Growth monitoring by reflectance anisotropy spectroscopy in MOVPE reactors for device fabrication

Reflectance anisotropy spectroscopy (RAS) has proved its capability to study surface processes during metalorganic vapour phase epitaxy (MOVPE) growth of a variety of III–V compounds. However, these investigations up to now have been mostly restricted to specialized research reactors. Therefore, we studied the feasibility of in-situ monitoring by RAS during growth on two production-type MOVPE reactors: horizontal 2 inch single wafer reactor AIX 200 and Planetary Reactor™ AIX 2000 for 5 × 3 inch. The slight modifications of the reactors necessary to gain normal incidence optical access to the sample do not alter the properties of the grown materials. While in the horizontal reactor the strain-free optical window allows one to obtain well-resolved RAS spectra the signals in the multiwafer reactor are affected by the anisotropy of the ceiling plate. Even in this case RAS spectra can be extracted. First measurements on rotating samples in the horizontal reactor demonstrate the possibility to obtain RAS spectra by multitransient spectroscopy. As an application monitoring of the growth of p-type layers for the base of GaInP/GaAs hetero-bipolar-transistors (HBTs) is discussed. The linear electro-optic effect (LEO) gives information on doping type and doping level. Time-resolved transients at specific energies are used to study the impact of different switching schemes on the properties of the base-emitter interface.     

AlN/Si(100)上CVD SiC薄膜的光致发光谱

本工作用化学气相淀积方法在AlN/Si(100)复合衬底上生长SiC薄膜.外延生长过程中,采用C4H4和SiH4作为反应气源,H2作为载气.样品的X-射线衍射谱和拉曼散射谱显示,所得到的外延层为六角对称的SiC薄膜.俄歇电子能谱及X-射线光电子能谱的测量结果表明,在外延膜中存在来自衬底的Al和N元素.样品的光致发光测量显示,所有的样品均可在室温下观察到位于3.03eV和3.17eV处的发光峰,这分别相应于4H-SiC能带中电子从导带到Al受主能级之间的辐射跃迁和电子从N施主能级到价带之间的辐射跃迁,从而表明所得的外延薄膜的多形体为4H-SiC.     

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.     

The characterization of the growth of sub-monolayer coverages (1/200th to 1 monolayer) of Si and Be on GaAs(001): A reflectance anisotropy spectroscopy and reflection high-energy electron diffraction study

The techniques of reflectance anisotropy spectroscopy (RAS) and reflection high-energy electron diffraction (RHEED) have been employed, for the first time in concert, to characterize the growth of sub-monolayer coverages of both Si and Be deposited onto the GaAs(001)-c(4×4) surface. The RHEED observations enabled the RAS spectra collected for a series of Si and Be coverages, in the range 0.005 to 1.000 monolayer (ML), to be interpreted in terms of changes in the sample surface structure. For the case of Si/GaAs(001) the following series of surface reconstructions were observed with increasing Si coverage: c(4×4), c(4×4)/(1×2), (1×2), (1×2)/(3×1) and, (3×1). During the deposition of Be/GaAs(001), c(4×4), c(4×4)/(1×2), c(4×4)/(1×3), (1×2)/(1×3), (1×3), and (1×2) reconstructions were noted to evolve. The fact that unique, but highly reproducible, RAS signatures were obtained for each of these surface phases demonstrates the applicability of a combined RHEED/RAS system for monitoring sub-monolayer heteroepitaxial growth with a surface sensitivity of the order of 1/200th of a monolayer.     

Chemical trend observed in anisotropic surface reflectance spectra of MOVPE by surface photoabsorption

This paper investigates the origin of the surface reflectance spectrum for the group-V-stabilized III–V surface during MOVPE by using surface photoabsorption. A chemical shift is observed for the stoichiometry sensitive peak in the anisotropic spectra of arsenides and phosphides. The peaks observed in the phosphides are located at higher energies than the arsenides, besides the peak in each compound shows a red-shift as the lattice constant increases. To investigate the possibility of the critical point of the bulk energy state appearing in the reflectance spectrum induced by surface modification, the anisotropic spectrum during InAs-on-GaAs heteroepitaxy are measured. One monolayer InAs growth on GaAs results in a drastic change that a peak sign is reversed, accompanied by a red-shift. This can be interpreted by the optical transition change corresponding to the surface conversion from a two-As-layer c(4 × 4)-like surface in GaAs to a one-As-dimer layer having a bond axis perpendicular to the c(4 × 4) As dimer. The contribution of the GaAs bulk electronic state in the reflectance spectrum is not observed. These results support the model that the anisotropic peak originates from an optical transition of the group-V dimer. The anisotropic spectrum measurement also makes it possible to monitor the P/As surface exchange and the As-atom segregation during the InP-on-InAs heteroepitaxy.     

Studies in the growth of ZnSe on GaAs(001)

This paper reports a study of the molecular beam epitaxial (MBE) growth of ZnSe on GaAs substrates using elemental sources. Growth rates of ZnSe as a function of Se:Zn flux ratio for constant Zn flux were determined over a wider range of values than previously reported. Careful measurements of atomic fluxes and sample thickness lead to a determination of the sticking coefficients of Zn and Se which are at variance with many previously reported values. The temperature dependence of the sticking coefficients of Zn and Se has been measured carefully and provides evidence for a greater desorption of Zn from the growing surface than previously thought, an effect which persists at low growth temperatures. Measurements at high flux ratios support the use of a precursor model to describe MBE growth of ZnSe on GaAs substrates.     

Investigations on the effect of InSb and InAsSb step-graded buffer layers in InAs0.5Sb0.5 epilayers grown on GaAs (0 0 1)

We report the structural and electrical properties of InAsSb epilayers grown on GaAs (0 0 1) substrates with mid-alloy composition of 0.5. InSb buffer layer and InAs_xSb_1−x step-graded (SG) buffer layer have been used to relax lattice mismatch between the epilayer and substrate. A decrease in the full-width at half-maximum (FWHM) of the epilayer is observed with increasing the thickness of the InSb buffer layer. The surface morphology of the epilayer is found to change from 3D island growth to 2D growth and the electron mobility of the sample is increased from 5.2×10³ to 1.1×10⁴ cm²/V s by increasing the thickness of the SG layers. These results suggest that high crystalline quality and electron mobility of the InAs_0.5Sb_0.5 alloy can be achieved by the growth of thick SG InAsSb buffer layer accompanied with a thick InSb buffer layer. We have confirmed the improvement in the structural and electrical properties of the InAs_0.5Sb_0.5 epilayer by quantitative analysis of the epilayer having a 2.09 μm thick InSb buffer layer and 0.6 μm thickness of each SG layers.     

Si和GaAs衬底上的ZnTe、CdTe分子束外延材料的晶向倾角

本文采用X射线双晶衍射二次测量法对φ76mm Si(211)和GaAs(211)B衬底上生长的ZnTe和CdTe外延层的晶向倾角进行了测量,发现对于Si和GaAs衬底,外延层的[211]均绕外延层与衬底的[0-11]复合轴朝[111]倾斜,其晶向倾角与晶格失配呈线性关系;通过实际测量验证了在外延层探测到的[133]峰代表[211]关于[111]旋转180°的[255]孪晶向.     

Effects of ultraviolet irradiation during growth of ZnSe epilayers by atmospheric pressure metalorganic vapor-phase epitaxy using dimethyl zinc and H2Se

This work has investigated the effects of ultraviolet irradiation on the epitaxial growth process of undoped ZnSe by atmospheric-pressure metalorganic vapor phase epitaxy. Dimethyl zinc and H₂Se at a [VI]/[II] mole ratio of 20 were the source gases used for growth onto (100)-just oriented semi-insulating GaAs substrates. Hydrogen was used as the carrier gas. A 500 W Hg-Xe lamp irradiated the substrate at 300 nm wavelength during growth. Growth temperature was varied from 210 to 450°C. Epilayers grown in the presence of irradiation experienced a prominent decrease in growth rate, which occurred even at high temperatures. Through a combination of surface and vapor-phase reactions, UV irradiation also affected the photoluminescence properties, crystalline quality, and surface morphology of the epilayers.     

The growth of ZnSe by photo-assisted metalorganic chemical vapor deposition (MOCVD)

ZnSe epitaxy layers were grown on (1 0 0)GaAs substrates by photo-assisted MOCVD using DMZn and DMSe as group II and VI sources, respectively. Irradiation can improve the growth rate efficiently, but the irradiation intensity influences the growth rate and the crystalline quality negligibly in a large range. Due to an oxidation reaction on the surface of ZnSe, the growth rate and the flow ratio of group II and VI sources influence the crystalline quality.     

GaAs---InP heteroepitaxy and GaAs---InP MESFET fabrication by MOVPE

Lattice-mismatched heteroepitaxy has attracted considerable attention in recent years. A great interest of these systems is the possibility of integrating devices from different materials on a single substrate. 1.3 and 1.5 μm InGaAs(P)/InP laser diodes are essential for optical communication, whereas InP field effect transistor technology is less developed than that of GaAs MESFET. The performances of laser diodes are much more sensitive to a high density of disclocations, so it would be interesting to grow GaAs MESFET on InP for integration with 1.3 and 1.5 μm lasers. Due to the large difference of the thermal expansion coefficient and lattice parameter between GaAs and InP, it is very difficult to grow GaAs epilayers of high quality on it is very difficult to grow of GaAs epilayer high quality on InP substrates due to the large difference of the thermal expansion coefficient and lattice parameter between GaAs and InP. A new method, metalorganic source modulation epitaxy (MOSME), which improves the crystal quality of GaAs epilayers on InP substrates by MOVPE, has been adopted in our laboratory. The lowest full width at half maximum (FWHM) of the double crystal X-ray (DCX) diffraction spectra reaches as low as 120 arcsec for a 5 μm thick layer. Structural properties (misorientation, lattice parameters and crystal quality) of 1.0–5.0 μm thick GaAs layers grown on InP have been measured by DCX diffraction. On GaAs MESFETs grown on InP, we have measured g_m = 100 ms/mm. For these transitions, the current gain cut-off frequency (F_t) is around 12 GHz and the maximum frequency of oscillation (F_max) is higher than 30 GHz.     

Investigation of preparation and properties of epitaxial growth GaN film on Si(1 1 1) substrate

In this paper, a single crystalline GaN grown on Si(1 1 1) is reported using a GaN buffer layer by a simple vacuum reactive evaporation method. Scanning electron microscopy (SEM), X-ray diffraction (XRD), photoluminescence measurement (PL), and Hall measurement results indicate that the single crystalline wurtzite GaN was successfully grown on the Si(1 1 1) substrate. The surface of the GaN films is flat and crack-free. A pronounced GaN(0 0 0 2) peak appears in the XRD pattern. The full-width at half-maximum (FWHM) of the double-crystal X-ray rocking curve (DCXRC) for (0 0 0 2) diffraction from the GaN epilayer is 30 arcmin. The PL spectrum shows that the GaN epilayer emits light at the wavelength of 365 nm with an FWHM of 8 nm (74.6 meV). Unintentionally doped films were n-type with a carrier concentration of 1.76×10¹⁸/cm³ and an electron mobility of 142 cm³/V s. The growth technique described was simple but very powerful for growing single crystalline GaN films on Si substrate.     

In situ monitoring of CdTe nucleation on GaAs (100) using spectroscopic ellipsometry

In situ spectroscopic ellipsometry was used to monitor the nucleation behavior of CdTe grown on vicinal GaAs (100) substrates by organometallic vapor phase epitaxy. CdTe was grown on GaAs (100) substrates of exact and 2° off towards 110 orientations. A spectroscopic ellipsometer was used to collect in situ data at 44 wavelengths from 4000–7000 Å. The Bruggeman's effective medium approximation was employed to determine the variation of the epilayer volume fraction with thickness, which was an indirect way of monitoring the expected island growth behavior. The Stranski-Krastonov (layer plus island) mode of growth was clearly observed for CdTe growth. The growth on the 2° off substrate was also “denser” than that on exact (100), which implied that coalescence of the islands occurred at lower thickness. This was expected since island nucleation is most favored along the ledges on the surface whose spacing decreases with increasing misorientation. A simple nucleation model, assuming cylinder-like islands, was able to fit the experimental data quite well, lending support to the island growth model.     

Excitation pattern of the blue emission in Ge-doped silica

The luminescence of Ge-doped glassy SiO₂ has been investigated at room temperature using a deuterium lamp as the excitation source in the ultraviolet and vacuum ultraviolet energy range. Two emission bands are observed around 3 and 4 eV as the excitation increases from 4.5 to 8 eV. The peak shift and bandwidth broadening of the emission around 3 eV indicate the overlapping of several bands. We carried out a Gaussian best-fit approach of the detected spectra and extracted the excitation spectra of three distinct emission: a 2.9 eV band with two excitation channels at 4.7 and 5.3 eV and no contribution above 6 eV and the well-known composite β-band (3.1 eV). The latter is resolved into two Gaussian components whose excitation spectra present three main excitations around 5.1, 6.5 and 7.3 eV.     

Growth and annealing effect of high-quality ZnSe:N/ZnSe by MOCVD

The ZnSe : N epitaxial layers were grown on (1 1 0) ZnSe substrates in a low-pressure metalorganic chemical vapor deposition (MOCVD) system using hydrogen as a carrier gas, and using ammonia as a dopant source. In order to obtain highly doped ZnSe : N epitaxial layers, the optimum growth and doping conditions were determined by studying the photoluminescence (PL) spectra from the ZnSe epitaxial layers grown at different ammonia flux and VI/II flux ratio. Furthermore, in order to enhance the concentration of active nitrogen in ZnSe epitaxial layer, a rapid thermal anneal technique was used for post-heat-treating. The results show that the annealing temperature of over 1023 K is necessary. Beside, a novel treatment method to obtain a smooth substrate surface for growing high quality ZnSe epitaxial layers is also described.     

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.     

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.     

MgZnO/ZnO异质结构的发光性质研究

本文利用等离子体辅助分子束外延(P-MBE)技术在蓝宝石 (Al2O3) 衬底上生长了Mg0.12Zn0.88O(100nm)/ZnO (20nm) /Mg0.12Zn0.88O (40nm) 异质结构,测得样品的X射线衍射谱表明,在34.56°的位置出现很强的(002)方向衍射峰,其半高宽度为0.20°,比Mg0.12Zn0.88O合金薄膜的半高宽度0.15°明显展宽.通过光致发光谱研究了MgZnO/ZnO/MgZnO异质结构的光学性质,室温下测得在370nm(3.35eV)位置有很强的紫外发光,而在348nm (3.56eV)的位置处有一个较弱的发光,这两个峰分别被归结于来自ZnO层和MgZnO盖层的发光.室温下的吸收光谱中,在上述两个峰的位置附近分别存在很明显的吸收,指示了带边吸收来自于MgZnO和ZnO两种材料.通过变温发光谱研究了异质结构中载流子弛豫、复合的规律.随着温度增加,来自于ZnO层和MgZnO层的发光强度比增加,这归结为MgZnO/ZnO异质结构存在界面势垒所致.     

Stranski-Krastanov formation of InAs quantum dots monitored during growth by reflectance anisotropy spectroscopy and spectroscopic ellipsometry

In this study the successful application of reflectance anisotropy spectroscopy (RAS) and spectroscopic ellipsometry (SE) for the in-situ investigation of InAs quantum dot growth on GaAs (001) in Stranski-Krastanov growth mode is reported. Both techniques provide the precise determination of the growth mode transition from two-dimensional InAs layer to three-dimensional island growth. In order to optimize the growth conditions, spectral and time-resolved measurements were performed for different growth parameters (temperatures, growth rates and V/III ratios). For high temperature deposition large additional anisotropies, caused by clusters elongated in the [110] direction were found. Decreasing the deposition rate (0.5 to 0.125 ML/s) also results in the formation of large clusters, as decreases in reflectivity due to larger stray light losses prove. Finally, increasing the AsH₃ partial pressure leads to an earlier onset of island formation and an enhanced tendency for cluster formation.     

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.