Optoelectronic properties of SnO_2 thin films sprayed at different deposition times

This article presents the elaboration of tin oxide(SnO_2) thin films on glass substrates by using a home-made spray pyrolysis system. Effects of film thickness on the structural, optical, and electrical film properties are investigated. The films are characterized by several techniques such as x-ray diffraction(XRD), atomic force microscopy(AFM), ultravioletvisible(UV–Vis) transmission, and four-probe point measurements, and the results suggest that the prepared films are uniform and well adherent to the substrates. X-ray diffraction(XRD) patterns show that SnO_2 film is of polycrystal with cassiterite tetragonal crystal structure and a preferential orientation along the(110) plane. The calculated grain sizes are in a range from 32.93 nm to 56.88 nm. Optical transmittance spectra of the films show that their high transparency average transmittances are greater than 65% in the visible region. The optical gaps of SnO_2 thin films are found to be in a range of 3.64 e V–3.94 e V. Figures of merit for SnO_2 thin films reveal that their maximum value is about 1.15 × 10-4-1?atλ = 550 nm. Moreover, the measured electrical resistivity at room temperature is on the order of 10-2?·cm.     

Nanomechanical characteristics of SnO2:F thin films deposited by chemical vapor deposition

The nanoindentation characterizations and mechanical properties of fluorine-doped tin oxide (SnO₂:F) films deposited on glass substrates, using chemical vapor deposition (CVD) method, were studied, which included the effects of the indentation loads, the loading time and the hold time on the thin film. The surface roughness, fractal dimension and frictional coefficient were also studied by varying the freon flow rates. X-ray diffraction (XRD), atomic force microscopy (AFM) and frictional force microscopy (FFM) were used to analyze the morphology of the microstructure. The results showed that crystalline structure of the film had a high intensity (1 1 0) peak orientation, especially at a low freon flow rate. According to the nanoindentation records, the Young's modulus ranged from 62.4 to 75.1 GPa and the hardness ranged from 5.1 to 9.9 GPa at a freon flow rate of 8000 sccm. The changes in measured properties were due to changing loading rate.     

Physical properties of ZnS thin films prepared by chemical bath deposition

Zinc sulphide thin films are deposited on SnO₂/glass using the chemical bath deposition technique. X-ray diffraction and atomic force microscopy are used to characterize the structure of the films; the surface composition of the films is studied by Auger electrons spectroscopy, the work function and the photovoltage are investigated by the Kelvin method. Using these techniques, we specify the effect of pH solution and heat treatment in vacuum at 500 °C. The cubic structure corresponding to the (1 1 1) planes of β-ZnS is obtained for pH equal to 10. The work function (Φ_material − Φ_probe) for ZnS deposited at pH 10 is equal to −152 meV. Annealing at 500 °C increases Φ_m (by about 43 meV) and induces the formation of a negative surface barrier. In all cases, Auger spectra indicate that the surface composition of zinc sulphide thin films exhibits the presence of the constituent elements Zn and S as well as C and O as impurity elements.     

Deposition of MgO films by pulsed mid-frequency magnetron sputtering

MgO films were deposited by pulsed mid-frequency magnetron sputtering from metallic targets in the mixture of Ar and O₂ gas. The surface morphology, crystalline structure, and optical properties were characterized by using atomic force microscopy (AFM), X-ray diffraction (XRD), and spectroscopic ellipsometry, respectively. The secondary electron emission coefficients of MgO films were measured by using a self-made apparatus in He gas. A pronounced hysteresis phenomenon of target voltage, current, and deposition rate with increasing and decreasing O₂ flow rate was observed. The structure of films deposited at a metallic mode changes from Mg phase to the mixed Mg and MgO phase, and the films have a very rough surface. All the films deposited at oxide mode have high transparency and smooth surface, and show (2 2 0) preferred orientation growth. The refractive index and extinction coefficient at a wavelength of 670 nm for MgO films deposited at oxide mode with a O₂ flow rate of 3 sccm are 1.698 and 1.16×10⁻⁴, respectively. The secondary emission coefficient at a E/p of 57.8 V/(cm Torr) for MgO films deposited at a O₂ flow rate of 3 sccm is 0.16, which is higher than that of MgO films deposited by e-beam evaporation.     

Surface structure and composition of flat titanium thin films as a function of film thickness and evaporation rate

To correlate flat titanium film surface properties with deposition parameters, titanium flat thin films were systematically deposited on glass substrates with various thicknesses and evaporation rates by electron-beam evaporation. The chemical compositions, crystal structure, surface topographies as well as wettability were investigated by using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM) and water contact angle measurement, respectively. The films consisted mainly of TiO₂. Small percentages of Ti₂O₃ and metallic Ti were also found at the film surface using high-resolution XPS analysis. Quantitative XPS showed little differences regarding elemental compositions among different groups of films. The films were obtained by varying the deposition rate and the film thickness, respectively. XRD data showed consistent reflection patterns of the different titanium samples deposited using different film thicknesses. Without exception measurements of all samples exhibited contact angles of 80° ± 5°. Quantitative AFM characterization demonstrated good correlation tendency between surface roughness and film thickness or evaporation rate, respectively. It is important to notice that titanium films with different sizes of grains on their surfaces but having the same chemistry and film bulk structure can be obtained in a controllable way. By increasing the film thickness and evaporation rate, the surface roughness increased. The surface morphology and grain size growth displayed a corresponding trend. Therefore, the control of these parameters allows us to prepare titanium films with desired surface properties in a controllable and reproducible way for further biological investigations of these materials.     

Thickness dependence of microstructures in La0.9Sr0.1MnO3 thin films grown on exact-cut and miscut SrTiO3 substrates

The thickness dependence of microstructures of La_0.9Sr_0.1MnO₃ (LSMO) thin films grown on exact-cut and miscut SrTiO₃ (STO) substrates, respectively, was investigated by high-angle X-ray diffraction (HXRD), X-ray small-angle reflection (XSAR), X-ray reciprocal space mapping and atomic force microscopy (AFM). Results show that the LSMO films are in pseudocubic structure and are highly epitaxial [0 0 1]-oriented growth on the (0 0 1) STO substrates. The crystalline quality of the LSMO film is improved with thickness. The epitaxial relationship between the LSMO films and the STO substrates is [0 0 1]_LSMO[0 0 1]_EXACT-STO, and the LSMO films have a slight mosaic structure along the q_x direction for the samples grown on the exact-cut STO substrates. However, an oriented angle of about 0.24° exists between [0 0 1]_LSMO and [0 0 1]_MISCUT-STO, and the LSMO films have a mosaic structure along the q_z direction for that grown on the miscut STO substrates. The mosaic structure of both groups of the samples tends to reduce with thickness. The diffraction intensity of the (0 0 4) peaks increases with thickness of the LSMO film. The XSAR and AFM observations show that for both groups, the interface is sharp and the surface is rather smooth. The mechanism was discussed briefly.     

不同Sb含量p-SnO2薄膜的制备和特性

采用化学气相沉积方法, 利用Sb₂O₃/SnO作为源材料, 在蓝宝石衬底上制备出不同Sb掺杂量的SnO₂薄膜, 并在此基础上制作出p-SnO₂:Sb/n-SnO₂同质p-n 结器件. 研究表明, 随着Sb含量的增加, 样品表面变得平滑, 晶粒尺寸逐渐增大, 且晶体质量有所改善, 发现少量Sb的掺入可以起到表面活化剂的作用. Hall测量结果证实适量Sb的掺杂可以使SnO₂呈现p型导电特性, 当Sb₂O₃/SnO的质量比为1:5时, 其电学参数为最佳值. 此外, p-SnO₂:Sb/n-SnO₂同质p-n结器件展现出良好的整流特性, 其正向开启电压为3.4 V.     

High pyroelectric Ba0.65Sr0.35TiO3 thin films with Ba0.65Sr0.35RuO3 seeding-layer for monolithic ferroelectric bolometer

Ba_0.65Sr_0.35TiO₃ (BST) thin films were deposited by RF sputtering with a very thin Ba_0.65Sr_0.35RuO₃ (BSR) seeding-layer on Pt/Ti/SiO₂/Si substrate. The crystallization of BST thin films and the surface morphology of BSR seeding-layer were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. XRD patterns show that the BSR seeding-layer affected the orientation of BST thin film, which is highly a-axis textured. It was also found that the BSR seeding-layer had a marked influence on the dielectric properties of BST thin films. Comparing with BST thin films directly deposited on Pt electrode, the dielectric relaxation can be suppressed and dielectric constant increased due to a possible reduction of interface oxygen vacancies at BST/BSR interface. Moreover, J–V measurement indicates that the leakage current density of BST thin films on BSR seeding-layer were greatly reduced compared with that of BST thin films directly on Pt electrodes. The pyroelectric coefficient of BST thin films with BSR seeding-layer is 7.57 × 10⁻⁷ C cm⁻² K⁻¹ at 6 V/μm at room temperature (RT). Our results reveal that high pyroelectric property of BST thin film could be achievable using BSR seeding-layer as a special buffer.     

Growth, structural, and magnetic properties of iron nitride thin films deposited by dc magnetron sputtering

FeN thin films were deposited on glass substrates by dc magnetron sputtering at different Ar/N₂ discharges. The composition, structure and the surface morphology of the films were characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and atomic force microscopy (AFM). Films deposited at different nitrogen pressures exhibited different structures with different nitrogen contents, and the surface roughness depended on the mechanism of the film growth. Saturation magnetization and coercivity of all films were determined using superconducting quantum interference device, which showed that if N₂/(Ar+N₂) flow ratio was equal to or larger than 30% the nonmagnetic single-phase γ″-FeN appeared. If N₂/(Ar+N₂) flow ratio was less than 10%, the films consisted of the mixed phases of FeN_0.056 and γ′-Fe₁₆N₂, whose saturation magnetizations were larger than that of -Fe. If N₂/(Ar+N₂) flow ratio was 10%, the phases of γ′-Fe₄N and -Fe₃N appeared, whose saturation magnetizations were lower than that of -Fe.     

Growth of β-MnO2 films on TiO2(110) by oxygen plasma assisted molecular beam epitaxy

We have used oxygen plasma assisted MBE to grow epitaxial films of pyrolusite (β-MnO₂) on TiO₂(110) for thicknesses of one to six bilayers (BL). We define a bilayer to be a layer of Mn and lattice O and an adjacent layer of bridging O within the rutile structure. The resulting surfaces have been characterized in situ by reflection high-energy electron diffraction, low-energy electron diffraction, X-ray photoelectron spectroscopy and diffraction, and atomic force microscopy. Well-ordered, pseudomorphic overlayers form for substrate temperatures between 400 and 500°C. Mn–Ti intermixing occurs over the time scale of film growth (1 BL/min) for substrate temperatures in excess of 500°C. Films grown at 400–500°C exhibit island growth, whereas intermixed films grown at temperatures of 500–600°C are more laminar. 1 BL films grown at 450°C are more laminar than multilayer films grown at the same temperature, and form a well-ordered surface cation layer of Mn on the rutile structure with at most 10% indiffusion to the second cation layer.     

Investigations on non-stoichiometric zirconium nitrides

Non-stoichiometric zirconium nitride thin films were prepared by reactive dc magnetron sputtering. Structural, optical and electrical properties were investigated with respect to nitrogen gas flow. The film characterization was obtained through various techniques: Rutherford back scattering (RBS), X-ray diffraction (XRD), reflectometry and a four probe method. We found that the deposition rate decreases while the nitrogen flow increases. Also it was shown that a stoichiometric compound (ZrN) is formed at a 4 sccm nitrogen flow. It has a rock-salt structure and presents a minimum of resistivity and a gold-like color. As nitrogen flow increases, films become more and more amorphous, semi-transparent and electrically resistive. Furthermore, at a nitrogen flow of 9 sccm, the nitrogen to zirconium atomic concentration ratio is near 1.33 and the film exhibits properties close to those of a Zr₃N₄ phase.     

Formation of high quality gallium nitride thin films on Ga-diffused Si(1 1 1) substrate

High quality gallium nitride thin films have been successfully grown on the Ga-diffused Si(1 1 1) substrates through ammoniating Ga₂O₃ thin films deposited by r.f. magnetron sputtering. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), atomic force microscope (AFM) and photoluminescence (PL) were used to characterize the synthesized samples. The analyses reveal that the formed films are high quality polycrystalline hexagonal gallium nitride. The as-formed GaN films show a flat surface topography with RMS roughness varied from 29 to 48 Å. The strong near-band-edge-emission peak around 368 nm was observed at room temperature. This is a novel method to fabricate GaN thin films based on the direct reaction between Ga₂O₃ and NH₃ on the Ga-diffused Si(1 1 1) substrates.     

Structural, mechanical and hydrophobic properties of fluorine-doped diamond-like carbon films synthesized by plasma immersion ion implantation and deposition (PIII–D)

Fluorine-doped diamond-like carbon (a-C:F) films with different fluorine content were fabricated on Si wafer by plasma immersion ion implantation and deposition (PIII–D). Film composition and structure were characterized by X-ray photoelectron spectroscopy (XPS) and Raman scattering spectroscopy. Surface morphology and roughness were analyzed by atomic force microscopy (AFM). Hardness and scratch resistance were measured by nano-indentation and nano-scratch, respectively. Water contact angles were measured by sessile drop method. With the increase of the CF₄ flux, fluorine content was gradually increased to the film. Raman spectra indicates that these films have a diamond-like structure. The addition of fluorine to diamond-like carbon films had a critical influence on the film properties. The film surface becomes more smoother due to the etching behavior of F⁺. Hardness was significantly reduced, while the scratch resistance results show that these films have a fairly good adhesion to the substrate. Evident improvements of the hydrophobicity have been made to these films, with contact angles of double-stilled water approaching that of polytetrafluoroethylene (PTFE). Our study suggests that broad application regions of the fluorine-doped amorphous carbon films with diamond-like structure, synthesized by PIII–D, can be extended by combining the non-wetting properties and mechanical properties which are far superior to those of PTFE.     

基于FTO/VO2/FTO结构的VO2薄膜电压诱导相变光调制特性

采用直流磁控溅射和后退火工艺在掺氟的SnO₂(FTO)导电玻璃衬底上制备VO₂薄膜, 研究了不同退火时间和不同比例的氮氧气氛对VO₂薄膜性能的影响, 对VO₂薄膜的结晶取向、表面形貌、表面元素的相对含量和透过率随波长变化进行了测试分析, 结果表明在最佳工艺条件下制备得到了组分相对单一的VO₂薄膜. 基于FTO/VO₂/FTO结构在VO₂薄膜两侧的透明导电膜上施加电压并达到阈值电压时, 观察到了明显的电流突变. 当接触面积为3 mm×3 mm时, 阈值电压为1.7 V, 阈值电压随接触面积的增大而增大. 与不加电压的情况相比, FTO/VO₂/FTO结构在电压作用下高低温的红外透过率差值可达28%, 经反复施加电压, 该结构仍保持性能稳定, 具有较强的电致调控能力.     

YMnO_3薄膜的铁电行为及其纳米尺度铁电畴的研究

六方YMnO_3是一种特殊的多铁性材料,因其具有介电常数低、单一极化轴、无挥发性元素等特点,在磁电领域具有独特的优势,但目前关于YMnO_3薄膜的铁电性特别是畴结构的研究相对较少.本文采用溶胶-凝胶法在Si(100)基片上制备了多铁性YMnO_3薄膜,利用掠入射X-射线衍射、原子力显微镜对薄膜的结构及表面形貌进行了分析,用压力显微镜(PFM)技术研究了纳米尺度畴结构及微区电滞行为,并通过I-V,P-E曲线进一步研究了薄膜的漏电流和宏观电滞行为.结果表明,该薄膜为六方钙钛矿结构,YMnO_3晶粒大小均匀并且结晶性较好,薄膜表面粗糙度为7.209 nm.PFM图显示出清晰的电畴结构,结合典型的微区振幅蝴蝶曲线和相位电滞回线,证实该YMnO_3薄膜具有较好的铁电性.由于受内建电场的作用,振幅曲线和相位曲线都向正向偏移,表现出非对称特征.该薄膜的漏电流密度低于10~(-6)A·cm~(-2),因而其电滞回线基本能够达到饱和.     

Optical properties and electronic transitions of SnO2 thin films by reflection electron energy loss spectroscopy

Optical properties of SnO₂ thin films in the 4–60 eV energy range are determined by reflection electron energy loss spectroscopy. Bulk and surface electron loss functions, real and imaginary parts of the dielectric function, refraction index, extinction and absorption coefficients are obtained from the analysis of the electron energy loss spectra. Electronic transitions are identified through the interpretation of the optical data. The samples (250–500 nm thick) were produced by ion beam-induced chemical vapor deposition. It is found that the compacity of the SnO₂ thin films affects their optical properties and therefore the relative intensity of the observed electronic transitions. The advantages of this method to determine optical properties of thin films are discussed. Inelastic mean free paths (6.2, 17 and 41 Å for electrons traveling in SnO₂ with kinetic energies of 300, 800 and 2000 eV, respectively) are obtained from the corresponding inelastic electron scattering cross-sections.     

溶胶-凝胶-蒸镀法制备高性能FTO薄膜

以SnCl_4·5H_2O为锡源,SnF_2为氟源,采用溶胶-凝胶-蒸镀法制备F掺杂的SnO_2透明导电氧化物薄膜(FTO薄膜).通过正交实验研究确定最佳反应温度、反应时间和蒸镀温度等制备条件.主要研究元素F的掺杂和膜的结构对FTO薄膜性能的影响,并采用傅里叶变换红外光谱仪、热重-差热分析、X射线衍射、高分辨透射电子显微镜和扫描电子显微镜等进行样品的性能表征.研究结果表明,当反应温度50?C、反应时间5 h、烧结(蒸镀)温度600?C、镀膜次数1次、而F/Sn=14 mol%时,FTO薄膜性能指数ΦTC最大,综合光电性能最优,表面电阻为14.7?·cm-1,平均透光率为74.4%.FTO薄膜内颗粒的平均粒径为20 nm,呈四方金红石型结构,F的掺入替代了部分的O,形成了SnO_(2-x)F_x晶体结构.F的掺杂量是影响FTO薄膜的主要因素,F过多或过少均不利于SnO_(2-x)F_x晶体的生长;FTO薄膜的结构、颗粒形状、大小等三维信息也是影响薄膜性能的因素,主要表现为分形维数越小,薄膜表面越平整,势垒越低,导电性能越好.     

Ni/SnO_2复合薄膜的制备与光电性能

采用旋涂法将溶胶-凝胶法制备的Ni/Sn O2凝胶在玻璃基底上镀膜,得到了Ni/Sn O2复合薄膜,探讨了镍掺杂量、煅烧温度对薄膜结构和形貌的影响。通过X射线衍射、红外光谱、扫描电子显微镜等测试手段对Ni/Sn O2复合膜的结构和形貌进行表征。结果显示,500℃下煅烧的薄膜样品的结晶度较高,粒径小,颗粒分布均匀。用紫外-可见分光光度计和四探针电阻仪对其进行光学、电学性能测试,结果显示:适量的Ni掺杂可以提高Sn O2薄膜在近紫外光区的吸收,Ni/Sn O2薄膜在近紫外光区的吸收随着Ni2+掺杂摩尔分数从5%增加到10%而逐渐减小。当Ni2+掺杂摩尔分数为6%时,Ni/Sn O2复合薄膜的导电性能最好。     

Picosecond nonlinear optical response of Ba0.5Sr0.5TiO3 thin films fabricated by pulsed laser deposition

Well-crystallized Ba_0.5Sr_0.5TiO₃ thin films with good surface morphology were prepared on MgO(1 0 0) substrates by pulsed laser deposition technique at a deposition temperature of 800 °C under the oxygen pressure of 2 × 10⁻³ Pa. X-ray diffraction and atomic force microscopy were used to characterize the films. The full width at half maximum of the (0 0 2) Ba_0.5Sr_0.5TiO₃ rocking curve and the root-mean-square surface roughness within the 5 μm × 5 μm area were 0.542° and 0.555 nm, respectively. The nonlinear optical properties of the films were determined by a single beam Z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that Ba_0.5Sr_0.5TiO₃ thin films exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 5.04 × 10⁻⁶ cm²/kW and β = 3.59 × 10⁻⁶ (m/W), respectively.     

Structural, optical and electrical studies on pulse electrodeposited CdIn2S4 thin films

CdIn₂S₄ thin films were prepared by pulse electrodeposition technique over F:SnO₂ glass and stainless steel substrates in galvanostatic mode from an aqueous acidic bath containing CdSO₄, InCl₃ and Na₂S₂O₃. The growth kinetics of the film has been studied and the deposition parameters such as electrolyte bath concentration, bath temperature, time of deposition, deposition current and pH of the bath are optimized. X-ray diffraction (XRD) analysis of the as deposited and annealed films shows polycrystalline nature. Energy dispersive analysis by X-ray (EDAX) confirms nearly stoichiometric CdIn₂S₄ nature of the film. Scanning electron microscope (SEM) studies show that, the deposited films are well adherent and grains are uniformly distributed over the surface of the substrate. The optical transmission spectra show a direct band gap of 2.16 eV. Conductivity measurements have been carried out at different temperatures and electrical parameters such as activation energy, trapped energy state and barrier heights etc. have been determined.