The growth and the interfacial layer of CdZnTe nano-crystalline films by vacuum evaporation

Nano-crystalline CdZnTe films were fabricated by thermal vacuum evaporation. The structure and surface morphology of the CdZnTe films were determined by XRD and SEM. The CdZnTe films were poly-crystalline with preferential (111) orientation. The CdZnTe films exhibited a typical particle size of 15 nm and a blue shift in the absorption with an effective band gap of 2.26 eV. An amorphous Te interfacial layer with thickness of 3 nm was observed with high resolution transmission electron microscopy, which should be formed at the initial stage of the growth. This is because the equilibrium vapor pressure of Cd is largely higher than that of Te₂ at the growth temperature, and the desorption rate of Cd atoms is much higher than that of and Te₂ molecules. The amorphous interfacial layer should be favorable for the formation of nano-crystalline CdZnTe film.     

Medium-term thermal stability of amorphous Ge2Sb2Te5 flash-evaporated thin films with regards to change in structure and optical properties

The stability of flash-evaporated amorphous Ge₂Sb₂Te₅ thin films has been studied under medium-term temperature treatment (30 - 80 °C, with a step of 10 °C) in ten subsequent heating and cooling cycles. The significant changes in structure and optical properties are reported. The temperature cycling of the films resulted in formation of an isolated 5 - 7 nm nano-crystalline phase in the amorphous phase. The corresponding increase in refractive index and change in optical bandgap energy and sheet resistance are also presented. The formation of Ge₂Sb₂Te₅ nano-crystals (~ 5 - 7 nm) even under temperature below 80 °C could contribute to the explanation of mechanism of resistivity fluctuation (drift) of the “amorphous phase” films. We also show that the optical and electrical properties of flash evaporated Ge₂Sb₂Te₅ thin films are very similar to those reported for sputtered films.     

Synthesis and characterization of 10% Sb doped CdTe thin films by stacked elemental layer (SEL) method

Antimony doped CdTe thin films have been prepared by stacked elemental layer (SEL) method. The X-ray diffraction spectra have demonstrated that the structure of the annealed films are polycrystalline in nature and mixed CdTe and Sb₂Te₃ phases have been observed at high annealing temperature (500 °C). The increased texture coefficient has been observed for planes (311) and (220) rather than (111) plane of CdTe in annealed stack (Te/Cd/Sb). Transmission spectra have been recorded and the calculated band gap lies between 1.45 and 1.68 eV. A pronounced PL spectrum has been noticed at 532 nm and depicted the presence of nano size particles in annealed thin films.     

Structural and optical properties of In doped Se–Te phase-change thin films: A material for optical data storage

Se_75−xTe₂₅In_x (x = 0, 3, 6, & 9) bulk glasses were obtained by melt quench technique. Thin films of thickness 400 nm were prepared by thermal evaporation technique at a base pressure of 10⁻⁶ Torr onto well cleaned glass substrate. a-Se_75−xTe₂₅In_x thin films were annealed at different temperatures for 2 h. As prepared and annealed films were characterized by X-ray diffraction and UV–Vis spectroscopy. The X-ray diffraction results show that the as-prepared films are of amorphous nature while it shows some poly-crystalline structure in amorphous phases after annealing. The optical absorption spectra of these films were measured in the wavelength range 400–1100 nm in order to derive the extinction and absorption coefficient of these films. It was found that the mechanism of optical absorption follows the rule of allowed non-direct transition. The optical band gap of as prepared and annealed films as a function of photon energy has been studied. The optical band gap is found to decrease with increase in annealing temperature in the present glassy system. It happens due to crystallization of amorphous films. The decrease in optical band gap due to annealing is an interesting behavior for a material to be used in optical storage. The optical band gap has been observed to decrease with the increase of In content in Se–Te glassy system.     

Binary semiconductor In2Te3 for the application of phase-change memory device

Nonvolatile phase-change memory devices with 500 nm contact hole based on In₂Te₃ were successfully fabricated by using focused ion beam, pulsed laser deposition, and dc magnetic sputtering techniques. In₂Te₃ films were characterized by using differential thermal analysis, X-ray diffraction, and UV–vis diffuse absorption spectroscopy, respectively. The devices can be switched between high and low resistance states repeatedly with the programmed voltage pulses. The reset operation (crystalline to amorphous) was done by the voltage pulse with a magnitude of 3.5 V and a duration of 30 ns, and the set operation (amorphous to crystalline) was done by the voltage pulse with a magnitude of 1.4 V and a duration of 100 ns. A dynamic resistance switching ratio (OFF/ON ratio) of 3.2 × 10³ has been obtained.     

Characteristics of high-k gate oxide prepared by oxidation of multi-layered Hf/Zr/Hf/Zr/Hf metal films

We investigated the physical and electrical properties of Hf-Zr mixed high-k oxide films obtained by the oxidation and annealing of multi-layered metal films (i.e., Hf/Zr/Hf/Zr/Hf, ∼ 5 nm). We demonstrated that the oxidation of multi-layered metal films results in two distinctive amorphous layers: That is, Hf-Zr mixed oxide film was formed on the top of silicate film due to inter-diffusion between Hf and Zr layer. This film shows the improved dielectric constant (k) and the raised crystallization temperature. Compared with HfO₂ and ZrO₂ gate dielectric, the crystallization temperature of Hf-Zr mixed oxides was raised by more than 200 °C. Using AES and XPS, we observed that Zr oxide has more fully oxidized stoichiometry than Hf oxide, irrespective of annealing temperatures. We also found that the thickness of an interfacial layer located between Hf-Zr mixed oxide and Si substrate also increases as annealing temperature increases. Especially, the thin SiO_x interfacial layer starts to form if annealing temperature increases over 700 °C, deteriorating the equivalent oxide thickness.     

Preparation of polycrystalline CdZnTe thick film Schottky diode for ultraviolet detectors

High resistivity (3 × 10⁹ Ω cm) polycrystalline CdZnTe thick films with thickness of 25 μm–150 μm were grown on SnO₂: F-coated glass substrates by close-spaced sublimation method. The properties of polycrystalline CdZnTe films were studied by XRD, SEM and EDS, respectively. A CdZnTe film Schottky diode detector was also fabricated and investigated using current–voltage and capacitance–voltage methods. The photo-current density of the device was about 1508.69 nA/mm² under light illumination (λ = 260 nm), at an applied negative voltage of 15 V. The results showed that polycrystalline CdZnTe thick film was suitable for application in ultraviolet detectors.     

Electron beam evaporation deposition and properties of Abrupt GST/Si heterojunction structure

The ternary alloy, Ge₂Te₂Sb₅ is one of the most important compounds of the GeTe-Sb₂Te₃ pseudobinary systems. Ge₂Te₂Sb₅ thin films of thickness of 100 nm-300 nm were deposited by electron beam evaporation. After annealing at different temperatures, we did X-ray diffraction measurement to characterize the structure transformation of the material. In-situ resistance measurement depending on the temperature shows that there is about three orders of magnitude change between the high resistance state (amorphous state) and the low resistance state (face-centered cubic state). To construct a heterojunction diode, we deposited Ge₂Te₂Sb₅ thin films on n-type silicon wafers. Rectification effects were observed in voltage-current measurements of the abrupt heterojunctions. Traditional voltage-current relationship of p-n junctions and metal-semiconductor junctions are used to explain the characteristics of Ge₂Te₂Sb₅/n-Si heterojunctions.     

Effect of substrate temperature on the optical parameters of thermally evaporated Ge-Se-Te thin films

Thin films of Ge₁₀Se_90 − xTe_x (x = 0, 10, 20, 30, 40, 50) glassy alloys were deposited at three substrate temperatures (303 K, 363 K and 423 K) using conventional thermal evaporation technique at base pressure of ~ 10^− 4 Pa. X-ray diffraction results show that films deposited at 303 K are of amorphous nature while films deposited at 363 K and 423 K are of polycrystalline nature. The optical parameters, refractive index and optical gap have been derived from the transmission spectra (using UV-Vis-NIR spectrophotometer) of the thin films in the spectral region 400-1500 nm. This has been observed that refractive index values remain almost constant while the optical gap is found to decrease considerably with the increase of substrate temperature. The decrease in optical gap is explained on the basis of change in nature of films, from amorphous to polycrystalline state, with the increase of substrate temperature. The optical gap has also been observed to decrease with the increase of Te content.     

Structural and electrical properties of room temperature pulsed laser deposited and post-annealed thin SrRuO3 films

Good quality strontium ruthenate (SrRuO₃) thin continuous films (15 to 125 nm thick) have been synthesized on silicon (100) substrates by room temperature pulsed laser deposition under vacuum followed by a post-deposition annealing, a route unexplored and yet not reported for SrRuO₃ film growth. The presence of an interfacial Sr₂SiO₄ layer has been identified for films annealed at high temperature, and the properties of this interface layer as well as the properties of the SrRuO₃ film have been analyzed and characterized as a function of the annealing temperature. The room temperature resistivity of the SrRuO₃ films deposited by laser ablation at room temperature and post-annealed is 2000 μΩ·cm. A critical thickness of 120 nm has been determined above which the influence of the interface layer on the resistivity becomes negligible.     

Properties and thermal stability of solution processed ultrathin,high-k bismuth titanate (Bi2Ti2O7) films

Ultrathin bismuth titanate films (Bi₂Ti₂O₇, 5–25 nm) are deposited onto SiO₂/Si substrates by aqueous chemical solution deposition and their evolution during annealing is studied. The films crystallize into a preferentially oriented, pure pyrochlore phase between 500 and 700 °C, depending on the film thickness and the total thermal budget. Crystallization causes a strong increase of surface roughness compared to amorphous films. An increase of the interfacial layer thickness is observed after anneal at 600 °C, together with intermixing of bismuth with the substrate as shown by TEM-EDX. The band gap was determined to be ～3 eV from photoconductivity measurements and high dielectric constants between 30 and 130 were determined from capacitance voltage measurements, depending on the processing conditions.     

Comparison of microstructure and phase transformation for nanolayered CrN/AlN and TiN/AlN coatings at elevated temperatures in air environment

CrN/AlN and TiN/AlN multilayer coatings with modulation period of 4 nm and thickness ratio equal to 1.0 were manufactured by RF magnetron sputtering. Both films were annealed at temperatures of 800 °C in air for 1 h and then for an additional 9 h. Both coatings in as-deposited and after heat treatment were evaluated with a transmission electron microscope (TEM) equipped with EDS. After heat treatment at 800 °C for 1 h, a thick oxide layer around 260 nm was formed on the surface of the TiN/AlN coating. The oxide layer which formed on the coating was composed of three different regimes, including Al-enriched oxide with excess oxygen on the top surface, a crystalline Al-depleted TiO₂ layer 30-80 nm thick above the nitride coating and in between, mixed nano-crystalline Al₂O₃ and TiO₂ films. In comparison, only one oxide layer smaller than 50 nm in thickness was found in the annealed CrN/AlN coating. This amorphous or nanocrystalline oxide layer identified by EDS was a metal-deficient oxide, in which Al₂O₃ and Cr₂O₃ were mixed together forming a solid solution. As a result, the CrN/AlN coating exhibited superior stability compared to the TiN/AlN coating at elevated temperatures.     

Growth of Ge nanoparticles on SiO2/Si interfaces during annealing of plasma enhanced chemical vapor deposited thin films

Multilayer germanosilicate (Ge:SiO₂) films have been grown by plasma enhanced chemical vapor deposition. Each Ge:SiO₂ layer is separated by a pure SiO₂ layer. The samples were heat treated at 900 °C for 15 and 45 min. Transmission electron microscopy investigations show precipitation of particles in the layers of highest Ge concentration. Furthermore there is evidence of diffusion between the layers. This paper focuses mainly on observed growth of Ge particles close to the interface, caused by Ge diffusion from the Ge:SiO₂ layer closest to the interface through a pure SiO₂ layer and to the interface. The particles grow as spheres in a direction away from the interface. Particles observed after 15 min anneal time are 4 nm in size and are amorphous, while after 45 min anneal time they are 7 nm in size and have a crystalline diamond type Ge structure.     

Thermoelectric properties of the bismuth-antimony-telluride and the antimony-telluride films processed by electrodeposition for micro-device applications

Thermoelectric properties of the electrodeposited bismuth-antimony-telluride (Bi-Sb-Te) and the antimony-telluride (Sb-Te) films were characterized. The electrodeposited Bi-Sb-Te films exhibited the Seebeck coefficients of 21-71 µV/K and a maximum power factor of 1.2 × 10^− 4 W/K²-m. The Sb-Te films electrodeposited at potentials of 10 mV-30 mV were amorphous with compositions close to the Sb₂Te₃ stoichiometry. The electrodeposited Sb-Te films exhibited the Seebeck coefficients larger than 250 µV/K due to their noncrystallinity. The amorphous Sb-Te films of the stoichiometric composition exhibited a maximum power factor of 57 × 10^− 4 W/K²-m.     

Manipulating the Interfacial Band Bending For Enhancing the Thermoelectric Properties of 1T′-MoTe2/Bi2Te3 Superlattice Films

Interfacial charge effects, such as band bending, modulation doping, and energy filtering, are critical for improving electronic transport properties of superlattice films. However, effectively manipulating interfacial band bending has proven challenging in previous studies. In this study, (1T′-MoTe₂)_x(Bi₂Te₃)_y superlattice films with symmetry-mismatch were successfully fabricated via the molecular beam epitaxy. This enables to manipulate the interfacial band bending, thereby optimizing the corresponding thermoelectric performance. These results demonstrate that the increase of Te/Bi flux ratio (R) effectively tailored interfacial band bending, resulting in a reduction of the interfacial electric potential from ≈127 meV at R = 16 to ≈73 meV at R = 8. It is further verified that a smaller interfacial electric potential is more beneficial for optimizing the electronic transport properties of (1T′-MoTe₂)_x(Bi₂Te₃)_y. Especially, the (1T′-MoTe₂)₁(Bi₂Te₃)₁₂ superlattice film displays the highest thermoelectric power factor of 2.72 mW m⁻¹ K⁻² among all films, due to the synergy of modulation doping, energy filtering, and the manipulation of band bending. Moreover, the lattice thermal conductivity of the superlattice films is significantly reduced. This work provides valuable guidance to manipulate the interfacial band bending and further enhance the thermoelectric performances of superlattice films.     

Phase change and optical band gap behavior of Ge-Te-Ga thin films prepared by thermal evaporation

The amorphous Ge_11.4Te_86.4Ga_2.2 chalcogenide thin films were prepared by thermal evaporation onto chemically cleaned glass substrates. Properties measurements include X-ray diffraction (XRD), Scanning electron microscopy (SEM), Differential scanning calorimetry (DSC), Four-point probe and VIS-NIR transmission spectra. The allowed indirect transition optical band gap and activation energy of samples were calculated according to the classical Tauc equation and Kissinger's equation, respectively. The results show that there is an amorphous-to-crystalline phase transition of Ge_11.4Te_86.4Ga_2.2 thin film. The investigated film has high crystallization temperature (∼200 °C) and activation energy (2.48 eV), indicating the film has good amorphous stability. The sheet resistance of the crystalline state is ∼10 Ω/and the amorphous/crystalline resistance ratio is about 10⁵. Besides, a wide optical band gap (0.653 eV) of Ge_11.4Te_86.4Ga_2.2 is obtained, indicating that the material possesses a low threshold current from amorphous-to-crystalline state for phase-change memory application.     

Characterization of phase transition in silver photo-diffused Ge2Sb2Te5 thin films

Surface activity of thermally evaporated amorphous chalcogenide films of Ge₂Sb₂Te₅ has been investigated. Silver (Ag) is readily deposited on such films from appropriate aqueous ionic solution and Ag diffuses into the films upon irradiation with energetic photons. The composition of Ge₂Sb₂Te₅ thin films and the amount of Ag photo-diffused has been gathered from electron probe micro-analyzer having a wavelength dispersive spectrometer. The composition of the films was found to be very close to the bulk used to deposit films and the amount of Ag photo-diffused was ∼ 0.38 at. %. X-ray diffraction and temperature dependent sheet resistance studies have been used for the structural analysis of the bulk alloy, as-deposited, Ag photo-diffused and annealed films at different temperatures. The films remain amorphous after Ag photo-diffusion into the amorphous Ge₂Sb₂Te₅ films. The reflectivity, reflectivity contrast and extinction coefficient of the crystalline and amorphous photo-diffused thin films are presented. The optical band gaps of the amorphous and crystalline photo-diffused (Ge₂Sb₂Te₅)_100−xAg_x=0.38 phase change thin films have also been calculated from absorption data using UV-VIS spectroscopy.     

Characterization of Agx(Ge2Sb2Te5)1 − xthin film by RF magnetron sputtering

We reported the Ag adding effects on the crystallization behavior in Ge₂Sb₂Te₅ film. Ag_x(Ge₂Sb₂Te₅)_1 − x films (where x = 0–0.2) were deposited on SiO₂ wafer and glass substrate by RF magnetron co-sputtering and annealed by RTA (rapid thermal annealing) at various temperature to crystallize. The effects of Ag adding on the structural, thermal and electrical properties were measured by X-ray diffraction, X-ray reflectivity, AFM, SEM, DSC and 4-point probe analysis. It was found that the crystallization temperature increased by Ag adding in Ge₂Sb₂Te₅ films. However, the surface of Ag_x(Ge₂Sb₂Te₅)_1 − x films got rough when annealing temperature and Ag contents increased. According to the Kissinger method, the activation energy for crystallization increased as the Ag content increased. It is thought that Ag atoms in Ge₂Sb₂Te₅ act as an amorphous stabilizer and they make it hard to switch from amorphous to crystalline phase. From this study, we would show the Ag_0.06(Ge₂Sb₂Te₅)_0.94 film is suitable for phase change memory material because of its higher crystallization temperature and structural stability.     

Structural characterization and novel optical properties of defect chalcopyrite ZnGa2Te4 thin films

Stoichiometric thin film samples of the ternary ZnGa₂Te₄ defect chalcopyrite compound were prepared and characterized by X-ray diffraction technique. The elemental chemical composition of the prepared bulk material as well as of the as-deposited film was determined by energy-dispersive X-ray spectrometry. ZnGa₂Te₄ thin films were deposited, by conventional thermal evaporation technique onto highly cleaned glass substrates. The X-ray and electron diffraction studies revealed that the as-deposited and the annealed ZnGa₂Te₄ films at annealing temperature t_a ≤ 548 K are amorphous, while those annealed at t_a ≥ 573 K (for 1 h), are polycrystalline. The optical properties of the as-deposited films have been investigated for the first time at normal incidence in the spectral range from 500 to 2500 nm. The refractive index dispersion in the transmission and low absorption region is adequately described by the Wemple–DiDomenico single oscillator model, whereby, the values of the oscillator parameters have been calculated. The analysis of the optical absorption coefficient revealed an in-direct optical transition with energy of 1.33 eV for the as-deposited sample. This work suggested that ZnGa₂Te₄ is a good candidate in solar cell devices as an absorbing layer.     

Fabrication of polycrystalline silicon thin films on glass substrates using fiber laser crystallization

Laser crystallization of amorphous silicon (a-Si), using a fiber laser of λ = 1064 nm wavelength, was investigated. a-Si films with 50 nm thickness deposited on glass were prepared by a plasma enhanced chemical vapor deposition. The infrared fundamental wave (λ = 1064 nm) is not absorbed by amorphous silicon (a-Si) films. Thus, different types of capping layers (a-CeO_x, a-SiN_x, and a-SiO_x) with a desired refractive index, n and thickness, d were deposited on the a-Si surface. Crystallization was a function of laser energy density, and was performed using a fiber laser. The structural properties of the crystallized films were measured via Raman spectra, a scanning electron microscope (SEM), and an atomic force microscope (AFM). The relationship between film transmittance and crystallinity was discussed. As the laser energy density increased from 10-40 W, crystallinity increased from 0-90%. However, the higher laser density adversely affected surface roughness and uniformity of the grain size. We found that favorable crystallization and uniformity could be accomplished at the lower energy density of 30 W with a-SiO_x as the capping layer.