低温溶液加工CsPbBr<sub>3</sub>纳晶薄膜制备钙钛矿太阳电池

张喜生; 晏春愉; 胡李纳; 王景州; 姚陈忠

doi:10.7498/aps.73.20241152

低温溶液加工CsPbBr₃纳晶薄膜制备钙钛矿太阳电池

1.
运城学院, 山西省智能光电传感应用技术创新中心, 运城　044000
2.
运城学院, 山西省光电信息科学与技术实验室, 运城　044000

通讯作者: E-mail: zhangxisheng@ycu.edu.cn.;

中图分类号: 81.05.-t, 84.60.Jt, 88.40.hj

Perovskite solar cells prepared by processing CsPbBr₃ nanocrystalline films in low temperature solution

1.
Shanxi Province Intelligent Optoelectronic Sensing Application Technology Innovation Center, Yuncheng University, Yuncheng 044000, China
2.
Shanxi Province Optoelectronic Information Science and Technology Laboratory, Yuncheng University, Yuncheng 044000, China

Corresponding author: E-mail: zhangxisheng@ycu.edu.cn.;

MSC: 81.05.-t, 84.60.Jt, 88.40.hj

摘要: 溶液法制备钙钛矿多晶薄膜过程中, 不仅使用有毒溶剂配置前驱液, 而且热处理仍是诱导钙钛矿晶粒生长的主要途径, 这项工艺会增加能耗, 还阻碍柔性电池的发展. 为消除有毒溶剂的使用和高温处理, 本文通过低温溶液加工CsPbBr₃纳晶薄膜获得相应的多晶薄膜, 应用到太阳电池中. 首先热注入法制备CsPbBr₃纳米晶墨汁前驱液, 并采用旋涂法制备其纳晶薄膜. 大气环境下, CsPbBr₃纳晶薄膜经Pb(SCN)₂与NH₄Br乙酸甲酯饱和溶液处理制备CsPbBr₃多晶薄膜, 将其作为吸收层制备钙钛矿太阳电池, 有效提高了电池的性能, 电池效率达到8.43%. 研究表明, Pb(SCN)₂与NH₄Br乙酸甲酯(MA)饱和溶液不仅可以使纳晶继续结晶生长, 同时还可以有效地钝化钙钛矿薄膜中的缺陷. 采用该方法制备CsPbBr₃多晶薄膜过程中, 既无高温处理, 也无高沸点毒性溶剂的使用, 同时适用于刚性和柔性电池的制备.
- CsPbBr₃ /
- 纳米晶 /
- 多晶 /
- 钙钛矿太阳电池
Abstract: In the process of preparing perovskite polycrystalline films by solution method, toxic solvents are used, and heat treatment is still the main way to induce perovskite grain growth, which not only increases energy consumption, but also hinders the development of flexible solar cells. In order to avoid the use of toxic solvents and high-temperature process, CsPbBr₃ nanocrystal films are treated with low temperature solution to obtain corresponding polycrystalline thin films, which are applied to solar cells. Firstly, CsPbBr₃ nanocrystalline (nanocrystalline NC) ink precursor is prepared by hot injection method, and nanocrystalline film is prepared by spinning coating method. In atmospheric environment, CsPbBr₃ nanocrystalline films are prepared by saturated solution of Pb(SCN)₂ and NH₄Br methyl acetate. Using the CsPbBr₃ nanocrystalline film as an absorbing layer, the perovskite solar cell is prepared and the performance of the cell is effectively improved, and the efficiency of the cell reaches 8.43%. The results show that the saturated solution of Pb(SCN)₂ and NH₄Br methyl acetate (MA) can not only continue the nanocrystalline crystallization, but also effectively passivate the defects in the perovskite films. In the process of preparing CsPbBr₃ polycrystalline films, neither high temperature treatment nor the high boiling point toxic solvent is used, which is suitable for the preparation rigid and flexible solar cells.The inorganic halide perovskite nanocrystals are developed and used as “ink” to fabricate fully air-processed, electrically stable solar cells. Although the prepared film is composed of mosaic nanocrystals capped with a large number of organic ligands and surface traps, this method provides a new approach for single-step, large-scale fabrication of inorganic perovskite devices. Moreover, the flexible control of the material composition provides a platform for uncovering the optimal conditions for optoelectronics and photonics.
- CsPbBr₃ /
- nanocrystalline /
- polycrystalline /
- perovskite solar cells .

图 1 CsPbBr₃纳晶　(a) X射线衍射图; (b) TEM图; (c) SEM图; (d) 多晶薄膜的SEM图, 内插照片分别为纳晶墨汁、纳晶及多晶薄膜在自然光和紫外灯照射下荧光; (e), (f) CsPbBr₃纳晶墨汁、纳米晶薄膜和多晶薄膜的(e) 紫外-可见吸收光谱和(f)光致发光光谱图, NC代表纳米晶

Figure 1. CsPbBr₃ nanocrystalline: (a) XRD spectrum, (b) TEM image; (c) SEM image; (d) SEM image of polycrystalline film, the interpolated photos show the fluorescence emission of nanocrystalline ink, nanocrystalline and polycrystalline films under natural light and ultraviolet lamps, respectively; (e) UV-VIS absorption spectra and (f) photoluminescence spectra of CsPbBr₃ nanocrystalline ink, nanocrystalline film and polycrystalline film, NC in the figures represents nanocrystalline.

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图 2 CsPbBr₃钙钛矿太阳电池的截面图　(a) 纳晶薄膜; (b) 纳晶团聚结晶; (c), (d) 纳晶薄膜经饱和溶液分别处理15 s和30 s所得的多晶薄膜. 钙钛矿薄膜表面形貌　(e) 纳晶薄膜; (f) 纳晶团聚薄膜; (g), (h) 分别对应图(c), (d)多晶薄膜

Figure 2. Cross-sectional SEM images of CsPbBr₃ perovskite solar cells: (a) Nanocrystalline; (b) nanocrystalline agglomerative crystals; (c), (d) polycrystalline films obtained by treating nanocrystalline films with saturated solution for 15 s and 30 s, respectively. Morphology of perovskite films: (e) Nanocrystalline film; (f) nanocrystalline agglomerative film; (g), (h) corresponding to panels (c), (d) polycrystalline films, respectively.

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图 3 CsPbBr₃钙钛矿太阳能电池的(a) J-V和(b) EQE曲线, 图中NC film表示纳晶薄膜器件, 15 s PC film和30 s PC film分别代表纳晶薄膜经饱和溶液分别处理15 s和30 s所得的多晶薄膜器件

Figure 3. (a) J-V curves and (b) EQE curve of CsPbBr₃ perovskite solar cells, where NC represents nanocrystalline film, 15 s PC film and 30 s PC film represent devices of polycrystalline film obtained by nanocrystalline film treated with saturated solution for 15 s and 30 s, respectively.

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图 4 (a) CsPbBr₃纳晶及经饱和溶液处理15 s和30 s所得多晶薄膜的XRD谱; (b) 薄膜正面照射所得PL光谱(激光激发波长为375 nm); (c) 时间分辨荧光光谱图; (d) 单电子器件的暗态I-V曲线 (内插图单电子器件的结构)

Figure 4. (a) XRD patterns of CsPbBr₃ nanocrystalline and polycrystalline films obtained by treating it with saturated solution for 15 s and 30 s; (b) PL spectrum obtained by positive irradiation of the films (laser excitation wavelength is 375 nm); (c) time-resolved fluorescence spectrum; (d) dark state I-V curves of single electron device (internal illustration of the structure of single electron device).

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表 1 3种薄膜所制备太阳能电池光伏性能及电学参数

Table 1. Photovoltaic properties and electrical parameters of solar cells prepared by three thin films.

Device		V_OC/V	J_SC/ (mA·cm^–2)	FF/%	PCE/%	R_s/Ω
NC film	最大值	1.49	5.62	64.1	5.36	261.4
NC film	平均值	1.46	5.61	63.8	5.23	—
15 s PC film	最大值	1.47	6.34	74.2	6.92	71.7
15 s PC film	平均值	1.46	6.34	73.5	6.80	—
30 s PC film	最大值	1.55	6.96	78.1	8.43	65.9
30 s PC film	平均值	1.54	6.94	77.9	8.35	—

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表 2 3种薄膜薄膜的时间分辨荧光的拟合参数

Table 2. Fitting parameters of time-resolved photoluminescence of three thin films.

器件类型	平均寿命 τ_ave /ns	寿命 τ₁ /ns	权重 A₁	寿命 τ₂/ ns	权重 A₂
FTO/TiO₂/NC film	14.60	19.71	261945	9.73	556783
FTO/TiO₂/15 s PC film	4.36	4.36	875893	4.36	875893
FTO/TiO₂/30 s PC film	2.13	2.13	3112950	2.13	3112950

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1. 引　言

无机铯铅钙钛矿材料(CsPbX₃, X = Cl, Br, I)在高效太阳电池、光电探测器、LED、激光器等光电子领域具有广阔的应用前景, 其优异性能归功于钙钛矿材料独特的光电特性, 包括高载流子迁移率、弱束缚激子、强吸收系数等^[1–6]. 全无机铯铅卤化CsPbBr₃因其对湿度和光照的耐受性强, 合适的带隙, 在室温下具有稳定的正交相结构等优点而受到广泛关注^[7–13]. 尽管功率转换效率(PCE)相对较低, 但CsPbBr₃太阳电池可提供高达1.7的高开路电压(V_OC), 可作为叠层电池的理想窗口层选择^[14–16].

溶液加工的钙钛矿材料因其低成本和易于制造的高性能光伏薄膜而受到广泛关注^[16–20]. 然而, 用于传统钙钛矿前驱溶液通常包括有毒的极性溶剂, 如氮, 氮-二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、氮-甲基–2-吡罗烷酮(NMP)等, 以及其他一些高沸点溶剂, 如二甲基亚砜(DMSO)、丁内酯(GBL)或高浓度的二甲基乙酰胺(DMA)^[17–20]. 替代或减少这些溶剂的使用成为钙钛矿太阳电池的一个研究方向, 但尚未得到科学的解决. 虽然有少许绿色溶剂被开发出来取代这些有毒溶剂, 但由此制备的器件性能仍然无法与基于DMF前驱体制备的器件相比^[21,22]. 除此之外, 溶液法制备钙钛矿多晶薄膜过程中, 热处理仍是诱导钙钛矿晶粒长大的主要途径, 这项工艺步骤不仅会增加能耗, 还阻碍柔性电池的发展. 纯无机钙钛矿纳米晶(NCs)制备过程中, 常用的溶剂包括十八烯(ODE)、油酸(OA)、油胺(OLA)、乙酸甲酯(MA)等, 均为无毒绿色溶剂, 而且基于纳米晶墨汁前驱液, 低温下便可通过旋涂或者刮涂一步法制备成膜, 该方法为大规模制造无机钙钛矿太阳电池提供了新的途径^[23–25].

本文基于CsPbBr₃纳晶墨汁制备高质量纳晶薄膜, 并在大气环境中, CsPbBr₃纳晶薄膜经Pb(SCN)₂与NH₄Br的乙酸甲酯(MA)饱和溶液处理制备了多晶薄膜, 将其作为钙钛矿太阳能电池中的吸收层, 制备了具有高效率的CsPbBr₃太阳电池. 该饱和溶液不仅可以促使纳晶体生长为均匀致密、晶粒尺寸大、缺陷密度低的多晶颗粒, 还可以有效地钝化钙钛矿薄膜的缺陷态密度, 所得钙钛矿太阳能电池的效率达到8.43%的效率. 基于纳晶低温溶液加工制备钙钛矿多晶薄膜, 不用在手套箱中进行, 也无需GBL, DMSO, DMF, DMSO, 氯苯等有毒有机溶剂的使用, 该方法对低成本的尤其是柔性钙钛矿电池的开发和应用具有很好的指导意义.

2. 实验部分

2.1. 主要试验试剂

溴化铅(PbBr₂)(纯度99.999%)购于Alfa Aesar公司; 碳酸铯(Cs₂CO₃), (纯度99.9%)、1-十八烯(ODE)(纯度90%)、油酸(OA)(纯度90%)、油胺 (OAm)(纯度70%)等溶剂均采购于阿拉丁试剂公司; 聚芳胺衍生物 (PTAA), M_w = 30000 g/mol, 采购于上海瀚丰化工科技有限公司. 乙酸甲酯MA(AR)、正辛烷(AR)、无水甲醇(AR)、金丝(Au)(纯度99.99%), 均来自国药集团化学有限公司; FTO玻璃(2.5 cm × 2.5 cm)用1.5% Hellmanex清洗液水溶液、超纯水(三次)和乙醇分别超声清洗10 min, 然后用N₂流干燥. 在沉积TiO₂之前, 所有衬底进一步用UV-臭氧清洗15 min. 根据之前的报道^[22], 通过化学浴沉积在清洁的FTO衬底上涂覆一层致密的TiO₂层. 将FTO/ TiO₂基底在200 ℃空气中退火40 min待用.

2.2. CsPbBr₃纳晶的合成

CsPbBr₃钙钛矿纳晶合成过程为: 将0.8 g碳酸铯和3 mL油酸加入圆底三口烧瓶中, 倒入30 mL十八烯(ODE), 将烧瓶放于加热套, 抽真空30 min去除空气和水后, 通入氩气保护, 在120 ℃条件下加热反应 30 min, 得到透明的Cs⁺油酸盐混合溶液. 与此同时, 将PbBr₂ (0.69 g)和ODE (60 mL)加入另一个三口圆底烧瓶中搅拌, 并将温度升至120 ℃抽真空去除空气和水, 结束后换成氩气保护, 分别加入5 mL OLA和5 mL OA, 再抽真空去空气和水, 当PbBr₂完全溶解溶液变透明后, 温度升高至反应温度160 ℃. 最后迅速注入之前合成好的Cs⁺油酸盐, 反应30 s后, 迅速将反应混合物放在冰浴中冷却, 得到的最终沉淀物即为CsPbBr₃纳晶, 产物经乙酸甲酯(MA)去除部分纳晶表面支链后离心清洗, 最终的纳晶溶解在5 mL正辛烷中形成墨汁, 用于旋涂薄膜所用的前驱液, 浓度约50 mg/mL, 产物通过旋蒸的方式得到颗粒物可用于样品表征.

2.3. CsPbBr₃钙钛矿太阳电池的制备

在大气环境中, 首先取60 μL的50 mg/mL CsPbBr₃纳晶墨汁前驱液滴到FTO玻璃/TiO₂表面, 2500 rad/min转速旋涂30 s, 过程中(旋涂开始5 s后)将300 μL乙酸甲酯滴到薄膜表面, 旋涂停止后, 分别将100 μL Pb(SCN)₂乙酸甲酯饱和溶液和100 μL NH₄Br乙酸甲酯(MA)饱和溶液滴到薄膜表面, 静置30 s后, 以3000 rad/min再旋涂30 s. 然后重复上述过程5次, 可形成500 nm的薄膜, 氮气吹干后在70 ℃加热台上烘干3 min后, 将配置好的PTAA溶液在钙钛矿表面以5000 rad/min的转速下旋转30 s, 形成大概100 nm厚的薄膜, 放置在干燥器中10 h, 最后, 用掩膜版热蒸发厚度为80 nm的Au作为阳极, 电池面积为0.1 cm².

CsPbBr₃纳晶墨汁及薄膜的荧光照片采用325 nm紫外灯激发, 频域荧光光谱及时域寿命检测采用脉冲激光器(PicoQuant Fluo Time 300)激发, 波长选用375 nm. X射线衍射仪(D8-Advance, Bruker)和紫外可见分光光度计(JASCO V-570) 分别对样品进行晶相和吸收光谱分析. 采用场发射扫描电子显微镜(FE-SEM, SU-8020, Hitachi), 透射电子显微镜(JEM-2100 JEOLTEM)对薄膜表面形貌进行表征. 太阳能电池的J-V电学特性测试时, 光源采用太阳模拟器(Pharos Technology)稳态模拟器, 辐照强度为100 mW/cm², 数据源表(Keithley 2400)得到J-V特性曲线. 利用EQE测试系统(QTest Station 2000 ADI)通过与已知入射单色光子-电子转化效率(IPCE)的标准硅探测器进行比较, 得出器件的EQE值, 所用的氙灯光源功率为300 W.

低温溶液加工CsPbBr₃纳晶薄膜制备钙钛矿太阳电池

通讯作者: E-mail: zhangxisheng@ycu.edu.cn.;

Perovskite solar cells prepared by processing CsPbBr₃ nanocrystalline films in low temperature solution

Corresponding author: E-mail: zhangxisheng@ycu.edu.cn.;

计量

低温溶液加工CsPbBr₃纳晶薄膜制备钙钛矿太阳电池

通讯作者: E-mail: zhangxisheng@ycu.edu.cn.;

English Abstract