JOURNAL OF APPLIED PHYSICS 97, 073706 2005

Finite depth square well model: Applicability and limitations

Giovanni Pellegrini, Giovanni Mattei,a and Paolo Mazzoldi
INFM, Dipartimento di Fisica, Universit di Padova, via Marzolo 8, I-35131, Padova, Italy

Received 17 September 2004; accepted 18 January 2005; published online 22 March 2005 An investigation of the nite depth square well model is presented in this article: model features and limitations, concerning size dependent band gap of semiconductor quantum structures, are presented and discussed. Model predictions are compared with large sets of experimental data for IIIV, IIVI and lead salt semiconductor quantum dots and quantum wires. Matrix inuence on the connement is studied by modeling experimental results for colloidal CdS, CdSe, CdTe and InP quantum dots. The effect of quantum structure dimensionality is investigated and successfully simulated for colloidal CdSe and InP experimental data and Si rst-principle calculations. Finally, model limitations for narrow band gap semiconductors are studied and discussed. 2005 American Institute of Physics. DOI: 10.1063/1.1868875
I. INTRODUCTION

Size dependent band gap of semiconductor quantum structures is a well known and studied quantum connement effect. The band gap of IIVI,16 IIIV712 and lead salt1318 semiconductor quantum dots QDs has been extensively investigated while quantum wires1923 QWs and quantum rods2428 have attracted much interest in the last few years. In order to understand the size dependent band gap, different theoretical approaches have been adopted, including effective mass approximation EMA ,2938 mostly relying on innite-well potentials outside the QDs, variational calculations,3945 k p method,4648 tight binding TB ,49,50 linear combination of atomic orbitals51 LCAO and empirical pseudopotential method EPM .5264 In the present article we will adopt the nite depth square well effective mass approximation,37,38,45 since recently it has been shown that including a nite depth well in the EMA considerably improves the model,37,38 making it suitable for quantitative predictions. It has also been shown, in the case of PbS, that the band gap depends on the different matrices surrounding the crystallites.37 The model has been applied only to a few systems thus, in order to further test its validity, it would be desirable to dispose of large sets of experimental data for QDs embedded in different matrices, though data of this kind are scarce in literature. We present an alternative and somehow specular approach to the problem, in order to easily overcome this difculty. Instead of choosing a single semiconductor embedded in different matrices, we shall use different semiconductors embedded in matrices that have experimentally shown to provide the same connement. In the present case colloidal quantum dots capped with organic ligands will be considered. Such systems have the signicative advantage to provide high quality monodispersed clusters, in a wide size range. Once we have established the validity of the model we shall study comparatively the band gap in QDs and QWs, investigating the effect of structure dimensionality
a

on the connement. Finally, the validity of the model will be checked for narrow band gap semiconductors, characterized by strongly nonparabolic bands.
II. THEORY: FINITE DEPTH WELL MODEL

In the present article we focus the study on nanoclusters with radius r0 approximately smaller than 5 nm. This corresponds, in the frame of the EMA, to the strong connement regime: electron and hole will be considered as independent particles of effective mass m* and m* inside the dot, and of e h mass m0 outside the dot, where m0 is the free electron mass. Their Coulomb interaction will be calculated by rst-order perturbation theory, since it may be considered small if compared to connement energy.39 The strong connement approximation is valid for r0 aB where r0 is indifferently the dot or wire radius and aB is the Bohr exciton radius.30 Its use CdS is justied since typical aB values range from aB InAs 2.5 nm for CdS to aB 30 nm for InAs. The stationary Schrdinger equation for a particle of mass m in a potential V r may be expressed as
2

2m

+V r

r =E

r .

We choose V r = V r centro symmetric and given by Vr = 0, r r0 r0 V0 , r , 2

for both quantum wires and quantum dots of radius r0: in these two different cases the potential is characterized by spherical and cylindrical symmetry, respectively. V0 is dened as33,37 2V0 = V0e + V0h = Eg M Eg S , 3

Author to whom correspondence should be addressed; electronic mail: mattei@padova.infm.it

where Eg M stands for the matrix band gap and Eg S for the semiconductor one. V0e and V0h are the conning potentials for electrons and holes, respectively. In the following we choose V0e = V0h = V0 with the exception of free standing Si QDs and QWs, for which experimental conning potential are available34 . Indeed, different combinations of V0e and V0h give a difference in the blueshift of the band gap of less
2005 American Institute of Physics

0021-8979/2005/97 7 /073706/8/$22.50

97, 073706-1

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Pellegrini, Mattei, and Mazzoldi

J. Appl. Phys. 97, 073706 2005

than 10% for PbS in silica:38 an even smaller difference would be obtained for semiconductors characterized by heavier electrons and holes. Moreover, it has to be underlined that while it is possible to establish the band offset for two different semiconductors,33 since their Fermi energies are often known, this is not always so for QDs capped with organic ligands. According to the spherical or cylindrical symmetry of the problem the radial and angular coordinates may be separated, and the energy eigenvalues may be deduced from the boundary conditions of the radial equations.

2. Coulomb interaction

The Coulomb interaction between electron and hole is treated in the frame of rst-order perturbation theory, thus obtaining37 Ee-h = 1se,1sh = 2e 4
0 2

4 0 r

0 r0 0

e2 1se,1sh 0 re rh r R2 rh rhdrh d
rh 0

R2 re r2dre . d e

10

A. Spherical potential well: Quantum dots

1. Energy eigenvalues

The radial Schrdinger equations in spherical coordinates for the = 0 ground state are 2 dRd r d 2R d r + k2 Rd r = 0, + in 2 dr r dr 2 dRd r d 2R d r 2 koutRd r = 0, + 2 dr r dr with k2 = in 2m*E
2 2 and kout =

The integral is calculated only inside the cluster volume since the contribution of the outer volume has been shown to be two or three orders of magnitude smaller than the inner one.36 A size dependent dielectric constant, developed originally by Hanken66 and then readapted to treat Coulomb perturbation in quantum dots, is used38,52 1 1 = 0 r 1 1 1
0

r0 ,

4a

exp 0/ r

r0 ,

4b

+ exp 0/ r 2

11

Here 0 is the mean electron-hole distance, r static and optical dielectric constants and 5
1/2 e,h

and are the are given as38 e,h

0

2m0 E V0
2

* 2me,h

,
LO

12

where m* stands for the electron or hole effective mass. The ground state wave function may be expressed as spherical Bessel functions of rst and third kind of zeroth order j0 kinr = Rd r sin kinr , kinr r r0 , 6 r r0 .

where LO is the LO phonon frequency. Finally the band gap Eg r0 for a cluster with radius r0 and its variation Eg r0 with respect to the bulk value are calculated as Eg r0 = Ee r0 + Eh r0 + Eeh r0 + Eg bulk , Eg r0 = Ee r0 + Eh r0 + Eeh r0 . 13a 13b

h01 koutr =

exp koutr , koutr

The proper matching conditions for the two branches of Rd r are obtained by imposing the continuity of the logarithmic derivative at the well edge weighted for the particle masses34 1 m Rd r
*

B. Cylindrical potential well: Quantum wires

The radial equations in cylindrical coordinates become 1 dRw r d 2R w r + k2 Rw r = 0, + in dr2 r dr 1 dRw r d 2R w r 2 koutRw r = 0, + 2 dr r dr r r0 , 14a

dRd r dr

=
rr 0

1 m 0R d r

dRd r dr

.
rr+ 0

This is done in order to preserve the current probability density at the semiconductor-matrix interface.34,65 By substituting
2 m0k2 r2 + m*koutr2 = in 0 0

r0 .

14b

m 0V 0

and

2m*r2 0
2

The ground state solutions are now Bessel functions of rst and second kind of zeroth order Rw r J0 kinr , K0 koutr , r r r0 , r0 . 15

in Eq. 7 and after some rearrangements the energy eigenvalues Ee and Eh are obtained solving for x the equation x cot x = 1 where x = kinr0. m* m0 m* m0 V0 x2 , 9

The boundary conditions are as in Eq. 7 . The energy eigenvalues Ee and Eh are now found by solving numerically for kin the following system of equations:

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Pellegrini, Mattei, and Mazzoldi

J. Appl. Phys. 97, 073706 2005 TABLE I. Sample characteristics.

rr+ 0

dJ0 kinr * m J0 kinr dr

2 m0k2 r2 + m*koutr2 = in 0 0

=
rr 0

1 dK0 koutr m0K0 koutr dr

m 0V 0

Connement

Matrix Oleic acid 1-thyoglicerol Oleic acid TOP/TOPO Phenyl n-Propil groups Oleic acid TOP/TOPO Tryoctilamine E-MAA Phosphate glasses TOP/TOPO Vacuum

Eg S eV 2.53 1.75

Eg M eV 5.0 5.0

. 16

CdSa CdSeb

3D 2D,3D

The band gap of a quantum wire of radius r0 is then Eg r0 = Ee r0 + Eh r0 + Eg bulk , Eg r0 = Ee r0 + Eh r0 . 17a 17b
CdTec InPd PbSe PbSef InAsg Sih
a b

3D 2D,3D 3D 3D 3D 2D,3D

1.60 1.35 0.41 0.26 0.36 1.17

5.0 5.0 3.91 3.5 5.0

Coulomb interaction is not included in the computation for wire band gap, since correlation between electron and hole positions along QW length are not easily taken into account within this kind of approach: consequences of this approximation will be discussed in Sec. III A. It is interesting to underline that a numerical expression has been given for the determination of Ee and Eh, by means of an approximated wave function, in the following form:37 x 2.334 tan x 2.334 m* + m0 m* V0 x2 , m0 18

Samples, Refs. 3 and 5, Eg S Ref. 67, Eg M Ref. 5. Samples, Refs. 2, 5, and 19, Eg S Ref. 67, Eg M Ref. 5. c Samples, Ref. 5, Eg S Ref. 68, Eg M Ref. 5. d Samples, Refs. 810 and 23, Eg S Ref. 69, Eg M Ref. 5. e Samples, Ref. 13, Eg S Ref. 37, Eg M Ref. 37. f Samples, Ref. 16, Eg S Ref. 67, Eg M Ref. 70. g Samples, Ref. 12, Eg S Ref. 67, Eg M Ref. 5. h Samples, Ref. 51, Eg S Ref. 53.

where x is as in Eq. 9 . Differences between approximated and exact solution are negligible, becoming signicant only for very narrow wires 2r0 1.6 nm , with a blueshift underestimation of about 0.3 and 0.1 eV for InP and CdSe wires, respectively. Anyway, we preferred to use the exact calculation of Eq. 16 .
III. THEORY VS EXPERIMENTAL RESULTS

In the present section nite depth well model predictions will be compared with a wide variety of experimental and theoretical results taken from the literature. First the model will be applied to four different semiconductor quantum dots CdS, CdSe, CdTe and InP and then to CdSe and InP quantum wires. Results will be discussed, focusing also on differences between three-dimensional and two-dimensional connement, by comparing our results to CdSe and InP experimental data and to Si rst-principle calculations. Finally, the size dependent band gap for three narrow band gap semiconductor quantum dots PbS, PbSe and InAs will be computed, discussing limitations of the present model in the case of strong nonparabolicity of the bands. Sample characteristics and simulation parameters are resumed in Table I and II, respectively. The effective mass values considered are the most widely used in literature,3538 while in the case of Si we relied on simple isotropic effective mass concepts.32,62,63 The rst of the two Si m* values in Table II refers to QDs, e the second to 001 oriented QWs.
A. Quantum dots and quantum wires

In the following only QDs and QWs capped with organic ligands like trioctylphosphine oxide TOPO , oleic acid and 1-thioglycerol have been taken into account.2,3,5 Interestingly, in the case of CdSe, it has been experimentally demonstrated that the size dependent band gap shows no measurable dependence on the capping agents considered and that

the strength of the connement is constant despite the different organic ligands.5 Thus we may reasonably assume for all the ligands considered the same energy gap of oleic acid 5.0 eV , as far as the connement properties are concerned. The crucial point is that once assigned matrix and semiconductor band gaps, the conning potential V0 dened as in Eq. 3 is univocally determined for all the four semiconductors considered, thus providing quite a restrictive test for the model. In this context our approach can be retained as selfconsistent in the sense that an agreement between experimental data and our calculations veried as we shall see in the present section would justify the choice of the same band gap for all the organic ligands. The results of our calculation are presented in Figs. 1 and 2. As may be seen a good agreement between experimental data, rst-principle calculations and our results have been obtained on a wide size range, though it is worth pointing out that for CdS and CdSe, characterized by a small Bohr CdS CdSe exciton radius aB 2.5 nm, aB 5 nm , the band gap values are underestimated for large dots probably because of strong connement approximation breakdown. On the other hand we obtained accurate predictions for very small clusters 2r0 1.5 nm even if effective mass approximation is expected to fail in that size range. While surprising at rst sight, it may be easily shown that the nite depth square well model is quite insensitive to effective mass values in that size range, thus even a noticeable change in the band structure may produce minor effects on band gap computation as demonstrated in Fig. 3. In all the systems studied the agreement between our calculation and literature values can anyway be retained as very satisfactory, therefore indicating that EMA coupled with nite well is indeed a fast and reliable model for band gap calculation. Focusing the attention on rst-principle calculations, it may be noticed that the agreement for CdSe and InP is excellent, while that for CdS and CdTe is worse though still

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073706-4

Pellegrini, Mattei, and Mazzoldi TABLE II. Parameters utilized for nite depth square well calculations. V0 eV CdSa CdSeb CdTec InPd PbSe PbSef InAsg Sih
a * me m0 unit

J. Appl. Phys. 97, 073706 2005

m* h m0 unit 0.53 0.3 0.35 0.4 0.085 0.06 0.33 0.28

LO 0

eV 5.23 6.23 7.1 10.6 17.2 25.0 12.3 38 26.46 19.8 43.4 26.03 16.8 30.1

1.25 1.63 1.7 1.83 1.75 1.61 2.3 V0h = 4.0 V0e = 5.1

0.18 0.13 0.11 0.065 0.085 0.07 0.028 0.26,0.31

8.28 9.56 10.3 15.0 161.0 227.0 15.2

* me and m* Ref. 37, 0 and Ref. 71, LO Ref. 72. h * me Ref. 37, m* Ref. 46, 0 and Ref. 73, LO Ref. 73. h c * me and m* Ref. 67, 0 and Ref. 74, LO Ref. 75. h d * me Ref. 67, m* Ref. 22, 0 and Ref. 76, LO Ref. 77. h e * me and m* Ref. 37, 0 and Ref. 38, LO Ref. 38. h f * me and m* Ref. 67, 0 and Ref. 78, LO Ref. 78. h g * me and m* Ref. 67, 0 and Ref. 79, LO Ref. 79. h h * V0e and V0h Ref. 34, me and m* Refs. 32 and 62. h b

quite good. This is probably because, in the case of CdSe and InP QDs, EPM surface conditions are specically designed to reproduce organic surface passivation,23,54 while in the other two cases this is no longer true. The same set of parameters has been used to simulate the size dependent band gap of CdSe and InP quantum wires.19,23 The blueshift of the band gap is accurately reproduced in a wide size range as can be seen in Fig. 4: the agreement is excellent for very narrow wires, similarly to small dots, and now also for large ones. Concerning CdSe the accordance for very large wires is remarkable but we must be reminded that, in the frame of nite depth square well EMA, wire wave

functions are not suitable for a perturbative calculation of Coulomb interaction since electron and hole correlation along wire length may not be taken into account, thus possibly leading to a small overestimation of the band gap: a variational approach should be more suitable for this kind of computation. Still focusing on CdSe it has to be underlined that quantum rods experimental band gap values have been included in our data set Fig. 4 a .25 We considered rods with high aspect ratio L / 2r0 10 and about 40 nm long. Their behavior is analog to that of quantum wires as can be seen in Fig. 4, while this is no longer true for shorter rods, where the connement along the rod length becomes

FIG. 1. a Comparison between experimental and theoretical results for CdS dots; , experimental values from Ref. 3 and Ref. 5; , EPM from Ref. 52; solid line, present work. Small dot radii values have been corrected following the procedure described in Ref. 3. b Comparison between experimental and theoretical results for CdSe dots; , experimental values from Ref. 2 and Ref. 5; , EMP from Ref. 54; solid line, present work.

FIG. 2. a Comparison between experimental and theoretical results for CdTe dots; , experimental values from Ref. 5; , TB from Ref. 50; solid line, present work. b Comparison between experimental and theoretical results for InP dots; , experimental values from Ref. 8 and Ref. 10; , EPM from Ref. 58; solid line, present work.

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Pellegrini, Mattei, and Mazzoldi

J. Appl. Phys. 97, 073706 2005

FIG. 3. Inuence of effective mass values on theoretical predictions: , experimental values from Ref. 2 and Ref. 5 with r0 1 nm; solid, dashed and dotted lines, present work. Experimental point have been reported in the present gure in order to show that agreement between theoretical predictions and experimental data is little affected by effective mass values in this size range.

important.25 We note that the present single band nite depth square well EMA cannot be adapted to compute quantum rod size dependent band gap for two main reasons: i the nonseparable character of the conning potential48 and ii the crossing of the two lowest energy levels for decreasing aspect ratios.59 The obtained good agreement between experimental results and our calculations justies and self-consistently proves the choice of a 5.0 eV band gap for all the capping agents, since it gives excellent quantitative predictions for all six quantum structures studied.
B. Two- versus three-dimensional connement

FIG. 5. a Comparison between experimental and theoretical results for CdSe wires and dots; , dots experimental values from Ref. 2 and Ref. 5; , wires experimental values from Ref. 19; , rods experimental values from Ref. 25; solid and dashed line, dot and wire present work; , CdSe dots in silicate glass, present work. b Comparison between experimental and theoretical results for InP wires and dots; , dots experimental values from Ref. 8 and Ref. 10; , wires experimental values from Ref. 23; solid and dashed line, dot and wire present work.

We are now able to investigate the effect of the dimensionality on a quantum structure. At the present time an ex-

FIG. 4. a Comparison between experimental and theoretical results for CdSe wires; , experimental values from Ref. 19; , rod experimental values from Ref. 25; , EPM from Ref. 19; solid line, present work. b Comparison between experimental and theoretical results for InP wires; , experimental values from Ref. 23; , EPM from Ref. 23; solid line, present work.

cellent study of this kind as been accomplished on InP and CdSe wires and dots,19,23 by means of experimental measurements combined with pseudopotential calculations. We have focused our attention on the same two systems, using larger sets of experimental data and obviously of the nite depth square well model. Results for QWs and QDs, obtained in Sec. III A, have now been plotted together in Fig. 5. In order to have a better insight into dimensionality effects, we also compared nite depth square well results with rst-principle calculation for free standing Si QDs and 001 oriented QWs. Focusing rst on experimental results it has to be noticed that the difference between 2D and 3D connement is small, though very clear particularly for smaller radii. The difference between 1 nm radius dot and wire band gap is about 0.21 and 0.34 eV for CdSe and InP, respectively, and it goes usually from some tenths to some hundredths of eV on increasing the radius. Dimensionality effect is much more pronounced in InP structures than in CdSe ones for a xed size since InP is characterized by a large Bohr exciton radius InP aB 8 nm and therefore by a stronger connement than CdSe CdSe 5 nm . In the case of large radii r0 aB CdSe aB we underline that CdSe wire and dot simulation lines cross as a consequence of the strong connement approximation breakdown, differently from what happens for InP. Indium phosphide stronger dimensionality effect is qualitatively explained in the frame of the innite depth well model since, dening the reduced mass as 1 / = 1 / m* + 1 / m*, the dife h ference between dot and wire band gaps can be written as23

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Pellegrini, Mattei, and Mazzoldi

J. Appl. Phys. 97, 073706 2005

FIG. 6. Comparison between rst-principle calculations and effective mass predictions for Si wires and dots; , LCAO dots from Ref. 51; , LCAO wires from Ref. 51; , EPM dots from Ref. 53; solid and dashed line, dot and wire present work. Coulomb interaction is neglected in present Si rstprinciple results and accordingly in our calculations.
2 2

FIG. 7. , , LCAO dots and wires from Ref. 51; solid and dashed lines, linear t of r2Vs. Eg r plots on the whole size range then restricted to r0 1 nm: smaller sizes correspond to lower slopes, wider size ranges and smaller sizes correspond to a more pronounced nonlinearity.

Edots r Ewires r = g g

8 r2

2 1.17 .

19

It is clear now from Eq. 19 that, for a xed particle size, the smaller the reduced mass the bigger the dimensionality effect on the quantum connement. The same good level of agreement obtained for compound semiconductors QDs and QWs is also achieved with literature Si rst-principle calculations: higher level theoretical data are well reproduced in their whole size range as may be seen in Fig. 6. It this latter case it is important to underline that dimensionality effect is much more evident since the conning potentials are 23 times stronger than for CdSe and InP. We may nally state that nite depth square well model has been shown to be able to discriminate QD from QW behavior in all the studied cases, even when the difference is very small as in CdSe. It would be of great interest to establish a general rule to distinguish quantum wire from quantum dot behavior. Dening d a particle or wire diameter, relying on the innite depth well model, Yu et al. proposed in Ref. 23 that the slope A of an experimental Eg vs d2 line for a set of quantum wires should be approximately 0.6 times that of a corresponding set of quantum dots, obtaining Awires / Adots = 0.53 0.05 for CdSe and Awires / Adots = 0.62 0.03 for InP.19,23 An approach of this kind poses several problems. First of all, once having established the role of the surrounding matrix in the connement, it is important to underline that the problem of nding a simple rule to discriminate dot from wire behavior must be restricted to quantum structures embedded in the same matrix or in matrices with similar conning behavior. In fact, as can be clearly seen in Fig. 5 a , CdSe wires embedded in a silicate glass show the same kind of connement of dots capped with organic ligands. This is an interesting result also because dimensionality of a system appears now not only as a function of geometry, but also as a function of the surrounding environment.38 It has then to be noticed that the Eg dependence from d2 is far from being linear,52,5461 with a decreasing slope for smaller sizes as may be seen in Fig. 7. The natural consequences are rst that the obtained slope is a function of the experimental data size range and second that the error of Awires / Adots increases the wider the experimental data size range, since nonlinearity becomes

much more pronounced. This can be seen as follows: with the whole experimental data sets used in the present work with no restriction on size we obtained Awires / Adots = 1.26 0.13 for CdSe and Awires / Adots = 1.54 0.21 for InP, apparently indicating that connement in wires should be stronger than in dots, while for Si rst-principle calculations we would obtain Awires / Adots = 0.93 0.07, which is incompatible with 0.6 value; nevertheless these results can be easily explained if we consider that CdSe and InP dot data sets are characterized by smaller sizes and then by smaller slopes than wire ones. Therefore, when homogeneous data sets are derived by restricting the QD data sets to that of QWs, we obtain Awires / Adots = 0.77 0.07 and Awires / Adots = 0.90 0.21 for CdSe and InP, respectively, in better agreement with 0.6. Concerning Si, if we remove data for r0 1 nm which deviate more evidently from linearity , we obtain Awires / Adots = 0.59 0.02 as slope ratio. In summary, it might be concluded that i the rule proposed in Ref. 23 is still valid, if one takes care to compare semiconductors embedded in the same matrix and data sets in the same size range, neglecting small radius values r0 / aB 0.25 as a guide , ii the nite depth square well model proposes itself as a simple, general and somehow solid method to distinguish QD from QW behavior.
C. Narrow band gap semiconductors

In order to better investigate model validity and limitations we compared theoretical predictions and experimental data for three narrow band gap semiconductors, namely PbS, PbSe and InAs: the characteristic gures of each sample are listed in Table I. As may be seen in Fig. 8 simulation results are now far from being satisfactory. Experimental results are systematically underestimated and the Eg r vs r slope is usually lower for experimental data than for theoretical ones. The same poor agreement, with the exception of PbS tight binding, holds in the comparison with higher level theoretical calculations. The reason for these discrepancies is most probably the breakdown of the effective mass approximation induced by two phenomena: i narrow band gap semiconductor bands are strongly nonparabolic, with effective masses no longer constants but a function of the wavevector k, ii Bohr exciton radii for narrow band gap semiconductors are quite large

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J. Appl. Phys. 97, 073706 2005

has been proven self-consistently by analyzing different semiconductors embedded in the same matrix. System dimensionality has been modeled accurately, partially validating the rule of thumb proposed by authors of Ref. 23 in order to distinguish QD from QW behavior. Finally, model limitations for narrow band gap semiconductors have been shown and attributed to deviation from band parabolicity, proposing some possible future implementations.
ACKNOWLEDGMENTS

The authors gratefully acknowledge Dr. Enrico Trave and Dr. Francesco Enrichi for useful discussions and suggestions.
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2 1

FIG. 8. a Comparison between experimental and theoretical results for PbS dots; , experimental values from Ref. 13; , TB from Ref. 37; solid line, present work. b Comparison between experimental and theoretical results for PbSe dots; , experimental values from Ref. 16; , k p method from Ref. 47; solid line, present work. c Comparison between experimental and theoretical results for InAs dots; , experimental values from Ref. 11 and Ref. 12; , EPM from Ref. 60; solid line, present work.

aB 20 30 nm causing electron and hole in a small cluster for instance, a 1 nm radius cluster to be strongly conned and consequently far away from band edges. Since interaction between valence and conduction bands is at the ground of their nonparabolicity, the model could be improved by implementing a multiband envelope function approximation, in order to take these effects into account;48 on the other hand, an hyperbolic band model, thus deviating from the simple parabolic dispersion relation, could also be used.13
IV. CONCLUSION

The reliability and limitations of the nite depth square well EMA has been systematically discussed. This model has proven to be a simple and effective method to predict size dependent band gap of semiconductor QDs and QWs, characterized by good exibility for the compound and monoelemental semiconductors studied, and by low computational demand. Model predictions are quantitatively accurate and effect of the sourrounding matrix on the band gap blueshift

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