Correlation between interfacial structure and c-axis-orientation of LiNbO3 films grown on Si and SiO2 by electron cyclotron resonance plasma sputtering

Thin films of crystalline lithium niobate (LN) grown on Si(1 0 0) and SiO₂ substrates by electron cyclotron resonance plasma sputtering exhibit distinct interfacial structures that strongly affect the orientation of respective films. Growth at 460–600 °C on the Si(1 0 0) surface produced columnar domains of LiNbO₃ with well-oriented c-axes, i.e., normal to the surface. When the SiO₂ substrate was similarly exposed to plasma at temperatures above 500 °C, however, increased diffusion of Li and Nb atoms into the SiO₂ film was seen and this led to an LN–SiO₂ alloy interface in which crystal-axis orientations were randomized. This problem was solved by solid-phase crystallization of the deposited film of amorphous LN; the degree of c-axis orientation was then immune to the choice of substrate material.     

Segregation of Ga during growth of Si single crystal

Segregation phenomenon of Ga in Czochralski (CZ)–Si crystal growth has been investigated. The effective segregation coefficient, k_eff, of Ga was obtained for different growth rates by assuming the simple relationship between the concentration of Ga in Si crystal and the bulk Ga concentration in melt. Applying BPS theory to effective segregation coefficients which is valid for the melt-solidified fraction up to 0.38, an equilibrium segregation coefficient of Ga was obtained, k₀=0.0079.     

Structure and thermal stability of MOCVD ZrO2 films on Si (1 0 0)

The structure and thermal stability of ZrO₂ films grown on Si (1 0 0) substrates by metalorganic chemical vapor deposition have been studied by high-resolution transmission electron microscopy, selected area electron diffraction and X-ray energy dispersive spectroscopy. As-deposited films consist of tetragonal ZrO₂ nanocrystallites and an amorphous Zr silicate interfacial layer. After annealing at 850°C, some monoclinic phase is formed, and the grain size is increased. Annealing a 6 nm thick film at 850°C in O₂ revealed that the growth of the interfacial layer is at the expense of the ZrO₂ layer. In a 3.0 nm thick Zr silicate interfacial layer, there is a 0.9 nm Zr-free SiO₂ region right above the Si substrate. These observations suggest that oxygen reacted with the Si substrate to grow SiO₂, and SiO₂ reacted with ZrO₂ to form a Zr silicate interfacial layer during the deposition and annealing. Oxygen diffusion through the tetragonal ZrO₂ phase was found to be relatively easier than through the monoclinic phase.     

Cracking assisted nucleation in chemical vapor deposition of silicon nanoparticles on silicon dioxide

Deposition of sub-monolayer silicon on SiO₂/Si(1 0 0) greatly facilitates nucleation in subsequent thermal chemical vapor deposition (CVD) of silicon nanoparticles. Sub-monolayer seeding is accomplished using silicon atoms generated via disilane decomposition over a hot tungsten filament. The hot-wire process is nonselective towards deposition on silicon and SiO₂, is insensitive to surface temperature below 825 K, and gives controlled coverages well below 1 ML. Thermal CVD of nanoparticles at 1×10⁻⁴ Torr disilane and temperatures ranging from 825 to 925 K was studied over SiO₂/Si(1 0 0) surfaces that had been subjected to predeposition of Si or were bare. Seeding of the SiO₂ surface with as little as 0.01 ML is shown to double the nanoparticle density at 825 K, and densities are increased twenty fold at 875 K after seeding the surface with 30% of a monolayer.     

Crystallization behavior and hydrophilic performances of V2O5–TiO2 films prepared by sol–gel dip-coating

Homogeneous and transparent V₂O₅–TiO₂ composite nanometer thin films were prepared on glass substrates by sol–gel processing and dip-coating technique. The films as well as the dried powder of bulk gel were characterized by different techniques like X-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM), atomic force microscope (AFM) and thermogravimetry–differential thermal analysis (TG–DTA). The hydrophilicity of the films was determined by measuring the water contact angles on the films. The results showed that the dopant of V₂O₅ on TiO₂ thin films could produce a visible-light response to the films, and the introduction of V₂O₅ could suppress the structural phase transition and crystal growth of TiO₂ crystal. Finally, the relationship between crystalline size and hydrophilicity under sunlight was investigated in this article.     

Influence of oxygen, hydrogen, helium, argon and vacuum on the surface behavior of molten InSb, other semiconductors, and metals on silica

Sessile drop experiments were performed on molten indium antimonide on clean quartz (fused silica) surfaces. A cell was constructed through which argon, helium, oxygen, hydrogen or a mixture of these was flowed at 600 °C. Some of the InSb was doped with 0.1% Ga. The surface tension σ of oxide-free molten InSb was smaller in Ar than in He, may have increased with increasing O₂ in the gas, and was not influenced by Ga or H₂. The contact angle θ on silica was higher in the presence of Ar, was lowered by O₂, and was not influenced by H₂ or Ga. The work of adhesion W and the surface energy σ_sv of the silica were higher in He than in Ar. The surface remained free of solid oxide only in flowing gas containing 0.8 ppm O₂. This behavior is attributed to reaction of O₂ at the surface of the melt to form In₂O gas. When solid oxide formed on Ga-doped material, it was strongly enriched in Ga, with the Ga/In ratio increasing with the concentration of O₂ in the gas.

Examination of published sessile-drop results for liquid metals and semiconductors on silica revealed that W and σ_sv were highest for reactive melts, in which SiO₂ dissolves. For non-reactive melts, W and σ_sv were lower and θ higher in a gas than in a vacuum, regardless of whether the experiments had been carried out in sealed ampoules, a flowing gas, or dynamic vacuum. The implication is that the surface of silica was different in a vacuum than in a gas at 1 bar.     

Growth and properties of (Pb0.90La0.10)TiO3 thick films prepared by RF magnetron sputtering with a PbO buffer layer

The (Pb_0.90La_0.10)TiO₃ [PLT] thick films (3.0 μm) with a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering method. The PLT thick films comprise five periodicities, the layer thicknesses of (Pb_0.90La_0.10)TiO₃ and PbO in one periodicity are fixed. The PbO buffer layer improves the phase purity and electrical properties of the PLT thick films. The microstructure and electrical properties of the PLT thick films with a PbO buffer layer were studied. The PLT thick films with a PbO buffer layer possess good electrical properties with the remnant polarization (P_r=2.40 μC cm⁻²), coercive field (E_c=18.2 kV cm⁻¹), dielectric constant (ε_r=139) and dielectric loss (tan δ=0.0206) at 1 kHz, and pyroelectric coefficient (9.20×10⁻⁹ C cm⁻² K⁻¹). The result shows the PLT thick film with a PbO buffer layer is a good candidate for pyroelectric detector.     

Ga segregation during Czochralski-Si crystal growth with Ge codoping

The segregation of Ga during the growth of Czochralski-Si crystals with Ge codoping was investigated. The effective segregation coefficient of Ga in Ga/Ge-codoped Si crystal growth was nearly constant over a wide Ge concentration range, even at high Ge concentrations of about 10²¹ cm⁻³. In contrast, the effective segregation coefficient increased at high B concentrations in Ga/B-codoped CZ-Si crystal growth. The segregation behavior of Ga in Ga/Ge- and Ga/B-codoped CZ-Si crystal growth was theoretically compared. The difference in the segregation coefficients of Ga as a function of the codoped impurity (Ge or B) between the two Si crystals was attributed to a difference in the excess enthalpy due to impurity incorporation into the Si crystal between Ga–Ge pairs and Ga–B pairs     

基于抛光基材的热蒸镀铜箔生长高平整单层石墨烯薄膜

在石墨烯的化学气相沉积工艺中,铜箔是决定石墨烯薄膜质量的重要因素。传统铜箔由于制备工艺的限制,存在大量的缺陷,导致石墨烯薄膜的成核密度较高。本工作选用抛光铝板、抛光不锈钢板、微晶玻璃和SiO₂/Si作为基材,用热蒸镀法制备了不同粗糙度的铜箔,并详细讨论了以该系列铜箔生长高平整度石墨烯薄膜的条件及铜箔对石墨烯薄膜品质的影响。实验结果表明,铜箔以(111)取向为主,与基材分离后,表面具有纳米级平整度。在生长石墨烯后,从SiO₂/Si剥离的铜箔成核密度是4种基材中最小的。同时,从SiO₂/Si剥离的铜箔晶体结构变化最不明显,具有良好的结晶性,表面几乎不存在铜晶界缺陷。当压强为3 000 Pa,氢气和甲烷流速分别为300 mL/min和0.5 mL/min时,可以获得约1 mm横向尺寸的石墨烯单晶晶畴。     

TOPCon太阳电池发射极Al2O3/SiNx与SiO2/Al2O3/SiNx叠层膜钝化性能的比较

本文对TOPCon电池发射结的叠层钝化膜进行了研究,对比了3种不同叠层钝化膜(SiO₂/SiN_x、Al₂O₃(1.5 nm)/SiN_x、SiO₂/Al₂O₃(1.5 nm)/SiN_x)的钝化性能。结果表明:Al₂O₃(1.5 nm)/SiN_x的钝化性能优于SiO₂/SiN_x,SiO₂/Al₂O₃(1.5 nm)/SiN_x的钝化水平最佳,隐开路电压均值可达到705 mV。基于Al₂O₃/SiN_x叠层膜研究了Al₂O₃厚度(1.5 nm、3 nm和5 nm)对钝化性能和电池转换效率的影响。当Al₂O₃厚度由1.5 nm增加到3 nm时,钝化性能得到明显提升,隐开路电压均值提高了20 mV,达到707 mV,对应电池的光电转换效率升高了0.23个百分点,与SiO₂/Al₂O₃(1.5 nm)/SiN_x叠层膜电池的转换效率持平。然而,当Al₂O₃厚度继续增加至5 nm时,隐开路电压均值保持不变。因此可以使用Al₂O₃(3 nm)/SiN_x叠层膜代替SiO₂/Al₂O₃(1.5 nm)/SiN_x叠层膜,不仅简化了电池的工艺步骤,而且降低了生产成本。     

Correlations between photoluminescence and Hall mobility in GaN/sapphire grown by metalorganic chemical vapor deposition

We have investigated photoluminescence (PL) and electron Hall mobility for unintentionally doped GaN epitaxial layers grown by low-pressure metalorganic chemical vapor deposition on c-plane Al₂O₃ substrates. Four GaN films having identical dislocation density but remarkably different electron Hall mobility were exploited. At low temperature (12 K), a PL line associated with a bound exciton was observed and strong correlations were found between the Hall mobility and the PL intensity of the exciton transition. That is, relative PL intensity of the bound exciton to a donor-bound exciton monotonously increased with decreasing the electron mobility of the GaN films. This correlation was interpreted in terms of electrical compensation. Efforts to find the chemical origin of the PL line led to the conclusion that the BE line originated neither from threading dislocations nor from extrinsic point defects. Intrinsic acceptors such as Ga vacancy and GaN anti-site were suspected as plausible origin.     

Agglomeration control during the selective epitaxial growth of Si raised sources and drains on ultra-thin silicon-on-insulator substrates

We have studied the impact of several Si selective epitaxial growth (SEG) process on the agglomeration of ultra-thin, patterned silicon-on-insulator (SOI) layers. Through a careful analysis of the effects of the in situ H₂ bake temperature (that followed an ex situ “HF-last” wet cleaning) and of the silicon growth temperature on the SOI film quality, we have been able to develop a low-temperature SEG process that allows the growth of Si on patterned SOI layers as thin as 3.4 nm without any agglomeration or Si moat recess at the Si window/shallow trench isolation edges. This process consists of an in situ H₂ bake at 650 °C for 2 min, followed by a ramping-up of the temperature to 750 °C, then some SEG of Si at 750 °C using a chlorinated chemistry (i.e. SiH₂Cl₂+HCl).     

Hexagonal AlN films grown on nominal and off-axis Si(0 0 1) substrates

Nucleation and growth of wurtzite AlN layers on nominal and off-axis Si(0 0 1) substrates by plasma-assisted molecular beam epitaxy is reported. The nucleation and the growth dynamics have been studied in situ by reflection high-energy electron diffraction. For the films grown on the nominal Si(0 0 1) surface, cross-sectional transmission electron microscopy and X-ray diffraction investigations revealed a two-domain film structure (AlN¹ and AlN²) with an epitaxial orientation relationship of [0 0 0 1]_AlN || [0 0 1]_Si and AlN¹ || AlN² || [1 1 0]_Si. The epitaxial growth of single crystalline wurtzite AlN thin films has been achieved on off-axis Si(0 0 1) substrates with an epitaxial orientation relationship of [0 0 0 1]_AlN parallel to the surface normal and 0 1 1 0_AlN || [1 1 0]_Si.     

Solvothermal growth of ZnO

The growth of ZnO single crystals and crystalline films by solvothermal techniques is reviewed. Largest ZnO crystals of 3 inch in diameter are grown by a high-pressure medium-temperature hydrothermal process employing alkaline-metal mineralizer for solubility enhancement. Structural, thermal, optical and electrical properties, impurities and annealing effects as well as machining are discussed. Poly- and single-crystalline ZnO films are fabricated from aqueous and non-aqueous solutions on a variety of substrates like glass, (100) silicon, -Al₂O₃, Mg₂AlO₄, ScAlMgO₄, ZnO and even some plastics at temperatures as low as 50 °C and ambient air conditions. Film thickness from a few nanometers up to some tens of micrometers is achieved. Lateral epitaxial overgrowth of thick ZnO films on Mg₂AlO₄ from aqueous solution at 90 °C was recently developed. The best crystallinity with a full-width half-maximum from the (0002) reflection of 26 arcsec has been obtained by liquid phase epitaxy employing alkaline-metal chlorides as solvent. Doping behavior (Cu, Ga, In, Ge) and the formation of solid solutions with MgO and CdO are reported. Photoluminescence and radioluminescence are discussed.     

Study of group-III binary and ternary nitrides using X-ray absorption fine structure measurements

It is demonstrated that the NEXAFS spectra are a “fingerprint” of the symmetry and the composition of the binary nitrides GaN, AlN and InN, as well as of their ternary alloys In_0.16Ga_0.84N and Al_yGa_1−yN. From the angular dependence of the N-K-edge NEXAFS spectra, the hexagonal symmetry of the under study compounds is deduced and the (p_x, p_y) or p_z character of the final state is identified. The energy position of the absorption edge (E_abs) of the binary compounds GaN, AlN and InN is found to red-shift linearly with the atomic number of the cation. The E_abs of the Al_yGa_1−yN alloys takes values in between those corresponding to the parent compounds AlN and GaN. Contrary to that, the E_abs of In_0.16Ga_0.84N is red-shifted relative to that of GaN and InN, probably due to ordering and/or phase separation phenomena. The EXAFS analysis results reveal that the first nearest-neighbour shell around the N atom, which consists of Ga atoms, is distorted in both GaN and Al_xGa_1−xN for x<0.5.     

Effects of SiO2 overlayer at initial growth stage of epitaxial Y2O3 film growth

We investigated the dependence of the Y₂O₃ film growth on Si surface at initial growth stage. The reflection high-energy electron diffraction, X-ray scattering, and atomic force microscopy showed that the film crystallinity and morphology strongly depended on whether Si surface contained O or not. In particular, the films grown on oxidized surfaces revealed significant improvement in crystallinity and surface smoothness. A well-ordered atomic structure of Y₂O₃ film was formed on 1.5 nm thick SiO₂ layer with the surface and interfacial roughness markedly enhanced, compared with the film grown on the clean Si surfaces. The epitaxial film on the oxidized Si surface exhibited extremely small mosaic structures at interface, while the film on the clean Si surface displayed an island-like growth with large mosaic structures. The nucleation sites for Y₂O₃ were provided by the reaction between SiO₂ and Y at the initial growth stage. The SiO₂ layer known to hinder crystal growth is found to enhance the nucleation of Y₂O₃, and provides a stable buffer layer against the silicide formation. Thus, the formation of the initial SiO₂ layer is the key to the high-quality epitaxial growth of Y₂O₃ on Si.     

Surface and interfacial structure of epitaxial SrTiO3 thin films on (0 0 1) Si grown by molecular beam epitaxy

Effects of relaxation of interfacial misfit strain and non-stoichiometry on surface morphology and surface and interfacial structures of epitaxial SrTiO₃ (STO) thin films on (0 0 1) Si during initial growth by molecular beam epitaxy (MBE) were investigated. In situ reflection high-energy electron diffraction (RHEED) in combination with X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectrometry (XPS) and transmission electron microscopy (TEM) techniques were employed. Relaxation of the interfacial misfit strain between STO and Si as measured by in situ RHEED indicates initial growth is not pseudomorphic, and the interfacial misfit strain is relaxed during and immediately after the first monolayer (ML) deposition. The interfacial strain up to 15 ML results from thermal mismatch strain rather than lattice mismatch strain. Stoichiometry of STO affects not only surface morphology but interfacial structure. We have identified a nanoscale Sr₄Ti₃O₁₀ second phase at the STO/Si interface in a Sr-rich film.     

Microstructure and ferroelectric properties of BaTiO3 films on LaNiO3 buffer layers by rf sputtering

We have fabricated LaNiO₃ and BaTiO₃ films using the rf sputtering method. The LaNiO₃ were deposited on Si substrates, demonstrating a (1 0 0) highly oriented structure and nanocrystalline characteristic with a grain size of 30 nm. The BaTiO₃ thin films were deposited on the LaNiO₃ buffer layers, and have exhibited a (1 0 0) texture with a thickness of 400 nm. A smooth interface is obtained between the LaNiO₃ bottom electrode and the BaTiO₃ film from cross-section observations by scanning electron microscopy. The bi-layer films show a dense and column microstructure with a grain size of 60 nm. Ferroelectric characterizations have been obtained for the BaTiO₃ films. The remnant polarization and coercive field are 2.1 μC/cm² and 45 kV/cm, respectively. The leak current measurements have shown a good insulating property.     

An EXAFS study of the local structure of Ce---Si---O amorphous thin films

An EXAFS study has been made on the structure of three composition ranges of Ce---Si---O amorphous thin films prepared by RF sputtering. The measurements, carried out on the K edge of silicon and the L₃ edge of cerium, reveal that in the stoichiometric oxygen films of the general formula (Ce, Si) O₂, both cerium and silicon are four-coordinated by oxygen regardless of the O : Si ratio. In the oxygen-deficient films cerium remains four-coordinated by oxygen, but, around silicon, the oxygen atoms are progressively replaced by silicon as the oxygen content of the films is reduced. In silicon-rich films which are very deficient in oxygen, the oxygen atoms prefer to ramain coordinated with cerium, rather than silicon.

A definite decrease in the Si---O distance with increase in Si---O coordination has been found. The effect is attributed to an increase in the charge of silicon with oxygen coordination, and supports a randomly bonded model for the structure.

The total oxygen coordination, derived from a consideration of bond conservation, indicates that the film structures are probably SiO₂-type continuous random networks.     

CrO2 (1 0 0) and TiO2 (1 0 0) film heteroepitaxy on a BaF2 (1 1 1)/Si (1 0 0) substrate

Multi-domained heteroepitaxial rutile-phase TiO₂ (1 0 0)-oriented films were grown on Si (1 0 0) substrates by using a 30-nm-thick BaF₂ (1 1 1) buffer layer at the TiO₂–Si interface. The 50 nm TiO₂ films were grown by electron cyclotron resonance oxygen plasma-assisted electron beam evaporation of a titanium source, and the growth temperature was varied from 300 to 600 °C. At an optimal temperature of 500 °C, X-ray diffraction measurements show that rutile phase TiO₂ films are produced. Pole figure analysis indicates that the TiO₂ layer follows the symmetry of the BaF₂ surface mesh, and consists of six (1 0 0)-oriented domains separated by 30° in-plane rotations about the TiO₂ [1 0 0] axis. The in-plane alignment between the TiO₂ and BaF₂ films is oriented as [0 0 1] TiO₂ || BaF₂ or [0 0 1] TiO₂ || BaF₂ . Rocking curve and STM analyses suggest that the TiO₂ films are more finely grained than the BaF₂ film. STM imaging also reveals that the TiO₂ surface has morphological features consistent with the BaF₂ surface mesh symmetry. One of the optimally grown TiO₂ (1 0 0) films was used to template a CrO₂ (1 0 0) film which was grown via chemical vapor deposition. Point contact Andreev reflection measurements indicate that the CrO₂ film was approximately 70% spin polarized.