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The performance of the electron transport layer in perovskite solar cells is a key factor in achieving stable device efficiency and a primary consideration for flexible devices. In this study,the SnO2 nanoparticle synthesis pathway is introduced for the low-temperature (40-90 ℃) synthesis of tin oxide nanocrystals using anhydrous SnCl4 as the tin source,which is directly hydrolyzed with deionized water without the addition of an acid or alkali. The grain size of SnO2 has a direct impact on its performance as an electron transport layer,and a smaller grain size can form a dense,flat,smooth,and thin film,which is favorable for the subsequent deposition of the perovskite layer and reduces the leakage current. The optimized SnO2 exhibits excellent optical and electrical properties, and the photovoltaic conversion efficiency of the device reaches 20.4% (effective area: 0.13 cm²). The electron transport layer accelerates the extraction and transport of carriers,and its formation of a good interface with the perovskite film leads to significant improvements in terms of solar cell fill factor and short-circuit current.

, authors=Yinbin ZHU, Yingchen LI, Qinwen GUO, Hongkun CAI, Jian NI, Jianjun ZHANG, authorsList=Yinbin ZHU, Yingchen LI, Qinwen GUO, Hongkun CAI, Jian NI, Jianjun ZHANG, authorCompany=null, correspAuthors=Hongkun CAI, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1321967848512139887, articleId=1321967841750921821, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=基于水解法SnO2薄膜性能研究及其对钙钛矿太阳电池的影响, columnId=1220689384622445292, journalTitle=材料工程, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

钙钛矿太阳电池中电子传输层性能是器件效率稳定上升的一个关键因素,也是柔性器件首要考虑的问题。本工作探究了一种SnO2纳米颗粒合成路径,采用无水SnCl4作为锡源,在不外加酸碱的情况下直接与去离子水发生水解反应,用于低温(40~90 ℃)合成氧化锡纳米晶体。SnO2的晶粒尺寸直接影响作为电子传输层时的性能,较小的晶粒尺寸可以形成致密平整光滑的薄膜,有利于后续钙钛矿层的沉积,减少漏电流的产生。经优化的SnO2具有优异的光学和电学特性,应用于钙钛矿太阳电池中,器件的光电转换效率达到20.4%(有效面积0.13 cm2)。电子传输层加速提取和输运载流子,其与钙钛矿形成良好的界面,使得太阳电池填充因子和短路电流方面都有显著提高。

, authors=朱银斌, 李迎晨, 郭沁文, 蔡宏琨, 倪牮, 张建军, authorsList=朱银斌, 李迎晨, 郭沁文, 蔡宏琨, 倪牮, 张建军, authorCompany=null, correspAuthors=蔡宏琨, authorNote=null, correspAuthorsNote=
蔡宏琨(1980—),女,教授,博士,主要研究半导体材料与器件,联系地址:天津市津南区同砚路南开大学新校区电子信息与光学工程学院(300350),E-mail:
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基于水解法SnO2薄膜性能研究及其对钙钛矿太阳电池的影响
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朱银斌 , 李迎晨 , 郭沁文 , 蔡宏琨 , 倪牮 , 张建军
材料工程 | 研究论文 2026,54(6): 181-188
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材料工程 |研究论文 2026 , 54 (6) : 181 -188
基于水解法SnO2薄膜性能研究及其对钙钛矿太阳电池的影响
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朱银斌, 李迎晨, 郭沁文, 蔡宏琨 , 倪牮, 张建军
作者信息
  • 南开大学 电子信息与光学工程学院 电子科学与工程系,天津 300350
通讯作者:
蔡宏琨(1980—),女,教授,博士,主要研究半导体材料与器件,联系地址:天津市津南区同砚路南开大学新校区电子信息与光学工程学院(300350),E-mail:
Study on the properties of SnO2 thin film based on hydrolysis and its effect on perovskite solar cells
Yinbin ZHU, Yingchen LI, Qinwen GUO, Hongkun CAI , Jian NI, Jianjun ZHANG
Affiliations
  • Department of Electronic Science and Technology,College of Electronic Information and Optical Engineering,Nankai University,Tianjin 300350,China
出版时间: 2026-06-20 doi: 10.11868/j.issn.1001-4381.2024.000267
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钙钛矿太阳电池中电子传输层性能是器件效率稳定上升的一个关键因素,也是柔性器件首要考虑的问题。本工作探究了一种SnO2纳米颗粒合成路径,采用无水SnCl4作为锡源,在不外加酸碱的情况下直接与去离子水发生水解反应,用于低温(40~90 ℃)合成氧化锡纳米晶体。SnO2的晶粒尺寸直接影响作为电子传输层时的性能,较小的晶粒尺寸可以形成致密平整光滑的薄膜,有利于后续钙钛矿层的沉积,减少漏电流的产生。经优化的SnO2具有优异的光学和电学特性,应用于钙钛矿太阳电池中,器件的光电转换效率达到20.4%(有效面积0.13 cm2)。电子传输层加速提取和输运载流子,其与钙钛矿形成良好的界面,使得太阳电池填充因子和短路电流方面都有显著提高。

水解法  /  SnO2  /  晶粒尺寸  /  钙钛矿  /  太阳电池

The performance of the electron transport layer in perovskite solar cells is a key factor in achieving stable device efficiency and a primary consideration for flexible devices. In this study,the SnO2 nanoparticle synthesis pathway is introduced for the low-temperature (40-90 ℃) synthesis of tin oxide nanocrystals using anhydrous SnCl4 as the tin source,which is directly hydrolyzed with deionized water without the addition of an acid or alkali. The grain size of SnO2 has a direct impact on its performance as an electron transport layer,and a smaller grain size can form a dense,flat,smooth,and thin film,which is favorable for the subsequent deposition of the perovskite layer and reduces the leakage current. The optimized SnO2 exhibits excellent optical and electrical properties, and the photovoltaic conversion efficiency of the device reaches 20.4% (effective area: 0.13 cm²). The electron transport layer accelerates the extraction and transport of carriers,and its formation of a good interface with the perovskite film leads to significant improvements in terms of solar cell fill factor and short-circuit current.

hydrolysis  /  SnO2  /  grain size  /  perovskite  /  solar cell
朱银斌, 李迎晨, 郭沁文, 蔡宏琨, 倪牮, 张建军. 基于水解法SnO2薄膜性能研究及其对钙钛矿太阳电池的影响. 材料工程, 2026 , 54 (6) : 181 -188 . DOI: 10.11868/j.issn.1001-4381.2024.000267
Yinbin ZHU, Yingchen LI, Qinwen GUO, Hongkun CAI, Jian NI, Jianjun ZHANG. Study on the properties of SnO2 thin film based on hydrolysis and its effect on perovskite solar cells[J]. Journal of Materials Engineering, 2026 , 54 (6) : 181 -188 . DOI: 10.11868/j.issn.1001-4381.2024.000267
在钙钛矿太阳电池中,电子传输层的作用是提取输运电子并阻挡空穴,它是高效、稳定、无迟滞太阳电池的基础[1-3]。电子传输层的关键特性包括与钙钛矿层匹配的能级排列、宽带隙、高透过率和高电导率[4-7]。目前,常用的电子传输层包括n型半导体氧化物(如二氧化钛、氧化锡、氧化锌、Zn2SnO4和BaSnO3)和有机物(PCBM和C60)[8-11]。致密二氧化钛/介孔二氧化钛层由于其成熟的沉积工艺和较好的光电性能,一直是制备高效n-i-p钙钛矿太阳电池的首选电子传输层[12]。然而,二氧化钛也存在一定的弊端,如退火温度较高且紫外光照射下的稳定性差等,限制了其在商业化进程中的发挥[13],研究者致力于寻找探索二氧化钛的替代方案。在各种备选材料中,氧化锡表现出一些优秀的特性,如高的带隙透射率、良好的电荷迁移率、适当的能带结构、可低温加工合成、制备工艺简单和良好的化学稳定性等[14-17],这使得氧化锡成为最有前途的电子传输层材料,近年来受到了广泛的关注。
2015年,Dai团队[18]首次将SnO2作为电子传输层引入钙钛矿太阳电池,电子传输层/钙钛矿界面良好的电荷抽取是降低器件迟滞的主要原因。近年来,报道了多种SnO2电子传输层的制备方法,如原子层沉积(ALD)、溶液法、化学浴沉积(CBD)、电化学沉积和原位水热生长等[13,19-21]。ALD已成为制备高质量SnO2薄膜的有效替代方法,该技术可以精确控制薄膜厚度,具有优越的均匀性和良好的一致性,使其在生产致密、无缺陷的电子传输层(ETLs)方面具有独特优势[22-24]。相比之下,湿法化学路线更受欢迎,其与真空沉积技术相比具有许多优势,例如成本低和易于加工,能更好适应未来的大规模生产[18,25]。目前,低温合成和制备高质量氧化锡仍是光伏领域的研究热点之一[26]。为进一步降低氧化锡制备温度,关键是控制化学反应路径和降低氧化锡纳米颗粒形成能[14]。
本工作提出了一种简单高效的合成路径,采用无水SnCl4作为锡源,在不外加酸碱的情况下直接与去离子水发生水解反应,用于低温(40~90 ℃)合成氧化锡纳米晶体(NCs),通过控制水解条件来调控生成的SnO2纳米晶体的尺寸。经过室温老化,得到直径在10 nm以内的稳定氧化锡纳米晶体,可应用于刚性和柔性钙钛矿太阳电池。
无水四氯化锡(SnCl4,纯度99.9%),购自上海毕得医药;碘化铅(PbI2,纯度99.999%)、甲脒碘(FAI,纯度99.5%)、溴化铅(PbBr,99.999%)和甲基溴化胺(MABr,纯度99.9%),均购自上海迈拓威;异丙醇(IPA,纯度99.5%),购自上海阿拉丁生化科技。
常用的商业SnO2水系分散液中,加入了KOH来抑制纳米颗粒团聚,溶液本身呈碱性,这也可能在器件的稳定性方面埋下隐患。相比于以SnCl2·2H2O、SnCl4·5H2O作为锡源的水热反应,无水SnCl4的水解过程较为缓慢,不需要额外的引入酸或碱来控制不溶性无定形氧化锡的形成。因此采用无水SnCl4作为锡源,将无水SnCl4溶液用常温去离子水稀释至0.15 mol/L,随后转移至密闭恒温烘箱中水解,经过洗涤、离心、过滤、烘干等操作得到白色SnO2晶体粉末。水解反应如式(1)所示:
SnCl4+H2O→HeatSnO2+HCl↑
本实验中Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3三元阳离子体系的钙钛矿太阳电池采用正式结构(n-i-p),如图1所示,具体器件结构为ITO衬底/SnO2/PVK/spiro-OMeTAD/Au。器件制备工艺流程包括:ITO玻璃衬底的清洗处理、采用旋涂法制备电子传输层(SnO2)、钙钛矿吸光层和空穴传输层(spiro-OMeTAD)、蒸镀背金属电极(Au)。其中SnO2层的旋涂工艺参数为120 µL-800 r/min旋涂2 s后3000 r/min下旋涂30 s,最后150 ℃的热板上退火30 min;钙钛矿层为50 µL-1000 r/min旋涂10 s,6000 r/min下旋涂30 s,在高速旋涂15 s时滴加180~200 µL的反溶剂CB,最后100 ℃的热板上退火60 min。空穴传输层的旋涂工艺参数为45~50 µL-800 r/min旋涂2 s,4000 r/min高速旋涂30 s,旋涂结束后自然冷却至室温。
XRD(Rigaku MiniFlex Ⅱ型)表征材料微观结构;紫外-可见-近红外分光光度计(QTEST STA TION 500AD型,550 nm)表征钙钛矿层对光的吸收能力;AFM(Dimension Icon型)表征样品表面形貌特征及其均方根(root mean square,RMS)粗糙度测试。
伏安特性曲线(J-V)测试是表征太阳电池器件整体性能的常用手段。在1个标准太阳光的照射下(81904型氙灯,光照强度100 mW/cm2),测试过程中给太阳电池器件提供连续的电压扫描(Keithley 2611光源计),扫描电压可根据不同吸收层的带隙设置,得到相应的电流值,通过J-V曲线可得到器件的开路电压VOC、短路电流ISC、填充因子FF、光电转换效率EPC等重要参数。光电转换效率如式(2)所示:
EPC=PmaxPinc×100%=FF×ISC×VOCPinc×100%
在半导体或其他电子器件中,当存在较高强度电场或器件尺寸较小时,此时电子或空穴在材料中移动时,由于空间中的电荷分布不均匀而限制电流密度,它们会受到周围空间电荷的影响,从而导致电荷在器件内部积累并形成电场,限制载流子的移动,进而影响到整个器件的电流输出特性。通过制备双电子或双空穴结构的单载流子器件,对其进行J-V测试(暗态条件下),通过分析暗态J-V特性曲线得到器件的缺陷密度等信息。其中主要用到了陷阱填充极限电压(VTFL),即欧姆区和缺陷填充区的交点对应的电压,用来计算器件的缺陷密度,如式(3)所示:
VTFL=eNtL22εε0
式中:e代表电子电荷值;Nt代表器件的缺陷密度;L为薄膜厚度;ε是材料的相对介电常数;ε0为真空介电常数。
作为电子传输层时,SnO2纳米颗粒的尺寸直接影响到整个器件的性能,在无水SnCl4的水解过程中,反应时间和反应温度共同决定着最终生成SnO2的粒径,可通过反应时间来调控生成的SnO2的晶粒尺寸,结果如图2(a)所示。随着反应时间的增加,溶液透明度下降,从最初的无色透明逐渐变浑浊,利用红色激光笔测试其丁达尔效应,激光笔照射形成的光路逐渐清晰再变得不透光,这主要是因为反应时间超过90 min后,溶液中粒子数增多,比表面积大,表面能高,处于能量不稳定状态,纳米颗粒发生团聚现象,SnO2颗粒的尺寸变大,从胶体变为悬浊液。
图2(b)为水解时间为60、90、120、180 min时制备的氧化锡粉末样品的XRD谱图。从XRD图谱中可以看出,在26.6°、33.9°、37.9°、51.9°处均有衍射峰,具有正方金红石结构,同时未发现金属锡或其他锡氧化物的衍射峰,说明不同水解时间下SnO2粉末都是结晶的,不会产生其他锡的氧化物杂质。但不同水解温度下的XRD图谱略有不同,60、90 min条件下的SnO2在(110)、(101)方向上的衍射峰较强且衍射峰的半高宽较小;随着时间增长,衍射峰的半高宽增大,这可能是因为水解生成的SnO2在结晶质量和晶粒尺寸方面有所不同,从XRD谱图中可以看出,水解时间为60、90 min时所得到的SnO2在晶体质量和晶粒尺寸方面的表现最佳。
动态光散射技术(DLS)是通过一定波长的光照射悬浮颗粒的溶液或气溶胶样品,利用颗粒对光的散射特性,结合布朗运动理论,通过分析散射光的模式和频率,来确定颗粒的尺寸和浓度。采用动态光散射技术进一步测试了SnO2异丙醇溶液中的纳米颗粒的尺寸,测试结果如图3所示。当水解时间不超过120 min时,制备的SnO2在晶粒尺寸方面均具有较强的单一性,分布比较集中,对平均晶粒尺寸的贡献全都来自小尺寸颗粒,溶液中不存在大尺寸的颗粒。超过120 min时,SnO2纳米颗粒团聚现象加剧,出现了大尺寸的粒子,晶粒尺寸的分布范围分为明显的两部分。水解时间在30、60、90、120、150、180 min条件下对应的平均晶粒尺寸分别为7.891、8.364、8.719、8.966、9.642、10.57 nm。
图4(a)可以看出,SnO2纳米颗粒的大小与水解时间近似成正相关,水解时间越长,得到的SnO2纳米颗粒的尺寸越大,这是因为随着反应的进行,溶液中的粒子浓度变大,小尺寸的粒子会发生团聚现象,导致晶粒尺寸增大,温度超过120 ℃时,变化的幅度增大这也与水解过程中溶液逐渐变浑浊的实验现象相一致。
为了进一步探究水解得到的SnO2的光学和电学特性,采用旋涂法将氧化锡前驱体涂覆在玻璃衬底上,测试了不同水解时间下的氧化锡薄膜的横向电导(图4(b))和光透过率(图4(c)),可以看到60 min对应的薄膜的横向电导率较大,180 min对应的薄膜的横向电导较小。这主要是因为较小的晶粒尺寸意味着更大的比表面积,随着溶剂的挥发,处于能量不稳定状态的粒子相互吸附结晶,形成致密平整的薄膜,这将减少电子的传递势垒,导电性能有所提高。总体来说,不同水解时间下得到的SnO2薄膜的光透过率的变化相对较小,说明晶粒尺寸的微小变化并不会对薄膜的光学特性产生较大的影响。图4(d)为不同水解时间下制备的SnO2薄膜的AFM图像,可以看出,水解法制备的SnO2的薄膜粗糙度普遍较小,水解时间为30、60、90、120、150、180 min时对应的粗糙度分别为1.68、1.38、1.44、1.64、1.61、1.76 nm。随着水解时间的增加,SnO2薄膜的粗糙度逐渐变大,这主要是因为反应时间越长,SnO2纳米颗粒出现团聚的现象越明显,晶粒尺寸变大,最终导致旋涂得到的SnO2薄膜的粗糙度增大。当作为电子传输层时,薄膜会因涂覆不均匀而出现孔洞,这将导致钙钛矿层直接与ITO衬底接触而产生漏电流。此外,电子传输层的粗糙度也会影响到上层钙钛矿的沉积,粗糙度变大,会对钙钛矿层与电子传输层的界面接触产生影响,从而加剧了载流子在界面处的复合,影响到整体钙钛矿太阳电池器件的性能。但粗糙度在1~2 nm之间的SnO2薄膜致密性都满足器件要求,此时更多的是材料电学和光学特性影响器件性能。
图5(a)为基于不同水解时间下得到的SnO2制备的太阳电池的器件光电转换效率统计箱线图,随着水解时间的增长,器件效率先上升后下降,水解时间在60 min条件下器件性能表现最好,平均效率达到18.5%,水解时间为180 min时器件的整体效率最低。可以看出,不同水解时间下得到的SnO2对太阳电池器件的短路电流密度(图5(b))和开路电压(图5(c))都有一定的影响,JSC和VOC的变化趋势和效率的变化一致,均为先上升后下降,最高的短路电流和开路电压都出现在60 min条件下;填充因子方面(图5(d)),各个实验组之间的变化趋势不明显,基本都分布在69~76的区间内。这就说明,水解法制备的SnO2晶粒尺寸越小,旋涂出的薄膜更加平整光滑,当钙钛矿吸收层涂覆在上面时可以形成更好的界面接触,减少了漏电损失,对开压的提高有一定的帮助。同时材料电学特性的提高使得载流子快速抽取,在界面处的复合损失减少,从而使器件的短路电流密度增大。
为了进一步分析载流子在界面处的传输,测试标准模拟光(AM 1.5G,100 mW/cm2)照射下的电化学阻抗谱,得到了对应的奈奎斯特曲线,如图6(a)所示,能够发现在Nyquist图中高频区域出现了明显的圆弧,代表了器件的电荷传输电阻(Rct),圆弧的半径与电荷转移电阻成正比,半径越大,则表示载流子的电荷转移势垒越大。对比可以发现水解时间为60 min时制备的器件在高频区域的Rct最小,表明SnO2导电性能的提高使得载流子在界面处的传输势垒减小,插图为用ZSimpWin软件对高频半圆拟合的等效电路模型。图6(b)的暗态J-V测试结果所示,水解时间为60 min时对应的器件的漏电流最小,载流子产生率降低,陷阱密度减小。这主要归因于60 min条件下的SnO2电导率较高,较小的晶粒尺寸可以形成光滑平整的电子传输层,与钙钛矿层的接触更加充分,减小了载流子的传输势垒,有利于载流子在界面处的转移和在传输层上的传输。
图7(a)为水解时间为60 min条件下的冠军器件的J-V测试结果,最高效率为20.4%(有效面积为0.13 cm2),开路电压为1.13 V,短路电流密度为23.0 mA/cm2,填充因子为76.5%,结合外量子效率(external quantum efficiency,EQE)测试,如图7(b)所示,钙钛矿吸光层在400~600 nm波段的响应均超过了80%,积分电流为22.5 mA/cm2,这也与J-V测试的短路电流密度结果相一致。同时,以广泛使用的商业SnO2作为对照组,相同条件下制备的钙钛矿太阳电池效率为19.35%(图8(a),(b)),可以看出,水解法制备的SnO2在电流、开压和填充方面均有一定的优势,这主要得益于晶粒尺寸的变小,能够形成致密光滑的薄膜,改善了电子传输层的导电性能和界面接触。
(1)采用无水SnCl4作为锡源,水解法制备SnO2纳米颗粒作为电子传输层。在无水SnCl4的水解过程中,随着反应时间的增加,溶液中的粒子浓度变大,小尺寸的粒子会发生团聚现象,导致出现较大尺寸的晶粒,形成的薄膜可能会因涂覆不均匀而出现孔洞,导电性能下降。
(2)较小晶粒尺寸的SnO2可以形成致密平整的电子传输层,与钙钛矿层的接触更加充分,有利于载流子在界面处的转移。水解时间为60 min时生成的SnO2的平均晶粒尺寸为8.36 nm,具有优异的光学和电学特性,制备成的薄膜质量较高,粗糙度为1.38 nm,有利于加速载流子的提取和输运,减少界面处电荷因堆积而造成的非辐射复合损失。
(3)制备的钙钛矿太阳电池器件填充因子和短路电流方面都有提高,最高光电转换效率可达20.4%(有效面积0.13 cm2)。
  • 国家自然科学基金(61974074)
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doi: 10.11868/j.issn.1001-4381.2024.000267
  • 接收时间:2024-04-15
  • 首发时间:2026-10-27
  • 出版时间:2026-06-20
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  • 收稿日期:2024-04-15
  • 录用日期:2024-07-17
基金
国家自然科学基金(61974074)
作者信息
    南开大学 电子信息与光学工程学院 电子科学与工程系,天津 300350

通讯作者:

蔡宏琨(1980—),女,教授,博士,主要研究半导体材料与器件,联系地址:天津市津南区同砚路南开大学新校区电子信息与光学工程学院(300350),E-mail:
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2种不同金属材料的力学参数
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属
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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