ZnO growth on Si with low-temperature ZnO buffer layers by ECR-assisted MBE

High-quality ZnO films were grown on Si(1 0 0) substrates with low-temperature (LT) ZnO buffer layers by an electron cyclotron resonance (ECR)-assisted molecular-beam epitaxy (MBE). In order to investigate the optimized buffer layer temperature, ZnO buffer layers of about 1.1 μm were grown at different growth temperatures of 350, 450 and 550 °C, followed by identical high-temperature (HT) ZnO films with the thickness of 0.7 μm at 550 °C. A ZnO buffer layer with a growth temperature of 450 °C (450 °C-buffer sample) was found to greatly enhance the crystalline quality of the top ZnO film compared to others. The root mean square (RMS) roughness (3.3 nm) of its surface is the smallest, compared to the 350 °C-buffer sample (6.7 nm), the 550 °C-buffer sample (7.4 nm), and the sample without a buffer layer (6.8 nm). X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurements were carried out on these samples at room temperature (RT) in order to characterize the crystalline quality of ZnO films. The preferential c-axis orientations of (0 0 2) ZnO were observed in the XRD spectra. The full-width at half-maximum (FWHM) value of the 450 °C-buffer sample was the narrowest as 0.209°, which indicated that the ZnO film with a buffer layer grown at this temperature was better for the subsequent ZnO growth at elevated temperature of 550 °C. Consistent with these results, the 450 °C-buffer sample exhibits the highest intensity and the smallest FWHM (130 meV) of the ultraviolet (UV) emission at 375 nm in the PL spectrum. The ZnO characteristic peak at 438.6 cm⁻¹ was found in Raman scattering spectra for all films with buffers, which is corresponding to the E₂ mode.     

Insights into effects of annealing on microstructure from SnO2 thin films prepared by pulsed delivery

Tin dioxide thin films were prepared by pulsed laser deposition techniques on clean glass substrates, and the thin films were then annealed for 30 min from 50 to 550 °C with a step of 50 °C, respectively. The influence of the annealing temperature on the microstructural and morphological properties of the tin dioxide thin films was investigated using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and selected area electron diffraction. The experimental results showed that the amorphous microstructure almost transformed into a polycrystalline tin dioxide phase exhibiting a preferred orientation related to the (1 1 0), (1 0 1) and (2 1 1) crystal planes with increased temperatures. The thin film annealed at 200 °C demonstrated the best crystalline properties, viz. optimum growth conditions. However, the thin film annealed at 100 °C revealed the minimum average root-mean-square roughness of 20.6 nm with average grain size of 26.6 nm. These findings indicate that the annealing temperature is very important parameter to determining the thin film quality, which involves the phase formation, microstructure and preferred orientation of the thin films.     

Low-temperature metal-induced crystallization of Mn-containing amorphous Ge thin films

This work focuses on the crystallization of amorphous germanium (a-Ge) thin films induced by manganese species. A series of Mn-containing a-Ge films ([Mn] ~ 0?3.7 at.% range) was deposited at 150 °C by the cosputtering technique. After deposition, all films were submitted to isochronal thermal annealing treatments up to 600 °C and analyzed by Raman scattering, optical transmission spectroscopy and electrical resistivity measurements. The experimental results indicate that: (a) Mn impurity lowers the crystallization temperature of a-Ge in ~ 100 °C, as confirmed by the Raman analyses, (b) the optical properties of the films are affected by both the insertion of Mn and the temperature of thermal treatment, with the optical bandgap staying in the range of ~ 0.7?1 eV, and (c) the electrical resistivity of the samples is also influenced by the Mn concentration and by the temperature of annealing, varying between ~ 1.0×10¹ and 1.6×10⁴ Ω cm. These experimental observations were systematically studied and the possible reasons associated to them are presented and discussed.     

Crystallization of polymer-derived SiC/BN/C composites investigated by TEM

The crystallization behavior of two polymer-derived Si/B/C/N ceramics with similar compositions lying close to the three-phase field BN + SiC + C was investigated by (high-resolution) transmission electron microscopy. The materials were high-temperature mass stable up to T = 2000 °C. During thermolysis at 1050 °C a homogeneous amorphous solid formed. SiC crystallization started at about 1400 °C. Further annealing to higher temperatures up to 2000 °C led to formation of microstructures composed of SiC crystals embedded into a structured BNC_x matrix phase. With increasing temperature, both the size of the crystallites and the ordering of the matrix phase increased.     

Structural and optical properties of TiO2 thin films derived by sol–gel dip coating process

Nanocrystalline thin films of titanium dioxide have been fabricated on glass and silica substrates from partially hydrolyzed precursor solution. These films were subjected to heat treatment for 1 h at temperatures 100, 200, 300, 400, 500, 600, 700, 800 and 900 °C and characterized by XRD, SEM, XPS and optical techniques. As deposited films are found to be amorphous and also contain hydroxyl and organic functional groups. Films heat treated above 100 °C do not contain hydroxyl and organic functional groups. Microcrystalline behavior is observed in the films heat treated above 300 °C. Crystallite size increases from ∼5 to 50 nm as sintering temperature is increased from 300 to 700 °C. Formation of anatase phase with c-axis length 7.03 Å is observed in the films annealed up to 700 °C. These films peel off from the substrate beyond 700 °C annealing temperature. Density as well as refractive index of the films increases with increase in annealing temperature up to 700 °C. Refractive index is found to show Cauchys behavior. Transmission better than 70% is observed in the visible range. There is a strong absorption around 370 nm, which is attributed to band gap absorption of the material.     

Plasma enhanced chemical vapor deposition of ZnO thin films

Zinc oxide thin films were deposited on silicon and corning-7059 glass substrates by plasma enhanced chemical vapor deposition at different substrate temperatures ranging from 36 to 400 °C and with different gas flow rates. Diethylzinc as the source precursor, H₂O as oxidizer and argon as carrier gas were used for the preparation of ZnO films. Structural and optical properties of these films were investigated using X-ray diffraction, reflection high energy electron diffraction, atomic force microscopy and photoluminescence. Highly oriented films with (0 0 2) preferred planes were obtained on silicon kept at 300 °C with 50 ml/min flow rate of diethylzinc without any post annealing. Reflection high energy electron diffraction pattern also showed the crystalline nature of these films. A textured surface with rms roughness ∼28 nm was observed by atomic force microscopy for the films deposited at 300 °C. A sharp peak at 380 nm in the PL spectra indicated the UV band-edge emission.     

Fabrication and ionic conductivity of amorphous Li–Al–Ti–P–O thin film

Li⁺ ion conducting Li–Al–Ti–P–O thin films were fabricated on ITO-glass substrates at various temperatures from 25 to 400 °C by RF magnetron sputtering method. When the substrate temperature is higher than 300 °C, severe destruction of ITO films were confirmed by XRD (X-ray diffraction) and the abrupt transformation of one semi-circle into two semi-circles on the impedance spectra. These as-deposited Li–Al–Ti–P–O solid state electrolyte thin films have an amorphous structure confirmed by XRD and a single semicircle on the impedance spectra. Good transmission higher than 80% in the visible light range of these electrolyte thin films can fulfill the demand of electro-chromic devices. Field emission scanning electron microscopy and atomic force microscopy showed the denser, smoother and more uniform film structure with the enhanced substrate temperature. Measurements of impedance spectra indicate that the gradual increased conductivity of these Li–Al–Ti–P–O thin films with the elevation of substrate temperature from room temperature to 300 °C is originated from the increase of the pre-exponential factor (σ₀). The largest Li-ion conductivity can come to 2.46 × 10^? 5 S cm^? 1. This inorganic solid lithium ion conductor film will have a potential application as an electrolyte layer in the field such as lithium batteries or all-solid-state EC devices.     

Fabrication and characterization of transparent conductive ZnO:Al thin films prepared by direct current magnetron sputtering with highly conductive ZnO(ZnAl2O4) ceramic target

Using a highly conductive ZnO(ZnAl₂O₄) ceramic target, c-axis-oriented transparent conductive ZnO:Al₂O₃ (ZAO) thin films were prepared on glass sheet substrates by direct current planar magnetron sputtering. The structural, electrical and optical properties of the films (deposited at different temperatures and annealed at 400°C in vacuum) were characterized with several techniques. The experimental results show that the electrical resistivity of films deposited at 320°C is 2.67×10⁻⁴ Ω cm and can be further reduced to as low as 1.5×10⁻⁴ Ω cm by annealing at 400°C for 2 h in a vacuum pressure of 10⁻⁵ Torr. ZAO thin films deposited at room temperature have flaky crystallites with an average grain size of ∼100 nm; however those deposited at 320°C have tetrahedron grains with an average grain size of ∼150 nm. By increasing the deposition temperature or the post-deposition vacuum annealing, the carrier concentration of ZAO thin films increases, and the absorption edge in the transmission spectra shifts toward the shorter wavelength side (blue shift).     

Properties of n-type hydrogenated nanocrystalline cubic silicon carbide films deposited by VHF-PECVD at a low substrate temperature

n-Type hydrogenated nanocrystalline cubic silicon carbide (nc-3C–SiC:H) films have been deposited by very high-frequency plasma-enhanced chemical vapor deposition at a low substrate temperature of about 360 °C to apply this material to the window layer of heterojunction crystalline silicon (HJ-c-Si) solar cells. We investigated the effect of in situ doping on deposition rate, crystalline volume fraction and dark conductivity to optimize properties of the material. We also fabricated HJ-c-Si solar cells with a n-type nc-3C–SiC:H window layer. The solar cells shows high internal quantum efficiency of 0.90 at a wavelength of 400 nm, indicating that n-type nc-3C–SiC:H deposited by VHF-PECVD is a promising candidate of the window layer of HJ-c-Si solar cells.     

High-quality AlN layers grown by hot-wall MOCVD at reduced temperatures

We report on a growth of AlN at reduced temperatures of 1100 °C and 1200 °C in a horizontal-tube hot-wall metalorganic chemical vapor deposition reactor configured for operation at temperatures of up to 1500–1600 °C and using a joint delivery of precursors. We present a simple route—as viewed in the context of the elaborate multilayer growth approaches with pulsed ammonia supply—for the AlN growth process on SiC substrates at the reduced temperature of 1200 °C. The established growth conditions in conjunction with the particular in-situ intervening SiC substrate treatment are considered pertinent to the accomplishment of crystalline, relatively thin, ～700 nm, single AlN layers of high-quality. The feedback is obtained from surface morphology, cathodoluminescence and secondary ion mass spectrometry characterization.     

Self-aggregated Si quantum dots in amorphous Si-rich SiC

Amorphous silicon quantum dots (Si-QDs) self-aggregated in silicon-rich silicon carbide are synthesized by growing with plasma-enhanced chemical vapor deposition on (100)-oriented Si substrate. Under the environment of Argon (Ar)-diluted Silane (SiH₄) and pure methane (CH₄), the substrate temperature and RF power are set as 350 °C and 120 W, respectively, to provide the Si-rich SiC with changing fluence ratio (R = [CH₄ ]/[SiH₄] + [CH₄]). By tuning the fluence ratio from 50% to 70%, the composition ratio x of Si-rich Si_1 ? xC_x film is varied from 0.27 to 0.34 as characterized by X-ray photoelectron spectroscopy (XPS), which reveals the component of Si_2p decreasing from 66.3 to 59.5%, and the component of C_1s increasing from 23.9% to 31% to confirm the formation of Si-rich SiC matrix. Annealing of the SiC sample from 650 °C to 1050 °C at 200 °C increment for 30 min induces the very tiny shift on the wavenumber of the crystalline Si (c-Si) related peak due to the precipitation of Si-QDs within the SiC matrix, and the Raman scattering spectra indicate a broadened Raman peak ranging from 410 to 520 cm^? 1 related to the amorphous Si accompanied with the significant enhancement for SiC bond related peak at 980 cm^? 1. From the high resolution transmission electron microscopy images, the critical temperature for Si-QD precipitation is found to be 850 °C. The self-assembly of the crystallized Si-QDs with the size of 3 ± 0.5 nm and the volume density of (3 ± 1) × 10¹⁸ (#/cm³) in Si-rich SiC film with R = 70% are observed after annealing at higher temperature.     

Structural,electrical and optical properties of in-situ phosphorous-doped Ge layers

We have studied the impact of temperature and pressure on the structural and electronic properties of Ge:P layers grown with GeH₄+PH₃ on thick Ge buffers, themselves on Si(0 0 1). The maximum phosphorous atomic concentration [P] exponentially decreased as the growth temperature increased, irrespective of pressure (20 Torr, 100 Torr or 250 Torr). The highest values were however achieved at 100 Torr (3.6×10²⁰ cm^?3 at 400 °C, 2.5×10¹⁹ cm^?3 at 600 °C and 10¹⁹ cm^?3 at 750 °C). P atomic depth profiles, “box-like” at 400 °C, became trapezoidal at 600 °C and 750 °C, most likely because of surface segregation. The increase at 100 Torr of [P] with the PH₃ mass-flow, almost linear at 400 °C, saturated quite rapidly at much lower values at 600 °C and 750 °C. Adding PH₃ had however almost no impact on the Ge growth rate (be it at 400 °C or 750 °C). A growth temperature of 400 °C yielded Ge:P layers tensily-strained on the Ge buffers underneath, with a very high concentration of substitutional P atoms (5.4×10²⁰ cm^?3). Such layers were however rough and of rather low crystalline quality in X-ray Diffraction. Ge:P layers grown at 600 °C and 750 °C had the same lattice parameter and smooth surface morphology as the Ge:B buffers underneath, most likely because of lower P atomic concentrations (2.5×10¹⁹ cm^?3 and 10¹⁹ cm^?3, respectively). Four point probe measurements showed that almost all P atoms were electrically active at 600 °C and 750 °C (1/4th at 400 °C). Finally, room temperature photoluminescence measurements confirmed that high temperature Ge:P layers were of high optical quality, with a direct bandgap peak either slightly less intense (750 °C) or more intense (600 °C) than similar thickness intrinsic Ge layers. In contrast, highly phosphorous-doped Ge layers grown at 400 °C were of poor optical quality, in line with structural and electrical results.     

Surface morphology of spin-coated As–S–Se chalcogenide thin films

Surface morphology and roughness of amorphous spin-coated As–S–Se chalcogenide thin films were determined using atomic force microscopy. Prepared films were coated from butylamine solutions with thicknesses d ∼ 100 nm and then annealed in a vacuum furnace at 45 °C and 90 °C for 1 h for their stabilization. The root mean square surface roughness analysis of surfaces of as-deposited spin-coated As–S–Se films indicated a very smooth film surface (with R_q values 0.42–0.45 ± 0.2 nm depending on composition). The nanoscale images of as-deposited films confirmed that surface of the films is created by domains with dimensions 20–40 nm, which corresponds to diameters of clusters found in solutions. The domain character of film surfaces gradually disappeared with increasing annealing temperature while the solvent was removed from the films. Middle-infrared transmission spectra recorded a decrease of intensities of vibration bands connected to N–H (at 3367 and 3292 cm⁻¹) and C–H (at 2965, 2935 and 2880 cm⁻¹) stretching vibrations. Temperature regions of solvent evaporation T = 60–90 °C and glass transformation temperatures T_g = 135–150 °C of spin-coated As–S–Se thin films were determined using a modulated differential scanning calorimetry.     

Growth and characterization of GaN and AlN films on (1 1 1) and (0 0 1) Si substrates

GaN and AlN films were grown on (1 1 1) and (0 0 1) Si substrates by separate admittances of trimethylgallium (or trimethylaluminum) and ammonia (NH₃) at 1000°C. A high temperature (HT) or low temperature (LT) grown AlN thin layer was employed as the buffer layer between HT GaN (or HT AlN) film and Si substrate. Experimental results show that HT AlN and HT GaN films grown on the HT AlN-coated Si substrates exhibit better crystalline quality than those deposited on the LT AlN-coated Si substrates. Transmission electron microscopy (TEM) of the HT GaN/HT AlN buffer layer/(1 1 1)Si samples shows a particular orientation relationship between the (0 0 0 1) planes of GaN film and the (1 1 1) planes of Si substrate. High quality HT GaN films were achieved on (1 1 1) Si substrates using a 200 Å thick HT AlN buffer layer. Room temperature photoluminescence spectra of the high quality HT GaN films show strong near band edge luminescence at 3.41 eV with an emission linewidth of ∼110 meV and weak yellow luminescence.     

Incipient amorphous-to-crystalline transition in HfO2 as a function of thickness scaling and anneal temperature

A series of 1.4, 1.8, and 4.0 nm thick HfO₂ films deposited on Si(1 0 0) substrates have been measured by extended X-ray absorption fine-structure prior to anneal processing, following a standard post deposition anneal of 700 °C for 60 s in NH₃ ambient, and following an additional rapid thermal anneal cycle of 1000 °C for 10 s in N₂ ambient. Analysis of the second coordination shell gives clear evidence of increased ordering with increasing film thickness at each temperature. Similarly, increased ordering with increasing anneal temperature is evident for each film thickness. Although X-ray diffraction and high resolution transmission electron microscopy indicated the 1.4 nm HfO₂ samples to be amorphous, EXAFS has distinguished nanocrystalline from amorphous states for these films.     

Correlation between the method of preparation and the properties of the sol–gel HfO2 thin films

This work describes the preparation of HfO₂ thin films by the sol–gel method, starting with different precursors such as hafnium ethoxide, hafnium 2,4-pentadionate and hafnium chloride. From the solution prepared as mentioned above, thin films on silicon wafer substrates have been realized by ‘dip-coating’ with a pulling out speed of 5 cm min^?1. The films densification was achieved by thermal treatment for 10 min at 100 °C and 30 min at 450 °C or 600 °C, with a heating rate of 1 °C min^?1. The structural and optical properties of the films are determined employing spectroellipsometric (SE) measurements in the visible range (0.4–0.7 μm), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The main objective of this paper was to establish a correlation between the method of preparation (precursor, annealing temperature) and the properties of the obtained films. The samples prepared from pentadionate and ethoxide precursors are homogenous and uniform in thickness. The samples prepared starting from chloride precursor are thicker and proved to be less uniform in thickness. Higher non-uniformity develops in multi-deposition films or in crystallized films. A nano-porosity is present in the quasi-amorphous films as well in the crystallized one. For the samples deposited on silicon wafer, the thermal treatment induced the formation of a SiO₂ layer at the coating–substrate interface.     

Crystallization of bismuth titanate and bismuth silicate grown as thin films by atomic layer deposition

Bismuth silicate and bismuth titanate thin films were deposited by atomic layer deposition (ALD). A novel approach with pulsing of two Bi-precursors was studied to control the Si/Bi atomic ratio in bismuth silicate thin films. The crystallization of compounds formed in the Bi₂O₃–SiO₂ and Bi₂O₃–TiO₂ systems was investigated. Control of the stoichiometry of Bi–Si–O thin films was studied when deposited on Si(1 0 0) and crystallization was studied for films on sapphire and MgO-, ZrO₂- and YSZ-buffered Si(1 0 0). The Bi–Ti–O thin films were deposited on Si(1 0 0) substrate. Both Bi–Si–O and Bi–Ti–O thin films were amorphous after deposition. Highly a-axis oriented Bi₂SiO₅ thin films were obtained when the Bi–Si–O thin films deposited on MgO-buffered Si(1 0 0) were annealed at 800 °C in nitrogen. The full-width half-maximum values for 200 peak were also studied. An excess of bismuth was found to improve the crystallization of Bi–Ti–O thin films and the best crystallinity was observed with Ti/Bi atomic ratio of 0.28 for films annealed at nitrogen at 1000 °C. Roughness of the thin films as well as the concentration depth distribution were also examined.     

Evaluation of structural and mechanical properties of aluminum oxide thin films deposited by a sol–gel process: Comparison of microwave to conventional anneal

Thin films of Al₂O₃ have been deposited on polished silica glass substrates at room temperature by sol–gel dip coating technique followed by two different exposure methods. One set was annealed at different temperatures ranging from 200 °C to 800 °C for 10 h and a second set was exposed to microwave (2.45 MHz) radiation at different powers for 10 min. The lower temperature and shorter time with microwave irradiation might be ascribed to the activating and facilitating effect of microwaves on solid phase diffusion. Unlike other preparation methods, microwave heating is generally quite faster, and energy efficient. X-ray diffraction (XRD) and scanning electron microscopy (SEM), energy dispersive X-ray analysis techniques have been employed to characterize structural, morphological and elemental compositions of the films. Adhesion strength failure measurements on films performed by scratch test in progressive loading sequence have shown critical loads up to 25 N (partial perforation) for both annealed films and films exposed to microwave irradiation. Nanohardness indentation tests of the films exposed (800 W) to microwave have shown hardness of 8.3 GPa with elastic modulus of 120 GPa compared to the conventional annealed film (800°) of 4.5 GPa with elastic modulus of 90 GPa.     

Characterization of pure ZnO thin films prepared by a direct photochemical method

In this paper, amorphous ZnO thin films were obtained by direct UV irradiation of β-diketonate Zn(II) precursor complexes spin-coated on Si(1 0 0) and fused silica substrates. ZnO films were characterized by means of XPS, X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). These analyses revealed that as-deposited films are amorphous and have a rougher surface than thermally treated films. Optical characterization of the films showed that these are highly transparent in the visible spectrum with an average transmittance of up to 95% over 400 nm, and an optical band-gap energy of 3.21 eV for an as-deposited film, and 3.27 eV for a film annealed at 800 °C. Low resistivity values were obtained for the ZnO films (1.0 × 10⁻² Ω cm) as determined by Van der Pauw four-point probe method.     

Structural study of undoped and (Mn, In)-doped SnO2 thin films grown by RF sputtering

Undoped and 5%(Mn, In)-doped SnO₂ thin films were deposited on Si(1 0 0) and Al₂O₃ (R-cut) by RF magnetron sputtering at different deposition power, sputtering gas mixture and substrate temperature. X-ray reflectivity was used to determine the films thickness (10–130 nm) and roughness (～1 nm). The combination of X-ray diffraction and Mössbauer techniques evidenced the presence of Sn⁴⁺ in an amorphous environment, for as-grown films obtained at low power and temperature, and the formation of crystalline SnO₂ for annealed films. As the deposition power, substrate temperature or O₂ proportion are increased, SnO₂ nanocrystals are formed. Epitaxial SnO₂ films are obtained on Al₂O₃ at 550 °C. The amorphous films are quite uniform but a more columnar growth is detected for increasing deposition power. No secondary phases or segregation of dopants were detected.