Study of Cu diffusion behavior in low dielectric constant SiOC(-H) films deposited by plasma-enhanced chemical vapor deposition

Carbon doped silicon oxide (SiOCH) thin films deposited using plasma-enhanced chemical vapor deposition (PECVD) are commonly used in multilevel interconnect applications. To enhance the electrical performance, the deposited SiOC(-H) films were annealed in a vacuum at various temperatures ranging from 250 to 450 °C. A Cu electrode was then deposited using thermal evaporation. The drift rate of Cu⁺ ions in the SiOC(-H) films with the Cu/SiOC(-H)/p-Si(100)/Al metal-insulator-semiconductor (MIS) structures after annealing was evaluated by C-V measurements with a flatband shift caused by bias-temperature stress (BTS). The samples were stressed at different temperatures of 150 to 275 °C and electric fields up to 1.5 MV/cm to examine the penetration of Cu⁺ ions into the SiOC(-H) films. The Cu⁺ ion drift diffusion behavior was observed by high-resolution transmission electron microscopy and depth profile analysis of the Auger electron spectra. The drift diffusion experiments suggested that the Cu⁺ ion drift rate in the of SiOC(-H) films increased with increasing annealing temperature. A thermal stress and BTS were used to evaluate the impact of Cu penetration on the dielectric properties of the SiOC(-H) films.     

The structures of low dielectric constant SiOC thin films prepared by direct and remote plasma enhanced chemical vapor deposition

Two structures of low dielectric constant (low-k) SiOC films were elucidated in this work. Low-k thin film by remote plasma mode was mainly composed of inorganic Si-O-Si backbone bonds and some oxygen atoms are partially substituted by CH₃, which lowers k value. The host matrix of low-k thin films deposited by direct plasma mode, however, was mainly composed of organic C-C bonds and “M” and “D” moieties of organosilicate building blocks, and thus the low dipole and ionic polarizabilities were the important factors on lowering k value.     

Properties of aluminum oxide thin films deposited by pulsed laser deposition and plasma enhanced chemical vapor deposition

The chemical, structural, mechanical and optical properties of thin aluminum oxide films deposited at room temperature (RT) and 800 °C on (100) Si and Si-SiO₂ substrates by pulsed laser deposition and plasma enhanced chemical vapor deposition are investigated and compared. All films are smooth and near stoichiometric aluminum oxide. RT films are amorphous, whereas γ type nano-crystallized structures are pointed out for films deposited at 800 °C. A dielectric constant of ∼ 9 is obtained for films deposited at room temperature and 11-13 for films deposited at 800 °C. Young modulus and hardness are in the range 116-254 GPa and 6.4-28.8 GPa respectively. In both cases, the results show that the deposited films have very interesting properties opening applications in mechanical, dielectric and optical fields.     

Electrical, mechanical, and optical properties of the organic-inorganic hybrid-polymer thin films deposited by PECVD

Hybrid thin films have been deposited on silicon substrates under several conditions such as different annealing temperatures and RF power by plasma enhanced chemical vapor deposition method using single molecular precursors. The result of the FT-IR measurement showed that the plasma polymerized thin films have highly cross-linked density with increasing RF power and annealing temperature. An impedance analyzer was utilized for the measurements of I-V and C-V curves. From the electrical properties measurements, the lowest dielectric constant and best leakage constant were obtained to be 2.26 and 10^− 9 A/cm² at 1 MV/cm, respectively. Also, the mechanical properties of the films were determined with nano-indentation.     

Characterisation of silicon carbide films deposited by plasma-enhanced chemical vapour deposition

The paper presents a characterisation of amorphous silicon carbide films deposited in plasma-enhanced chemical vapour deposition (PECVD) reactors for MEMS applications. The main parameter was optimised in order to achieve a low stress and high deposition rate. We noticed that the high frequency mode (13.56 MHz) gives a low stress value which can be tuned from tensile to compressive by selecting the correct power. The low frequency mode (380 kHz) generates high compressive stress (around 500 MPa) due to ion bombardment and, as a result, densification of the layer achieved. Temperature can decrease the compressive value of the stress (due to annealing effect). A low etching rate of the amorphous silicon carbide layer was noticed for wet etching in KOH 30% at 80 °C (around 13 A/min) while in HF 49% the layer is practically inert. A very slow etching rate of amorphous silicon carbide layer in XeF₂ -7 A/min- was observed. The paper presents an example of this application: PECVD-amorphous silicon carbide cantilevers fabricated using surface micromachining by dry-released technique in XeF₂.     

Ultraviolet irradiation effect on the properties of leakage current and dielectric breakdown of low-dielectric-constant SiOC(H) films using comb capacitor structure

Low-dielectric constant SiOC(H) films were deposited on p-type Si(100) substrates by plasma-enhanced chemical-vapor deposition (PECVD) using dimethyldimethoxy silane (DMDMS, C₄H₁₂O₂Si) and oxygen gas as precursors. To improve the physicochemical properties of the SiOC(H) films, the deposited SiOC(H) films were exposed to ultraviolet (UV) irradiation in a vacuum. The bonding structure of the SiOC(H) films was investigated by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The electrical characterization of SiOC(H) films were carried out through I-V measurements using the comb-like patterns of the TiN/Al/Ti/SiOC(H)/TiN/Al/Ti metal-insulator-metal (MIM) structure. Excessive UV treatment adversely affected the SiOC(H) film, which resulted in an increased dielectric constant. Our results provide insight into the UV irradiation of low-k SiOC(H) films.     

Post deposition annealing of aluminum oxide deposited by atomic layer deposition using tris(diethylamino)aluminum and water vapor on Si(100)

Thin stoichiometric aluminum oxide films were deposited using tris(diethylamino)aluminum precursor and water. Changes in aluminum oxide film and interfacial regions were studied after post deposition annealing under inert ambience at 600, 800 and 1000 °C using Fourier Transform InfraRed (FTIR) spectroscopy, X-ray Photoelectron Spectroscopy, and Scanning Transmission Electron Microscopy (STEM)/Electron Energy Loss spectroscopy (EELS) techniques. STEM/EELS analyses were also done on samples annealed in situ, i.e., inside the electron microscope at temperatures as high as 800 °C. Up to an annealing temperature of 600 °C, the atomic layer deposited alumina film was thermally stable and remained amorphous with no interfacial silica growth observed. After annealing at 800 °C for 5 min, the only change observed was a small increase in the interfacial layer thickness which was found to be mainly silicon oxide without any significant silicate content. Annealing at 1000 °C induced a significant increase in the interfacial layer thickness which consisted of a mixture of silicon oxide and aluminum silicate. The composition of the interfacial layer was found to change with depth, with silicate concentration decreasing with distance from the Si substrate. Also, the FTIR spectra exhibited strong absorption features due to Al-O stretching in condensed AlO₆ octahedra which indicate crystallization of the alumina film after annealing at 1000 °C for 5 min.     

Evolution of optical properties with deposition time of silicon nitride and diamond-like carbon films deposited by radio-frequency plasma-enhanced chemical vapor deposition method

The paper presents investigations of the optical properties of thin high-refractive-index silicon nitride (SiN_x) and diamond-like carbon (DLC) films deposited by the radio-frequency plasma-enhanced chemical vapor deposition method for applications in tuning the functional properties of optical devices working in the infrared spectral range, e.g., optical sensors, filters or resonators. The deposition technique offers the ability to control the film's optical properties and thickness on the nanometer scale. We obtained thin, high-refractive-index films of both types at deposition temperatures below 350 °C, which is acceptable under the thermal budget of most optical devices. In the case of SiN_x films, it was found that for short deposition processes (up to 5 min long) the refractive index of the film increases in parallel with its thickness (up to 50 nm), while for longer processes the refractive index becomes almost constant. For DLC films, the effect of refractive index increase was observed up to 220 nm in film thickness.     

Characterization and tribological application of diamond-like carbon (DLC) films prepared by radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique

Diamond-like carbon (DLC) films were successfully prepared on glass substrates and surfaces of selenium drums via radio frequency plasma enhanced chemical vapor deposition method. The microstructure, surface morphology, hardness, film adhesion, and tribological properties of the films were characterized and evaluated by X-ray photoelectron spectroscopy, atomic force microscopy, and micro-sclerometer and friction-wear spectrometer. The results showed that DLC films have smooth surfaces, homogeneous particle sizes, and excellent tribological properties, which can be used to improve the surface quality of the selenium drums and prolong their service life.     

Plasma enhanced chemical vapor deposition of low dielectric constant SiOC(-H) films using MTES/O2 precursor

Low dielectric constant SiOC(-H) thin films were deposited by plasma enhanced chemical vapor deposition (PECVD) using methyltriethoxysilane (MTES) and oxygen as precursors. The SiOC(-H) films were prepared with MTES/O₂ flow rate ratio of 80%, rf power of 700 W and the working pressure was varied from 110 to 150 mTorr. Then the films were annealed at different temperatures in an Ar ambient for 30 min in order to study their thermal stability. Film thickness and refractive index were measured by SEM and ellipsometry, respectively. Bonding characteristics of the films were investigated by Fourier transform infrared (FTIR) spectroscopy. The dielectric constant of SiOC(-H) film was evaluated by C-V measurements using Al/SiOC(-H)/p-Si structure. The dielectric constants as low as 2.4 have been obtained for the film annealed at 500 °C with the working pressure of 150 mTorr. The annealing treatment was found to reduce dielectric constant significantly due to abundant incorporation of methyl group into the Si-O network. These results demonstrated the promising characteristics of SiOC(-H) thin films deposited by using oxygen and MTES precursor.     

Study on chemical vapor deposited copper films on cyano and carboxylic self-assembled monolayer diffusion barriers

Thin copper films were produced by chemical vapor deposition using the precursor Cu^IIbis-hexafluoroacetylacetonate on the SiO₂/Si substrate modified with cyano and carboxylic self-assembled monolayers (SAMs) as diffusion barriers. The characterizations of the deposited copper films were measured by various thin film analysis techniques, i.e., scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The comparison between copper deposited on SiO₂ and on the SAM-modified SiO₂ substrates indicates that the copper films tend to be deposited onto the SAM-modified substrate, which is further proved by the calculation results of the interaction energies of copper and the SAMs with density functional theory method.     

Effect of nickel oxide seed layers on annealed-amorphous titanium oxide thin films prepared using plasma-enhanced chemical vapor deposition

The effect of a nickel oxide (NiO_x) seed layer on the crystallization and photocatalytic activity of the sequentially plasma-enhanced chemical vapor deposited amorphous titanium oxide (TiO_x) thin film processed by a post-annealing process was investigated. The evolution of the crystalline structures, chemical bond configurations, and surface/cross-sectional morphologies of the annealed TiO_x films, with and without a NiO_x seed layer, was examined using X-ray diffractometer, Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, atomic force microscopy, and field emission scanning electron microscope measurements. Thermo- and photo-induced hydrophilicity was determined by measuring the contact angle of water droplet. Photocatalytic activity after UV light irradiation was evaluated from the decolorization of a methylene blue solution. The crystallization temperature of the TiO_x film, deposited on a NiO_x seed layer, was found to be lower than that of a pure TiO_x film, further improving the thermo- and photo-induced surface super-hydrophilicity. The TiO_x film deposited onto the NiO_x seed layer, resulting in significant cluster boundaries, showed a rough surface morphology and proved to alleviate the anatase crystal growth by increasing the post-annealing temperature, which yielded a more active surface area and prohibited the recombination of photogenerated electrons and holes. The photocatalytic activity of the NiO_x/TiO_x system with such a textured surface therefore was enhanced and optimized through an adequate post-annealing process.     

The preparation and characterization of preferred (110) orientation aluminum nitride thin films on Si (100) substrates by pulsed laser deposition

The preferred (110) oriented aluminum nitride (AlN) thin films have been prepared by pulsed laser deposition on p-Si (100) substrates. The films were characterized with X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and atomic force microscope (AFM). The results indicate that the AlN thin films are well-crystallized when laser energy is higher than 300 mJ/puls. The AFM images show that the surface roughness of the deposited AlN thin films gradually increases with increasing laser energy, but the surface morphologies are still very smooth. The crystallinity and morphology of the thin films are found to be strongly dependent on the laser energy.     

Synthesis of boron carbonitride (BCN) films by plasma-enhanced chemical vapor deposition using trimethylamine borane as a molecular precursor

Boron carbonitride (BCN) films were deposited on Si substrates by plasma-enhanced chemical vapor deposition (PECVD) using a powdered precursor of trimethylamine borane (C₃H₁₂NB). The effect of using different carrier gasses and microwave powers was investigated. Field emission scanning electron microscopy (FE-SEM) revealed that the films have a nanofibrous structure with elongated features 20 nm in diameter and 200 nm in length. Fourier transfer infrared (FT-IR) spectroscopy was used to investigate chemical bonding states present in the deposited films. The FT-IR results suggested that the films have multiple chemical bonding states including C-N, B-N, and B-C bonds, as well as oxygen incorporation in the form of B-O bonds. Mixing the powdered precursor with molecular sieve was found to reduce the oxygen content in the films by removing surface adsorbed water from the precursor.     

Effects of applied power on hydrogenated amorphous carbon (a-C:H) film deposition by low frequency (60 Hz) plasma-enhanced chemical vapor deposition (PECVD)

Hydrogenated amorphous carbon (a-C:H) films were deposited onto glass substrates using low frequency (60 Hz) plasma-enhanced chemical vapor deposition and the effects of the applied power on a-C:H films deposition were investigated. During deposition, the electron temperature and the density of CH₄-H₂ plasma were 2.4-3.1 eV and about 10⁸ cm⁻³, respectively. The main optical emission peak of the carbon species observed in the CH₄-H₂ plasma is shown to be excited carbon CH* at 431 nm. The sp³/sp² ratio, band gap, hydrogen content, and refractive index of a-C:H films gradually increased up to a power of 25 W and then saturated at higher power. This tendency is similar to the variation of plasma parameters with varying applied power, thereby indicating that a strong relationship exists between the properties of the films and the plasma discharge.     

Annealing effects on structural and electrical properties of fluorinated amorphous carbon films deposited by plasma enhanced chemical vapor deposition

The annealing effects on the structural and electrical properties of fluorinated amorphous carbon (a-C:F) thin films prepared from C₆F₆ and Ar plasma are investigated in a N₂ environment at 200 mTorr. The a-C:F films deposited at room temperature are thermally stable up to 250 °C, but as the annealing temperature is increased beyond 300 °C, the fluorine incorporation in the film is reduced, and the degree of crosslinking and graphitization in the film appears to be enhanced. At the annealing temperature of 250 °C, the chemical bond structures of the film are unchanged noticeably, but the interface trapped charges between the film and the silicon substrate are reduced significantly. The increased annealing temperature contributes the decrease of both the interface charges and the effective charge density in the a-C:F film. Higher self-bias voltage is shown to reduce the charge density in the film.     

Growth and morphological studies of (100) textured diamond thin films by microwave plasma-enhanced chemical vapor deposition

Textured (100) diamond films have been successfully grown using the plasma-enhanced chemical vapor deposition technique and characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction. The thickness of such a (100)-oriented diamond film can be as thin as 4 μm, and the just-emerged transitional layer is found to be only 1.5 μm, which is very thin compared with the computer simulation value of 700d₀, where d₀ is the average distance between the nuclei. A systematic study of various parameters in the carburization and bias steps on the growth of textured (100) diamond films and the subsequent change of surface morphology has been investigated. Experimental results show that these two pre-growth steps seem to ease the growth of textured (100) diamond films and they should be optimized for a set of growth conditions. It is suggested that varying these parameters in the pre-growth steps may cause a change of microstructure, alignment of nuclei, and defect states in the diamond-like layer, resulting in the morphological change of textured (100) diamond films.     

热灯丝CVD金刚石膜的微结构和形貌对其电子性质的影响

利用热灯丝CVD法在硅衬底上合成出了金刚石膜。金刚石膜的质量和电子性质由扫描电子显微镜、拉曼谱、阴极发光及霍尔系数测量来表征。实验结果表明,沉积条件对金刚石膜电子性质和质量有重要影响。载流子迁移率随甲烷浓度增加而减少,但场发射随其增加而增强。压阻效应随微缺陷增多而降低。异质外延金刚石膜压阻因子在室温下100微形变时为1200,但含有大量缺陷的多晶金刚石膜压阻因子低于200,这是由于薄膜中缺陷态密度增加,并依赖于膜结构的变化。     

Influence of technological conditions on electronic transitions in chemical vapor deposited poly(azomethine) thin films

Thin films of poly(1,4-phenylenemethilidynenitrilo-1,4-phenylenenitrilomethilidyne) (PPI) have been prepared by chemical vapor deposition in the horizontal geometry using gaseous argon as a transport agent. PPI thin films have been grown by polycondensation of para-phenylene diamine (PPDA) and terephtal aldehyde (TPA). Fourier Transform Infrared spectra confirm formation of PPI layers without end groups. The strongest absorption band with discernible vibronic progression has been found to be due to superposition of 2.64, 2.82 and 3.03 eV bands corresponding to interband transitions connecting electronic ground state and vibrational levels of electronic excited state. A feature seen at about 2.6 eV in the spectra of PPI films prepared at higher temperatures of PPDA and TPA sources are attributed to excitons connected with the π-π? gap. Shoulder at 3.31 eV is attributed to interband transitions between delocalized states, while a peak at 4.2 eV is attributed to excitons formed by localized holes and delocalized electrons and vice versa and interband transitions connecting delocalized and localized bands, with the binding energy of about 0.8 eV. Thin films prepared at low temperatures of monomers consist of randomly distributed PPI chains weakly bound together.     

Microstructure and electrical properties of Cu films obtained by chemical vapor deposition of copper(I) pentafluoropropionate complexes with vinyltrialkylsilanes

Copper thin layers were deposited on Si(111) and glass substrates by chemical vapor deposition method using [Cu(OOCC₂F₅)(L)], L = vinyltrimethylsilane (1), vinyltriethylsilane (2) as precursors. Application of multistage depositions of Cu films on a glass surfaces resulted in formation of the metallic membranes. Fabricated crystalline copper layers, which contains some carbon (5-9%) and oxygen (1-5%) impurities, have been characterized by grazing incidence X-ray diffraction and X-ray photoelectron methods. The morphology studies exhibited metallic layers composed of copper grains, their size and packed density depends on deposition parameters. Electrical properties of metallic films were studied by four-point probe, as a function of temperature in 103-333 K range.