surface s c i e n c e

ELSEVIER Surface Science 357-358 (1996) 555-559

H2-TPD study on the difference in the growth kinetics between Sill4- and Si2H6-GSMBE
M. Suemitsu, H. Nakazawa *, N. Miyamoto
Research Institute of Electrical Communication, Tohoku University, 2-1-1 Katahima, Sendal 980, Japan

Received22 August 1995; accepted for publication 1 November 1995

Abstract

Hydrogen desorption kinetics from a Si(100) surface grown by gas-source molecular beam epitaxy (GSMBE) using either silane or disilane has been studied with temperature-programmed-desorption (TPD) measurements. For each source gas, a series of TPD spectra was obtained from surfaces quenched from the growth at various temperatures. The TPD spectra from disilane-GSMBEgrown surfaces showed no shift in the peak temperature, while those from the silane-grown surfaces showed a peak shift towards higher temperatures by 25C at hydrogen coverages below 0.3 ML. This shift, indicative of the presence of higher-order desorption kinetics, suggests a more isolated configuration of the adsorbed hydrogen on the silane-grown surfaces. Difference in the growth kinetics between silane and disilane is also discussed.

1. Introduction

Both silane (Sill4) and disilane (SizH6) are the c o m m o n Si-bearing source gases equally used in Si chemical v a p o r deposition or Si gas-source molecular beam epitaxy. They, however, show dissimilarities in their temperature-dependence or the doping effect of the growth rate; reactive sticking coefficient (RSC) of disilane is about two orders of magnitude higher than that of silane 1-1,2], while doping with phosphine significantly reduces the poly-silicon growth rate by silane, but not so much by disilane [-3 ]. One of the mechanisms underlying the different growth behavior is the different adsorption state of the source gases. Adsorption state is responsible for both the adsorption rate of the source gas

*Corresponding author. Fax: +81 22 2175482; e-mail: Nakazawa@miyamoto.riec.tohoku:ac.jp.

molecule and the hydrogen desorption rate therefrom. A good example of the former is the number of required adsorption sites for the growth. The high RSC of disilane is partly understood in terms of its fewer (two) necessary adsorption sites 1-4] as compared to that of silane (four) [-5,6]. The influence of the adsorption s t a t e on hydrogen desorption can be best described in terms of the reaction o r d e r of the process, In general, it is well established that the hydrogen desorption from Si(100) 2 x 1 monohydride phase follows a first-order reaction 1-7 ] . T h e prepaired model [,7 ], in which the doubly occupied dimer ( D O D ) acts as the desorption precursor, has been widely accepted to account for the first order reaction. However, if the arrangement of surface hydrogen is such that it interferes with their association process for forming D O D s , the desorption would be of higher order kinetics. The aim of this paper is to obtain insight on the difference in the growth

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M. Suemitsu et aL /Surface Science 357-358 (1996) 555-559

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kinetics between the two source gases through studies on the hydrogen desorption kinetics of the grown surfaces.

SiH4/Si(100) PsiH4=2.0xl 0-4Torr //~J

.450oc (0.83ME)

2. Experiment
v

Experiments were made in an aluminum-alloy ultrahigh vacuum chamber whose base pressure was below 1.0 x 10 -9 Torr. Samples were borondoped Si(100) (p = 20-50 f~. cm) wafers which were cut to 5 x 33 mm 2. Prior to introduction to the chamber, samples were chemically cleaned by 1HzSO2:lH20 z and 1HF:20HzO followed by a 1 min ultraviolet ozone cleaning. Samples were resistively heated in vacuo and were degassed at 700C for 15 rain and flash annealed at 1200C for 30 s to obtain the clean 2 1 + 1 x 2 reconstructed surface by reflection high energy electron diffraction (RHEED). Growth was conducted by using either 2.0 x 10 -4 Torr silane or 1.0 x 10 -5 Torr disilane. The different choice of the pressure was to obtain similar hydrogen coverage after 10 rain of stationary growth. After 10 rain of the growth, the growing surface was quenched by stopping both the source gas and the sample current supplies. As reported previously [ 8 ], the amount of the quenched surface hydrogens decreases with increasing growth temperature, which was utilized to control the former quantity. The reaction order n of the hydrogen desorption process was obtained from a series of temperatureprogrammed desorption (TPD) measurements, in which the quenched hydrogen coverage 0 was varied; the T P D peak temperature Tp is independent of 0 when n= > i, while it shifts towards higher temperatures with decreasing 0 when n > I. T P D measurements were conducted at m/e=2 (H2) b y using a quadrupole mass spectrometer with a ramp rate of 5.7C/s.

/y

/ ', \ / 5 0 0

09 0

/ / ! ~"~5207) I1 ' , , ~ ./600 ////~\~" (0.13) //2t '__ ,2~\J 650

400 600 l-emperature(C)

Fig. 1. Hydrogen coverage dependence of H 2 TPD spectrum from SiH4-GSMBE grown Si(100) surface.

Si2H6/Si(100) " PSi2H6=1.0xl0-5Torr

i . m -.

:. ~ /~
/

450 C (0.77M L) /500

(0.44)

c-

/!~

i..~

co 03 (2

/ 550 (0.26) // ~ \ /600 / / / / : \~..."" (0.11) /// ; e-N~,L~ 650 ' (0.07)
400 '

/ /If \

Temperature(C)

'

6()0

Fig. 2. Hydrogen coverage dependence of H2 TPD spectrum from Si2H6-GSMBE grown Si(100) surface.

3 . Results and discussion

Figs. 1 and 2 are series of T P D spectra obtained from the grown surfaces using silane and disilane, respectively. All the spectra present a single,

so-called fll peak at around 500C, which can be attributed to hydrogen desorption from the monohydride phase. This fact, together with our R H E E D observation of the 2 1 reconstruction, indicates that the hydrogen desorptions relevant to the present study are all from the Si(100)-2 x 1 monohydride phase. In spite of this identical origin of the surface hydrogen, the silane-and the disilane-grown surfaces present quite a contrast in their T P D peak

M. Suemitsu et al./Surface Science 357-358 (1996) 555-559

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behavior. For the silane-grown surface (Fig. 1), the spectrum presents a Tp shift by more than 25C for hydrogen coverages below 0.3 ML. Since the lower coverage surfaces correspond to a growth at higher temperatures, where the surface migrations are enhanced, the presence of the shift indeed indicates the rate-limitation by a higher order process in the hydrogen desorption. In fact, our previous analysis [8] on the identical system yielded n = 1.59 for the reaction order. Quite contrary to this, the surface quenched from disilane growth (Fig. 2) presented no Tp shift down to 0 = 0.1 ML. This shows that the hydrogen desorption from disilane-grown surfaces is dominated by a first order process. This difference in the reaction order can be best interpreted as being caused by the different hydrogen association rate at the surface to form the desorption precursor, DOD. One possible factor that is responsible for the surface association process is the surface morphology or the surface roughness. As far as the atomic force microscopy and Nomarski optical microscopy are concerned, however, no differences were observed between silane-and disilane-grown surfaces. Therefore, we focus here to another more likely factor, the surface hydrogen arrangement. If the hydrogen atoms from the source gas molecules are readily paired as DOD just after the adsorption, the desorption kinetics should be of first order. On the other hand, if the adsorbed hydrogen atoms are sitting separately as-Sill2 or singly occupied dimers (SOD), the desorption kinetics should be more limited by higher order processes. In order to proceed further, detailed knowledge on the adsorption state of silane and disilane is indispensable. The initial stage of disilane adsorption onto Si(100) has been rather well clarified by Fourier-transformed infrared absorption [9], electron energy loss spectroscopy [10], or static secondary ion-mass spectrometry [11], which all presents a common view that disilane utilizes two neighboring dangling bonds to form two adjacent-Sill3 adsorbates (Figs. 3a and 3b). They are then combined together to form DODs (Fig. 3c). In contrast to the well established understanding of the Si(100)/disilane system, studies on the silane

(b)

(c)

(d)

Fig. 3. Model of Si2H 6 adsorption on Si(100) during SizH 6GSMBE: (a) before adsorption, (b) just after the adsorption, (c) the second stage after the adsorption and (d)surface during growth. adsorption process have been insufficient. The number of required adsorption sites itself has been an issue. Our contribution, however, is the finding [ 5,6] that a silane molecule most probably requires four adjacent adsorption sites on its adsorption (Figs. 4a and 4b). This conclusion has its basis on our observation that the growth rate shows a fourth power dependence on the free site density of the surface. From this knowledge on the initial stages of the silane and disilane adsorption, the difference in the hydrogen desorption kinetics between the two source gases is explained as follows. On disilanegrown surfaces (Fig. 3d), the two Si adatoms from

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M. Suemitsu et al./Surface Science 357-358 (1996) 555-559

(a)

,A

(b)

(c)

(d)

Fig. 4. Model of Sill4 adsorption on Si(100) during SiH4GSMBE: (a) before adsorption, (b) just after the adsorption, (c) the second stage after the adsorption and (d) surface during growth. a source gas molecule adsorb as an adatom dimer. The six hydrogens of the molecule are mostly forming DODs, a part of which has however desorbed due to the elevated temperature of the growing surface. This exclusive presence of surface hydrogens as D O D s is responsible for the first order desorption kinetics of the hydrogens on the disilane-grown surface. The silane-grown surface differs from the disilane-grown surface by the fact that the source gas molecule presents only one Si adatom. In the model illustrated in Fig. 4b, the adsorbate precursors are two atomic hydrogens and a =Sill2. The two atomic hydrogens may readily be combined

to form a DOD, but the = S i l l 2 starts migrating on the surface (Fig. 4c). On the growing surface (Fig. 4d), a part of the D O D s may have desorbed and the = Sill2 precursors are predominantly left. In order for the hydrogens of this = Sill2 to desorb, the precursor must migrate on the surface to form an adatom dimer or D O D . The higher-order hydrogen desorption kinetics from the silanegrown surfaces is understood from the sparsely distributed =Sill2. Here we have assumed that the two hydrogens of a ~-SiH2 precursor by themselves are hard to desorb as H 2 as evidenced from the absence of the f12 peak in the T P D spectra (Fig. 1). Finally, let us briefly discuss the hydrogen desorption from the atomic-hydrogen-adsorbed Si(100) surface. From the argument above, one might raise a question as to why an atomichydrogen dosed Si(100) 2 x 1 surface presents a first-order desorption, or no Tp shift, when most of the surface hydrogen atoms are considered to be adsorbing randomly. For this, a recent T P D observation by Widdra et al. is instructive [12]. The Si(100) surface dosed with atomic hydrogens, to our surprise, showed a dominance of D O D s for a substrate temperature as low as 150 K. The superthermal energy of the impinging atomic hydrogen was proposed to account for the nonthermally activated surface migration. The present adsorption model can also explain the different RSC for the two source gases. Firstly, disilane is more readily dissociated during adsorption. This is so because the energy required to break the Si-Si bond (1.80 eV) to dissociate disilane is much lower than the one required to break the Si-H bond (3.05eV) to dissociate silane. Secondly, the adatoms from disilane are more readily stabilized at the surface by forming an adatom dimer, while the adatoms from silane must migrate to find a counterpart to form an adatom dimer. Thirdly, the surface hydrogen desorption process is more enhanced on disilane-grown surfaces. To summarize, the difference in the growth kinetics between silane-and disilane-GSMBE on Si(100) surfaces has been investigated, by using the hydrogen desorption process from the grown surface as a probe. The observed higher-order desorp-

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tion kinetics for the silane-grown surface, in contrast to the first-order one for the disilanegrown surface, has been given the interpretation that the surface hydrogens are more sparsely distributed on the silane-grown surface. A model has been proposed, which successfully explains the different distribution of the surface hydrogens in terms of the different content of Si atoms in the source gas molecule.

References
[ 1] K. Weaner, S. Butzke, S. Radelaar and P. Balk, J. Crystal Growth 136 (1994) 322. [2] M. Suemitsu, K.-J. Kim, H. Nakazawa and N. Miyamoto, Appl. Surf. Sci., to be published.

1-3] S. Nakayama, H. Yonezawa and J. Murota, Jpn. J. Appl. Phys. Part 2 23 (1984) 493. [4] K. Weaner, S. Bntzke, S. Radelaar and P. Balk, J. Crystal Growth 136 (1994) 338. [5] K.-J. Kim, M. Suemitsu, M. Yamanaka and N. Miyamoto, Appl. Phys. Lett. 62 (1993) 3461. [6] F. Hirose, M. Suemitsu and N. Miyamoto, J. Appl. Phys. 70 (1991) 580. 1-7] J.J. Boland, Phys. Rev. Lett. 67 (1991) 1539. [8] M. Suemitsu, K.-J. Kim and N. Miyamoto, Phys. Rev. B 4 (1994) 48. [9] A.C. Dillon, M.B. Robinson and S.M. George, Surf. Sci. Lett. 295 (1993) L998. [10] Y. Suda, D. Lubben, T. Mottoka and J.E. Greene, J. Vac. Sci. Technol. A 8 (1990) 61. 1-11] S.M. Gates and C.M. Chiang, Chem. Phys. Lett. I84 (1991) 448. [12] W. Widdra, S.I. Yi, R. Maboudian, G.A.D. Briggs and W.H. Weinberg, Phys.