以氧化铟、氧化锑和氯化铯为基本原料,浓盐酸作为溶剂,采用低温水热法合成Sb3+掺杂全无机Cs2InCl5·H2O(Cs2InCl5·H2O∶Sb3+)钙钛矿。研究了Sb3+的掺杂量(0、2%、4%、6%、8%、10%、20%)对Cs2InCl5·H2O钙钛矿发光性能的影响。采用紫外-可见分光光谱、荧光光谱和X射线衍射仪(XRD)等表征该样品的吸收光谱、发光性能和晶体结构。结果表明,少量Sb3+掺杂Cs2InCl5·H2O钙钛矿不会改变其结构。当Sb3+的掺杂量为10%时,达到最强荧光发射,发射峰波长约为620nm,荧光寿命为8.13μs。采用荧光转换法,将实验合成的Cs2InCl5·H2O∶Sb3+钙钛矿纳米晶与商用蓝色发光的BaMgAl10O17∶Eu和绿色发光的(Sr,Ba)2SiO4∶Eu荧光粉混合涂于365nm的紫外芯片上,封装得到显色指数(CRI)为91.8,CIE色坐标为(0.326,0.316),色温为5843K的白光LED。说明Cs2InCl5·H2O∶Sb3+钙钛矿纳米晶在白光LED领域具有很好的应用前景。
Sb3+-doped all-inorganic Cs2InCl5·H2O(Cs2InCl5·H2O∶Sb3+) perovskite was synthesized by low-temperature hydrothermal method with indium oxide,antimony oxide,and cesium chloride as raw materials and concentrated hydrochloric acid as solvent.The effects of doping amounts of Sb3+(0,2%,4%,6%,8%,10%,20%) on the luminescence performance of Cs2InCl5·H2O perovskite were studied in detail.The absorption spectra,luminescence properties and crystal structure of the samples were characterized via X-ray diffraction,fluorescence spectroscopy and UV-Vis absorption spectrometry.The results showed that the crystal structure of Cs2InCl5·H2O perovskite was not changed with the introduction of a small amount of Sb3+.The maximum fluorescence emission was achieved,with an emission peak wavelength of about 620nm and a fluorescence lifetime of 8.13 us when the doping amount of Sb3+ was 10%.A white LED was fabricated by coating the phosphors,mixing the red light-emitting Cs2InCl5·H2O∶Sb3+ perovskite,blue light-emitting BaMgAl10O17∶Eu,and green light-emitting(Sr,Ba)2SiO4∶Eu,onto a 365nm UV chip.The white LED showed a high color rendering index (CRI) of 91.8,CIE color coordinates of (0.326,0.316),and a color temperature of 5843 K,which indicated that Cs2InCl5·H2O∶Sb3+ perovskite had significant potential for application in white LEDs.
[1] Wei J H,Liao J F,Zhou L,et al.Indium-antimony-halide single crystals for high-efficiency white-light emission and anti-counterfeiting[J].Science Advances,2021,7(34):3989.
[2] Zhou J,Rong X,Molokeev M S,et al.Exploring the transposition effects on the electronic and optical properties of Cs2AgSbCl6 via a combined computational-experimental approach[J].Journal of Materials Chemistry A,2018,6:2346-2352.
[3] Braly I L,de Quilettes D W,Pazos-Outoń L M,et al.Hybrid perovskite films approaching the radiative limit with over 90% photoluminescence quantum efficiency[J].Nature Photonics,2018,12:355-361.
[4] Yang W S,Park B W,Jung E H,et al.Iodide management in formamidinium-lead-halide-based perovskite layers for efficient solar cells[J].Science,2017,356:1376-1379.
[5] Bai T X,Yang B,Chen J S,et al.Efficient luminescent halide quadruple-perovskite nanocrystals via trap-engineering for highly sensitive photodetectors[J].Advanced Materials,2021,33(8):2007215.
[6] Nedelcu G,Protesescu L,Yakunin S,et al.Fast anion-exchange in highly luminescent nanocrystals of cesium lead halide perovskites (CsPbX3,X=Cl,Br,I)[J].Nano Letters,2015,15(8):5635-5640.
[7] Mao X,Wang Z,Zhang F,et al.All-inorganic zero-dimensional Sb3+-doped Rb2ScCl5 (H2O) perovskite single crystals:efficient self-trapped exciton emission and X-ray detection[J].The Journal of Physical Chemistry Letters,2023,14(6):1521-1527.
[8] Schileo G,Grancini G.Lead or no lead？availability,toxicity,sustainability and environmental impact of lead-free perovskite solar cells[J].Journal of Materials Chemistry,2021,9:67-76.
[9] 李登,崔灿.金属卤化物杂化钙钛矿材料及其光电器件的研究进展[J].浙江理工大学学报:自然科学版,2019,41(6):730-739.
[10] Swarnkar A,Ravi V K,Nag A.Beyond colloidal cesium lead halide perovskite nanocrystals:analogous metal halides and doping[J].ACS Energy Letters,2017,2(5):1089-1098.
[11] Ye T,Wang K,Hou Y,et al.Ambient-air-stable lead-free CsSnI3 solar cells with greater than 7.5% efficiency[J].Journal of the American Chemical Society,2021,143(11):4319-4328.
[12] Jellicoe T C,Richter J M,Glass H F J,et al.Synthesis and optical properties of lead-free cesium tin halide perovskite nanocrystals[J].Journal of the American Chemical Society,2016,138(9):2941-2944.
[13] Lu C,Itanze D S,Aragon A G,et al.Synthesis of lead-free Cs3Sb2Br9 perovskite alternative nanocrystals with enhanced photocatalytic CO2 reduction activity[J].Nanoscale,2020,12(5):2987-2991.
[14] Wang A,Yan X,Zhang M,et al.Controlled synthesis of lead-free and stable perovskite derivative Cs2SnI6 nanocrystals via a facile hot-injection process[J].Chemistry of Materials,2016,28(22):8132-8140.
[15] Zhang Y,Yin J,Parida M R,et al.Direct-indirect nature of the bandgap in lead-free perovskite nanocrystals[J].The journal of physical chemistry letters,2017,8(14):3173-3177.
[16] Zhou L,Liao J F,Huang Z G,et al.A highly red-emissive lead-free indium-based perovskite single crystal for sensitive water detection[J].AngewandteChemie,2019,131(16):5331-5335.
[17] Ge Q,Zheng R,Lin J,et al.Cs2InCl5 (H2O):a moisture-stable defective double halide perovskite analogue with broadband emission[J].Materials Letters,2020,277:128280.
[18] Jing Y Y,Liu Y,Jiang X X,et al.Sb3+dopant and halogen substitution triggered highly efficient and tunable emission in lead-free metal halide single crystals[J].Chemistry of Materials,2020,32:5327-5334.
[19] Jing L,Cen Q M,Pang Q,et al.Enhancing photoluminescence and stability of Mn-doped Cs2InCl5· H2O microcrystals with introduced Bi3+ Ion[J].The Journal of Physical Chemistry C,2023,127(5):2448-2455.
[20] Wei J H,Luo J B,Liao J F,et al.Te4+-doped Cs2InCl5 center dot H2O single crystals for remote optical thermometry[J].Science China-Materials,2022,65(3):764-772.
[21] Chang T,Wang H,Gao Y,et al.Component engineering to tailor the structure and optical properties of Sb-doped indium-based halides[J].Inorganic Chemistry,2022,61(3):1486-1494.
[22] Cao R P,Shi Z H,Quan J G,et al.Li3Mg2NbO6∶Mn4+ red phosphor for light-emitting diode synthesis and luminescence properties[J].Optical Materials,2016,57:212-216.
[23] Jiang X,Zhang Y,Zhang J.White-emission in single-phase Ba2Gd2Si4O13∶Ce3+,Eu2+,Sm3+ phosphor for white-LEDs[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2018,192:194-201.
