Physics Letters A 319 (2003) 191–197

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Binding energies of donors in quantum wells

under hydrostatic pressure
G.J. Zhao b,∗ , X.X. Liang a,b , S.L. Ban a,b
a CCAST (World Laboratory), P.O. Box 8730, Beijing 100080, People’s Republic of China
b Department of Physics, Inner Mongolia University, Hohhot 010021, People’s Republic of China

Received 25 July 2003; accepted 2 October 2003

Communicated by R. Wu

Abstract
The binding energies of donors in quantum wells are investigated with a variational method considering the influence of finite
barriers under hydrostatic pressure. In the calculation, we take into account the electronic effective mass, dielectric constant,
and conduction band offset between the well and barriers varying with pressure. The numerical result shows that the donor
binding energy linearly increases with the pressure from 0 to 40 kbar. The pressure effect for GaAs/Alx Ga1−x As quantum
wells is more obvious than that for GaN/Alx Ga1−x N quantum wells. We also calculate the binding energy as a function of
the Al concentration, which can influences the barrier height. The result indicates that the donor binding energy monotonically
increases with increasing the barrier height.
 2003 Elsevier B.V. All rights reserved.

PACS: 62.50.+p; 73.21.Fg; 71.55.-i

Keywords: Hydrostatic pressure; Quantum well; Donors; Binding energies

1. Introduction cal research on the pressure influence on the physi-

Hydrostatic pressure can shift effectively the en-
ergy levels of tetrahedral semiconductors without al-
tering the crystal symmetry. The study of the pressure
dependences of the electrical and the optical proper-
ties of the semiconductors provides information on the
band structure and other parameters. In recent years,
there was a great deal of experimental and theoreti-
* Corresponding author.
E-mail address: stzhaogj@imu.edu.cn (G.J. Zhao).
0375-9601/$ – see front matter  2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.physleta.2003.10.006
cal properties of bulk and low-dimensional semicon-
ductors [1–8]. Since GaAs/Alx Ga1−x As quantum well
(QW) structure has been applied in modern high speed
electronic and photo electronic devices, the pressure
dependence of the optical and electric properties in
the related systems have been extensively investigated.
Lefebvre, Gil and Mathieu [3] presented a theoretical
calculation about the pressure coefficients of carrier
effective mass and the well-width and barrier-height
dependent excitonic transitions in GaAs/Alx Ga1−x As
QWs. Their results show that the effective masses of
electrons and light holes increase with pressure. But
192 G.J. Zhao et al. / Physics Letters A 319 (2003) 191–197
the effective masses of heavy holes do not change ev-
idently with pressure. Goni, Syassen, and Cardona [9]
measured the dispersion of the refractive index of Ge
and GaAs between 0.6 and 1.4 eV under a hydrostatic
pressure up to 8 GPa and also obtained the variation
of high frequency dielectric constant with the pres-
sure. Their results show that the refractive index and
high frequency dielectric constant decrease monoton-
ically with increasing the pressure up to 8 GPa. The
pressure effect on the optical absorption of excitons
in GaAs at low temperatures has been investigated by
Goni, Cantareno, Syassen, and Cardona [10] by ob-
serving the effective Rydberg energy of excitons. They
found that the binding energies of direct excitons in-
crease linearly with the pressure.
It is well known that the lattice vibration plays an
important role in the properties of semiconductors.
Nakahara et al. [11] measured the Raman spectra dif-
ferent alloy compositions and pressures. They found
that the LO and TO phonon modes shift to the higher
frequencies under pressure. Recently, Holtz and his
collaborators [12] have performed an extensive Ra-
man scattering study for the effect of hydrostatic pres-
sure on the phonon modes in ternary mixed crystal
Alx Ga1−x As of 0
x
0.70, and obtained the x de-
pendence of the mode-Grüneisen parameter.
Although there were many experimental and theo-
retical researches on the pressure effect in the bulk ma-
terial and QW structures, the electronic complex states
have been rarely reported to our knowledge. Sukumar
and Navaneethakrishnan [13] discussed the effect of
hydrostatic pressure on the binding energies of Wan-
nier excitons in a GaAs/Alx Ga1−x As QW structure
and found the binding energies increasing with pres-
sure. However, an infinite barrier approximation was
adopted in their calculation. More recently, Ban and
Liang [14] investigated the binding energy of a donor
near the interface of a GaAs/Alx Ga1−x As hetero-
junction under hydrostatic pressure. They developed
a variational method and considered the influence of
a realistic interface potential. The results showed that
the donor binding energy increases with pressure ob-
viously. Based on this work, the authors [15] adopted
a variational method to calculate the exciton binding
energy including the exciton–phonon interaction in
GaAs/Alx Ga1−x As QWs under hydrostatic pressure.
There, we have assumed that the excitons are confined
in the well under an infinite barrier approximation.
However, the infinite barrier approximation fails when
the width of the QW becomes very narrow, because
the effect of the electronic wave-function penetration
into the barrier region no longer can be neglected.
In this Letter, we adopt a variational method to cal-
culate the binding energy of a donor in a QW struc-
ture with finite barriers under hydrostatic pressure.
The pressure effects of the electron effective mass, the
dielectric constant and the band offsets between the
well and barrier materials are considered in the calcu-
lations. Meanwhile, the effect of the electronic wave-
function penetrating into the barrier regions is also
taken into account. The results show that the donor
binding energy monotonically increases with pressure
in the region from 0 to 40 kbar. The binding energy is
also sensitive to the barrier height variation, which is
related to the Al concentration.
2. Theory
Let us consider a GaAs/Alx Ga1−x As (GaN/Alx -
Ga1−x N) QW, for which the well region GaAs (GaN)
denoted by material 1 is located at |z|
d and the
barrier regions Alx Ga1−x As (Alx Ga1−x N) denoted by
material 2 are located at |z| > d, respectively. The
coordinate origin is chosen as the well center. A donor
impurity bearing a charge e located at (0, 0, z0) binds
a conduction electron with an isotropic effective mass
mi (i = 1, 2 refers to material i) and charge −e
to form impurity states. Here, we only consider the
case of |z0 | < d. By adopting the effective mass
approximation, the Hamiltonian of the electron and
impurity system can be written as
H = H + H⊥ + HC , (1)
where the first term denotes the kinetic energy of the
electron in the x–y plane and satisfies
h̄2 1 ∂ ∂
H = − ρ . (2)
2m(z) ρ ∂ρ ∂ρ


Here, ρ = x 2 + y 2 is the radial component of the
electron coordinate in the x–y plane. In Eq. (1),
h̄2 ∂ 1 ∂
H⊥ = − + V (z) (3)
2 ∂z m(z) ∂z
represents the kinetic energy of electron along the z-
direction.
 G.J. Zhao et al. / Physics Letters A 319 (2003) 191–197 193

In the above equations m(z) is the electron effective The wave vectors of the electron in the well and
mass with different values in the well and barriers, barriers can be obtained simultaneously as


m1 for |z|
d,
m(z) = (4) 2m1 E
2m2 (V0 − E)
m2 for |z| > d. k= , k = . (13)
h̄2 h̄2
In Eq. (3), V (z) is the height of potential barriers for
electrons and is given by

0 for |z|
d, 3. Pressure coefficient
V (z) = (5)
V0 for |z| > d.
The third term in Eq. (1) is the Coulomb interaction We now turn to consider the influence of hydrosta-
between the electron and impurity, and is given by tic pressure on the energies of the impurity states in
GaAs/Alx Ga1−x As and GaN/Alx Ga1−x N QWs. For
e2 this purpose, we first discuss the dependence of the
HC = −
, (6)
ε(z, z0 ) ρ 2 + (z − z0 )2 electronic effective mass, dielectric constants and band
in which the position dependent dielectric constant is offset in GaAs (GaN) and Alx Ga1−x As (Alx Ga1−x N)
chosen as on the hydrostatic pressure. Here we confine our dis-
 cussion for pressure being not very high, i.e., below
ε01 for |z|
d,
ε(z, z0 ) = (7) 40 kbar. The well material GaAs then can be treated
(ε01 + ε02 )/2 for |z| > d. as a direct band-gap semiconductor.
Here ε0i is the static dielectric constant of the ith As applying hydrostatic pressure on the material,
material. it changes the structure of energy band, in addition
We choose the following variational trial wave- the electronic effective mass change with pressure.
function for the impurity ground state According to the kp theory, the pressure dependence
   of the electronic effective mass is given by [17],
λ
|Φ = exp − (z − z0 ) + ρ ζ (z),
2 2 (8)
2 m0 C
=1+ , (14)
where λ is the variational parameter and m(p) Eg (p)

cos(kz) for |z|
d, where Eg is the band gap and C is constants for differ-
ζ (z) =  
 (9)
cos(kd) exp − |k |z − d for |z| > d. ent materials. C = 19.8297 eV for GaAs, 12.2853 eV
for AlAs, 14.0684 eV and 12.1818 eV for GaN and
In Eq. (9), k and k
are the wave vectors of the electron
AlN, respectively.
in the well and barriers, respectively, and can be
For the pressure dependence of high frequency
determined by the first subband energy of the electron.
dielectric constant, we use the equation given by Goni,
Using Eq. (8), we obtained the variational energy
Syassen, and Cardona [9]
for the impurity ground state in a QW with finite
barriers ∂ ln ε∞ 5(ε∞ − 1)
≈ (0.9 − fi ), (15)
Φ|H |Φ ∂ ln V 3ε∞
Ev = . (10)
Φ|Φ where fi is the ionicity of the material under pres-
Then the binding energy for the ground state can be sure. The volume V of the material can be determined
obtained by subtracting Ev from the “free electron” by the Murnaghan state equation. It satisfies approxi-
energy E: mately the following linear relation [1] in the low pres-
sure range:
EB = E − Ev . (11)
∂P
Here E is determined by numerically solving the B(P ) = −V = B0 + B0
P . (16)
transcendental equation ∂V

  
 Here B is the bulk modulus and is assumed being lin-
m1 V 0 2m1 d 2 E ear with the pressure for not very high pressures. B0
− 1 − tan = 0. (12)
m2 E h̄2 and B0
are the bulk modulus at zero pressure and its
194 G.J. Zhao et al. / Physics Letters A 319 (2003) 191–197

Table 1
Parameters used in the computation. Phonon energies are measured in units of meV, electronic effective mass in units of the bare electron mass
m0 , bulk modulus B0 in units of kbar, energy band gap in units of eV, pressure coefficient of band gap α = dEg /dP in units of meV/kbar
ε∞ h̄ωLO h̄ωTO me fi B0 B0
Eg α γLO γTO
GaAsa 10.89 36.25 33.29 0.067 0.310 770b 4.6b 1.424 11.5 1.01c 1.12c
AlAsa 8.16 50.09 44.88 0.15 0.274 748b 4.6b 2.168 10.2 0.85c 1.08c
GaN 5.41d 92.99f 69.43f 0.19g 0.5h 2054i 4.6i 3.3g 3.6i 1.02f 1.19f
AlN 4.46e 112.5f 82.08f 0.33g 0.499h 2158i 4.2i 6.0g 4.7i 0.89f 1.14f
a Adachi, Ref. [16]. b Lam et al., Ref. [8]. c Holtz et al., Ref. [12]. d Karch et al., Ref. [18]. e Karch et al., Ref. [19]. f Wagner
et al., Ref. [6]. g Wang et al., Ref. [20]. h Phillips, Ref. [21]. i Wei et al., Ref. [5].

first order pressure deviation at zero pressure, respec- GaN/Alx Ga1−x N (b) QW structure with well widths
tively. Thus we can write the pressure coefficient for d = 10, 20 and 50 Å for GaAs/Alx Ga1−x As QW,
the high frequency dielectric constant as d = 5, 15 and 100 Å for GaN/Alx Ga1−x N QW and the
∂ε∞ 5(ε∞ − 1) Al concentration x = 0.15 for the ternary mixed crys-
=− (0.9 − fi ). (17) tal barriers. It is found that the donor binding energies
∂P 3B
nearly linearly increase with pressure in the calculated
The static dielectric constant is then determined by the
pressure range, from 0 to 40 kbar. The donor bind-
famous Lyddane–Sachs–Teller relation:
ing energy is elevated about 34–36% in comparison

h̄ωLO 2
ε0 = ε∞ , (18)
h̄ωTO
where h̄ωTO and h̄ωLO are, respectively, the transverse
optical (TO) and longitudinal optical (LO) phonon
energies.
According to the mode-Grüneisen parameter
1 ∂ω
γ = B0 , (19)
ω0 ∂p
we can obtain the optical phonon energy dependence
on pressure. In the above equation, B0 is the bulk mod-
ulus, ω and ω0 are the optical phonon frequencies un-
der hydrostatic pressure p = 0 and p = 0, respectively.
The values of the mode-Grüneisen parameter γ are
given in Table 1.
4. Results and discussion
In order to understand the pressure dependence
of the donor binding energy, we have preformed
numerically computation for GaAs/Alx Ga1−x As and
GaN/Alx Ga1−x N QW structures. The parameters used
in the computation are listed in Table 1. The calculated
results are shown in Figs. 1–4 for the impurities being
at the well center.
Fig. 1 shows the donor binding energies as func-
tions of pressure in GaAs/Alx Ga1−x As (a) and
with that without pressure for the same well widths for
a GaAs/Alx Ga1−x As QW, and the value is about 6%
for a GaN/Alx Ga1−x N QW. This indicates that the
pressure effect is more obvious for the former than
that for the latter. On the other hand, the pressure influ-
ence on the binding energies of the impurity states is
also sensitive to the well width for GaAs/Alx Ga1−x As
QWs. The curve with the largest pressure effect corre-
sponds to the well width around 20 Å where the pres-
sure effect is about 36%. The same conclusion can be
obtained for GaN/Alx Ga1−x N QWs.
To understand the well-width effect clearly, we
have also plotted the binding energies as functions of
the well width for three given pressures, P = 0, 20
and 40 kbar with Fig. 2(a) and (b) corresponding to
the GaAs/Alx Ga1−x As and GaN/Alx Ga1−x N QWs,
respectively. It is shown in Fig. 2 that the three curves
of the donor binding energies versus well width for
pressures P = 0, 20 and 40 kbar are almost paral-
lel. One can see that the pressure effects for different
pressures are qualitatively similar. Therefore, that the
character of the binding energy variation with the well
width under pressure is similar to that without pres-
sure is expected. In bulk materials, the calculated ef-
fective Rydberg energies (Ry) and effective Bohr radii
(EBR) for donors are respectively 7.373233 meV and
80.68553 Å for bulk Al0.15 Ga0.85 As, 5.460948 meV
and 102.094 Å for GaAs, 31.7458 meV and 23.8609 Å
 G.J. Zhao et al. / Physics Letters A 319 (2003) 191–197
(a)
(b)
Fig. 1. The donor binding energies as functions of the hydrostatic
pressure for the given Al concentration x = 0.15 and well width
d = 10 (5) Å, 20 (15) Å and 50 (100) Å corresponding to the dotted,
solid and dashed lines, respectively. (a) is for GaAs/Alx Ga1−x As
QWs and (b) for GaN/Alx Ga1−x N QWs.
for Al0.15 Ga0.85 N, 27.4215 meV and 27.0551 Å for
GaN. When the well width is much larger than the
EBR of the well, the electronic wave-function al-
most does not penetrate into the barriers and the
donor binding energy decreases with increasing the
well width and finally (d → ∞) tends to the 3D re-
sult, i.e., Ry for GaAs or GaN. With decreasing the
well width, the size of the quantum confinement in
z-direction reduces and the donor binding energy in-
creases and finally tends exactly to 4 Ry of the 2D
result for an infinite quantum well with zero width.
However, in the finite barriers case, the electronic
wave-function cannot be confined completely in the
195
(a)
(b)
Fig. 2. The donor binding energies as functions of the well width for
the given pressure P = 0, 20, 40 kbar and Al concentration x = 0.15
corresponding to the solid, dotted and dashed lines, respectively.
(a) is for GaAs/Alx Ga1−x As QWs and (b) for GaN/Alx Ga1−x N
QWs.
well and partly penetrates into the barriers when the
well width is getting narrower than the EBR of the
impurity state. Finally, most of the wave-function of
the electron penetrates into the barrier regions so that
the donor binding energy does not reach to the 2D
limit, but reasonably closes to the effective Ry in
Al0.15 Ga0.85 As or Al0.15 Ga0.85 N, when the well be-
comes very much narrow (d → 0). There is a max-
imum value of the donor binding energy at the well
width around 20 Å for GaAs/Alx Ga1−x As QW and
15 Å for GaN/Alx Ga1−x N QW. It is also found in
Fig. 2 that the maximum value of the donor binding
energy slightly move to the narrow well width as the
196 G.J. Zhao et al. / Physics Letters A 319 (2003) 191–197
(a)
(b)
Fig. 3. The energy differences as functions of the well width for
(a) GaAs/Alx Ga1−x As QWs and (b) GaN/Alx Ga1−x N QWs. The
solid lines denote $E1 = EB (p = 40 kbar) − EB (p = 0) and the
dotted lines denote $E2 = EB (p = 20 kbar) − EB (p = 0).
pressure increases because the EBR of the donor state
decreases with pressure.
From Fig. 2, we found that the upward shifts
of donor binding energies caused by pressure are
quantitatively different in dependence on the well
width. In order to understand this phenomenon, we
plot the pressure dependence of the differences of
donor binding energies between with and without
pressure varying with well width in Fig. 3. From
the figures we found that this dependence also have
a maximum value, which increases with well width in
both GaAs/Alx Ga1−x As and GaN/Alx Ga1−x N QWs.
It is the same with the maximum value of donor
(a)
(b)
Fig. 4. The donor binding energies as functions of the Al con-
centration x for given well width d = 20 Å and pressure P = 0,
20, and 40 kbar corresponding to the solid, dotted and dashed
lines, respectively. (a) is for a GaAs/Alx Ga1−x As QW and (b) for
a GaN/Alx Ga1−x N QW.
binding energy. As the well width is large enough, it
trends to a steady value.
As mentioned above, the wave-functions of impu-
rity states partly penetrate into the barriers for the prac-
tical QWs with finite barriers. This is different from
the infinite barrier situation. The barrier height influ-
ences the penetration and then the donor energy. We
have illustrated in Fig. 4 the calculated donor bind-
ing energies as functions of the Al concentration x
(and also the barrier height) in the given well width
d = 20 Å and pressure P = 0, 20 and 40 kbar. It is
shown that the donor binding energy monotonically
increases with the Al concentration x in the given pres-
 G.J. Zhao et al. / Physics Letters A 319 (2003) 191–197
sure and well width, since the Al composition raises
the barrier height and enhances the confinement of im-
purity states.
The dependence of the donor binding energy on
the impurity-center position z0 was also considered.
For the given well width and pressure, the donor
binding energy firstly increases, and then decreases
with moving the impurity position from z = −d to
z = d. It gets a maximum value when the impurity
center is at the well center, i.e., z0 = 0. We do not give
the results here for simplification.
In conclusion, we have calculated variationally
the binding energies of donors in GaAs/Alx Ga1−x As
and GaN/Alx Ga1−x N quantum wells with finite bar-
riers under hydrostatic pressure by taking into ac-
count the pressure influence on the effective mass
of electrons, dielectric constant and the band off-
set. The results show that the donor binding en-
ergy increases almost linearly with the pressure, and
monotonically with the barrier height. The pressure ef-
fect for GaAs/Alx Ga1−x As quantum wells is more ob-
vious than that for GaN/Alx Ga1−x N quantum wells.
The pressure effect qualitatively agrees with the result
for donors in heterojunctions [14] and quantum wells
with an infinite barrier approximation [13].
Acknowledgements
This work was supported by the National Natural
Science Foundation of China (Grant Nos. 60166002
and 10264003), and the Educational Science Founda-
tion of Inner Mongolia Autonomous Region of PR
China (Grant NJ02054). The author (G.J. Zhao) is
197
thankful to Prof. Z.W. Yan for useful discussions and
helps.
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