无机材料学报 ›› 2026, Vol. 41 ›› Issue (9): 1310-1318.DOI: 10.15541/jim20250461
张剑(
), 申慧(
), 杨迎, 张熏涛, 田甜, 徐家跃(
)
收稿日期:2025-11-20
修回日期:2025-12-27
出版日期:2026-09-20
网络出版日期:2026-01-21
通讯作者:
申 慧, 教授. E-mail: hshen@sit.edu.cn;作者简介:张 剑(1999-), 男, 硕士研究生. E-mail: 17638416686@163.com
基金资助:
ZHANG Jian(
), SHEN Hui(
), YANG Ying, ZHANG Xuntao, TIAN Tian, XU Jiayue(
)
Received:2025-11-20
Revised:2025-12-27
Published:2026-09-20
Online:2026-01-21
Contact:
SHEN Hui, professor. E-mail: About author:ZHANG Jian (1999-), male, Master candidate. E-mail: 17638416686@163.com
Supported by:摘要:
以CsPbBr3为代表的金属卤化物钙钛矿具有高光致发光量子效率、窄带发射及宽色域等优异特性, 在光电探测、太阳能电池和光电显示等领域具有广阔应用前景。高质量图案化制备对于高分辨率、集成化光电器件至关重要。本研究旨在探究聚乙烯吡咯烷酮(Polyvinylpyrrolidone, PVP)浓度对喷墨打印CsPbBr3纳米阵列的结晶形貌、发光性能及环境稳定性的影响规律。采用喷墨打印法, 在不同浓度(0、50、100、150 mg/mL) PVP修饰的聚对苯二甲酸乙二醇酯(Polyethylene Terephthalate, PET)衬底上, 制备了一系列CsPbBr3纳米阵列。结果表明, 当PVP浓度为50 mg/mL时, CsPbBr3平均粒径为92 nm, 发光强度最高, 荧光寿命达到91.5 ns。这主要是由于PVP分子中的羰基(C=O)与钙钛矿中的Pb2+之间的配位作用, 有效钝化了表面缺陷, 抑制了非辐射复合。在30 ℃、65%~75%相对湿度条件下保存30 d, 当PVP浓度为0、50、100和150 mg/mL时, 柔性CsPbBr3阵列的发光强度分别达到初始强度的16.20%、73.44%、66.57%和54.91%。PVP对CsPbBr3晶粒的空间限域与包覆作用, 有效增强了环境稳定性。本工作为优化柔性CsPbBr3图案化制备、推动其在光电器件中的集成应用提供了理论依据与实验指导。
中图分类号:
张剑, 申慧, 杨迎, 张熏涛, 田甜, 徐家跃. PVP浓度对喷墨打印CsPbBr3结晶形貌、发光与稳定性的影响规律[J]. 无机材料学报, 2026, 41(9): 1310-1318.
ZHANG Jian, SHEN Hui, YANG Ying, ZHANG Xuntao, TIAN Tian, XU Jiayue. Influence of PVP Concentration on the Crystalline Morphology, Luminescence and Stability of Inkjet-printed CsPbBr3 Patterns[J]. Journal of Inorganic Materials, 2026, 41(9): 1310-1318.
图1 喷墨打印CsPbBr3实验流程图, 包括在PET衬底上旋涂PVP修饰层, 在PVP修饰层上打印CsPbBr3和热处理过程
Fig. 1 Experimental flowchart of inkjet printing CsPbBr3, including spin-coating PVP layer on PET substrate, printing CsPbBr3 on PVP modified PET layer and anealing treatment process
图2 不同浓度PVP上打印的CsPbBr3阵列的(I)荧光显微镜图像、(II) SEM照片和(III)结晶颗粒尺寸分布图
Fig. 2 (I) Fluorescence microscope images, (II) SEM images and (III) crystal particle size distribution diagrams of CsPbBr3 arrays printed on PVP of different concentrations (a) 0 mg/mL; (b) 50 mg/mL; (c) 100 mg/mL; (d) 150 mg/mL
图3 (a)不同浓度PVP上打印的CsPbBr3的XRD图谱(热处理时间为120 s); (b)打印在150 mg/mLPVP上, CsPbBr3进行30、60、120 s热处理后的XRD图谱; (c)打印在50 mg/mL PVP上的CsPbBr3与PVP的FT-IR光谱; (d)不同浓度PVP上打印CsPbBr3的PL图谱
Fig. 3 (a) XRD patterns of CsPbBr3 printed on PVP with different concentrations (annealing treatment for 120 s); (b) XRD patterns of CsPbBr3 printed on 150 mg/mL PVP after annealing treatment for 30, 60, and 120 s; (c) FT-IR spectra of CsPbBr3 printed on 50 mg/mL PVP and pristine PVP; (d) PL spectra of CsPbBr3 printed on PVP with different concentrations
图4 不同浓度PVP上打印CsPbBr3的(a)瞬态荧光光谱和(b)衰减寿命柱状图
Fig. 4 (a) Transient photoluminescence spectra and (b) histograms of photoluminescence decay time of CsPbBr3 printed with different PVP concentrations Colorful figures are available on website
图5 (a~d)不同浓度PVP上打印的CsPbBr3阵列在30 d内的PL图谱(30 ℃, 65%~75%相对湿度)及(e)发光强度随时间变化曲线
Fig. 5 (a-d) PL spectra of CsPbBr3 patterns over 30 d period under conditions of 30 ℃ and 65%-75% relative humidity and (e) changes of PL intensities with time (a) 0 mg/mL; (b) 50 mg/mL; (c) 100 mg/mL; (d) 150 mg/mL
图6 (a~c)在PVP上打印乌龟、雪人与马的图案(紫外灯照射); (d)在PVP上打印的矩形阵列; (e)图案的色坐标图; (f~h)弯曲测试程序的示意图
Fig. 6 (a-c) Various patterns (turtle, snowman, horse) printed on flexible PVP substrates under UV light; (d) Rectangular arrays inkjet printed on PVP substrate; (e) Color coordinate diagram of the patterns; (f-h) Schematic diagrams of the bending test procedure
| [1] | BAUMANN F, RAGA S R, LIRA-CANTU M. Monitoring the stability and degradation mechanisms of perovskite solar cells by in situ and operando characterization. APL Energy, 2023, 1(1): 011501. |
| [2] | BOVESECCHI G, PETITTA M, PIERRO M, et al. Outdoor performance monitoring method for degradation studies of perovskite modules. Progress in Photovoltaics, 2025, 33(3): 445. |
| [3] |
GU Z W, XING K, CAO S, et al. Boosting photoluminescence efficiency and stability of Mn2+-doped CsPbCl3 perovskite nanocrystals via europium ion cooping. Journal of Rare Earths, 2025, 43: 1835.
DOI URL |
| [4] | ALAMRI A M, LEUNG S, VASEEM M, et al. Fully inkjet-printed photodetector using a graphene/perovskite/graphene heterostructure. IEEE Transactions on Electron Devices, 2019, 66(6): 2657. |
| [5] | LIU X, YANG Q, LI G, et al. Synthesis and properties of undoped and Tb3+-doped CsPbF3 QDs-in-glasses for ultraviolet emitter and optical thermometry. Journal of Rare Earths, 2025, 43(7): 1337. |
| [6] | ZHANG L L, XUE Z X, SUN L, et al. Metal halide perovskite single crystal scintillators for radiation detection. Journal of Synthetic Crystals, 2025, 54(8): 1330. |
| [7] | ZHANG L, CHEN S, ZENG J, et al. Inkjet-printing controlled phase evolution boosts the efficiency of hole transport material free and carbon-based CsPbBr3 perovskite solar cells exceeding 9%. Energy & Environmental Materials, 2024, 7(2): e12543. |
| [8] | JIA X F, RUAN M, YE L F, et al. Imidazolium ionic liquid-modified perovskite solar cells and its performance characteristics. Journal of Synthetic Crystals, 2025, 54(5): 864. |
| [9] | ZHANG B, SUN T, WANG L, et al. Inkjet printing preparation of AgCuTe thermoelectric thin films. Journal of Inorganic Materials, 2024, 39(12): 1325. |
| [10] | WEI C, SU W, LI J, et al. A universal ternary-solvent-ink strategy toward efficient inkjet-printed perovskite quantum dot light- emitting diodes. Advanced Materials, 2022, 34(10): 2107798. |
| [11] | CHEN T, LUO Y, ZHU L, et al. Organic-inorganic co-addition to improve mechanical bending and environmental stability of flexible perovskite solar cells. Journal of Inorganic Materials, 2024, 39(5): 477. |
| [12] | WANG Q, ZHANG G, ZHANG H, et al. High-resolution, flexible, and full-color perovskite image photodetector via electrohydrodynamic printing of ionic-liquid-based ink. Advanced Functional Materials, 2021, 31(28): 2100857. |
| [13] | LI H, HAO X, CHANG B, et al. Stiffening the Pb-X framework through a π-conjugated small-molecule cross-linker for high-performance inorganic CsPbI2Br perovskite solar cells. ACS Applied Materials & Interfaces, 2021, 13(34): 40489. |
| [14] | SATALE V V, CHOUWDHURY S, MOHAMED A, et al. Green solvent enabled perovskite ink for ambient-air-processed efficient inkjet-printed perovskite solar cells. Advanced Functional Materials, 2025, 35(40): 2503717. |
| [15] | ZHENG Y, DUAN Y, YE Y, et al. Effect of polymethyl methacrylate on in situ patterning of perovskite quantum dots by inkjet printing. Luminescence, 2024, 39(2): e4691. |
| [16] | FALLAH K, NOROUZIANALAM S, GHAFFARY B, et al. Enhancement of the environmental stability of perovskite thin films via AZ5214-photoresist and PMMA coatings. Optical Materials Express, 2024, 14(8): 2083. |
| [17] | WANG S, CHEN D, XU K, et al. Boosting stability and inkjet printability of pure-red CsPb(Br/I)3 quantum dots through dual-shell encapsulation for micro-LED displays. ACS Energy Letters, 2024, 9(6): 2517. |
| [18] | LIU M, LIN C, OU W, et al. Electrohydrodynamic printing of PCL@CsPbBr3 composite fibers with high luminescence for flexible displays. Coatings, 2023, 13(3): 500. |
| [19] | PEI F, LIN S, TANG J, et al. Perovskite/CIGS tandem solar cells with over 1000 h operational stability through interconnection stress relief. Journal of the American Chemical Society, 2025, 147(40): 36815. |
| [20] | ZHAO C, ZHANG H, ALMALKI M, et al. Stabilization of FAPbI3 with multifunctional alkali-functionalized polymer. Advanced Materials, 2023, 35(28): 2211619. |
| [21] | ZHANG G, ZHANG H, YU R, et al. Critical size/viscosity for coffee-ring-free printing of perovskite micro/nanopatterns. ACS Applied Materials & Interfaces, 2022, 14(12): 14712. |
| [22] | HAN T, NING D, QIN H, et al. Interface engineering with polymer interlayers: achieving uniform and stable perovskite thick films for X-ray detection. ACS Applied Materials & Interfaces, 2025, 17(18): 27545. |
| [23] | GU Z, HUANG Z, HU X, et al. In situ inkjet printing of the perovskite single-crystal array-embedded polydimethylsiloxane film for wearable light-emitting devices. ACS Applied Materials & Interfaces, 2020, 12(19): 22157. |
| [24] | KIM G E, MOON S, PARK J D, et al. Spray-printed light-emitting diodes with perovskite/polymer composite emitters on various transparent substrates. ACS Applied Materials & Interfaces, 2025, 17(5): 8349. |
| [25] |
MENG Y, AHMADI M, WU X, et al. High performance and stable all-inorganic perovskite light emitting diodes by reducing luminescence quenching at PEDOT:PSS/perovskites interface. Organic Electronics, 2019, 64: 47.
DOI URL |
| [26] | KIM D B, YU J C, NAM Y S, et al. Improved performance of perovskite light-emitting diodes using a PEDOT:PSS and MoO3 composite layer. Journal of Materials Chemistry C, 2016, 4(35): 8161. |
| [27] | SHEN Y, LI M N, LI Y, et al. Rational interface engineering for efficient flexible perovskite light-emitting diodes. ACS Nano, 2020, 14(5): 6107. |
| [28] | LIU X, LV D, LI Y, et al. Improving the uniformity of the inkjet-printed polymer film in a bank by Marangoni flow and contact line sliding. Journal of Materials Chemistry C, 2024, 12(17): 6074. |
| [29] | YANG X, WU M M, DOI M, et al. Evaporation dynamics of sessile droplets: the intricate coupling of capillary, evaporation, and Marangoni flow. Langmuir, 2022, 38(16): 4887. |
| [30] | LI Y, XU J, SHEN H, et al. Morphology, luminescence and the gravity sedimentation effect of flexible and highly stable CsPbBr3 nanocrystal patterns by the inkjet printing method. CrystEngComm, 2024, 26(36): 5046. |
| [31] | CHEN T, WANG C, XING X, et al. Integration of highly luminescent lead halide perovskite nanocrystals on transparent lead halide nanowire waveguides through morphological transformation and spontaneous growth in water. Small, 2022, 18(11): 2105009. |
| [32] | PROTESESCU L, YAKUNIN S, BODNARCHUK M I, et al. Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): novel optoelectronic materials showing bright emission with wide color gamut. Nano Letters, 2015, 15(6): 3692. |
| [33] | YU X, FANG Z, LIN S, et al. Polyvinyl pyrrolidone induced “confinement effect” on PbI2 and the improvement on crystallization and thermal stability of perovskite. Small, 2024, 20(5): 2306101. |
| [34] | SONG L, HUANG L, LIU Y, et al. Efficient and stable blue perovskite light-emitting devices based on inorganic Cs4PbBr6 spaced low-dimensional CsPbBr3 through synergistic control of amino alcohols and polymer additives. ACS Applied Materials & Interfaces, 2021, 13(28): 33199. |
| [35] | TANG W, CHEN Y, SHI R, et al. Unveiling the effect of polymerization values on the crystallization behavior of perovskite films for efficient and stable solar cells. Small, 2025, 21(24): 2502851. |
| [36] | LIU P, ZHANG X, ZHANG B, et al. Molecular engineering enables high-performance hybrid perovskite photodetector. Chip, 2025, 4(1): 100125. |
| [37] | CHAUDHARY B, KULKARNI A, JENA A K, et al. Poly(4-vinylpyridine) based interfacial passivation to enhance voltage and moisture stability of lead halide perovskite solar cells. ChemSusChem, 2017, 10(11): 2473. |
| [38] | YAVARI M, MAZLOUM-ARDAKANI M, GHOLIPOUR S, et al. Reducing surface recombination by a poly(4-vinylpyridine) interlayer in perovskite solar cells with high open-circuit voltage and efficiency. ACS omega, 2018, 3(5): 5038. |
| [39] | HUANG Y L, LI W, YANG F Q. Eco-friendly synthesis and stability analysis of CsPbBr3 and poly(methyl methacrylate)-CsPbBr3 films. Nanotechnology, 2025, 36(17): 175601. |
| [40] | LIN H S T, ZHANG S K, ZHAO D F, et al. Flexible polyphosphazene nanocomposite films: enhancing stability and luminescence of CsPbBr3 perovskite nanocrystals. Chinese Chemical Letters, 2025, 36(4): 109795. |
| [41] | GAO R, ZHANG Q, ZHAO Y, et al. Regulating polysulfide redox kinetics on a self-healing electrode for high performance flexible lithium sulfur batteries. Advanced Functional Materials, 2022, 32(15): 2110313. |
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