Metalorganic chemical vapor deposition of silver thin films for future interconnects by direct liquid injection system

Deposition of Ag films by direct liquid injection-metal organic chemical vapor deposition (DLI-MOCVD) was chosen because this preparation method allows precise control of precursor flow and prevents early decomposition of the precursor as compared to the bubbler-delivery. Silver(I)-2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionato-triethylphosphine [Ag(fod)(PEt₃)] as the precursor for Ag CVD was studied, which is liquid at 30 °C. Ag films were grown on different substrates of SiO₂/Si and TiN/Si. Argon and nitrogen/hydrogen carrier gas was used in a cold wall reactor at a pressure of 50–500 Pa with deposition temperature ranging between 220 °C and 350 °C. Ag films deposited on a TiN/Si diffusion barrier layer have favorable properties over films deposited on SiO₂/Si substrate. At lower temperature (220 °C), film growth is essentially reaction-limited on SiO₂ substrate. Significant dependence of the surface morphology on the deposition conditions exists in our experiments. According to XPS analysis pure Ag films are deposited by DLI-MOCVD at 250 °C by using argon as carrier gas.     

The epitaxial growth of ZnO on sapphire and MgAl spinel using the vapor phase reaction of Zn and H2O

The gas phase reaction of Zn and H₂O in a He carrier gas has been used as the basis for the chemical vapor deposition of ZnO on sapphire and MgAl spinel. Deposit characteristics were studied as a function of reactor linear gas stream velocity, Zn/H₂O vapor phase ratio, temperature and substrate preparation. It was round that the substrate support can influence the surface morphology significantly and that in situ pretreatment can affect epitaxial relationships between deposit and substrate. Transparent, visually smooth deposits of (11–24) ZnO can be obtained on chemically polished (0001) sapphire at 815°C using average linear gas stream velocities, ν, of 6-12 cm/sec referenced to room temperature in conjunction with a Zn/H₂O reactor input-pressure ratio of 0.02–0.09 (using Zn reactor pressures of 1.2–5.0 × 10⁻³ atm) . The substrates are given an H₂O in situ pretreatment at 900°C prior to deposition at ν = 3 cm/sec with the partial pressure of H₂O in He = 5.7 × 10 atm.     

Mechanistic study of borosilicate glass growth by low-pressure chemical vapor deposition from tetraethylorthosilicate and trimethylborate

A reaction mechanism and film morphology as a function of reactor conditions and post growth thermal annealing for borosilicate glass (BSG), (SiO₂)_x(B₂O₃)_1−x, films deposited from tetraethylorthosilicate (TEOS), trimethylborate (TMB), and oxygen (O₂) precursors by low-pressure chemical vapor deposition (LPCVD) was determined. An empirically derived reaction model for BSG film growth is proposed that predicts the growth rate and composition of BSG films up to 70 mole% B₂O₃. The BSG reaction model includes a strongly adsorbed TEOS-derived intermediate that forms SiO₂ and a direct surface reaction of TMB, in O₂, to form B₂O₃. This model is supported by growth rate and mass spectroscopic data. The BSG film morphology, investigated using atomic force microscopy, was found to have a root-mean-square roughness of 0.5 nm, with the precise film morphology being a function of reactor conditions. The BSG film roughness increases with film thickness, temperature, and boron content. Thermal annealing of the films in a water-free environment leads to planarization of the BSG governed by the film composition and anneal temperature.     

Deposition and characterization of Pb TiO3 thin films on silicon wafers using metalorganic sources

Ferroelectric PbTiO₃ thin films were deposited on bare silicon and Pt/SiO₂/Si substrates by metalorganic chemical vapor deposition in a temperature range from 270 to 550°C. The deposition of a single phase PbTiO₃ thin film did not occur on bare silicon substrates. Instead a double layer of lead-silicate and PbTiO₃ was formed owing to a serious diffusion of lead and oxygen ions into silicon substrates. But on Pt/SiO₂/Si substrates, a single phase PbTiO₃ oriented parallel to a-and c-axis was grown at a substrate temperature as low as 350°C even without a high temperature post-annealing. To get an optimal film, a precise control of input gas composition and also a deposition in a low temperature range from 350 to 400°C are necessary.     

SiO2 film deposition in a low-pressure RF inductive discharge SiH4 + O2 plasma

SiO₂ films were deposited in an rf inductive discharge plasma (13.56 MHz) at a substrate temperature of-550 K and an ion energy of 35 eV. Variable parameters were silane and oxygen flow rates, pressure (0.3–1.2 Pa), and ion current density (1–2.5 mA/cm²). In these ranges of the process parameters, good silicon dioxide films with a composition close to that of thermally oxidized SiO₂ were obtained. The film growth rate was found to be 65 nm/min. The deposition nonuniformity was <4% over 100-mm silicon wafers.     

The effects of process conditions and substrate on copper MOCVD using liquid injection of (hfac)Cu(vtmos)

Copper MOCVD (metalorganic chemical vapor deposition) using liquid injection for effective delivery of the (hfac)Cu(vtmos) [1,1,1,5,5,5-hexafluoro-2,4-pentadionato(vinyltrimethoxysilane) copper(I)] precursor has been performed to clarify growth behavior of copper films onto TiN, <100> Si, and Si₃N₄ substrates. Especially, we have studied the influences of process conditions and the substrate on growth rates, impurities, microstructures, and electrical characteristics of copper films. As the reactor pressure was increased, the growth rate was governed by a pick-up rate of (hfac)Cu(vtmos) in the vaporizer. The apparent activation energy for copper growth over the surface-reaction controlled regime from 155°C to 225°C was in the range 12.7–32.5 kcal/mol depending upon the substrate type. It revealed that H₂ addition at 225°C substrate temperature brought about a maximum increase of about 25% in the growth rate compared to pure Ar as the carrier gas. At moderate deposition temperatures, the degree of a <111> preferred orientation for the deposit was higher on the sequence of <Cu/Si<Cu/TiN<Cu/Si₃N₄. The relative impurity content within the deposit was in the range 1.1 to 1.8 at.%. The electrical resistivity for the Cu films on TiN illustrated three regions of the variation according to the substrate temperature, so the deposit at 165°C had the optimum resistivity value. However, the coarsened microstructures of Cu on TiN prepared above 275°C gave rise to higher electrical resistivities compared to those on Si and Si₃N₄ substrates.     

Influences of ZnO buffer layers on the quality of ZnO films synthesized by the metal-organic chemical vapor deposition process

High-quality ZnO thin films were prepared by metal-organic chemical vapor deposition (MOCVD) on a sapphire (a-Al₂O₃) substrate. The synthesis of ZnO films was performed over a substrate temperature of 400–700°C and at chamber pressures of 0.1–10 torr. The structural and optical properties of ZnO films were investigated in terms of deposition conditions, such as substrate temperature, working pressure, and the ratio of Zn precursor (Diethylzinc (DEZn)) to oxygen. The ZnO films, preferentially oriented to 34.42° diffraction because of the (002) plane, were obtained under processing conditions of 700°C and 3 torr. This film shows a full-width at half-maximum (FWHM) of 0.4–0.6°. The results of photoluminescence (PL) spectroscopy also show a strong near band-edge emission at 3.36 eV at 10 K as well as a very weak emission at deep levels around 2.5 eV at room temperature. In addition, we are interested in the introduction of ZnO buffer-layer growth by the sputtering process to reduce lattice mismatch stress. This paper addresses how to advance the crystalline and optical properties of film. The ZnO film grown with the aid of a buffer layer shows a FWHM of 0.06–0.1° in the x-ray diffraction (XRD) pattern. This result indicates that crystalline properties were highly improved by the ZnO buffer layers. The PL spectroscopy data of ZnO film also shows a strong near band-edge emission and very weak deep-level emission similar to films synthesized without a buffer layer. Accordingly, synthesized ZnO films with buffer layers indicate fairly good optical properties and low defect density as well as excellent crystallinity.     

Laser processing of TiSi2 and CoSi2 thin films on silicon (100) substrates

We have investigated the formation of TiSi₂ and CoSi₂ thin films on Si(100) substrates using laser (wave length 248 nm, pulse duration 40 ns and repetition rate 5 Hz) physical vapor deposition (LPVD). The films were deposited from solid targets of TiSi₂ and CoSi₂ in vacuum with the substrate temperature optimized at 600° C. The films were characterized using x-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and four point probe ac resistivity. The films were found to be polycrystalline with a texture. The room temperature resistivity was found to be 16 μΩ-@#@ cm and 23 μΩ-cm for TiSi₂ and CoSi₂ films, respectively. We optimized the processing parameters so as to get particulate free surface. TEM results show that the silicide/silicon interface is quite smooth and there is no perceptible interdiffusion across the interface.     

Remote plasma-enhanced CVD of silicon: Reaction kinetics as a function of growth parameters

The reaction kinetics in Remote Plasma-enhanced Chemical Vapor Deposition (RPCVD) have been studied for a chamber pressure of 200 mTorr, rf powers between 4 and 8 W, diluted silane flow rates between 5 and 40 sccm, and temperatures between 190 and 480° C. The observed temperature dependence of growth rate reveals a change in activation energy at 300–325° C, suggesting that hydrogen desorption is the rate limiting step in the deposition reaction. A strong dependence of growth rate on rf power has been attributed in part to the extension of the glow discharge region closer to the substrate at higher rf powers. Growth rate has been shown to increase when the sample is positioned closer to the glow, indicating that the reaction precursor is a short-lived species, probably SiH₂ or SiH₃. Growth rate has been shown to exhibit a sublinear dependence on silane partial pressure. Oxygen incorporation in the deposited films has been studied using Secondary Ion Mass Spectroscopy (SIMS), and it has been found that the main source of oxygen contamination is the process gases. However, it has also been found that “point of use” purification of the process gases reduces water and oxygen contamination significantly, reducing the oxygen incorporation in the films by an order of magnitude.     

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.     

Atmospheric pressure chemical vapor deposition of blanket tungsten films on silicon substrates for integrated circuit applications

Atmospheric pressure chemical vapor deposition (APCVD) of tungsten films using WF₆/H₂ chemistry has been studied. A statistical design of experiments approach and a surface response methodology were used to determine the most important process parameters and to obtain the best quality film possible in the parameter range studied. It was found that the deposition rate depends strongly on WF₆ flow rate, temperature, and the interaction between hydrogen flow rate and temperature. The resistivity was found to have a strong dependence on WF₆ and H₂ flow rates and temperature. An activation energy of 0.4 eV was calculated for the reaction rate limited growth regime. Empirical equations for predicting the deposition rate and resistivity were obtained. The resistivity decreases with both increasing film thickness and grain size. The films grown in the studied process parameter range indicate that (110) is the preferred orientation for films deposited with low WF₆/H₂ flow rate ratios at all deposition temperatures (350–450°C), whereas, the (222) orientation dominates at high WF₆/H₂ flow ratios and high deposition temperatures. Also, the grain size is larger for (222) oriented films than for (110) oriented films. The results of this study suggest that high-quality, thin film tungsten can be deposited using APCVD.     

Structural and Passivative Behaviors of Cu(In) Thin Film

This investigation prepares a low-resistivity and self-passivated Cu(In) thin film. The dissociation behaviors of dilute Cu-alloy thin films, containing 1.5–5at.%In, were prepared on glass substrates by a cosputter deposition, and were subsequently annealed in the temperature range of 200–600 °C for 10–30 min. Thus, self-passivated Cu thin films in the form In₂O₃/Cu/SiO₂ were obtained by annealing Cu(In) alloy films at an elevated temperature. Structural analysis indicated that only strong copper diffraction peaks were detected from the as-deposited film, and an In₂O₃ phase was formed on the surface of the film by annealing the film at an elevated temperature under oxygen ambient. The formation of In₂O₃/Cu/SiO₂ improved the resistivity, adhesion to SiO₂, and passivative capability of the studied film. A dramatic reduction in the resistivity of the film occurred at 500 °C, and was considered to be associated with preferential indium segregation during annealing, yielding a low resistivity below 2.92 μΩcm. The results of this study can be potentially exploited in the application of thin-film transistor–liquid crystal display gate electrodes and copper metallization in integrated circuits.     

A large-scale parametric study of InP deposition on patterned substrates

Selective Area Epitaxy (SAE) is the process of locally depositing a semiconductor film on a substrate which has been patterned with an inert masking material such as SiO₂. During deposition by metalorganic chemical vapor deposition (MOCVD), the build up of precursors over the SiO₂ mask causes material to diffuse into the open areas leading to a growth rate increase. SAE is an important technique for electronic and photonic device fabrication, and for the monolithic integration of these devices. The present work is a single comprehensive study, which reports on the impact of all major MOCVD parameters to SAE indium phosphide films. The parameters include pressure, V/III pressure ratio, growth rate, temperature and mask geometry.     

Large-Scale Synthesis of Graphene Films by Joule-Heating-Induced Chemical Vapor Deposition

We report large-area synthesis of few-layer graphene films by chemical vapor deposition (CVD) in a cold-wall reactor. The key feature of this method is that the catalytic metal layers on the SiO₂/Si substrates are self-heated to high growth temperature (900°C to 1000°C) by high-current Joule heating. Synthesis of high-quality graphene films, whose structural and electrical characteristics are comparable to those grown by hot-wall CVD systems, was confirmed by transmission electron microscopy images, Raman spectra, and current–voltage analysis. Optical transmittance spectra of the graphene films allowed us to estimate the number of graphene layers, which revealed that high-temperature exposure of Ni thin layers to a carbon precursor (CH₄) was critical in determining the number of graphene layers. In particular, exposure to CH₄ for 20 s produces very thin graphene films with an optical transmittance of 93%, corresponding to an average layer number of three and a sheet resistance of ~600 Ω/square.     

Basic studies of gallium nitride growth on sapphire by metalorganic chemical vapor deposition and optical properties of deposited layers

We have studied the growth of gallium nitride on c-plane sapphire substrates. The layers were grown in a horizontal metalorganic chemical vapor deposition reactor at atmospheric pressure using trimethylgallium (TMG) and ammonia (NH₃). Variation of the V/III ratio (150–2500) shows a distinct effect on the growth rate. With decreasing V/III ratio, we find an increasing growth rate. Variation of the growth temperature (700–1000°C) shows a weak increase in growth rate with temperature. Furthermore, we performed secondary ion mass spectroscopy measurements and find an increasing carbon incorporation in the GaN films with decreasing ammonia partial pressure and a growing accumulation of carbon at the substrate interface. Photoluminescence measurements show that samples with high carbon content show a strong yellow luminescence peaking at 2.2 eV and a near band gap emission at 3.31 eV. With increasing carbon content, the intensity of the 3.31 eV line increases suggesting that a carbon related center is involved.     

Low temperature plasma enhanced chemical vapor deposition of silicon oxide films using disilane and nitrous oxide

Silicon oxide films have been deposited between room temperature and 300°C using disilane and nitrous oxide by plasma enhanced chemical vapor deposition. Film deposition was investigated as a function of the gas flow ratio of nitrous oxide to disilane, the substrate temperature, the total gas flow rate, the radio frequency discharge power, and the process pressure. The stoichiometric SiO₂ films were obtained when the gas ratio of nitrous oxide to disilane was in the range of 50-150. The deposition was found to be nearly temperature independent indicating the mass transport limited regime.     

Fabrication of Bismuth Telluride-Based Alloy Thin Film Thermoelectric Devices Grown by Metal Organic Chemical Vapor Deposition

Bismuth–antimony–telluride based thin film materials were grown by metal organic vapor phase deposition (MOCVD). A planar-type thermoelectric device was fabricated with p-type Bi_0.4Sb_1.6Te₃ and n-type Bi₂Te₃ thin films. The generator consisted of 20 pairs of p-type and n-type legs. We demonstrated complex structures of different conduction types of thermoelectric elements on the same substrate using two separate deposition runs of p-type and n-type thermoelectric materials. To demonstrate power generation, we heated one side of the sample with a heating block and measured the voltage output. An estimated power of 1.3 μW was obtained for the temperature difference of 45 K. We provide a promising procedure for fabricating thin film thermoelectric generators by using MOCVD grown thermoelectric materials that may have a nanostructure with high thermoelectric properties.     

The CVD growth of Cu films using H2 as carrier gas

Copper chemical vapor deposition from Cu(hexafluoroacetylacetonate)trimethylvinylsilane (Cu(hfac)TMVS) was studied using a low pressure chemical vapor deposition system of a cold wall vertical reactor. The Cu films deposited using H₂ as a carrier gas revealed no impurities in the films within the detection limits of Auger electron spectroscopy and x-ray photoelectron spectroscopy. Using hydrogen as a carrier gas, the hydrogen not only acts as a reducing agent, but also reacts with the residual fragment of precursor. As a result, using H₂ as a carrier gas for Cu(hfac)TMVS resulted in Cu films of lower resistivity, denser microstructure and faster deposition rate than using Ar or N₂ as the carrier gas. Moreover, we found that N₂ plasma treatment on the substrate surface prior to Cu deposition increased the deposition rate of Cu films.     

Interface properties of ZnO nanotips grown on Si substrates

ZnO nanotips have been grown on Si (100) using metalorganic chemical vapor deposition (MOCVD). The growth temperature is optimized for good crystallinity, morphology, and optical properties. ZnO nanotips exhibit a strong near band edge emission of ∼376 nm at room temperature with negligible green band emission. Pregrowth substrate treatment using diluted hydrofluoric acid (HF) and minimized oxygen exposure before the initial growth significantly reduces the interfacial SiO₂ thickness, while maintaining good morphology. An n-ZnO nanotips/p-Si diode is fabricated and its I–V characteristic is measured. The threshold voltage of the diode is found to be below 2.0 V with small reverse leakage current. The ZnO/p-Si diodes provide the possibility of integrating the ZnO nanotips with Si-based electronic devices.     

Formation of aluminum oxide films from aluminum hexafluoroacetylacetonate at 350–450° c

A study of the thermally activated decomposition of Al(hfa)₃ (aluminum hexafluoroacetylacetonate) from the gas phase to form Al₂O₃ on silicon substrates is reported. The decomposition process was carried out in an open tube atmospheric pressure reactor in either argon or oxygen/argon mixtures in the temperature range, 350–450° C. The chemical vapor deposition process resulted in the formation of aluminum oxide films in all instances. The dielectric strength of Al/Al₂O₃/Si capacitors which received a post-metal anneal, but did not receive a high temperature annealing treatment, with aluminum oxide films prepared from Al(hfa)₃ in argon, was found to be in the range 2–6 MV/cm. The difference between the flatband voltage of the MOS structures and the metal-silicon work function difference was positive, indicative of a net negative oxide charge with a density of approximately 3 × 10¹¹ – 3 × 10¹² cm^-2, assuming the charge is located at the oxide-silicon interface. Decomposition of Al(hfa)₃ was also carried out in oxygen/argon mixtures with the oxygen concentration in the range 10–60 vol %. This process led to the deposition of aluminum oxide films with breakdown fields in the range 8–9 MV/cm. However, the flatband voltages of the Al/Al₂O₃/Si capacitors were even more positive than those obtained with Al₂O₃ formed in pure argon. High temperature (800–1000° C) oxygen or nitrogen annealing treatments of alumina films deposited in either argon or oxygen/argon mixtures were evaluated from the point of view of their influence on the oxide film properties. In particular, an annealing process in oxygen at 1000° C for 15 min was found to result in a reduction of the net negative oxide charge, and an improvement of the dielectric strength of films deposited in argon. Films formed in oxygen/argon mixtures did not change appreciably following oxygen annealing, as far as breakdown fields are concerned, but the oxide net negative charge was reduced. As in an earlier study by the authors, of copper film deposition from Cu(hfa)₂, it was found that essentially carbon free films could be obtained under appropriate conditions.