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.     

Low temperature II–VI nanowire growth using Au–Sn catalysts

Epitaxial lateral overgrowth is reported for semi-polar (Al,Ga)N(1 1 .2) layers. The mask pattern consisted of periodic stripes of SiO₂ oriented parallel to either the GaN[1 1 .0] or the GaN[1 1 .1] direction. Lateral growth occurred either along GaN[1 1 .1] or along GaN[1 1 .0]. For growth along the [1 1 .0] direction, coalescence was achieved for layer thicknesses >4 μm. However, planarization was not observed yielding extremely corrugated surfaces. For growth in [1 1 .1] direction, coalescence was delayed by a diminishing lateral growth rate. Growth of AlGaN during ELOG resulted in coalescence. Improvement in crystal quality of such buffer layers for the growth of InGaN/GaN quantum wells was confirmed by X-ray diffraction and photoluminescence spectroscopy.     

MOVPE Growth of Wide Band-Gap II—VI Compounds for Near-UV and Deep-Blue Light Emitting Devices

We report on the growth by metalorganic vapour phase epitaxy of high structural and optical quality ZnS, ZnSe and ZnS/ZnSe multiple quantum well (MQW) based heterostructures for applications to laser diodes operating in the 400 nm spectral region. High purity ^tBuSH, ^tBu₂Se and the adduct Me₂Zn:Et₃N were used as precursors of S, Se and Zn, respectively. The effect of the different MOVPE growth parameters on the growth rates and structural properties of the epilayers is reported, showing that the crystallinity of both ZnS and ZnSe is limited by the kinetics of the incorporation of Zn, S and Se species at the growing surface. Very good structural and optical quality ZnS and ZnSe epilayers are obtained under optimized growth conditions, for which also dominant (excitonic) band-edge emissions are reported. The excellent ZnS and ZnSe obtained by our MOVPE growth matches the stringent requirements needed to achieve high quality ZnS/ZnSe MQWs. Their structural properties under optimized MOVPE conditions are shown to be limited mostly by the formation of microtwins, a result of the intrinsic high lattice mismatch involved into the ZnS/ZnSe heterostructure. Despite the large amount of defects found, the optical quality of the MQWs turned out to be high, which made possible the full characterization of their electronic and lasing properties. In particular, photopumped lasing emission up to 50 K in the 3.0 eV energy region are reported for the present MQWs heterostructures under power excitation density above 100 kW/cm².     

X-Ray Diffraction Studies on Point Defects in II–VI Compounds

The point defect concentration in Te-rich CdTe and Hg_1-xCd_xTe annealed at various temperatures has been estimated from precision lattice parameters using a simple continuum inclusion model and compared with densities of electrically charged defects determined by high-temperature Hall and conductivity measurements. The nonstoichiometry is realized by cation vacancies. Dependent on the CdTe content, the ratio of total to charged defect concentrations varies between about unity for HgTe-rich composition and 75 for CdTe. Therefore, it is necessary to distinct between “electrical” and “chemical” stability regions.     

Dynamic crystallization of II–VI compounds from vapours of the component elements

Dynamic crystallization in II–VI compounds synthesis from the vapour phase has been discussed. The method consists in the displacement of the growth zone by the predetermined change of the evaporation temperatures of the initial elements at constant flows of the transport gas. It leads to uniform distribution of grown crystals in the crystallization region and to the increase of the size and of the yield of crystals. Dynamic crystallization makes it possible to control the photoelectrical properties of the crystals and to increase the yield of the crystals with the required photosensitivity by changing the rate and the direction of the displacement of the growth zone.     

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.     

Relationship between refractive index,optical electronegativities and electronic polarizability in alkali halides,III–V,II–VI group semiconductors

Refractive indices have been evaluated from DUFFY'S optical electronegativities. The validity of the proposed empirical relation has been tested in the case of II–Vi, III–V compound semiconductors and alkali halides by comparing the calculated values of n with those in the literature. The estimated refractive indices are used in Classius-Mossotti relation to evaluate electronic polarizabilities in the above compounds. The nature of the bonding in terms of Δχ and n is discussed. Good agreement is observed between the computed and literature values of electronic polarizability.     

MOVPE of InP Using Trimethylindium – Trimethylamine Adduct

Growth of InP layers by MOVPE using trimethylindium-trimethylamine (TMIn–TMN) is described. Low temperature photoluminescence results reveal the high crystal quality indicated by the well resolved excitonic spectra and high internal quantum efficiency. A strong near-gap luminescence degradation with decreasing substrate temperature during the growth corresponds with the increasing deep level concentration estimated by the DLTS-investigations. In the specimens prepared at higher temperatures carbon and zinc are believed to be the main residual acceptors. From C–V data free carrier concentrations of 10¹⁵ cm⁻³ were obtained.     

Debye temperature and melting point of II‐VI and III‐V semiconductors

In this paper, simple relations are proposed for the calculation of Debye temperature θ_D and melting point T_mof II‐VI and III‐V zincblende semiconductors. Six relations are proposed to calculate the value of θ_D. Out of these six relations, two are based on plasmon energy data and the others on molecular weight, melting point, ionicity and energy gap. Three simple relations are proposed to calculate the value of T_m. They are based on plasmon energy, molecular weight and ionicity of the semiconductors. The average percentage deviation of all nine equations was calculated. In all cases, except one, it was estimated between 3.34 to 17.42 % for θ_D and between 2.37 to 10.45 % for T_m. However, in earlier correlations, it was reported between 10.59 to 33.38% for θ_D and 6.96 to 14.95% for T_m. The lower percentage deviation shows a significant improvement over the empirical relations proposed by earlier workers. The calculated values of θ_D and T_m from all equations are in good agreement with the available experimental values and the values reported by different workers. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dynamic crystallization of II—VI compounds with a gaseous control of vapour concentrations

The method for dynamic crystallization of II—VI compounds with a gaseous control of vapour concentrations in the growth zone is developed. The predeterminated change of the transport gas flows which carry the vapours of the initial elements into the reaction zone together with the change of additional inert gas flows conducted directly to the crystallizer entries gives the posibility to displace the growth zone during the process of synthesis. It results in the considerable increase in crystal number and size and leads to best quality of grown crystals.     

Compositional effects accompanying near equilibrium vapour growth of solid solution crystals of the types IV‐VI and II‐VI

Near equilibrium evaporation‐condensation in a sealed ampoule leads to almost full compositional reproduction of a solid solution if it consists of components having comparable vapour pressures; this can be qualitatively interpreted by domination of entropy increase. Nevertheless, even vestigial separation requires closer characteristics, since it may prove crucial – particularly for properties of semiconducting solid solutions. Maximum component separation allowed by a small temperature difference is described here in terms of thermodynamics and kinetics of solid‐vapour and vapour‐solid phase transitions. Theoretical models of the determining effects having different character are shortly described, and their applicability areas are determined. Experimental data collected for crystal growth of numerous semiconducting solid solutions of the II‐VI and IV‐VI type support the conclusion drawn from the models that the near equilibrium crystal growth from the vapour in a closed system ensures the highest degree of compositional uniformity. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Replacement of hydrides by TBAs and TBP for the growth of various III–V materials in production scale MOVPE reactors

Besides the standard group V precursors AsH₃ and PH₃, so-called alternative precursors like TBAs and TBP (tertiary-butyl-arsine and tertiary-butyl-phosphine) are more and more important in today's MOVPE processes. A lot of publications have demonstrated that these precursors can be successfully used for the growth of different III–V materials. In this study we want to demonstrate that TBAs and TBP can be used as the group V precursor in a complete family of production scale reactors. It is shown that these precursors can be used for the growth of InP-based as well as for GaAs-based materials. The reactors that have been employed are medium scale reactors (AIX 200/4; 1 × 2 inch, 3 or 4 inch or 3 × 2 inch capability) and large scale Planetary Reactors®, in particular the AIX 2400 system (15 × 2 inch or 5 × 4 inch). Materials that have been grown are (Al)GaInP on GaAs and GaInAsP on InP. The lower cracking energy of these precursors compared to PH₃ and AsH₃ allows one to use lower growth temperatures and lower V/III ratios, particularly in combination with the high cracking efficiencies of the used reactors. For the growth of GaInAsP on InP, the consumption of TBP and TBAs is up to 8 times lower than using PH₃ and AsH₃. GaInP on GaAs could be grown with a V/III ratio as low as 25 in a Planetary Reactor®. Good crystalline quality is demonstrated by DCXD (e.g. for GaInP: FWHM = 35 arcsec, substrate 32 arcsec). PL intensity and growth rate are not affected by using the alternative precursors. The compositional uniformity is similar to layers grown with arsine and phosphine (e.g. 1.5 nm uniformity for GaInAsP (λ = 1.5 μm) on 2 inch; approximately 1 nm uniformity for GaInP) [1,2]. The purity of the grown layers depends mainly on the quality of the TBP and TBAs. Using high purity TBP, InP revealed background carrier concentration in the mid 10¹⁴ cm⁻³ regime. Our investigation shows that TBP and TBAs can replace phosphine and arsine in state of the art MOVPE reactors. Both for single and multi-wafer production MOVPE reactors these compounds can be used successfully for the growth of the entire material spectrum in the Al---Ga---In---As---P system.     

Temperature dependence of the tetragonal distortion in I–III–VI2 compounds

On the basis of free energy considerations with anharmonic contributions included a model is developed for the temperature dependence of the tetragonal distortion Δ of the I–III–VI₂ compounds. Agreement with experimental data can be only achieved if compounds with Δ < 0.05 and Δ > 0.05 are considered separately. It is suggested that this result is related to the structural order-disorder behaviour of the I–III–VI₂ compounds.     

Characterization of BGO glass–ceramic materials

Glass–ceramics of the compositions Bi₄Ge₃O₁₂ (BGO) and Bi₂O₃–GeO₂ have been obtained by pouring molten materials onto graphite plates heated below and above the glass transition temperatures. Glass transitions temperatures have been measured by DSC. T_g is lower in the case of BGO than with the Bi₂O₃–GeO₂ glass ceramics material. Crystallization is evaluated by X-ray diffraction and microscopic observations. The XRD measurements confirm the amorphous structure of the samples cast below T_g. The Hruby factor, which measures the stability of the glass–ceramics, is about 0.21 in the case of BGO glass ceramics suggesting a rather stable glass. The fluorescence under U.V. excitation is larger by one order of magnitude in the case of BGO glass–ceramics by comparison to the Bi₂O₃–GeO₂ glasses, suggesting it is a good candidate for scintillation materials. The images obtained under U.V. excitation shows structured luminescent centers in the case of BGO glass–ceramics.     

Crystalline–amorphous and amorphous–amorphous transitions in phase-change materials

The transition from the crystalline state to amorphous state and back has been studied in the particular case of the GeSb₂Te₄ phase-change material by a computer simulation procedure. Modelling at the nanoscale indicates specific structural characteristics, especially the multiplicity of the amorphous phase as opposite to the uniqueness of the crystalline phase. In the particular case of the Si₁₂Ge₁₀As₃₀Te₄₈ switching glass two types of ordering have been pointed out and characterized.     

In situ surface passivation of III–V semiconductors in MOVPE by amorphous As and P layers

A new process for chemical passivation of III–V semiconductor surfaces in metalorganic vapour phase epitaxy (MOVPE) is developed. A passivation layer is deposited directly after growth in the reactor. It consists of amorphous arsenic or a double-layer package of amorphous phosphorus and arsenic, which are grown by photo-decomposition of the group-V hydrides. These layers (caps) serve to protect the surfaces against contamination in air after removing the samples from the MOVPE growth reactor. Such passivation is applicable e.g. for a two-step epitaxy or for further surface characterizations.     

Investigation of II –VI alloy lattice dynamics by IR spectroscopic ellipsometry

Optical properties related to lattice vibrations of bulk Zn_1‐xBe_xSe, Zn_1‐x‐yBe_xMn_ySe and Cd_1‐xBe_xSe alloys are reported. Optical phonons of the mixed crystals grown by the Bridgman method have been investigated by infrared spectroscopic ellipsometry in the wave‐number range 300‐8000 cm^‐1. The complex dielectric functions can be reproduced using a model with two or three classical damped oscillators corresponding to the BeSe‐like transverse‐optical phonon‐modes and a Drude contribution from the free carriers. The frequencies of longitudinal‐optical phonons have been found from the imaginary parts of the dielectric loss functions. The influence of the alloy composition on the zone‐centre optical phonon frequencies is discussed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Zur Kristallzüchtung von Cadmiumsulfid und anderen II–VI-Verbindungen (III) Gleichgewichtsdrucke über den Sulfiden in Wasserstoff enthaltenden Gasen

Starting from the reaction formulas 2 MS_f = 2M + S₂ and H₂ + 1/2 S₂ = H₂S vapour pressures of Mg, Zn, Cd, Hg from their sulphides are calculated for various H₂ H₂S-inert gas mixtures and temperatures. They are discussed, compared with values from literature and transpiration experiments and evaluated for crystal growth.     

Comment on “Debye temperature and melting point of II‐VI and III‐V semiconductors” [Cryst. Res. Technol. 45, No. 9, 920–924 (2010)]

In the present work, we have readjusted some empirical parameters obtained by Kumar et al. in their work which contains some numerical errors.