Highly uniform AlGaAs/GaAs and InGaAs(P)/InP structures grown in a multiwafer vertical rotating susceptor MOVPE reactor

Highly uniform AlGaAs/GaAs and InGaAs(P)/InP epitaxial layers have been grown in a vertical rotating susceptor MOVPE reactor capable of accommodating three 2′ wafers. The unique water-cooled “showerhead”-type injection distributor which is located 1.5 cm above the substrates ensures a uniform reactant distribution, resulting in uniform growth over a wide range of growth conditions. Periodic multilayer and single layer structures have been used to investigate the thickness and compositional uniformities. The thickness variations over a radial distance of 48 mm for three wafers grown in the same run are within ± 2% for both AlGaAs and InGaAs layers, resulting in a standard deviation of only 0.9%. The gallium concentration of an InGaAs layer varies from 46.88% to 47.01% over the same radial distance with the standard deviation of 0.043%. Measurements of InGaAsP layers grown onto 2′ InP wafers with different alloy compositions show good compositional uniformity yielding standard deviations within 4.4 nm in PL wavelength and 135 ppm in lattice mismatch over a 46 mm radial distance.     

Anisotropy in InGaAs/GaAs heterostructures grown by low-pressure MOVPE and CBE

InGaAs/GaAs heterostructures grown on (001) substrates by low-pressure MOVPE exhibit a measurable anisotropy in their structural, optical and electrical properties. This anisotropy occurs in structures which have undergone partial or complete strain relaxation and it can be strongly reduced by using slightly misoriented substrates. A comparison with similar structures grown by CBE indicates that this anisotropy is less important. This study suggests that strain relaxation is achieved by a combination of several mechanisms whose relative importance depends on the orientation of the substrate and on growth temperature which varies with the growth technique.     

The kinetics of parasitic growth in GaAs MOVPE

Gallium arsenide (GaAs) deposition was carried out in a horizontal quartz reactor tube with trimethylgallium (TMGa) and arsine (AsH₃) as precursors, using a hydrogen (H₂) carrier gas. Temperatures were in the range 400–500 °C, where surface reactions limit deposition rate. Nucleation time and deposition rate were monitored using laser interferometry, optimum reflectance was gained by aligning a quartz wafer to back reflect the incident beam. The 980 nm infrared laser beam was sufficiently long in wavelength to be able to penetrate the wall deposit. Results showing the effect of temperature and V/III ratio on the nucleation time and deposition rate are presented, where with temperature the nucleation delay was observed to reduce and the growth rate to increase. The nucleation delay is consistent with a thermally activated surface nucleation for the parasitic GaAs. A theoretical growth rate model, based on a restricted set of reaction steps was used to compare with the experimental growth rates. Without any free parameters, the growth rates from theoretical calculation and experiment agreed within a factor of two and showed the same trends with V/III ratio and temperature. The non-linearity of the theoretical growth rates on an Arrhenius plot indicates that there is more than one dominant reaction step over the temperature range investigated. The range of experimental activation energies, calculated from Arrhenius plots, was 17.56–23.59 kJ mol⁻¹. A comparison of these activation energies and minimum deposition temperature with the literature indicates that the wall temperature measurement on an Aixtron reactor is over 100 °C higher than previously reported.     

Initial growth behavior of GaAs on ZnSe in MOVPE

We have used atomic force microscopy to investigate the initial stages of the growth of GaAs on ZnSe by metalorganic vapor phase epitaxy. Underlying ZnSe with an atomically flat surface is achieved by growth at 450°C and post-growth annealing at the same temperature. The growth modes of GaAs on the ZnSe surface strongly depend on growth temperatures. The growth carried out at 450°C is 2-dimensional, while that at 550°C is highly 3-dimensional (3D), where the 3D islands are elongated in the [110] direction. The growth behavior, unlike homoepitaxy, is well interpreted in terms of low sticking coefficient and anisotropic lateral growth rate in the heterovalent heteroepitaxy.     

MOVPE growth of InN films using 1,1-dimethylhydrazine as a nitrogen precursor

InN films have been successfully grown on sapphire substrates by MOVPE using trimethylindium (TMIn) and 1,1-dimethylhydrazine (DMHy) with N₂ carrier. DMHy is an advantageous precursor of N as it decomposes efficiently at relatively low temperature (T₅₀=420 °C) compatible with the InN growth. The reactor is specially designed so as to avoid parasitic reaction between TMIn and DMHy occurring at room temperature. The growth feature was studied by varying growth temperature, V/III ratio, TMIn flow and reactor pressure. The InN films were obtained at 500–570 °C and 60–200 Torr with a V/III ratio optimized to 100–200. The In droplets are seen on the grown surfaces, indicating an excess supply of TMIn. It is demonstrated that the InN films grows on the sapphire substrate in a single domain with an epitaxial relationship, [1 01¯ 0]_InN//[1 1 2¯ 0]_sapphire.     

MOVPE growth of GaAs on Ge substrates by inserting a thin low temperature buffer layer

High quality GaAs layers have been grown by low pressure MOVPE on Ge(001) and Ge(001) 9° off oriented in [110] direction by using a thin low temperature (LT) GaAs layer. Investigations of the initial growth step were performed at different V/III ratios and temperatures. To show the good buffer layer quality solar cell structures were grown on off oriented n‐Ge(001) and n‐GaAs(001) substrates. The surface morphology was studied by atomic force microscopy which showed the step‐flow growth mode on 1.2 µm thick GaAs/Ge structures. The crystalline qualities of this structures and the smooth surface morphology were investigated by double crystal X‐ray diffraction (XRD) and atomic force microscopy (AFM). (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nitrogen content of GaAsN quantum wells by in situ monitoring during MOVPE growth

Metal–organic vapor phase epitaxial growth of GaAsN quantum wells is monitored by in situ reflectance measurements. Correlation between the change in the reflectance intensity and nitrogen content of the quantum well is established. The reflectance as a function of time also reveals if there is deterioration of the crystalline quality during growth. This method together with X-ray diffraction and photoluminescence characterization is applied to analyze GaAsN growth using various reactor pressures and TBAs/III molar flow ratios.     

Selective etching of dislocations in GaN grown by low-pressure solution growth

This work presents an experimental study on the identification and quantification of different types of dislocations in GaN grown by low-pressure solution growth. A reliable defect selective etching procedure in a NaOH-KOH melt is developed and validated using transmission electron microscopy that permits to define groups of etch pits that belong each to dislocations with a specific Burgers vector. This way a comparably fast method is provided for determining the total, the specific dislocation densities and the type of dislocation in a statistically representative way. The results for the solution grown samples are compared to those obtained for MOCVD GaN.     

Recent developments in the MOVPE growth of low H content ZnSe-based compounds and heterostructures

The origin of unintentional hydrogen (H) incorporation during metalorganic vapour phase epitaxy (MOVPE) of ZnSe-based compounds is reviewed and discussed. Hydrogen enters in MOVPE-grown ZnSe as a result of alkyls surface reactions, effectively passivating intentional nitrogen (N) acceptors in p-doped ZnSe during the fabrication of blue-light emitting diodes and laser diodes. The existence of a marked trade-off between the proclivity of common Se alkyls to incorporate H and their thermal stability is pointed out. Current strategies to overcome this process limitation are then described along with results achieved and technological drawbacks. The use of a novel class of VI-group alkyl precursors of the form R₂X₂ [where X=Se, S and R is an ethyl (Et) or methyl (Me) radical] is proposed as an alternative solution. These alkyls allow a reduction of H incorporation in ZnSe-based materials, whilst retaining the low temperatures required for the growth of device quality wide band-gap II–VI compounds. Dimethyldiselenide (Me₂Se₂) and diethyldisulphide (Et₂S₂) allow the pyrolytic MOVPE growth of Zn(S)Se compounds below 400 °C. Mass spectrometry fragmentation experiments performed on the alkyl molecular ions allowed to investigate their relative bond strengths and likely decomposition paths. The reduced thermal stability of these alkyls is attributed to a weakening of the XC bonds in the R₂X₂ molecule induced by the stronger XX bond. Secondary ion mass spectrometry (SIMS) analysis showed that as-grown ZnSe have [H]≈(1–3)×10¹⁷ cm⁻³, i.e. among the lowest ever reported for MOVPE-grown layers. The functional validation of the new S and Se alkyls is completed by the structural and optical characterisation of Zn(S)Se-based heterostructures grown on (100)GaAs. High-resolution X-ray diffraction studies are presented along with cathodoluminescence (CL) measurements and compared to what reported in the literature. The epilayer structural properties compare well with that of molecular beam epitaxy and MOVPE grown Zn(S)Se heterostructures. CL spectra of ZnSe epilayers appear of good quality, with pronounced band-edge emissions and reduced deep level contributions. Specific emissions in the spectra of ZnS and ZnSe confirm the occurrence of several impurities in the layers, whose origin can be in part attributed to the yet insufficient purity of the novel alkyls.     

MOVPE growth of nonpolar a-plane GaN with low oxygen contamination and specular surface on a freestanding GaN substrate

We investigated unintentionally doped nonpolar a- and m-plane GaN layers grown by metalorganic vapor phase epitaxy under several sets of conditions on freestanding a- and m-plane GaN substrates. Oxygen contamination in a-plane GaN is greatly reduced by increasing the V/III ratio during growth. As a result, a high-resistivity GaN buffer layer for an AlGaN/GaN heterostructure field-effect transistor was realized.     

Heat transfer and mass transport in a multiwafer MOVPE reactor: modelling and experimental studies

An improved detailed model for the calculation of the temperature distribution in a multiwafer Planetary Reactor™ has been developed. The temperature field of the reactor has been calculated in dependence of the reactor parameters for (Al,Ga)As growth as well as on the kind and the thickness of the wall and susceptor deposits. The amount of parasitic wall deposits can be minimized by a proper tuning of the reactor temperature distribution. Calculated GaAs growth rate profiles on 3 inch wafers show a strong dependence on the temperature field in the reactor and the amount of parasitic deposits. These predicted relationships have been used to optimize the reactor temperature distribution in order to minimize parasitic wall depositions. By this procedure a growth rate uniformity of < 1% on 3 inch wafers can be reproducibly achieved.     

Minimization of wafer bowing in GaN-based vertical light-emitting diodes by selective area growth using metal-organic chemical vapor deposition

The effect of selective area growth (SAG) on wafer bowing of GaN-based light-emitting diodes (LEDs) is investigated. The SAG of LED structures was carried out on a silicon dioxide (SiO₂) mask pattern with periodic 1000×1000 μm openings, along the sapphire 〈1?1 0 0〉 and 〈?1?1 2 0〉 directions. The morphology of a selectively-grown n-GaN epilayer was examined in relation to various growth parameters such as temperature, pressure, and V/III ratio. Under optimized growth conditions, formation of a ridge-shaped epilayer with a v-pit free smooth surface was realized. Furthermore, the ridge-shaped vertical LED structure, after the removal of the sapphire substrate by laser lift-off (LLO) showed less wafer bowing compared with conventional vertical LED structures. This is attributed to the suppression of lateral strain and dislocations during the site-selective growth process, due to a reduction in the lateral dimensions.     

Simulation of temperature and gas density field distribution in diamond films growth on silicon wafer by hot filament CVD

In the present study, the temperature and gas density field inside the hot filament chemical vapor deposition (HFCVD) reactor, which play a determinate role on the growth rate and quality of as-deposited diamond films, are simulated using the finite volume method, and the influence of the size and arrangement of filaments and inlets are investigated. Firstly, the correctness of the simulation model is verified by comparing the temperature data obtained from the simulation with that measured in an actual depositing process, and the results show that the error between them is less than 3%. Thereafter, the deposition parameters are optimized using this model as N(filament number)=6, r(filament radius)=0.4 mm, D(filament separation)=16–18 mm, H(substrate–filament distance)=8–9 mm, and 25 inlets. Finally, diamond films are deposited on silicon (100) wafers using above parameters and the results of characterization by SEM and Raman spectrum exhibit that the deposited diamond films appear homogeneous surface with fine-faceted crystals.     

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.     

The role of hydrogen in low-temperature MOVPE growth and carbon doping of In0.53Ga0.47As for InP-based HBT

Hydrogen radicals are decisive for the low-temperature growth and carbon doping of In_0.53Ga_0.47As in LP-MOVPE. This is demonstrated for the growth of highly p-type doped In_0.53Ga_0.47As layers with CCl₄ as dopant source. Perturbed angular correlation measurements (PAC) were used to investigate the passivation of acceptors by hydrogen in low-temperature grown In_0.53Ga_0.47As. Based on the above analysis an InP-based layer stack is developed which employs low-temperature growth of the base layer, high-temperature growth of the remaining HBT layers, and an in situ post-growth annealing under TMAs/N₂ ambient.     

Numerical investigation of induction heating and heat transfer in a SiC growth system

A global simulation model is applied for a silicon carbide growth system heated by induction coils. A finite‐volume method (FVM) and a global model are applied to solve the equations for electromagnetic field, conductive and radiative heat transfer. The growth rate is predicted by Hertz‐Knudsen equation and one‐dimensional mass transfer equation. Further, simulations for five different coil positions are carried out to investigate the effects of coil position on temperature distribution in the furnace. The numerical results reveal that the variation of temperature in the radial direction along the substrate surface and the temperature difference between the powder and substrate are greatly affected by the coil position. The predicted growth rate along the substrate surface for five coil positions is also studied. Finally, a reasonable range of coil positions maintaining a balance between large‐diameter crystal, high growth rate, temperature limitation of material and lower electrical power consumption is obtained. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of SiGe bulk crystals with uniform composition by utilizing feedback control system of the crystal–melt interface position for precise control of the growth temperature

We developed an automatic feedback control system of the crystal–melt interface position to keep the temperature at the interface constant during growth, and demonstrate its successful application to grow Ge-rich SiGe bulk crystals with uniform composition. In this system, the position of the crystal–melt interface was automatically detected by analyzing the images captured using in situ monitoring system based on charge-coupled-devices camera, and the pulling rate of the crucible was corrected at every 1 min. The system was found to be effective to keep the crystal–melt interface position during growth even when the variation of the growth rate is quite large. Especially, the interface position was kept for 470 h during growth of Ge-rich SiGe bulk crystal when we started with a long growth melt of 80 mm. As a result, a 23 mm-long Si_0.22Ge_0.78 bulk crystal with uniform composition was obtained thanks to the constancy of the growth temperature during growth through the control of the interface position. Our technique opens a possibility to put multicomponent bulk crystal in a practical use.     

Rough surface growth by random deposition in colloidal system

We report the study of the random deposition process in polystyrene colloidal solution film. We analysed the morphology of the formed interface and measured the scaling exponents and β, defining the interface width w(L, t) ≈ Lf(t/L^/β), where f(x) ≈ 1 for x 1 and f(x) ≈ x^β for x 1, the values of which are 0.5 and 0.26, respectively. We also compared the result with the theoretical model describing the deposition process.     

Numerical simulation of a new SiC growth system by the dual-directional sublimation method

A new SiC growth system using the dual-directional sublimation method was investigated in this study. Induction heating and thermal conditions were computed and analyzed by using a global simulation model, and then the values of growth rate and shear stress in a growing crystal were calculated and compared with those in a conventional system. The results showed that the growth rate of SiC single crystals can be increased by twofold by using the dual-directional sublimation method with little increase in electrical power consumption and that thermal stresses can be reduced due to no constraint of the crucible lid and low temperature gradient in crystals.     

Gas bubble associated mass transport in Bridgman-Stockbarger melt growth system

Experimental evidence has been obtained showing that gas bubbles may be responsible for melt stirring in Bridgman-Stockbarger growth system which results in Pfann type impurity distribution profiles along the crystal length. The hypothesis of the gas bubble associated mass transfer mechanism is supported by the production of Y₃Al₅O₁₂–Nd³⁺ single crystals under conditions which eliminate or limit gas bubble nucleation in the melts with Nd³⁺ distribution profiles similar to those generally observed in melt growth systems where the mass transport in the melts is limited to diffusion.