences in geminate recombination. In order to understand the influence of morphology and mobility on the carrier dynamics and recombination, we utilized grazing incident wide-angle X-ray scattering (GIWAXS), resonant soft X-ray scattering (RSoXS) and diode mobility measurements. Our results indicate that the difference in performance is difficult to explain with the small differences observed in morphology and packing, and seems to be dominated by the changes in intrinsic mobility that the side-chain modification engenders, which impact both charge creation and extraction. The results highlight the difficulties of predicting the impact of synthetic structural modifications on performance and on a specific device-relevant parameter.

Impact of exciton transfer dynamics on charge generation in polymer/nonfullerene solar cells (Conference Presentation)

The initial steps in organic photovoltaic cell (OPV) operation involve the formation of neutral excitons through photo absorption, exciton diffusion to and separation into free charges at the donor acceptor interface.1, 2As the usable solar spectrum spans a large range from the visible to the infra-red (IR), an obvious direction for improved light harvesting is to synthesize donor and acceptor materials with complementary absorption. In such devices, specifically those involving polymer donors and small molecule acceptors, both charge transfer from donor and acceptor moieties, and energy (exciton) transfer from high band gap to low band gap material are possible. Here we show that when charge and exciton transfer processes are present, the co-existence of excitons in both domains can cause a loss mechanism. Charge separation of excitons in a low band-gap polymer is hindered due to exciton population in the larger band-gap acceptor domains. Our results further show that excitons in the lower bandgap material should have a relatively long lifetime compared to the transfer time of excitons from the higher band gap material, in order to contribute to the charge separation. These observations provide significant guidance for design and development of new materials in OPV applications.