Enhancing the near-infrared upconversion photocatalytic activity of ZnO/Bi3Ti2O8F:Yb3+, Er3+ by modulating the internal electric field through Z-scheme heterojunction construction.

Exploring strategies to improve the near-infrared response of photocatalysts is an urgent challenge that can be overcome by utilizing upconversion (UC) luminescence to enhance photocatalysis. This paper reports the fabrication of a ZnO/Bi3Ti2O8F:Yb3+, Er3+ (ZnO/BTOFYE) Z-scheme heterojunction based on a Bi3Ti2O8F:Yb3+, Er3+ (BTOFYE) UC photocatalyst via electrostatic self-assembly. Fermi energy difference at the interface of BTOFYE and ZnO generates a strong internal electric field (IEF) in the Z-scheme heterojunction, offering a novel charge transfer mode that promotes carrier transfer and separation while retaining the strong redox capability. These results are confirmed through in situ X-ray photoelectron spectroscopy, in situ Kelvin probe force microscopy, electron spin resonance, and density functional theory calculations. In addition, the effect of the IEF on the UC luminescence process of Er3+ enhances the luminescence intensity, considerably improving the UC utilization efficiency. The optimal ZnO/BTOFYE degrades 64 % of ciprofloxacin in 120 min, which is 2.3 times more than that degraded by BTOFYE. Overall, the results of this study offer a reference for the rational development of high efficiency UC photocatalysts by generating IEF in Z-scheme heterojunctions.

Self-doping induced oxygen vacancies and lattice strains for synergetic enhanced upconversion luminescence of Er3+ ions in 2D BiOCl nanosheets.

Rare earth (RE) ions combined with two-dimensional (2D) semiconductors can exhibit unexpected optical properties. However, fluorescence quenching has always been inevitable due to defects associated with the synthesis and doping of 2D materials. In this work, we reported an efficient upconversion (UC) enhancement of Er3+ doped BiOCl nanosheets, utilizing a defect engineering strategy conversely rather than eliminating defects. Experiments and theoretical calculations provide evidence that oxygen vacancies (OVs) and lattice strain are simultaneously formed in the BiOCl:Er3+ nanosheets through self-doping of Cl- ions. Under 980 nm excitation, samples doped with 300 mol% Cl- ions exhibit the best luminescent emission, and the green and red UC emissions are enhanced 3.5 and 15 times, respectively. We showed that the OVs in the 2D semiconductor can act as energy bridges to transfer charges to the Er3+ energy level, enriching the electron population at the excited levels; while, the lattice strain enhances the energy transfer and charge accumulation, which synergistically enhance the UC luminescence. This research provides a new insight into the development of defect engineering for UC PL in 2D nanomaterials.

Reversible 3D optical data storage and information encryption in photo-modulated transparent glass medium.

Transparent glass has been identified as a vital medium for three-dimensional (3D) optical information storage and multi-level encryption. However, it has remained a challenge for directly writing 3D patterning inside a transparent glass using semiconductor blue laser instead of high-cost femtosecond laser. Here, we demonstrate that rare earth ions doped transparent glass can be used as 3D optical information storage and data encryption medium based on their reversible transmittance and photoluminescence manipulation. The color of tungsten phosphate glass doped with rare earth ions change reversibly from light yellow to blue upon alternating 473 nm laser illumination and temperature stimulation, resulting in the reversible luminescence modulation. The information data could be repeatedly written and erased in arbitrary 3D space of transparent glass, not only showing the ability of the excellent reproducibility and storage capacity, but also opening opportunities in information security. The present work expands the application fields of luminescent glass, and it is conducive to develop a novel 3D data storage and information encryption media.

Intermediate excited state suppression and upconversion enhancement of Er3+ ions by carbon-doping boosting photocarrier separation in bismuth oxychloride nanosheets.

Low luminescence efficiency of rare-earth ions dopedupconversion (UC) nanomaterials is still a major limitation for their applications.Here, based on bismuth oxychloride nanosheets that show efficient photocarriers separation due to combining spontaneous polarization and layered semiconductor, we report a new carbon heterovalent doping strategy for efficient UC luminescence enhancement by suppressing the intermediate excited states of Er3+ ions. The first-principles calculations and photoelectrochemical characterizations provide evidences that the replacement of C ions for Cl strengthen the spontaneous polarization and inter electric field (IEF) of bismuth oxychloride nanosheets, which further improve the photocarriers separation efficiency. Under 808 or 980 nm excitation, the emission intensity of 4I13/2 energy level of Er3+ ions (1550 nm) increase slightly with C doping, but the its decay time and the visible UC emission are improved tremendously at the same time. We show that the recombination rate of intermediate excited state electrons of Er3+ ions with the ground state is inhibited by the enhanced IEF, which promotes the energy reabsorption transition to upper energy levels, thus enhancing the visible UC emission. This work not only may provide a new insight into the method for engineering of UC emissions but also deepen the understanding for layered semiconducting material to modify the transition of Lanthanide ions.

Novel Strategy for Designing Photochromic Ceramic: Reversible Upconversion Luminescence Modification and Optical Information Storage Application in the PbWO4:Yb3+, Er3+ Photochromic Ceramic.

Inorganic photochromic material is an available medium to obtain optical information storage. The photochromic property of the inorganic material is mainly from the defects of the host. However, the formation of defects in the host is uncontrollable, in particular, the revisable formation and removement of defects are difficult. Thus, there are few inorganic materials with the revisable photochromism upon the entire light stimulation. Therefore, it is an urgent need to find a suitable approach to design inorganic photochromic materials. Here, the photochromic PbWO4:Yb3+, Er3+ ceramic was designed with the help of valence state change of W6+ → W5+ and Pb2+ → Pb4+. Upon the 532 nm laser stimulation, the photochromism of the PbWO4:Yb3+, Er3+ ceramic was obtained based on the Pb2+ + hν (532 nm) → Pb4+ + 2e- and W6+ + e- + hν (532 nm) → W5+ reaction, resulting in the optical information writing. Under the stimulation of an 808 nm laser, the written optical information was erased based on the W5+ + hν (808 nm) → W6+ + e- and Pb4+ + 2e- + hν (808 nm) → Pb2+ reaction. In addition, the photochromism-induced upconversion emission modification was obtained in the PbWO4:Yb3+, Er3+ ceramic, realizing the effective and nondestructive reading out of optical information. The cyclic experiment demonstrated a good reproducibility of both photochromism and upconversion emission modification, exhibiting the potential application of the PbWO4:Yb3+, Er3+ ceramic as the optical data storage medium.

Reversible Modulated Upconversion Luminescence of MoO3:Yb3+,Er3+ Thermochromic Phosphor for Switching Devices.

Reversible modulation of upconversion luminescence induced by the external field stimuli exhibits potential applications in various fields, such as photoswitches, optical sensing, and optical memory devices. Herein, a new MoO3:Yb3+,Er3+ thermochromic phosphor was synthesized via a high-temperature solid-state method, and the reversible color modification of the MoO3:Yb3+,Er3+ phosphor was obtained by alternating the sintering conditions either in a reducing atmosphere or in air. The color of the MoO3:Yb3+,Er3+ phosphor changed from light-yellow to blue under sintering in the reducing atmosphere and returned back after sintering again in air. The influence of reversible thermochromism on the upconversion luminescence of MoO3:Yb3+,Er3+ phosphor was investigated. The MoO3:Yb3+,Er3+ phosphor prepared in air exhibited visible upconversion luminescence, while the MoO3:Yb3+,Er3+ phosphor has no upconversion luminescence after sintering in the reducing atmosphere. This up-conversion luminescence modulation shows excellent reproducibility after several cycles. The thermochromic MoO3:Yb3+,Er3+ phosphor with reversible modulated upconversion luminescence shows great potential for practical applications in optical switches and optoelectronic multifunctional devices.

Phase transformation induced reversible modulation of upconversion luminescence of WO3:Yb3+, Er3+ phosphor for switching devices.

The upconverting luminescence properties of phosphors are dependent on the hosts. In this work, the WO3:Yb3+, Er3+ phosphor was prepared, and the reversible phase transformation from the WO3 to the WO2 was obtained by alternating the sintering in a reducing atmosphere or in air. The influence of reversible phase transformation on the upconversion luminescence was investigated first. The WO3:Yb3+, Er3+ phosphor exhibits the visible upconversion luminescence, while no upconversion luminescence was observed in the WO2:Yb3+, Er3+ phosphor. The reversible modulation of upconversion luminescence of the WO3:Yb3+, Er3+ phosphor retains the excellent reproducibility, exhibiting the potential applications in data storage and optical switches.

Thermomchromic Reaction-Induced Reversible Upconversion Emission Modulation for Switching Devices and Tunable Upconversion Emission Based on Defect Engineering of WO3:Yb3+,Er3+ Phosphor.

Reversible luminescence modulation of upconversion phosphors has the potential applications as photoswitches and optical memory and data storage devices. Previously, the photochromic reaction was extensively used for the realization of reversible luminescence modulation. It is very necessary to develop other approaches such as thermomchromic reaction to obtain the reversible upconversion luminescence modulation. In this work, the WO3:Yb3+,Er3+ phosphors with various colors were prepared at various temperatures, exhibiting tunable upconversion luminescence attributed to the formation of oxygen vacancies in the host. Upon heat treatment in the reducing atmosphere or air, the WO3:Yb3+,Er3+ phosphors show a reversible thermomchromic property. The reversible upconversion luminescence modulation of WO3:Yb3+,Er3+ phosphors was observed based on thermomchromic reaction. Additionally, the upconversion luminescence modulation is maintained after several cycles, indicating its excellent stability. The WO3:Yb3+,Er3+ phosphors with reversible upconversion luminescence and excellent reproducibility have potential applications as the photoswitches and optical memory and data storage devices.

Emergence of photoluminescence enhancement of Eu3+ doped BiOCl single-crystalline nanosheets at reduced vertical dimensions.

Here, we report that a reduction in scale leads to an enhancement in the photoluminescence (PL) of Eu3+ doped BiOCl nanosheets, challenging the long-standing notion that PL is inevitably suppressed at a scale of tens of nanometers. The oriented depolarization effect of layered ferroelectrics was utilized for the first time to improve the PL efficiency of lanthanide doped nanomaterials. The probing effect of the electric dipole transitions of the Eu3+ ions and their PL measurements provides evidence that the depolarization field and the PL of Eu3+ ions increase synchronously as the thickness of the BiOCl single-crystalline nanosheets decreases from hundreds to tens of nanometers. We show that the scale-dependent internal electric field (IEF) induced by the depolarization field as well as its excitation field enhancement are responsible for the appearance of an abnormal scale-dependent PL enhancement. This finding may be useful for the development of low-dimensional material systems with enhanced photophysical properties, relevant for use in new nano-optoelectronic devices.

Comprehensive investigations of near infrared downshift and upconversion luminescence mechanisms in Yb3+ single-doped and Er3+,Yb3+ co-doped SiO2 inverse opals.

Comprehensive investigations of near infrared (NIR) downshift and visible upconversion luminescence (UCL) mechanisms were carried out for Yb3+ single-doped and Er3+,Yb3+ co-doped SiO2 inverse opals under excitation at 256, 378, 520 and 980 nm. NIR emission at 976 nm from the Yb3+-O2- charge transfer state and UCL emission at 500 nm due to the cooperative emission of two Yb3+ ions were observed in SiO2:Yb3+ inverse opal upon excitation at 256 and 980 nm, respectively. The cooperative UCL of two Yb3+ ions was suppressed due to the photon trap created by the photonic band gap. For the SiO2:Er3+,Yb3+ inverse opals, NIR emission of Yb3+ at 976 nm and of Er3+ at 1534 nm were observed upon excitation at 256, 378 and 520 nm, respectively. Upon excitation at 378 and 520 nm, the 976 nm NIR emission of Yb3+ does not arise from (2H11/2/4S3/2) + 2Yb3+(2F7/2) → Er3+(4I15/2) + 2Yb3+(2F5/2) traditional quantum cutting. The NIR emission of Yb3+ at 976 nm may be due to the Er3+(2H11/2) + Yb3+(2F7/2) → Yb3+(2F5/2) + Er3+(4I11/2) cross-relaxation energy transfer process upon excitation at 520 nm. The NIR emission of Yb3+ at 976 nm may arise from the cross-relaxation energy transfer of Er3+(4G11/2) + Yb3+(2F7/2) → Yb3+(2F5/2) + Er3+(4F9/2) and Er3+(4F9/2) + Yb3+(2F7/2) → Yb3+(2F5/2) + Er3+(4I13/2) upon excitation at 378 nm.

Detection of Hemodynamically Significant Coronary Artery Stenosis With CT Enhancement Ratio: A Validation Study in a Porcine Model.

OBJECTIVE: Although numerous techniques that are based on CT number analysis have been proposed, the assessment of hemodynamically significant coronary artery stenosis remains a great challenge. The purpose of this study is to validate use of the CT enhancement ratio in the detection of hemodynamically significant coronary artery stenosis in a porcine model. MATERIALS AND METHODS: Experiments involving eight closed-chest swine were performed. A balloon catheter was placed into the left anterior descending coronary artery to simulate different degrees of luminal stenosis. The myocardial blood flow (MBF) ratio was measured using the colored microsphere technique. The fractional flow reserve was measured using an invasive pressure wire. CT scans were performed during the first-pass phase, while the pigs were undergoing adenosine stress tests. The CT enhancement ratio and the CT attenuation ratio were calculated using data from the CT images obtained. RESULTS: Results suggested that the CT enhancement ratio had a strong correlation (y = 0.07245 + 0.09963x; r2 = 0.898; p < 0.001) with the MBF ratio measured using the microsphere technique, whereas only moderate correlation (y = -1.5508 + 2.2684x; r2 = 0.498; p < 0.001) was noted between the CT attenuation ratio and the MBF ratio measured using the microsphere technique. In ROC curve analysis, the AUC values of the CT enhancement ratio and the CT attenuation ratio were 0.927 and 0.829, respectively, with regard to the detection of significant ischemia during adenosine stress tests, as defined by the fractional flow reserve. CONCLUSION: The CT enhancement ratio provides a reliable prediction of the MBF ratio measured using the microsphere technique, indicating that this metric has good diagnostic performance in the detection of hemodynamically significant coronary artery stenosis. The CT enhancement ratio may have potential for use as an imaging biomarker for the relative quantitative assessment of myocardial perfusion.

Modification on upconversion luminescence of Er3+-Yb3+ co-doped BiOCl semiconductor nanosheets through interaction between nanohost and doping lanthanide.

We reported the upconversion luminescence (UCL) properties of Er3+-Yb3+ co-doped BiOCl semiconductor nanosheets synthesized by hydrothermal method. Under 980nm excitation, the red and green UCL of Er3+ ions were observed to be populated by a four and three-photon process in the case of absent or low concentration Yb3+ dopant. However, an increase of Yb3+ dopants show a completely opposite effect on the emission intensity of red and green one, accompanying with the change of upconverting process. It indicates that the red-shifting absorption edge of semiconductor and the super saturation UC processes involved with Yb3+ and Er3+ doping in BiOCl semiconductor nanosheets, respectively, are mainly responsible for the above UC phenomena.

Color Tunable and Upconversion Luminescence in Yb-Tm Co-Doped Yttrium Phosphate Inverse Opal Photonic Crystals.

For this paper, YPO4: Tm, Yb inverse opals with the photonic band gaps at 475 nm and 655 nm were prepared by polystyrene colloidal crystal templates. We investigated the influence of photonic band gaps on the Tm-Yb upconversion emission which was in the YPO4: Tm Yb inverse opal photonic crystals. Comparing with the reference sample, significant suppression of both the blue and red upconversion luminescence of Tm3+ ions were observed in the inverse opals. The color purity of the blue emission was improved in the inverse opal by the suppression of red upconversion emission. Additionally, mechanism of upconversion emission in the inverse opal was discussed. We believe that the present work will be valuable for not only the foundational study of upconversion emission modification but also the development of new optical devices in upconversion lighting and display.

Coupling of Ag Nanoparticle with Inverse Opal Photonic Crystals as a Novel Strategy for Upconversion Emission Enhancement of NaYF4: Yb(3+), Er(3+) Nanoparticles.

Rare-earth-ion-doped upconversion (UC) nanoparticles have generated considerable interest because of their potential application in solar cells, biological labeling, therapeutics, and imaging. However, the applications of UC nanoparticles were still limited because of their low emission efficiency. Photonic crystals and noble metal nanoparticles are applied extensively to enhance the UC emission of rare earth ions. In the present work, a novel substrate consisting of inverse opal photonic crystals and Ag nanoparticles was prepared by the template-assisted method, which was used to enhance the UC emission of NaYF4: Yb(3+), Er(3+) nanoparticles. The red or green UC emissions of NaYF4: Yb(3+), Er(3+) nanoparticles were selectively enhanced on the inverse opal substrates because of the Bragg reflection of the photonic band gap. Additionally, the UC emission enhancement of NaYF4: Yb(3+), Er(3+) nanoparticles induced by the coupling of metal nanoparticle plasmons and photonic crystal effects was realized on the Ag nanoparticles included in the inverse opal substrate. The present results demonstrated that coupling of Ag nanoparticle with inverse opal photonic crystals provides a useful strategy to enhance UC emission of rare-earth-ion-doped nanoparticles.

Energy transfer and visible-infrared quantum cutting photoluminescence modification in Tm-Yb codoped YPO(4) inverse opal photonic crystals.

YPO4: Tm, Yb inverse opal photonic crystals were successfully synthesized by the colloidal crystal templates method, and the visible-infrared quantum cutting (QC) photoluminescence properties of YPO4: Tm, Yb inverse opal photonic crystals were investigated. We obtained tetragonal phase YPO4 in all the samples when the samples sintered at 950°C for 5 h. The visible emission intensity of Tm3+ decreased significantly when the photonic bandgap was located at 650 nm under 480 nm excitation. On the contrary, the QC emission intensity of Yb3+ was enhanced as compared with the no photonic bandgap sample. When the photonic bandgap was located at 480 nm, the Yb3+ and Tm3+ light-emitting intensity weakened at the same time. We demonstrated that the energy transfer between Tm3+ and Yb3+ is enhanced by the suppression of the red emission of Tm3+. Additionally, the mechanisms for the influence of the photonic bandgap on the energy transfer process of the Tm3+, Yb3+ codoped YPO4 inverse opal are discussed.

[Synthesis and Luminescence Properties of BiOCL: Dy3⁺Phosphors for NUV Excited White Light-Emitting Diodes].

Abstract In the present paper, we reported the luminescence properties of BiOCl:Dy(3+) and BiOCl:Dy(3+), Li+ phosphor synthesized by conventional solid state method. X-ray diffraction (XRD) and excitation and emission spectroscopy were used to characterize the samples. Results show that pure tetragonal BiOCl:Dy(3+) crystals can be synthesized successfully at 500 °C, and Li+ ion dopant improves the crystallinity of samples furtherly. Under near UV light excitation, the samples,give the characteristic luminescence of Dy(3+) ions located at 478 (blue) and 574 nm (yellow), which show a low yellow-to-blue intensity ratio (Y/B) of Dy(3+) emission and white light emission. Moreover, codoping of Li+ ion can realize the enhancement of emission intensity and the adjustment of emission color. The characteristics of BiOCl:Dy(3+) phosphor, low temperature preparation, good near ultraviolet excitation and white light emission make it to a promising near-ultraviolet WLED phosphor.

Investigation on the upconversion emission in 2D BiOBr:Yb(3+)/Ho(3+) nanosheets.

As lanthanide doped upconverting host, two dimensional (2D) nanostructure materials have remarkable advantages compare with the bulk materials, but excellent 2D upconversion nanohost is still few up to date. In this work, Yb(3+)/Ho(3+) co-doped BiOBr nanosheets have been successfully prepared via a facile hydrothermal method, which were characterized by X-ray diffraction, transmission electron microscopy, Atomic Force Microscope, Raman spectra, Fourier transform infrared absorption and UC luminescence spectra. Under excitation at 980 nm, bright green UC emission centered at 550 nm accompanied with weak red (663 nm) and near infrared (NIR) UC emissions (760 nm) were observed. Power dependence studies revealed that NIR and red UC emissions were both dominated by a two and one-photon process due to saturation effects that is related to the special crystal structure of BiOBr nanosheets, and a different UC mechanism of NIR emission from Ho(3+) was proposed accordingly.

Preparation and upconversion emission modification of crystalline colloidal arrays and rare earth fluoride microcrystal composites.

In this paper, highly ordered crystalline colloidal arrays containing rare earth fluoride microcrystals were fabricated. The upconversion emission property of rare earth fluoride microcrystals in crystalline colloidal arrays was studied and modified. A significant suppression and enhancement of the upconversion emission from the rare earth fluorides can be observed in the regions of the photonic band gap and its band edge, respectively. The suppression or enhancement factor was shown to be related to the ordered degree of the crystalline colloidal arrays and is critical in the preparation of upconversion displays and low-threshold lasers.

[Preparation and up-conversion luminescence properties of Yb3+/Tm3+ co-doped Sb2O4 powder].

The Sb2O4:Yb3+, Tm3+ up-conversion luminescence powder with excellent physical, chemical stability and relative low phonon energy was synthesized by the high temperature solid-state reaction and its up-conversion luminescence property was investigated. Under the 980 nm excitation, infrared and blue up-conversion emissions centered at 800 and 480 nm were observed, which were assigned to the 1G4-->3H6 and 3H4-->3 He transitions of Tm2+, respectively. The influence of Yb3+ and Tm3+ concentration on the up-conversion emission property was also obtained. The up-conversion luminescence increases with increasing of Yb3+ and Tm3+ concentration. Additionally, the up-conversion luminescence mechanism was discussed based on the dependence of Tm3+ up-conversion luminescence on pump power. It is interesting that two photon excitation processes for blue and infrared emission were observed in the Sb2O04: Yb3+, Tm3+ powder under a 980 nm excitation. Based on the energy level diagram of Tma3 and Yb2+ ions, we think that two photons blue emission is contributed to the cooperation energy transfer between Tm"+ and Yb3+ ions. We believe that the Sbz04 : Yb3 , Tm2+ up-conversion luminescence powder will have potential application for new optical devices in up-conversion color displays, sensors, detection of infrared radiation, and lasers.