溶胶—凝胶法制备Al掺杂ZnO纳米颗粒膜及其性能研究
摘要
ZnO是一种新型的宽禁带半导体材料,室温时禁带宽度为3.4eV,具有六角纤锌矿结构。ZnO薄膜由于具有优异的压电、光电、气敏、压敏等特性,近年来受到广泛关注。Al~(3+)掺杂的ZnO(简称AZO)薄膜因其具有优良的光电性能已成为研究热点之一。此外,ZnO是对人体完全无毒的绿色材料,其在生物方面的应用也极具潜力。随着纳米技术和薄膜技术的飞速发展,研究发现独特的极性晶体结构使ZnO具有形态各异的纳米结构,并随之产生许多奇特的光学特性和量子效应,极大的提高了器件的性能。因此,ZnO低维材料的应用研究已经成为当前的热点,具有重要的实际意义。
本文采用溶胶-凝胶法,选择二水合乙酸锌(Zn(CH_3COO)_2·2H_2O)作为前驱体,无水乙醇为溶剂,乙醇胺(MEA)作为络合剂(ZnAc∶MEA=1∶1.5),硝酸铝(Al(NO_3)_3·9H_2O)作为Al掺杂来源,配制出锌离子浓度为0.8mol/L并具有不同Al掺杂浓度(0～10%)的透明均质溶胶。分别在玻璃和硅片衬底上成功制备出ZnO薄膜,平均晶粒尺寸在纳米级别。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、电阻率测量、紫外-可见光透射光谱的表征和分析,研究了掺杂对ZnO薄膜结晶状态、电阻率、能带结构的影响。
结果表明,使用溶胶-凝胶法在非晶玻璃和Si(100)衬底上制备了c轴择优取向生长的AZO薄膜,薄膜为众多纳米颗粒构成的纳米颗粒薄膜。不同浓度的Al掺杂(1-10%)均能提高其导电性能,Al掺杂浓度为1-2%时ZnO薄膜Al掺杂水平相对较高,电阻率显著降低,在掺杂浓度为2%时具有最小值0.671Ω·cm。SEM显示,Al含量的增加使薄膜的平均晶粒尺寸明显减小,掺杂浓度较高(7-10%)时,Al掺杂会影响ZnO薄膜的结晶状态。分析认为,未形成掺杂的Al原子以非晶Al_2O_3的形式在ZnO晶界上形成了对晶界运动的钉扎,导致晶粒尺寸的减小;杂质含量增加与晶粒细化的竞争使Al在ZnO薄膜中的掺杂水平存在极限。Al掺杂会对ZnO的能带结构产生影响,使其在紫外光区的透射率有所增加。
ZnO is a novel kind of semiconductor material,which has hexagonal wurtzite cystal structure,with a wide band-gap of 3.4eV at room temperature.The Al~(3+)-doped ZnO(AZO) thin films have become one of the focuses research because of its excellent optical and electrical properties.ZnO is a green material that is absolutely nontoxic for human being and it is favorable for the potential application in biomaterials.With the fast development of nanotechnology and thin films technology,it is found that due to the unique polar crystal structure,ZnO has rich nanostructures,which bring many peculiar optical properties and quantum effect.This can extremely improve the devices performance.Thus,application researches on low dimensional ZnO materials have become hot topics and have significant values.
In this paper,ZnO thin films were prepared by sol-gel method. Zn(CH_3COO)_2·2H_2O was employed as the precursor,anhydrous alcohol was the solvent,monoethanolamine was the complexant(ZnAc:MEA=1:1.5) and Al(NO_3)_3·9H_2O was used as the source of the Al-dopant in the experiment to yield the transparent and homogeneous solution with the density of the Zn ion of 0.8 mol/L and different Al-doping concentration from 0-10%.The nanocrystalline ZnO thin films have been successfully prepared with the average grain size in nanoscale,on the substrate of glass and n-type Si(100) wafer respectively.The effect of the doping proportion on the crystallization,electric resistivity and energy band structure of the ZnO thin film were characterized by X-ray diffraction(XRD),scanning electron mocroscope(sem),the electric resistivity measurement and the ultraviolet-visible transmission spectra(UV-Vis).
The results show that Preferential c-axis oriented AZO thin films were fabricated on the amorphous glass and n-type Si(100) substrates by sol-gel method.The films are the nanocrystalline thin films,which are composed by many nanograins.The conductivity of the films can be improved with different dopant concentration(1-10%). the doping proportion in the ZnO films is relatively high while the Al-doping concentration is 1-2%and the crystallization of the Al-doped ZnO thin films would be affected when the doping concentration lifted(7%-10%).The Al-doping can dramatically decrease the electric resistivity and the minimum value of 0.671Ω·cm was detected with the doping concentration of 2%.EDX mapping shows that the Al component undoped into ZnO lattice is rich on the grain boundary.It is presented that the Al atoms may form a state of amorphous Al_2O_3 and pin the movement of ZnO grain boundary,which leads to the decrease of grain size.The competition between the dopant contents increase and the grain refining makes the Al-doping in ZnO thin film has a maximum.Moreover,the Al-doping can also influence the energy band structure of the ZnO thin film,which increases the transmittivity of the film in the ultraviolet region.
本文采用溶胶-凝胶法,选择二水合乙酸锌(Zn(CH_3COO)_2·2H_2O)作为前驱体,无水乙醇为溶剂,乙醇胺(MEA)作为络合剂(ZnAc∶MEA=1∶1.5),硝酸铝(Al(NO_3)_3·9H_2O)作为Al掺杂来源,配制出锌离子浓度为0.8mol/L并具有不同Al掺杂浓度(0～10%)的透明均质溶胶。分别在玻璃和硅片衬底上成功制备出ZnO薄膜,平均晶粒尺寸在纳米级别。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、电阻率测量、紫外-可见光透射光谱的表征和分析,研究了掺杂对ZnO薄膜结晶状态、电阻率、能带结构的影响。
结果表明,使用溶胶-凝胶法在非晶玻璃和Si(100)衬底上制备了c轴择优取向生长的AZO薄膜,薄膜为众多纳米颗粒构成的纳米颗粒薄膜。不同浓度的Al掺杂(1-10%)均能提高其导电性能,Al掺杂浓度为1-2%时ZnO薄膜Al掺杂水平相对较高,电阻率显著降低,在掺杂浓度为2%时具有最小值0.671Ω·cm。SEM显示,Al含量的增加使薄膜的平均晶粒尺寸明显减小,掺杂浓度较高(7-10%)时,Al掺杂会影响ZnO薄膜的结晶状态。分析认为,未形成掺杂的Al原子以非晶Al_2O_3的形式在ZnO晶界上形成了对晶界运动的钉扎,导致晶粒尺寸的减小;杂质含量增加与晶粒细化的竞争使Al在ZnO薄膜中的掺杂水平存在极限。Al掺杂会对ZnO的能带结构产生影响,使其在紫外光区的透射率有所增加。
ZnO is a novel kind of semiconductor material,which has hexagonal wurtzite cystal structure,with a wide band-gap of 3.4eV at room temperature.The Al~(3+)-doped ZnO(AZO) thin films have become one of the focuses research because of its excellent optical and electrical properties.ZnO is a green material that is absolutely nontoxic for human being and it is favorable for the potential application in biomaterials.With the fast development of nanotechnology and thin films technology,it is found that due to the unique polar crystal structure,ZnO has rich nanostructures,which bring many peculiar optical properties and quantum effect.This can extremely improve the devices performance.Thus,application researches on low dimensional ZnO materials have become hot topics and have significant values.
In this paper,ZnO thin films were prepared by sol-gel method. Zn(CH_3COO)_2·2H_2O was employed as the precursor,anhydrous alcohol was the solvent,monoethanolamine was the complexant(ZnAc:MEA=1:1.5) and Al(NO_3)_3·9H_2O was used as the source of the Al-dopant in the experiment to yield the transparent and homogeneous solution with the density of the Zn ion of 0.8 mol/L and different Al-doping concentration from 0-10%.The nanocrystalline ZnO thin films have been successfully prepared with the average grain size in nanoscale,on the substrate of glass and n-type Si(100) wafer respectively.The effect of the doping proportion on the crystallization,electric resistivity and energy band structure of the ZnO thin film were characterized by X-ray diffraction(XRD),scanning electron mocroscope(sem),the electric resistivity measurement and the ultraviolet-visible transmission spectra(UV-Vis).
The results show that Preferential c-axis oriented AZO thin films were fabricated on the amorphous glass and n-type Si(100) substrates by sol-gel method.The films are the nanocrystalline thin films,which are composed by many nanograins.The conductivity of the films can be improved with different dopant concentration(1-10%). the doping proportion in the ZnO films is relatively high while the Al-doping concentration is 1-2%and the crystallization of the Al-doped ZnO thin films would be affected when the doping concentration lifted(7%-10%).The Al-doping can dramatically decrease the electric resistivity and the minimum value of 0.671Ω·cm was detected with the doping concentration of 2%.EDX mapping shows that the Al component undoped into ZnO lattice is rich on the grain boundary.It is presented that the Al atoms may form a state of amorphous Al_2O_3 and pin the movement of ZnO grain boundary,which leads to the decrease of grain size.The competition between the dopant contents increase and the grain refining makes the Al-doping in ZnO thin film has a maximum.Moreover,the Al-doping can also influence the energy band structure of the ZnO thin film,which increases the transmittivity of the film in the ultraviolet region.
引文
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