Structural and optical properties of Mg‐doped ZnO thin films prepared by a modified Pechini method

ZnO thin films with different Mg doping contents (0%, 3%, 5%, 8%, 10%, respectively) were prepared on quartz glass substrates by a modified Pechini method. XRD patterns reveal that all the thin films possess a polycrystalline hexagonal wurtzite structure. The peak position of (002) plane for Mg‐doped ZnO thin films shifts toward higher angle due to the Mg doping. The crystallite size calculated by Debey‐Scherrer formula is in the range of 32.95–48.92 nm. The SEM images show that Mg‐doped ZnO thin films are composed of dense nanoparticles, and the thickness of Mg‐doped ZnO thin films with Mg doped at 8% is around 140 nm. The transmittance spectra indicate that Mg doping can increase the optical bandgap of ZnO thin films. The band gap is tailored from 3.36 eV to 3.66 eV by changing Mg doping concentration between 3% and 10%. The photoluminescence spectra show that the ultraviolet emission peak of Mg‐doped ZnO thin films shifts toward lower wavelength as Mg doping content increases from 3% to 8%. The green emission peak of Mg‐doped ZnO thin films with Mg doping contents were 3%, 8%, and 10% is attributed to the oxygen vacancies or donor‐acceptor pair. These results prove that Mg‐doped ZnO thin films based on a modified Pechini method have the potential applications in the optoelectronic devices.     

PET上沉积Al掺杂ZnO薄膜的光电特性研究

采用脉冲激光沉积技术(PLD),室温下在柔性衬底PET上制备了高度c轴择优取向的Al掺杂ZnO薄膜.XRD分析表明,不同Al掺杂浓度的样品均呈现单一的ZnO相.荧光光谱和透射光谱分析显示,低温低氧压下制备的Al掺杂ZnO薄膜在紫光区域有很强的荧光发射,在可见光区域具有较高的透射率;并且可以通过Al掺杂浓度调节薄膜紫色发光强度和薄膜带隙.薄膜的电阻率随着Al掺杂浓度的增加先降低后增加,在掺杂浓度为3;原子分数时达到最小值.     

Structural,optical and electrical properties of Ga-doped and (Ga,Co)-codoped ZnO films

The Ga-doped and (Ga, Co)-codoped ZnO films were grown on quartz glass substrate by inductively coupled plasma enhanced physical vapor deposition. The effect of Co doping and oxygen pressure on the structural, optical, electrical and magnetic properties of the as-grown films was investigated. The structural characterization revealed that high-quality films were grown with wurtzite structure and c-axis preferred crystalline orientation. The surface morphology was affected by Co doping and oxygen pressure. Room-temperature ferromagnetism was observed in (Ga, Co)-codoped ZnO films. We found that the optical and electrical properties were degraded with Co doping. The Ga-doped ZnO films had an average transmittance of above 88% in the visible wavelength, while (Ga, Co)-codoped ZnO showed a lower average transmittance (∼65%) due to the d-d transitions of Co²⁺. The resistivity and Hall mobility of (Ga, Co)-doped ZnO samples were lower than those of Ga-doped ZnO films when grown at the same oxygen pressure.     

UV,violet and blue‐green luminescence from RF sputter deposited ZnO:Al thin films

The mechanism of ultraviolet (UV), violet and blue green emission from ZnO:Al (AZO) thin films deposited at different radio frequency (r.f.) powers on glass substrates was investigated. The structure and surface morphology of AZO films have also been observed. The optical transmittance spectra shows more than 80% transmittance in the visible region and the band gap is found to be directly allowed. From the photoluminescence measurement, intense UV and blue green luminescence is obtained for the samples deposited at higher sputtering powers. The mechanism of luminescence suggests that UV luminescence of AZO thin film is related to the transition from near band edge to the valence band and the concentration of antisite oxide (O_zn) increases with increase in r.f. power which in turn increases the intensity of green band emission while the violet PL is due to the defect level transition in the grain boundaries of AZO films. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoluminescence from screen printed ZnO based nanocrystalline films

Photoluminescence from ZnO based films deposited by screen printing is studied. PL spectra of undoped films show strong broad green emission around 500 nm and a weak (nearly one fourth of visible) UV emission around 398 nm. Further enhancement of 30% in the green emission is observed as 5 at.% Ca is doped in ZnO which for higher dopant concentration falls monotonously. The films are polycrystalline and the particle size lies between 33 to 47 nm as determined by Debye‐Scherrer method. Film with 5 at.% doping is under tensile strain and the others are under compressive strain. SEM shows microclusters, consisting of nanoparticles, scattered throughout the substrate which club together with increase in dopant amount. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Grain boundary defects induced room temperature ferromagnetism in V doped ZnO thin films

Vanadium (V) doped ZnO thin films (Zn_1‐xV_x O, where x = 0, 0.05, 0.10) have been grown on sapphire substrates by RF magnetron sputtering to realize room temperature ferromagnetism (RTFM). The grown films have been subjected to X‐ray diffraction (XRD), resonant Raman scattering, photoluminescence (PL) and vibrating sample magnetometer (VSM) measurements to investigate their structural, optical and magnetic properties, respectively. The full width at half maximum of XRD and Raman scattering peaks increases with V ion concentration indicates that the V ions have been substituted on Zn²⁺ ions in the ZnO matrix. The increase in oxygen vacancies with V concentration is evidenced by PL measurements. Rutherford backscattering spectrometry analysis confirms the presence of the V ions in the films. The room temperature VSM measurements reveal the signature of ferromagnetism in V doped ZnO thin films. It has been observed that the grain boundary defects, i.e., oxygen vacancies play a crucial role in inducing RTFM in V doped ZnO films. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thickness and substrate orientation dependence of ferromagnetism in Mn doped ZnO thin films

The effect of film thickness and substrate orientation on ferromagnetism in Mn doped ZnO thin films have been studied. The Mn doped ZnO films of different thickness (15, 35 and 105 nm) have been grown on both Si (100) and Si (111) substrates. The structural, electrical, optical, elemental and magnetic properties of the films have been investigated by X‐ray diffraction (XRD), Hall Effect measurements, photoluminescence (PL), energy dispersive spectroscopy (EDS) and vibrating sample magnetometer (VSM), respectively. It is found that all the properties are strongly influenced by the film thickness and substrate orientation. The XRD analysis confirmed that the formation of high quality monophasic hexagonal wurtzite structure for all the grown films. The room temperature VSM measurements showed that the films of lower thickness have better ferromagnetism than that of the thicker films grown on both the substrates. Among the lower thickness films, the film grown on Si (111) substrate has higher saturation magnetization (291×10^‐5 emu cm^‐3) due to high density of the defects. The observed ferromagnetism has been well justified by XRD, Hall measurements and PL. The presence of Mn atoms in the film has been confirmed by EDS. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

水热法制备Co掺杂CeO2纳米晶的微观形貌及磁学性能研究

以Ce(NO3)3·6H2O和Co(NO3)3·6H2O为原料,Na3PO4·12H2O为沉淀剂,用水热法制备了不同浓度Co掺杂的CeO2纳米晶.利用XRD、Raman、SEM、PPMS等测试手段研究纳米晶的晶体结构、微观形貌和磁学性能.XRD和Raman研究结果表明,不同浓度Co掺杂的CeO2纳米晶仍保持纯CeO2的立方莹石结构.没有出现Co以及Co氧化物的特征峰,说明Co掺杂替换了CeO2中的Ce晶格位.XRD的特征峰未出现明显的平移,Co掺杂导致CeO2的晶格畸变也不明显.SEM研究发现纳米晶的形状都是棱长约为600～800 nm的八面体,Co掺杂CeO2纳米晶的微观形貌与Co掺杂浓度存在明显关系,随着Co掺杂浓度的增加,八面体的棱从清晰变为模糊,各个面从光滑变为粗糙.PPMS测量表明所有样品都表现出室温铁磁性,随着Co掺杂浓度的增加,饱和磁化强度先增加后减小,5;Co掺杂CeO2纳米晶具有最大的饱和磁化强度.不同Co掺杂浓度导致纳米晶的磁性有了明显的变化,可见通过改变Co掺杂浓度可以调制纳米晶的室温铁磁性能.     

Growth,structure and optical characterization of Al‐doped ZnO nanoparticle thin films

Al‐doped ZnO nanoparticle thin films were prepared on glass substrate at the optimum temperature of (410±10) °C by spray pyrolysis technique using zinc nitrate as a precursor solution and aluminium chloride as a dopant. The dopant concentration (Al/Zn at%) was varied from 0 to 2 at%. Structural analysis of the films shows that all the films are of polycrystalline zinc oxide in nature, possessing hexagonal wurtzite structure. The films exhibit variation in peak intensities corresponding to (100), (002) and (101) reflection planes on Al‐doping. The crystallite size calculated by Scherrer formula has been found to be in the range of 35‐65 nm. The optical absorption study shows that the optical band gap in the Al‐doped films varies in the range of 3.11 – 3.22 eV. The width of localized states in the band gap estimated by the Urbach tail analysis has been found to be minimum in case of the 1 at% Al‐doped zinc oxide thin film. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of the effect of aluminum doped zinc oxide (ZnO:Al) thin films by spray pyrolysis

ABSTRACT

In this study, aluminum doped zinc oxide thin films were deposited on ordinary glass substrates at the temperature of 425°C by spray pyrolysis technique for various doping concentrations of aluminum ranging from 1 to 5 at.%. The effect of dopant concentration on structural, morphological and optical properties of ZnO:Al thin films was studied. Optical band gap of the films increased with doping percentage and started to decrease from 2 at.% of dopant. The average transmittance for 2at.% ZnO:Al film is significantly increased over 90% in the visible region at 450 nm which is crucial for optoelectronic applications.     

p-ZnO薄膜及其异质结的光电性质

采用射频磁控溅射法,在不同的Ar∶O2条件下,以高掺磷n型Si衬底为磷掺杂源制备了p型ZnO薄膜和p-ZnO/n-Si异质结.对ZnO∶P薄膜进行了光致发光谱(PL)、霍尔参数、Ⅰ-Ⅴ特性、扫描电镜(SEM)和X射线衍射谱(XRD)等测试.结果表明,获得的ZnO∶P薄膜沿(0002)晶面高取向生长,以3.33 eV近带边紫外发光为主,伴有2.69 eV附近的深能级绿色发光峰,空穴浓度为8.982 × 1017/cm3,空穴迁移率为9.595 cm2/V·s,p-ZnO/n-Si异质结I-V整流特性明显,表明ZnO∶P薄膜具有p型导电特性.     

ZnO薄膜结构缺陷与发光性能研究(二)

在ZnO发光材料中存在的各种结构缺陷是制约ZnO发光性能的一个关键因素。本文在查阅文献的基础上,总结了ZnO薄膜材料中可能存在的缺陷类型,并就位错及界面的性质及其对发光性能影响的研究现状做了重点评述。位错作为非辐射复合中心大大降低了半导体器件的发光效率及使用寿命。ZnO颗粒晶界附近的电子耗尽区使绿光发射减弱甚至消失。ZnO薄膜表面的V型缺陷作为光学通道,使近带边发射穿过ZnO层时不被空间激子层吸收,而异质结、超晶格、量子阱中的界面对ZnO的发光性能则具有更重要的影响。     

In掺杂量对ZnO薄膜微结构和光学性质的影响

采用溶胶-凝胶法分别制备未掺杂和In掺杂ZnO薄膜,用X射线衍射仪、扫描电镜和紫外可见分光光度计测试分析薄膜的微结构、表面形貌和光学性质.结果表明:In掺杂ZnO薄膜仍为六角纤锌矿结构,但In的掺入抑制ZnO薄膜的结晶,使得薄膜的结晶度降低.In掺杂ZnO薄膜表面呈网络状结构,随着In掺杂量的增加,表面起伏程度减小,空隙减少,表面平整,致密度提高.In掺杂ZnO薄膜的光学带宽Eg值均小于未掺杂ZnO薄膜,且随In掺杂量的增加先增大后减小,并用Burstein-Moss效应和缺陷浓度变化对光学带宽变化进行了解释.     

Dopant concentration dependence of structure,optical, and magnetic properties of ZnO:Fe thin films

The effects of Fe-dopant concentration on the structure, optical, and magnetic properties of ZnO thin films were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), optical transmittance, absorption, photoluminescence (PL), and magnetic measurements. XRD spectra indicated that the doping of Fe atoms could not only change the lattice constant of ZnO but also improve the crystalline quality of ZnO thin films. And the Zn (0 0 2) diffraction peak at round 36.34°(2θ) was detected with increasing Fe content for the substitution of the Zn in the ZnO film. The band gap edge shifted toward longer wavelength with increase in Fe doping. Moreover, near band edge emission gradually increased with increase in Fe content (up to about 0.82 wt%), and then abruptly decreased due to the concentration quenching effect. Magnetic measurements confirmed that the ferromagnetic behavior of Fe-doped ZnO was correlated with the dopant concentration.     

Cu掺杂ZnO薄膜的制备及其光谱特性

采用溶胶-凝胶法在铟锡氧化物(ITO)导电玻璃基底上制备了不同掺杂浓度的Cu∶ ZnO薄膜.采用X射线衍射仪和扫描电子显微镜分析了薄膜样品的晶相结构和形貌,用荧光光谱仪测量了薄膜样品的光致发光谱.结果表明:Cu∶ ZnO薄膜均为六角纤锌矿结构,呈c轴择优取向,且因压应力的存在使其晶格常数略小于未掺杂薄膜样品的晶格常数;低温和高温退火处理的薄膜样品的光致发光谱(PL)中分别观察到414 nm、438 nm的蓝光双发射峰和510 nm左右的绿光发射峰.蓝光发射峰与样品中的Vzn和Zni有关,而绿光发射峰与样品中的Vo -Zni有关.     

Growth of nitrogen-doped p-type ZnO films by spray pyrolysis and their electrical and optical properties

Nitrogen-doped ZnO films were deposited on silicon (1 0 0) substrate using zinc acetate and ammonium acetate aqueous solution as precursors by ultrasonic spray pyrolysis. Successful p-type doping can be realized at optimized substrate temperature. The p-type ZnO films show excellent electrical properties such as hole concentration of 10¹⁸ cm⁻³, hole mobility of 10² cm² V⁻¹ s⁻¹ and resistivity of 10⁻² Ω cm. In the photoluminescence measurement, a strong near-band-edge emission was observed, while the deep-level emission was almost undetectable in both undoped and N-doped ZnO films. The growth and doping mechanism of N-doped ZnO films were discussed.     

不同缓冲层对ZnO薄膜的性能影响

用射频反应磁控溅射法在玻璃基底上分别以SnO2、SiO2和Al2O3为缓冲层制备ZnO薄膜.利用X射线衍射仪(XRD)、扫描电镜(SEM)、紫外-可见分光光度计和荧光分光光度计对薄膜的结构和光学性能进行了表征.XRD和SEM的分析结果表明,在SiO2和Al2O3缓冲层上生长的ZnO薄膜具有较好的c轴择优取向,薄膜表面光滑平整,薄膜的结晶质量得到改善;透射光谱表明所有样品在可见光范围内的平均透过率超过70;;通过对薄膜光致发光谱的分析,认为422 nm左右的紫峰来自于电子从晶粒边界的界面缺陷能级到价带的辐射跃迁;PL谱中蓝光和绿光的发光机制与薄膜中的本征缺陷有关.     

Properties of InAs co‐doped ZnO thin films prepared by pulsed laser deposition

InAs co‐doped ZnO films were grown on sapphire substrates by pulsed laser deposition. The grown films have been characterized using X‐ray diffraction (XRD), Hall effect measurements, Atomic force microscope (AFM) and Field emission scanning electron microscope (FESEM) in order to investigate the structural, electrical, morphological and elemental properties of the films respectively. XRD analysis showed that all the films were highly orientated along the c‐axis. It was observed from Hall effect measurements that InAs co‐doped ZnO films were of n‐type conductivity. In addition, the presence of In and As has been confirmed by Energy dispersive X‐ray analysis. AFM images revealed that the surface roughness of the films was decreased upon the co‐doping. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

ZnO薄膜结构缺陷与发光性能研究(一)

在ZnO发光材料中存在的各种结构缺陷是制约ZnO发光性能的一个关键因素。本文总结了ZnO薄膜材料中可能存在的缺陷类型,并就点缺陷的性质及其对发光性能影响的研究现状做了重点评述。对ZnO薄膜发光光谱常见的三个发光带,即紫外、绿光和黄光而言,紫外发光普遍被认为是带-带直接辐射复合发光或激子发光;而对可见光,尤其是绿光的发光机理却有着不同的说法,人们早期认为是铜杂质,近年来普遍认为是氧空位、锌空位等点缺陷所致,确切机理仍有争论。此外,点缺陷作为非辐射中心对ZnO薄膜的发光寿命有一定的影响。     

Properties of Co‐doped ZnO films prepared by electrochemical deposition

We prepared Co‐doped ZnO films by the electrochemical deposition. X‐ray diffraction (XRD), high resolution transmission microscopy (HRTEM), x‐ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), x‐ray absorption near‐edge structure (XANES), vibrating sample magnetometer (VSM), optical absorption, and photoluminescence (PL) measurements were carried out on the samples. The results showed Co atoms substituted Zn atoms in the ZnO lattice without the formation of the impurity phase. VSM measurements showed the ferromagnetic properties for the Co‐doped ZnO samples. When the Co doping concentration increased, the band gaps were widened and the PL peak positions shifted towards the short wavelength direction. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)