One Dimensional Finite Crystal: Quantum Confinement and

Parametrically Resonated Surface States

Syed Minhaz Hossaina, Krishnendu Mukherjeea, Mallar Rayb

a Department of Physics, Indian Institute of Engineering Science and Technology, Shibpur, PO: Botanic

Garden, Howrah: 711103

b Dr. M. N. Dastur School of Materials Science and Engineering, Indian Institute of Engineering Science

and Technology, Shibpur, PO: Botanic Garden, Howrah: 711103

Abstract

We present an analytical method for obtaining exact solutions for fully confined electronic

states in a finite one dimensional crystal with arbitrary surface termination. The calculation

leads to an analytical expression for the band states, parametrically resonated surface states

and band gap energy.

Keywords: Finite crystal, Mathieu equation, surface state, parametric resonance,

nanostructure

1. Introduction

It is well known that as we make the size of a crystal smaller and smaller its surface to volume

ratio increases and consequently when such a piece of crystal is exposed to external

perturbation such as electromagnetic radiation, the states lying near the surface interact more

dominantly with the radiation than its bulk. Therefore, we may expect that in case of finite

crystals there should exist some states having maximum support near the surface and

decaying rapidly inside the bulk of the solid, and such states would play more significant

roles for small systems. It is a theoretical challenge to predict the existence of such surface

states using the basic principles of solid state physics. Analytical solution for obtaining states

of an electron confined in a finite lattice has remained a challenging problem. The absence of

translational invariance in a crystal of finite size poses the major difficulty for obtaining exact

solutions of Schrödinger’s equation (SE) for an electron moving in a periodic potential that is

terminated at the crystal boundaries. Most of the theoretical investigations in this regard have

so far been based on approximate and/or numerical approaches and usually modelled to
explain a specific system [1, 2]. This letter provides an exactly solvable analytical model that

is applicable to any one-dimensional (1-D) finite system with a periodic (sinusoidal) potential

that is truncated at the crystal boundaries. Effect of finite size on the surface states and

electronic structure becomes more pronounced with decreasing particle size, particularly for

quantum structures that has drawn considerable attention in recent time [3, 4, 5]. The theory

of quantum structures has so far been primarily dominated by the effective mass

approximation (EMA) and its extension to the k.p theory [6]. Semi empirical methods like

tight binding (TB) approaches and pseudo potentials have also been widely employed but

these theories are clouded by the fact that the parameters are usually fitted to the data of the

nanostructure itself and have consequently failed to provide a general approach [7, 8, 9]. Based

on the solution of truncated Hill's equation, an analytical theory for treating an ideal finite 1-

D crystal in an inversion symmetric potential has been proposed by Ren [10]. The origin of

two types of electronic states due to complete quantum confinement of Bloch waves has been

reported for such an ideal system [11]. He and Qin have obtained the electronic structure of

quantum well with infinite barrier having arbitrary geometries [12]. A surface state model

accounting for ionic, metallic and covalent types of states for a semi-infinite 1-D crystal with

arbitrary truncation has been reported by Levine [13]. However, a general theory that takes

into account the finite size effect of a real crystal as well as the surface defect induced

variations in electronic structure is much awaited.

2. The Model Potential

Since every crystal enjoys lattice structure, an electron confined in the system finds itself in a

periodic potential with the period being equal to the lattice constant of the solid. Let V(x)

denote the potential energy of an electron in a 1-D lattice of lattice constant ac. Since the

potential energy is invariant under a crystal lattice translation: V(x) = V(x + ac), it can be

expanded as a Fourier series in the reciprocal lattice vector G:

V ( x )   U G e iGx (1)
G

UG for actual crystal potentials tend to decrease rapidly with increasing magnitude of G. For

bare Coulomb potential UG decreases as: 1 . The reality of the potential energy function
G2
requires the following expansion of V(x) in terms of the Fourier coefficients:
 V ( x)  2  U G cosGx 
G 0

Where, U*G = UG and U0 can be set equal to 0 for convenience. In case of a lattice of infinite

2s
extent the reciprocal lattice vector reads as, G  , where s  Z+ (Z+ denoting the set of
ac

positive integers). So the potential energy takes the form:

2
V ( x )   U s cos x

sZ ac

Keeping only the leading term (s = 1) of the expansion, the potential energy function of the

electron in the lattice becomes:

 2 
V x   V0 cos x 
 ac 

where, V0 = 2U1.

3. Results and discussion

3.1. Stable solutions of Mathieu equation: Bulk states and band gap widening

As we are dealing with a 1-D finite crystal of length L = Nac, where N is a positive integer

denoting the number of atoms in the crystal, the problem is to solve the following SE:

d 2 ( x)  2me E 2mV0  2 
2
  2  2 cos x  ( x)  0 (2)
dx     ac 


Introducing a new variable z  x the SE takes the canonical form of ME, given by:
ac

 ( z )    2q cos 2 z  ( z )  0 (3)

where, ε and q are two dimensionless quantities given by,

2me ac2 E me ac2V0

The general solution of equation (3) can be expressed as a linear combination of fractional sine

and cosine elliptic functions:

 ( z )  Ase m  p ( z , q )  Bce m p ( z , q ) (5)

To make the crystal finite, boundaries are introduced at z = δ and z = δ + Nπ so that N number

of lattice sites are enclosed between the boundaries. Since the effect of those boundaries are

felt only by the electrons confined in the crystal, following BC are imposed on ψ(z):

 ( z   )  0   (  N ) (6)

Imposing the BC in equation (5) we get:

se m  p ( , q ) j
B  A and p  ; j = 1,2…,(N-1) (7)
ce m  p ( , q ) N

  N
  ( z ) dz  1 and using the orthogonality
2
Imposing the normalization condition


properties of fractional sine and cosine elliptic functions given in Ref. [14], we obtain the

normalized wave function::

2  
 m , j ( z,  )   se j  z, q    ( )ce j z , q  (8)

N 1      m N
2
 m
N 

se
m
j  , q 
where,     N
(9)
ce
m
j  , q 
N

and the corresponding energy eigenvalues are,

2
 j
5 m    7
 m , j q   m  Nj 
2 1  N
 q2  q4 
 j
2
  j
2 3
  j
2

2  m    1 32  m    1  m    4
 N  N N
   
(10)
4 2
 j  j
9 m    58 m    29
 N
5
 N
q6  O q8  
 j
2
  j
2
  j
2

64  m    1  m    4  m    9
 N   N   N 

Here,  m, j q  s depend upon q and the system size N. For a given m, as N→∞,

 m , j 1   m , j   0 and thereby forms a continuum in the case of a semi-infinite crystal. Thus

m-the band, respectively, and the expression for the band gap is given by:

 gm    m1,1   m, N 1 (11)

It is evident from equation (11) and also from Figure 1 that the band gap widens with a

decrease in the system size N.

1
Figure 1: Plot of band edge energy as a function of system size, for q  . The energies of
2
the surface states corresponding to the unstable solutions of ME falls inside the forbidden gap.

The variations of the energies of the surface states with δ for the first two band gaps are shown.

3.2. Unstable solutions of Mathieu equation: Surface states

According to Floquet’s theory, ME also admits solutions of the form:  ( z )  e  ( z ) where

 (z ) is a periodic function with period 2π [15]. So we can write  (z ) as a linear combination

 n  z   C n e z se n ( z , q )    ce n ( z , q ) (12)

se n  , q 
where,     and n = 1,2,… (13)
ce n  , q 
   N
The constant Cn can be determined from the normalization condition   ( z ) 2 dz  1 .


Following method outlined in Ref. [14] and also used in Ref. [13], we obtain µ and the n-th

state energy eigenvalue as:

  bn  an 

 
2     1 K nn
2
(14)

 2 an  bn   2 2 bn  an 2
 n  bn   (15)
2 1 4 2  1 K nn
2 2

2 2
where, K nn   ce n  z , q sen  z, q dz    se n  z, q cen  z , q dz . an and bn are functions of q only
0 0

and those are the values of ε of ME when the eigenfunctions are cen and sen, respectively

[14,15]. It is clear from equations (13) and (14) that in the region 0    2 , µ = 0 for

 3
  0, , and 2π and the corresponding  n  z  s are omnipresent near the boundaries as
2 2
well as in the bulk. This is evident from Figure 1 for the states present at the edges of the bands


corresponding to m = 1 and m = 2 for the cases δ =0 and , respectively. Thus a system size
2
independent electronic state with energy equal to the band edge energy is obtained, which is

similar to the observation of Ren [11], and also in agreement with the calculations of

Franceschetti and Zunger [45], who has reported the presence of such a state for free standing

GaAs quantum films. Barring these values of δ, µ attains non-zero values when δ lies between

0 and 2π and the corresponding  n  z  s shoot up near the boundaries, thus giving rise to the

“parametrically resonated” surface states. The words “parametrically resonated” indicate the

fact that in spite of not being perturbed externally, there is a shooting up of  n  z  for non-

zero values of µ near the boundaries [17]. Here εns depend upon δ and q but are independent

of the system size N as evident from Figure 1. Consequently,  n  z  s will be present even in

case of a semi-infinite crystal [13].

3.3. ε-k dispersion relation

The ε-k dispersion relation represented in Figure 2 (a) clearly indicates the presence of the

parametrically resonated surface states (represented by open circles) within the band gap. It
is also clear from equation (15) and Figures 1 and 2 that the energies of the system size

independent surface states are strongly dependent on δ implying that the position of the

surface state within the band gap is governed by the crystal termination. From Figure 2 (b) we

see that the resonated surface state oscillates between the lower and the upper band edges for

δ varying between 0 and π/2 for the first band gap, i.e. between (m = 1, j = N − 1) and (m = 2, j

= 1) bulk band edge states. Whereas, for the higher order band gaps this state always fall

within the gap and oscillates between much smaller energy range compared to the

corresponding band gap energy, which is evident from Figures 1 and 2 (b).

Figure 2: (a) ε-k diagram corresponding to the first 4 bands (m = 1, 2, 3 and 4) showing the

j
surface states within the forbidden gaps, where k  and ε for the bulk and the surface
Nac

states are given by equations (10) and (15), respectively. The variations of the surface state

energies as a function of δ for the above four band gaps are shown in (b). The plot is for q =

1/π2 and N = 30.

Concentrating only on the first band gap and the corresponding surface state, it is found that

l
for all values of δ, except for   (l = 0, 1,…) there is a state inside the “forbidden gap”.
2
Thus, for systems that exhibit metallic characteristics in the bulk state (N →∞), size reduction

may affect a transformation of the material to semiconductor or insulator, depending on δ.

nanoparticles, carbon nanotubes, etc. [18,19]. However, this is not explained simply by the

formation and widening of band gap for small N given by equation (11). The property

(metallic, semiconducting or insulating) of a system will obviously be governed by the relative

position of the Fermi level. Now, for an N particle system with N accessible electronic states,

the Fermi surface will fall inside the band gap only for the above-mentioned values of  ,

thereby affecting a metal to semiconductor transition with decrease in system size. Following

similar arguments, we can assert that a reverse transformation (semiconductor to metal) will

also be primarily determined by δ, i.e. on the location of the surface defect states. This implies

that for a given system with small size, a metal-semiconductor or semiconductor-metal

transformation may be affected by shifting the position of these states relative to the Fermi

level. The assertion is supported by well documented experimental and theoretical studies on

pressure induced semiconductor to metal transformations of various nanostructures [20]. In

keeping with this argument, experimental works have demonstrated that metal like

conductivity of ZnO nanowires due to strain induced shifting of surface defect states can be

explained by relative change in the position of Fermi level [21]. In addition, such oscillation

of the position of surface states can also account for donor-to-acceptor or the reverse

transitions for semiconductor nanocrystals. Such donor-to-acceptor or acceptor-to donor

transitions due to surface modification of nanostructures have also been experimentally

observed [22, 23].

3.4. Wave functions

The different electronic wave functions for N =30, of some of the bulk and the surface states

are represented in Figure 3. As expected the nature of the wave function corresponding to the

state (m = 1, j = 1) and (m = 1, j = 2) for perfect truncation i.e. δ = 0, is similar to that of an electron

confined in an infinite potential well. The only difference here is that the wave forms are

modulated by the crystal potential. For the bulk edge states (m = 1, j = 29) and (m = 2, j = 1),

standing wave patterns are observed, both for perfect and imperfect truncations. Hasegawa

et al. [24] has reported direct observation of formation of such standing waves at surface steps

and defects of Au (111) surface. It is also evident from Figure 3 that the surface states for δ = 0

and π/2 behaves like a free electron, whereas, the wave functions for imperfect truncations (δ

= π/4 and 3π/4) decays rapidly.

surface states for different values of δ for the first band gap corresponding to n = 1.(q = 1/π2

and N = 30).

3.5. Model prediction and experimental findings

We now briefly compare the results of our analytical solutions with some important

experimental findings. By far the most widely examined size dependent property of small

systems (nanocrystals) is the optical spectrum. It is well established that the energy of

electronic transition in such systems blue shifts with decreasing size indicating widening of

the band gap [25, 26], which is an obvious outcome of this model. The effect of surface states

on the optical spectrum has been extensively investigated, particularly for semiconducting
nanostructures and significant conclusions about band structure modifications and surface

states have been made from experimental stand point. For example, from photoluminescence

and electrogenerated chemiluminescnce characteristics of Si nanocrystals it has been

concluded that core band gaps depend on nanocrystal size, whereas, energy separation of the

surface states is only slightly affected by particle size [25, 27]. These results are also well

explained by our solution.

4. Conclusion

In summary, we have presented an exactly solvable model representing a finite 1D crystal.

The much observed size induced band gap widening for small crystals is successfully

explained and an expression for band gap has been obtained. Surface defects produce

parametrically resonated states within the band gaps and the energies of these states are

independent of system size but depends on truncation. Whereas the energies of the bulk states

vary with system size but do not depend on the crystal termination location. For the first band

gap the position of the surface state oscillates between the lower and the upper band edges

depending upon truncation. The model results are in very good agreement with experimental

findings related to quantum structures.

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