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PII: S0042207X(98)00150X

Vacuum/volume 51/number 2/pages 161 to 164/1998 1998 Elsevier Science Ltd All rights reserved. Printed in Great Britain 0042207X/98 $19.00+.00

Aluminium nitride thin lms deposited by DC reactive magnetron sputtering

V. Dimitrova,a* D. Manova,a T. Paskova,b Tz. Uzunov,c N. Ivanov,c D. Dechev,c aDepartment of Physics, University of Rousse, 8 Studentska Str., 7017 Rousse, Bulgaria; bDepartment of Solid State Physics, University of Soa, 5 J. Baucher Str., 1164 Soa, Bulgaria; cLaboratory of New Technologies, Technical University of Sliven, 59 Bourgasko Shousse, 8800 Sliven, Bulgaria

AlN-lms prepared by dc reactive magnetron sputtering. AlN in an Ar+N2 gas mixture have been prepared and their microstructure, hardness, refractive index and IR transmittance examined. At l = 640 nm the refractive index was 1.93 and k = 3103; high transmission occurred between [??] structure and oxygen on microhardness is discussed. 1998 Elsevier Science Ltd. All rights reserved

0[ Introduction The widespread technological application of nitride thin _lms is the reason for increasing interest in the investigation of these compounds[ In particular AlN is an attractive material because of its high melting point "1399>C#\ thermal conductivity "159 Wm0K0#\ extreme hardness "about 1092 kgf mm1#\ chemical and thermal stability\ and high electrical resistivity "r 0980900 Vm# et al[02 AlN is an interesting optical _lm material with a high refractive index "n 0[71[1#3 and low absorption "k092#4[ Its thin _lms are transparent in the visible\ infrared and ultra!violet regions with high optical transmission between 9[101[4 mm4[ It is also a promising material for optical applications in corrosive and high temperature environments5\6[ Aluminium nitride is not an easy material to study because its growth of good quality AlN thin _lms requires a high purity source and an oxygen!free environment\ because of the alu! minium reactivity[ The _lms have been deposited by several tech! niques] molecular beam epitaxy "MBE#7\8\ reactive sputtering2\09\00\ chemical vapour deposition "CVD#01\02 etc[ A most common deposition method is d[c[ reactive magnetron sput! tering\ because of its simplicity\ relatively low cost and the ability to obtain _lms of a good quality[ In this work polycrystalline AlN!_lms were deposited on glass\ monocrystal KCl and low carbon steel substrates by the d[c[ reactive magnetron sputtering[ The microstructure\ morphology\ microhardness\ refractive index and transmission in the IR region of the _lms were studied using TEM\ microhardness tester\ optical and IR transmission spectrophotometers respectively[

1[ Experimental details 1[0[ Thin _lm deposition[ AlN!_lms\ 215255 nm thick\ were deposited by d[c[ reactive magnetron sputtering of a water cooled aluminium target in a gas mixture of argon and nitrogen[ The diameter of aluminium target was 09 cm and the Al purity was 88\84)[ The vacuum chamber was evacuated to 67[093 Pa and high purity argon introduced up to 0[090 Pa[ The target was cleaned at 329 W for 04 minutes[ The vacuum chamber was then evacuated again and nitrogen "88[88)# was introduced with partial pressures of 0[4091 Pa "regime I# and 8092 Pa "regime II#[ Afterwards argon was continuously admitted in addition to the nitrogen until the total pressure "N1Ar# reached 2091 Pa "regime I# and 6091 Pa "regime II#[ Each regime was established for 04 minutes[ During deposition the total pres! sure and the d[c[ power were kept constant[ AlN!_lms were deposited on glass\ KCl and low carbon steel substrates\ because of the speci_c requirements of TEM\ IR spectral analysis and the possibility of various AlN applications[ The deposition times were 1 h "regime I# and 0[4 h "regime II#[ The substrate was unheated and its temperature depended on heating from the plasma[ The substrate to target distance was 029 mm[ 1[1[ Structure[ Structural details of the _lms were revealed by transmission electron microscopy "TEM#[ Films for these inves! tigations were deposited onto monocrystal KCl substrates for 09 minutes and afterwards detached dissolving the substrates in distilled water[ 1[2[ Microhardness[ Microhardness measurements were made with a PMT!2 tester equipped with a diamond Knoop pyramid[ By applying increasing loads to the indenter\ it was possible to gather information on layer hardness at increasing penetration

To whom all correspondence should be addressed[ $Paper presented at the 09th International School on Vacuum Electron and Ion technologies\ 1116 September 0886\ Varna\ Bulgaria[

V. Dimitrova et al.: Aluminium nitride thin lms deposited by DC reactive magnetron sputtering

depths[ Ten impressions were made at each load and the average microhardness values were taken[ The statistic error did not exceed 5)[ 1[3[ Optical properties[ The optical transmittance was measured as a function of the wavelength "9[29[7 mm# by a spec! trophotometer {Specord UV VIS|[ The refractive index n of the layers was determined from the interference maxima and minima in the visible spectral region of the transmittance spectra accord! ing to Swanepoel 03[ The region of high optical transmission and absorption IR band were studied by means of IR transmission spectroscopy using a spectrophotometer {Specord 64 IR|[

2[ Results and discussion 2[0[ Structure[ Figure 0 shows the microstructure of AlN _lms\ deposited on KCl substrates at a N1 pressure of 0[4091 Pa and total sputtering pressure of 2091 Pa "regime I#[ It can be seen that the _lms have a relatively smooth\ homogeneous\ uncracked surface and a uniform microstructure[ The TEM photograph picture\ taken normal to the _lm surface\ shows that the _lm surface is composed of crystals with a di}erent size and high density[ The polycrystalline hexagonal structure of all investigated AlN _lms was con_rmed by electron beam di}raction "EBD#[ Figure 1 shows the electron di}raction pattern of AlN _lms deposited at a nitrogen partial pressure of 8092 Pa and total sputtering pressure of 6091 Pa "regime II#[ In this EBD pattern the pres! ence of "009#\ "091#\ "991# and "099# rings can be seen clearly\ which indicates once again a polycrystalline structure of the _lms[ The presence of a weak a!Al1O2 ring is due to oxygen in the residual gas in the vacuum chamber[ On the EBD pattern many single re~ections can be seen\ which con_rm the results from TEM analysis[ The results from EBD and TEM analysis are in good agreement with the observations of other authors 00[ TEM photographs and EBD patterns clearly showed that all investigated AlN thin _lms had a microcrystalline structure "Fig! ures 0 and 1#[
Figure 1[ Electron di}raction pattern of AlN _lms deposited on KCl substrates at a nitrogen partial pressure of 8092 Pa and a total pressure of 6091 Pa[

2[1[ Microhardness depth pro_les of AIN thin _lms[ The variation of the measured composite hardness Hc of the investigated sam! ples "regime I# with the identation height\ i[e[ the penetration depth\ h\ is given in Figure 2[ The penetration depth is expressed by h d:29[41\ where d is the identation diagonal[ The micro! hardness of the low carbon steel substrate\ Hs\ was measured on an uncovered sample[ Its variation with h is also shown in the same _gure[ The results of this measurement show\ that the Hs vs[ h plot is typical for a system\ in which the layer is harder than the used substrate material[ As shown in Figure 2\ with the indenter tip approaching the interface both curves tend to con! verge and coincide beneath the interface Hc and Hs[ To separate the _lm hardness\ Hf\ from that of the composite Hc the model proposed by Jonson and Hogmark 04 for metallic bilayer and veri_ed by Navratil and Stejskalova 05 for semi! conductor bilayer systems is used[ The following expression for hard ductile _lms on softer substrates applies]

Figure 0[ TEM picture "magni_cation 4093# of a reactively dc mag! netron sputtered AlN thin _lm "N1 partial pressure of 0[4091 Pa and total pressure of 2091 Pa# taken normal to the _lm surface[ 162

Figure 2[ Microhardness Hk of an AlN thin _lm on a low carbon steel substrate as a function of the identation depth h[

V. Dimitrova et al.: Aluminium nitride thin lms deposited by DC reactive magnetron sputtering



HcHs t t 1C C1 h h



where C sin 061> 29?\ for hard ductile _lm and t is the layer thickness[ The calculated Hf values varying with h are given also in Figure 2[ The three curves from this _gure show an expected character of varying[ It is well known that the microhardness doesn|t depend on the load P used and penetration depth h respectively[ But in practice there is a load dependence particularly for small load "indentation!size e}ect#[ The experimental points were _tted with the function Hk Hkoexp "k:L#\ where Hk is the measured microhardness\ L is the load\ K is a constant for every speci_c sample and Hko is the load independent bulk microhardness[ The load independent micro! hardness of the low carbon steel substrate obtained here is 105[147 kg[mm1[ The so called bulk microhardness value of the AlN layer "255 nm# is about 634[277 kg[mm1[ This value is lower than the one measured for AlN monocrystalline thin _lms reported in the literature\ according to Refs[ 5\ 06 and 07\ the Knoop microhardness of AlN thin _lms is in the range 0199 0799 kg[mm1[ In our case the lower value of microhardness is normal for microcrystalline structure of the grown layers[ Ano! ther reason for the lower layer hardness could be the presence of a small oxygen amount "8)# in the _lms from the residual gas in the chamber[ 2[2[ Optical properties[ Figures 3 and 4 show an optical trans! mission spectrum T"l# of AlN _lms\ which are deposited at a nitrogen partial pressure of 8092 Pa and a total sputtering pressure of 6091 Pa "regime II#\ and the relationship between the calculated _lm refractive index and the wavelength of light n"l# respectively[ It can be seen in Figure 3\ that the interference maxima are not located very close to the uncoated substrate transmittance curve Ts"l# and this indicates\ that the _lms have

Figure 4[ AlN _lm refractive index as a function of the wavelength of light[

observable absorption[ In our case\ the average value of AlN transmission is about 79) at a glass substrate transmission 89)[ The refractive index n"l# was calculated using envelope curves of transmittance maxima and minima according to Swanepoel 03[ The results are shown in Figure 4[ At a wavelength of 539 nm the _lm refractive index n was found to be 0[82[ The extinction coe.cient for these _lms in the visible range is k 2092 at l 539 nm[ The _lm thickness obtained by Swanepoel|s method is 215 nm[ These results are in accordance with the ones reported for a refractive index and coe.cient of extinction of poly! crystalline AlN _lms 0\3 and con_rm the possibility for the depo! sition of AlN thin _lms with the expected optical properties by dc reactive magnetron sputtering[ An infrared transmission spectrum of AlN _lms grown on KCl substrates "regime II# is shown in Figure 5[ This spectrum displays the strong absorption band at 569 cm0[ The deposited _lms have an IR characteristic of AlN[ The region of high IR transmission was found to be between 1[4 and 01 mm[ 3[ Conclusions The AlN thin _lms produced in this study are polycrystalline with a smooth surface and a dense\ homogeneous microstructure[ The measured microhardness values of the grown layers are nor! mal for microcrystalline AlN[ The _lms are found to have good optical properties!refractive index\ extinction coe.cient and high transmission in the visible and IR regions\ depending on the deposition conditions[ The mentioned above results of this work con_rm the possi! bility for the production of AlN thin _lms with a polycrystalline microstructure\ good optical and mechanical characteristics by d[c[ reactive magnetron sputtering[ Further work is necessary to determine the in~uence of process parameters like nitrogen pressure\ current power and target!sub! strate distance on the composition\ structure\ morphology\ electrical\ mechanical and optical properties of the _lms[

Figure 3[ Spectral transmittance of an AlN _lm on a glass substrate[

V. Dimitrova et al.: Aluminium nitride thin lms deposited by DC reactive magnetron sputtering

Figure 5[ Infrared transmission spectrum of an AlN _lm on a KCl substrate[

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