Electrical and optical properties of oxygen doped GaN grown by MOCVD using N2O

Oxygen doped GaN has been grown by metalorganic chemical vapor deposition using N₂O as oxygen dopant source. The layers were deposited on 2″ sapphire substrates from trimethylgallium and especially dried ammonia using nitrogen (N₂) as carrier gas. Prior to the growth of the films, an AIN nucleation layer with a thickness of about 300? was grown using trimethylaluminum. The films were deposited at 1085°C at a growth rate of 1.0 μm/h and showed a specular, mirrorlike surface. Not intentionally doped layers have high resistivity (>20 kW/square). The gas phase concentration of the N₂O was varied between 25 and 400 ppm with respect to the total gas volume. The doped layers were n-type with carrier concentrations in the range of 4×10¹⁶ cm⁻³ to 4×10¹⁸ cm⁻³ as measured by Hall effect. The observed carrier concentration increased with increasing N₂O concentration. Low temperature photoluminescence experiments performed on the doped layers revealed besides free A and B exciton emission an exciton bound to a shallow donor. With increasing N₂O concentration in the gas phase, the intensity of the donor bound exciton increased relative to that of the free excitons. These observations indicate that oxygen behaves as a shallow donor in GaN. This interpretation is supported by covalent radius and electronegativity arguments.     

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.     

Structural, optical and electronic properties of oxidized AIN thin films at different temperatures

We report on the properties of a novel insulator, AlO:N for application in semiconductors produced by thermally oxidizing AlN thin films. The process steps were similar to those used for SiO₂, creating the possibility of a new technology for metal-insulator-semiconductor field effect devices and integrated circuits. Thin films of AlN were deposited by radio-frequency magnetron reactive sputtering on p-type silicon or fused quartz substrates. As-deposited AlN film thickness ranged from 0.05 to 0.7 μm, with polycrystalline structure revealed by x-ray diffraction. Oxidation was performed under O₂ flow at 800 to 1100°C for 1–4 h. AlN films were oxidized partially or fully into Al₂O₃, depending on initial thickness, oxidation temperature and time. X-ray diffraction indicates the presence of several phases of Al₂O₃ at 1000°C, whereas at 1100°C, only the α-Al₂O₃ phase was found. Considering the importance of surface field effect device applications, the surfaces of oxidized films were examined with atomic force microscopy in air, and a clear change was observed in the surface structure of the oxidized film from that of as-deposited AlN films. Capacitance-voltage measurements of metal-oxide-semiconductor structures yielded a dielectric constant of AlO:N between 8–12 and a net oxide-trapped-charge density of ∼10¹¹ cm⁻². Using Fourier transform infrared spectrometry transmittance and reflectance, some α-Al₂O₃ modes were observed. In this paper, we describe the general properties of the oxide thin films, bulk and interface, at different temperatures.     

Microstructure and enhanced morphology of planar nonpolar m-plane GaN grown by hydride vapor phase epitaxy

Nonpolar ( ) m-plane gallium nitride has been grown heteroepitaxially on (100) γ-LiAlO₂ by several groups. Previous attempts to grow m-plane GaN by hydride vapor phase epitaxy (HVPE) yielded films unsuitable for subsequent device regrowth because of the high densities of faceted voids intersecting the films’ free surfaces. We report here on the growth of planar m-plane GaN films on (100) γ-LiAlO₂ and elimination of bulk and surface defects. The morphology achieved is smooth enough to allow for fabrication of m-plane GaN templates and free-standing substrates for nonpolar device regrowth. The GaN films were grown in a horizontal HVPE reactor at 860–890°C. Growth rates ranged from 30 μm/h to 240 μm/h, yielding free-standing films up to 250-μm thickness. The m-plane GaN films were optically specular and mirror-like, with undulations having 50–200-nm peak-to-valley heights over millimeter length scales. Atomic force microscopy revealed a striated surface morphology, similar to that observed in m-plane GaN films grown by molecular beam epitaxy (MBE). Root-mean-square (RMS) roughness was 0.636 nm over 25-μm² areas. Transmission electron microscopy (TEM) was performed on the m-plane GaN films to quantify microstructural defect densities. Basal-plane stacking faults of 1×10⁵ cm⁻¹ were observed, while 4×10⁹ cm⁻² threading dislocations were observed in the g=0002 diffraction condition.     

Optical properties of thick-film GaN grown by hydride vapor phase epitaxy on MgAl2O4 substrate

A hydride vapor phase epitaxy was employed to grow the 10∼240 μm thick GaN films on a (111) MgAl₂O₄ substrate. The GaN films on a MgAl₂O₄ substrate revealed characteristics of photoluminescence (PL) in impurity doped GaN, which may be due to the out-diffusion and auto-doping of Mg from the MgAl₂O₄ substrate during GaN growth. The PL peak energy of neutral donor bound exciton emission and the frequency of Raman E₂ mode were decreased by increasing the GaN thickness, due to the residual strain relaxation in the epilayers. The dependence of Raman E₂ mode of GaN films on residual strain can be estimated as Δ ω/Δ σ=3.93 (cm⁻¹/GPa).     

Surface etching of 6H-SiC (0001) and surface morphology of the subsequently grown GaN via MOCVD

The correlation between surface morphological properties of the GaN epilayers and the surface conditions of 6H-SiC (0001) substrates etched in H₂, C₂H₄/H₂, and HCl/H₂ was studied. Etching 6H-SiC in H₂ produced a high quality surface with steps and terraces, while etching in HCl/H₂ produced either a rough surface with many pits and hillocks or a smooth surface similar to that etched in H₂, depending on the HCl concentration and temperature. The GaN epilayers were subsequently deposited on these etched substrates using either a low temperature GaN or a high temperature AlN buffer layer via MOCVD. The substrate surface defects increased the density and size of the “giant” pinholes (2–4 μm) on GaN epilayers grown on a LT-GaN buffer layer. Small pinholes (<100 nm) were frequently observed on the samples grown on a HT-AlN buffer layer, and their density decreased with the improved surface quality. The non-uniform GaN nucleation caused by substrate surface defects and the slow growth rate of planes of the islands were responsible for the formation of “giant” pinholes, while the small pinholes were believed to be caused by misfit dislocations.     

Pendeo-epitaxial growth of gallium nitride on silicon substrates

Pendeo-epitaxy (PE)¹ from raised, [0001] oriented GaN stripes covered with silicon nitride masks has been employed for the growth of coalesced films of GaN(0001) with markedly reduced densities of line and planar defects on Si(111)-based substrates. Each substrate contained previously deposited 3C-SiC(111) and AlN(0001) transition layers and a GaN seed layer from which the stripes were etched. The 3C-SiC transition layer eliminated chemical reactions between the Si and the NH₃ and the Ga metal from the decomposition of triethylgallium. The 3C-SiC and the GaN seed layers, each 0.5 μm thick, were also used to minimize the cracking and warping of the GaN/SiC/silicon assembly caused primarily by the stresses generated on cooling due to the mismatches in the coefficients of thermal expansion. Tilting in the coalesced GaN epilayers of 0.2° was confined to areas of lateral overgrowth over the masks; no tilting was observed in the material suspended above the trenches. The strong, low-temperature PL band-edge peak at 3.456 eV with a FWHM of 17 meV was comparable to that observed in PE GaN films grown on AlN/6H-SiC(0001) substrates.     

Effect of copper and chlorine on the properties of SiO2 encapsulated polycrystalline CdSe films

The effects of different copper doping concentrations on the properties of SiO₂ encapsulated CdSe films have been investigated. Two methods were used to dope the films with copper: ion implantation and diffusion from a surface layer. The room temperature dark resistivity of films annealed in oxygen at 450°C was found to increase as the copper concentration was increased until a maximum resistivity of 10⁸ ohm cm occurred at a copper concentration of 10²⁰ atoms cm⁻³. The room temperature resistivity in the light was found to be independent of the copper concentration and whether the films were annealed in argon or oxygen. During annealing the grains grew from 0.03 μm to 0.3 μm and this growth was independent of the doping or the annealing ambient. The energy levels, carrier mobilities, and microstructure of the annealed films were dependent on the method of doping. The ion implanted films had an additional energy level at 0.33 eV and their mobility was a factor of 4 smaller than films doped by the surface diffusion method, whose mobilities were 20 to 35 cm²V⁻¹ s⁻¹. The addition of chlorine to copper doped films had no effect on either the resistivity or photosensitivity but slowed the response times of the photocurrent by a factor of 10. No energy levels were observed which could be associated with the copper nor was the copper found to affect the density of the observed intrinsic levels at 0.65 and 1.1 eV.     

Growth and characterization of GaN thin films on SiC SOI substrates

SiC semiconductor-on-insulator (SOI) structures have been investigated as substrates for the growth of GaN films. The SiC SOI was obtained through the conversion of Si SOI wafers by reaction with propane and H₂. (111) SiC SOI have been produced by this carbonization process at temperatures ranging from 1200 to 1300°C. X-ray diffraction (XRD) and infrared spectroscopy (FTIR) are used to chart the conversion of the Si layer to SiC. Under our conditions, growth time of 3 min at 1250°C is sufficient to completely convert a 1000? layer. XRD of the SiC SOI reveals a single SiC peak at 2θ = 35.7° corresponding to the (111) reflection, with a corrected full width at half-maximum (FWHM) of ~590±90 arc-sec. Infrared spectroscopy of SiC SOI structures obtained under optimum carboniza-tion conditions exhibited a sharp absorption peak produced by the Si-C bond at 795 cm⁻¹, with FWHM of ∼ 20–25 cm⁻¹. Metalorganic CVD growth of GaN on the (111) SiC SOI was carried out with trimethylgallium and NH₃. The growth of a thin (≤200?), low temperature (500°C) GaN buffer layer was followed by the growth of a thick (∼2 μm) layer at 1050°C. Optimum surface morphology was obtained for zero buffer layer. XRD indicates highly oriented hexagonal GaN, with FWHM of the (0002) peak of ~360±90 arc-sec. Under high power excitation, the 300°K photoluminescence (PL) spectrum of GaN films exhibits a strong near band-edge peak (at λ_p~371 nm, with FWHM = 100–150 meV) and very weak yellow emission. Under low power excitation, the 370 nm PL emission from the GaN/SiC SOI structure increases rapidly with SiC carbonization temperature, while the yellow band (∼550–620 nm) correspondingly decreases.     

Evaporated InSb thin films and their application to bubble domain devices

Indium antimonide thin films were deposited by the three-temperature method onto various kinds of amorphous substrates such as Corning 7059 glass using source materials of 99.9999 % purity. The optimum ratio of vapor pressures of indium and antimony, and the optimum temperature of the substrate, T_sub, were investigated for each substrate in order that the deposited film had the highest carrier mobility, μH, and Hall coefficient, R_H, as well as being perfectly stoichiometric when tested by the x-ray diffraction method. The microstructure of the films was also investigated as a function of T_sub. The thickness of the film varied between 1.0 – 3.2 μm. Among the films thus obtained the best one gave the characteristics of μ_H = 23,000 cm²/V·sec and R_H = 480 cm₃/C at room temperature. The latter value is entirely the same as that of the purest bulk material. This film was photo—etched to a cross—shaped Hall detector; the width of both the current lead and the output lead was 4μm. The device was applied to the detection of magnetic bubble domains of 10 μm diameter. The output voltage of 1.4 mV is larger than those ever reported for a bubble of the same order of diameter.     

Correlation between the structural, morphological, optical, and electrical properties of In2O3 thin films obtained by an ultrasonic spray CVD process

Indium oxide (In₂O₃) thin films are successfully deposited on glass substrate at different deposition times by an ultrasonic spray technique using Indium chloride as the precursor solution; the physical properties of these films are characterized by XRD, SEM, and UV-visible. XRD analysis showed that the films are polycrystalline in nature having a cubic crystal structure and symmetry space group Ia3 with a preferred grain orientation along the (222) plane when the deposition time changes from 4 to 10 min, but when the deposition time equals 13 min we found that the majority of grains preferred the (400) plane. The surface morphology of the In₂O₃ thin films revealed that the shape of grains changes with the change of the preferential growth orientation. The transmittance improvement of In₂O₃ films was closely related to the good crystalline quality of the films. The optical gap energy is found to increase from 3.46 to 3.79 eV with the increasing of deposition time from 4 to 13 min. The film thickness was varied between 395 and 725 nm. The film grown at 13 min is found to exhibit low resistivity (10^-2 Ω·cm), and relatively high transmittance (~ 93%).     

Ammonothermal synthesis of aluminum nitride crystals on group III-nitride templates

Polycrystalline aluminum nitride (AlN) crystals were synthesized using the ammonothermal technique at temperatures between 525°C and 550°C. The growth of AlN was conducted in alkaline conditions with potassium azide (KN₃) as the mineralizer. The growth mechanism was found to be reversegradient soluble, necessitating the placement of the GaN and AlN seeds at a higher temperature than the aluminum metal source. Growth on the GaN seeds varied from 100 to 1500 μm in thickness at a gestation period of 21 days. Additionally, scanning electron micrographs revealed varying microstructure ranging from pointed hexagonal rods, which are approximately 5 μm wide and 20 μm long, to highly densified and contiguous films. Formation of hexagonal AlN was verified using x-ray powder diffraction measurements. Oxygen was detected at 3.7 at.% by inert gas fusion analysis on AlN nucleated on the walls of the autoclave and a qualitative indication of unintentionally incorporated impurities in the AlN grown on the GaN seeds was obtained using energy-dispersive x-ray analysis. Photoluminescence spectroscopy conducted at 20 K revealed a deep-level emission at 3.755 eV due to unintentionally incorporated impurities.     

Structural, optical and electrical properties of SnxSy thin films grown by spray ultrasonic

Tin sulfide(Sn_xS_y) thin films were prepared by a spray ultrasonic technique on glass substrate at 300℃. The influence of deposition time t=2, 4, 6, 8 and 10 min on different properties of thin films, such as(XRD), photoluminescence(PL) and(UV) spectroscopy visible spectrum and four-point were investigated. X-ray diffraction showed that thin films crystallized in SnS₂, SnS, and Sn₂S₃ phases, but the most prominent one is SnS₂. The results of the(UV) spectroscopy visible spectrum show that the film which was deposited at 4 min has a large transmittance of 60% in the visible region. The photoluminescence spectra exhibited the luminescent peaks in the visible region, which shows its potential application in photovoltaic devices. The electrical resistivity(ρ) values of Sn_xS_y films have changed from 8.1×10^-4 to 1.62Ω·cm with deposition time.     

Synthesis and characterization of Pb(Zr0.54Ti0.46)O3 thin films on (100)Si using textured YBa2Cu3O7−δ and yttria-stabilized zirconia buffer layers by laser physical vapor deposition technique

We have fabricated high-quality <001> textured Pb(Zr_0.54Ti_0.46)O₃ (PZT) thin films on (00l)Si with interposing <001> textured YBa₂Cu₃O_7−δ (YBCO) and yttria-stabilized zirconia (YSZ) buffer layers using pulsed laser deposition (KrF excimer laser, λ, = 248 nm, τ = 20 nanosecs). The YBCO layer provides a seed for PZT growth and can also act as an electrode for the PZT films, whereas YSZ provides a diffusion barrier as well as a seed for the growth of YBCO films on (001)Si. These heterostructures were characterized using x-ray diffraction, high-resolution transmission electron microscopy, and Rutherford backscattering techniques. The YSZ films were deposited in oxygen ambient (∼9 × 10⁻⁴ Torr) at 775°C on (001)Si substrate having <001>YSZ // <001>Si texture. The YBCO thin films were deposited in-situ in oxygen ambient (200 mTorr) at 650°C. The temperature and oxygen ambient for the PZT deposition were optimized to be 530°C and 0.4-0.6 Torr, respectively. The laser fluence to deposit this multilayer structure was 2.5-5.0 J/cm². The <001> textured perovskite PZT films showed a dielectric constant of 800-1000, a saturation polarization of 37.81 μC/cm², remnant polarization of 24.38 μC/cm² and a coercive field of 125 kV/cm. The effects of processing parameters on microstructure and ferroelectric properties of PZT films and device implications of these structures are discussed.     

LaNiO3 and Cu3Ge contacts to YBa2Cu3O7-x films

Metallization of high-T_c superconductors using low resistivity metal oxides and Cu-Ge alloys has been investigated on high quality pulsed laser deposited epitaxial YBa₂Cu₃O_7-x (YBCO) films. Epitaxial LaNiO₃ (LNO) thin films have been grown on YBCO films at 700°C using pulsed laser deposition. The specific resistivity of LNO was measured to be 50 μΩ-cm at 300K which decreases to 19 μΩ-cm at 100K indicating good metallicity of the LNO films. The contact resistance of LNO-YBCO thin film interface was found to be reasonably low (of the order of 10^-4Ω-cm² at 77K) which suggests that the interface formed between the two films is quite clean and LNO can emerge as a promising metal electrode-material to YBCO films. A preliminary investigation related to the compatibility of Cu₃Ge alloy as a contact metallization material to YBCO films is discussed. The usage of other oxide based low resistivity materials such as SrRuO₃ (SRO) and SrVO₃ (SVO) for metallization of high-T_c YBCO superconductor films is also discussed.     

Correlation of in-situ reflectance spectra and resistivity of GaN/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> interfacial layer in metalorganic chemical vapor deposition

The correlation between the resistivity of an undoped GaN/Al₂O₃ interfacial layer and in-situ reflectance spectrum in metalorganic chemical vapor deposition and the mechanism of this correlation were investigated. The first minimum reflectance during the initial high-temperature GaN growth was found to be a good indicator of the resistivity of the GaN buffer. The background electron concentration and mobility were both higher in the samples with higher indicative reflectance at that point. The resistivity of the GaN buffer layer was predominantly determined by an ∼0.25-μm-thick layer near the GaN/Al₂O₃ interface. Atomic force microscope (AFM) and high-resolution x-ray diffraction (HRXRD) results showed that the samples with higher indicative reflectance had smaller sized but higher density nuclei before the high-temperature GaN growth and lower screw threading dislocation (TD) density in the initially grown GaN. The difference in the background electron concentration and mobility of the interfacial layer was related to the relatively higher concentration of the O and Al diffused from Al₂O₃, which is also dependent on the size and density of the nuclei. These differences were found not to affect the structural and electrical properties or the surface morphology of AlGaN/GaN high electron-mobility transistors (HEMTs, except for the buffer conduction) when the GaN buffer is thick enough (e.g., ∼2.5 μm).     

The effect of film thickness and doping content of SnO2:F thin films prepared by ultrasonic spray method

This paper reports on the effects of film thickness and doping content on the optical and electrical properties of fluorine-doped tin oxide. Tin (II) chloride dehydrate, ammonium fluoride dehydrate, ethanol and HCl were used as the starting materials, dopant source, solvent and stabilizer, respectively. The doped films were deposited on a glass substrate at different concentrations varying between 0 and 5 wt% using an ultrasonic spray technique. The SnO₂:F thin films were deposited at a 350 ℃ pending time (5, 15, 60 and 90 s). The average transmission was about 80%, and the films were thus transparent in the visible region. The optical energy gap of the doped films with 2.5 wt% F was found to increase from 3.47 to 3.89 eV with increasing film thickness, and increased after doping at 5 wt%. The decrease in the Urbach energy of the SnO₂:F thin films indicated a decrease in the defects. The increase in the electrical conductivity of the films reached maximum values of 278.9 and 281.9 (Ω·cm^-1) for 2.5 and 5 wt% F, respectively, indicating that the films exhibited an n-type semiconducting nature. A systematic study on the influence of film thickness and doping content on the properties of SnO₂:F thin films deposited by ultrasonic spray was reported.     

Physical properties of sprayed antimony doped tin oxide thin films: Role of thickness

Transparent conducting antimony doped tin oxide (Sb:SnO₂) thin films have been deposited onto preheated glass substrates using a spray pyrolysis technique by varying the quantity of spraying solution. The structural, morphological, X-ray photoelectron spectroscopy, optical, photoluminescence and electrical properties of these films have been studied. It is found that the films are polycrystalline in nature with a tetragonal crystal structure having orientation along the (211) and (112) planes. Polyhedrons like grains appear in the FE-SEM images. The average grain size increases with increasing spraying quantity. The compositional analysis and electronic behaviour of Sb:SnO₂ thin films were studied using X-ray photoelectron spectroscopy. The binding energy of Sn3d_5/2 for all samples shows the Sn⁴ bonding state from SnO₂. An intensive violet luminescence peak near 395 nm is observed at room temperature due to oxygen vacancies or donor levels formed by Sb⁵ ions. The film deposited with 20 cc solution shows 70% transmittance at 550 nm leading to the highest figure of merit (2.11 × 10^-3 Ω^-1). The resistivity and carrier concentration vary over 1.22 × 10^-3 to 0.89 × 10^-3Ωcm and 5.19 × 10²⁰ to 8.52 × 10²⁰ cm^-3, respectively.     

Au schottky barrier diodes on β-SiC thin films deposited on silicon substrates by reactive magnetron sputtering technique

β-SiC thin films have been grown on (100) silicon substrates using reactive magnetron sputtering of a silicon target in an Ar/CH₄ mixed plasma. For the first time it has been possible to make gold Schottky diodes on β-SiC grown by reactive magnetron sputtering. Current-voltage measurements showed an ideality factor of 1.27 and a leakage current density of 4 μA/cm². Capacitance-voltage measurements gave a barrier height of 1.04 eV. The static dielectric constant for β-SiC was determined to be 9.     

Title:Spray pyrolysis of tin selenide thin film semiconductor: effect of the selenium concentration on the thin film properties

Thin films of tin selenide (Sn_xSe_y) with an atomic ratio of r=≤[y/x]=0.5, 1 and 1.5 were prepared on a glass substrate at T= 470 ℃ using a spray pyrolysis technique. The initial materials for the preparation of the thin films were an alcoholic solution consisting of tin chloride (SnCl₄·5H₂O) and selenide acide (H₂SeO₃). The prepared thin films were characterized by X-ray diffraction (XRD), scanning electron microscopy, scanning tunneling microscopy, scanning helium ion microscopy, and UV-vis spectroscopy. The photoconductivity and thermoelectric effects of the Sn_xSe_y thin films were then studied. The Sn_xSe_y thin films had a polycrystalline structure with an almost uniform surface and cluster type growth. The increasing atomic ratio of r in the films, the optical gap, photosensitivity and Seebeck coefficient were changed from 1.6 to 1.37 eV, 0.01 to 0.31 and-26.2 to-42.7 mV/K (at T= 350 K), respectively. In addition, the XRD patterns indicated intensity peaks in r=1 that corresponded to the increase in the SnSe and SnSe₂ phases.