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Boundary scattering of phonons

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1978 J. Phys. C: Solid State Phys. 11 1787 (http://iopscience.iop.org/0022-3719/11/9/017) View the table of contents for this issue, or go to the journal homepage for more

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J. Phys. C : Solid State Phys., Vol. 11, 1978. Printed in Great Britain. Q 1978

Boundary scattering of phonons

C M Bhandarit and D M Rowe
Department of Physics, Electronics and Electrical Engineering UWIST, King Edward VI1 Avenue, Cardiff, CF13NU UK

Received 14 November 1977

Abstract. The role of boundary scattering of phonons in reducing the lattice thermal conductivity is investigated in silicon, germanium and silicon-germanium alloy. The theoretical model gives a satisfactory explanation to the reduction in thermal conductivity observed in thin undoped films of silicon compared to bulk material. The magnitude of the reduction in heavily-doped hot-pressed Si-Ge alloys is somewhat less than previously reported and discrepancies still remain between theory and experimental data.

1. Introduction

The role of boundary scattering in limiting the phonon mean free path has long been considered as a low-temperature phenomenon, where in the absence of other phonon scattering mechanisms, boundary scattering effects are observed as the phonon mean free path approaches the sample dimensions. In solid solutions however because a large proportion of the heat is carried by low frequency phonons, boundary scattering effects can manifest themselves at high temperatures (Goldsmid and Penn 1968).The magnitude of the effect has been estimated for the case of sintered semiconductor alloys, and an increase in thermal resistivity of about 9 % has been predicted in Si,,Ge,, alloy possessing a particle size of 40 pm (Parrott 1969).A somewhat different value has been obtained by considering thin films of neutron irradiated silicon (Savvides and Goldsmid 1973). In recent years interest has grown in the use of hot-pressed techniques in fabricating heavily doped semiconductor thermocouples for use in thermoelectric application. The combination of hot pressing and heavy doping however complicates the situation and a satisfactory quantitative description of the thermal and electronic behaviour has so far proved elusive (Meddins and Parrott 1976). In this paper, an analysis based upon our earlier work (Bhandari and Rowe 1977)is employed in investigating the role of boundary scattering on thermal conductivity. Due to thedifficulties encountered in analysing experimental data on heavily-doped hot-pressed silicon-germanium alloy we approach the problem in a number of stages and consider systems of increasing complexity.

2. Theory
In an earlier communication (Bhandari and Rowe 1977)an analysis was presented based
t On leave from the University of Allahabad, India

1787

1788

C A4 Bhandari and D A4 Rowe

upon Parrott's work (1969) and an expression for the thermal conductivity obtained by considering longitudinal and transverse phonon branches separately. Following Meddins and Parrott (1976) we extend our theory to doped semiconductor alloys and define a phonon relaxation time due to scattering by charged carriers as

re;' = B'z

where z

hw/kT

and include this, in our expressions for the thermal conductivity which is now given by:

where L n =

jol + .x"+
Ax4
Bx

d.x
x2

+ C'

and the symbols k,, k and A,, have the same meaning as in Parrott's paper.

The exact form of B,, is not important in the present context as it can be taken as an adjustable parameter for single crystal material. The two parameters are related by
B 0 3 T = BL w2 Consequently only one of the two parameters needs to be adjusted and in undoped and A T , , are related by materials B T , , = 0. The two sets of parameters C T , L

and as the parameters C T , are temperature dependent (inversely proportional to temperature) we introduce another parameter D T , , = C,,,T. D, is now varied to cover a large range ofgrain sizes and the corresponding change in thermal conductivity expressed in terms of the quantity Ksintered/Ksingle or Kfilm/Kbulk as the case may be. The deviation of this ratio from unity being a measure of the effectiveness of boundary scattering.

Boundary scattering of phonons

1789

Although more exact expressions for the phonon-phonon relaxation time are available which take into account the frequency and temperature dependences of the various three phonon relaxation times (Guthrie 1966, Holland 1963, Joshi and Verma 1970), a more rigorous approach is unlikely to affect the analysis in any significant way. The use of different relaxation times for normal and umklapp processes for the two polarisations and at two different temperature ranges involves a number of adjustable parameters whose inclusion would effectively cancel out any gain derived from the more exact expressions. Important phonon parameters used in our calculations are given in table 1.
Tablel. Material Dopant
1/R,e ioi9 cm-3

v, ( x 10-5)
cm s - ' 3.55 5.86

v, ( x 10-5) cm s - l
4.90 8.50 7.10
730
~ ~~

u2(
5-1

x 10-13)
~~~ ~~~

w 3( x
S-l

Undoped germanium Undoped silicon Doped Geo.30Sio.,o (MPI): B Doped Geo,20Sio.80 (SN1)S P

1.5 1.8~ 2.1

1.9
~~

4.3 7.0 6.5 6.8

17.5 14.0

4.90 5.20

7 This value is appreciably smaller than that reported by Brockhouse (1959) However as frequency values for various compositions of Si rich alloys were required we have obtained all these values from Braunstein (1963) though w2 values may be somewhat uncertain $ Meddins and Parrott sample 1 5 Alloy obtained from Sandia Laboratories, USA

J
\

e:

0981

; 0-9L

k 0860 :

0.2 O

O t'

0.6g

0.8 O 10 L 1.2

D L

Figure 1. Calculated values of Ksintered/Kringle CryIta, or (Kfilm/Kbuik) as a function of grain size (film thickness) for undoped germanium at 300 K.

3. Results The results of our calculations on undoped germanium and silicon are shown in figures 1-3. Figure 1 shows the predicted reduction in thermal conductivity in pure elemental germanium (when A T , L= 0, B T , L= 0). The reduction expressed as Ksintered/ Ksinglecrysta, or Kfilm/Kbulk has been obtained as a function of the parameter D, which

1790

C M Bhandari and D A 4 Rowe

depends upon grain size. The correction term is significant for vanishing A T , values and has been taken into account in all our calculations. Even in irradiated silicon, the concentration of point defects is small enough to make the correction term appreciable. In pure germanium we estimate that a grain size of 10 pm would give rise to a reduction in thermal conductivity of -7 % while measurements on hot pressed germanium (Fox,

652 326 163

I I

L Ihml 815
I

652
I

c3
I

0%-

> - 090-

0% -

02

OL

06
DL

08

1 0

12

tL

Figure 2. Krllm/KbUk for undoped unirradiated silicon at 300K. 0, calculated values; experimental values (Savvides and Goldsmid 1974).

+,

unpublished) show a much greater reduction. However the specimens on which measurements were made were less than 95 % dense and the discrepancy could be partially due to porosity effects. Much better agreement between theory and experimental data is obtained in the analysis of thin film data. Films are well characterised and their thickness known accurately (Savvides and Goldsmid 1974).In figures 2 and 3 the results of our calculations are displayed together with the experimental data on unirradiated and irradiated silicon. as a fraction of D, for unirradiated undoped silicon Figure 2 shows the plot of Kfilm/Kbulk films where A , = BT, = 0. A change in grain size to 8 pm corresponds to a 12 % change in thermal conductivity. The effect of point defect scattering in enhancing the

Figure 3. Kri,m/Kbu,k as a function of l / L and k, for neutron irradiated silicon films at 300 K. 0, calculated values; , experimental values.

Boundary scattering of phonons

1791

role of boundary scattering is displayed in figure 3. In the absence of information relating to the concentration of point defects in the neutron irradiated samples, A , has been adjusted to fit the thermal conductivity of bulk material. Agreement is excellent with k , = 1.0 while k , = 2.5 gives good agreement in unirradiated silicon films. The model is considerably simplified by assuming the same frequency and temperature dependences for normal and umklapp processes and there appears little justification for the choice of k, value. At point defect values typical of an alloy A , = 40 and k , = 1.0 at 300 K and for a grain size of 7 pm the ratio Kfilm/Kbulk = 0.62. This can be compared to the reduction obtained in heavily doped material (figure 4).
Table 2.

(TI
Temperature 300 500 700 900

Sample MP1 A, BL 59.43 35.66 25.47 19.81 0.32 022 0.19 0.15

Sample SNl A, BL 52.73 31.64 22.60 17.58 0.49 0.35 0.28 0.23

4
Figure 4. Calculated values of KSintcred/Ksingle as a function of grain size for heavily doped

silicon-germanium alloys.

The electronic contribution K e to the thermal conductivity is given by

K,
=

9 ( k / e ) oT.

The parameter 2 depends upon the scattering mechanism of the charge carriers and upon the degree of degeneracy. Estimates have usually been made by considering only one scattering mechanism. In real systems however, a multiplicity of mechanisms are in operation, the dominant of which are acoustic phonons and impurities with associated relaxation times of the form

1792

C M Bhandari and D M Rowe

where y~ is the reduced carrier energy. 2 has been calculated as a function of Fermi potential 4 and the degree of mixing tl where
a2 = L 1 / 2 / 2 , / 2 .

Over the range of interest 2 2.9 and this value has been used to calculate K e . In thin films of germanium the carrier mean free path is unaffected by boundary scattering down to thicknesses of l0WA (Suzuki and Maki 1977) and recent measurements of high density ( > 99.5 %) hot-pressed silicon-germanium alloys (Madani and Rowe, unpublished) suggest that the carrier mean free path remains unaffected by grain size over the range of interest. This indicates that K , may not be adversely affected by hot pressing and offers a possibility, at least in principle, of obtaining an increased figure of merit. Two problems are encountered in extending the theory to doped materials, (a) obtaining an accurate value of the electronic contribution to the thermal conductivity, (b) assessing the part played by the electron-phonon interaction in limiting the phonon mean free path. Our analysis in common with that of Meddins and Parrott (1976) assumes that as far as the lattice thermal conductivity is concerned the addition of dopant only serves to increase the scattering of phonons. This assumption may not be justified.
N

4. Discussion

Our calculations indicate that the magnitude of the reduction in thermal conductivity as a function of grain size should be somewhat less than previously reported (Meddins and Parrott 1976). Reasonably good agreement between theory and experimental data is obtained apart from that on heavily doped materials, figures 5 and 6t. Initially it was thought that sub-grain structure may have been responsible for the anomalous behaviour

181 I 300 LOO

500 600 700 800 900

T IK1

Figure 5. Thermal resistivity ( W )against temperature for heavily-doped hot-pressed silicongermanium alloy (MP1, Plessey UK). Solid curve-calculated values, dashed curve-best fit to experimental data (Parrott 1969).

Thermal diffusivity measurements on SN1 kindly made at UMIST by Dr R Taylor.

Boundary scattering of phonons

1793

of heavily doped materials and although the hot pressing method of preparation may introduce additional scattering mechanisms into the system, preliminary electron microscopic examination has failed to reveal culpable agencies of a scale or in sufficient number to significantly affect the thermal conductivity. A possible explanation may lie in the shortcomings of the theoretical model adopted. Although in our analysis we have attempted to allow for doping through the inclusion of an additional scattering mechanism, difficulties arise because the electron-phonon interaction is significant for low-frequency phonons. Steigmeier and Abeles (1964)
I

26

18

300

LOO

500

600
T iK)

700

800

900

Figure 6. Thermal resistivity ( W )against temperature for heavily-doped hot-pressed silicongermanium alloy (SNI, Sandia Laboratories, USA). Solid curve--calculated values, dashed curve-best fit to experimental data.

explain the reduction in thermal conductivity with doping in single crystal Si-Ge alloys 1 by considering the additional scattering of phonons by charge carriers. Erofeev et a (1966) however failed to detect phonon drag effects on the thermoelectric power and attributed the reduction in thermal conductivity to ionised impurity scattering and assumed an associated frequency independent relaxation time. This view is not shared by Steigmeier (1969) who criticises their interpretation on the ground that whereas the electron-phonon interaction is important in the scattering of phonons, it is not the dominant scattering mechanism for electrons. Erofeevs approach would not assist in explaining the present situation as a frequency independent scattering mechanism would also compete with the boundary scattering. A more appropriate model may be that adopted by Korzhevykh (1976) in his analysis of data on heavily doped semiconductors. He considers the electron contribution to the elastic constants in the long-wavelength approximation which is equivalent to the influence of the electron-phonon scattering on the phonon-phonon interaction. This approach leads to a renormalisation of the anharmonic scattering. He also reports good agreement of his theory with the experimental data on heavily doped Si and GaAs in the temperature range 60 K-300 K. It appears that the reduction in thermal conductivity of a doped semiconductor may partly be due to the renormalisation of anharmonic constants and the rest due to the scattering of phonons by carriers.

1794

C M Bhandari and D M Rowe

Another source of error which could give rise to discrepancies is an incorrect assignment of the carrier concentration values. Comparisons between hot pressed materials and the corresponding single crystals are made on the basis of composition and carrier concentration. Any appreciable error in the later would lead to an incorrect value for the reduction in thermal conductivity.

5. Conclusion
This rather simplified theoretical model gives a satisfactory explanation to the reduction in thermal conductivity observed in thin films of silicon compared to their bulk, single crystal counterparts although the explanation is not as satisfactory in sintered materials, particularly if heavily doped. The magnitude of the reduction in thermal conductivity of hot-pressed heavily-doped Si-Ge alloys is somewhat less than previously reported, although discrepancies still remain between the theory and experimental data. Doping is believed to exert a considerable influence on the phonon-phonon relaxation time. Any attempt to put forward a more rigorous theory should be preceeded by more accurate measurements to establish the correct magnitude of the reduction in thermal conductivity. It is suggested that this may be facilitated by measurements made on thin films of doped materials. Acknowledgments The authors acknowledge SRC for supporting the project, Professor D J Harris for Departmental facilities, Professor J E Parrott for helpful discussions and Mr A R Rowlands for assistance with computing. Acknowledgment is also made to Dr Valvo Raag of the Sandia Laboratories, USA, for his help in supplying silicon-germanium alloy samples. References
Bhandari C M and Rowe D M 1977 J . Phys. D : Appl. Phys. 10 L59 and L247 Braunstein R 1963 Phys. Rev. 130 879 Brockhouse B N 1959 Phys. Rev. Lett. 2 256 Erofeev R S, Iordanishvili E K and Petrov A V 1966 Sou. Phys.-Solid St. 7 2470 Goldsmid H J and Penn A W 1969 Phys. Lett. 27A 523 Guthrie G L 1966 Phys. Rev. 152 801 Holland M G 1963 Phys. Rev. 132 2461 Joshi Y P and Verma G S 1970 Phys. Rev. B1 750 Korzhevykh E 1976 Sou. Phys.-Solid St. 17 2174 Meddins H R andParrott J E 1976 J . Phys. C: Solid St. Phys. 9 1263 Parrott J E 1969 J . Phys. C: Solid St. Phys. 2 147 Savvides N and Goldsmid H J 1973 J . Phys. C ;Solid St. Phys. 6 1701 __ 1974 Phys. Stat. Solidi (6) 63 K89 Steigmeier E F 1969 Thermal Conductivity Ed R P Tye (London, New York: Academic Press) 2 p 299 Steigmeier E F and Abeles B 1964 Phys. Rev. 136 A 1149 Suzuki K and Maki M 1977 J . Appl. Phys. Japan 16 667