Selective growth of InP on patterned,nonplanar InP substrates by low-pressure organometallic vapor phase epitaxy

The effects of indium sources, mask materials and etched mesa profiles on growth mor-phology of Fe-doped semi-insulating InP on patterned, nonplanar InP substrates were studied for low-pressure organometallic vapor phase epitaxy (OMVPE). The presence or absence of polycrystalline InP layers deposited on the mask was found to depend on the indium source but not on the mask material. Trimethylindium was found to be the preferable indium source for prevention of polycrystalline InP deposits on the mask. The etched mesa shape was found to dominate the final geometry of the OMVPE re-grown InP layer. Inclusion of an interfacial layer of 1.16 μm bandgap wavelength InGaAsP between the dielectric mask and InP substrate produces a favorable mesa shape by con-trolling the level of undercut during mesa etching, so as to form a smooth mesa profile. After selective regrowth of InP over the resulting mesa, a planar surface is typically achieved for mesa stripes with a mask overhang length as long as 2.6 μm and a mesa height as high as 4 μm.     

An investigation on hydride VPE growth and properties of semi-insulating InP:Fe

Growth of highly resistive semi-insulating InP : Fe has been achieved by the Hydride VPE technique in an ambient consisting mostly of nitrogen. After dealing with some thermodynamic considerations pertinent to InP:Fe growth, the experimental growth parameters are described. It is shown that various amounts of iron can be introduced into the InP crystal just by varying the temperature of the iron source. The crystal quality of the grown material is estimated to be good by etch pit density and x-ray diffraction analyses. Current-voltage behaviour and capacitance studies on ann ⁺-SI-n ⁺ structure are explained by invoking the theory of current injection in solids by Lampert and Mark: the experimental current densities at the threshold of each observed regime are compared with the theoretically derived current densities; in the absence of current injection, the measured capacitance is found to be the same as the geometrical capacitance.     

不同熔体配比的InP分析研究

原位磷注入合成 Ｌ Ｅ Ｃ晶体生长法可分别合成得到富铟、近化学配比或富磷的 Ｉｎ Ｐ熔体, 并进行 Ｌ Ｅ Ｃ晶体生长。我们对不同配比程度的材料进行了 Ｆ Ｔ Ｉ Ｒ、 Ｐ Ｌ、变温 Ｈａｌｌ等测试工作, 得到了一些相当有意义的结果, 对研究非掺杂半绝缘 Ｉｎ Ｐ提供了非常有意义的实验证据     

The inverted horizontal reactor: Growth of uniform InP and GaInAs by LPMOCVD

The uniformity of InP and GalnAs lattice matched to InP has been studied for three different types of horizontal reactors. Employing the conventional approach,i.e. the susceptor is positioned in the centre or at the bottom of the reactor cell with the wafer surface facing upward, the uniformity in film thickness and ternary composition perpendicular to the direction of gas flow could be substantially improved by using an obstacle which spreads the incoming gas over the entire width of the reactor. In the direction of flow however, a compositional grading of the GalnAs films was observed. This gradient could be avoided by using a novel design in which the substrate is located at the highest and hottest point of the reaction cell and facing downwards.     

Advances in LEC growth of InP crystals

By reducing the temperature gradients in the vicinity of the crystal-melt interface, 35-mm-diameter InP boules with much reduced dislocation densities have been grown by the liquid-encapsulated Czochralski technique. A reduction in the residual donor concentration of InP grown by this technique has been achieved by using In-rich charges prepared by adding elemental In to polycrystalline InP ingot material. Nominally undoped crystals with carrier concentrations as low as 1–2 x₄ 10¹⁵ Cm − 1 and 77 K mobilities as high as 7.0 × 10 cm² V⁻¹ s⁻¹ have been obtained. By growing doped crystals at increased seed or crucible rotation rates, short-range longitudinal variations in dopant concentration have been reduced to a few per cent, as determined by optical absorption measurements with a scanning CO₂ laser.     

Zn doping of InP, InAsP/InP, and InAsP/InGaAs heterostructures through metalorganic vapor phase diffusion (MOVPD)

Zinc incorporation by post-growth metalorganic vapor phase diffusion (MOVPD) is used to achieve high p-doping, which is desirable for the fabrication of photodiodes. Diethylzinc (DEZ) is used as precursor and Zn is diffused into InP and InAs_0.6P epitaxial layers grown by low pressure metalorganic vapor phase epitaxy (MOVPE) on different substrate orientations, enabling the investigation of the dislocation density on the Zn incorporation. Diffusion depths are measured using cleave-and-stain techniques, resistivity measurements, electrochemical profiling, and secondary ion mass spectroscopy. High hole concentrations of, respectively, 1.7 10¹⁹ and 6 10¹⁸ cm⁻³, are obtained for, respectively, InAs_0.60P and InP. The diffusion coefficients are derived and the Zn diffusion is used for the fabrication of lattice-mismatched planar PIN InAsP/InGaAs photodiodes.     

Selective area LPE growth and open tube diffusion in InGaAs/InP

Techniques are described in which selective chemical etching, localised LPE growth and localised diffusion in In_0.53Ga_0.47As and InP were carried out. Spun-on silica films were employed as masks in these processes and its performance was found to be comparable with pyrolytic or rf deposited films. Localised LPE growth of In_0.53Ga_0.47As and in-situ etching enabled well-controlled islands of In_0.53Ga_0.47As embedded in InP to be produced. Orientation dependent growth rates were also identified. An open-tube diffusion technique based on an LPE growth system has been successfully used for diffusion of Zn into InP and In_0.53 Ga_0.47As from Sn solutions. A strong variation of diffusion depth in InP with Zn concentration in Sn has been observed at low Zn concentrations but a constant depth is approached for Zn concentrations greater than ∼0.08 atomic fraction.     

Effects of pressure and temperature on epitaxial growth of InP on non-planar substrates using OMVPE

The effects of pressure and temperature on the epitaxial growth of InP on the mesastructured substrate have been investigated using OMVPE. At 550° C and 700 Torr, the reverse-mesa profile was observed. As the pressure decreases, the epitaxial growth profile changes from the reverse-mesa shape to the mesa shape. As the growth temperature increases, the growth profile follows the mesa-structured substrate even at high growth pressure. We propose that two major factors contributed to the formation of the reverse-mesa shape at low temperature and high pressure. We can explain the pressure effects on the epitaxial growth profile with these two factors at all growth temperatures ranging from 550 to 650° C. One factor is the growth rate enhancement on the (111)A facet compared to the growth rate on the (001) facet at low growth temperature, the other is the deficiency of constituent at the recess region of the epitaxial layer caused by reduced gas phase diffusivity at high pressure.     

Liquid encapsulated czochralski pulling of InP crystals

The growth of bulk indium phosphide crystals via liquid encapsulated Czochralski pulling from both stoichiometric and nonstoichiometric melts is described. Nominally un-doped crystals with carrier concentration N_D-N_A = 6 × 10¹⁵ cm⁻³ and Hall mobilities of 4510 cm²/Vsec at room temperature were grown. Also, we prepared Zn-or Cd-doped p-type crystals in the range 10¹⁶ ≤ N_A-N_D ≤ 10¹⁸ cm⁻³ with Hall mobilities ≤ 130 cm²/Vsec and Sn-doped n-type crystals in the range 4 × 10¹⁷ ≤ N_A-N_D ≤ 10¹⁸ cm^-3 with Hall mobilities ≤ 2400 cm²/Vsec. The dislocation density of LEC pulled InP crystals is typically ~ 10⁴ cm⁻².     

The growth of InP crystals from the melt

The growth of InP crystals from the melt is discussed on the basis of new data on the pTx relations for the In/P system in the vicinity of stoichiometric InP. The preparation of nominally undoped n-type material by the gradient-freeze technique with visual control of the seeding process is described. Zn- and Cd-doped p-type crystals were prepared in a modified almost-isothermal apparatus in order to obtain uniform stoichiometry and regular dopant distribution. The crystals were characterized in terms of their chemical purity, dopant distribution, physical defects and electrical properties.     

Electronic properties of low-temperature InP

We have investigated InP layers grown by low-temperature (LT) gas source molecular beam epitaxy. Using high-pressure hall effect measurements, we have found that the electronic transport in the LT epilayers is determined by the presence of the dominant deep donor level which is resonant with the conduction band (CB) located 120 meV above the CB minimum (E_CB). We find that its pressure derivative is 105 meV/GPa. This large pressure derivative reveals the highly localized character of the donor which via auto-ionization gives rise to the high free electron concentration n. From the deep level transient spectroscopy and Hall effect measurements, we find two other deep levels in the band gap at E_CB−0.23 eV and E_CB−0.53 eV. We assign the two levels at E_CB 0.12 eV and E_CB−0.23 eV to the first and second ionization stages of the phosphorus antisite defect.     

Compositional non-uniformities in selective area growth of GaInAs on InP grown by OMVPE

Selective area epitaxial growth of Ga_0.47In_0.53As on InP substrates patterned with silicon nitride was done by low pressure organometallic vapor phase epitaxy. Good surface morphology and clean side walls of the epitaxial layers were obtained in most of the areas of selective GalnAs growth. However, both GaAs incorporation and InAs incorporation increased near the edges of the selective growth areas due to the extra flux of Gacontaining and In-containing species migrating on the surface of silicon nitride. The increase in InAs incorporation was found at a higher rate when the adjacent silicon nitride area was large, hence, cross-hatching appeared near the edges. A characteristic length of adjacent silicon nitride seemed to be connected with the enhanced InAs incorporation, which was about 40μm at 600°. The non-uniformities in composition appeared in all wafers grown in the temperature range between 570 and 650°.     

Photoluminescence characterization of solution and lec grown InP

Low temperature photoluminescence and electrical measurements on bulk grown polycrystalline and single crystal InP indicate the purity and crystal perfection to be equivalent to that of LPE and VPE samples. This work was supported in part by the U.S. Army Research Office, Research Triangle Park, N.C.; Defense Research Projects Agency, Arlington, VA; and Rome Air Development Center, Hanscom Air Force Base, Massachusetts.     

Metalorganic vapor phase epitaxial growth,characterization and annealing experiments on InP doping superlattices

InP doping superlattices (DSLs) were grown by atmospheric pressure metalorganic vapor phase epitaxy (MOVPE) and their stability was examined by annealing at high temperatures. Diethylzinc (DEZ) and H₂S were used asp- andn-type doping sources, respectively. Photoluminescence (PL) measurements performed on as grown layers show a shift of the main emission peak with increasing excitation power in very good agreement with theoretical models. A comparison of the PL results between these structures and the annealed samples show that even at very high temperatures (up to 850° C) the tunability of the effective bandgap of the annealed superlattices is possible, although less pronounced than for the as grown layers. This is due to diffusion of the dopants, into adjacent layers and partial compensation of each other. Secondary ion mass spectrometry (SIMS) done on the as grown and annealed samples shows that only the Zn atoms diffuse. Diffusion coefficients obtained from the SIMS profiles give values in the range 1 × 10⁻¹⁴ <D < 9 × 10⁻¹⁴ cm²/s, still smaller than other published values estimated on layers, which did not suffer any treatment. This shows the high quality and stability of our layers even at high temperatures.     

Electrical properties of the hydrogen defect in InP and the microscopic structure of the 2316 cm−1 hydrogen related line

We have studied the microscopic structure of a hydrogen related defect by measuringits vibrational IR absorption at 2315.6 cm⁻¹ in bulk InP crystals doped with deuterium. In contrast to the spectrum observed in nominally undoped samples (with only hydrogen present), the 2315.6 cm⁻¹ line in these samples containing both hydrogen and deuterium is split into at least three components approximately 0.5 cm⁻¹ apart. This can be explained if the defect contains more than one hydrogen atom; the additional lines are caused by mixed vibrational modes containing various combinations of hydrogen and deuterium. We present evidence that the formation of defect-hydrogen complexes leads to creation of a shallow intrinsic donor which can be annihilated under certain annealing conditions.     

国外InP HEMT和InP HBT的发展现状及应用

在毫米波段,InP基器件由于其具有高频、高功率、低噪声及抗辐射等特点,成为人们的首选,尤其适用于空间应用.InP HEMT和InP HBT已在卫星、雷达等军事应用中表现出了优异的性能.分别介绍了InP HEMT和InP HBT器件及电路的发展现状,现在能达到的最高性能及主要生产公司等,其中InP HEMT又分别按低噪声和功率进行了详细介绍.介绍了它们在军事上的主要应用,以具体的应用实例介绍了在卫星相控阵雷达系统天线中的T/R模块中、航天器和地面站的接收机中、以及雷达和通信系统中的应用情况、达到的性能及可靠性等.并根据国外InP器件和电路的发展现状总结了其未来发展趋势.     

Study on microscopic defects in Fe-Doped InP single crystals

Effect of crystal growth conditions on the density of microscopic defects, observed on polished Fe-doped InP LEC single crystal wafers, has been investigated by an interference contrast microscope and a laser scattering tomography (LST) system. It was found that microscopic defects have no correlation with dislocations. Crystal rotation speed affects the density of microscopic defects. In addition, the density depends on the time that the InP melt is held in the molten state before crystal growth. On the other hand, it was found that the H₂O concentration in B₂O₃ has no correlation with the generation of microscopic defects. The relationship between the microscopic defects and the stoichiometry of grown crystals was investigated by coulometric titration analysis. Since the density of microscopic defects is reduced as the indium concentration decreases, it is speculated that their origin is indium or indium oxide.     

Improved selective growth of InP around dry-etched mesas by metalorganic chemical vapor deposition at low growth temperature

A comparative study has been carried out regarding selective embedding growth of InP by metalorganic chemical vapor deposition (MOCVD) around dry-etched mesas, using two types of reactors: a conventional horizontal type and a highspeed rotating-susceptor type. In the case of the conventional horizontal-type MOCVD, overgrowth on the mask was observed when the growth temperature was low (600°C). On the other hand, an almost planar grown surface without such overgrowth was achieved by using the high-speed rotating-susceptor MOCVD for a wide range of growth temperatures, especially even at a low growth temperature of 580°C. Regarding the high-speed rotating-susceptor MOCVD, we have also investigated the effects of dopants on the growth behaviors and have found a remarkable difference between n-type S-doped and p-type Zn-doped InP in the growth behaviors. The mechanism for suppressing overgrowth in case of the high-speed rotating-susceptor MOCVD, as well as the cause for the different effects between the dopants, are discussed.     

MLEK crystal growth of (100) indium phosphide

We have used a combined magnetic liquid encapsulated Kyropoulos/Czochralski (MLEK/ MLEC) technique to produce twin-free indium phosphide (InP) crystals. This technique has advantages over the standard LEC method used for commercial production of InP. By stabilizing convective flows with a magnetic field and controlling the angle between solid and liquid, one can grow large diameter twin-free (100) InP crystals; they are shaped with a flat top as is typical for Kyropoulos growth, and then pulled from the magnetically stabilized melt as in Czochralski growth. This shaping method has the benefit of maximizing the number of single crystal wafers which can be sliced from the boule. MLEK InP growth is distinguished from other methods such as LEC and MLEC with respect to solid-liquid interface shape, dislocation density, and impurity distribution. This process has demonstrated that twin-free InP (100) crystals can be consistently grown.     

Temporally resolved selective regrowth of InP around [110] and [-110] mesas

Temporally resolved selective regrowth of InP around reactive ion etched [110] and [-110] directional mesas is studied by hydride vapor phase epitaxy at the growth temperatures of 600, 650, 685, and 700°C. The regrowth profiles are strikingly different depending upon the mesa orientation. The results are interpreted by invoking the difference in the bonding configurations of these mesas as well as the growth facility in a direction leading to the largest reduction of dangling bonds under the growth conditions. Various emerging planes during regrowth are identified and arehhl planes with initial values of 1/h ≤ 3 but ≥ 3 as the planarization is approached. Initial lateral growth defined as the growth away from the mesa at half of its height in the very first minute is a decreasing function of temperature when plotted as Arrhenius curves. Such a behavior is attributed to the exothermicity of the reaction and to an enhanced pyrolysis of PH₃ to P₂. The lateral growth rate is much larger than that on the planar substrate. This should be taken into account when regrowth of a doped layer (e.g. InP:Fe or InP:Zn) is carried out to fabricate a buried heterostructure device since the dopant concentration can be very much lower than the one optimized on the planar substrates.