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ISSN 1063 7826, Semiconductors, 2010, Vol. 44, No. 13, pp. 16441648. Pleiades Publishing, Ltd., 2010.

. Original Russian Text N.M. Manzha, 2010, published in Izvestiya vysshikh uchebnykh zavedenii. Elektronika.

MICROELECTRONICS TECHNOLOGY

A Study of Vapor Phase Deposition of Silicon Nitride Layers by Ammonolysis of Dichlorosilane at Lowered Pressure
N. M. Manzha
Technological Center Research and Production Company, Moscow Institute of Electronic Technology, Moscow, Russia e mail: magazine@miee.ru
Submitted December 24, 2008

AbstractDeposition kinetics of silicon nitride layers at lowered reactor pressures of 10130 Pa and temper atures in the range 9731073 K has been studied. The equilibrium constant of the bimolecular reaction of dichlorosilane with ammonia has been calculated. The apparent activation energies calculated taking into account the experimental growth rate nearly coincide with the experimental data. Recommendations for improving the quality of silicon nitride layers are made. DOI: 10.1134/S1063782610130051

Silicon nitride layers (SNLs) are widely used in industry and, in particular, in the technology of inte grated circuits. The application field of SNLs is so wide and the requirements on these layers are so diverse and, occasionally, contradictory that there is no universal method for synthesis of SNLs. The known techniques for SNL deposition can be classed as follows. (i) High temperature direct interaction of silicon with nitrogen or ammonia [1, 2]. (ii) Plasmochemical deposition and reactive sput tering [3]. (iii) Low pressure chemical vapor deposition (LPCVD) [46]. The choice of a particular process for formation of silicon nitride layers and of the corresponding equip ment for its implementation must be primarily deter mined by the functional role to be played by the mate rial in a given particular device, with the whole sequence of technological procedures for its fabrica tion and performance characteristics taken into account. In the late 1970s, the LPCVD technique with monosilane and ammonia became the main method for formation of SNLs as a mask in fabrication of iso lating regions [isoplanar, LOCOS (local oxidation of silicon), etc.] [6]. However, this process provides a layer thickness nonuniformity over the substrate of no less than 7% and is highly sensitive to a geometric factor related to arrangement of substrates within the reactor impairing the output capacity of the process [7]: d/ ( R r r s ) 2, (1)

One of the ways to improve the layer thickness uni formity and raise the output capacity of the process is to synthesize SNLs by means of ammonolysis of dichlorosilane. Our study is concerned with the kinet ics of SNL deposition by ammonolysis of dichlorosi lane and the properties of silicon nitride layers. SNLs were synthesized on an Isotron 2M installa tion on KDB 10 (111) substrates 102 mm in diameter subjected to the standard chemical treatment. The SNL thickness was measured with an LEM 3 ellip someter. The temperature within the reactor was mon itored using a built in thermocouple with an accuracy of 1C in the entire working deposition zone, and the pressure in the reactor was measured at its outlet with a 13VTZ 003 vacuum gage. The substrates were mounted in the reactor perpendicularly to the gas flow at a step of 2.38 mm. According to Hess law, the heat effect of a reaction depends only on the nature and state of the starting substances, being independent of the process pathway, i.e., of the number and type of intermediate elementary stages. Dropping intermedi ate elementary stages of the vapor phase bimolecular reaction of dichlorosilane with ammonia in accor dance with the equation 3SiH2Cl2 + 4NH3
T

Si3N4 + 6HCl + 6H2

(2)

and assuming that the SiN bond is formed by the reaction [8] * * SiH2Cl 2 + NH 3
K

SiN + 2HCl + 3/2H2,

where d is the distance between substrates, Rr is the inner radius of the reactor, and rs is the substrate radius.

which is a slower process as compared with the subse quent reaction of SiN with NH3 to give a stable Si3N4 phase, we find the rate of the surface bimolecular reac tion (2) as d[SiN]/dt = K[SiH2Cl2]*[NH3]*, (3) where K is the equilibrium constant.

1644

A STUDY OF VAPOR PHASE DEPOSITION OF SILICON NITRIDE LAYERS

1645

At adsorption equilibrium attained for each of the reactants, we obtain the following equations: [SiH2Cl2]* = {K1[SiH2Cl2]N}/{[SiH2Cl2] + K2[NH3] + N}, [NH3]* = {K2[NH3]N}/{[SiH2Cl2] + K2[NH3]}, where [SiH2Cl2] N SiH2 Cl2 and [NH3] N NH3 are the reactant concentrations, K1 is the equilibrium con stant for dichlorosilane adsorption, K2 is the equilib rium constant for ammonia adsorption, N is the sur
0 t t

face concentration of adsorbed centers (cm2), and the symbol * denotes the adsorbent. At low reactant concentrations (N K1[SiH2Cl2], N K2[NH3]), we have [SiH2Cl2]* = K1[SiH2Cl2], [NH3]* = K2[NH3]. Then, taking into account (3), we obtain d[SiN]/dt = KK1K2N SiH2 Cl2N NH3 = K0N SiH2 Cl2N NH3, (4) where K0 = KK1K2 is the reaction rate constant. Integrating (4), we obtain [9]
0 0 0

K 0 = 1 [ ln ( N SiH2 Cl2 N NH3 )/ ( N SiH2 Cl2 N NH3 ) ]/t ( N NH3 N SiH2 Cl2 ) ,
0 0

(5)

where N SiH2 Cl2 and N NH3 are the dichlorosilane and ammonia concentrations at the reactor inlet (at t = 0); t t N SiH2 Cl2 and N NH3 , dichlorosilane and ammonia con centrations in the reactor after a time t. Since ammo nia is present in excess, we can disregard the decrease 0 t in its concentration, i.e., N NH3 = N NH3 . The variation of the dichlorosilane concentration over the deposi tion zone can be found if the distribution of the growth rate of silicon nitride over the deposition zone is known (Fig. 1). Let the number of dichlorosilane 0 moles at the reactor inlet be M SiH2 Cl2 and the number of dichlorosilane moles after a time t of contact with the substrate be given by
t t

M SiH2 Cl2 = M SiH2 Cl2 ( 1 X SiH2 Cl2 ), where X SiH2 Cl2 is the depletion of the dichlorosilane flow. The change in volume as a result of reaction (2) is given by V SiH2 Cl2 = ( V xSiH2 Cl2 = 1 V xSiH2 Cl2 = 0 )/V xSiH2 Cl2 = 0 = ( 12/7V V )/V = 0.7. The concentration of dichlorosilane after a time t is N SiH2 Cl2 = N SiH2 Cl2 ( 1 X SiH2 Cl2 )/ ( 1 + 0.7X SiH2 Cl2 ). (6) Substituting (6) into (5), we have
0 0 t 0 t t 0 0 0 t

K 0 = 1 [ ln ( 1 + 0.7X SiH2 Cl2 )/ ( 1 0.7X SiH2 Cl2 ) ]/t ( N NH3 N SiH2 Cl2 ) [cm3 mol1 min1]. We find the depletion of the dichlorosilane concen tration from the expression X SiH2 Cl2 = [ 3S Si3 N4 V 0 v gr ( T ) ]/ ( M Si3 N4 Q SiH2 Cl2 ), (8) where S = 2Rd + 2r s , R is the inner radius of the reactor (7 cm), d is the distance between the substrates (0.476 cm), rs is the substrate radius (5.1 cm), Si3 N4 is the density of silicon nitride (3.4 g cm3), V0 is the vol ume under standard conditions (1 g mol1 of dichlo av rosilane = 21 400 cm3 mol1), v gr ( T ) is the growth rate of silicon nitride averaged along the deposition zone length L at 0 < L 30 cm, M Si3 N4 is the molecular mass of silicon nitride (140 g mol1), and Q SiH2 Cl2 is the expenditure of dichlorosilane. The time during which the reactants pass the deposition zone is given by the expression
SEMICONDUCTORS Vol. 44 No. 13 2010
2 t av

(7)

t = L/v fl = ( LPT room A )/ [ ( Q SiH2 Cl2 + Q NH3 )P atm T dep ],

(9)

where vfl is the linear flow velocity; P is the pressure in the reactor (40 Pa); is the Troom room temperature (300 K); A is the area of the gap between substrate edges and inner surface of the reactor (75 cm2); Q SiH2 Cl2 and Q NH3 are the flow rates of dichlorosilane and ammonia, respectively; Patm is the atmospheric pressure (105 Pa); and Tdep is the reactor temperature in deposition of sil icon nitride. The flow velocity along the reactor axis is determined beginning at the first substrate. The concentrations of dichlorosilane and ammo nia at the reactor inlet (at an insignificant pressure dif ference across the reactor) are given by N SiH2 Cl2 ( Q SiH2 Cl2 P )/ [ ( Q SiH2 Cl2 + Q NH3 )RT ], N NH3 ( Q NH3 P )/ [ ( Q SiH2 Cl2 + Q NH3 )RT ].
0 0

(10) (11)

1646 p, /min 90 80 70 60 50 40 30 20 10 0 10 20 30 40 50 2 1 60 70 80 L, cm 3 4

MANZHA p, /min 102 K0 109, cm3 mol1 min1

101

101

100 100

0.88

0.92 0.96 1.00 1000/T, K1

1.04

Fig. 1. Variation of the growth rate of silicon nitride along the deposition zone at various temperatures Tdep = (1) 973, (2) 1023, (3) 1073, and (4) 1123 K. (Q SiH Cl =
2 2

Fig. 2. Temperature dependences of the growth rate of sil icon nitride and reaction rate constant.

1.8 l h1, Q NH = 5.4 l h1, P = 40 Pa).


3

and the equilibrium rate constant of the bimolecular reaction, calculated by formula (12), depend on tem perature.
t

Substituting (9)(11) into (7), we obtain K 0 = 2.47 10 T ln (1 + 0.7X SiH2 Cl2)/ (1 0.7X SiH2 Cl2). Taking into account that X SiH2 Cl2 X) X at X 1, we have K 0 = 2.47 10 T dep 1.7X SiH2 Cl2 .
t 6 2 t t 6 2 t

1 and ln(1 + (12)

Calculation of X SiH2 Cl2 (8) and substitution of the data into (12) yields K 0 = 2.47 10 T dep v gr ( T dep ).
2 2 av

(13)

It can be seen in Fig. 1 that the depletion of the gas mixture in the reactants over the deposition zone, which is the reason the growth rate decreases, is insig nificant only at Tdep = 973 K and increases with the deposition temperature. Using the data in Fig. 1 and Eq. (12), we can calculate the equilibrium constant K0 (Table 1). Figure 2 shows how the rate of SNL growth on sub strates situated at the beginning of the deposition zone
Table 1. Equilibrium constant of the bimolecular reaction Tdep, K 923 1023 1073 1123 K0 109, cm3 mol1 min1 1.76 5.45 10.8 19.7

In the temperature ranges 9731023 and 1023 1073 K of silicon nitride deposition, the experimental values of the apparent activation energy are 43 and 28.8 kcal mol1 and those calculated from the equilib rium constant are 44.5 and 29.3 kcal mol1, respec tively. The silicon nitride deposition process was fur ther studied with a positive temperature gradient along the deposition zone (in the temperature intervals 106310731088 K) in order to compensate for the depletion of the dichlorosilane concentration. It fol lows from the dependences in Fig. 3 that the SNL growth rate decreases over the deposition zone to a greater extent as the flow rates of dichlorosilane and ammonia become lower: at dichlorosilane and ammo nia flow rates of 1.8 and 5.4 l h1, respectively, the growth rate decreases by 1.5 min1 at the end of the deposition zone, compared with its beginning; at dichlorosilane and ammonia flow rates of 0.45 and 1.35 l h1, respectively, the growth rate decreases by 7 min1 at the end of the deposition zone, compared with its beginning. The SNL grow rate depends more heavily on the dichlorosilane flow rate and less so on the ammonia flow rate. In contrast to deposition from monosilane and ammonia [7], the growth rate and the thickness nonuniformity are barely dependent on the geometric factor related to the arrangement of the substrates in the reactor, i.e., on relation (1). As the pressure in the reactor is raised from 40 to 130 Pa, the layer thickness nonuniformity increases from 1 to 3%, with the posi tive temperature gradient along the deposition zone becoming higher. The SNL thickness nonuniformity is
SEMICONDUCTORS Vol. 44 No. 13 2010

A STUDY OF VAPOR PHASE DEPOSITION OF SILICON NITRIDE LAYERS p, /min 40 35 30 25 20 2 15 1 10 0 10 20 30 40 50 60 70 80 90 L, cm Number of processes 70 70 (a) (b) 3 1 2

1647

Fig. 4. SEM image of an SNL with defects: (1) SNL and (2) defect.

Fig. 3. Variation in the growth rate of silicon nitride along the deposition zone l length at various pressures. (1) P = 10 Pa (Q SiH Cl = 0.45 l h1, Q NH = 1.35 l h1); (2) P =
2 2 3

40

40

20 Pa (Q SiH 40 Pa (Q SiH

2 Cl 2

= 0.9 l h1, Q NH = 2.7 l h1); (3) P =


3

2 Cl 2

= 1.8 l h1, Q NH = 5.4 l h1).


3

10

10 0.16 0.32 0 0.10 0.15 SNL porosity, cm2

improved if the centers of the substrates coincide with the axial line of the reactor. One of the most important problems to be solved in SNL deposition in a hot wall reactor is to diminish the number of inclusions and the layer porosity. Inclusions are a consequence of reactions in the vapor phase and result from formation of chlorosilanes deposited onto the inner reactor walls, powdered ammonium chloride deposited onto cold parts of the reactor, and finely dis persed silicon nitride particles falling off from inner reactor walls and buffer substrates. Figure 4 shows an SEM image of a silicon nitride layer, in which finely dispersed inclusions (defects) 12 m in size can be seen. Saturation of the inner walls of the quartz reactor with chlorosilanes leads to formation of matte stripes on substrates situated at the end of the deposition zone. Purging the reactor with oxygen with nitrogen at a pressure of 300400 Pa for 3040 min after the dep osition process precludes formation of matte stripes on the substrates and favors hardening of ammonium chloride. It was experimentally found that the inner walls of the reactor and buffer substrates should be cleaned to remove silicon nitride at its thickness of 1.71.9 m on the substrates and 1.21.5 m on the inner walls of the reactor. Figures 5 and 6 show histo grams of the SNL porosity distribution over 70 pro cesses (150 substrates in a process, and 3 of these taken as a sample) and the refractive index distribution over 120 processes. Table 2 lists characteristics of the SNL studied.
SEMICONDUCTORS Vol. 44 No. 13 2010

Fig. 5. Porosity distribution histograms for SNLs with thicknesses of (a) 0.1 and (b) 0.15 m.

Number of substrates 320

180

60

0 1.98 2.00 2.02 Refractive index of SNL


Fig. 6. The histogram for refractive index distribution of SNL.

Using the experimental values of the growth rate of a silicon nitride layer obtained in this study, we calcu lated the equilibrium constant of the bimolecular

1648 Table 2. Characteristics of a silicon nitride layer SNL characteristic At dichlorosilane/NH3 flow rate ratio of (0.160.5) Refractive index n Dielectric constant Breakdown strength E, V cm1 Density of the effective carrier charge N, cm2 Tensile stresses , GPa

MANZHA

Measurement data

Stoichiometric SNL 2 0.2 7.5 0.1 (1.2 0.1) 107 (3.4 0.2) 1011 h = 100 nm; 0.15 0.01 h = 200 nm; 0.8 0.01 With a 50 nm thick silicon dioxide sublayer Tensile stresses , GPa h = 100 nm; 0.055 0.005 h = 200 nm; 0.7 0.02 Nonuniformity of the SNL thickness over wafer, % 1 Nonuniformity of the SNL thickness in a batch, % 2 Number of substrates processed in a cycle, pieces 200
Note: h is the SNL thickness.

reaction of dichlorosilane with ammonia. The appar ent activation energies calculated taking into account the experimental growth rate at silicon nitride deposi tion temperatures in the ranges 9731023 K and 10231073 K are 44.5 and 29.3 kcal mol1, respec tively, and nearly coincide with the experimental apparent activation energies of 43 and 28.8 kcal mol1. REFERENCES
1. T. Ito, T. Nozaki, H. Arakawa, and M. Shimoda, Elec trochem. Soc. 125, 448 (1978). 2. S. P. Myrarka, C. C. Chang, and A. C. Adams, J. Elec trochem. Soc. 125, 1875 (1978). 3. S. I. Patyukov, V. P. Zakharova, and N. M. Manzha, Zarub. lektron. Tekh., No. 6 (337), 63 (1989).

4. L. L. Vasileva, A. S. Ginovker, V. P. Popov, and S. M. Re pinskii, Izv. SO AN SSSR, Ser. Khim. 5 (12), 54 (1979). 5. O. I. Semenova, L. A. Nenasheva, and S. M. Repinskii, Neorg. Mater. 17, 1223 (1981). 6. R. S. Rosler, Solid State Technol. 20 (4), 63 (1977). 7. V. N. Kokin, N. M. Manzha, S. I. Patyukov, et al., le ktron. Promyshl. 31 (2), 26 (1986). 8. G. Peev, L. Zambov, and Y. Yanakiev, Thin Solid Films 189, 275 (1990). 9. Yu. V. Fillipov and M. P. Popovich, Physical Chemistry (Mosc. Gos. Univ., Moscow, 1980), pp. 242, 243 [in Russian].

Translated by M. Tagirdzhanov

SEMICONDUCTORS

Vol. 44

No. 13

2010