Silicon Nitride Films Deposited by RF Sputtering for Microstructure Fabrication in MEMS

In the present work, we report silicon nitride films deposited by a radio- frequency (RF) sputtering process at relatively low temperatures (<260°C) for microelectromechanical system (MEMS) applications. The films were prepared by RF diode sputtering using a 3-inch-diameter Si₃N₄ target in an argon ambient at 5 mTorr to 20 mTorr pressure and an RF power of 100 W to 300 W. The influence of the film deposition parameters, such as RF power and sputtering pressure, on deposition rate, Si-N bonding, surface roughness, etch rate, and stress in the films was investigated. The films were deposited on single/double-side polished silicon wafers and transparent fused-quartz substrates. To explore the RF-sputtered silicon nitride film as a structural material in MEMS, microcantilever beams of silicon nitride were fabricated by bulk, surface, and surface-bulk micromachining technology. An RF-sputtered phosphosilicate glass film was used as a sacrificial layer with RF-sputtered silicon nitride. Other applications of sputtered silicon nitride films, such as in the local oxidation of silicon (LOCOS) process, were also investigated.     

Electroless deposition of Co(W) thin films

Thin films of cobalt that contain small amounts of tungsten [Co(W)] were deposited by the electroless process. Those films do not contain either phosphorus or boron which are included in most electroless cobalt films processes. The deposition bath for Co(W) thin films include Co ions, tungstate ions as a source for tungsten, di-methyl-amine-borane (DMAB) complex as a reducing agent, ammonium hydrate as a complexing agent, acetic acid for buffering and surfactants. Co(W) layers were deposited on two types of seed layers: (a) thin sputtered cobalt or copper films on 100 nm SiO₂/Si and (b) bare silicon wafers activated by an aqueous Pd/PdCl₂ solution. The deposited layer thickness range was 40–1000 nm with deposition rate at 90 °C and pH 9 of 7 nm/s for both Pd activated Si and sputtered Co seed, and 5 nm/s for the sputtered Cu seed. Lowering the temperature to 70 °C lowered the deposition rate to 0.7 nm/s for the Pd activated Si. The deposited layers were bright coloured, uniform, and with low defect density under visual inspection. The thin films composition was found to be Cobalt with 3–4 at.% tungsten for all types of seed layers. The Co(W) thin films specific resistivity was in the range of 60–90 μΩ cm. Finally we present the thin film morphology as it was characterized using atomic force microscopy and scanning electron microscopy.     

Effects of thermal annealing on the structural properties of sputtered W–Si–N diffusion barriers

W–Si–N thin films were deposited via rf-magnetron sputtering from a W₅Si₃ target in Ar/N₂ reactive gas mixtures over a large range of compositions, obtained by varying the partial flow of nitrogen within the reaction chamber. The samples of each set were then thermally annealed in vacuum at different temperatures up to 980 °C.Film composition was determined by Rutherford backscattering spectrometry (RBS), surface film morphology by scanning electron microscopy (SEM), micro-structure by transmission electron microscopy (TEM), vibrational properties by FT-IR absorption and Raman scattering spectroscopy, and electrical resistivity by four-point probe measurements.Independently of the deposition conditions, all the as-deposited films have an amorphous structure, while their composition varies, showing an increase of Si/W ratio from 0.1 up to 0.55 when the nitrogen concentration in the films increases from 0 to 60 at%. Thermal treatments in vacuum induce an important loss of nitrogen in the nitrogen-rich samples, especially at temperatures higher than 600 °C. Samples with high nitrogen content preserve their amorphous structure even at the highest annealing temperature, despite the chemical bonding ordering observed by means of FT-IR measurements. Raman spectroscopy of as-deposited films rich in nitrogen suggests the presence of an important amorphous silicon nitride component, but fails to detect any structural rearrangement either within the composite matrix of film or within silicon nitride component. Segregation of metallic tungsten was detected by TEM in the annealed sample with lowest nitrogen content (W₅₈Si₂₁N₂₁). Finally, the resistivity of the films increases with the N content, while the loss of nitrogen accompanies the decrease of resistivity especially of samples with high nitrogen content.     

Structural Properties of AlN Grown on Sapphire at Plasma Self-Heating Conditions Using Reactive Magnetron Sputter Deposition

Aluminum nitride (AlN) films were grown on sapphire by reactive magnetron sputter deposition in N₂ discharges at plasma self-heating conditions. The growth temperature was as low as 94°C. The structural properties resulting from different substrate biases and growth pressures were investigated by atomic force microscopy, x-ray diffraction (XRD) measurements, and transmission electron microscopy (TEM). At 20 mTorr of N₂ with most sputtered species thermalized, films exhibited both AlN (0002) and (10[`1] 1) (10\overline{1} 1) XRD peaks, with the AlN (0002) intensity initially increasing with ion energy above 15 eV, showing enhanced film quality with an optimum of 25 eV. At a lower growth pressure of 5 mTorr with energetic sputtered species, the AlN (10[`1] 1) (10\overline{1} 1) peak disappeared and the crystallinity of AlN improved, exhibiting relaxed epitaxial AlN. The measured lattice parameter was 0.4975 nm, which was 0.10% smaller than that of bulk. The epitaxial relationship of a single-crystal AlN film was confirmed by pole figure and cross-sectional TEM. These results demonstrate that control of ion energy and energy of the sputter-deposited species is critical for film deposition at low temperature.     

Investigation of RF sputtered PSG films for MEMS and semiconductor devices

In this work, we report the preparation of phospho-silicate-glass (PSG) films using RF magnetron sputtering process and its application as a sacrificial layer in surface micromachining technology. For this purpose, a 76 mm diameter target of phosphorus-doped silicon dioxide was prepared by conventional solid-state reaction route using P₂O₅ and SiO₂ powders. The PSG films were deposited in a RF (13.56 MHz) magnetron sputtering system at 200-300 W RF power, 10-20 mTorr pressure and 45 mm target-to-substrate spacing without external substrate heating. To confirm the presence of phosphorus in the deposited films, hot-probe test and sheet resistance measurements were performed on silicon wafers following deposition of PSG film and a drive-in step. As a final confirmatory test, a p-n diode was fabricated in a p-type Si wafer using the deposited film as a source of phosphorus diffusion. The phosphorus concentration in the target and the deposited film were analyzed using energy dispersive X-rays (EDAX) tool. The etch rate of the PSG film in buffered HF was measured to be about 30 times higher as compared to that of thermally grown SiO₂ films. The application of RF sputtered PSG film as sacrificial layer in surface micromachining technology has been explored. To demonstrate the compatibility with MEMS process, micro-cantilevers and micro-bridges of silicon nitride were fabricated using RF sputtered PSG as a sacrificial layer in surface micromachining. It is envisaged that the lower deposition temperature in RF sputtering (<150 °C) compared to CVD process for PSG film preparation is advantageous, particularly for making MEMS on temperature sensitive substrates.     

Enhancement of the Schottky Barrier Height using a Nitrogen-Rich Tungsten Nitride Thin Film for the Schottky Contacts on AlGaN/GaN Heterostructures

Tungsten, stoichiometric W₂N, and nitrogen-rich W₂N films were used as Schottky contacts on AlGaN/GaN heterostructures. The nitrogen content in the film was controlled by varying the nitrogen-to-argon gas flow ratio during the reactive sputter deposition. The diode with the nitrogen-rich film exhibited a higher Schottky barrier height and the leakage current was comparable to that of the Ni/Au Schottky contact. Analysis suggested that this was due to the increase of the tungsten nitride work function as the result of higher nitrogen incorporation. Furthermore, after 600°C thermal annealing, the diode was stable and showed no change in the leakage current.     

Investigation on doping behavior of copper in ZnO thin film

An experiment to determine the electronic and chemical states of Cu in a ZnO crystal was performed using Hall measurement, X-ray photoelectron spectroscopy (XPS) and low-temperature photoluminescence (PL). Cu atoms showed different behaviors in the ZnO matrix as a function of oxygen gas pressure. Metallic copper (Cu⁰)-related Cu 2p_3/2 peak was observed in highly n-type ZnO:Cu film deposited in 10 mTorr. In the Cu-doped p-type ZnO film prepared in 50 mTorr, Cu_Zn¹⁺-related peak and small Cu_Zn²⁺-related satellite peak exhibited and the optical acceptor binding energies of Cu3d⁹ and Cu3d¹⁰ were 173 and 213 meV, respectively.     

Thickness dependence of the structural and electrical properties of copper films deposited by dc magnetron sputtering technique

This paper addresses the influences of film thickness on structural and electrical properties of dc magnetron sputter-deposited copper (Cu) films on p-type silicon. Cu films with thicknesses of 130-1050 nm were deposited from Cu target at sputtering power of 125 W in argon ambient gas pressure of 3.6 mTorr at room temperature. The electrical and structural properties of the Cu films were investigated by four-point probe, atomic force microscopy (AFM) as well as X-ray diffraction (XRD). Results from our experiment show that the grain grows with increasing film thickness, along with enhanced film crystallinity. The root mean square (RMS) roughness as well as the lateral feature size increase with the Cu film thickness, which is associated with the increase in the grain size. On the other hand, the Cu film resistivity decreases to less than 5 μΩ-cm for 500 nm thick film, and further increase in the film thickness has no significant effects on the film resistivity. Possible mechanisms of film thickness dependent microstructure formation of these Cu films are discussed in the paper, which explain the interrelationship of grain growth and film resistivity with increasing Cu film thickness.     

The self-formation graded diffusion barrier of Zr/ZrN

In this paper, the 5 nm ZrN diffusion barrier was deposited by high vacuum magnetron sputtering method on Si substrate and the 300 nm Cu(Zr) alloy film or Cu film was sputtered on ZrN barrier without break vacuum. The self-formation graded Zr/ZrN diffusion barrier was obtained by annealing Cu(Zr)/ZrN bilayer system in N₂/H₂ (10% H₂) atmosphere. The X-ray diffraction (XRD) and four-point probe method were used to study graded Zr/ZrN diffusion barrier. The results revealed that the self-formation Zr barrier and ZrN barrier all obviously improved the thermal stability of Cu/Si system.     

Study of ultrathin vanadium nitride as diffusion barrier for copper interconnect

Ultrathin Vanadium nitride (VN) thin film with thickness around 10 nm was studied as diffusion barrier between copper and SiO₂ or Si substrate. The VN film was prepared by reactive ion beam sputtering. X-ray diffraction, Auger electron spectroscopy, scanning electron microscopy and current-voltage (I-V) technique were applied to characterize the diffusion barrier properties for VN in Cu/VN/Si and Cu/VN/SiO₂ structures. The as-deposited VN film was amorphous and could be thermal stable up to 800 °C annealing. Multiple results show that the ultrathin VN film has good diffusion barrier properties for copper.     

Electroless CoWP as a Diffusion Barrier between Electroless Copper and Silicon

In this work, an electroless CoWP film deposited on a silicon substrate as a diffusion barrier for electroless Cu and silicon has been studied. Four different Cu 120 nm/CoWP/Si stacked samples with 30, 60, 75, and 100 nm electroless CoWP films were prepared and annealed in a rapid thermal annealing (RTA) furnace at 300°C to 800°C for 5 min. The failure behavior of the electroless CoWP film in the Cu/CoWP/Si sample and the effect of CoWP film thickness on the diffusion barrier properties have been investigated by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and sheet resistance measurements. The composition of the electroless CoWP films was 89.4 at.% Co, 2.4 at.% W, and 8.2 at.% P, as determined by energy dispersive X-ray spectrometer (EDS). A 30 nm electroless CoWP film can prevent copper penetration up to 500°C, and a 75 nm electroless CoWP film can survive at least up to 600°C. Therefore, increasing the thickness of electroless CoWP films effectively increases the failure temperature of the Cu/CoWP/Si samples. The observations of SEM and TEM show that interdiffusion of the copper and cobalt causes the failure of the electroless CoWP diffusion barriers in Cu/CoWP/Si during thermal annealing.     

Enhancing the reliability of n-p junction diodes using plasma treated tantalum barrier film

The properties of Ta barrier films treated with various plasma nitridations have been investigated by Cu/barrier/Si. An amorphous layer is formed on Ta barrier film after plasma treatments. The thickness of the amorphous layer is about 3 nm. Plasma treated Ta films possess better barrier performance than sputtered Ta and TaN films. It is attributed to the formation of a new amorphous layer on Ta surface after the plasma treatment. Cu/Ta(N,H)/Ta (10 nm)/Si remained stable after annealing at 750 °C. Ta(N,H)/Ta possesses the best thermal stability and excellent electrical properties. Cu/Ta/n⁺-p and Cu/Ta(N,O)/Ta/n⁺-p diodes resulted in large reverse-bias junction leakage current after annealing at 500 °C and 600 °C, respectively. On the other hand, Ta(N,H)/Ta and Ta(N)/Ta diffusion barriers improve the thermal stability of junction diodes to 650 °C. Ta(N,H)/Ta barrier film possesses lowest resistivity among Ta, Ta(N,O)/Ta, and Ta(N)/Ta films. Hydrogen plays an important role in enhancement of barrier properties. It is believed that hydrogen not only induces amorphization on Ta, but also eliminates the oxygen in the film. It is believed that the enhancement of ability against the copper diffusion is due to the combined effects of the hydrogen reaction and nitridation.     

Optical and structural properties of CuCrO2 thin films on c-face sapphire substrate deposited by reactive RF magnetron sputtering

Reactive sputtering with Ar/N₂ mixture gas was introduced to improve stoichiometry of p-type transparent CuCrO₂ films, and effects of N₂ partial pressure ratio (α_N) on optical and structural properties were investigated. Film composition was changed from Cu rich (i.e. Cr poor) to Cr rich (i.e. Cu poor) by N₂ addition, and the stoichiometric film was grown at α_N of about 20%. Although N atoms were not incorporated into the films from analyses of crystal structure and chemical bonding state, both transmittance from visible to near-infrared wavelength and crystallinity were improved at α_N up to 10%. These improvements were attributed to suppression of the CuO formation and promotion of the O-Cu-O dumbbell bonds formation. This was confirmed by the decrease of diffraction intensity from CuO and the increase of vibrational intensity corresponding A_1g mode. From these results, it can be considered that N atoms decreased not only Cu but also excess O in the film. At α_N of 20% or above, transmittance at wavelength of 450 nm and crystallinity deteriorated. This is supposed that excessive N₂ addition probably generated both O and Cu deficiencies. As a result, it was found that slightly Cu-rich composition is suitable to obtain high-transparency CuCrO₂ thin films for practical use.     

钨粉化学镀铜对压制性能的影响

通过钨粉表面化学镀铜,使其表面包覆一层均匀的诱导铜膜,以此制备W-15Cu电子封装材料。采用扫描电镜和双对数压制方程理论分析,研究钨粉表面化学镀铜含量对钨粉压制性能的影响,结果表明钨粉表面化学镀铜可改善其压制性能,且随化学镀铜含量的增加,压制同等生坯密度的制品压力增大。     

Effect of a silicon nitride buffer layer on the electrical properties of tantalum pentoxide films

Ta₂O₅ films with a buffer layer of silicon nitride of various thicknesses were deposited on Si substrate by reactive sputtering and submitted to annealing at 700 °C in nitrogen atmosphere. The microstructure and the electrical properties of thin films were studied. It was found that with a buffer layer of silicon nitride the electrical properties of Si_xN_y/Ta₂O₅ film can be improved than Ta₂O₅ film. When the thickness of the buffer layer was 3 nm, the Si_xN_y/Ta₂O₅ film has the highest dielectric constant of 27.4 and the lowest leakage current density of 4.61 × 10⁻⁵ A/cm² (at −1 V). For the Si_xN_y (3 nm)/Ta₂O₅ film, the conduction mechanism of leakage current was also analyzed and showed four types of conduction mechanisms at different applied voltages.     

Characterization of sputtered Ta-C-N film in the Cu/barrier/Si contact system

Characterization of sputtered tantalum carbon nitride (Ta-C-N) film in Cu/barrier/Si system was reported for the first time. With a 50∶50 wt.% TaC target and an optimum N₂/Ar flow rate (in sccm) ratio of 2/24, a 600 Å-thick sputtered Ta-C-N layer was shown metallurgically stable up to 650°C annealing for 30 min, which is about 100°C higher as compared to the case without nitrogen doping. Cu diffusion through the local defects or grain boundaries of the Ta-C-N barrier layer into Si substrate is the dominant factor responsible for the failure of the Ta-C-N barrier layer after high temperature annealing.     

Copper chemical vapor deposition from Cu(hexafluoroacetylacetonate)trimethylvinylsilane

Copper chemical vapor deposition using Cu-hexafluoroacetylacetonate (hfac) trimethylvinylsilane (TMVS) as precursor was performed in a cold-wall low pressure chemical vapor deposition (CVD) reactor. The design and operation of the reactor are described. Copper deposition on thermal SiO₂, W, and CoSi₂ substrate surfaces was investigated over the temperature range of 160–300°C and pressure range of 10–1000 mTorr. The activation energies of Cu CVD were determined to be 13.33 and 11.54 kcal/mole for the W and CoSi₂ substrates, respectively. The dependence of film resistivity, grain size, and growth rate on deposition pressure and temperature were also investigated. The film uniformity was found to be better than ten percent over a 4-inch diameter substrate. Experimental results also show that selective deposition can be achieved at a pressure of 10 mTorr within the temperature range of 160–200°C. In addition, hydrofluoric acid dipping was found to modify the SiO₂ surface and influence the copper deposition on it.     

The microstructure,mechanical stress,texture, and electromigration behavior of Al-Pd alloys

As the minimum feature size of interconnect lines decreases below 0.5 urn, the need to control the line microstructure becomes increasingly important. The alloy content, deposition process, fabrication method, and thermal history all determine the microstructure of an interconnect, which, in turn, affects its performance and reliability. The motivation for this work was to characterize the microstructure of various sputtered Al-Pd alloys (Al-0.3wt.%Pd, Al-2Cu-0.3Pd, and Al-0.3Nb-0.3Pd) vs sputtered Al-Cu control samples (Al-0.5Cu and Al-2Cu) and to assess the role of grain size, mechanical stress, and crystallographic texture on the electromigration behavior of submicrometer wide lines. The grain size, mechanical stress, and texture of blanket films were measured as a function of annealing. The as-deposited film stress was tensile and followed a similar stress history on heating for all of the films; on cooling, however, significant differences were observed between the Al-Pd and Al-Cu films in the shape of their stress-temperature-curves. A strong (111) crystallographic texture was typically found for Al-Cu films deposited on SiO₂. A stronger (111) texture resulted when Al-Cu was deposited on 25 nm titanium. Al-0.3Pd films, however, exhibited either a weak (111) or (220) texture when deposited on SiO₂, which reverted to a strong (111) texture when deposited on 25 nm titanium. The electromigration lifetimes of passivated, ≈0.7 μm wide lines at 250°C and 2.5 × 10⁶ A/cm² for both single and multi-level samples (separated with W studs) are reported. The electromigration behavior of Al-0.3Pd was found to be less dependent on film microstructure than on the annealing atmosphere used, i.e. forming gas (90% N₂-10%H₂) annealed Al-0.3Pd films were superior to all of the alloys investigated, while annealing in only N₂ resulted in poor lifetimes.     

Properties of the Mo Back Contact for the Formation of a Thin-Film Photovoltaic Absorber

A Taguchi experimental design was used to find which deposition parameter has the most dominant effect on the electrical resistivity of molybdenum (Mo) films. Based on the most important parameter, the Mo films were further characterized by structural, electrical, and adhesive methods. Then, a copper indium gallium selenide (CIGS) thin film was fabricated by a two-stage process on the obtained Mo layer. The results show that working pressure had a dominant effect on electrical resistivity. The Mo films deposited at 1 mTorr and 2 mTorr exhibited compressive strain and dense polycrystalline microstructure, whereas those deposited at 3 mTorr and 4 mTorr exhibited tensile strain and an elongated grain with open boundaries. A Mo film with open porous structure, tensile strain, and lower resistivity was suitable for the formation of CIGS films. After selenization at 560°C, a single-phase chalcopyrite CIGS film with a layer of MoSe₂ at the Mo/CIGS interface was obtained.     

Electroless deposition and electrical resistivity of sub-100 nm Cu films on SAMs: State of the art

Self-assembled organic monolayers (SAMs) of silanes with -SH, -NH₂ and -C₅H₄N functional groups have been shown recently to act as ultra-thin, robust diffusion barriers at the Cu/SiO₂ and Cu/ultra low-k dielectric interfaces. More generally, SAMs with their tunable surface chemistry are essential elements of future all-wet ULSI metallization with Cu deposited by electroless (ELD) over SAM-functionalized dielectrics. Far too small is known however on the electrical properties of thin metal films formed onto SAM/dielectric substrates. In this paper, we give first a brief literature survey of what is known about Cu films deposited by electroless over dielectrics modified by SAMs. Second, we present our observations of electrical resistivity ρ of sub-100 nm ELD Cu films deposited over the surface of amino-silane SAM/SiO₂ activated by Au monodispersed nano-particles and show that this techniques helps to obtain considerably smaller ρ compared to the previously reported data.