Characterization of single-crystal sapphire substrates by X-ray methods and atomic force microscopy

The possibility of characterizing a number of practically important parameters of sapphire substrates by X-ray methods is substantiated. These parameters include wafer bending, traces of an incompletely removed damaged layer that formed as a result of mechanical treatment (scratches and marks), surface roughness, damaged layer thickness, and the specific features of the substrate real structure. The features of the real structure of single-crystal sapphire substrates were investigated by nondestructive methods of double-crystal X-ray diffraction and plane-wave X-ray topography. The surface relief of the substrates was investigated by atomic force microscopy and X-ray scattering. The use of supplementing analytical methods yields the most complete information about the structural inhomogeneities and state of crystal surface, which is extremely important for optimizing the technology of substrate preparation for epitaxy.     

Epitaxial growth of ferroelectric PLZT [(Pb,La)(Zr,Ti)O3] thin films

Thin films of PLZT were epitaxially grown at around 700°C on sapphire and SrTiO₃ substrates: (111) PLZT  (0001) sapphire and (100) PLZT  (100) SrTiO₃. PLZT films on semiconductor substrates were also grown at around 620°C. The crystal quality of these PLZT films was investigated by X-ray diffraction, reflection electron diffraction, scanning electron microscopy (SEM), and Auger electron spectroscopy (AES). The epitaxy of PLZT films grown on different single crystal substrates is discussed. The refractive index of the film on the sapphire substrate was determined as 2.49₇ by an optical waveguide technique.     

In situ study of the growth and degradation processes in tetragonal lysozyme crystals on a silicon substrate by high-resolution X-ray diffractometry

The results of an in situ study of the growth of tetragonal lysozyme crystals by high-resolution X-ray diffractometry are considered. The crystals are grown by the sitting-drop method on crystalline silicon substrates of different types: both on smooth substrates and substrates with artificial surface-relief structures using graphoepitaxy. The crystals are grown in a special hermetically closed crystallization cell, which enables one to obtain images with an optical microscope and perform in situ X-ray diffraction studies in the course of crystal growth. Measurements for lysozyme crystals were carried out in different stages of the crystallization process, including crystal nucleation and growth, developed crystals, the degradation of the crystal structure, and complete destruction.     

Sapphire shaped crystals for waveguiding,sensing and exposure applications

Second half of the XX century was marked by a rapid development of sapphire shaped crystal growth technologies, driven by the demands for fast, low-cost, and technologically reliable methods of producing sapphire crystals of complex shape. Numerous techniques of shaped crystal growth from a melt have been proposed relying on the Stepanov concept of crystal shaping. In this review, we briefly describe the development of growth techniques, with a strong emphasize on those that yield sapphire crystals featuring high volumetric and surface quality. A favorable combination of physical properties of sapphire (superior hardness and tensile strength, impressive thermal conductivity and chemical inertness, high melting point and thermal shock resistance, transparency to electromagnetic waves in a wide spectral range) with advantages of shaped crystal growth techniques (primarily, an ability to produce sapphire crystals with a complex geometry of cross-section, along with high volumetric and surface quality) allows fabricating various instruments for waveguiding, sensing, and exposure technologies. We discuss recent developments of high-tech instruments, which are based on sapphire shaped crystals and vigorously employed in biomedical and material sciences, optics and photonics, nuclear physics and plasma sciences.     

表面处理对蓝宝石衬底的影响

蓝宝石衬底是目前最为普遍的一种衬底材料,是生长GaN、ZnO材料最常用的衬底.本文用光学显微镜、原子力显微镜(AFM)和高分辨X射线双晶洐射对蓝宝石衬底进行了分析测试,系统研究了经过机械抛光、化学机械抛光、化学腐蚀等表面处理对蓝宝石衬底表面性能的影响.结果表明经过化学机械抛光随后再经腐蚀后的蓝宝石衬底的表面性能最好.     

Modeling habit forms of sapphire crystals using the principles of periodic-bond-chain method

The potential of the periodic-bond-chain method for calculating the sequence of manifestation of faces of corundum single crystals is considered. The leading role of the faces of the pinacoid, high rhombohedron, and hexagonal prism is demonstrated. The calculation results are compared with the experimental data on faceting the lateral surface of cylindrical sapphire single crystals grown by the Stepanov method and with the faceting data for crystals grown by the flux method and natural crystals.

     

The influence of thermal screens on the temperature distribution,thermal stress,and defect structure during growth of shaped sapphire crystals

The ways in which a block structure is formed in shaped sapphire single crystals grown from melt by the Stepanov method are considered. The measured temperature distributions and results of a mathematical modeling of the heat exchange in the growth zones, as well as the calculated thermoelastic fields and measured residual stresses, are reported. The possibility of effectively controlling the thermal fields and growth of block-free crystals by choosing optimal screening is shown for single crystals in the form of tubes and basal-plane-faceted ribbons.     

Deposition of bulk GaN from solution in gallium under high N2 pressure on silicon carbide and sapphire substrates

Results of high-pressure directional growth of GaN on foreign substrates: SiC, sapphire and GaN/sapphire MOCVD templates are presented. The role of nitrogen pressure and supersaturation in the growth process is discussed. The conditions for stable growth of the nitride are determined. The results of the crystallization process are compared with those obtained for directional growth on pressure grown GaN crystals.     

Application of the periodic bond chain method for calculating sapphire crystallographic forms

The application of the periodic bond chain method for calculating the sequence of the development of corundum single crystal faces is considered. The key role of the faces of pinacoid, high rhombohedron, and hexagonal prisms is demonstrated. The calculated data are compared with the experimental results on faceting of the lateral surface of cylindrical sapphire single crystals grown by the Stepanov technique and with the faceting data on flux-grown and natural crystals.     

Structural contribution to the roughness of supersmooth crystal surface

Technological advances in processing crystals (Si, sapphire α-Al₂O₃, SiC, GaN, LiNbO₃, SrTiO₃, etc.) of substrate materials and X-ray optics elements make it possible to obtain supersmooth surfaces with a periodicity characteristic of the crystal structure. These periodic structures are formed by atomically smooth terraces and steps of nano- and subnanometer sizes, respectively. A model surface with such nanostructures is proposed, and the relations between its roughness parameters and the height of atomic steps are determined. The roughness parameters calculated from these relations almost coincide with the experimental atomic force microscopy (AFM) data obtained from 1 × 1 and 10 × 10 μm areas on the surface of sapphire plates with steps. The minimum roughness parameters for vicinal crystal surfaces, which are due to the structural contribution, are calculated based on the approach proposed. A comparative analysis of the relief and roughness parameters of sapphire plate surfaces with different degrees of polishing is performed. A size effect is established: the relief height distribution changes from stochastic to regular with a decrease in the surface roughness.     

Homoepitaxial growth and electrical characterization of GaN-based Schottky and light-emitting diodes

Homoepitaxial growth of GaN epilayers on free-standing hydride vapor phase epitaxy (HVPE) GaN substrates offered a better control over surface morphology, defect density, and doping concentration compared to conventional heteroepitaxial growth. The FWHM of the (0 0 0 2) X-ray diffraction (XRD) rocking curve from homoepitaxial GaN was measured to be as low as 79 arcsec, much smaller than 230 arcsec for GaN grown on sapphire. Schottky diodes grown on GaN substrates exhibited sharper breakdown characteristics and much lower reverse leakage than diodes on sapphire. However, the homoepitaxial devices had poor scalability due to the presence of yield-killing defects originating from the substrate surface. Vertical InGaN/GaN light-emitting diodes (LEDs) on GaN substrates showed reduced series resistance and reverse leakage compared to lateral LEDs on sapphire. Wafer mapping demonstrated that the distribution of leaky homoepitaxial devices correlated well with that of macroscopic defects in the GaN substrates.     

Multilayer X-ray mirrors for the (4.4–5)-nm carbon-window spectral region

Cr/C-based multilayer X-ray mirrors intended for the reflection of X-ray radiation in the “carbon-window” spectral region (λ = 4.4–5 nm) are fabricated and studied. The structures are formed by magnetron sputtering at different deposition parameters. Under normal incidence, record reflection coefficients up to 15% are reached. The structural parameters of the mirrors are investigated by reflectometry at wavelengths of 0.154 and 4.47 nm.     

Suppression of phase separation in InGaN layers grown on lattice-matched ZnO substrates

Sapphire and SiC are typical substrates used for GaN growth. However, they are non-native substrates and result in highly defective materials. The use of ZnO substrates can result in perfect lattice-matched conditions for 22% indium InGaN layers, which have been found to suppress phase separation compared to the same growths on sapphire. InGaN layers were grown on standard (0 0 0 2) GaN template/sapphire and (0 0 0 1) ZnO substrates by metalorganic chemical vapor deposition. These two substrates exhibited two distinct states of strain relaxation, which have direct effects on phase separation. InGaN with 32% indium exhibited phase separation when grown on sapphire. Sapphire samples were compared with corresponding growths on ZnO, which showed no evidence of phase separation with indium content as high as 43%. Additional studies in Si-doping of InGaN films also strongly induced phase separation in the films on sapphire compared with those on ZnO. High-resolution transmission electron microscopy results showed perfectly matched crystals at the GaN buffer/ZnO interface. This implied that InGaN with high indium content may stay completely strained on a thin GaN buffer. This method of lattice matching InGaN on ZnO offers a new approach to grow efficient emitters.     

Study of GaN and InGaN films grown by metalorganic chemical vapour deposition

In this paper GaN and InGaN films are examined, which are grown on basal plane (0001) sapphire substrates. Growth is performed in a novel type of vertical rotating disk reactor. The effects of several growth parameters on the film quality are discussed. The GaN and InGaN layers were evaluated by surface morphology studies, DC X-ray diffraction, electrical and optical characterisation.     

Specific features of the formation of terrace-step nanostructures on the (0001) surface of sapphire crystals

The terrace-step structures on atomically smooth vicinal surfaces of sapphire crystals subjected to thermal annealing after mechanical and chemical treatments have been investigated by atomic-force microscopy. The influence of the vicinal angles and conditions of thermal treatment (including annealings in air and vacuum) of sapphire plates on the metric parameters of terrace-step structures has been analyzed. It is shown that steps with a height from monoatomic (0.22 nm) to 3 nm or more can be formed on the sapphire surface by changing the vicinal angle and thermal-treatment conditions. The results are interpreted in terms of the minimum surface energy and surface diffusion processes.     

Rhombohedral epitaxy of cubic SiGe on trigonal c-plane sapphire

Highly [1 1 1]-oriented rhombohedral hetero-structure epitaxy of cubic SiGe semiconductor on trigonal c-plane sapphire was achieved and characterized with two new advanced X-ray diffraction methods to control the formation of primary-twin crystals. The formation of twin crystals on (1 1 1) plane was controlled with growth parameters such that the volume percentage of primary-twin crystal was reduced from 40% to 0.3% compared to the majority single crystal. The control of stacking faults can yield single-crystalline semiconductors without defects or improved thermoelectric materials with twinned crystals for phonon scattering while maintaining electrical integrity. In this study, about 94% of all epitaxial layers were fabricated in a single-crystalline phase. We propose the temperature-dependent alignment model of energetically favored majority single-crystalline SiGe layer on c-plane sapphire. This study shows that nearly single-crystalline cubic semiconductors can be grown in the [1 1 1] orientation on the basal (0 0 0 1) planes of selected trigonal crystal substrates.     

Growth, dielectric, ferroelectric and optical properties of Ca0.28Ba0.72Nb2O6 single crystals

Calcium barium niobate Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystals were grown by the Czochralski method. The effective segregation coefficients of Ca, Ba, Na elements in CBN-28 crystal growth were measured, and the rocking curve from 0 0 2 reflection of CBN-28 wafer was also measured by the high-resolution X-ray diffractometer D5005, and the full-width at half-maximum value was measured to be 70.6″. The measured dependence of dielectric constants on temperature showed the Curie temperature of the CBN-28 crystals is between 246.8 and 260 °C. Typical polarization–electric field (P–E) hysteresis loops were measured at room temperature. Ferroelectric 180° domains were observed by scanning electron microscopy (SEM) on the etched (0 0 1) surface of the CBN-28 crystals. The transmittance of [0 0 1]-oriented CBN-28 crystals was measured and the result shows that optical properties of CBN-28 crystal are almost the same as those of SBN for wavelengths between 2500 and 7500 nm.     

多片导模法蓝宝石晶体的缺陷研究

使用导模法(EFG)生长了多片a面蓝宝石晶体。显微拉曼光谱结合电感耦合等离子体发射光谱(ICP-AES)测试得出晶体的气泡中可能存在含S化合物。晶体表面明显的生长条纹主要与温度、生长速度的波动以及模具的加工精度有关。化学腐蚀分析表明晶体位错密度在4.2×10⁴ cm^-2,未存在小角度晶界缺陷,双晶摇摆曲线半峰宽(FWHM)为70.63″。由于采用石墨保温材料,晶体中存在F心与F⁺色心。晶体在400~3 000 nm波段透过率高于80%,空气中退火后可减弱色心吸收。本文研究结果可为蓝宝石晶体缺陷形成理论研究提供参考,也可为导模法蓝宝石工业生产技术改进提供借鉴。     

Metalorganic vapor phase epitaxy and characterizations of nearly-lattice-matched AlInN alloys on GaN/sapphire templates and free-standing GaN substrates

The epitaxy optimization studies of high-quality n-type AlInN alloys with different indium contents grown on two types of substrates by metalorganic vapor phase epitaxy (MOVPE) were carried out. The effect of growth pressure and V/III molar ratio on growth rate, indium content, and surface morphology of these MOVPE-grown AlInN thin films were examined. The surface morphologies of the samples were characterized by scanning electron microscopy and atomic force microscopy. By varying the growth temperatures from 860 °C to 750 °C, the indium contents in AlInN alloys were increased from 0.37% up to 21.4% as determined by X-ray diffraction (XRD) measurements. The optimization studies on the growth conditions for achieving nearly-lattice-matched AlInN on GaN templates residing on sapphire and free-standing GaN substrates were performed, and the results were analyzed in a comparative way. Several applications of AlInN alloy for thermoelectric and light-emitting diodes are also discussed.     

Manifestation of the Sapphire Crystal Structure in the Surface Nanopattern and Its Application in the Nitride Film Growth

The “quenching” technique was used to investigate the initial stage of the formation of a terracestep nanostructure on the R-cut surface of sapphire crystal upon high-temperature annealing in air. The morphological features of the formation of A- and R-sapphire planes are experimentally shown in dependence on the misorientation direction and qualitatively interpreted with allowance for the surface energy density for the main sapphire faces. The possibilities of forming AlN layers on the R-sapphire surface with a terrace-step nanostructure under thermochemical effect and high-temperature substrate annealing in a mixture of nitrogen and reducing gases are considered.