JOURNAL OF APPLIED PHYSICS 107, 083503 2010

Thermal conductivity of silicon bulk and nanowires: Effects of isotopic composition, phonon connement, and surface roughness
M. Kazan,1,a G. Guisbiers,2 S. Pereira,2 M. R. Correia,3 P. Masri,4 A. Bruyant,1 S. Volz,5 and P. Royer1
1

Laboratoire de Nanotechnologie et dInstrumentation Optique, ICD, CNRS (FRE2848), Universit de Technologie de Troyes, 10010 Troyes, France 2 Department of Physics, CICECO, University of Aveiro, Aveiro 3810-193, Portugal 3 Department of Physics, I3N, University of Aveiro, Aveiro 3810-193, Portugal 4 Groupe dEtude des Semiconducteurs, CNRS-UMR 5650, University of Montpellier II, Montpellier 34095, France 5 Laboratoire dEnergie Molculaire et Macroscopique, Combustion CNRS UPR 288, Ecole Centrale Paris, Grande Voie des Vignes, F-92295 Chtenay-Malabry Cedex, France

Received 24 March 2009; accepted 30 January 2010; published online 21 April 2010 We present a rigorous analysis of the thermal conductivity of bulk silicon Si and Si nanowires Si NWs which takes into account the exact physical nature of the various acoustic and optical phonon mechanisms. Following the Callaway solution for the Boltzmann equation, where resistive and nonresistive phonon mechanisms are discriminated, we derived formalism for the lattice thermal conductivity that takes into account the phonon incidence angles. The phonon scattering processes are represented by frequency-dependent relaxation time. In addition to the commonly considered acoustic three-phonon processes, a detailed analysis of the role of the optical phonon decay into acoustic phonons is performed. This optical phonon decay mechanism is considered to act as acoustic phonon generation rate partially counteracting the acoustic phonon scattering rates. We have derived the analytical expression describing this physical mechanism which should be included in the general formalism as a correction to the resistive phonon-point-defects and phonon-boundary scattering expressions. The phonon-boundary scattering mechanism is taken as a function of the phonon frequency, incidence angles, and surface roughness. The importance of all the mechanisms we have involved in the model is demonstrated clearly with reference to reported data regarding the isotopic composition effect in bulk Si and Si NW samples. Namely, our model accounts for previously unexplained experimental results regarding i the isotope composition effect on the thermal conductivity of bulk silicon reported by Ruf et al. Solid State Commun. 115, 243 2000 , ii the size effect on T of individual Si NWs reported by Li et al. Appl. Phys. Lett. 83, 2934 2003 , and iii the dramatic decrease in the thermal conductivity for rough Si NWs reported by Hochbaum et al. Nature London 451, 163 2008 . 2010 American Institute of Physics. doi:10.1063/1.3340973
I. INTRODUCTION

Experimental results show that the thermal conductivity of bulk semiconductor materials has a general qualitative behavior as a function of the temperature T .19 At very low T few Kelvins , depends on the size of the crystal and increases with T mirroring the temperature dependence of the lattice specic heat T3 , to reach a maximum at around Tmax = 0.05 D, where D is the acoustic Debye temperature. Near this maximum, is T independent but sensitive to the crystal imperfections and isotopic composition. At T slightly above Tmax, T decreases with T due to phonon scattering via normal N processes. At T approaching 0.1 D, T decreases with T due to Umklapp U processes. For the case of semiconductor nanowires NWs , precise experiments have shown that T has a different behavior from what has been previously described. As such, Li et al.10 measured T of silicon NWs Si NWs with diameters of 22, 37, 56, and 115 nm. They reported on T values two
a

Electronic mail: michel.kazan@utt.fr.

orders of magnitude lower than bulk Si, with a clear deviation from the Debye T3 law at low T. The authors suggested that these experimental observations could be due to an increased phonon-boundary scattering and possible phonon spectrum modication due to spatial phonon connement. More recently, Boukai et al.11 demonstrated that by varying the Si NW size and doping levels, Seebeck coefcient12 values representing an approximately 100-folded improvement over bulk Si can be achieved over a wide T range. Moreover, Hochbaum et al.13 reported on rough Si NW having Seebeck coefcient and electrical resistivity values that are the same as doped bulk Si but exhibit 100-folded reduction in T . So far, the remarkable differences regarding the experimentally observed T behavior in bulk Si and NWs with different sizes and surface conditions could not be explained by current theories. It is highly desirable to have a theoretical approach which can describe the physical phenomena responsible for the experimental observations in the full T range. With this theoretical tool in hand, one can gain insight into the effects
2010 American Institute of Physics

0021-8979/2010/107 8 /083503/14/$30.00

107, 083503-1

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of the size and temperature on the harmonic and anharmonic terms of the interatomic forces and rationally tailor materials for efcient design of fast heat removals, or alternatively, thermoelectric devices. The usual approach to calculate T in semiconductor materials is to consider a Boltzmann equation with a relaxation time approximation. Then, the scattering cross section can be calculated by perturbation theories.14 In such a treatment, the temperature and frequency dependences of anharmonic three-phonon processes are strongly affected by the details of the phonon branch and anharmonic coefcients, which makes the expressions derived valid for only specic phonons and limited T range. In order to obtain the expressions for the three-phonon processes in a wide T range, an ab initio approach involving the combination of Boltzmann formalism with density functional calculation of the harmonic and anharmonic interatomic constants was proposed recently.15 This calculation method showed the possibility to obtain good agreement with the experimental data on T of bulk Si and germanium Ge without the use of any tting parameters. However, it is limited to the case of bulk materials because for the case of nanostructures such calculation becomes computationally prohibitive. On the other hand, the formalism for T established by Callaway16 for low T and modied later by several authors1719 to t T in a wide T range has been widely used to describe several effects on T . Although the modied-Callaway formalisms allow including, in addition to the phonon normal processes, various resistive processes such as the scattering by lattice imperfections and sample boundaries their forms established for the case of bulk semiconductors fail to describe the isotopic composition effect on T of bulk Si and to provide a reasonable representation of even the qualitative behavior of the experimentally measured Si NW T .18,19 Mingo et al.20,21 attributed the poor predictions obtained with Callaway model to the use of the approximation of linearized dispersion relations and inadequate forms of the anharmonic scattering rates. They attempted to calculate the Si NW T by using the real dispersion relations of Si, omitting the normal processes, and considering, in addition to the resistive phonon mechanisms arisen from Umklapp processes and crystal imperfections scattering, a boundary scattering expression which depends on a constant F related to the phonon specularity. When the reection from the surface is completely specular, F is zero. When the boundary scattering is completely diffusive, F is one. Whenever partial specular reection occurs, F takes values between zero and one. The approach of Mingo requires only bulk data as inputs and thus, can be used to estimate theoretically the NWs T with higher accuracy than that provided by the modied-Callaway models. Nevertheless, even with the use of the exact phonon dispersion relation, the best representation of T for the Si NWs of cross section 37 is obtained with F values larger than one.20,21 The authors attributed the physically unreasonable value of F obtained to possible errors on the measurements of the NW cross section and to a very diffusive boundary scattering. However, it is well known that the specular reection rate from the surface decreases, or alternatively the diffuse scattering rate increases, with increasing the surface roughness see below in Sec. II the physics behind , what

leads to a decrease in T .8,2230 Thus, the dramatic decrease in T for rough Si NWs reported recently by Hochbaum et al.13 clearly indicates that the boundary scattering in the soconsidered smooth single Si NWs initially measured by Li et al.10 and modeled by Mingo et al.20,21 were far from completely diffusive and the corresponding F value should be well below one. Consequently, even with the use of the exact phonon dispersion relation, the T behavior in Si NWs as a function of size could not be well described with the commonly considered phonon physical mechanisms. This, together with the fact that the experimental T curve for Si NW of 22 nm cross section could not at all be represented with the exact bulk Si dispersion spectrum, strongly suggest that some phonon mechanisms contributing signicantly to T have not been taken into account in the previous approaches. Here, we propose a theoretical approach based on the solution of Boltzmann equation by taking into account the physical aspects of the relevant phonon mechanisms. The model considers the normal three-phonon processes which, in contrast to the resistive processes, tend to displace the Planck distribution. These normal phonon processes do not have a complete resistive nature and, therefore, should not be neglected even when the resistive processes rates are too high. Moreover, in order to approach to realistic and reasonable phonon mechanisms at the surface we consider that the probability for phonon specularity and diffuse scattering is judged by the phonon incidence angles to the surface and the phonon wavelength compared to the surface roughness. The relevance of such effect is supported by reection measurements of heat pulses from free solid surfaces which have shown that the assumption of specular phonon reection breaks down for high frequency phonon 100 GHz , unless the surfaces are cleaved in situ or laser annealed.31 Thus, in our approach the parameter F in the expression of the boundary scattering is no longer a constant but depends on the specic characteristics of each phonon. In the case of NWs we also take into account the phonon connement and the consequent quantization of the phonon spectrum. Another key development presented is that the decay of optical phonons into acoustic phonons is considered in detail. The importance of this physical mechanism has been previously shown in the description of the effect of crystallographic orientation and isotopic composition on T of bulk aluminum nitride Ref. 32 and Ge.33 Here we show that the optical phonon decay effect on T is particularly relevant for the case of NWs. As a result we show that, even when using linearized dispersion relations, a rigorous and appropriate analysis of the phonon physical mechanisms allows to consistently explain the effects observed on T for bulk and NW semiconductor structures.
II. THEORIES A. General formalism for the lattice thermal conductivity

The phonon heat current density 1 / A JQ is the sum of phonons with given frequency, j, and incidence angles

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J. Appl. Phys. 107, 083503 2010

and that are incident on a unit area A per unit time, times the phonon energy j. Here j refers to a particular phonon branch, is the angle between the phonon wave vector and the normal to the unit area A and is the azimuthal angle. Let v j,q . cos be the normal component of velocity, d = sin d d , q the phonon wave vector, and N = N0,j Nq,j the q deviation in the phonon distribution Nq,j from its equilibrium 0 value Nq,j. Then the phonon heat current density can be written as
2

equation in the following form which is physically valid for small T variation and can maintain the difference in the physical aspects of the collision processes described above N t =
v

N
N

N0 N
R

1/A JQ =
j q 0 0

j,qv j,q

cos 4

sin Nd d . 1

Here N is a relaxation time for normal processes and R is a relaxation time for the overall resistive processes. The term N is the displaced Planck distribution and is a constant vector in the direction of the temperature gradient. The displaced Planck distribution N can be written as a function of the Planck distribution at the equilibrium state N0 in the following form16,34 N = N0 + exp /kBT q , /kBT 1 2 kBT exp 6

Assuming small T variation along well-dened direction the thermal conductivity T is 1 / A JQ / T and thus its expression can be written as T = 1 4
2 j,qv j,q cos j q 0 0

where kB is the Boltzmann constant. Substituting Eq. 6 in Eq. 4 we can write 2

v

sin

N d d . T

k BT

exp /kBT exp /kBT 1

Assuming now linearized dispersion relations v j q = j / q and using the Debye density of states approximation for one 3 d3q = 1 / 2 2 q2dq unit volume, i.e., q=1/ 2 2 2 3 / v d , we can write =1/2 T = 1 8
3 j 2 0 0 0
D,j

exp /kBT q 1 + 1 = 0. +N /kBT 1 NkBT exp N R

3 2 j vj

cos

Thus, we can have an expression for N that depends on the normal and resistive relaxation times. Its substitution in Eq. 3 , after performing mathematical arrangements similar to those in Ref. 16, allows writing an incidence-angledependent expression for the thermal conductivity T =
j

sin

N d d d , T

3 where

k B k BT 8 3v j

I1,j + I2,j ,

8a

where D,j is the Debye frequency or the cut-off frequency for the jth phonon branch. In principle, T can be calculated if N is known. In order to do this we need to solve the Boltzmann equation for N N t v
v

D,j/T

2 c,j 0 0

I1,j =
0

x 4e x cos2 ex 1 2

sin d d dx, 8b

dN = 0. dT

and
0
D,j/T 2

In the Boltzmann equation Eq. 4 the second term describes the changes in the distribution function due to temperature gradient. Since we assumed a small T variation, N in the second term can be replaced by N0. The rst term describes the change in the phonon distribution function due the various phonon collision processes. Here, one should discriminate between two types of processes. The normal processes in which the momentum is conserved and the resistive processes in which the momentum is not conserved. The normal processes tend to displace the Planck distribution, while the resistive processes tend to bring back the Planck distribution to its initial position. Thus, the strong difference between the nature of the normal processes and that of the resistive processes should be taken into account while solving the Boltzmann equation. Following Callaway approximation16 we can write the rst term of the Boltzmann

I2,j =
0

D,j/T 2

2 x 4e x 2 sin d d dx 2 cos N,j e 1 . x 4e x c,j 2 sin d d dx x 2 cos N,j R,j e 1 c,j x

8c Thus, T can be described as the sum of two components; 1 T and 2 T with

1

T =
j

kB/8 kB/8
j

v j kBT/ v j kBT/

I1,j I2,j .

and

Here we dene a combined relaxation time and a dimensionless parameter x = / kBT.

1 1 1 c,j = N,j + R,j ,

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B. Expressions for the various phonon relaxation times

F , ,

=4 +

p
0

0,

After writing an expression for T in which the phonon incidence angles are taken into account and the normal and resistive processes are fully considered, let us now discuss the phonon physical mechanisms which contribute to the normal and resistive processes and approximate their contribution to T by phonon relaxation times.

1 ps c 0

0,

11

where 0 = 0 , 0 and = , refer to the directions of the incident and emerging wave vectors, respectively,
0, 0, 0,

= 2 / = 2 / = cos
0

sin sin

cos sin

sin sin

cos sin ,

III. PHONON-POINT-DEFECTS SCATTERING

The rate of the scattering of the phonon by point-defects or mass different from that of the host crystal in an otherwise perfect lattice is provided by Klemens.35 For a given phonon branch j the scattering rate can be written as
1 I,j

+ cos ,
2 2

0,

= exp

4 VkB

x,y = 2 / ps
0

. z x,y , , d

x 4 3 vj

4 4

T ,

9a

=p =

0, 0

where V is the volume per atom and is the massuctuation-phonon scattering parameter dened by =
i

c i M i ic i M i . 2 ic i M i

9b c
0,

Here ci and M i denote the concentration and the mass of the constituent isotopes and impurities.

= L2/4 exp

2 n=1

2 n

/n!n
0

exp R2/4n = c
0,

and

d .

IV. PHONON-BOUNDARY SCATTERING

The phonon-boundary scattering has been rst investigated by Casimir.28 Later, Berman et al.29 have extended the Casimir theory to include the effect of nite size l and nonzero specularity factor of the phonon P. The authors proposed for the phonon-boundary scattering rate the following form
1 B,j

= vj

1 1 1 Pj + , L 1 + Pj l

10

where L is the effective diameter of the sample which is equal twice the radius for a cylindrical cross section and the square root of the side lengths product for a square or rectangular cross section. If we replace the term 1 P j / 1 + P j by 1 / F with P j a constant independent from the phonon branch we get the expression for the phonon-boundary scattering used by Mingo et al.20,21 However, Zimann30 and later Soffer36 developed a statistical model for the reection of plane wave from a rough surface. It has been shown that the reectivity of a plane wave from a rough surface leads to a plane wave in the specular direction and to a diffused plane wave in a direction that depends on the incident plane wave, the surface roughness, and the tangential correlation of the surface asperities. Thus, reducing the surface specularity and diffuse scattering to a constant would be inadequate for describing accurately the phonon-boundary scattering. A more realistic expression is thus essential to investigate the experimentally observed effects. Soffer described the average scattered ux density by the following expression:

The rst term on the right hand in Eq. 11 is the specular part and the second term is the diffuse part, with the wavelength and R the tangential correlation length. In the case of cylindrical-like NW, the term x , y which is present in both specular and diffuse part is the one way phase shift caused by a diameter uctuation around the value L. The quantity 2 can thus be considered as the rms height deviation h . Only the diffuse part depends on the tangential correlation be the transition probability of pholength R. Let P 0 , after an internon wave per unit solid angle, from 0 to is the action with the boundary . By denition, P 0 , average ux density of Eq. 11 normalized to unity transition probability for all allowed angles. Thus, it can be expressed as P
0,

= 1/

P
0

0,

+
0,

0 0

1P

/c

12

Now, the total transition probability is d

0P 0,

13

Substituting Eq. 12 in Eq. 13 we nd d

0P 0,

=P c

+
0,

1P
0

/c

14 equal to exp

with a specular reection probability P

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3 2 k B LV

J. Appl. Phys. 107, 083503 2010

4 2 k B TV 2 M 3v T

2 cos2 . In order to express the specular reection probability as a function of measurable physical parameters we write

BN,L = where stants.

LT

M 2v L

5,

and

BN,T =

18c

Pj

2h cos , ,h = exp vj

is the longitudinal transversal Grneisen con-

15

In the case of a temperature gradient along the length of the sample, the angle should be replaced by / 2 in the expression of the specularity probability. Substituting Eq. 15 in Eq. 10 , one can certainly obtain a more realistic expression for the phonon-boundary scattering.

VI. UMKLAPP THREE-PHONON SCATTERING

The Umklapp three-phonon processes can be described by the same cubic anharmonic term given by Eq. 16 . Nevertheless, in the Umklapp processes V 3 vanishes unless q0 + q + q1 = b , 19

V. NORMAL THREE-PHONON SCATTERING

The normal three-phonon processes can be understood from the cubic anharmonic term in the Hamiltonian H3 q =
q,j,q ,j ,q ,j

V 3 q, j,q , j ,q , j a q, j a q , j a+ q , j , 16

where a and a+ are the annihilation and creation operators, respectively. As shown from Eq. 16 , in the normal threephonon processes, two acoustic phonons of polarizations j and j and wave vectors q and q are annihilated and one higher energy phonon optical phonon of polarization j and wave vector q is created. The term V 3 is the coefcient of the cubic anharmonicity. In the case of normal processes, V 3 vanishes unless = and q0 + q + q1 = 0. 17b
0

where b is a nonzero reciprocal lattice vector. Thus, in the Umklapp three-phonon scattering processes two acoustic phonons are annihilated and one higher energy phonon is created without conserving the total momentum. At temperatures in the region of T 0.1 D, the dominant phonon scattering mechanism is the Umklapp scattering. The thermal conductivity of several high purity, isotopically clean crystals have been measured and the results for T 0.1 D could be approximated by a universal curve.3840 This universal curve is the ratio of at T to at D and is assumed to depend only on the reduced temperature T / D . This assumption is founded on the same basis as those used to derive the Debye specic-heat function Cv T / D . It has been demonstrated that the expression for the Umklapp processes which can t T of several pure crystals at T 0.1 D is of the form18,19,3840
1 U,j

= BU,j

T exp

D,j/3T

20a

with BU,j =
2 j

= 0,

17a

M v2 j

.
D

20b

In a pure and relatively large samples larger than the phonon mean free path in the full T range , where the phonon-pointdefects scattering and the phonon-boundary scattering can be neglected, T at T slightly above Tmax = 0.05 D, can be determined by the normal three-phonon processes alone. Note that in the T range around Tmax, the higher order normal processes, as well as Umklapp processes are unlikely. This led to an experimental determination of analytical expression for the normal three-phonon scattering rates.2,3,24 For the class of cubic semiconductor materials such as Ge, diamond, and Si, it has been found that the expression of the normal three phonon scattering rate for longitudinal phonons is of the form
1 N,L

Several other expressions for the Umklapp scattering rate or attempts to ignore the Umklapp phonon mechanism have appeared in the literature.4145 However, in the tting of the theoretical expression for T to the experimentally measured data, they lead to physically unreasonable values for the phonon dispersion curves characteristics. Since Eq. 20 has been derived by a physically reasonable experimental method and described the Umklapp processes in several high purity crystals belonging to the class of materials to which Si belongs, we choose here to use Eq. 20 as an analytical expression describing the Umklapp scattering rate in Si.
VII. DECAY OF OPTICAL PHONONS INTO ACOUSTIC PHONONS

= BN,L

2 3

T ,

18a

and that for transversal phonons is of the form

1 N,T

= BN,T T4 .

18b

The magnitudes of the coefcients BN are chosen to satisfy the following dependence on phonon velocity19,37

After describing the annihilation of acoustic phonons and the creation of higher energy phonons via the various acoustic phonon scattering processes, we should consider the reverse process, i.e., the decay of high energy phonons, such as the optical phonons, into acoustic phonons. In fact, due to its low group velocity, an optical phonon by itself cannot conduct a noticeable amount of heat. However, in order to maintain the lattice thermal equilibrium, it should decay and interchange energy with low energy phonons which conduct

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J. Appl. Phys. 107, 083503 2010

the heat. The relevancy of this phonon process has been widely observed experimentally.4648 Thus, the rate of the decay of optical phonon into acoustic phonon of a given should be considered as an acoustic phonon frequency generation rate partially counteracting the scattering rate of the acoustic phonons of the same frequency. There is no expression for the anharmonic optical phonon scattering rates deduced from systematic experimental measurements. The reason is the incapability of detecting the optical phonons lifetimes of nonvanishing wave vectors. Therefore, we will approximate analytical expression for the optical phonon decay from the total potential energy of Si crystalline lattice. The unperturbed harmonic Hamiltonian for each lattice normal-mode takes the form H0 = 1/2M
2

d NOP dt

3 3

=2

Mr
2

V3 2
j,j1,q,b 0

1
1

1 cos
2

t 0 NOP + NOP N0 + 1 N0 + 1 1 24a

0 NOP + NOP + 1 N0N0 , 1

and that due to four-phonon processes as t d NOP dt

4 4

=2

Mr
2

V4 2
j,j1,j2,q,q1,b 0

1
1 2

1 cos
2

t 0 NOP + NOP N0 + 1 N0 + 1 1 24b

a+ j,q a j,q + a j,q a+ j,q ,

21

0 N0 + 1 NOP + NOP + 1 N0N0N0 . 2 1 2

where M is the atomic mass. The term in the cubic anharmonic Hamiltonian HA 3 which describes the strength of the interaction between one optical phonon of frequency 0 and wave vector q0 with two acoustic phonons of frequencies and 1 and wave vectors q and q1 takes the form HA 3 =
q0,j0,q,j,q1,j1

The resonance factor ensures that the principal contributions in the summation arise from processes for which the energy is conserved =0 . At the thermal equilibrium
0 0 NOP N0 + 1 N0 + 1 NOP + 1 N0N0 = 0, 1 1

25a

V3 q0, j0,q, j,q1, j1 a j0,q0 a+ j,q a+ j1,q1 . 22a

and
0 0 NOP N0 + 1 N0 + 1 N0 + 1 NOP + 1 N0N0N0 = 0. 1 2 1 2

25b Equations 25a and 25b can be used to reduce the term between brackets in Eq. 24a to NOP 1 + N0 + N0 and that in 1 0 0 Eq. 24b to NOP 1 + N0 + N1 + N2 + N0N0 + NN0 + N0N0 . 1 2 1 2 On the other hand, we dene the phonon scattering rate 1 by
1

The term in the quartic anharmonic Hamiltonian HA 4 which describes the strength of the interaction between one optical phonon of frequency 0 and wave vector q0 with three acoustic phonons of frequencies , 1, and 2 and wave vectors q , q1 and q2 takes the form HA 4 =
q0,j0,q,j,q1,j1,q2,j2

V4 q0, j0,q, j,q1, j1,q2, j2 = a j0,q0 a+ j,q a+ j1,q1 a+ j2,q2 . 22b

1 d NOP . NOP dt

26

Here, the cubic and quartic anharmonic coefcients are dened by V3 q0, j0,q, j,q1, j1 = g3 and
0 1

Thus, we can write the expression of the optical phonon scattering rate due to three-phonon processes as
3 1 A3

q0 + q + q1 ,

23a

=2

1 t j,j
2

V3 2
1,q,b

1
0 1

1 cos V4 q0, j0,q, j,q1, j1,q2, j2 = g4

0 1 2 2

1 + N0 + N0 , 1

27a

q0 + q + q1 + q2 ,

23b

and that due to four-phonon processes as

4 1 A4

where g3 and g4 are constants and q = 1 if q = b and 0 otherwise. The Hamiltonians HA 3 and HA 4 give rise, in rst-order perturbation, to three-phonon and four-phonon processes, respectively. If we consider NOP the occupation number of the optical phonon 0,q0,j0 equal to the sum of its deviation from the initial value NOP and its thermal equilib0 rium value NOP, and N0 , N0 , N0 the occupation numbers of 1 2 the created acoustic phonons q,j, 1,q1,j1, and 2,q2,j2 at thermal equilibrium, the rate of change in the optical phonon occupation number due to three-phonon processes can be written as

=2

1 t j,j

V4 2
1,j 2,q,q1,b

1
0 1 2

1 cos
2 2

1 + N 0 + N 0 + N 0 + N 0N 0 + N 0N 0 + N 0N 0 . 1 2 1 2 1 2 27b One can notice that Eqs. 27a and 27b depend on T only through the occupation numbers which have the form 1 / e /kBT 1 . At T = 0, the occupation numbers are omitted and the expressions of the optical phonon scattering rate can be reduced to

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3

J. Appl. Phys. 107, 083503 2010

1 A3

=2

1 t j,j

V3 2
1,q,b

1
0 1

1 cos
2 2

27c

and
4 1 A4

=2

1 t j,j

V4 2
1,j 2,q,q1,b

1
0 1 2

1 cos
2 2

27d and at Thus, one can perform the calculation of T = 0 independently from T and then add to the result the T dependent factor. Let us consider now Eq. 27c . Assuming that J and B are integers representing, respectively, the number of the phonon branches and the number of the reciprocal lattice vectors for which the total energy is conserved and the total momentum is conserved or equal to a reciprocal lattice vector, j,j1 can be replaced by J and b can be replaced by B. On the other hand, the concept of phonon density of states allows writing =
q 1 A3 1 A4

= 1 0 and 1 = 1 1 0, where 1 is a constant number below unity. This comes from the principle of energy conservation. We can notice that 1 = 1 1 / 1 . Since 1 is a positive constant which can take some positive values below unity, we can reasonably assume for it an average value of 0.5 and then, consider the Klemens channel,51 which assumes that the optical phonon decays into acoustic phonons of equal energies i.e., = 1 = 0 / 2 for the three-phonon processes and = 1 = 2 = 0 / 3 for the four-phonon processes . The use of Klemens approximation and Eqs. 30a 30c in Eq. 29 allows expressing the optical threephonon processes at T = 0 as
1 A3

12 g3JBGV t M r 2v 3 1 +

1 cos
2

31

We note that 1 cos t / 2d = t. Thus, the optical phonon scattering rate due to the three-phonon processes at T = 0 can be written as
1 A3

GV 2 3

d 3q =

GV 4 2 3

2 g3JBGV M r v3 1 +

32a

q2dq,

28

We can introduce now the T dependent factor to describe the optical phonons decay as function of T
1 A3

where G is the number of atoms and V is the volume per atom. By using Eqs. 22a , 27c , and 28 we can write that for T = 0
3 1 A3

T =

2 g3JBGV M r v3 1 +

1 + N0 + N0 . 1

32b

=2

Mr
2

1 1 g2JBGV 3 4 t 2 2 3 t q2dq.

Since we are assuming for the optical phonon decay the Klemens channel = 1 and consequently N0 = N0 , Eq. 32b 1 can be reduced to 29
1 A3

1 cos

T = CA 3

coth

2kBT

33

For the three-phonon processes, within the approximation of a linearized dispersion relations, we can write = vqq vq1q1 = 0, 30a

where CA 3 is a temperature and frequency independent constant equal to 2 /M r g3JBGA3/ v3 1 + .

where vq and vq1 are the velocities of the waves q and q1, respectively. However, we can nd a constant such as vq1q1 = vqq. Then, we can write = and d = 1+ dq
vq .

1+

vqq,

30b

30c

Indeed an optical phonon 0j0,q0 cannot decay into any two acoustic phonons j,q and 1j1,q1 or any three acoustic phonons j,q, 1j1,q1, and 2j2,q2. It should decay only to other phonons where the total energy is conserved and the total momentum is conserved or equal to a reciprocal lattice vector. The all allowed decay channels can be approximated from several approaches, such as Debye isotropic continuum model,49 anisotropic continuum model, and full lattice dynamical model.50 However, such a treatment would make the numerical calculation of T extremely cumbersome, if not impossible. To avoid this problem one can assume the following. The optical phonon of frequency 0 decays into two and 1 with acoustic phonons of lower frequencies,

Equation 33 describes only the anharmonic decay of optical phonon into two acoustic phonons. However, in the most of the materials, the decay of the optical phonons is due to the combined effects of anharmonic decay, which determines the intrinsic decay, together with scattering of the optical phonon by point defects. Let us now introduce the additional effect of defects scattering on the optical phonon scattering rate. The best convenient method to do so is to convolute the point-defect scattering with the anharmonic process.5254 The experimentally observed52,55,56 enhancement in the optical phonon scattering rate due point-defects scattering was considered as creation of additional favorable channels for the optical phonon decay with introducing point-defects. We assume here that these additional channels consist on anharmonic optical phonon scattering into a neighbor mode q followed by point-defect scattering into acoustic modes q and q1. According to the coherent potential approximation,57 if there is overlap between an optical phonon mode q0 of frequency 0 and other optical phonon mode q of frequency , the total optical phonon relaxation rate, which we will refer to as a generation rate of two acoustic phonons of frequency , can be written as

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sion of the optical phonon decay into two acoustic phonons, or the expression of the two acoustic phonon generation rate as
1/2 1 G3

1 A+I, 3

= CG 3

coth

2kBT

39

Similar treatment for Eq. 27d allows us to write the expression of the generation rate of three acoustic phonons of frequency as
1 G4

= CG 4

1+

3 e
/kBT

3 e
/kBT

1/2

. 40

FIG. 1. Phonon dispersion curves for silicon calculated from the full Weber adiabatic bond charge model.
2 0

1 G3

1 A+I, 3

12

Nd ,

34

where Nd is the density of modes q . Within the isotropic medium approximation Nd can be considered as being the number of modes in the sphere of radius q , divided by the pure anharmonic scattering rate. Thus, it can be written as Nd = GV 4 2 33
3

When the scattering processes are independent, the scattering probabilities are additive. Since the scattering processes of the optical phonons are independent from those of the acoustic phonons and since the rates of the decay of the optical phonons is considered as a rate of generation of acoustic phonons partially counteracting the resistive processes we can reasonably consider that the total resistive scattering probability is the sum over the various acoustic phonons scattering probabilities minus the probability of the decay of the optical phonons
1 R,j

1 A3

35

1 B,j

1 I,j

1 G 3 ,j

1 G 4 ,j

1 U,j .

41

Let 0C be the optical phonon frequency at the zone center for the phonon branch branch j, and Kq0 the curvature of the phonon branch j around the wave vector q0. We can then write
0= 0C

q2 0
2 Kq
0

36

2 Indeed, Eq. 36 is valid only when the quantity q2 / Kq is 0 0 smaller than unity. The Si phonon dispersion spectrum presented in Fig. 1 was calculated by using the full Weber adiabatic bond charge model58,59 which is based on the theories of Phillips60 and Martin.61 This spectrum shows that the curvature of the phonon branches is sufciently large in the whole Brillouin zone, so that Eq. 36 is valid in the whole Brillouin zone and thus can be adopted to describe the pointdefects scattering of an average optical phonon. Now, taking 1 A 3 = 0C 0, the expression of Nd takes the form

The phonon polarization or branch j can be either longitudinal L or transversal T . Thus, in Eq. 41 we separate the decay of optical phonon into longitudinal acoustic phonons from that into transversal acoustic phonons. This separation splits the two free adjustable parameters of the model, CG 3 and CG 4 to four free adjustable parameters CG 3 ,L, CG 3 ,T, CG 4 ,L, and CG 4 ,T, which is physically reasonable because these constants depend on phonon branches of different characteristics. Thus, they should be different for different phonon branches. Since the four-phonon processes are noticeable only at high temperatures, CG 3 ,L and CG 3 ,T should be adjusted to describe T at relatively low T, while CG 4 ,L and CG 4 ,T should be adjusted to describe T at higher T. Indeed, an optical phonon can combine with other phonons and produces optical phonons of higher energies. These created optical phonons will certainly have higher energies and thus relatively very low velocities. Consequently, this event cannot inuence the thermal conductivity and, therefore, is not taken into account.
VIII. COMPARISION WITH EXPERIMENTS A. Isotopic composition effect on the thermal conductivity of bulk Si

Nd =

4 GV 3 K 3 2 3 q0

1 1/2 A3 . 3/2 0C

37

After substituting in Eq. 34 , we obtain

1 G3

3 2GVKq

1/2

72

3/2 2

1 1/2 A

= CI 3

1/2

1 1/2 , A

38

3 where, CI 3 = 2GVKq / 72 3/2 and 2 = 0 / 0C. The term 2 0 2 is a constant below unity, introduced to express an average optical phonon frequency as a function of the zone center optical phonon frequency. The factor 2 comes from the assumption of Klemens channel for the decay of the optical phonon i.e., 0 = 2 . Thus, we can write the total expres-

Experimental measurements regarding the isotope composition effect on T of bulk Si showed an enhancement in T of the isotopically enriched over the natural abundance Si of almost 60%. The most recent modications brought to the model of Callaway model of Morelli et al.19 , could not account for this effect. Thus, it is interesting to apply the approach proposed to describe T for natural abundance Si natural Si and isotopically enriched Si 99.8588% 28Si in the full T range.

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FIG. 2. Color online Thermal conductivity of natural abundance and isotopically enriched silicon bulk samples. Symbols: experimental data. Dashed lines: theoretical results obtained from the conventional full Callaway model and single mode approximation. Solid lines: theoretical results obtained from the theoretical approach described in the present work which includes the contribution of the decay of the optical phonon into acoustic phonons to the lattice thermal conductivity.

The symbols in Fig. 2 present the experimental data on T of naturalSi and 99.8588% 28Si. The data on naturalSi and 99.8588% 28Si are obtained from Refs. 62 and 63, respectively. For the sake of comparison, we plot these experimental results together with the calculated T curves obtained by using the model of Morelli et al., and those obtained by using the theoretical approach proposed. In our calculations we have used the same values for the transversal and longitudinal acoustic phonon Debye temperatures and phonon velocities given by Morelli et al. These values are presented in Table I. The theoretical results obtained from the model of Morelli et al. for T of naturalSi and 9.8588% 28Si are plotted in Fig. 2 by using dashed lines. Although the model of Morelli et al. provides a good description of T of naturalSi at low T and T 200 K, it underestimates T near the temperature corresponding to the maximum thermal conductivity, Tmax, i.e., 20120 K. For enriched Si, the disagreement between the data and the theoretical curves becomes much more important; the model of Morelli et al. signicantly underestimates T when T exceeds Tmax. It is believed by the present authors that their model does not account for the isotopic composition effect on T of Si.

Several changes in the scattering rates involved in the model of Morelli et al. were attempted in order to improve the t. Namely, we tried to decrease and bring the theoretical curves closer to the experimental data at T around Tmax but this leads to a larger discrepancy at lower T. Also, we have considered longitudinal and transversal normal scatter2 a+b2 /3 V / M v a+b ing rate having the general form b a b KB / T and tuned a between 1.0 and 2.0 for each value of b between 2.0 and 4.0. In spite of using several reported forms for the three-phonon processes,1619,43,44,64,65 we did not nd any combination of a and b which could further improve the t. The theoretical T curves for naturalSi and 9.8588% 28Si obtained with our approach are plotted in Fig. 2 by using solid lines. Since the deduced expressions for the scattering rates are all independent from the azimuthal angle , the integral 2 d in the formalism for T proposed in this 0 work contributed 2 . Then, the numerical calculation of the remaining double integral was carried out by solving in a rst step the inner integral, using recursive adaptive Simpson quadrature,66 and in a second step the outer integral by using the same numerical method. Since the three-phonon processes are likely at relatively low T and the four phononprocesses are likely at higher T, the free adjustable parameters CG 3 ,L and CG 3 ,T were tuned to obtain the best t to the experimental data at low T, while the free adjustable parameters CG 4 ,L and CG 4 ,T were tuned to obtain the best t to the experimental data at higher T. The values of these free adjustable parameters, as obtained from the least-squares method, are shown in Table I. The excellent agreement between the theoretical approach proposed and the experimental results regarding the isotopic composition effects on T of Si highlights the importance of taking into account the expression for the decay of optical phonons into acoustic phonons as correction to the expression for the phononpoint-defects scattering rate. Moreover, these results show that, in contrast to the common accepted view, the optical phonons have an indirect, yet crucial role in the thermal conductivity. In order to illustrate the magnitude of the acoustic phonon generation rate relatively to the different scattering rates we plot in Fig. 3 1 T and 2 T , the two components of the full lattice thermal conductivity formalism, for the case of

TABLE I. Parameters obtained from the least-squares best t to the experimental data on the lattice thermal conductivity of Si bulk samples differing in their isotope composition and NWs differing in their cross section and surface roughness. L m 4 14 115 56 37 22 115 98 50 103 103 109 109 109 109 109 109 109 h m 1 109 1 109 1 109 1 109 6 109 5 109 5.7 109
vT m/s vL m/s
D,T D,L

Sample
natural Si 99.8588% 28Si natural Si NW natural Si NW natural Si NW natural Si NW natural Si NW natural Si NW natural Si NW

K 240 240 125 121 118 116 125 123 119

K 586 586 311 302 294 289 311 307 297

C 3 ,L 29.75 29.75 7.33 7.33 7.33 7.33 7.33 7.33 7.33 104 104 106 106 106 106 106 106 106

C 3 ,T 1.25 1.25 2.4 2.4 2.4 2.4 2.4 2.4 2.4 107 107 107 107 107 107 107 107 107

C 4 ,L 2.625 2.625 64.68 64.68 64.68 64.68 64.68 64.68 64.68

C 4 ,T 9.375 9.375 18 18 18 18 18 18 18

5840 5840 5759 5575 5436 5344 5759 5574 5483

8430 8430 8228 7900 7782 7646 8228 8122 7858

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FIG. 3. Color online Contribution of 1 T and 2 T components to the overall lattice conductivity of natural bulk silicon. Dashed lines: when the optical phonon decay is not taken into account. Solid lines: when the optical phonon decay is taken into account.

Si. As we can notice, the introduction of the acoustic phonon generation rate has inuence on 2 T in the temperature range where the model of Morelli et al. underestimates the thermal conductivity but not on 1 T . From the expressions of 1 T and 2 T , one can readily notice that the acoustic phonon generation rate is much less than the combined scattering rate 1 = 1 + 1 in the full temperac,j N,j R,j ture range. However, it becomes comparable to and counteracts the overall resistive scattering rate 1 in the temperaR,j ture range where the model of Morelli underestimates the thermal conductivity.
B. Thermal conductivity of individual silicon NWs

natural

of Si phonon dispersion spectrum shown in Fig. 1 within the single mode relaxation time model.49,67,68 It can be observed that in spite the fast decrease in A T with T, A T remains larger than the cross section of a Si NW in a wide T range e.g., A T remains larger than 100 nm up to 450 K . This clearly shows that for Si NWs the phonon-boundary scattering is the dominant scattering mechanism in a wide T range. Thus, an expression for the phonon-boundary scattering rate describing all the phonon mechanisms at the surface is crucial to explain all the effects which are observed experimentally. An additional mechanism might also contribute to T of NWs. It is the enhanced scattering of optical phonons due to an additional scattering by the sample boundary. This phenomenon is likely when the optical phonon mean free path O T is comparable to the sample cross section. However, as can be noticed from Fig. 4, for low T 300 K , O T is comparable to the cross sections of some of the NWs investigated 22 nm but A T is orders of magnitude larger than it. Consequently, at relatively low T the enhancement in the optical phonon scattering due to boundary scattering cannot have a noticeable inuence on the acoustic-phononboundary scattering rate. At higher T, A T is only one order of magnitude higher than O T but O T becomes smaller than the cross sections of the NWs investigated. For these reasons, in the present investigation we do not consider the enhancement in the acoustic phonon generation rate due to the scattering of optical phonons by the sample boundary
IX. SIZE EFFECT ON THE THERMAL CONDUCTIVITY OF SI NWS

Let us now apply the theoretical approach proposed to describe available experimental data on T of individual Si NWs. As mentioned earlier, for the case of NWs the phononboundary scattering is expected to be the most dominant scattering mechanism in a wide T range. This can be well noticed if we compare the T dependent intrinsic mean free path of the acoustic phonon A T and that of the optical phonon O T to the NW cross section L. In Fig. 4, we illustrate A T and O T which are calculated by using the data

In order to describe T of Si NWs, in addition to an accurate phonon-boundary scattering expression, we should take into account the modication of the acoustic phonon dispersion due to connement induced by boundary. For small cross section NW, typically below 8 nm, calculation of the size dependent phonon spectrum can be carried out by using molecular dynamics simulation.6971 For larger NW cross sections the molecular dynamics simulation becomes computationally prohibitive and the only way for calculating the size dependent phonon dispersion spectrum is the use of the elastic continuum approximation.7280 Although the elastic continuum approximation is valid only for phonons of wavelengths much larger than the interatomic spacing, a number of experiments conrm its usefulness in describing qualitatively the effect of size on the Debye temperatures and the phonons velocities,8184 which are the only phonon spectrum characteristics involved in the present formalism for T . Within the elastic continuum approximation,76,80,85 for a longitudinal wave propagating along the axis of a NW of cross section L, the dispersion relations are given by
2 q2 qT 2

qLL/2 J0 qLL/2 2 2 2qL q2 + qT J1 qLL/2 qTL/2 J0 qTL/2 = 0, J1 qTL/2 42a

2 + 4q2qL

FIG. 4. Color online Calculated mean free paths for the optical, acoustic, A, phonons as a function of temperature.

O,

and

where J0 and J1 are the ordinary Bessel functions and qL and qT are two parameters related by

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FIG. 5. Color online Elastic continuum approximation prediction of the dispersion relations for longitudinal solid lines and transversal dashed lines modes in silicon NWs of cross sections 115, 56, 37, and 22 nm.
2 L,n 2 vL T

FIG. 6. Color online Thermal conductivity of individual silicon NWs. Symbols: experimental data. Solid lines: theoretical results obtained from the theoretical approach described in the present work which considers the optical phonons decay into acoustic phonons as acoustic phonon generation rate. Dashed lines: theoretical results obtained from the theoretical approach described in the present work without accounting for the optical phonon decay.

2 qL T =

q2 .

42b to take into account the decrease in L T and D,L T when the v NW cross section decreases is to set them as free adjustable parameters with permitted values below those of vL T and D,L T for bulk Si. As can be noticed from Fig. 4, at low T the anharmonic effect is very weak. This allows us to consider that, at low T, the acoustic phonon generation probabilities almost vanish and hence L T and D,L T can be set v as the only free adjustable parameters. Furthermore, the Debye temperatures D,L T are involved only in the expressions of the acoustic phonon scattering rate due to Umklapp processes, which does not have noticeable inuence on T at very low T below 30 K for Si . Thus, L T can be obtained v from the least-squares best t to the experimental data below 30 K, whereas D,L T can be obtained from that between 30 and 50 K. The experimental T data for individual Si NWs with diameters 115, 56, 37, and 22 nm reported in Ref. 10 are plotted in Fig. 6. Assuming an rms value of 1 nm for all the Si NWs investigated in Ref. 10 see Fig. 2 in Ref. 10 we have plotted in Fig. 6 the calculated T curves obtained from the formalism proposed with solid lines and without dashed lines taking into account the effect of optical phonons decay into acoustic phonons. The averaged values for the phonon velocities L T and Debye temperatures v obtained from the least-squares best t to the experiD,L T

The dispersion relations for a shear wave or transversal wave are given by
T,n 2 = vT qz,n + q2 ,

43

where qz,n = 2 n / L and n is a quantization integer. By numerically solving Eqs. 42 and 43 we can obtain the dispersion relations of conned acoustic phonon modes in the single Si NWs investigated. At each q one can nd many solutions for qL, qT, and qz. The index n is used as quantization index to indicate the different solutions so that n is the phonon frequency for the nth branch. In Fig. 5 we show the dispersion relations of the seven lowest conned longitudinal and transversal acoustic phonon branches in the single Si NW investigated, together with the longitudinal and transversal bulk dispersion relations. Because of the quantization and manifold nature of a conned phonon spectrum and because the elastic continuum model is limited to phonons of wave vectors very close to the zone center, it is not possible to provide quantitative averaged values for the transversal and longitudinal velocities L T and Debye temv of conned phonons from the size depenperatures
D,L T

dent Si acoustic phonon spectrum. However, their qualitative trends with the NW cross section can be clearly understood. As can be noticed, the slopes of the conned acoustic phonon branches decrease with decreasing the cross section of the NW, which implies a decrease in the transversal and longitudinal averaged phonon velocities. Furthermore, within the elastic continuum approximation the longitudinal and transversal Debye temperatures are given by86
2 D,L T

= 2

/kB

3NA/4 V L T , v3

44

where NA is the Avogadro number. They are proportional to the averaged phonon velocities. Thus, they should also decrease with decreasing the NW cross section. The best way

mental data are given in Table I. At T close to 0 K the anharmonic processes optical phonons decay are negligible and both the theoretical curves coincide. At higher T, without taking into account the optical phonons decay into acoustic phonons as acoustic phonon generation rate, the theoretical model clearly underestimates T for all the NWs investigated. Any readjustment of L T and/or D,L T to bring the v theoretical curve closer to the experimental data at high T causes strong deviation between the theoretical curve and the

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experimental data at low T and around Tmax. However, when the optical phonon decay into acoustic phonons is introduced, an accurate description of the size dependent T in the full T range is obtained. It is worth to note here that the calculations of T were carried out with a unique set of CG 3 ,L, CG 3 ,T, CG 4 ,L, and CG 4 ,T listed in Table I in purpose to provide approximate values for these constants that can be used to predict T for Si NWs of cross sections not investigated in the present work. The adjustment of these constants for a particular cross section certainly leads to a better agreement between the theoretical and the experimental results. Although our approach gives satisfactory description of T of the NW of 22 nm cross section, we can notice from the experimental curve a light positive curvature above 150 K, while the theoretical curve in this T region shows a light negative curvature. This small disagreement is probably due to an alteration in the expression of the normal threephonon processes caused by strong phonon connement. An additional connement effect can be observed from Table I. The Cs are enhanced for the conned structure, which implies an enhancement in the optical phonon decay. To understand the physical reasons for this enhancement, consider the decay conditions for an optical phonon. An optical phonon of wave vector q0 and frequency 0 can decay into, for instance, two other phonons of wave vectors q and q1 and frequencies and 1 if the total energy is conserved and the total momentum is conserved or equal to a reciprocal lattice vector. In the case of a bulk material, for one wave vector q we can associate one longitudinal acoustic phonon frequency and two transversal acoustic frequencies. However, for the case of a NW, as demonstrated previously, for one wavevector q we can associate many longitudinal and many transversal acoustic phonon frequencies and thus the decay conditions become satised for much higher number of wavevectors q. In other words, due to the manifold nature of a conned phonon dispersion spectrum the number of the decay channels for optical phonons increases signicantly, which can explain the enhancement in the optical phonon decay in NWs and the enhancement in Cs. On the other hand, it has been reasonably suggested that in nanostructured materials, in addition to the short range mechanical force and the long range Coulomb force in the case of polar materials , there are long range mechanical forces in nonpolar and polar materials which give rise to spatial dispersion and dene the periodicity conditions for the displacement elds.87,88 Due to these forces, the radial wavevectors for longitudinal optical phonons and those for transversal optical phonons are quantized according to two different formalisms. This fact results in raising the frequency of an optical longitudinal phonon over that of an optical transversal phonon. From the electrodynamics point of view this splitting can be seen as a connement induced macroscopic electric eld associated with the longitudinal phonon. This electric eld serves to stiffen the force constant of the phonon and thereby raise the frequency of the longitudinal phonon over that of the transversal phonon. Since the longitudinal optical phonon has a frequency higher than that of the transversal phonon, its decay channels number in manifold phonon spectrum must be higher than that for the transversal phonon.

FIG. 7. Color online Thermal conductivity of rough silicon NWs. Symbols: experimental results. Solid lines: theoretical results obtained from the theoretical approach described in the present work.

This effect can explain the fact that the Cs for a longitudinal phonon have undergone two orders of magnitude enhancement, while the Cs for the transversal phonon have increased by a factor of two only.

X. SURFACE ROUGHNESS EFFECT ON THE THERMAL CONDUCTIVITY OF SI NWS

Considering that the expression for the phonon-boundary scattering involved in the present formalism for T imposes criteria for specular reection and diffuse scattering mechanisms, it should enable providing accurate description of the experimental results which show dramatic decrease in T for rough Si NWs.13 According to Ref. 13 the mean roughness height of these NWs varies from a wire to a wire but is typically 15 nm with a roughness period of the order of several nanometers. This roughness is attributed in Ref. 13 to randomness of the lateral oxidation and etching in the corrosive aqueous solution or slow HF etching and faceting of the lattice during synthesis. The experimental results showing the dramatic decrease in T for rough Si NWs are plotted in Fig. 7 together with the calculated T curves obtained from the model proposed with: i keeping the same set of CG 3 ,L, CG 3 ,T, CG 4 ,L, and , ii estimating and from their trends in C v
G 4 ,T LT D,L T

Table I, and iii setting the surface roughness rms value as the only free adjustable parameter since there is no precise experimental data on the rms values for the Si NWs surfaces investigated. The rms value obtained for each Si NW is given in Table I. The very good agreement between the theoretical and experimental results for these rather complex nanostructures adds support to the wide scope and applicability of the model proposed. Now, the strong decrease in T of Si NWs when the surface roughness increases can be explained. This effect can be understood with reference to Eqs. 8 , 10 , and 15 . When the surface roughness parameter, h, increases, the surface specularity, P , , h , decreases exponentially. This leads to a strong enhancement in the phonon-boundary scat1 tering rate B and consequently, to a signicant decrease in T.

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FIG. 8. Color online Contribution of 1 T and 2 T components to the overall lattice thermal conductivity of T . Symbols: experimental data on rough silicon nanowire with diameter of 115 nm. Dashed lines: contribution of 1 T and 2 T . Solid line: the total thermal conductivity T , i.e., 1 T + 2 T .

generation rate counteracting the acoustic phonon scattering rates. In addition, the commonly used expression for the phonon-boundary scattering has been corrected by including a phonon specularity probability depending on the phonon frequency, incidence angle, and surface roughness. We have demonstrated the importance of the corrections brought and wide scope of the formalism proposed with reference to reported data regarding the effect of the isotope composition on the thermal conductivity of bulk Si samples and the effects of size and surface roughness on the thermal conductivity of Si NWs. The experimental thermal conductivity curves, for all cases could be well described in the full temperature range. The formalism proposed for the thermal conductivity is exible to include additional phonon scattering mechanisms to describe the thermal conductivity of even more complex semiconductor structures with technological interest.
ACKNOWLEDGMENTS

Although the present approach is more computationally demanding than the commonly used Botlzmann transport equation approach which includes mainly phonon scattering at the wire surfaces and neglects the nonresistive processes,77,89,90 it allows understanding the effects of the various phonon mechanisms on T , especially in circumstances where the phonon-boundary and phonon-pointdefects scattering are the dominant mechanisms. In Fig. 8 we present both the contributions of 1 T = jkB / 8 3v j kBT / 3I1,j and 2 T = jkB / 8 3v j kBT / 3I2,j to the overall lattice thermal conductivity T for the 115 nm rough Si NW. As can be noticed, at low T say below 70 K the I2 T integrals may be omitted and thus the numerical complexity for the calculation of T of NWs can be signicantly reduced. It is worth to note here that the model proposed in this section for the size effect on the thermal conductivity of NWs, which is based on the elastic continuum approximation, holds only for NWs of diameters much larger than the atomic spacing. For the case of ultrathin NWs L 4 nm , recent atomistic simulation showed that, in contrast to what would be predicted from our model, the thermal conductivity becomes insensitive to the NW diameter and phonon connement may lead to an increase in T at low temperatures due to the occurrence of long wavelength acoustic phonons of very long mean free paths.91 On the other hand, the atomistic simulation is consistent with our model in describing the roughness effect on the thermal conductivity of Si NWs.
XI. CONCLUSION

M. Kazan would like to acknowledge nancial support of Rgion-Champagne Ardene and Agent National de la Recherche ANR . S. Pereira and M. R. Correia would like to acknowledge nancial support by FCT, Portugal Grant No. PTDC/FIS/65233/2006 .
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2 1

In summary, we have used the Boltzmann equation solution of Callaway, which discriminates between the nonresistive nature of the normal three-phonon processes and the resistive nature of the other phonon mechanisms, to establish formalism for the thermal conductivity that takes into account the phonons incidence angles. The acoustic phonon scattering processes have been represented by frequencydependent relaxation time and the optical phonons decay into acoustic phonons has been considered as acoustic phonons

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