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Sihan Yang, Changshuai Gong, Ziying Wang, Liang Dong, Xuejiao Wang, [Ji-Guang Li](https://orcid.org/0000-0002-5625-7361)

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[Blue Light Excitable Near-Infrared Luminescence Material Yb2−2xCr2xW3O12: Cr3+ → Yb3+ Energy Transfer, Mechanisms of Antithermal Quenching, and High-Performance pc-LED Applications](https://mdr.nims.go.jp/datasets/427c95a1-9b26-45ff-bdb4-79239dff8be9)

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Blue Light Excitable Near-Infrared Luminescence Material Yb2-2xCr2xW3O12: Cr3+→Yb3+ Energy Transfer, Mechanisms of Antithermal Quenching, and High-Performance pc-LED ApplicationsSihan Yang,a$ Changshuai Gong,a$ Ziying Wang,a Liang Dong,c Xuejiao Wang,a* Ji-Guang Lib*aSchool of Materials and Environmental Engineering, Bohai University, Jinzhou, Liaoning 121007, ChinabResearch Center for Electronic and Optical Materials, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044, JapancKey Laboratory for Anisotropy and Texture of Materials (Ministry of Education), School of Materials Science and Engineering, Northeastern University, Shenyang, Liaoning 110819, China*Corresponding authorDr. Xuejiao WangBohai UniversityJinzhou, ChinaTel: +86-416-3400708Email: wangxuejiao@bhu.edu.cnDr. Ji-Guang LiNational Institute for Materials ScienceTsukuba, JapanTel: +81-29-860-4394Email: li.jiguang@nims.go.jp$Sihan Yang and Changshuai Gong made equal contributions to this work1mailto:wangxuejiao@bhu.edu.cnmailto:li.jiguang@nims.go.jpABSTRACTTo overcome the problem of severe thermal quenching of near-infrared (NIR) phosphors, the NIR phosphor with anti-thermal quenching performance is urgently needed. In this work, negative thermal expansion (NTE) material Yb2-2xCr2xW3O12 was prepared. Through a comprehensive analysis involving in-situ XRD, thermogravimetry (TG) and Rietveld refinement, it was concluded that, at room temperature, the sample adopts a trihydrate orthorhombic structure (Yb2W3O12·3H2O) and does not exhibit negative thermal expansion (NTE) behavior. However, after dehydration at 373 K, anhydrous orthorhombic Yb2W3O12 (space group Pbcn), which exhibits obvious NTE properties, was obtained. The underlying mechanism is that, when water molecules enter the crystal and occupy vacancies, the Yb-O-W bonds bend, restricting the transverse thermal vibrations of the Yb-O-W bonds. The characteristic emission of Yb3+ within the range of 800-1300 nm was observed under 468 nm blue light irradiation due to the efficient energy transfer from Cr3+→Yb3+. Remarkably, the prepared NIR phosphor has anti-thermal quenching performance, and at 398 K the intensity of the strongest emission can maintain 1.89 times that of the room temperature, surpassing most NIR phosphors. The anti-thermal quenching phenomenon is attributed to cell contraction, which reduces the distance between the sensitizer and activator, thereby enhancing the energy transfer efficiency and increasing the luminous intensity. The combination of 460 nm excitable strong NIR emission and anti-thermal quenching suggests potential application in biomedical imaging and infrared night-vision technologies. The NIR pc-LED device, prepared by coating the Yb1.94Cr0.06W3O12 phosphor on a commercial 460 nm chip, demonstrated a high optoelectronic efficiency and high output power, making it well-suited for night vision applications. Furthermore, the efficient NIR-I/II emission from Yb1.94Cr0.06W3O12 was proved to be highly effective for compositional analysis. This study offers valuable insights for designing NIR phosphors with excellent thermal quenching resistance.KEYWORDS: blue light excitable phosphor; near-infrared luminescence; anti-thermal quenching; efficient energy transfer; negative thermal expansion21. INTRODUCTIONNIR spectroscopy has many benefits, such as rapid detection, non-invasive inspection, and contactless measurements.1-5 Practical applications of the traditional NIR light sources, however, are restricted due to the low efficiency, large size, and high energy consumption. Intelligence and miniaturization of integrated spectrometers are still facing challenges. Another NIR light source currently being developed is the NIR pc-LED. Compared with conventional light sources, it has a small size, low cost, stable spectrum, and a tunable spectral distribution.6 Additionally, the NIR pc-LED is suitable as a light source for micro NIR spectrometers owing to the inherent benefits of white LEDs.7 Active ions that can realize broadband NIR luminescence can primarily be categorized as 4f-5d electron transition type (Ce3+, Eu2+, etc.), 6s-6p electron transition type (Bi3+/Bi2+/Bi+, etc.), and 3d-3d electron transition type (Cr3+/Cr4+, Ni2+, Fe3+, etc.). Cr3+ has garnered significant academic attention due to its ultra-wide emission band, capacity for tunable broadband NIR emission within the 700-1200 nm range, and efficient excitation by blue LED chips. It is thus widely regarded as the most promising activator for the development of commercial NIR pc-LEDs.8,9 However, the emission of Cr3+-activated phosphors primarily located in the NIR-I region (650-900 nm). Emission in the NIR-II region (1000-1700 nm) has the advantages of covering multiple functional group vibration frequencies, deeper tissue penetration, higher sensitivity, and superior spatial resolution,10,11 although potential eye safety risk exists for NIR emission >1400 nm in practical use.12 The emission of Yb3+, originating from f-f transitions, lies at the end of the NIR-I region and the beginning of the NIR-II region (＜1400 nm), making it suitable for applications like biological imaging and spectral analysis. However, the intrinsic f-f absorption of Yb3+ is weak and poorly matches with3commercial blue LED chips. When co-doped with Cr3+, effective Cr3+→Yb3+ energy transfer may occur, enabling the phosphor to be efficiently excited by blue light and emit high-efficiency NIR light.In addition, NIR phosphors face a critical challenge, that is, thermal quenching (TQ). Especially, NIR phosphors with longer emission wavelengths often exhibit severe thermal quenching due to strong electron-phonon coupling, which promotes non-radiative transitions. Materials exhibiting negative thermal expansion (NTE) or near-zero thermal expansion (NZTE) behavior provides a new solution for this issue. Among these, the A2M3O12 family stands out due to its excellent chemical flexibility and adjustable thermal expansion coefficient.13,14 These compounds consist of co-cornered AO6 octahedra and MO4 tetrahedra, and the transverse vibration of the A-O-M bridging bonds can induce NTE behavior at the macroscopic scale. Sumithra et al.15 systematically studied the thermal expansion properties of the Ln2W3O12 series (Ln: lanthanide elements) and found that their thermal expansion behavior is regulated by the radius of Ln3+ and crystal structure. The tungstates of larger Ln3+ (Ln = La, Nd, Dy) exhibit a co-edge monoclinic structure (space group C2/c) at room temperature, which suppresses the negative thermal expansion effect. In contrast, the tungstates of smaller Ln3+ (Ln = Y, Yb, Er) exhibit a trihydrate orthorhombic structure. Upon dehydration at elevated temperatures, these compounds transform into an orthorhombic phase (space group Pnca) and exhibit pronounced NTE behavior. Among them, Yb2W3O12, as a typical negative thermal expansion material, has a linear thermal expansion coefficient of -8.35× 10-6 K-1@373-873 K, in sharp contrast to traditional positive thermal4expansion materials such as YAG (8.5×10-6 K-1@300-600 K) and YAP (8.325×10-6 K-1@298-774 K).15−17 The lattice contraction during heating reduces the distance between activator ions, thereby enhancing energy transfer efficiency and improving luminescence performance.18,19 Based on this background, this study attempts to incorporate Cr3+ into the Yb2W3O12 matrix, aiming to exploit its negative thermal expansion properties and build an efficient energy transfer pathway from Cr3+ to Yb3+. This will facilitate the realization of high-performance NIR-I/II emission and allow to explore the correlation between anomalous thermal quenching behavior and lattice contraction. In this work, we doped Cr3+ into Yb2W3O12 to study NIR luminescence characteristics and energy transfer mechanism. The mechanism of anti-thermal quenching and multi-functional applications were also explored. The Yb2-2xCr2xW3O12 series samples were synthesized via traditional solid-state reaction method. The NIR emission from the Yb3+ ions can be produced under blue light irradiation owing to the energy transfer of Cr3+→Yb3+. The representative Yb1.94Cr0.06W3O12 sample maintains 189% of its luminescence intensity at 398 K, surpassing the performance of most long-wavelength-emitting NIR phosphors. An NIR pc-LED device was also constructed using a commercial 460 nm blue LED chip and Yb1.94Cr0.06W3O12 phosphor. The results showed that Yb1.94Cr0.06W3O12 phosphor has potential application in high-performance NIR pc-LED.2. EXPERIMENTAL SECTION2.1 Sample preparationThe conventional solid-state reaction method was selected over wet-chemical synthesis sol-gel, due to its superior scalability for potential industrial applications. The5rare earth source for the synthesis is Yb2O3 (99.99% pure), which was purchased from Huizhou Ruier Rare Chemical Hi-Tech Co. Ltd. (Huizhou, China). The other reagents of H40N10O41W12xH2O (AR grade) and Cr2O3 (99.99% pure) were purchased from Aladdin Corporation (Shanghai, China) and were used without further purification. The starting materials were weighed based on the calculated molar stoichiometric ratios, and then transferred into an agate mortar, where a suitable quantity of alcohol was added to achieve full grinding. The powder mixture was transferred into a corundum crucible after drying, and the crucible was then put inside a tube furnace and heated for 4 h at 1100 ℃. Thereafter, the sample was cooled to room temperature followed by grounding into powder for further experiments.2.2 Characterization The phases of the obtained specimens were determined with an Ultima IV X-ray diffractometer (XRD) from Rigaku using a Cu-Kα1 radiation (λ = 0.15406 nm) in step-scan mode. The inductively coupled plasma-mass spectrometry (ICP-MS; Model ICPE-9820, Shimadzu, Japan) was used to evaluate the Cr3+ concentration in the products. The EDS and morphological analyses of the prepared phosphors were conducted utilizing a Tescan MIRA LMS field emission SEM (FE-SEM) system. Diffuse reflectance spectra were acquired using a PE-750 UV-Vis spectroscopy system from PerkinElmer. The Raman and Fourier transform infrared (FT-IR) spectra were acquired utilizing a HORIBA-LabRAM HR confocal micro-Raman spectrometer and an IRTracer-100 spectrometer, respectively. Thermogravimetric curves were measured with an STA 8000 thermal analyzer from PerkinElmer. The PL/PLE and fluorescence decay curves were obtained utilizing an FLS 1000 fluorospectrophotometer from Edinburgh Instru-ments Ltd. Temperature-dependent luminescence spectra were also acquired utilizing the same setup coupled to a TAP-02 high-temperature controller.62.3 Testing and packaging of pc-LEDThe NIR pc-LED devices were fabricated utilizing the synthesized Yb1.94Cr0.06W3O12 phosphor and a 460 nm LED (3 W) from San'an Optoelectronics Co., Ltd. The chip material used is InGaN, while the bracket pin material is copper alloy with a silver-plated surface. Epoxy resin is used as the encapsulating material. The encapsulation process is as follows: First, the phosphor and epoxy resin are mixed in a specific ratio to ensure the materials are fully dispersed. Next, the mixture is degassed using a degassing machine to remove any air bubbles, ensuring high uniformity and stability of the mixture. Finally, the mixture is applied to the LED chip for further testing.3. RESULTS AND DISCUSSION3.1 Phase, crystal structure, morphology and compositionFigure 1. (a) The XRD patterns for the Yb2-2xCr2xW3O12 (x = 0-0.10) phosphors and enlarged view of the XRD peak in the 2θ = 24.5-27.5o range. (b) The crystal structure of orthorhombic Yb2W3O12. (c) The survey XPS spectrum of Yb1.94Cr0.06W3O12. (d) High-resolution XPS spectra of Cr 2p and (e) O 1s. (f) The acquired FE-SEM images and EDS mapping results for the Yb1.94Cr0.06W3O12 phosphor.A series of Yb2W3O12 based phosphors doped with different concentrations of Cr3+7were prepared and the actual amounts of Cr3+ in the samples were further determined by ICP-MS. The results in Table S1 show that the actual content is quite close to the designed value. The XRD patterns for the series of samples Yb2-2xCr2xW3O12 (x = 0-0.10) are provided in Figure 1a. All the diffraction peaks of each sample match well with the standard data (JCPDS-18-1451)20 without detectable impurity signals, indicating the successful synthesis of pure-phase materials and that Cr3+ doping did not affect the phase composition. A magnified view of the main diffraction peaks between 24.5°-27.5° reveals a gradual shift toward higher angles with increasing Cr3+ concentration. This observation suggests lattice contraction, which can be attributed to the smaller ionic radius of Cr3+ (0.615 Å, CN = 6) than Yb3+ (0.87 Å CN = 6).21 The structure of Yb2W3O12 is presented in Figure 1b, where [YO6] octahedron and [WO4] tetrahedron are connected through an oxygen atom. Figure 1c depicts the XPS survey spectrum for the Yb1.94Cr0.06W3O12 sample. It is evident that all the constituent elements of the tested sample can be clearly identified. The high-resolution XPS spectrum of the Cr 2p orbital is presented in Figure 1d. The sub-peaks corresponding to Cr 2p1/2 and Cr 2p3/2 exhibit central energies of approximately 587.43 eV and 577.26 eV, indicating a trivalent state of Cr.22 In previously reported studies on Yb2W3O12, the presence of oxygen vacancies has been documented, making it necessary to use XPS to verify the changes in vacancy concentrations in the samples. Figure 1e displays the O 1s spectra of two representative samples, where the fitted high-energy and low-energy peaks are assigned to adsorbed oxygen (OA) and oxygen vacancies (OV), respectively.23 The content of oxygen vacancies can be roughly estimated by the OV/OA peak area ratio. Upon Cr3+ doping, this ratio decreased from 4.79 to 3.15, indicating a reduction in oxygen vacancy concentration. This reduction would decrease the non-radiative8recombination centers, thereby enhancing luminescence efficiency. Additionally, electron paramagnetic resonance (EPR) spectroscopy was conducted, as displayed in Figure S1. Compared with pristine Yb2W3O12, the EPR signal of oxygen vacancies (g = 2.003) in Yb1.94Cr0.06W3O12 is significantly reduced, further supporting the conclusion that Cr3+ doping leads to a decrease in oxygen vacancy concentration. The SEM and EDS mapping results obtained for the Yb1.94Cr0.06W3O12 phosphor are summarized in Figure S2 and Figure 1f. It was found that the microscopic morphology under different magnifications was not uniform, and the product is agglomerated particles. The mapping results confirmed that all the elements, especially the doped Cr element, were distributed evenly within the prepared sample.24Figure 2. (a) DR spectra of Yb2-2xCr2xW3O12 (x = 0-0.10). (b) Band gap determination of Yb2W3O12. (c) Raman spectra, (d) FT-IR spectra obtained for the Yb2-2xCr2xW3O12 (x = 0-0.10) phosphors.The DR spectra acquired for the Yb2-2xCr2xW3O12 (x = 0-0.10) phosphors are presented in Figure 2a, where the Yb2W3O12 matrix exhibits an absorption band in the 200–350 nm region. Upon Cr3+ doping, new absorption bands appeared at 400–550 and9600–800 nm, corresponding to the transitions of Cr3+ from the ground state 4A2 to 4T1 (4F) and 4T2 (4F), respectively. The band gap energy for Yb2W3O12 was determined by the Kubelka-Munk function:25[    (1)左方括号 大写 F 左第二个圆括号 大写 R 下标 无穷大 设备控制 4 , 右第二个圆括号 设备控制 4 h Nu 右方括号 ...次方 停顿 1 除 n 结束 上标 等于 大写 A. 左圆括号 h Nu 减 大写 E 下标 g 设备控制 4 , 右圆括号𝐹(𝑅∞)ℎ𝜈]1/𝑛 = 𝐴(ℎ𝜈 − 𝐸𝑔)大写 F 左圆括号 大写 R 下标 无穷大 设备控制 4 , 右圆括号 等于 左圆括号 1 减 上标 基线 , 大写 R 下标 无穷大 右圆括号 , 结束 基线 , 平方 除 2 左圆括号 大写 R 下标 无穷大 设备控制 4 , 右圆括号𝐹(𝑅∞) = (1 − 𝑅∞)2/2(𝑅∞)(2)Here, F(R∞) denotes the reflection coefficient, Eg corresponds to the band gap, A represents a constant, hν denotes the energy of the incident photons, whereas n denotes the band gap type, with n = 1/2 for a direct allowed transition, n = 3/2 for a direct forbidden transition, n = 2 for an indirect allowed transition, and n = 3 for an indirect forbidden transition.26 According to previous reports, the electronic band structure of Yb2W3O12 is an indirect allowed transition, so the n value is 2. The correlation between hν and [F(R∞)hν]1/2 for Yb2W3O12 is shown in Figure 2b, and the resulting Eg value is 4.38 eV. The Raman and FT-IR spectra were acquired to gather lattice vibration information, which was used to evaluate the phonon energy of both the host lattice and the doped samples. The lattice vibration information was obtained by monitoring Raman and FT-IR spectra to obtain the phonon energy of the prepared samples. As depicted in Figure 2c, the three distinct signals, observed at 250-400 cm-1, 750-900 cm-1 and 900-1050 cm-1 in the Raman curves, can be identified as the bending vibrations, asymmetric stretching vibrations, and symmetric stretching vibrations of [WO4] tetrahedra, respectively.27,28 As illustrated in Figure 2d, the FT-IR spectra of both the host lattice and the series of doped samples exhibited an absorption signal at 874 cm-1, corresponding to the vibrations of W-O-W. Additionally, the signals at 1620 and 3404 cm-1 were linked to the H-O-H bending vibration and O-H stretching vibrational modes, respectively.29103.2 Near-infrared luminescence characteristics and efficient Cr3+-Yb3+ energy transferFigure 3. (a) Normalized PL and PLE spectra of Yb2W3O12 and Yb1.94Cr0.06W3O12. (b) The PL spectra under 468 nm excitation of Yb2W3O12 and Yb1.94Cr0.06W3O12. (c) The energy transfer schematic diagram between Yb3+ and Cr3+. (d) The PLE spectra and (e) PL spectra of Yb2-2xCr2xW3O12 (x = 0-0.10). (f) Decay curves of the 1048 nm emission of Yb2-2xCr2xW3O12 (x = 0.01-0.10).The PL and PLE spectra of the host and Cr3+-doped samples are displayed in Figure 3a and Figure S3. The optimal excitation band of the host sample is located at 314 nm, which does not match commercially available blue LED chips. Under 314 nm excitation, an emission band ranging from 900 to 1100 nm can be observed, attributable to the 2F5/2→2F7/2 transition of Yb3+. The splitting observed in the emission spectrum can be ascribed to the transitions from the Stark split energy levels of 2F5/2 to ground state 2F7/2.30 After doping with Cr3+, no characteristic emission band of Cr3+ was detected aside from the Yb3+ emission. Furthermore, when monitoring the excitation spectrum at the Yb3+ emission wavelength, excitation bands corresponding to the characteristic transitions of Cr3+ were observed, indicating an effective energy transfer of Cr3+→Yb3+. To further verify the existence of energy transfer, as depicted in Figure 3b, the host and Cr3+-doped Yb2W3O12 samples were excited with blue light under11identical conditions. It can be seen that only the Cr3+-doped sample could be effectively excited by blue light and exhibited Yb3+ emission. The absence of Cr3+ emission can be attributed to the exceptionally high efficiency of energy transfer from Cr3+ to Yb3+. The energy transfer mechanism is illustrated in Figure 3c. Under the blue light irradiation, the electrons within Cr3+ transited from the 4A2 ground level to the excited level 4T1, before relaxing down to the excited state 4T2. After that, some of them returned to the ground state 4A2 to produce the NIR light. The other part transferred energy to the Yb3+ ions from the 4T2 state of Cr3+ to the 2F5/2 state of Yb3+. Finally, the electrons at the 2F5/2 energy level return to 2F7/2, producing the emission of 1048 nm.31,32 The excitation spectra obtained for the Yb2-2xCr2xW3O12 (x = 0-0.10) phosphors are depicted in Figure 3d. The characteristic 4A2→4T1 (4P), 4A2→4T2 (4F), and 4A2→4T1 (4F) transitions of Cr3+ were observed as the emission wavelength was being monitored at the 1048 nm emission of Yb3+, exhibiting effective Cr3+→Yb3+ energy transfer. Under 468 nm excitation, Yb2W3O12 exhibits no emission peak in the 900-1100 nm region. In contrast, all the Yb2-2xCr2xW3O12 (x = 0.01-0.10) phosphors displayed the characteristic Yb3+ emission at 1048 nm, covering both the NIR-I and NIR-II regions. In summary, it is the highly efficient Cr3+→Yb3+ energy transfer that enables Yb2-2xCr2xW3O12 to be effectively excitable by blue light and produce efficient NIR-I/II emission. The emission intensity reached a maximum value at x = 0.03 with an increase in the doping concentration of Cr3+ and subsequently decreased (Figure 3e). The full width at half maximum (FWHM) values of the samples were calculated and summarized in Table S2. The decay spectra of the 970 nm, 1004 nm, and 1048 nm emissions of the Yb2-122xCr2xW3O12 (x = 0.01-0.10) phosphors were measured., and the results are shown in Figure 3f and Figure S4. Bi-exponential fitting demonstrated the best fitting results and goodness-of-fit factors compared to single and triple exponential fitting (Figure S5). The fitting formula is as follows:33(3)大写 I. 中等阴影 t , 等于 大写 A. 下标 1 设备控制 4 exp 左圆括号 减 t 除 tau 下标 1 设备控制 4 , 右圆括号 加 大写 A. 下标 2 设备控制 4 exp 左第二个圆括号 分子 停顿 减 t 结束 分子 , 杠 tau 下标 2 设备控制 4 , 右第二个圆括号𝐼(𝑡) = 𝐴1exp(−𝑡/𝜏1) + 𝐴2 exp(−𝑡 𝜏2⁄ )where I(t) indicates the emission intensity at time t, τ1 and τ2 refer to the lifetimes of the two exponential decaying components, while A1 and A2 are constants. The mean lifetime τ* was determined via eq. (4):(4)tau ...次方 星号运算符 等于 分子 停顿 大写 A. 下标 1 设备控制 4 上标 基线 , tau 下标 1 , 结束 基线 , 平方 加 大写 A. 下标 2 设备控制 4 上标 基线 , tau 下标 2 , 结束 基线 , 平方 结束 分子 , 除 分母 停顿 大写 A. 下标 1 设备控制 4 tau 下标 1 加 大写 A. 下标 2 设备控制 4 tau 下标 2 设备控制 4 结束 分母𝜏∗ =𝐴1𝜏12+𝐴2𝜏22𝐴1𝜏1+𝐴2𝜏2The lifetime of the Yb3+ ions was calculated by eqs. (3)-(4), with the fitted parameter values and fitting factors χ2 being summarized in Table S3-5. It was found that as the Cr3+ concentration increased, the lifetimes of the three split emission peaks gradually decreased. Additionally, the lifetime values for the three emission peaks at each concentration point showed minimal differences. This suggests that all the three peaks correspond to the 2F5/2→ 2F7/2 transition of Yb3+, and thus similar lifetimes and consistent lifetime variations were resulted. Besides, the internal quantum efficiency of Yb1.94Cr0.06W3O12 is 23.6% (Figure S6). Broadband NIR phosphors with emission wavelengths toward NIR-II region have rarely been reported and often have low quantum efficiency, as exemplified by CaScAlSiO6: Cr3+ (IQE = 21%, λem = 950 nm), InTaO4: Cr3+ (IQE = 26%, λem = 975 nm), Cs2NaInCl6: Cr3+ (IQE = 19.7%, λem = 958 nm), Cs2AgInCl6: Cr3+ (IQE = 5.8%, λem = 998 nm), and ZnWO4: Cr3+ (IQE = 12.5%, λem = 987 nm).34−37133.3 Anti-thermal quenching NIR luminescenceFigure 4. (a) In-situ XRD patterns, (b) the TG cures of Yb1.94Cr0.06W3O12. (c) The variation trend of cell parameters a, b, c and V with temperature. (d) Temperature-dependent emission spectra, (e) the normalized emission intensity for different emissions of Yb1.94Cr0.06W3O12. (f) Decay curves of the 1048 nm emission for the Yb1.94Cr0.06W3O12 phosphor under varying temperatures.To evaluate the NTE properties, the in-situ XRD patterns of the representative Yb1.94Cr0.06W3O12 sample were taken. As shown in Figure 4a, a phase transition occurred with increasing temperature. When the temperature exceeds 323 K, the XRD patterns can be indexed to the standard reference (mp-759447) of orthorhombic Yb2W3O12 with Pbcn space group. The A2M3O12 phase is reported to possess microchannels along the a-axis. Larger microchannels allow the free entering of water molecules, which disrupt the local structure and lead to partial amorphization of the Yb2W3O12 phase at room temperature, accompanied by the loss of NTE behavior.38 At moderately elevated temperatures (~373 K), dehydration occurs and Yb2W3O12 crystallizes into the orthorhombic system (Pbcn space group). This transformation has been observed in all hygroscopic tungstates and orthorhombic tungstates. To verify this phenomenon, we examined the TG curve (Figure 4b), which shows a 4.84% weight loss between 323-388 K by the release of hydration water, indicating a phase transition14during the water release process. The number of water molecules calculated from the TG analysis is approximately equal to 3. For further analysis, Rietveld refinement on the in-situ XRD spectra was performed. Since no CIF file is available for hydrated Yb2W3O123H2O, we obtained basic crystallographic parameters by unit cell refinement in Jade software using the monoclinic system according to literature reports.38,39 For the anhydrous sample (orthorhombic system), refinement was conducted using the GSAS software package with the results shown in Figure S7. Detailed crystallographic parameters are listed in Table S6, and the refinement further confirmed the occupation of Yb3+ sites by Cr3+. The trend of change in unit cell parameters with temperature is plotted in Figure 4c. It is evident that the hydrated Yb2W3O123H2O sample has smaller unit cell parameters, which is due to the bending of Yb-O-W bonds when water molecules enter the crystal framework and occupy vacancies. After water release, the Yb-O-W bonds become unbent, causing the lattice parameters to increase. Due to the bent Yb-O-W bonds, the hydrated Yb2W3O123H2O may not exhibit negative thermal expansion.40 When the temperature rises from 298 K to 323 K, the vibrations of the water molecules become more intense. With increasing vibrational activity, the water molecules undergo a transition from a bound sate to a free state, resulting in significant expansion of the unit cell.41 After complete release of water (373-573 K), cell volume gradually decreases, confirming the presence of NTE characteristics. Additionally, using relevant formulas, the coefficient of thermal expansion in the 373-573 K temperature range was determined to be -2×10-5 K-1, further confirming the NTE behavior of the sample. The lattice contraction is caused by the transverse thermal vibrations of the bridging oxygen atoms at the vertices of the Yb-O-W chains, accompanied by slight distortions of the rigid [YbO6] and [WO4] polyhedrons.42 Generally, the NTE property would lead to thermal enhancement of luminescence.15To investigate this effect, the temperature-dependent luminescence spectra of the sample were taken in Figure 4d. It was found that the emission intensity initially decreased, which is followed by an increasing trend before decreasing again with an increase in temperature. As analyzed above, the hydrated Yb2W3O123H2O sample exhibits no NTE. However, upon dehydration, it clearly demonstrates characteristic NTE behavior. The relationship between emission intensity and temperature can be seen by the normalized spectra of different emissions in Figure 4e. The emission peaks at 970 nm, 1004 nm, and 1048 nm show consistent changes with increasing temperature. At 398 K, the emission intensities increased to 263%, 242%, and 189% of their room temperature values, respectively. These values significantly surpass those of typical NIR-II emitting phosphors, confirming the excellent anti-thermal quenching property of the sample in practical applications. This fluorescence enhancement phenomenon is attributed to the lattice contraction of Yb1.94Cr0.06W3O12 at high temperatures, which shortens the distance between the sensitizer and activator ions, thereby enhancing energy transfer and improving the emission intensity. Additionally, the lattice contraction helps to increase the structural rigidity of the matrix, further enhancing the thermal stability of the phosphor. Upon exceeding 398 K, the fluorescence intensity begins to decline. In this temperature regime, the energy loss caused by thermally activated non-radiative processes outweighs the energy gain from enhanced energy transfer, resulting in an overall reduction of luminescence intensity.43 Furthermore, batch-to-batch consistency tests were performed and the quantitative reproducibility metrics for PL intensity and temperature-dependent luminescence are shown in Figure S8 and S9. The normalized decay curves of the 1048 nm emission of the Yb1.94Cr0.06W3O12 phosphor at various temperatures are presented in Figure 4d. The lifetime values have been calculated utilizing eqs. (3)-(4), and the fitting parameters16and goodness factor of fitting are listed in Table S7. It can be seen that the lifetime first increased and then followed a decreasing trend as temperature increases.3.4 Applications in night vision and NIR pc-LEDFigure 5. (a) Luminescence spectra obtained at different driving currents for the developed NIR pc-LED. (b) Relationships between photoelectric efficiency/NIR output power and the driving current. (c) Photographs demonstrating the practical application of the prepared NIR pc-LED device. (d) The thermographs obtained for the prepared device at varying driving current values (20-300 mA).To evaluate the application potential of the obtained Yb1.94Cr0.06W3O12 phosphor, an NIR pc-LED device was fabricated by integrating this phosphor with a blue LED chip as the excitation source. The electroluminescence spectra of the prepared NIR pc-LED covered the NIR range extending from 900 to 1300 nm, as presented in Figure 5a. The FWHM of the spectra at different driving currents was calculated, and the spectral purity, an important parameter for applications such as biological imaging and composition identification, was obtained in Table S8. The small FWHM and high spectral purity may improve signal-to-noise ratio provide high accuracy in distinguishing different tissue absorption/scattering characteristics. The absolute NIR output power increases steadily at a higher driving current, reaching a value of 44 mW17and an irradiance of 1100 mA/cm2 at 320 mA. The photoelectric efficiency for the prepared NIR pc-LED was found to be 15.4% at 20 mA (Figure 5b). Table S9 compares the performance of the Yb1.94Cr0.06W3O12 phosphor with those of previously reported Cr3+-doped NIR phosphors. The outstanding photoelectric properties of our phosphor, combined with its anti-thermal quenching performance, demonstrate that the fabricated NIR pc-LED device holds great promise for practical applications. Taking into consideration the non-invasive and high penetration characteristics of NIR light, the prepared NIR pc-LED was employed as a light source for non-invasive imaging of human hand, and the results are shown in Figure 5c. Under the NIR light, the distribution of the endoskeleton in the finger was observed clearly. Meanwhile, a smartphone was used to take photos of fruits under natural light and were then passed through an NIR camera employing the fabricated NIR pc-LED as a light source, and the damage of the banana skin could be observed clearly with the NIR camera, which proved that our phosphor also has immense potential for night vision applications. As depicted in Figure 5d, the operating temperature of the fabricated device increased from 25.5 to 57.7 °C as the drive current increased from 20 to 300 mA, which is due to increased production of heat at higher current values. The temperature (T) and temperature rise (ΔT) as a function of the current are plotted in Figure S10. Figure 6. (a) Schematic diagram of the designed absorption spectroscopy testing system. The absorption spectra of (b) water and (c) methanol.In order to highlight the potential application of the NIR-II pc-LED in the field of18NIR spectroscopy, a miniaturized real-time absorption spectroscopy testing system using this NIR pc-LED as the light source was designed, as shown in Figure 6a. The NIR-II region covers the vibrational frequencies of the functional groups such as C-H, O-H, and N-H in organic molecules. In this study, the NIR absorption spectra of water and methanol were measured. The results show that both the substances exhibit distinct absorption in the NIR region. Specifically, the spectrum of water in Figure 6b shows absorption bands at 970–1020 nm, which are attributed to the second overtone of O-H bond vibrations.44,45 In Figure 6c, the absorption of methanol in the 900–1100 nm range is due to C-H bond vibrations.46 The successful distinguishment of these two solutions highlights that the Yb1.94Cr0.06W3O12 phosphor may have good suitability for various portable NIR detection instruments. Inspired by previous research,47−49 the application of the NIR phosphor in LiDAR technology can be expected since the excellent anti-thermal feature can effectively withstand the significant heat generated during LiDAR system operation to maintain a stable performance. Additionally, integrating the phosphor into flexible substrates to reduce hygroscopicity, which negatively impacts NTE properties, may allow wider applications of the phosphor.4. CONCLUSIONSYb2-2xCr2xW3O12 phosphor has been proposed in this study as a potential NIR light source material for developing NIR pc-LEDs. The results showed that trihydrate Yb2W3O12·3H2O exhibits positive thermal expansion at room temperature. This behavior is attributable to the water molecules, which restrict the transverse thermal vibrations of Yb-O-W bonds. Upon heating to 373 K, dehydration occurs and the resulting orthorhombic Yb2W3O12 demonstrates negative thermal expansion. The characteristic emission of Yb3+ within the range of 800-1300 nm was observed under 468 nm blue light irradiation due to efficient Cr3+→Yb3+energy transfer. Notably, the19luminescence intensity of the Yb1.94Cr0.06W3O12 sample at 398 K is 1.89 times higher than that at room temperature. Such an anti-thermal quenching performance is superior over most long-wavelength-emitting NIR phosphors. This significant luminescence enhancement can be attributed to enhanced energy transfer from Cr3+ to Yb3+ by negative thermal expansion. This study thus provides a new strategy for developing NIR phosphors with anti-thermal quenching properties. Furthermore, the NIR pc-LED fabricated by combining the Yb1.94Cr0.06W3O12 phosphor with a blue LED chip exhibited an outstanding optoelectronic performance for potential application in night vision, non-invasive imaging, and compositional analysis.ASSOCIATEDCONTENTSupporting InformationICP-MS results; EPR spectra; FE-SEM images; PLE/PL spectra of the matrix; decay curve and the decay fitting results; FWHM data and spectral purity; Rietveld refinement of XRD; The batch-to-batch consistency of PL intensity and thermal stability; A summary of performance parameter comparison (PDF)AUTHOR INFORMATIONCorresponding AuthorsXuejiao Wang − School of Materials and Environmental Engineering, Bohai University, Jinzhou, Liaoning 121007, P. R. China; orcid.org/0000-0003-4327-2340; Email: wangxuejiao@bhu.edu.cnJi-Guang Li − Research Center for Electronic and Optical Materials, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044, Japan; orcid.org/0000-0002-5625-7361; Email: li.jiguang@nims.go.jpAuthors20mailto:wangxuejiao@bhu.edu.cnmailto:li.jiguang@nims.go.jpSihan Yang − School of Materials and Environmental Engineering, Bohai University, Jinzhou, Liaoning 121007, P. R. ChinaChangshuai Gong − School of Materials and Environmental Engineering, Bohai University, Jinzhou, Liaoning 121007, P. R. ChinaZiying Wang − School of Materials and Environmental Engineering, Bohai University, Jinzhou, Liaoning 121007, P. R. ChinaLiang Dong − Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), School of Materials Science and Engineering, Northeastern University, Shenyang, Liaoning 110819, P. R. ChinaNotesThe authors declare no competing financial interest. The authors also confirm that there are no undisclosed conflicts of interest related to citations of references.ACKNOWLEDGEMENTS This study was endorsed by the Liaoning Revitalization Talents Program (Grant No. XLYC2403017), the Natural Science Foundation of the Education Department of Liaoning Province (Grant No. JYTMS20231627), the Young Talents Program of Jinzhou (Grant No. JXYC230103), and the Innovation Fund Project for Graduate Student of Bohai University (Grant No. YJC2024-003). The authors would also like to acknowledge the support from Scientific Compass (www.shiyanjia.com).REFERENCES [1] Beć , K. B.; Grabska, J.; Huck, C. W. Near-infrared spectroscopy in bio-applications. Molecules 2020, 25(12), 2948. [2] Vatansever, F.; Hamblin M. R. Far infrared radiation (FIR): Its biological effects and medical applications: Ferne Infrarotstrahlung: Biologische effekte und21 medizinische anwendungen. Photonics Lasers Med. 2012, 1(4), 255-266. [3] Hayashi, D.; van Dongen, A. 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