Wide bandgap II–VI compounds grown by MOMBE

Recent developments of MOMBE for wide bandgap II–VI compounds are reviewed by considering both film properties and a novel growth technique such as atomic layer epitaxy (ALE). MOMBE using dimethylzinc and hydrogen has enabled growth of p-type ZnSe doped with nitrogen by using ammonia as a dopant source. Ideal ALE was obtained for ZnSe by using various gas source conditions. Furthermore, applications of MOMBE of II–VI compounds to the growth of strained layer superlattices are also reviewed.     

Charge transfer in CdTe at 200 and 300 K

Using a perfect single crystal sample of CdTe grown using PVT method, the electronic charge transfer in the II–VI compound semiconductor CdTe at 200 and 300 K has been evaluated using two different approaches: (1) by solving a quadratic equation involving the observed structure factors of h+k+l=4n+2 type reflections; and (2) by a graphical approach in which the observed and calculated atomic form factors are extrapolated to sinθ/λ=0, to determine the transferred charge. Precise X-ray structure factors collected using MoK radiation have been used for the analysis. The results obtained are reasonable and clearly indicate the ionicity by which charge is transferred from Cd to Te in CdTe.     

Growth of highly doped p-type ZnTe layers on GaAs using a nitrogen DC plasma cell

In this paper we report about the use of a DC plasma cell for nitrogen doping of ZnTe layers grown on GaAs substrates by molecular beam epitaxy (MBE). The samples, characterized by high resolution X-ray diffraction, photoluminescence and Hall measurements, show good crystalline quality and carrier concentrations as high as 1×10²⁰ cm^-3 with mobilities up to 30 cm²/V·s at room temperature. To our knowledge, this is the highest hole doping level reported so far in the literature for any wide-gap II–VI compound. The achieved hole concentration is one order of magnitude larger than values reported using an RF plasma source.     

The characterization of semiconductor layer and interface quality with special reference to raman spectroscopy

This article gives a survey over the application of Raman spectroscopy (inelastic light scattering) for the characterization of semiconductor heterostructures, considering the quality of epitaxial layers and their interfaces. Theoretical considerations of Raman scattering are briefly reviewed. Experimental results are presented for various systems of III–V and II–VI compounds. Aspects of interest are crystalline quality, strain, composition of mixed compounds, chemical reactions at interfaces, doping efficiency and implications of interface quality for electronic properties.     

MOVPE of II–VI materials

The development of II–VI MOVPE is reviewed, contrasting the narrow bandgap materials with the wide bandgap. Common issues are the need to grow the layers at lower temperatures than their III–V cousins in order to avoid point defects. This means that II–VI MOVPE occurs in a surface kinetic regime for precursor decomposition and has stimulated a lot of research on alternative precursors. The narrow bandgap II–VI growers have settled on dimethyl cadmium (DMCd) combined with diisopropyl telluride (DIPTe) and a liquid Hg source but wide bandgap growers are split between pyrolytic and photo-assisted growth. Recent progress in p-type doping has enabled the demonstration of some new devices, including two colour infrared detectors and the first MOVPE grown green emitting laser structure. The common theme appears to be hydrogen passivation of the Group V dopant and some novel precursor solutions to this problem are discussed.     

The electrical, optical and crystalline properties of GaAs: C grown by GSMBE using TMG and AsH3 for application to HBTs

We report the results of a comprehensive study on the electrical, optical and crystalline properties of heavily carbon doped p-type (100) GaAs epilayers (p = 6.3 × 10¹⁸−1.3 × 10²⁰ cm^-3; THICKNESS = 250−420 nm) grown by gas source molecular beam epitaxy using trimethylgallium and arsine. X-ray analysis showed epilayer lattice contraction with a mismatch of δa/a = -1.8 × 10^-3 at p = 1.3 × 10²⁰ cm^-3. Room temperature photoluminescence peak energy shifted from 1.40 eV (p = 6.3 × 10¹⁸ cm^-3) to 1.37 eV (p = 1.3 × 10²⁰ cm^-3). Stokes Raman spectra showed two modes assigned as the unscreened LO phonon (292 cm^-1) and the low frequency branch of the coupled hole-plasmon-LO-phonon (266 cm^-1). Conservation of Raman scattering rules under all incident light configurations showed that the (100) GaAs:C epilayers were of high crystalline quality without the presence of faceting or other such crystalline defects. Annealing at 900°C for between 30 s to 45 min, resulted in a significant reduction in the hole concentration, lattice contraction and photoluminescence intensity for all epilayers. The implications of these results for the development of GaAs/AlGaAs HBTs are discussed.     

High-resolution XRD study of stress-modulated YBCO films with various thicknesses

High-quality epitaxial YBa₂Cu₃O_7−δ (YBCO) superconducting films with thicknesses between 0.2 and 2 μm were fabricated on (0 0 l) LaAlO₃ with direct-current sputtering method. The influence of film thickness on the structure and texture was investigated by X-ray diffraction conventional θ–2θ scan and high-resolution reciprocal space mapping (HR-RSM). The films grew with strictly c-axis epitaxial, and no a-axis-oriented growth was observed up to a thickness of 2 μm. Lattice parameters of the YBCO films with different thicknesses were extracted from symmetry and asymmetry HR-RSMs. The X-ray lattice parameter method was used to determine the residual stress in YBCO films by measuring the a-, b-, c-axis strains, respectively. The results showed that YBCO films within thinner than 1 μm were under compressive stress, which was relieved increasing of film thickness. However, beyond 1 μm in thickness, YBCO films exhibited a tensile stress. Based on the experimental analysis, the variety of residual stresses in the films is mainly attributed to oxygen vacancies with thickness of YBCO film increasing.     

Metalorganic chemical vapor epitaxy and doping of ZnMgSSe heterostructures for blue emitting devices

Blue-green semiconductor laser diodes operating at room temperature are still the domain of wide bandgap II–VI compound semiconductors. CW operation at room temperature and hours of lifetime were reported. However, the conductivity control, defect generation and the ohmic contacts still need improvement. Therefore we focused our work on the MOVPE growth and the optimization of ZnMgSSe/ZnSSe/ZnSe heterostructures as well as on nitrogen doping of ZnSe. To verify the layer quality characterization was carried out by X-ray diffraction, electron probe microanalysis, electrical measurements and photoluminescence. ZnMgSSe/ZnSSe/ZnSe and ZnSSe/ZnSe quantum wells and superlattices were grown to investigate structural as well as interface properties. Electron beam and optical pumping was used to clarify the laser mechanism and to clarify the suitability of a MOVPE process to grow laser quality material. The electrical compensation of ZnSe doped with nitrogen is still controversially discussed whereas high n-type doping with chlorine was reproducible achieved. ZnSe: N doped at different growth conditions (II/VI ratio, growth temperature, nitrogen supply) using N₂ excited in a plasma source or by the use of nitrogen containing precursors was investigated to study the compensation mechanisms.     

A SAXS study of V2O5·nH2O sols and gels

Small-angle X-ray scattering (SAXS) measurements on V₂O₅·nH₂O sols and gels, prepared by dissolving V₂O₅ glass into water at room temperature, show that there are V₂O₅ polymeric fibers entangled like random coils in the sol of n 5000, while the deviation from the random coil behavior occurs in the dilute sol of n 6000.

A Bragg peak appears at the scattering vector h 0.02 Å⁻¹ to be superimposed on an asymptotic h⁻²-course in the SAXS curve of the concentrated sol of n 680. This means that the spatial correlation between V₂O₅ polymeric fibers takes place even in the fluid state.

V₂O₅·nH₂O sols completely lose fluidity at n 250 to transfer to the gel state, where V₂O₅ polymeric fibers begin to pile up in the parallel with a substrate surface. Such a layer structure is preserved up to the gel of n 4. However, V₂O₅ polymeric fibers are randomly oriented within each layer.     

高温扩散工艺制备带隙可调的β-(AlxGa1-x)2O3薄膜

β-(Al_xGa_1-x)₂O₃因其优异的抗击穿及带隙可调节性在现代功率器件及深紫外光电探测等领域展现出巨大的应用前景,然而传统直接生长工艺的复杂性和难度限制了其进一步的发展。因此,本文采用较为简单的高温扩散工艺在c面蓝宝石衬底上成功制备了β-(Al_xGa_1-x)₂O₃纳米薄膜。利用X射线衍射、原子力显微镜、扫描电子显微镜和紫外-可见分光光度计对其进行了表征。由于高温下蓝宝石衬底中的Al原子向Ga₂O₃层扩散,β-Ga₂O₃薄膜将转变为Al、Ga原子比例不同的β-(Al_xGa_1-x)₂O₃薄膜。实验结果显示：当退火温度从1 010℃增加到1 250℃时,薄膜中Al的平均含量从0.033增加到0.371;当退火温度从950℃增加到1 250℃时...     

化学计量比对镓酸镁尖晶石陶瓷微波介电性能的影响

尖晶石型微波介质陶瓷因高品质因数和可调的谐振频率温度系数在无线通信等领域应用广泛。本文通过无压烧结制备了MgO·nGa₂O₃(n=0.975、1.00、1.08和1.17)尖晶石陶瓷,采用XRD Rietveld全谱拟合研究了化学计量比对晶体结构的影响,并结合键价理论模型探究了微波介电性能与晶体结构的关系。结果表明:MgO·nGa₂O₃陶瓷相对介电常数(ε_r)的变化与晶格常数和离子极化率有关;品质因数(Q×f)受键强和阳离子有序度的共同影响,随n值增大从165 590 GHz下降至109 413 GHz;而谐振频率温度系数(τ_f)与晶体热膨胀系数相关。制备的MgO·0.975Ga₂O₃陶瓷具有优异的微波介电性能:ε_r=9.69、Q×f=165 590 GHz(频率14 GHz下)和τ_f=-7.12×10^-6/℃。     

Growth of carbon-doped base GaAs/AlGaAs HBT by gas-source MBE using TEG, TEA, TMG, AsH3, and Si2H6

High-performance carbon-doped-base GaAs/AlGaAs heterobipolar transistors (HBTs) were grown by gas-source MBE using only gaseous sources including dopant sources. The AlGaAs emitter layer was doped with Si from uncracked SI₂H₆ (n = 9 × 10¹⁷ cm^-3), and the base layer (92.5 nm) was doped with carbon from TMG (p = 4 × 10¹⁹ cm^-3). From SIMS analysis it was confirmed that a well-defined emitter-base junction with sharp carbon profile was obtained. The base-current ideality factor from the Gummel plot was 1.47, and the emitter-base junction ideality factor was 1.12. A high DC current gain of 53 was obtained at a current density of 4 × 10⁴ A/cm². The device characteristics of our carbon-doped HBTs were found to be stable under current stress.     

Pyrolysis characteristics of iodine precursors for gas source n-type doping of II–VI compounds

The selection criteria and pyrolysis characteristics of iodine precursors were investigated to determine the best compounds for the n-type doping of CdTe during gas source molecular beam epitaxy. Ethyliodide and allyliodide were found to have the most suitable properties and to produce iodine dimers for pyrolysis temperatures above 650 and 600°C, respectively. The ethyliodide doping of CdTe was studied and produced highly conductive CdTe layers with room temperature electron concentrations as high as 3 × 10¹⁸ cmsu-3 with a mobility of ˜ 460 cm²/V·s.     

Brillouin scattering and pockels coefficients in silicate glasses

The Brillouin spectra of binary and ternary silicate glasses were investigated and absolute values for the Pockets coefficients p₁₂ and p₄₄ and (p₁₁ – p₁₂) were calculated from the measured spectra. The results were interpreted as to the density and refractive index dependence of the Pockels coefficients in terms of the theoretical treatments by Carleton, Mueller and Sipe. From the measured p₁₂ and p₄₄ values the quantity (∂ε/∂p), the change of the dielectric constant with respect to density, was calculated and compared with (∂ε/∂) evaluated from the Lorentz-Lorenz equation, Drude equation and the Carleton model. The Lorentz-Lorenz and Drude equations overestimated the magnitude of (∂ε/∂), while the Carleton model with its two limiting cases set upper and lowe bounds to (∂ε/∂). From the (∂ε/∂) results the strain polarizability constant (λ₀) was determined and its physical significance discussed. In general, the alkali-oxide concentration dependence of the Pockels coefficients of various silicate glasses has been measured and qualitatively explained by several existing theoretical formulations.     

MOVPE homoepitaxy of high-quality GaN: Crystal growth and devices

Epitaxial growth on GaN bulk single crystal substrates sets new standards in GaN material quality. The outstanding properties provide insights into fundamental material parameters (e.g. lattice constants, exciton binding energies, etc.) with a precision not obtainable from heteroepitaxial growth on sapphire or SiC. With metalorganic vapor phase epitaxy (MOVPE) we realized unstrained GaN layers with dislocation densities about six orders of magnitude lower than in heteroepitaxy. By the use of dry etching techniques for surface preparation, an important improvement of crystal quality is achieved. Those layers reveal an exceptional optical quality as determined by a reduction of the low-temperature photoluminescence (PL) linewidth from 5 meV to 0.1 meV and a reduced X-ray diffraction (XRD) rocking curve width from 400 to 20 arcsec. As a consequence of the narrow PL linewidths, new features as, e. g. a fivefold fine structure of the donor-bound exciton line at 3.471 eV was detected. Additionally, all three free excitons as well as their excited states are visible in PL at 2 K.

Dry etching techniques for surface preparation allow morphologies of the layers suitable for device applications. We report on InGaN/GaN multi-quantum-well (MQW)_ structures as well as GaN pn- and InGaN/GaN double heterostructure light emitting diodes (LEDs) on GaN bulk single crystal substrates. Those LEDs are twice as bright as their counterparts grown on sapphire. In addition they reveal an improved high power characteristics, which is attributed to an enhanced crystal quality and an increased p-doping.     

Structural study of magnesium polyphosphate glasses

Magnesium polyphosphate glasses with molar ratios, y=n(MgO)/n(P₂O₅), ranging from 1.0 to 1.9 have been examined by X-ray and neutron scattering and ³¹P magic angle spinning nuclear magnetic resonance spectroscopy to extract information on their short-range, intermediate-range and submicroscopic structure. The depolymerization of the PO₄ chains with rising MgO content is quantitatively described by the increasing concentration of Q¹ and Q⁰ groups determined by NMR. In the pyrophosphate region the Q¹ sites disproportionate to Q⁰ and Q² groups, whereas there is no disproportionation of the Q² sites at metaphosphate composition. The shortening of the real-space distances, r_m, indicates that the structure of the glasses becomes more compact with progressive depolymerization which is due to the increasing connection of the MgO_n polyhedra by sharing the non-bridging oxygen atoms. The Mg–O co-ordination sphere was found to change not significantly in dependence on composition. Heterogeneities about 1 nm in diameter exist in the glasses with MgO content exceeding 46.6 mol% indicated by a weak small angle X-ray scattering.     

High carbon doping of Ga1−xInxAs (x≈0.01) grown by molecular beam epitaxy

We have grown layers of Ga_1−xIn_xAs:C (x ≈ 0.01) on (100) GaAs by molecular beam epitaxy. As C source a graphite filament was used. Structures coherent with the substrate were obtained by adjusting properly the In and C concentrations. With simultaneous incorporation of In and C the strain is compensated and, consequently, the defect density is reduced. A maximum hole concentration value of p = 6×10¹⁹ cm⁻³ was achieved, which is twice higher than the saturation value of C doping of GaAs produced under the same conditions. There is evidence that this value is not in the saturation limit. The product of the hole density times the mobility increases, so the resistance decreases with higher C doping. Raman spectra show that the C_As peak broadens and shifts to lower frequencies for increasing concentration of indium. In H-passivated samples, Raman spectroscopy shows that C_As is surrounded by Ga atoms only. Indium atoms are thus present only in the second group III shell.     

Raman spectroscopic study on the structure of ZnCl2---ZnX2 and ZnCl2---KX (X = Br, I) glasses

Raman spectra have been measured for ZnCl₂---ZnX₂ and ZnCl₂---KX (X = Br, I) glasses to investigate the structure of the glasses with varying composition. The assignment of each band was made, and the change of the spectra with composition was explained in terms of the bridging and non-bridging states of halide ions and the change of the tetrahedral units, ZnX_nCl_4−n²⁻ (n = 0–4), formed in the glasses. As the content of ZnX₂ in ZnCl₂---ZnX₂ glasses increases (20 → 80 mol%), the peak frequency of the Zn---Cl stretching mode increases (238 → 248 cm⁻¹ in X = I glasses, 238 → 259 cm⁻¹ in X = Br glasses) while the Zn---I and Zn---Br stretching frequencies decrease (173 → 120 cm⁻¹ for Zn---I, 196 → 157 cm⁻¹ for Zn---Br). The decrease of the Zn---I and Zn---Br band frequencies was attributed to the increase of the number n of the ZnX_nCl_4−n²⁻ tetrahedra. The increase of the Zn---Cl frequency suggests the existence of the bonding state of Cl⁻ ions which is intermediate between the bridging and the non-bridging states. In ZnCl₂---KX glasses, the Zn---Cl_non-bridging band at about 300 cm⁻¹ was observed in addition to the bands observed in ZnCl₂---ZnX₂ glasses. The addition of KX produces non-bridging anions while the tetrahedral units, ZnX_nCl_4−n²⁻ are also formed.     

Mg掺杂调制铜铁矿结构CuAlO2多晶的微结构和电热传导

采用固相反应法制备铜铁矿结构的CuAl_1-xMg_xO₂ (x=0、0.005、0.01、0.02、0.03、0.04)多晶,研究了Mg掺杂对CuAlO₂多晶结构和性能的影响。Mg掺杂量x从0增加到0.02,样品均为菱方R3m单相,密度依次提高;所有样品呈半导体的热激活电输运行为,x=0.02样品在室温下的电阻率是未掺杂样品的1/19,热激活能显著下降(x=0时,ρ_{300 K}~5.54 Ω·m,E_a~0.328 eV;x=0.02时,ρ_{300 K}~0.29 Ω·m,E_a~0.218 eV),载流子浓度增加1个量级,主要因为Mg²⁺取代Al³⁺,引入新的受主能级。x>0.02时,MgAl₂O₄尖晶石杂相出现,使其电导率和热导率降低。CuAl_1-xMg_xO₂多晶的晶格热导率在总热导率中占绝对优势,且随温度升高(300~500 K)而下降,晶格热导Callaway模型模拟表明,所有样品的热阻主要源于点缺陷-声子散射。与x=0相比,x=0.02样品的室温热导率增大1倍(κ~13.065 0 W/(m·K)),声速增大,点缺陷-声子散射减弱,分析认为掺Mg形成强的Mg—O键,提高了晶体的弹性模量和声子频率,减弱了本征点缺陷、Mg掺杂引起的质量波动和应变场波动对声子的散射,同时Mg掺杂样品的密度提高也有利于增加热导率。     

Thick single crystalline vanadyl phthalocyanine film epitaxially grown on KBr crystal by molecular beam epitaxy

Structural analyses are reported of 5 μm thick VOPc films grown on a KBr(001) surface by the MBE technique. The crystal is monoclinic with lattice parameters a = 14.2 Å, b = 13.1 Å, c = 12.7 Å and β = 103.2°. The orientation of the unit cell is influenced by the crystal lattice of the substrate even in this thickness range: The projections of the a- and b-axes of VOPc onto the (001) plane of KBr coincide with the [110] directions of KBr. Four kinds of crystal orientations were observed in pole figure measurements.