Influence of Zn Doped SnO₂ Nanocrystals as Photoanode Materials on Photoelectric Performance of Dye-sensitized Solar Cells Enhanced Publication

SnO 2 ∶Zn纳米晶光阳极对染料敏化太阳能电池光电性能的影响 Influence of Zn Doped SnO 2 Nanocrystals as Photoanode Materials on Photoelectric Performance of Dye-sensitized Solar Cells 1 corresp first-author E-mail: cuiling.yu@hit.edu.cn E-mail: cuiling.yu@hit.edu.cn 于翠玲(1979-)，女，吉林长春人，博士，讲师，2008年于吉林大学获得博士学位，主要从事光电材料与器件的研究。E-mail: cuiling.yu@hit.edu.cn http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=22919371&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=22919376&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=22919379&type= 于翠玲 (1979-)，女，吉林长春人，博士，讲师，2008年于吉林大学获得博士学位，主要从事光电材料与器件的研究。E-mail: cuiling.yu@hit.edu.cn cuiling.yu@hit.edu.cn 1 1 1 1 1 2 哈尔滨工业大学　物理学院，黑龙江　哈尔滨　150001 哈尔滨工业大学　物理学院，黑龙江　哈尔滨　150001 School of Physics, Harbin Institute of Technology, Harbin 150001, China School of Physics, Harbin Institute of Technology, Harbin 150001, China 长春希达电子科技有限公司，吉林　长春　130103 长春希达电子科技有限公司，吉林　长春　130103 Changchun Cedar Electronics Technology Co., Ltd., Changchun 130103, China Changchun Cedar Electronics Technology Co., Ltd., Changchun 130103, China 利用水热法合成不同Zn掺杂含量的SnO 2 (SnO 2 ∶Zn)纳米晶，并通过丝网印刷技术制备了SnO 2 ∶Zn纳米晶光阳极，研究不同含量Zn掺杂SnO 2 纳米晶光阳极对染料敏化太阳能电池光电性能的影响。实验结果表明，Zn掺杂含量增加能够引起SnO 2 光阳极的平带电位负向偏移和等电点增加。与未掺杂SnO 2 染料敏化太阳能电池相比，当Zn掺杂量为2% 时，SnO 2 ∶Zn基染料敏化太阳能电池的功率转换效率(PCE)最高，为4.2%，这归因于Zn掺杂能够增加染料在SnO 2 光阳极的担载量和提高染料敏化太阳能电池的光生电子寿命( τ e )。此外，2% Zn掺杂SnO 2 光阳极进一步经过TiCl 4 处理，其电池功率转换效率可提高到7.7%。 Zn-doped SnO 2 nanocrystals under hydrothermal conditions were synthesized and subsequently the photoanodes were prepared via the screen printing technology for dye-sensitized solar cells. The effect of Zn-doped SnO 2 on the performance of dye-sensitized solar cells was investigated. It is found that Zn doping into SnO 2 can induce a negative shift in the flat-band potential and enhance the isoelectric point. As a result, the power conversion efficiency(PCE) of 4.2% was achieved for 2% Zn-doped SnO 2 based dye-sensitized solar cell compared with undoped SnO 2 based dye-sensitized solar cell. The enhancement in performance was ascribed to improve photogenerated electron lifetime( τ e ) and dye-uptake capabilities. Moreover, after the TiCl 4 treatment of the photoanode, the 2% Zn-doped SnO 2 based dye-sensitized solar cell exhibited an impressive power conversion efficiency of 7.7%. 染料敏化太阳能电池 SnO 2 Zn掺杂 光阳极 dye-sensitized solar cell SnO 2 Zn doped photoanode 引言 1 随着社会对可再生能源需求的日益增长，太阳能电池开发利用越来越引起世界各国的重视。在过去的二十多年里，染料敏化太阳能电池因其高性价比而被广泛研究 [ 1 1 - 5 5 1-5 ] 。作为染料敏化太阳能电池关键组成部分，宽禁带半导体金属氧化物扮演着两个重要角色:染料分子载体和光注入电子的输运体。目前报道的高功率转换效率的染料敏化太阳能电池所使用的光阳极都是基于介孔TiO 2 纳米晶的光阳极 [ 6 6 - 9 9 6-9 ] 。而其他金属氧化物，如ZnO、SnO 2 和Nb 2 O 5 ，作为潜在的TiO 2 替代者也已被研究 [ 10 10 - 14 14 10-14 ] 。与TiO 2 相比，SnO 2 具有更高的电子迁移率(100~200 cm 2 ·V -1 ·s -1 ) [ 15 15 ] ，有利于光注入电子快速传输到电流集流体上。此外，由于SnO 2 有更宽的带隙(3.6 eV)，其价带有较少氧化性空穴，能够减少紫外线对染料分子的降解，进而提高染料敏化太阳能电池的长期稳定性 [ 16 16 ] 。 然而，与TiO 2 基染料敏化太阳能电池相比，SnO 2 基染料敏化太阳能电池功率转换效率仍很低。其原因是:(1)相对于TiO 2 导带边，SnO 2 导带边正偏移~300 mV，这会导致光注入电池与电解质快速电子复合，进而影响电池的开路电压( V oc ) [ 17 17 ] ;(2)SnO 2 等电点(pH 4~5)低于TiO 2 等电点(pH 6~7) [ 18 18 ] ，不利于带有羧酸官能团的染料分子的吸附。为了解决这些问题，研究者们通过对SnO 2 元素掺杂和/或表面包覆的方法来抑制电子复合和提高染料分子在光阳极的担载量，进而提高SnO 2 基染料敏化太阳能电池的功率转换效率 [ 19 19 - 22 22 19-22 ] 。Wang等采用TiO 2 包覆的分级SnO 2 八面体结构作为光阳极，实现了功率转换效率达6.8%的染料敏化太阳能电池 [ 19 19 ] 。Ramasamy等报道了一种采用Zn掺杂二维六角结构SnO 2 作为染料敏化太阳能电池光阳极，这种掺杂结构可以调节SnO 2 子带边缘的表面态，从而将染料敏化太阳能电池的功率转换效率从0.8%提高到了3.73% [ 20 20 ] 。之后，Dou等报道了一种具有SnO 2 ∶Zn 纳米花结构的染料敏化太阳能电池，这种结构进一步用TiO 2 包覆后，其功率转换效率从3.0%增加到了6.78% [ 21 21 ] 。Mao等基于SnO 2 ∶Zn纳米线构筑的微米管分级结构制备的染料敏化太阳能电池功率转换效率也可达到4.22% [ 22 22 ] 。Duan等采用Al 2 O 3 包覆SnO 2 光阳极抑制电池界面载流子复合，其电池功率转换效率从3.50%提高到4.15% [ 23 23 ] 。 因此，SnO 2 光阳极的适当元素掺杂和表面处理是提高其染料敏化太阳能电池功率转换效率的一种有效方法。 目前，高效染料敏化太阳能电池所使用的光阳极由具有高比表面积的纳米晶颗粒构成。然而，基于SnO 2 ∶Zn纳米晶制备的染料敏化太阳能电池光阳极研究较少。本文采用水热法合成了SnO 2 ∶Zn纳米晶，通过丝网印刷技术制备SnO 2 ∶Zn纳米晶光阳极，主要研究Zn掺杂对SnO 2 基染料敏化太阳能电池光电性能的影响。 实验 1 SnO 2 ∶Zn纳米晶制备 2 SnO 2 ∶Zn纳米晶采用水热法合成。其合成方法如下:首先，将20 mL含有0.6 mol·L -1 的SnCl 4 ·5H 2 O和一定原子比的Zn(CH 3 COO) 2 ·2H 2 O的水溶液缓慢加入配制好的氨水溶液中，这种氨水溶液包含16 mL NH 4 OH和24 mL去离子水。将混合溶液搅拌2 h后倒入反应釜中，然后放置在干燥箱中，在200 ℃条件下保温12 h。待反应结束后，将反应釜冷却至室温，得到白色产物，经离心、洗涤、干燥后备用。 光阳极制备与电池组装 2 SnO 2 ∶Zn纳米晶浆料采用标准的染料敏化太阳能电池浆料制作方法 [ 24 24 - 25 25 24-25 ] 。光阳极采用丝网印刷技术制作，其面积为0.283 cm 2 ，厚度约为8.5 μm。SnO 2 ∶Zn光阳极经烧结或TiCl 4 处理后，将其浸泡于C106钌染料溶液中敏化20 h。然后将敏化完的光阳极薄膜朝上放置在热压机工作平台上，上面覆盖铂化的对电极，两个电极中间用拜劳热熔环分开，热压组合后，在对电极的小孔注入电解液，最后用拜劳圆膜和盖玻片将小孔以热封，完成电池制备。 样品表征与电池性能测试 2 采用Rigaku D/max-2500 X射线衍射仪对样品进行XRD表征。利用透射电子显微镜(JEOL JEM-2100)进行样品TEM和HRTEM表征。用JEOL JEM-6700F扫面电子显微镜对样品进行SEM表征。用PHI 5700 ESCA系统对材料进行XPS表征。用BELSORP-max比表面积测试仪进行样品的比表面积测量。UV-Vis吸收光谱在Shimadzu 3600 UV-Vis光谱仪上测得。利用染料的解吸附法，通过测染料解吸附溶液的吸收光谱来估算染料分子在光阳极上的担载量。电极平带电位是利用Autolab-PGSTAT302N电化学工作站测量Mott-Schottky曲线推算得到。采用500 W的氙灯光源(CHF-XM500,Trusttech)，用全自动光栅单色仪(Omni- λ 300,Zolix)分光，标准单晶硅太阳能电池(S1337-1010BQ,Hamamatsu)为参比电池，Keithley 2400型数字源表作为电流记录表，由LabVIEW 8.0软件自动控制完成外量子效率(EQE)测试。采用LS1000-4S-AM1.5G-1000W型太阳光模拟器(Solar Light Com. Inc.)为辐照光源，用Keithley 2602数字源表对电池两端施加偏压，测量其外电路的电流值，获得 J-V 曲线。利用Autolab-PGSTAT302N电化学工作站进行瞬态光电衰减测试。 结果与讨论 1 SnO 2 ∶Zn纳米晶结构与形貌分析 2 图1(a) 图1(a) 为不同Zn掺杂SnO 2 纳米晶的XRD光谱。所有的衍射峰都对应于正方金红石相的SnO 2 晶体(JCPDS,41-1445)，没有其他的杂质衍射峰，这说明Zn的掺杂并没有引起SnO 2 晶格结构的明显改变。然而，随着Zn掺杂含量的增加，衍射峰的强度降低，半高宽增加，这可能是由于Zn的掺入导致SnO 2 晶粒尺寸变小 [ 26 26 ] 。此外，利用TEM对比了未掺杂和2% Zn掺杂的SnO 2 晶体形貌差异。从 图1(b)、(c) 图1(b)、(c) 中可以看出，2% Zn掺杂SnO 2 晶粒尺寸略小于未掺杂的SnO 2 晶粒，2% Zn掺杂SnO 2 晶粒尺寸大约为15 nm。2% Zn掺杂SnO 2 纳米晶的典型HRTEM如 图1(d) 图1(d) 所示。从图中的清晰晶格条纹可以推断出SnO 2 为单晶结构，其面间距为0.334 nm，该间距对应于金红石相SnO 2 的(110)面。 图2 图2 为未掺杂的和2% Zn掺杂的SnO 2 纳米晶的XPS光谱。 图2(a) 图2(a) 代表两种材料Sn 3d 5/2 和3d 3/2 峰的变化。由于氧化缺陷的影响，与未掺杂的SnO 2 纳米晶相比，2% Zn掺杂的SnO 2 纳米晶Sn 3d 5/2 和3d 3/2 结合能分别从原来的487.4 eV和495.9 eV降到486.6 eV和495.1 eV [ 27 27 ] 。另外，如 图2(b) 图2(b) 所示，Zn掺杂以后，O 1s峰也由原来的531.1 eV 降到 529.8 eV。Zn掺杂后在O 1s峰上出现的肩峰可能是Sn-O-Zn的结合峰 [ 28 28 ] 。从 图2(c) 图2(c) 中可以看出，2% Zn掺杂的SnO 2 纳米晶在1 020.4 eV和1 044.3 eV出现两个峰，这个峰是Zn 2p 3/2 和 Zn 2p 1/2 的归属峰，这也证明了SnO 2 纳米晶中有Zn元素的存在。 电池的光电性能分析 2 基于SnO 2 ∶Zn纳米晶的染料敏化太阳能电池在AM1.5G模拟太阳光照射条件下(辐照度为100 mW·cm -2 )的 J - V 曲线如 图3(a) 图3(a) 所示。未掺杂SnO 2 染料敏化太阳能电池的开路电压( V oc )、短路电流( J sc )、填充因子(FF)和功率转换效率(PCE)分别为335 mV、9.2 mA/cm 2 、0.43和1.3%。当使用不同Zn掺杂含量的SnO 2 纳米晶为光阳极时，电池的 V oc 随着Zn掺杂量增加而增大；在Zn掺杂量为2%时，电池的 J sc 达到最大，为13.5 mA/cm 2 ，功率转换效率达到最高，为4.2%，是未掺杂SnO 2 染料敏化太阳能电池效率的3倍多。 对染料敏化太阳能电池来说，当电解质固定后，其 V oc 大小主要由光阳极材料的电子准费米能级决定。为了证明Zn掺杂对SnO 2 光阳极准费米能级的影响，我们通过Mott-Schottky曲线对各个SnO 2 光阳极的平带电位( V FB )进行推算 [ 29 29 ] 。 V FB 可通过Mott-Schottky公式得到 [ 30 30 ] : http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=22919485&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=22919490&type= http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=22919494&type= 其中， C 是空间电荷区的微分电容， e 为电子电荷， ε 为半导体介电常数， ε 0 为真空介电常数， N D 为施主浓度， A 为电极的表面积， V 为电极电势， k 为玻尔兹曼常数， T 代表绝对温度。通过测得Mott-Schottky曲线，然后求解空间电荷区电容对电极电势函数关系来得到 V FB 。从 图3(b) 图3(b) 中可以看出，随着Zn掺杂含量的增加，引起 V FB 逐渐负向偏移，从未掺杂的0.19 V到3% Zn掺杂的-0.16 V。这种移动可能是通过Zn掺杂使得SnO 2 光阳极表面态钝化引起的，这种钝化会导致SnO 2 光阳极准费米能级上移，从而提高染料敏化太阳能电池的开路电压 [ 31 31 ] 。 为了理解Zn掺杂对染料敏化太阳能电池 J sc 的影响，测试了染料敏化太阳能电池的外量子效率(EQE)光谱，如 图3(c) 图3(c) 所示。EQE光谱与测得的 J sc 具有相同的趋势。未掺杂SnO 2 染料敏化太阳能电池的EQE值在波长为540 nm时为59%，随着Zn掺杂量增加，其电池的EQE在全光谱范围内明显增加，在2% Zn掺杂浓度条件下，波长为540 nm处EQE值可达74%。但是，当Zn掺杂含量增加到3%时，EQE又出现下降情况，但是仍高于未掺杂SnO 2 染料敏化太阳能电池的EQE值。通过上面的结果分析， V FB 的负向偏移可解释为Zn掺杂导致SnO 2 的导带提高 [ 27 27 ] 。导带位置的提高会抑制载流子的注入，从而引起EQE降低。与未掺杂SnO 2 相比，Zn掺杂SnO 2 染料敏化太阳能电池的EQE和 J sc 的提高与染料的负载量和界面电子复合有关 [ 32 32 ] 。不同光阳极染料分子的吸附量可以通过解吸附的UV-Vis曲线计算获得。未掺杂与掺杂量为1%、2%和3% Zn的SnO 2 光阳极的染料担载量分别为3.9×10 7 ,4.7×10 7 ,5.2×10 7 ,5.6×10 7 mol/cm 2 ，如 表1 表1 所示。由此看见，阳极的染料分子担载量随着Zn掺杂量的增加而增加。染料分子担载量与SnO 2 光阳极的等电点密切相关。 图3(d) 图3(d) 为Zn掺杂SnO 2 纳米晶的等电点与pH值关系曲线。从图中可以看出，随着Zn掺杂含量的增加，SnO 2 光阳极的等电点从4.3提高到5.0。随等电点的增加，染料分子的羧基更容易与SnO 2 光阳极结合而附着在SnO 2 光阳极上 [ 10 10 ] ，从而导致EQE与 J sc 提高。 1 1   1 1 Zn doping/% 1 1 Dye loading/(10 -7 mol·cm -2 ) 1 1 V oc /mV 1 1 J sc /(mA·cm -2 ) 1 1 FF 1 1 PCE/% 1 1 No TiCl 4 treatment 1 1 0 1 1 3.9 1 1 335 1 1 9.2 1 1 0.43 1 1 1.3 1 1   1 1 1 1 1 4.7 1 1 542 1 1 12.9 1 1 0.52 1 1 3.6 1 1   1 1 2 1 1 5.2 1 1 560 1 1 13.5 1 1 0.55 1 1 4.2 1 1   1 1 3 1 1 5.6 1 1 574 1 1 12.7 1 1 0.52 1 1 3.8 1 1 TiCl 4 treatment 1 1 2 1 1 6.4 1 1 673 1 1 16.9 1 1 0.68 1 1 7.7 测试了不同Zn掺杂SnO 2 染料敏化太阳能电池在暗处的 J-V 曲线，如 图4(a) 图4(a) ，分析Zn掺杂对SnO 2 染料敏化太阳能电池电子复合的影响。虽然暗电流不能直观地反映电极处的电子复合过程，但对于同一类型的电池来说，通过对比也可以得到一定的载流子复合信息。从 图4(a) 图4(a) 中可以看出，随着Zn掺杂含量的增加，其电池的暗电流逐渐降低，这意味着Zn的掺杂可以有效地抑制电子在半导体电极与电解质之间的复合。进一步利用瞬态光谱技术测量了未掺杂与Zn掺杂染料敏化太阳能电池中的光生电子寿命( τ e )，如 图4(b) 图4(b) 所示。Zn掺杂电池中的 τ e 远远高于未掺杂电池中的光生电子寿命。在一定提取电荷时， τ e 随着Zn掺杂浓度的增加而增加，这与得到的暗电流趋势是相符的。众所周知，染料敏化太阳能电池中的 τ e 是决定电池载流子复合动力学中的关键因素。 τ e 的增加意味着Zn掺杂可以有效地抑制光生电子与电解质之间的复合。较低的载流子复合速率是实现较高电子收集效率的必要条件。收集效率增加可以提高染料敏化太阳能电池EQE、 J sc 和 V oc 值，进而提高电池功率转换效率。然而，当Zn掺杂含量增加到3%时，尽管光生电子寿命增加，但电池功率转换效率有所降低，主要还是归因于Zn掺杂导致SnO 2 的导带位置提高在一定程度上抑制了载流子的注入，进而降低了电池的 J sc 。 为了进一步提高染料敏化太阳能电池光电性能，我们对2% Zn掺杂SnO 2 光阳极进行TiCl 4 处理。 图5(a)、(b) 图5(a)、(b) 分别为2% Zn掺杂SnO 2 光阳极被TiCl 4 处理前后的SEM形貌。与未经TiCl 4 处理2% Zn掺杂SnO 2 光阳极相比，经TiCl 4 处理的2% Zn掺杂SnO 2 光阳极表面变得致密和平整，进而增加了纳米晶颗粒间的连接点。 图5(c) 图5(c) 为经TiCl 4 处理的2% Zn掺Zn掺SnO 2 染料敏化太阳能电池在AM1.5G模拟太阳光照射条件下(辐照度为100 mW·cm -2 )的 J - V 曲线，其光伏参数如 表1 表1 所示。与未经TiCl 4 处理的染料敏化太阳能电池相比，经过TiCl 4 处理的2% Zn掺杂SnO 2 染料敏化太阳能电池的功率转换效率提高到7.7%。 图5(c) 图5(c) 插图为2% Zn掺杂SnO 2 染料敏化太阳能电池的EQE，其EQE值在波长470~610 nm范围内均超过了80%，明显高于未经TiCl 4 处理光阳极电池的EQE。这主要归因于2% Zn掺杂SnO 2 光阳极经TiCl 4 处理后其染料担载量明显增加(如 表1 表1 所示)，吸附染料光阳极颜色也加深(如 图5 图5 插图所示)，提高了其光捕获能力。此外，如 图4 图4 所示，2% Zn掺杂SnO 2 光阳极经TiCl 4 处理后，其电池暗电流和界面电子复合都得到明显抑制，这主要归因于TiCl 4 处理能够提高邻近SnO 2 纳米晶紧密连接，可以有效地提高电子传输和抑制SnO 2 与电解质间电子复合过程，从而提高了电池的V oc [ 33 33 - 34 34 33-34 ] 。因此，经TiCl 4 处理后，2% Zn掺杂SnO 2 光阳极的染料担载量的增加和界面电子复合的抑制使得电池的功率转换效率显著提高。 结论 1 本文采用水热法成功地制备了不同Zn掺杂含量的SnO 2 纳米晶，并将其应用在染料敏化太阳能电池中。结果表明，Zn掺杂含量增加能够引起SnO 2 光阳极的平带电位负向偏移，导致SnO 2 光阳极准费米能级上移，从而提高染料敏化太阳能电池的开路电压。同时，Zn掺杂含量增加能够提高SnO 2 光阳极的等电点，进而提高染料分子在光阳极的担载量，增加其光捕获能力。此外，通过瞬态光谱技术证明了Zn掺杂能抑制光生载流子的复合，进而提高染料敏化太阳能电池的光电性能。与未掺杂SnO 2 染料敏化太阳能电池相比，2% Zn掺杂SnO 2 染料敏化太阳能电池的功率转换效率最高，达到4.2%，是未掺杂SnO 2 染料敏化太阳能电池效率的3倍多。2% Zn掺杂SnO 2 光阳极经过TiCl 4 处理后，增加其染料担载量并抑制了电池中光生电子的复合，进而使电池功率转换效率提高到7.7%。 本文专家审稿意见及作者回复内容的下载地址:http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20210285. 参考文献: O'REGAN B , GRÄTZEL M . 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Enhanced photovoltaic properties in dye sensitized solar cells by surface treatment of SnO2 photoanodes 10.37188/CJL.20210285 O482.31;TM914 A 1000-7032(2021)12-1936-08 国家自然科学基金（51502056）；中央高校基本科研业务费专项基金（HIT. NSRIF. 2020100）资助项目 Supported by National Natural Science Foundation of China (51502056); Fundamental Research Funds for The Central Universities (HIT. NSRIF. 2020100) 2021-08-27 2021-09-10 2021-12-16 2021 发光学报 12 42