Metalorganic chemical vapor deposition of HgCdTe for photodiode applications

Metalorganic chemical vapor depositon (MOCVD) in situ growth of p-on-n junctions for long wavelength infrared (LWIR) and medium wavelength infrared (MWIR) photodiodes is reported. The interdiffused multilayer process was used for the growth of the HgCdTe junctions on CdTe and CdZnTe substrates. The n-type region was grown undoped while the p-type layer was arsenic doped using tertiarybutylarsine. Following a low temperature anneal in Hg vapor, carrier densities of (0.2-2) x 10¹⁵ cm³ and mobilities of (0.7-1.2) x 10⁵ cm²/V-s were obtained for n-type LWIR (x ~ 0.22) layers at 80K. Carrier lifetimes of these layers at 80 K are ~l-2 μs. For the p-type region arsenic doping was controlled in the range of (1-20) x 10¹⁶ cm^-3. Arsenic doping levels in the junctions were determined by calibrated secondary ion mass spectroscopy depth profile measurements. Composition and doping of the p-on-n heterojunctions could be independently controlled so that the electrical junction could be located deeper than the change in the composition. The graded composition region between the narrow and wide (x = 0.28-0.30) bandgap regions are 1–2 μm depending on the growth temperature. Backside-illuminated variable-area circular mesa photodiode arrays were fabricated on the grown junctions as well as on ion implanted n-on-p MWIR junctions. The spectral responses are classical in shape. Quantum efficiencies at 80K are 42–77% for devices without anti-reflection coating and with cutoff wavelengths of 4.8–11.0 μm. Quantum efficiencies are independent of reverse bias voltage and do not decrease strongly at lower temperatures indicating that valence band barrier effects are not present. 80K R_oA of 15.9 Ω-cm² was obtained for an array with 11.0 μm cutoff. Detailed measurements of the characteristics of the MOCVD in situ grown and implanted photodiodes are reported.     

Metalorganic chemical vapor deposition of HgCdTe p/n junctions using arsenic and iodine doping

We report new results on metalorganic chemical vapor deposition (MOCVD)in situ growth of long wavelength infrared (LWIR) P-on-n and medium wavelength infrared (MWIR) n-on-P HgCdTe heterojunction photodiodes using the interdiffused multilayer process (IMP). The n-type regions are doped with iodine using the precursor ethyl iodide (El). I-doped HgCdTe using El has mobilities higher than that obtained on undoped background annealed films and are comparable to LPE grown In-doped HgCdTe. The p-type layers are doped with arsenic from either tertiarybutylarsine (TBAs) or a new precursor,tris-dimethylaminoarsenic (DMAAs). The substrates used in this work are lattice matched CdZnTe oriented (211)B or (100)4°→«110». Junction quality was assessed by fabricating and characterizing backside-illuminated arrays of variable-area circular mesa photodiodes. This paper presents four new results. First, carrier lifetimes measured at 80K on arsenic doped single HgCdTe layers are generally longer for films doped from the new precursor DMAAs than from TBAs. Second, we present data on the first P-on-n HgCdTe photodiodes grownin situ with DMAAs which have R₀A products limited by g-r current at 80K for λ_co = 7–12 μm, comparable to the best R₀A products we have achieved with TBAs. Third, we report the first experimental data on a new HgCdTe device architecture, the n-on-P heterojunction, with a wide gap p-type layer which allows radiation incident through the substrate to be absorbed in a narrower gap n-type layer, thereby eliminating interface recombination effects. With the n-on-P architecture, MWIR photodiodes were obtained reproducibly with classical spectral response shapes, high quantum efficiencies (70-75%) and R₀A products above 2 x 10⁵ ohm-cm² for λ_co = 5.0 μm at 80K. Fourth, we report 40K data for LWIR P-on-n HgCdTe heterojunction photodiodes (using TBAs), with R₀A values of 2 x 10⁴ ohm-cm² for λ_co = 11.7 μm and 5 x 10⁵ ohm-cm² for λ_co - 9.4 μm. These are the highest R₀A values reported to date for LWIR P-on-n heterojunctions grownin situ by MOCVD.     

The interface of metalorganic chemical vapor deposition-CdTe/HgCdTe

The metalorganic chemical vapor deposition (MOCVD) growth of CdTe on bulk n-type HgCdTe is reported and the resulting interfaces are investigated. Metalinsulator-semiconductor test structures are processed and their electrical properties are measured by capacitance-voltage and current-voltage characteristics. The MOCVD CdTe which was developed in this study, exhibits excellent dielectric, insulating, and mechano-chemical properties as well as interface properties, as exhibited by MIS devices where the MOCVD CdTe is the single insulator. Interfaces characterized by slight accumulation and a small or negligible hysteresis, are demonstrated. The passivation properties of CdTe/ HgCdTe heterostructures are predicted by modeling the band diagram of abrupt and graded P-CdTe/n-HgCdTe heterostructures. The analysis includes the effect of valence band offset and interface charges on the surface potentials at abrupt hetero-interface, for typical doping levels of the n-type layers and the MOCVD grown CdTe. In the case of graded heterojunctions, the effect of grading on the band diagram for various doping levels is studied, while taking into consideration a generally accepted valence band offset. The MOCVD CdTe with additional pre and post treatments and anneal form the basis of a photodiode with a new design. The new device architecture is based on a combination of a p-on-n homojunction in a single layer of n-type HgCdTe and the CdTe/HgCdTe heterostructure for passivation.     

Copper outdiffusion from CdZnTe substrates and its effect on the properties of metalorganic chemical vapor deposition-grown HgCdTe

We report that HgCdTe (MCT) epilayers grown by metalorganic chemical vapor deposition can be doped by copper outdiffusing from CdZnTe substrates. The copper content in the substrates was determined by the choice of the purity of the starting raw materials. Copper diffusion could be controlled by adjusting the tellurium precipitate density in the substrates. Growing on substrates with a high concentration of tellurium precipitates resulted in low doped MCT epilayers whereas a high copper concentration was found in MCT grown on substrates with a lower concentration of tellurium precipitates. A mechanism whereby tellurium precipitates getter copper during the post-growth cooldown of CdZnTe boules and trap copper in the substrates is proposed.     

Independently accessed back-to-back HgCdTe photodiodes: A new dual-band infrared detector

We report the first data for a new two-color HgCdTe infrared detector for use in large dual-band infrared focal plane arrays (IRFPAs). Referred to as the independently accessed back-to-back photodiode structure, this novel dual-band HgCdTe detector provides independent electrical access to each of two spatially collocated back-to-back HgCdTe photodiodes so that true simultaneous and independent detection of medium wavelength (MW, 3–5 μm) and long wavelength (LW, 8–12 μm) infrared radiation can be accomplished. This new dual-band detector is directly compatible with standard backside-illuminated bump-interconnected hybrid HgCdTe IRFPA technology. It is capable of high fill factor, and allows high quantum efficiency and BLIP sensitivity to be realized in both the MW and LW photodiodes. We report data that demonstrate experimentally the key features of this new dual-band detector. These arrays have a unit cell size of 100 x 100 μm², and were fabricated from a four-layer p-n-N-P HgCdTe film grown in situ by metalorganic chemical vapor deposition on a CdZnTe substrate. At 80K, the MW detector cutoff wavelength is 4.5 μm and the LW detector cutoff wavelength is 8.0 μm. Spectral crosstalk is less than 3%. Data confirm that the MW and LW photodiodes are electrically and radiometrically independent.     

Dislocation profiles in HgCdTe(100) on GaAs(100) grown by metalorganic chemical vapor deposition

We studied dislocation etch pit density (EPD) profiles in HgCdTe(lOO) layers grown on GaAs(lOO) by metalorganic chemical vapor deposition. Dislocation profiles in HgCdTe(lll)B and HgCdTe(lOO) layers differ as follows: Misfit dislocations in HgCdTe(lll)B layers are concentrated near the HgCdTe/CdTe interfaces because of slip planes parallel to the interfaces. Away from the HgCdTe/CdTe interface, the HgCdTe(111)B dislocation density remains almost constant. In HgCdTe(lOO) layers, however, the dislocations propagate monotonically to the surface and the dislocation density decreases gradually as dislocations are incorporated with increasing HgCdTe(lOO) layer thicknesses. The dislocation reduction was small in HgCdTe(lOO) layers more than 10 μm from the HgCdTe/CdTe interface. The CdTe(lOO) buffer thickness and dislocation density were similarly related. Since dislocations glide to accommodate the lattice distortion and this movement increases the probability of dislocation incorporation, incorporation proceeds in limited regions from each interface where the lattice distortion and strain are sufficient. We obtained the minimum EPD in HgCdTe(100) of 1 to 3 x 10⁶ cm^-2 by growing both the epitaxial layers more than 8 μm thick.     

A CdTe passivation process for long wavelength infrared HgCdTe photo-detectors

Passivant-Hg_1−xCd_xTe interface has been studied for the CdTe and anodic oxide (AO) passivants. The former passivation process yields five times lower surface recombination velocity than the latter process. Temperature dependence of surface recombination velocity of the CdTe/n-HgCdTe and AO/n-HgCdTe interface is analyzed. Activation energy of the surface traps for CdTe and AO-passivated wafers are estimated to be in the range of 7–10 meV. These levels are understood to be arising from Hg vacancies at the HgCdTe surface. Fixed charge density for CdTe/n-HgCdTe interface measured by CV technique is 5×10¹⁰ cm⁻², which is comparable to the epitaxially grown CdTe films. An order of magnitude improvement in responsivity and a factor of 4 increase in specific detectivity (D*) is achieved by CdTe passivation over AO passivation. This study has been conducted on photoconductive detectors to qualify the CdTe passivation process, with an ultimate aim to use it for the passivation of p-on-n and n-on-p HgCdTe photodiodes.     

Metalorganic chemical vapor deposition and characterization of ZnO materials

Zinc oxide is attracting growing interest for potential applications in electronics, optoelectronics, photonics, and chemical and biochemical sensing, among other applications. We report herein our efforts in the growth and characterization of p- and n-type ZnO materials by metalorganic chemical vapor deposition (MOCVD), focusing on recent nitrogen-doped films grown using diethyl zinc as the zinc precursor and nitric oxide (NO) as the dopant. Characterization results, including resistivity, Hall measurements, photoluminescence, and SIMS, are reported and discussed. Electrical behavior was observed to be dependent on illumination, atmosphere, and heat treatment, especially for p-type material.     

Direct growth of CdTe on (100), (211), and (111) Si by metalorganic chemical vapor deposition

CdTe epilayers were grown directly on (100), (211), and (111) silicon substrates by metalorganic chemical vapor deposition (MOCVD). The crystallinity and the growth orientation of the CdTe film were dependent on the surface treatment of the Si substrate. The surface treatment consisted of exposure of the Si surface to diethyltelluride (DETe) at temperatures over 600°C prior to CdTe growth. Direct growth of CdTe on (100) Si produced polycrystalline films whereas (lll)B single crystals grew when Si was exposed to DETe prior to CdTe growth. On (211) Si, single crystal films with (133)A orientation was obtained when grown directly; but produced films with (211)A orientation when the Si surface was exposed to DETe. On the other hand, only (lll)A CdTe films were possible on (111) Si, both with and without Te source exposure, although twinning was increased after exposure. The results indicate that the exposure to a Te-source changes the initial growth stage significantly, except for the growth on (111) Si. We propose a model in which a Te atom replaces a Si atom that is bound to two Si atoms.     

Reaction kinetics control in preparation of CdTe and HgCdTe by hot wall metalorganic vapor phase epitaxy

The growth rates of CdTe and HgCdTe by hot wall metalorganic vapor phase epitaxy were studied as functions of growth temperatures and partial pressures of precursors. It is suggested that the growth of CdTe and HgCdTe was controlled by reaction kinetics. The relationship between growth processes and epilayer properties was discussed and high quality epilayers were obtained.     

Metalorganic chemical vapor deposition growth of high optical quality and high mobility GaN

Hall mobilities as high as 702 and 1230 cm²/Vs at 300 and 160K along with low dislocation densities of 4.0 × 10⁸ cm^-2 have been achieved in GaN films grown on sapphire by metalorganic chemical vapor deposition. High growth temperatures have been established to be crucial for optimal GaN film quality. Photoluminescence measurements revealed a low intensity of the deep defect band around 550 nm in films grown under optimized conditions.     

Electrical and structural properties of epitaxial CdTe/HgCdTe interfaces

In this study, CdTe epilayers were grown by metalorganic chemical vapor deposition on epitaxial HgCdTe with the purpose of developing suitable passivation for HgCdTe photodiodes. Two types of CdTe layers were investigated. One was grown directly,in situ, immediately following the growth of HgCdTe. The second type of CdTe was grown indirectly, on top of previously grown epitaxial HgCdTe samples. In this case, the surface of the HgCdTe was exposed to ambient atmosphere, and a surface cleaning procedure was applied. The material and structural properties of the CdTe/HgCdTe interfaces were investigated using secondary ion mass spectroscopy, Auger electron spectroscopy, Rutherford back scattering, and x-ray double crystal diffractometry techniques. Electrical properties of the CdTe/HgCdTe heterostructure were determined by capacitance-voltage (C-V) characterization of Schottky barrier devices and metal insulator semiconductor devices. Also, a preliminary current-voltage characterization of n⁺ p photodiodes was performed. A theoretical model suitable for analysis of graded heterojunction devices was used for interpretation of C-V measurements.     

Metalorganic chemical vapor deposition growth and characterization of InGaP/GaAs superlattices

Lattice-matched In_0.49Ga_0.51P/GaAs superlattices were grown on (001) GaAs substrates using metalorganic chemical vapor deposition. The interface properties were characterized by photoluminescence, transmission electron microscopy, and x-ray diffraction. By varying the growth temperature, the precursor flow rates, and the growth interruption at the interfaces, we found that, while arsenic and phosphorus carry over have some effect on the formation of a low-bandgap InGaAsP quaternary layer at the interfaces, the In surface segregation seems to play an important role in the formation of the interface quaternary layer. Evidence of this indium segregation comes from x-ray and photoluminescence studies of samples grown at different temperatures. These studies show that the formation of an interfacial layer is more prominent when the growth temperature is higher. Growing a thin (∼1 monolayer thick) GaP intentional interfacial layer on top of the InGaP before the growth of the GaAs layer at the P→As transition effectively suppresses the formation of the low-bandgap unintentional interface layer. On the other hand, the growth of a thin GaAsP (or GaP) layer before the growth of the InGaP layer, at the As→P transition increases the formation of a low-bandgap interfacial layer. This nonequivalent effect of a GaP layer at the two interfaces on the PL properties is discussed.     

Improved arsenic doping in metalorganic chemical vapor deposition of HgCdTe andin situ growth of high performance long wavelength infrared photodiodes

Controlled and effective p-type doping is a key ingredient forin situ growth of high performance HgCdTe photodiode detectors. In this paper, we present a detailed study of p-type doping with two arsenic precursors in metalorganic chemical vapor deposition (MOCVD) of HgCdTe. Doping results from a new precursortris-dimethylaminoarsenic (DMAAs), are reported and compared to those obtained from tertiarybutylarsine (TBAs). Excellent doping control has been achieved using both precursors in the concentration range of 3 × 1015-5 × 10¹⁷ cm⁻³ which is sufficient for a wide variety of devices. Arsenic incorporation efficiency for the same growth temperature and partial pressure is found to be higher with DMAAs than with TBAs. For doping levels up to 1 × 10₁₇ cm⁻³, the alloy composition is not significantly affected by DMAAs. However, at higher doping levels, an increase in the x-value is observed, possibly as a result of surface adduct formation of DMAAs dissociative products with dimethylcadmium. The activation of the arsenic as acceptors is found to be in the 152–50% range for films grown with DMAAs following a stoichiometric anneal. However, a site transfer anneal increases the acceptor activation to near 100%. Detailed temperature dependent Hall measurements and modeling calculations show that two shallow acceptor levels are involved with ionization energies of 11.9 and 3.2 meV. Overall, the data indicate that DMAAs results in more classically behaved acceptor doping. This is most likely because DMAAs has a more favorable surface dissociation chemistry than TBAs. Long wavelength infrared photodiode arrays were fabricated on P-on-n heterojunctions, grownin situ with iodine doping from ethyl iodide and arsenic from DMAAs on near lattice matched CdZnTe (100) substrates. At 77K, for photodiodes with 10.1 and 11.1 (im cutoff wavelengths, the average (for 100 elements 60 × 60 μm² in size) zero-bias resistance-area product, R₀A are 434 and 130 ohm-cm², respectively. Quantum efficiencies are ≥50% at 77K. These are the highest R₀A data reported for MOCVDin situ grown photodiodes and are comparable to state-of-the-art LPE grown photodiodes processed and tested under identical conditions.     

Characterization of CdTe for HgCdTe surface passivation

The objectives of this work are to study the physical and chemical structure of CdTe films using secondary ion mass spectrometry (SIMS) and atomic force miroscopy (AFM) and to demonstrate the usefulness of these analytical techniques in determining the characteristics of CdTe-passivation films deposited by different techniques on HgCdTe material. Three key aspects of CdTe passivation of HgCdTe are addressed by different analytical tools: a) morphological microstructure of CdTe films examined by atomic force microscopy; b) compositional profile across the interface determined by Matrix (Te)—SIMS technique; c) concentration of various impurities across the CdTe/HgCdTe structure profiled by secondary ion-mass spectrometry.     

Characteristics of GaN stripes grown by selective-area metalorganic chemical vapor deposition

We report on the selective-area metalorganic chemical vapor deposition of GaN stripes in the size range of 50 to 125 urn and the characterization of the morphology, topography, and optical properties of these stripes. GaN films (∼1–3 μm) grown on (0001) sapphire are used as the substrates. Excellent surface morphology is achieved under optimized growth conditions which include a higher V/III ratio than broad area growth. It is found that, under certain growth conditions, (0001) terraces of ~5 μm in width develop at the edges of all stripes, independent of stripe size and orientation. The selectively grown GaN yields stronger band-edge emission than the “substrate” GaN which indicates an improvement in optical quality. However, the donor-acceptor pair recombination (or conduction band to acceptor transition) and yellow emission are also enhanced in certain areas of the stripes. The spatial correlation of these emission bands is established by cathodoluminescence wavelength imaging, and the origin of these emissions is speculated.     

The growth of AlInSb by metalorganic chemical vapor deposition

We have grown Al_xIn_1−xSb epitaxial layers by metalorganic chemical vapor deposition using tritertiarybutylaluminum (TTBAl), trimethylindium (TMIn), and triethylantimony (TESb) as sources in a high speed rotating disk reactor. Growth temperatures of 435 to 505°C at 200 Torr were investigated. The V/III ratio was varied from 1.6 to 7.2 and TTBAl/(TTBAl+TMIn) ratios of 0.26 to 0.82 were investigated. Al_xIn_1−xSb compositions from x=0.002 to 0.52 were grown with TTBAl/(TTBAl+TMIn) ratios of 0.62 to 0.82. Under these conditions, no Al was incorporated for TTBAl/(TTBAl+TMIn) ratios less than 0.62. Hall measurements of Al_xIn_1−xSb showed hole concentrations between 5×10¹⁶ cm⁻³ to 2 × 10¹⁷ cm⁻³ and mobilities of 24 to 91 cm²/Vs for not intentionally doped Al_xIn_1−xSb.     

Metalorganic chemical vapor deposition growth of GaAs:Er using Er(C4H9C5H4)3

Erbium doped GaAs has been grown by metalorganic chemical vapor deposition using a novel liquid precursor: Tris (n-butylcyclopentadienyl) erbium, Er(C₄H₉C₅H₄)₃. Erbium doping as high as 1.2 × 10¹⁹cm⁻³ has been realized. The morphology was excellent at growth temperatures near 620°C. The erbium concentration was found to depend on growth temperatures due to incomplete pyrolysis of the erbium metalorganic compound. The erbium-related PL intensity was decreased when the erbium concentration exceeded ∼1.2 × 10¹⁹cm⁻³.     

Metalorganic vapor phase epitaxyin-situ growth of p-on-n and n-on-p Hg1-xCdxTe junction photodiodes using tertiarybutylarsine as the acceptor source

We report arsenic doping of Hg_1-xCd_xTe (0.2 < x < 0.3) grown using metalorganic vapor phase epitaxy (MOVPE) by the direct alloy growth (DAG) technique. Tertiarybutylarsine (TBAs) was used as a precursor for As doping. Several epilayers were grown at different Hg partial pressures and TBAs bubbler temperatures in order to study the doping characteristics. The amount of As incorporated in the layer as well as the acceptor concentration were found to be a strong function of the Hg pressure. Secondary ion mass spectrometric studies on heterostructures showed that the compositional interdiffusion is less than the diffusion of As during growth. P-N junctions were grown using TBAs for the first time and several of these layers were processed to fabricate photodiodes. A p-on-n grown junction photodiode with a cutoff wavelength of 8.2 μm had an R_oA value of 241 ohm-cm² at 80K and is the highest reported value for p-on-n DAG-MOVPE devices. Methods to improve the device R_oA of the grown junctions are also proposed.