Suchergebnisse

Fano resonance is a fundamental physical process that strongly affects the electronic transport, optical, and vibronic properties of matter. Here, we provide the first experimental demonstration of its profound effect on spin properties in semiconductor nanostructures. We show that electron spin generation in InAs/GaAs quantum-dot structures is completely quenched upon spin injection from adjacent InGaAs wetting layers at the Fano resonance due to coupling of light-hole excitons and the heavy-hole continuum of the interband optical transitions, mediated by an anisotropic exchange interaction. Using a master equation approach, we show that such quenching of spin generation is robust and independent of Fano parameters. This work therefore identifies spin-dependent Fano resonance as a universal spin loss channel in quantum-dot systems with an inherent symmetry-breaking effect. ; Funding Agencies|Swedish Research CouncilSwedish Research CouncilEuropean Commission [2016-05091, 2020-04530]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]

Dynamic nuclear polarization (DNP) is well recognized as being important in spintronics and quantum-information processing. DNP gives rise to high nuclear spin polarization that not only can prolong electron-spin lifetime by generating an Overhauser field (OHF), but also has fertilized the idea to explore nuclear spin qubits. In strained quantum-dot structures (QDSs), a nuclear spin is coupled to a strain field via its quadrupole moment. It has been shown that such nuclear quadrupole interaction (NQI) can be used to achieve appreciable DNP and hence electron-spin polarization. Here, we uncover magneto-optical anomalies from a series of laterally arranged (In,Ga)As QDSs that arise from the NQI and DNP in these nanostructures. We find that the principal axis of NQI in symmetry-lowered QDSs significantly deviates from the growth direction, resulting in tilting of OHF with an angle exceeding 37 degrees. The resulting transverse component of OHF is probed with respect to the crystallographic orientations and its influence on the DNP and ensemble spin dephasing is analyzed. We show that a high-symmetry electronic confinement potential for excitons does not guarantee a high-symmetry NQI for nuclei within the same nano-object, thereby calling for correlated optimization in the symmetry of the electronic confinement potential and that of the nuclear spin bath. Our results underline the role of oblique NQI in electron-spin decoherence and depolarization, which has so far largely been overlooked. This work thus sheds light on design rules for engineering the electronic and spin landscape of QDSs for better performance of DNP desirable for applications in spintronics and quantum computation. ; Funding Agencies|Linkoping University; Swedish Research CouncilSwedish Research Council [2016-05091]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]

We show by electron spin resonance (ESR) and Raman spectroscopies that the crystal phase transition of the lead-free double-perovskite Cs2AgBiBr6 has a profound symmetry-breaking effect on the high spin states of, for example, a transition-metal ion Fe3+ and the vibrational modes. It lifts their degeneracy when the crystal undergoes the cubic-tetragonal phase transition, splitting the six-fold degenerate S = 5/2 state of Fe3+ to three Kramer doublets and the enharmonic breathing mode T-g of the MBr6 octahedra (M = Ag, Bi, Fe) into E-g + A(g). The magnitudes of both spin and Raman line splitting are shown to directly correlate with the strength of the tetragonal strain field. This work, in turn, demonstrates the power of the ESR and Raman spectroscopies in probing structural phase transitions and in providing in-depth information on the interplay between the structural, spin, and vibrational properties of lead-free double perovskites, a newly emerging and promising class of materials for low-cost and high-efficiency photovoltaics and optoelectronics. ; Funding Agencies|Swedish Research CouncilSwedish Research Council [VR-2017-05285]; Linkoping University; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW 2019.0082]

The ultimate goal for singlet fission is that each photo-excited singlet exciton, S1, will result in two triplet excitons with unity yield. However, the singlet fission is now recognized to be complicated, involving bright/dark excited states of different spin multiplicity. Identifying the role of such states is vital to optimize singlet fission yield but difficult due to their elusive spectral signature. Here, we develop an experimental protocol based on a refined magneto-optical probe to access the fast time evolution of various excited states. In diphenylhexatriene crystal, the S1 is found to undergo two competing processes?to form one of the two dark triplet pair intermediates having different exchange energies or to form a bright state, Sx, exhibiting excimer-like delayed photoluminescence. Our result provides a clear picture of a competition event in singlet fission, which is beneficial for the development and tailoring of singlet fission materials with high yield. ; Funding agencies: Swedish Research CouncilSwedish Research CouncilEuropean Commission [VR-2017-05285]; Linkoping University; Knut and Alice Wallenberg Foundation (KAW)Knut & Alice Wallenberg Foundation; Royal Thai Government Scholarship under the Development and Promotion of Science and Technology Talents Project (DPST); EPSRCUK Research & Innovation (UKRI)Engineering & Physical Sciences Research Council (EPSRC) [EP/M005143/1, EP/P027741/1, EP/L011972/1]; Spanish Government MINECO/FEDERSpanish Government [PID2019109555GB-l00]; Basque governmentBasque Government [PIBA19-0004]; CONACYT-MexicoConsejo Nacional de Ciencia y Tecnologia (CONACyT) [591700]

Doping of organic semiconductors is a powerful tool to optimize the performance of various organic (opto)electronic and bioelectronic devices. Despite recent advances, the low thermal stability of the electronic properties of doped polymers still represents a significant obstacle to implementing these materials into practical applications. Hence, the development of conducting doped polymers with excellent long-term stability at elevated temperatures is highly desirable. Here, we report on the sequential doping of the ladder-type polymer poly-(benzimidazobenzophenanthroline) (BBL) with a benzimidazole-based dopant (i.e., N-DMBI). By combining electrical, UV-vis/infrared, X-ray diffraction, and electron paramagnetic resonance measurements, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and microstructure of the sequentially doped polymer films as a function of the thermal annealing temperature. Importantly, we observed that the electrical conductivity of N-DMBI-doped BBL remains unchanged even after 20 h of heating at 190 degrees C. This finding is remarkable and of particular interest for organic thermoelectrics. ; Funding Agencies|Swedish Research CouncilSwedish Research Council [2016-03979]; AForsk [18-313, 19310]; Olle Engkvists Stiftelse [204-0256]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Finnish Cultural FoundationFinnish Cultural Foundation; Finnish Foundation for Technology Promotion; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [Dnr KAW 2014.0041]

A common way of determining the majority charge carriers of pristine and doped semiconducting polymers is to measure the sign of the Seebeck coefficient. However, a polarity change of the Seebeck coefficient has recently been observed to occur in highly doped polymers. Here, it is shown that the Seebeck coefficient inversion is the result of the density of states filling and opening of a hard Coulomb gap around the Fermi energy at high doping levels. Electrochemical n-doping is used to induce high carrier density (>1 charge/monomer) in the model system poly(benzimidazobenzophenanthroline) (BBL). By combining conductivity and Seebeck coefficient measurements with in situ electron paramagnetic resonance, UV-vis-NIR, Raman spectroelectrochemistry, density functional theory calculations, and kinetic Monte Carlo simulations, the formation of multiply charged species and the opening of a hard Coulomb gap in the density of states, which is responsible for the Seebeck coefficient inversion and drop in electrical conductivity, are uncovered. The findings provide a simple picture that clarifies the roles of energetic disorder and Coulomb interactions in highly doped polymers and have implications for the molecular design of next-generation conjugated polymers. ; Funding Agencies|Swedish Research CouncilSwedish Research CouncilEuropean Commission [2020-03243]; Olle Engkvists Stiftelse [204-0256]; European CommissionEuropean CommissionEuropean Commission Joint Research Centre [GA-955837, GA-799477]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]; Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germanys Excellence Strategy via the Excellence Cluster 3D Matter Made to OrderGerman Research Foundation (DFG) [EXC-2082/1-390761711]; Carl Zeiss Foundation; Deutsche ForschungsgemeinschaftGerman Research Foundation (DFG) [FA 1502/1-1]; National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [52173156]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [ITM17-0316]

A common way of determining the majority charge carriers of pristine and doped semiconducting polymers is to measure the sign of the Seebeck coefficient. However, a polarity change of the Seebeck coefficient has recently been observed to occur in highly doped polymers. Here, it is shown that the Seebeck coefficient inversion is the result of the density of states filling and opening of a hard Coulomb gap around the Fermi energy at high doping levels. Electrochemical n-doping is used to induce high carrier density (>1 charge/monomer) in the model system poly(benzimidazobenzophenanthroline) (BBL). By combining conductivity and Seebeck coefficient measurements with in situ electron paramagnetic resonance, UV–vis–NIR, Raman spectroelectrochemistry, density functional theory calculations, and kinetic Monte Carlo simulations, the formation of multiply charged species and the opening of a hard Coulomb gap in the density of states, which is responsible for the Seebeck coefficient inversion and drop in electrical conductivity, are uncovered. The findings provide a simple picture that clarifies the roles of energetic disorder and Coulomb interactions in highly doped polymers and have implications for the molecular design of next-generation conjugated polymers. ; Research funding the Swedish Research Council. Grant Number: 2020-03243 Olle Engkvists Stiftelse. Grant Number: 204-0256 European Commission. Grant Numbers: GA-955837, GA-799477 Swedish Government Strategic Research. Grant Number: 2009-00971 Deutsche Forschungsgemeinschaft. Grant Numbers: EXC-2082/1-390761711, FA 1502/1-1 National Natural Science Foundation of China. Grant Number: 52173156 the Swedish Foundation for Strategic Research

Conducting polymers, such as the p-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), have enabled the development of an array of opto- and bio-electronics devices. However, to make these technologies truly pervasive, stable and easily processable, n-doped conducting polymers are also needed. Despite major efforts, no n-type equivalents to the benchmark PEDOT:PSS exist to date. Here, we report on the development of poly(benzimidazobenzophenanthroline):poly(ethyleneimine) (BBL:PEI) as an ethanol-based n-type conductive ink. BBL:PEI thin films yield an n-type electrical conductivity reaching 8Scm(-1), along with excellent thermal, ambient, and solvent stability. This printable n-type mixed ion-electron conductor has several technological implications for realizing high-performance organic electronic devices, as demonstrated for organic thermoelectric generators with record high power output and n-type organic electrochemical transistors with a unique depletion mode of operation. BBL:PEI inks hold promise for the development of next-generation bioelectronics and wearable devices, in particular targeting novel functionality, efficiency, and power performance. The development of n-type conductive polymer inks is critical for the development of next-generation opto-electronic devices that rely on efficient hole and electron transport. Here, the authors report an alcohol-based, high performance and stable n-type conductive ink for printed electronics. ; Funding Agencies|Knut and Alice Wallenberg foundationKnut & Alice Wallenberg Foundation; Swedish Research CouncilSwedish Research CouncilEuropean Commission [2016-03979, 2020-03243]; AForsk [18-313, 19-310]; Olle Engkvists Stiftelse [204-0256]; VINNOVAVinnova [2020-05223]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]; National Research Foundation of KoreaNational Research Foundation of Korea [NRF2020M3H4A3081814, 2019R1A6A1A11044070]; National Science FoundationNational Science Foundation (NSF) [DMR-2003518]

Spintronics holds great potential for next-generation high-speed and low-power consumption information technology. Recently, lead halide perovskites (LHPs), which have gained great success in optoelectronics, also show interesting magnetic properties. However, the spin-related properties in LHPs originate from the spin-orbit coupling of Pb, limiting further development of these materials in spintronics. Here, we demonstrate a new generation of halide perovskites, by alloying magnetic elements into optoelectronic double perovskites, which provide rich chemical and structural diversities to host different magnetic elements. In our iron-alloyed double perovskite, Cs2Ag(Bi:Fe)Br-6, Fe3+ replaces Bi3+ and forms FeBr6 clusters that homogenously distribute throughout the double perovskite crystals. We observe a strong temperature-dependent magnetic response at temperatures below 30 K, which is tentatively attributed to a weak ferromagnetic or antiferromagnetic response from localized regions. We anticipate that this work will stimulate future efforts in exploring this simple yet efficient approach to develop new spintronic materials based on lead-free double perovskites. ; Funding Agencies|Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW 2019.0082]; Swedish Energy AgencySwedish Energy Agency [2018004357, P43288-1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]; Grant Agency of the Czech RepublicGrant Agency of the Czech Republic [GA19-05259S]; China Scholarship Council (CSC)China Scholarship Council; U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering DivisionUnited States Department of Energy (DOE); European CommunityEuropean Community (EC) [312284]; Czech Ministry of EducationMinistry of Education, Youth & Sports - Czech Republic [LM2015057]; CERIC users grant; International Synchrotron Access Program of the Australian Synchrotron

Engineering a low singlet-triplet energy gap (Delta E-ST) is necessary for efficient reverse intersystem crossing (rISC) in delayed fluorescence (DF) organic semiconductors but results in a small radiative rate that limits performance in LEDs. Here, we study a model DF material, BF2, that exhibits a strong optical absorption (absorption coefficient = 3.8 x 10(5) cm(-1)) and a relatively large Delta E-ST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 mu s), but in aggregated films, BF2 generates intermolecular charge transfer (inter-CT) states on picosecond timescales. In contrast to the microsecond intramolecular rISC that is promoted by spin-orbit interactions in most isolated DF molecules, photoluminescence-detected magnetic resonance shows that these inter-CT states undergo rISC mediated by hyperfine interactions on a similar to 24 ns timescale and have an average electron-hole separation of >= 1.5 nm. Transfer back to the emissive singlet exciton then enables efficient DF and LED operation. Thus, access to these inter-CT states, which is possible even at low BF2 doping concentrations of 4 wt%, resolves the conflicting requirements of fast radiative emission and low Delta E-ST in organic DF emitters. ; Funding Agencies|Simons Foundation [601946]; EPSRCUK Research & Innovation (UKRI)Engineering & Physical Sciences Research Council (EPSRC) [EP/M01083X/1, EP/M005143/1, EP/L01551X/1]; European Research Council (ERC) under the European Unions Horizon 2020 research and innovation programmeEuropean Research Council (ERC) [670405]; Swedish Energy AgencySwedish Energy AgencyMaterials & Energy Research Center (MERC) [EM-48594-1]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [VR-2017-05285]; Aix Marseille Universite; CNRSCentre National de la Recherche Scientifique (CNRS)European Commission; Basque GovernmentBasque Government [PIBA19-0004]; Spanish Government MINECO/FEDERSpanish Government [PID2019-109555GB-I00]; European Unions Horizon 2020 research and innovation programme under Marie Skodowska Curie Grant [722651]; Fonds de la Recherche Scientifiques de Belgique (F.R.S.-FNRS)Fonds de la Recherche Scientifique - FNRS [2.5020.11]; Tier-1 supercomputer of the Federation Wallonie-Bruxelles; Walloon Region [1117545]; FRS-FNRSFonds de la Recherche Scientifique - FNRS [F.4534.21]; Fonds pour la formation a la Recherche dans lIndustrie et dans lAgriculture (F.R.I.A.) of the F.R.S.-F.N.R.S