Similar admittance behavior of amorphous silicon carbide and nitride dielectrics within the MIS structure

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Vacuum 82 (2008) 566–573 www.elsevier.com/locate/vacuum

Similar admittance behavior of amorphous silicon carbide and nitride dielectrics within the MIS structure Orhan O¨zdemira,, I˙smail Atılganb, Bayram Katırcıogˇlub Physics Department, Yildiz Technical University, Esenler, I˙stanbul, Turkey Physics Department, Middle East Technical University, Balgat, Ankara, Turkey a

b

Received 8 April 2007; received in revised form 1 July 2007; accepted 19 August 2007

Abstract PECVD grown a-SiNx:H and a-SiCx:H films were investigated as dielectric films in the form of metal/insulator/p-silicon (MIS) structures. AC admittance of MIS structures was measured as a function of dc gate bias voltages and frequencies (1–1000 kHz) of the superimposed ac bias voltage (10 mV). For each applied bias voltage (from accumulating to inverting bias regimes), temperature (T) dependence of both capacitance (C) and conductance ðG=oÞ were measured to investigate majority/minority carrier behavior under various frequencies o (kHz-MHz) as parameters. C and G=o  T  o measurements reveal that observed pairs of capacitance steps and conductance peaks are related to traps lying on the same energy value, residing in the insulator and at the interface of insulator/ semiconductor structure and differing only through capture cross-sections. On the other hand, surface band bending ðcs Þ of silicon and activation energy (EA) deduced from the Arrhenius plot of the frequency vs. reciprocal temperature as a function of gate bias (VG) seem linearly dependent, implying that EA reflects the cs variation. r 2007 Elsevier Ltd. All rights reserved. Keywords: a-SiCx:H; a-SiNx:H; MIS; PECVD; Capacitance (conductance) steps; Temperature; Surface band bending

1. Introduction Apart from passivation layers of IC devices and protective coating in electronic packaging[1,2], amorphous hydrogenated silicon (a-Si:H) alloyed with nitrogen (N) and carbon (C) is of considerable interest, especially for a dielectric film in a thin film transistor (TFT) which is constitued by a-Si:H as the semiconductor and a-SiNx:H as a dielectric. TFT are mostly utilized as switching devices for large area liquid crystal displays (LCD) and image sensing arrays. Recently, investigations of these two materials keep going in order to adapt the TFT on flexible plastic substrates and organic light emitting diodes (OLED) by (i) lowering deposition temperature (to less than 200 1C) [3] and (ii) forming a-Si:H micro and/or nanocrystals via excimer laser crystallization [4] and microwave plasma chemical vapor deposition (ECR) [5] to enhance the mobility. Corresponding author. Tel.: +90 212 449 1864; fax: +90 212 449 1514.

E-mail address: [email protected] (O. O¨zdemir). 0042-207X/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.vacuum.2007.08.006

On the other hand, image sensing elements ( ¼ pixels) in optical sensors can take the form of a p–i–n diode component (with low leakage current compared to Schottky type diode) and a switching component (i.e., TFT transistor). Therefore, p-i-n structure (intrinsic semiconductor sandwiched between doped layers) seems an acceptible candidate for an imaging system. Hence, hydrogenated amorphous silicon carbide (a-SiCx:H) thin films grown by plasma enhanced chemical vapor deposition (PECVD) in p–i–n form has become a promising material for visible light emitting/sensing devices [6]. Obviously, bringing two amorphous layers together (i.e., a-SiNx:H/a-Si:H or p-a-SiCx:H/i-a-SiCx:H) will complicate characterizations of the resultant structure, such as low field effect mobility, high density of states (DOS) that yields charge trapping and causing the shifts in ON/OFF (threshold) voltage of TFT and flat band voltage in MIS (abbreviation of metal-insulator-semiconductor) structures [7,8]. Therefore, in order to avoid ambiguity between two amorphous materials, a single a-SiNx:H and a-SiCx:H film alone might be deposited on c-Si to find out

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Table 1 Growth conditions of a-SiNx:H and a-SiCx:H films Sample

Pressure (Torr)

Subs.temp. (C)

SiH4 (ccm)

NH3 (ccm)

C2H4 (ccm)

RF power (mW cm2)

a-SiNx:H a-SiCx:H

0.3 0.1

300 250

3 30

36 –

– 30

45 60

5000 100 B

100 Cr/a-SiNx:H/p-Si structrue

dielectric film substrate

80

80

60

60

40

40

20

20

Capacitance (pF)

Film Thickness (Å)

a-SiNx:H 3000

2000 a-SiCx:H 1000

Conductance/frerquency (pF)

A

4000

C

D

Frequency = 5 kHz T = 300 K

0

100000

200000 600000 650000 Scanned Region (nm)

-20

700000

Fig. 1. Thickness measurements of a-SiNx:H and a-SiCx:H films determined by Ambios XP2 profilometer. Several runs performed (denoted as A, B, C, D path in the inset) on a-SiNx:H and a-SiCx:H films, and the closest profiles to the dot of admittance measurements are picked for each film.

2. Experimental 2.1. Sample preparation Both a-SiNx:H and a-SiCx:H films were deposited on 12–18 O cm (1 0 0) oriented p-type silicon substrate after following standard RCA cleaning procedure by PECVD system at hand. The growth parameters were given in Table 1. MIS structures were obtained by e-beam coated

-14

-16

-10

-12

-8

-6

0 -4

Cr/a-SiCx:H/p-Si structure

600

Capacitance (pF)

the film properties and interface related problems. Besides, exploration of a-SiNx:H(a-SiCx:H)/c-Si interface might contribute to solar cell technology [1]. MIS structure together with admittance spectroscopy is a suitable tool to study the electronic properties of a-SiNx:H and a-SiCx:H films. In this work, the ac admittance of MIS structures was measured in the frequency range of 1–1000 kHz. For each applied bias (from accumulating to inverting biases), the temperature of both capacitance (C) and conductance (T) dependence  G=o was determined to investigate majority/minority carrier behavior under the various frequencies o (kHz–MHz) as parameters in the C; G=o  T  o measurements.

-18

600

400

400

200

200

Conductance/frequency (pF)

0

0

Frequency = 5kHz T = 300 K

0 -6

-5

-4

-3

-1

-2 0 Gate Bias (V)

1

2

3

0

Fig. 2. Admittance as a function of gate bias on (a) Cr/a-SiNx:H/p-cryst. Si and (b) Cr/a-SiCx:H/p-cryst. Si MIS structures at room temperature with 5 kHz as measuring frequency.

cromium electrode through a shadow mask of diameter 0.11 and 0.14 cm on a-SiNx:H and a-SiCx:H films, respectively. Hereafter, films will be denoted in the text as sample A and B for Cr/a-SiNx:H/p-Si and Cr/a-SiCx:H/ p-Si structures, respectively. Thickness (dI) of a-SiNx:H and a-SiCx:H films were determined through an Ambios XP2 profilometer that

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By this way, n was calculated as 1.89 and 2.15 and consistent with ones measured with UV-visible transmittance and ellipsometry results for a-SiNx:H and a-SiCx:H films, respectively [10–12]. Moreover, energy gap of the films (EG) by means of UV-visible transmittance were found to be 5.0 and 2.67 eV, respectively.

necessitates a step within the film on the substrate. For this reason, firstly, a-SiNx:H and a-SiCx:H films were partly coated with photoresist and then baked at 90 1C for 30 min. Secondly, uncovered portions of a-SiNx:H and a-SiCx:H films were removed by wet and dry etching (plasma etching), respectively. Wet etching was obtained by HF/H2O (1:5 volume ratio) solution, whereas 10% O2 in CF4 gas was used for plasma etching with 150 W RF power at a pressure of 0.1 Torr for 4 min. Finally, photoresist layer on the films was removed with acetone and then films were cleaned in isopropil alcohol. Then, thickness measurements of the films were performed with several runs on distinct paths (A, B, C, D). The closest profiles to the dot of admittance measurements for a-SiNx:H and a-SiCx:H films are illustrated in Fig. 1. The thicknesses of the films used in this work are determined to be 334 and 126 nm for a-SiNx:H and a-SiCx:H, respectively. Then, the obtained results were used pffiffi to determine index (or permittivity of the films via n   ) through the highest frequency capacitance–voltage curve at accumulation mode C¼

A , dI

2.2. Measurement procedure The computer controlled admittance spectroscopy system consists of impedance analyzer (HP4192A) and a helium closed cycle cryostat (Material Research System CSW-202S) with a temperature control unit (Lakeshore 331) used to record admittance versus temperature scans at different constant gate biases under kHz–MHz frequency range. Initially the room temperature C(G/o)-VG characteristics (depicted in Fig. 2) for a-SiNx:H and a-SiCx:H films were measured to define the biases that drive the MIS capacitor to accumulation, inversion, and depletion regimes. Then, for each selected bias (corresponding to mentioned regimes in MIS), a temperature scan was performed at various measuring frequencies (from 1 kHz to 1 MHz). During the scan, temperature is initially set at a

(1)

with A ¼ area of electrode.

600 VG = -5 V

-3.5

-1.5

VG -15 V

-11

-10

-8

-13

β α

40

Capacitance (pF)

Capacitance (pF)

80

400

β 1.5

200 α

0

0

16

12000

Conductance /frequency (pF)

Conductance / frequecny (pF)

Frequency = 30 kHz Cr/a-SiNx:H/p-cryst.Si

β 8

Frequency = 10 kHz Cr/a-SiCx:H/p-cryst.Si

β

8000

4000 α

0

0 0

100

200 300 Temperature (K)

400

70

170 270 Temperature (K)

370

Fig. 3. Representative set of admittance (capacitance together with conductance/frequency) versus temperature scans are given under constant frequency with applied gate bias as parameters on: (a,b) a-SiNx:H, (c,d) a-SiCx:H film based MIS structure, respectively.

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high temperature and lowered by 2 K between frequency scans under predetermined gate biases, corresponding to the onset of accumulation, near flatband and weak inversion regimes of MIS structure. For a-SiNx:H/p-Si structure, as illustrated in Fig. 2a, gate biases of 15 and 13 V correspond to the onset of accumulation, 11 V is near flatband, 10 V is in depletion region and finally 8 V is used for the weak inversion regime. Similarly, for a-SiCx:H/p-Si structure, 5 V is for the onset of accumulation, 3.5 V is near flatband, 1.5 and +1.5 V are used for inversion region (see Fig. 2b). Here, frequency scans for the mentioned films vary between 0.5 kHz and 1 MHz. For sample B, a slightly narrow temperature interval (77–370 K) is used owing to usage of a N2 bath cryostat. This tedious and time consuming process explained above was accomplished by a computer controlled LABVIEW program. As a result, frequency and temperature scans of admittance (C and G/o) of MIS structures are obtained at various gate biases.

Temperature dependence of admittance measurements (Cm and Gm/o) under predetermined dc gate biases and small amplitude ac excitation frequencies of 30 and 10 kHz for the sample A and B are illustrated in Fig. 3a,b and c,d, respectively. First of all, at the low T side, a sharp bias independent decrease in Cm and corresponding peak in Gm/o are clearly seen around 30 K for sample A. This effect might be a consequence of freezing out of the extrinsic carriers in p-type c-Si. Therefore, the substrate behaves as a dielectric below this temperature. The second step, called a around 200 K appears due to the freeze out of inversion charges. Below this temperature, deep depletion effect in c-Si is dominant for samples A and B and manifests itself as voltage dependent behavior of capacitance. Deep depletion effect vanishes for accumulating gate biases as expected (see Fig. 3a). The third step called b is thought to be caused by percolation of charges

600

1kHz 5 30 100 500 1000

60

Cr/a-SiCx:H/p-cryst.Si MIS structure at -3.5 V Frequency

Capacitance (pF)

Capacitance (pF)

3. Results

Cr/a-SiNx:H /p-cryst.Si MIS structure at -10 V Frequency

80

569

β

40 α

0.5 kHz 1 5 10 100

400

β

200

20 α 0

0 16

Conductance /frequenc (pF)

Conductance /frequency (pF)

β β

8

1500 x 1/500

1000

500 α

x 1/5

0

0 0

100

200 300 Temperature (K)

400

70

170 270 Temperature (K)

Fig. 4. Capacitance together with conductance/frequency versus temperature curves at different measuring frequencies (kHz–MHz) under constant gate bias (10 V)on Cr/a-SiNx:H/p-cryst.Si MIS structure in a and b. Similarly, (c,d) reports the same analysis for Cr/a-SiCx:H/p-cryst.Si MIS stucture at 3.5 V. Note that different temperature regimes with two steps in capacitance together with corresponding conductance peaks (the main and secondary ones denoted as a and b, respectively) appear as temperature increases. Also note that the conductivity of c-si substrate near 30 K is freezing out.

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accumulated at the interface into a-SiNx:H and a-SiCx:H films. Since both kind of charges (majority and minority charges) can be injected into the films and keep going by hopping mechanism [7,9,11]. Therefore, this step is observed for all applied bias regimes. The mechanisms behind the mentioned steps are investigated through frequency dependence; examples for sample A and B are given in Fig. 4a,b and c,d at the gate biases of 10 V and 3.5 V respectively, corresponding to depletion regime. The above mentioned first type distinct temperature regime appears at low temperatures in admittancetemperature scan on the investigated films. As seen in Fig. 4a, b, the conductivity of c-Si substrate near 30 K is frozen out where Cm goes to zero whereas Gm/o passes by a peak. The Arrhenius plot of the frequency versus the inverse temperature (deduced from either the peak position of Gm/o or the middle of capacitance steps) is illustrated in Fig. 5 and the activation energy (EA) of acceptor dopants was determined as 50 meV at 13 V gate bias, in agreement with the boron energy level in p-type Si [13]. Increasing temperature allows the observation of Cm that exhibits a plateau and corresponds to two capacitors in series; one corresponding to the a-SiNx:H (and/or a-SiCx:H) layer together with the capacitance, CD, associated with the width of the depletion region, dD, extending into the c-Si substrate. Since the investigated films are not conducting, in this temperature interval, barrier potential at the c-Si side of the interface, cs , could be determined from thelow  temperature capacitance plateau via cs ¼ qN A d 2D =2s . In this manner, the extracted cs plotted against VG and linear variation was observed, as depicted in Fig. 6a.

Cr/a-SiNx:H/p-cryst.Si

Frequency (kHz)

1000

100

EA =50 meV VG = -13 V

10 28

32

36

40

44

48

1000 /T(K-1) Fig. 5. Arrhenius plot of the frequency versus inverse temperature to determine activation energy (EA) of acceptor dopants. Note that EA was determined as 50 meV; in agreement with the boron energy level in p-type Si, deduced from the peak position of conductance/frequency.

A second temperature regime where frequency dependent b step of Cm as well as Gm/o peaks are distinguished in the temperature range of 200–400 K for sample A (see Fig. 4a,b). On the other hand, for sample B, within 100–200 and 200–300 K temperature intervals, corresponding a and b steps appear, as shown in Fig. 4c,d. These temperature activated processes are Arrhenius type (see Fig. 6b,c). The remarkable point is that the activation energies EA, deduced from the steps a and b in capacitance for sample B, remain at the same energy values but appear at different temperature interval in C–T curve, as shown in Fig. 6c. Also note that as applied gate biases increases towards positive values, so does EA. In addition, it is worth noting that calculated barrier potential and activation energies deduced from the capacitance steps are nearly equal in magnitude, suggesting EA reflects the band bending variation [9]. As a last remarkable point, at a temperature range following the b step, nearly frequency independent (dependent) capacitance plateau arises for a-SiNx:H (a-SiCx:H) film and designates the film geometric capacitances at high frequency. 4. Discussion The variations of Cm and Gm/o as a function of VG were performed at room temperature on sample A and B at 5 kHz and depicted in Fig. 2. Similar to C; G=o  T  o measurement, the Cm-VG curves exhibit a main step (a) together with relevant Gm/o peaks apart from a smaller one (b step) appearing at the negative voltage side at room temperature. Besides, following b steps, the maximum capacitances reflect the film geometric capacitances at high frequency in accumulating gate biases (discussed in Section 1 and see the Relation (1)). On the other hand, for inverting  gate biases, the lowest measured capacitance, C; G=o  T  o and C–V curves are constituted by film and depletion capacitances, connected in series. Recall that the capacitance is inversely proportional to the first moment of charge variation induced by gate bias modulation dQ (depicted in Fig. 7) and could be expressed by [9] Z 1 Z 1  hxidQ dx= C¼ where hxi ¼ dQ dx, (2) hx i 0 0 where gate bias modulation dQ is a combination of induced dQt ( ¼ injected charges in the film), dQss ( ¼ interface trap charges), dQA ( ¼ accumulated charges at the interface) and dQD ( ¼ charges at the edge of c-Si semiconductor), respectively. In other words, the measured capacitance, scanned either via gate bias or temperature as parameters would be inversely proportional to the weighted average distance of the ‘fictitous’ electrode to the gate electrode and could be related through following expression:   ðd I  xt ÞdQt þ dQss þ dQA d I þ dQD ðd I þ d D Þ hd i ¼ dQt þ dQss þ dQD þ dQA (3)

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1

Surface band bending (eV)

(a-SiNx:H)

0.8

0.6

0.4 (a-SiCx:H)

0.2 -16

-12

-8 Gate Bias (V)

-10 -11 Cr/a-SiNx:H/p-cryst.Si

0

Cr/a-SiCx:H/p-cryst.Si

VG = -13 (V)

1000

-4

100

EA (eV)

β

0.26 ~0.4 0.42 ~0.8 0.85

Frequency (kHz)

Frequency (kHz)

-8 100

10

10

-5

1

1 0.72

EA = 0.25 eV

0.51 0.43

VG = -1.5 V

0

α

-3.5

0 2

4

6

8

1000 /Temperature (K-1)

10

3

5

7

9

1000 /Temperature (K-1)

  Fig. 6. (a) Surface band bending variation, determined from the low temperature capacitance plateau via cs ¼ qN A d 2D =2s , as a function of applied gate biases for sample A and B, respectively. (b) Arrhenius plot of the frequency versus inverse temperature for the middle of b step at various gate biases for sample A. Note that EA increases with applied gate biases as it changes from accumulating type to inverting one.(c) EA deduced from a (filled symbol) and b (open symbols) steps in capacitance lies on the nearly same value, demonstrated through sample B.

with xt denoting the inverted/injected distance away from film/semiconductor interface. Within this frame, frequency dispersion observed in C–T scan at high temperature side could be imagined as additive contribution of dQt over the existent film capacitance rather than the series resistance effect [7,9–11]. That is, since modulation of dQt together with dQss is believed to be a slow process, reduced dQt under high measuring frequency (as illustrated in Fig. 7 for both accumulation and depletion regimes) leads to increase in hd i and overall, the lower measured capacitance would be observed. Equivalently, this phenomenon could   be interpreted with capture/emission time, t ¼ eqcs =kT : changing gate bias (temperature) toward accumulating bias regime (high temperature zone) leads to a decrease in cs , hence only

fast states could follow the ac modulation. Increasing the gate bias values towards positive side, the flat band voltage cs  0 is first reached and then the depleting gate bias regime starts. Further increase in gate bias induces the increase of cs (40) in turn widening the depletion width. This phenomenon appears as steps (a; b) in Cm and peaks in Gm/o These steps might be correlated as follows: first, the trapped holes in a-SiNx:H(a-SiCx:H) film hop or multi-tunnel toward interface states, then emitted from the interface states to the valance band edge of c-Si substrate. Analytically, this could be explained in terms of two characteristic times ta and tb : a release time ta of trapped charges from the interface states to the valance band edge by the well known Shockley–Read–Hall statistics (that is a single mechanism) and tb release time of trapped charges

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a

b a-SiCx:H a-SiNx:H

Al

a-SiCx:H a-SiNx:H

p-Si

p-Si Ec

Al

EF Ec

qVG

EF

Energy Band Diagrams

qVG

Ev

Ev ρ

ρ

Qss QA

Qt

x

Space Charge QG Distribution

qNA

QG

x

δQt

Low freq.

δQG

δQA x

High freq.

Qss

Modulated Charge

Modulated Charge

Qt

a.c. Charge Modulation

xt dI

δQG

High freq. Low freq.

δQt δQss xt dI

x δQD dD

Fig. 7. Schematic illustration of effective charge distribution in accumulation (a) and depletion (b) regimes under gate bias modulation.

Table 2 Comparison of activaiton energy obtained through C–T–o and DLTS measurements in this work and in Ref. [9] at depleting bias regime This work Ac conductance Activation energy (eV) a E0.4

b 0.42

Ref. [9] DLTS Ac conductance

DLTS

a –

a b E0.4 0.42

b –

a 0.42

b 0.43

within the film to the valance band edge via interface states (that is, a two step mechanism) [9]     1 ta ¼ sp nth pe exp qcs kT      2xt 1 tb ¼ sp nth pe exp  exp qcs =kT , l

ð4Þ

where pe is the free carrier concentration in c-Si, nth the thermal velocity of carriers, k Boltzman constant and l the localization length. In this work, the C–T–o measurement has carried out that EA (or cs ) was the same for a and b steps. This double appearance of the same activation energy along the temperature axis has been already

detected in Ref. [9]. The comparison is given in Table 2. The similarity is interpreted as follows: the duplication of capacitance steps might be in temperature is due to crosssection difference of traps located at the interface and deep inside the dielectric [10]. As for the single activation energy, it is interpreted as due to the surface band bending cs of silicon and its Fermi level location for both traps. 5. Conclusion The admittance measurements were performed as a function of temperature (from 400 to 25 K) under various frequencies and gate biases via MIS structure. Different temperature regions with two steps (the main and secondary ones denoted as a and b, respectively) in capacitance and corresponding peaks in conductance appear along the temperature interval of 30–400 K. The step a and b associated with interface trap around the fermi level and appearing at shifted along the reciprocal temperature. Arrhenius plot of the frequency versus the inverse temperature states that activation energies EA of both steps are almost the same and increase when gate bias changes from accumulating to inverting biases. Moreover, the band bending, determined from the low temperature  capacitance plateau via cs ¼ qN A d 2D =2s is the same as the corresponding with activation energy EA. In other

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words, linear dependence of activation energy EA on the applied gate bias implies that EA variations reflects cs variation along depletion biases. Acknowledgments This work was carried out with the financial support of both the Turkish Scientific and Technical Research Council (TUBITAK-TBAG-Project No. 104M195) and State Planning Organization (DPT Project No. DPT2002K120540-15). References [1] Vetter M, Martin I, Orpella A, Puigdollers J, Voz C, Alcubilla R. Thin Solid Films 2004;451–452:340–4. [2] Wang YH, Moityeree MR, Kumar R, Shen L, Zheng KY, Chai JW, et al. Thin Solid Films 2004;460:211–6.

573

[3] Sazonov A, McArthur C. J. Vac Sci Technol 2004;A22(5): 2052. [4] Han S-M, Lee M-C, Shin M-Y, Park J-H, Han M-K. Proc. IEEE 2005;93:1297. [5] Theng LH, Anderson WA. Solid State Electron 2004;48:309–14. [6] Kruongom D. Amorphous and microcrystaline semiconductor: optoelectronic devices. In: Kanicki J, editor. Artech House: London; 1991 [chapter 6]. [7] O¨zdemir O, Atılgan I˙, Katırcıogˇlu B. J Non-Crsyt Solids 2001; 296:27. [8] Fortunato G, Mariucci L, Reito C. Appl Phys Lett 1991;59:826. [9] Atılgan I˙, O¨zdemir O, Kaogˇlu B, Sel K, Katırcıogˇlu B. Philos Mag B 2006;86:2771. [10] Atılgan I˙, O¨zder S, O¨zdemir O, Katırcıogˇlu B. J Non-cryst Solids 1999;249:131. [11] O¨zdemir O, Atılgan I˙, Akaogˇlu B, Sel K, Katırcıogˇlu B. Thin Solid Films 2006;497:149. [12] Demichelis F, Crovini G, Giorgis F, Piri CF, Tresso E. JAP 1996; 79:1730. [13] Sze SM. Physics of semiconductor devices, vol. 2. New York: Wiley; 1981.