Optical thermometry as an important local temperature-sensing technique,has received increasing attention in scientific and industrial areas.However,it is still a big challenge to develop luminescent materials with se...Optical thermometry as an important local temperature-sensing technique,has received increasing attention in scientific and industrial areas.However,it is still a big challenge to develop luminescent materials with self-activated dual-wavelength emissions toward high-sensitivity optical thermometers.Herein,a novel ratiometric thermometric strategy of Bi^(3+)-activated dual-wavelength emission band was realized in the same lattice position with two local electronic states of La_(3)Sb_(1-x)Ta_xO_(7):Bi^(3+)(0≤x≤1.0)materials based on the different temperature-dependent emission behaviors,benefiting from the highlysensitive and regulable emission to the coordination environment of Bi^(3+).The structural and spectral results demonstrate that the emission tremendously shifted from green to blue with 68 nm and the intensity was enhanced 2.6 times.Especially,the visual dual-wavelength emitting from two emission centers was presented by increasing the Ta^(5+)substitution concentration to 20%or 25%,mainly originating from the two local electronic states around the Bi^(3+)emission center.Significantly,the dual-wavelength with different thermal-quenching performance provided high-temperature sensitivity and good discrimination signals for optical thermometry in the range between 303 and 493 K.The maximum relative sensitivity reached 2.64%/K(La_(3)Sb_(0.8)Ta_(0.2)O_(7):0.04Bi^(3+)@383 K)and 1.91%/K(La_(3)Sb_(0.75)Ta_(0.25)O_(7):0.04Bi^(3+)@388 K).This work reveals a rational design strategy of different local electronic states around the singledoping multiple emission centers towards practical applications,such as luminescence thermometry and white LED lighting.展开更多
Chemical short-range orders(CSROs),as the built-in sub-nanoscale entities in a high-/medium-entropy alloy(H/MEA),have aroused an ever-increasing interest.With multi-principal elements in an H/MEA to form a complex con...Chemical short-range orders(CSROs),as the built-in sub-nanoscale entities in a high-/medium-entropy alloy(H/MEA),have aroused an ever-increasing interest.With multi-principal elements in an H/MEA to form a complex concentrated solution,a variety of sub-systems of species exist to induce the metastable ordered compounds as candidates for ultimate CSROs.The issues remain pending on the origin of CSROs as to how to judge if CSRO will form in an H/MEA and particularly,what kind of CSROs would be stably produced if there were multiple possibilities.Here,the first-principles method,along with the proposed local formation energy calculation in allusion to the atomic-scale chemical heterogeneities,is used to predict the CSRO formation based on the mechanical stability,thermodynamic formation energy,and electronic characteristics.The simulations are detailed in an equiatomic ternary VCoNi MEA with three kinds of potential compounds,i.e.,L1_(1),L1_(2),and B2,in the face-centered cubic matrix.It turns out that L1_(1)is stable but hard to grow up so as to become the final CSRO.L1_(1)is further predicted as CSROs in CrCoNi,but unable to form in FeCoNi and CrMnFeCoNi alloys.These predictions are consistent with the experimental observations.Our findings shed light on understanding the formation of CSROs.This method is applicable to other H/MEAs to design and tailor CSROs by tuning chemical species/contents and thermal processing for high performance.展开更多
Luminogens with aggregation-induced emission(AIE)characteristics(or AIEgens)have been widely used in various applications due to their excellent luminescent properties in molecular aggregates and the solid state.A dee...Luminogens with aggregation-induced emission(AIE)characteristics(or AIEgens)have been widely used in various applications due to their excellent luminescent properties in molecular aggregates and the solid state.A deep understanding of the AIE mechanism is critical for the rational development of AIEgens.In this work,the“state-crossing from a locally excited to an electron transfer state”(SLEET)model is employed to rationalize the AIE phenomenon of two(bi)piperidylanthracenes.According to the SLEET model,an electron transfer(ET)state is formed along with the rotation of the piperidyl group in the excited state of(bi)piperidylan-thracene monomers,leading to fluorescence quenching.In contrast,a bright state exists in the crystal and molecular aggregates of these compounds,as the intermolecular interactions restrict the formation of the dark ET state.This mechanistic understanding could inspire the deployment of the SLEET model in the rational designs of various functional AIEgens.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52072101,51972088,52172205)the Fundamental Research Funds for the Provincial Universities of Zhejiang(No.GK229909299001-003)the Postgraduate Research Innovation Fund of Hangzhou Dianzi University(No.CXJJ2022032)。
文摘Optical thermometry as an important local temperature-sensing technique,has received increasing attention in scientific and industrial areas.However,it is still a big challenge to develop luminescent materials with self-activated dual-wavelength emissions toward high-sensitivity optical thermometers.Herein,a novel ratiometric thermometric strategy of Bi^(3+)-activated dual-wavelength emission band was realized in the same lattice position with two local electronic states of La_(3)Sb_(1-x)Ta_xO_(7):Bi^(3+)(0≤x≤1.0)materials based on the different temperature-dependent emission behaviors,benefiting from the highlysensitive and regulable emission to the coordination environment of Bi^(3+).The structural and spectral results demonstrate that the emission tremendously shifted from green to blue with 68 nm and the intensity was enhanced 2.6 times.Especially,the visual dual-wavelength emitting from two emission centers was presented by increasing the Ta^(5+)substitution concentration to 20%or 25%,mainly originating from the two local electronic states around the Bi^(3+)emission center.Significantly,the dual-wavelength with different thermal-quenching performance provided high-temperature sensitivity and good discrimination signals for optical thermometry in the range between 303 and 493 K.The maximum relative sensitivity reached 2.64%/K(La_(3)Sb_(0.8)Ta_(0.2)O_(7):0.04Bi^(3+)@383 K)and 1.91%/K(La_(3)Sb_(0.75)Ta_(0.25)O_(7):0.04Bi^(3+)@388 K).This work reveals a rational design strategy of different local electronic states around the singledoping multiple emission centers towards practical applications,such as luminescence thermometry and white LED lighting.
基金supported by the National Key Re-search and Development Program of the Ministry of Science and Technology of China(No.2019YFA0209902)the Natural Sci-ence Foundation of China(Nos.11988102 and 11972350).
文摘Chemical short-range orders(CSROs),as the built-in sub-nanoscale entities in a high-/medium-entropy alloy(H/MEA),have aroused an ever-increasing interest.With multi-principal elements in an H/MEA to form a complex concentrated solution,a variety of sub-systems of species exist to induce the metastable ordered compounds as candidates for ultimate CSROs.The issues remain pending on the origin of CSROs as to how to judge if CSRO will form in an H/MEA and particularly,what kind of CSROs would be stably produced if there were multiple possibilities.Here,the first-principles method,along with the proposed local formation energy calculation in allusion to the atomic-scale chemical heterogeneities,is used to predict the CSRO formation based on the mechanical stability,thermodynamic formation energy,and electronic characteristics.The simulations are detailed in an equiatomic ternary VCoNi MEA with three kinds of potential compounds,i.e.,L1_(1),L1_(2),and B2,in the face-centered cubic matrix.It turns out that L1_(1)is stable but hard to grow up so as to become the final CSRO.L1_(1)is further predicted as CSROs in CrCoNi,but unable to form in FeCoNi and CrMnFeCoNi alloys.These predictions are consistent with the experimental observations.Our findings shed light on understanding the formation of CSROs.This method is applicable to other H/MEAs to design and tailor CSROs by tuning chemical species/contents and thermal processing for high performance.
基金This work was supported by A^(*)STAR under Its Advanced Manufacturing and Engineering Program of Singapore(No.A2083c0051).
文摘Luminogens with aggregation-induced emission(AIE)characteristics(or AIEgens)have been widely used in various applications due to their excellent luminescent properties in molecular aggregates and the solid state.A deep understanding of the AIE mechanism is critical for the rational development of AIEgens.In this work,the“state-crossing from a locally excited to an electron transfer state”(SLEET)model is employed to rationalize the AIE phenomenon of two(bi)piperidylanthracenes.According to the SLEET model,an electron transfer(ET)state is formed along with the rotation of the piperidyl group in the excited state of(bi)piperidylan-thracene monomers,leading to fluorescence quenching.In contrast,a bright state exists in the crystal and molecular aggregates of these compounds,as the intermolecular interactions restrict the formation of the dark ET state.This mechanistic understanding could inspire the deployment of the SLEET model in the rational designs of various functional AIEgens.