Energy Structure of an Individual Mn Acceptor in GaAs : Mn

The energy structure of the Mn acceptor, which is a complex of Mn²⁺ ion plus valence band hole, is investigated in the external magnetic field and under presence of an uniaxial stress has been studied. The spin-flip Raman spectra are studied under resonant excitation of exciton bound to the Mn acceptor. The gfactors of the ground F = 1 and the first excited F = 2 states are determined and selection rules for the optical transitions between the acceptor states are described. The value of the random field (stress or electric field) acting on manganese acceptor and the deformation potential for the exchange interaction constant of the Mn²⁺ + hole complex are obtained. A theoretical model is developed that takes into account the influence of random internal and uniaxial external stress and magnetic field. The proposed model describes well the lines of spin-flip Raman scattering of Mn acceptor.     

Far-infrared magneto-absorption of donor-bound excitons in germanium: Pseudo-acceptor model

The magneto-oscillatory absorption spectrum of the arsenic-bound excitons in germanium observed at 118.6 μm reveals a series of absorption lines similar to the Zeeman spectrum of the acceptor impurity. This fact indicates that the bound excitons have the excited states associated with the light-hole Landau ladders and these excited states can be described by the model of a hole bound to the D^- state, i.e. the pseudo-acceptor model. The hole binding energy of the ground state of the bound excitons has been obtained to be 4.7 meV, which is smaller compared with the binding energy of the acceptor impurity.     

Optical properties of individual manganese-doped quantum dots

The magnetic state of a single magnetic ion (Mn²⁺) embedded in an individual quantum dot is optically probed using micro-spectroscopy. The fine structure of a confined exciton in the exchange field of a single Mn²⁺ ion (S=) is analyzed in detail. The exciton–Mn²⁺ exchange interaction shifts the energy of the exciton depending on the Mn²⁺ spin component and six emission lines are observed at zero magnetic field. The emission spectra of individual quantum dots containing a single magnetic Mn atom differ strongly from dot to dot. The differences are explained by the influence of the system geometry, specifically the in-plane asymmetry of the quantum dot and the position of the Mn atom. Depending on both these parameters, one has different characteristic emission features which either reveal or hide the spin state of the magnetic atom. The observed behavior in both zero field and under magnetic field can be explained quantitatively by the interplay between the exciton–Mn²⁺ exchange interaction (dependent on the Mn position) and the anisotropic part of the electron–hole exchange interaction (related to the asymmetry of the quantum dot).     

Lattice relaxation and charge-transfer optical transitions due to self-trapped holes in nonstoichiometric LaMnO3 crystal

We explore the role of electronic and ionic polarization energies in the physics of “colossal” magnetoresistive (CMR) materials. We use the Mott-Littleton approach to evaluate polarization energies in the LaMnO₃ lattice associated with holes localized on both the Mn³⁺ cation and the O^2?anion. The full (electronic and ionic) lattice relaxation energy for a hole localized at the O site is estimated at 2.4 eV, which is appreciably greater than that of 0.8 eV for a hole localized at the Mn site, indicating a strong electron-phonon interaction in the former case. The ionic relaxation around the localized holes differs for anion and cation holes. The relaxation associated with Mn⁴⁺ is approximately isotropic, whereas ionic displacements around O^? holes show axial symmetry with the axis directed towards the apical oxygens. Using the Born-Haber cycle, we examine thermal and optical energies of the hole formation associated with the electron ionization from Mn³⁺, O^2?, and La³⁺ions in the LaMnO₃ lattice. For these calculations, we derive a phenomenological value for the second electron affinity of oxygen in the LaMnO₃ lattice by matching the optical energies of the La⁴⁺ and O^? hole formation with maxima of binding energies in the experimental photoemission spectra. The calculated thermal energies predict that the electronic hole is marginally more stable in the Mn⁴⁺ state in the LaMnO₃ host lattice, but the energy of a hole in the O^? state is only higher by a small amount, 0.75 eV, suggesting that both possibilities should be treated seriously. We examine the energies of a number of fundamental optical transitions, as well as those involving self-trapped holes of Mn⁴⁺ and O^? in the LaMnO₃ lattice. The reasonable agreement of our predicted energies, linewidths, and oscillator strengths with experimental data leads us to plausible assignments of the optical bands observed. We deduce that the optical band near 5 eV is associated with the O(2p)-Mn(3d) transition of a charge-transfer character, whereas the band near 2.3 eV is rather associated with the presence of Mn⁴⁺ and/or O^? self-trapped holes in the nonstoichiometric LaMnO₃ compound.     

Spin dependent conductivity and photovoltage in ZnSe:Mn2+ Schottky barrier diodes

Light emitting ZnSe:Mn²⁺ Schottky barrier diodes have been investigated by magnetic resonance and for the first time a deep centre resonance, Mn²⁺, has been observed by monitoring the forward and reverse conductivity. In the same experiments a donor resonance was also observed as an increase in conductivity. Using two ohmic contacts the Mn²⁺ resonance and a hole centre resonance, most probably a (V_Zn-Cl) acceptor, were recorded by monitoring the photoconductivity. The Mn²⁺ could also be detected in the photovoltaic signal. These experiments suggest new techniques to investigate deep centres in semiconductors.     

退火温度对N+注入ZnO:Mn薄膜结构及室温铁磁性的影响

采用射频磁控溅射法在石英玻璃衬底上制备了ZnO:Mn薄膜, 结合N⁺ 注入获得Mn-N共掺ZnO薄膜, 进而研究了退火温度对其结构及室温铁磁性的影响. 结果表明, 退火后ZnO:(Mn, N) 薄膜中Mn²⁺和N^3-均处于ZnO晶格位, 没有杂质相生成. 退火温度的升高 有助于修复N⁺注入引起的晶格损伤, 同时也会让N逸出薄膜, 导致受主(N_O)浓度降低. 室温铁磁性存在于ZnO:(Mn, N)薄膜中, 其强弱受N_O浓度的影响, 铁磁性起源可采用束缚磁极化子模型进行解释.     

Energy spectrum of the A + + e complex in a quantum dot in the adiabatic approximation

The energy states of an A ⁺ + e complex in a quantum dot described within the hard-wall potential model are considered using the zero-range potential method in the adiabatic approximation. These complexes can be formed under nonequilibrium conditions (for example, under photoexcitation). A relationship describing the dependence of the binding energy of a hole located at a neutral acceptor on the parameters of the zero-range potential of the system and the quantum state of the electron is obtained analytically. It is demonstrated that, in quantum dots of small radius, the binding energy of a hole in the A ⁺ + e complex can be considerably higher than the ground-state energy of the A ⁺ stationary center.     

Thermally stimulated luminescence of Ca3(PO4)2 and Ca9Ln(PO4)7 (Ln = Pr,Eu, Tb,Dy, Ho,Er, Lu)

The series of whitlockite compounds Ca₃(PO₄)₂ and Ca₉Ln(PO₄)₇ (Ln = Pr, Eu, Tb, Dy, Ho, Er, Lu) was studied in radioluminescence (RL) and thermally stimulated luminescence (TSL) excited by X-rays. f-f emission lines of Ln³⁺ were observed in RL for Ca₉Ln(PO₄)₇ (Ln = Pr, Eu, Tb, Dy, Ho, Er) whereas d-d emission band of the impurity Mn²⁺ was observed in Mn:Ca₃(PO₄)₂ and Mn:Ca₉Lu(PO₄)₇ at 655 nm. In TSL, the Eu, Ho and Er compounds did not show any signal. As Eu³⁺, Ho³⁺ and Er³⁺ present the highest Ln³⁺/Ln⁴⁺ ionization potential (IP) of the series, this was interpreted as the inability of these lanthanides to trap a hole. On the contrary Pr³⁺ in Ca₉Pr(PO₄)₇, Tb³⁺ in Ca₉Tb(PO₄)₇, Dy³⁺ in Ca₉Dy(PO₄)₇, Mn²⁺ in Mn:Ca₃(PO₄)₂ and Mn:Ca₉Lu(PO₄)₇ were identified as hole traps and radiative recombination centers in the TSL mechanism. Ca₉Tb(PO₄)₇ was found to be a high intensity green persistent phosphor whereas Mn:Ca₉Lu(PO₄)₇ is a red persistent phosphor suitable for in vivo imaging application.     

Modification of the properties of ferromagnetic layers based on A<Superscript>3</Superscript>B<Superscript>5</Superscript> compounds by pulsed laser annealing

Laser annealing experiments were performed in order to increase the concentration of electrically active manganese in the layers of A³B⁵: Mn semiconductors. An LPX-200 KrF excimer laser with a wavelength of 248 nm and a pulse duration of ~30 ns was used. It is shown experimentally that at a pulse energy of an excimer laser of >230 mJ/cm², the hole concentration in GaAs: Mn layers increases to 3 × 10²⁰ cm^–3. The negative magnetoresistance and the anomalous Hall effect with a hysteresis loop for annealed GaAs: Mn samples remain the same up to 80–100 K. Similar changes are observed for InAs: Mn layers as a result of laser annealing.     

<Superscript>57</Superscript>Fe emission Mössbauer spectroscopy following dilute implantation of <Superscript>57</Superscript>Mn into In <Subscript>2</Subscript>O<Subscript>3</Subscript>

Emission Mössbauer spectroscopy has been utilised to characterize dilute ⁵⁷Fe impurities in In ₂O₃ following implantation of ⁵⁷Mn (T _1/2 = 1.5 min.) at the ISOLDE facility at CERN. From stoichiometry considerations, one would expect Fe to adopt the valence state 3 + , substituting In ³⁺, however the spectra are dominated by spectral lines due to paramagnetic Fe²⁺. Using first principle calculations in the framework of density functional theory (DFT), the density of states of dilute Fe and the hyperfine parameters have been determined. The hybridization between the 3d-band of Fe and the 2p band of oxygen induces a spin-polarized hole on the O site close to the Fe site, which is found to be the cause of the Fe²⁺ state in In ₂O₃. Comparison of experimental data to calculated hyperfine parameters suggests that Fe predominantly enters the 8b site rather than the 24d site of the cation site in the Bixbyite structure of In ₂O₃. A gradual transition from an amorphous to a crystalline state is observed with increasing implantation/annealing temperature.     

Free and localized positively charged excitons in the emission spectrum of GaAs/AlGaAs quantum wells

The recombination emission spectra of an excitonic complex (A ⁰ X) localized on a neutral acceptor, which have previously been attributed to a positively charged exciton (X ⁺), are investigated. Satellites arising around the main luminescence line as a result of recoil processes during recombination of the complex which leave the surviving hole in an excited state are observed and investigated. It is shown in a computational model based on the Luttinger Hamiltonian that the energy splittings between the main line and the satellites correspond to an in-barrier impurity center located a definite distance from the well. It is shown that as the magnetic field increases, a transition is observed from the singlet ground state of the complex to a multiplet state. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 3, 223–228 (10 August 1998)     

Anomalous hall effect in Mn δ-doped GaAs/In0.17Ga0.83As/GaAs quantum wells with high hole mobility

Magnetic and magnetotransport properties of GaAs(δ〈Mn〉)/In_0.17Ga_0.83As/GaAs quantum wells with different Mn concentrations are studied. The delta-doped manganese layer has been separated from the GaAs quantum well with a spacer with an optimal thickness (3 nm), which has provided a sufficiently high hole mobility (≥10³ cm²V^?1 s^?1) in the quantum wells and their effective exchange with Mn atoms. It is found that the anomalous Hall effect (AHE) is exhibited only in a restricted temperature range above and below the Curie temperature, while the AHE is not observed in quantum wells with quasi-metallic conductivity. Thus, it is shown that the use of the AHE is inefficient in studying magnetic ordering in semiconductor systems with high-mobility carriers. The features observed in the behavior of the resistance, magnetoresistance, and Hall effect are discussed in terms of the interaction of holes with magnetic Mn ions with regard to fluctuations of their potential, hole transport on the percolation level, and hopping conduction.     

Ab initio calculations of neutral and charged impurity centers of manganese and chromium in strontium titanate

This paper presents the results of ab initio calculations of the equilibrium geometry, the electronic structure, and the spin and charge densities for neutral and negatively charged defects produced by the Mn and Cr impurities in the B position of the SrTiO₃ structure. It has been shown that, in both cases, the neutral defect is an acceptor center, while the singly charged defect is a donor center. It has been found that doubly charged defects are polar, have the symmetry C _4v, and reside in the ionic configurations ⁵Mn³⁺ + ³Ti³⁺ and ⁴Cr³⁺ + ³Ti³⁺, respectively. In each case, there is a pair of almost energy-degenerate electronic states (⁴ B ₁ and ⁶ B ₁ for Mn and ³ A ₁ and ⁵ A ₁ for Cr), which differ only in the direction of the spin of the electron polaron localized at one of the neighboring titanium atoms. For the manganese impurity, the energy of the polar state ⁶ B ₁ is only 0.174 eV lower than that of the state ⁶ A _1g (O _h ) with the Mn²⁺ ion in the high-spin state. A new mechanism of dielectric relaxation in STO: Mn has been proposed.     

Ferromagnetism induced by oxygen-vacancy complex in (Mn,in) codoped ZnO

Mn doped Zinc oxide (ZnO) thin films were prepared by metal organic chemical vapor deposition (MOCVD) technique. Structural characterizations by X-ray diffraction technique (XRD) and photoluminescence (PL) indicate the crystal quality of ZnO films. PL and Raman show a large fraction of oxygen vacancies (V_O²⁺) are generated by vacuum annealed the film. The enhancement of ferromagnetism in post-annealed (Mn, In) codoped ZnO could result from V_O²⁺ incorporation. The effect of V_O²⁺ on the magnetic properties of (Mn, In) codoped ZnO has been studied by first-principles calculations. It is found that only In donor cannot induce ferromagnetism (FM) in Mn-doped ZnO. Besides, the presence of V_O²⁺ makes the Mn empty 3d-t_2g minority state broadened, and a t_2g-V_O²⁺ hybrid level at the conduction band minimum forms. The presence of V_O²⁺ can lead to strong ferromagnetic coupling with the nearest neighboring Mn cation by BMP model based on defects reveal that the ferromagnetic exchange is mediated by the donor impurity state, which mainly consists of Mn 3d electrons trapped in oxygen vacancies.     

Spectroscopy studies of highly acceptor doped GaAs/AlGaAs quantum wells

We present a theoretical and experimental study of optical properties on highly acceptor doped QWs. Steady state photoluminescence (PL) and PL excitation (PLE) results are compared with theoretical calculations involving exchange and correlation effects for the electron-hole system and their interaction with acceptor ions. We have studied the effects of impurity doping at levels varying from 10⁸ up to 10¹³ cm^-2. Excitons can still be detected at high hole concentrations above the degenerate limit. They survive due to the inefficiency of screening in the 2D system.     

Dopant diffusion and segregation in semiconductor heterostructures: Part 1. Zn and Be in III-V compound superlattices

chemical effect on the neutral species; and (ii) a Fermi-level effect on the ionized species, because, in addition to the chemical effect, the solubility of the species also has a dependence on the semiconductor Fermi-level position. For Zn and Be in GaAs and related compounds, their diffusion process is governed by the doubly-positively-charged group III element self-interstitials (I²⁺ _III), whose thermal equilibrium concentration, and hence also the diffusivity of Zn and Be, exhibit also a Fermi-level dependence, i.e., in proportion to p². A heterojunction consists of a space-charge region with an electric field, in which the hole concentration is different from those in the bulk of either of the two layers forming the junction. This local hole concentration influences the local concentrations of I²⁺ _III and of Zn^- or Be^-, which in turn influence the distribution of these ionized acceptor atoms. The process involves diffusion and segregation of holes, I²⁺ _III, Zn^-, or Be^-, and an ionized interstitial acceptor species. The junction electric field also changes with time and position. Received: 20 August 1998/Accepted: 23 September 1998     

Electron spin resonance and optical identification of Fe4+-V0 in SrTiO3

The electron spin resonance of the minority defect Fe⁴⁺-V₀ has been observed in SrTiO₃. It is the first pair center identified with a two-fold positive charge with respect to the lattice. For Fe⁴⁺ it occurs in the unusual high spin S = 2 state. Optically-induced conversion to the neighbor Fe³⁺-V₀ charge state served to identify the acceptor transfer bands, showing the potentiality of the conversion-rate method.     

Valence band contributions to photoluminescence excitation spectra of tightly bound holes in zincblende semiconductors

Photoluminescence excitation (PLE) spectra of deep acceptor states in ZnSe, for example the Cu-related luminescence band at ≈1.95 eV, contain a prominent excitation band at ≈3.25 eV. This band lies above the structure marking the lowest direct E_O band gap E_g by the spin-orbit splitting energy Δ of the valence bands at Γ. The higher energy feature is either absent or greatly de-emphasised in the PLE spectra of shallow acceptor states in ZnSe and of the oxygen iso-electronic trap in ZnTe, where the electron rather than the hole is tightly bound. However, a significant PLE component at E_g + Δ is observed for deep acceptor-like states in ZnTe, where Δ is ≈0.95 eV. Efficient PLE at E + Δ for luminescence from deep acceptor-like states is shown to be consistent with the extended wave-vector contributions to the bound state wave-functions of holes of binding energies ≈Δ.     

A selective hole burning method applied to determine distances between paramagnetic species in photosystems

A method of selective hole burning in EPR spectra was applied to determine the distances from a radical to the acceptor quinone-iron in bacterial and plant photosystems. A low amplitude hole burning 180° pulse and high amplitude 90° and 90° pulses applied to detect ESE of P870⁺ inRb. Sphaeroides and the distance from the primary electron donor P870⁺ to the acceptor Q _A ^? Fe²⁺ was determined to be 26±2 Å from the dipolar broadening of the burned hole in P870⁺ EPR. This result is consistent with that given by X-ray analysis and susceptibility measurement. In plant photosystem II the same method was applied to the EPR spectrum of tyrosine D⁺, but the effect of crystalline field splitting of Fe²⁺ ion was taken into consideration. The effective spin value for the ferrous iron in PS II was found to be 0.8 and the distance between the radical and the non-heme iron was obtained to be 42±2 Å.     

Electronic States and Spatial Charge Distribution of Single Mn Impurity in Diluted Magnetic Semiconductors

The electronic and magnetic properties as well as the spatial charge distribution of single Mn impurity in III--V diluted magnetic semiconductors are obtained when the degeneracy of the p orbits contributed from the four nearest-neighbouring As(N) atoms is taken into account. We show that in the ground state, the Mn spin is strongly antiferromagnetically coupled to the surrounding As(N) atoms when the p-d hybridization V_pd is large and both the hole level E_v and the impurity level E_d are close to the Fermi energy. The spatial charge distribution of the Mn acceptor in the (110) plane is non-spherically symmetric, in good agreement with the recent STM images.