Optical properties and recombination mechanisms in GaN and GaN:Mg grown by metalorganic vapor phase epitaxy

Photoluminescence (PL) and reflection spectra of undoped and Mg-doped GaN single layers grown on sapphire substrates by metalorganic vapor phase epitaxy (MOVPE) were investigated in a wide range of temperatures, excitation intensities, and doping levels. The undoped layers show n-type conductivity (μ=400 cm²/Vs, n=3×10¹⁷ cm⁻³). After annealing at T=600–700°C, the Mg-doped layers showed p-type conductivity determined by the potential-profiling technique. A small value of the full width at half maximum (FWHM=2.8 meV) of the excitonic emission and a high ratio between excitonic and deep level emission (≈5300) are evidences of the high layer quality. Two donor centers with activation energies of 35 and 22 meV were observed in undoped layers. A fine structure of the PL band with two narrow lines in the spectral range of the donor-acceptor pair (DAP) recombination was found in undoped layers. An anomaly was established in the temperature behavior of two groups of PL lines in the acceptor-bound exciton and in donor-acceptor pair regions in Mg doped layers. The lower energy line quenched with increasing temperature appreciably faster than the high energy ones. Our data does not agree with the DAP recombination model. It suggests that new approaches are required to explain the recombination mechanisms in undoped and Mg-doped GaN epitaxial layers.     

Electrical and optical properties of oxygen doped GaN grown by MOCVD using N2O

Oxygen doped GaN has been grown by metalorganic chemical vapor deposition using N₂O as oxygen dopant source. The layers were deposited on 2″ sapphire substrates from trimethylgallium and especially dried ammonia using nitrogen (N₂) as carrier gas. Prior to the growth of the films, an AIN nucleation layer with a thickness of about 300? was grown using trimethylaluminum. The films were deposited at 1085°C at a growth rate of 1.0 μm/h and showed a specular, mirrorlike surface. Not intentionally doped layers have high resistivity (>20 kW/square). The gas phase concentration of the N₂O was varied between 25 and 400 ppm with respect to the total gas volume. The doped layers were n-type with carrier concentrations in the range of 4×10¹⁶ cm⁻³ to 4×10¹⁸ cm⁻³ as measured by Hall effect. The observed carrier concentration increased with increasing N₂O concentration. Low temperature photoluminescence experiments performed on the doped layers revealed besides free A and B exciton emission an exciton bound to a shallow donor. With increasing N₂O concentration in the gas phase, the intensity of the donor bound exciton increased relative to that of the free excitons. These observations indicate that oxygen behaves as a shallow donor in GaN. This interpretation is supported by covalent radius and electronegativity arguments.     

Optical properties of undoped and iodine-doped CdTe

A comprehensive study of the properties of undoped and iodine-doped CdTe structures by photoluminescence (PL) and photoreflectance (PR) is reported. Undoped bulk CdTe and iodine-doped CdTe layers grown by metalorganic molecular beam epitaxy on (lOO)-oriented CdTe and (211)B-oriented GaAs substrates with electron concentrations ranging from 10¹⁴ to mid-10¹⁸ cm^-3 were included in this study. Lineshape modeling of 80KPL and PR spectra indicated the presence of both free exciton and donor-hole transitions at the higher doping levels. Strong PL and PR signals were also observed at room temperature. If only a single transition is considered for the analysis of the 300K spectra, the PL emission peak and the PR transition energy both exhibit a strong dependence on electron concentration for doped layers. However, lineshape modeling of the room-temperature spectra indicated the presence of multiple transitions consisting of free exciton and direct band-to-band transitions. The use of two transitions resulted in a constant value of bandgap over the entire range of conductivities studied. A strong correlation remained between the broadening of the PR and PL spectra and excess carrier concentration N_D-N_A. In addition, the E₁ transition energy measured by PR was found to vary dramatically with growth conditions.     

Variable temperature hall effect on p-Hg1−xCdxTe grown on CdTe and sapphire substrates by liquid phase epitaxy

Variable temperature Hall effect measurements have been made down to 9–10K on p-type Hg_1−xCd_xTe grown by liquid phase epitaxy on both CdTe and sapphire substrates. Carrier freeze-out was usually observed throughout the measured temperature range. For most samples, the hole mobility was well-behaved and exhibited a maximum at ˜ 35K. Values of acceptor ionization energy E_A and donor concentration N_D were estimated from the data, using a model assuming significant compensation, which provided a good fit to the low temperature data. In addition, values of N_D were also estimated from an analysis of the low temperature mobility using the hole effective mass as a parameter to provide reasonable agreement between the N_D values calculated from the Hall coefficient and mobility data. The measured carrier concentration is a result of close compensation between stoichiometric acceptors and donors, with N_D usually in the low-10¹⁷ cm⁻³ range. Average values of E_A for as-grown, undoped x = 0.32 layers on CdTe and sapphire substrates are 7.4 and 6.6 meV, respectively. An activation energy of 0.84 meV was determined for a Cu-doped x = 0.32 layer that was annealed in Hg vapor to reduce the number of Hg vacancies. The average E_A for undoped Hg-annealed x = 0.22 layers on CdTe substrates is 2.35 meV. Layers with x = 0.32 grown on sapphire substrates have average carrier concentrations of 2.92 (σ = 0.54) × 10¹⁶ cm⁻³, compared with 4.64 (θ = 1.26) × 10¹⁶ cm⁻³ for the same composition layers grown on CdTe substrates.     

Growth condition of iodine-doped n+-CdTe layers in metal-organic vapor phase epitaxy

Iodine doping of CdTe layers grown on (100) GaAs by metal-organic vapor phase epitaxy (MOVPE) was studied using diethyltelluride (DETe) and diisopropyltelluride (DiPTe) as tellurium precursors and ethyliodine (EI) as a dopant. Electron densities of doped layers increased gradually with decreasing the growth temperature from 425°C to 325°C. Doped layers grown with DETe had higher electron densities than those grown with DiPTe. When the hot-wall temperature was increased from 200°C to 250°C at the growth temperature of 325°C, doped layers grown with DETe showed an increase of the electron density from 3.7×10¹⁶ cm⁻³ to 2.6×10¹⁸ cm⁻³. On the other hand, such an increase of the electron density was not observed for layers grown with DiPTe. The mechanisms for different doping properties for DETe and DiPTe were studied on the basis of the growth characteristics for these precursors. Higher thermal stability of DETe than that of DiPTe was considered to cause the difference of doping properties. With increasing the hot-wall temperature from 200°C to 250°C, the effective ratio of Cd to Te species on the growth surface became larger for layers grown with DETe than those grown with DiPTe. This was considered to decrease the compensation of doped iodine and to increase the electron density of layers grown with DETe. The effective ratio of Cd to Te species on the growth surface also increased with decreasing growth temperature. This was considered to increase the electron density with decreasing growth temperature.     

Point defects in Cd1−xZnxTe: A correlated photoluminescence and EPR study

Cd_1−xZn_xTe (CZT) is an emerging material for room-temperature x-ray and gamma-ray detectors. The identification and control of point defects and charge compensators in the bulk material are currently important issues. We have used photoluminescence (PL), photoluminescence excitation, and electron paramagnetic resonance (EPR) to characterize point defects in a series of bulk CZT crystals grown by the high-pressure Bridgman technique. Luminescence peaks due to shallow donors, shallow acceptors, and deeper levels, such as V_Cd-D_Cd complexes (D = shallow donor), were monitored. This was followed by a detailed study of photo-induced EPR, using a tunable Ti:sapphire laser. There were no EPR signals in the “light off” condition; however, during illumination, an isotropic EPR spectrum due to neutral donors could be observed. The dependence of the donor g value on zinc molar fraction, x, has been determined for the range 0.07<x<0.14. We show that PL and EPR can be combined to give increased quantitative defect analysis in CZT. With resonant tuning of the Ti:sapphire laser, we detected donor concentrations as low as mid-10¹⁴cm⁻³ in detector-grade CZT crystals.     

Low-Temperature Photoluminescence Study of CdTe:In Crystals Annealed in Molten Bismuth

We used a low-temperature photoluminescence (PL) technique to investigate CdTe:In crystals after annealing in molten bismuth (Bi). The two annealed samples showed different resistivities after the treatment. For both samples, we observed very strong emissions in the excitonic spectral region and revealed fine structures of exciton emissions in the PL spectrum. In the sample with high resistivity, we found one ionized donor-bound exciton peak, (D⁺,X), that we ascribed to incorporated Bi atoms occupying Cd sites in the CdTe. The temperature dependence of the (D⁺,X) peak emission had an associated activation energy of 3.59 meV for the exciton bound to this ionized donor. Meanwhile, a donor–acceptor pair peak at 1.5315 eV, which was absent from the PL of the low-resistivity sample, suggested the likelihood of some Bi atoms occupying Te sites in the high-resistivity sample. Our findings highlight the need for detailed investigation of annealing conditions to ensure precise control of the electrical properties of the material during annealing in molten Bi.     

Effect of features of the technology of polycrystalline CdTe growth on the conductivity and deep level spectrum after annealing

The conductivity, morphology, and deep levels in polycrystalline CdTe are studied. Undoped p-CdTe is grown from the vapor phase by low-temperature methods of direct Cd and Te chemical reaction and CdTe vacuum sublimation at P _min. Chlorine-doped CdTe is also grown. The resistivity of the grown samples is ～105–109 Ω cm. After annealing in liquid cadmium or in cadmium vapor at ～500°C, the conductivity type changes, the free-carrier concentration in the undoped and doped samples increases to 4 × 10¹⁵ and ～2 × 10¹⁶ cm^?3, respectively. For all samples, a defect ground level of ～0.84 eV and continuous background are observed in DLTS spectra after annealing. A correlation between the primary-defect and free-carrier concentrations in undoped and doped CdTe is observed. Chlorine is a main residual impurity in the undoped samples. It is assumed that the defect is a complex including chlorine and observed structural defects in CdTe.     

Assessment of electrical inhomogeneity of undoped and doped Hg1−xCdxTe MOVPE (IMP) layers by variable magnetic field hall profile measurements

A Hall profiling technique in which measurements are made at 77K as a function of magnetic field (0.01–1T) and layer thickness (by chemical thinning) has been developed for the characterization of Hg_1−xCd_xTe epitaxial layers. The technique has been applied to undoped and lightly In doped MOVPE interdiffusion multilayer process (IMP) layers grown on (100) GaAs and CdTe with x values between 0.19 and 0.30 in order to investigate the parameters controlling the electrical homogeneity. Results show unpassivated layers with x>0.25 are uniformly p-type with 77K hole concentrations consistent with Hg vacancy concentrations for the growth conditions while layers with x<0.25 are anomalous, being either inhomogeneous or uniformly n-type depending on x. The inhomogeneous layers are mainly n on p layer structures, in which the junction depth, Xj, but not the carrier concentration is found to be a function of x and can be comparable to layer thickness at x=0.20. Carrier levels in the n and p-type regions are consistent with the net background impurity donor and Hg vacancy concentrations respectively, suggesting that the n-type properties occur through post growth Hg in-diffusion filling in the vacancies. This model was partly confirmed by capping layers with CdTe, which significantly reduced the extent of the n-type region, and by ex-situ annealing experiments to simulate the inhomogeneity. Results show the low temperature process responsible for the type conversion in MOVPE CMT is highly x dependent, suggesting a variation in the electrical “Hg diffusion coefficient” of over an order of magnitude between 0.20 and 0.30 at 200°C. Carrier and mobility profiles of both as-grown and annealed n-p structures are abrupt and consistent with an interstitial Hg diffusion mechanism.     

Time of flight experimental studies of CdZnTe radiation detectors

A time of flight technique was used to study the carrier trapping time, τ, and mobility, μ, in CdZnTe (CZT) and CdTe radiation detectors. Carriers were generated near the surface of the detector by a nitrogen-pumped pulsed dye laser with wavelength ∼500 nm. Signals from generated electrons or holes were measured by a fast oscilloscope and analyzed to determine the trapping time and mobility of carriers. Electron mobility was observed to change with temperature from 1200 cm²/Vs to 2400 cm²/Vs between 293 K and 138 K, respectively. Electron mobilities were observed between 900 cm²/Vs and 1350 cm²/Vs at room temperature for various CZT detectors. Electron mobilities in various CdTe detectors at room temperature were observed between 740 cm²/Vs and 1260 cm²/Vs. Average electron mobility was calculated to be 1120 cm²/Vs and 945 cm²/Vs for CZT and CdTe, respectively. Hole mobilities in both CZT and CdTe were found to vary between 27 cm²/Vs and 66 cm²/Vs. Electron trapping times in CZT at room temperature varied from 1.60 μs to 4.18 μs with an average value of about 2.5 μs. Electron trapping time in CdTe at room temperature varied between 1.7 μs and 4.15 μs with an average value of about 3.1 μs.     

Doping of LPE layers of CdTe grown from te solutions

Good quality epitaxial layers of CdTe have been grown by LPE from Te-rich solutions at ˜ 500‡C onto (111) CdTe substrates. The layers have been characterised by a wide variety of techniques including capacitance-voltage profiling, photoluminescence at 4K and secondary-ion mass spectrometry (SIMS) . Undoped layers had good electrical properties (p ˜ 1 × 10¹⁶ cm⁻³, L_e ˜ 3 μm) and SIMS showed the layers to be of high purity. Those doped with In and Al however, had low n-type carrier concentrations and very short diffusion lengths, while the photoluminescence spectra showed a strong peak at ˜ 1.4 eV commonly seen in n-type bulk CdTe. The most heavily doped layers showed marked decreases in lattice parameter.     

Photoluminescence excitation spectroscopy of the dense exciton gasinvolved in the lasing transition in ZnSe epitaxial layers

The lasing transition in ZnSe epitaxial layers has been investigated at 77 K. The lowest lasing threshold (I_th) was achieved when the layers were resonantly excited at the photon energy of the exciton level. It was found that the exciton level at the excitation intensity just above the I_th was red-shifted by about 16 meV compared with the free exciton line (2.792 eV) under weak excitation condition. The energy difference between the exciton line and the lasing peak was about 19 meV at I=I_th and increased with increasing excitation intensity up to I=8×I_th. This suggests that the stimulated emission occurs due to the inelastic exciton-exciton scattering process at this temperature     

Cadmium(1−x)zinc(x)telluride thin films deposited by sequential pulsed laser deposition

In this work, sequential pulsed laser deposition was used for the deposition of cadmium zinc telluride (CZT) thin films. CZT is a ternary II–VI compound semiconductor with a tunable band gap between 1.51 and 2.26 eV. In this work, three different CZT film compositions were achieved at room temperature by sequential deposition of nanometric layers with a precise number of laser shots on the cadmium telluride (CdTe) and zinc telluride (ZnTe) targets. XPS, XRD and UV–vis transmittance techniques were used to characterize the CZT films. The atomic content of zinc ranged from 60% down to 13%. This represents an enlargement of the lattice constant from 6.19 to 6.41 Å, and a band gap decrement from 1.94 to 1.55 eV. In addition, the CZT film resistivity can be modulated between the CdTe (4.1×10⁷ Ω-cm) and ZnTe (2.8×10⁵ Ω-cm) values. Our results demonstrated that the sequential pulsed laser deposition can be used to obtain several CZT film compositions with precise control of its stoichiometry and can be extended to the production of other ternary compounds.     

Photoluminescence measurements on undoped CdZnTe grown by the high-pressure bridgman method

The low temperature photoluminescence of Cd_0.91Zn_0.09Te grown by the high-pressure Bridgman (HPB) method exhibits a neutral donor bound exciton emission (D⁰X) at 1.65603 eV with its excited state (D⁰X^*) at 1.65798 eV and neutral acceptor bound exciton emissions (A⁰X) at 1.64566 eV and 1.65201 eV. Assuming a direct generation and subsequent relaxation of excitons at the D⁰X^* state, we demonstrate that the temporal evolution of the above emission bands is well reproduced by a set of rate equations. The resultant radiative-lifetime of 1.4 ns for the D⁰X and 1.5 and 2.0 ns for the A⁰Xs are compared with various CdZnTe's (CZTs) grown by the other methods to demonstrate the particular nature of the HPB CZT.     

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.     

掺氮ZnSe外延层的光致发光研究

报导了掺氮ＺｎＳｅ外延层的光致发光,研究了与氮受主有关的发光峰随温度和激发强度的变化关系．１０Ｋ下施主－受主对发光峰随激发强度的增加向高能方向移动,且峰强呈现饱和趋势．在１０～３００Ｋ温度范围光致发光谱表明,随着温度增加,由于激子在受主束缚激子态和施主束缚激子态之间转移,施主束缚激子发光峰强度相对受主束缚激子发光峰强度增加     

UV and IR emission intensity in ZnO films,nanorods, and bulk single crystals doped with Er and additionally introduced impurities

For ZnO films, nanorods, and bulk single crystals doped with Er⁺ ions, it is shown that the effect of codopants introduced into the cation and ion sublattices and the observation of a high-intensity emission band at the wavelength λ_max = 1535 nm are defined by the local environment of the Er⁺ ion. Doping of the films and single crystals with Er⁺ ions by diffusion brings about an infrared (IR) emission band with a low intensity because of an inadequate concentration of impurity ions. The emission intensity of this band can be raised by introducing additional Ag, Au, or N⁺ impurities into the ZnO films. The UV-emission intensity of the Er-doped films and single crystals at λ_max = 368–372 nm is identical to that of the undoped films. ZnO nanorods doped with Er only or together with Al or Ga codopants exhibit only one IR band (at λ_max = 1535 nm), whose intensity decreases upon the introduction of codopants. Doping of the nanorods with the N⁺ gaseous impurity during growth (930 < T < 960°C) and then with the Er⁺ impurity by diffusion does not yield a substantial increase in the IR-emission intensity compared to the that of the corresponding band for nanorods not doped with the N⁺ impurity. In the Er-doped nanorods, whose photoluminescence spectra exhibit a high-intensity band at λ_max = 1535 nm, the UV emission band at λ_max = 372 nm is practically lacking.     

Luminescence of stepped quantum wells in GaAs/GaAlAs and InGaAs/GaAs/GaAlAs structures

Luminescence spectra of doped and undoped GaAs/GaAlAs and InGaAs/GaAs/GaAlAs structures containing several tens of stepped quantum wells (QW) are investigated. The emission bands related to free and bound excitons and impurity states are observed in QW spectra. The luminescence excitation spectra indicate that the relaxation of free excitons to the e1hh1 state proceeds via the exciton mechanism, whereas an independent relaxation of electrons and holes is specific to bound excitons and impurity states. The energy levels for electrons and holes in stepped QWs, calculated in terms of Kane’s model, are compared with the data obtained from the luminescence excitation spectra. The analysis of the relative intensities of emission bands related to e1hh1 excitons and exciton states of higher energy shows that, as the optical excitation intensity increases, the e1hh1 transition is more readily saturated at higher temperature, because the lifetime of excitons increases. Under stronger excitation, the emission band of electron-hole plasma arises and increases in intensity superlinearly. At an excitation level of ～10⁵ W/cm², excitons are screened and the plasma emission band dominates in the QW emission. Nonequilibrium luminescence spectra obtained in a picosecond excitation and recording mode show that the e1hh1 and e2hh2 radiative transitions are 100% polarized in the plane of QWs.     

非掺杂n型氮化镓外延层的光致发光

研究了热处理对非掺杂 n型氮化镓外延层光致发光谱的影响和光谱中各发光带强度与温度之间的关系 .热处理后 ,光谱中的带边峰和黄光峰的强度较热处理前都有明显降低 .黄光峰强度随温度升高的衰减速度要比带边峰慢得多 .由这些实验结果得出结论 :光谱中的带边峰是由自由激子和束缚在一浅施主能级的束缚激子的谱线重合而成 ,这个浅施主能级很有可能是由氮空位产生 ;黄色荧光的机制应为自由电子或施主能级向深受主能级的跃迁 ,并且黄色荧光肯定和氮化镓中的一内部缺陷产生的深受主能级有关 ,该内部缺陷很有可能是镓空位 .     

Investigation of HgCdTe p-n device structures grown by liquid-phase epitaxy

The microstructure of p-n device structures grown by liquid-phase epitaxy (LPE) on CdZnTe substrates has been evaluated using transmission electron microscopy (TEM). The devices consisted of thick (∼21-μm) n-type layers and thin (∼1.6-μm) p-type layers, with final CdTe (∼0.5 μm) passivation layers. Initial observations revealed small defects, both within the n-type layer (doped with 8×10¹⁴/cm³ of In) and also within the p-type layer but at a much reduced level. These defects were not visible, however, in cross-sectional samples prepared by ion milling with the sample held at liquid nitrogen temperature. Only isolated growth defects were observed in samples having low indium doping levels (2×10¹⁴/cm³). The CdTe passivation layers were generally columnar and polycrystalline, and interfaces with the p-type HgCdTe layers were uneven. No obvious structural changes were apparent in the region of the CdTe/HgCdTe interfaces as a result of annealing at 250°C.