Effects of annealing temperature on crystallisation kinetics and properties of polycrystalline Si thin films and solar cells on glass fabricated by plasma enhanced chemical vapour deposition

Solid-phase crystallisation of Si thin films on glass fabricated by plasma enhanced chemical vapour deposition is compared at different annealing temperatures. Four independent techniques, optical transmission microscopy, Raman and UV reflectance spectroscopy, and X-ray diffraction, are used to characterise the crystallisation kinetics and film properties. The 1.5 μm thick films with the n+/p−/p+ solar cell structure have incubation times of about 300, 53, and 14 min and full crystallisation times of about 855, 128, and 30 min at 600 °C, 640 °C, and 680 °C respectively. Estimated activation energies for incubation and crystal growth are 2.7 and 3.2 eV respectively. The average grain size in the resulting polycrystalline Si films measured from scanning electron microscopy images gradually decreases with a higher annealing temperature and the crystal quality becomes poorer according to the Raman, UV reflection, and X-ray diffraction results. The dopant activation and majority carrier mobilities in heavily doped n+ and p+ layers are similar for all crystallisation temperatures. Both the open-circuit voltage and the spectral response are lower for the cells crystallised at higher temperatures and the minority carrier diffusion lengths are shorter accordingly although they are still longer than the cell thickness for all annealing temperatures. The results indicate that shortening the crystallisation time by merely increasing the crystallisation temperature offers little or no merits for PECVD polycrystalline Si thin-film solar cells on glass.     

Al and Ti/Al contacts on n-GaN

Al(60 nm) and Ti(40 nm)/Al(160 nm) metal layers have been deposited by thermal evaporation onto n-GaN epitaxial layers grown by metal organic chemical vapour deposition (MOCVD) on a c-plane sapphire substrate. The samples have been annealed at 300, 400, 700 or 900 °C for 10 min in vacuum. The microstructural and electrical properties of the contacts have been investigated by electron microscopy, X-ray diffraction and by current-voltage measurements. As-deposited Al and Ti/Al contacts were rectifying with Schottky barrier heights below 0.35 eV and 0.38 eV, respectively. After heat treatment at 300 °C and 400 °C both contacts exhibited linear current-voltage characteristics. After annealing at 700 °C Al contacts became rectifying with a barrier height of 0.42 eV, while Ti/Al contacts remained nearly linear at the same temperature. The electrical characteristics and XRD analysis indicated that the upper metal in Ti/Al contact diffused in the Ti layer already during deposition. Cross-sectional transmission electron microscopy revealed that in the case of Ti/Al contacts, the continuity of the Ti layers ceased when annealing above 700 °C. X-ray diffractions showed, that a Ti₂N interface phase formed in Ti/Al contacts at 700 and 900 °C, and an AlN interface phase developed in the same contact at 900 °C.     

Structural, optical and electrical study of undoped GaN layers obtained by metalorganic chemical vapor deposition on sapphire substrates

We investigate optical, structural and electrical properties of undoped GaN grown on sapphire. The layers were prepared in a horizontal reactor by low pressure metal organic chemical vapor deposition at temperatures of 900 °C and 950 °C on a low temperature grown (520 °C) GaN buffer layer on (0001) sapphire substrate. The growth pressure was kept at 10,132 Pa. The photoluminescence study of such layers revealed a band-to-band emission around 366 nm and a yellow band around 550 nm. The yellow band intensity decreases with increasing deposition temperature. X-ray diffraction, atomic force microscopy and scanning electron microscopy studies show the formation of hexagonal GaN layers with a thickness of around 1 μm. The electrical study was performed using temperature dependent Hall measurements between 35 and 373 K. Two activation energies are obtained from the temperature dependent conductivity, one smaller than 1 meV and the other one around 20 meV. For the samples grown at 900 °C the mobilities are constant around 10 and 20 cm² V⁻¹ s^− 1, while for the sample grown at 950 °C the mobility shows a thermally activated behavior with an activation energy of 2.15 meV.     

Thermal stability of advanced gate stacks consisting of a Ru electrode and Hf-based gate dielectrics for CMOS technology

Metallic Ru and Hf-based dielectrics such as HfO₂, HfSiO_x and HfSiON, are promising materials for the gate electrode and gate dielectrics, respectively. This paper reports on the thermal stability of gate stack systems comprised of Ru/Hf-based dielectrics. Layers of both types of material were prepared on Si substrate by metal-organic chemical vapour deposition (MOCVD). The stacks underwent exposure by rapid thermal annealing (RTA) in pure nitrogen ambience at temperatures 800, 900, and 1000 °C for 10 s. The samples were analysed using Rutherford backscattering spectrometry (RBS). Small changes were found in the stacks treated at 800 and 900 °C. The most stable stack was found to be one with a HfSiON dielectric layer, which was resistant also at temperature 900 °C. However, the annealing at 1000 °C induced massive diffusion at both interfaces for all types of stack. The results imply a limited thermal stability of the Ru/Hf-based dielectric gate stacks during the source/drain activation step.     

Substrate and annealing temperature effects on the crystallographic and optical properties of MoO3 thin films prepared by laser assisted evaporation

MoO₃ thin Films were prepared using the assisted laser evaporation technique. Samples were grown on glass and silicon substrates at different substrates temperatures. The effect on structural and optical properties of the substrate and on annealing temperatures was evaluated. A phase transition was found around 200 °C in all samples from the amorphous to the β phase with a small percentage of α phase, and another one was found around 500 °C from the α + β to the α phase. The percentage errors between the lattice parameter a₀ of the crystallographic index card for the MoO₃ alpha phase and the indexed lattice parameters were 1.4% and 0.3% for the samples deposited on glass and silicon respectively, indicating the crystalline structure of the silicon substrate favors the formation of the MoO₃ alpha orthorhombic phase. The spectral variation of the refractive index and the absorption coefficient were theoretically determined. The amorphous samples presented a constant gap of 3.2 eV while the optical properties critically depended on the substrate and annealing temperatures.     

Structural and electrical properties of Au and Ti/Au contacts to n-type GaN

Au and Ti/Au layers were deposited on n-GaN. The samples were annealed at 400, 700 and 900 °C for 10 min in vacuum. The contacts were rectifying up to 700 °C and the highest Schottky barrier height of 1.07 eV was obtained for an Au single layer by current-voltage measurements. A binary phase of Au₂Ga was identified at the interface of the n-GaN/Ti/Au contact after annealing at 900 °C. The formation of Ti₂N and TiN (twin) phases epitaxially grown on GaN was also observed in the same contact as well as some gold diffusion into the topmost region of the GaN epilayer.     

Broad band optical characterization of sol-gel TiO2 thin film microstructure evolution with temperature

Titanium dioxide (TiO₂) thin films have been produced by spin coating a titanium isopropoxide sol on silicon wafer substrates. The structural evolution of the thin films in terms of decomposition, crystallization and densification has been monitored as a function of annealing temperature from 100 to 700 °C using optical characterization and other techniques. The effect of annealing temperature on the refractive index and extinction coefficient of these TiO₂ thin films was studied in the range of 0.62 to 4.96 eV photon energy (250-2000 nm wavelength) using spectroscopic ellipsometry. Thermal gravimetric analysis and atomic force microscopy support the ellipsometry data and provide information about structural transformations in the titania thin films with respect to different annealing temperatures. These data help construct a coherent picture of the decomposition of the sol-gel precursors and the creation of dense layers of TiO₂. It was observed that the refractive index increased from 2.02 to 2.45 at 2.48 eV (500 nm) in sol-gel spin coated titania films for annealing temperatures from 100 °C to 700 °C.     

Annealing and recrystallization of amorphous ZnO thin films deposited under cryogenic conditions by pulsed laser deposition

This article deals with the annealing of amorphous ZnO thin films prepared by pulsed laser deposition (PLD) under cryogenic conditions. The substrate holder was cooled by liquid nitrogen. X-ray diffraction analysis evidenced that as-deposited films had amorphous structures: analysis by scanning electron microscopy (SEM) revealed their fine grained surface and inner structure. Annealing at temperatures in the range of 200-800 °C resulted in a transition in the thin film crystal structure from amorphous to polycrystalline. Various properties of the ZnO films were found depending on the recrystallization temperature. In depth investigations employing SEM, X-ray diffraction, atomic force microscopy and secondary ion mass spectroscopy provided comparisons of the recrystallizations of undoped ZnO thin films during the phase transition processes from amorphous to hexagonal wurtzite structures.     

Ag diffusion in ZnS thin films prepared by spray pyrolysis

ZnS thin films were deposited by spray pyrolysis method on glass substrates. Diffusion of Ag in ZnS thin films was performed in the temperature range 80-400 °C under a nitrogen atmosphere. The diffusion of Ag is determined with XRF, and the obtained concentration profile allows to calculate the diffusion coefficient. The temperature dependence of Ag diffusion coefficient is determined by the equation D = 8 × 10^− 9 exp(− 0.10 eV / kT). It was found that the as-grown undoped high resistive n-type ZnS thin films were converted to the p-type upon Ag doping with a slight increase in resistivity only by rapid thermal annealing at 400 °C in N₂ atmosphere. In addition, the band gap of the p-type film was decreased as compared with the undoped sample annealed under the same conditions. The results were attributed to the migration of Ag atoms in polycrystalline ZnS films by means of both along intergrain surfaces and intragrain accompanied by interaction with native point defect.     

Thermal relaxation of residual stresses in shot peened surface layer of (TiB + TiC)/Ti-6Al-4V composite at elevated temperatures

As an effective and important surface treatment method, shot peening can introduce high residual compressive stress and microstructure variation at near surface deformation layers. In this work, residual stresses relaxation behaviors of the shot peened layer of (TiB + TiC)/Ti-6Al-4V composite were investigated during thermal exposure, and the microstrain was calculated according to the integral breadth after isothermal annealing. The microstrain decreased fast and reached the minimum at 500 °C, which resulted from the thermal recovery and dynamic recrystallization. At elevated temperatures, the residual compressive stresses were relaxed in the whole deformation layers, which were caused by the thermally activated gliding of dislocations. The processes of relaxation can be described using a Zener-Wert-Avrami function and the activation energy of the residual stresses relaxation was higher than that of titanium self diffusion, which was ascribed to the hindrance effects of reinforcements as sink sources of dislocations during annealing.     

Recrystallization behavior of a supersaturated Al-Mn alloy

The effect of concurrent precipitation on recrystallization behavior during the isothermal annealing of a supersaturated and deformed Al-Mn alloy was investigated. It is found that concurrent precipitation strongly affects the recrystallization behavior of this alloy. At low temperatures, concurrent precipitation retards recrystallization and results in large flat grains. The size of recrystallized grains decreases significantly with increasing temperature. The kinetics of recrystallization was determined by measurements of hardness. The JMAK exponent decreases from 3.0 to 0.8 as the annealing temperature increases from 371 °C to 427 °C. The activation energy for recrystallization of the alloy is about 456 kJ/mol. Concurrent precipitation enhances the activation energy for recrystallization of aluminum alloys.     

Susceptor-assisted microwave annealing for activation of arsenic dopants in silicon

Microwave annealing of arsenic-doped silicon was employed to achieve nearly complete dopant activation and repair of damage caused by ion implantation. Analysis of Rutherford backscattering spectra suggested that volumetric heating from microwaves can repair ion-implantation damage. Secondary ion mass spectroscopy depth profiling revealed that even with high damage due to implanted arsenic, microwave annealing achieves repair of lattice damage, and electrical activation of dopants without allowing any significant dopant diffusion into the silicon substrate. Surface temperatures greater than 700 °C were achieved within ~ 100 s with assisted microwave heating, marking this as a quick annealing technique when compared to un-assisted annealing. This temperature was sufficient for solid phase epitaxial growth in Si. The temperature profile recorded by a thermocouple-calibarated IR pyrometer was explained based upon the type of losses the sample undergoes while heating. The mechanism for susceptor-assisted microwave heating was dominated by dipole polarization losses in the initial stages of anneal and by Ohmic conduction losses at higher temperatures. Cross-section transmission electron microscopy, along with ion channeling spectra indicated that the silicon lattice regained nearly all of its crystallinity during the microwave anneal. Hall measurement and sheet resistance characterization were used to assess the extent of dopant activation.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

Effects of substrate temperature and post-deposition anneal on properties of evaporated cadmium telluride films

The effects of substrate temperature and post-deposition heat treatment steps on the morphology, structural, optical and electrical properties of thin film CdTe layers grown by vacuum evaporation were investigated. Scanning electron microscopy and X-ray diffraction (XRD) techniques were employed to study the structural changes. It was observed that the grain sizes and morphologies of as-deposited layers were similar for substrate temperatures of − 173 °C and − 73 °C. However, CdTe films produced at a substrate temperature of 27 °C had substantially larger grain size and clearly facetted morphology. Annealing at 200-400 °C in air did not cause any appreciable grain growth in any of the films irrespective of their growth temperature. However, annealing at 400 °C reduced faceting in all cases and initiated fusing between grains. XRD studies showed that this behavior after annealing at 400 °C coincided with an onset of a degree of randomization in the originally strong (111) texture of the as-grown layers. Optical band gap measurements showed sharpening of the band-edge upon annealing at 400 °C and a band gap value in the range of 1.46-1.49 eV. Resistivity measurements indicated that annealing at 400 °C in air forms a highly resistive compensated CdTe film. All results point to 400 °C to be a critical annealing temperature at which optical, structural and electrical properties of CdTe layers start to change.     

Effect of annealing temperature on ZnO:Al/p-Si heterojunctions

Al-doped, zinc oxide (ZnO:Al) films with a 1.2 at.% Al concentration were deposited on p-type silicon wafers using a sol-gel dip coating technique to produce a ZnO:Al/p-Si heterojunction. Following deposition and subsequent drying processes, the films were annealed in vacuum at five different temperatures between 550 and 900 °C for 1 h. The resistivity of the films decreased with increasing annealing temperature, and an annealing temperature of 700 °C provided controlled current flow through the ZnO:Al/p-Si heterojunction up to 20 V. The ZnO:Al film deposited on a p-type silicon wafer with 1.2 at.% Al concentration was concluded to have the potential for use in electronic devices as a diode after annealing at 700 °C.     

Investigation of Sb diffusion in amorphous silicon

Amorphous silicon materials and its alloys became extensively used in some technical applications involving large area of the microelectronic and optoelectronic devices. However, the amorphous-crystalline transition, segregation and diffusion processes still have numerous unanswered questions. In this work we study the Sb diffusion into an amorphous Si film by means of Secondary Neutral Mass Spectrometry. Amorphous Si/Si_1−xSb_x/Si tri-layer samples with 5 at% antimony concentration were prepared by direct current magnetron sputtering onto Si substrate at room temperature. Annealing of the samples was performed at different temperatures in vacuum (p<10⁻⁷ mbar) and 100 bar high purity (99.999%) Ar pressure. During annealing a rather slow mixing between the Sb-alloyed and the amorphous Si layers was observed. Supposing concentration independent of diffusion, the evaluated diffusion coefficients are in the range of ∼10⁻²¹ m²s⁻¹ at 550 °C.     

Formation and transformation of ZnTiO3 prepared by sputtering process

Zinc titanate (ZnTiO₃) films were prepared using RF magnetron sputtering at substrate temperatures ranging from 30 to 400 °C. Subsequent annealing of the as-deposited films was performed at temperatures ranging from 600 to 900 °C. It was found that all as-deposited films were amorphous, as confirmed by XRD. This was further confirmed by the onset of crystallization that took place at annealing temperatures 600 °C. The phase transformation for the as-deposited films and annealed films were investigated in this study. The results revealed that pure ZnTiO₃ (hexagonal phase) can exist, and was obtained at temperatures between 700 and 800 °C. However, it was found that decomposition from hexagonal ZnTiO₃ to cubic Zn₂TiO₄ and rutile TiO₂ took place with a further increase in temperature to 900 °C.     

Fabrication of a n-ZnO/p-Si heterojunction diode by ultra-high vacuum magnetron sputtering

Heterojunction diodes of n-type ZnO were fabricated on a p-type Si(100) substrate using an ultra-high vacuum radio frequency magnetron sputtering method at room temperature. A short-time post-annealing process was performed to prevent inter-diffusion of Zn, dopants, and Si atoms. The post-annealing process at 600 °C enhanced the crystallinity of ZnO films and produced a high forward to reverse current ratio of the heterojunction diode with a barrier height of approximately 0.336 eV. A thin SiO_x layer at the interface of the ZnO film and Si substrate appeared distinctly at the 600 °C annealing, however the post-annealing at 700 °C showed an a-(Zn_2xSi_1 − xO₂) structure caused by diffusion of silicon into the ZnO film. In the n-ZnO/p-Si sample annealed at 700 °C, a rapid change in the barrier height was considered due to the effect of the dopant segregation from the substrate and deformation of the a-SiO_x structure.     

Polycrystalline silicon films on glass grown by amorphous-liquid-crystalline transition at temperatures below 330 °C

An approach to deposit polycrystalline silicon layers on amorphous substrates is presented. It is shown that metastable amorphous silicon can be transformed into its more stable microcrystalline structure at a temperature below 330 °C via an intermediate liquid solution stage. In particular, the interaction of liquid indium nanodroplets in contact with amorphous silicon is shown to lead to the formation of circular polycrystalline domains. Crystallinity of these domains is analyzed by micro-Raman spectroscopy. The droplet size necessary for the onset of crystallization is related to the temperature of the film. Full coverage of the substrate with microcrystalline silicon has been obtained at 320 °C within less than one hour. These films might act as seeding layers for further enlargement by steady-state liquid phase epitaxy.     

Copper diffusion in thin In2S3 layers investigated by Rutherford Backscattering Spectroscopy

Copper diffusion in thin In₂S₃ layers was investigated by measuring copper concentration profiles with Rutherford Backscattering Spectroscopy (RBS). For this purpose In₂S₃ layers (thickness 100 nm) were evaporated on crystalline silicon substrates and Cu was diffused from a CuSCN surface layer at temperatures between 150 and 250 °C. The CuSCN source layer was removed in pyridine solution before RBS measurements were performed. Diffusion coefficients of Cu in In₂S₃ were obtained by simulating the diffusion process in a one-dimensional model and comparing measured and simulated Cu concentration profiles. The values of the exponential prefactor of the diffusion coefficient and of the activation energy were 9 × 10^− 11 cm²/s and 0.3 eV, respectively.