Effects of oxygen doping on properties of microcrystalline silicon film grown using rapid thermal chemical vapor deposition

An oxygen doped microcrystalline silicon (μc-Si) deposition process is developed by mixing small amounts of nitrous oxide (N₂O) with silane (SiH₄) in a rapid thermal chemical vapor deposition (RTCVD) reactor. The effects of oxygen doping on the properties of RTCVD μc-Si films are studied. Experimental results show that the RTCVD process provides high deposition rates for μc-Si and polycrystalline silicon (polySi) films at elevated deposition temperatures and pressures. The surface roughness of the RTCVD μc-Si films can be significantly reduced compared to that of conventional LPCVD polySi films. Steep side walls can be realized due to the small grain size of the μc-Si films. The sheet resistance of BF₂ doped μc-Si films is slightly higher than that of BF₂ doped polySi films, whereas sheet resistances of P and As doped μc-Si films are much higher than those of the corresponding P and As doped polySi films. Measurements of the catastrophic breakdown strength of metal-oxide-semiconductor (MOS) capacitors indicate that the quality of gate electrodes fabricated using μc-Si is improved relative to that of MOS capacitors fabricated using polySi gate electrodes.     

Synthesis of low resistivity complex oxides on MgO using Pt as buffer layer

Highly crystalline SrRuO₃ (SRO) and La_0.5Sr_0.5CoO₃ (LSCO) thin films were deposited on (100) Pt/ MgO by pulsed laser deposition. The films were mainly (001) textured normal to the substrate surface with a high degree of in-plane orientation with respect to the substrate’s major axes. These films were characterized using x-ray diffraction, Rutherford backscattering, four-point probe resistivity measurement, and transmission electron microscopy. The room temperature resistivity for LSCO and SRO films on Pt/MgO was found to be ∼35 and ∼40 μΩ-cm, respectively. An ion beam minimum channeling yield of ∼43% and ∼33% was obtained for LSCO and SRO films, respectively. The interface between Pt and oxide was found to be smooth and free from any interfacial diffusion. This result showed that high-quality low resistivity oxide thin films can be deposited on Pt.     

Characteristics of PECVD grown tungsten nitride films as diffusion barrier layers for ULSI DRAM applications

We have developed tungsten nitride (W-Nitride) films grown by plasma enhanced chemical vapor deposition (PECVD) for barrier material applications in ultra large scale integration DRAM devices. As-deposited W-Nitride films show an amorphous structure, which transforms into crystalline, β-W₂N and α-W phases upon annealing at 800°C. The resistivity of the as-deposited films grown at the NH₃/WF₆ gas flow ratio of 1 is about 160 μω-cm, which decreases to 50 μω-cm after an rapid thermal annealing treatment at 800°C. In the contact holes with the size of 0.35 μm and aspect ratio of 3.5, the bottom step coverage of the tungsten nitride films is about 60%, which is about three times higher than that of collimated-TiN films. We obtained contact resistance and leakage current with the tungsten nitride barrier layer comparable to those with conventional collimated TiN films. The contact resistance and leakage current are stable upon thermal stressing at 450°C up to 48 h.     

In situ B-doped Si epitaxial films grown at 450‡ C by remote plasma-enhanced chemical vapor deposition: Physical and electrical characterization

In situ boron doping of Si epitaxial films grown at 450‡ C by remote plasma-enhanced chemical vapor deposition (RPCVD) has been studied using secondary ion mass spectroscopy (SIMS), Hall effect measurements, defect etching in conjunction with Nomarski microscopy, cross-sectional transmission electron microscopy (XTEM), and current-voltage measurements. Boron incorporation is shown to be controllable and electrically active from 7 × 10¹⁷ to over 10²⁰ cm^-3, with no dependence on process parameters (temperature, rf power, and substrate bias) in the ranges studied, other than the B₂H₆/SiH₄ gas-phase ratio. No change in deposition rate upon introduction of B₂H₆ dopant gas is seen, contrary to what has been observed in several higher-temperature CVD processes. No defects such as stacking faults are seen under Nomarski microscopy, but a visible haze covers some areas ofin situ B-doped wafers. This haze appears to consist of amorphous cone-shaped structures with their apexes at the substrate-epilayer interface. The origin of the conical defects is believed to be related to some phenomenon at the initiation of growth. In order to evaluate the electrical quality ofin situ B-doped epilayers,P ⁺/N mesa diodes have been fabricated using both homoepitaxial and heteroepitaxial (Ge_xSi_1-x)p-type epitaxial films. The electrical junction in these diodes coincides with the (epi-substrate)—interface in the grown films. To avoid interdiffusion or annealing effects during diode fabrication, all processing temperatures were kept at or below 450‡ C. Ideality factors are 1.2-1.3 for all diodes, indicating diffusion-limited transport rather than recombination in the depletion region.     

Investigation of Laser-Assisted Microcrystalline SiGe Films Deposited at Low Temperature

SiGe films deposited by conventional plasma-enhanced chemical vapor deposition (PECVD) were compared with microcrystalline SiGe (μc-SiGe) films deposited at a low temperature using a laser-assisted plasma-enhanced chemical vapor deposition (LAPECVD). In the LAPECVD system, a CO₂ laser was used to assist the pyrolytic decomposition of SiH₄ and GeH₄ reactant gases. The μc-SiGe structure was identified using electron diffraction patterns from high-resolution transmission electron microscopy images. Microcrystalline SiGe films were analyzed using various measurements.     

Chalcopyrite/Si Heterojunctions for Photovoltaic Applications

Films of CuInSe₂ (CIS) and CuGaSe₂ (CGS) were deposited on (100) Si by radiofrequency (RF) magnetron sputtering from stoichiometric CIS and CGS targets. Rutherford backscattering (RBS) analysis yielded a composition of Cu_0.8In_1.1Se_1.9 for CuInSe₂, which indicates that these films were Cu and Se poor. A composition of Cu_0.3Ga_1.5Se_2.0 for CuGaSe₂ shows Ga-rich and Cu-poor layers. Transmission electron microscopy (TEM) of cross-sectional samples established that the films were polycrystalline in nature and free of pinhole defects that normally short-circuit devices fabricated on glass with submicron absorber layers. From the electron and x-ray diffraction patterns, tetragonal chalcopyrite phases of the material were identified. Circular diodes, with a diameter between 100 μm and 400 μm, were fabricated on the grown films with a common Au back-contact. Diodes on both CIS and CGS films exhibited rectifying characteristics. From the polarity corresponding to the high and low currents, it was inferred that the grown films were p-type. These diodes exhibited photovoltaic response, and the forward-bias current increased by as much as two orders of magnitude when illuminated by a 75-W halogen lamp. The open-circuit voltages (V _OC) for these devices are expected to approach the turn-on voltage of the diodes, 0.5 V and 0.7 V, for the CGS/Si and the CIS/Si heterojunctions, respectively. Shunting caused by degenerate phases present in the CGS film is believed to have resulted in the observed lower turn-on voltage for the CGS/n-Si heterojunction diode.     

Growth and characterization of inTISb for IR-detectors

Epitaxial In_1-xTl_xSb films with compositions up to x = 0.1 have been demonstrated using the metalorganic chemical vapor deposition technique on InSb and GaAs substrates. A specially designed high-temperature source delivery system was used for the low vapor pressure cyclopentadienylthallium source. Tl-compositions in the deposited films were measured by Rutherford backscattering spectroscopy which confirmed the incorporation of up to 10% Tl. Room temperature infrared transmission spectra of InTISb exhibited considerable absorption beyond 7 μm. Photoconductive detectors were fabricated in InTISb films grown on semi-insulating GaAs. Spectral response measurements showed substantial photoresponse at 8.5 to 14 μm. In spite of the large lattice-mismatch (≈14%) between InTISb and GaAs, photoconductive detectors exhibited black-body detectivities (D^* _bb) of 5.0 × 10⁸ cm-Hz^1/2W⁻¹ at 40K.     

Low temperature aluminum oxide deposition using trimethylaluminum

Aluminum oxide films (amorphous and γ-Al₂O₃) have been deposited by the oxidation of trimethy1aluminum. Process parameters have been evaluated and optimized to obtain reasonable growth rates and film properties for deposition temperatures between 300 and 400° C. Values of the dielectric constant (7.5 – 7.8), the dielectric strength (7.5 – 7.9 × 10⁶ V/cm), the index of refraction (1.54 – 1.67), and the resistivity (> 10 ohm-cm) compare favorably with Al₂O₃, films grown with other processes at higher deposition temperatures. Film analysis by secondary ion mass spectrometry identified a distribution of carbon and sodium impurities.     

Low-Resistivity Ru-Ta-C Barriers for Cu Interconnects

Ru-Ta-C films deposited on silicon substrates were evaluated as barriers for copper metalization. The films were prepared by magnetron cosputtering using a Ru target and a Ta-C target. Compositions and structure of resultant films were optimally tuned by the respective deposition power of each target. The fabricated Ru-Ta-C films were characterized via four-point probe measurement, x-ray diffractometry, field-emission electron probe microanalysis, and transmission electron microscopy. Failure temperature was evaluated by the sudden rise in electrical resistivity after annealing the Cu/Ru-Ta-C/Si sandwich films, and a reference bilayer Cu/(5 nm Ru)/(5 nm Ta-C)/Si scheme. The optimal compositions were 10 nm Ru₇₇Ta₁₅C₇ and (5 nm Ru)/(5 nm Ta-C), both of which showed failure temperature of 650°C for 30 min and electrical resistivity less than 150 μΩ cm. Because of their high thermal stability and low electrical resistivity, both Ru-Ta-C and Ru/Ta-C films are promising barriers for Cu metalization.     

Field Emission and Electric Discharge of Nanocrystalline Diamond Films

Nanocrystalline diamond (NCD) films were produced by microwave plasma-enhanced chemical vapor deposition (MPECVD) using gas mixtures of Ar, H₂, and CH₄. The structural properties, electron emission, and electric discharge behaviors of the NCD films varied with H₂ flow rates during MPECVD. The turn-on field for electron emission at a pressure of 2.66 × 10⁻⁴ Pa increased from 4.2 V μm⁻¹ for the NCD films that were deposited using a H₂ flow rate of 10 cm³ min⁻¹ to 7 V μm⁻¹ for films deposited at a H₂ flow rate of 20 cm³ min⁻¹. The NCD film with a low turn-on field also induced low breakdown voltages in N₂. The grain size and roughness of the NCD films may influence both the electron emission and the electric discharge behaviors of the NCD cathodes.     

Pulsed laser deposition and processing of wide band gap semiconductors and related materials

The present work describes the novel, relatively simple, and efficient technique of pulsed laser deposition for rapid prototyping of thin films and multi-layer heterostructures of wide band gap semiconductors and related materials. In this method, a KrF pulsed excimer laser is used for ablation of polycrystalline, stoichiometric targets of wide band gap materials. Upon laser absorption by the target surface, a strong plasm a plume is produced which then condenses onto the substrate, kept at a suitable distance from the target surface. We have optimized the processing parameters such as laser fluence, substrate temperature, background gas pressure, target to substrate distance, and pulse repetition rate for the growth of high quality crstalline thin films and heterostructures. The films have been characterized by x-ray diffraction, Rutherford backscattering and ion channeling spectrometry, high resolution transmission electron microscopy, atomic force microscopy, ultraviolet (UV)-visible spectroscopy, cathodoluminescence, and electrical transport measurements. We show that high quality AlN and GaN thin films can be grown by pulsed laser deposition at relatively lower substrate temperatures (750–800°C) than those employed in metal organic chemical vapor deposition (MOCVD), (1000–1100°C), an alternative growth method. The pulsed laser deposited GaN films (∼0.5 μm thick), grown on AlN buffered sapphire (0001), shows an x-ray diffraction rocking curve full width at half maximum (FWHM) of 5–7 arc-min. The ion channeling minimum yield in the surface region for AlN and GaN is ∼3%, indicating a high degree of crystallinity. The optical band gap for AlN and GaN is found to be 6.2 and 3.4 eV, respectively. These epitaxial films are shiny, and the surface root mean square roughness is ∼5–15 nm. The electrical resistivity of the GaN films is in the range of 10⁻²–10² Θ-cm with a mobility in excess of 80 cm²V⁻¹s⁻¹ and a carrier concentration of 10¹⁷–10¹⁹ cm⁻³, depending upon the buffer layers and growth conditions. We have also demonstrated the application of the pulsed laser deposition technique for integration of technologically important materials with the III–V nitrides. The examples include pulsed laser deposition of ZnO/GaN heterostructures for UV-blue lasers and epitaxial growth of TiN on GaN and SiC for low resistance ohmic contact metallization. Employing the pulsed laser, we also demonstrate a dry etching process for GaN and AlN films.     

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.     

Influence of Ga vs As prelayers on GaAs/Ge growth morphology

The surface morphology of GaAs films grown on Ge substrates is studied by scanning force microscopy. We find a dramatic difference arising from Ga as opposed to As prelayers in the formation of anti-phase boundaries (APBs), surface features near threading dislocations, and surface roughness, for films as thick as 1 μm. Ga prelayer samples are smooth; thin films display some APBs with predominantly one growth domain while the 1 μm thick film displays the morphology of a homoepitaxial GaAs film. In contrast, As prelayer samples are rough with complicated APB structures, which can be attributed to the increase in single steps during As₂ deposition.     

Amorphous chromium silicide formation in hydrogenated amorphous silicon

The interaction between thin films of hydrogenated amorphous silicon and sputter-deposited chromium has been studied. Following deposition of the chromium films at room temperature, the films were annealed over a range of times and temperatures below 350°C. It was found that an amorphous silicide was formed only a few nanometers thick with the square of thickness proportional to the annealing time. The activation energy for the process was 0.55±0.05 eV. The formation process of the silicide was very reproducible with the value of density derived from the thickness and Cr surface density being close to the value for crystalline CrSi₂ for all films formed at temperatures ≤300°C. The specific resistivity of the amorphous CrSi₂ was ≈600 μΩ·cm and independent of annealing temperature.     

Development of (Bi,Sb)<Subscript>2</Subscript>(Te,Se)<Subscript>3</Subscript>-Based Thermoelectric Modules by a Screen-Printing Process

In major applications, optimal power will be achieved when thermoelectric films are at least 100 μm thick. In this paper we demonstrate that screen-printing is an ideal method to deposit around 100 μm of (Bi,Sb)₂(Te,Se)₃-based films on a rigid or flexible substrate with high Seebeck coefficient value (90 μV K⁻¹ to 160 μV K⁻¹) using a low-temperature process. Conductive films have been obtained after laser annealing and led to acceptable thermoelectric performance with a power factor of 0.06 μW K⁻² cm⁻¹. While these initial material properties are not at the level of bulk materials, the complete manufacturing process is cost-effective, compatible with large surfaces, and affords a mass-production technique.     

Sputter deposition of phosphors for electroluminescent flat panel displays

Thin film electroluminescent (TFEL) phosphors for flat panel displays have been produced by several different growth methods including atomic layer epitaxy, chemical vapor deposition, and sputter deposition. There is a great deal of interest in sputter deposition due to the extensive knowledge base and equipment from other existing thin film manufacturing. However, deposition of sulfide-based TFEL phosphors by conventional radio frequency magnetron sputtering has proven to be difficult due to the formation of negative sulfur ions near the target which are accelerated to the growing film by the self-bias developed on the target. This negative-ion resputtering can result in amorphization or re-sputtering of the phosphor films. In severe cases, a net sputtering of the substrate can result. In order to remedy this negative ion resputtering problem, modifications of the magnetron geometry and ion-beam sputtering have been evaluated for production of Ca_xSr_1−xGa₂S₄:Ce and SrS:Ce TFEL phosphors. Sputter deposited TFEL films also typically require a postdeposition anneal which adds to expense and can cause other problems for the flat panel display. Ion-beam assist during deposition of undoped ZnS was studied as a method to induce surface-atom mobility and a more crystalline as-deposited film for use in monochrome TFEL displays.     

Photosensitivity of thin-film structures based on laser-deposited CuIn(TexSe1−x )2 layers

Thin films of the solid solutions CuIn(Te_xSe_1−x )₂ (0<x<1) exhibiting chalcopyrite structure were obtained by the method of laser deposition. Using half-transmitting indium layers, Schottky diodes were prepared on the basis of the films obtained. The spectral dependence of the sensitivity as a function of the ratio between Te and Se was investigated by illuminating the structures through the In contact. Analysis of the experimental results showed that the region of spectral sensitivity of such thin-film structures depends on the tellurium content in the CuIn(Te_xSe_1−x )₂ layers. Fiz. Tekh. Poluprovodn. 32, 458–460 (April 1998)     

Study of the emission extraction efficiency of mesa-LEDs with a narrow-gap InAsSb active region

A series of light-emitting diodes (LEDs) (emission peak wavelength λ_max = 3.6 μm) with cone-shaped mesas, which have concave lateral surfaces and heights between 10 to 130 μm, has been developed. The dependence of the emission efficiency for these LEDs on mesa height has been studied at different injection currents at the temperatures 77 and 298 K. The form of the dependence observed is in agreement with the results of theoretical calculations. It is shown that the effective absorption coefficient, caused by emission extraction from the crystal, may be as large as 3 cm⁻¹ for LEDs with the highest mesa (130 μm) among the diodes in this series. The emission extraction coefficient is close to 30% at the temperature 298 K and 94% at 77 K.     

Growth of (GaAs)1_x(Ge2)x by metalorganic chemical vapor deposition

We report deposition of (GaAs)_{1_x}(Ge₂)_x on GaAs substrates over the entire alloy range. Growth was performed by metalorganic chemical vapor deposition at temperatures of 675 to 750°C, at 50 and 760 Torr, using trimethylgallium, arsine, and germane at rates of 2–10 μ/h. Extrinsic doping was achieved using silane and dimethylzinc in hydrogen. Characterization methods include double-crystal x-ray rocking curve analysis, Auger electron spectroscopy, 5K photoluminescence, optical transmission spectra, Hall-effect, and Polaron profiling. Results achieved include an x-ray rocking curve full-width at half maximum as narrow as 12 arc-s, Auger compositions spanning the alloy range from x = 0.03 to x = 0.94, specular surface morphologies, and 5K photoluminescence to wavelengths as long as 1620 nm. Undoped films are n type, with n ≈ 1 × 10¹⁷ cm⁻³. Extrinsic doping with silane and dimethylzinc have resulted in films which are n type (10¹⁷ to 10¹⁸ cnr⁻³) or p type (5 × 10¹⁸ to 1 × 10²⁰ cm⁻³). Mobilities are generally ≈ 50 cm²/V-s and 500 cm²/V-s, for p and n films, respectively.     

Low-temperature metal-organic chemical vapor deposition (LTMOCVD) of device-quality copper films for microelectronic applications

Copper films for potential use in multilevel metallization in ULSIC’s were produced by low temperature (250–350° C) metal-organic chemical vapor deposition (LTMOCVD) in atmospheres of pure H₂ or mixture Ar/H₂ from the β-diketonate precursor bis(1,1,1,5,5,5-hexafluoroacetylacetonato) copper(ll), Cu(hfa)₂. The films were analyzed by x-ray diffraction (XRD), Rutherford backscattering (RBS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and energy-dispersive x-ray spectroscopy (EDXS). The results of these studies showed that the films were uniform, continuous, adherent and highly pure—oxygen and carbon contents were below the detection limits of AES. Four point resistivity measurements showed that the copper films had very low resistivity, as low as 1.9 μΩcm for the films deposited in pure hydrogen atmosphere. Our preliminary results seem to indicate that LTMOCVD is a very attractive technique for copper multilevel metallizations.