Differences between chloro‐carbon and hydro‐carbon precursors in low‐temperature epitaxial growth of 4H‐SiC

The advantages of using the chlorinated carbon precursor chloromethane instead of the hydrocarbon precursor propane in low‐temperature (1300 °C) epitaxial growth of 4H‐SiC were investigated. Chloromethane was found to provide a much wider process window for variation of the C/Si ratio between the lower boundary corresponding to the formation of condensed silicon face and the upper boundary corresponding to polytype inclusions and polycrystalline degradation, which is critical for achieving high growth rates without epilayer quality degradation. Use of a high Cl/Si ratio provided by HCl addition in the propane‐based epitaxial growth did not eliminate the critical differences between chloro‐carbon and hydro‐carbon precursors. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Very high crystalline quality of thick 4H‐SiC epilayers grown from methyltrichlorosilane (MTS)

200 µm thick 4H‐SiC epilayers have been grown by chloride‐based chemical‐vapor deposition using methyltrichlorosilane (MTS) as single precursor. The very high crystalline quality of the grown epilayer is demonstrated by high resolution X‐Ray Diffraction rocking curve with a full‐width‐half‐maximum value of only 9 arcsec. The high quality of the epilayer is further shown by low temperature photoluminescence showing strong free exciton and nitrogen bound exciton lines. The very high crystalline quality achieved for the thick epilayer grown in just two hours at 1600 °C suggests that MTS is a suitable precursor molecule for SiC bulk growth. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Use of chlorinated carbon and silicon precursors for epitaxial growth of 4H‐SiC at very high growth rates

A possibility to apply the advantages of chlorinated carbon precursors, which had been previously used in low‐temperature epitaxial growth of 4H‐SiC, to achieve very high growth rates at higher growth temperatures was investigated. Silicon tetrachloride was used as the silicon precursor to suppress gas‐phase homogeneous nucleation. The temperature increase from 1300 °C (which is the temperature of the previously reported low‐temperature halo‐carbon epitaxial growth) to 1600 °C enabled an increase of the precursor flow rates and consequently of the growth rate from 5 to more than 100 μm/h without morphology degradation. High quality of the epilayers was confirmed by low‐temperature photoluminescence spectroscopy and time‐resolved luminescence. No evidences of homogeneous nucleation were detected, however, liquid Si droplet formation on the epilayer surface seems to remain a bottleneck at very high growth rate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spray pyrolysis deposition of ZnO thin films on FTO coated substrates from zinc acetate and zinc chloride precursor solution at different growth temperatures

ZnO thin films were fabricated using zinc chloride and zinc acetate precursors by the spray pyrolysis technique on FTO coated glass substrates. The ZnO films were grown in different deposition temperature ranges varying from 400 to 550 °C. Influences of substrate temperature and zinc precursors on crystal structure, morphology and optical property of the ZnO thin films were investigated. XRD patterns of the films deposited using chloride precursor indicate that (1 0 1) is dominant at low temperatures, while those deposited using acetate precursor show that (1 0 1) is dominant at high temperatures. SEM images show that deposition temperature and type of precursor have a strong effect on the surface morphology. Optical measurements show that ZnO films are obviously influenced by the substrate temperatures and different types of precursor solutions. It is observed that as temperature increases, transmittance decreases for ZnO films obtained using zinc chloride precursor, but the optical transmittance of ZnO films obtained using zinc acetate precursor increases as temperature increases.     

Molecular-mediated crystal growth of PbTiO3 nanostructure on silicon substrate

A simple approach based on an organically modified sol-gel process has been developed to fabricate PbTiO₃ (PT) nanocrystals on Si (1 0 0) substrate, where the amorphous powder modified by acetylacetone (acac) was used as precursor. After dropping the amorphous powder precursor prepared by freeze-drying process, PT nanocrystals on Si (1 0 0) substrate were obtained after heat treatment at 720 °C for 30 min in air. PT nanocrystals have been detected by XRD to be tetragonal perovskite structure. With the increase of acac/Pb molar ratio, the relative (1 0 0)/(0 0 1) diffraction peak intensity gradually increases, which probably suggested an oriented growth of PT nanocrystal along [1 0 0] on Si (1 0 0) substrates. In addition, Atomic force microscopy (AFM) results indicated that the height and the average lateral size of PT nanocrystal increased and then decreased as the acac/Pb molar ratio increased. Piezoelectric force microscopy (PFM) results demonstrated that all the samples show obvious piezoelectric activity. These results implied that the acetylacetone molecular mediated the growth of PT nanocrystals on Si (1 0 0) substrates possibly by the acac/Pb molar ratio. This simple method has been suggested to be attractive for tailoring an oriented growth of the nanostructures of perovskite oxide systems on Si substrates.     

Selective MOCVD of titanium oxide and zirconium oxide thin films using single molecular precursors on Si(1 0 0) substrates

Titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films have been deposited on modified Si(1 0 0) substrates selectively by metal-organic chemical vapor deposition (MOCVD) method using new single molecular precursor of [M(OⁱPr)₂(tbaoac)₂] (M=Ti, Zr; tbaoac=tertiarybutyl-acetoacetate). For changing the characteristic of the Si(1 0 0) surface, micro-contact printing (μCP) method was adapted to make self-assembled monolayers (SAMs) using an octadecyltrichlorosilane (OTS) organic molecule which has -CH₃ terminal group. The single molecular precursors were prepared using metal (Ti, Zr) isopropoxide and tert-butylacetoacetate (tbaoacH) by modifying standard synthetic procedures. Selective depositions of TiO₂ and ZrO₂ were achieved in a home-built horizontal MOCVD reactor in the temperature range of 300-500 °C and deposition pressure of 1×10⁻³-3×10⁻² Torr. N₂ gas (5 sccm) was used as a carrier gas during film depositions. TiO₂ and ZrO₂ thin films were able to deposit on the hydrophilic area selectively. The difference in surface characteristics (hydrophobic/hydrophilic) between the OTS SAMs area and the SiO₂ or Si-OH layer on the Si(1 0 0) substrate led to the site-selectivity of oxide thin film growth.     

Photoelectron spectroscopic investigation of transformation of trifluoroacetate precursors into superconducting YBa2Cu3O7−δ films

X-ray photoelectron spectroscopy (XPS) has been used to investigate the evolution of surface chemistry of YBa₂Cu₃O_7−δ (Y123) films prepared by the metalorganic deposition (MOD) process using trifluoroacetate (TFA) precursors. Detailed XPS core-level spectra obtained from the samples quenched from various points during the calcining and firing stages have been reported for the first time and are used to identify surface species. The XPS data show evidence of formation of intermediate phases such as Y-O-F, BaF₂, and CuO during the calcining process, which are the decomposition products of yttrium, barium, and copper trifluoroacetates, respectively. The TFA precursors are completely decomposed at the end of calcination. The change of binding energies for Y 3d_5/2, Ba 3d_5/2, and O 1s during the firing process indicates that Y123 starts to form at 800 °C after 0.5 h firing. Based on the experimental results, an alternative mechanism of the chemical evolution from precursor to final film in the TFA-MOD process is proposed.     

Silicon carbonitride by remote microwave plasma CVD from organosilicon precursor: Growth mechanism and structure of resulting Si:C:N films

The remote microwave hydrogen plasma chemical vapor deposition (RP-CVD) from bis(dimethylamino)methylsilane precursor was used for the synthesis of silicon carbonitride (Si:C:N) films. The effect of thermal activation on the RP-CVD process was examined by determining the mass- and the thickness-based film growth rate and film growth yield, at different substrate temperature (T_S). It was found that the mechanism of the process depends on T_S and for low substrate temperature regime, 30 °C ≤ T_S ≤ 100 °C, RP-CVD is limited by desorption of film-forming precursors, whereas for high substrate temperature regime, 100 °C < T_S ≤ 400 °C, RP-CVD is a non-thermally activated and mass-transport limited process. The Si:C:N films were characterized by X-ray photoelectron and Fourier transform infrared spectroscopies, as well as by atomic force microscopy. The increase of T_S enhances crosslinking in the film via the formation of nitridic Si-N and carbidic Si-C bonds. On the basis of the structural data a hypothetical crsosslinking reactions contributing to silicon carbonitride network formation have been proposed.     

Critical diameters and temperature domains for MBE growth of III–V nanowires on lattice mismatched substrates

We report on the growth properties of InAs, InP and GaAs nanowires (NWs) on different lattice mismatched substrates, in particular, on Si(111), during Au‐assisted molecular beam epitaxy (MBE). We show that the critical diameter for the epitaxial growth of dislocation‐free III–V NWs decreases as the lattice mismatch increases and equals 24 nm for InAs NWs on Si(111), 39 nm for InP NWs on Si(111), 44 nm for InAs NWs on GaAs(111)B, and 110 nm for GaAs NWs on Si(111). When the diameters exceed these critical values, the NWs are dislocated or do not grow at all. The corresponding temperature domains for NW growth extend from 320 °C to 340 °C for InAs NWs on Si(111), 330 °C to 360 °C for InP NWs on Si(111), 370 °C to 420 °C for InAs NWs on GaAs(111)B and 380 °C to 540 °C for GaAs NWs on Si(111). Experimental values for critical diameters are compared to the previous findings and are discussed within the frame of a theoretical model. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optimising uniformity of InAs/(InGaAs)/GaAs quantum dots grown by metal organic vapor phase epitaxy

A route towards optimisation of uniformity and density of InAs/(InGaAs)/GaAs quantum dots grown by metal organic vapor phase epitaxy (MOVPE) through successive variations of the growth parameters is reported. It is demonstrated that a key parameter in obtaining a high density of quantum dots is the V/III ratio, a fact which was shown to be valid when either AsH₃ (arsine) or tertiary-butyl-arsine (TBA) were used as group V precursors. Once the optimum V/III ratio was found, the size distribution was further improved by adjusting the nominal thickness of deposited InAs material, resulting in an optimum thickness of 1.8 monolayers of InAs in our case. The number of coalesced dots was minimised by adjusting the growth interruption time to approximately 30 s. Further, the uniformity was improved by increasing the growth temperature from 485 °C to 520 °C. By combining these optimised parameters, i.e. a growth temperature of 520 °C, 1.8 monolayers InAs thickness, 30 s growth stop time and TBA as group V precursor, a full-width-half-maximum (FWHM) of the low temperature luminescence band of 40 meV was achieved, indicating a narrow dot size distribution.     

Growth parameters and shape specific synthesis of silicon nanowires by the VLS method

In this paper the effect of varying temperature, pressure and chemical precursors on the vapour–liquid–solid (VLS) growth of silicon nanowires (Si NWs) have been investigated. Some aspects of nucleation and growth mechanisms are discussed. Control on Si NW morphology by varying the choice of gaseous precursor (silane or dichlorosilane) at elevated temperatures is reported.     

Low-macroscopic field emission from silicon-incorporated diamond-like carbon film synthesized by dc PECVD

Silicon-incorporated diamond-like carbon (Si-DLC) films were deposited via dc plasma-enhanced chemical vapor deposition (PECVD), on glass and alumina substrates at a substrate temperature 300 °C. The precursor gas used was acetylene and for Si incorporation, tetraethyl orthosilicate dissolved in methanol was used. Si atomic percentage in the films was varied from 0% to 19.3% as measured from energy-dispersive X-ray analysis (EDX). The binding energies of C 1s, Si 2s and Si 2p were determined from X-ray photoelectron spectroscopic studies. We have observed low-macroscopic field electron emission from Si-DLC thin films deposited on glass substrates. The emission properties have been studied for a fixed anode-sample separation of 80 μm for different Si atomic percentages in the films. The turn-on field was also found to vary from 16.19 to 3.61 V/μm for a fixed anode-sample separation of 80 μm with a variation of silicon atomic percentage in the films 0% to 19.3%. The turn-on field and approximate work function are calculated and we have tried to explain the emission mechanism there from. It was found that the turn-on field and effective emission barrier were reduced by Si incorporation than undoped DLC.     

TEM studies on the formation of nano crystallites of Si by metal induced crystallization

In the present investigations, we have grown the nano-crystallites of Si by metal induced crystallization process. Layers of two different metals (Al and Au) were deposited on either side of Si using thermal evaporation technique to study metal induced crystallization. Annealing of such samples was carried out in the hot stage of TEM. We have found that the crystallization of amorphous silicon starts at 150 °C through the formation of metal silicides. Formation of metal silicides was observed through selected area diffraction. Nearly complete formation of nano crystallites of Si throughout the sample was observed at 200 °C. High-resolution TEM studies confirm the formation of nano-crystallites of Si all along the film.     

TiO2 chemical vapor deposition on Si(111) in ultrahigh vacuum: Transition from interfacial phase to crystalline phase in the reaction limited regime

The interaction between the metal organic precursor molecule titanium(IV) isopropoxide (TTIP) and three different surfaces has been studied: Si(111)-(7 × 7), SiO_x/Si(111) and TiO₂. These surfaces represent the different surface compositions encountered during TTIP mediated TiO₂ chemical vapor deposition on Si(111). The surface chemistry of the titanium(IV) isopropoxide precursor and the film growth have been explored by core level photoelectron spectroscopy and x-ray absorption spectroscopy using synchrotron radiation. The resulting film morphology has been imaged with scanning tunneling microscopy. The growth rate depends on both surface temperature and surface composition. The behavior can be rationalized in terms of the surface stability of isopropoxy and isopropyl groups, confirming that growth at 573 K is a reaction limited process.     

Microstructures and electrical properties of La0.8Sr0.2MnO3 films synthesized by sol-gel method

La_0.8Sr_0.2MnO₃ (LSMO) thin films were fabricated on alumina substrates by an improved sol-gel dip-coating process. It was found that multiple dip-coating process could not be performed until the pre-firing temperature reached 600 °C. Different amounts of LSMO powders were added to precursor solution with an aim to avoid cracks in LSMO thin films during calcining caused by the shrinkage mismatch between the film and the substrate. The structure and surface morphology of the films prepared from precursors with and without LSMO powders were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that the addition of 56.4 wt.% LSMO powders into the sol-gel precursor solution significantly modified the microstructure of films. A single LSMO perovskite phase was obtained on alumina substrate after calcining at 800 °C for 4 h by the improved sol-gel method. The sheet resistance of the films prepared with different processing parameters was measured by four-point dc method. Results indicated that the sheet resistance of films decreased with increasing the number of coating applications and the amount of LSMO powders.     

Real-time study of phase transformations in Cu-In chalcogenide thin films using in situ Raman spectroscopy and XRD

The growth of polycrystalline CuInSe₂ and CuInS₂ thin films from metallic precursor layers is investigated using two complementary in situ methods which give bulk sensitive (XRD) and surface sensitive (Raman) information. From the time evolution of the XRD and Raman peak intensities the phase transformation sequences and the reaction kinetics can be derived. In both cases the chalcogenization of the Cu-In precursors proceeds at the top surface. Thus, the process is at least limited by cation diffusion through the metallic precursor. However, the growth kinetics of CuInSe₂ and CuInS₂ films differ. While the CuInSe₂ growth is limited by the reaction of binary phases, CuInS₂ growth is controlled by fast diffusion which is solely restricted to the period of raising temperature during the process.     

Influence of precursor feeding rate on vapor–liquid–solid nanowire growth

The yield of Ge nanowires (NWs) synthesized using the vapor–liquid–solid (VLS) method was discovered to be highly sensitive to the rate of precursor feeding. When other parameters were fixed, fast filling of precursors yielded nearly 100% Ge NWs with regard to the growth seeds. By contrast, slow feeding produced nearly no or very low yield of Ge NWs. The dramatic difference was attributed to a layer of Ge coating on the surface of growth seeds. The coating formed at relatively low precursor pressures as a result of the imbalance in the VLS process. The results shed new light on the VLS mechanism in general. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

UHV-MOCVD growth of TiO2 on SiOx/Si(1 1 1): Interfacial properties reflected in the Si 2p photoemission spectra

Metal–organic chemical vapour deposition growth of titanium oxide on moderately pre-oxidised Si(1 1 1) using the titanium(IV) isopropoxide precursor has been studied for two different growth modes, reaction-limited growth at 300 °C and flux-limited growth at 500 °C. The interfacial properties have been characterized by monitoring synchrotron radiation excited Si 2p photoemission spectra. The cross-linking from oxidised Si to bulk Si after TTIP exposure has been found to be very similar to that of SiO_x/Si(1 1 1). However, the results show that the additional oxidation of Si most probably causes a corrugation of the SiO_x/Si interface. Those conclusions are valid for both growth modes. A model is introduced in which the amorphous interface region is described as (TiO₂)_x(SiO₂)_y where x and y changes linearly and continuously over the interface. The model quantifies how (TiO₂)_x(SiO₂)_y mixing changes the relative intensities of the signals from silicon oxide and silicon. The method can be generalised and used for the analyses of other metal-oxides on silicon.     

Deposition and growth kinetics studies of thin zirconium dioxide films by UVILS-CVD

We report the deposition of thin zirconium dioxide films on Si(1 0 0) by a technique of ultraviolet-assisted injection liquid source chemical vapor deposition (UVILS-CVD) by using ultraviolet with 222 nm radiation. The alkoxide zirconium(IV) tert-butoxide (Zr[OC(CH₃)₃]₄) was used as precursor while nitrous oxide was driven into the reaction chamber as an oxidizing agent. The ZrO₂ films were deposited under various conditions and characterized by ellipsometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and scanning electron microscopy. The growth rate decreased with the increasing of substrate temperatures from 200 to 400 °C. Deposition rate of 20 nm/min was observed at a substrate temperature of 350 °C. There was a liner relation between the thicknesses of the films and deposition times. As a result the thicknesses can be accurately controlled by changing the number of drops of precursor introduced by the injection liquid source. The growth rate increased with the increasing concentrations of the precursor, nevertheless the trend stopped when the concentration exceeded 8.5%. The growth kinetics were also studied and the results were fit to a three-step kinetic model involving a photo chemical reaction, a reversible precursor absorption process and a following irreversible deposition reaction.     

Surfactant effect of Sb on the growth of MnSi1.7 layers on Si(0 0 1)

Deposition of one monolayer of Sb prior to the deposition of Mn at 600 °C is observed to increase the MnSi_1.7 island density by about two orders of magnitude as well as to change the crystalline orientation of the silicide grains. The preferential epitaxial orientation of MnSi_1.7 grains grown by this process is determined to be MnSi_1.7(1 0 0)[0 1 0]||Si(0 0 1)[1 0 0]. This growth procedure results in the silicide growth into the Si matrix. For comparison, the same deposition process carried out without Sb leads to silicide formation on top of the substrate surface. The observed morphological changes of the MnSi_1.7 layers can be explained by a reduced surface diffusion of the Mn atoms on Si(0 0 1) in presence of the Sb monolayer. Additionally, lateral Si diffusion is considered to be nearly suppressed, which is responsible for the observed silicide growth into the substrate.