Photoluminescence spectra of Ga-doped and Al-doped 4H-SiC

Blue and violet photoluminescences of Ga-doped and Al-doped 4H-SiC single crystals grown from a Si melt have been studied at 2 ~ 200 K. Luminescence spectra under continuous excitation and their dependences on temperature and excitation intensity as well as temperature dependence of the luminescence intensity are measured. Time-resolved spectra and decay curves after pulsed excitation also are observed at various temperatures. The luminescences at 2 K are found to be due to pair recombination between the N donor introduced unintentionally and the Ga or Al acceptor. The spectra of the two samples resemble each other in shape, and each consists of a zero-phonon peak and its phonon replicas. At higher temperatures, another emission appears due to the recombination of free electrons with bound holes at the acceptors in place of the pair emission. From the energies of the zero-phonon peaks of these two kinds of emissions, the ionization energies of the Ga and the Al acceptors are determined to be 249 ± 3meV+E_x and 168 ± 3 meV + E_x, respectively, where E_x is the exciton binding energy of 4H-SiC, and that of the N donor is estimated to be 55 ± 7 me V using an appropriate approximation.     

Luminescence of CuInS2: II. Exciton and near edge emission

The near-edge (exciton) emission of CuInS₂ is investigated for various material-compositions as a function of temperature. From these investigations the exciton ionization energy (20 meV) and the temperature dependence of the energy gap were determined. For the first time, recombination of the free exciton belonging to the deeper lying Γ₇ valence bands has been observed. Moreover, six different bound exciton emission lines and a donor to valence band transition were detected. These emissions could be assigned in terms of the defect-chemical model presented in Part I.     

Shallow impurity states and the free exciton binding energy in gallium phosphide

A new set of donor and acceptor ionization energies in GaP is deduced from photoexcitation spectra. Energy spectrum of donor states confirms an existence of the “camel's back” with a conduction band minima displacement ≈ 0.08(2π/a) from the X, and the corresponding energy shift ≈ 3meV. The free exciton binding energy in GaP is correctly determined: E_ex = 21 ± 2 meV.     

Photoluminescence of thermally treated n+ Si-doped and semi-insulating Cr-doped GaAs substrates

Photoluminescence measurements are used to investigate the nature of the surface layers formed on n⁺ Si-doped and semi-insulating Cr-doped GaAs substrates after heat-treatment at 780–830°C in H₂ or He flow. At 5.5 K the heat-treated n⁺ substrates exhibit a band near 1.44 eV while the semi-insulating substrates are characterized by a phonon assisted transition with the zero-phonon band at 1.41 eV. Both these bands are identified with donor-acceptor pair recombination. The ionization energy of both the donor and acceptor for the 1.44 eV band is estimated to be ～ 35–40 meV and it is suggested that the acceptor is Si_As. The identities of the donor in the 1.44 eV band as well as that of the centers responsible for the emission at 1.41 eV are unknown.     

Optical properties of the Ge donor and acceptor in GaP

The observation of discrete pair line emission and the analysis of the spectra from Ge donor - C acceptor and S donor - Ge acceptor pairs in GaP is reported. The Ge donor binding energy is 0.200 ± 0.002 eV and the Ge acceptor binding energy is 0.258 ± 0.002 eV. The bound exciton recombination at neutral Ge donors was observed at 2.265 eV corresponding to an exciton binding energy of 0.063 eV. This is the most tightly donor bound exciton observed in GaP.     

Band-edge emission in CuI single crystals

The photoluminescence spectra of CuI single crystals have been studied at T = 4.2 K and at various excitation levels. The emission band of donor-acceptor pairs (DAP) with a maximum at about 4200 Å has been shown to possess a complex structure. Theoretical analyses and exciton spectroscopy data make it possible to calculate the ionization energies for the donors and acceptors participating in the formation of DAP, which are equal to E_D = = 0.045?0.065 eV and E_A = 0.155?0.170 eV, respectively. The fine structure of emission due to the annihilation of excitons bound on acceptor pairs (band maximum 4075 Å) has been detected and calculated. The energy of the longitudinal optical phonon participating in the exciton-phonon interaction (LO ? 18.7 meV) has been determined.     

Optical absorption and electrical conductivity of flash evaporated CuGaTe2 thin films

The optical absorption edge of CuGaTe₂ thin films in the energy range 1 to 2·3 eV was studied. The characteristic band gaps were found to be 1·23 eV and 1·28 eV whereas the acceptor ionization energy was 170 meV. Electrical conductivity measurements were carried out in the temperature range 300–550 K and two acceptor states with ionization energies 400 meV and 140 meV were found. The origin of acceptor states is explained based on covalent model.     

Impurity absorption and luminescence of CuGaSe<Subscript>2</Subscript> crystals

A comparison of the experimental and calculated absorption spectra of CuGaSe₂ crystals revealed the existence of two acceptor levels with ionization energies of 66 and 167 meV in the samples under study. It was found that the luminescence spectra of CuGaSe₂ measured at 77 K exhibit four impurity-band transitions with impurity ionization energies of 66, 99, 136, and 190 meV. An analysis of the temperature dependence of the luminescence intensity in the temperature range 11–77 K revealed a band peaking at 1.671 eV due to the radiation of donor-acceptor pairs. The calculated sum of the ionization energies of the impurities responsible for the formation of donor-acceptor pairs and the temperature dependence of the relative intensities of impurity-band emission were used to determine the ionization energies of the corresponding donor and acceptor.     

A PTIS study of quenched-in acceptors in germanium

The shallow acceptors produced in germanium crystals by quenching from 820–925 C have been studied for the first time using Photo-Thermal Ionization Spectroscopy (PTIS). We have found two acceptor-continua, which correspond to the E_v + 8.4 meV and E_v + 12 meV levels observed in earlier Hall measurements. With the lower energy continuum there are associated two previously unobserved hydrogenic acceptors. They are shallower than any known acceptor in germanium: their ionization energies are 8.69 ±0.01 meV and 9.48 ±0.01 meV. We attribute the acceptors to two different defects because of differences in their creation and annealing behaviour. No discrete lines were found to be associated with the higher energy continuum. We estimate the acceptor ionization energy to be about 14 meV. Finally, we have observed a number of as yet unexplained negative lines superimposed on both acceptor-continua.     

Reevaluation of bandgap and free exciton binding energy of GaP

Very sensitive measurements on the spectral behaviour of the free-to-bound excitation σ_pl^°(hν) from the valence band to the deep 0 donor in GaP at low temperatures are presented. Evaluation of the threshold energy for the electronic transition, together with the known value of the 0 binding energy, provides a simple and accurate way to determine the indirect bandgap E_g of GaP. Our new value is E_g = 2.3525 ± 0.003 eV at 1.5 K, which gives an exciton binding energy E_x = 24 ± 3 meV, considerably larger than previously used values. These data also imply an upward revision of acceptor binding energies in GaP with 10 ± 2 meV.     

Deep level transient spectroscopy measurement on tin-doped n-indium selenide

Deep level transient spectroscopy measurements in indium selenide samples doped with different amounts of tin are reported. Three tin-related electron traps have been detected with activation energies for emission of 56, 74, and 110 meV. The capture cross-section has also been measured and it is very low and weakly dependent on temperature for the 74 and 110 meV deep levels that are attributed to electron trap states related to ionized acceptor centers. For the 56 meV level the apparent capture cross-section shows an activated temperature dependence with an activation energy of 35 meV, which yields an ionization energy of 21 meV for the related level, which corresponds to the tin-related shallow donor. That behaviour is interpreted through the presence in InSe of stacking-fault-related barriers. When one of these barriers is swept by the depletion zone edge during the emptying or filling pulses, electrons must overcome that barrier in order to be emitted or captured, which results in a reduction of the effective capture and emission rates of shallow donors which thus become observable through capacitance transients.     

Effects of S incorporation on Ag substitutional acceptors in ZnO:(Ag, S) thin films

Ag–S codoped ZnO thin films have been fabricated on Si substrates by radio frequency (RF) magnetron sputtering using a thermal oxidation method. XRD and SEM measurements showed that the sample has hexagonal wurtzite structure with a preferential (002) orientation and the surface is composed of compact and uniform grains. Ag_Zn–nS_O defect complexes were observed in the Ag–S codoped ZnO films by XPS analysis. Low temperature PL spectra showed neutral acceptor bound exciton emission related to Ag_Zn–nS_O. The corresponding acceptor ionization energy of 150 meV is much lower than that of monodoped Ag (246 meV), which is favorable for p-type doping of ZnO.     

The nature of the predominant acceptors in high quality zinc telluride

We report very sharp bound exciton luminescence spectra in high quality melt-grown very lightly compensated ZnTe, p-type with N_A-N_D in the low 10⁺¹⁵ cm^-3. Bound exciton localisation energies at seven shallow neutral acceptors with E_A between ~55 and ~150 meV are very insensitive to E_A. Optical absorption and dye laser luminescence excitation spectroscopy were necessary to obtain a full separation of the transitions due to different acceptors, together with a study of certain ‘two-hole’ luminescence satellites in which the acceptor is left in a series of orbital states after bound exciton decay. Two shallow acceptors are P_Te and As_Te, a third possibly Li_Zn while a fourth, relatively prominent in our best undoped crystals, may be a complex. A deeper, 150 meV acceptor, frequently reported in the ZnTe literature and electrically dominant in most of our undoped crystals has the Zeeman character of a point defect. We present clear evidence from our spectra that this energy does not represent the binding of a single hole at a doubly ionized cation vacancy, a popular attribution since 1963. This acceptor may be covered by another impurity, possibly Cu_Zn. We also report bound phonon effects, lifetime broadening of excited bound exciton states and observe a single unidentified donor with E_D ~18.5 meV. This energy is determined using selective dye laser excitation at the weak neutral donor bound exciton line and from the onset of valence band to ionized donor photo-absorption.     

The location and shape of the conduction band minima in cubic silicon carbide

We have measured the inter-bound state excitation spectrum of the N_C donor in cubic β-SiC through the ‘two-electron’ transition satellites observed in the luminescent recombination of excitons bound to neutral N donors. Transitions are seen to p as well as s-like donor states although the transition oscillator strength is derived from interaction with the impurity core since parity is conserved through inter-valley scattering by p-like X phonons. The Zeeman splitting of a luminescence line involving the 2p± donor state yield the electron mass parameter m_t = 0.24 ± 0.01 m₀. This and the directly measured energy separations of the 2p₀ and 2p± states yields m_t/m₁ = 0.36 ± 0.01 with the static dielectric constant K = 9.92 ± 0.1. Mutually consistent central cell corrections of 1.1 and 8.4 meV are observed for the 2s(A₁) and 1s(A₁) donor states, the latter being in agreement with a recent estimate from electronic Raman scattering by Gaubis and Colwell. The ionization donor energy of the N_C donor, 53.6 ± 0.5 meV is consistent with earlier, less accurate estimates from donor-acceptor pair and free to bound luminescence. There is no evidence for a ‘camel's back’ conduction band structure in cubic SiC, unlike GaP. The two-phonon sidebands of the N_C donor exciton luminescence spectrum in SiC can be constructed by X and Г phonons only.     

Site-dependent donor and acceptor levels in 6 H-SiC

The photoluminescence of N- and Al- or Ga-doped 6 H-SiC has been studied. Radiative transitions between free electrons and holes bound to acceptors in cubic-like and hexagonal-like sites are assigned. Donor-acceptor pair transitions between donor and acceptor impurities in cubic-like and hexagonal-like sites are analyzed. From studies on these transitions, the ionization energies of impurities in cubic-like and hexagonal-like sites in 6 H-SiC are estimated to be 248.5 and 239 meV for Al acceptors, 333 and 317 meV for Ga acceptors, and 155 and 100 meV for N donors, respectively. The ratios of the ionization energies of acceptors in the cubic-like sites to the hexagonal-like sites are almost constant, ≈1.04-1.05. The origin of the difference of the ionization energies of impurities in the different sites is discussed on the basis of the quantum defect model. For acceptors this is mainly caused by differences in the local dielectric constants.     

Impurity centers in ZnSe:Na crystals

The influence of sodium impurity on photoluminescence (PL) spectra of ZnSe crystals doped in a growth process from a Se+Na melt is investigated. It is shown that the introduction of the impurity results in emergence of emission bands in the PL spectra due to the recombination of exciton impurity complexes associated with both donors and hydrogen-like acceptors. Apart from that, four bands generated by donor-acceptor pairs recombination and a band produced by electronic transitions from the conduction band to a shallow acceptor are discussed. As a result of the analysis it is concluded that Na impurity forms in ZnSe lattice Na_Zn hydrogen-like acceptors with activation energy of 105±3 meV, Na_i donor centers with activation energy of 18±3 meV, as well as Na_ZnV_Se and Na_iNa_Zn associative donors with activation energy of 35±3 and 52±9 meV, respectively.     

Photoluminescence study of Si doped and undoped Chalcopyrite CuGaSe2 thin films

Photoluminescence (PL) characteristics have been studied on undoped and Si-doped CuGaSe₂ single crystal thin films grown on GaAs (001) substrate by migration-enhanced epitaxy. Room temperature PL spectrum of an undoped layer clearly shows free excitonic emission bands related to the minimum band-edge and to the split-off valence band, but no discernible emission has been observed in the low energy area. At 4.2 K, the excitonic emission due to the split-off valence band disappears. Instead, two additional emissions appear at 1.68 and 1.715 eV which are attributed to the bound exciton and band-to-acceptor transition. The Si doping to CuGaSe₂ produces two additional PL bands around 1.61 and 1.64 eV. These PL bands are attributed to the donor acceptor pair emissions due to the doped Si impurity which probably occupies Cu or Ga sites and intrinsic Cu vacancy.     

Optical properties of p-type ZnO doped by lithium and nitrogen

A lithium and nitrogen doped p-type ZnO (denoted as ZnO: (Li, N)) film was prepared by RF-magnetron sputtering and post annealing techniques with c-Al₂O₃ as substrate. Its transmittance was measured to be above 95%. Three dominant emission bands were observed at 3.311, 3.219 and 3.346 eV, respectively, in the 80 K photoluminescence (PL) spectrum of the p-type ZnO:(Li, N), and are attributed to radiative electron transition from conduction band to a Li_Zn-N complex acceptor level (eFA), radiative recombination of a donor-acceptor pair and recombination of the Li_Zn-N complex acceptor bound exciton, respectively, based on temperature-dependent and excitation intensity-dependent PL measurement results. The Li_Zn-N complex acceptor level was estimated to be about 126 meV above the valence band by fitting the eFA data obtained in the temperature-dependent PL spectra.     

Optically detected electron resonance in phosphorus-doped ZnTe

Samples of ZnTe showing near gap edge luminescence predominantly due to exciton recombination at shallow neutral acceptors and donor- acceptor pair recombination have been investigated using optically detected magnetic resonance (ODMR). Emission polarization changes at 2.318 eV were observed due to magnetic resonance of electrons at g_e = + 0.401 ± 0.004. The observations are consistent with the donor trapped electron resonance resulting from microwave induced changes in donor-acceptor pair photoluminescence.     

Photoluminescence and recombination centers in phosphorus-doped and undoped CdTe heat-treated under component vapour pressures

Photoluminescence spectra in heat-treated CdTe : P and undoped CdTe were studied at temperatures of 4.2–77 K in the edge emission and the exciton emission region. Temperature dependences and excitation intensity dependences were measured, and the recombination mechanism of each emission line was identified. A change in recombination centers with p_Cd was studied. In a heavily doped crystal an acceptor A₂ (66 meV) was dominant at low p_Cd and the phosphorus acceptor (78 meV) at high p_Cd. A rather deep donor (about 35 meV) was also observed. In a lightly doped crystal the spectra were intermediate between those of the undoped and the heavily doped crystas, and the emission line due to the phosphorus acceptor was not observed. In an undoped crystal an acceptor A₁ (52 meV) was dominat at low p_Cd and the A₂ acceptor at medium and high p_Cd.