phys. stat. sol. (a) 201, No. 13, 2966 2979 (2004) / DOI 10.1002/pssa.

200406849

Inter-trap tunnelling in thin SiO2 films

S. Simeonov*, I. Yourukov, E. Kafedjiiska, and A. Szekeres
Institute of Solid State Physics, Bulgarian Academy of Sciences, Sofia 1784, Bulgaria Received 23 February 2004, revised 21 June 2004, accepted 2 July 2004 Published online 23 September 2004 PACS 71.55.Jv, 73.40.Gk, 73.40.Qv An expression for the currentvoltage characteristics of insulators in the case of inter-trap tunnelling is obtained. This expression gives an opportunity to estimate the energy position and concentration of traps responsible for charge transport by inter-trap tunnelling. Tunnelling currents at 77 and 300 K are observed in p-Si/SiO2 structures with 13 and 65 nm SiO2 films subjected to hydrogen plasma treatment at 20, 100 and 300 C. It has been shown that these currents together with tunnelling currents in some other insulator films, mainly SiO2, are carried out by inter-trap tunnelling.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction
With the continuous reduction of the thickness of gate insulators in contemporary advanced MOS integrated circuits the problem of tunnelling currents through the gate SiO2 film acquires great importance. Besides the indispensable tunnelling current from the metal to the Si conduction/valence band or the tunnelling current in the opposite direction, it is established that deep levels in the SiO2 energy gap also contribute to the tunnelling currents through SiO2 films. The indispensable tunnelling current from metal to Si and vice versa as a function of the applied electrical field is given by the FowlerNordheim expression. It is also established that deep levels generated by high electrical fields in SiO2 films create an additional path for charge carrier tunnelling, namely the stress-induced leakage current (SILC) (e.g. see [1]). Similar paths for trap-assisted tunnelling (TAT) are connected with deep levels in SiO2 films generated by ion implantation [2], X-ray exposure [3] or deep levels generated during SiO2 growth by thermal oxidation of Si [4]. It is widely accepted that the rate-limiting step of the TAT process is the tunnelling of charge carriers from the occupied deep levels to the conduction or valence band of SiO2 films. Another possible tunnelling mechanism for charge carrier transport via deep levels is inter-trap tunnelling. In this case the charge carrier tunnels from an occupied deep level to the next-nearest unoccupied one. When the inter-trap distance is smaller than the charge carrier path from the occupied deep level to the insulator conduction or valence band, this mechanism will prevail over the FowlerNordheim-type tunnelling from deep levels. Because of the high density of deep levels in SiO2 films this inter-trap tunnelling should be taken into account for explaining the excess tunnelling currents in SiO2 films prepared by different methods. By establishing the relation between the trap concentration and the tunnelling current via these traps it becomes possible to estimate the trap density in different SiO2 and other insulator films. Such estimation is needed for further development and control of the growth, deposition and other preparation methods of insulator films in the contemporary semiconductor technology. At present, radio frequency (rf) plasma processes are widely applied in semiconductor device technology. During plasma treatment Si/SiO2 structures are subjected to ion bombardment and UV light exposure. Because of this, defects are introduced in the SiO2 film, at the Si/SiO2 interface and in the Si bulk
*

Corresponding author: e-mail: simeon@issp.bas.bg, Phone: +359 2 71 44 228, Fax: +359 2 975 36 32
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

phys. stat. sol. (a) 201, No. 13 (2004) / www.pss-a.com

2967

(e.g. see [5]). Therefore it is interesting to study the role of deep levels, introduced during plasma exposure of Si/SiO2 structures, in the charge carrier transport through SiO2 films. In this paper an expression for the currentvoltage characteristics in insulators for the case of intertrap tunnelling is derived. An expression for inter-trap tunnelling current density as a function of applied electrical field is described in Section 2. The sample preparation, plasma treatment and characterization of p-Si/SiO2 structures are described in Section 3. The observation of tunnelling currents in these p-Si/SiO2 structures is considered in Section 3.3, where also the analysis of these tunnelling currents is presented. This analysis shows that the current in these SiO2 films is indeed caused by the inter-trap tunnelling. In Section 4 it is shown that currents of tunnelling type in some other MIS structures are also due to inter-trap tunnelling.

Inter-trap tunnelling conduction in insulators

As the traps in SiO2 are distributed in broad bands, in some cases with a single dominant trap, the energy distribution, D(q t), of these traps should be taken into account. The inter-trap tunnelling is governed by the position of the electron quasi-Fermi level, F. It is assumed that when an electrical field is applied to the SiO2 film this level remains parallel to the energy bands of SiO2. It is a constant value below the SiO2 conduction band edge along the SiO2 film thickness. In these circumstances the electron tunnelling current density, Jd, from occupied traps, with energy position q t (measured from the conduction band edge), to the unoccupied ones in the direction where the electrical field decreases the energy barrier for electron tunnelling is given by
J d = q Dt ( q t ) ft ( q t ) (1 ft ( q t ) wPd d ( q t ) )
0 g

(1)

where is the electron attempt to escape frequency in the occupied trap, w is the distance from the occupied trap to the next-nearest unoccupied trap, ft is the trap occupation function and Pd is the probability factor for this tunnelling. In many cases the change of fixed oxide charge in SiO2 films during electrical conduction can be neglected. Then from the time-dependent continuity equation (the Esaki equation)
dft = J in (1 ft ) J out ft , dt

where Jin and Jout are, respectively, the ingoing and outgoing electron fluxes, in the steady state it follows that Jin = Jout and ft = 1/2. With
ft = 1 , q F 1 + exp t kTeff

where Teff is the effective temperature of tunnelling electrons in the SiO2 film, this mean that the tunnelling current contribution is a maximum when the trap energy coincides with the quasi-Fermi level F. Taking into account that

(1 ft ) f ( t ) =

1 2

1 q t F 1 + cosh kTeff

(2)

it is clear that electron tunnelling from traps with other energies decreases sharply.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2968

S. Simeonov et al.: Inter-trap tunnelling in thin SiO2 films

Equation (1) can then be transformed to

g Dt ( q t ) ( Pd Pup ) dq t 1 J = q w 2 q F 0 1 + cosh t kTeff

(1a)

where Pup is the probability factor for an electron tunnelling from an occupied trap to the next-nearest unoccupied one in the direction where the electrical field increases the energy barrier. Taking into account that the factor 1 + cosh [(q t F)/kTeff] as a function of q t increases sharply when q t is moving away from F, in comparison with Pd and Pup also as functions of q t one may transform Eq. (1a) to
1 J = q w ( Pd Pup ) 2 0
g

Dt ( q t ) dq t q F 1 + cosh t kTeff

(1b)

where Pd and Pup are calculated for q t* = F. As will be shown later the errors introduced by this approximation for calculation of inter-trap tunnelling are practically negligible. Taking into account that

q F dq t = kTeff tanh t . q F 2kTeff 1 + cosh t kTeff

Equation (1b) can be transformed to J = qwNt(Pd Pup) (1c)

where trap concentration Nt is equal to D( F)kTeff. For the calculation of Pd in accordance with [4] it is assumed that under an electrical field, E, the shape of the energy barrier between two adjacent deep levels with energy depth q t and distance w is trapezoidal (see Fig. 1). For simplicity it is assumed that the distances from the occupied deep level to next-nearest unoccupied ones along or against the electrical field are equal. It will be shown later that this assumption does not put any constraint for practical use on the expression obtained for tunnelling current. If the electrical field, E, decreases the electron energy barrier for electron tunnelling from an occupied trap to the next-nearest unoccupied one, the probability factor, Pd, for this tunnelling in the

q(t+E.w) w

qt w

q(t-E.w)

Fig. 1 Schematic of electron potential barriers at nearest traps in an insulator under an electrical field.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

phys. stat. sol. (a) 201, No. 13 (2004) / www.pss-a.com

2969

WKB approximation is given by the integral

2w Pd = exp (2 m q )1/ 2 ( t Ex )1/ 2 dx . 0

(3)

After an integration of Eq. (3) Pd is transformed to

4(2 m q)1/ 2 [( t Ew)3 / 2 t3 / 2 ] Pd = exp . 3 E

(4)

When Ew t and taking into account that

( t Ew)3 / 2 t3/2 3 t1/ 2 Ew 3( Ew)2 3( Ew)2 + . + 1/2 2 4 t 4 t1/ 2

(5)

Equation (4) can be transformed to

2(2 m q )1/ 2 t1/ 2 w (2 m q )1/ 2 w 2 E Pd = exp exp . t1/2

(6)

When the electrical field increases the energy barrier for an electron tunnelling in the opposite direction from the same occupied deep level to the next-nearest unoccupied one the derivation of the probability factor for this tunnelling, Pup, is similar to that for Pd. In this case the probability factor is given by
2(2 m q )1/ 2 t1/ 2 w (2 m q )1/ 2 w 2 E Pup = exp exp . t1/2

(7)

The concentration of traps, Nt, near to the electron quasi-Fermi level is approximately 1/w3; taking into account Eqs. (1c), (6) and (7) the net electron current density from the occupied deep levels to unoccupied ones is expressed by
J= q w ( Pd Pup ) . 2w3

(8)

When Pd and Pup in Eq. (8) are replaced by Eqs. (6) and (7), respectively, the current density is given by
J = 2q

2(2 m q )1/ 2 t1/ 2 w (2 m q )1/ 2 w 2 E 1 exp sinh . 2 w t1/2

(9)

Both the field-dependent and field-independent terms in Eq. (9) depend on the energy position in the insulator energy gap, q t, and the inter-trap distance, w. Therefore, measuring the I V characteristics of a metalinsulatorsilicon structure it is possible to determine the energy position and concentration of traps in the insulator if inter-trap tunnelling takes place.

Characterization of hydrogen plasma-treated p-Si/SiO2 structures

3.1 Sample preparation Float-zone grown boron-doped Si(100) wafers with a specific resistivity of 3.64.5 cm were thermally oxidized in dry oxygen (H2O < 3 ppm) at 1050 C. Two sets of Si/SiO2 structures were prepared. One set, D1 samples, with 13.5 nm thick SiO2, and the other set, D6, with 65 nm thick SiO2. The thickness of the SiO2 layers was determined from the ellipsometric measurements.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2970

S. Simeonov et al.: Inter-trap tunnelling in thin SiO2 films

The p-Si/SiO2 structures were subjected to rf hydrogen plasma exposure at temperatures of 20, 100 and 300 C for 15 min in a home-built planar reactor similar to the one described in [6]. The plasma was excited between two parallel electrodes by a 13.56 MHz rf generator with a power density of 75 mW cm2 delivered to the upper electrode. The hydrogen gas pressure was kept at 13.3 mbar. The metal body of the reactor and the lower electrode were grounded. The samples were placed on this grounded electrode. During plasma exposure the SiO2 surface was charged up to the floating potential in the reactor (2 V) measured by a Langmuir probe. 3.2 C V characteristics of p-Si/SiO2 structures To study electrically active defects in these p-Si/SiO2 structures capacitancevoltage (C V) measurements using a 1 MHz E7 10 LCR meter and currentvoltage (I V) measurements were performed at 77 K and room temperature. The C V characteristics of the hydrogen plasma-treated p-Si/SiO2 structures were compared with those of p-Si/SiO2 structures formed in the same oxidation runs but without plasma treatment. Such unexposed structures will be further denoted as reference samples. Using the expression for the capacitance,
1 1 w = , C Cox s

and for the electrical potential

Vfb V = qN A w 2 qN A wd + 2 s ox

of a MOS structure, where Vfb and V are the flat-band and applied voltages, respectively, w and d are the thickness of the space charge layer and the oxide film, respectively, s and ox are dielectric constants of the same layer and film, respectively, and all other symbols have their usual meaning, one may obtain the expression
2(Vfb V ) 1 1 2 1 1 = + qN A S C Cox Cox C Cox
2

for the capacitance in the depletion mode of a MOS structure. Using this expression, from C V measexp urements in the depletion mode of MOS structures, the flat-band voltage, Vfb , and the doping concentration in the Si substrate, NA, are determined by plotting the dependence of
1 1 2 1 1 + C Cox Cox C Cox
2

Table 1 Density of traps, Nox, in the SiO2 film.

sample measurement temperature reference treated in plasma at 20 C treated in plasma at 100 C treated in plasma at 300 C
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Nox for the D1 set (cm2) 300 K 5.80 1011 3.71 1012 3.07 1012 6.90 1011 89 K 1.40 1011 5.95 1012 4.85 1012 1.06 1012

Nox for the D6 set (cm2) 300 K 4.30 1011 1.19 1012 1.07 1012 3.70 1011 77 K 4.70 1011 1.87 1012 1.47 1012 5.30 1011

phys. stat. sol. (a) 201, No. 13 (2004) / www.pss-a.com

300K

2971
10
2

1.0
77K

reference 0 treated at 100 C reference 0 treated at 100 C

300K 77K

10 10 10 10 10

0.8

J(Acm )

0.6

-1

C/Cox

-2

-2

0.4

-3

0.2
10
-4

0.0

-12 -10 -8 -6 -4 -2 0 2 4 6 8 10

10

-5

10

15

20

25

30

Voltage (V)
Fig. 2 Normalized CV characteristics of reference and hydrogen plasma-treated at 100 C D6 p-Si/SiO2 structures measured at 77 and 300 K.

Voltage (V)
Fig. 3 IV characteristics of D6 p-Si/SiO2 structure treated in hydrogen plasma at 100 C measured at 77 and 300 K.

on the applied voltage. The slope of this plot gives the NA value and the intersection with the voltage axis exp of the extrapolated curve determines the Vfb value. With this value of NA the ideal flat-band voltage i ideal Vfb for the corresponding Si/SiO2 structure is determined by qVfb = m Eg + kTln[Nv(T)/NA], where m is the metal work function, is the electron affinity and Nv is the effective density of states in the Si valence band. The CV characteristics of all samples subjected to hydrogen plasma are shifted towards negative voltages. This is evidence that hydrogen plasma exposure generates positive charge in the SiO2. As an illustration, in Fig. 2 the C V characteristics, measured at 77 and 300 K, of the reference and the sample treated in hydrogen plasma at 100 C from the D6 set are shown. exp i The density of fixed oxide charge in the SiO2 film, qNox, is given by qNox = Cox( Vfb Vfb ). The values of trap density, Nox, for different samples are given in Table 1. For the references and the samples treated in plasma at 300 C the trap density at room temperature is in the range of 1011 cm2. The trap density values of reference samples are close to the same values of corresponding samples treated at 300 C. The trap density for both D1 and D6 samples treated in plasma at 20 and 100 C is in the range of 1012 cm2. This observation shows that the majority of plasma-induced defects are annealed out at 300 C. The Nox values for the D1 set of samples are approximately three times higher than the corresponding values for the D6 samples. The C V characteristics of all samples measured at 77 K are shifted towards more negative voltages in relation of the corresponding characteristics measured at 300 K. This is evidence that donor-like localized traps exist at the Si/SiO2 interface [7]. In accordance with [7] their energy density, Nit, in the Si energy gap can by estimated by the expression
exp V exp (77) Vfb (300) N it = Cox fb , F

where F is the shift of the Fermi level towards the Si valence band when the temperature decreases from 300 to 77 K. The values of the energy density Nit are given in Table 2.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2972

S. Simeonov et al.: Inter-trap tunnelling in thin SiO2 films Table 2 Energy density of interface traps, Nit, in p-Si/SiO2 structures.

sample reference treated in plasma at 20 C treated in plasma at 100 C treated in plasma at 300 C

Nit for the D1 set (eV1 cm2) 3.85 1012 12.3 1012 7.88 1012 2.35 1012

Nit for the D6 set (eV1 cm2) 1.76 1011 3.84 1012 1.85 1012 7.51 1011

3.3 Tunnelling currents in p-Si/SiO2 structures The I V characteristics of the structures were measured at both forward and reverse bias applied voltages. Here only the forward current at negative voltages applied to the dot electrode on the oxide is considered. The current densities of different samples are close to each other, but the lowest densities are observed in the references and in the samples treated in plasma at 300 C, while the highest densities are for samples treated at 100 C. In Fig. 3 the I V characteristics, measured at 77 and 300 K, of D6 sample treated in plasma at 100 C are shown. The C V curves show that at applied voltages larger than 10 V this p-Si/SiO2 structure is in the accumulation mode and, therefore, the whole electrical field is applied across the SiO2 film. With decreasing the temperature from 300 to 77 K the electrical conduction changes a little. Even at voltages larger than 10 V the conductivity at 77 K is slightly higher than that at 300 K. Such behaviour of the conductivity, i.e. a small increase with decrease of temperature, is observed in Ge tunnelling diodes [8]. The small change in the conductivity with temperature suggests that under an accumulation the conduction through the oxide is of tunnelling type. As the oxide thickness in the studied structures is 13.5 or 65 nm, FowlerNordheim tunnelling through the SiO2 film is excluded. Therefore, the observed conductivity is due to trap-assisted tunnelling of charge carriers in the SiO2 film. The electron and hole effective masses in SiO2 are 0.5m0 and 0.46m0, respectively [4]. One can expect that the observed tunnelling currents through the oxide of the plasma-treated structures may be carried either by electrons or holes. In the first case the electrons tunnel from the Al dot electrode through the SiO2 film towards the p-Si substrate. In the second case the holes tunnel from the hole-accumulation layer at the p-Si/SiO2 interface through the SiO2 film towards the Al dot electrode. It has been established that in the case of hole accumulation at the Si/SiO2 interface the current through the 4 5 nm SiO2 films on p-Si substrate is carried by electrons injected from the metal [9]. Because of this, only the electron current will be considered further for an explanation of tunnelling currents in our 13.5 and 65 nm thick SiO2 films. However, possible intertrap tunnelling currents by holes in other insulator films can be treated by a simple replacement of the electron effective mass with that of holes in Eq. (9). If one assumes that Fowler Nordheim trap emission is responsible for tunnelling currents, then for the tunnelling current analysis two expressions are applied. In some cases such current density is expressed by
4(2 m q )1/ 2 t3 / 2 J = AE 2 exp 3 E

(10)

where A = q3/[162(qt)] (e.g. see [10, 11]), or by

4(2 m q )1/ 2 t3 / 2 J = J 0 exp 3 E

(11)

where J0 is unspecified [12]. Equation (8) is correct for the tunnelling of electrons from the gate metal to the semiconductor or vice versa through the SiO2 layer with an energy barrier at the metal/SiO2 interface, qt.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

phys. stat. sol. (a) 201, No. 13 (2004) / www.pss-a.com

2973

Taking into account that the fixed oxide charge in these Si/SiO2 structures is positive, the electrical field in the SiO2 layer, E, in the accumulation mode is expressed as
E=
exp V Vfb d

exp is the flat-band voltage and d is the SiO2 film thickness. Using where V is the applied voltage, Vfb 2 exp 1 Eq. (10) from the plot of ln(JE ) versus (V Vfb ) it is possible to determine q t either by the slope of this dependence or by the pre-exponential term. From the I V characteristics, measured at 300 K, of the sample from the D6 set, treated in plasma at 300 C, the q t values are calculated from both the slope and pre-exponential term and are 0.077 and 1.83 107 eV, respectively. These values calculated from the I V characteristics, measured at 77 K, are 0.16 and 6.29 105 eV, respectively. For the D6 reference, the corresponding values at 300 K are 0.21 and 3.8 106 eV, respectively, while at 77 K they are 0.15 and 4.1 106 eV, respectively. The large discrepancies in the values of q t determined from the plot of exp 1 ) show that Eq. (10) is not appropriate to account for electron tunnelling via ln(JE2) versus (V Vfb traps in the SiO2 layer. As is known, the tunnelling current is given by a product of the probability factor for tunnelling with the supply function of tunnelling charge carriers and subsequent integration of this product. The electron supply function depends on the character and density of electron states. The character and density of electron states in the SiO2 conduction band are very different from the character and density of localized electron states at traps in SiO2. Therefore the supply function for electrons that tunnel from traps in the SiO2 is different from the supply function for electrons in metal or SiO2 conduction band. Because of this the current density due to electrons tunnelling from traps to the SiO2 conduction band cannot be accounted for by Eq. (10) as is shown above. The probability factor for electron tunnelling from traps to conduction band in SiO2 is given by exp [(4(2m q)1/2 t3/2)/3E]. In this case one has to use Eq. (11) which takes into account only the probability factor for tunnelling from traps and J0 remains unspecified [12]. In this case it is possible to exp 1 ) . The q t values for the determine only q t from the slope of the dependence of ln(J) on (V Vfb samples of the D1 set, treated in plasma at 20 and 100 C, are in the range of 0.11 0.26 eV. From the D1 set the q t values for the reference and the sample treated in plasma at 300 C are in the range 0.260.36 eV. The corresponding values of q t for the D6 set are in the range 0.0830.15 eV and 0.140.29 eV, respectively. Such low values of q t are not compatible with the WKB approach to the tunnelling by which approach Eqs. (10) and (11) are obtained. The WKB approximation is valid when

E 2(2 m q )1/ 2 ( t Ex )3 / 2

1.

The mean values of are 0.15 and 0.18 only for the D6 samples at 100 and 300 C. In all other cases ranges from 0.76 to 6.42. Therefore the use of both Eqs. (10) and (11) is not justified at least for these latter cases. Moreover these values of qt are considerably lower than the values of trap energy positions in the SiO2 film established by measurements other than I V ones [13 15]. For these other measurements qt values are in the range 1.82.8 eV. Therefore, one can reach to a conclusion that charge carrier tunnelling via deep levels in these SiO2 films is not the FowlerNordheim-type emission described by Eqs. (10) and (11). Another possibility for trap-assisted tunnelling is inter-trap tunnelling. In this case one has to use Eq. (9) for analysis of the tunnelling current. The plots of the natural logarithm of the current density, exp measured at 77 K and room temperature, as a function of (V Vfb ) for the D1 sample treated in plasma exp at 300 C are shown in Fig. 4. As is seen, at applied voltages larger than Vfb the slope of the plot of ln(J) exp 1 versus (V Vfb ) is constant. This slope is 0.538 and 0.398 V for 77 and 300 K measurements, respecexp tively. Also, extrapolating the curve to the intersection with the ln(J) axis at (V Vfb ) = 0 the ln(J0) 2 value is obtained. The values of J0 are 0.51 and 0.413 A cm for 77 and 300 K measurements, respectively. Then one may evaluate the distance between the nearest traps, w, and the trap position in the SiO2
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2974
4 2 0 -2
300K 77K

S. Simeonov et al.: Inter-trap tunnelling in thin SiO2 films Fig. 4 Plot of ln(J) versus (V Vfbexp) of measured current density at 77 and 300 K of D1 p-Si/SiO2 structure treated in hydrogen plasma at 300 C.

ln [J(Acm )]

-4 -6 -8 -10 -12 -14 -16 -2 -1 0 1 2 3 4 5 6 7 8 9 10

(V - VFB)(V)

energy gap, q t, by comparing the value of this slope and that of J0 with the corresponding values of the slope and J0 in Eq. (9) for inter-trap tunnelling, which are equal to
(2 m q )1/ 2 w 2 E t1/ 2

and
q 2(2 m q )1/ 2 t1/ 2 w 1 exp , 2 w

respectively. For an estimation of the order of magnitude of the attempt to escape frequency, , Mott proposed a relation h = kT where T is the Debye temperature [16]. With a Debye temperature of 552 K [17] the estimated value for in SiO2 is 1.15 1013 s1. The frequency of dominant phonons in SiO2 at 100 K estimated from Fig. 9 of [17] is = 1013 s1. In our calculations the value of = 1013 s1 will be used. The inter-trap tunnelling current density given by Eq. (9) depends exponentially on q t and w and it is proportional to . Because of this if = 1013 s1 is replaced by = 1012 s1 the calculated value for q t decreases by 15%, while the value for w decreases by 4%. If = 1013 s1 is replaced by = 1014 s1 the calculated value for q t increases by 15%, while the value for w increases by 4%. This means that one needs only the order of magnitude of the attempt to escape frequency to evaluate the values of w and q t. The effective electron mass in SiO2 is taken as m* = 0.5me. From the I V measurements at 77 K of the D1 sample treated at 300 C the values of w and qt are 1.73 107 cm and 2.18 eV, respectively. From the room temperature measurements of the same sample these values are w = 1.57 107 cm and qt = 2.74 eV, respectively. Using these values of q t and w one may estimate the error of replacement of Pd(q t) in Eq. (1b) with Pd(q t*) where q t* = F. It is smaller than 1 2% for q t in the range F 4kTeff < q t < F + 4kTeff where 96.5% of total inter-trap tunnelling current flows. The results for Pup are similar. Using the same
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

-2

phys. stat. sol. (a) 201, No. 13 (2004) / www.pss-a.com

2975

the errors are similar but for D6 samples they are smaller. Therefore, one can use Eq. (9) for analysis of the tunnelling currents in D1 and D6 samples. The values of the slope in these plots for applied voltages corresponding to the accumulation mode show that the hyperbolic sine function can be replaced by the exponential function. This means that practically all electrons trapped at deep levels always tunnel in the direction where the electrical field decreases the electron energy barriers. Therefore in these circumstances one can neglect the Pup term in relation to the Pd one for these values of applied voltage. The distance w has the meaning of the mean value of the inter-trap distance and it does not depend on the electrical field direction. Because of this w values used for calculation of Pd and Pup as shown in Fig. 1 are taken as equal to one another. In Table 3 the values of the energy depth, qt, and the distance, w, for samples from D1 and D6 sets are summarized. As is seen, the values of q t are in the range 1.53.9 eV for both D1 and D6 sets. With these values of q t and w the mean values of the parameter
= E 2(2 m q ) ( t Ex )3 / 2
1/ 2

are from 3.8 103 to 0.044. As all values of are many times smaller than 1 this means that the WKB approximation is valid for analysis of the inter-trap tunnelling in these MOS structures. For a given sample, the observed difference of the values of q t by several tenths of eV is due to the uncertainties of I V measurements and the change of the position of the quasi-Fermi level in the SiO2 layer with changing temperature. These values of qt are in the same range as the broad bands of defects at 1.82 and 2.25 eV observed by electroluminescence in SiO2 layers [13]. They are also in the range of deep levels at 2.7 2.8 eV by which two-step TAT takes place in 5 nm thick SiO2 layers [14] and deep levels at 2.1 eV, established by noise measurements of SILC currents in 5 nm thick SiO2 layers [15].
Table 3 The energy depth, qt, and the distance, w, of traps in the SiO2 energy gap, obtained with values of m = 0.5me and = 1013 s1 for samples of the D1 and D6 sets.

sample

D1 set at 77 K w (cm) q t (eV) 3.53 1.95 2.35 2.18 Nt (cm3) 3.29 1020 1.77 1020 1.83 1020 1.93 1020 at 300 K w (cm) 1.38 107 1.81 107 1.82 107 1.57 107 q t (eV) 3.71 2.17 2.37 2.74 Nt (cm3) 3.79 1020 1.69 1020 1.66 1020 2.57 1020

reference treated in plasma at 20 C treated in plasma at 100 C treated in plasma at 300 C sample reference treated in plasma at 20 C treated in plasma at 100 C treated in plasma at 300 C

1.45 107 1.78 107 1.76 107 1.73 107 D6 set 2.08 107 1.75 107 1.28 107 1.82 107

1.55 1.84 3.02 1.90

1.11 1020 1.86 1020 4.8 1020 1.65 1020

1.99 107 1.63 107 1.19 107 1.80 107

1.59 2.35 3.9 1.9

1.26 1020 2.30 1020 5.93 1020 1.71 1020

2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2976

S. Simeonov et al.: Inter-trap tunnelling in thin SiO2 films

Using the values of inter-trap distance, w, one may evaluate the density of traps, Nt, by which the tunnelling takes place (Nt 1/w3). The calculated values of Nt are in the range 1.1 1020 2.45 1020 cm3 and are also presented in Table 3. The values of Nt for the D6 reference sample are the smallest. Observation of tunnelling currents even in the reference samples, without any plasma treatment, means that traps are initially present in the oxides and they are responsible for the appearance of inter-trap tunnelling. However, the concentration of these traps in reference samples is lower in relation to the trap concentration in plasma-treated samples. This result is analogous to the observation of TAT even in virgin SiO2 layers without electrical stress [4]. The values of Nt obtained for D1 and D6 samples plasma treated at 300 C are higher than the corresponding reference sample values. The comparison of the Nt values with the Nox values of the corresponding samples shows that the lowest values of Nt and Nox are observed in the reference samples. The values of Nt and Nox in samples treated in plasma at 300 C are higher than in the reference samples but smaller than those for samples treated in plasma at 20 and 100 C. The highest values of Nox are observed in samples treated at 20 C, while the highest values of Nt are observed in samples treated at 100 C. This shows that traps different from traps connected to the fixed oxide charges are responsible for inter-trap tunnelling. The concentration of Nox is in the range 6.6 10164.4 1018 cm3 in these SiO2 layers. This concentration is smaller than the Nt concentration, which is in the range 1.1 1020 2.45 1020 cm3. It is known that Nox is a superposition of positively and negatively charged defects in SiO2 layers [18]. Tunnelling via neutral traps unoccupied by electrons is also possible, as is suggested in Ref. [1]. Therefore, the concentration of Nt can exceed the concentration of Nox as these concentrations are related to different properties of SiO2 layers. Trap concentrations of the order of 3 1019 1020 cm3 are considered for analysis of the temperature-dependent SILC in 10 nm SiO2 layers [19]. Trap concentrations of the order of 3 1019 7 1019 cm3 are used for modelling of trap-assisted inelastic tunnelling in MOS structures [15]. These trap concentrations are of the same order of magnitude as the values of Nt obtained from the analysis of the tunnelling-type I V characteristics of the studied p-Si/SiO2 structures. Therefore, both quantities, the trap energy positions in SiO2 energy gap q t and the trap concentrations Nt obtained from the inter-trap tunnelling dependence of I V characteristics, are consistent with the corresponding investigations of other Si/SiO2 structures. This consistency leads to the conclusion that the inter-trap tunnelling is the real conduction mechanism in the investigated p-Si/SiO2 structures. One may also notice that Eq. (9) is similar to the so-called Poole law for inter-trap conduction in the case of thermally activated electron emission from insulator traps (see Ref. [19] and references therein). In this law ln(J) is also a linear function of applied electrical field E, as it is in Eq. (9). However, the relationships connecting ln(J) with w and q t and Eq. (7) are different because the charge carrier transfer from an occupied trap to next-nearest unoccupied one is thermally activated in the Poole law and it is of tunnelling type in the case of Eq. (9). The measured I V characteristics at 77 and 300 K do not depend on the temperature. This means that the effective temperature of electrons in traps in SiO2 under these electrical fields is not equal to the lattice temperature and it is at least equal or greater than 300 K. Because of this it is not possible to estimate the energy distribution of traps responsible for inter-trap tunnelling, D( F), from their concentration, Nt, by the relation Nt = D( F)kTeff used in Eq. (1c). Defects in SiO2 films generate broad trap bands and because of this the values of the trap energy position q t discussed so far have a meaning of the energy position of traps which dominate in the particular tunnelling process. Because of this it is interesting to estimate the energy distribution of traps, N, responsible for tunnelling in D1 and D6 SiO2 films. In these circumstances N is equal to 1/w3qEw as qEw eV is the energy position of the next-nearest trap to which the electrical field makes possible the electron tunnelling. With the values of w and E in these D1 and D6 SiO2 films N is in the range 2.2 1020 7.15 1020 cm3 eV1. Similar or even higher energy densities of states are reported for amorphous materials (e.g. see [20] where the values of N are in the range 6.37 1021 1.28 1022 cm3 eV1 for V2O5 B2O3 BaO glasses).
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

phys. stat. sol. (a) 201, No. 13 (2004) / www.pss-a.com

2977

Tunnelling currents in other insulator films

For a further check of the inter-trap approach to the tunnelling currents in some SiO2, SiO and other insulator films, their I V characteristics given in Refs. [2, 21 27] have been analysed with Eq. (9) in the same way as is described in Section 3.3 for the tunnelling currents in p-Si/SiO2 structures treated in hydrogen plasma. In [21] the I V characteristics of 380 nm SiO layer measured at 4.2 and 77 K have been reported. These characteristics are very close to each other suggesting that in this SiO film at these temperatures a conduction of tunnelling type takes place. Assuming that the inter-trap electron tunnelling is the real charge transport mechanism, from the 4.2 K I V measurements by Eq. (9) one may obtain an energy position of q t = 1.8 eV and a concentration of Nt = 6.7 1018 cm3 for traps responsible for tunnelling in this SiO film. The same values obtained from 77 K measurements are 1.79 eV and 7.26 1018 cm3, respectively. Similar I V characteristics of 410 nm SiO film have also been reported [22]. In this case from the 4.2 K I V measurements the values of q t = 1.9 eV and Nt = 1.38 1019 cm3 are calculated. These values obtained from the 77 K measurements are 1.83 eV and 1.22 1019 cm3, respectively. In [2] it has been shown that in 300 nm SiO2 films after a 100 200 keV Ge implantation with a dose of (1.5 1.8) 1016 cm2 the current does not depend on temperature in the range 25 150 C for applied electrical field in the range (2 4.5) MV cm1. Using Eq. (7) the calculated q t and w values for this tunnelling-type current are 3.16 eV and 2.91 107 cm, respectively. The corresponding value of Nt is 4 1019 cm3. In [23] a weak temperature dependence of the gate leakage currents of 11.5 nm thick nitrided oxide and re-oxidized nitrided oxide in the 300 400 K temperature range is also reported. For electrical fields above 4.5 MV cm1, applying Eq. (7) the estimated values of qt and w are 3.11 eV and 2.17 107 cm for nitrided oxide, 3.17 eV and 2.18 107 cm for re-oxidized nitrided oxide and 3.32 eV and 2.33 107 cm for nitrided oxides annealed in nitrogen. The corresponding trap concentrations are 9.78 1019, 9.64 1019 and 7.89 1019 cm3, respectively. In many present day MOS structures the thickness of the SiO2 layer is of the order of several nanometres and, therefore, trap-assisted tunnelling exists in these SiO2 layers. In these cases the charge carriers from the metal or the semiconductor tunnel firstly to a trap in the SiO2 layer and then to the semiconductor or the metal. Although Eq. (9) is obtained for the case of inter-trap tunnelling, the probability factors (exponential terms) for the inter-trap tunnelling in an insulator and the tunnelling from an insulator trap to either metal or semiconductor bands are essentially the same. The corresponding I V expressions differ only by the pre-exponential terms in them. Therefore, Eq. (9), valid for inter-trap tunnelling, can be also applied for evaluation of energy position and concentration of traps in such MOS structures. A weak temperature dependence of the gate leakage currents in 3 nm SiO2 films of an MOS capacitor in the accumulation mode in the temperature range 50 300 K has been observed [24]. From these I V characteristics at gate voltages greater than 2 V using Eq. (9) the values of q t = 2.8 eV, w = 2.42 107 cm and Nt 7 1019 cm3 are estimated. If the stress-induced leakage current in MOS structures with 4.5, 7 and 12 nm SiO2 layers in Fig. 11 of [25] is re-plotted using Eq. (9) one may obtain q t and w values. These are 5.9, 4.5 and 3.1 eV and 2.25 107, 2.9 107 and 4.09 107 cm for 4.5, 7 and 12 nm SiO2 layers, respectively. Further we show the applicability of Eq. (9) for TAT currents in the case when it is possible to estimate the inter-trap distance, w, independently. From the observed TAT given in Fig. 11 of [26] it is deduced that w is less than 5 nm but greater than 3.5 nm. Using Eq. (9) one may re-plot TAT for 5, 7 and 10 nm SiO2 films. The values obtained for q t and w are 4.58 eV and 2.7 107 cm, 4.55 eV and 3.02 107 cm and 4.9 eV and 3.06 107 cm, respectively. The most reliable values are for 10 nm SiO2 films because in this case the inter-trap tunnelling is an indispensable step in the whole tunnelling charge transfer. Therefore, the value obtained of w = 3.06 107 cm is close to the independently estimated value of w, 3.5 nm < w < 5 nm. This comparison is another example that Eq. (9) is reliable for calculation of the energy position and concentration of traps in insulators in which inter-trap tunnelling or TAT take place.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2978

S. Simeonov et al.: Inter-trap tunnelling in thin SiO2 films

In AlN/GaN heterostructures with 6 nm AlN insulating film the observed currents in accumulation mode are 1013 1017 times higher than the tunnelling currents calculated without taking into account the trap-assisted tunnelling [27]. If one assumes that the observed current is of tunnelling type then using Eq. (9) the values of q t and w are 0.973 eV and 3.144 107 cm, respectively, and the corresponding trap density is 3.21 1019 cm3. From the above considerations the usefulness of Eq. (9) is clearly demonstrated. The possibility of using Eq. (9) will give a quick and straightforward opportunity for an estimation of the concentration of traps in insulator films under the conditions where tunnelling currents prevail. The estimated trap densities could be beneficial for the comparison of different preparation methods of new insulator layers, for example high-permittivity insulator films on SiO2.

Conclusion

An expression for the currentvoltage characteristics in insulators for the case of inter-trap tunnelling, Eq. (9), has been presented. This expression gives an opportunity to estimate the energy position and concentration of traps by which the inter-trap tunnelling takes place. It is used to analyse TAT currents in p-Si/SiO2 structures subjected to hydrogen plasma treatment, and in other SiO2 and other insulator films. The thickness of these films and current densities in them are very different. Nevertheless the values of energy position in SiO2 can be estimated using this expression for currentvoltage dependence for intertrap tunnelling. The energy gap and concentration of traps in the SiO2 films are in the range 1.5 3.9 eV and 6 1018 2.14 1020 cm3, respectively, for oxide thickness changing from 3 to 410 nm in D1 and D6 samples and some other SiO2 layers where TAT is observed. These results show that the inter-trap tunnelling can account for tunnelling-type currents in SiO2 and some other insulator films. The obtained values of energy position and concentration of traps are consistent with the same values estimated by other methods in similar SiO2 films. Therefore the inter-trap tunnelling is a more suitable mechanism than the FowlerNordheim trap emission for explaining TAT in SiO2 and some other insulator films. The obtained values of energy position and concentration of traps in these films, especially the concentration of traps responsible for inter-trap tunnelling, can be used in the development of preparation methods for contemporary semiconductor technology.

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] D. J. Di Maria and J. Cartier, J. Appl. Phys. 78, 3883 (1995). J. Zhao et al., Solid State Electron. 46, 66 (2002). B. J. Cho et al., Solid State Electron. 44, 1289 (2000). A. Ghetti, Microelectron. Eng. 59, 127 (2001). S. Simeonov et al., Vacuum 61, 199 (2001). A. R. Reinberg, Electrochemical Society Meeting, San Francisco, US patent 3 757 733 (1974). P. V. Gray and D. M. Brown, Appl. Phys. Lett. 8, 31 (1966). L. Esaki, Phys. Rev. 109, 603 (1958). J. Maserjian and N. Zamani, J. Appl. Phys. 53, 559 (1982). D. Goguenheim et al., Solid State Electron. 45, 1355 (2001). Y. L. Chiou et al., Solid State Electron. 45, 1787 (2001). W. J. Chang et al., Semicond. Sci. Technol. 16, 961 (2001). C. G. Quin et al., J. Phys.: Condens. Matter 13, 11751 (2001). F. Jimenes-Molinos et al. J. Appl. Phys 90, 3396 (2001). K. Komiya and O. Yasuhisa, J. Appl. Phys. 92, 2593 (2002). N. F. Mott and R. S. Allgaier, phys. stat. sol. 21, 343 (1967). R. C. Zeller and R. O. Pohe, Phys. Rev. B 4, 2029 (1971). M. Pepper, Proc. R. Soc. A 353, 225 (1977). B. De Salvo et al., Solid State Electron. 44, 895 (2000). M. M. El-Desoky, phys. stat. sol. (a) 195, 422 (2003). A. Servini and A. K. Jonscher, Thin Solid Films 3, 341 (1969).

2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

phys. stat. sol. (a) 201, No. 13 (2004) / www.pss-a.com [22] [23] [24] [25] [26] [27] N. Klein and Z. Lisak, Proc. IEEE 54, 979 (1966). S. Fleisher et al., J. Appl. Phys. 73, 8354 (1993). A. P. Jacobs et al., Semicond. Sci. Technol. 17, 942 (2002). D. Vuillaune et al., Microelectron. Reliab. 38, 7 (1998). G. Ghibaudo et al., C. R. Acad. Sci. Paris 1, Serie 4, 911 (2000). S. Imanaga et al., Jpn. J. Appl. Phys. 40, 1194 (2001).

2979

2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim