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# Ab initio molecular dynamics study of liquid methanol

## 1. Introduction

Liquid methanol is of fundamental interest in natural sciences and of significant importance in technical and industrial applications. The liquid phase of the simplest alcohol is widely studied, both experimentally and theoretically. Among the alcohols, methanol is the closest analog to water. The characteristic hydroxyl group allows methanol to form hydrogen bonds that dominate the structural and dynamical behavior of the liquid phase. The methyl group does not participate in the hydrogen bonding and constitutes the distinction with water. This difference is apparent in the microscopic structure of the liquid, with water having a tetrahedral-like coordination, whereas for methanol experiments and molecular simulation suggest a local structure consisting of chains, rings, or small clusters.

The precise quantification of the microscopic structural and dynamical picture of liquid methanol has been a long-time subject in both experimental and molecular simulation studies. Recently, a series of state-of-the-art studies have been reported. Among these are the neutron diffraction (ND) experiments of Refs. . Simulation studies include work based on empirical force-fields, mixed empirical and ab-initio interactions, and a full ab initio molecular dynamics study. The recent ND experiments have provided a detailed microscopic picture of the structure of liquid methanol, including the pair distribution functions among all atoms. Yet, some of these atom-atom distribution functions are still subject to some uncertainty as they are obtained indirectly.

Molecular simulation provides a complementary approach to study the microscopic behavior of liquids. Most molecular simulations studies of liquid methanol are based on empirical force fields potentials that are designed to reproduce a selection of experimental data. Obviously, molecular simulations based on these potentials do not provide a picture completely independent from experiment. Moreover, the reliability of the results at conditions that are significantly different from those where the potential was designed for, may be questionable. Density functional theory (DFT) based molecular dynamics (MD) simulation, such as the Car-Parrinello molecular dynamics method, where the interactions are calculated by accurate electronic structure calculations provides a route to overcome these limitations. This has been demonstrated in studies of liquid water and aqueous solvation. Important advantages of DFT-MD over force-field MD are that it intrinsically incorporates polarization, that it accounts for the intra-molecular motion and therefore allows for a direct comparison with spectroscopy of intra-molecular vibrations, and that it yields detailed information on the electronic properties, such as the energy levels of electronic states and the charge distribution. In a broader chemical perspective it is important to note that DFT-MD is capable of the study of chemical reactions in solution, where force-field MD would fail completely as it cannot account for the change in chemical bonding.

Here, we report a DFT-MD study of liquid methanol that addresses the liquid structure, the inter- and intra-molecular dynamics, and the electronic charge distribution.

## 2. Methods and Validation

Electronic structure calculations are performed using the Kohn-Sham formulation of DFT. We employed the gradient-corrected BLYP functional. The choice for the BLYP functional was guided by its good description of the structure and dynamics of water where hydrogen bonds are, as in liquid methanol, the dominant interactions. Furthermore, it has been shown that DFT-BLYP gives a proper description of solvation of methanol in water.

The DFT-based MD simulations are performed with the Car-Parrinello method  using the CPMD package. Semi-local norm-conserving Martins-Troullier pseudopotentials are used to restrict the number of electronic states to those of the valence electrons. The pseudopotential cut-off radii were taken $`0.50`$, $`1.11`$ and $`1.23`$ a.u, for H, O, and C, respectively. The electronic states are expanded in a plane-wave basis with a cut-off of $`70`$ Ry yielding energies and geometries converged within $`0.01`$ Å and $`1`$ kJ/mol, respectively. Vibrational frequencies are converged within $`1`$ %, except for C-O and O-H stretch modes that are underestimated by $`3`$ % and $`5`$ % compared to the basis-set limit values.

To validate our computational approach we compared results for the gas-phase monomer and hydrogen-bonded dimer against state-of-the-art atomic-orbital DFT calculations obtained with ADF,111 Kohn-Sham orbitals are expanded in an even-tempered, all-electron Slater type basis set augmented with 2p and 3d polarization functions for H and 3d and 4f polarization functions for C and O. and against the B3LYP and MP2 calculations of Ref. . The CPMD-BLYP calculations were performed using a cubic box with an edge of 12.9 Å, with the interactions among the periodic images eliminated by a screening technique. Results for geometry and complexation energy of the dimer are given in Fig. 1 and Table 1. Deviations among CPMD and ADF are 1 kJ/mol for the complexation energy, smaller than 0.01 Å for the intra-molecular bonds, and smaller than 0.02 Å for the hydrogen bond. This indicates a state-of-the-art accuracy for the numerical methods employed in CPMD. Compared to the MP2 and B3LYP results, the BLYP bond lengths are slightly longer, with deviations up to $`0.03`$ and $`0.05`$ Å for the intra- and inter-molecular bond lengths, respectively. Differences among BLYP, B3LYP and MP2 complexation energies are within acceptable limits, with the BLYP energies smaller by 2-4 kJ/mole. The deviations are similar to the comparison between BLYP and MP2222MP2 limit estimate. See for example  for the water dimer and the water-methanol dimer. We obtained a zero-Kelvin association enthalpy $`\mathrm{\Delta }H^0(0)`$ of $`10.6`$ kJ/mol using the B3LYP zero-point energy of Ref. . This is in reasonable agreement with the experimental value of 13.2(4) kJ/mol. The calculated hydrogen bond length ($`r_{\mathrm{O}\mathrm{}\mathrm{O}}=2.94`$ Å, $`r_{\mathrm{H}\mathrm{}\mathrm{O}}=1.95`$ Å) is in good agreement with the experimental values of $`r_{\mathrm{O}\mathrm{}\mathrm{O}}=2.98(2)`$Å and $`r_{\mathrm{H}\mathrm{}\mathrm{O}}=1.96(2)`$ Å of Refs.  and , respectively.

Current gradient corrected functionals such as BLYP do not account for dispersion forces. For methanol this could be important as attraction to the methyl group is fully due to the dispersion force. To estimate the effect of the absence of the dispersion we computed the BLYP binding energy of two dimer configurations that are sensitive to this: one with methyl groups approaching (M-M) and the other with the methyl and hydroxyl group approaching each other (M-OH). State-of-the art MP2 calculations, that incorporate to a good approximation the dispersion force, serves as a reference. The dimer configurations were taken from Ref.  and chosen such that the carbon-carbon (M-M dimer) and carbon-oxygen (M-OH dimer) distances were close to the peak position of their atom-atom distribution function in the liquid state.333 Configuration from Ref. . M-M dimer: geometry M with $`r_{\mathrm{CC}}=3.75`$ Å. M-OH dimer: geometry I with $`r_{\mathrm{CO}}=3.50`$ Å. Both monomers in the dimer are kept fixed to their isolated geometries. The comparison yields for the M-M dimer values of $`2.3`$ kJ/mol and $`2.0`$ kJ/mol for BLYP and MP2, respectively. For the M-OH dimer these values are $`1.2`$ kJ/mol and $`4.9`$ kJ/mol, respectively. The too repulsive nature of the BLYP interaction is consistent with DFT calculations of dispersion dominated systems. However, although by far not insignificant, the magnitude of the deviation is much smaller than the hydrogen-bond interaction and of the same order of magnitude as the error in the latter. It can therefore be argued that for a study of liquid methanol on the accuracy level of BLYP, neglecting the dispersion interaction is acceptable.

In Ref.  we have shown that for the gas-phase monomer CPMD-BLYP vibrational frequencies are in excellent agreement with ADF results and, compared to experiment, underestimate allmost all modes by $`10\%`$, a known feature of the BLYP functional.

Overall, we conclude that our level theory is satisfactory in comparison with experimental and other theoretical gas-phase data.

## 3. Liquid

Liquid methanol was modeled by 32 molecules in a periodic cubic box with an edge of 12.9 Å, reproducing the experimental density of 0.791 g/cm3 at 293 K. The temperature was fixed at 293 K using the Nosé-Hoover thermostat . The fictitious mass associated with the plane-wave coefficients is chosen at 900 a.u., which allowed for a time step in the numerical integration of the equations-of-motion of 0.145 fs. The system was equilibrated for 1 ps from an initial configuration obtained from a force-field simulation. Subsequently, we gathered statistical averages from a 6 ps trajectory.

### 3.1 Structure

In Fig. 2 we have plotted the most characteristic atom-atom radial distribution functions (RDFs), i.e. the hydrogen bonding O-O, O-HO, and HO-HO RDF and the C-O RDF. For comparison we also plotted results of recent ND results and the peak positions obtained using Haugney’s empirical potential, the latter being considered one of the most accurate empirical force fields to date.

The pronounced structure in the first three RDFs are a clear indication of the presence of hydrogen bonds. Comparison with the experimental data shows that the positions of the first peaks match within the statistical error for the O-O and O-HO RDFs and is slightly smaller ($`0.1`$ Å) for the HO-HO RDF. The height of the first peak is in good agreement for the O-HO and HO-HO RDFs, that both can be determined accurately from the ND data. However, the O-O RDF shows a calculated first peak height that is significantly lower than the experimental result. Given the small system of 32 molecules in our simulation, the discrepancy could well be a system-size effect. On the other hand, the indirect way by which the the O-O RDF is extracted from ND data could yield an overestimate of the O-O correlation. Comparison with force field results, that yield significant higher peak values for the O-O and O-HO RDFs, suggests that the Haugney potential overestimates the hydrogen bonding structure in the liquid, in line with the observation of Ref. .

The number of H-bonds as calculated by integrating the O-HO and O-O RDFs up to the first minimum, and using the geometrical criterion of Ref. , yields values of $`1.9`$, $`2.0`$, and $`1.6`$, respectively. This is in good agreement with the experimental ND results of Ref.  yielding $`1.8`$ and $`1.9`$ obtained by integrating the O-HO and O-O RDFs. Applying the geometrical criterion to the Haugney force-field simulation yields a slightly higher value of $`1.9`$.

The hydrogen bonding in the liquid phase is accompanied by an elongation of the OHO bond of $`0.15`$ Å. A direct comparison with the experimental results for this change in the geometry of the methanol molecule is rather difficult due to the large spread in the reported values. However, similar change in the geometry is observed in the DFT-MD study of liquid methanol reported in Ref.  and in ab initio studies of small methanol clusters.

The calculated C-O RDF is in reasonable agreement with the ND results, with the overall shape well reproduced but the first peak clearly less pronounced than in the ND result. This is consistent with the, in the previous section found, underestimation of the BLYP binding energy of the M-O dimer with a C-O distance at the RDF peak position. This is due to the absence of the dispersion interaction in BLYP. However, the absence of the dispersion interaction clearly does not lead to a completely distorted C-O positional correlation. The comparison of the calculated C-C RDF with the ND result (not plotted) is very similar.

### 3.2 Dynamics

The time scale of the present simulation (6 ps) allows for an analysis of the short-time dynamics of liquid methanol. Figure 3 shows the power spectrum of the velocity auto correlation function (VACF) of the hydroxyl hydrogen. For comparison we have also plotted the calculated 200 K monomer spectrum of Ref. . The three distinct peaks correspond to the OH stretch (3100 cm-1), C-O-H bend (1600 cm-1), and the CO stretch (1000 cm-1). The broad feature below 1000 cm-1 indicates the librational-translational (500 cm-1) modes of the methanol molecules. Compared to the gas phase, the liquid OH stretch mode has red-shifted by approximately 200 cm-1 and broadened considerably. On the other hand, the C-O-H bending is blue-shifted by approximately 70 cm-1. The observed shifts and broadening are characteristic for hydrogen bonded liquids and also observed in the spectrum of water or hydrated methanol. The calculated shifts compare reasonably well with experimental infrared spectra that yield values of $``$354 cm-1 and +78 cm-1 for the O-H stretch and C-O-H bend. The calculated positions and shifts of the modes match within statistical errors with those of methanol in aqueous solution determined using the same computational approach. This indicates that the intra-molecular dynamics of methanol is affected in a similar way by an aqueous environment and a methanol environment.

The diffusion constant $`D`$ is a key measure of the collective dynamics. In view of the limited length of the calculated trajectory we can only provide a rough estimate. From the mean square displacement of the oxygen atoms we obtained $`D=2.0\pm 0.6\times 10^9m^2/s`$, in reasonable agreement with the experimental value of $`2.42\pm 0.05\times 10^9m^2/s`$ .

### 3.3 Electronic properties

As the electronic structure is an intrinsic part of a CPMD simulation, detailed information on the electronic charge distribution is obtained. To quantify the charge distribution we used the method of maximally localized Wannier functions that transforms the Kohn-Sham orbitals into Wannier functions whose centers (WFC) can be assigned with a chemical meaning such as being associated with an electron bonding- or lone-pair (LP).

We calculated the positions of the WFCs for the monomer, the dimer, and 6 independent configurations of the liquid simulation. Table 2 lists the (average) distances of the WFCs associated with the oxygen electrons. Most notably is the small but significant shift of $`0.024`$ Å for the OH bond WFC towards the oxygen atom when going from the monomer to the liquid. At the same time, one of the LP WFCs shifts away from the oxygen by $`0.023`$Å. These changes should be considered a manifestation of the hydrogen bonding and the induced polarization among the dipolar methanol molecules in the liquid state.

To quantify the change in the charge distribution in a single number we calculated the molecular dipole moment assuming the electronic charge to be distributed as point charges located on the WFCs. For liquid water it has been shown that such a partitioning of the charges over the molecules yields a unique assignment of the WFCs over distinct molecules. From Table 3, that lists the values for the monomer, dimer, and liquid, we observe a significant enhancement of the dipole moment going from the monomer via the dimer to the liquid. A comparable liquid-state value of 2.39 D has been observed in a coupled empirical and ab initio MP2 study. Note that the value of the dipole moment is somewhat larger than in the Haugney (2.33 D) or AMBER (2.2 D) force field. A second important feature of the electronic charge distribution in the liquid is its fluctuating character due to the thermally driven configurational changes. In Fig. 4 we have plotted the calculated distribution of the dipole moments in the liquid phase. It shows that there is a significant variation ranging from 1.7 D to 3.5 D.

## Conclusions

We have demonstrated that *ab initio* MD is a valuable approach to study the structural, dynamical, and electronic properties of liquid methanol. The calculated pair distribution functions involving the hydroxyl hydrogens correlate well with recent state-of-the-art neutron diffraction experiments of Soper and co-workers. It confirms their finding that one of the benchmark empirical potentials overestimates the hydrogen bonding structure. The calculated oxygen-oxygen radial distribution function shows significantly less structure than the experimental neutron diffraction results. Currently we are studying a larger simulation sample to see whether this is due to the small system size in the present calculation. It could also be a result from an inaccuracy in the experimental result that is obtained in an indirect way. Results for the dimer binding energies and the oxygen-carbon RDF suggest that the absence of the dispersion interaction is notable but has no major impact. Comparing the vibrational spectra of the liquid phase against that of the gas phase monomer shows a significant red shift of the O-H stretch accompanied by a smaller blue shift of the C-O-H bend mode, in reasonable agreement with experimental observations with the O-H shift somewhat underestimated in our calculation. We quantified the electronic charge distribution using a Wannier function decomposition. A small but measurable shift of the positions of the Wannier function centers when going from the gas-phase to the liquid is accompanied by a substantial enhancement of the dipole moment. Moreover we have found that in the liquid the dipole moment fluctuates significantly with variations up to half the average magnitude. The latter suggest that the assumption made in empirical potentials using a fixed dipole moment is a strong simplification. The present results may be considered valuable data for improvement of empirical potentials for the study of liquid methanol.

We are grateful to A.K. Soper for providing us data of the RDFs of Ref. . J.-W.H. and T.S.v.E acknowledges NWO-CW (Nederlandse Organisatie voor Wetenschappelijk Onderzoek, Chemische Wetenschappen), J.-W.H through PIONIER. E.J.M. acknowledges the Royal Netherlands Academy of Art and Sciences for financial support. We acknowledge support from the Stichting Nationale Computerfacileiten (NCF) and the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO) for the use of supercomputer facilities.


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# Ultrafast carrier relaxation in GaN, In0.05Ga0.95N and an In0.05Ga0.95N/In0.15Ga0.85N Multiple Quantum Well

## I Introduction

Technological advances in group-III nitride-based optoelectronics have been possible with extensive materials research, resulting in the commercialization of short wavelength emitters and detectors.NakamuraBLD1997 ; NakamuraJJAP95 ; NakamuraJJAP1997-2 ; CarranoJAP1998  The active layers in high efficiency emitters, such as blue/green light emitting diodes and blue/purple laser diodes, contain InGaN alloys. Time scales for carrier recombination, transport, and quantum well capture in the ultrafast regime determine the efficiency of optoelectronic devices. Therefore it is important to understand the carrier relaxation and recombination mechanisms in InGaN structures. In addition to many studies on recombination times,ChichibuJVST1998 ; ChichibuMSEB1999 ; BerkowiczPRB2000  there have been a limited number of reports on ultrafast carrier dynamics in InGaN heterostructuresChoiPRB2001-2 ; OmaePSSA2002  and multiple quantum wells (MQW).KawakamiAPL2000 ; SatakePRB1999  Measurements on heterostructures, single QWs, and MQWs have emphasized different aspects of carrier relaxation in nitrides. In this paper, we report comprehensive room temperature ultrafast measurements on a bulk GaN, an InGaN epilayer, and an InGaN MQW sample having barriers with the same In composition as the epilayer sample.

In achieving the current state of nitride device development, overcoming material growth difficulties has been the main focus. The efficiencies of InGaN-based emitters are strongly affected by material inhomogeneities such as compositional fluctuations and indium-phase separation. However, inhomogeneities in the form of quantum dot-sized In-rich regions are observed to increase lateral confinement, thereby increasing the emission efficiencies of InGaN devices. The effect of these In-rich regions on electron-hole recombination through spontaneous emission (SPE) has been studied extensively.ChichibuJVST1998 ; MartinAPL1999 ; RibletAPL1999  In spite of imperfect material properties, high emission efficiencies are observed not only through enhanced SPE but also through stimulated emission (SE) generated at moderate pump powers. There have been many reports on SE in InGaN epilayersSatakePRB1998 ; ShmaginJAP1997 and MQW structures.SchmidtAPL1998 ; SchmidtAPL1998-2 ; BidnykAPL1998  However SE and its effects on carrier relaxation is poorly understood. In this study, ultrafast dynamics in the presence and absence of SE are investigated.

Three samples, a GaN epilayer, an InGaN epilayer, and an InGaN MQW structure, were grown on c-plane double polished sapphire by metalorganic chemical vapor deposition at the University of California, Santa Barbara.KellerJCG1998  The GaN sample is $``$ 3 $`\mu `$m thick, and the buffer layers in the other two samples are $``$ 2 $`\mu `$m thick GaN:Si. InGaN epilayer sample consists of a 60 nm thick In0.05Ga0.95N:Si layer, capped with another 15 nm thick GaN layer. The InGaN MQW is a typical laser active layer structure with 10 periods of 8.5 nm In0.05Ga0.95N:Si barriers and 3.5 nm In0.15Ga0.85N quantum wells. There is a 100 nm GaN cap layer on top of the MQW. The doping in the barriers and in the InGaN epilayer is $``$ 1018 cm-3.

In section II, techniques used in the experiment are introduced. Then the results for each sample are respectively considered as subsections of section III. In each subsection, first continuous-wave (cw) and time integrated measurements are presented to identify the band structures. The investigation of carrier relaxation dynamics follows, using non-degenerate time-resolved differential transmission (TRDT) spectroscopy. To understand the effects of the underlying buffer and cap GaN layers, and to understand the effects of the 3D InGaN barriers in the MQW sample, measurements on the bulk GaN sample and on the InGaN epilayer sample are discussed, respectively. Above- and below-bandgap excitation data are presented to explore the excitation wavelength dependence of the GaN and InGaN relaxation phenomena.

Similarly, measurements on the MQW sample are reported for above-, at-, and below-barrier energy excitations. Time-resolved data for the MQW sample are compared with results from a previous study of carrier capture times using degenerate TRDT.OzgurAPL2000

## II Experimental Techniques

### II.1 Continuous wave and time-integrated characterization

Continuous-wave (cw) photoluminescence (PL), PL excitation (PLE), and absorption measurements were performed at room temperature. Cw-PL was measured at excitation power densities of 100 W/cm2 using a 25 mW HeCd laser operating at 325 nm (3.82 eV). A 300 W Xe Lamp was used for PLE and cw-absorption measurements. Xe Lamp was dispersed by a 30 cm double grating spectrometer for the PLE, and both cw-PL and PLE were detected by a photomultiplier tube attached to a 75 cm grating spectrometer. Another 30 cm grating spectrometer with a charge coupled device (CCD) was used for the absorption measurements.

Pulsed excitation, time-integrated PL (TI-PL) is performed on the samples at room temperature using 1 kHz, $``$10 $`\mu `$J pulses from an optical parametric amplifier, at excitation power densities varied between 20 $`\mu `$J/cm2 and 2 mJ/cm2, either by changing the focus or using neutral density filters. For high enough excitation densities, SE features are observed for all the samples. To obtain the SE threshold densities, PL from the samples was detected both normal to the surface from the front and parallel to the surface from the edges. Edge detection produced stronger SE signals, making it the preferred detection scheme. The samples were excited normal to the surface, and the PL was collected from the edge using a 600 $`\mu `$m diameter UV-VIS fiber. A CCD attached to the 30 cm spectrometer was used for detection. Both the spectrally-integrated PL intensity and the emission linewidth were plotted as a function of pump power density and found to give identical SE thresholds.

### II.2 Time-resolved characterization

Previously, standard wavelength-degenerate, time-resolved differential transmission (TRDT) measurements were performed on the MQW sample, using a frequency-doubled mode-locked Ti:Sapphire laser. OzgurAPL2000  In this study, non-degenerate TRDT spectroscopy was applied at room temperature. A Ti:Sapphire laser-seeded, 1 kHz Quantronix Titan regenerative amplifier (RGA) with 1.8 mJ , 100 fs pulses at 800 nm was used. Half of the RGA output power is used to pump a Quantronix TOPAS optical parametric amplifier (OPA). The signal output from the tunable OPA is frequency quadrupled and used as the pump in the DT experiment. The other half of the RGA output is frequency doubled in a BBO crystal and focused on a quartz cell filled with D2O to generate a broadband continuum probe centered near 400 nm (3.11 eV). The continuum probe, which has relatively minor amplitude fluctuations over its $`>`$ 100 nm bandwidth, is highly attenuated by spatial filtering, then collected and focused on the sample using a spherical mirror. The pump beam is delayed with respect to the probe beam using a retroreflector mounted on a 1 $`\mu `$m-resolution translational stage. The probe, transmitted through the sample, is then collected by a UV liquid light guide, sent to the 30 cm grating spectrometer, and detected by a CCD camera attached to the output port. It is important to note that the excitation regime in this study is much higher ($`>`$100 $`\mu `$J/cm2) than the previous study of degenerate TRDT ($``$1 $`\mu `$J/cm2).OzgurAPL2000  Using a pump intensity-independent absorption constant of 105 cm-1, MuthAPL1997  the number of photo-injected carriers in the MQW sample is estimated to be 1017 cm-3 for the previous study, and $`>`$1019 cm-3 for this work. These carrier densities are larger for the GaN sample due to its larger thickness.

First, the continuum probe spectrum is recorded. Next, the pulsed absorption spectrum of the sample is obtained by comparing the continuum probe spectrum and the spectrum of the probe transmitted through the unpumped sample. Some absorption features that were not clear in the cw-absorption data were easily observed in the pulsed absorption spectra due to larger excitation density. Then, pump-probe measurements are made by comparing the transmission of the probe through the sample with and without the pump beam for various delays up to 0.4 ns. The absolute DT signal at energy h$`\nu `$ is

$$DT(h\nu )=\frac{T_{PumpON}(h\nu )T_{PumpOFF}(h\nu )}{T_{PumpOFF}(h\nu )}=\mathrm{}\alpha (h\nu )d,$$
(1)
where $`T_{PumpON}`$ and $`T_{PumpOFF}`$ are the probe transmission signal magnitudes with the pump beam on and off, respectively. $`\mathrm{}\alpha `$ is the change in the absorption coefficient, and $`d`$ is the thickness of the sample over which the change in absorption is induced. Pump and probe spot diameters on the samples were $``$1 mm and $``$0.2 mm, respectively. The absorption from the bare probe beam was observed to be much smaller than the absorption due to the pump beam, suggesting that the modulation in the DT signal is purely from the pump.

TRDT data is presented in two different ways, spectrally-integrated and spectrally-resolved, in order to elucidate different aspects of the relaxation processes. Spectrally-integrated DT gives an indication of the total population of carriers (i.e. density of states) and their aggregate decay, while spectrally-resolved DT describes the distribution of carriers and indicates their energy relaxation pathways.

Due to the thick GaN layers, strong absorption at the GaN band edge allows only weak transmission of the probe beam for all the samples. Therefore, a small pump-induced change in the absorption at the GaN energy will yield a large TRDT signal. Spectrally-resolved TRDT data for all the samples show oscillations that arise from the interference of the multiple reflections in the sample.

Similar non-degenerate TRDT measurements have been performed on GaN,OmaePRB2002 ; ChoiPRB2001  InGaN epilayersChoiPRB2001-2 ; OmaePSSA2002 , and InGaN MQWs KawakamiAPL2000 ; SatakePRB1999 ; OmaePSSA2002 ; KawakamiJPCM2001 , by different groups. These studies provide insights on important aspects of carrier relaxation dynamics. In this study, a more comprehensive investigation is made, focusing on relaxation over many time scales, sub-picosecond to nanosecond, as a function of excitation wavelength and density. The role of stimulated emission on carrier dynamics is also studied in both spectrally-integrated and spectrally-resolved data.

## III Results and Discussion

### III.1 Differential transmission of bulk GaN

The cw-PL from the bulk GaN sample is centered at 3.41 eV (Fig. 1) when excited above (3.82 eV) the bandgap, in agreement with the 3.41 eV GaN band edge obtained from pulsed absorption measurements. Pulsed-PL showed another peak at 3.31 eV due to electron-hole plasma (EHP) induced SEHerzogAPL2000 ; HolstMRSIJNSR1997 ; JursenasAPL2001  with a threshold of 70 $`\mu `$J/cm2. The SE peak is observed to redshift by 25 meV and broaden (from 37 meV to 66 meV) with increasing pump intensity (from 40$`\mu `$J/cm2 to 2 mJ/cm2). When the sample is excited below (3.34 eV) the bandgap, no PL is observed.

The spectrally-integrated TRDT data for the GaN at excitation energies above (3.82 eV) and below (3.34 eV) the bandgap are shown in Fig. 2. For below bandgap excitation, increased transmission is observed for a very short time, less than 1 ps. Data for the above bandgap excitation shows a similarly rapid rise ($`<`$ 1 ps), a $``$2 ps-wide peak, and a fast decay (3-6 ps), followed by a much slower relaxation (100’s of ps). For both excitations, the early, strong increase in transmission at the GaN band edge is due to photo-excited carriers and the dynamic (AC) Stark effect.OmaePRB2002 ; ChoiPRB2002  The wide peak and fast relaxation are due to the operation and removal of carriers through SE, which occurs when the pump density is above threshold (70 $`\mu `$J/cm2) and ends when the number of carriers is reduced below threshold. The time constant for SE decay at excitation density of 300 $`\mu `$J/cm2 is measured to be $``$2 ps.

Spectrally-resolved results from the TRDT measurements on the GaN sample (Fig. 3) confirm these findings for excitations above and below the GaN band edge. For above bandgap excitation (Fig. 3a), the carrier distribution is broad ($``$80 meV) and extends below the bandgap ($``$3.34 eV) during the first 1.2 ps. The carriers relax to the GaN band edge in $``$ 2ps through multiple LO-phonon and carrier scattering events required to cool the carriers as much as 400 meV.GaNabsorption  The 2 ps-wide SE feature in the spectrally-integrated DT is observed during this cooling. After 2 ps when the carrier redistribution is finished, a clear decay due to SE becomes visible, with a decay constant of $`2`$ ps. At later times (17 ps), the lower energy part (3.34 eV - 3.37 eV) of the distribution disappears, while carriers near the GaN band edge show increasing absorption. The decay of the low energy part might be explained by the blueshift of the SE, and carrier energy, in the EHP after the number of carriers is decreased through SE. This is supported by the fact that SE redshifts with increasing carrier density due to increased coulombic repulsion.HolstMRSIJNSR1997

For excitation 80 meV below the bandgap (Fig. 3b), the generation of carriers may seem more surprising, especially because it cannot be explained as an assist from room temperature thermal energy kBT (26 meV) or from the pulse bandwidth (25 meV). It is well known that the excitonic resonances are visible even at room temperature for GaNMuthAPL1997 , and AC Stark effect has been observed for GaN for detunings as large as 159 meV below the excitonic resonance.ChoiPRB2002  The bleaching which exists during the intense pump pulse and lasts less than 500 fs is an indication of the AC Stark effect. This short-lived AC Stark feature in Fig. 3b is observed in all the samples as the very fast increase and decay of the spectrally-integrated DT for below band gap excitations (e.g. Fig. 2). The residual change in the DT which persists as long as 400 ps is due to real excitation of carriers by the two-photon absorption of the intense pump pulse (300 $`\mu `$J/cm2).

At longer delays, induced absorption is observed at the GaN energy for both above and below band gap excitations. The observed slow relaxation is due to decaying remnant carriers and excitons at the GaN band edge. The rate of this decay is observed to be slower than 300 ps, which is consistent with the recombination lifetimes obtained for GaN.MuthAPL1997 ; JursenasAPL2001

### III.2 Differential transmission of an In0.05Ga0.95N epilayer

The PL emission from the In0.05Ga0.95N epilayer (Fig. 1) occurred at $``$3.20 eV for cw excitation (100W/cm2) from the HeCd laser (3.82 eV). This is slightly lower than the band gap values for In0.05Ga0.95N in the literature, constrained between $`3.220`$ eV to $`3.224`$ eV.wetzelAPL98 ; mccluskeyAPL98  TI-PL is only observed for above bandgap excitation, never for below bandgap excitation. The cw-absorption (Fig. 1) suggests an In0.05Ga0.95N band edge of 3.26 eV. When the broadening of the band edge is taken into account, an effective band edge of 3.22 eV is obtained from a sigmoidal fitMartinAPL1999 , giving a 20 meV Stokes’ shift. Since the piezoelectric (PZE) field in the InGaN epilayer is already reduced remarkably with Si doping, the band edge changes very little with pulsed laser excitation. Thus, screening of the PZE field does not produce a remarkable blueshift. This is verified by pulsed absorption measurements which suggest an In0.05Ga0.95N band edge of $``$3.26 eV, similar to the cw-absorption.

The spectrally-resolved TRDT data for the InGaN sample is shown in Fig. 4. Pump wavelengths for Fig. 4a and Fig. 4b were above (3.35 eV) and just below (3.23 eV) the InGaN bandgap, respectively. Before considering carrier dynamics in the InGaN layer, it is useful to reconsider carrier dynamics in the GaN layers in this sample. The pump energies are 60 meV, and 180 meV below the GaN bandgap, respectively. As in the below bandgap data for bulk GaN (Fig. 3b), it is first observed that the transmission increases from carrier generation and AC Stark effect in the GaN, reaching a maximum in $``$ 300 fs at the GaN band edge (3.41 eV) for both pump energies. AC Stark effect is observed in the GaN layers of the InGaN epilayer sample in a manner similar to the below band gap excitation of the GaN sample. The magnitude of the AC Stark effect is smaller for the larger detuning of 190 meV in Fig. 4b. Real carriers are also generated at the GaN band edge due to two-photon absorption, but unlike the GaN sample they can quickly ($`<`$1 ps) decay into lower InGaN states through carrier-LO phonon and carrier-carrier scattering processes. This makes the distinction between the two-photon absorption and the AC-Stark effect more difficult. The small decreases (above bandgap) or increases (below bandgap) in absorption at the GaN band edge (3.41 eV) after 5 ps are due to the remnant carriers and excitons at the GaN interface and trap states. The two-photon induced carrier absorption feature in bulk GaN (Fig. 3b) remains visible after 408 ps with no remarkable reduction in its amplitude. This contrasts with the more complex induced absorption and transmission in the GaN cap and buffer layers of the InGaN sample (Fig. 4b) which varies with excitation energy and time but remains for at least 400 ps. The differences can be attributed to carrier relaxation from the GaN layers to the InGaN epilayer and the reduced role of SPE in the GaN layers and trap states.

Regarding carrier dynamics in the InGaN layer, SE appears at 3.21 eV, near the InGaN band edge and slightly on the blue side (10 meV) of the PL, for excitation above (3.35 eV) the InGaN bandgap. Since the SE peak is broad and very close to the main PL peak, the onset of SE is observed as the emergence of a narrower linewidth PL whose strength increases with increasing pump intensity. From PL measurements of spectrally-integrated intensity and linewidth, a pump threshold of $``$80 $`\mu `$J/cm2 is obtained. Spectrally-integrated TRDT data for above bandgap, above threshold (300 $`\mu `$J/cm2) excitation shows a fast decay during the first 14 ps due to carrier removal through SE, followed by a much slower relaxation through SPE after the carrier density decreases below the SE threshold (Fig. 5). The fast rising edge of the spectrally-integrated dt for both excitations include the contribution from the AC Stark effect at the GaN band edge, as observed in Fig.2.

The fast relaxation feature of the spectrally-integrated TRDT is spectrally-resolved in Fig. 4a as a redistribution of the carriers. The broad distribution of carriers becomes clearly visible after 400 fs as a bleaching of the InGaN photo-absorption. The carrier distribution extends from the GaN band edge to the InGaN band edge and reaches a maximum in 1 ps at $``$ 3.30 eV. Afterwards, the blue edge of this bleaching, $``$ 70 meV above the InGaN band edge, is observed to decay rapidly ($`<`$ 14 ps) while the red edge (3.18-3.27 eV) remains almost constant. The red shift of the bleaching arises from carrier cooling, and the peak reaches the In0.05Ga0.95N band edge (3.26 eV) by 14 ps when SE ceases. Thus the fast decay feature of the spectrally-integrated TRDT is due to the fast removal of the carriers at the InGaN band edge through SE, while carriers at higher energies relax down to refill the lost carriers. After the number of carriers is reduced below the SE threshold, only SPE remains.

By contrast, for the below bandgap excitation (3.23 eV), SE is not observed, and the DT signal, shown in Fig. 4b, does not exhibit SE-related features. The number of induced carriers is smaller, and the DT signal shows them narrowly distributed close (3.27 eV) to the band edge, reaching a maximum in 600 fs. Of particular noteworthiness is the absence of the SE-mediated fast decaying blue edge seen in above bandgap excitation. During the first 3 ps, there is also a more complex absorption change at the GaN band edge due to a combined effect of the AC Stark effect and the two-photon absorption. Induced absorption is observed after 400 fs until 3 ps, and increased transmission at the GaN energy persists for as long as 346 ps due to carriers and excitons in GaN trap states.

Spectrally-integrated DT data for both excitations show an additional decay component in the InGaN with a much larger time constant of several 100 ps. Spectrally-resolved TRDT reveals that carriers decay very slowly, and the carrier distribution continues to narrow, after 24 ps in above bandgap excitation (Fig. 4a) and after 600 fs in below bandgap excitation (Fig. 4b). The slow decay of these cooled carriers is due to radiative recombination-induced SPE. From the data, the radiative recombination time in this InGaN layer is estimated to be 0.98$`\pm `$0.08 ns, a value consistent with the reports in the literature. ChichibuJVST1998 ; KoronaMSEB2002  Other TRDT measurements on InGaN epilayers ChoiPRB2001-2 ; OmaePSSA2002  show similar slow decay behavior as in In0.05Ga0.95N epilayer investigated here.

### III.3 Differential transmission of an InGaN MQW

#### III.3.1 Investigation of Sample Structure

As seen in Fig. 1, the cw-PL for the MQW sample shows a single emission centered at $``$3.01 eV associated with the confined QW minimum. The corresponding PLE and cw-absorption measurements indicate the In0.05Ga0.95N barrier energy is $``$3.23 eV. This barrier energy is 30 meV below the band edge energy obtained for the In0.05Ga0.95N epilayer because the barrier composition is slightly different, most probably due to In incorporation into the barriers from the wells.

Simple 1-D calculations predict the minimum confined QW energy level within 60 meV of the measured 3.01 eV, given reasonable values for conduction:valence band offsets (20:80 TO 80:20) and bowing parameter (1.75 eV)wetzelAPL98 . The difference between the measured and calculated values is satisfactory given the large but uncertain PZE field strength arising from lattice mismatch-induced strain between the layers. TakeuchiAPL1998

PLE at room temperature (Fig. 1) shows clear edges at the GaN and the In0.05Ga0.95N barrier energies consistent with the cw-absorption. The contribution from the confined QW states is not observed in cw-absorption. However, the logarithmic plot of the PLE signals at 303 K and 83 K (Fig. 1 inset) shows the broad QW edge at $``$3.11 eV and $``$3.14 eV, respectively. At room temperature the emission is 100 meV lower than this PLE edge, but a sigmoidal fit to this QW edge gives an effective band edge of 3.06 eV, and a Stokes’ shift of 50 meV. Shifts even larger than 300 meV have been observed for higher In composition MQWs under cw excitation.ChichibuMSEB1999 ; MartinAPL1999

High excitation density TI-PL from the MQW sample produced a blueshift as large as 90 meV from the low intensity cw-PL peak. Similar to the SE feature of the InGaN epilayer, the MQW SE emission peak is not observed as a narrow feature on the main PL. Instead, just above the threshold ($``$95 $`\mu `$J/cm2), the emission peak narrows and blueshifts 20 meV. As excitation intensity increases, this narrowed emission continues to blueshift. This blueshift is primarily due to increased screening of the PZE field and to lateral carrier confinement in the MQW. As in the InGaN epilayer, the strain-induced PZE field of the MQW is decreased through Si doping and through screening by the large number of carriers induced by the pulsed laser.ChichibuMSEB1999  MQW lateral carrier confinement arises from the formation of In-rich quantum dot-like regions in the QWs which grow with increasing In composition.ChichibuJVST1998  Such inhomogeneities have been observed for InGaN MQWs having even less than 15 $`\%`$ In.ChichibuMSEB1999 ; ChichibuAPL1998-2  Carrier localization due to inhomogeneities is also expected to decrease with Si doping in the barriers.ChoAPL1998  As the size of In-rich regions grow, the confinement within large dots is reduced and the Stokes’ shift increases. The degree of confinement added to the screening of the PZE field make the blueshift in the MQW TI-PL larger than it is for the InGaN epilayer sample.

#### III.3.2 Spectrally-integrated and -resolved TRDT

To examine the relaxation of the total number of carriers, DT signals are integrated over the spectrum 2.92 - 3.41 eV for excitation energies above (3.35 eV), at (3.23 eV), and below (3.14 eV) the barrier energy.integratedDT  As seen in Fig. 7, all three spectrally-integrated TRDT signals show a fast decay at early times, followed by a very slow relaxation. The fast components are observed to decay in less than 10 ps. Spectrally-integrated DT data were fit by a bi-exponential decay function, $`Ae^{t/\tau _1}+Be^{t/\tau 2}`$, where $`\tau _1`$ and $`\tau _2`$ are the decay times for the fast and the slow decaying components, and A and B are the corresponding amplitudes. A fractional strength value ($`f=A/(A+B)`$) is defined to observe the relative strength of the fast decaying component.

The fractional strength ($`f`$) of the fast decaying component is largest for at-barrier excitation, and is larger for above-barrier excitation than for below-barrier excitation (Inset, Fig. 7). As with the GaN and InGaN epilayers, the fast decay in the MQW sample is caused by the accelerated relaxation of carriers through SE. However, SE is observed even for below-barrier excitation of the MQW sample. For at-barrier energy excitation (SE threshold $``$ 95 $`\mu `$J/cm2), the magnitude of the fast feature is observed to decrease ($`f`$=0.74, 0.65 , 0.26) and its decay constant slowed (2.6, 4.6, and 13.5 ps) as the excitation density decreased (300, 160, and 60 $`\mu `$J/cm2)(Fig. 6).SEbelowThreshold  For a given excitation density (300 $`\mu `$J/cm2), the fast feature decay times for at-, above-, and below- barrier excitations increased (2.6, 2.6, and 3.7 ps, respectively)(Fig. 7), and the magnitude of the feature decreased ($`f`$=0.74, 0.73, 0.56), in a manner consistent with the strength of the PLE measured at the respective excitation energies (Fig. 1).

SE decay times faster than 10 ps have been observed for similar MQW structures at room temperature and at 2 K.SatakePRB1999 ; KawakamiJPCM2001  In one study, a three-level rate equation model was also developed, consisting of 2D QW, 3D barrier, and ground (recombined) states.SatakePRB1999  This model suggested that the fast relaxation was due to carriers decaying from the 3D states to refill the 2D states emptied by SE. The fact that higher energy 3D states supply carriers to lower energy states undergoing SE has been confirmed in the GaN (Fig. 3a) and InGaN (Fig. 4a) data presented above. As will be discussed below, a similar process occurs in the MQWs, in which 3D states supply carriers for the saturated 2D states undergoing SE. Thus, SE reduces the total number of carriers in a similar manner for all samples studied.

To elucidate the carrier redistribution and relaxation processes, spectrally-resolved TRDT data for the InGaN MQW sample for various delays at different pump energies above, at, and below the barrier energy are shown in Fig. 8. The fast decaying AC-Stark and the two-photon absorption feature at the GaN energy (3.41 eV) is observed at all pump excitation energies and behaves analogously to the below GaN bandgap excitation for the GaN and InGaN epilayer samples discussed above. The strength of this feature decreased both with decreasing pump intensity and increasing detuning.

In further analogy with the InGaN epilayer, a broad bleaching is observed in the InGaN MQW barrier region (3.13 - 3.30 eV) for all excitation energies. The peak of the carrier distribution is observed at the 3.23 eV barrier energy. For above- and near-bandgap excitation in Fig. 8a and Fig. 8b, the blue edge of this carrier distribution rises faster (300 fs, 360 fs) than the red edge (540 fs, 560 fs) in the QWs. This is reminiscent of the carrier redistribution for above bandgap (3.35 eV) excitation in the InGaN epilayer (Fig. 4a).

Likewise, the blue edge of the MQW carrier distribution, centered at the 3-D barrier band edge (3.23 eV), is observed to decay much faster than the red edge (blue:10ps, red:$`>`$100ps). As in the InGaN epilayer (Fig. 4a), this initial fast decay of the blue edge corresponds to the SE-related fast decay in the spectrally-integrated TRDT. However, the carriers cool down to the barrier band edge more quickly ($`<`$1 ps) than they did for above bandgap excitation of the InGaN epilayer, resulting in a very broad (170 meV) carrier distribution extending from the GaN edge down into the QWs. This difference between epilayer and MQW barrier carrier relaxation arises because capture into the QWs removes carriers from the InGaN barrier much faster than recombination removes them from the InGaN epilayer.OzgurAPL2000

The role of SE-mediated carrier relaxation is most clearly seen by comparing the at-bandgap excitation TRDT data above (300 $`\mu `$J/cm2) (Fig. 8b) and below (60 $`\mu `$J/cm2) (Fig. 8d) threshold. In the first 1 ps, the larger, asymmetric carrier distribution for the above threshold data is obvious, indicating the greater carrier concentration in the barriers and the role of SE in effectively depleting the higher energy barrier states faster than the band edge barrier states. Although carrier capture is apparent, a large percentage of carriers remain in the barrier region while SE is operating. By contrast, the below threshold TRDT data indicates a more symmetric carrier distribution whose relaxation rates are much less sensitive to carrier energy and whose peak drops below the barrier band energy in only 300 fs. By 1.5 ps, the below threshold carrier distribution is fully 50 meV below that of the above threshold case, and the barriers are virtually depopulated. It may be surmised that SE assists in the carrier capture process by quickly depopulating QW states which are refilled by captured barrier band edge carriers which in turn are refilled by higher energy carriers in the barriers. The normal cooling of the carrier distribution observed below threshold is altered above threshold by SE through the continued emptying of energetically accessible states near the barrier band edge. By 6 ps when SE is over, however, the distributions appear quite similar and exhibit the same relaxation behavior thereafter.

In addition to elucidating the action of SE and carrier redistribution, Fig. 8 reveals the mechanism of QW carrier capture. Due to their higher density of states, holes are expected to be captured from the 3-D barriers to the 2-D QW levels much faster than the electrons.MansourJAP1995  Pulse widths of 100 fs used here limit our observations to the electron capture. A significant number of carriers are observed at and above the barriers after 240 fs for above- and at-barrier excitations, while carriers are just beginning to appear in the QWs (Fig. 8b). The carrier distribution at the barrier band edge (3.23 eV) peaks in $``$ 0.5 ps, while the carrier distribution at the QWs (3.11 eV) reaches its maximum in $``$ 0.8 ps (Fig. 9). This delay of 0.3 ps confirms that the carriers are reaching the barriers faster than they arrive at the QWs, an indication of the electron capture process. This result is consistent with previous measurements of electron capture time (340-510 fs) using degenerate TRDT spectroscopy.OzgurAPL2000

In addition, degenerate TRDT showed optimal emission efficiency and most efficient carrier capture occurred when the carrier injection was within $`\pm `$ 40 meV of the 3.23 eV barrier energy. OzgurAPL2000  Similar to the cw-absorption measurements (Fig. 1), the pulsed absorption spectrum in Fig. 8 clearly shows an 80 meV-wide peak centered at 3.23 eV. This broad absorption suggests potential fluctuations in the barriers due to the compositional inhomogeneities. The spectrally-integrated DT data obtained here verifies that the most efficient carrier capture occurs for pump energies near the barrier energy.

Measurements by Satake *et al.*SatakePRB1999  also show a broad distribution of carriers around the barrier energy and SE-related decays faster than 5 ps in the spectrally-resolved DT. However, the QW capture rate could not be observed. Other studies on InGaN-based laser diode structures by Kawakami *et al.*KawakamiAPL2000 ; KawakamiJPCM2001  also observed the same fast carrier accumulation at the barriers and much slower SPE decay from the QWs. It is not clear if those samples, excited at power densities above the SE threshold, show the same initial fast decay feature in the spectrally-integrated DT signals as seen here. However, carrier capture to the lower energy localized QW states appears to occur in less than 1 ps, similar to our measurements. Surprisingly, a sizable carrier population remains at barrier energies for at least 200 ps in their samples, which they claim is due to the capture of carriers in a high lying, nearly delocalized QW state. However, this feature bears some similarity to the long-lived excitonic relaxation in GaN interfacial traps observed in our InGaN TRDT data (FIG. 4). By contrast, the broad, quickly decaying distribution of carriers observed in our MQW sample is probably due to rapid carrier capture from the broad absorption at the barrier energy (Fig. 8).

For an excitation energy (3.14 eV) below the barriers, total carrier generation is smaller, and the peak carrier distribution appears at a slightly lower energy than the other two excitation energies (Fig. 8c). Unlike below-band edge (3.23 eV) excitation in the InGaN epilayer, the MQW carrier distribution is observed to peak 50 meV below the barrier edge. Nevertheless, both the InGaN and MQW carrier distributions reach their maximum in a very short time ($``$400 fs), and the rise times for both blue and red edges of the respective carrier distributions (Fig. 4b and Fig. 8c) are similar. This behavior contrasts with the above- and at- bandgap excitation for the MQW in which the blue side rises faster than the red side. As observed in Fig. 7, the fast decaying component of the spectrally-integrated DT for the below-barrier excitation is smaller than for the other two excitations, indicating a weaker carrier decay through SE. Accordingly, $`f`$ is very small for the spectrally-integrated DT, and the blue edge decay of the TRDT signal in Fig. 8c is not noticeable.

The fast decaying component in the spectrally-integrated TRDT signal disappears as the carrier density falls below the SE threshold and emission goes from SE to SPE.KawakamiAPL2000 ; SatakePRB1999 ; KawakamiJPCM2001  After SE ends (5 \- 10 ps), the carriers at the QW band edge recombine only through SPE, and carriers at higher energies relax at a similar rate to replace those lost at the QW band edge. For all excitations this is observed as the redshift of the bleaching. The carrier distribution cools and redshifts to the QW band edge ($``$ 3.11 eV) after 400 ps. In addition to carrier recombination in the QWs, the redshift of the carrier distribution is also partly due to the reduced screening of the PZE field as carrier density decreases through SPE.KawakamiAPL2000  An exponential fit to the spectrally-resolved data at 3.11 eV gives a decay constant of 0.66$`\pm `$0.06 ns, consistent with the 0.69 ns value from previous degenerate TRDT measurements.OzgurAPL2000  The slow decay constant from the spectrally-integrated TRDT is slightly smaller (0.54$`\pm `$0.07 ns), but agrees satisfactorily when the carrier redistribution through different channels is taken into account.

## IV Conclusions

In summary, non-degenerate TRDT spectroscopy is performed on a bulk GaN layer, an InGaN epilayer, and an InGaN MQW. All the samples were observed to have SE features for excitation densities above a pump threshold density of $``$100$`\mu `$J/cm2. Spectrally-integrated TRDT data showed the effects of SE-mediated decay, which occurred in $`<`$10 ps for above band gap excitations. These fast decays are accompanied by carrier relaxation from higher to lower energy states which are emptied in turn by SE. After the total carrier density is reduced below threshold, SE disappeared and a slow relaxation through SPE is observed. For GaN, a spectrally narrow absorption of carriers decayed by SE at the band edge in 6 ps. A broader carrier distribution is observed for the InGaN sample which narrowed and decayed to the InGaN band edge through SE in $`<`$14 ps. Carrier recombination through spontaneous emission was observed with a time constant of approximately 1 ns.

Photo-excitation above, at, and below the barrier energy for the MQW sample showed more complex relaxation pathways in the QWs. Spectrally-integrated TRDT signals for above- and at-barrier bandgap energy excitations demonstrated SE as a fast decaying component in the first 10 ps. The strength and fast decay times of the SE feature were seen to vary as a function of excitation energy and density. For a given excitation density, the decay times varied inversely with the PLE magnitudes for the respective excitation energy. SE was observed to depopulate the higher energy barrier states faster than the lower energy barrier states through a process of cascaded refilling. Once SE ended, carrier capture and spontaneous emission from carrier recombination cools the carrier distribution into the wells and toward the lowest energy QW state. The wavelength non-degenerate TRDT data at QW and barrier energies provided sub-ps values for the electron capture time, and $``$660 ps for the recombination time. These values agree well with previous degenerate TRDT measurements on the same MQW sample.OzgurAPL2000

###### Acknowledgements.

The authors would like to thank Steven DenBaars, Stacia Keller and Amber Abare from University of California, Santa Barbara for supplying the samples, and Arup Neogi for helpful discussions. This work was supported by the Army Research Office.


text:
# Absorption systems in the spectrum of GRB 021004 Based on observations made with the Nordic Optical Telescope, operated on the island of La Palma jointly by Denmark, Finland, Iceland, Norway, and Sweden.

## 1 Introduction

More than 30 Optical Afterglows (OAs) to Gamma-Ray Bursts (GRBs) have been detected to date. Absorption lines due to metal enriched gas in the host galaxy of the GRB have been detected in all cases where a spectrum with a good signal-to-noise ratio of the OA has been obtained. Prior to GRB 021004 the redshift has been determined from such detected metal absorption for about a dozen OAs. Absorption line spectra of GRBs have primarily been used to constrain the redshift of the burst but also to gain insight into the nature of the burst, the gas phase of its host galaxy, and of its large scale environment (e.g. Vreeswijk et al. 2001; Mirabal et al. 2002).

Furthermore, it is interesting to consider how the GRB absorption line systems compare to the well-studied QSO absorption line systems, and to examine whether the physical conditions (e.g. column densities, metallicities, ionizations states, and kinematics) in the absorbers detected in GRB afterglow spectra are similar to any of the various classes of QSO absorbers (e.g. Jensen et al. 2001; Savaglio et al. 2002a; Salamanca et al. 2002).

In this Letter we present optical spectroscopy of the afterglow of GRB 021004. GRB 021004 was detected by the HETE-II satellite on October 4.5043 2002 UT (Shirasaki et al. 2002). An optical afterglow was reported already 10 minutes after the burst (Fox 2002). The first optical spectroscopy reported two absorption systems at z=1.38 and 1.60 (Fox et al. 2002), which were later confirmed by Eracleous et al. (2002), Anupama et al. (2002) and Castander et al. (2002). Ly$`\alpha `$ absorption at z=2.323 was first reported by Chornock & Filippenko (2002). The presence of this system was confirmed by Salamanca et al. (2002b), Savaglio et al. (2002b), Sahu et al. (2002) and Castro-Tirado et al. (2002). Its lightcurve showed strong deviations from the usual power-law decay indicating structure in the surrounding medium (Lazzati et al. 2002; Holland et al. in prep).

## 2 Observations and data reduction

### 2.1 Observations

The spectrum of GRB 021004 presented in Fig. 1 was obtained with the 2.56-m Nordic Optical Telescope (NOT) using the Andalucía Faint Object Spectrograph (ALFOSC). The detector was a 20482 pixels thinned Loral CCD with a pixel scale of 0$`\stackrel{}{.}`$189. We used a grism covering 3850Å– 6850 Å and a slit of 1.3 arcsec providing a resolution of 6.5 Å and a sampling of 1.5 Å per pixel.

The spectroscopic observations consisted of a single 3600 s exposure started at Oct. 4.9505 (10.71 hrs after the burst). Photometric observations obtained on the same and the following nights at the NOT and elsewhere made it possible to closely follow the GRB light-curve. The brightness of the OA at the start of the exposure was R=18.48$`\pm `$0.03 and B=19.15$`\pm `$0.10. During the one-hour exposure the OA faded by 0.08 magnitudes. These broad band magnitudes were used for the flux calibration.

### 2.2 Data reduction and absorption line-list

Standard techniques were used for bias, dark and flat field corrections. For the optimal 1D extraction, and for the line-search, measurement, identification, and fitting we used a code originally developed for 2D spectral PSF fitting (Møller 2000) and for QSO spectral analysis (for details see Møller & Kjærgaard 1992).

In Table 1 we list centroid (vacuum corrected) and observed equivalent width of all absorption lines found above our 5$`\sigma `$ detection limit. Several of the listed lines are complex blends, and for those we provide the total observed quantities with no attempt at this point to deblend them. Inferred redshifts are listed only for the single unblended lines. The absorption lines are marked above the normalised spectrum shown in Fig. 1.

We have identified five absorption systems at redshifts 1.3806, 1.6039, 2.2983, 2.3230, and 2.3292 and we shall in what follows refer to them as systems A, B, C, D, and E. The identification of those systems was carried out independently of the early GCNCs, but is seen to agree well with the circulars summarised in Sect. 1.

For systems C, D, and E our spectrum covers Ly$`\alpha `$. No line redwards of the Ly$`\alpha `$ line of system E is unidentified, and we conclude that line No 4 in Table 1 marks the onset of the Lyman forest. System E is therefore most likely associated with the GRB itself, and could mark the redshift of the GRB host galaxy. There are however a few caveats and we shall return to this question in Sect. 4.

Most of the absorption lines are blended, making it impossible to obtain a good redshift directly from line centroiding. The redshifts given above were therefore derived through line profile fitting. Detailed fits to the blends are shown in Fig. 2, and the redshifts required to fit each species are listed in Table 2.

The lines are heavily saturated and the resolution low enough that the line profiles are dominated by the resolution. Therefore the column densities used in the fits are mostly too poorly constrained to be useful. Nevertheless, from the Ly$`\alpha `$ line profiles we can set a strict upper limit of $`1.1\times 10^{20}`$ cm-2 on the H i column density. The total H i column actually used in the fit of systems C, D, and E was $`5.7\times 10^{19}`$ cm-2.

## 3 Ly$`\alpha `$ in emission

Inspection of the top panel of Fig. 2 shows that what is mostly a very good fit of the Ly$`\alpha `$ absorption lines of systems C, D, and E, becomes very poor on the red shoulder of the last line. Subtraction of the fit (Fig. 3) reveals that the poor fit is caused by the presence of an emission line shortly redwards of the Ly$`\alpha `$-E line. As suggested in several GCN Circulars (Chornock & Filippenko 2002; Salamanca et al. 2002b; Djorgovski et al. 2002; Castro-Tirado et al. 2002), this line is likely Ly$`\alpha `$ emission from the host galaxy. The line (Fig. 3, right panel) is unresolved, has its centroid at 4054.4 Å, and a flux of $`2.46\pm 0.50\times 10^{16}`$ erg s-1 cm-2 identical to other reported measurements to within $`1\sigma `$. The flux is comparable to the Ly$`\alpha `$ flux of the GRB 000926 host galaxy (Fynbo et al. 2002). The inferred redshift (2.3351) is 530 km s-1 higher than that of the E system. At the time of writing the limit on the host galaxy magnitude is B$`>`$24, providing a lower limit on the observed emission line equivalent width of 170 Å.

## 4 Discussion

### 4.1 Properties of Ly$`\alpha `$ absorption and emission lines

A shift of a few hundred km s-1 between redshifts determined from Ly$`\alpha `$ absorption and emission is commonly seen for DLA galaxies (Møller et al. 2002) and for Lyman-Break galaxies (e.g. Adelberger at al. 2002, their Figures 2 and 3). Two effects are thought to contribute to this observed velocity shift: if the absorbing gas is in a galactic wind moving towards us, that will blueshift the absorber and at the same time cause the resonantly scattered Ly$`\alpha `$ photons to become redshifted in order to escape the cloud. A spread in absorption/emission redshifts as large as that seen in systems C–E and host Ly$`\alpha `$ emission (3300 km s-1) has never been seen in Lyman-Break Galaxy spectra, and in fact equation 2 from Adelberger et al. (2002) shows that the velocity shift of the Ly$`\alpha `$ emission line should be less than 200 km s-1 for an emission line rest equivalent width larger than 50 Å. Therefore the large velocity range spanned here cannot be explained in terms of normal host galaxy properties, and we conclude that the absorbers must be in the local environment of the GRB.

### 4.2 The nature of the GRB absorption systems

Any absorption seen in the spectra of high-redshift QSOs may be classified as belonging to one of three basic categories (Weymann et al. 1979). The “intervening systems” are cosmologically distributed and can have any redshift lower than that of the source, “local cluster systems” will have the same redshift as the source to within $`\pm `$ the velocity dispersion of the local cluster or filament, and “ejected systems” (physically closest) can be radiatively accelerated to large velocities.

In QSOs the ejected systems are often seen as BALs (P-Cygni type broad absorption line systems) and/or as line-locked systems (Foltz et al. 1987). Ejection velocities as high as 0.1c have been reported (Vilkoviskij & Irwin 2001), and the systems are found to be highly ionized and to have extremely high metallicities (Savaglio et al. 1994; Møller et al. 1994). The high ionization is easily understood because of the intense UV flux of the QSO. The line-locking is explained as an effect of cloudlets being accelerated via absorption at a given transition until its wavelength falls into the shadow of another line in a cloud in front of it (Vilkoviskij et al. 1999).

In this scheme we would classify systems A and B as intervening systems, while systems C, D and E display a surprising similarity to the ejected systems of QSOs. They all have strong absorption of highly ionized C IV and Si IV but no detectable Si II absorption, they have high column densities compared to stellar winds, and at intermediate resolution they show evidence for line-locking in C IV, Si III/Ly$`\alpha `$ and possibly Si IV (see also Savaglio et al. 2002b; Salamanca et al. 2002b). For confirmation of the line-locking higher resolution spectra (already obtained) are needed.

It is difficult to understand why there is this resemblance between systems C–E and ejected systems of QSOs. We concluded above that the systems arise in the local environment of the GRB. They may therefore be related either directly or indirectly to the GRB or the GRB progenitor itself, or they may be caused by an unrelated phenomenon which just happens to be sharing the same volume of space. Firstly we would consider it unlikely that the systems are directly related to the burst itself. So soon after the burst any material ejected simultaneous with the GRB itself should undergo significant changes on relatively short timescales, yet there is no evidence for such changes between our spectrum and that of Matheson et al. 2002. Secondly one may ask if stellar winds could create such signatures. Radiatively driven winds with terminal velocities of up to several 1000 km s-1 are ubiquitous for very hot stars such as O stars and WR stars (Lucy & Abbott 1994; Kudritzki 2002) but these winds cannot reach the required column densities. Also, presumably for the same reason, actual line-locking has never been observed in stellar winds.

We cannot exclude that the GRB is located close to the inner region of a recently deceased QSO, especially at z$``$2, where the QSO density is high. However, given the existing evidence that GRBs seem to be related to the deaths of massive stars it is more likely that the GRB progenitor was a massive, hot star and that this star radiatively drove the fast outflow now observed in absorption against the light of the afterglow. Other massive stars and supernova explosions could be contributing to the wind if the progenitor was located in a compact star-forming region similar to that of GRB 980425 (Fynbo et al. 2001). A similar scenario was suggested for GRB 971214 by Ahn (2000).

Alternatively, as suggested by Lazzati et al. (2002), in the supra-nova scenario (Vietri & Stella 1998) the wind and the clumpy surrounding medium could be the result of a supernova predating the GRB by several years.

###### Acknowledgements.

We thank E. Y. Vilkoviskij for helpful discussions and our referee Davide Lazzati for fast, thorough and constructive criticism. We are grateful to the staff at the Nordic Optical Telescope for keeping the Telescope working so well and for excellent support. JPUF gratefully acknowledge support from the Carlsberg foundation. This work is supported by the Danish Natural Science Research Council (SNF).