We report the observation of thermal annealing and nitrogeninduced effects on electronic transport properties of asgrown and annealed n and ptype modulationdoped Ga_{1  x}In_{
x
}N_{
y
}As_{1  y} (x = 0.32, y = 0, 0.009, and 0.012) strained quantum well (QW) structures using magnetotransport measurements. Strong and wellresolved Shubnikov de Haas (SdH) oscillations are observed at magnetic fields as low as 3 T and persist to temperatures as high as 20 K, which are used to determine effective mass, 2D carrier density, and Fermi energy. The analysis of temperature dependence of SdH oscillations revealed that the electron mass enhances with increasing nitrogen content. Furthermore, even the current theory of dilute nitrides does not predict a change in hole effective mass; nitrogen dependency of hole effective mass is found and attributed to both strain and confinementinduced effects on the valence band. Both electron and hole effective masses are changed after thermal annealing process. Although all samples were doped with the same density, the presence of nitrogen in ntype material gives rise to an enhancement in the 2D electron density compared to the 2D hole density as a result of enhanced effective mass due to the effect of nitrogen on conduction band. Our results reveal that effective mass and 2D carrier density can be tailored by nitrogen composition and thermal annealinginduced effects.
PACS
72.00.00; 72.15.Gd; 72.80.Ey
Keywords
GaInNAsMagnetotransportShubnikov de HaasTransportNitrogendependent effective mass
Review
Background
Dilute nitrides are technologically important materials due to their promising physical properties and potential application in optoelectronic technology. The strong nitrogen dependence of the bandgap energy makes dilute nitrides promising candidate for device applications, operating in near infrared region [1–3]. Therefore, in order to fully determine fundamental physical properties of this unconventional alloy system, an intense research has been devoted since its discovery. Much effort has been spent developing theoretical models and understanding peculiar nitrogeninduced effects on optical properties of dilute nitrides [1, 4–6]. Although the strong composition dependence of the bandgap energy compared to the conventional IIIV alloys is attractive, it has been soon realized that the presence of nitrogen severely degrades the optical quality. Therefore, thermal annealing is commonly used a standard procedure to improve the optical quality of dilute nitrides, but at the expense of the blueshift of the bandgap [1, 7].
From the electronic properties' point of view, it has been demonstrated that incorporation of nitrogen gives rise to drastic decrease in electron mobility due to the Ninduced scattering centers and enhanced electron effective mass [8–13]. On the contrary, in the presence of the nitrogen, it has been theoretically demonstrated that hole effective mass and hole mobility remain unaffected [14–16]. So far, much effort has been focused on nitrogen dependence of electron effective mass and electron mobility, ignoring the composition dependence of hole effective mass and hole mobility. Moreover, even it has been accepted as a standard procedure to improve optical quality, the effects of thermal annealing on electronic properties has not been considered.
The aim of the study presented here is to investigate the effect of nitrogen composition and thermal annealing on electronic transport properties of n and ptype modulationdoped Ga_{0.68}In_{0.32}N_{
y
}As_{1  y}/GaAs (y = 0, 0.009, and 0.012) strained quantum well (QW) structures.
Methods
The samples were grown on semiinsulating GaAs (100) substrates using solid source molecular beam epitaxy, equipped with a radio frequency plasma source for nitrogen incorporation. XRD measurements were used to determine nitrogen and indium compositions. The sample structures are comprised of 7.5nmthick QW with indium concentration of 32% and various nitrogen concentration (N% = 0, 0.9, and 1.2) and 20 nm doped (Be for ptype and Si for ntype) GaAs barriers. A 5nm GaAs was used between GaInNAs and GaAs layer to separate charge and doping regions. The growth temperatures of GaInNAs, GaInAs, and GaAs were 420°C, 540°C, and 580°C, respectively. Post growth rapid thermal annealing was applied at 700°C for 60 and 600 s. The doping density was the same for both n and ptype samples as 1 × 10^{18} cm^{3}. The samples were fabricated in Hall bar shapes, and ohmic contacts were formed by alloying Au/Ge/Ni and Au/Zn for n and ptype samples, respectively.
Magnetotransport measurements were carried out using a ^{4}He cryostat equipped with a 7 T superconducting magnet. Inplane effective mass, 2D carrier density, and Fermi energy were determined by analyzing the Shubnikov de Haas (SdH) oscillations as a function of temperature between 6.1 and 20 K. In order to evaluate the obtained results from SdH analysis, influence of nitrogen and thermal annealing on the bandgap was probed using photoluminescence (PL) measurements. PL was excited with an argon ion laser (514 nm), dispersed with a 0.5m monochromator and detected with a thermocooled GaInAs photodetector.
Results and discussion
Figure 1a shows the experimental data of magnetoresistance measurements at various temperatures for one set of the Ncontaining and Nfree asgrown samples. It is known that SdH oscillations can be observed in high magnetic fields (μB > 1) in low mobility samples and at low temperatures (k_{B}T < ℏω_{
C
}). Since doping amount is the same in all samples, carrier mobility is an important factor to be able to observe SdH oscillations. As seen in Figure 1, the SdH oscillations start at lower magnetic fields for Nfree samples as an indication of higher carrier mobility in Nfree samples. It is worth noting that we observed higher mobility in Nfree samples in a previous work (see [8]).
The observed decrease of the amplitude of SdH oscillations with increasing temperature can be expressed by an analytical function [17–19]:
where Δρ_{
xx
}, ρ_{0}, E_{F}, E_{1}, ω_{
c
}, m *, τ_{
q
}, and μ_{
q
} are the oscillatory magnetoresistivity, zerofield resistivity, Fermi energy, first subband energy, cyclotron frequency, effective mass, quantum lifetime of 2D carriers, and carrier mobility, respectively. The i represents the subbands. In Equation 1, the temperature dependence of the amplitude of the oscillations is included in the function D(χ). The exponential function in Equation 1 represents the damping of the oscillations due to the collisioninduced broadening of Landau levels. The contribution of the higher subbands appears in SdH oscillations with different periodicity. We observed that the SdH oscillations has only one period, indicating that only the lowest subband is occupied. The observation of diminishing minima is an indication of absence of background magnetoresistance and presence of 2D carrier gas.
As seen in Figure 1a, the SdH oscillations are suppressed by either a positive (for Nfree sample) or a negative (especially for ntype Ncontaining sample) background magnetoresistance. The minima of SdH oscillations decrease as the magnetic field increases for ptype Ncontaining samples due to negligible negative magnetoresistance than that of ntype sample. As for Nfree samples, a pronounced positive magnetoresistance causes minima to increase with the magnetic field. The origin of the positive magnetoresistance is parallel conduction due to undepleted carriers in barrier layer, herein GaAs. On the other hand, the weak localization effect leads to negative magnetoresistance [19, 20]. The background magnetotransport makes the analysis of SdH oscillations difficult especially at low magnetic fields and high temperatures. In order to exclude the effect of the background magnetoresistance and to extract the SdH oscillations, we used the negative second derivative with respect to the magnetic field of raw magnetoresistance data (∂^{2}R_{
xx
}/∂B^{2}) (see Figure 1b). As can be easily seen from Equation 1, this method does not change the position of the peak or period of the oscillations and enables to subtract the slowly changing background magnetoresistance and amplifies the shortperiod oscillations [18, 19] as depicted in Figure 1b.
The thermal damping of the SdH oscillations at a fixed magnetic field is determined by temperature, magnetic field, and effective mass using Equations 1 to 5 as follows [19–22]:
where A(T, B_{
n
}) and A(T_{0}, B_{
n
}) are the amplitudes of the SdH oscillations at a constant magnetic field B_{
n
} and at temperatures T and T_{0}. Using Equation 6 and SdH oscillations data at different temperatures, we derived the effective mass which we plotted in Figure 2.
An enhancement of the electron effective mass compared to the Nfree sample is observed in Ncontaining asgrown samples, which obeys the band anticrossing (BAC) model [4]. After thermal annealing, the electron effective mass increases, which can be attributed to the change of bandgap. It is known that incorporation of nitrogen into GaInAs lattice causes a redshift of the bandgap; on the other hand, thermal annealing blueshifts the bandgap and the amount of blueshift increases with increasing nitrogen content (see Table 1). The origin of the blueshift has been explained in terms of interdiffusion of InGa and restructure of the nearest neighbor configuration of nitrogen [1, 9].
Table 1
PL peak energies and observed blueshift amounts at 30 K
Samples
PL peak energy (eV)
Blueshift (meV)
ptype
ntype
ptype
ntype
Ga_{0.68}In_{0.32}As
Asgrown
1.180
1.172


Annealed (60 s)
1.182
1.184
2
12
Annealed (600 s)
1.194
1.194
14
22
Ga_{0.682}In_{0.32} N_{0.009}As_{0.991}
Asgrown
1.089
1.120


Annealed (60 s)
1.118
1.129
29
9
Annealed (600 s)
1.146
1.137
57
17
Ga_{0.68}In_{0.32} N_{0.012}As_{0.988}
Asgrown
1.033
1.076


Annealed (60 s)
1.065
1.088
32
12
Annealed (600 s)
1.103
1.096
70
20
As a result of blueshift of the bandgap, conduction band states approaches localized N level, giving rise a stronger interaction; therefore, electron effective mass increases compared to the values in asgrown Ncontaining samples. In Nfree sample, indium atoms diffuse out from the QW, leading to a decrease in In content and weaker confinement due to the reduction of the conduction band offset as a result of blueshifted bandgap. An enhancement in electron effective mass in compressively strained GaInAs layer with decreasing In content and weaker confinement was also observed by Meyer et al. [23], which is consistent with our result. As for hole masses, although BAC model does not predict a change in effective hole mass, a decrease with increasing N content from y = 0 to y = 0.009 resulted in a decrease in hole effective mass. In order to understand the unpredicted N dependence of hole effective mass, both compressive strain and confinementinduced effects should be considered. With increasing N content, compressive strain decreases and confinement becomes stronger due to the redshift of the bandgap. Stronger confinement decreases the hole effective mass, while less compressive strain increases the hole mass. Moreover, a reduction of the hole concentration decreases the hole effective mass due to change of the valence band nonparabolicity. Therefore, the value of hole effective mass depends on several competing mechanisms. We can conclude that in our Ncontaining samples, stronger confinement and reduced 2D hole density (see Table 2) are the dominant mechanisms, affecting hole effective mass. A more detailed study of N dependency of hole effective mass and effect of thermal annealing on hole effective mass in these samples can be found in our previous paper [14].
Table 2
Effective mass, 2D carrier density, and Fermi energy values found from analysis of SdH oscillations
Samples
n_{2D}(×10^{12} cm^{2})
(E_{F}E_{1}) (meV)
ptype
ntype
ptype
ntype
Ga_{0.62}In_{0.38}As
Asgrown
1.38
2.02
36.8
113.8
Annealed (60 s)
1.34
1.95
41.5
101.7
Annealed (600 s)

1.92

90.9
Ga_{0.62}In_{0.38} N_{0.009}As_{0.991}
Asgrown
1.18
2.30
52.7
99.5
Annealed (60 s)
1.16
2.29
52.0
82.1
Annealed (600 s)
1.17
2.32
52.8
83.1
Ga_{0.62}In_{0.38} N_{0.012}As_{0.988}
Asgrown
1.20
2.50
40.0
0.0686
Annealed (60 s)
1.06
2.59
55.5
0.0699
Annealed (600 s)

2.71

0.0788
The analysis of SdH is also useful to obtain both 2D carrier density and Fermi energy. A plot of the reciprocal magnetic field versus the peak number n gives the period of the SdH oscillations, Δ(1/B). The 2D carrier density and the Fermi energy can be calculated from the obtained period of SdH oscillations using [18, 22, 24]
where E_{F}  E_{1} is the energy difference between the Fermi level and occupied first subband level; m*, effective mass; and n_{2D}, 2D carrier density. Figure 3 shows the plot of 1/B_{
i
} versus n and the slope of the lines for n and ptype samples with 0.9% nitrogen composition. The fact that the plots have the same slope is an indication of only one occupied subband. We obtained that slopes are independent of temperature. Using the slope of the plot, both 2D carrier density and Fermi energy are calculated and tabulated in Table 2.
Although all samples were doped with the same doping concentration, among ntype samples, among ntype samples, Nfree ones have the lowest electron density. Moreover, the hole density is less than the electron density for the samples with the same nitrogen content. An enhancement of electron concentration in Ncontaining samples compared to the Nfree ones was also observed in previous studies [8, 14–16] and explained in accordance with the BAC model, since Ninduced flattening of conduction band leads to an increased density of states of electrons therefore a significant increase in 2D electron density. Upon thermal annealing, 2D electron density tends to increase in Ncontaining samples as a result of enhanced electron effective mass. As a result of almost thermal annealing insensitive effective hole mass, 2D hole density remains unaffected for the sample with 0.9% nitrogen. As nitrogen composition increases to 1.2%, the observed decrease in effective hole mass causes to reduce 2D hole density. The calculated Fermi energies change depending on both 2D carrier and effective mass, which are influenced by nitrogen composition and thermalannealinginduced effects.
Conclusions
We have investigated the effect of nitrogen and thermal annealing on electronic transport properties of n and ptype Nfree and Ncontaining alloys using magnetotransport measurements. With an analysis of SdH oscillations at different temperatures, we have calculated inplane effective carrier mass, 2D carrier density, and Fermi energy of the samples. Nitrogendependent enhancement of the both electron and hole masses has been observed in asgrown samples. Upon thermal annealing, the electron effective mass increased, whereas hole mass tends to decrease. The observed nitrogen dependence of electron mass has been explained in terms of strengthened interaction between localized nitrogen level and conduction band states. A tendency to decrease in hole mass upon annealing can be attributed to the reduction of well width and/or decrease in hole density. Even all samples have the same dopant density, the observation of higher 2D electron density than that of ptype samples with the same nitrogen composition and Nfree samples has been explained with a stronger interaction of N level and conduction band states, which gives rise to enhancement of the density of states. The results revealed that effective mass in dilute nitride alloys can be tailored by nitrogen composition and also thermalannealinginduced effects.
Abbreviations
2D:
twodimensional
QW:
quantum well
SdH:
Shubnikov de Haas.
Declarations
Acknowledgements
This work is supported by the TUBITAK project (project number 110 T874) and Istanbul University Scientific Research Projects Unit (project number IRP 9571) and The Ministry of Development, Turkey (project number 2010 K121050). We also acknowledge to the COST Action MP085 for enabling collaboration possibilities.
Authors’ Affiliations
(1)
Department of Physics, Faculty of Science, Istanbul University
(2)
Material Engineering, Adana Science and Technology University, Seyhan
(3)
Optoelectronics Research Centre, Tampere University of Technology, Korkeakoulunkatu
References
Klar PJ, Grüning H, Koch J, Schäfer S, Volz K, Stolz W, Heimbrodt W, Saadi A, Lindsay A, O’Reilly EP: (Ga, In)(As, N)fine structure of the bandgap due to nearestneighbor configuration of isovalent nitrogen. Phys Rev B 2001, 64: 121203.View Article
Sun Y, Erol A, Yilmaz M, Arikan MC, Ulug B, Ulug A, Balkan N, Sopanen M, Reentilä O, Mattila M, Fontaine C, Arnoult A: Optical and electrical properties of modulationdoped n and ptype GaInNAs/GaAs quantum wells for 1.3 μm laser applications. Opt Quant Electron 2007, 40: 467.View Article
Erol A: Dilute Nitride Semiconductors and Materials Systems: Physics and Technology. Berlin: Springer; 2008.View Article
O’Reilly EP, Lindsay A, Fahy S: Theory of the electronic structure of dilute nitride alloys: beyond the bandanticrossing model. J Phys Condens Matter 2004, 16: 3257. 10.1088/09538984/16/18/025View Article
Fahy S, Lindsay A, Ouerdane H, O’Reilly EP: Alloy scattering of ntype carriers in GaN _{x}As_{1 x}. Phys Rev B 2006, 74: 035203.View Article
Balkan N, Mazzucato S, Erol A, Hepburn CJ, Potter RJ, Vickers AJ, Chalker PR, Joyce TB, Bullough TJ: Effect of fast annealing on optical spectroscopy in MBE and CBEgrown GaInNAs/GaAs QWs: blueshift versus redshift. IEEE Proc Optoelectron 2004, 151: 5.
Erol A, Akcay N, Arikan MC, Mazzucato S, Balkan N: Spectral photoconductivity and inplane photovoltage studies of asgrown and annealed GaInNAs/GaAs quantum well structures. Semicond Sci Technol 2004, 19: 1086. 10.1088/02681242/19/9/003View Article
Sarcan F, Donmez O, Gunes M, Erol A, Arikan MC, Puustinen J, Guina M: An analysis of Hall mobility in asgrown and annealed n and ptype modulationdoped GaInNAs/GaAs quantum wells. Nanoscale Res Lett 2012, 7: 1. 10.1186/1556276X71View Article
Shan W, Walukiewicz W, Ager JW: Effect of nitrogen on band structure of GaInNAs alloys. J Appl Phys 1999, 86: 2349. 10.1063/1.371148View Article
Tiras E, Balkan N, Ardali S, Gunes M, Fontaine C, Arnoult A: Philosophical Magazine. 2011, 91: 628. 10.1080/14786435.2010.525543View Article
Tiras E, Ardali S: Contactless electron effective mass determination in GaInNAs/GaAs quantum wells. Eur Phys J B 2013, 86: 2.View Article
Baldassarri G, Hogersthal H, Polimeni A, Masia F, Bissiri M, Capizzi M: Magnetophotoluminescence studies of (InGa)(AsN)/GaAs heterostructures. Phys Rev B 2003, 67: 233304.View Article
Wartak MS, Weetman P: The effect of well coupling on effective masses in the InGaAsN material system. J Phys Condens Matter 2007, 19: 276202. 10.1088/09538984/19/27/276202View Article
Sarcan F, Donmez O, Erol A, Gunes M, Arikan MC, Puustinen J, Guina M: Influence of nitrogen on hole effective mass and hole mobility in ptype modulation doped GaInNAs/GaAs quantum well structures. Appl Phys Lett 2013, 103: 082121. 10.1063/1.4819233View Article
Sun Y, Balkan N, Erol A, Arikan MC: Electronic transport in n and ptype modulationdoped GaInNAs/GaAs quantum wells. Microelectron J 2009, 40: 403. 10.1016/j.mejo.2008.06.010View Article
Sun Y, Balkan N, Aslan M, Lisesivdin SB, Carrere H, Arikan MC, Marie X: Electronic transport in n and ptype modulation doped Ga_{x}In_{1x}N_{y}As_{1y}/GaAs quantum wells. J Phys Condens Matter 2009, 21: 174210. 10.1088/09538984/21/17/174210View Article
Ando T: Theory of quantum transport in a two dimensional electron system under magnetic field. J Phys Soc Jpn 1974, 41: 1233.View Article
Patane A, Balkan N: Semiconductor Research Experimental Techniques. Berlin: Springer; 2012:63.View Article
Balkan N, Celik H, Vickers AJ, Cankurtaran M: Warmelectron power loss in GaAs/Ga_{1x} Al_{x} As multiple quantum wells: wellwidth dependence. Phys Rev B 1995, 52: 24. 10.1103/PhysRevB.52.24View Article
Celik H, Cankurtaran M, Balkan N, Bayraklı A: Hot electron energy relaxation via acousticphonon emission in GaAs/Ga_{1x}Al_{x} As multiple quantum wells: wellwidth dependence. Semicond Sci Technol 2002, 17: 18. 10.1088/02681242/17/1/304View Article
Bauer G, Kahlert H: Hot electron Shubnikovde Haas effect in nInSb. J Phys Condens Matter 1973, 6: 1253.
Bauer G, Kahlert H: Lowtemperature nonohmic galvanomagnetic effects in degenerate ntype InAs. Phys Rev B 1972, 5: 566. 10.1103/PhysRevB.5.566View Article
Meyer BK, Drechsler M, Wetzel C, Harle V, Scholz F, Linke H, Omling P, Sobkowicz P: Composition dependence of the inplane effective mass in latticemismatched, strained Ga_{1x}In_{x}As/InP single quantum wells. Appl Phys Lett 1993, 63: 657. 10.1063/1.109948View Article
Arikan MC, Straw A, Balkan N: Warm electron energy loss in GaInAs/AlInAs high electron mobility transistor structures. J Appl Phys 1993, 74: 6261. 10.1063/1.355170View Article
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