纳米ZnO基有机/无机复合光伏器件研究
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摘要
ZnO是一种宽禁带直接带隙的半导体材料,在紫外发光与激光、探测器和太阳能电池等很多方面都具有非常广泛的应用。并且与其它材料相比,ZnO具有多种一维纳米结构,这些纳米结构具有较大的比表面积,并且是单晶结构,从而成为制备新型纳米光电器件的构筑单元。本论文就是利用ZnO一维纳米结构的这些特点,设计并制备了有机/无机复合结构光伏器件。并通过在界面处引入CdS和PbS量子点,有效的提高了太阳能电池的效率。论文工作中取得的主要结果如下:
1.采用电化学沉积的方法生长了ZnO纳米棒阵列,并通过对籽晶层、反应时间和反应溶液的浓度等参数的调节,初步实现了ZnO纳米棒密度、尺寸和长径比的可控生长。
2.采用电化学沉积方法制备的ZnO纳米棒和聚乙烯咔唑(PVK)成功的制备了具有类p-n结结构的ZnO/PVK复合紫外探测器,并利用ITO,ZnO和PVK特定的吸收位置获得了具有高选择性的紫外响应。这种探测器的响应峰值位于365 nm,响应度可达110 mA/W,响应峰半高宽仅为26 nm。
3.在带有ZnO籽晶层的ITO玻璃上,用电化学沉积的方法生长ZnO纳米棒,与聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯撑乙烯撑](MEH-PPV)成功制备了类p-n结结构的有机/无机复合的太阳能电池器件。通过采用化学浴方法在有机无机界面处引入不同的CdS量子点,显著提高了太阳能电池器件的效率。其中六次生长的CdS量子点的电池效率可达到0.65%,是未经敏化电池效率的6.5倍。并发现随着CdS量的增加,电池的效率是先增加后减小,在利用生长六次的CdS量子点进行敏化的电池效率达到了最大值。
4.通过引入带隙更窄、吸收范围更宽的PbS量子点作为敏化层,利用ZnO纳米棒和MEH-PPV制备了有机/无机复合的太阳能电池器件。其中利用生长四次的PbS量子点进行敏化的电池效率可达到0.42%,是未经敏化电池效率的四倍多。并发现由于PbS量子点之间的导电性不好,很大程度限制了光生载流子的传输,器件的短路电流的较低,导致PbS量子点敏化的太阳能电池的转换效率并不高。
As one of the typical semiconductors with a wide and direct band gap, ZnO has a lot of applications such as ultraviolet lasers, ultraviolet photodetectors, and solar cells. ZnO nanostructures of many versatile appearances have many remarkable properties such as big specific surface area and monocrystalline, which are different with other materials. Therefore, ZnO nanostructures become to one of the units of preparing the new nanostructure optoelectronics. In this work, the hybrid photovoltaic devices were demonstrated based on these merits of ZnO nanostructures. The efficency of the soalr cells sensitized with the CdS and PbS quantum dots were increased greatly. The research is outlined as follows.
(1) The ZnO nanorods in this work were fabiricated by the electrodeposition method. The ZnO nanorods could be electrodeposited controlled by the seed layer, reaction time and the concentration of the aqueous solution.
(2) High spectrum selectivity hybrid ultraviolet photodetector was demonstrated by using electrodeposited ZnO nanorods and poly-N-vinylcarbazole as the electron acceptor and donor, respectively. The high spectrum selectivity hybrid ultraviolet photodetector was obtained based on the particular absoption of ITO glass, ZnO nanorods and poly-N-vinylcarbazole. The photoresponse of the photodetector showed a narrow band centered at 365 nm with a responsibilith of 110 mA/W and with a full width at half maximum of only 26 nm.
(3) Poly[2-methoxy-5-(2-ethylhexyloxy-pphenylenevinylene)]/ZnO nanorods hybrid solar cells were demonstrated sensitized by CdS quantum dots prepared by a chemical bath deposition method. A thin ZnO film was adopted to well control the length of the ZnO nanorods and act as a hole-blocking layer. An appropriate coating of the CdS quantum dots on the ZnO nanorods leads to a maximum power conversion efficiency of 0.65%, which was increased 6.5 times compared with the one without using quantum dots. The efficiency of the devices were increased with the quantum of CdS at first and after that decreased with the quantum of CdS. The efficiency reached the maximum value of 0.65% when the CdS quantum dots were coated by 6 cycles.
(4) Poly[2-methoxy-5-(2-ethylhexyloxy-pphenylenevinylene)] (MEH-PPV)/ZnO nanorods hybrid solar cells consisting of PbS quantum dots prepared by a chemical bath deposition method were fabricated. An optimum coating of the quantum dots on the ZnO nanorods could strongly improve the performance of the solar cells. And a maximum power conversion efficiency of 0.42% was achieved for the PbS Q quantum dots sensitive solar cell coated by 4 cycles, which was increased almost 5 times compared with the solar cell without using PbS quantum dots. For large clusters the band alignment at the ZnO/PbS interface appears to be unfavorable for carrier transfer due to that the PbS quantum dots are electrically isolated from each other, which result in the decrease of the JSC values and efficiency.
1.采用电化学沉积的方法生长了ZnO纳米棒阵列,并通过对籽晶层、反应时间和反应溶液的浓度等参数的调节,初步实现了ZnO纳米棒密度、尺寸和长径比的可控生长。
2.采用电化学沉积方法制备的ZnO纳米棒和聚乙烯咔唑(PVK)成功的制备了具有类p-n结结构的ZnO/PVK复合紫外探测器,并利用ITO,ZnO和PVK特定的吸收位置获得了具有高选择性的紫外响应。这种探测器的响应峰值位于365 nm,响应度可达110 mA/W,响应峰半高宽仅为26 nm。
3.在带有ZnO籽晶层的ITO玻璃上,用电化学沉积的方法生长ZnO纳米棒,与聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯撑乙烯撑](MEH-PPV)成功制备了类p-n结结构的有机/无机复合的太阳能电池器件。通过采用化学浴方法在有机无机界面处引入不同的CdS量子点,显著提高了太阳能电池器件的效率。其中六次生长的CdS量子点的电池效率可达到0.65%,是未经敏化电池效率的6.5倍。并发现随着CdS量的增加,电池的效率是先增加后减小,在利用生长六次的CdS量子点进行敏化的电池效率达到了最大值。
4.通过引入带隙更窄、吸收范围更宽的PbS量子点作为敏化层,利用ZnO纳米棒和MEH-PPV制备了有机/无机复合的太阳能电池器件。其中利用生长四次的PbS量子点进行敏化的电池效率可达到0.42%,是未经敏化电池效率的四倍多。并发现由于PbS量子点之间的导电性不好,很大程度限制了光生载流子的传输,器件的短路电流的较低,导致PbS量子点敏化的太阳能电池的转换效率并不高。
As one of the typical semiconductors with a wide and direct band gap, ZnO has a lot of applications such as ultraviolet lasers, ultraviolet photodetectors, and solar cells. ZnO nanostructures of many versatile appearances have many remarkable properties such as big specific surface area and monocrystalline, which are different with other materials. Therefore, ZnO nanostructures become to one of the units of preparing the new nanostructure optoelectronics. In this work, the hybrid photovoltaic devices were demonstrated based on these merits of ZnO nanostructures. The efficency of the soalr cells sensitized with the CdS and PbS quantum dots were increased greatly. The research is outlined as follows.
(1) The ZnO nanorods in this work were fabiricated by the electrodeposition method. The ZnO nanorods could be electrodeposited controlled by the seed layer, reaction time and the concentration of the aqueous solution.
(2) High spectrum selectivity hybrid ultraviolet photodetector was demonstrated by using electrodeposited ZnO nanorods and poly-N-vinylcarbazole as the electron acceptor and donor, respectively. The high spectrum selectivity hybrid ultraviolet photodetector was obtained based on the particular absoption of ITO glass, ZnO nanorods and poly-N-vinylcarbazole. The photoresponse of the photodetector showed a narrow band centered at 365 nm with a responsibilith of 110 mA/W and with a full width at half maximum of only 26 nm.
(3) Poly[2-methoxy-5-(2-ethylhexyloxy-pphenylenevinylene)]/ZnO nanorods hybrid solar cells were demonstrated sensitized by CdS quantum dots prepared by a chemical bath deposition method. A thin ZnO film was adopted to well control the length of the ZnO nanorods and act as a hole-blocking layer. An appropriate coating of the CdS quantum dots on the ZnO nanorods leads to a maximum power conversion efficiency of 0.65%, which was increased 6.5 times compared with the one without using quantum dots. The efficiency of the devices were increased with the quantum of CdS at first and after that decreased with the quantum of CdS. The efficiency reached the maximum value of 0.65% when the CdS quantum dots were coated by 6 cycles.
(4) Poly[2-methoxy-5-(2-ethylhexyloxy-pphenylenevinylene)] (MEH-PPV)/ZnO nanorods hybrid solar cells consisting of PbS quantum dots prepared by a chemical bath deposition method were fabricated. An optimum coating of the quantum dots on the ZnO nanorods could strongly improve the performance of the solar cells. And a maximum power conversion efficiency of 0.42% was achieved for the PbS Q quantum dots sensitive solar cell coated by 4 cycles, which was increased almost 5 times compared with the solar cell without using PbS quantum dots. For large clusters the band alignment at the ZnO/PbS interface appears to be unfavorable for carrier transfer due to that the PbS quantum dots are electrically isolated from each other, which result in the decrease of the JSC values and efficiency.
引文
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