直流溅射工艺参数对Mo薄膜结构及电性能的影响

采用直流磁控溅射法在SLG衬底上沉积Mo薄膜,对不同溅射功率和溅射工作气压下沉积的薄膜进行X射线衍射、SEM(扫描电子显微镜)、电阻率测试,讨论了工艺参数对沉积Mo薄膜相结构、表面微观形貌、薄膜沉积速率和电学性能的影响。结果表明,随着溅射功率的增加,薄膜的结晶性能变好,沉积速率提高,在沉积功率范围内薄膜均匀致密,表面无空隙,电阻率较低;随着溅射工作气压增加,薄膜结晶性能变差,沉积速率先增加后降低,在沉积工作气压范围内,薄膜致密;随气压降低,电阻率急剧减小。因此,较高的溅射功率和较低的工作气压沉积的Mo薄膜更适合作CIGS薄膜太阳电池的BC层(背接触层)。     

Property variations of direct-current reactive magnetron sputtered copper oxide thin films deposited at different oxygen partial pressures

Cuprous oxide (Cu₂O) and cupric oxide (CuO) thin films were deposited on glass substrates at different oxygen partial pressures by direct-current reactive magnetron sputtering of pure copper target in a mixture of argon and oxygen gases. Oxygen partial pressure was found to be a crucial parameter in controlling the phases and, thus, the physical properties of the deposited copper oxide thin films. Single-phase Cu₂O thin films with cubic structure were obtained at low oxygen partial pressure between 0.147 Pa and 0.200 Pa while higher oxygen partial pressure promoted the formation of CuO thin films with base-centered monoclinic structure. Polycrystalline Cu₂O thin films deposited with oxygen partial pressure at 0.147 Pa possessed the lowest p-type resistivity of 1.76 Ω cm as well as an optical band gap of 2.01 eV. On the other hand, polycrystalline CuO thin films deposited with oxygen partial pressure at 0.320 Pa were also single phase but showed a n-type resistivity of 0.19 Ω cm along with an optical band gap of 1.58 eV.     

The effect of argon pressure, residual oxygen and exposure to air on the electrical and microstructural properties of sputtered chromium thin films

Chromium thin films were deposited on SiO₂/Si wafers using two sputtering systems with different levels of cleanliness, and at argon sputtering pressures varying between 0.13 and 0.93 Pa. Films from the two systems grown under identical sputtering conditions had significantly different resistivity values that are shown to be due to differences in residual oxygen in the chambers. Electrical transport measurements were conducted on the series of grown films to investigate the influence of argon pressure on film electrical resistivity. The films morphology, microstructure and composition were characterized using scanning electron microscopy and X-ray photoelectron spectroscopy. Significant differences were found in Cr thin films sputtered at different sputtering pressures; differences in resistivity performance and microstructure were noted. This change was shown to be due to the transition from porous structure to a denser microstructure. The Cr films sputtered at high pressure contained large quantities of oxygen when exposed to air. Some of the oxygen is added to the film during the deposition depending on the deposition rate and the base pressure of the sputtering system. The rest is incorporated into the film once it is exposed to air. The amount of oxygen added at this stage depends on the structure of the film and would be minimal for the films deposited at low sputtering pressures.     

Electrical,morphological and structural properties of RF magnetron sputtered Mo thin films for application in thin film photovoltaic solar cells

Molybdenum (Mo) thin films were deposited using radio frequency magnetron sputtering, for application as a metal back contact material in “substrate configuration” thin film solar cells. The variations of the electrical, morphological, and structural properties of the deposited films with sputtering pressure, sputtering power and post-deposition annealing were determined. The electrical conductivity of the Mo films was found to increase with decreasing sputtering pressure and increasing sputtering power. X-ray diffraction data showed that all the films had a (110) preferred orientation that became less pronounced at higher sputtering power while being relatively insensitive to process pressure. The lattice stress within the films changed from tensile to compressive with increasing sputtering power and the tensile stress increased with increasing sputtering pressure. The surface morphology of the films changed from pyramids to cigar-shaped grains for a sputtering power between 100 and 200 W, remaining largely unchanged at higher power. These grains were also observed to decrease in size with increasing sputtering pressure. Annealing the films was found to affect the resistivity and stress of the films. The resistivity increased due to the presence of residual oxygen and the stress changed from tensile to compressive. The annealing step was not found to affect the crystallisation and grain growth of the Mo films.     

ZnO thin films prepared by atomic layer deposition and rf sputtering as an active layer for thin film transistor

Recently, the application of ZnO thin films as an active channel layer of transparent thin film transistor (TFT) has become of great interest. In this study, we deposited ZnO thin films by atomic layer deposition (ALD) from diethyl Zn (DEZ) as a metal precursor and water as a reactant at growth temperatures between 100 and 250 °C. At typical growth conditions, pure ZnO thin films were obtained without any detectable carbon contamination. For comparison of key film properties including microstructure and chemical and electrical properties, ZnO films were also prepared by rf sputtering at room temperature. The microstructure analyses by X-ray diffraction have shown that both of the ALD and sputtered ZnO thin films have (002) preferred orientation. At low growth temperature T_s ≤ 125 °C, ALD ZnO films have high resistivity (> 10 Ω cm) with small mobility (< 3 cm²/V s), while the ones prepared at higher temperature have lower resistivity (< 0.02 Ω cm) with higher mobility (> 15 cm²/V s). Meanwhile, sputtered ZnO films have much higher resistivity than ALD ZnO at most of the growth conditions studied. Based upon the experimental results, the electrical properties of ZnO thin films depending on the growth conditions for application as an active channel layer of TFT were discussed focusing on the comparisons between ALD and sputtering.     

Highly adherent bioactive glass thin films synthetized by magnetron sputtering at low temperature

Thin (380–510 nm) films of a low silica content bioglass with MgO, B₂O₃, and CaF₂ as additives were deposited at low-temperature (150°C) by radio-frequency magnetron sputtering onto titanium substrates. The influence of sputtering conditions on morphology, structure, composition, bonding strength and in vitro bioactivity of sputtered bioglass films was investigated. Excellent pull-out adherence (~73 MPa) was obtained when using a 0.3 Pa argon sputtering pressure (BG-a). The adherence declined (~46 MPa) upon increasing the working pressure to 0.4 Pa (BG-b) or when using a reactive gas mixture (~50 MPa). The SBF tests clearly demonstrated strong biomineralization features for all bioglass sputtered films. The biomineralization rate increased from BG-a to BG-b, and yet more for BG-c. A well-crystallized calcium hydrogen phosphate-like phase was observed after 3 and 15 days of immersion in SBF in all bioglass layers, which transformed monotonously into hydroxyapatite under prolonged SBF immersion. Alkali and alkali-earth salts (NaCl, KCl and CaCO₃) were also found at the surface of samples soaked in SBF for 30 days. The study indicated that features such as composition, structure, adherence and bioactivity of bioglass films can be tailored simply by altering the magnetron sputtering working conditions, proving that this less explored technique is a promising alternative for preparing implant-type coatings.     

Effect of temperature on the properties of Al:ZnO films deposited by magnetron sputtering with inborn surface texture

Al:ZnO (AZO) films were deposited on glass substrate with inborn surface texture by magnetron sputtering at a power density as high as 7 W/cm². The sputtering parameters, such as argon working pressure and substrate temperature were varied from 1.0 to 6.0 Pa and from room temperature to 500 °C, respectively. All the films exhibited perfect (002) orientations with very weak (004) peaks measured by X-ray diffraction. A linear relationship between the growth rate of AZO film and working pressure was found. The AZO film with best electrical properties of all films obtained at room temperature was deposited at working pressure of 2.0 Pa. And the root-mean-square roughness tested by atomic force microscopy was 37.50 nm, which indicated that surface texture was successfully fabricated without further etching process. For higher substrate temperature a decrease in the resistivity was observed due to an increase in the mobility and the carrier concentration. Resistivity low as 9.044 × 10⁻⁴ ohm/cm was obtained at 500 °C and 2.0 Pa, the corresponding mobility and carrier concentration were 20.45 m²/Vs and 3.379 × 10²⁰/cm³, respectively. The grain size and the surface texture size tested by scanning electron microscopy also peaked at 500 °C. All the films showed a relatively high transmittance about 80%.     

Effect of sputtering pressure on the properties of ZnMgO: Ti transparent conducting thin films

ZnMgO: Ti transparent conducting thin films have been deposited on glass substrates by DC-magnetron sputtering, and the effects of sputtering pressure on their properties have been investigated. Electrical resistivity as low as 7.84*10⁻⁴Ω cm was achieved for ZnMgO: Ti thin film. All thin films provided high optical transparencies in the visible region. Thin films deposited at 6 Pa, 8 Pa and 10 Pa showed “blue shift”. These results have not only clarified the effects of the sputtering pressure on the properties of ZnMgO: Ti films, but also revealed the potential of ZnMgO: Ti films in solar cells application. Efficiency of solar cells may be improved by choosing ZnMgO: Ti thin film as transparent electrode.     

Deposition of Al-doped ZnO films on polyethylene naphthalate substrate with radio frequency magnetron sputtering

100 nm Al-doped ZnO (AZO) thin films were deposited on polyethylene naphthalate (PEN) substrates with radio frequency magnetron sputtering using 2 wt.% Al-doped ZnO target at various deposition conditions including sputtering power, target to substrate distance, working pressure and substrate temperature. When the sputtering power, target to substrate distance and working pressure were decreased, the resistivity was decreased due to the improvement of crystallinity with larger grain size. As the substrate temperature was increased from 25 to 120 °C, AZO films showed lower electrical resistivity and better optical transmittance due to the significant improvement of the crystallinity. 2 wt.% Al-doped ZnO films deposited on glass and PEN substrates at sputtering power of 25 W, target to substrate distance of 6.8 cm, working pressure of 0.4 Pa and substrate temperature of 120 °C showed the lowest resistivity (5.12 × 10^− 3 Ω cm on PEN substrate, 3.85 × 10^− 3 Ω cm on glass substrate) and high average transmittance (> 90% in both substrates). AZO films deposited on PEN substrate showed similar electrical and optical properties like AZO films deposited on glass substrates.     

Growth and characterization of indium tin oxide thin films deposited on PET substrates

Transparent and conductive indium tin oxide (ITO) thin films were deposited onto polyethylene terephthalate (PET) by d.c. magnetron sputtering as the front and back electrical contact for applications in flexible displays and optoelectronic devices. In addition, ITO powder was used for sputter target in order to reduce the cost and time of the film formation processes. As the sputtering power and pressure increased, the electrical conductivity of ITO films decreased. The films were increasingly dark gray colored as the sputtering power increased, resulting in the loss of transmittance of the films. When the pressure during deposition was higher, however, the optical transmittance improved at visible region of light. ITO films deposited onto PET have shown similar optical transmittance and electrical resistivity, in comparison with films onto glass substrate. High quality films with resistivity as low as 2.5 × 10^− 3 Ω cm and transmittance over 80% have been obtained on to PET substrate by suitably controlling the deposition parameters.     

Characterization of copper oxide nanolayers deposited by direct current magnetron sputtering

Direct current reactive magnetron sputtering was used to deposit the thin layers of copper oxide (Cu₂O) on glass substrates. A solid disc of pure copper as the target was sputtered in an argon gas under sputtering pressures varying from 0.133 to 4 Pa. The effects of the sputtering power and pressure on the structural and optical properties of Cu₂O thin films were systematically studied. The deposited layers were characterized using X-ray diffraction, atomic force microscopy, profilometry and spectrophotometry. The optical transmission of the films was measured in the visible region. The increase in pressure resulted in a higher growth rate than increasing sputtering power. The increase in power produced Cu₂O thin films that were detrimental to the optical transmission of the films.     

Investigation of thermal stability of Mo thin-films as the buffer layer and various Cu metallization as interconnection materials for thin film transistor-liquid crystal display applications

Cu/Mo/Si multi-layer structures were fabricated to investigate diffusion behaviors and thermal stability between Cu and Mo. Physical vapor deposition (PVD), chemical vapor deposition, electroplating and electrolessplating were used to grow 100 nm thick Cu films as interconnection materials, and radio-frequency sputtering system was introduced to grow 37.5 nm thick Mo films as a buffer layer. All Cu/Mo/Si multi-layer specimens were annealed at 350 to 700 °C for 30 min. When the annealing temperature was over 600 °C, the Cu diffused through Mo into Si, and the Cu₃Si phase and Mo-Si intermetallic compounds formed at the Mo/Si interface. The diffusion mechanism is the grain boundary diffusion. The results indicate that Cu film deposited by PVD had best crystallinity, lower roughness, large adhesive energy and resistivity. The values of the resistivity, diffusion activity energy and large adhesive energy are 5.47 μΩ-cm, 0.948 eV and 2.46 N/m, respectively.     

Effect of ZnO buffer layer on AZO film properties and photovoltaic applications

Aluminum-doped ZnO (AZO) transparent conducting films were deposited on glass substrates with and without intrinsic ZnO (i-ZnO) buffer layers by a home made and low cost radio-frequency (RF) magnetron sputtering system at room temperature in pure argon ambient and under a low vacuum level. The films were examined and characterized for electrical, optical, and structural properties for the application of CIGS solar cells. The influence of sputter power, deposition pressure, film thickness and residual pressure on electrical and optical properties of layered films of AZO, i-ZnO and AZO/i-ZnO was investigated. The optimization of coating process parameters (RF power, sputtering pressure, thickness) was carried out. The effects of i-ZnO buffer layer on AZO films were investigated. By inserting thin i-ZnO layers with a thickness not greater than 125 nm under the AZO layers, both the carrier concentration and Hall mobility were increased. The resistivity of these layered films was lower than that of single layered AZO films. The related mechanisms and plasma physics were discussed. Copper indium gallium selenide (CIGS) thin film solar cells were fabricated by incorporating bi-layer ZnO films on CdS/CIGS/Mo/glass substrates. Efficiencies of the order of 7–8% were achieved for the manufactured CIGS solar cells (4–5 cm² in size) without antireflective films. The results demonstrated that RF sputtered layered AZO/i-ZnO films are suitable for application in low cost CIGS solar cells as transparent conductive electrodes.     

Effects of substrate on the structural, electrical and optical properties of Al-doped ZnO films prepared by radio frequency magnetron sputtering

Transparent and conductive Al-doped ZnO (AZO) thin films were deposited on substrates including alkali-free glass, quartz glass, Si, and SiO₂ buffer layer on alkali-free glass by using radio frequency magnetron sputtering. The effects of different substrates on the structural, electrical and optical properties of the AZO films were investigated. It was found that the crystal structures were remarkably influenced by the type of the substrates due to their different thermal expansion coefficients, lattice mismatch and flatness. The AZO film (100 nm in thickness) deposited on the quartz glass exhibited the best crystallinity, followed sequentially by those deposited on the Si, the SiO₂ buffer layer, and the alkali-free glass. The film deposited on the quartz glass showed the lowest resistivity of 5.14 × 10^− 4 Ω cm among all the films, a carrier concentration of 1.97 × 10²¹ cm^− 3 and a Hall mobility of 6.14 cm²/v·s. The average transmittance of this film was above 90% in the visible light spectrum range. Investigation into the thickness-dependence of the AZO films revealed that the crystallinity was improved with increasing thickness and decreasing surface roughness, accompanied with a decrease in the film resistivity.     

Physical properties of hydrogenated Al-doped ZnO thin layer treated by atmospheric plasma with oxygen gas

Hydrogenated Al-doped ZnO (H:AZO) thin films were deposited on glass substrates at room temperature by radio-frequency magnetron sputtering at various hydrogen flow rates. The addition of hydrogen improved the resistivity of the H:AZO films significantly. A thin insulating layer was produced on H:AZO films by atmospheric pressure plasma with Ar/O₂ reactive gas. The resistivity degenerated and the optical band gap of the oxygen plasma-treated H:AZO films decreased from 3.7 eV to 3.4 eV. This was attributed to a decrease in the hydrogen concentration at the film surface according to elemental depth analysis.     

Cu(In,Ga)Se2 films prepared by sputtering with a chalcopyrite Cu(In,Ga)Se2 quaternary alloy and In targets

This study reports the successful preparation of Cu(In,Ga)Se₂ (CIGS) thin film solar cells by magnetron sputtering with a chalcopyrite CIGS quaternary alloy target. Bi-layer Mo films were deposited onto soda lime glass. A CIGS quaternary alloy target was used in combination with a stack indium target for compensating the loss of indium during annealing process. A one-stage annealing process was performed to form CIGS chalcopyrite phase. Experimental results show that the optimal adhesion strength, residual stress, and resistivity were obtained at a thickness ratio of 67% of bi-layer Mo films and a working pressure of 0.13 Pa. The CIGS precursor was layered through selenization at 798 K for 20 min. The stoichiometry ratios of the CIGS film were Cu/(In + Ga) = 0.91 and Ga/(In + Ga) = 0.23, which approached the device-quality stoichiometry ratio (Cu/(In + Ga) <0.95, and Ga/(In + Ga) <0.3). The resistivity of the sample was 11.8 Ωcm, with a carrier concentration of 3.6 × 10¹⁷ cm⁻³ and mobility of 1.45 cm²V⁻¹s⁻¹. The resulting film exhibited p-type conductivity.     

Influences of film composition and annealing on the mechanical and electrical properties of W–Mo thin films

In this article, the mechanical and electrical characteristics of co-sputtered W–Mo thin films investigated for the application to microelectromechanical systems are described. W–Mo thin films with various compositions were deposited by co-sputtering onto a cover glass and silicon oxide (SiO _x ) film-coated Si wafer. The internal stress measured by Newton-ring method depended on film composition and Ar pressure, but were independent on annealing at 623 K. The hardness gradually decreased with an increase in Ar pressure, whereas the effective Young’s modulus stayed constant throughout Ar pressures ranging from 0.2 to 0.4 Pa. Both the mechanical properties showed no dependences of film composition and annealing. The resistivity was proportional to Ar pressure, but was not related to film composition. Annealing slightly affected the resistivity. Auger spectroscopy clarified that, by annealing, an oxide layer of approximately 10 nm thick was produced on the top surface, but film composition did not change. From the experimental results obtained, annealing at 623 K did not affect the mechanical and electrical properties of W–Mo films. This indicates that the co-sputtered film is very stable at temperatures ranging from RT to 623 K. By controlling Ar pressure, stress-free W–Mo films with superior mechanical characteristics and low resistivity can be produced regardless of film composition.     

Preparation of ITO thin films applied in nanocrystalline silicon solar cells

ITO thin films were prepared by changing the experimental parameters including gas flow ratio, sputtering pressure and sputtering time in DC magnetron sputtering equipment. The stable experimental parameters of Ar flow at 70 sccm, O₂ flow at 2.5 sccm ∼ 3.0 sccm, sputtering pressure around 0.5 Pa, and sputtering time of 80 s were obtained. Under these parameters, we had achieved the ITO thin films with low resistivity (<4 × 10⁻⁴ Ω ∙ cm) and high average transmissivity (95.48%, 350 nm ∼ 1100 nm). These ITO thin films were applied in nanocrystalline silicon solar cells as top transparent conductive layer. The solar cell test result showed that the open circuit voltage (Voc) was up to 534.9 mV and the short circuit current density (Jsc) was 21.56 mA/cm².     

Structural and electrical properties of Al doped ZnO thin films deposited at room temperature on poly(vinilidene fluoride) substrates

Transparent, conducting, Al-doped ZnO films have been deposited, by dc and pulsed dc magnetron sputtering, on glass and electroactive polymer (poly(vinylidene fluoride)–PVDF) substrates. Samples have been prepared at room temperature varying the argon sputtering pressure, after optimizing other processing conditions. All ZnO:Al films are polycrystalline and preferentially oriented along the [002] axis. Electrical resistivity around 3.3 × 10^− 3 Ω cm and optical transmittance of ~ 85% at 550 nm have been obtained for AZOY films deposited on glass, while a resistivity of 1.7 × 10^− 2 Ω cm and transmittance of ~ 70% at 550 nm have been attained in similar coatings on PVDF. One of the main parameters affecting film resistivity seems to be the roughness of the substrate.     

Enhancement of the crystalline quality of reactively sputtered yttria-stabilized zirconia by oxidation of the metallic target surface

Yttria-stabilized zirconia (YSZ) thin films were fabricated on glass substrates by direct current magnetron reactive sputtering. We found out that the crystalline quality of the YSZ film was improved by an oxidation process of the metallic target surface prior to the sputtering deposition process. It is speculated that, at the initial stage of the sputtering, the sputtered particles from the oxidized target surface form a layer with higher degree of crystallization on the substrate, compared with those particles from the metallic target surface. This crystallized layer can enhance the crystallization of the film deposited subsequently. Other sputtering conditions such as sputtering pressure, oxygen flow rate, substrate temperature, and Y₂O₃ content in the film were investigated, for optimization of the crystalline quality of the deposited YSZ film.