Role of surface states and adsorbates in time-resolved photocurrent measurements and photovoltage generation at phthalocyaninatozinc(II)-photocathodes

1999 ◽  
Vol 462 (2) ◽  
pp. 222-234 ◽  
Author(s):  
T. Oekermann ◽  
D. Schlettwein ◽  
N.I. Jaeger
Keyword(s):  
Author(s):  
TORSTEN OEKERMANN ◽  
DERCK SCHLETTWEIN ◽  
NILS I. JAEGER ◽  
DIETER WÖHRLE

The influence of electron-withdrawing substituents on the photoelectrochemical properties of phthalocyanines is shown in a comparison between hexadecafluorophthalocyaninatozinc(II) ( F 16 PcZn ) and the unsubstituted phthalocyaninatozinc(II) ( PcZn ). The role of surface states in the photoelectrochemistry of both materials has been investigated by time-resolved photocurrent measurements in the millisecond range. The charging and discharging of surface states could clearly be seen as spikes at the beginning and the end of illumination. Surface states were filled with photogenerated electrons at PcZn and with photogenerated holes at F 16 PcZn . In the steady state under illumination only cathodic photocurrents were detected at PcZn , while at F 16 PcZn both cathodic and anodic photocurrents were observed. An adsorption step of electroactive species prior to the charge transfer was derived from the dependence of the steady state photocurrents on the electrolyte concentration for both materials. The concentration dependence of the charging and discharging currents, however, showed that charge transfer from surface states to the electrolyte occurs at PcZn , while at F 16 PcZn the surface states only represent recombination centres.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Hamoon Hedayat ◽  
Davide Bugini ◽  
Hemian Yi ◽  
Chaoyu Chen ◽  
Xingjiang Zhou ◽  
...  

AbstractWe use circular dichroism (CD) in time- and angle-resolved photoemission spectroscopy (trARPES) to measure the femtosecond charge dynamics in the topological insulator (TI) $$\hbox {Bi}_{2}\hbox {Te}_{3}$$ Bi 2 Te 3 . We detect clear CD signatures from topological surface states (TSS) and surface resonance (SR) states. In time-resolved measurements, independently from the pump polarization or intensity, the CD shows a dynamics which provides access to the unexplored electronic evolution in unoccupied states of $$\hbox {Bi}_{2}\hbox {Te}_{3}$$ Bi 2 Te 3 . In particular, we are able to disentangle the unpolarized electron dynamics in the bulk states from the spin-textured TSS and SR states on the femtosecond timescale. Our study demonstrates that photoexcitation mainly involves the bulk states and is followed by sub-picosecond transport to the surface. This provides essential details on intra- and interband scattering in the relaxation process of TSS and SR states. Our results reveal the significant role of SRs in the subtle ultrafast interaction between bulk and surface states of TIs.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Ivan Ramirez ◽  
Alberto Privitera ◽  
Safakath Karuthedath ◽  
Anna Jungbluth ◽  
Johannes Benduhn ◽  
...  

AbstractStability is now a critical factor in the commercialization of organic photovoltaic (OPV) devices. Both extrinsic stability to oxygen and water and intrinsic stability to light and heat in inert conditions must be achieved. Triplet states are known to be problematic in both cases, leading to singlet oxygen production or fullerene dimerization. The latter is thought to proceed from unquenched singlet excitons that have undergone intersystem crossing (ISC). Instead, we show that in bulk heterojunction (BHJ) solar cells the photo-degradation of C60 via photo-oligomerization occurs primarily via back-hole transfer (BHT) from a charge-transfer state to a C60 excited triplet state. We demonstrate this to be the principal pathway from a combination of steady-state optoelectronic measurements, time-resolved electron paramagnetic resonance, and temperature-dependent transient absorption spectroscopy on model systems. BHT is a much more serious concern than ISC because it cannot be mitigated by improved exciton quenching, obtained for example by a finer BHJ morphology. As BHT is not specific to fullerenes, our results suggest that the role of electron and hole back transfer in the degradation of BHJs should also be carefully considered when designing stable OPV devices.


2009 ◽  
Vol 53 (3) ◽  
pp. 368-373 ◽  
Author(s):  
Alessandro Clayton Souza Ferreira ◽  
Karina Braga Gomes ◽  
Ivan Barbosa Machado Sampaio ◽  
Vanessa Cristina de Oliveira ◽  
Victor Cavalcanti Pardini ◽  
...  

INTRODUCTION:Type 1A diabetes mellitus (T1ADM) is a multifactorial disease in which genetic and environmental aspects are important to its development. The association of genetic variations with disease has been demonstrated in several studies; however, the role of some gene loci has not yet been fully elucidated. OBJECTIVE:To compare the frequency of HLA alleles and polymorphism in CTLA-4 and insulin genes in Brazilians with T1ADM and individuals without the disease, as well as to identify genetic markers that are able to discriminate between diabetic and non-diabetic individuals. METHODS: The presence of HLA DQB1, DQA1 and DRB1 alleles, as well as the -2221 MspI polymorphism in the insulin gene and 49 A/G in the CTLA-4 gene were identified by the "Time-resolved fluorometer" technique after hybridization with probes labeled with Eu (III) / Sm (III) and Tb (III). RESULTS: The DQB1 *0302 and DQA1 *03 alleles were identified as predisposed to T1ADM, and the DQB1 *0301 allele presented a protective effect against the disease.The DQA1 label proved to be able to differentiate between 71.13% of the diabetic and non-diabetic individuals.This value increased to 82.47% when the DQB1 label was added. No significant difference in the frequency of polymorphisms in the insulin and CTLA-4 genes was observed between the two groups. CONCLUSIONS: The genetic markers that best characterized and discriminated diabetic and non-diabetic individuals were the HLA DQA1 and DQB1.alleles.


eLife ◽  
2019 ◽  
Vol 8 ◽  
Author(s):  
Michael Puljung ◽  
Natascia Vedovato ◽  
Samuel Usher ◽  
Frances Ashcroft

The response of ATP-sensitive K+ channels (KATP) to cellular metabolism is coordinated by three classes of nucleotide binding site (NBS). We used a novel approach involving labeling of intact channels in a native, membrane environment with a non-canonical fluorescent amino acid and measurement (using FRET with fluorescent nucleotides) of steady-state and time-resolved nucleotide binding to dissect the role of NBS2 of the accessory SUR1 subunit of KATP in channel gating. Binding to NBS2 was Mg2+-independent, but Mg2+ was required to trigger a conformational change in SUR1. Mutation of a lysine (K1384A) in NBS2 that coordinates bound nucleotides increased the EC50 for trinitrophenyl-ADP binding to NBS2, but only in the presence of Mg2+, indicating that this mutation disrupts the ligand-induced conformational change. Comparison of nucleotide-binding with ionic currents suggests a model in which each nucleotide binding event to NBS2 of SUR1 is independent and promotes KATP activation by the same amount.


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