The effect of Pb doping on the characteristic properties of spin coated ZnO thin films: Wrinkle structures

Un-doped and lead (Pb) doped ZnO thin films were deposited by sol–gel spin coating technique. Structural, morphological and optical properties of the films were investigated by means of Pb doping, in the range of 1–4% (with 1 at% step). X-ray diffraction results indicated that all films have hexagonal wurtzite crystal structure. (002) Reflection peak has been seen as the most intense peak and the highest texture coefficient value. Grain size values of the films varied from 19.68 nm to 13.37 nm with the increasing Pb incorporation. The top-view and cross sectional scanning electron microscope images demonstrated that the films were made up of wrinkle network structures and the films' thicknesses changed in the range of 400–276 nm. The direct optical band gap was calculated in 3 different functions and a significant harmony was observed among them. Additionally, all results indicated that the direct optical band gap and the Urbach values of the films increase with the increasing Pb doping content. Besides, the effects of Pb content on the photoluminescence properties of ZnO films were evaluated and it was observed that the decrease in the photoluminescence intensity was based on the Pb content. Moreover, the correlation between the optical and structural properties suggested that the optical band gap of Pb doped ZnO films were influenced by the lattice parameters a and c.     

Europium incorporation dynamics and some physical investigations within ZnO sprayed thin films

Europium doped ZnO thin films were deposited on glass substrates using a simple mini spray technique at 460 °C. The structural properties of as-prepared thin films were characterized by X-ray diffraction (XRD). Both undoped and Eu-doped films show strong preferred c-axis orientation. The maximum value of the volume cells was obtained at 1% doping level. The texture coefficient (TC) of the films along (002) direction changes with the doping level due to Eu incorporation.The optical band gap calculated from transmittance and reflectance spectra show the effect of concentration on this energy. They equally outlined the direct gap absorption of these materials. Analysis of Urbach–Martienssen model parameters allows nano-scale explanations of the doping-related divergence of Urbach tailing evolution.     

Band gap widening and narrowing in moderately and heavily doped n-ZnO films

In semiconductors, a widening of the optical band gap occurs because the lower states in the conduction band are blocked. At the same time band gap narrowing also occurs due to many body interactions on doping. This paper reports the analysis of widening and narrowing of optical band gap in sol–gel derived ZnO films moderately doped with Yttrium and heavily doped sputtered ZnO films with aluminum and scandium. The band gap was evaluated using optical transmission data. Carrier concentration was known from the Hall measurements. At high concentrations the effective change in band gap is found to be the difference of the band gap widening and band gap narrowing. At low concentration of dopant the many body theories do not apply and the experiments also show that the band gap narrowing is practically negligible at these concentrations and the effective band gap widening is determined by the band gap widening alone. The chemical nature of the dopant played practically no role.     

Effect of Al dopant concentration on structural,optical and photoconducting properties in nanostructured zinc oxide thin films

Thin films of undoped and doped ZnO, with different Al concentrations (1–5 wt%) were deposited onto glass substrates, by the sol–gel spin coating method. Grazing incidence X-ray diffraction (GIXRD) studies confirmed the nature of films as poly-crystalline, with typical hexagonal wurtzite structure. The films showed variation in crystallite size and change in relative intensities, upon different Al doping concentrations. The surface morphology of the films examined using FE-SEM, showed the grain size becoming smaller upon Al doping. The influence of Al with different concentrations, onto ZnO on the optical absorption and transmittance was studied using UV–Vis–NIR spectrophotometer in the wavelength range 300–2500 nm. The UV absorption shifted towards shorter wavelength upon Al doping. The average transmittance in the visible region increased for Al doped films up to 1–2 wt% and decreased for other concentration. The dark and photo conductivity measurements of the films indicated increase in the current values upon doping up to 1–2 wt% of Al and decreased for further concentrations. The rise and decay time measured from the photoresponse study, indicate larger values of rise time for the doped films compared to undoped ZnO. However, the film with 1–2 wt% doping of Al showed better response within the doping concentration. The thermal activation energy obtained from temperature-dependant conductivity showed decrease in the value upon Al doping up to 2 wt% and increased beyond this concentration in the temperature range 300–400 K.     

Properties of antimony doped ZnO thin films deposited by spray pyrolysis technique

Antimony (Sb) doped zinc oxide (ZnO) thin films were deposited on the glass substrate at 450°C using spray pyrolysis technique. Effect of Sb doping on surface morphology structural, optical and electrical properties were studied. X-ray diffraction (XRD) analysis showed that both the undoped and doped ZnO thin films are polycrystalline in nature with (101) preferred orientation. SEM analysis showed a change in surface morphology of Sb doped ZnO thin films. Doping results in a marked increase in conductivity without affecting the transmittance of the films. ZnO films prepared with 3 at % Sb shows the lowest resistivity of 0.185 Ohm cm with a Hall mobility of 54.05 cm² V^–1 s^–1, and a hole concentration of 6.25 × 10¹⁷ cm^–3.     

透明导电ZnO：Sn薄膜光学和电学性能的研究进展

纯ZnO电阻率高,电学性能不稳定,通过掺杂其他元素提高其光电性能,制备出高质量的ZnO薄膜是实现其应用的关键。文章从制备方法、掺杂浓度和退火等方面综述了Sn掺杂ZnO(ZnO:Sn)薄膜光电性能的研究进展,提出了降低ZnO:Sn薄膜电阻率和提高透光率的有效途径。     

锰掺杂对钛酸锶铅铁电薄膜带-带跃迁和带尾吸收特性的影响

通过透射光谱研究了锰掺杂量对钛酸锶铅铁电薄膜光学特性尤其是带-带跃迁和带尾吸收特性的影响,并利用柯西色散关系获得了光学透明区的光学常数.研究表明:随着锰掺杂量的增加,钛酸锶铅铁电薄膜的禁带宽度减小而带尾能增加.禁带宽度随锰掺杂的收缩可以归因为锰3d轨道降低了导带底的能级及掺杂后晶格的减小.掺杂锰离子的随机占位和非等价掺杂后氧空位浓度的增加则是导致局域带尾态拓宽的主要原因.     

Synthesis,Optical and Photoluminescence Properties of Cu-Doped Zno Nano-Fibers Thin Films: Nonlinear Optics

Different concentrations of copper-doped zinc oxide thin films were coated on a glass substrate by sol–gel/spin-coating technique. The structural properties of pure and Cu-doped ZnO films were characterized by different techniques, i.e., atomic force microscopy (AFM), photoluminescence and UV–Vis-NIR spectroscopy. The AFM study revealed that pure and doped ZnO films are formed as nano-fibers with a granular structure. The photoluminescence spectra of these films showed a strong ultraviolet emission peak centered at 392 nm and a strong blue emission peak cantered at 450 nm. The optical band gap of the pure and copper-doped ZnO thin films calculated from optical transmission spectra (3.29–3.23 eV) were found to be increasing with increasing copper doping concentration. The refractive index dispersion curve of pure and Cu-doped ZnO film obeyed the single-oscillator model. The optical dispersion parameters such as E _o , E _d , and \(n_{{\infty }}^{2}\) were calculated. Further, the nonlinear refractive index and nonlinear optical susceptibility were also calculated and interpreted.     

溶胶-凝胶旋涂法制备In掺杂ZnO薄膜结构和光学性能的研究

采用溶胶-凝胶(sol-gel)旋涂法在常规玻璃衬底 上生长了In掺杂浓度分别为1at%、2at%、3at%、4at%、5at%的ZnO薄膜。借助X射线衍射仪(X RD)、扫描电子显微镜(SEM)、紫外- 可见分光光度计(UV-Vis)对样品的晶粒生长、结构以及光学性能进行表征。结果如下:所 制 备的薄膜均沿(002)方向择优生长,且随着In³⁺掺杂浓度增加 ,衍射峰的峰型及半高宽均呈 先降低后升高的趋势;In³⁺掺入后,ZnO薄膜晶粒由原来的六边形状发展成类似蠕虫 状,同 时粒径变小且大小不一;与本征样品相比,掺杂后的ZnO光透过率提高了10%,且吸收边向短 波长方向偏移,同时随着In³⁺的掺入,薄膜的光学带隙值从3.49 eV增加到3.80 eV。当In³⁺掺 杂浓度为4at%时,薄膜(002)峰的峰形最为尖锐、峰值最大,晶粒较为均匀、 晶格间距更小,光透过率最高,光学带隙值相对较大为3.77 eV。     

Al掺杂对ZnO薄膜形貌和光学性能的影响

采用溶胶-凝胶旋涂法在FTO玻璃衬底上制备得到了不同Al掺杂浓度的ZnO薄膜(AZO)。利用XRD、FESEM、UV-vis和PL等测试手段对样品结构、形貌和光学性能进行了表征。结果表明,合成的AZO薄膜均为六方纤锌矿结构且峰强随掺杂浓度的升高而减弱;同时,颗粒形貌由不规则向规则球形转变且尺寸逐渐减小;PL谱中的近紫外发射峰和晶格缺陷峰值随掺杂浓度的升高先增大后降低;由UV-vis吸收光谱可知,AZO薄膜在设定波长内的光吸收处于波动状态,且当Al掺杂浓度为3%时,光吸收强度最高,禁带宽度减小到3.12eV。     

Mg and Al co-doping of ZnO thin films: Effect on ultraviolet photoconductivity

Thin films of Zinc Oxide were deposited by the sol-gel technique on glass substrates. The films were doped with Al, Mg or co-doped with both by introduction of appropriate compounds in the solution before dip-coating and annealing in air at 500 °C. Energy Dispersive X-Ray Spectroscopy was employed to measure the dopant incorporation. X-ray diffraction studies indicate that Mg doping increases grain size, while Al doping reduces it. Photoluminescence (PL) measurements indicate that undoped and Al-doped films show, along with a broad near band-edge (NBE) peak, additional peaks at longer wavelengths related to various defect states. However Mg doped films show only a sharp NBE peak, which is blue shifted compared to undoped ZnO, and there are no prominent sub band gap luminescence peaks. This is also the case for Mg and Al co-doped ZnO samples, provided the Mg content is low. Photocurrent measurements were carried out using silver contacts using a De source under atmospheric conditions. Undoped and Mg doped ZnO films showed high resistances and low photocurrent levels. With low Al doping, both the dark current and the photocurrent increase significantly, but the films show very long photocurrent transients. With optimized concentration of Mg/Al co-doping in ZnO, the photocurrent increased by ~98 times compared to ZnO films doped only with Mg. Simultaneously, the photocurrent transients became ~44 times faster than ZnO films doped only with Al.     

Structural,optical and electrical properties of MgxZn1−xO ternary alloy films

The structural, optical and electrical properties of Mg_xZn_1−xO (x=0.05–0.3) ternary alloy thin films deposited by the sol–gel method on the glass substrate were investigated. The presence of Mg in deposited samples was confirmed through EDAX. XRD spectra revealed that the deposited Mg doped ZnO films were polycrystalline in nature. The optical band gap of the films was tailored between 3.2 and 3.45 eV by varying Mg mole concentration between 0.05 and 0.3. I–V characteristics showed decrease in current with increase in the Mg mole concentration. These results explore the applicability of MgZnO to form effective and efficient heterostructures with ZnO as an active layer for efficient carrier confinement in light emitting devices.     

Structural, Optical, and Electrical Properties of Nb-Doped ZnO Thin Films Prepared by Spray Pyrolysis Method

Niobium (Nb) doping (0 at.% to 3 at.%) in ZnO thin films prepared by the chemical spray pyrolysis method at a substrate temperature of 400°C enhances the optical and electrical properties but deteriorates the structural quality of the films. The films are polycrystalline with hexagonal structure having a preferential orientation along the (002) crystallographic direction. The film doped with 3 at.% Nb demonstrates a maximum average transmittance of ~83% in the visible region. A strong blue emission is recorded for both pure and doped films, and the intensity is substantially enhanced with Nb doping due to interface and valence-band transitions. Vacuum annealing at 400°C for 60 min improves the electrical characteristics of the films, and the highest mobility of 71 cm²/V s is achieved for the 1 at.% Nb-doped ZnO films.     

Luminescence Properties of Cobalt-Doped ZnO Films Prepared by Sol–Gel Method

Pure ZnO and Co-doped ZnO films have been deposited on coverslip substrates by sol–gel spin coating. The morphological, structural, and optical properties of the films were investigated. The microstructure of the ZnO films became increasingly fine and the crystalline size decreased with Co doping. Analysis of x-ray diffraction (XRD) and Raman spectra reveals that Co²⁺ ions are substituted for Zn²⁺ ions in the ZnO lattice without changing its wurtzite structure. Co doping induces a decrease of the band-gap energy and fluorescence quenching of the emission bands. The spectra related to transitions within the tetrahedral Co²⁺ ions in the ZnO host crystal were observed in absorption and luminescence spectra. Photoluminescence (PL) spectra under different excitation energies and PL excitation spectra for the visible emissions suggest that the orange–red emission and green emission could be related to interstitial zinc (Zn_i) shallow donors and oxygen vacancy (V _O) deep donors, respectively. The red emission of Co-doped ZnO film could be assigned to the radiative transitions within the tetrahedral Co²⁺ ions in the ZnO host crystal after band-to-band excitation. A consistent explanation for the pure and Co-doped ZnO films is that the red emission under the excitation energy below the band gap is probably associated with extended Zn_i states.     

Enhanced photoluminescence properties of Cu-doped ZnO thin films deposited by simultaneous RF and DC magnetron sputtering

Copper (Cu)-doped ZnO thin films were grown on unheated glass substrates at various doping concentrations of Cu (0, 5.1, 6.2 and 7.5 at%) by simultaneous RF and DC magnetron sputtering technique. The influence of Cu atomic concentration on structural, electrical and optical properties of ZnO films was discussed in detail. Elemental composition from EDAX analysis confirmed the presence of Cu as a doping material in ZnO host lattice. XRD patterns show that the films were polycrystalline in nature with (002) as a predominant reflection of ZnO exhibited hexagonal wurtzite structure toward c-axis. From AFM analysis, films displayed needle-like shaped grains throughout the substrate surface. The electrical resistivity was found to be increased with increase of Cu content from 0 to 7.5 at%. Films have shown an average optical transmittance about 80% in the visible region and decreased optical band gap values from 3.2 to 3.01 eV with increasing of Cu doping content from 0 to 7.5 at% respectively. Furthermore, remarkably enhanced photoluminescence (PL) properties have been observed with prominent violet emission band corresponding to 3.06 eV (405 nm) in the visible region through the increase of Cu doping content in ZnO host lattice.     

Investigation of characteristics of ZnO:Ga nanocrystalline thin films with varying dopant content

In this study, undoped and Ga doped ZnO thin films were synthesized by the sol–gel spin coating technique. The effect of Ga contribution on the structural, morphological and optical properties of the ZnO thin films was examined. XRD results showed that all films had a hexagonal wurtzite crystal structure with polycrystalline nature. The intensity of the (002) peak changed with the variable Ga content. The scanning electron microscopy (SEM) results revealed that the surface morphology of the ZnO thin films was affected by Ga content. Moreover, it consisted of nanorods as a result of the increased function of the Ga content. Additionally, the presence of Ga contributions was evaluated by energy dispersive x-ray (EDX) measurements. Although the transparency and the optical band gap of the ZnO thin films increased with Ga contribution, Urbach energy values decreased from 221 meV to 98 meV. In addition, these steepness parameters increased with the increased Ga content from 0% to 6%. The correlation between structural and optical properties was investigated and significant consistency was found.     

Sb掺杂ZnO电子结构和光学性质

为了研究ZnO掺Sb后电子结构和光学性质的变化,采用基于密度泛函理论对纯净ZnO和Sb掺杂ZnO两种结构进行第一性原理的计算。计算结果表明：随着Sb的掺入,体系的晶格常数变大,键长增加,体积变大,系统总能增大。能带中价带和导带数目明显变密,费米能级进入导带,体系逐渐呈金属性,带隙明显展宽。在光学性质方面,主吸收峰的左边出现了新的吸收峰,是由导带上的Zn-4s和Sb-5p轨道杂化电子跃迁所致;同时介电函数虚部波峰发生一定程度的升高,实部静态介电常数也明显增大。     

Optical and electrical properties of epitaxial (Mg,Cd)xZn1−xO, ZnO, and ZnO:(Ga,Al) thin films on c-plane sapphire grown by pulsed laser deposition

A consistent set of epitaxial, n-type conducting ZnO thin films, nominally undoped, doped with Ga or Al, or alloyed with Mg or Cd, was grown by pulsed laser deposition (PLD) on single-crystalline c-plane sapphire (0 0 0 1) substrates, and characterized by Hall measurement, and UV/VIS optical transmission spectroscopy.The optical band gap of undoped ZnO films at nearly 3.28 eV was shifted by alloying with Mg up to 4.5 eV and by alloying with Cd down to 3.18 eV, dependent on the alloy composition. In addition, highly doped ZnO:Al films show a blue-shifted optical absorption edge due to filling of electronic states in the conduction band.The Hall transport data of the PLD (Mg,Zn,Cd)O:(Ga,Al) thin films span a carrier concentration range of six orders of magnitude from 3 × 10¹⁴ to 3 × 10²⁰ cm⁻³, which corresponds to a resistivity from 5 × 10⁻⁴ to 3 × 10³ Ω cm. Structurally optimized, nominally undoped ZnO films grown with ZnO nucleation and top layer reached an electron mobility of 155 cm²/V s (300 K), which is among the largest values reported for heteroepitaxial ZnO thin films so far.Finally, we succeeded in combining the low resistivity of ZnO:Ga and the band gap shift of MgZnO in MgZnO:Ga thin films. This results demonstrate the unique tunability of the optical and electrical properties of the ZnO-based wide-band gap material for future electronic devices.     

Electrical and optical properties of zinc-oxide films deposited by the ion-beam sputtering of an oxide target

The influence of the parameters of the deposition process on the stoichiometric composition and electrical and optical properties of ZnO films deposited by the ion-beam sputtering of a ZnO target is studied. It is established that, upon sputtering of a ZnO target with stoichiometric composition, there is a deficit of oxygen in the films deposited. Even for the case of target sputtering in a pure O₂ atmosphere, the stoichiometry index of the films is no higher than 0.98. A decrease in the oxygen content in the films is accompanied by a sharp decrease in the resistivity to 35–40 Ω m, narrowing of the optical band gap, and a shift of the optical transmittance edge from 389 to 404 nm. All of the variations in the optical and electrical properties of the ZnO films can be attributed to variations in the concentration and mobility of free charge carriers in the films.     

Properties of cobalt-doped zinc oxide thin films grown by pulsed laser deposition on glass substrates

Undoped and cobalt-doped zinc oxide (CZO) polycrystalline piezoelectric thin films (Co: 3, 5 at.%) using a series of high quality ceramic targets have been deposited at 450 °C onto glass substrates using a pulsed laser deposition method. The used source was a KrF excimer laser (248 nm, 25 ns, 2 J∕cm²). X-ray diffraction patterns showed that the Co-doped ZnO films crystallize in a hexagonal wurtzite type structure with a strong (0 orientation, and the grain sizes calculated from these patterns decrease from 37 to 31 nm by increasing Co doping. The optical waveguiding properties of the films were characterized by using a prism-coupling method. The distinct M-lines of the guided transverse magnetic (TM) and transverse electric (TE) modes of the ZnO films waveguide have been observed. With the aim of study the optical properties of the ZnO films, an accurate refractive index and thickness measurement apparatus was set up, which is called M-lines device. An evaluation of experimental uncertainty and calculation of the precision of the refractive index and thickness were developed on ZnO films. The optical transmittance spectra showed a good transparency in the visible region. Calculated optical band gap varying from 3.23 to 3.37 eV when the content of Co doping increases from 0 to 5 at.%.