Activation Of Mg Acceptors Research Articles

Reduction in Gap State Density near Valence Band Edge at Al2O3/p‐type GaN Interface by Photoelectrochemical Etching and Subsequent SiO2 Cap Annealing

The process‐dependent properties of Al2O3/p‐type GaN (p‐GaN) interfaces formed by atomic layer deposition at 300 °C after photoelectrochemical (PEC) etching are reported. For investigating the gap states at the Al2O3/p‐GaN interface, metal‐oxide‐semiconductor (MOS) diodes are fabricated and examined by sub‐bandgap‐light‐assisted and temperature‐dependent capacitance–voltage (C–V) measurements. PEC etching prior to Al2O3/p‐GaN interface formation is conducted with the etching depth varied in the range between 12.5 and 32.1 nm. The C–V characteristics of the MOS diodes without PEC etching indicate Fermi‐level pinning due to the near‐surface defect level in p‐GaN at 0.7 eV above the valence band edge EV and a high density of gap states around the midgap. However, all samples with PEC etching exhibit C–V characteristics, indicating a reduction in the density of the defect states at EV + 0.7 eV and midgap states. Still, PEC etching after capless annealing at 800 °C for the activation of Mg acceptors cannot reduce the density of gap states near the valence band edge. On the other hand, annealing of a sample with a SiO2 cap layer at 800 °C after PEC etching can reduce the gap state density near the valence band edge.

Interface state density distribution near conduction band edge at Al2O3/Mg-ion-implanted GaN interface formed after activation annealing using AlN cap layer

An interface state density (Dit) distribution near the conduction band edge (EC) at the Al2O3/Mg-ion-implanted GaN interface was measured after ion implantation, annealing with an AlN protective cap, and cap layer removal. Mg ions were implanted into n-GaN with a Si concentration of 6 × 1017 cm−3 at a maximum Mg concentration of 2 × 1017 cm−3, resulting in the maintenance of the n-type conduction in GaN even after the activation of Mg dopants. Activation annealing was carried out at 1250 °C for 1 min using an AlN cap layer. The complete removal of the AlN cap layer was accomplished by wet etching, which was confirmed by x-ray photoelectron spectroscopy. The photoluminescence spectrum showed donor–acceptor-pair emission after annealing, indicating the activation of Mg acceptors. By applying the capacitance–voltage method to a completed metal–oxide–semiconductor diode, we derived a continuous distribution of relatively low Dit below 5 × 1012 cm−2 eV−1, which increased monotonically toward EC in the range from EC − 0.15 to EC − 0.45 eV. Compared with the Dit distribution of the as-implanted sample, the density of the discrete level at EC − 0.25 eV generated by divacancies markedly decreased upon 1250 °C annealing.

Impact of defects on the electrical properties of p–n diodes formed by implanting Mg and H ions into N-polar GaN

The relationship between the junction properties and point defects in p–n diodes, formed by implanting magnesium (Mg) and hydrogen (H) ions into a GaN layer, was investigated. Vertical diodes were fabricated by implanting Mg ions with and without H ions into nitrogen-polar n-type GaN substrates, followed by annealing at 1150 °C or 1230 °C without the use of protective layers. Samples annealed at 1150 °C showed Schottky-barrier-diode (SBD)-like properties with an insufficient build-in potential, indicating surface depletion due to poor activation of Mg acceptors. The Mg/H-ion-implanted diode annealed at 1230 °C exhibited an improved rectifying property with a build-in potential around 3 V, close to an ideal p–n junction of GaN, whereas the sample with only implanted Mg-ions exhibited mixed properties of a p–n junction and SBD due to imperfect activation. In addition, leakage currents in the forward bias below 3 V for the Mg/H-ion-implanted diodes can be explained by a recombination current based on the Shockley–Read–Hall model with an estimated recombination lifetime of 3 to 10 ps. To clarify the sources of the difference in the junction properties, positron annihilation spectroscopy was employed. The samples annealed at 1150 °C contained high-density vacancy clusters such as (VGaVN)3, whose concentrations were reduced by the higher temperature annealing. We found that introduced H atoms can enhance the activation of Mg acceptors and/or reduce the defect concentrations. The results indicate the combination of the H ion introduction and higher temperature annealing improves the junction properties.

Improving p-type doping efficiency in Al0.83Ga0.17N alloy substituted by nanoscale (AlN)5/(GaN)1 superlattice with MgGa-ON δ-codoping: Role of O-atom in GaN monolayer

We calculate Mg-acceptor activation energy EA and investigate the influence of O-atom, occupied the Mg nearest-neighbor, on EA in nanoscale (AlN)5/(GaN)1 superlattice (SL), a substitution for Al0.83Ga0.17N disorder alloy, using first-principles calculations. We find that the N-atom bonded with Ga-atom is more easily substituted by O-atom and nMgGa-ON (n = 1-3) complexes are favorable and stable in the SL. The O-atom plays a dominant role in reducing EA. The shorter the Mg-O bond is, the smaller the EA is. The Mg-acceptor activation energy can be reduced significantly by nMgGa-ON δ-codoping. Our calculated EA for 2MgGa-ON is 0.21 eV, and can be further reduced to 0.13 eV for 3MgGa-ON, which results in a high hole concentration in the order of 1020 cm−3 at room temperature in (AlN)5/(GaN)1 SL. Our results prove that nMgGa-ON (n = 2,3) δ-codoping in AlN/GaN SL with ultrathin GaN-layer is an effective way to improve p-type doping efficiency in Al-rich AlGaN.

Light-extraction efficiency and forward voltage in GaN-based light-emitting diodes with different patterns of V-shaped pits

We present a new method of making a textured V-pit surface for improving the light extraction efficiency in GaN-based light-emitting diodes and compare it with the usual low-temperature method for p-GaN V-pits. Three types of GaN-based light-emitting diodes (LEDs) with surface V-pits in different densities and regions were grown by metal—organic chemical vapor deposition. We achieved the highest output power and lowest forward voltage values with the p-InGaN V-pit LED. The V-pits enhanced the light output power values by 1.45 times the values of the conventional LED owing to an enhancement of the light scattering probability and an effective reduction of Mg-acceptor activation energy. Moreover, this new technique effectively solved the higher forward voltage problem of the usual V-pit LED.

Control of Eu Luminescence Centers by Codoping of Mg and Si into Eu-Doped GaN

The effects of Mg and Si codoping on Eu luminescence properties have been investigated in Eu-doped GaN (GaN:Eu). The Mg codoping into GaN:Eu produced novel luminescence centers consisting of Eu and Mg, and increased photoluminescence (PL) intensity in Eu,Mg-codoped GaN (GaN:Eu,Mg). However, this increased PL intensity was quenched by thermal annealing in N2 ambient, which is due to activation of Mg acceptors. In GaN:Eu,Mg codoped additionally with Si (GaN:Eu,Mg,Si), on the other hand, the Eu–Mg centers disappeared, while an additional luminescence center appeared. Furthermore, the additional luminescence center showed no quenching under N2 annealing because Si donors compensated for the Mg acceptors in GaN. Thermal quenching of the luminescence center was also approximately half of that in GaN:Eu. These results indicate that the codoping with additional impurities in GaN:Eu is a powerful technique to control Eu luminescence centers for realization of improved device performance in red light-emitting diodes using GaN:Eu.

Saturation of the junction voltage in GaN-based laser diodes

Saturation of the junction voltage in GaN-based laser diodes (LDs) is studied. It is found that there is a bump above the lasing transition in the I(dV/dI)-I curve, instead of a dip as that for GaAs-based LDs. The bump in I(dV/dI)-I curve moves to higher currents along with the lasing threshold. A model considering ambipolar conduction and electron overflow into p-AlGaN cladding layer due to poor carrier confinement in active region is used to explain the anomaly. The characteristic temperature of GaN-based LD is obtained by fitting threshold currents determined from I(dV/dI)-I curves. Moreover, it is found that GaN-based LDs show characteristics with a nonlinear series resistance, which may be due to the electron overflow into p-AlGaN cladding layer and the enhanced activation of Mg acceptors.

Passivation and activation of Mg acceptors in heavily doped GaN

Electron paramagnetic resonance measurements are used to monitor the passivation and activation of the Mg-related acceptor in GaN doped with different concentrations of Mg, up to 2 × 1020 cm−3. Samples were annealed in either forming gas (H2:N2) or pure N2 between 200 and 900 °C. As expected, the Mg-related EPR signal is reduced by at least a factor of ten during the forming gas treatment; while the pure N2 environment revives the signal. However, the study also shows that reactions between Mg and hydrogen occur at a temperature as low as 525 °C in the 1020 cm−3 Mg doped samples; while in more lightly doped samples, temperatures greater than 700 °C are required to observe changes in the Mg signal intensity. While the observations support the model in which a hydrogen atom ionizes at the Mg impurity and the remaining proton bonds at a near neighbor, the different temperature dependence suggests that hydrogen diffusion is affected by the increased Mg concentration.

Microwave annealing of Mg-implanted and in situ Be-doped GaN

An ultrafast microwave annealing method, different from conventional thermal annealing, is used to activate Mg-implants in GaN layer. The x-ray diffraction measurements indicated complete disappearance of the defect sublattice peak, introduced by the implantation process for single-energy Mg-implantation, when the annealing was performed at ≥1400 °C for 15 s. An increase in the intensity of Mg-acceptor related luminescence peak (at 3.26 eV) in the photoluminescence spectra confirms the Mg-acceptor activation in single-energy Mg-implanted GaN. In case of multiple-energy implantation, the implant generated defects persisted even after 1500 °C/15 s annealing, resulting in no net Mg-acceptor activation of the Mg-implant. The Mg-implant is relatively thermally stable and the sample surface roughness is 6 nm after 1500 °C/15 s annealing, using a 600 nm thick AlN cap. In situ Be-doped GaN films, after 1300 °C/5 s annealing have shown Be out-diffusion into the AlN layer and also in-diffusion toward the GaN/SiC interface. The in-diffusion and out-diffusion of the Be increased with increasing annealing temperature. In fact, after 1500 °C/5 s annealing, only a small fraction of in situ doped Be remained in the GaN layer, revealing the inadequateness of using Be-implantation for forming p-type doped layers in the GaN.

Catalytic Activation of Mg-Doped GaN by Hydrogen Desorption Using Different Metal Thin Layers

The annealing of Mg-doped GaN with Pt and Mo layers has been found to effectively improve the hole concentration of such material by more than 2 times as high as those in the same material without metal. Compared with the Ni and Mo catalysts, Pt showed good activation effect for hydrogen desorption and ohmic contact to the Ni/Au electrode. Despite the weak hydrogen desorption, Mo did not diffuse into the GaN epilayer in the annealing process, thus suppressing the carrier compensation phenomenon with respect to Ni and Pt depositions, which resulted in the high activation of Mg acceptors. For the GaN activated with the Ni, Pt, and Mo layers, the blue emission became dominant, followed by a clear peak redshift and the degradation of photoluminescence signal when compared with that of GaN without metal.

Hydrogen depassivation of the magnesium acceptor by beryllium in p-type GaN

Under nitrogen-rich growth conditions, the present ab initio study predicts that hydrogen passivation is more effective on the acceptor Be instead of Mg in a co-doped p-type GaN. The formation energy is 0.24 eV for (H–Be Ga) complex, and 0.46 eV for (H–Mg Ga) complex. Congruently, the binding energy is 1.40 eV for (H–Be Ga), and 0.60 eV for (H–Mg Ga). Owing to the lower binding energy, (H–Mg Ga) is not thermally stable. As Be is incorporated in Mg-doped GaN, a (H–Mg Ga) may release a H + cation at relatively elevated temperatures. Consequently, the H + diffuses swiftly away from a Mg − Ga, across a barrier of 1.17 eV, towards a Be − Ga and forms a stable (H–Be Ga) with it. The activation of Mg acceptors can be thus facilitated. In this view, the process of hydrogen depassivation of the Mg acceptor by Be can convert the as-grown high-resistivity Mg-doped GaN into a p-conducting material, as observed in the experiments.

Enhancement of p-type conductivity by modifying the internal electric field in Mg- and Si-δ-codoped AlxGa1−xN/AlyGa1−yN superlattices

The internal electric field is modified by using Mg- and Si-δ-codoped AlxGa1−xN/AlyGa1−yN superlattices (SLs). The first-principles simulation results show that the internal electric field in SL has been significantly intensified due to the charge transferring from Si-doped interface to Mg-doped interface. Accordingly, the Mg- and Si-δ-codoped p-type Al0.2Ga0.8N/GaN SLs are grown by metalorganic vapor phase epitaxy and higher hole concentration as much as twice of that in modulation-doped SL has been achieved, as determined by Hall effect measurements. Furthermore, by applying Mg- and Si-δ-codoped AlxGa1−xN/AlyGa1−yN SLs with high Al content as the p-type layers, we have fabricated deep ultraviolet light emitting diodes with superior current-voltage characteristics by lowering Mg-acceptor activation energy.

Short period p-type AlN/AlGaN superlattices for deep UV light emitters

AbstractThe Mg doped AlN/AlxGa1-xN (0.03 ≤ x ≤ 0.05) short period superlattices (SPSLs) were grown by gas source molecular beam epitaxy on (0001) sapphire substrates. The average AlN mole fraction is ∼ 0.7 and the hole concentration is ∼ 7×1017 cm-3. Contacts formed to the SPSLs using Ni/Au bilayer are found to have specific contact resistance ∼ 5×10-5 Ωcm2 near room temperature and to show weak temperature dependence attributed to activation of Mg acceptors in the AlN barriers of SPSLs. These p-SPSLs are attractive for fabrication of transparent low resistive ohmic contacts for deep UV LEDs.

Reliability analysis of GaN-based light emitting diodes for solid state illumination

In this paper, we have discussed the effect of electrical stress on GaN light emitting diode (LED). With the lapse of time, the LED with an applied large current stress can reduce its current more than without such a stress under a large forward-voltage drop. Its scanning electron microscopy (SEM) image shows that there exist several pits on the surface of the p-metal. With an electrical stress applied, the number of pits greatly increases. We also find that the degradation of GaN LED is related to the oxidized Ni/Au ohmic contact to p-GaN. The electrical activation of H-passivated Mg acceptors is described in detail. Annealing is performed in ambient air for 10 min and the differential resistances at a forward-voltage drop of 5 V are taken to evaluate the activation of the Mg acceptors. These results suggest some mechanisms of degradation responsible for these phenomena, which are described in the paper.

Optimum Rapid Thermal Activation of Mg-Doped p-Type GaN

In this paper, we describe the electrical properties of Mg-doped GaN annealed using rapid thermal annealing. Metal–organic vapor phase epitaxy (MOVPE)-grown samples with Mg concentrations ranging from 1.25 ×1019 to 1 ×1020 cm-3 were annealed at various temperatures in a nitrogen atmosphere. It was found that the maximum hole concentration achieved after rapid thermal annealing is limited to approximately 8 ×1017 cm-3 at room temperature and its optimum annealing temperature decreases with increasing Mg concentration. The temperature dependence of hole concentration suggested that the formation of donor complex defects is responsible for the suppressed electrical activation of Mg acceptors after annealing at high temperatures higher than the optimum annealing temperature.

Kinetics of low-temperature activation of acceptors in magnesium-doped gallium nitride epilayers grown by metal-organic vapor-phase epitaxy

The annealing process of magnesium-doped gallium nitride (GaN:Mg) epilayers grown by metal-organic vapor-phase epitaxy was investigated by in situ measurements of electrical transport properties. The resistivity ρ and the Hall effect were studied as functions of time and temperature in the range of 20–600°C. A time-dependent p-type conductivity was observed at temperatures as low as 350°C. Activation energy of about Eact=1.5eV was found for the magnesium acceptor (Mg) from the isothermal measurements of ρ(t) kinetics in the range of 350–550°C. This value corresponds well to the theoretical prediction for the thermal dissociation of magnesium-hydrogen complexes (Mg–H). The annealing at temperatures higher than 600°C leads obviously to the activation of Mg acceptors, but the final resistivity of the sample is higher than the result obtained after annealing at 520°C. The ionization energy of electrically active Mg acceptor level of about EA=170meV was found from the temperature dependences of the resistivity ρ(T).

Mg-acceptor activation mechanism and transport characteristics in p-type InGaN grown by metalorganic vapor phase epitaxy

The Mg-acceptor activation mechanism and transport characteristics in a Mg-doped InGaN layer grown by metalorganic vapor phase epitaxy are systematically investigated through their structural, optical, and electrical properties. The In mole fraction was from 0 to 0.13, and the Mg concentration varied from 1×1019 to 1×1020 cm−3. X-ray rocking curves for Mg-doped InGaN layers indicate that the structural quality is comparable to that of undoped and Si-doped InGaN layers. Their photoluminescence spectra show emissions related to deep donors emerged at lower energy when Mg doping concentrations are above 2−3×1019 cm−3. The electrical properties also support the existence of these deep donors in the same Mg concentration range because the hole concentration starts to decrease at around the Mg concentration of 2−3×1019 cm−3. These results indicate that self-compensation occurs in Mg-doped InGaN at higher-doping levels. The temperature dependence of the hole concentration in Mg-doped InGaN indicates that the acceptor activation energy decreases with increasing In mole fraction. This is the reason the hole concentration in Mg-doped InGaN is higher than that in Mg-doped GaN at room temperature. In addition, the compensation ratio increases with doping concentration, which is consistent with the deep donor observed in PL spectra. For Mg-doped InGaN, impurity band conduction is dominant in carrier transport up to a relatively higher temperature than that for Mg-doped GaN, since the acceptor concentration for Mg-doped InGaN is higher than that of Mg-doped GaN.

Low-temperature activation of Mg-doped GaN with thin Co and Pt films

The activation of metallorganic chemical vapor deposition-grown Mg-doped GaN by N 2 annealing with thin Co and Pt films has been investigated. The Hall effect measurements revealed that both the Co and Pt films enhance activation of Mg acceptors as catalysts at low temperatures. A maximum hole concentration of p-type GaN was achieved at annealing temperature of 600 °C for the samples activated with both the Co and Pt films. It was also revealed that the activation of the acceptors is strongly affected by the thickness of the Co film.

Correlation between deep levels and the persistent photoconductivity in Mg-doped GaN grown MOCVD

Electrical properties of Mg-doped GaN epilayers grown by metal organic chemical vapour deposition (MOCVD) were investigated using photocapacitance measurements and deep level transient spectroscopy (DLTS). Annealing at different temperatures and different time durations gave gradual activation of Mg acceptors in samples taken from the same as-grown wafer. The samples exhibit a clear persistent photocapacitance (PPC) at low temperature. The photocapacitance versus illumination energy measurements shows the presence of energy levels labelled O1 and O2 at 1.1 and 1.9 eV, respectively, from the valence band. Their concentrations increase with the annealing duration and the temperature and thus they can be inferred to originate from Mg. They are found to be metastable. Our results support the hypothesis that the PPC observed in GaN : Mg originates from these metastable deep centres related to Mg. DLTS measurements show the presence of a deep level T1 at 0.35 eV from the valence band. When the sample has been illuminated at 80 K with photon energy of 1 eV or higher, the DLTS signal from this centre decreases with the illumination time. The energy 0.35 eV is therefore likely to be the thermal activation energy of the O1 centre.

Activation of Mg acceptors in GaN:Mg monitored by electron paramagnetic resonance spectroscopy.

ABSTRACTHydrogen removal from Mg-doped GaN is necessary to activate p-type conductivity, but the exact chemical process is not yet clear. We have investigated this issue by monitoring the intensity of an electron paramagnetic resonance (EPR) signal attributed to Mg through a series of isochronal and isothermal anneals between 600 and 1000 °C. Measurements made on GaN:Mg epitaxial layers deposited on SiC and annealed between 700 and 850 °C indicate that the Mg-related EPR signal increases with temperature as expected for depassivation of a Mg complex by removal of hydrogen. However, data obtained outside this temperature range suggest that additional processes may occur. For example, as-deposited films contain a signal resembling the Mg acceptor that is quenched by a 650 °C N2 anneal. Also, for all samples, N2 annealing at T>850 °C irreversibly decreases the signal thought to be due to Mg. Although the presence of the signal in the as-grown films is not fully understood, the effects observed at T>850 °C may be attributed to preferential N-desorption from Mg-N-H complexes.