Sm3+ as effective deactivator for enhanced ∼3 µm laser emission in Er,Sm:SrLaAlO4 crystal.

A promising mid-infrared (MIR) laser crystal with Er, Sm co-doped SrLaAlO4 (Er,Sm:SLA) crystal was successfully grown using the Czochralski (CZ) method. It was the first time that co-doped Sm3+ ion as deactivator for Er3+ activated âˆ¼ 3.0 µm laser. The crystal structure, absorption spectra, emission spectra, and energy level lifetime were discussed in detail. The band structure and density of states were calculated by the density functional theory. The spectral parameters were calculated using Judd-Ofelt (J-O) theory and the deactivate effect of Sm3+ was systematically studied. The introduction of Sm3+ ions enhance the 2.7 µm mid infrared emission intensity by three times, and decrease the lifetime of 4I13/2 energy level of Er3+ ion from 4.35 ms to 0.98 ms. The lifetime ratio of upper and lower levels for 2.7 µm emission was calculated to be 0.63, which is 2.6 times of Er:SLA crystal and comparable to some commercial crystals. All the results indicate that the Sm3+ ion is an effective deactivator for âˆ¼3 µm laser emission. The long upper level lifetime, as well as the large lifetime ratio, the broadening spectra characteristics and the appropriate emission cross-section show the Er,Sm:SLA crystal a good gain material for ultrafast and tunable lasers at âˆ¼3.0 µm.

Simultaneously tuning the luminescent color and realizing an optical temperature sensor by negative thermal expansion in Sc2(WO4)3:Tb/Eu phosphors.

At present, many researchers are focusing on trivalent lanthanide (Ln3+)-doped thermally enhanced upconversion luminescent (UCL) materials with negative thermal expansion (NTE) properties. However, selective anti-thermal quenching downshifting emissions of the activator and thermal quenching of the sensitizer in a phosphor with NTE properties are not implemented. Herein, Tb3+/Eu3+ co-doped Sc2(WO4)3 phosphors synthesized by the solid-state method are explored in selectively enhanced red emission (Eu3+:5D0 → 7F2) due to the energy-transfer efficiency from Tb3+ to Eu3+ and the promoted radiative transition probability. The selective thermally quenched green emission (Tb3+:5D4 → 7F5) is owing to the change of energy transfer from Tb3+ to Eu3+ as the temperature increased. Moreover, under ultraviolet 365 nm excitation, the thermally stimulated color emission tuned from yellow to red with the increase in temperature. Based on the radically different thermal response downshifting the luminescence of the activator and sensitizer, the luminescence intensity ratio (LIR) of non-thermally coupled levels (NTCLs) for 5D0 (Eu3+) and 5D4 (Tb3+) is adopted for optical temperature sensing. The optimal relative sensitivity of temperature sensing in the Sc2(WO4)3:25%Tb3+/3%Eu3+ sample could reach 2.94% K-1 at 347 K. All these indicate that this Sc2(WO4)3:Tb3+/Eu3+ material is a promising candidate for high-sensitivity optical temperature sensing.

Site regulation and luminescence properties of Eu3+, Eu2+ in (La, Mg):SrAl12O19 matrix.

The partially and equivalent substitution of La + Mg â†’ Sr + Al in SrAl12O19 lattice is an effective strategy to provide trivalent sites, reduce the site occupation splitting of Al and stabilize the entire lattice. When excited by 397 nm, the Eu3+ activated La, Mg:SrAl12O19 (ASL) phosphor shows intense linear emission through the 5D0→7F4 transition at 707 nm when compared with SrAl12O19:Eu3+. Especially, the Eu, Mg co-doped Sr1-xLaxMgxAl12-xO19 with certain amount of x = 1/3 exhibits the significant intense photoluminescence, which was demonstrated through a lattice evolutional model. Eu2+ in the host with 1/3 ratio of (La, Mg) substitution shows broad blue emission and as short fluorescence lifetime as 248 ns. The temperature-depended fluorescence quenching behavior confirms the essence of strong electric-phonon coupling originated from distorted and polarized crystal field around Eu2+/Sr2+ site. Basing on site regulation of SrAl12O19 matrix, our study provides a reference for exploration on efficient rare earth ions activated luminescent laser or scintillation materials.

Preparation of REE-doped NaY(WO4)2 single crystals for quantitative determination of rare earth elements in REE:NaY(WO4)2 laser crystals by LA-ICP-MS.

In REE:NaY(WO4)2 laser crystals, optical properties like laser conversion efficiency are dependent on the doped rare earth element (REE) concentration, which necessitates the importance for accurate determination of the REE concentration in these precious samples. However, in situ microanalysis of these samples by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is often hampered by the lack of matrix-matched reference materials. In this work, a REE-doped NaY(WO4)2 single crystal (NaYW-500) that has a nominal REE concentration of 500 µg g-1 was synthesized and employed as a candidate reference material. Its homogeneity (1 RSD of elemental concentration or 89Y-normalized signal intensity) was measured by electron probe microanalysis (EPMA) and LA-ICP-MS to be less than 2% for major elements and mainly <3% for REEs, respectively. Then, an LA-ICP-MS analytical method was developed by using 89Y as the internal standard and using NaYW-500 as the external calibrator under the optimal operating conditions. Quantitative determination of the REE concentration in the other two REE:NaY(WO4)2 single crystals NaYW-50 and NaYW-5000 show that these samples can be accurately measured with relative deviations (Dr) of -6.00 to 12.33% and -9.86 to 6.94%, respectively. Further application of the proposed analytical method to quantitative determination of the Ho concentration in a Ho:NaY(WO4)2 laser crystal shows that desirable accuracy was obtained with a Dr of 4.62%. It demonstrates that the proposed method by preparing REE-doped NaY(WO4)2 single crystals for quantitative determination of the REE concentration in NaY(WO4)2 laser crystals is valid and robust.

A novel approach for forensic identification of automotive paints using optical coherence tomography and multivariate statistical methods.

Automotive paint is one of the most important evidence in solving vehicle-related criminal cases. It contains the critical information about the suspected vehicle, providing essential clues for the investigation. In this study, a novel approach based on optical coherence tomography combined with multivariate statistical methods was proposed to facilitate rapid, accurate and nondestructive identification of different brands of automotive paints. 164 automotive paint samples from 8 different manufacturers were analyzed by a spectral-domain optical coherence tomography system (SD-OCT). Two-dimensional cross-sectional OCT images and three-dimensional OCT reconstruction of vehicle paints of different paints were obtained to show the internal structural differences. Visual discrimination of A-scan data after registration and averaging processing was first used to distinguish different samples. An scanning electron microscope was utilized to obtain the cross-sectional image of the sample to evaluate the effectiveness of OCT technique. Then the original A-scan data, first derivative data and second derivative data of 136 paints with four layers from 7 different manufacturers were collected. Multivariate statistical methods, including principal component analysis (PCA), multi-layer perceptron (MLP), k-nearest neighbor (KNN) algorithm and Bayes discriminant analysis (BDA), were used to analyze different datasets. The results show the hybrid PCA and BDA model based on the first derivative OCT data achieved the best result of 100% accuracy on the testing dataset for identifying automotive paints. It is demonstrated that the OCT technique combined with multivariate statistics could be a promising method for identifying the automotive paints rapidly and accurately.

NaLaMgWO6:Mn4+/Pr3+/Bi3+ bifunctional phosphors for optical thermometer and plant growth illumination matching phytochrome PR and PFR.

Phytochromes PR and PFR distributed in different organs of plant can effectively absorb red and far-red light, respectively. Therefore, plant growth can be controlled by changing the ratio of red light to far-red light. The emission of Pr3+ (transition from 3P0→3F2,3) and Mn4+(transition from 2Eg→4A2g) is located at the red and far-red range which matches with the absorption band of PR and PFR, respectively. Herein, NaLaMgWO6:Mn4+/Pr3+/Bi3+ phosphors with improving luminescence properties via Bi3+ doping have been successfully prepared by the sol-gel method. With the variation of temperature, the photoluminescence (PL) of Pr3+/Mn4+ (corresponding to PFR/PR) of titled phosphors can be tuned, which is very useful for controlling the plant growth. Moreover, based on the fluorescence intensity ratios (FIR) of the two activator Mn4+ and Pr3+, the maximum relative sensitivity was approximately 3.39%/K at 298 K. All the results indicated that the titled phosphor is a bifunctional material for plant growth illumination with high matching phytochrome (PR and PFR) and temperature sensing with high sensitivity.

High efficient and broadband ∼3.5 µm emission of Er3+:YAG crystal.

The YAG single crystals doped with 10 at.%, 20 at.% and 50 at.% Er3+ were successfully grown by the micro-pulling down method and spectroscopic properties of the crystals were investigated. The main interest was focus on the relation between the Er3+ concentration and ∼3.5 µm emission of Er3+:YAG crystals. Room temperature absorption spectra were analyzed by the Judd-Ofelt theory. The stimulated emission cross-sections were calculated by the Füchtbauer-Ladenburg equation. The fluorescence intensities and peak emission cross-sections of the crystals at ∼3.5 µm are slightly decreasing with the increase of Er3+ concentration. The trend of the emission properties in NIR and visible region with the Er3+ concentration was also discussed and compared. The results indicate that the highly doped Er3+ concentration is beneficial to realize the ∼3.5 µm laser output.

Spectral analyses of Dy3+/Sr2+: LaF3 and Dy3+/Ca2+: LaF3 mixed crystals for laser applications.

Mixed crystals of Dy3+/Sr2+: LaF3 and Dy3+/Ca2+: LaF3 were grown by Bridgman technique and their spectral properties were investigated. Spectra broadening and peak shifts were observed, indicating the co-doping of Sr2+/Ca2+ brings about a more disordered local symmetry of Dy3+, which makes both crystals favorable for tunable lasing action. Low-temperature high resolution excitation and emission spectra were carried out for exploring the types of luminescent center of Dy3+ in crystals. Room-temperature absorption and emission spectra, together with the fluorescence decay curves were studied in both crystals for estimating their potentials for yellow and MIR lasers. Under 450 nm excitation, the largest emission cross-sections at 571 nm of 1.51 × 10-21 cm2 for Dy3+/Sr2+: LaF3 crystal and 1.56 × 10-21 cm2 for Dy3+/Ca2+: LaF3 crystal, along with the lifetimes of Dy3+: 4F9/2 level as 0.983 ms for Dy3+/Sr2+: LaF3 crystal, 1.143 ms for Dy3+/Ca2+: LaF3 crystal were obtained, respectively. Besides yellow emissions, MIR emissions approximately at 3 µm are more appealing. Under 1280 nm excitation, the largest emission cross-sections of 0.304 × 10-20 cm2 at 2885 nm in Dy3+/Sr2+: LaF3 crystal, and 0.319 × 10-20 cm2 at 2880 nm in Dy3+/Ca2+: LaF3 crystal, together with rather long lifetimes of Dy3+: 6H13/2 in the level of milliseconds were achieved, making them useful media for MIR lasers.

Sb2Te3 as the saturable absorber for the ∼2.0 µm passively Q-switched solid state pulsed laser.

We demonstrated a passively Q-switched Tm:YAP solid state pulsed laser based on an Sb2Te3 saturable absorber. This saturable absorber was prepared by a facile hydrothermal method. The maximum pulse energy was up to 5.366 µJ at the absorbed pump power of 6.6 W. The corresponding pulse width, output power and repetition rate were 533 ns, 542 mW and 101 kHz, respectively. The results indicated that the hydrothermally synthesized Sb2Te3 nanosheet was a promising saturable absorber for near-infrared pulsed lasers.

High performance of a passively Q-switched mid-infrared laser with Bi2Te3/graphene composite SA.

We report passively Q-switched ∼2 and ∼3 µm mid-infrared (MIR) solid-state lasers with a self-assembly solvothermal-synthesized Bi2Te3/graphene heterostructure saturable absorber (SA) for the first time. Based on the oxidation resistance and high thermal conductivity of graphene, and large modulation depth of Bi2Te3 nanosheets, two high-performance Q-switching lasers were realized. One is a Tm:YAP laser with a maximum average output power of 2.34 W and a pulse width of 238 ns at ∼2 µm. The corresponding maximum pulse peak power was 91 W, which was much improved in comparison with the pure graphene-based Tm laser. The other one is an Er:YSGG laser producing a pulse width of 243 ns, which is the shortest among the 2D SAs-based ∼3 µm solid-state lasers, as far as we know. Our results indicate that such a composite Bi2Te3/graphene material is a promising SA for generating high-performance mid-infrared pulse lasers.

Ultrasensitive nonlinear absorption response of large-size topological insulator and application in low-threshold bulk pulsed lasers.

Dirac-like topological insulators have attracted strong interest in optoelectronic application because of their unusual and startling properties. Here we report for the first time that the pure topological insulator Bi2Te3 exhibited a naturally ultrasensitive nonlinear absorption response to photoexcitation. The Bi2Te3 sheets with lateral size up to a few micrometers showed extremely low saturation absorption intensities of only 1.1 W/cm(2) at 1.0 and 1.3 µm, respectively. Benefiting from this sensitive response, a Q-switching pulsed laser was achieved in a 1.0 µm Nd:YVO4 laser where the threshold absorbed pump power was only 31 mW. This is the lowest threshold in Q-switched solid-state bulk lasers to the best of our knowledge. A pulse duration of 97 ns was observed with an average power of 26.1 mW. A Q-switched laser at 1.3 µm was also realized with a pulse duration as short as 93 ns. Moreover, the mode locking operation was demonstrated. These results strongly exhibit that Bi2Te3 is a promising optical device for constructing broadband, miniature and integrated high-energy pulsed laser systems with low power consumption. Our work clearly points out a significantly potential avenue for the development of two-dimensional-material-based broadband ultrasensitive photodetector and other optoelectronic devices.