CN111293182A - 一种溶胶-凝胶法制备大晶粒czts吸收层的方法 - Google Patents
一种溶胶-凝胶法制备大晶粒czts吸收层的方法 Download PDFInfo
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Abstract
本发明公开了一种溶胶‑凝胶法制备大晶粒CZTS吸收层的方法,属于薄膜太阳电池领域。本发明通过旋涂5次制备第一前驱体薄膜,通过一次硫化,先得到较薄的第一吸收层,然后,在此基础上再旋涂5次制备第二前驱体薄膜,通过二次硫化,最终得到完整的大晶粒CZTS吸收层薄膜。结果表明,两次硫化所得薄膜结晶性好,表面致密连续,并且形成了从底部到顶部完整的大晶粒。
Description
技术领域
本发明涉及太阳电池领域,具体涉及一种溶胶-凝胶法制备大晶粒CZTS吸收层的方法。
背景技术
由于化合物半导体薄膜太阳电池具有生产成本低并且易于实现工业化生产等优点,所以具有广泛的应用前景。铜铟镓硒(CIGS)电池在薄膜太阳能电池中单结转换效率最高,达21.7%,且长期稳定性好、对环境污染小,但所含In、Ga元素稀缺,使其大规模产业化严重受限。将In、Ga和 Se替换为无毒无污染的 Zn、Sn和S,可得到晶体结构与物性类似于CIGS的半导体材料Cu2ZnSnS4(CZTS)。其中CZTS为P型直接带隙半导体材料,禁带宽度为1.45eV~1.50eV,光吸收系数超过10 4 cm -1,只需要1.5μm~2.5μm厚的材料,就可以吸收绝大多数可见光,并且相比于钙钛矿太阳电池,CZTS太阳电池的稳定性更好,采用的Cu、Zn、Sn、S元素矿藏丰富无毒,因此CZTS已经成为薄膜的太阳能电池吸收层最佳候选材料之一。
常见的制备CZTS薄膜的方法可大致分为真空法和非真空法两类。真空类制备方法包括溅射法、蒸发法等,非真空类方法包括溶胶-凝胶法、电沉积法、喷雾热解法等。其中溶胶-凝胶法不需要昂贵和复杂的真空设备和条件,而且生产成本低,实验操作简便,能够实现大面积生产,因此溶胶-凝胶法制备CZTS薄膜备受国内外科研人员关注。
目前CZTS类薄膜太阳电池的最高效率是基于无小颗粒层存在的大晶粒CZTS吸收层薄膜,溶胶-凝胶法制备的CZTS薄膜在传统的一步硫化工艺下往往呈现上下分层的现象,上层是大晶粒层,下层是尺寸非常小的纳米颗粒层的双层结构,即表面的大晶粒层和底部细小的纳米颗粒层,原因可能是硫蒸气不能完全渗透整个薄膜,反应不够完全所致,纳米颗粒层会增加薄膜的串联电阻,也会在晶界处增加电子与空穴的复合几率,降低光生载流子的寿命,进而最终影响薄膜电池的效率。
发明内容
鉴于现有制备方法存在的薄膜晶粒尺寸小、底部存在纳米颗粒层等缺陷,本发明的目的是提供一种溶胶-凝胶法制备大晶粒CZTS吸收层的方法,可以增大吸收层晶粒大小,解决薄膜底部存在碎小晶粒的问题。
实现本发明目的的技术方案是:一种溶胶-凝胶法制备大晶粒CZTS吸收层的方法,包括如下步骤:
(1)在洁净的钠钙玻璃衬底上采用直流法溅射双层结构的Mo背电极;
(2)配制前驱体溶液;
(3)以所述前驱体溶液采用旋涂法在Mo背电极上制备第一前驱体薄膜;
(4)用硫粉作为硫源,将步骤(3)所得样品在N2环境下进行硫化处理,得到第一吸收层薄膜;
(5)再次采用旋涂法在步骤(4)所得第一吸收层薄膜制备第二前驱体薄膜;
(6)用硫粉作为硫源,将步骤(5)所得样品在N2环境下进行退火处理,得到所述的大晶粒CZTS吸收层。
进一步的,步骤(1)中,双层结构的Mo背电极包括高阻层和低阻层Mo薄膜,通过如下步骤制备:在洁净的钠钙玻璃衬底上溅射高阻层Mo薄膜,溅射功率为200W,工作气压为1.2Pa,溅射时间为15min;接着溅射低阻层Mo薄膜,溅射功率为200W,工作气压为0.3Pa,溅射时间为100min。
更进一步的,双层结构的Mo背电极通过如下步骤制备:抽真空至5×10 -4 Pa,溅射时通入Ar作为工作气体,在洁净的钠钙玻璃衬底上溅射高阻层Mo薄膜,溅射功率为200W,工作气压为1.2Pa,溅射时间为15min;接着溅射低阻层Mo薄膜,溅射功率为200W,工作气压为0.3Pa,溅射时间为100min。
进一步的,步骤(2)中,以Cu(CO2CH3)2·H2O,C4H6O4Zn·2H2O,SnCl2·2H2O,CH4N2S作为溶质,以N,N-二甲基甲酰胺(DMF)作为溶剂,配制前驱体溶液,其中,Cu/(Zn+Sn)=0.7,Zn/Sn=1.2,S/金属元素 =2.0,比值为原子摩尔比;前驱体溶液中金属元素的浓度为1.2mol/L。
进一步的,步骤(2)中,前驱体溶液制备过程如下:先将Cu(CO2CH3)2·H2O、C4H6O4Zn·2H2O和SnCl2·2H2O放入容器中,再加入DMF作为溶剂,置于50℃水浴锅中搅拌15min,然后加入CH4N2S,在50℃水浴锅中继续搅拌50min,制得所述前驱体溶液。
进一步的,步骤(2)中,对所述前驱体溶液进行离心,离心机转速为8000rad/min,离心时间为5min。
进一步的,步骤(3)和步骤(5)中,旋涂次数为5次。
进一步的,步骤(3)和步骤(5)中,旋涂法的过程如下:涂覆前驱体溶液后,置于300℃下预加热5min,室温冷却2min,重复涂覆、预加热、室温冷却过程5次。
更进一步的,步骤(3)和步骤(5)中,旋涂法的过程如下:使用一次性针筒吸取前驱体溶液,滴在Mo背电极上,使其完全覆盖表面,启动匀胶机,转速为3000rad/min,时间为20s,涂覆前驱体溶液后,置于300℃下预加热5min,室温冷却2min,重复涂覆、预加热、室温冷却过程5次。
进一步的,步骤(4)和步骤(6)中,退火处理的过程如下:将样品置于石墨舟中,加入过量的硫粉,然后将石墨舟置于硫化炉中,通入高纯N2,设定硫化炉升温曲线为45分钟内从室温线性变化至650℃,并保温35~40分钟,然后自然冷却至室温。
更进一步的,步骤(4)和步骤(6)中,退火处理的过程如下:将样品置于石墨舟中,按照每片样品0.25g的比例加入硫粉,然后将石墨舟置于硫化炉中,通入高纯N2,设定硫化炉升温曲线为45分钟内从室温线性变化至650℃,并保温35~40分钟,然后自然冷却至室温,在加温前,保持N2流量为1250sccm通气10min,排净硫化炉管道内的空气,然后保持N2流量为30sccm,启动加温程序。
与现有技术相比,本发明具有以下优点:(1)本发明通过两次旋涂-硫化退火,将两层较薄的吸收层薄膜叠加生长在一起,使硫化退火时硫分压能够完全渗透整个薄膜,增大晶粒尺寸,减少底部碎小晶粒,使吸收层薄膜具有更好的结晶性。(2)本发明减少了吸收层表面的孔洞,使薄膜表面更加致密连续,从而降低载流子的界面复合,从而减小暗电流。
附图说明
附图不意在按比例绘制。在附图中,在各个图中示出的每个相同或近似相同的组成部分可以用相同的标号表示。为了清晰起见,在每个图中,并非每个组成部分均被标记。现在,将通过例子并参考附图来描述本发明的各个方面的实施例,其中:
图1为本发明实施例1硫化升温曲线图。
图2为旋涂5次硫化1次所得吸收层薄膜的表面形貌图(a)和截面形貌图(b)。
图3为本发明实施例1和2制备的吸收层薄膜表面形貌图。
图4为本发明实施例1和2制备的吸收层薄膜截面形貌图。
图5为本发明实施例1和2制备的吸收层薄膜X射线衍射谱。
图6为本发明实施例1和2制备的吸收层薄膜拉曼光谱。
具体实施方式
为了使本发明的制备顺序等内容更容易被清楚理解,下面根据具体实施例并结合附图,对本发明作进一步详细的说明。
溶胶-凝胶法制备大晶粒CZTS吸收层薄膜的制备工艺包含两个步骤:第一步在钠钙玻璃上溅射双层结构的Mo背电极。第二步是将前驱体溶液使用旋涂法涂覆在玻璃衬底上,然后进行硫化退火,并将旋涂-硫化退火过程重复两次。本文的主旨就是采用两次硫化退火处理,减少吸收层表面孔洞,增大晶粒尺寸,减少底部碎小晶粒,从而形成大晶粒结构的CZTS吸收层薄膜。
本发明所述的溶胶-凝胶法制备完整大晶粒CZTS吸收层薄膜所得样品由下到上包括依次连接的钠钙玻璃衬底、双层结构的Mo背电极和吸收层薄膜。所述双层结构的Mo背电极,厚度为1.5μm;经过5次涂覆、预加热、冷却后得到的前驱体层的厚度约为350~450nm;大晶粒CZTS吸收层薄膜通过两次旋涂-硫化退火处理得到,在第一次旋涂-硫化退火后的吸收层薄膜厚度约为400~600nm,经两次旋涂-硫化退火后的吸收层薄膜总厚度约为900~1200nm。
本发明的原理在于:所述的吸收层薄膜由前驱体溶液旋涂在双层结构的Mo背电极上再进行硫化退火获得,其中为了去除前驱体溶液中的易挥发的有机溶剂和杂质,旋涂之后要放在300℃的加热板上预加热5min。由于有机残留物的挥发会导致薄膜疏松多孔,两次旋涂除了增加薄膜厚度外,对改善薄膜致密程度也具有重要作用。CZTS薄膜硫化过程中的硫化硫分压较低时,CZTS薄膜表面会分解为Cu、Zn和Sn的硫化物,其分解过程由如下反应方程式表示:
同时,旋涂层数过厚会导致硫化退火时硫化硫分压不能完全渗透到薄膜底部,以至于薄膜底部不能完全形成晶粒结构或出现晶粒结构分解的现象,因此本发明通过减少单次硫化前的旋涂次数,使用两次旋涂-硫化退火的方法,使硫分压能够完全渗透整个前驱体薄膜,减少薄膜表面孔洞,促进薄膜晶粒生长,以形成大晶粒结构。
实施例1
(1)玻璃衬底清洗:
将钠钙玻璃衬底依次用去污粉、洗衣粉清洗,然后放入酒精、丙酮中各超声30分钟,超声结束后,依次使用Ⅰ号液(溶液体积比为氨水:过氧化氢:水=1:2:5)、Ⅱ号液(溶液体积比为盐酸:过氧化氢:水=1:2:8)各加热煮沸10分钟,最后待样品冷却后用去离子水冲洗后用N 2吹干;
(2)沉积Mo背电极:
将清洗好的样品放入磁控溅射腔室内,抽真空至5×10 -4 pa。再通入高纯氩气作为工作气体。调整基片台转速为8.0rpm。采用直流法溅射高、低阻层的双层Mo薄膜作为背电极,首先溅射高阻层Mo薄膜,溅射功率为200W,工作气压为1.2Pa,溅射时间为15min;接着溅射低阻层Mo薄膜,溅射功率为200W,工作气压为0.3Pa,溅射时间为100min。
(3)前驱体溶液的制备:
先将0.9583g Cu(CO2CH3)2·H2O,0.7339g C4H6O4Zn·2H2O,0.7446g SnCl2·2H2O放入30ml广口瓶中,再加入10mlDMF作为溶剂,并加入磁子,置于50℃水浴锅中磁力搅拌15min,然后加入1.9791gCH4N2S,在50℃水浴锅中继续磁力搅拌50min。使用移液枪将所得前驱体溶液分装于4ml的离心管中,然后设定离心机转速为8000rad/min,离心时间为5min,分装的目的在于便于离心,离心目的在于去除前驱体溶液中由于药品品质问题产生的细微沉淀,实验环境洁净度达到标准的话这一步可以省略。
(4)制备第一前驱体薄膜:
使用一次性针筒吸取前驱体溶液,滴在上述双层结构的Mo背电极上,使其完全覆盖表面,启动匀胶机,转速为3000rad/min,时间为20s,涂覆前驱体溶液完成后,将所述样品其放在300℃加热板上预加热5min后取下冷却2min。将涂覆、预加热、冷却过程重复5次(即旋涂次数为5次),得到第一前驱体薄膜,重复次数只会影响薄膜厚度,对薄膜性能影响不大。
(5)第一次硫化:
将样品置于20cm长石墨舟中,按照每片样品0.25g的比例加入硫粉(过量),然后将石墨舟置于硫化炉中,通入高纯N2,在加温前,保持N2流量为1250sccm通气10min,排净硫化炉管道内的空气,然后保持N2流量为30sccm,启动加温程序,硫化炉升温曲线为45分钟内从室温线性变化至650℃,并保温40分钟,然后自然冷却至室温得到较薄的第一吸收层薄膜,其厚度约为400~600nm。
(6)制备第二前驱体薄膜:
使用一次性针筒吸取前驱体溶液,滴在上述第一吸收层薄膜上,使其完全覆盖表面,启动匀胶机,转速为3000rad/min,时间为20s,涂覆前驱体溶液完成后,然后将所述样品其放在300℃加热板上预加热5min后取下冷却2min。将涂覆、预加热、冷却过程重复5次(即旋涂次数为5次),得到第二前驱体薄膜。
(7)第二次硫化:
将样品置于20cm长石墨舟中,按照每片样品0.25g的比例加入硫粉(过量),然后将石墨舟置于硫化炉中,通入高纯N2,在加温前,保持N2流量为1250sccm通气10min,排净硫化炉管道内的空气,然后保持N2流量为30sccm,启动加温程序,硫化炉升温曲线为45分钟内从室温线性变化至650℃,并保温40分钟,然后自然冷却至室温,最终得到经两次旋涂-硫化退火后的大晶粒CZTS吸收层薄膜,其总厚度约为900~1200nm,硫化升温曲线图如图1所示。
实施例2
观察适当改变硫化保温时间后是否符合预期。
实施例2与实施例1的区别在于,实施例1硫化保温时间为40min,实施例2中硫化保温时间为35min。时间过长或过短一般会使CZTS晶体生长不完整,我们经过大量实验,发现保温时间在35~40分钟范围内,都可以得到晶体质量好的CZTS吸收层薄膜。本实施例对比两次硫化方法在不同硫化保温时间时薄膜的质量。从图3、图4薄膜表面形貌和截面图可以看出CZTS晶体生长情况良好,两次旋涂、两次硫化后的CZTS薄膜的晶粒很大,说明两次旋涂、两次硫化可以促使晶粒生长,可消除底部碎晶粒,从而形成大晶粒结构。
综上所述,图2表明涂覆5次硫化1次所得吸收层薄膜虽然形成了晶粒结构,但晶粒尺寸较小,薄膜表面不够致密。
图3样品SEM表面图表明本发明所述方法有效的改善了薄膜表面致密程度,增大了晶粒尺寸,晶粒尺寸在1~3µm,这对载流子的传输非常有利。
图4样品SEM截面图表明经过第二次硫化处理后,吸收层不存在分层现象,第二次旋涂的前驱体薄膜经过第二次硫化与第一层吸收层完全生在在一起,形成一层总厚度约为900~1200nm的吸收层薄膜。
图5为实施例1-2所制备的吸收层薄膜的X射线衍射谱。两个图都与CZTS的标准衍射峰吻合,衍射峰的强度较高,表明样品结晶性较好。
图6为实施例1-2所制备的薄膜吸收层的拉曼谱。显示位于254cm-1,285cm-1、337cm-1和371cm-1波数处出现了特征散射峰,与铜锌锡硫拉曼峰基本吻合。
Claims (10)
1.一种溶胶-凝胶法制备大晶粒CZTS吸收层的方法,其特征在于,包括如下步骤:
(1)在洁净的钠钙玻璃衬底上制备双层结构的Mo背电极;
(2)配制前驱体溶液;
(3)以所述前驱体溶液采用旋涂法在Mo背电极上制备第一前驱体薄膜;
(4)用硫粉作为硫源,将步骤(3)所得样品在N2环境下进行硫化处理,得到第一吸收层薄膜;
(5)再次采用旋涂法在步骤(4)所得第一吸收层薄膜制备第二前驱体薄膜;
(6)用硫粉作为硫源,将步骤(5)所得样品在N2环境下进行退火处理,得到所述的大晶粒CZTS吸收层。
2.如权利要求1所述的方法,其特征在于,步骤(1)中,双层结构的Mo背电极包括高阻层和低阻层Mo薄膜,采用直流溅射法制备,其具体步骤如下:在洁净的钠钙玻璃衬底上溅射高阻层Mo薄膜,溅射功率为200W,工作气压为1.2Pa,溅射时间为15min;接着溅射低阻层Mo薄膜,溅射功率为200W,工作气压为0.3Pa,溅射时间为100min。
3.如权利要求1所述的方法,其特征在于,步骤(2)中,以Cu(CO2CH3)2·H2O,C4H6O4Zn·2H2O,SnCl2·2H2O,CH4N2S作为溶质,以N,N-二甲基甲酰胺作为溶剂,配制所述前驱体溶液,其中,Cu/(Zn+Sn)=0.7,Zn/Sn=1.2,S/金属元素 =2.0,比值为摩尔比,金属元素的总浓度为1.2mol/L。
4.如权利要求1或3所述的方法,其特征在于,步骤(2)中,前驱体溶液制备过程如下:先将Cu(CO2CH3)2·H2O、 C4H6O4Zn·2H2O和SnCl2·2H2O放入容器中,再加入N,N-二甲基甲酰胺作为溶剂,置于50℃水浴锅中搅拌15min,然后加入CH4N2S,在50℃水浴锅中继续搅拌50min,制得所述前驱体溶液。
5.如权利要求1所述的方法,其特征在于,步骤(2)中,对所述前驱体溶液进行离心,离心机转速为8000rad/min,离心时间为5min。
6.如权利要求1所述的方法,其特征在于,步骤(3)和步骤(5)中,旋涂次数为5次。
7.如权利要求1所述的方法,其特征在于,步骤(3)和步骤(5)中,旋涂法的过程如下:涂覆前驱体溶液后,置于300℃下预加热5min,室温冷却2min。
8.如权利要求1所述的方法,其特征在于,步骤(3)和步骤(5)中,旋涂法的过程如下:使用一次性针筒吸取前驱体溶液,滴在Mo背电极上,使其完全覆盖表面,启动匀胶机,转速为3000rad/min,时间为20s,涂覆前驱体溶液后,置于300℃下预加热5min,室温冷却2min。
9.如权利要求1所述的方法,其特征在于,步骤(4)和步骤(6)中,退火处理的过程如下:将样品置于石墨舟中,加入过量的硫粉,然后将石墨舟置于硫化炉中,通入高纯N2,设定硫化炉升温曲线为45分钟内从室温线性变化至650℃,并保温35~40分钟,然后自然冷却至室温。
10.如权利要求1所述的方法,其特征在于,步骤(4)和步骤(6)中,退火处理的过程如下:将样品置于石墨舟中,按照每片样品0.25g的比例加入硫粉,然后将石墨舟置于硫化炉中,通入高纯N2,设定硫化炉升温曲线为45分钟内从室温线性变化至650℃,并保温35~40分钟,然后自然冷却至室温,在加温前,保持N2流量为1250sccm通气10min,排净硫化炉管道内的空气,然后保持N2流量为30sccm,启动加温程序。
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