Influence of phosphine flow rate on Si growth rate in gas source molecular beam epitaxy

As reported by other authors, we have also observed that the Si growth rate decreases with increasing phosphine (PH₃) flow rate in gas source Si molecular beam epitaxy using phosphorous (P) as a n-type dopant. Why small quantity PH₃ can affect Si growth rate? Up to now, the quantitative characterization of PH₃ flow influence on Si growth rate is little known. In this letter, the PH₃ influence will be analyzed in detail and a model considering strong P surface segregation and its absorption of hydrogen will be proposed to characterize the effect.     

Use of V/III ratio to produce heterostructures in ordered GaInP

Compositional ordering in Ga_0.52 In_0.48 P results in a significant reduction in bandgap energy. The degree of order is known to be a strong function of the input partial pressure of the P precursor during growth due to the effect of this parameter on the surface reconstruction. This raises the possibility of producing heterostructures by simply changing the flow rate of the P precursor during growth. The change in bandgap energy at order/disorder (O/D) heterostructures formed by decreasing the P partial pressure during the OMVPE growth cycle is graded over several thousands of Å when PH₃ is used as the P precursor. Examination of the transmission electron microscope image and the photoluminescence (PL) spectrum reveals that the ordered structure in the lower layer persists far into the upper layer. Similarly, disorder/order (D/O) structures produced in this way yield PL spectra indicative of graded composition at the heterostructure when the P precursor is PH₃. The abruptness is not affected by interruptions in the growth cycle for as long as one hour. Similar heterostructures produced using tertiarybutylphosphine (TBP) as the P precursor are distinctly different. Both D/O and O/D heterostructures can be produced by abruptly increasing the TBP flow rate during the growth cycle. PL studies show two distinct peaks closely corresponding to those observed for single layers grown using these conditions. Surface photoabsorption spectroscopy was used to monitor the transition in surface reconstruction. The change was found to be limited by the dynamics of the mass flow controller. The only difference detected which might explain the difference in behavior between PH₃ and TBP is that atomic force microscopy scans show the layers grown using TBP are covered by monolayer and bilayer (6 Å in height) steps. Growth under similar conditions using PH₃ produces bunched steps, much larger than 6 Å in height.     

Evaluation of cracking efficiency of As and P precursors

The cracking behaviour of PH₃, TBP and DitBuPH, AsH₃ and TBAs was studied by mass spectrometry in a production-type MOMBE growth chamber. The measurements were performed varying the cracking temperature of the injector cells and the total material flux. The pyrolysis of the hydrides PH₃/AsH₃ essentially leads to the production of hydrogen and the dimers P₂/As₂. The decomposition of these source materials reaches about 90% at beam pressures in the range of 10⁻⁷ Torr. Under identical conditions TBP, TBAs and DitBuPH are cracked better than 97%. However, the pyrolysis of the alkyl-compounds is accompanied by the formation of isobutene and hydrides. Consequently the decomposition of this PH₃ and AsH₃ produced during cracking is limiting the growth relevant cracking efficiency to the values obtained for the hydrides. The additional occurrence of dihydrides at beam pressures in the range of 10⁻⁵ Torr suggests an initial decomposition process of the source materials via a radical formation mechanism. With respect to the stability of the compounds a self-dissociation of TBAs in the bubbler under the production of isobutane C₄H₁₀ and AsH₃ was detected.     

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.     

MOVPE growth and characterization of GaInAs(P) on (001) InP using diethyltertiarybutylarsine (DEtBAs) and tertiarybutylphosphine (TBP) as the group-V sources

We report on low pressure MOVPE results of (GaIn)As grown with the arsenic precursor DEtBAs as well as (GaIn)(AsP) grown on InP using the precursor combinations DEtBAs/TBP, DEtBAs/PH₃ which we carefully compared with samples grown in the standard system (AsH₃/PH₃). Lattice matched (GaIn)As layers have been obtained at a growth temperature of 600°C, a V/III ratio of 3 and at a growth rate of 1 μm/h at a reactor pressure of 50 mbar. Changing the As precursor from AsH₃ to DEtBAs simultaneously alters the incorporation coefficient ratio k_Ga/k_In from 1.15 to 1. At room temperature n-type mobilities of 9060 cm²/V s have been achieved for (GaIn)As grown with DEtBAs at a V/III ratio of 2. Besides the excitonic luminescence at 802 meV a lower energy peak appears in the photoluminescence (PL) spectra at 753 meV (carbon-carbon donor-acceptor pair). The excitonic luminescence peak has a FWHM of about 9 meV. The (GaIn)(AsP) layers have been grown at a growth temperature of 625°C and V/III ratios of 15–25 with DEtBAs/TBP and about 60 with DEtBAs/PH₃. Layers grown with higher V/III ratios show an enhanced As content. However, considering the P incorporation we have observed a qualitative difference between the standard hydride system and systems using alternative group-V precursors. Even in the system DEtBAs/PH₃ the phosphorus incorporation is much higher than in the AsH₃/PH₃ system indicating the influence of vapor phase exchange reactions.     

Temperature dependency of the composition of GaInAsP grown by GSMBE

We have grown GaInAsP layers on InP substrates by gas-source molecular beam epitaxy and observed an abrupt change in the alloy composition as a function of growth temperature in the GaInAsP alloys for the wavelengths 1.05<λ1.3 μm. In this study we have concentrated on the alloys in the region of wavelength 1.1 μm. We have studied the influence of growth parameters such as growth rate and AsH₃ and PH₃ pressures on As concentration and on the magnitude of the abrupt change in more detail.     

On the use of remote RF plasma source to enhance III–V MOCVD technology

A remote RF (13.56 MHz) plasma source, assembled on a metalorganic chemical vapour deposition (MOCVD) system, was used to investigate the processes of (a) cleaning and passivation of InP substrates with H atoms (H₂ plasmas), (b) deposition of InP epilayers from In(CH₃)₃ and PH_x radicals (PH₃/H₂ plasmas), and (c) deposition of InN on sapphire from In(CH₃)₃ and N atoms (N₂---H₂---Ar plasmas). From kinetic and spectroscopic ellipsometric in situ analysis, the removal of native oxide from InP surface was found to be complete, without surface damage (phosphorus depletion), at 230°C and 7 min of H atoms exposure. The growth of InP epilayers with PH₃ plasma pre-activation was successful (stoichiometric InP) even at low V/III ratio. During InN growth, the use of optical emission spectroscopy (OES) and of in situ ellipsometry (SE) was determinant for the process control.     

Growth of 1.55 μm DH laserstructures using TBAs and TBP in MOMBE

In a comparative study we have chosen TBAs and TBP as well as AsH₃ and PH₃ for the growth of InP/GaInAs(P) heterostructures for laser applications in a production metalorganic molecular beam epitaxy (MOMBE) system. The n-type doping was performed with Si from an effusion cell, whereas for the p-type doping Be and DEZn were utilized. InP layers using TBP under optimized cracking conditions exhibit excellent surface morphology with good electrical properties in the low 10¹⁵ cm⁻³ range of carrier concentrations. The MOMBE growth mechanism is not disturbed by the hydride replacement compound. This allows for a convenient replacement without losing calibration data from the hydride process. Broad-area DH laserstructures with GaInAsP (λ = 1.55 μm) active regions were grown with AsH₃/PH₃ and TBAs/TBP. Comparable threshold current densities in the range of 1.6-2.3 kA/cm² are achieved for the lasers, grown with both sets of precursors combined with DEZn source doping. These results are in good agreement with the standard set by the hydride MOVPE process.     

GaN-MOVPE气相自由基反应的量子化学研究

利用量子化学的密度泛函理论(DFT),对TMG/NH₃/H₂体系中自由基参与的金属有机气相外延(MOVPE)反应进行计算分析,特别针对H、NH₂自由基对Ga(CH₃)₃(简称TMG)热解路径、氢解路径以及加合路径的影响进行研究。通过计算不同反应路径的吉布斯自由能差ΔG和能垒ΔG^*/RT,确定了自由基参与的气相反应在不同温度下不同的反应路径。研究发现:当T<683 K时,TMG与NH₃反应生成加合物TMG:NH₃。当T>683 K时,TMG:NH₃重新分解为TMG和NH₃。TMG在MOVPE温度下很难直接热解,在H自由基作用下则易热解产生Ga(CH₃)₂(简称DMG)、GaCH₃(简称MMG)和Ga原子。当T<800 K时,TMG与NH₃的氨基反应速率大于自由基参与的热解反应,故氨基反应占主导;当T>800 K时,自由基参与的TMG热解反应速率大于氨基反应,故热解反应占主导。氢解反应由于能垒很高,因此可忽略。TMG及其热解产物与NH₂自由基反应很容易产生氨基物。氨基物DMGNH₂可以与H自由基继续反应,最终生成表面反应前体GaNH₂。     

The effect of dopants on the microstructure of polycrystalline silicon thin film grown by MILC method

The effect of dopants on the crystal growth and the microstructure of poly-crystalline silicon (poly-Si) thin film grown by metal induced lateral crystallization (MILC) method was intensively investigated. PH₃ and B₂H₆ were used as source gases in ion mass doping (IMD) process to make n-type and p-type semiconductor respectively. It was revealed that the microstructure of MILC region varies significantly as the doping type of the samples varied from intrinsic to n-type and p-type, which was investigated by field emission (FE)-SEM. The microstructure of MILC region of the intrinsic was bi-directional needle network structure whose crystal structure has a (1 1 0) preferred orientation. For p-type doped sample, the microstructure of MILC region was revealed to become unidirectional parallel growth structure more and more as MILC growth proceed, which was led by unidirectional division of needlelike grain at the front of MILC region. And for n-type doped sample, the microstructure was random-directional needlelike growth structure. These phenomena can be explained by an original model of Ni ion and Ni vacancy hopping in the NiSi₂ phase and its interface at the front of MILC region.     

In situ mesa etching and immediate regrowth in a HVPE reactor for buried heterostructure device fabrication

Mesa etching in a hydride vapour-phase epitaxy (HVPE) reactor has been studied. Etched depth, underetching and shape of the mesas have been analysed as a function of partial pressures of active gases (HCl, PH₃ and InCl), stripe orientation and etching temperature. The experimental results show that the depth and undercut can be etched independently. We propose qualitative mechanisms for etching each of the emerging crystallographic planes ((0 0 1), (1 1 0) and {1 1 1}). In situ mesa etching with immediate regrowth was applied to the fabrication of buried heterostructure Fabry–Perot lasers. No surface contamination due to exposure to ambient and low process time are advantages of this technique.     

Non-linear As(P) incorporation in GaAs1−yPy on GaAs and InAs1−yPy on InP

We find anion incorporation into both GaAs_1−yP_y on GaAs and InAs_1−yP_y on InP during gas source molecular beam epitaxy (GSMBE) is not linearly related to the hydride gas fluxes within our reactor. The deviation from an ideal model, i.e., y = ƒ_P/(ƒ_P+ƒ_As), where As(P) is the flux of AsH₃ (PH₃), can be as large as a factor of two. GaAsP exhibits the largest degree of nonlinearity and incorporation is found to depend quadratically on the fluxes over a wide range of flux ratio. Significant deviations are also found for InAsP; however, anion incorporation can be modeled with y = ƒ_P/(ƒ_P+βƒ_As).     

A comparative study of GaAs- and InP-based HBT growth by means of LP-MOVPE using conventional and non gaseous sources

Low-pressure metalorganic vapor phase epitaxy (LP-MOVPE) growth of carbon doped (InGa)P/GaAs and InP/(InGa)As heterojunction bipolar transistors (HBT) is presented using a non-gaseous source (ngs-) process. Liquid precursors TBAs/TBP for the group-V and DitBuSi/CBr₄ for the group-IV dopant sources are compared to the conventional hydrides AsH₃/PH₃ and dopant sources Si₂H₆/CCl₄ while using TMIn/TEGa in both cases. The thermal decomposition of the non gaseous sources fits much better to the need of low temperature growth for the application of carbon doped HBT. The doping behavior using DitBuSi/CBr₄ is studied by van der Pauw Hall measurements and will be compared to the results using Si₂H₆/CCl₄. Detailed high resolution X-ray diffraction (HRXRD) analysis based on 004 and 002 reflection measurements supported by simulations using BEDE RADS simulator enable a non-destructive layer stack characterization. InGaP/GaAs HBT structures designed for rf-applications are grown at a constant growth temperature of T_gr=600°C and at a constant V/III-ratio of 10 for all GaAs layers. P-type carbon concentrations up to P = 5·10¹⁹cm⁻³ and n-type doping concentrations up to N = 7·10¹⁸cm⁻³ are achieved. The non self-aligned devices (A_E = 3·10 μm²)_show excellent performance, like a dc-current gain of B_max = 80, a turn on voltage of V_offset = 110 mV (Breakdown Voltage V_CEBr,0 > 10 V), and radio frequency properties of f_T/f_max = 65 GHz/59 GHz.

In the non-gaseous source configuration the strong reduction in the differences of V/III-ratios and temperatures during HBT structure growth enable easier LP-MOVPE process control. This is also found for the growth InP/InGaAs HBT where a high dc-current gain and high transit frequency of f_T= 120 GHz are achieved.     

High-quality InP grown by chemical beam epitaxy

InP films were grown by chemical beam epitaxy using trimethylindium (TMI) and pure phosphine (PH₃) in a flow control mode with hydrogen as the carrier gas, with the TMI flow rate fixed at 3 SCCM. Substrate temperatures were varied between 505 and 580°C and V/III ratios from 3 to 9. InP layers with high optical quality (intense and narrow excitonic transition lines) and high crystalline quality (narrow and symmetric X-ray diffraction peaks) could be grown only within a narrow parameter window around a substrate temperature of 545°C (δT_s ≤ 25°C) and a V/III ratio of 5.5 (δ(V/III) ≤ 2). Carrier densities of 8 × 10¹⁴ cm^-3 with mobilities of 70000 cm²/V.s measured at 77 K were obtained for growth conditions close to the edge of this parameter window towards low V/III ratios. The growth rate of inP was also clearly at its maximum in the given parameter window. Leaving the window, by changing either the growth temperature or the V/III ratio, significantly decreased the growth rate. This reduced growth rate was accompanied by a degradation in the crystalline quality. We also demonstrate that for higher TMI flow the parameter window shifts to higher growth temperatures. The InP could be doped effectively with Si in the range from 9 × 10¹⁵ to 3 × 10¹⁸ cm^-3.     

Low temperature growth of AlGaAs by MOMBE (CBE) using trimethylamine alane

In order to gain further insight into the surface chemistry of AlGaAs growth by metalorganic molecular beam epitaxy, we have investigated the deposition behavior and material quality of AlGaAs grown at temperatures from 350 to 500°C using trimethylamine alane (TMAA), triethylgallium (TEG) and arsine (AsH₃). Though the Al incorporation rate decreases with decreasing temperature, Ga-alkyl pyrolysis, and hence Ga incorporation rate, declines more rapidly. Thus the Al content increases from X_AlAs = 0.25 at 500°C to X_AlAs = 0.57 at 350°C. Below 450°C, the Ga incorporation rate appears to be determined by the desorption of diethylgallium species, rather than interaction with adsorbed AlH₃. Similarly, carbon incorporation is enhanced by 2 orders of magnitude over this temperature range due to the increasingly inefficient pyrolysis of the Ga-C bond in TEG. Additionally, active hydrogen from the TMAA1, which normally is thought to getter the surface alkyls, is possibly less kinetically active at lower growth temperatures. Contrary to what has been observed in other growth methods, low growth temperatures produced a slight decrease in oxygen concentration. This effect is likely due to reduced interaction between Ga alkoxides (inherent in the TEG) and the atomic hydrogen blocked Al species on the growth surface. This reduction in oxygen content and increase in carbon concentration causes the room temperature PL intensity to actually increase as the temperature is reduced from 500 to 450°C. Surprisingly, the crystalline perfection as measured by ion channeling analysis is quite good, χ_min≤5%, even at growth temperatures as low as 400°C. At 350°C, the AlGaAs layers exhibit severe disorder. This disorder is indicative of insufficient Group III surface mobility, resulting in lattice site defects. The disorder also supports our conclusions of kinetically limited surface mobility of all active surface components.     

喷淋式MOCVD反应器中AlN的生长速率和化学反应路径的数值模拟研究

利用数值模拟方法,结合反应动力学和气体输运过程,研究喷淋式MOCVD反应器中AlN的生长速率和气相反应路径与反应前体流量(NH3和H2)、进口温度、压强、腔室高度等参数的关系.研究发现:薄膜生长前体和纳米粒子前体的浓度决定了不同的生长速率和气相反应路径.在低Ⅴ/Ⅲ比(2000)、高H2流量(12 L/min)、高进口温...     

Hydrogen and nitrogen ambient effects on epitaxial growth of GaN by hydride vapour phase epitaxy

This study presents the influence of the composition of the carrier gas on the growth of GaN by HVPE. Since no hydrogen is introduced in the vapour phase, the deposition is expected to be controlled by Cl desorption in the form of GaCl₃, as has been proposed for GaAs. However, our published model predicts much lower growth rates than those observed. We can account for both the observed parasitic deposition and GaN growth rate if we assume that GaCl₃ is not at its equilibrium pressure in the deposition zone and where nucleation takes place on the walls as well as on the substrate. This yields a high rate of parasitic nucleation even though the nominal supersaturation is vanishing small. Very little growth takes place on the substrate where the equilibrium pressure of GaCl₃ is reached. We describe similar experiments performed with a H₂/N₂ mixture as the carrier gas. In this case, we expect GaN deposition to be controlled by desorption of Cl as HCl, which is known as the H₂ mechanism. It is speculated that the results show the existence of a new growth mechanism.     

Behaviour of vicinal InP surfaces grown by MOVPE: exploitation of AFM images

InP substrates and epilayers grown by MOVPE have been studied by AFM. For different misorientation angles, we observed the surface of the substrate after annealing under phosphine (PH₃) and of the epilayers under different growth conditions such as growth temperature T_g and trimethylindium (TMI) partial pressure. After annealing the terrace width corresponds to the nominal value of misorientation angle measured by X-ray diffraction. We observed different topographies and roughnesses for the grown layers corresponding to different growth modes. We propose, taking into account the roughness of the surface, a calculation of the step height and terrace width. For 2D nucleation (θ ≤ 0.2° and T_g = 500°C) and step flow mode, the roughness is low while it is increased by step bunching (θ ≥ 0.5° and T_g ≥ 580°C). Moreover we have examined the surface morphology for different misorientation angles and determined the influence of growth conditions (growth temperature, indium partial pressure) on the growth mechanism. At T_g = 580°C the increase of the TMI partial pressure in the reactor enhances the step bunching and leads to larger terraces.     

The growth of Si/SiGe/Si structures for heterojunction bipolar transistor by gas source molecular beam epitaxy

Three n–p–n Si/SiGe/Si heterostructures with different layer thickness and doping concentration have been grown by a home-made gas source molecular-beam epitaxy (GSMBE) system using phosphine (PH₃) and diborane (B₂H₆) as n-and p-type in situ doping sources, respectively. Heterojunction bipolar transistors (HBTs) have been fabricated using these structures and a current gain of 40 at 300 K and 62 at 77 K have been obtained. The influence of thickness and doping concentration of the deposited layers on the current gain of the HBTs is discussed.     

Growth of Cr : LiCaAlF6 and Cr : LiSrAlF6 by the Czochralski method

Single crystals of chromium-doped LiCAF and LiSAF can be grown from nearly stoichiometric melts of the components LiF, AlF₃, CrF₃ and CaF₂ or SrF₂, respectively, by the Czochralski method. The optical quality of LiSAF crystals is usually better, as LiCAF contains more scattering particles. This different behavior can be attributed to different thermodynamic properties of both substances: The higher melting point of LiCAF leads to higher evaporation losses of volatile LiF and AlF₃. Moreover, LiCAF melts incongruently. The main problem during the growth and application of LiSAF crystals is the highly anisotropic thermal expansion that may lead to thermal cracking. The extreme hygroscopicity of the doping agent CrF₃ has to be considered for the growth of both substances.