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All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Zirconium nitride films deposited in (Ar + N{sub 2} + H{sub 2}) sputtering atmosphere: Optical, structural, and electrical properties

Zr-N films were grown on glass substrates via radio-frequency magnetron sputtering using an Ar + N{sub 2} + H{sub 2} mixture. Hydrogen was employed in order to reduce oxygen contamination coming from background pressure, as confirmed by secondary ion mass spectroscopy analysis. The tuned process parameter was the nitrogen flux percentage (R{sub N2}) in the mixture. The crystallographic structure of the films was studied using x-ray diffraction. The measurements show that the films deposited at low R{sub N2} (lower than or equal to 50%) crystallize in the rocksalt ZrN structure. As R{sub N2} exceeds 50%, the film exhibits the co-presence of ZrN and Zr{sub 3}N{sub 4} (denoted as o-Zr{sub 3}N{sub 4}) phases. When the deposition is performed in only nitrogen atmosphere (R{sub N2} = 100%), a broad peak located at 2{theta}{approx_equal} 32.2 deg. is mainly attributed to the contribution coming from (320) planes of the o-Zr{sub 3}N{sub 4}. An envelope method, based on the optical reflection and transmission spectra taken at normal incidence, has been applied for the optical characterization of the nitride films. Such a method allows the determination of the samples' average thickness and optical constants (refractive index n and extinction coefficient k) in the ultraviolet-visible-near infrared regions. The evaluated thickness was about 2500 nm, which is in good agreement with the value obtained from profilometry. The absorption coefficient {alpha} was calculated from reflectance and transmittance spectra. The energy bandgap ranges from 2.3 eV to 2.4 eV. Electrical characterization was performed using capacitance-voltage measurements, which showed that the films evolve from insulating to semiconductor behavior when the nitrogen content in the sputtering atmosphere is decreased, confirming structural and optical results.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Plasma etch characteristics of aluminum nitride mask layers grown by low-temperature plasma enhanced atomic layer deposition in SF{sub 6} based plasmas

The plasma etch characteristics of aluminum nitride (AlN) deposited by low-temperature, 200 deg. C, plasma enhanced atomic layer deposition (PEALD) was investigated for reactive ion etch (RIE) and inductively coupled plasma-reactive ion etch (ICP-RIE) systems using various mixtures of SF{sub 6} and O{sub 2} under different etch conditions. During RIE, the film exhibits good mask properties with etch rates below 10r nm/min. For ICP-RIE processes, the film exhibits exceptionally low etch rates in the subnanometer region with lower platen power. The AlN film's removal occurred through physical mechanisms; consequently, rf power and chamber pressure were the most significant parameters in PEALD AlN film removal because the film was inert to the SF{sub x}{sup +} and O{sup +} chemistries. The etch experiments showed the film to be a resilient masking material. This makes it an attractive candidate for use as an etch mask in demanding SF{sub 6} based plasma etch applications, such as through-wafer etching, or when oxide films are not suitable.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Characterization of hydrogen-plasma interactions with photoresist, silicon, and silicon nitride surfaces

For the 45 nm technology node and beyond, a major challenge is to achieve reasonably high photoresist ash rates while minimizing the loss of the silicon (Si) substrate and its nitride (Si{sub 3}N{sub 4}). Accordingly, an objective of this work is to characterize the photoresist strip rate under varying conditions of H{sub 2} plasma and the effects of these conditions on Si and Si{sub 3}N{sub 4} etch rates. In addition, we discuss in detail the fundamental mechanisms of the reactions between H atoms and the above substrates and successfully reconcile the process trends obtained with the reaction mechanisms. In this work, photoresist, Si, and Si{sub 3}N{sub 4} films were exposed to downstream pure-H{sub 2} discharges and their removal rates were characterized by ellipsometry as a function of the following parameters: substrate temperature, reactor pressure, H{sub 2} flow rate, and source power. The authors found that the H{sub 2}-based dry ash and Si{sub 3}N{sub 4} etch are both thermally activated reactions, evidenced by the steady increase in etch rate as a function of temperature, with activation energies of {approx}5.0 and {approx}2.7 kcal/mol, respectively. The Si substrate exhibits a rather unique behavior where the etch rate increases initially to a maximum, which occurs at {approx}40 deg. C, and then decreases upon a further increase in temperature. The decrease in the Si etch rate at higher temperatures is attributed to the activation of competing side reactions that consume the chemisorbed H atoms on the Si surface, which then suppresses the Si-etch step. The photoresist and Si{sub 3}N{sub 4} removal rates increase initially with increasing pressure, reaching maxima at {approx}800 and 2000 mTorr, respectively, beyond which the removal rates drop with increasing pressure. The initial increase in removal rate at the low-pressure regime is attributed to the increased atomic-hydrogen density, whereas the decrease in ash rate at the high-pressure regime could be attributed to the recombination of H atoms that could occur by various mechanisms. At temperatures where the reaction rates are relatively fast, the photoresist and Si removal rates both increase continuously with the H{sub 2} flow rate, indicating that both reactions are in the supply-limited regime. For the range of process conditions explored here, we find that the etch rates of Si are generally much higher than those for Si{sub 3}N{sub 4} with Si:Si{sub 3}N{sub 4} etch-rate ratios that vary from 25 to >>520. Based on the process trends obtained here, we have identified a process window--high temperature and intermediate pressure--that attains relatively high photoresist ash rates and low Si and Si{sub 3}N{sub 4} etch rates.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Biaxial texture development in aluminum nitride layers during off-axis sputter deposition

Polycrystalline aluminum nitride (AlN) layers were deposited by pulsed-dc reactive magnetron sputtering from a variable deposition angle {alpha} = 0 Degree-Sign -84 Degree-Sign in 5 mTorr pure N{sub 2} at room temperature. X-ray diffraction pole figure analyses show that layers deposited from a normal angle ({alpha} = 0 Degree-Sign ) exhibit fiber texture, with a random in-plane grain orientation and the c-axis tilted by 42 Degree-Sign {+-} 2 Degree-Sign off the substrate normal, yielding wurtzite AlN grains with the {l_brace}1012{r_brace} plane approximately parallel ({+-}2 Degree-Sign ) to the substrate surface. However, as {alpha} is increased to 45 Degree-Sign , two preferred in-plane grain orientations emerge, with populations I and II having the c-axis tilted toward and away from the deposition flux, by 53 Degree-Sign {+-} 2 Degree-Sign and 47 Degree-Sign {+-} 1 Degree-Sign off the substrate normal, respectively. Increasing {alpha} further to 65 Degree-Sign and 84 Degree-Sign , results in the development of a single population II with a 43 Degree-Sign {+-} 1 Degree-Sign tilt. This developing biaxial texture is attributed to a competitive growth mode under conditions where the adatom mobility is sufficient to cause intergrain mass transport, but insufficient for the thermodynamically favored low energy {l_brace}0001{r_brace} planes to align parallel to the layer surface. Consequently, AlN nuclei are initially randomly oriented and form a kinetically determined crystal habit exposing {l_brace}0001{r_brace} and {l_brace}1120{r_brace} facets. The expected direction of its highest growth rate is 49 Degree-Sign {+-} 5 Degree-Sign tilted relative to the c-axis, in good agreement with the 42 Degree-Sign -53 Degree-Sign measured tilt. The in-plane preferred orientation for {alpha} > 0 Degree-Sign is well explained by the orientation dependence in the cross section of the asymmetric pyramidal nuclei to capture directional deposition flux. The observed tilt is ideal for shear mode electromechanical coupling, which is maximized at 48 Degree-Sign .

36 MATERIALS SCIENCE↗
DOE OSTI2013

Low-temperature ({<=}200 Degree-Sign C) plasma enhanced atomic layer deposition of dense titanium nitride thin films

Titanium nitride (TiN) has been widely used in the semiconductor industry for its diffusion barrier and seed layer properties. However, it has seen limited adoption in other industries in which low temperature (<200 Degree-Sign C) deposition is a requirement. Examples of applications which require low temperature deposition are seed layers for magnetic materials in the data storage (DS) industry and seed and diffusion barrier layers for through-silicon-vias (TSV) in the MEMS industry. This paper describes a low temperature TiN process with appropriate electrical, chemical, and structural properties based on plasma enhanced atomic layer deposition method that is suitable for the DS and MEMS industries. It uses tetrakis-(dimethylamino)-titanium as an organometallic precursor and hydrogen (H{sub 2}) as co-reactant. This process was developed in a Veeco NEXUS Trade-Mark-Sign chemical vapor deposition tool. The tool uses a substrate rf-biased configuration with a grounded gas shower head. In this paper, the complimentary and self-limiting character of this process is demonstrated. The effects of key processing parameters including temperature, pulse time, and plasma power are investigated in terms of growth rate, stress, crystal morphology, chemical, electrical, and optical properties. Stoichiometric thin films with growth rates of 0.4-0.5 A/cycle were achieved. Low electrical resistivity (<300 {mu}{Omega} cm), high mass density (>4 g/cm{sup 3}), low stress (<250 MPa), and >85% step coverage for aspect ratio of 10:1 were realized. Wet chemical etch data show robust chemical stability of the film. The properties of the film have been optimized to satisfy industrial viability as a Ruthenium (Ru) preseed liner in potential data storage and TSV applications.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Influence of inert gases on the reactive high power pulsed magnetron sputtering process of carbon-nitride thin films

The influence of inert gases (Ne, Ar, Kr) on the sputter process of carbon and carbon-nitride (CN{sub x}) thin films was studied using reactive high power pulsed magnetron sputtering (HiPIMS). Thin solid films were synthesized in an industrial deposition chamber from a graphite target. The peak target current during HiPIMS processing was found to decrease with increasing inert gas mass. Time averaged and time resolved ion mass spectroscopy showed that the addition of nitrogen, as reactive gas, resulted in less energetic ion species for processes employing Ne, whereas the opposite was noticed when Ar or Kr were employed as inert gas. Processes in nonreactive ambient showed generally lower total ion fluxes for the three different inert gases. As soon as N{sub 2} was introduced into the process, the deposition rates for Ne and Ar-containing processes increased significantly. The reactive Kr-process, in contrast, showed slightly lower deposition rates than the nonreactive. The resulting thin films were characterized regarding their bonding and microstructure by x-ray photoelectron spectroscopy and transmission electron microscopy. Reactively deposited CN{sub x} thin films in Ar and Kr ambient exhibited an ordering toward a fullerene-like structure, whereas carbon and CN{sub x} films deposited in Ne atmosphere were found to be amorphous. This is attributed to an elevated amount of highly energetic particles observed during ion mass spectrometry and indicated by high peak target currents in Ne-containing processes. These results are discussed with respect to the current understanding of the structural evolution of a-C and CN{sub x} thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Dry etching techniques for active devices based on hexagonal boron nitride epilayers

Hexagonal boron nitride (hBN) has emerged as a fundamentally and technologically important material system owing to its unique physical properties including layered structure, wide energy bandgap, large optical absorption, and neutron capture cross section. As for any materials under development, it is necessary to establish device processing techniques to realize active devices based on hBN. The authors report on the advancements in dry etching techniques for active devices based on hBN epilayers via inductively coupled plasma (ICP). The effect of ICP radio frequency (RF) power on the etch rate and vertical side wall profile was studied. The etching depth and angle with respect to the surface were measured using atomic force microscopy showing that an etching rate ∼1.25 μm/min and etching angles >80° were obtained. Profilometer data and scanning electron microscope images confirmed these results. This work demonstrates that SF{sub 6} is very suitable for etching hBN epilayers in RF plasma environments and can serve as a guide for future hBN device processing.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Low sheet resistance titanium nitride films by low-temperature plasma-enhanced atomic layer deposition using design of experiments methodology

A design of experiments methodology was used to optimize the sheet resistance of titanium nitride (TiN) films produced by plasma-enhanced atomic layer deposition (PE-ALD) using a tetrakis(dimethylamino)titanium precursor in a N{sub 2}/H{sub 2} plasma at low temperature (250 °C). At fixed chamber pressure (300 mTorr) and plasma power (300 W), the plasma duration and N{sub 2} flow rate were the most significant factors. The lowest sheet resistance values (163 Ω/sq. for a 20 nm TiN film) were obtained using plasma durations ∼40 s, N{sub 2} flow rates >60 standard cubic centimeters per minute, and purge times ∼60 s. Time of flight secondary ion mass spectroscopy data revealed reduced levels of carbon contaminants in the TiN films with lowest sheet resistance (163 Ω/sq.), compared to films with higher sheet resistance (400–600 Ω/sq.) while transmission electron microscopy data showed a higher density of nanocrystallites in the low-resistance films. Further significant reductions in sheet resistance, from 163 Ω/sq. to 70 Ω/sq. for a 20 nm TiN film (corresponding resistivity ∼145 μΩ·cm), were achieved by addition of a postcycle Ar/N{sub 2} plasma step in the PE-ALD process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Low-temperature growth of gallium nitride films by inductively coupled-plasma-enhanced reactive magnetron sputtering

Gallium nitride (GaN) films were grown on sapphire substrate by reactive magnetron sputtering. Inductively coupled-plasma (ICP) source was installed between the substrate holder and the sputtering target to increase the plasma density and the degree of ionization of nitrogen gas. Liquid Ga and Ar/N{sub 2} were used as the sputtering target and sputtering gases, respectively. X-ray diffraction measurements confirmed that the authors could grow high quality GaN crystallites at 500 °C. However, the crystalline GaN (0002) peak remained even by lowering the growth temperature down to 300 °C. The N:Ga ratio of the film grown at 500 °C was almost 1:1, and the nitrogen composition became higher toward the 1:1 N:Ga ratio with increasing the growth temperature. The high degree of ionization induced by ICP source was essential to the growth of high crystalline quality GaN films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Synthesis of copper nitride films doped with Fe, Co, or Ni by reactive magnetron sputtering

Copper nitride (Cu{sub 3}N) and Fe-, Co-, and Ni-doped Cu{sub 3}N films were prepared by reactive magnetron sputtering. The films were deposited on silicon substrates at room temperature using pure Cu target and metal chips. The molar ratio of Cu to N atoms in the as-prepared Cu{sub 3}N film was 2.7:1, which is comparable with the stoichiometry ratio 3:1. X-ray diffraction measurements showed that the films were composed of Cu{sub 3}N crystallites with anti-ReO{sub 3} structure and adopted different preferred orientations. The reflectance of the four samples decreased in the wavelength range of 400–830 nm, but increased rapidly within wavelength range of 830–1200 nm. Compared with the Cu{sub 3}N films, the resistivity of the doped Cu{sub 3}N films decreased by three orders of magnitude. These changes have great application potential in optical and electrical devices based on Cu{sub 3}N films.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Al capping layers for nondestructive x-ray photoelectron spectroscopy analyses of transition-metal nitride thin films

X-ray photoelectron spectroscopy (XPS) compositional analyses of materials that have been air exposed typically require ion etching in order to remove contaminated surface layers. However, the etching step can lead to changes in sample surface and near-surface compositions due to preferential elemental sputter ejection and forward recoil implantation; this is a particular problem for metal/gas compounds and alloys such as nitrides and oxides. Here, the authors use TiN as a model system and compare XPS analysis results from three sets of polycrystalline TiN/Si(001) films deposited by reactive magnetron sputtering in a separate vacuum chamber. The films are either (1) air-exposed for ≤10 min prior to insertion into the ultrahigh-vacuum (UHV) XPS system; (2) air-exposed and subject to ion etching, using different ion energies and beam incidence angles, in the XPS chamber prior to analysis; or (3) Al-capped in-situ in the deposition system prior to air-exposure and loading into the XPS instrument. The authors show that thin, 1.5–6.0 nm, Al capping layers provide effective barriers to oxidation and contamination of TiN surfaces, thus allowing nondestructive acquisition of high-resolution core-level spectra representative of clean samples, and, hence, correct bonding assignments. The Ti 2p and N 1s satellite features, which are sensitive to ion bombardment, exhibit high intensities comparable to those obtained from single-crystal TiN/MgO(001) films grown and analyzed in-situ in a UHV XPS system and there is no indication of Al/TiN interfacial reactions. XPS-determined N/Ti concentrations acquired from Al/TiN samples agree very well with Rutherford backscattering and elastic recoil analysis results while ion-etched air-exposed samples exhibit strong N loss due to preferential resputtering. The intensities and shapes of the Ti 2p and N 1s core level signals from Al/TiN/Si(001) samples do not change following long-term (up to 70 days) exposure to ambient conditions, indicating that the thin Al capping layers provide stable surface passivation without spallation.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Observation of ultraslow stress release in silicon nitride films on CaF{sub 2}

Silicon nitride thin films are deposited by plasma-enhanced chemical vapor deposition on (100) and (111) CaF{sub 2} crystalline substrates. Delaminated wavy buckles formed during the release of internal compressive stress in the films and the stress releasing processes are observed macroscopically and microscopically. The stress release patterns start from the substrate edges and propagate to the center along defined directions aligned with the crystallographic orientations of the substrate. The stress releasing velocity of SiN{sub x} film on (111) CaF{sub 2} is larger than that of SiN{sub x} film with the same thickness on (100) CaF{sub 2}. The velocities of SiN{sub x} film on both (100) and (111) CaF{sub 2} increase with the film thickness. The stress releasing process is initiated when the films are exposed to atmosphere, but it is not a chemical change from x-ray photoelectron spectroscopy.

42 ENGINEERING↗
DOE OSTI2015

Low-temperature growth of low friction wear-resistant amorphous carbon nitride thin films by mid-frequency, high power impulse, and direct current magnetron sputtering

The potential of different magnetron sputtering techniques for the synthesis of low friction and wear resistant amorphous carbon nitride (a-CN{sub x}) thin films onto temperature-sensitive AISI52100 bearing steel, but also Si(001) substrates was studied. Hence, a substrate temperature of 150 °C was chosen for the film synthesis. The a-CN{sub x} films were deposited using mid-frequency magnetron sputtering (MFMS) with an MF bias voltage, high power impulse magnetron sputtering (HiPIMS) with a synchronized HiPIMS bias voltage, and direct current magnetron sputtering (DCMS) with a DC bias voltage. The films were deposited using a N{sub 2}/Ar flow ratio of 0.16 at the total pressure of 400 mPa. The negative bias voltage, V{sub s}, was varied from 20 to 120 V in each of the three deposition modes. The microstructure of the films was characterized by high-resolution transmission electron microscopy and selected area electron diffraction, while the film morphology was investigated by scanning electron microscopy. All films possessed an amorphous microstructure, while the film morphology changed with the bias voltage. Layers grown applying the lowest substrate bias of 20 V exhibited pronounced intercolumnar porosity, independent of the sputter technique. Voids closed and dense films are formed at V{sub s} ≥ 60 V, V{sub s} ≥ 100 V, and V{sub s} = 120 V for MFMS, DCMS, and HiPIMS, respectively. X-ray photoelectron spectroscopy revealed that the nitrogen-to-carbon ratio, N/C, of the films ranged between 0.2 and 0.24. Elastic recoil detection analysis showed that Ar content varied between 0 and 0.8 at. % and increased as a function of V{sub s} for all deposition techniques. All films exhibited compressive residual stress, σ, which depends on the growth method; HiPIMS produces the least stressed films with values ranging between −0.4 and −1.2 GPa for all V{sub s}, while CN{sub x} films deposited by MFMS showed residual stresses up to −4.2 GPa. Nanoindentation showed a significant increase in film hardness and reduced elastic modulus with increasing V{sub s} for all techniques. The harder films were produced by MFMS with hardness as high as 25 GPa. Low friction coefficients, between 0.05 and 0.06, were recorded for all films. Furthermore, CN{sub x} films produced by MFMS and DCMS at V{sub s} = 100 and 120 V presented a high wear resistance with wear coefficients of k ≤ 2.3 × 10{sup −5} mm{sup 3}/Nm. While all CN{sub x} films exhibit low friction, wear depends strongly on the structural and mechanical characteristics of the films. The MFMS mode is best suited for the production of hard CN{sub x} films, although high compressive stresses challenge the application on steel substrates. Films grown in HiPIMS mode provide adequate adhesion due to low residual stress values, at the expense of lower film hardness. Thus, a relatively wide mechanical property envelope is presented for CN{sub x} films, which is relevant for the optimization of CN{sub x} film properties intended to be applied as low friction and wear resistant coatings.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Plasma enhanced atomic layer deposition of silicon nitride using neopentasilane

Progress in transistor scaling has increased the demands on the material properties of silicon nitride (SiN{sub x}) thin films used in device fabrication and at the same time placed stringent restrictions on the deposition conditions employed. Recently, low temperature plasma enhanced atomic layer deposition has emerged as a viable technique for depositing these films with a thermal budget compatible with semiconductor processing at sub-32 nm technology nodes. For these depositions, it is desirable to use precursors that are free from carbon and halogens that can incorporate into the film. Beyond this, it is necessary to develop processing schemes that minimize the wet etch rate of the film as it will be subjected to wet chemical processing in subsequent fabrication steps. In this work, the authors introduce low temperature deposition of SiN{sub x} using neopentasilane [NPS, (SiH{sub 3}){sub 4}Si] in a plasma enhanced atomic layer deposition process with a direct N{sub 2} plasma. The growth with NPS is compared to a more common precursor, trisilylamine [TSA, (SiH{sub 3}){sub 3 }N] at identical process conditions. The wet etch rates of the films deposited with NPS are characterized at different plasma conditions and the impact of ion energy is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Stoichiometry and thickness dependence of superconducting properties of niobium nitride thin films

The current technology used in linear particle accelerators is based on superconducting radio frequency (SRF) cavities fabricated from bulk niobium (Nb), which have smaller surface resistance and therefore dissipate less energy than traditional nonsuperconducting copper cavities. Using bulk Nb for the cavities has several advantages, which are discussed elsewhere; however, such SRF cavities have a material-dependent accelerating gradient limit. In order to overcome this fundamental limit, a multilayered coating has been proposed using layers of insulating and superconducting material applied to the interior surface of the cavity. The key to this multilayered model is to use superconducting thin films to exploit the potential field enhancement when these films are thinner than their London penetration depth. Such field enhancement has been demonstrated in MgB{sub 2} thin films; here, the authors consider films of another type-II superconductor, niobium nitride (NbN). The authors present their work correlating stoichiometry and superconducting properties in NbN thin films and discuss the thickness dependence of their superconducting properties, which is important for their potential use in the proposed multilayer structure. While there are some previous studies on the relationship between stoichiometry and critical temperature T{sub C}, the authors are the first to report on the correlation between stoichiometry and the lower critical field H{sub C1}.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Nitrogen incorporation in sputter deposited molybdenum nitride thin films

In this paper, the authors report on the high temperature performance of sputter deposited molybdenum (Mo) and molybdenum nitride (Mo{sub 2}N) thin films. Various argon and nitrogen gas compositions are applied for thin film synthetization, and the amount of nitrogen incorporation is determined by Auger measurements. Furthermore, effusion measurements identifying the binding conditions of the nitrogen in the thin film are performed up to 1000 °C. These results are in excellent agreement with film stress and scanning electron microscope analyses, both indicating stable film properties up to annealing temperatures of 500 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Silicon nitride and silicon etching by CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams

Silicon nitride (SiN, where Si:N ≠ 1:1) films low pressure-chemical vapor deposited on Si substrates, Si films on Ge on Si substrates, and p-Si samples were exposed to plasma beams emanating from CH{sub 3}F/O{sub 2} or CH{sub 3}F/CO{sub 2} inductively coupled plasmas. Conditions within the plasma beam source were maintained at power of 300 W (1.9 W/cm{sup 3}), pressure of 10 mTorr, and total gas flow rate of 10 sccm. X-ray photoelectron spectroscopy was used to determine the thicknesses of Si/Ge in addition to hydrofluorocarbon polymer films formed at low %O{sub 2} or %CO{sub 2} addition on p-Si and SiN. Polymer film thickness decreased sharply as a function of increasing %O{sub 2} or %CO{sub 2} addition and dropped to monolayer thickness above the transition point (∼48% O{sub 2} or ∼75% CO{sub 2}) at which the polymer etchants (O and F) number densities in the plasma increased abruptly. The C(1s) spectra for the polymer films deposited on p-Si substrates appeared similar to those on SiN. Spectroscopic ellipsometry was used to measure the thickness of SiN films etched using the CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams. SiN etching rates peaked near 50% O{sub 2} addition and 73% CO{sub 2} addition. Faster etching rates were measured in CH{sub 3}F/CO{sub 2} than CH{sub 3}F/O{sub 2} plasmas above 70% O{sub 2} or CO{sub 2} addition. The etching of Si stopped after a loss of ∼3 nm, regardless of beam exposure time and %O{sub 2} or %CO{sub 2} addition, apparently due to plasma assisted oxidation of Si. An additional GeO{sub x}F{sub y} peak was observed at 32.5 eV in the Ge(3d) region, suggesting deep penetration of F into Si, under the conditions investigated.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Structural and chemical analysis of annealed plasma-enhanced atomic layer deposition aluminum nitride films

Plasma-enhanced atomic layer deposition was utilized to grow aluminum nitride (AlN) films on Si from trimethylaluminum and N{sub 2}:H{sub 2} plasma at 200 °C. Thermal treatments were then applied on the films which caused changes in their chemical composition and nanostructure. These changes were observed to manifest in the refractive indices and densities of the films. The AlN films were identified to contain light element impurities, namely, H, C, and excess N due to nonideal precursor reactions. Oxygen contamination was also identified in the films. Many of the embedded impurities became volatile in the elevated annealing temperatures. Most notably, high amounts of H were observed to desorb from the AlN films. Furthermore, dinitrogen triple bonds were identified with infrared spectroscopy in the films. The triple bonds broke after annealing at 1000 °C for 1 h which likely caused enhanced hydrolysis of the films. The nanostructure of the films was identified to be amorphous in the as-deposited state and to become nanocrystalline after 1 h of annealing at 1000 °C.

36 MATERIALS SCIENCE↗