Preparation and Transparent Property of the n—ZnO／p—Diamond Heterostructure

Heterostructures of an n-type ZnO film/p-type diamond film on the {111} crystalline diamond substrate have been prepared for the first time.The electrodes of the n-and p-type semiconductors are experimentally verified to be ohmic.The diode shows a good rectification characteristic and the ratio of forward current to the reverse current exceeded 200 within the range of applied voltages of -2 to 2V.The turn-on voltage of the diode is 0.34V and the highest current is about 5.0mA as the forward voltage reaches 2V.Moreover,the diode is optically transparent in the region of 500-700nm wavelength.     

Effects of a carbon convection field on large diamond growth under high-pressure high-temperature conditions

Large diamond crystals were successfully synthesized by a FeNi-C system using the temperature gradient method under high-pressure high-temperature conditions. The assembly of the growth cell was improved and the growth process of diamond was investigated. Effects of the symmetry of the carbon convection field around the growing diamond crystal were investigated systematically by adjusting the position of the seed crystal in the melted catalyst/solvent. The results indicate that the morphologies and metal inclusion distributions of the synthetic diamond crystals vary obviously in both symmetric and non-symmetric carbon convection fields with temperature. Moreover, the finite element method was applied to analyze the carbon convection mode of the melted catalyst/solvent around the diamond crystal. This work is helpful for understanding the growth mechanism of diamond.     

Synthesis and characterization of p-type boron-doped IIb diamond large single crystals

High-quality p-type boron-doped IIb diamond large single crystals are successfully synthesized by the temperature gradient method in a china-type cubic anvil high-pressure apparatus at about 5.5 GPa and 1600 K.The morphologies and surface textures of the synthetic diamond crystals with different boron additive quantities are characterized by using an optical microscope and a scanning electron microscope respectively.The impurities of nitrogen and boron in diamonds are detected by micro Fourier transform infrared technique.The electrical properties including resistivities,Hall coefficients,Hall mobilities and carrier densities of the synthesized samples are measured by a four-point probe and the Hall effect method.The results show that large p-type boron-doped diamond single crystals with few nitrogen impurities have been synthesized.With the increase of quantity of additive boron,some high-index crystal faces such as {113} gradually disappear,and some stripes and triangle pits occur on the crystal surface.This work is helpful for the further research and application of boron-doped semiconductor diamond.     

Atomic—Scale Kinetic Monte Carlo Simulation of {100}—Oriented Diamond Film Growth in C—H and C—H—CI Systems by Chemical Vapour Deposition

We simulate the {100}-oriented diamond film growth of chemical vapour deposition (CVD) under different models in C-H and C-H-Cl systems in an atomic scale by using the revised kinetic Monte Carlo method.The simulation results show that:(1) the CVD diamond film growth in the C-H system is suitable for high substrate temperature,and the film surface roughness is very coarse;(2) the CVD diamond film can grow in the C-H-Cl system either at high temperature or at low temperature,and the film quality is outstanding;(3) atomic Cl takes an active role for the growth of diamond film,especially at low temperatures.The concentration of atomic Cl should be controlled in a proper range.     

GaInN light-emitting diodes with omni-directional reflector using nanoporous SnO_2 film

Enhancement of light extraction in a GaInN light-emitting diode （LED） employing an omni-directional reflector （ODR） consisting of GaN, SnO2 nanorod and an Ag layer was presented. The ODR comprises a transparent, quarterwave layer of SnO2 nanorod claded by silver and serves as an ohmic contact to p-type GaN. Transparent SnO2 sols were obtained by sol-gel method from SnCl2·2H2O, and SnO2 thin films were prepared by dip-coating technique. The average size of the spherical SnO2 particles obtained is 200 nm. The refractive index of the nanorod SnO2 film layer is 2.01. The GaInN LEDs with GaN/SnO2/Ag ODR show a lower forward voltage. This was attributed to the enhanced reflectivity of the ODR that employs the nanorod SnO2 film layer. Experimental results show that ODR-LEDs have lower optical losses and higher extraction efficiency as compared to conventional LEDs with Ni/Au contacts and conventional LEDs employing a distributed Bragg reflector （DBR）.     

Effect of Metallic Film in Diamond Growth from an Fe—Ni—C System at High Temperature and High Pressure

The metallic film surrounding a diamond single crystal,which plays an important role the diamond growth from and Fe-Ni-C system,has been successfully investigated by using transmission-electron microscopy(TEM),Raman layer(near diamond)of the film by TEM and Raman spectroscopy,but a parallel relationship exists between the(111) plane of γ-(Fe,Ni) and the (100) plane of (Fe2Ni)3C in this region.Compared with that of the film has an increase of 0.9V.According to the microstructures on the film obtained by the TEM.Raman spectra,and XPS,the catalytic mechanism of the film may be assumed as follows.In the surface layer of the film,iron and nickel atoms in the γ-(Fe,Ni) lattice can absorb carbon atoms in the (Fe,Ni)3C lattice and make them transform to an sp^3-like state.Then carbon atoms with the sp^3-like structure are separated from the (Fe,Ni)3C and stack on the growing diamond crystal.This study provides a direct evidence for the diamond growth from a metallic catlayst-graphite system under high temperature and high pressure.     

Electroluminescence and Photoluminescence from Scored Si—Rich SiO2 Film／p—Si Structure

Electroluminescence(EL)is observed from the Au/Si-rich SiO2 film/p-Si diodes,in which the Si-rich SiO2 films are scroed deliberately by a diamond tip.The EL intensity of the scroed diode annelaed at 800℃ is about 6 times of that of the unscored counterpart,The EL sectrum of the usscored diode could be decomposed into two Gaussian luminescence bands with peaks at about 1.83 and 2.23eV,while for the EL spectrum of the scored diode,an additional Gaussian band at about 3.0eV appears,and the 1.83-eV peak increases significantly in intensity,The photoluminescence(PL) spectrum of an unscored Si-rich SiO2 film has only one band peaking at about 1.48eV,whereas the Pl spectrum of the scored one has two bands at about 1.48 and 1.97eV.We consider that the high-density defect regions produced by the scoring provide new luminescence centres and become some types of nonradiative centres in the Si oxide layer,which thus result in changes of the EL and PL spectra.     

Structures and local ferroelectric polarization switching properties of orthorhombic YFeO_3 thin film prepared by a sol–gel method

Orthorhombic YFeO_3 thin film was prepared on La_(0.67)Sr_(0.33)MnO_3/LaAlO_3 substrate by a sol-gel spin-coating method. The structures of the YFeO_3/La_(0.67)Sr_(0.33)MnO_3/LaAlO_3(YFO/LSMO/LAO) sample were detected by x-ray diffraction pattern, Raman spectrometer, scanning electron microscopy, and atomic force microscope. The local ferroelectric polarization switching properties of the orthorhombic YFO film were confirmed by piezoresponse force microscopy(PFM) for the first time. The results show that the YFO film deposited on LSMO/LAO possesses orthorhombic structure,with ultra-fine crystal grains and flat surface. The leakage current of the YFO film is 8.39 × 10~(-4) A·cm~(-2) at 2 V,with its leakage mechanism found to be an ohmic behavior. PFM measurements indicate that the YFO film reveals weak ferroelectricity at room temperature and the local switching behavior of ferroelectric domains has been identified. By local poling experiment, polarization reversal in the orthorhombic YFO film at room temperature was further observed.     

Current transport in ZnO/Si heterostructure grown by laser molecular beam epitaxy

The n-ZnO/p-Si heterojunction was fabricated by depositing high quality single crystalline aluminium-doped n-type ZnO film on p-type Si using the laser molecular beam epitaxy technique. The heterojunction exhibited a good rectifying behavior. The electrical properties of the heterojunction were investigated by means of temperature dependence current density-voltage measurements. The mechanism of the current transport was proposed based on the band structure of the heterojunction. When the applied bias V is lower than 0.15 V, the current follows the Ohmic behavior. When 0.15V 0.6 V), the space charge limited effect becomes the main transport mechanism. The current-voltage characteristic under illumination was also investigated. The photovoltage and the short circuit current density of the heterojunction aproached 270 mV and 2.10 mA/cm 2 , respectively.     

FEM simulations and experimental studies of the temperature field in a large diamond crystal growth cell

We investigate the temperature field variation in the growth region of a diamond crystal in a sealed cell during the whole process of crystal growth by using the temperature gradient method (TGM) at high pressure and high temperature (HPHT). We employ both the finite element method (FEM) and in situ experiments. Simulation results show that the temperature in the center area of the growth cell continues to decrease during the process of large diamond crystal growth. These results are in good agreement with our experimental data, which demonstrates that the finite element model can successfully predict the temperature field variations in the growth cell. The FEM simulation will be useful to grow larger high-quality diamond crystal by using the TGM. Furthermore, this method will be helpful in designing better cells and improving the growth process of gem-quality diamond crystal.     

The influence of electronic transport across interface junction between Si substrate and the root of ZnO micro-prism on field emission performance

ZnO micro-prisms are prepared on the p-type and n-type Si substrates, separately. The $I$--$V$ curves analysed by AFM show that the interface junctions between the ZnO micro-prisms and the p-type substrate and between the ZnO micro-prisms and the n-type Si substrate exhibit p--n junction behaviour and ohmic contact behaviour, respectively. The formation of the p--n heterojunction and ohmic contact is ascribed to the intrinsic n-type conduction of ZnO material. Better field emission performance (lower onset voltage and larger emission current) is observed from an individual ZnO micro-prism grown on the n-type Si substrate. It is suggested that the n-Si/n-ZnO interfacial ohmic contact benefits the electron emission; while the p-Si/n-ZnO interface heterojunction deteriorates the electron emission.     

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba（N3）2

Additive Ba(N 3) 2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure (about 6.0 GPa) by employing the temperature gradient method.Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus.The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated.It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets.The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra.The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form,and the aggregated nitrogen concentration in diamond increases with temperature and duration.In addition,it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature.Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy.Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress,whereas diamond crystals heavily doped with the addition of Ba(N 3) 2 display the tensile stress.     

Probing thermal properties of vanadium dioxide thin films by time-domain thermoreflectance without metal film

Vanadium dioxide(VO_2) is a strongly correlated material, and it has become known due to its sharp metal–insulator transition(MIT) near room temperature. Understanding the thermal properties and their change across MIT of VO_2 thin film is important for the applications of this material in various devices. Here, the changes in thermal conductivity of epitaxial and polycrystalline VO_2 thin film across MIT are probed by the time-domain thermoreflectance(TDTR) method.The measurements are performed in a direct way devoid of deposition of any metal thermoreflectance layer on the VO_2 film to attenuate the impact from extra thermal interfaces. It is demonstrated that the method is feasible for the VO_2 films with thickness values larger than 100 nm and beyond the phase transition region. The observed reasonable thermal conductivity change rates across MIT of VO_2 thin films with different crystal qualities are found to be correlated with the electrical conductivity change rate, which is different from the reported behavior of single crystal VO_2 nanowires. The recovery of the relationship between thermal conductivity and electrical conductivity in VO_2 film may be attributed to the increasing elastic electron scattering weight, caused by the defects in the film. This work demonstrates the possibility and limitation of investigating the thermal properties of VO_2 thin films by the TDTR method without depositing any metal thermoreflectance layer.     

Synthesis of large diamond crystals containing high-nitrogen concentration at high pressure and high temperature using Ni-based solvent by temperature gradient method

This paper reprots that with Ni-based catalyst/solvent and with a dopant of NaN 3,large green single crystal diamonds with perfect shape are successfully synthesized by temperature gradient method under high pressure and high temperature in a China-type cubic anvil high-pressure apparatus (SPD-6×1200),and the highest nitrogen concentration reaches approximately 1214-1257 ppm calculated by infrared absorption spectra.The synthesis conditions are about 5.5 GPa and 1240-1300 C.The growth behaviour of diamond with high-nitrogen concentration is investigated in detail.The results show that,with increasing the content of NaN 3 added in synthesis system,the width of synthesis temperature region for growth high-quality diamonds becomes narrower,and the morphology of diamond crystal is changed from cube-octahedral to octahedral at same temperature and pressure,the crystal growth rate is slowed down,nevertheless,the nitrogen concentration doped in synthetic diamond increases.     

Electronic properties of hydrogen- and oxygen-terminateddiamond surfaces exposed to the air

The electronic properties of hydrogen- and oxygen-terminated diamond surfaces exposed to the air are investigated by scanning probe microscopy (SPM). The results indicate that for the hydrogen-terminated diamond surface a shallow acceptor above the valence-band-maximum (VBM) appears in the band gap. However, the oxygen-terminated diamond film exhibits a high resistivity with a wide band gap. Based on the density-functional-theory, the densities of states, corresponding to molecular adsorbate in hydrogenated and oxygenated diamond (100) surfaces, are studied. The results show that the shallow acceptor in the band gap for the hydrogen-terminated diamond film can be attributed to the interaction between the surface C--H bonding orbitals and the adsorbate molecules, while for the oxygen-terminated diamond film, the interaction between the surface C--O bonding orbitals and the adsorbate molecules can induce occupied states in the valence-band.     

Investigation of optical emission spectroscopy in diamond chemical vapor deposition by Monte Carlo simulation

The optical emission spectra(atomic hydrogen(H_α,H_β,H_γ),atomic carbon C(2p3s→2p~2:λ=165.7 nm)and radical CH(A~2Δ→X~2Π:λ=420-440 nm))in the gas phase process of the diamond film growth from a gas mixture of CH4 and H_2 by the technology of electron-assisted chemical vapor deposition (EACVD)have been investigated by using Monte Carlo simulation.The results show that the growth rate may be enhanced by the substrate bias due to the increase of atomic hydrogen concentration and the mean temperature of electrons.And a method of determining the mean temperature of electrons in the plasma in-situ is given.The strong dependence on substrate temperature of the quality of diamond film mainly attributes to the change of gas phase process near the substrate surface.     

Investigation of optical emission spectroscopy in diamond chemical vapor deposition by Monte Carlo simulation

The optical emission spectra(atomic hydrogen(Hα,Hβ,Hγ),atomic carbon C(2p3s→2p2:λ=165.7 nm) and radical CH(A2△→X2П:λ=420-440 nm))in the gas phase process of the diamond film growth from a gas mixture of CH4 and H2 by the technology of electron-assisted chemical vapor deposition (EACVD)have been investigated by using Monte Carlo simulation.The results show that the growth rate may be enhanced by the substrate bias due to the increase of atomic hydrogen concentration and the mean temperature of electrons.And a method of determining the mean temperature of electrons in the plasma in-situ iS given.The strong dependence on substrate temperature of the quality of diamond film mainly attributes to the change of gas phase process near the substrate surface.     

Pinhole defects in MPCVD diamond films

Diamond films were deposited in microwave plasma chemical vapor deposition (MPCVD) method on plain silicon substrates with (100) orientation. And the pinhole defects on them were investigated by optical microscopy and scanning electron microscopy (SEM). X-ray masks were fabricated with the films deposited by us. We found the pinhole defects in the film destroyed the gold absorber. The corrosion-resistance tests conducted in 30% KOH solution under 80℃showed that the diamond films with pinhole defects have lower corrosion-resistance. In addition, the possible mechanism of the formation of pinhole defects in diamond films was discussed. And we deduced that the defects on substrates, competitive growth of multi-phase in diamond films, lattice dislocation between substrates and diamond films could be associated with the defect formation.     

Influence of annealing treatment on as-grown Ib-type diamond crystal at a high temperature and high pressure

In this paper,we report on the influence of annealing treatment on as-grown Ib-type diamond crystal under high pressure and high temperature in a china-type cubic anvil high-pressure apparatus.Experiments are carried out at a pressure of 7.0 GPa and temperatures ranging from 1700 C to 1900 C for 1 h.Annealing treatment of the diamond crystal shows that the aggregation rate constant of nitrogen atoms in the as-grown Ib-type diamond crystal strongly depends on diamond morphology and annealing temperature.The aggregation rate constant of nitrogen remarkably increases with the increase of annealing temperature and its value in octahedral diamond is much higher than that in cubic diamond annealed at the same temperature.The colour of octahedral diamond crystal is obviously reduced from yellow to nearly colorless after annealing treatment for 1 h at 1900 C,which is induced by nitrogen aggregation in a diamond lattice.The extent of nitrogen aggregation in an annealed diamond could approach approximately 98% indicated from the infrared absorption spectra.The micro-Raman spectrum reveals that the annealing treatment can improve the crystalline quality of Ib-type diamond characterized by a half width at full maximum at first order Raman peak,and therefore the annealed diamond crystals exhibit nearly the same properties as the natural IaA-type diamond stones of high quality in the Raman measurements.     

Effect of FeS doping on large diamond synthesis in FeNi-C system

The large single-crystal diamond with FeS doping along the(111) face is synthesized from the FeNi–C system by the temperature gradient method(TGM) under high-pressure and high-temperature(HPHT). The effects of different FeS additive content on the shape, color, and quality of diamond are investigated. It is found that the(111) face of diamond is dominated and the(100) face of diamond disappears gradually with the increase of the FeS content. At the same time, the color of the diamond crystal changes from light yellow to gray-green and even gray-yellow. The stripes and pits corrosion on the diamond surface are observed to turn worse. The effects of FeS doping on the shape and surface morphology of diamond crystal are explained by the number of hang bonds in different surfaces of diamond. It can be shown from the test results of the Fourier transform infrared(FTIR) spectrum that there exists an S element in the obtained diamond. The N element content values in different additive amounts of diamond are calculated. The XPS spectrum results demonstrate that our obtained diamond contains S elements that exist in S–C and S–C–O forms in a diamond lattice. This work contributes to the further understanding and research of FeS-doped large single-crystal diamond characterization.