Effect of substrate temperature on spontaneous gan nanowire growth and optoelectronic properties

Đây là một bài báo khoa học về dây nano silic trong lĩnh vực nghiên cứu công nghệ nano dành cho những người nghiên cứu sâu về vật lý và khoa học vật liệu.Tài liệu có thể dùng tham khảo cho sinh viên các nghành vật lý và công nghệ có đam mê về khoa học

Effect of substrate temperature on spontaneous GaN nanowire growth and optoelectronic properties

A.P Vajpeyia,b, , A Georgakilasa,b, G Tsiakatourasa,b, K Tsagarakia,b, M Androulidakia,b,

S.J Chuac, S Tripathyc

a

Microelectronics Research Group, Department of Physics, University of Crete, P.O Box 2208, 71003 Herakilon-Crete, Greece

b

Institute of Electronic Structure and Laser (IESL), FORTH, P.O Box 2208, 71110, Herakilon-Crete, Greece

c

Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology, and Research), 3 Research Link, Singapore 117602, Singapore

a r t i c l e i n f o

Article history:

Received 11 July 2008

Received in revised form

2 September 2008

Accepted 3 September 2008

Available online 10 October 2008

PACS:

78.67.Lt

Keywords:

Plasma-assisted molecular beam epitaxy

(PAMBE)

GaN nanowires (NWs)

a b s t r a c t

The catalyst-free growth and the optoelectronic properties of GaN nanowires (NWs) grown on (111) Si substrates by plasma-assisted molecular beam epitaxy have been investigated At constant N/Ga flux ratio, the NW morphology, density and growth rate are controlled by the substrate temperature, which affects the gallium adatom diffusion length before desorption An increase in substrate temperature results in lower growth rate and smaller diameter of NWs with lower areal density NWs Low-temperature photoluminescence spectra at 20 K revealed that PL intensity ratio of donor-bound exciton peak (D1X at 3.470 eV) with defect-related peak (Y2at 3.424 eV) increased with increase in substrate temperature Micro-Raman spectra showed that the GaN NWs are completely stress free irrespective of the growth conditions

&2008 Elsevier B.V All rights reserved

III-nitrides are promising semiconductor materials because of

their application in optoelectronics and high-power electronic

devices One of the major problems of III-nitride materials

hetroepitaxial growth is high density of threading dislocations,

of the order of 108–1010cm2, which adversely affect the device

performance Nanodimensional nitrides such as nanowires

(NWs)/nanopillars are attractive materials for the reduction of

the dislocation density The NWs could be free of threading

dislocations as their small lateral length could allow initially

formed threading dislocations to move out of the crystal The free

surface at the sidewalls also permits elastic relaxation of the

strain[1] In addition to the elimination of threading dislocations,

the NW geometry also allows the device dimensions to be scaled

down Different techniques such as metal-organic vapor phase

epitaxy[2,3], molecular beam epitaxy (MBE)[4,5], chemical beam

epitaxy [6] and laser ablation [7,8] have been used to grow a

variety of semiconductor NWs with high crystalline quality

Recently, Calarco et al.[9]studied the nucleation density of MBE

grown GaN NWs and their evolution in terms of growth time for a

fixed set of growth parameters It has also been reported that the

GaN NW morphology is affected by the N/Ga flux ratio and the

substrate temperature [10–12] However, it is desirable to independently control the rod-like morphology of NWs in order

to optimize their crystalline quality

In this paper, we report on the effect of substrate temperature

on the surface morphology, density, growth rate and optoelec-tronic properties of GaN NWs spontaneously grown on n-type (111) silicon, by nitrogen radio-frequency plasma source MBE (RFMBE) The results suggest that during growth, Ga adatoms are transferred from uncovered substrate areas to the GaN NWs and the amount of transferred Ga atoms is limited by the Ga adatom residence time on the surface, which decreases as the substrate temperature increases Photoluminescence spectra at 20 K showed that PL intensity ratio of donor-bound exciton peak (D1X) with defect-related peaks increased in the smaller diameter NWs, grown at higher substrate temperatures

The GaN NWs were grown without any external catalyst on n-type (111) silicon substrates at a constant N/Ga flux ratio of 5, using RFMBE.[13]The Si wafers were chemically cleaned[14]and then loaded into the MBE system The Si surface oxide was removed by heating in the growth chamber at 800 1C for 10 min Then, the plasma was turned on at 300 W with a 1.35 standard cubic centimeter per minute (sccm) nitrogen flow rate In order to study the effect of substrate temperature on GaN NW morphol-ogy, the growth was performed at (a) 700 1C (sample A), (b) 750 1C (sample B) and (c) 800 1C (sample C) for 3 h with a Ga-limited

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Physica E

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Corresponding author.

E-mail addresses: agam@physics.uoc.gr (A.P Vajpeyi) , alexandr@physics.uoc.gr

(A Georgakilas)

nominal GaN growth rate of 166 nm/h The substrate temperature

was monitored by a manipulator thermocouple and the

un-certainty in the substrate temperature measurement is within

1 1C The growth experiments were monitored by in situ reflection

high-energy electron diffraction (RHEED) The sample surface

morphology was characterized by field-emission high-resolution

scanning electron microscopy (JEOL 6700FESEM) The optical

properties of the GaN NWs were investigated by low-temperature

photoluminescence at 20 K (20 K PL), and Raman spectroscopy PL

spectra were recorded using 325 nm line excitation wavelength

from a He–Cd laser Micro-Raman measurements were carried out

using 514.5 nm line excitations, where the scattered light was

dispersed through the JY-T64000 triple monochromatic system

attached to a liquid nitrogen cooled charge coupled device

detector The spatial and spectral resolution of the Raman setup

is about 1.0mm and 0.2 cm1, respectively

During the initial stage of the growth, the RHEED shows a rings

pattern, indicating the formation of polycrystalline GaN and

silicon nitride on the major part of the Si surface The formation of

amorphous silicon nitride layer has been previously reported by

Kim et al and Grandal et al.[5–15]After MBE growth of 5–15 min,

the ring-like RHEED pattern gradually changed into a spotty one,

indicative for the formation of (0 0 0 1)-oriented GaN NWs The

transition from a ring-like RHEED pattern to a spotty one

depended on the growth temperature and N/Ga flux ratio In

general, growth at higher temperature needed longer time for the

appearance of the spotty RHEED pattern, because of reduced

coverage of the substrate surface by the GaN NWs at higher

temperature

Fig 1 shows the plane and cross-sectional view of the SEM

images of the GaN NWs samples A, B and C grown on (111) Si,

with N/Ga flux ratio kept constant at 5 SEM images revealed that

nanowires density decreased from 9  109to 2.6  109cm2, while

the average diameter of the nanowires decreased from 90 to

70 nm, when the substrate temperature was increased from 700

and 800 1C The GaN NWs grown at lower temperature (p750 1C) exhibited a tapering morphology effect The tapering of a NW can be evaluated by the diameter difference between the top and bottom of the individual NW In the case of sample B, the

when measured from bottom to top part of the NW The sample

C did not show any tapering effect Such a tapering effect for GaN NWs grown on silicon was also reported by Meijers et al.[10] Our results suggest that the tapering effect can be controlled

by growth conditions such as substrate temperature and N/Ga flux ratio In our experiments, the growth rate of the NWs along the [0 0 0 1] axis was decreased with increasing growth tempera-ture The growth rate of the NWs grown at 700 and 750 1C was found to be 20% higher than the nominal growth rate of compact film formation, which would correspond to a NW height of 498 nm The higher growth rate of NWs compared to a compact film suggests that Ga has redistributed to form taller nanowires with a lower area fill factor relative to a compact film This could occur either by a substrate diffusion mechanism (at low nanowire heights) or by Ga striking the sidewalls and then diffusing to the ends (for taller nanowires) The height of the GaN NWs grown at 800 1C (sample C) was slightly lower than the nominal value, but within a possible range of experimental inaccuracies of the thickness measurements A slight NW height reduction cannot be explained by initiation of GaN decomposition

at 800 1C, since GaN could be regrown under the high-excess flux

of nitrogen species, as N/Ga flux ratio of 5 was used We believe that the reduction of the GaN NW growth rate at 800 1C is due

to a reduced residence time (t) of Ga adatoms on the substrate surface The diffusion length of Ga adatoms before desorption

is proportional to (Dt)1/2, where D is the diffusion coefficient

temperature is increased, diffusion coefficient increases but residence time is decreased and the overall effect is a reduction

in the Ga adatom diffusion length before desorption Hence less

Ga is transferred from the uncovered substrate area to the NWs.

The limited supply of Ga adatoms to the apex of the NWs limits

the growth rate and also reduces the tapering effect at higher

growth temperature The reduction of the Ga adatom residence

time on the surface with increasing growth temperature is also

consistent with the observed temperature dependence of the

density of the GaN NWs

Fig 2presents LT-PL spectra at 20 K where all the GaN NWs

samples exhibited emission peaks at 3.470 and 3.424 eV while the

reference GaN film showed an emission peak at 3.466 eV Both the

GaN NWs and film showed donor–acceptor pair (DAP) band at

3.260–3.333 eV The PL emission at 3.470 eV is associated with

free exciton bound to a neutral or shallow donor (D1X) and such a

PL peak was also observed by Calleja et al.[17]The PL intensity of

(D1X) peak increased with increase in growth temperature The

slight reduction in PL intensity of sample C may be due to the less

amount of GaN NW material excited by the laser beam (reduced

NW density) The PL emission peak at 3.424 eV, observed in all

GaN NW samples, might arise from dislocations formed when

nanowires coalesce Cheng et al [18] and Calleja et al [19]

reported that this peak was attributed to an exciton bound to

structural defects at the GaN/Si interfaces The PL intensity of DAP

band was decreased significantly with increase in growth

temperature of GaN NWs, which reflects that optical quality of

the NWs increased with increase in growth temperature Besides

reduction of DAP emission intensity, PL intensity ratio of

donor-bound exciton peak (D1X) with defect-related peak (Y2 at

3.424 eV) was found to be increased with increase in growth

temperature, and further confirms improvement in optical quality

of NWs sample grown at higher substrate temperature Finally, a

blue shift of about 4.070.5 meV is observed for the D1X transition

from the GaN NWs when compared to the GaN film and such a

blue-shifted (D1X) emission is associated with relaxation of the

tensile stress in the NW samples Micro-Raman spectra further

confirm that NWs are grown stress free compared to the reference

GaN film

Fig 3presents the Raman spectra of the GaN NWs and the

reference GaN film grown on Si(111) The spectra were recorded

in the zðxxÞ¯z scattering geometry The spectra are dominated by

the strong E2 (high) optical phonon peaks besides the strong

silicon peaks at 520.5 cm1 The Raman spectrum of the GaN film

shows strong E2(high) and A1(LO) modes at 566.4 and 734.0 cm1, respectively, which are in agreement with Raman selection rules for wurtzite GaN The inset inFig 3is an expansion of the Raman spectrum in the vicinity of the E2(high) phonon peak of GaN NWs and the GaN film The E2(high) phonon line of the GaN

0.2570.05 GPa when compared to strain-free, 400mm thick, freestanding GaN grown by HVPE [16] The amount of strain was evaluated using the proportionality factor of 4.3 cm1GPa1

for hexagonal GaN The E2(high) phonon line from the GaN NWs

is centered at 567.5 cm1, which is the value reported for the freestanding GaN film The E2(high) phonon frequency was the same for all the GaN NW samples grown from 700 to 800 1C Therefore all these GaN NWs are grown stress free on the Si substrate The GaN NWs samples showed very weak and broad

A1(LO) phonon mode Such a broad and weak A1(LO) phonon mode could be associated with residual n-type doping as high-temperature growth on the bare Si surface induces Si migration from the substrate and incorporate into GaN NWs [20] It was shown in Ref.[20]that doping level of 2.5  1018 cm3is sufficient

to broaden the peak Infact we have performed electrochemical CV measurements which confirmed that doping level in GaN NWs is

of the order of 1019cm3

In conclusion, we have studied the effect of growth tempera-ture on GaN NW morphology SEM results revealed that the density, diameter and growth rate of GaN NWs decrease with increase in growth temperature This behavior is attributed

to the reduction of Ga adatom residence time on the surface with increase in growth temperature which limits the lateral supply of Ga atoms to the NWs Low-temperature photolumines-cence at 20 K showed that PL intensity ratio of D1X peak with defect-related peaks increased indicative of improvement in optical quality of GaN NWs with increase in growth temperature

PL and Raman spectra revealed that all the GaN NWs are stress free irrespective of the used growth temperature Such GaN NWs are promising for the fabrication of nanostructure devices as well

as for the overgrowth of low density and stress-free III-Nitrides films since the NWs form an air-bridge-like structure with a high aspect ratio They may also be used as compliant buffer layer for the growth of compact III-Nitride films and device hetrostruc-tures

20K

Emission Energy (eV)

A

B

C

GaN film

Fig 2 Low temperature PL spectra at 20 K of the GaN NWs grown at (A) 700 1C, (B)

750 1C, (C) 800 1C, and a reference GaN film grown on (111) Si.

A1(LO)

E2(high)

E2(high)

Raman-shift (cm -1 )

A B C Film

A B C Film

Fig 3 Raman spectra of GaN NWs grown at (A) 700 1C, (B) 750 1C, (C) 800 1C, and a reference GaN film grown on (111) Si The inset shows an expansion of the spectrum in the vicinity of the E 2 (high) phonon peak.

This research was carried out in the framework of the ‘‘PARSEM’’

Marie Curie Project (MRTN-CT-2004-005583) funded by European

Union

References

[1] F Glas, Phys Rev B 74 (2006) 121302(R).

[2] F Qian, Y Li, S Gradecak, D.L Wang, C.J Barrelet, C.M Lieber, Nano Lett 4

(2004) 1975.

[3] J Su, et al., Appl Phys Lett 86 (2005) 13105.

[4] R Calarco, M Marso, T Richter, A.I Aykanat, R Meijers, A.V Hart, T Stoica, H.

Luth, Nano Lett 5 (2005) 981.

[5] Y.H Kim, J.Y Lee, S.H Lee, J.E Oh, H.S Lee, Appl Phys A 80 (2005) 1635.

[6] L.E Jensen, M.T Bjo¨rk, S Jeppesen, A.I Persson, B.J Ohlsson, L Samuelson,

Nano Lett 4 (2004) 1961.

[7] A.M Morales, C.M Lieber, Science 279 (1998) 208.

[8] X.F Duan, C.M Lieber, J Am Chem Soc 122 (2000) 188.

[9] R Calarco, R.J Meijers, R.K Debnath, T Stoica, E Sutter, H Luth, Nano Lett 7

(2007) 2248.

[10] R Meijers, T Richter, R Calarco, T Stoica, H.P Bochem, H Marso, H Luth,

J Cryst Growth 289 (2006) 381.

[11] K.A Bertness, A Roshko, N.A Sanford, J.M Barker, A.V Davydov, J Cryst Growth 287 (2006) 522.

[12] Y.S Park, S.H Lee, J.E Ob, C.M Park, T.W Kang, J Cryst Growth 282 (2005) 313.

[13] E Iliopoulos, A Adikimenakis, E Dimakis, K Tsagaraki, G Konstantinidis,

A Georgakilas, J Cryst Growth 278 (2005) 426.

[14] M Kayambaki, R Callec, G Constantinidis, C Papavassiliou, E Loechtermann,

H Krasny, N Papadakis, P Panayotatos, A Georgakilas, J Cryst Growth 157 (1995) 300.

[15] J Grandal, M.A Sa´nchez-Garcı´a, E Calleja, E Luna, A Trampert, Appl Phys Lett 91 (2007) 021902.

[16] L.S Wang, K.Y Zang, S Tripathy, S.J Chua, Appl Phys Lett 85 (2004) 5881.

[17] E Calleja, M.A Sanchez-Garcıa, F Calle, F.B Naranjo, E Munoz, U Jahn,

K Ploog, J Sanchez, J.M Calleja, K Saarinen, P Hautojarvi, Mater Sci Eng.

B 82 (2001).

[18] Hung-Ying Chen, Hon-Way Lin, Chang-Hong Shen, Shangjr Gwo, Appl Phys Lett 89 (2006) 243105.

[19] E Calleja, M.A Sa´nchez-Garcı´a, F.J Sa´nchez, F Calle, F.B Naranjo, E Munoz,

U Jahn, K Ploog, Phys Rev B 62 (2000) 16826.

[20] T Kozawa, T Kachi, Y Taga, M Hashimoto, N Koide, K Manabe, J Appl Phys.

75 (2) (1993).