溶胶凝胶法制备钼掺杂氧化锌薄膜及性质研究

利用溶胶凝胶法在Al₂O ₃衬底上制备出了c轴择优取向的钼掺杂氧化锌（MZO）透明导电薄膜,研究了钼的掺杂量(0~1 at%)对钼掺杂氧化锌薄膜光电性能的影响。研究结果表明：所制备的薄膜为六方纤锌矿型结构且表面平整、致密,通过高温真空退火,MZO薄膜的电阻率明显降低,且随着钼含量的增加,MZO薄膜的电阻率呈现出先减小后增大的趋势,当钼含量为0.4at.%时,获得最小电阻率为0.13 Ωcm。薄膜在近红外区域(800~2000 nm)的平均透过率大于85%,这可以有效地拓宽光电器件的光谱范围。     

Investigation of aluminum and gallium co-doped ZnO powders and their effects on the properties of targets

Aluminum and gallium co-doped ZnO (AGZ) powders were synthesized by the chemical co-precipitation method with the same Al doping concentration (3 at%) and different Ga doping concentrations (0–0.5 at%). The microstructure, lattice distortion and surface morphology of AGZ powders were investigated because the properties of targets were related to corresponding powders. Both AZO and AGZ targets were prepared by molding and atmospheric pressure sintering. The microstructure, morphologies, electrical properties and densification of sintered targets were also studied. The measured results showed that the grain sizes of AGZ powders are smaller than AZO powder, the former has a larger specific area, and the distribution of AGZ particles are more homogeneous, which are good for preparation of a high-density target. Besides, the extent of ZnO lattice distortion exhibits a downward trend with the increase of the Ga doping concentration. The AGZ target with appropriate concentration of Ga (0.3 at%) has the lowest resistivity of 2.518×10⁻³ Ω cm and the highest relative density of 99.2%. In general, the moderate Al–Ga co-doping proportion leads to finer grain size, lower resistivity, higher Hall mobility and higher sintered density.     

Studies on morphology,electrical and optical characteristics of Al-doped ZnO thin films grown by atomic layer deposition

Al doped ZnO (AZO) films deposited on glass substrates through the atomic layer deposition (ALD)technique are investigated with various temperatures from 100 to 250 ℃ and different Zn ∶ Al cycle ratios from 20 ∶ 0 to 20 ∶ 3.Surface morphology,structure,optical and electrical properties of obtained AZO films are studied in detail.The Al composition of the AZO films is varied by controlling the ratio of Zn ∶ Al.We achieve an excellent AZO thin film with a resistivity of 2.14 × 10-3 Ω·cm and high optical transmittance deposited at 150 ℃ with 20 ∶ 2 Zn ∶ Al cycle ratio.This kind of AZO thin films exhibit great potential for optoelectronics device application.     

改善玻璃衬底上ZnO薄膜特性的方法

利用磁控溅射法在玻璃衬底上淀积铝掺杂氧化锌(AZO)薄膜作为缓冲层,在其上制备了ZnO薄膜。重点研究了AZO薄膜作为缓冲层对玻璃衬底上ZnO薄膜特性的影响。扫描电子显微镜(SEM)图像和X射线衍射(XRD)图谱分析结果表明,玻璃衬底上加入厚度为1μm的AZO缓冲层后,提高了衬底材料和ZnO薄膜之间的晶格匹配程度,有助于增大ZnO薄膜晶粒尺寸,提高其(002)取向择优生长特性、薄膜结晶特性及晶格结构完整性。室温下的透射光谱结果表明玻璃/AZO和玻璃衬底上ZnO薄膜的透光特性没有显著不同。光致发光(PL)谱研究结果表明AZO缓冲层可以有效阻止衬底表面硅原子从ZnO薄膜中"俘获"氧原子,减少ZnO薄膜中的缺陷,改善ZnO薄膜的结晶质量。     

Al_2O_3过渡层厚度对AZO薄膜性能的影响研究

采用磁控溅射法,在预先沉积了Al2O3过渡层的玻璃衬底上制备了性能优良的AZO薄膜。借助XRD、AFM、四探针仪和分光光度计对AZO薄膜的结构、表面形貌以及电学和光学性质进行了表征,并研究了Al2O3过渡层厚度对AZO薄膜性能的影响。结果表明:Al2O3过渡层的添加对AZO薄膜的表面形貌有一定影响;AZO薄膜的结晶质量随着过渡层厚度的增加先上升后下降;AZO薄膜的电阻率因过渡层的添加而明显降低,特别是在AZO薄膜较薄时;在添加了1～3 nm厚的过渡层后,160 nm厚的AZO薄膜的电阻率下降了44%左右;AZO薄膜的可见光透射率和光学带隙基本不受过渡层影响。     

Effects of oxygen concentration on the properties of Al-doped ZnO transparent conductive films deposited by pulsed DC magnetron sputtering

The effect of oxygen concentration on the properties of Al-doped ZnO (AZO) transparent conductive films has been investigated on the films deposited by pulsed DC magnetron sputtering using a cylindrical ZnO target containing 2 wt% Al. AZO films were deposited at 230 °C to the thickness of about 1000 nm and the oxygen concentration was controlled by varying the O₂/Ar supply ratio from 0 to 0.167. With the increasing O₂/Ar ratio, crystallinity of the AZO films deteriorated while the film surface became smooth. Accompanying this, electrical properties also deteriorated significantly. When the O₂/Ar ratios were 0 and 0.033, the AZO films showed metallic conduction behavior with the electrical resistivity in the mid 10^?4 Ω cm range. However, when the ratios were 0.100 and 0.167, the films showed poor electrical conduction behavior similar to semiconductors as deduced from the transmittance behavior. Spectroscopic analysis showed that such deteriorating properties are due to the formation of condensed oxide group through the reaction between excess oxygen and dopant aluminum.     

缓冲层厚度对透明导电薄膜ZnO:Zr性能的影响

利用直流磁控溅射法在有ZnO:Zr缓冲层的水冷玻璃衬底上成功制备出了ZnO:Zr透明导电薄膜,缓冲层的厚度介于35～208 nm.利用XRD、SEM、四探针测试仪和紫外-可见分光光度计研究ZnO:Zr薄膜的结构、形貌、电光性能.结果表明,薄膜的颗粒尺寸和电阻率对缓冲层厚度具有较强的依赖性.当缓冲层厚度从35 nm增加到103 nm时,薄膜的颗粒尺寸增大,电阻率减小.而当缓冲层厚度从103 nm增加到208 nm时,薄膜的颗粒尺寸减小,电阻率增大.当缓冲厚度为103 nm时,薄膜的电阻率最小为2.96×10-3 Ω·cm,远小于没有缓冲层时的12.9×10-3 Ω·cm.实验结果表明,在沉积薄膜之前先沉积一层适当的缓冲层是提高ZnO:Zr薄膜质量的一种有效方法.     

AZO透明导电薄膜的结构与光电性能

采用射频溅射工艺制备了Zn1-xAlxO透明导电薄膜。通过XRD、UV透射和电学性能测试等分析手段,研究了Al浓度对薄膜的组织结构和光电性能的影响规律。结果表明:薄膜具有c轴择优取向,随着Al浓度的增加,(002)衍射峰向高角度移动,峰强度逐渐减弱,x(Al)为15%掺杂极限浓度。x(Al)为2%时,薄膜电阻率是3.4×10–4Ω.cm。随着掺杂量x(Al)从0增加到20%,薄膜的禁带宽度从3.34 eV增加到4.0 eV。     

电学性能不反常的本征GaAs基InSb异质外延研究

采用三步工艺进行了GaAs基InSb的异质外延生长并结合实验数据和文献资料研究了生长温度和速率、InSb层的厚度、低温缓冲层质量和双In源工艺对材料Hall电学性能等的影响。发现温度和生长速率对室温载流子迁移率和本征载流子浓度影响不太大;晶体XRD FWHM随膜厚的增加而逐渐地减小;低温缓冲层的界面质量和厚度对表面形貌具有一定的影响,低温缓冲层的界面厚度不应小于30 nm,ALE低温缓冲层的方法可以降低局部表面粗糙度;实验发现在优化的工艺参数基础上采用双In源生长工艺可以生长出电学性能不发生反常的理想本征InSb异质外延薄膜材料。获得2μm厚GaAs基InSb层在300 K和77 K的Hall迁移率分别为3.6546×104 cm^2 V^-1 s^-1和7.9453×104 cm^2 V^-1 s^-1,本征载流子迁移率和电子浓度随温度的变化符合理论公式的预期。     

Structural and Electrical Properties of Atomic Layer Deposited Al‐Doped ZnO Films

Structural and electrical properties of Al‐doped ZnO (AZO) films deposited by atomic layer deposition (ALD) are investigated to study the extrinsic doping mechanism of a transparent conducting oxide. ALD‐AZO films exhibit a unique layer‐by‐layer structure consisting of a ZnO matrix and Al₂O₃ dopant layers, as determined by transmission electron microscopy analysis. In these layered AZO films, a single Al₂O₃ dopant layer deposited during one ALD cycle could provide ≈4.5 × 10¹³ cm^?2 free electrons to the ZnO. The effective field model for doping is suggested to explain the decrease in the carrier concentration of ALD‐AZO films when the interval between the Al₂O₃ layers is reduced to less than ≈2.6 nm (>3.4 at% Al). By correlating the electrical and structural properties, an extrinsic doping mechanism of ALD‐AZO films is proposed in which the incorporated Al atoms take oxygen from the ZnO matrix and form doubly charged donors, such as oxygen vacancies or zinc interstitials.     

ZnO和Al2O3缓冲层对AZO透明导电膜薄膜性能的影响

采用射频磁控溅射法,以纯度为99.9%,质量分数98%ZnO、2%Al2O3陶瓷靶为溅射靶材,在预先沉积了ZnO和Al2O3的玻璃衬底上制备了Al2O3掺杂的ZnO薄膜。研究并对比了两种不同的缓冲层对ZnO∶Al(AZO)薄膜的微观结构和光电性能的影响。并借助X线衍射(XRD)仪、扫描电子显微镜(SEM)、紫外可见光谱仪(UV-Vis)等方法测试和分析了不同缓冲层,对AZO薄膜的形貌结构、光电学性能的影响。结果表明:加入缓冲层后,在衬底温度为200℃时,溅射30min,负偏压为60V、在氮气气氛下经300℃退火处理后,制得薄膜的可见光透过率为83%～87%,AZO薄膜的最低电阻率,从9.2×10-4Ω.cm(玻璃)分别下降到8.0×10-4Ω.cm(ZnO)和5.4×10-4Ω.cm(Al2O3)。     

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.     

Effect of NaOH solution on surface textured ZnO: Al films prepared by pulsed direct current magnetron sputtering

Transparent conducting Al-doped ZnO (ZnO:Al, AZO) thin films were prepared at substrate temperature of 270 °C by pulsed direct current magnetron sputtering. NaOH solution (5 wt%) was employed to etch the AZO films at room temperature, and the surface textured AZO films were obtained successfully. The relationship between the surface textured structures and the etching process controlled by etching time was discussed. The textured morphology of the etched AZO films became clear as increasing the etching time, and the AZO film etched for 30 min exhibited uniformly and distinctly crater-like surface textured structure. Correspondingly, the haze and the resistivity increased with the increasing etching time. And the resistivity of the AZO film etched for 30 min was 3.2×10⁻³ Ω cm.     

Highly conductive ZnO films with high near infrared transparency

We present an approach for deposition of highly conductive nominally undoped ZnO films that are suitable for the n‐type window of low band gap solar cells. We demonstrate that low‐voltage radio frequency (RF) biasing of growing ZnO films during their deposition by non‐reactive sputtering makes them as conductive as when doped by aluminium (ρ≤1·10⁻³Ω cm). The films prepared with additional RF biasing possess lower free‐carrier concentration and higher free‐carrier mobility than Al‐doped ZnO (AZO) films of the same resistivity, which results in a substantially higher transparency in the near infrared region (NIR). Furthermore, these films exhibit good ambient stability and lower high‐temperature stability than the AZO films of the same thickness. We also present the characteristics of Cu(InGa)Se₂, CuInSe₂ and Cu₂ZnSnSe₄‐based solar cells prepared with the transparent window bilayer formed of the isolating and conductive ZnO films and compare them to their counterparts with a standard ZnO/AZO bilayer. We show that the solar cells with nominally undoped ZnO as their transparent conductive oxide layer exhibit an improved quantum efficiency for λ > 900 nm, which leads to a higher short circuit current density J_SC. This aspect is specifically beneficial in preparation of the Cu₂ZnSnSe₄ solar cells with band gap down to 0.85 eV; our champion device reached a J_SC of nearly 39 mAcm⁻², an open circuit voltage of 378mV, and a power conversion efficiency of 8.4 %. Copyright © 2015 John Wiley & Sons, Ltd.     

掺铝氧化锌陶瓷靶材的制备及其薄膜的光学性能

以Al(NO3)3.9H2O和ZnO粉体为原料,采用常压烧结方法制备了高致密度和高导电性的ZnO:Al(AZO)陶瓷靶材。研究了烧结温度对AZO靶材微观结构、相对密度和电性能的影响。当Al和Zn的摩尔比为3:100,烧结温度为1 400℃时,所制AZO靶材的致密度达96%,电阻率为2.5×10–2.cm。以烧结温度为1400℃的AZO陶瓷靶为靶材并通过直流磁控溅射在玻璃基片上制备出了高度c轴择优取向的AZO薄膜,其可见光透过率为90%,禁带宽度为3.63 eV,电阻率为1.7×10–3.cm。     

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.     

本征和Al3+掺杂ZnO薄膜的特性研究

采用溶胶-凝胶方法在载玻片衬底上制备了本征及不同Al3+掺杂浓度的ZnO:Al薄膜,利用X射线衍射(XRD)、原子力显微镜,紫外-可见光吸收光谱及霍尔效应研究了Al3+掺杂浓度对ZnO:Al薄膜结构和光电性能的影响。结果显示,ZnO:Al薄膜为六角纤锌矿晶体结构,具有很高的沿c轴的(002)择优取向,Al3+掺杂并没有改变ZnO的晶体结构,只是Al取代了Zn;掺杂前后薄膜样品均在ZnO带边吸收的位置有较强的吸收而在可见光范围吸收较小;并且当Al3+掺杂浓度为1.5%(摩尔百分比)时所获得的ZnO:Al薄膜具有最小的电阻率,为26Ωcm。     

Effect of Al Nanoparticles on the Microstructure,Electrical, and Optical Properties of AZO/Al/AZO Trilayer Thin Film

In this work, designed growth of aluminum (Al)/aluminum-doped zinc oxide (AZO), AZO/Al/AZO, and AZO/Al multilayer electrodes by radiofrequency (RF) magnetron sputtering on glass substrates was studied. The microstructures, optical properties, and electrical characteristics of the multilayer electrode thin films were analyzed, their structural denseness and thickness were observed by field-emission scanning electron microscopy (FE-SEM), and their crystal orientation was identified by x-ray diffraction (XRD). The resistivity and transmittance of the films were measured by four-point probe and UV–Vis–NIR spectrophotometer, respectively. The resistivity of the AZO/Al/AZO multilayer electrode thin film was 1.55 Ω cm. The average transmittance of the AZO/Al/AZO thin film over wavelengths from 400 nm to 800 nm was much better than that of other thin films, since Al nanoparticles distribute in the AZO thin film during the sputtering process, as observed by high-resolution transmission electron microscopy (HRTEM). In addition, the figure of merit of the AZO/Al/AZO trilayer film was much larger than those of the other structures.     

Thickness dependence of the properties of transparent conducting ZnO:Zr films deposited on flexible substrates by RF magnetron sputtering

Transparent conducting zirconium-doped zinc oxide(ZnO:Zr)thin films with high transparency,low resistivity and good adhesion were successfully prepared on water-cooled flexible substrates(polyethylene glycol terephthalate,PET)by RF magnetron sputtering.The structural,electrical and optical prooerties of the films were studied for different thicknesses in detail.X-ray diffraction(XRD)and scanning electron microscopy(SEM)revealed that all the deposited films are polycrystalline with a hexagonal structure and a preferred orientation perpendicular to the substrate．The lowest resistivity achieved is 1.55×10-3 Ω·cm for a thickness of 189 nm with a Hall mobility of 17.6cm2/(V·s)and a carrier concentration of 2.15×1020cm-3.All the films present a high transmittance of above 90％in the wavelength range of the visible spectrum.     

P-type ZnO thin films prepared by in situ oxidation of DC sputtered Zn3N2:Ga

The feasibility of a new fabrication route for N and Ga codoped p-type ZnO thin films on glass substrates, consisting of DC sputtering deposition of Zn3N2:Ga precursors followed by in situ oxidation in high purity oxygen, has been studied. The effects of oxidation temperature on the structural, optical and electrical properties of the samples were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), optical transmittance and Hall effect measurements. The results were compared to a control film without Ga. XRD analyses revealed that the Zn3N2 films entirely transformed into ZnO films after annealing Zn3N2 films in oxygen over 500 ℃ for 2 h. Hall effect measurements confirmed p-type conduction in N and Ga codoped ZnO films with a low resistivity of 19.8 Ω·cm, a high hole concentration of 4.6 × 1018 cm-3 and a Hall mobility of 0.7 cm2/(V·s). These results demonstrate a promising approach to fabricate low resistivity p-type ZnO with high hole concentration.