旋涂法制备WO_3薄膜电致变色性能
|
摘要
"智能窗"大规模推广顺应可持续发展潮流,三氧化钨(WO_3)是生产"智能窗"的一种重要电致变色材料,但调控WO_3薄膜电致变色性能机制仍待进一步研究。采用旋涂法制备WO_3薄膜,重点研究了溶液浓度和旋涂次数对调控WO_3薄膜电致变色性能的影响。通过表面轮廓仪测量薄膜厚度,X射线衍射(XRD)测量薄膜结晶情况,原子力显微镜(AFM)和扫描电子显微镜(SEM)分析薄膜表面形貌,光谱仪测量薄膜初始态、着色态和褪色态的透射率。实验结果表明,随着溶液浓度增加(0. 2～1. 0 mol/L),薄膜厚度从9. 7 nm增加到33. 3 nm,透射率调制能力从0%提升到37. 0%;多次旋涂薄膜厚度线性增长,线性拟合优度(R~2)达0. 98,5次旋涂后透射率调制能力达51. 3%。改变溶液浓度和旋涂次数都是调控薄膜透射率调制能力的有效手段,精准调控薄膜透射率调制能力对设计不同应用场景的电致变色器件具有重大意义。
Large-scale promotion of"smart windows"is to conform to the trend of sustainable development. Tungsten trioxide (WO_3) is an important electrochromic material for producing"smart window"but the mechanism of regulating the electrochromic properties of WO_3 thin films remains to be further studied. WO_3 films were prepared by spin-coating process. The thickness of films was measured by surface profiler. The crystallinity of films was measured by X-ray diffraction (XRD) and the surface morphology was measured by atomic force microscope (AFM) and scanning electron microscope (SEM). Finally,the transmittance of the films was measured by spectrometer. The experiment results indicated that the thickness of the films increased from 9. 7 nm to 33. 3 nm with the solution concentration increasing (0. 2 mol/L to 1. 0 mol/L),and the transmittance modulation capability of this film increased from 0% to 37. 0%. The thickness of multiple spin-coated films increased linearly,and goodness of fit (R~2) was 0. 98. After 5 times of spin-coating,the transmittance modulationcapability reached 51. 3%. Both changing the concentration of solution and the times of spin-coating are the effective means to regulate transmittance modulation capability and it is of great significance to accurately regulate the transmittance modulation capability of the film to design the electrochromic devices for different application scenarios.
Large-scale promotion of"smart windows"is to conform to the trend of sustainable development. Tungsten trioxide (WO_3) is an important electrochromic material for producing"smart window"but the mechanism of regulating the electrochromic properties of WO_3 thin films remains to be further studied. WO_3 films were prepared by spin-coating process. The thickness of films was measured by surface profiler. The crystallinity of films was measured by X-ray diffraction (XRD) and the surface morphology was measured by atomic force microscope (AFM) and scanning electron microscope (SEM). Finally,the transmittance of the films was measured by spectrometer. The experiment results indicated that the thickness of the films increased from 9. 7 nm to 33. 3 nm with the solution concentration increasing (0. 2 mol/L to 1. 0 mol/L),and the transmittance modulation capability of this film increased from 0% to 37. 0%. The thickness of multiple spin-coated films increased linearly,and goodness of fit (R~2) was 0. 98. After 5 times of spin-coating,the transmittance modulationcapability reached 51. 3%. Both changing the concentration of solution and the times of spin-coating are the effective means to regulate transmittance modulation capability and it is of great significance to accurately regulate the transmittance modulation capability of the film to design the electrochromic devices for different application scenarios.
引文
[1]杨秀,江亿.中外建筑能耗比较[J].中国能源,2007,29(6):21-26.YANG X,JIANG Y.Comparison of building energy consumption data between China and developed countries[J].Energy China,2007,29(6):21-26.(in Chinese)
[2]JITTIARPORN P,BADILESCU S,AL SAWAFTA M N,et al..Electrochromic properties of sol-gel prepared hybrid transition metal oxides-a short review[J].J.Sci.Adv.Mater.Dev.,2017,2(3):286-300.
[3]WANG Y,RUNNERSTROM E L,MILLIRON D J.Switchable materials for smart windows[J].Annu.Rev.Chem.Biomol.Eng.,2016,7(1):283-304.
[4]GRANQVIST C G.Electrochromic tungsten oxide films:review of progress 1993-1998[J].Sol.Energy Mater.Sol.Cells,2000,60(3):201-262.
[5]NEO W T,YE Q,CHUA S J,et al..Conjugated polymer-based electrochromics:materials,device fabrication and application prospects[J].J.Mater.Chem.C,2016,4(31):7364-7376.
[6]方成,汪洪,施思齐.氧化钨电致变色性能的研究进展[J].物理学报,2016,65(16):168201-1-13.FANG C,WANG H,SHI S Q.Research progress of electrochromic performances of WO3[J].Acta Phys.Sinica,2016,65(16):168201-1-13.(in Chinese)
[7]ESMAIL A,HASHEM H M,SOLTANS,et al..Thickness dependence of electro-optical properties of WO3films as an electrochromic functional material for energy-efficient applications[J].Phys.Status Solidi(A),2017,214(1):1600478.
[8]ARVIZU M A,QU H Y,NIKLASSON G A,et al..Electrochemical pretreatment of electrochromic WO3films gives greatly improved cycling durability[J].Thin Solid Films,2018,653:1-3.
[9]KAMALISARVESTANI M,SAIDUR R,MEKHILEF S,et al..Performance,materials and coating technologies of thermochromic thin films on smart windows[J].Renew Sustain.Energy Rev.,2013,26:353-364.
[10]VERNARDOU D,PSIFIS K,LOULOUDAKIS D,et al..Low pressure CVD of electrochromic WO3at 400°C[J].J.Electrochem.Soc.,2015,162(9):H579-H582.
[11]LIN Y S,CHEN H T,LAI J Y.Electrochromic performance of PECVD-synthesized WOxCythin films on flexible PET/ITOsubstrates for flexible electrochromic devices[J].Thin Solid Films,2009,518(5):1377-1381.
[12]ZHAO B W,ZHANG X,DONG G B,et al..Efficient electrochromic device based on sol-gel prepared WO3films[J].Ionics,2015,21(10):2879-2887.
[13]STOENESCU S,BADILESCU S,SHARMA T,et al..Tungsten oxide-cellulose nanocrystal composite films for electrochromic applications[J].Opt.Eng.,2016,55(12):127102-1-7.
[14]REN Y,ZHOU X G,WANG Q H,et al..Combined redox and plasmonic electrochromic effects in WO3/ITO double-layer films[J].J.Sol-Gel Sci.Technol.,2018,85(3):732-742.
[15]GARG D,HENDERSON P B,HOLLINGSWORTH R E,et al..An economic analysis of the deposition of electrochromic WO3via sputtering or plasma enhanced chemical vapor deposition[J].Mater.Sci.Eng.B,2005,119(3):224-231.
[16]BREEDON M,SPIZZIRRI P,TAYLOR M,et al..Synthesis of nanostructured tungsten oxide thin films:a simple,controllable,inexpensive,aqueous sol-gel method[J].Cryst.Growth Des.,2011,10(1):430-439.
[17]PEHLIVAN E,KOC K,TEPEHAN F Z,et al..Structural,optical and electrochromic properties of tantalum pentoxidedoped niobium pentoxide thin films[J].J.Sol-Gel Sci.Technol.,2016,77(1):172-178.
[18]RAJA M,CHANDRASEKARAN J,BALAJI M,et al..Impact of annealing treatment on structural and dc electrical properties of spin coated tungsten trioxide thin films for Si/WO3/Ag junction diode[J].Mater.Sci.Semicond.Process.,2016,56:145-154.
[19]ZHI M Y,HUANG W X,SHI Q W,et al..Sol-gel fabrication of WO3/RGO nanocomposite film with enhanced electrochromic performance[J].RSC Adv.,2016,6(72):67488-67494.
[20]WU C L,LIN C K,WANG C K,et al..Annealing induced structural evolution and electrochromic properties of nanostructured tungsten oxide films[J].Thin Solid Films,2013,549:258-262.
[21]LIN Y S,TSAI T H,CHEN P C,et al..Flexible electrochromic tungsten/titanium mixed oxide films synthesized onto flexible polyethylene terephthalate/indium tin oxide substrates via low temperature plasma polymerization[J].Thin Solid Films,2018,651:56-66.
[22]BAE J,SEO D G,PARK S M,et al..Optimized low-temperature fabrication of WO3films for electrochromic devices[J].J.Phys.D:Appl.Phys.,2017,50(46):465105.
[23]代富平,吕淑媛,冯博学,等.非晶态WO3薄膜电致变色特性的研究[J].物理学报,2003,52(4):1003-1008.DAI F P,LS Y,FENG B X,et al..Study on electrochromic performances of amorphous WO3films[J].Acta Phys.Sinica,2003,52(4):1003-1008.(in Chinese)
[24]HILL J C,CHOI K S.Effect of electrolytes on the selectivity and stability of n-type WO3photoelectrodes for use in solar water oxidation[J].J.Phys.Chem.C,2012,116(14):7612-7620.
[25]HO C,RAISTRICK I D,HUGGINS R A.Application of A-C techniques to the study of lithium diffusion in tungsten trioxide thin films[J].J.Electrochem.Soc.,1980,127(2):343-350.
[2]JITTIARPORN P,BADILESCU S,AL SAWAFTA M N,et al..Electrochromic properties of sol-gel prepared hybrid transition metal oxides-a short review[J].J.Sci.Adv.Mater.Dev.,2017,2(3):286-300.
[3]WANG Y,RUNNERSTROM E L,MILLIRON D J.Switchable materials for smart windows[J].Annu.Rev.Chem.Biomol.Eng.,2016,7(1):283-304.
[4]GRANQVIST C G.Electrochromic tungsten oxide films:review of progress 1993-1998[J].Sol.Energy Mater.Sol.Cells,2000,60(3):201-262.
[5]NEO W T,YE Q,CHUA S J,et al..Conjugated polymer-based electrochromics:materials,device fabrication and application prospects[J].J.Mater.Chem.C,2016,4(31):7364-7376.
[6]方成,汪洪,施思齐.氧化钨电致变色性能的研究进展[J].物理学报,2016,65(16):168201-1-13.FANG C,WANG H,SHI S Q.Research progress of electrochromic performances of WO3[J].Acta Phys.Sinica,2016,65(16):168201-1-13.(in Chinese)
[7]ESMAIL A,HASHEM H M,SOLTANS,et al..Thickness dependence of electro-optical properties of WO3films as an electrochromic functional material for energy-efficient applications[J].Phys.Status Solidi(A),2017,214(1):1600478.
[8]ARVIZU M A,QU H Y,NIKLASSON G A,et al..Electrochemical pretreatment of electrochromic WO3films gives greatly improved cycling durability[J].Thin Solid Films,2018,653:1-3.
[9]KAMALISARVESTANI M,SAIDUR R,MEKHILEF S,et al..Performance,materials and coating technologies of thermochromic thin films on smart windows[J].Renew Sustain.Energy Rev.,2013,26:353-364.
[10]VERNARDOU D,PSIFIS K,LOULOUDAKIS D,et al..Low pressure CVD of electrochromic WO3at 400°C[J].J.Electrochem.Soc.,2015,162(9):H579-H582.
[11]LIN Y S,CHEN H T,LAI J Y.Electrochromic performance of PECVD-synthesized WOxCythin films on flexible PET/ITOsubstrates for flexible electrochromic devices[J].Thin Solid Films,2009,518(5):1377-1381.
[12]ZHAO B W,ZHANG X,DONG G B,et al..Efficient electrochromic device based on sol-gel prepared WO3films[J].Ionics,2015,21(10):2879-2887.
[13]STOENESCU S,BADILESCU S,SHARMA T,et al..Tungsten oxide-cellulose nanocrystal composite films for electrochromic applications[J].Opt.Eng.,2016,55(12):127102-1-7.
[14]REN Y,ZHOU X G,WANG Q H,et al..Combined redox and plasmonic electrochromic effects in WO3/ITO double-layer films[J].J.Sol-Gel Sci.Technol.,2018,85(3):732-742.
[15]GARG D,HENDERSON P B,HOLLINGSWORTH R E,et al..An economic analysis of the deposition of electrochromic WO3via sputtering or plasma enhanced chemical vapor deposition[J].Mater.Sci.Eng.B,2005,119(3):224-231.
[16]BREEDON M,SPIZZIRRI P,TAYLOR M,et al..Synthesis of nanostructured tungsten oxide thin films:a simple,controllable,inexpensive,aqueous sol-gel method[J].Cryst.Growth Des.,2011,10(1):430-439.
[17]PEHLIVAN E,KOC K,TEPEHAN F Z,et al..Structural,optical and electrochromic properties of tantalum pentoxidedoped niobium pentoxide thin films[J].J.Sol-Gel Sci.Technol.,2016,77(1):172-178.
[18]RAJA M,CHANDRASEKARAN J,BALAJI M,et al..Impact of annealing treatment on structural and dc electrical properties of spin coated tungsten trioxide thin films for Si/WO3/Ag junction diode[J].Mater.Sci.Semicond.Process.,2016,56:145-154.
[19]ZHI M Y,HUANG W X,SHI Q W,et al..Sol-gel fabrication of WO3/RGO nanocomposite film with enhanced electrochromic performance[J].RSC Adv.,2016,6(72):67488-67494.
[20]WU C L,LIN C K,WANG C K,et al..Annealing induced structural evolution and electrochromic properties of nanostructured tungsten oxide films[J].Thin Solid Films,2013,549:258-262.
[21]LIN Y S,TSAI T H,CHEN P C,et al..Flexible electrochromic tungsten/titanium mixed oxide films synthesized onto flexible polyethylene terephthalate/indium tin oxide substrates via low temperature plasma polymerization[J].Thin Solid Films,2018,651:56-66.
[22]BAE J,SEO D G,PARK S M,et al..Optimized low-temperature fabrication of WO3films for electrochromic devices[J].J.Phys.D:Appl.Phys.,2017,50(46):465105.
[23]代富平,吕淑媛,冯博学,等.非晶态WO3薄膜电致变色特性的研究[J].物理学报,2003,52(4):1003-1008.DAI F P,LS Y,FENG B X,et al..Study on electrochromic performances of amorphous WO3films[J].Acta Phys.Sinica,2003,52(4):1003-1008.(in Chinese)
[24]HILL J C,CHOI K S.Effect of electrolytes on the selectivity and stability of n-type WO3photoelectrodes for use in solar water oxidation[J].J.Phys.Chem.C,2012,116(14):7612-7620.
[25]HO C,RAISTRICK I D,HUGGINS R A.Application of A-C techniques to the study of lithium diffusion in tungsten trioxide thin films[J].J.Electrochem.Soc.,1980,127(2):343-350.