Atomic layer deposition of ZnS via in situ production of H2S

Atomic layer deposition (ALD) of ZnS films utilizing diethylzinc and in situ generated H₂S was performed over a temperature range of 60 °C-400 °C. This method for generating H₂S in situ was developed to eliminate the need to store high pressure H₂S gas. The H₂S precursor was generated by heating thioacetamide to 150 °C in an inert atmosphere, producing acetonitrile and H₂S as confirmed with mass spectroscopy. ALD behavior was confirmed by investigation of growth behavior and saturation curves. The properties of the films were studied with X-ray diffraction, transmission electron microscopy, ellipsometry, atomic force microscopy, scanning electron microscopy, ultraviolet-visible spectroscopy, and X-ray photoelectron spectroscopy. The results show a growth rate that monotonically decreases with temperature, and films that are stoichiometric in Zn and S. The root mean square roughness of the films increases with temperature above 100 °C. A change in crystal phase begins at ∼ 300 °C. The band gap is dependent on the crystal phase and is estimated to be 3.6-4 eV.     

Enhanced conductivity of pulsed laser deposited n-InGaZn6O9 films and its rectifying characteristics with p-SiC

Wide band gap InGaZn₆O₉ films of thickness ~ 350 nm were deposited on sapphire (0001) at room temperature by using the pulsed laser deposition technique. The transparent films showed the optical transmission of > 80% with the room temperature Hall mobility of ~ 10 cm²/V s and conductivity of 4 × 10² S/cm at a carrier density > 10²⁰ cm^− 3. The electrical properties as a function of deposition temperatures revealed that the conductivity and mobility almost retained up to the deposition temperature of 200 °C. The films annealed in different atmospheres suggested oxygen vacancy plays an important role in determining the electrical conductivity of the compound. Room temperature grown heterostructure of n-InGaZn₆O₉/p-SiC showed a good rectifying behavior with a leakage current density of less than 10^− 9 A/cm², current rectifying ratio of 10⁵ with a forward turn on voltage ~ 3 V, and a breakdown voltage greater than 32 V.     

Synthesis and luminescent properties of ZnNb2O6 nanocrystals for solar cell

The phase formation, morphology and luminescent properties of ZnNb₂O₆ nanocrystals by the sol-gel method were investigated at a lower temperature than that of the traditional solid-state reaction method. The products were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), photoluminescence spectroscopy (PL) and absorption spectra. The activation energy of ZnNb₂O₆ grain growth is obtained about 18.4 kJ/mol. The diameters of the nanocrystals are in the range of 20-40 nm. The PL spectra excited at 276 nm have a broad and strong blue emission band maximum at 450 nm, corresponding to the self-activated luminescence of the niobate octahedra group [NbO₆]⁷⁻. The optical absorption spectrum of the sample at a calcination temperature of 800 °C has a band gap energy of 3.68 eV.     

Influence of hydrogen introduction on structure and properties of ZnO thin films during sputtering and post-annealing

ZnO thin films were prepared in Ar and Ar + H₂ atmospheres by rf magnetron sputtering, and then they were annealed in vacuum and Ar + H₂ atmosphere, respectively. The structure and optical-electrical properties of the films were investigated by X-ray diffraction, transmittance spectra, and resistivity measurement, and their dependences on deposition atmosphere, annealing treatment, and aging were studied. The results showed that adding H₂ in deposition atmosphere improved the crystallinity of the films, decreased lattice constant, increased band gap, decreased the resistivity by the order of 10⁴ Ω cm, but exhibited poor conductive stability with aging. After Ar + H₂ and vacuum annealing, crystallinity of the films deposited in Ar and Ar + H₂ was further improved; their resistivity was decreased by the order of 10⁵ and 10¹ Ω cm, respectively, and exhibited high conductive stability with aging. We suggest that the formed main defect is V_O and H_i when H₂ is introduced during deposition, which decreases the resistivity but cannot improve the conductive stability; hydrogen would remove negatively charged oxygen species near grain boundaries during Ar + H₂ annealing to decrease the resistivity, and grain boundaries are passivated by formation of a number of V_O-H complex (H_O) to improve the conductive stability at the same time. Under vacuum annealing, the hydrogen that is introduced non-intentionally from deposition chamber maybe plays an important role; it exists as H_O in the films to improve the conductive stability of the films.     

Crystal structure of a new organic condensed phosphate (C6H9N3O)H2P2O7

Crystals of a new organic compound, the isonicotinic acid hydrazide dihydrogendiphosphate, (C₆H₉N₃O)H₂P₂O₇ (denoted INHDP) were prepared and grown at room temperature. The INHDP crystallizes in the triclinic system with the space group. Its unit cell dimensions are: a = 7.316(3) Å, b = 7.783(3) Å, c = 10.802(4) Å, α = 82.41(3)°, β = 75.19(3)°, γ = 72.57(3)°, with V = 566.3(4) Å³ and Z = 2. Crystal structure has been determined and refined to a reliability R factor of 0.0389. The atomic arrangement can be described as inorganic infinite ribbons of H₂P₂O₇²⁻ anions spreading parallel to the b-axis. These ribbons are themselves interconnected by the organic (C₆H₉N₃O)⁺ cations so as to build a three dimensional arrangement. In the present work, we describe the crystal structure, thermal behaviour and IR analysis of this new compound.     

Influence of excitation wavelengths on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol-gel-combustion processing

Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ red-emitting long afterglow phosphor was synthesized by sol-gel-combustion methods using Sr(NO₃)₂, Al(NO₃)₃·9H₂O, Eu₂O₃, Dy₂O₃, H₃BO₃ and C₆H₈O₇·H₂O as raw materials. The crystalline structure of the phosphors were characterized by X-ray diffraction, luminescent properties of phosphors were analyzed by fluorescence spectrophotometer. The effect of excitation wavelengths on the luminescent properties of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors was discussed. The emission peak of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor lays at 516 nm under the excitation of 360 nm, and at 612 nm under the excitation of 468 nm. The results reveal that the Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphor will emit a yellow-green light upon UV illumination, and a bright red light upon visible light illumination. The emission mechanism was discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions in Sr₃Al₂O₆. The afterglow time of (Sr_0.94Eu_0.03Dy_0.03)₃ Al₂O₆ phosphors lasts for over 600s after the excited source was cut off.     

Structural and luminescence correlation of annealed Er-ZnO/Si thin films deposited by AACVD process

Er doped ZnO thin films have been synthesized from zinc acetates dihydrate (C₄H₆O₄Zn·2H₂O) and Erbium tris (2,2,6,6-tetramethyl-3,5-heptadionate) (Er(TMHD)₃) by aerosol assisted chemical vapor deposition AACVD atmospheric pressure technique. Films were deposited in the temperature range of [370–500 °C] on Si (1 1 1) substrate. Nano-disk shaped grains were grown on the top of the film surface. The morphology of the as-deposited films was found to be dependent on the substrate temperature. After annealing in air atmosphere, XRD patterns revealed a highly oriented c-axis Er:ZnO films with hexagonal wurtzite structure without any second phase. Under 488 nm excitation, the intra 4f–4f green emission (²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) gradually increased with increasing annealing temperature. Also, the local structure of Er changes to a pseudo-octahedral structure with C_4v symmetry. The ZnO film with 2.504 at.% Er³⁺ doping has the best crystalline structure and the best resolved PL spectra. Using 325 nm excitation, all the samples showed an ultraviolet emission centered at 380 nm originating from a near band EDGE emission and a broad band green emission centered at 520 nm from deep levels. The optical response was correlated with crystallinity of the synthesized thin films.     

Influence of Ga2O3 addition on transparent conductive oxide films of In2O3-ZnO

Influence of incorporation of Ga in amorphous In-Zn-O transparent conductive oxide films was investigated as a function of Zn/(Zn + In). For In-Zn-O films with no Ga₂O₃, the range of Zn/(Zn + In) ratio where the amorphous phase appears became narrow at a substrate temperature of 250 °C. With increasing Ga₂O₃ quantity, amorphous films were obtained even at a high substrate temperature of 250 °C in a wider range of Zn/(Zn + In) than that of In-Zn-O films with no Ga₂O₃. This means that the trend of crystallization at higher substrate temperature was disturbed with additional Ga incorporation. For the film deposited from ZnO:Ga (Ga₂O₃: 4.5-7.5 wt%) and In₂O₃ targets, we obtained a resistivity of 2.8 × 10⁻⁴ Ω cm, nearly the same value as that for an In-Zn-O film with no Ga₂O₃. The addition of more than 7.5 wt% Ga₂O₃ induced a widening of the optical band gap.     

Optical properties of nanocrystalline SnS2 thin films

Thin films of nanocrystalline SnS₂ on glass substrates were prepared from solution by dip coating and then sulfurized in H₂S (H₂S:Ar = 1:10) atmosphere. The films had an average thickness of 60 nm and were characterized by X-ray diffraction studies, scanning electron microscopy, EDAX, transmission electron microscopy, UV-vis spectroscopy, and Raman spectroscopy. The influence of annealing temperature (150-300 °C) on the crystallinity and particle size was studied. The effect of CTAB as a capping agent has been tested. X-ray diffraction analysis revealed the polycrystalline nature of the films with a preferential orientation along the c-axis. Optical transmission spectra indicated a marked blue shift of the absorption edge due to quantum confinement and optical band gap was found to vary from 3.5 to 3.0 eV with annealing temperature. Raman studies indicated a prominent broad peak at ∼314 cm⁻¹, which confirmed the presence of nanocrystalline SnS₂ phase.     

Synthesis of V-doped TiO2 films by chemical bath deposition and the effect of post-annealing on their properties

Amorphous composite films, composed of a Ti_1 − xV_xO₂ solid-solution phase and a V₂O₅ phase, were produced by chemical bath deposition and subsequently air-annealed at various temperatures up to 550 °C. The microstructure and chemical composition of the as-prepared and annealed films were investigated by a combinatorial experimental approach using Scanning electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy. Ultraviolet-Visible Spectrometry was applied to determine the optical band gap of the as-prepared and annealed films. It followed that the incorporation of vanadium in the as-deposited films reduces the optical band gap of TiO₂ from about 3.8 eV to 3.2 eV. Annealing of the films up to 350 °C leads to slight increase of band gap, as attributed to a reduction of the defect density in the initially amorphous oxide films due to the gradual development of long-range order and a concurrent reduction of the V⁴⁺-dopant concentration in the Ti_1 − xV_xO₂ solid-solution phase. The films crystallized upon annealing in air at 550 °C, which resulted in drastic changes of the phase constitution, optical absorbance and surface morphology. Due to the lower solubility of V⁴⁺ in crystalline TiO₂, V⁴⁺ segregates out of the crystallizing Ti_1 − xV_xO₂ solid-solution phase, forming crystalline V₂O₅ at the film surface.     

Low-energy electron interaction with nitrobenzene: C6H5NO2

Low-energy electron attachment to C₆H₅NO₂ (nitrobenzene) in the gas phase is reported in the electron energy range from about 0 up to 10 eV with an energy resolution of 120 meV. Dissociative and nondissociative electron attachment to nitrobenzene were observed. From the numerous ions observed, the two most abundant were NO₂⁻ and C₆H₅NO₂⁻. Based on comparison of the abundance of studied ions with Cl⁻ in the dissociative electron attachment to CCl₄ at 0.8 eV, estimates of cross sections for the all observed ions were obtained for the first time (e.g. σ(NO₂⁻)=4.6×10⁻²⁰ m² and σ(C₆H₅NO₂⁻)=3.8×10⁻²¹ m²).     

Reactively sputtered TiO2 layers on SnO2:F substrates: A Raman and surface photovoltage study

DC reactively sputtered TiO₂ layers on SnO₂:F substrates were investigated by Raman and surface photovoltage spectroscopy. The stoichiometry and layer thicknesses were investigated by elastic recoil detection analysis. The deposition temperature, the O₂/(O₂ + Ar) ratio and the deposition time were varied systematically. With increasing temperature, the layers become crystalline with the rutile modification dominating. Rutile phase preferentially forms on vertical facets of SnO₂ crystallites. Anatase phase starts to form during prolonged deposition and at lower O₂/(O₂ + Ar) ratios. The energy of the exponential absorption tails below the band gap, a measure of the defect density of the films, is determined by the deposition temperature and not by other parameters if the deposition temperature is relatively high, irrespective of the content of crystalline phases or the value of the band gap. Charge separation takes place at length scales significantly shorter than the layer thicknesses (diffusion length less than 6 nm). TiO₂ films sputtered at 380 °C show rectifying behaviour with a carbon contact.     

Preparation and mobile ion transport studies of Ta and Nb doped Li6Zr2O7 Li-fast ion conductors

Pure and doped Li_6−x(Zr_2−xM_x)O₇, M = Nb and Ta; x = 0, 0.15 compounds have been prepared by the urea combustion method followed by annealing at 950 °C for 8 h. The samples are characterized by X-ray diffraction and impedance spectroscopy. Ionic conductivities, σ_ionic, were determined in the temperature range of 60-360 °C by impedance spectroscopy. We observe that the Ta doped Li₆Zr₂O₇ has a measurable σ_ionic at ∼160 °C, and at 300 °C exhibits a conductivity value of 1 × 10⁻³ S/cm. The temperature dependence of the conductivity in the range 100-360 °C obeys an Arrhenius relation, yielding an activation energy of E_a = 0.95 eV (for M = Ta and x = 0.15).The bond valence approach has been used to visualise Li⁺ ion migration pathways and the conductivity mechanism in these compounds. The lowest energy pathway is found to extend along the [0 1 2] direction. The Bond valence analysis also indicates a significantly anisotropic Li-ion conductivity in compounds with Li₆Zr₂O₇ type structure, predicting activation energies of 1.1 and 0.9 eV for the low energy pathway in undoped and doped Li₆Zr₂O₇.     

Electronic structure and photoluminescence properties of Eu-activated Ca4Si2O7F2

The blue-emitting phosphors Ca_(4−x)Eu_xSi₂O₇F₂ (0 < x ? 0.05) have been prepared by solid-state reaction and the photoluminescence properties have been studied systematically. The electronic structure of calcium fluoride silicate Ca₄Si₂O₇F₂ was calculated using the CASTEP code. The calculation results of electronic structure show that Ca₄Si₂O₇F₂ has an indirect band gap with 5 eV. The top of the valence band is dominated by O 2p and Si 3p states, while the bottom of the conduction band is mainly composed of Ca 3d states. Under the 350 nm excitation, the obtained sample shows a broad emission band in the wavelength range of 400-500 nm with peaks of 413 nm and 460 nm from two different luminescence centers, respectively. The relative intensity of the two peaks changes with the alteration of the Eu²⁺ concentration. The strong excitation bands of the powder in the wavelength range of 200-420 nm are favorable properties for the application as lighting-emitting-diode conversion phosphor.     

Synthesis, crystal structure and thermal decomposition of [La2(CH3CH2COO)6·(H2O)3]·3.5H2O precursor for high-k La2O3 thin films deposition

Lanthanum acetylacetonate La(C₅H₇O₂)₃·xH₂O has been used in the preparation of the precursor solution for the deposition of polycrystalline La₂O₃ thin films on Si(1 1 1) single crystalline substrates. The precursor chemistry of the as-prepared coating solution, precursor powder and precursor single crystal have been investigated by Fourier Transformed Infrared Spectroscopy (FTIR), differential thermal analysis coupled with quadrupole mass spectrometry (TG-DTA-QMS) and X-ray diffraction. The FTIR and X-ray diffraction analyses have revealed the complex nature of the coating solution due to the formation of a lanthanum propionate complex. The La₂O₃ thin films deposited by spin coating on Si(1 1 1) substrate exhibit good morphological and structural properties. The films heat treated at 800 °C crystallize in a hexagonal phase with the lattice parameters a = 3,89 Å and c = 6.33 Å, while at 900 °C the films contain both the hexagonal and cubic La₂O₃ phase.     

Preparation of Magnéli phases of Ti27O52 and Ti6O11 films by laser chemical vapor deposition

Magnéli phases of Ti₂₇O₅₂ and Ti₆O₁₁ films were prepared by laser chemical vapor deposition using Ti(dpm)₂(O-i-Pr)₂ as a precursor. Ti₆O₁₁ film was obtained at a laser power (P_L) of 200 W and a deposition temperature (T_dep) of 1270 K. Ti₂₇O₅₂ film was obtained at P_L = 150 to 200 W and T_dep = 1120 to 1250 K. Ti₆O₁₁ and Ti₂₇O₅₂ films had a faceted texture about 2 μm in grain size and a columnar cross section. The deposition rate of Ti₂₇O₅₂ and Ti₆O₁₁ films were 90 and 70 μm h^− 1, respectively.     

Synthesis, characterization and photoluminescence properties of (Gd0.99,Pr0.01)2O2S sub-microphosphor by homogeneous precipitation method

Homogeneous precipitation method for synthesizing (Gd_0.99,Pr_0.01)₂O₂S sub-microphosphor was developed, using the commercially available Gd₂O₃, Pr₆O₁₁, H₂SO₄ and (NH₂)₂CO (urea) as the starting materials. It was found that the as-synthesized precursor is mainly composed of (Gd_0.99,Pr_0.01)₂(OH)₂(CO₃)(SO₄)·nH₂O. Pure quasi-spherical shaped (Gd_0.99,Pr_0.01)₂O₂S particles can be synthesized by calcining the precursor at a temperature higher than 700 °C for 1 h in flowing hydrogen. The (Gd_0.99,Pr_0.01)₂O₂S particles have a narrow size distribution with a mean grain size of about 300-400 nm. Photoluminescence spectra of (Gd_0.99,Pr_0.01)₂O₂S under 303 nm UV excitation show a green emission at 515 nm as the most prominent peak, which corresponds to the ³P₀ → ³H₄ transition of Pr³⁺ ions. Decay study reveals that the ³P₀ → ³H₄ transition of Pr³⁺ ions in Gd₂O₂S host lattice has a single exponential decay behavior.     

A reddish La2O2S-based long-afterglow phosphor with effective absorption in the visible light region

Sm³⁺-activated La₂O₂S phosphors with good crystallinity were prepared by solid-state reaction. The formation mechanism of La₂O₂S formation was assumed and the phase change with different temperatures was discussed. The luminescence properties of phosphors with different sintering temperatures and different doping concentrations of Sm³⁺were investigated. The emission peak at 605 nm showed a well intensity can be attributed to the ⁴G_5/2 → ⁶H_7/2 transition of Sm³⁺. The optical absorption of La₂O₂S phosphors showed a stronger intensity in UV-vis region comparing with the Y₂O₂S phosphors. The long afterglow properties were investigated after the phosphors were excited with a fluorescent lamp. Phosphorescence lasted for about 3 min in the limit of light perception of the dark-adapted human eye (0.32 mcdm⁻²).     

Photoconductive properties of organic-inorganic hybrid perovskite (C6H13NH3)2(CH3NH3)m − 1PbmI3m + 1:TiO2 nanocomposites device structure

Photoconductive devices, with remarkable photoconductive performance, of fluorine doped tin oxide/TiO₂/(C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2):TiO₂/Pt were fabricated. An electron injection mechanism from the (C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2) to TiO₂ was proposed for the photoconductive effects, where organic-inorganic hybrid perovskite (C₆H₁₃NH₃)₂(CH₃NH₃)_m − 1Pb_mI_3m + 1 (m = 1, 2), self-organized into mesoscopic TiO₂ films from solution directly, served as the electron donor. The photoconductive performance of the devices can be adjusted by the inorganic sheet thickness (tuned by m) of the hybrid perovskite. The photocurrent value increased as m value increased at the same illumination. Further, when bias voltage was 1.0 V, the ratio of photocurrent and dark current for (C₆H₁₃NH₃)₂(CH₃NH₃)_2⁻ Pb₂I₇:TiO₂ reached as high as 7.05 × 10³. The devices could be potentially used as light detectors and light-controlled switch.     

Preparation and analysis of amorphous carbon films deposited from (C6H12)/Ar/He chemistry for application as the dry etch hard mask in the semiconductor manufacturing process

Amorphous carbon layers (ACL) were deposited on Si (100) wafers by plasma enhanced chemical vapor deposition (PECVD) by using 1-hexene (C₆H₁₂) as a carbon source for dry etch hard mask of semiconductor devices manufacturing process. The deposition characteristics and film properties were investigated by means of ellipsometry, Raman spectroscopy, X-ray photo electron spectroscopy (XPS) and stress analysis. Hardness, Young's modulus, and surface roughness of ACL deposited at 550 °C were investigated by using nano-indentation and AFM. The deposition rate was decreased from 5050 Å/min to 2160 Å/min, and dry etch rate was decreased from 2090 Å/min to 1770 Å/min, and extinction coefficient was increased from 0.1 to 0.5. Raman analysis revealed a higher shift of the G-peak and a lower shift of the D-peak and the increase of I(D)/I(G) ratio as the deposition temperature was increased from 350 °C to 550 °C. XPS results of ACL deposited at 550 °C revealed a carbon 1s binding energy of 284.4 eV. The compressive film stress was decreased from 2.95 GPa to 1.28 GPa with increasing deposition temperature. The hardness and Young's modulus of ACL deposited at 550 °C were 5.8 GPa and 48.7 GPa respectively. The surface roughness RMS of ACL deposited at 550 °C was 2.24 Å, and that after cleaning in diluted HF solution (H₂O:HF = 200:1), SC1 (NH₄OH:H₂O₂:H₂O = 1:4:20) solution, and sulfuric acid solution (H₂SO₄:H₂O₂ = 6:1) was 2.28 Å, 2.30 Å and 7.34 Å, respectively. The removal amount of ACL deposited at 550 °C in diluted HF solution, SC1 solution and sulfuric acid solution was 6 Å, 36 Å and 110 Å, respectively. These results demonstrated the viability of ACL deposited by PECVD from C₆H₁₂ at 550 °C for application as the dry etch hard mask in fabrication of semiconductor devices.