CN108075001A - 一种化合物半导体-铁电耦合的太阳电池 - Google Patents
一种化合物半导体-铁电耦合的太阳电池 Download PDFInfo
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Abstract
一种化合物半导体‑铁电耦合的太阳电池,是以BaTiO3铁电纳米颗粒为纳米偶极子,CZTSe为吸收层。本发明的特点是:(1)提出将光伏介质CZTSe和铁电纳米极化颗粒BaTiO3耦合生长在一起形成化合物半导体‑铁电耦合的薄膜,利用CZTSe较高的光吸收系数和BaTiO3铁电纳米颗粒自发极化构建的内建电场分离光生电子和空穴。提高太阳电池的开路电压和效率。(2)通过简单的溶胶凝胶方法,制备出了立方相的BaTiO3。所制备的BaTiO3纳米颗粒的平均粒径为25nm。(3)通过溶液法制备了BaTiO3/CZTSe化合物半导体‑铁电耦合的太阳电池。
Description
技术领域
本发明属于太阳电池制造技术领域,特别涉及一种化合物半导体-铁电耦合的太阳电池。本发明可应用于太阳电池制造方面的技术领域,并可应用于半导体器件制造领域。
背景技术
目前的光伏电池基本都是通过P-N异质结、或染料敏化界面等方法分离光生载流子。根据细致平衡原理计算,这种机制的光伏电池的最高转换效率为32%,太阳光中的大部分能量均没有得到很好的利用。为了利用有限的资源获得更多的能源,一个有效的办法是突破Schockley-Queisser效率,即将太阳电池的转换效率提高,这样既能提高能量的利用率,又能降低材料的使用量。但是,目前的太阳能电池基本都是通过P-N结实现光生载流子的收集,因此转换效率很难突破30%。
2008年V.Karpov等人创造性的提出将光伏介质和铁电纳米极化颗粒耦合生长在一起形成纳米偶极子薄膜,并提出了纳米偶极子太阳电池的初始结构模型。这里所谓偶极子,即一对等值异号的电荷相聚一个小的距离。与传统的P-N结太阳电池相比,它的优点及发电机理如下:
(1)传统P-N结电池,是依靠在异质结界面附近的空间电荷区来分离载流子,即只有处于空间电荷区和扩散长度在耗尽区内的载流子能够被利用。而对于纳米偶极子太阳电池,该器件是由同向排列、在光伏介质中均匀分布的纳米小颗粒电偶极子来产生内建电场,因此电场分布在整个纳米偶极子存在的区域内,这不但能显著提高了载流子的收集,而且大大降低了复合几率。
(2)传统P-N结电池由于有严重的复合,因此电场一般为弱结场。而纳米偶极子电池极化场是P-N结电池的10倍,使得纳米偶极子电池具有更大的开路电压和短路电流。
(3)纳米偶极子薄膜中的极化特性是一种铁电性,具有自发极化的偶极子颗粒在外场干预下进行强极化的特征。因此,纳米偶极子电池同时具有铁电光伏电池的优势,即该光伏效应的光电压不受限于材料的禁带宽度(Eg),其产生的开路电压理论上可比Eg高2~4个数量级,达到103~105V/cm。
综上所述,通过溶液法,把CZTSe和BaTiO3纳米偶极子进行耦合,制备一种化合物半导体-铁电耦合的太阳电池,提高电池的开路电压,提高器件效率。
综上,我们提出制备化合物半导体-铁电耦合的太阳电池。
发明内容
本发明的目的是解决现有基于P-N结太阳电池光生电子与空穴复合严重,太阳电池开路电压低,太阳电池的转换效率低的问题,提供一种化合物半导体-铁电耦合的太阳电池。
本发明采用溶液法制备化合物半导体-铁电耦合的太阳电池。所提供的化合物半导体-铁电耦合的太阳电池具有以下几个方面的作用:(1)提出了化合物半导体-铁电耦合的太阳电池的初始结构模型。(2)对化合物半导体-铁电耦合的太阳电池的机理进行了分析和推理。(3)提出了化合物半导体-铁电耦合的太阳电池的制备方法。
化合物半导体材料具有光吸收高的优点,因此非常适合于与铁电材料耦合以薄膜的形式来制备纳米偶极子电池。铜基化合物是一类重要的半导体材料,目前在光伏方面有重要应用,他们对可见光的吸收率均在104cm-1。其中的如Cu(In,Ga)Se2和Cu2ZnSn(S,Se)4材料储量丰富、无毒,并且具有合适的带隙1.0-1.5eV,吸收系数高达104cm-1,在可见光范围内吸收率很容易达到80%,并且制备方法多种多样,实验操作简单易行,被选为合适的光吸收层。
大多数关于铁电光伏的研究主要集中在:LiNbO3(LNO),BaTiO3(BTO),Pb(Zr,Ti)O3(PZT)和BiFeO3(BFO)。使用半导体材料制造的光伏器件,太阳能转化依赖于有效的光吸收,电子-空穴对载流子或激子的电荷分离,以及快速传输和电荷传输抑制复合过程。铁电材料能够保持永久电极化,能对体相和界面区域中的电场分布进行控制。并且铁电材料具有极化诱导的内部电场,由于在铁电/电极界面处产生有效的内建场,可以帮助分离载流子。与传统的半导体光伏不同,铁电材料光伏效应的光电压不受限于材料的禁带宽度(Eg)的限制,其产生的开路电压理论上可比Eg高2~4个数量级,达到103~105V/cm,所以又被称为反常光生伏特。
本发明的具体技术方案是:
一种化合物半导体-铁电耦合的太阳电池,所述太阳电池由下至上依次包括基底、背电极、化合物半导体-铁电耦合吸收层、缓冲层、窗口层和前电极,所述化合物半导体-铁电耦合吸收层是以BaTiO3铁电纳米颗粒为纳米偶极子,以CZTSe为吸收层制备而成,从图4中可以看到,在可见光区域内,电池的吸收率达到80%以上。
所述化合物半导体-铁电耦合吸收层中形成纳米偶极子部分的材料为铁电纳米颗粒:BaTiO3(BTO)、LiNbO3(LNO)或Pb(Zr,Ti)O3(PZT)。
所述化合物半导体-铁电耦合吸收层中形成纳米偶极子的光吸收材料是:CZTSe、CZTSSe或者CIGS光伏材料。
以化合物光伏材料作为化合物半导体-铁电耦合的太阳电池的吸收层,铁电纳米颗粒作为化合物半导体-铁电耦合的太阳电池的纳米偶极子,其特点是将铁电纳米颗粒添加到化合物光伏材料前驱体溶液中,通过后硒化处理,制备化合物半导体-铁电耦合的太阳电池的吸收层。
所述化合物半导体-铁电耦合的太阳电池,吸收层可以是铜锌锡硫硒(CZTSSe)、铜铟镓硒(CIGS)薄膜,BaTiO3铁电纳米颗粒作为化合物半导体-铁电耦合的太阳电池的纳米偶极子,也可以是LiNbO3(LNO),BaTiO3(BTO),Pb(Zr,Ti)O3(PZT)铁电纳米颗粒。
本发明公开的化合物半导体-铁电耦合的太阳电池采用溶液法制备而成。具体步骤如下:
所述铁电纳米偶极子颗粒采用溶胶凝胶法制备的BaTiO3纳米颗粒。
所述CZTSe吸收层采用溶液法制备。
所述化合物半导体-铁电耦合的太阳电池吸收层的制备,通过将BaTiO3纳米颗粒添加到CZTSe前驱体溶液中,再Mo层上旋涂混合溶液制成薄膜,然后将制备的薄膜进行硒化或者硫化处理。薄膜厚度为1.0-2.0um。
所述缓冲层可采用化学水浴法、原子层沉积法和蒸发法制备CdS、ZnS、(Cd,Zn)S、Zn(O,S)、In2S3层,薄膜的厚度为30~100nm。
所述本征氧化锌(i-ZnO)层采用磁控溅射法制备,薄膜厚度为30~150nm。
所述掺杂氧化锌为磁控溅射法制备的掺铝氧化锌(AZO)、掺镓氧化锌(GZO)或掺镁氧化锌(MZO)薄膜,薄膜的厚度为300~1500nm。
所述前电极层为蒸发或溅射制备的铝(Al)或者镍(Ni)铝合金层,厚度为0.5~4μm。
本发明的优点和有益效果:
所述化合物半导体-铁电耦合的太阳电池,突破Schockley-Queisser效率,即将太阳电池的转换效率提高,这样既能提高能量的利用率,又能降低材料的使用量。而纳米偶极子电池极化场是P-N结电池的10倍,使得纳米偶极子电池具有更大的开路电压和短路电流。每加1V的偏压,电池的开路电压增加6mV,效果显著。
附图说明
图1为化合物半导体-铁电耦合的太阳电池结构示意图。
图2为化合物半导体-铁电耦合的太阳电池结构原理图。
图3为BaTiO3铁电纳米偶极子颗粒的X射线衍射图。
图4为化合物半导体-铁电耦合的太阳电池EQE曲线。
图5(a)为CZTSe化合物太阳电池在不同偏压下的J-V曲线;(b)为CZTSe-BaTiO3化合物半导体-铁电耦合的太阳电池在不同偏压下的J-V曲线。
具体实施方式
下面介绍化合物半导体-铁电耦合的太阳电池发明的实施例,但本发明绝非限于实施例。通过溶胶凝胶法制备BaTiO3纳米颗粒作为铁电纳米偶极子,将BaTiO3纳米颗粒添加到CZTSe前驱体溶液中,在Mo层上旋涂化合物半导体-铁电耦合的太阳电池的预制层,然后通过后硒化处理,成功制备了CZTSe-BaTiO3化合物半导体-铁电耦合的太阳电池吸收层,薄膜厚度为1.0-2.0um。在通过水浴法制备CdS,薄膜的厚度为30~100nm。采用磁控溅射法制备i-ZnO和Al-ZnO,通过电子束制备Ni-Al栅线,厚度为0.5~4μm。
实施例1
如图1与图2所示,一种化合物半导体-铁电耦合的太阳电池,所述太阳电池结构由下至上依次包括基底、背电极、化合物半导体-铁电耦合吸收层、缓冲层、窗口层和前电极,所述化合物半导体-铁电耦合吸收层是以BaTiO3铁电纳米颗粒为纳米偶极子,图3所示XRD即是BaTiO3峰,以CZTSe为吸收层制备而成,采用化合物半导体与铁电材料耦合形成纳米偶极子作为太阳能电池的吸收层,如图4所示,为CZTSe-BaTiO3化合物半导体-铁电耦合的太阳电池的EQE曲线。从图中可以看到,在可见光区域内,电池的吸收率达到80%以上。从图5中可以看出,CZTSe化合物太阳电池在不同偏压下的J-V曲线不会发生变化,而CZTSe-BaTiO3化合物半导体-铁电耦合的太阳电池随着所加偏压的增大,电池的开路电压也在相应的增大,每加1V的偏压,电池的开路电压增加6mV,从而提高效率。
下面以溶液法制备CZTSe薄膜,以BaTiO3铁电纳米颗粒作为纳米偶极子,此作为化合物半导体-铁电耦合的太阳电池具体实施来阐述本发明。通过对样品加电压进行极化处理,电池的开路电压得到了提高,并且开路电压不会随着极化处理的撤离而降低。每加1V的偏压,电池的开路电压增加6mV,效果显著。
参照图1和图2,电池制备步骤如下所述:
(1-1)将0.02mol的钛酸丁酯溶于10ml的无水乙醇,记做A溶液,将0.02mol的醋酸钡溶于20ml的乙酸,记做B溶液,将A、B两溶液进行混合超声,在40℃水浴锅中进行回流3小时,得到湿凝胶。在80℃条件下烘干,研磨,在800℃条件下煅烧3小时,得到BaTiO3纳米颗粒;
(1-2)在钠钙玻璃上利用磁控溅射方法制备Mo背电极,薄膜厚度为1μm;
(1-3)配制CZTSe吸收层的前驱体溶液;
(1-4)采用溶液法制备CZTSe吸收层,取2.5ml CZTSe吸收层前驱体溶液,添加0.001g BaTiO3,纳米颗粒超声溶解,然后旋涂在Mo衬底的钠钙玻璃上,制备化合物半导体-铁电耦合的太阳电池吸收层,后硒化处理,薄膜厚度约为1-2um。
(1-5)图3为BaTiO3纳米颗粒的X射线衍射图。通过测试,成功制备了BaTiO3纳米颗粒;
(1-6)缓冲层CdS利用化学水浴方法制备,厚度为50nm;
(1-7);本征氧化锌(i-ZnO)层采用磁控溅射法制备,薄膜厚度为50nm;
(1-8)窗口层掺铝氧化锌(AZO)采用直流磁控溅射方法制备,薄膜的厚度为500nm;
(1-9)前电极镍(Ni)铝合金层采用蒸发方法制备。
实施例2
化合物半导体-铁电耦合的太阳电池的具体结构同实施例1.
步骤(2-1)采用实施例一(1-1)~(1-3);
图2为BaTiO3纳米颗粒的X射线衍射图。
(2-2)取2.5ml CZTSe吸收层前驱体溶液,添加0.001g BaTiO3,超声溶解,然后旋涂在Mo衬底的钠钙玻璃上,制备化合物半导体-铁电耦合的太阳电池吸收层,后硫化处理,薄膜厚度约为1-2um;
以下各层的制备同实施例一。
Claims (6)
1.一种化合物半导体-铁电耦合的太阳电池,其特征在于,所述太阳电池由下至上依次包括基底、背电极、化合物半导体-铁电耦合吸收层、缓冲层、窗口层和前电极,所述化合物半导体-铁电耦合吸收层是以BaTiO3铁电纳米颗粒为纳米偶极子,以CZTSe为吸收层制备而成,采用化合物半导体与铁电材料耦合形成纳米偶极子作为太阳能电池的吸收层,从而提高开压和效率。
2.根据权利要求1所述的化合物半导体-铁电耦合的太阳电池,其特征在于,所述化合物半导体-铁电耦合吸收层中形成纳米偶极子部分的材料为铁电纳米颗粒:BaTiO3(BTO)、LiNbO3(LNO)或Pb(Zr,Ti)O3(PZT)。
3.根据权利要求1所述的化合物半导体-铁电耦合的太阳电池,其特征在于,所述化合物半导体-铁电耦合吸收层中形成纳米偶极子的光吸收材料是:CZTSe、CZTSSe或者CIGS光伏材料。
4.根据权利要求1所述的化合物半导体-铁电耦合的太阳电池,其特征在于铁电材料采用溶胶凝胶法制备BaTiO3纳米颗粒。
5.根据权利要求1所述的化合物半导体-铁电耦合的太阳电池,其特征在于所述化合物半导体-铁电耦合吸收层中的光吸收层CZTSe是采用溶胶凝胶法制备前驱体后硒化处理得到,吸收层厚度为1.0-2.0μm。
6.根据权利要求1所述的化合物半导体-铁电耦合的太阳电池,其特征在于,所述化合物半导体-铁电耦合的太阳电池的制备流程:在玻璃基底上溅射制备背电极Mo;将铁电纳米偶极子加入到化合物光伏材料前驱体溶液中;将铁电纳米偶极子和化合物光伏材料混合溶液超声溶解;将铁电纳米偶极子和化合物光伏材料混合溶液旋涂在Mo层上;将旋涂好的铁电纳米偶极子和化合物光伏材料的样品进行后硒化处理;在铁电纳米偶极子和化合物光伏材料层上通过化学水浴法、原子层沉积法或蒸发法制备CdS层缓冲层;溅射窗口层i-ZnO和Al-ZnO;蒸发前电极Ni-Al,得到化合物半导体-铁电耦合的太阳电池。
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