沉积时间对聚醚醚酮表面类金刚石薄膜的结构和性能的影响

采用直流磁控溅射技术在聚醚醚酮(PEEK)表面制备不同厚度的类金刚石(DLC)薄膜,研究了沉积时间对其表/界面结构、组分、疏水、力学和光透过性能的影响。结果表明,在平均沉积速率为5.71 nm/min的条件下,随着沉积时间的延长DLC薄膜的厚度线性增大、碳原子的致密性提高、界面互锁结构增强,而界面结合强度逐渐降低。沉积时间≤15 min时,基体结构的影响使拟合计算出的I_D/I_G值为0.23~0.25和sp²/sp³比值较小(0.58~0.74);沉积时间>15 min时基体的影响较小,I_D/I_G值突增大至0.81,sp²/sp³值也比较大(0.96~1.12)。沉积时间的延长使PEEK基体的温度逐渐升高,使膜内的sp²/sp³值逐渐增大。薄膜表面的氧含量先降低然后趋于平缓,部分C=O转化为C-O。随着沉积时间的延长,PEEK/DLC复合薄膜的硬度、弹性模量及防紫外线和阻隔红外线性能都逐渐提高,其表面粗糙度和疏水性的变化趋势是先提高后降低。沉积时间为32 min的薄膜,其表面粗糙度和水接触角达到最大值,分别为495 nm和108.29°。     

Characterization of ion-beam-deposited diamond-like carbon films

Diamond-like carbon (DLC) films are excellent prospects for a wide range of high-technology applications but their precise structure and properties are not well understood. The purpose of the present work was to use several complementary techniques to characterize the nature, structure and microstructure of DLC films. Thin DLC films were deposited on various substrates in the presence of a Si interlayer (500 Å thick) using CH₄ ion-beam deposition at an acceleration energy of 750 eV and a current density of about 2.5 mA cm⁻². The Si interlayer was deposited by either e-beam evaporation or Si evaporation enhanced by Ar⁺ beam bombardment (1 keV). The produced DLC films were featureless, very smooth and of high hardness (2900–3300 kg mm⁻²). Auger electron spectroscopy and electron diffraction showed that the films were mainly amorphous. Their microstracture was characterized by a three-dimensional network structure with a medium-range order of about 25 nm. Fourier transform infrared and Raman spectroscopies showed that the films were mainly composed of sp³ and sp² carbon-bonded hydrogen. The sp³/sp² ratio varied from 3.2 to 4.1 and was found to depend on the nature of the Si bond layer. The results showed that the nucleation of the diamondlike structure was promoted on the Si interlayer that was deposited under Ar⁺ beam bombardment. This effect can be explained by the higher surface roughness produced in this interlayer as suggested by the reflectivity measurements. Spectroscopic ellipsometry revealed that the films had an optical band gap between 1.56–1.64 eV. The present results are consistent with previous proposals suggesting that the DLC structure is composed of small graphitelike clusters (involving fused six-fold rings) that are interconnected by sp³-bonded carbon.     

Catalytic CVD growth and properties of a-C:H and a-C:N

Hydrogenated amorphous carbon (a-C:H) and nitrided amorphous carbon (a-C:N) films have been synthesized on quartz substrates at a substrate temperature of 700 °C using a catalytic chemical vapor deposition (Cat-CVD) method. Raman spectra of a-C:H films showed two principal bands, the G-band at 1600 cm⁻¹ and the D-band at 1350 cm⁻¹. Those of a-C:N films showed similar spectra, with a G′ band at 1640 cm⁻¹, the peak energy of which is higher than that of the G-band in a-C:H. The intensity ratio /I_D, which is a measure of the degree of order in a-C:H, decreased for a-C:H with increasing CH₄/H₂ gas-flow ratio. On the contrary, the /I_D ratio increased with increasing CH₄/H₂ gas-flow ratio.     

Implantation effect of diamond-like carbon films by 110 keV nitrogen ions

Diamond-like carbon films, grown on microscope slides by a dual-ion beam sputtering system, were implanted by 110 keV N⁺ under the doses of 1 × 10¹⁵, 1 × 10¹⁶ and 1 × 10¹⁷ions cm⁻² respectively. The implantation induced changes in electrical resistivity of the films and in infrared (IR) transmittance of the specimens were investigated as a function of implantation dose. The structural changes of the films were also studied using IR spectroscopy and Raman spectroscopy. It was observed that, with the increase of implantation dose, the diamond-like carbon films display two different stages in electrical and optical behaviours. The first is the increase of both the film resistivity and the IR transmittance of specimen at the dose of 1 × 10¹⁵ ions cm⁻² which, we consider, is attributed to the implantation-induced increase sp³ C---H bonds. However, when the doses are higher than 1 × 10¹⁵ ions cm⁻², the film resistivity and the IR transmittance of specimen decrea significantly and the decrease rates at dose range of 1×10¹⁶ to 1×10¹⁷ ions cm⁻² are smaller than those between 1×10¹⁵ and 1 × 10¹⁶ ions cm⁻². We conclude that the significant reductions of the two parameters at high doses are caused by the decreases of bond-angle disorder and of sp³ C---H bonds, the increases of sp² C---C bonds dominated the crystallite size and/or number and also the sp² C---H bonds. The smaller decrease rates at a dose range of 1 × 10¹⁶ to 1 × 10¹⁷ ions cm⁻² may be caused by further recombination of some retained hydrogen atoms to carbon atoms.     

Low temperature internal friction of diamond-like carbon films

We have studied the internal friction of amorphous diamond-like carbon films prepared by pulsed-laser deposition from 0.4 to 300 K. The low temperature internal friction below 10 K is dominated by the atomic tunneling states for amorphous solids, which is a measure of structure disorder. We have tried to vary the content of sp³ carbon atoms versus sp² ones by changing laser fleunce, by doping with N and Ar, and by annealing at 500 °C for 20 min. Our results show that the internal friction varies about one order of magnitude from 2×10⁻⁵ to 2×10⁻⁴, and its value is higher with higher sp³ content when the film quality is generally considered superior. However, it is known that as-deposited diamond-like carbon films with high sp³ content are heavily stressed. Annealing and doping are used to release the stress. We conclude that in addition to tetrahedral bonding, low stress is also important in reducing structure disorder associated with the low energy tunneling states in amorphous solids.     

Electrical properties of reactively sputtered carbon nitride films

Carbon nitride films with β-C₃N₄ crystals of 200 nm grain size were grown on Si (1 0 0) substrates using magnetron sputtering. These films were characterized by transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Carbon nitride films had low surface roughness. Maximum N/C ratio of 0.5 was achieved in the films. Chemical bonds of sp, sp² and sp³ coexisted in the films. The fraction of each bond was related to the deposition conditions. The resistivities of the films were measured, which ranged from 1×10³ to 1×10⁷ Ω cm. The measured resistivity results indicated that the carbon nitride films had semiconductive properties. The resistivity largely depended on the sp³/sp² ratio. Effects of N₂ fraction, target current and substrate bias were investigated. All these deposition parameters had influence on the chemical bonds of the films, and on the resistivities too. High sp³/sp² ratio resulted in high resistivity.     

Structural, electrical, and optical studies on rapid thermally processed ferroelectric BaTiO3 thin films prepared by metallo-organic solution deposition technique

Polycrystalline BaTiO₃ thin films having the perovskite structure were successfully produced on platinum coated silicon, bare silicon, and fused quartz substrate by the combination of the metallo-organic solution deposition technique and post-deposition rapid thermal annealing treatment. The films exhibited good structural, electrical, and optical properties. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) and metal-ferroelectric-semiconductor (MFS) capacitors. The typical measured small signal dielectric constant and dissipation factor at a frequency of 100 kHz were 255 and 0.025, respectively, and the remanent polarization and coercive field were 2.2 μC cm⁻² and 25 kV cm⁻¹, respectively. The resistivity was found to be in the range 10¹⁰–10¹² Ω·cm, up to an applied electric field of 100 kV cm⁻¹, for films annealed in the temperature range 550–700 °C. The films deposited on bare silicon substrates exhibited good film/substrate interface characteristics. The films deposited on fused quartz were highly transparent. An optical band gap of 3.5 eV and a refractive index of 2.05 (measured at 550 nm) was obtained for polycrystalline BaTiO₃ thin film on fused quartz substrate. The optical dispersion behavior of BaTiO₃ thin films was found to fit the Sellmeir dispersion formula well.     

The effect of thermal annealing on aerosol-gel deposited SiO2 films: a FTIR deconvolution study

Aerosol-gel process has been used for the deposition of SiO₂ thin films. Layers were deposited from a solution with pH = 3.5 and water to TEOS molar ratio (rw) 2.2 and then treated at various temperatures ranging from room temperature to 700°C. As-prepared thin films have been characterized by FTIR spectroscopy. Spectra were acquired in transmission at 65° angle of incidence or at perpendicular incidence. Characteristic absorption bands of the SiO₂ sol-gel system have been studied with respect to the posttreatment temperature. Bands located at 1250–1000 cm⁻¹ and around 960 cm⁻¹ have been deconvoluted in several peaks. The origin and temperature dependence of these peaks are discussed.     

电弧离子镀CrAlN-DLC硬质复合薄膜的成分、结构与性能

为了改善CrAlN薄膜的摩擦性能, 本研究在增强磁过滤脉冲偏压电弧离子镀设备上, 用分离靶弧流调控技术在硬质合金基体上分别制备了不同成分的CrAlN-DLC硬质复合薄膜, 并采用不同手段表征了薄膜的表面形貌、成分、相结构以及力学和摩擦性能。结果表明, 不同成分薄膜表面均平整致密, 膜厚均在1.05 μm左右。随着靶弧流比I_C/I_CrAl的升高, 薄膜中碳的原子分数由33.1%升至74.6%。薄膜的相结构主要由晶体相和非晶相复合组成, 其晶体相主要为c-(Cr,Al)N相, 且随着碳含量增大晶体相减少、晶粒尺寸减小, 其非晶相主要为DLC, 其中sp²/sp³的比值随碳含量增大而减小。相应地, 薄膜的硬度随着碳含量增大而提高, 当碳的原子分数为74.6%时, 达到最大值(26.2±1.4) GPa, 且该成分点处薄膜摩擦系数也降至最小值0.107, 磨损率仅为3.3×10^-9 mm³/Nm。综合而言, 当非晶DLC相最多时, CrAlN-DLC复合薄膜的综合性能达到最佳, 较之CrAlN薄膜, 摩擦性能显著提高。     

Optically active Er–Yb codoped Y2O3 films produced by pulsed laser deposition

Optically active Er³⁺:Yb³⁺ codoped Y₂O₃ films have been produced on c-cut sapphire substrates by pulsed laser deposition from ceramic Er:Yb:Y₂O₃ targets having different rare-earth concentrations. Stoichiometic films with very high rare-earth concentrations (up to 5.5 × 10²¹ at cm^− 3) have been achieved by using a low oxygen pressure (1 Pa) during deposition whereas higher pressures lead to films having excess of oxygen. The crystalline structure of such stoichiometric films was found to worsen the thicker the films are. Their luminescence at 1.53 μm and up-conversion effects have been studied by pumping the Yb³⁺ at 0.974 μm. The highest lifetime value (up to 4.6 ms) is achieved in films having Er concentrations of ≈ 3.5 × 10²⁰ at cm^− 3 and total rare-earth concentration ≈ 1.8 × 10²¹ at cm^− 3. All the stoichiometric films irrespective of their rare-earth concentration or crystalline quality have shown no significant up-conversion.     

Electrical properties of evaporated polycrystalline Ge thin-films

Electrical properties of Ge thin films evaporated on Si₃N₄ CVD-coated Si substrate were improved by introducing a heat treatment after the deposition of Ge films. Evaporation conditions were optimized by changing the substrate temperature and deposition rate, and then, heat treatment was performed. At substrate temperatures during the evaporation lower than 300 °C and higher than 400 °C, deposited films were amorphous and polycrystalline, respectively. At substrate temperatures lower than 400 °C, Ge films were evaporated without degrading the surface roughness. The Hall mobility of films evaporated at room temperature increased with increasing the substrate and heating temperature and showed about 400 cm² V⁻¹ s⁻¹ for the hole concentration of 4 × 10¹⁷ cm⁻³ at the heating temperature of 900 °C. This value was almost comparable to that of p-type Ge single crystal.     

Al2O3 formation on Si by catalytic chemical vapor deposition

Catalytic chemical vapor deposition (Cat-CVD) has been developed to deposit alumina (Al₂O₃) thin films on silicon (Si) crystals using N₂ bubbled tri-methyl aluminum [Al(CH₃)₃, TMA] and molecular oxygen (O₂) as source species and tungsten wires as a catalyzer. The catalyzer dissociated TMA at approximately 600 °C. The maximum deposition rate was 18 nm min⁻¹ at a catalyzer temperature of 1000 °C and substrate temperature of 800 °C. Metal oxide semiconductor (MOS) diodes were fabricated using gates composed of 32.5-nm-thick alumina film deposited at a substrate temperature of 400 °C. The capacitance measurements resulted in a relative dielectric constant of 7.4, fixed charge density of 1.74×10¹² cm⁻², small hysteresis voltage of 0.12 V, and very few interface trapping charges. The leakage current was 5.01×10⁻⁷ A cm⁻² at a gate bias of 1 V.     

A study on the formation and characteristics of the Si---O---C---H composite thin films with low dielectric constant for advanced semiconductor devices

The Si---O---C---H composite thin films were deposited on a p-type Si(100) substrate using bis-trimethylsilane (BTMSM) and O₂ mixture gases by an inductively coupled plasma chemical vapor deposition (ICPCVD). High density plasma of approximately 10¹² cm⁻³ is obtained at low pressure (<320 mtorr) with an RF power of approximately 300 W in the inductively coupled plasma source where the BTMSM and oxygen gases are greatly dissociated. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra show that the film has Si---CH₃ and O---H related bonds. The CH₃ groups formed the void in the film and the Si atoms in the annealed sample have different chemical states from those in the deposited sample. It means that the void is formed due to the removing of O---H related bonds during the annealing process. The relative dielectric constant of the annealed sample with the flow rate ratio O₂/BTMSM as 0.3 at 500°C for 30 min is approximately 2.5.     

Dielectric properties of AlN films prepared by laser-induced chemical vapour deposition

The dielectric properties and electrical conductivity of AlN films deposited by laser-induced chemical vapour deposition (LCVD) are studied for a range of growth conditions. The static dielectric constant is 8.0 ± 0.2 over the frequency range 10²−10⁷ Hz and breakdown electric fields better than 10⁶ V cm⁻¹ are found for all films grown at temperatures above 130°C. The resistivity of the films grown under optimum conditions (substrate temperature above 170°C, NH₃/TMA flow rate ratio greater than 300 and a deposition pressure of 1–2 Torr) is about 10¹⁴ Ω cm and two conduction mechanisms can be identified. At low fields, F < 5 × 10⁵ V cm⁻¹ and conductivity is ohmic with a temperature dependence showing a thermal activation energy of 50–100 meV, compatible with the presumed shallow donor-like states. At high fields, F > 1 × 10⁶ V cm⁻¹, a Poole-Frenkel (field-induced emission) process dominates, with electrons activated from traps at about 0.7–1.2 eV below the conduction band edge. A trap in this depth region is well-known in AlN. At fields between 4 and 7 × 10⁵ V cm⁻¹ both conduction paths contribute significantly. The degradation of properties under non-ideal growth conditions of low temperature or low precursor V/III ratio is described.     

Electrical characterization of CVD diamond thin films grown on silicon substrates

Diamond thin films grown on high resistivity, 100 oriented silicon substrates by the hot filament chemical vapor deposition (HFCVD) method have been characterized by four-point probe and current-voltage (through film) techniques. The resistivities of the as-grown, chemically etched and annealed samples lie in the range of 10² Ω cm to 10⁸ Ω cm. The Raman measurements on these samples indicate sp³ bonding with a sharp peak at 1332 cm⁻¹. The surface morphology as determined by scanning electron microscope shows polycrystalline films with (100) or (111) faceted structures with average grain size of ≈2.5 μm. The through film current-voltage characteristics obtained via indium contacts on these diamond films showed either rectifying or ohmic behavior. The difference in Schottky and ohmic behavior is explained on the basis of the high or low sheet resistivities measured by four-point probe technique. 5% methane to hydrogen concentration during film growth resulted in poor surface morphology, absence of sp³ bonds, and low resistivity.     

Quantitative analysis of tungsten, oxygen and carbon concentrations in the microcrystalline silicon films deposited by hot-wire CVD

In order for hot-wire chemical vapor deposition to compete with the conventional plasma-enhanced chemical vapor deposition technique for the deposition of microcrystalline silicon, a number of key scientific problems should be cleared up. Among these points, the concentration of tungsten (nature of the filament), as well as the concentration of oxygen and carbon (elements issued when vacuum is broken between two runs), should not exceed threshold values, beyond which electronic properties of the films could be degraded, as in the case of monocrystalline silicon. Quantitative chemical analysis of these elements has been carried out using the secondary ion mass spectrometry technique through depth profiles. It has been shown that for a high effective filament surface area (S_f=27 cm²), the W content increases steadily from 5×10¹⁴ to 2×10¹⁸ atoms cm⁻³ when the filament temperature T_f increases from 1500 to 1800 °C. For a fixed T_f, the W content increases with the effective surface area S_f. Thus, considering our reactor geometry, the W content does not exceed the detection limit (5×10¹⁴ atoms cm⁻³) when T_f and S_f are limited to 1600 °C and 4 cm², respectively. For O and C elements, under deposition conditions of high dilution of silane in hydrogen (96%), O and C concentrations approaching 10²⁰ atoms cm⁻³ have been obtained. The introduction of an inner vessel inside the reactor, the addition of a load-lock chamber and a decrease in substrate temperature to 300 °C have led to a drastic decrease in these contents down to 3×10¹⁸ atoms cm⁻³, compatible with the realization of 6% efficiency HWCVD μc-Si:H solar cells.     

Preparation of highly c-axis-oriented Bi4Ti3O12 thin films and their crystallographic, dielectric and optical properties

Bismuth titanate (Bi₄Ti₃O₁₂) thin films with a high c-axis orientation up to 99% were prepared on (100)-oriented silicon wafers by r.f. planar magnetron sputtering using a Bi₂TiO₅ ceramic target at a substrate temperature of 600 °C. From the Auger electron spectroscopy depth profile of the film, there is no evidence of interdiffusion of a specific element between the film and the substrate. Relative dielectric constant of these films depends on film thickness. The behavior was explained assuming a low-dielectric-constant interface layer. Using this assumption, the relative dielectric constant of Bi₄Ti₃O₁₂ film was estimated to be approximately 140. This value is close to that along the c axis in a bulk form. The remanent polarization and the coercive field were 0.8 μC cm⁻² and 20 kV cm⁻¹, respectively.     

Enhanced ferroelectric properties of multilayer SrBi2Ta2O9/SrBi2Nb2O9 thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉/SrBi₂Nb₂O₉ (SBT/SBN) multilayer thin films with various stacking periodicity were deposited on Pt/TiO₂/SiO₂/Si substrate by pulsed laser deposition technique. The X-ray diffraction patterns indicated that the perovskite phase was fully formed with polycrystalline structure in all the films. The Raman spectra showed the frequency of the O–Ta–O stretching mode for multilayer and single layer SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBNT) samples was 827–829 cm⁻¹, which was in between the stretching mode frequency in SBT (813 cm⁻¹) and SBN (834 cm⁻¹) thin films. The dielectric constant was increased from 300 (SBT) to 373 at 100 kHz in the double layer SBT/SBN sample with thickness of each layer being 200 nm. The remanent polarization (2P_r) for this film was obtained 41.7 μC/cm², which is much higher, compared to pure SBT film (19.2 μC/cm²). The coercive field of this double layer film (67 kV/cm) was found to be lower than SBN film (98 kV/cm).     

Properties of GaAs solar cells coated with diamondlike carbon films

Thin films of amorphous diamondlike carbon (a:DLC) were deposited on GaAs solar cells, with and without antireflecting coating. The films were deposited by decomposition of CH₄ plasma using a r.f. generator (13.56 MHz). The reflected light from these cells, in the visible light, decreased after deposition of a:DLC film thickness (from 33% for t=0 nm to 14% for t=60 nm) which indicates antireflecting properties. The I–V measurements show an increase of the short circuit current (I_sc) with films thickness up to t40–60 nm, where it reaches a maximum and then decreases for higher thickness (t>60 nm). The efficiency (η) of the cells, as a function of the a:DLC thickness, shows a maximum value of 15% for t=50 nm. It was also shown, that the a:DLC films is a useful material as a protecting material for cells for operation in an abrasive environment. In abrasive environment, the efficiency of the coated cell maintains the level of about 12% whereas the efficiency of uncoated cells drop sharply from 15.5% to 6%.     

Microstructure and optical properties of GaN films on sapphire substrates

Transmission electron microscopy (TEM), double crystal X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurement were applied to study the correlation between the microstructure and material properties of the GaN films grown by light radiation heating metalorganic chemical vapor deposition (LRH-MOCVD), using GaN buffer layer on sapphire substrates. Corresponding to the density of the threading dislocation (TD) increasing approximately one order, the yellow luminescence (YL) intensity was strengthened from negligible to two orders higher than the band-edge emission intensity. The full width of half maximum (FWHM) of GaN (0002) peak of the XRD rocking curve was widened from 11 to 15 min, and in Raman spectra, the width of E₂ mode is broadened from 5 cm⁻¹ to 7 cm⁻¹. A ‘zippers’ structure of GaN buffer layer was discovered by high-resolution electron microscope (HREM).