MOVPE growth of GaInP/GaAs hetero-bipolar-transistors using CBr4 as carbon dopant source

Carbon doping of GaAs with carbon tetrabromide (CBr₄) in low pressure MOVPE has been investigated and applied to the fabrication of GaInP/GaAs HBTs. Especially the hydrogen incorporation and the associated acceptor passivation has been studied. The hydrogen found in single GaAs:C layers is predominantly incorporated during cooling the sample under AsH₃ after growth, n-Type capping layers can block this H indiffusion and GaAs:C base layers in HBTs show much lower H concentrations than GaAs:C single layers without a cap. A further reduction of acceptor passivation is possible by optimization of the growth procedure. First HBTs processed from layers with a base that was doped using CBr₄ show promising DC and HF performance (β = 45, for 2 × 20 μm² devices).     

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.     

Demonstration of the N2 carrier process for LP-MOVPE of III/V''s

The suitability of an N₂ carrier in LP-MOVPE of GaInAs/InP device structures and for the growth of (Al)GaInP is investigated for the first time. Al-free GaInAs/InP HEMTs and MSM photodetectors exhibit cutoff frequencies of f_t = 135 GHz and f_max = 200 GHz and a bandwidth of 16 GHz and responsivity of 0.27 A/W, respectively. AlGaInP and GaInP layers deposited using the optimized growth conditions showed excellent structural, optical and homogeneity properties. For example X-ray diffractograms with FWHMs as low as 15–16 arcsec for 1 μm thick layers and 300 K photoluminescence mappings over full 2 inch wafers with standard deviations of ±0.23 and ±0.26 nm were obtained for both materials.     

Magnesium-doped InGaAs using (C2H5C5H4)2Mg: application to InP-based HBTs

Heavily magnesium-doped p-type-InGaAs layers on InP(100) substrates were successfully grown, for the first time, by low-pressure metalorganic chemical vapor deposition (MOCVD) using bis-ethylcyclopentadienyl-magnesium, (C₂H₅C₅H₄)₂Mg (EtCp₂Mg), as organometallic precursor for the Mg. It was experimentally verified that the room-temperature hole concentration of Mg into InGaAs increased with increase of the V/III ratio and decrease of the growth temperature. A maximum hole concentration of over 4 × 10¹⁹ cm⁻³ was obtained. The diffusion coefficient of Mg in InGaAs was experimentally derived to be 10⁻¹² cm²/s at 800°C, which was comparable to that of Be. Finally, InP/InGaAs heterojunction bipolar transistors (HBTs) with Mg-doped bases were fabricated successfully. Measured maximum current gain was about 320 with a 90 nm thick base and a sheet resistance of the base layer of 1.28 kΩ/sq.     

Selective epitaxial growth by UHV-CVD using Si2H6 and Cl2

The conditions under which selective epitaxial growth (SEG) is achieved in UHV-CVD with Si₂H₆ are determined by the amount of Si₂H₆ molecules being supplied, and there is a critical gas supply amount (F_c) beyond which SEG will break down and lose its selectivity. The value of F_c is itself determined by two factors, growth temperature and the material used for masking, i.e. SiO₂, Si₃N₄. We found that this limiting factor of F_c was increased through the addition of a small amount of Cl₂, and that after such addition, the resulting decrease in growth rate is minimal.     

RHEED studies of the growth of Si(001) by gas source MBE from disilane

The growth of Si(001) from a gas source molecular beam epitaxy system (Si-GSMBE) using disilane (Si₂H₆) was investigated using reflection high-energy electron diffraction (RHEED). The surface reconstructions occurring between 100 and 775°C were studied as a function of both substrate temperature and surface coverage. We report the first observation of (2x2) and c(4x4) reconstructions during growth at substrate temperatures near 645°C using Si₂H₆. All growth was found to be initiated by the formation of three-dimensional (3D) islands which coalesced at substrate temperatures above 600°C. The surface reconstruction was found to change from a disordered to an ordered (2x1)+(1x2) structure at 775°C via intermediate (2x2) and c(4x4) phases. Thereafter, growth was found to proceed in a 2D layer-by-layer fashion, as evidenced by the observation of RHEED intensity oscillations. This technique has been used, for the first time, to calibrate growth rates during Si-GSMBE. The intensity oscillations were measured as a function of both substrate temperature and incident beam flux. Strong and damped oscillations were observed between 610 and 680°C, in the two-dimensional growth regime. At higher temperatures, growth by step propagation dominated while at lower temperatures, growth became increasingly three-dimensional and consequently oscillations were weak or absent. Similarly, there was a minimum flux limit ( <0.16 SCCM), below which no oscillations were recorded.     

Photoassisted growth and nitrogen doping of ZnSe

ZnSe was grown on GaAs(100) substrates by photoassisted MOVPE using the precursors dimethylzinc-triethylamine (DMZn-TEN) and ditertiarybutylselenide (DtBSe). The optimal growth temperature was T_g = 300°C. Above 300°C no enhancement of growth rate was observed under illumination. Furthermore, nitrogen doping experiments were performed using phenylhydrazine, allylamine and tert-butylamine as nitrogen precursors. Nitrogen concentrations up to 10¹⁹ cm⁻³ (SIMS) were achieved with input flow ratios as low as [PhHz]/[Se] = 4 × 10⁻⁴. All as-grown samples were highly compensated. Successful nitrogen incorporation was also observed with allylamine. However, the use of tert-butylamine together with the adduct compound DMZn-TEN showed no incorporation of nitrogen.     

p-Type GaAs doped by diiodomethane (CI2H2) in molecular beam epitaxy, metalorganic molecular beam epitaxy, and chemical beam epitaxy

Highly p-type carbon-doped GaAs epitaxial layers were obtained using diiodomethane (CI₂H₂) as a carbon source. In the low 10¹⁹ cm⁻³ range, almost all carbon atoms are electrically activated and at 9×10¹⁹ cm⁻³, 91% are activated. The carbon incorporation efficiency in GaAs layers grown by metalorganic molecular beam epitaxy (MBE) and chemical beam epitaxy (CBE) is lower than that by MBE due to the site-blocking effect of the triethylgallium molecules. In addition, in CBE of GaAs using tris-dimethylaminoarsenic (TDMAAs), the carbon incorporation is further reduced, but it can be increased by cracking TDMAAs. Annealing studies indicate no hydrogenation effect.     

Properties of (Ga0.47In0.53)As epitaxial layers grown by metalorganic vapor phase epitaxy (MOVPE) using alternative arsenic precursors

In this study, the use of novel, liquid, organic arsenic precursors as substitutes for the highly toxic hydride gas arsine (AsH₃) in low pressure metalorganic vapor phase epitaxy (LP-MOVPE) of (GaIn)As lattice matched on InP has been investigated. The model precursors out of the classes of (alkyl)3-nAsH_n (n = 0,1,2) are tertiarybutyl arsine (TBAs), ditertiarybutyl arsine (DitBAsH) and diethyltertiarybutyl arsine (DEtBAs). The MOVPE growth has been investigated in the temperature range of 570–650°C using V/III ratios from 2 to 20. The obtained epitaxial layer quality as examined by means of optical and scanning electron microscopy (SEM), high resolution double crystal X-ray diffraction, temperature-dependent van der Pauw-Hall, as well as photoluminescence (PL) measurements, will be compared for the different source molecules. Under optimized conditions almost uncompensated n-type (GaIn)As layers with carrier concentrations below 1 × 10¹⁵ cm⁻³ and corresponding mobilities above 80 000 cm²/V · s have been realized. For TBAs and DitBAsH in combination with the corresponding P sources TBP and DitBuPH, respectively, we have worked out a process parameter area for the growth of layers with device quality, as proven by the realization of a pin-detector structure.     

Growth of GaAs/AlGaAs HBTs by MOMBE (CBE)

In this paper, we will discuss how the unique growth chemistry of MOMBE can be used to produce high speed GaAs/AlGaAs heterojunction bipolar transistors (HBTs). The ability to grow heavily doped, well-confined layers with carbon doping from trimethylgallium (TMG) is a significant advantage for this device. However, in addition to high p-type doping, high n-type doping is also required. While elemental Sn can be used to achieve doping levels up to 1.5×10¹⁹ cm^-3, severe segregation limits its use to surface contact layers. With tetraethyltin (TESn), however, segregation does not occur and Sn doping can be used throughout the device. Using these sources along with triethylgallium (TEG), trimethylamine alane (TMAA), and AsH₃, we have fabricated Npn devices with 2 μm×10 μm emitter stripes which show gains of ≥ 20 with either ƒ_t = 55 GHz and ƒ_max = 70 GHz or ƒ_t = 70 GHz and ƒ_max = 50 GHz, depending upon the structure. These are among the best RF values reported for carbon doped HBTs grown by any method, and are the first reported for an all-gas source MOMBE process. In addition, we have fabricated a 70 transistor decision circuit whose performance at 10 Gb/s equals or exceeds that of similar circuits made from other device technologies and growth methods. These are the first integrated circuits reported from MOMBE grown material.     

Metalorganic vapor-phase epitaxy of III/V phosphides with tertiarybutylphosphine and tertiarybutylarsine

Indium phosphide, gallium arsenide phosphide, and aluminum indium phosphide have been deposited by metalorganic vapor-phase epitaxy using tertiarybutylphosphine and tertiarybutylarsine. The effects of growth temperature and V/III ratio on the amount of silicon, sulfur, carbon, and oxygen in InP have been determined. Minimum incorporation was observed at 565 °C and a V/III ratio of 32. In this case, the material contained a background carrier concentration of 2.7×10¹⁴ cm⁻³, and the Hall mobilities were 4970 and 135,000 cm²/V s at 300 and 77 K. The oxygen contamination in AlInP was found to be only 9.0×10¹⁵ cm⁻³ for deposition at 650 °C and a V/III ratio of 35. The relative distribution of arsenic to phosphorus in GaAs_yP_1−y was determined at temperatures between 525 and 575 °C. The distribution coefficient [(N_As/N_P)_film/(P_TBAs/P_TBP)_gas] ranged from 25.4 to 8.4, and exhibited an Arrhenius relationship with an apparent activation energy of 1.2 eV.     

Influence of oxygen contamination during Si low presure vapour phase epitaxy on epitaxial layer quality

The influence of oxygen contamination on Si low pressure vapour phase epitaxy (LPVPE) at 800°C in the SiCl₂H₂−H₂ system has been investigated. O₂ was added intentionally with partial pressures between 10⁻⁸ and 2×10⁻⁴ mbar. The quality of the epitaxially grown silicon layers was determined by comparing surface morphology, defect density, Schottky diode characteristics and SIMS measurements. These four parameters are correlated and they reveal a drastic decrease in epitaxial layer quality for O₂ pressures above 15×10⁻⁶ mbar. The critical oxygen pressure which has been until now considered as a limit for epitaxial growth can therefore be exceeded by one order of magnitude.     

Electronic traps in mixed Si1−xGexO2 films

Thermally stimulated luminescence (TSL) and infrared (IR) spectroscopy were measured in plasma grown Si_1−xGe_xO₂ (x=0, 0.08, 0.15, 0.25, 0.5) with different thicknesses (12–40 nm). A comparison with the TSL properties of thermally grown SiO₂ and GeO₂ was also performed. A main IR absorption structure was detected, due to the superposition of the peaks related to the asymmetric O stretching modes of (i) Si–O–Si (at ≈1060 cm⁻¹) and (ii) Si–O–Ge (at 1001 cm⁻¹). Another peak at ≈860 cm⁻¹ was observed only for Ge concentrations, x>0.15, corresponding to the asymmetric O stretching mode in Ge–O–Ge bonds. A TSL peak was observed at 70°C, and a smaller structure at around 200°C. The 70°C peak was more intense in all Ge rich layers than in plasma grown SiO₂. Based on the thickness dependence of the signal intensity we propose that at Ge concentrations 0.25x0.5 TSL active defects are localised at interfacial regions (oxide/semiconductor, Ge poor/Ge rich internal interface, oxide external surface/atmosphere). Based on similarities between TSL glow curves in plasma grown Si_1−xGe_xO₂, thermally grown GeO₂ and SiO₂ we propose that oxygen vacancy related defects are trapping states in Si_1−xGe_xO₂ and GeO₂.     

Growth of heavily C-doped GaAs/AlGaAs MQW structures by MOVPE for 2–3 μm normal incidence photodetectors

The growth and intersubband optical properties of high quality heavily doped p-type GaAs/AlGaAs multiple quantum well (MQW) structures are reported. The MQWs were fabricated by the atmospheric pressure metalorganic vapor phase epitaxy process using liquid CCl₄ to dope the wells with C acceptors (N_a ≈ 2 × 10¹⁹ cm⁻³). A constant growth temperature was maintained for the entire structure while different V/III ratios were used for the well and barrier regions. By this process it is possible to achieve both high C doping densities in the wells and to simultaneously obtain good quality AlGaAs barriers. Fourier transform infrared spectroscopy measurements on heavily doped 10-period MQW structures reveal a new absorption peak at 2 μm with an effective normal incidence absorption coefficient of 4000 cm⁻¹. Photocurrent measurements on mesa-shaped diodes show a corresponding peak at 2.1 μm. The photodiodes exhibit a symmetrical current-voltage characteristic and a low dark current, which are indicative of a high quality MQW structure and a well-controlled C doping profile. The 2 μm absorption represents the shortest wavelength ever reported for any GaAs/AlGaAs or InGaAs/AlGaAs MQW structure and should be very useful for implementing multicolor infrared photodetectors.     

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.     

Formation of oxygen-deficient type structural defects and state of ions in SiO2 glasses implanted with transition metal ions

The properties and concentrations of oxygen-deficient type structural defects in type III SiO₂ glasses implanted with Ti⁺, Cr⁺, Mn⁺, Fe⁺, or Cu⁺ to doses from 0.5×10¹⁶ to 6×100¹⁶ ions/cm² at an energy of 160 keV have been measured by using vacuum UV and EPR spectroscopies. An intense absorption band centered around 7.5 eV is observed in all the samples except for Cu-implanted ones and is attributed primarily to Si---Si homo-bonds with the bond distance close to that of the Si₂H₆ molecule. The homo-bond and implanted ion concentrations are of the same order of magnitude in the implanted layers. An E′ type center associated with the homo-bond is observed in all the samples except for Cu-implanted ones. Anomalous behaviors of the Cu-implanted samples are attributed to the formation of Cu-colloids. An enhanced formation of metallic particles or colloids is suggested for the samples implanted with Cr, Mn or Fe to doses higher than 3×10¹⁶ ions/cm².     

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.     

TiO2-SiO2 monolithic glass formation from sol-gel

This study demonstrates that hydrolysis should be carried out in a step manner in gel synthesis. The key to the increase in the amount of water added is the control of the hydrolysis rate of Ti(OC₄H₉)₄. The hydrolysis of Si(OC₂H₅)₄ can be carried out at about 75°C. The amount of added water (γ_WI), which varied with TiO₂ content (in mol%), was about 64–88% of the total amount of added water. The hydrolysis reaction should be performed at room temperature while Ti(OC₄H₉)₄ is added. The total amount of added water (γ_W) is related to the amount of solvent (R). For example, if TiO₂ is 40mol%, γ_W will vary from 3.2 to 8.0 when R varies from 0.8 to 2.0. The amount of added water was affected by the distribution of solvent in the metal alkoxides. The amount of added water can be increased when R_Si(OC2H5)4 = 1, R_Ti(OC4H9)4 > 1. The rate of rise in temperature of the thermolysis of the dried gel should be less than 10°C per hour, and the heat treatment temperatyre is related to the TiO₂ content (in mol%). Gel glasses without devitrification can only be obtained by thermolysis at 600°C from the gel with no less than 20 mol% TiO₂.     

Structural and electrical properties of GaSb, AlGaSb and their heterostructures grown on GaAs by metalorganic chemical vapor deposition

A systematic study of structural and electrical properties of GaSb and AlGaSb grown on GaAs by metalorganic chemical vapor deposition is reported. In general, the results obtained from surface morphologies, X-ray linewidths and Hall properties are consistent with each other and indicate that the optimal growth conditions for GaSb are at 525°C around V/III = 1. A highest hole mobility of 652 cm²/V · s at RT (3208 cm²/V · s at 77 K) and a lowest concentration of 2.8 × 10¹⁶ cm⁻³ (1.2 × 10¹⁵ cm⁻³ at 77 K) were obtained for GaSb grown under this optimal condition. Compared to the GaSb growth, a smaller V/III ratio is needed for the AlGaSb growth to protect the surface morphology. When Al was incorporated into GaSb growth, mobility decreased and carrier concentration increased sharply. The AlGaSb grown at 600°C had a background concentration about one order of magnitude lower than the AlGaSb grown at 680°C. Room-temperature current-voltage characteristics of GaSb/Al_xGa_{1 − x}Sb/GaSb show a rectifying feature when Al composition x is higher than 0.3, suggesting a valence-band discontinuity at the AlGaSb/GaSb interface. A leakage current much higher than the value predicted by the thermionic emission theory is observed at 77 K, presumably due to a large number of dislocations generated by the huge lattice mismatch between GaSb and GaAs.     

Heavily carbon-doped p-type (In)GaAs grown by gas-source molecular beam epitaxy using diiodomethane

Heavily carbon-doped p-type In_xGa_1−xAs (0≤x<0.49) was successfully grown by gas-source molecular beam epitaxy using diiodomethane (CH₂I₂), triethylindium (TEIn), triethylgallium (TEGa) and AsH₃. Hole concentrations as high as 2.1×10²⁰ cm⁻³ were achieved in GaAs at an electrical activation efficiency of 100%. For In_xGa_1−xAs, both the hole and the atomic carbon concentrations gradually decreased as the InAs mole fraction, x, increased from 0.41 to 0.49. Hole concentrations of 5.1×10¹⁸ and 1.5×10¹⁹ cm⁻³ for x = 0.49 and x = 0.41, respectively, were obtained by a preliminary experiment. After post-growth annealing (500°C, 5 min under As₄ pressure), the hole concentration increased to 6.2×10¹⁸ cm⁻³ for x = 0.49, probably due to the activation of hydrogen-passivated carbon accepters.