Materials Transactions, Vol. 48, No. 10 (2007) pp.

2782 to 2786
#2007 The Japan Institute of Metals RAPID PUBLICATION

High Thermal Conductivity of Gallium Nitride (GaN) Crystals

Grown by HVPE Process
Hiroyuki Shibata1 , Yoshio Waseda1;2 , Hiromichi Ohta3 , Kazumasa Kiyomi4 , Kenji Shimoyama5 ,
Kenji Fujito4 , Hirobumi Nagaoka4 , Yuji Kagamitani1 , Rayko Simura1; * and Tsuguo Fukuda1
1
Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Sendai 980-8577, Japan
2
Centre for Advanced Nitride Technology, Institute of Multidisciplinary Research for Advanced Materials (IMRAM),
Tohoku University, Sendai 980-8577, Japan
3
Faculty of Engineering, Ibaragi University, Nakanarusawamachi, Hitachi 316-8511, Japan
4
Optoelectronics Laboratory, Mitsubishi Chemical Corporation, Ushiku 300-1295, Japan
5
Optoelectronics Department, Mitsubishi Chemical Corporation, Tokyo 108-0014, Japan

A relatively large sample of gallium nitride (GaN) was grown as a single crystal using the hydride vapor phase epitaxy (HVPE) process.
The thermal diffusivity of the single crystal has been measured using a vertical-type laser flash method. The thermal expansion was measured
using a dilatometer in order to estimate the thermal diffusivity with sufficient reliability. The effect of sample thickness and temperature on
thermal diffusivity was evaluated. The specific heat capacity of GaN was also measured by using a differential scanning calorimeter. The
thermal properties of single-crystal GaN have been compared with the measured thermal properties of single-crystal silicon carbide (SiC). The
thermal conductivity of single-crystal GaN at room temperature is found to be 253
8:8% W/mK, which is approximately 60% of the value
obtained for SiC. The excellent thermal property that is obtained in this study clearly indicates that GaN crystals are one of the promising
materials for use in high-power-switching devices. [doi:10.2320/matertrans.MRP2007109]

(Received May 9, 2007; Accepted July 23, 2007; Published September 5, 2007)
Keywords: gallium nitride, thermal diffusivity, thermal conductivity, thermal expansion, laser flash method

1. Introduction studied the effect of oxygen on thermal conductivity and

obtained an approximate value of 200 W/mK at 300 K for a
Silicon carbide (SiC) is utilized for many applications flat plate-shaped sample, which was 200 mm thick and 3 mm
because of its high thermal conductivity. A thermal con- wide. In 2003, Jezowski et al.9) also obtained the value of
ductivity of over 360 W/mK at room temperature1) has been 226 W/mK for a bulk-shaped sample with a thickness of
reported for SiC. This intrinsic thermal property of SiC 100 mm and lateral dimensions of a few millimeters at 300 K.
allows us to fabricate devices such as thyristors for high It is understood that the defects in GaN as well as impurities
power switching. Gallium nitride (GaN) has also received in it should be minimized in order to use the material in
attention for many years due to its unique electrical proper- thyristors for manufacturing high-power-switching devices
ties. Since it has a large and tunable band gap of 3.4 eV at and high-brightness light-emitting diodes. It may also be
room temperature, GaN finds application in injection lasers suggested that a large bulk-shaped sample is strongly
and light-emitting diodes in the visible and ultraviolet required for measuring the thermal properties of GaN in
regions. GaN is also used in high-electron-mobility transis- order to reduce the experimental uncertainties in the
tors, quantum wells, photodetectors, and display devices.1) measurements. However, it was previously not an easy task
On the other hand, the thermal properties of GaN are very to produce large bulk-shaped samples. In this regard, a bulk-
important to make the devices work properly. In particular, shaped sample of single-crystal GaN with a relatively large
the thermal conductivity of GaN is an essential property for size can now be prepared using the hydride vapor phase
estimating the suitability of devices. To the best of the epitaxy (HVPE) process. This prompts us to measure the
authors knowledge, Sichel and Pankove2) were the first to thermal properties of GaN again for checking the possibility
report (1977) that the measured thermal conductivity of bulk of the application of GaN in high-power-switching devices.
GaN of 400 mm thickness at room temperature is 130 W/mK. The purpose of this study is to report the experimental
This is not far from the upper limit of 170 W/mK for a results of thermal diffusivity of single-crystal GaN using a
perfect GaN crystal, as predicted by Slack.3) In 1998, Witek4) laser flash method10–13) in the temperature range of 298 to
had theoretically estimated the value of the thermal con- 849 K. The thermal diffusivity of single-crystal SiC was also
ductivity of GaN as 410 W/mK, which is considerably higher measured for the purpose of comparison. The specific heat
than that predicted by Slack. The experimental thermal capacity of GaN was also measured using a differential
conductivity values of GaN obtained at room temperature, scanning calorimeter,14) and its thermal expansion coefficient
using a scanning thermal microscope, are scattered in the was measured by a thermal dilatometer in order to estimate
range of 50 to 210 W/mK.5,6) This is attributed to the effects the value of the thermal conductivity with sufficient
of impurities and dislocations on the thermal properties. Luo accuracy.
et al.7) reported the thermal conductivity value of 155 W/mK
using a third-harmonic electrical technique. Slack et al.8) 2. Experimental

*Present address: Institute for Materials Research, Tohoku University, 2.1 Thermal diffusivity measurement
Sendai 980-8577 The single-crystal GaN sample was grown on a sapphire
 High Thermal Conductivity of Gallium Nitride (GaN) Crystals Grown by HVPE Process 2783

Pulse laser 200

Temperature response (a.u.)

2 -1
Thermal diffusivity, α / 10 m s
-6
150

Thin carbon layer 100

GaN at room temperature
Sample Thin gold layer
50

Sample holder
0 5000 10000 15000 20000 0
GaN c axis 6H-SiC Sapphire Copper
Time, t/µ s
InSb infrared detector
Fig. 3 Comparison of thermal diffusivity val-
Fig. 2 Measured temperature response of GaN
Fig. 1 Schematic diagram of the sample ar- ues of GaN and 6H-SiC, which are obtained in
with 1 mm thickness along the c axis at room
rangement in a vertical-type laser flash appa- this study, with those of sapphire and copper.
temperature.
ratus.

substrate in a conventional vertical-type HVPE reactor at the axis of the sample is one-dimensional. To prevent a fracture
Optoelectronics Laboratory, Mitsubishi Chemical Corpora- in the thin metal film coating, an optical filter was inserted in
tion. The growth rate of GaN was approximately 120 mm/h, the path of the laser beam to reduce the intensity of the laser
and the temperature at a reactor wall was maintained between beam. An InSb infrared detector was employed to measure
1248 and 1293 K. A free-standing GaN sample was sponta- the temperature response from the rear surface of the sample.
neously separated from the sapphire substrate. The high The measurements were carried out under vacuum to
crystalline quality of the free-standing GaN crystal was minimize the heat leakage from the sample to its surround-
supported by X-ray diffraction(XRD)analysis. The measured ings. The thermal diffusivity (
) of the sample can be readily
full width at half maximum (FWHM) of X-ray !-rocking obtained using the following equation:15)
curves were 62.0 and 98.8 arcsec for the (002) and (102) d2
reflections, respectively. The impurity concentration was
¼ 0:1388 ð1Þ
investigated using secondary-ion mass spectroscopy (SIMS). t1=2
The GaN crystal was unintentionally, nominally undoped where d is the sample thickness and t1=2 is the time required
with a silicon impurity of concentration 2:1  1017 cm3 . for the rear surface of the sample to reach half the value of the
The concentration of the other impurities (H, Li, Be, B, C, O, maximum temperature rise.
F, Na, Mg, Al, Cl, K, Fe, Cu, Zn, As, Br, I, and At) was below
the detection limit. The dislocation density was determined 2.2 Thermal expansion measurement
from the dark spot density, which was obtained by the In order to examine the effect of the sample thickness and
cathode luminescence method. The typical value of the dark temperature on thermal diffusivity, the thermal expansion
spot density was approximately 5  106 cm2 . The sample coefficient of GaN was measured using a conventional
used in the present study was octagonal in shape with a thermal dilatometer at the Institute of Multidisciplinary
thickness of 1 mm along the c axis. The radius of the Research for Advanced Materials, Tohoku University. This
inscribed circle of the octagonal-shaped sample was 5 mm. dilatometer allows measuring the size variation within 1 mm.
This sample was used for measuring the thermal diffusivity in A rectangular sample of single-crystal GaN was prepared and
the temperature range of 298 to 849 K. used for the thermal expansion measurement. The temper-
The thermal diffusivity measurement of single-crystal ature during the experiments was varied between 298 to
GaN was performed using a vertical-type laser flash 473 K.
method.10–14) The single-crystal GaN is transparent for an
Nd:glass laser; hence, a thin gold layer of approximately 2.3 Specific heat capacity measurement
100 nm thickness was sputtered on both the sides of the GaN The specific heat capacity was measured using a conven-
sample. One layer acts as an absorber for the pulsed laser tional differential scanning calorimeter (DSC) at the Institute
beam and the other acts as an emitter of infrared rays. Carbon of Multidisciplinary Research for Advanced Materials,
powder was also sprayed on both the surfaces of the sample Tohoku University. The measurement was made under an
in order to increase the absorbance of the heating laser pulse atmosphere of high purity nitrogen with a flow rate of 50 ml/
and the emissivity of infrared rays for detecting the change in min. The specific heat capacity of sapphire was used as a
temperature of the sample after the laser irradiation. Such reference. The DSC curve was analyzed by the enthalpy
metal coating with carbon was found to work well for method. The experimental details and the data processing of
measuring the thermal diffusivity of the transparent sam- DSC measurements have been reported elsewhere14) and are
ples.10,11) not repeated here.
Figure 1 shows a schematic diagram of the sample
arrangement used for measuring the thermal diffusivity in 3. Results and Discussion
this study. The front surface of the sample was irradiated with
a pulse of Nd:glass laser as the heat source (output 7 J) with a Figure 2 shows the typical temperature response curve for
beam diameter of approximately 10 mm. The beam diameter single-crystal GaN obtained in this study. The temperature
was large enough to homogeneously heat the octagonal- increases rapidly and reaches a maximum value within 7 ms.
shaped sample surface. Therefore, the heat flow along the c The time required to reach half the value of the maximum
2784 H. Shibata et al.

120 10
0.6
GaN 65.58 mg

Specific heat capacity, Cp/ Jg-1K-1

GaN c axis Sapphire 92.39 mg
100 8
2 -1

0.5
Thermal diffusivity, α / 10 m s

Empty cell
-6

80

DSC signal (a.u.)

6
0.4

60 4 0.3

40 2 0.2
Present work
Jacob et al.
20 0 0.1

0 0.0
300 400 500 600 700 800 900 -2 300 400 500 600 700 800
5000 6000
Temperature, T/K Temperature, T/K
Elapsed time, t /s

Fig. 4 Thermal diffusivity values of GaN Fig. 5 DSC signals of GaN (65.58 mg), sap- Fig. 6 Specific heat capacity values (open
along the c axis as a function of temperature. circle) of GaN using DSC. The solid line is
phire (92.39 mg), and empty platinum cell in
The fitted line is expressed by
¼ the temperature range of 548 to 598 K. obtained from the data of Jacob et al.18)
93:85 6 2 1
T201  10 m s .

temperature rise, t1=2 , is estimated to be 1.64 ms, which is Cpr Wr Ss

very short and is approximately twice the laser pulse width. Cps ¼ ð3Þ
W s Sr
This phenomenon is known as the pulse width effect and is a
typical characteristic of laser flash measurements of high where Ws is the weight of the sample and Ss is the area
thermal diffusivity samples.16) In such a case, equation (1) between the DSC curves of GaN and the empty cell. The
gives an overestimation of the thermal diffusivity value. For subscript r denotes the reference material, which is sapphire
this reason, we also carried out thermal diffusivity measure- in this case. Sr is the area between the DSC curves of the
ments of pure copper (thermal conductivity = 398 W/mK) reference material and the empty cell. The data obtained for
with different thicknesses in the range of 0.889 to 3.179 mm. the specific heat capacity of GaN are shown in Fig. 6 as open
The pulse width effect was found to be insignificant in the circles. Recently, Jacob et al.18) have obtained an empirical
measurement of copper disks with a thickness larger than equation to calculate the heat capacity of GaN above room
2.44 mm. On the basis of these results, a correction factor temperature. This equation is valid in the temperature range
could be determined for thin samples with a thickness of less of 350 to 1075 K and is represented as
than 1 mm. Hence, the pulse width effect for the measure- Cp ¼ 74:424  0:00106T þ 46720=T 2
ments of GaN was corrected with reference to copper.
The thermal diffusivity values of GaN and SiC at room  685:9=T 0:5 J/molK ð4Þ
temperature are shown in Fig. 3 together with those of Equation (4) has also been plotted in Fig. 6 as a solid line for
sapphire and pure copper, which are known as high thermal the purpose of comparison. The measured values in this study
conductivity materials.17) The thermal diffusivity of GaN are well represented by eq. (4). Therefore, in order to obtain
obtained in this study is 98:6  106 m2 /s at room temper- the value of the thermal conductivity of GaN, equation (4)
ature, whereas the thermal diffusivity of 6H-SiC is was used to estimate the value of the specific heat capacity
198  106 m2 /s at room temperature. for temperatures ranging from room temperature to 849 K.
The thermal diffusivity measurements were also made The thermal conductivity  can be estimated using thermal
above the room temperature up to 849 K. The thermal diffusivity (
) and specific heat capacity (CP ) data with the
expansion coefficient of 3:53  106 K1 was obtained for help of the following equation (5):
GaN along the c axis. This clearly indicates that the change in
 ¼
Cp ð5Þ
the thickness of GaN due to thermal expansion is negligible
and thus no correction due to the sample thickness is needed where  is the density of the material. As the value of the
for estimating the thermal diffusivity using equation (1) at thermal expansion coefficient of GaN is very small
elevated temperatures. The thermal diffusivity of GaN is (3:53  106 K1 ), a constant density (6.15 g/cm3 )1) has
plotted in Fig. 4 as a function of temperature. The measure- been used to estimate the thermal conductivity by using
ments are repeated five times at the measured temperature. equation (5). The calculated thermal conductivities of GaN,
From this figure, one can clearly see a good reproducibility in for comparison, are shown in Fig. 7 as a function of the
the results. The thermal diffusivity of GaN is found to temperature along with the results of SiC. The thermal
decrease with increasing temperature and it may be repre- conductivity of GaN decreases almost exponentially with
sented with an uncertainty of
1:8%13) by the following increase in temperature. This is obvious because the density
equation: and specific heat are almost constant; however, thermal
939 diffusivity changes exponentially with temperature (Fig. 4),

¼  105 m2 /s ð2Þ as mentioned before. The thermal conductivity of GaN is
T  201 found to rapidly decrease with increasing temperature. The
The measured DSC signal of GaN is shown in Fig. 5 along data obtained by Sichel and Pankov2) also suggests the
with two other curves of the reference material sapphire and decreasing trend in thermal conductivity with increasing
an empty cell. It may be noted that the value of the specific temperature above room temperature. Slack et al.8) and
heat capacity of the sample, Cps , can be estimated using the Jezowski et al.9) have presented a negative temperature
following equation: coefficient of thermal conductivity above approximately 20
and 45 K, respectively, since the contribution of the Umklapp
 High Thermal Conductivity of Gallium Nitride (GaN) Crystals Grown by HVPE Process 2785

450

Present work
4. Summary
400
GaN along c axis

Thermal conductivity, λ / Wm-1K-1

6H-SiC
350
Literature value
6H-SiC by Nilsson et al.
The thermal diffusivity of single-crystal GaN grown by the
300

250
GaN by Sichel and Pankove
HVPE process was measured not only at room temperature
200
but also at high temperatures of up to 849 K using the
150
vertical-type laser flash method. The results were summa-
100 rized as a function of the temperature. The measurement of
50 the thermal expansion of GaN along the c axis clearly
200 300 400 500 600

Temperature, T/K
700 800 900
indicates that no correction due to the sample thickness is
needed for estimating the thermal diffusivity value; this is
Fig. 7 Thermal conductivity values of GaN as a function of temperature because the thermal expansion coefficient of GaN is very low
together with the values reported by Sichel and Pankove.2) The filled (3:53  106 K1 ).
square mark shows the thermal conductivity of SiC-6H estimated from the
The specific heat capacity of GaN was also measured using
measured thermal diffusivity data in this study. The broken line is the data
61100
from Nilsson et al.19) given by  ¼ T115 W/mK. a differential scanning calorimeter in order to obtain the
values of the thermal conductivity of GaN as a function of
temperature. The thermal properties of single-crystal GaN at
Table 1 Summary of the thermal properties of GaN and 6H-SiC at room
temperature obtained in this study.
room temperature, which are obtained in this study, are
summarized in Table 1 together with those of SiC for
Specific heat Thermal Thermal comparison. The thermal conductivity value of 253 W/mK
Density
Sample capacity diffusivity conductivity
(J/gK)
(g/cm3 )
(106 m2 /s) (W/mK)
for GaN along the c axis is the highest reported value among
the previously reported ones for single-crystal GaN; this
GaN
(along the c 0.417 6.15 98.6 253
corresponds to approximately 60% of the value reported for
axis) SiC. Although thermal properties of single-crystal GaN are
6H-SiC 0.69 3.21 198 438 known to be very sensitive to defects, the present results at

obtained from equation (4) and  taken from Ref. 1).
least suggest that the thermal conductivity value of single-
crystal GaN could be significantly improved when a perfect
crystal is produced, which is the case in the current study. It is
processes may dominate in this temperature range. The value also worth mentioning that GaN is undoubtedly one of the
of thermal conductivity obtained in the present study has candidates for next generation high-power-switching devices
been compared with the reported values of the free-standing due to its high thermal conductivity.
bulk-shaped samples. The obtained thermal conductivity of
253 W/mK in this study at room temperature is higher than Acknowledgement
those previously reported. The major impurity in the present
sample is silicon (2:1  1017 cm3 ), and the dislocation This project was supported by Japan Science and Tech-
density is approximately 5  106 cm2 . However, the sample nology Agency and the MEXT program ‘‘Development of
used by Sichel and Pankove,2) which has a thermal Growth Method of Semiconductor Crystals for Next Gen-
conductivity value of approximately 130 W/mK, had many eration Solid State Lighting.’’ The authors are grateful to Mr.
impurities as pointed out by Slack et al.8) The thermal Yasuhiro HOSHINO and Mr. Ryo OKADA, undergraduates
conductivity value of 200 W/mK was obtained by Slack et of the faculty of engineering, IBARAGI University, for their
al.8) for a GaN sample with impurities of oxygen (2:1  help in the thermal diffusivity measurements. The authors
1016 cm3 ) and silicon (0:37  1016 cm3 ). Jezowski et al.9) appreciate the permission granted for the use of the data of
reported the impurities and Ga vacancy (O: 1  1020 cm3 , specific heat capacity of GaN provided by Professor K. T.
Si: 1  1017 cm3 , H: 7  1017 cm3 , C: 1  1019 cm3 , Mg: Jacob (Indian Institute of Science).
1  1018 cm3 , Ga vacancy: 1  1018 cm3 ) in their sample
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