Synthesis and properties of close packed ZnO:Al submicro-rods deposited by pulsed laser ablation

Al-doped ZnO (AZO) semiconducting thin films consisting of perpendicularly aligned submicro-rods were deposited on silicon substrate by conventional pulsed laser ablation. No catalyst was used in this process. It was found that the rod structure can be grown at relatively high oxygen pressures (1-20 Torr) and relatively high substrate temperatures (550-700 °C). Low resistivity and high carrier concentration can be obtained in these Al-doped ZnO rods with relatively high Al concentrations. Increasing Al doping reduces the electric resistivity and increase carrier concentration. The photoluminescence property measurement indicates an increased UV emission with a small amount Al doping and reduced UV emission with further increase of Al concentration.     

Polycrystalline ZnO: B grown by LPCVD as TCO for thin film silicon solar cells

Conductive zinc oxide (ZnO) grown by low pressure chemical vapor deposition (LPCVD) technique possesses a rough surface that induces an efficient light scattering in thin film silicon (TF Si) solar cells, which makes this TCO an ideal candidate for contacting such devices. IMT-EPFL has developed an in-house LPCVD process for the deposition of nanotextured boron doped ZnO films used as rough TCO for TF Si solar cells. This paper is a general review and synthesis of the study of the electrical, optical and structural properties of the ZnO:B that has been performed at IMT-EPFL.The influence of the free carrier absorption and the grain size on the electrical and optical properties of LPCVD ZnO:B is discussed. Transport mechanisms at grain boundaries are studied. It is seen that high doping of the ZnO grains facilitates the tunnelling of the electrons through potential barriers that are located at the grain boundaries. Therefore, even if these potential barriers increase after an exposition of the film to a humid atmosphere, the heavily doped LPCVD ZnO:B layers show a remarkable stable conductivity. However, the introduction of diborane in the CVD reaction induces also a degradation of the intra-grain mobility and increases over-proportionally the optical absorption of the ZnO:B films. Hence, the necessity to finely tune the doping level of LPCVD ZnO:B films is highlighted. Finally, the next challenges to push further the optimization of LPCVD ZnO:B films for thin film silicon solar cells are discussed, as well as some remarkable record cell results achieved with LPCVD ZnO:B as front electrode.     

Effect of Al concentrations on the electrodeposition and properties of transparent Al-doped ZnO thin films

Al-doped zinc oxide (AZO) thin films are prepared on polycrystalline fluorine-doped tin oxide-coated conducting glass substrates from nitrates baths by the electrodeposition process at 70 °C. The electrochemical, morphological, structural and optical properties of the AZO thin films were investigated in terms of different Al concentration in the starting solution. It was found that the carrier density of AZO thin films varied between ?3.11 and ?5.56 × 10²⁰ cm^?3 when the Al concentration was between 0 and 5 at.%. Atomic force microscopy images reveal that the concentration of Al has a very significant influence on the surface morphology and roughness of thin AZO. X-ray diffraction spectra demonstrate preferential (002) crystallographic orientation having c-axis perpendicular to the surface of the substrate and average crystallites size of the films was about 33–54 nm. With increasing Al doping, AZO films have a strong improved crystalline quality. As compared to pure ZnO, Al-doped ZnO exhibited lower crystallinity and there is a shift in the (002) diffraction peak to higher angles. Due to the doping of Al of any concentration, the films were found to be showing >80 % transparency. As Al concentration increased the optical band gap was also found to be increase from 3.22 to 3.47 eV. The room-temperature photoluminescence spectra indicated that the introduction of Al can improve the intensity of ultraviolet (UV) emission, thus suggesting its greater prospects in UV optoelectronic devices. A detailed comparison and apprehension of electrochemical, optical and structural properties of ZnO and ZnO:Al thin films is done for the determination of optimum concentration of Al doping.     

磁控溅射法制备的CdS:Al薄膜的性质研究

采用Al和CdS双靶共溅射的方法, 调控Al和CdS源的沉积速率, 制备出不同Al掺杂浓度的CdS:Al薄膜。通过XRD、SEM、AFM、紫外-可见透射光谱分析、常温霍尔测试对CdS: Al薄膜的结构、形貌、光学和电学性质进行表征。XRD结果表明, 不同Al掺杂浓度的CdS:Al薄膜均为六方纤锌矿结构的多晶薄膜, 并且在(002)方向择优生长。SEM和AFM结果表明, CdS:Al薄膜的表面均匀致密, 表面粗糙度随着Al掺杂浓度的增加略有增加。紫外-可见透射光谱分析表明, CdS:Al薄膜禁带宽度在2.42~2.46 eV 之间, 随着Al掺杂浓度的增加而略微减小。常温霍尔测试结果证明, 掺Al对CdS薄膜的电学性质影响显著, 掺Al原子浓度3.8%以上的CdS薄膜, 载流子浓度增加了3个数量级, 电阻率下降了3个数量级。掺Al后的CdS薄膜n型更强, 有利于与CdTe形成更强的内建场, 从而提高太阳电池效率。用溅射方法制备的CdS:Al薄膜的性质适合用作CdTe薄膜太阳电池的窗口层。     

Effects of Al concentration on microstructural characteristics and electrical properties of Al-doped ZnO thin films on Si substrates by atomic layer deposition

Al-doped ZnO (AZO) thin films with various Al concentrations were synthesized on Si(001) substrates with native oxide layers by atomic layer deposition process. The effects of the Al concentration on the microstructural characteristics of the AZO thin films grown at 250 degrees C and the correlation between their microstructural characteristics and electrical properties of the AZO thin films were investigated by AFM, XRD, HRTEM and Hall measurements. The XRD and HRTEM results revealed that the crystallinity and electrical properties of the undoped ZnO thin films were enhanced by 2.48 at% Al doping. However, 12.62 at% Al doping induced the deterioration of their crystallinity and electrical properties due to the formation of nano-sized metallic Al clusters and randomly oriented ZnO-based nano-crystals. To enhance the electrical properties of the AZO thin films while maintaining their crystallinity and electrical properties, a moderate Al concentration has to be chosen under the solubility limit of Al in ZnO.     

Influence of Al concentration on structural and optical properties of Al-doped ZnO thin films

Undoped ZnO and Al-doped zinc oxide (ZnO:Al) thin films with different Al concentrations were prepared onto Si (100) substrate by pulsed filtered cathodic vacuum arc deposition system at room temperature. The influence of doping on the structural and optical properties of thin films was investigated. The preferential (002) orientation was weakened by high aluminum doping in films. Raman measurement was performed for the doping effects in the ZnO. Atomic force microscopy images revealed that the surface of undoped ZnO film grown at RT was smoother than that of the Al-doped ZnO (ZnO:Al) films. The reflectance of all films was studied as a function of wavelength using UV–Vis–NIR spectrophotometer. Average total reflectance values of about 35 % in the wavelength range of 400–800 nm were obtained. Optical band gap of the films was determined using the reflectance spectra by means of Kubelka–Munk formula. From optical properties, the band gap energy was estimated for all films.     

Control of aluminum doping of ZnO:Al thin films obtained by high-power impulse magnetron sputtering

This work reports a method used to control Al doping of ZnO thin films deposited by high-power impulse magnetron sputtering of a pure Zn target in low-pressure Ar/O₂ gas mixture. The method uses sputtering of an electrically negative biased aluminum electrode placed in the proximity of the negative glow of the magnetron discharge. Resonant laser absorption measurements of Al atom concentration in vapor phase and the X-ray Photoelectron Emission Spectroscopy measurements of Al concentration in the deposited ZnO:Al films confirm that the electrode biasing potential is the key parameter that controls the Al doping process. Optically transparent ZnO:Al films with resistivity as low as 3.6 × 10^− 3 Ω × cm have been obtained at an optimum value of Al concentration of 1.5 at.%. It has been found that the film electrical conductivity is limited by the effect of decreasing of crystalline grain size in the films with the increased Al doping concentration.     

Optical and electronic properties of highly stable and textured hydrogenated ZnO:Al thin films

We have experimentally investigated the effects of hydrogen-annealing on the structural, electrical, and optical properties of Al-doped ZnO (ZnO:Al) thin films prepared by RF magnetron sputtering at room temperature. From the X-ray diffraction observations, the orientation of ZnO:Al films was found to be a c-axis in the hexagonal structure. We found that intentionally incorporated hydrogen plays an important role in n-type conduction as a donor, improving free carrier concentration and electrical stability. We simultaneously obtained improved optical transmission and enhanced absorption edge of the ZnO:Al film due to hydrogen-annealing. Our experimental data suggest the hydrogen-annealing process as an important role in the enhancement of electrical and optical properties, which is promising as a back reflector material for thin-film solar cells.     

Growth behaviors and characteristics of low temperature spin-sprayed ZnO and Al-doped ZnO microstructures

The influence of growth parameters of the spin-spray technique upon the microstructure and electrical and optical properties of ZnO and Al-doped ZnO microstructures was investigated. This investigation was carried out by varying the pH and concentration of the solutions utilized. With increasing pH from 9 to 12, the ZnO films changed from membrane-like microstructures at a pH of 9 to single crystal ZnO rods with hexagonal ends at the pH of 10, and to polycrystal ZnO needle-like tips with random crystalline orientation at the pH of 12. Varying the concentration of the solution brought about a dramatic change in the crystal growth behavior and crystalline orientation, with the least concentration producing rods more uniform and oriented in the c-axis direction. The optical absorption dependence of the ZnO microstructures was also studied by ultraviolet visible spectrophotometer. This investigation will enable optimized low temperature (<100 °C) fabrication of ZnO films by the spin-spray technique with controllable microstructure and properties based on their processing conditions. Furthermore, the influence of Al doping on the electric property, optical property microstructures of the Al-doped ZnO thin films was examined. Increase in Al concentration from 0 to 2 % further reduced the resistivity of the ZnO films by 3 orders of magnitudes from 3.4 × 10⁴ to 14 Ω cm; while the Hall mobility increases from 1 to 140 cm²/V s at the same time. The optical photoluminescence measurement of Al-doped ZnO thin films in ultra violet (UV) was also demonstrated.     

Structural,optical and electrical characterization on ZnO film grown by a spray pyrolysis method

Undoped ZnO poly crystalline films were successfully grown by a spray pyrolysis method at 300–500∘C. The samples grown at 500∘C indicated high quality because the (0002) orientation was strongly observed in the X-ray diffraction (XRD) spectrum. Surface roughness reduced with increasing substrate temperature and indium concentration. Indium doping caused the resistivity to decrease and the carrier concentration to increase. Electrical conduction types in the undoped and In-doped ZnO films indicated all n-types. From these results, this indicated that indium atoms could act as a donor type impurity.     

Low temperature synthesis of sol–gel derived Al-doped ZnO thin films with rapid thermal annealing process

A series of sol–gel derived Al-doped ZnO (AZO) thin films with rapid thermal annealing process at low temperature were studied to examine the influence of annealing temperature and the Al doping concentration on their microstructure, electrical and optical transport properties. Crystalline AZO thin films were obtained following an annealing process at temperatures between 400 and 600 °C for 10 min in argon gas ambient. AZO thin films with Al doping of 1 at% were oriented more preferentially along the (002) direction, and have larger grain size and lower electrical resistivity, while the highest average optical transmittances of 92% were observed in AZO films with Al doping of 2 at%. With the annealing temperature increasing from 400 to 600 °C, the grain size of AZO films increased, the optical transmittance became higher, and the electrical resistivity decreased to a lowest value of 1.2 × 10⁻⁴ Ω cm resulting from the increase of the carrier concentration and the mobility.     

Metal on metal oxide nanowire Co-catalyzed Si photocathode for solar water splitting

We report a systematic study of Si|ZnO and Si|ZnO| metal photocathodes for effective photoelectrochemical cells and hydrogen generation. Both ZnO nanocrystalline thin films and vertical nanowire arrays were studied. Si|ZnO electrodes showed increased cathodic photocurrents due to improved charge separation by the formation of a p/n junction, and Si|ZnO:Al (n(+)-ZnO) and Si|ZnO(N(2)) (thin films prepared in N(2)/Ar gas) lead to a further increase in cathodic photocurrents. Si|ZnONW (nanowire array) photocathodes dramatically increased the photocurrents and thus photoelectrochemical conversion efficiency due to the enhanced light absorption and enlarged surface area. The ZnO film thickness and ZnO nanowire length were important to the enhancements. A thin metal coating on ZnO showed increased photocurrent due to a catalyzed hydrogen evolution reaction and Ni metal showed comparable catalytic activities to those of Pt and Pd. Moreover, photoelectrochemical instability of Si|ZnO electrodes was minimized by metal co-catalysts. Our results indicate that the metal and ZnO on p-type Si serve as co-catalysts for photoelectrochemical water splitting, which can provide a possible low-cost and scalable method to fabricate high efficiency photocathodes for practical applications in clean solar energy harvesting.     

The effect of Sn concentration on some physical properties of zinc oxide films prepared by ultrasonic spray pyrolysis

The effect of Sn concentration on zinc oxide (ZnO) film properties has been investigated by depositing films with various Sn concentrations in the solution (Sn/Sn + Zn ratio from 0 to 50 at%) at a substrate temperature of 350°C by ultrasonic spray pyrolysis (USP) technique. The deposited films were characterized for their electrical, structural, morphological and elemental properties using current-voltage and conductivity-temperature measurements, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. Electrical investigations showed that the resistivity of ZnO films decreases for lower Sn concentration (at 10%) and then increases for higher Sn concentration (at 30–50%). Also, depending on the increasing Sn concentration, energies of donor-like traps for ZnO films decreased and activation energy of donors for ZnO films increased. The XRD patterns showed that the as-deposited films have polycrystalline structure and the crystalline nature of the films was deteriorated with increasing Sn concentration and a shift to amorphous structure was seen. The effect of Sn concentration was to increase the surface roughening and change considerably the morphologies of ZnO films. The most homogenous surface was seen in ZnO films. EDS results showed that all elements in the starting solutions were in the solid films and Zn element is more dominant than Sn on the surfaces. After all investigations, it was determined that Sn incorporation dramatically modifies the properties of ZnO films. ZnO and ZnO:Sn (10 at%) films have a low resistivity and high transparency in the visible range and may be used as window material and antireflecting coating in solar cells while the other films may be used in gas sensors where high conductivity is unnecessary.     

Structural, electrical and optical properties of Si doped ZnO films grown by atomic layer deposition

Si doped ZnO (SZO) films with various Si concentrations were deposited by atomic layer deposition at 300 °C using triethyzinc, tris(dimethylamino)silane and H₂O₂ as the precursors. The influences of Si doping concentration on structural, electrical and optical properties of ZnO films have been investigated. All the films exhibited a highly preferential c-axis orientation. A minimum resistivity of 9.2 × 10^?4 Ω cm, with a carrier concentration of 4.3 × 10²⁰ cm^?3 and a Hall mobility of 15.8 cm²/Vs, was obtained for SZO film prepared with the Si concentration of 2.1 at%. The increase of conductivity with Si doping was attributed to the presence of Si in +3 valence state acting as donor in ZnO and the increases of oxygen vacancies with Si concentration as proven by XPS measurements. The optical bandgap of SZO films initially increased from 3.25 to 3.55 eV with increasing of Si concentration to 2.1 at%, then decreased with further increase of Si concentration. The blue shift of band gap of SZO films with increasing carrier concentration can be explained by the Burstein-Moss (B-M) effects.     

Structures and properties of the Al-doped ZnO thin films prepared by radio frequency magnetron sputtering

Al-doped ZnO thin films were deposited by radio frequency magnetron sputtering using a ZnO target with 2 wt.% Al₂O₃. The structures and properties of the films were characterized by the thin film X-ray diffraction, high resolution transmission electron microscopy, Hall system and ultraviolet/visible/near-infrared spectrophotometer. The Al-doped ZnO film with high crystalline quality and good properties was obtained at the sputtering power of 100 W, working pressure of 0.3 Pa and substrate temperature of 250 °C. The results of further structure analysis show that the interplanar spacings d are enlarged in other directions besides the direction perpendicular to the substrate. Apart from the film stress, the doping concentration and the doping site of Al play an important role in the variation of lattice parameters. When the doping concentration of Al is more than 1.5 wt.%, part of Al atoms are incorporated in the interstitial site, which leads to the increase of lattice parameters. This viewpoint is also proved by the first principle calculations.     

Effect of Al Doping on Structural, Electrical, Optical and Photoluminescence Properties of Nano-Structural ZnO Thin Films

The nano-structural Al-doped ZnO thin films of different morphologies deposited on glass substrate were successfully fabricated at substrate temperature of 350 C by an inexpensive spray pyrolysis method. The structural, electrical, optical and photoluminescence properties were investigated. X-ray diffraction study revealed the crystalline wurtzite (hexagonal) structure of the films with nano-grains. Scanning electron mi- croscopy (SEM) micrographs indicated the formation of a large variety of nano-structures during film growth. The spectral absorption of the films occurred at the absorption edge of ～410 nm. In the present study, the optical band gap energy 3.28 eV of ZnO decreased gradually to 3.05 eV for 4 mol% of Al doping. The deep level activation energy decreased and carrier concentrations increased substantially with increasing doping. Exciting with the energy 3.543 eV (λ=350 nm), a narrow and a broad characteristic photoluminescence peaks that correspond to the near band edge (NBE) and deep level emissions (DLE), respectively emerged.     

Investigation of thin solid ZnO films prepared by sputtering

Zinc oxide (ZnO) thin films have attracted great attention in recent years due to their unique piezoelectric and piezooptic properties, making them suitable for various microelectronics and optoelectronics applications, such as surface acoustic wave devices, optical fibers, solar cells etc. ZnO is a semiconductor with a band gap of 3.3 eV and a large exciton binding energy of 60 meV. Undoped ZnO exhibits intrinsic n-type conductivity and it enables achieving high electron concentration. However, it may be doped to obtain low resistivity p-type thin films. Among group V of the periodic table, nitrogen is used as a popular p-type dopant due to its small atomic size. However, it is difficult to achieve p-type conduction in ZnO films due to the low solubility of nitrogen and its high intensity in self compensating process upon doping.Sputtering techniques enable us to form dense and homogeneous films due to the relatively high energy of the sputtered atoms. Thus we can grow high quality ZnO films with c-axis orientation, low growth temperature, high deposition rate, large area deposition, and availability in various growths ambient. In this work, the zinc oxide films were prepared using various DC sputtering methods in an atmosphere of pure argon and an atmosphere of mixed argon with nitrogen. Optical and electrical properties of the films were investigated.     

Structural and optical properties of ZnO films grown on the AAO templates

Structural and optical properties of ZnO films grown on Al substrate and anodic alumina oxide (AAO) templates by rf magnetron reactive sputtering deposition were investigated using X-ray diffraction (XRD), atomic-force microscope (AFM) and photoluminescence (PL). We found that ZnO thin films on Al substrate show good C-axis orientation, while the orientation of ZnO film on AAO templates is disordered, this due to the fact that the crystalline of ZnO is greatly influenced by surface morphology of substrates. PL measurements show a blue band in the wavelength range of 400–500 nm caused by the interstitial Zn in the ZnO films. The intensity of emission peak of ZnO films deposited on AAO templates increases compared with that on the Al substrate. Combining electrical resistivity and carrier concentration measurements, we found that that the blue emission intensity is consistent with the concentration for the interstitial zinc in the ZnO films.     

Influence of preparation condition and doping concentration of Fe-doped ZnO thin films: Oxygen-vacancy related room temperature ferromagnetism

Fe-doped and Fe-Ga co-doped ZnO diluted magnetic semiconductor thin films on quartz substrate were studied. Rapid annealing enhanced the ferromagnetism (FM) of the films grown in Ar/O₂. All the films grown in Ar are n-type and the carrier concentration could increase significantly when Ga is doped. The state of Fe in the films was investigated exhibiting Fe³⁺. Magnetic measurements revealed that room temperature ferromagnetism in the films were doping concentration dependent and would enhance slightly with Ga doping. The origin of the observed FM is interpreted by the overlapping of polarons mediated through oxygen vacancy based on the bound magnetic polaron model.     

Synthesis of nano-dimensional ZnO and Ga doped ZnO thin films by vapor phase transport and study as transparent conducting oxide

We report synthesis of polycrystalline ZnO and Ga doped ZnO (ZnO:Ga) thin films (approximately 80 nm) on Si and quartz substrates in a non-vacuum muffle furnace, a simple and cost-effective route, without any catalyst/reactive carrier gases, at relatively low processing temperature of 550 degrees C. The crystalline phases of the films are identified by grazing angle X-ray diffraction (GAXRD). The growth of ZnO films is examined with scanning electron microscope (SEM) as a function of deposition time. An optical transmission of approximately 90% is observed for pure ZnO film having a resistivity of approximately 2.1 Omega-cm as measured by van der Pauw technique. Doping with Ga results in single phase ZnO:Ga films, retaining an optical transmission of about 80% and three orders of magnitude decrease in resistivity as compared to pure ZnO film.