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.     

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.     

High mobility, transparent, conducting Gd-doped In2O3 thin films by pulsed laser deposition

Highly transparent and conducting thin films of gadolinium doped indium oxide, which have high electron mobility, were deposited on quartz substrate to study the effect of growth temperature and oxygen pressure on their structural, optical, and electrical properties. X-ray diffraction study reveals that these films are randomly oriented on the quartz surface. The average particle size of the films grown at 600 °C was calculated to be ∼ 23 nm. The optical transparency of the films increases with an increase in the growth temperature. The film transparency is also found to increase with increased oxygen pressure during deposition. The electrical properties of these films strongly depend on both the growth temperature and the oxygen pressure. Analysis of the electrical data shows that the mobility of the films increases with increase in the growth temperature.     

Investigation of the growth dynamics of pulsed laser-deposited RuO2 films using in situ resistance measurement and atomic force microscopy

RuO₂ thin films were grown on (001) LaAlO₃ utilizing the pulsed laser deposition technique. Atomic force microscopy was used to check the topography of films at different growth stages. The in situ resistivity measurement was used to monitor the resistance change during and post film growth with changes of resistivity associated with the change of film growth mode. Transmission electron microscopy was used to reveal film quality and crystalline information. The layer-plus-island Stranski–Krastanov growth mode is proposed according to above results. The ambient O₂ filled during growth is found to be the main oxygen source for the formed RuO₂.     

氧分压对磁控溅射ZnO薄膜生长行为和光学特性的影响

采用反应射频磁控溅射方法, 在Si(001)基片上制备了具有高$c$轴择优取向的ZnO薄膜. 利用原子力显微镜、X射线衍射、透射光谱和室温光致荧光光谱等分析技术, 研究了氧分压对薄膜的表面形貌和光学特性的影响. 研究结果显示: 0.04～0.23Pa的氧分压范围内, ZnO薄膜存在三个不同的生长模式, 薄膜生长模式转变的临界氧分压分别位于0.04～0.08Pa和0.16～0.19Pa之间; 在0.16Pa以下时, ZnO薄膜的表面岛呈+c取向的竹笋状生长; 当氧分压>0.19Pa时, 薄膜的表面岛以-c取向生长为主; ZnO薄膜的折射率、光学带隙宽度以及PL光谱强度均随着氧分压的增大而增大, 氧分压为0.19Pa时, 薄膜的发光峰最窄, 其半峰宽为88meV.     

辅助气体对RF-PECVD制备碳纳米管薄膜形貌的影响

采用射频等离子体增强化学气相沉积(RF-PECVD)技术,以Ni为催化剂,经600℃裂解C2H2在Si基底上制备出定向碳纳米管薄膜。采用扫描电子显微镜(SEM)表征了刻蚀后Ni颗粒与沉积的碳纳米管薄膜的形貌。研究了辅助气体对等离子体预处理催化剂与碳纳米管生长的影响。结果表明:辅助气体(H2与N2)流量比对催化剂颗粒尺寸、分布以及碳纳米管生长有显著影响;合适的气体流量比有利于减少碳纳米管薄膜的杂质颗粒,促进其定向生长。预处理过程中气体流量比H2:N2=20:5时,预处理后催化剂Ni颗粒分布密度大、粒径小且分布范围窄,适合碳纳米管均匀着床;沉积生长碳纳米管薄膜时,H2:N2=20:15可得到纯度高、定向性好的碳纳米管。     

Tungsten chemical vapor deposition using tungsten hexacarbonyl: microstructure of as-deposited and annealed films

Tungsten (W) films were deposited on Si(100) from tungsten hexacarbonyl, [W(CO)₆], by low-pressure chemical vapor deposition (CVD) in an ultra-high vacuum (UHV)-compatible reactor. The chemical purity, resistivity, crystallographic phase, and morphology of the deposited films depend markedly on the substrate temperature. Films deposited at 375°C contain approximately 80 at.% tungsten, 15 at.% carbon and 5 at.% oxygen. These films are polycrystalline β-W with a strong (211) orientation and resistivities of >1000 μΩ cm. Vacuum annealing at 900°C converts the metastable β-W to polycrystalline -W, with a resistivity of approximately 19 μΩ cm. The resultant -W films are porous, with small randomly oriented grains and nanoscale (<100 nm) voids. Films deposited at 540°C are high-purity (>95 at.%) polycrystalline -W, with low resistivities (18–23 μΩ cm) and a tendency towards a (100) orientation. Vacuum annealing at 900°C reduces the resistivity to approximately 10 μΩ cm, and results in a columnar morphology with a very strong (100) orientation.     

Effects of the deposition temperature on the resistivity of copper films produced by low-pressure metal-organic chemical vapour deposition on a TiN barrier layer

Copper was deposited on to TiN by low-pressure metal-organic chemical vapour deposition, using hexafluoroacetylacetonate-Cu⁺¹-trimethylvinylsilane (hfacCu(I)TMVS) and argon carrier gas. The resistivity of the deposited copper films was investigated by observing the effects of the deposition temperature on the composition, microstructure and surface morphology of the copper films. The resistivity of the copper films decreases as the deposition temperature decreases. The copper films deposited at high temperatures, tend to contain the pores and or/ channels as well as carbon and oxygen, which results in the increase of the resistivity of the deposited films. The pores and/or channels come from the island-like growth of the copper films, while carbon and oxygen are due to the concurrent thermal decomposition of hfac during the disproportionation reaction between hfacCu(I) molecules.     

Ultraflat indium tin oxide films prepared by ion beam sputtering

Indium tin oxide (ITO) films with a smooth surface (root-mean-square roughness; R_rms=0.40 nm) were made using a combination of the deposition conditions in the ion beam-sputtering method. Sheet resistance was 13.8 Ω/sq for a 150-nm-thick film grown at 150 °C. Oxygen was fed into the growth chamber during film growth up to 15 nm, after which, the oxygen was turned off throughout the rest of the deposition. The surface of the films became smooth with the addition of ambient oxygen but electrical resistance increased. In films grown at 150 °C with no oxygen present, a rough surface (R_rms=2.1 nm) and low sheet resistance (14.4 Ω/sq) were observed. A flat surface (R_rms=0.5 nm) with high sheet resistance (41 Ω/sq) was obtained in the films grown with ambient oxygen throughout the film growth. Surface morphology and microstructure of the films were determined by the deposition conditions at the beginning of the growth. Therefore, fabrication of ITO films with a smooth surface and high electrical conductivity was possible by combining experimental conditions.     

Microstructure and hardness of electroplated gold prepared by D.C., pulse and asymmetric A.C. plating

Initially procedures for preparing insulating carbon films of exceptional hardness by ion beam deposition and ion impact growth in hydrocarbon plasmas are reviewed; for completeness reference is also made to thermally cracked carbon films grown on diamond. We described experiments on the coating of germanium targets on a water-cooled electrode in a butane r.f. plasma (13.56 MHz) with the electrode capacitively coupled to the supply to provide a negative bias to enhance ion impact. Films prepared at a low power input-to-pressure ratio of 1–2 W cm^-2Torr^-1 were polymers with some oxygen contamination as shown by their infrared absorption bands. Raising the ratio to 40 W cm^-2 Torr^-1 produced carbon films without absorption in the measured region λ = 2–20 μm. The films were amorphous with a refractive index of 1.9–2.0 and a resistivity of 10¹² Ω cm. At higher power-to-pressure ratios or target temperatures the film resistivity fell with loss of the infrared transparency. A critical ratio exists at which energetic ion impact is sufficient to rupture all CH bonded species reaching the target and to damage any structure ordering which may otherwise arise. At high ratios the target cooling is considered to be insufficient to prevent the film temperature rising and resulting in a transition from a metastable to a graphitic form. In conclusion the properties of vacuum-deposited carbon and the nature of some reported defects in diamond are considered in relation to the characteristics of ion impact films.     

温度对BCl3-CH4-H2化学气相沉积掺硼碳沉积过程的影响

以三氯化硼、甲烷和氢气的混合气体为前驱体,利用磁悬浮天平热重系统研究了850～1200℃区间内化学气相沉积掺硼碳的原位动力学.探索了温度对沉积速率的影响,计算了该温度区间内沉积过程的表观活化能,同时借助SEM和EDS技术.测试了不同温度点(900℃、1000℃、1100℃和1200℃)沉积产物的微观结构和成分.结果表明,化学气相沉积掺硼碳属于典型的热激活反应过程;在所研究的温度区间内存在5种不同的反应控制机制;随着温度的升高,沉积产物的n(B)/n(C)和堆积密度都显著变小,说明高n(B)/n(C)和高致密度的掺硼碳涂层应在较低的温度下制备.     

Structure of ultrathin MgO films on Mo(001)

We have studied the structure of ultrathin MgO films grown on a single crystal Mo(001) surface. Scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) were used to investigate the effect of substrate temperature and oxygen partial pressure on the growth and morphology of these films. LEED indicates the growth of (100) films with MgO 〈110〉 directions oriented along 〈100〉 directions of the substrate. Despite the insulating nature of bulk MgO, films up to 25-Å thick are sufficiently conducting to perform STM measurements. STM reveals Mg deposition in an oxygen ambient at substrate temperatures from 300 to 900 K produces uniform films. Films as thick as eight atomic layers typically have only three layers exposed. These films consist of small domains between 20 and 60 Å in diameter. The domain shapes are random and the perimeters show no preferred orientation. In contrast, films grown at temperatures in excess of 1000 K exhibit larger three-dimensional MgO islands (Volmer-Weber growth). Steps on these high temperature films orient preferentially along thermodynamically favored MgO 〈100〉 directions. STM images of films deposited at high temperature exhibit a checkerboard pattern. The dimensions and symmetry of this pattern are consistent with the coincidence arising from the mismatch of the MgO(100) and Mo(001) lattice. Annealing room temperature deposited films results in island coalescence and produces uniform films with domains in excess of 100 Å. The perimeters of these domains are oriented along MgO 〈100〉 directions.     

Preparation and properties of TiN and AlN films from alkoxide solution by thermal plasma CVD method

Single phase TiN and AlN films were prepared on a Si wafer from titanium tetra-etoxide and aluminum tri-butoxide solutions dissolved in ethanol and toluene, respectively, using an Ar/N₂/H₂ radio-frequency (r.f.) inductive thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, measurement of electrical resistivity and Vickers microhardness. Factors affecting the formation of the films (lattice parameter, chemical composition, oxygen/carbon content, and deposition rate of the films) were examined in terms of the N₂ flow rate (2.5–4.5 slm), substrate temperature (300–700°C), feed rate of the solution (0.025–0.3 ml/min), and the mole ratio of the alkoxide solution (1:1–1:3). The optimum conditions for preparation of TiN films produced a film 0.2–3 μm thick with an oxygen content of 8 at.% and a free carbon content of 4 at.%, showing an electrical resistivity of 370 μΩ cm. The optimum conditions for AlN films produced a film 0.3 μm thick containing 14 at.% oxygen and 8 wt.% carbon. The deposition rate of the TiN film was determined to be 30–35 nm/min. The Vickers microhardness of the TiN and AlN films was found to be 10±1 and 13±3 GPa, respectively.     

Control of thickness uniformity and grain size in graphene films for transparent conductive electrodes

Large-scale and transferable graphene films grown on metal substrates by chemical vapor deposition (CVD) still hold great promise for future nanotechnology. To realize the promise, one of the key issues is to further improve the quality of graphene, e.g., uniform thickness, large grain size, and low defects. Here we grow graphene films on Cu foils by CVD at ambient pressure, and study the graphene nucleation and growth processes under different concentrations of carbon precursor. On the basis of the results, we develop a two-step ambient pressure CVD process to synthesize continuous single-layer graphene films with large grain size (up to hundreds of square micrometers). Scanning electron microscopy and Raman spectroscopy characterizations confirm the film thickness and uniformity. The transferred graphene films on cover glass slips show high electrical conductivity and high optical transmittance that make them suitable as transparent conductive electrodes. The growth mechanism of CVD graphene on Cu is also discussed, and a growth model has been proposed. Our results provide important guidance toward the synthesis of high quality uniform graphene films, and could offer a great driving force for graphene based applications.     

化学气相沉积制备钼钨合金

以MoF6、WF6以及H2为原料,用化学气相共沉积的方法,成功地在铜基片表面沉积出钼钨合金.实验分析表明:沉积层结构为单相均匀固溶体.在钼含量高时沉积层显微组织呈细晶层状结构,在钼含量较低时沉积层显微组织呈柱状晶生长.改变反应气体中WF6、MoF6相对含量可实现膜层成分可控.采用化学气相沉积法沉积钼钨等难熔金属合金,沉积纯度高,设备简单,沉积速率快,在高温抗烧蚀涂层及耐腐蚀涂层方面具有广泛的应用前景.     

Low Resistance Polycrystalline Diamond Thin Films Deposited by Hot Filament Chemical Vapour Deposition

Polycrystalline diamond thin films with outgrowing diamond (OGD) grains were deposited onto silicon wafers using a hydrocarbon gas (CH4) highly diluted with H2 at low pressure in a hot filament chemical vapour deposition (HFCVD) reactor with a range of gas flow rates. X-ray diffraction (XRD) and SEM showed polycrystalline diamond structure with a random orientation. Polycrystalline diamond films with various textures were grown and (111) facets were dominant with sharp grain boundaries. Outgrowth was observed in flowerish character at high gas flow rates. Isolated single crystals with little openings appeared at various stages at low gas flow rates. Thus, changing gas flow rates had a beneficial influence on the grain size, growth rate and electrical resistivity. CVD diamond films gave an excellent performance for medium film thickness with relatively low electrical resistivity and making them potentially useful in many industrial applications.     

Influence of bowl shaped substrate holder on growth of polymeric DLC film in a microwave plasma CVD reactor

The properties of diamond like carbon (DLC) films grown in modified microwave plasma CVD reactor is presented in this paper. By using bowl shaped steel substrate holder in a MW plasma CVD reactor (without ECR), films have been grown at relatively high pressure (20 Torr) and at low temperature (without heating). The input microwave power was about 300 W. Earlier, under the same growth conditions, no deposition was achieved when flat molybdenum/steel substrate holders were used. In this study, two different designs of bowl shaped steel substrate holder at different bias have been experimented. Raman spectra confirm the DLC characteristics of the films. FTIR results indicate that the carbon is bonded in the sp ³ form with hydrogen, and this characteristic is more pronounced when smaller holder is used. UV-visible spectra show high visible transmittance (~85%) for films grown in both the holders. The nanoindentation hardness of the films have a wide range, about 4–16 GPa. Field emission scanning electron microscope (FESEM) images reveal that the films have featureless and smooth surface morphology. These films are polymeric in nature with moderately high hardness, which may be useful as anti-scratch and anti-corrosive coatings.     

Electrochemical characterization of carbon nanotube forests grown on copper foil using transition metal catalysts

Growth of vertical, multiwalled carbon nanotubes (CNTs) on bulk copper foil substrates can be achieved by sputtering either Ni or Inconel thin films on Cu substrates followed by thermal chemical vapor deposition using a xylene and ferrocene mixture. During CVD growth, Fe nanoparticles from the ferrocene act as a vapor phase delivered catalyst in addition to the transition metal thin film, which breaks up into islands. Both the thin film and iron are needed for dense and uniform growth of CNTs on the copper substrates. The benefits of this relatively simple and cost effective method of directly integrating CNTs with highly conductive copper substrates are the resulting high density of nanotubes that do not require the use of additional binders and the potential for low contact resistance between the nanotubes and the substrate. This method is therefore of interest for charge storage applications such as double layer capacitors. Inconel thin films in conjunction with Fe from ferrocene appear to work better in comparison to Ni thin films in terms of CNT density and charge storage capability. We report here the power density and specific capacitance values of the double layer capacitors developed from the CNTs grown directly on copper substrates.     

Effects of molybdenum, silver dopants and a titanium substrate layer on copper film metallization

Annealing of 100 nm-thick Cu, Cu(Mo) and Cu(Ag) films was carried out to investigate the effect of dopant atoms on the films. Molybdenum (Mo) and silver (Ag) were selected as immiscible dopants for out-diffusion studies. A thermally grown SiO₂ layer and a sputtered Ti layer were used as substrates. The dopant and substrate effects were characterized in terms of surface morphology, resistivity, preferred orientation, and diffusional characteristics. The lowest observed resistivity was 2.32 · cm in the Cu(Ag) film, which was lower than that in a pure Cu film of the same thickness. Ag addition enhanced the surface morphology and thermal stability of the Cu(Ag) films. The highest thermal stability was obtained in the case of a Cu(Mo)/Ti film which maintained film integrity to 800°C. A Ti substrate enhanced Cu(111) texture growth. A highly oriented Cu(111)-texture was obtained in the Cu(Mo)/Ti films. Cu diffusion through the Ti layer was limited in the (111)-textured Cu(Mo)/Ti films, which showed good potential as a diffusion barrier.     

Optical properties of ZnO thin film on γ-LiAlO2 substrate grown by pulsed laser deposition

Optical properties were investigated of ZnO thin films grown on (100) γ-LiAlO₂ (LAO) substrates by pulsed laser deposition method. C-axis oriented ZnO film was grown on (100) LAO substrate at the substrate temperature of 550 °C. The transmittances of the films were over 85%. Peaks attributed to excitons were seen in the absorption spectra, indicating that the thin films have high crystallinity. Photoluminescence spectra were observed at room temperature; the peak at 550 nm is ascribed to oxygen vacancies in the ZnO films caused by the diffusion of Li from the substrate into the film during deposition.