CN109913814A - 一种氧化铜/硒复合材料薄膜 - Google Patents

一种氧化铜/硒复合材料薄膜 Download PDF

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CN109913814A
CN109913814A CN201910244517.8A CN201910244517A CN109913814A CN 109913814 A CN109913814 A CN 109913814A CN 201910244517 A CN201910244517 A CN 201910244517A CN 109913814 A CN109913814 A CN 109913814A
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material film
copper oxide
cuo
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高斐
高蓉蓉
刘浩
刘生忠
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Shaanxi Normal University
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Abstract

本发明公开了一种氧化铜/硒复合材料薄膜，将低熔点(为221℃)、强光敏性的Se引入CuO，从而得到晶性良好，光、电及光电性能优异的薄膜材料。本发明将Se引入CuO，并通过低温退火使Se熔化，利用熔化的Se对CuO的浸润来消除或减少CuO膜中的空洞和悬挂键等缺陷，从而提高薄膜的晶性、光、电及光电性能，克服了CuO结晶性差、熔点高且高温分解的缺点，在太阳能电池领域具有良好的应用前景。

Description

一种氧化铜/硒复合材料薄膜
技术领域
本发明属于半导体材料技术领域，具体涉及一种新型的半导体氧化铜/硒(CuO/Se)复合材料薄膜。
背景技术
氧化铜(CuO)是一种重要的p型半导体材料，其光学禁带宽度约为1.4eV。在地球上拥有大量的铜资源，因而CuO价格低廉。CuO是一种具有广泛用途的材料，可用在超导、磁性、催化、气敏、储能和太阳能电池等方面。由于CuO在其熔点附近(1026℃)会分解，因此不能用真空热蒸发制备和用高温退火的方法提高其结晶性。目前CuO薄膜的制备主要用磁控溅射、电化学沉积、化学溶液旋涂等方法。用这些方法制备的CuO薄膜结晶性差，缺陷多，导致载流子复合严重，器件性能差。
发明内容
为了解决目前现有技术制备的CuO薄膜结晶性差的问题，本发明提出将低熔点(为221℃)、强光敏性的Se引入CuO，制备一种氧化铜/硒复合材料薄膜，从而提高薄膜的结晶性和光、电及光电性能。
解决上述问题所采用的氧化铜/硒复合材料薄膜为CuO和Se的复合物薄膜，且CuO和Se的复合物中存在中间相CuSe2和CuSe中任意一种或两种；该薄膜中Cu元素的原子百分含量为10％～60％，O元素的原子百分含量与Cu元素相同，Se元素的原子百分含量为10％～60％。
作为优选，上述氧化铜/硒复合材料薄膜中，Cu元素的原子百分含量为20％～40％，O元素的原子百分含量与Cu元素相同，Se元素的原子百分含量为20％～50％。
作为进一步优选，本发明氧化铜/硒复合材料薄膜中还掺杂有Si、Fe、Ge中任意一种，其中掺杂的Si或Fe或Ge元素的原子百分含量为3％～10％。
本发明氧化铜/硒复合材料薄膜采用磁控溅射法制备，具体制备方法为：采用CuO和Se共溅射的方式在衬底上沉积一层CuO/Se复合材料薄膜，然后在空气或氮气中300～400℃退火1～3分钟，得到氧化铜/硒复合材料薄膜；或先用磁控溅射法在玻璃衬底上沉积一层CuO膜，再在CuO膜上热蒸发沉积一层Se膜，接着在空气或氮气中300～400℃退火10～60分钟，得到氧化铜/硒复合材料薄膜。
本发明氧化铜/硒复合材料薄膜还可采用化学溶液法制备，具体制备方法为：将CuO粉末和Se粉末按摩尔比为1:2～3研磨混合均匀后加入二甲亚砜中，在50～70℃下搅拌6～10小时，所得反应液旋涂于衬底上，然后在150～200℃下退火5～10分钟，制备成氧化铜/硒复合材料薄膜。
上述的衬底为单晶硅片、普通玻璃、石英玻璃、氧化铟锡导电玻璃、掺氟氧化锡导电玻璃中的任意一种。
本发明的有益效果如下：
本发明将低熔点(为221℃)、强光敏性的Se引入CuO，并通过低温退火(Se的熔点附近)，使Se熔化，利用熔化的Se对CuO的浸润来消除或减少CuO膜中的空洞和悬挂键等缺陷，从而得到一种结晶性良好的CuO/Se复合材料薄膜。该复合材料薄膜结合了CuO对光强吸收、带隙合适，Se的熔点低、适合低温制备和处理且具有强的光敏性的优点，克服了CuO熔点高且高温分解，Se带隙过大(约1.8eV)的缺点，是一种结晶性良好，光、电及光电性能优异的薄膜材料，在光电子器件及太阳能电池领域具有良好的应用前景。
附图说明
图1是实施例1所制备的CuO/Se复合材料薄膜的结构表征X射线衍射图。
图2是实施例1所制备的CuO/Se复合材料薄膜的扫描电镜图。
图3是实施例1所制备的CuO/Se复合材料薄膜的吸收光谱图。
图4是实施例1所制备的CuO/Se复合材料薄膜的光电流随载流子扩散距离的衰减。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
将普通玻璃衬底依次在丙酮、乙醇、去离子水中超声清洗10分钟，用氮气吹干，然后将玻璃衬底置于磁控溅射沉积室内，用机械泵和分子泵将沉积室抽真空至2×10-4Pa，调节玻璃衬底和靶材的距离为6cm，然后将玻璃衬底加热至200℃，接着打开氩气通气阀，向沉积室通入氩气，并打开质量流量计，控制氩气流量为30sccm，调节沉积室压强至0.6Pa。采用CuO和Se共溅射的方式，溅射功率为60W，并同时旋转衬底，在玻璃衬底上沉积CuO/Se复合材料薄膜，溅射时间为30分钟，薄膜厚度约4μm。沉积结束后，自然冷却至室温，在空气中350℃退火1分钟，得到CuO/Se复合材料薄膜。
采用霍尔效应仪测量得出所制备的CuO/Se复合材料薄膜为p型导电性，载流子浓度为2.05×1019cm-3，迁移率为98cm2V-1s-1，电阻率为3.12×10-3Ωcm。图1的X射线衍射测量表明，CuO/Se复合材料薄膜中CuO处于非晶态，一部分Se处于纳晶态(用Debye-Scherrer公式估算平均晶粒尺寸为48nm)，并出现CuSe2纳晶(平均晶粒尺寸为44nm)，说明该薄膜是一种非晶/纳晶复合薄膜，而没有退火的膜中CuO和Se都没有结晶。由能量色散X射线谱(EDX)测量出CuO/Se复合材料薄膜中Cu、O和Se的原子百分含量分别约为30％、32％和38％。图2是CuO/Se复合材料薄膜的表面扫描电子显微镜(SEM)照片，可以看出，该薄膜表面由10～30nm的颗粒组成。用紫外-可见-近红外分光光度计测量CuO/Se复合材料膜的吸收光谱，结果见图3。由图3可以看出，所制备的CuO/Se复合材料薄膜在整个太阳光谱波段(250～2500nm)对光都有强的吸收(平均吸收率接近80％)。用光电流扫描法直接测量CuO/Se复合材料薄膜的光电流随载流子扩散距离的衰减，结果见图4。由指数衰减方程I＝I0exp(-L/LD)，得出CuO/Se复合材料薄膜的光生载流子扩散长度LD＝3.147mm。这比最好的p型单晶硅的载流子扩散长度(1.95mm)还长许多！远远大于目前研究热点的有机-无机杂化钙钛矿材料的载流子扩散长度(如单晶CH3NH3PbI3为0.32mm，多晶薄膜为0.014mm)。这些特性说明本发明CuO/Se复合材料薄膜是一种性能非常优异的光电材料。
实施例2
本实施例中，采用CuO和Se、Si共溅射的方式，按照实施例1的条件制备Cu元素和O元素的原子百分含量均为30％，Se元素的原子百分含量为36％，Si元素的原子百分含量为4％的CuO/Se复合材料薄膜。所制备的CuO/Se复合材料薄膜仍在整个太阳光谱波段(250～2500nm)对光都有强的吸收(平均吸收率接近80％)。用光电流扫描法直接测量CuO/Se复合材料薄膜的光生载流子扩散长度LD＝3.124mm。
实施例3
先用磁控溅射法，按照实施例1的条件在玻璃衬底上沉积一层CuO膜，再在CuO膜上用常规的热蒸发沉积一层Se膜，接着在空气中300℃退火30分钟，制备成CuO/Se复合材料薄膜。
实施例4
将0.4g(5mmol)CuO粉末和0.34g(10mmol)Se粉末研磨并混合均匀后，加入3mLDMSO中，在60℃下搅拌8小时，所得反应液以1000转/分的转速旋涂于玻璃衬底上，然后在150℃下退火10分钟，制备成CuO/Se复合材料薄膜。

Claims (7)

1.一种氧化铜/硒复合材料薄膜，其特征在于：所述氧化铜/硒复合材料薄膜为CuO和Se的复合物薄膜，且CuO和Se的复合物中存在中间相CuSe2和CuSe中任意一种或两种；该薄膜中Cu元素的原子百分含量为10％～60％，O元素的原子百分含量与Cu元素相同，Se元素的原子百分含量为10％～60％。
2.根据权利要求1所述的氧化铜/硒复合材料薄膜，其特征在于：所述氧化铜/硒复合材料薄膜中Cu元素的原子百分含量为20％～40％，O元素的原子百分含量与Cu元素相同，Se元素的原子百分含量为20％～50％。
3.根据权利要求1或2所述的氧化铜/硒复合材料薄膜，其特征在于：所述氧化铜/硒复合材料薄膜中还掺杂有Si、Fe、Ge中任意一种。
4.根据权利要求3所述的氧化铜/硒复合材料薄膜，其特征在于：所述氧化铜/硒复合材料薄膜中掺杂的Si或Fe或Ge元素的原子百分含量为3％～10％。
5.根据权利要求1所述的氧化铜/硒复合材料薄膜，其特征在于：所述氧化铜/硒复合材料薄膜采用磁控溅射法制备而成，具体制备方法为：采用CuO和Se共溅射的方式在衬底上沉积一层CuO/Se复合材料薄膜，然后在空气或氮气中300～400℃退火1～3分钟，得到氧化铜/硒复合材料薄膜；
或先用磁控溅射法在玻璃衬底上沉积一层CuO膜，再在CuO膜上热蒸发沉积一层Se膜，接着在空气或氮气中300～400℃退火10～60分钟，得到氧化铜/硒复合材料薄膜。
6.根据权利要求1所述的氧化铜/硒复合材料薄膜，其特征在于：所述氧化铜/硒复合材料薄膜采用化学溶液法制备而成，具体制备方法为：将CuO粉末和Se粉末按摩尔比为1:2～3研磨混合均匀后加入二甲亚砜中，在50～70℃下搅拌6～10小时，所得反应液旋涂于衬底上，然后在150～200℃下退火5～10分钟，制备成氧化铜/硒复合材料薄膜。
7.根据权利要求5或6所述的氧化铜/硒复合材料薄膜，其特征在于：所述的衬底为单晶硅片、普通玻璃、石英玻璃、氧化铟锡导电玻璃、掺氟氧化锡导电玻璃中的任意一种。
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