Dynamics of energy transfer and charge carrier localization in Mn-doped CdS/ZnS core/shell nanocrystals correlated with doping location and concentration are studied via transient absorption measurement of exciton relaxation dynamics. The strong dependence of exciton-Mn energy transfer rate on doping location was directly resolved in the transient bleach recovery and electron intraband absorption data by using layer-by-layer synthesized Mn-doped nanocrystals. With 1.2 nm decrease in doping radius in the ZnS shell, energy transfer rate increases by 6 fold. We identified that hole trapping is the major competing process that inhibits the energy transfer in Mn-doped CdS/ZnS nanocrystals. From the branching ratio of the energy transfer and hole trapping, combined with luminescence quantum yield measurement, we also obtained doping location-dependent radiative relaxation quantum yield of Mn(2+) ions that is as high as 0.95.

Rapid hot carrier cooling is the key loss channel overriding all possible energy loss pathways that limit achievable solar conversion efficiency. Thus, delayed hot carrier cooling in the cell absorber layer can make hot carrier extraction a less cumbersome task, assisting in the realization of hot carrier solar cells. There have been plentitude of reports concerning the slow carrier cooling in perovskite materials, which eventually triggered interest in radical understanding of the native photophysics driving the device design. Here in this finding, a further dramatic dip in the cooling rate has been discerned upon a growing Cs 4 PbBr 6 shell over CsPbBr 3 core nanocrystals (NCs), in contrast to the bare CsPbBr 3 core NCs. Using transient absorption spectroscopy, we investigated the disparity in the hot carrier thermalization pathways in the CsPbBr 3 and CsPbBr 3 @Cs 4 PbBr 6 core−shell NCs under the same laser fluence, which can be validated as a corollary of polaron formation in the later NCs.

Charge carrier dynamics of multinary quantum dots like CuInS2 (CIS) nanocrystals (NCs) is not clearly understood, especially in ultrafast time scales. Herein we have synthesized colloidal CIS NCs that show defect-induced emission between donor (antisite) and acceptor (internal/surface) states as indicated from steady-state and time-resolved photoluminescence (PL) measurements. Subpicosecond transient absorption (TA) spectra of CIS NCs reveal a gradient of electronic states that exists above the conduction band edge. The electron cooling rate has been determined to be ∼0.1-0.15 eV/ps. The cascade of electron cooling dynamics was monitored after following the TA kinetics at different electronic states. Interestingly, the kinetics at the antisite state unveil a biexcitonic feature, which has been enlightened through a probe-induced biexciton mechanism. With progressively higher fluence (⟨N⟩), the biexciton binding energy increases, and the electron cooling to the antisite state considerably slows down. Extra energy released during Auger recombination of bi/multiexcitons are used to re-excite the electron to a further high energy level, resulting in longer electron cooling time to the antisite states.

Specially aligned surface-accumulated Mn-doped CdSe (MnCdSe) quantum dots (QDs) have been synthesized to study the effect of dopant atom on charge-carrier dynamics in QD materials. EPR studies suggest that the (4)T1 state of Mn(2+) lies above the conduction band of CdSe, and as a result no Mn-luminescence was observed from MnCdSe. Femtosecond transient absorption studies suggest that Mn atom introduces structural defects in surface-doped CdSe, which acts as electron trap center in doped QD for the photoexcited electron. Bromo-pyrogallol red (Br-PGR) were found to form strong charge-trasfer complex with both CdSe and MnCdSe QDs. Charge separation in both the CdSe/Br-PGR and MnCdSe/Br-PGR composites was found to take place in three different pathways by transferring the photoexcited hole of CdSe/MnCdSe QDs to Br-PGR, electron injection from photoexcited Br-PGR to the QDs, and direct electron transfer from the HOMO of Br-PGR to the conduction band of both the QDs. Hole-transfer dynamics are found to be quite similar (∼1.1 to 1.3 ps) for both of the systems and found to be independent of Mn doping. However, charge recombination dynamics was found to be much slower in the MnCdSe/Br-PGR system as compared with that in the CdSe/Br-PGR system, which confirms that the Mn dopant act as the electron storage center. As a consequence, the MnCdSe/Br-PGR system can be used as a better super sensitizer in quantum-dot-sensitized solar cell to increase efficiency further.

Detailed analysis on charge separation energetics and dynamics for CdTe/ZnS nanocrystals have been carried out with varying shell thickness to elucidate quasi-type-II behavior in a standard type-I system. Redshift in the absorption−photoluminescence spectra and increase of the excited state lifetime in the core/shell nanocrystals with a thick ZnS shell (2 and 4 ML of ZnS) indicate quasi-type-II behavior caused by charge separation. Separation of charge arises as the lattice strain at the core/shell interface alters the conduction band energy levels for both the core and the shell in an opposite way, extending the electronic wave function toward the shell. To find out the energetics of the charge separation, the steady-state spectra were analyzed in the realm of Marcus theory to reveal charge separation occurring in the inverted region with −ΔG°E T > λ. Slow electron cooling as observed from ultrafast transient absorption measurements with increasing shell thickness also confirms electron being decoupled from the hole as the electronic wave function spreads out to the shell. Consistent with the Marcus theory analysis, the separation of charge is clearly exhibited in the nanocrystal with the highest ZnS shell thickness because the excitonic bleach shows a slower electron cooling rate and increased amplitude of a slow recovery component in the red region of transient absorption spectrum.

Composition and size dependent band gap engineering with longer excited state charge carrier lifetime assist CdS x Se1–x alloy semiconductor quantum dots (QDs) as a promising candidate for quantum dot solar cell (QDSC). Colloidal CdS x Se1–x alloy QDs were synthesized using the hot injection method where a stoichiometric mixture of S-TOP and Se-TOP were injected at 270 °C in a mixture of Cd-oleate. The electron decoupled from hole in the alloyed structure due to delocalization of electron in electronically quasi type-II graded CdS x Se1–x alloyed structure. As a result, intraband electron cooling time increases from 100s of fs to sub 10 ps time scale in the alloyed graded structure. Extremely slow electron cooling time (∼8 ps) and less charge recombination (∼50% in >2 ns) as compared to both CdS and CdSe QDs are found to be beneficial for charge carrier extraction in QD solar cells. Using polysulfide electrolyte and Cu2S-deposited ITO glass plates as photocathode, the efficiency of the QD solar cell was measured to be 1.1 (±0.07)% for CdS, 3.36 (±0.1)% for CdSe, and 3.95 (±0.12)% for CdS0.7Se0.3 QDs. An additional nonepitaxial CdS quasi-shell followed by ZnS passivation layer (TiO2/ CdS0.7Se0.3 /quasi-CdS/ZnS) was deposited on top of the CdS0.7Se0.3 film which showed a photo current conversion efficiency (PCE) of 4.5 (±0.18) %. The overall 14% increase of PCE is due to the quasi CdS shell helps to separate more electrons through passivating the surface states of TiO2.

Singlet fission in tetracene generates two triplet excitons per absorbed photon. If these triplet excitons can be effectively transferred into silicon (Si), then additional photocurrent can be generated from photons above the bandgap of Si. This could alleviate the thermalization loss and increase the efficiency of conventional Si solar cells. Here, we show that a change in the polymorphism of tetracene deposited on Si due to air exposure facilitates triplet transfer from tetracene into Si. Magnetic field-dependent photocurrent measurements confirm that triplet excitons contribute to the photocurrent. The decay of tetracene delayed photoluminescence was used to determine a transfer efficiency of ∼36% into Si. Our study suggests that control over the morphology of tetracene during the deposition will be of great importance to boost the triplet transfer yield further.

We have synthesized Mn-doped CdTeSe gradient alloy nanocrystals (NCs) by a colloidal synthetic method, and charge carrier dynamics have been revealed through ultrafast transient absorption (TA) spectroscopy. Due to the reactivity difference between Te and Se, a CdTe-rich core and CdSe-rich shell have been formed in the CdTeSe alloy with the formation of a gradient type II core-shell structure. Electron paramagnetic resonance studies suggest Mn atoms are located in the surface of the alloy NCs. Steady-state optical absorption and emission studies suggest formation of a charge-transfer (CT) state in which electrons are localized in a CdSe-rich shell and holes are localized in a CdTe-rich core which appears in the red region of the spectra. Electron transfer in the CT state is found to take place in the Marcus inverted region. To understand charge-transfer dynamics in the CdTeSe alloy NCs and to determine the effect of Mn doping on the alloy, ultrafast transient absorption studies have been carried out. In the case of the undoped alloy, formation of the CT state is found to take place through electron relaxation to the conduction band of the CT state with a time of 600 fs and through hole relaxation (from the CdSe-rich state to the CdTe-rich state) to the valence band of the CT state with a time scale of 1 ps. However, electron relaxation in the presence of Mn dopants takes place initially via an electron transfer to the Mn 3d state (d(5)) followed by transfer from the Mn 3d state (d(6)) to the CT state, which has been found to take place with a >700 ps time scale in addition to the hole relaxation time of 2 ps. Charge recombination time of the CT state is found to be extremely slow in the Mn-doped CdTeSe alloy NCs as compared to the undoped one, where the Mn atom acts as an electron storage center.